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Unraveling the Role of H2 and NH3 in the Amination of Isohexides over a Ru/C Catalyst
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Unraveling the Role of H2 and NH3 in the Amination of Isohexides over a Ru/C Catalyst
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ACS Sustainable Chemistry & Engineering

Cite this: ACS Sustainable Chem. Eng. 2023, 11, 22, 8229–8241
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https://doi.org/10.1021/acssuschemeng.2c07501
Published May 22, 2023

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Abstract

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The direct amination of biomass-derived isohexides with NH3 over a Ru/C catalyst was systematically investigated to understand the role of H2 and NH3 in the production of isohexide diamines vs aminoalcohols, i.e., the transformation of one or both OH-groups in isohexides into NH2 groups. Only aminoalcohols with an exo-OH group were generated starting from isosorbide, which contains both an exo-OH and an endo-OH group, while a moderate yield of diamines was obtained from isomannide with two endo-OH groups due to the higher reactivity of the latter. The main byproducts were identified, including a variety of N- and O-containing cyclic compounds, such as 2,5-dimethylpyrrolidine, that arise from a decomposition path driven by hydrolysis/hydrodeoxygenation of a tricyclic amine intermediate. By combining density functional theory calculations with microkinetics, NH3 was found to adsorb strongly on the catalyst surface and generate adsorbed NH2 and NH species with variable coverage depending on the temperature and the nominal H2/NH3 ratio. Isomerization of isohexides was greatly suppressed by adsorbed NH3. Meanwhile, adsorbed NH3 discouraged the formation of byproducts driven by competing side reactions promoted by H2. The H2/NH3 ratio, which conditions the distribution of NH2 and NH species on the Ru surface, influences drastically the catalytic performance.

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Synopsis

The amination of isohexides to diamines over Ru/C is affected by ammonia poisoning and formation of byproducts by hydrogenolysis.

Introduction

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Amines are essential building blocks in the chemical industry that are used as intermediates for the synthesis of polymers, surfactants, dyes, pharmaceuticals, and agrochemicals. (1,2) Traditionally, aromatic and aliphatic amines are industrially manufactured using synthetic routes encompassing petrochemical precursors. (3) However, the synthesis of value-added N-compounds from biomass has grown considerably, and more sustainable routes for transforming biobased platform molecules into useful amines have been sought. (4−10)
Isosorbide (IS) along with its isomers isomannide (IM) and isoidide (II), collectively referred to as isohexides, constitute a group of biobased platform chemicals that have gained interest as potential replacements to fossil-fuel-based products. (5,11,12) Isosorbide is produced at an industrial scale from polysaccharides. In particular, IS and its diamine derivatives show great interest in manufacturing biobased polymers such as polyurethanes, polymethacrylates, and polyamides. (8,13−15) The three isohexides differ in the relative configuration of the two secondary OH groups: IS has OH groups in opposite (endo-exo) orientations relative to the ring skeleton, while IM (endo–endo) and II (exo–exo) have OH groups pointing in the same direction relative to the ring skeleton (Scheme 1A). Unlike exo-OH groups, endo-OH groups are better positioned to engage in intramolecular hydrogen bonding with the oxygen atoms of the adjoining furan ring. (16−19) These structural differences lead to differences in the physicochemical properties and reactivity of isohexides. (19,20)

Scheme 1

Scheme 1. Products Obtained from the Direct Amination of Isohexides with NH3 over Ru/Ca
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a(A) isohexide isomers, (B) isohexide monoamines, and (C) isohexide diamines.

Diamines can be prepared from isohexides using poorly sustainable synthetic routes encompassing a large number of steps. The first studies reported the transformation of the OH groups of the isohexides into diamines with high yield and good stereocontrol by intermediate tosylation into good leaving groups. Montgomery, Bashford, and Wiggins prepared 2,5-ditosyl isosorbide and isomannide. Further treatment with NH3 in methanol at 170 °C for 30 h resulted in isosorbide and isomannide diamines with 60 and 80% yields, respectively. (21,22) Cope and Shen developed an alternative route encompassing nucleophilic substitution of 2,5-ditosyl isosorbide with potassium phthalimide in DMF via an SN2 mechanism, followed by deprotection with hydrazine hydrate. (19) This route is limited by the low overall yield (<4%) and the toxicity of hydrazine. Van Es and co-workers reported DMSO as a convenient solvent in the nucleophilic substitution step to avoid byproduct formation due to hydrolysis. (23) Besides, a mixture of HCl/glacial acetic acid was used instead of hydrazine, followed by treatment with basic ion exchange resin, leading to a 66% overall yield. Van Es and co-workers also reported benzylamine as an alternative to potassium phthalimide. (24) Further hydrogenolysis in ethanol of the as synthesized isohexide benzyldiamines over Pearlman’s catalyst [Pd(OH)2/C] resulted in isosorbide and isoidide diamines with 90% overall yield, together with an aziridine byproduct. Kuszmann and Medgyes reported the synthesis of isomannide diamines by IM conversion into bismesylates, followed by nucleophilic substitution with azide and hydrogenation. (25) Despite the high yield achieved (88%), this route is limited by the explosive behavior of azides, which discourages its application for large-scale diamine production.
As an alternative to the above routes, the synthesis of isohexide diamines by the direct amination of alcohols with NH3 is an attractive option since the reaction proceeds in a single step and water is generated as the main byproduct. The direct amination of isohexides is regarded to proceed via a hydrogenation–rehydrogenation pathway (i.e., H2-borrowing hydrogen). (26,27) This pathway, also at play in isohexide isomerization under H2, encompasses alcohol dehydrogenation over a catalyst to generate a ketone intermediate that undergoes condensation with NH3 to produce an imine. Subsequent hydrogenation of the imine with the stored H2 affords the amine product. The direct amination of isosorbide IS with NH3 to diamines was first described by Beller et al. using a Ru(CO)ClH(PPh3)3 complex combined with a Xantphos ligand. (4) The catalyst operated at 170 °C without exogenous H2, providing a mixture of diamines with 96% yield at full IS conversion. However, the product distribution was not reported. Vogt et al. reported the direct amination of isomannide IM to isohexide diamines using Ru3(CO)12 and PNP pincer-type ligands with 96% yield. (28) The molar ratio between diamino isosorbide, isoidide, and isomannide after the reaction was 47:38:16, which is similar to the thermodynamic ratio achieved between IS, II, and IM achieved after isomerization under H2 (i.e., 39:55:6). (29,30) A similar catalytic system was patented in 2014 for the catalytic amination of isohexides in organic solvents and with different PNP pincer-type ligands. (31) This system produced a distribution of aminoalcohol and diamine products with a 60:40 molar ratio. Recently, Popowycz and co-workers described the amination of IS and IM with benzylamine using an Ir complex and diphenylphosphate, followed by hydrogenation. (32) In this route, only endo-OH groups were reactive, and benzyldiamine products could be accessed from IM with 59% yield.
The synthesis of amines from isohexides has also been attempted using heterogeneous catalysts. The efforts to date have concentrated on the amination of isohexides with NH3 over Ru/C in water. (33,34) Unlike with ruthenium complexes, 4 aminoalcohols with different stereochemistry were obtained as main products (Scheme 1B), together with small amounts of diamines (Scheme 1C). The product distribution varied depending on the isohexide isomer. The amination of IS produced only aminoalcohols AS1 and AS2 with unreacted exo-OH and trace amounts of II, showing that endo-OH groups are reactive, while exo-OH groups are not. The conversion of IS increased with the H2 pressure in the range of 0–10 bar, whereas it was unchanged at about 70% in the H2 pressure range of 10–30 bar. In the case of IM, aminoalcohols AM1 and AM2 were obtained as the main products. Noticeably, the second endo-OH was barely aminated, with little formation of diamines (DAM, DAS, and DAI). Although the reaction did not require exogenous H2, increasing the H2 pressure above 10 bar led to higher conversion (increasing almost linearly with the H2 pressure in the 10–40 bar range), but to the detriment of selectivity. A slight decline of the amine yield was observed, while a considerable amount of isomers, mainly II, were obtained due to competing reactions between isomerization and amination.
Herein, we present a combined experimental and computational study to rationalize the role of H2 and NH3 in the direct amination of isohexides over Ru/C. In particular, we investigated the influence of the isomerization reaction on the direct amination of IM and the nature of byproducts generated during amination.

Results and Discussion

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Influence of the Substrate on the Catalytic Performance

First, we measured the kinetic profiles for the direct amination of IS, IM, and II with NH3 at 180 °C (Figure 1). The product distribution varies depending on the starting isomer used. The amination of isosorbide IS only generates two aminoalcohols with exo-OH (i.e., AS1 with endo-NH2 and AS2 with exo-NH2) and very little II (Figure 1a). The complete absence of aminoalcohols with endo-OH (AM1 and AM2) clearly shows the low reactivity of the exo-OH groups, which is consistent with earlier observations by Pfützenreuter and Rose. (33) The amination reaction is complete at ca. 50% conversion of IS, i.e., after 12 h. Extending the reaction time to 120 h promotes the conversion of IS to almost 100%. The combined yield of aminoalcohols (AS1 and AS2) keeps almost unchanged at 50% to the detriment of the formation of byproducts, and only a very small amount of diamines (0.7%) is formed.

Figure 1

Figure 1. Kinetic profiles for the direct amination of (a) isosorbide IS, (b) isomannide IM, and (c) isoidide II, with NH3. Reaction conditions: 1 g isohexide, 15 mL NH3·H2O (25 wt %), pH = 13.5, 0.2 g Ru/C (5 wt %), 10 bar H2, and 180 °C.

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Starting from isomannide IM, the main products obtained after 12 h are aminoalcohols with endo-OH (i.e., AM1 with endo-NH2 and AM2 with exo-NH2) and diamine products DAM, DAS, and DAI, with an overall yield of ∼70% after 18 h at ∼70% IM conversion (Figure 1b). By contrast with the absence of diamines when starting from isosorbide IS (Figure 1a), this confirms the higher reactivity of endo-OH vs exo-OH groups. While the IM conversion gradually increases to completion after 168 h, the total yield of amines decreases, suggesting that the aminoalcohols AM1 and AM2 are not stable for extended times under the reaction conditions. After 168 h, more than 50% of IM is converted to byproducts, which is very similar to what was observed for IS (see Figure 1a). However, the diamine-to-aminoalcohol ratio increases over time while keeping the total yield of diamines almost unchanged, suggesting a slow conversion of the aminoalcohols to diamines over longer periods of time.
The above trends for IM and IS might be explained by the conversion of aminoalcohols and diamines into byproducts and/or by poisoning of Ru/C by excess NH3, thus limiting the adsorption of H2 and isohexides or favoring the degradation of isohexides. These hypotheses will be discussed in the forthcoming sections.
Finally, amination of isoidide II yields a very small amount of IS (3%) and aminoalcohols with exo-OH (AS1 and AS2, 7%) (Figure 1c), pointing out a first isomerization step of II to IS, followed by amination of the more reactive endo-OH groups of IS to yield said aminoalcohols. The amount of IS is surprisingly small since, in line of our previous study focusing on the isomerization of isohexides, (35) the isomerization equilibrium should be reached within 2 h at 160 °C, 10 bar H2, again suggesting the inhibition of this reaction when NH3 is present.

Analysis of the Byproducts Formed in the Amination of Isomannide

Since the mass loss in direct amination increases with the reaction time (Figure 1a,b), the amination of isomannide IM was stopped after 12, 72, and 168 h, and the reaction mixture was analyzed by MS to identify all possible byproducts formed (Figure 2). The starting solution of IM shows IM + Na (m/z 169) and 2 IM + 2 Na + 2 H (m/z 340) peaks (Figure 2a). Other peaks (m/z 210, 279, 301, 329, 337, 356, 378, 467, and 541) are attributed to contamination derived from the MS instrument by comparison with blank tests (Figure S1). Aminoalcohol AS2 and diamine DAS solutions were also analyzed by MS, showing no fragment peaks (Figure S2). Aminoalcohols at m/z 146 (+H) and unreacted IM at m/z 169 (+Na) are visible in the reaction mixture after 12 h reaction (Figure 2b). The peak appearing at 145 (+H) m/z, which at first sight can be ascribed to a satellite of 146 m/z (+H), can be attributed to isohexide diamines. Besides contamination peaks, no product is detected above 200 m/z, indicating no condensation of any product, resulting in a good carbon balance. A higher aminoalcohol (146 m/z) to IM (169 m/z) ratio is observed after 72 h compared to 12 h (Figure 2c), which is consistent with a higher IM conversion. The peaks above 200 m/z are more visible according to the smaller intensity scale (105) used, but can still be attributed to contamination. Two obvious peaks at m/z 100 (+H) and 116 (+H) are observed in the reaction mixture, especially at longer reaction times, which can be attributed to byproducts (Figure 2b–d). After 168 h, isohexide diamines become the main products and are observed at m/z 145 (+H) (Figure 2d). Additional byproducts are visible at m/z 86 (+H), 131 (+H), and 185 (+H).

Figure 2

Figure 2. Mass spectra of (a) initial isomannide IM solution and reaction mixture obtained from the amination of IM after (b) 18, (c) 72, and (d) 168 h. Reaction conditions: 1 g IM, 15 mL NH3·H2O (25 wt %), 0.2 g Ru/C (5 wt %), 10 bar H2, and 180 °C. A higher concentration was used for the injected solution to obtain the mass spectrum (d) (0.5 mg/mL vs 0.1 mg/mL).

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Table 1 lists the possible byproducts generated that are compatible with the MS spectra. All the compounds have at least one O- or N-containing heterocycle. To rationalize the formation of the most likely byproducts (highlighted with a dashed orange frame), plausible degradation routes from IM can be proposed (Figure 3). The byproduct with MW = 130 could be generated from hydrodeoxygenation of isohexide diamines since its peak at m/z 131 (+H) appears only after 168 h, while the conversion of IM already exceeds 90% after 48 h. We also identified 2,5-dimethylpyrrolidine, a bicyclic compound including a C5 N-heterocycle with MW = 99 and other byproducts with MW = 115 and MW = 85. All these byproducts could be formed from an intermediate tricyclic compound (i.e., 2,5-imino-1,4:3,6-dianhydro-2,5-dideoxy-D-mannitol, A, MW = 127), opening a path to degradation routes (and carbon loss) driven by ring opening, followed by hydrodeoxygenation, hydrogenolysis, and C–C cleavage.

Figure 3

Figure 3. Proposed reaction routes for the formation of detected byproducts during the amination of IM.

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Table 1. Possible Structures of C6–C4 Byproducts Detected during the Amination of IM, as Suggested by MSa
a

The most likely structures are circled by a dashed orange line. Unsaturation degree Ω = (C × 2 + 2 H + N)/2.

The tricyclic compound A could be generated by internal nucleophilic substitution (SN2) of AS1, exhibiting an anti configuration between the nucleophile (endo-NH2) and the leaving group (exo-OH), with a Gibbs free energy of reaction ΔrG = −10 kJ mol–1 at 200 °C computed using the M06-2X functional. Water may facilitate proton shuttling from −NH2 to −OH to yield compound A and H2O. Another possibility is an internal substitution (SN2) of DAS, with one endo-NH2 and one exo-NH2, to yield compound A and NH3, but this reaction is predicted to be endergonic with ΔrG = +3 kJ mol–1 at 200 °C. Finally, compound A might also be obtained by internal nucleophilic substitution (SN1) with an endo-OH or endo-NH2 leaving group and still an endo-NH2 as nucleophile in the AM1 aminoalcohol (ΔrG = −13 kJ mol–1) and the DAM diamine (ΔrG = −1 kJ mol–1). All in all, the most likely path based on the Gibbs free energy of the reaction appears to be the internal nucleophilic substitution in AS1 or AM1.
While we did not detect compound A, this compound has been reported by Bashford and Wiggins when reacting isoidide bistosylate with methanolic NH3. (22) Compound A has also been prepared by reacting isoidide bistosylate with benzylamine, followed by hydrogenolysis over a Pd(OH)2 catalyst. (23) Overall, these studies suggest that compound A can be accessed in our reaction system either in the bulk alkaline solution or over the Ru/C catalyst at high IM conversion (>70%).

Role of NH3 and H2 in the Amination of Isomannide IM

Effect of NH3 and Aminoalcohols on the Amination of IM

To assess the potential inhibition of aminoalcohols on the catalytic activity of Ru/C, the amination of isomannide IM was performed in the presence of aminoalcohol AS2 (with exo-NH2) in the starting solution and in excess of NH3 (Figure 4). This aminoalcohol was chosen since it was found to be not reactive from the experiments using IS (Figure 1a). Only 15 wt % of AS2 based on IM (almost the same molar percentage) was added to the starting solution to prevent competitive adsorption with the substrate. Interestingly, AS2 did not react and did not exert any influence on the product distribution or IM conversion compared to the direct amination of pure IM. These results suggest that aminoalcohols do not inhibit the reaction.

Figure 4

Figure 4. Conversion of isomannide IM and product distribution in the amination of IM without (left) and with (right) addition of 0.15 g AS2 (15 wt % to IM) to the starting solution. Reaction conditions: 1 g IM, 15 mL NH3·H2O (25 wt %), 0.2 g Ru/C (5 wt %), 10 bar H2, 180 °C, and 18 h.

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To investigate the role of NH3 on the catalytic activity and selectivity, the amination of IM was conducted at variable NH3 loading in the reactor by diluting 25 wt % aqueous NH3 with H2O, while the H2 pressure was kept unchanged at 10 bar (Figure 5). At about 70% conversion of IM, the total yield of amines increases with the NH3 loading from 0.5 to 3.4 g, while the amount of isomerization products (IS and II) declines. In parallel, the aminoalcohols-to-diamines molar ratio decreases from 4.1 to 1.9. Interestingly, the more NH3 is present, the higher the carbon balance, accompanied by an increase in the pH of the reaction mixture. These results underline the competitive role of hydrogenolysis/hydrodeoxygenation of IM over amination at lower NH3 loadings, resulting in the formation of acid byproducts not detectable by MS (e.g., short-chain carboxylic acids) (Figure 3) (36) and promoting the isomerization of isohexides. (35)

Figure 5

Figure 5. (a) Conversion of isomannide IM and product distribution, as a function of the amount of NH3, in the direction of amination of IM. Reaction conditions: 1 g IM, 15 mL solvent, 15 to 2.2 mL NH3·H2O (25 wt %), 0.2 g Ru/C (5 wt %), 10 bar H2, 180 °C, and 18 h. (b) Molar ratio of aminoalcohols-to-diamine products as a function of the amount of NH3.

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Effect of H2 Pressure on the Amination of Isomannide IM

The effect of H2 pressure on the amination of isomannide IM was further investigated at constant NH3 loading (3.4 g) (Figure 6). The IM conversion increases with the H2 pressure from 1 to 30 bar, with a concomitant decrease of the diamine yield and carbon balance due to byproduct formation for a H2 pressure higher than 10 bar. In parallel, IS is generated from the isomerization of IM, with a higher yield due to faster isomerization at higher H2 pressures. (34) Subsequent amination of IS produces aminoalcohols AS1 and AS2. This observation is further confirmed by MS analysis of the reaction solution after amination of IM under 30 bar of H2 (Figure S3). At this higher H2 pressure, a new peak is observed at 132 m/z (+H), not listed in Table 1, which can be ascribed to ring-opening products of compound A, while another peak at m/z 100 is ascribed to a product originating from further hydrodeoxygenation. Additional byproducts originating from hydrodeoxygenation/hydrogenolysis at higher H2 pressures are listed in the Supporting Information (Figure S4).

Figure 6

Figure 6. Conversion of isomannide IM and product distribution under different H2 pressures. Reaction conditions: 1 g IM, 15 mL NH3·H2O (25 wt %) (pH = 13), 0.2 g Ru/C (5 wt %), 180 °C, and 18 h.

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The effect of the H2 pressure on the amination of IM was investigated at two different IM loadings (i.e., 0.5 and 1.0 g) while keeping the Ru/C loading constant at 0.2 g (Figure 7). Under 5 bar H2 pressure, the IM conversion is 75% using 0.5 g of IM, whereas it decreases to 49% using 1.0 g of IM, while keeping in both cases a carbon balance higher than 90% (Figure 7a). The higher IM conversion in the former case can be attributed to a higher catalyst-to-substrate ratio. While under 10 bar H2 pressure, the conversion is higher (90% for 0.5 g of IM and 70% for 1 g of IM), and the trend in the conversion is similar to that found for 5 bar H2 pressure (compare Figure 7a,b). However, contrary to what was found with 5 bar H2 pressure, the total amine yield is much lower using 0.5 g of IM. An increase of the H2 pressure from 5 to 10 bar enhances the rate of amination, resulting in an increase of the total yield of amines from 47% at 5 bar H2 to 70% at 10 bar H2. In contrast, using 0.5 g of IM, side reactions are strongly promoted by increasing the H2 pressure from 5 to 10 bar. This results in a decline of the total yield of amines due to competitive hydrogenolysis/hydrodeoxygenation reactions of aminoalcohols or IM, leading to different byproducts (Figure 3).

Figure 7

Figure 7. Conversion of isomannide IM and product distribution at 1 and 0.5 g IM under (a) 5 bar and (b) 10 bar H2. Other reaction conditions: 15 mL NH3·H2O (25 wt %) (pH = 12), 0.2 g Ru/C catalyst, 180 °C, and 18 h.

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Reactivity of Ketones

Finally, we studied the role of monoketones as intermediates during the amination of isomannide IM. The endo-OH monoketone was synthesized by oxidation of IM with 10 bar O2 over Pt–Bi/C (see the Supporting Information for details), resulting also in the formation of the diketone. The IM/endo-OH ketone/diketone molar ratio of the resulting mixture was 26:48:10. This mixture was then subjected to reductive amination using aqueous NH3 over Ru/C at 100 °C and 10 bar H2 (Figure S5). Under such conditions, the reaction mixture is enriched with IM after 12 h, which can be attributed to the partial hydrogenation of the endo-OH group. Besides, two aminoalcohols with endo-OH (i.e., AM1 with endo-NH2 and AM2 with exo-NH2) are generated, as well as a few diamines.
We also investigated the product distribution in the reductive amination of the pure isohexide diketone over Ru/C. Despite full conversion of the diketone, neither isohexide monoketones nor amines are observed at 25 °C after 1 h or at 100 °C after 18 h. A dark brown-colored solution is obtained just by reacting the diketone with aqueous NH3 over Ru/C and 10 bar H2, suggesting fast imine formation, followed by polymerization.
The results above point out that the endo-OH monoketone is most likely an intermediate originating from IM dehydrogenation. However, the diketone is not expected to be generated on the catalyst surface during IM dehydrogenation and participate in the catalytic mechanism.

Competition of Amination and Isomerization of Isomannide over Ru/C

During the amination of isohexides, isomerization can also occur. In the absence of NH3, the three isohexide isomers can interconvert over Ru/C under a pressure of H2. In particular, we have recently shown that IS can isomerize, starting either from the endo-OH or exo-OH with a comparable energetic span. (35) In the absence of co-adsorbed H, chemisorbed monoketones are strongly bonded to the Ru surface because of the stabilizing interaction with the ether of the adjoining cycle. As a result, monoketones poison the Ru catalyst, with re-hydrogenation being the limiting process. In the presence of H2, monoketones are less strongly adsorbed and are more easily re-hydrogenated, producing IS, IM, or II. The isomerization equilibrium is reached within 2 h at 160 °C, 10 bar H2 (i.e., the II/IS/IM molar ratio of 61:35:4).
To rationalize the final distribution of products in the amination of isohexides, it is critical to understand the interplay between this reaction and the isomerization of isohexides, in the presence of both NH3 and H2. In this view, we first explored the evolution of IM over Ru/C at 200 °C in water solvent under 30 bar H2 (Figure 8). In line with our previous study, (35) IM isomerizes into II and IS, reaching thermodynamic equilibrium after 2 h. Next, we reacted IM with a small amount of NH3 (1 mL of 25 wt % NH3·H2O instead of 15 mL in the previous experiments) in water (15 mL) at 200 °C under 30 bar H2. Isomerization is suppressed and does not reach equilibrium. This observation is consistent with the low yield of isohexide isomers observed during amination in excess NH3 and suggests strong inhibition of isomerization in the amination reaction.

Figure 8

Figure 8. Product distribution and mass loss in the isomerization reaction of isomannide IM in the presence of NaOH (pH = 10) (left) and NH3·H2O (25 wt %, 1 mL) (pH = 8) (right). Reaction conditions: 1 g IM, 15 mL solvent, 0.05 g Ru/C (5 wt %), 30 bar H2, 200 °C, and 2 h.

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We conducted two further catalytic tests on mixtures resulting from the amination reaction (Figure 9). In these tests, we kept the pH at basic conditions to discourage the side effects of the pH on the reactivity. We first carried out the amination of IM at 180 °C for 18 h (pH 13), and then, NH3 was partially removed by bubbling N2 for 6 h until the pH was 11. The resulting mixture was then reacted with 30 bar of H2 (Step A, Figure 9a). The yield of isohexides and aminoalcohols remains almost unchanged, while the yield of diamines decreases slightly. NH3 was further added to the reactor, and the amination reaction was resumed (Step B, Figure 9a), leading to a moderate increase of the yield of diamines. We conducted a second catalytic test at 180 °C for 18 h and then fully removed NH3 under vacuum (pH 11) (Step A, Figure 9b). The yield of amines exhibits a remarkable decrease, especially in the case of diamines, reinforcing the idea that diamines are more vulnerable to H2 than aminoalcohols over Ru/C. Besides, the ratio of AM2 (with one exo-NH2) to AM1 (with one endo-NH2) increases dramatically, either due to partial isomerization from AM1 to AM2 or due to a higher decomposition rate of AM1. The isomerization of IM is also inhibited in the presence of the amine products, as described above.

Figure 9

Figure 9. Product distribution in consecutive isomerization–amination tests. Step A reaction conditions: 15 mL mixture, 0.05 g Ru/C (5 wt %), 30 bar H2, 200 °C, and 2 h. Step B reaction conditions: 15 mL mixture, 9 g NH3, pH > 13, 0.2 g Ru/C (5 wt %), 10 bar H2, 180 °C, and 18 h.

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Understanding the Role of NH3 and H2 in IM Amination

To improve our understanding of the role of NH3 and H2 in isomannide IM amination over Ru/C, we performed density functional theory (DFT) calculations, complementing our previous studies focusing on the isomerization reaction. (35) Aminoalcohols are the main products of the amination reaction in the case of IS, with only traces of the desired diamines produced. Further reaction of the aminoalcohols to the desired diamine products is observed in the case of IM, but to a limited extent. Alcohol amination is a multistep process that starts with the OH scission activated by the Ru/C catalyst. (37) Considering the adsorption on Ru(0001) followed by the O–H scission (TSOH), we compare IM with the four aminoalcohol intermediates (i.e., AS1, AS2, AM1, and AM2, see Scheme 1). The corresponding Gibbs free energy profiles are provided in Figure 10a. IM adsorbs weakly by building two Ru–O weak bonds with one O-ether and one hydroxyl group. The O–H breaks with an activation energy of 33 kJ mol–1. Adsorption of aminoalcohols is clearly much more favorable via their NH2 group (NH2*) than via their OH group (OH*) by at least 25 kJ mol–1, which means that the OH group points away from the catalyst surface in the most stable adsorption mode (>5 Å, see illustration for AM1 in Figure 10b). Starting from the OH* adsorption mode, the O–H scission barrier is comparable to that found for IM (around 30 kJ mol–1). However, the overall barrier rises to at least 59 kJ mol–1 by including the adsorption equilibrium between the most stable adsorption mode (NH2*) and the least stable but reactive adsorption mode (OH*). In other words, aminoalcohols are predicted to be less reactive than IM in agreement with our experimental findings (formation of aminoalcohol is comparatively easy, while further reaction to diamines is strongly inhibited), and this is mainly related to the over-stabilizing adsorption through the amino substituent (NH2*) compared to the reactive adsorption through the alcohol substituent (OH*).

Figure 10

Figure 10. (a) Gibbs free energy profiles, including adsorption and O–H scission (TSOH) of IM and the four aminoalcohol intermediates (AS1, AS2, AM1, and AM2) found in the amination reaction of isohexides. The entropic and enthalpic contributions were calculated at 200 °C and 1 atm using a harmonic ideal gas approximation. Reference energy is the pristine Ru(0001) slab, IM in the gas phase, and NH3 in the gas phase. When considering the aminoalcohols, the water molecule generated by the amination of IM is set in the gas phase. (b) Optimized structures of AM1 on Ru(0001). N in blue, O in red, C in gray, H in white, and Ru in green. Only selected top-most atoms of the Ru slabs are shown. The distance between the H of the −OH and the average height of the topmost layer of Ru is indicated with a black dash and given in Å. *OH and *NH2 stand for adsorption configuration through OH and NH2 functional groups, respectively.

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According to our previous work on the isomerization of isohexides over Ru/C (i.e., without NH3), (35) exogenous H2 is necessary to promote the isomerization of the isohexides (IS/II/IM). DFT calculations highlighted that isomerization is facilitated on a Ru(0001) surface covered by H compared to a pristine surface. (35) To elucidate the impact of NH3 on the isomerization of isohexides, we investigated the fate of NH3 on Ru(0001). Given the weak Gibbs free adsorption of IM (−8 kJ mol–1) compared to that of NH3 (−37 kJ mol–1), the co-adsorption of IM was ruled out in our calculations. The corresponding reaction profile is shown in the Supporting Information (Figure S7). NH3 adsorbs strongly on Ru(0001) and easily dissociates into NH2, NH, and N (barrier < 110 kJ mol–1). Noteworthy, recombination of N into N2 is limited by a very high barrier (295 kJ mol–1). These results are in agreement with previous work on the synthesis of NH3 and its decomposition over Ru surfaces. (38,39) These aforementioned surface species could be responsible for surface poisoning, as confirmed by microkinetic modeling, where the steady state was evaluated at increasing temperatures for a H2/NH3 ratio of 1.0 and at increasing H2/NH3 ratios at 200 °C. As shown in Figure 11, poisoning by NH* and N* increases with temperature but can be reduced by increasing the H2/NH3 ratio. More details about the micro-kinetic analysis can be found in the Supporting Information.

Figure 11

Figure 11. Predicted coverage obtained from microkinetics in combination with the energy barriers computed at the DFT level (Figure S6) as a function of (a) temperature at a H2/NH3 ratio of 1.0 and (b) H2/NH3 ratio at a temperature of 200 °C. The adsorbed species *OH, H2O*, NH2*, N2*, and H* have negligible coverage at H2/NH3 = 1.0 with increasing temperature; N* and O* become negligible with the increasing H2/NH3 ratio. The evolution of free sites is shown on the twin axis in cyan color.

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Combining the above insights from modeling with the experimental investigations, we can rationalize how NH3 and H2 control the fate of isomannide IM over Ru/C during amination, as summarized in Figure 12a. Both the isomerization and amination of IM share the same first step, namely the dehydrogenation of one OH group into a chemisorbed ketone. We have already shown that isomerization is accelerated by exogenous H2 due to co-adsorption of the substrate with H on the catalyst surface. (35) In the presence of both NH3 and H2, the main surface species are NH3 and NH, instead of H, according to combined DFT calculations and micro-kinetics (Figure 11), which modifies the catalytic properties of Ru/C, thus strongly inhibiting the isomerization of IM to IS (Figure 8). This high coverage in NH species is also in agreement with adsorption experiments dosing NH3 on Ru(0001). (40,41) A high NH and/or NH3 coverage should also facilitate imine production on the catalyst, with its hydrogenation being limited by the H2 coverage. As a matter of fact, a H2 pressure of at least 5 bar is necessary to accelerate imine hydrogenation and reach 70% conversion of IM within 18 h (Figure 6). However, the H2/NH3 ratio needs to be kept low to prevent carbon loss. Indeed, as depicted in Figure 9, removing NH3 and keeping H2 is detrimental to the stability of aminoalcohols and diamines. Finally, to obtain diamines, aminoalcohols need to bind through their −OH group, which is less likely than through their −NH2 group, discouraging their further amination.

Figure 12

Figure 12. Proposed reaction pathways for the amination of IM with NH3 over Ru/C in the presence of H2. (a) Direct amination of IM and (b) IM isomerization to IS, followed by direct amination.

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In parallel, even though adsorbed amine species slow down the isomerization of the isohexides, IM is still slowly converted to IS. The latter then transforms into AS1, which is regarded as the precursor of tricyclic amine A, which is further converted into byproducts (Figure 12b).

Conclusions

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To conclude, the direct amination of isohexides with NH3 favors the synthesis of aminoalcohols over Ru/C to the detriment of diamines. The key to this behavior is the inhibition of isomerization during amination (i.e., under NH3), with endo-OH groups in isosorbide and isomannide showing much higher reactivity than exo-OH groups. In contrast, exo-OH groups exhibit partial reactivity in isosorbide and isomannide isomerization under H2 (i.e., without NH3).
Isohexide diamines can be obtained in moderate yield by the direct amination of isomannide with NH3 over Ru/C. A panel of byproducts is obtained, which could be generated by hydrolysis and hydrodeoxygenation from a tricyclic amine, as determined by MS. Increasing the NH3 concentration (relative to that of H2) poisons the Ru surface because of strong NH3 adsorption and the concomitant generation of surface NH species. Furthermore, the isomerization of isomannide is hindered, thus avoiding the formation of AS1 and limiting, in turn, the carbon loss. Increasing the H2 pressure accelerates the amination of isohexides, but too high a pressure is to be avoided to limit AM1 formation and, in turn, the promotion of hydrolysis and hydrodeoxygenation reactions of the intermediate compound A. Therefore, the ratio of H2 to NH3, which conditions the distribution of NH2 and NH species on the Ru surface, drastically influences the catalytic performance.
All in all, we rationalize why the direct amination of isohexides to diamines over Ru/C is discouraged, as desirable as this reaction may be from an industrial point of view. The impossibility of obtaining high yields of diamines, even when starting from isomannide with two more reactive endo-OH groups, results from catalyst poisoning caused by ammonia and the formation of byproducts by hydrogenolysis. In the case of isosorbide and isoidide, the isomerization of the less reactive exo-OH groups to more reactive endo-OH groups is suppressed by ammonia and product amines.

Experimental Section

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Chemicals

Isoidide (98%) was purchased from FluoroChem. Isosorbide (98%) and isomannide (95%) were procured from Sigma-Aldrich. Aqueous ammonia (25 wt %) was procured from Merck. AS1 and DAS were synthesized by ChemPartner. Unless otherwise stated, all chemicals were used without any further purification. An activated carbon-supported ruthenium (Ru/C, 5 wt %, reduced) catalyst was purchased from Sigma-Aldrich.

General Procedure for Amination Reactions

The high-pressure amination reactions were carried out in a Parr 5000 Multiple Reactor System (75 mL) equipped with a thermocouple and a digital manometer. In a typical reaction with aqueous NH3, 1 g (6.8 mmol) of either IS, IM, or II, 0.2 g of Ru/C, and 15 mL of aqueous NH3 (25 wt %, 0.91 g mL–1, 0.2 mol of NH3) were added to the reactor. The reactor was then sealed, flushed 3 times with H2, and sealed at the target H2 pressure and temperature. After the reaction, the reactor was cooled down to room temperature using an ice–water mixture, and the internal pressure was released.

General Procedure for the Synthesis of Isohexide endo-OH Monoketone

The oxidation of isohexides was performed in a 50 mL double-neck flask. Typically, 1 g substrate, 15 mL H2O and 0.2 g Pt–Bi/C were added to the flask. An airflow [80 mL(STP)/min] was introduced to the suspension, and the reaction temperature was set to 60 °C. The endo-OH monoketone MK1 together with the diketone DK and was obtained after 72 h starting from IM at full conversion.

Identification of Products and Quantification

The crude product was filtered (perfluoroethylene, 0.2 μm) to remove the catalyst and was diluted in methanol. The mixture was analyzed by gas chromatography using a Bruker Scion 436 GC equipped with an Agilent HP-5MS column (30 m × 0.25 mm x 0.25 μm), a flame ionization detector (FID), and an autosampler. The calibration was performed using n-dodecanol as the internal standard.
GC methods A and B (see Figure S8 in the Supporting Information) were used to identify all possible products in the isomerization and amination of isohexides (Schemes 1 and 2). Representative GC spectra of the product mixture obtained from the amination of IS or IM are provided in Figure S9. The quantification of each substrate and conversion was carried out using method A, while method B was used to measure the molar ratio between DAI and AS1. Equal GC response factors was assumed for isohexides and the corresponding alcoholamines and diamines.

Scheme 2

Scheme 2. Possible Products Obtained from the Dehydrogenation of Isohexides and Reductive Amination of Isohexide Monoketones
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GC methods A and C (see Figure S10 in the Supporting Information) were used to identify the products in the oxidation of IM and IS, respectively. Representative GC spectra of the product mixture after oxidation are provided in Figure S11. Equal GC response factors were assumed for isohexides and ketones.
In each experiment, the substrate conversion and yield of each product were calculated using the following expressions
Conversion=(1−nan0)×100%
(1)
Yield=npn0×100%
(2)
where na is the molar amount of reactant after reaction, n0 is the initial molar amount of reactant, and np is the molar amount of product after reaction.
MS analysis was used to measure the molecular weight of the possible byproducts during the amination reaction. The analyses were conducted using a Thermo QExactive mass spectrometer (Source-type ESI, scan began at m/z 50, scan ended at m/z 1000, and ion polarity, positive or negative).

Computational Details

DFT implemented in Gaussian 16 (42) was used to investigate the thermodynamic stability of isohexides and their potential amination products using the MO6-2X functional (43) with the def2-TZVPP basis set. (44,45) SCF convergence and optimization criteria were set to tight, and the obtained optimized geometries were used to calculate the vibrational frequencies. These were subsequently used to calculate standard Gibbs free energies at 200 °C and 101 kPa using the GoodVibes python package under the harmonic ideal gas approximation. (44−46) After an initial rescaling of the normal modes recommended for the selected level of theory, (47) frequencies below 100 cm–1 were rescaled to 100 cm–1 for a quasi-harmonic treatment of both vibrational entropy (48) and vibrational enthalpy. (49)
For the study of on–surface reactions, periodic DFT, as implemented in the Vienna ab initio simulation package (VASP) (50) was used to investigate reaction pathways for various reaction species. Electronic energies were approximated at the GGA level using the Perdew–Burke–Ernzerhof (PBE) (51) exchange–correlation functional with dDSc dispersion correction. (52) Ion-electron interactions were treated using the Projector Augmented Wave (PAW) formalism (53,54) with an 850 eV cutoff for the augmentation charges, and the plan-wave basis set was truncated at 500 eV. The Ru catalyst was modeled by a 4 layer thick p(4 × 4) slab of Ru(0001) surface. The slab was cleaved from bulk Ru following a full optimization of the bulk, which resulted in lattice parameters of a = 2.702 Å and c/a ratio of 1.578. The bottom two layers were kept frozen in their bulk positions, while all other degrees of freedom were allowed to relax until the forces were lower than 0.01 eV Å–1 The cutoff for the electronic self-consistency cycle was set to 10–7 eV. The calculations for slab or slab-adsorbate systems used a Gamma-centered 5 × 5 × 1 k-point mesh to sample the Brillouin zone. Second order Methfessel-Paxton smearing scheme, AM2, was employed with a smearing width of 0.2 eV. To minimize the interactions between the different periodic images of the system in the direction normal to the slab, a minimum vacuum gap of 25 Å augmented by a dipole correction of both energy and forces was implemented in the given direction. The O–H transition states for IM and aminoalcohols were computed using a combination of DIMER and quasi-Newton methods.
Thermal and entropic contributions to the total energy were estimated under the harmonic approximation by calculating the normal modes for the adsorbate part of all reaction species using central finite differences with a step size of 0.01 Å. All normal modes (those with a vibration below 100 cm–1 were rescaled to 100 cm–1 to avoid spurious effects within the harmonic approximation) were used to calculate the zero-point energy (ZPE) and other thermal and entropic contributions under harmonic and ideal gas approximations.
The molecular species were optimized at the Gamma point in a 20 × 20 × 20 Å3 cubic box. Due to the polarity of the molecules, dipole correction was used in all directions. A reduced smearing width of 0.02 eV was employed for molecular species. The vibrational, rotational, and translational contributions to the enthalpy and entropy were calculated under the harmonic ideal gas approximation, taking into account the proper symmetry of the molecules.
The kinetic analysis was performed for two cases: surface coverage vs temperature and surface coverage vs NH3/H2 molar ratio. In the former case, the kinetic equations were solved to find the steady state for an initial condition of 25 wt % aqueous NH3 in a 15 mL reactor and a H2/NH3 ratio of 1.0; this sets the initial molar concentrations of NH3, H2O, and H2 gas phase species. In the latter case, the same initial condition for NH3 was used, and the H2 concentration was set according to the H2/NH3 ratio. The initial concentration of N2 gas was set to 0.0 molar in both cases. The binding energy of H* was scaled by 0.12 eV (∼20%) to take into account the lateral interactions in a mean-field approximation. The binding energy of H* was rescaled by ∼20% to mimic the lateral interactions in a mean-field approximation. However, little to no effect was found on the steady-state kinetics as a result of this rescaling. Figure S12 shows the steady-state coverage of surface species and empty sites as a function of temperature at a H2/NH3 ratio of 1.0 when H* is not rescaled, while Figure S13 shows the evolution of N2 gas as a function of temperature for a H2/NH3 ratio of 1.0.
The following elementary reactions were considered
NH3(g)+*↔NH3*
NH3*+*↔NH2*+H*
NH2*+*↔NH*+H*
NH*+*+*↔N*+H*
2N*↔N2*+*
N2*↔N2(g)+*
H2O(g)+*↔H2O*
H2O*+*↔OH*+H*
OH*+*↔O*+H*
2H*↔H2(g)+2*
The differential equations resulting from the elementary steps were solved using the find_steady_state subroutine implemented in the Micki program (55) with dt = 200 and a tolerance of 1 × 10–8. Adsorption of gas-phase species was modeled using a non-interacting 2D ideal gas (defined as the STICK method in Micki) and on–surface reactions were modeled using the Transition State Theory (defined as the TST method in Micki). A continuous stirred reactor (CSTR) with an infinite flowrate (i.e., a perfect mixture) was achieved by fixing the concentrations of NH3(g), H2O(g), and H2(g).

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c07501.

  • Coordinates for DFT calculations (ZIP)

  • Blank mass spectra of the MS system; mass spectra of AS2 and DAS; mass spectra of the reaction mixture after amination of isomannide IM under 30 bar H2; possible byproducts from IM amination; reductive amination of endo-OH ketone mixtures; optimized structures for different adsorption modes of aminoalcohols through either −OH or −NH2 functional groups; reaction profile corresponding to the dehydrogenation of NH3 to form NHx species on Ru(0001); GC methods A and B used for the analysis of product mixtures in the amination of IM; representative GC chromatograms obtained for reactant and product analysis using GC methods A and B; GC method C used for the analysis of product mixtures in the oxidation of IM and IS; representative GC chromatograms obtained for reactant and product analysis using GC methods A and C; steady-state coverage of surface species and empty catalytic sites as a function of temperature at a H2/NH3 ratio of 1.0; evolution of N2 gas as a function of temperature for H2/NH3 molar ratio of 1.0; and a table listing substrate conversion and product yield for figures in the main text (PDF)

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Author Information

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  • Corresponding Authors
    • Raphael Wischert - Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS-Solvay, 3966 Jin Du Road, Xin Zhuang Ind. Zone, 201108 Shanghai, China;  Email: [email protected]
    • Carine Michel - Université de Lyon, Ecole Normale Supérieure de Lyon, CNRS UMR 5182, Laboratoire de Chimie, 46 allée d’Italie, F69364 Lyon, France;  Orcidhttps://orcid.org/0000-0002-4501-7194;  Email: [email protected]
    • Karine de Oliveira Vigier - IC2MP UMR CNRS_Université de Poitiers 7285, ENSIP 1 rue Marcel Doré, TSA 41195, 86073 Poitiers Cedex 9, France;  Orcidhttps://orcid.org/0000-0003-3613-7992;  Email: [email protected]
    • Marc Pera-Titus - Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS-Solvay, 3966 Jin Du Road, Xin Zhuang Ind. Zone, 201108 Shanghai, China;  Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, CF10 3AT Cardiff, U.K.;  Orcidhttps://orcid.org/0000-0001-7335-1424;  Email: [email protected]
  • Authors
    • Hang Hu - Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS-Solvay, 3966 Jin Du Road, Xin Zhuang Ind. Zone, 201108 Shanghai, China;  IC2MP UMR CNRS_Université de Poitiers 7285, ENSIP 1 rue Marcel Doré, TSA 41195, 86073 Poitiers Cedex 9, France
    • Muhammad Akif Ramzan - Université de Lyon, Ecole Normale Supérieure de Lyon, CNRS UMR 5182, Laboratoire de Chimie, 46 allée d’Italie, F69364 Lyon, France;  Orcidhttps://orcid.org/0000-0002-1369-6356
    • François Jerôme - IC2MP UMR CNRS_Université de Poitiers 7285, ENSIP 1 rue Marcel Doré, TSA 41195, 86073 Poitiers Cedex 9, France;  Orcidhttps://orcid.org/0000-0002-8324-0119
  • Author Contributions

    H.H. and M.A.R. contributed equally to this work. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    The authors are grateful to Solvay for funding.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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The authors are grateful to the Pôle Scientifique de Modélisation Numérique at the École Normale Supérieure de Lyon for HPC resources. The authors also thank the SYSPROD project and AXELERA Pôle de Compétitivité for financial support (PSMN Data Center). M.A.R. is grateful to the ENS de Lyon and Solvay for the financial support for his PhD grant. H.H. is also grateful to Solvay for funding a PhD grant.

Abbreviations

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DAM

diaminoisomannide

DAS

diaminoisosorbide

DAI

diaminoisoidide

AM1

aminoisomannide

AM2

exo-NH2-aminoisosorbide

AS1

exo-OH-aminoisosorbide

AS1

exo-OH-aminoisosorbide

AS2

aminoiidide

II

isoidide

IM

isomannide

IS

isosorbide

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    Froidevaux, Vincent; Negrell, Claire; Caillol, Sylvain; Pascault, Jean-Pierre; Boutevin, Bernard
    Chemical Reviews (Washington, DC, United States) (2016), 116 (22), 14181-14224CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    Amines are key-intermediates in chem. industry due to their nucleophilic characteristic which confers a high reactivity to them. Thus, they are key-monomers for the synthesis of polyamides, polyureas, polyepoxydes···which are all of growing interest in automotive, aerospace, building or health applications. Despite a growing interest for biobased monomers and polymers, and particularly polyamides, it should be noticed that very few natural amines are available. Actually, there is only chitosan and poly(lysine). In this review, we present both fundamental and applied research on the synthesis of biobased primary and secondary amines with current available biobased resources. Their use is described as building block for material chem. Hence, we first recall some background on the synthesis of amines, including the reactivity of amines. Second we focus on the synthesis of biobased amines from all sorts of biomass, from carbohydrate, from terpenes, or from oleochem. sources. Third, because they need optimization and technol. developments, we discuss some examples of their use for the creation of biobased polymers. We conclude on the future of the synthesis of biobased amines and their use in different applications.
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  9. 9
    Brun, N.; Hesemann, P.; Esposito, D. Expanding the biomass derived chemical space. Chem. Sci. 2017, 8, 4724– 4738,  DOI: 10.1039/c7sc00936d
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    Expanding the biomass derived chemical space
    Brun, Nicolas; Hesemann, Peter; Esposito, Davide
    Chemical Science (2017), 8 (7), 4724-4738CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    A review. Biorefinery aims at the conversion of biomass and renewable feedstocks into fuels and platform chems., in analogy to conventional oil refinery. In the past years, the scientific community has defined a no. of primary building blocks that can be obtained by direct biomass decompn. However, the large potential of this "renewable chem. Space" to contribute to the generation of value added bio-active compds. and materials still remains unexplored. In general, biomass derived building blocks feature a diverse range of chem. functionalities. In order to be integrated into value-added compds., they require addnl. functionalization and/or covalent modification thereby generating secondary building blocks. The latter can be thus regarded as functional components of bio-active mols. or materials and represent an expansion of the renewable chem. space. This perspective highlights the most recent developments and opportunities for the synthesis of secondary biomass derived building blocks and their application to the prepn. of value added products.
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  10. 10
    Liang, G.; Wang, A.; Li, L.; Xu, G.; Yan, N.; Zhang, T. Production of primary amines by reductive amination of biomass-derived aldehydes/ketones. Angew. Chem., Int. Ed. 2017, 56, 3050– 3054,  DOI: 10.1002/anie.201610964
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    10
    Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones
    Liang, Guanfeng; Wang, Aiqin; Li, Lin; Xu, Gang; Yan, Ning; Zhang, Tao
    Angewandte Chemie, International Edition (2017), 56 (11), 3050-3054CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Transformation of biomass into valuable nitrogen-contg. compds. is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO2, which could catalyze the reductive amination of a variety of biomass-derived aldehydes/ketones in aq. ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two-step approach for prodn. of ethanolamine, a large-market nitrogen-contg. chem., from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO2-contg. multivalence Ru assocn. species worked as a bifunctional catalyst, with RuO2 as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation.
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  11. 11
    Flèche, G.; Huchette, M. Preparation, properties and chemistry. Starch/Stärke 1986, 38, 26– 30,  DOI: 10.1002/star.19860380107
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    11
    Isosorbide. Preparation, properties and chemistry
    Fleche, G.; Huchette, M.
    Starch/Staerke (1986), 38 (1), 26-30CODEN: STARDD; ISSN:0038-9056.
    Isosorbide (I) is obtained by dehydration of sorbitol and therefore can be considered as a valuable product from biomass. The acid-catalyzed reaction gives rise to different anhydro-compds., but also to polymer-like products. Kinetics of sorbitol decrease, followed with the help of HPLC, shows, remarkedly, the different reactions taking place during the dehydration. Physicochem. properties of isosorbide are also discussed: melting temp., sp. gr., soly. Emphasis is put on stereochem. aspect, pointing out the endo-exo position of hydroxyl groups vs. those of other isomers: exo-exo for isoiodide and endo-endo for isomannide. Some other properties such as: hygroscopicity ant thermal stability are also discussed. The chem. reactivity of the mols. is described and some reactions analyzed, proving the interest of the cyclic conformation. Finally, known applications are presented.
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  12. 12
    Wiggins, L. F. 2. The anhydrides of polyhydric alcohols. Part I. The constitution of isomannide. J. Chem. Soc. 1945, 4– 7,  DOI: 10.1039/jr9450000004
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    12
    Anhydrides of polyhydric alcohols. I. Constitution of isomannide
    Wiggins, L. F.
    Journal of the Chemical Society (1945), (), 4-7CODEN: JCSOA9; ISSN:0368-1769.
    Mannitol (I) (20 g.) in 70 cc. dichloroglycerol, ClCH2CH(OH)CH2Cl heated at 140-50° while HCl is passed through the suspension for 3.5 hrs., gives 5.4 g. of 1,4,3,6-dianhydromannitol (isomannide) (II), m. 87-8°, [α]D 91° (H2O, c 2.28). I (500 g.) in 3 l. fuming HCl, boiled 72 hrs., gives 140 g. of II. 1,6-Dichloromannitol, ClCH2[CH(OH)]4CH2Cl (III) (C.A. 38, 2628.6) (2 g.), heated in vacuo at 180°, gives 0.95 g. of II. II (4 g.) in 5.6 g. C5H5N, treated with SOCl2 at 0° and heated 0.5 hr. at 100°, gives 70% of the 2,5-di-Cl compd. (IV), m. 67°, [α]D 93.5° (CHCl3, c 2.054); this is unchanged on distn. with fused KOH. II (1 g.), treated 4 times with MeI and Ag2O at 45°, gives 0.9 g. of the 2,5-di-Me ether (IVA), m. 75-6°, [α]D18 175° (CHCl3, c 2.287). II (1 g.) in 20 cc. fuming HCl, heated 24 hrs. in a sealed tube, gives 0.25 g. of III; thus positions 1 and 6 are involved in the anhydro rings. II (1 g.), heated at 120° for 29 hrs. with 50 cc. MeOH satd. with NH3 at 0°, gives 0.8 g. unchanged II; it is also unaffected with 10% MeOH-MeONa under the same conditions. II is not oxidized by HNO3 (d. 1.14) on heating at 100° for 4 hrs. Pb(OAc)4 in AcOH is without action on II in 48 hrs., indicating that the 2 OH groups are not on adjacent C atoms. IV (7.2 g.) in 200 cc. fuming HCl, heated in a sealed tube for 72 hrs. at 110°, gives 1.6 g. of unchanged IV and 3.4 g. of 1,2,5,6-tetrachloromannitol (V), m. 69-70°, [α]D 28.3° (CHCl3, c 3.107); 3,4-di-Bz deriv., m. 109-10°, [α]D17 -95.4° (CHCl3, c 1.048). V and PCl5 at 130° for 1 hr. give hexachloromannitol; thus V possesses the configuration of I. With MeONa at room temp. for 4 hrs. 1 g. of V gives 0.5 g. of IV. V (0.3 g.), shaken overnight with 25 cc. Me2CO contg. 0.1 cc. H2SO4, gives 0.33 g. of the 3,4-acetone deriv. (VI), b0.05 115° (bath temp.), nD16 1.4954, [α]D 56.8° (CHCl3, c 2.405); VI results also in 0.4-g. yield from 1 g. of 1,6-dichloro-3,4-acetonemannitol (VII)(Micheel, C.A. 26, 4304) and SOCl2 in C5H5N (1 hr. at 100°). VII (5 g.), treated 5 times with MeI and Ag2O at 45° for 9 hrs., gives 1.6 g. of the 2,5-di-Me ether (VIII), m. 56°, [α]D 11.5° (CHCl3, c 2.253); 0.503 g. of VIII in 40 cc. of 75% EtOH contg. 5% H2SO4, kept at room temp. for 550 hrs. (change in [α]D from 9.5° to -35°), gives 0.21 g. of 1,6-dichloro-2,5-dimethylmannitol, m. 131°; with MeONa in MeOH 0.17 g. gives 0.09 g. of IVA; this shows that the HO groups of II are located at C2 and C5. Mannitan (IX) distils at 10 mm. practically without decompn.; distn. of 2 g. of IX with 2 drops of concd. H2SO4 at 10 mm. gives 1.1 g. of II. IX (5 g.) in 50 cc. C5H5N, treated at 0° with 6 g. p-MeC6H4SO2Cl and kept at room temp. for 96 hrs. (with addn. of 25 cc. Ac2O after 48 hrs.), gives 10.5 g. of 1-tosyl-2,4,5-triacetylmannitan (X), a liquid. Reaction of X with MeONa gives II. That the tosyl group is on a primary alc. group is shown by treatment of X with NaI in Me2CO to give 80% of p-MeC6H4SO3Na. The above facts prove that the rings are hydrofuranol in type.
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  13. 13
    Rose, M.; Palkovits, R. Isosorbide as a renewable platform chemical for versatile applications – quo vadis?. ChemSusChem 2012, 5, 167– 176,  DOI: 10.1002/cssc.201100580
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    13
    Isosorbide as a Renewable Platform chemical for Versatile Applications-Quo Vadis?
    Rose, Marcus; Palkovits, Regina
    ChemSusChem (2012), 5 (1), 167-176CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Isosorbide is a platform chem. of considerable importance for the future replacement of fossil resource-based products. Applications as monomers and building blocks for new polymers and functional materials, are conceivable. This minireview deals with all aspects of isosorbide chem., which includes its prodn., special properties, and chem. transformations for its utilization in biogenic polymers and other applications of interest.
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  14. 14
    Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J. P. Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): a review. Progr. Polym. Sci. 2010, 35, 578– 622,  DOI: 10.1016/j.progpolymsci.2009.10.001
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    14
    Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): A review
    Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J.-P.
    Progress in Polymer Science (2010), 35 (5), 578-622CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
    A review. The use of the 1,4:3,6-dianhydrohexitols isosorbide, isomannide, and isoidide in polymers is reviewed. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. In the field of polymeric materials, these diols are essentially employed to synthesize or modify polycondensates. Their attractive features as monomers are linked to their rigidity, chirality, non-toxicity, and the fact that they are not derived from petroleum. First, the synthesis of high glass transition temp. polymers with good thermomech. resistance is possible. Second, the chiral nature of 1,4:3,6-dianhydrohexitols may lead to specific optical properties. Finally, biodegradable polymers can be obtained. The prodn. of isosorbide on an industrial scale with a purity satisfying the requirements for polymer synthesis suggests that isosorbide will soon emerge in industrial polymer applications. However, a deciding factor will be the redn. of polymn. time of these low-reactivity monomers to values compatible with economically viable prodn. processes to give polyesters, polyamides, poly(amide esters), poly(ester imides), polycarbonates, polyurethanes, and polyethers.
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  15. 15
    Wu, J.; Jasinska-Walc, L.; Dudenko, D.; Rozanski, A.; Hansen, M. R.; van Es, D.; Koning, C. E. An investigation of polyamides based on isoidide-2,5-dimethyleneamine as a green rigid building block with enhanced reactivity. Macromolecules 2012, 45, 9333– 9346,  DOI: 10.1021/ma302126b
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    15
    An Investigation of Polyamides Based on Isoidide-2,5-dimethyleneamine as a Green Rigid Building Block with Enhanced Reactivity
    Wu, Jing; Jasinska-Walc, Lidia; Dudenko, Dmytro; Rozanski, Artur; Hansen, Michael Ryan; van Es, Daan; Koning, Cor E.
    Macromolecules (Washington, DC, United States) (2012), 45 (23), 9333-9346CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    Novel, semicryst. polyamides and copolyamides were synthesized from a new carbohydrate-based diamine, namely isoidide-2,5-dimethyleneamine (IIDMA). In combination with 1,6-hexamethylene diamine (1,6-HDA) as well as the biobased sebacic acid (SA) or brassylic acid (BrA), the desired copolyamides were obtained via melt polymn. of the nylon salts followed by a solid-state polycondensation (SSPC) process. Depending on the chem. compns., the no. av. mol. wts. (Mn) of the polyamides were in the range of 4000-49000 g/mol. With increasing IIDMA content in the synthesized copolyamides, their corresponding glass transition temps. (Tg) increased from 50 °C to approx. 60-67 °C while the melting temps. (Tm) decreased from 220 to 160 °C. The chem. structures of the polyamides were analyzed by NMR and FT-IR spectroscopy. Both differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analyses revealed the semicryst. character of these novel copolyamides. Variable-temp. (VT) 13C{1H} cross-polarization/magic-angle spinning (CP/MAS) NMR and FT-IR techniques were employed to study the crystal structures as well as the distribution of IIDMA moieties over the cryst. and amorphous phases of the copolyamides. The performed ab initio calcns. reveal that the stability of the IIDMA moieties is due to a pronounced "boat" conformation of the bicyclic rings. The incorporation of methylene segments in between the isohexide group and the amide groups enables the hydrogen bonds formation and organization of the polymer chain fragments. Given the sufficiently high Tm values (∼200 °C) of the copolyamides contg. less than 50% of IIDMA, these biobased semicryst. copolyamides can be useful for engineering plastic applications.
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  16. 16
    Montgomery, R.; Wiggins, L. F. 77. The anhydrides of polyhydric alcohols. Part IV. The constitution of dianhydro sorbitol. J. Chem. Soc. 1946, 390– 393,  DOI: 10.1039/jr9460000390
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    16
    Anhydrides of polyhydric alcohols. IV. Constitution of dianhydrosorbitol
    Montgomery, R.; Wiggins, L. F.
    Journal of the Chemical Society (1946), (), 390-3CODEN: JCSOA9; ISSN:0368-1769.
    cf. Hockett, et al., C.A. 40, 4677.3. Sorbitol (500 g.) and concd. HCl, refluxed 24 hrs., give 265 g. (66%) of 1,4,3,6-dianhydrosorbitol (I), b10 160-5°, m. 61-3°, [α]D 43.9° (H2O, c 0.8). I does not react with Pb(OAc)4 in AcOH or with BzH in the presence of ZnCl2. I (100 g.) in 200 cc. H2O at 40°, treated with 258 g. Me2SO4 and 360 cc. 30% NaOH in 10 portions during 2 hrs., gives 92 g. of the 2,5-di-Me deriv. (II), b0.1 93-5° (bath), nD19 1.4622, [α]D21 92.9° (CHCl3, c 1.51). I does not react with 5% MeONa in MeOH (20 hrs. at 120°) or with MeOH-NH3 (satd. at 0°) at 120° for 30 hrs. I (5 g.) and 50 cc. fuming HCl, heated at 100-10° for 24 hrs., give 5 g. of a dark brown sirup which, with (HCHO)3 and concd. H2SO4, yields 1,6-dichloro-2,4,3,5-dimethylenesorbitol, m. 116° (C.A. 38, 2628.6). 1,2-Acetoneglucose (40 g.) yields 30 g. of the 5,6-ditosyl deriv. (III) and 18.2 g. of the 3,5,6-tritosyl deriv., m. 129-30°, [α]D17 -3.4° (CHCl3, c 4.14), which results also on further tosylation of III (cf., however, Ohle, et al., C.A. 23, 103, who describe a 3,5,6-deriv. m. 95-6°, [α]D -5.2°). Reduction of 3,6-anhydro-glucose over Raney Ni at 110-20°/100 atm. gives 3,6-anhydrosorbitol (IV); distn. of 0.2 g. with a trace of H2SO4 gives 25 mg. of I. IV (1 g.) and 1.28 g. p-MeC6H4-SO2Cl in 10 cc. C5H5N, mixed at 0° and kept at room temp. for 60 hrs., Ac2O being added at 0° after the 1st 16 hrs., give 1.63 g. of 1-tosyl-2,4,5-triacetyl-3,6-anhydrosorbitol (V); 1.2 g. of V and 0.25 g. Na in 20 cc. MeOH and 10 cc. CHCl3, on standing overnight, give 73% of I. V (0.4 g.) and 0.29 g. NaI in 15 cc. Me2CO, heated at 110°, give 80% of p-MeC6H4SO3Na; the other product could not be crystd. Catalytic reduction of 1 g. of 2,5-dimethyl-3,6-anhydroglucose in H2O over 1 g. Raney Ni at 110-20°/100 atm. for 6 hrs., gives 1 g. of 2,5-dimethyl-3,6-anhydrosorbitol, m. 70-1°, [α]D22 -15.6° (CHCl3, c 0.173); treated as above with p-MeC6H4SO2Cl and Ac2O in C5H5N, 0.3 g. yields 0.23 g. of 1-tosyl-4-acetyl-2,5-dimethyl-3,6-anhydrosorbitol which, with MeONa in MeOH-CHCl3, gives 0.07 g. of II.
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  17. 17
    Fletcher, H. G., Jr; Goepp, R. M., Jr Hexitol Anhydrides.1 1,4,3,6-Dianhydro-L-iditol and the Structures of Isomannide and Isosorbide. J. Am. Chem. Soc. 1946, 68, 939– 941,  DOI: 10.1021/ja01210a007
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    17
    1,4,3,6-Dianhydro-L-iditol and the structure of isomannide and isosorbide
    Fletcher, Hewitt G., Jr.; Goepp, R. Max, Jr.
    Journal of the American Chemical Society (1946), 68 (), 939-41CODEN: JACSAT; ISSN:0002-7863.
    1,4,3,6-Dianhydrosorbitol (isosorbide) (I) (50 g.) and 10 g. Raney Ni in abs. EtOH, freed of EtOH in vacuo, heated 10 min. at 135-40°/2 mm., and then subjected to a pressure of 3750 lb./sq. in. of H at 190-200° for 2 hrs., gave a sirup which could not be crystd. Distn. of 46.1 g. at 140° (bath)/2 mm. gave 27.2 g. of distillate, [α]D25 44.2° in AcOH, and 18.1 g. of a residue (II), [α]D25 27.4° in AcOH. II (18.1 g.) in 50 ml. C5H5N at 0°, treated with 32 ml. BzCl, allowed to stand overnight at room temp., poured into 726 ml. ice water, and crystd. from EtOH, gave 31 g. of a product, m. 81.8-90°; the CHCl3, soln., shaken with aq. NaHCO3 to remove the BzOH and the product crystd. from EtOH and BuOH, gave 16.1 g. of the 2,5-di-Bz deriv. (III), m. 111-11.3° (m. ps. cor.), [α]D23.4 140.3° (CHCl3, c 2.03), [α]D28.2 110.5° (C5H5N, c 2.07), of 1,4,3,6-dianhydro-L-iditol (L-isoidide) (IV), m. 63.8-4.4°, [α]D24.5 20.8° (CHCl3, c 2.02), [α]D28.2 33.3° (C5H5N, c 2.24°). By the same method, 50 g. of isomannide (V) gives 0.92 g. of III. L-Iditol (0.97 g.) and 2 drops concd. H2SO4, heated at 140-5° (bath)/4 cm. for 1.25 hrs. and the product treated with BzCl in C5H5N, gave 31.4% of III. III (10 g.) in 40 ml. CHCl3 at 0°, treated with a chilled soln. of 0.1 g. Na in 40 ml. MeOH and kept at 0° for 23 hrs., gave 90.4% of IV, which is sparingly sol. in CHCl3. The prepn. of IV is best explained by the assumption that Raney Ni exerts a dehydrogenating action on the secondary alcs., converting 1 or both of the free HO groups to sym. CO groups, which are subsequently reduced with the formation of a mixt. of diastereoisomers. The isolation of IV from I and V proves the structure of IV and confirms those of I and V.
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  18. 18
    Fletcher, H. G., Jr; Goepp, R. M., Jr 1,4;3,6-Hexitol dianhydride L-isoidide. J. Am. Chem. Soc. 1945, 67, 1042– 1043,  DOI: 10.1021/ja01222a513
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    18
    1,4,3,6-Hexitol dianhydride. L-Isoidide
    Fletcher, Hewitt G., Jr.; Goepp, R. Max, Jr.
    Journal of the American Chemical Society (1945), 67 (), 1042-3CODEN: JACSAT; ISSN:0002-7863.
    Reduction of D-isomannide or D-isosorbide at 200° over Raney Ni at 250 atms. gives a mixt. of hexitol dianhydrides from which, by benzoylation and fractional crystn., there is sepd. 1,4,3,6-dianhydro-L-iditol (L-isoidide) (I), m. 63.7-4.5°, [α]D24.5 20.8° (H2O, c 2.02), [α]D28.2 33.27° (C5H5N, c 2.24); dibenzoate, m. 111-11.3°, [α]D25.2 141.9° (CHCl3, c 2.15), [α]D28.2 110.5° (C5H5N, c 2.07). Similar data are given for the D-sorbitol and D-mannitol derivs. I also results by the direct acid-catalyzed anhydrization of L-iditol.
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  19. 19
    Cope, C.; Shen, T. Y. The stereochemistry of 1,4: 3,6-dianhydrohexitol derivatives. J. Am. Chem. Soc. 1956, 78, 3177– 3182,  DOI: 10.1021/ja01594a055
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    19
    Stereochemistry of 1,4:3,6-dianhydrohexitol derivatives
    Cope, Arthur C.; Shen, T. Y.
    Journal of the American Chemical Society (1956), 78 (), 3177-82CODEN: JACSAT; ISSN:0002-7863.
    Ditosylate (I) (35 g.) of D-isomannide (II) and 40 g. Et4NOAc.H2O (III) refluxed 70 hrs. on the steam bath in 400 cc. Me2CO, concd. to 100 cc., dild. with 400 cc. H2O, and extd. with CHCl3, the extd. evapd., the residue distd., and the distillate (b0.7 120-50° bath) cooled gave 14.1 g. diacetate (IV) of 1,4:3,6-dianhydro-L-iditol (V), b0.5 100-10°, m. 57-7.6°, [α]D25 89.6° (c 1.5, CHCl3); all m.ps. are cor. II (4.0 g.) treated 2 days at 0-5° with 12 cc. Ac2O and 15 cc. pyridine, dild. with H2O, and extd. with CHCl3 gave 5.63 g. diacetate (VI) of 1,4:3,6-dianhydro-D-mannitol (VII), b0.5 118°, nD25 1.4680, [α]D25 194.5° (c 6.7, CHCl3). IV (12.5 g.) in 90 cc. abs. MeOH treated at 0° with 10 cc. N Ba(OMe)2 in MeOH, kept 18 hrs. at 5°, treated with powd. Dry Ice, and centrifuged, and the supernatant liquid worked up yielded 7.1 g. V, m. 43-3.5°, [α]D25 18.7° (c 2, H2O). IV (350 mg.) in 5 cc. 20% KOH shaken 20 min. with 1 cc. BzCl yielded 386 mg. dibenzoate of V, flakes, m. 110.6-11.4° (from aq. EtOH), [α]D26 134.2° (c 3, CHCl3). V (1.46 g.) treated 18 hrs. at 0-5° with 4.5 g. p-MeC6H4SO2Cl in 15 cc. pyridine and dild. with ice water yielded 3.96 g. di-p-toluene-sulfonate (VIII) of V, m. 105.5-106° (from MeOH), [α]D25 33.2° (c 2.5, CHCl3). Ditosylate (IX) (9.0 g.) of isosorbide refluxed 72 hrs. with 5.0 g. III in Me2CO, concd., dild. with H2O, and extd. with CHCl3 yielded 4.54 g. 5-O-acetyl-2-O-p-toluenesulfonyl-1,4:3,6-dianhydro-L-iditol (X), m. 95.5-6.3° (from MeOH), [α]D25 50.5° (c 4.7, CHCl3). X (1.0 g.) in 10 cc. abs. MeOH treated at 0° with 10 cc. 0.1N Ba(OMe)2 in MeOH, neutralized after 18 hrs. with powd. Dry Ice, centrifuged, and evapd. in vacuo, the oily residue treated 18 hrs. with 1.0 g. p-MeC6H4SO2Cl in 10 cc. pyridine at 5°, and the mixt. poured into ice water and filtered yielded 0.67 g. VIII, m. 105-6°. VIII (3.8 g.) and 1.75 g. III in 50 cc. Me2CO refluxed 72 hrs., concd. to 20 cc. and dild. with H2O gave 2.19 g. unchanged VIII, m. 104.5-5.3°. I (22.6 g.), 20 g. K phthalimide, and 300 cc. HCONMe2 heated 40 hrs. at 110° and dild. with 1.5 l. H2O, and the pptd. solid extd. with 300 cc. boiling EtOH left 6.9 g. 2,5-diphthalimido-2,5-dideoxy deriv. (XI) of V, prisms, m. 243.4-3.6° (from EtOAc-EtOH), [α]D25 168° (c 1, CHCl3). XI (8.08 g.), 1.51 g. 85% N2H4.H2O, and 200 cc. EtOH refluxed 2 days, treated with 20 cc. 4N HCl, refluxed 1 hr., and filtered, the filtrate evapd. to dryness in vacuo, the residue dissolved in 30 cc. H2O, filtered, treated with Darco, acidified to pH about 4.5 with aq. (CO2H)2, and dild. with EtOH to ppt. 2.1 g. oxalate, m. 242-3°, and the oxalate dissolved in H2O, treated with 0.7 g. NaOH in H2O, and distd. yielded 0.97 g. 2,5-di-NH2 analog (XII) of XI, b0.2 110°, m. 59-60°; picrate, m. 227.8-28.1°. I (39 g.) and 70 g. Me2NH shaken 72 hrs. at 120° in 500 cc. tetrahydrofuran in a steel bomb, the mixt. concd., treated with 100 cc. 20% aq. NaOH and extd. with Et2O, the ext. evapd., and the sirupy residue distd. yielded 7.5 g. 2,5-di-(Me2NCH2) analog (XIII) of XI, b0.2 80-100°, m. 57.5-8.5° (sublimed at 40° and 0.2 mm.), [α]D26 30.0° (c 2.1, H2O). XIII treated with excess MeI in boiling MeOH and recrystd. from aq. EtOH gave XIII.2MeI.H2O, m. 260° (decompn.), [α]D26 33.3° (c 2.2, H2O). XIII gave a dipicrate, m. 222° (decompn.) (from aq. EtOH). IX (45.2 g.) and 100 g. Me2NH in 600 cc. tetrahydrofuran heated at 120-30° with shaking in a bomb, cooled, concd., treated with 150 cc. 20% NaOH, and extd. with Et2O, and the ext. worked up gave 0.68 g. crude low boiling fraction, b0.3 41°, and 14.5 g. residue; the distillate treated with MeI in MeOH yielded 1.13 g. 5-dimethylamino-5-deoxy-1,4:3,6-dianhydro-1,2-L-iditoleen methiodide, plates, m. 202-3° (decompn.), [α]D31 33.1° (c 2.5, H2O); the nonvolatile residue in Et2O washed with H2O, dried over KOH, and concd. gave a brown sirup, which treated with picric acid yielded the picrate of 2-O-p-toluenesulfonyl-5-dimethylamino-5-deoxy-1,4:3,6-dianhydro-L-iditol (XIV), m. 179.4-80.8°. The sirup treated with MeI in MeOH gave XIV.MeI, prisms, m. 177.6-8.6° (from EtOH). IX (45.2 g.) and 100 g. Me2NH in 600 cc. tetrahydrofuran shaken 48 hrs. at 165°, concd., treated with 150 cc. 20% aq. NaOH, and extd. with Et2O, and the ext. worked up yielded 13.4 g. 2,5-bis(dimethylamino)-2,5-dideoxy-1,4:3,6-dianhydro-D-glucitol (XV), white prisms, m. 54.6-5.4° (sublimed at 80° and 0.5 mm.), [α]D25 106.3° (c 1.6, H2O). Cryst. oxalate (1.17 g.) of 2,5-di-NH2 analog (XVI) of XV in 10 cc. 98% HCO2H and 8 cc. 37% CH2O refluxed 18 hrs., treated with 10 cc. 4N HCl and evapd. to dryness in vacuo, the residue dissolved in 30 cc. N NaOH and extd. with Et2O, the ext. worked up, and the residue sublimed at 80° and 0.5 mm. gave 0.67 g. XV, m. 54-4.5°, which gave XV.2MeI.H2O, m. 292-5° (decompn.). XVI (3.0 g.) and 25 g. MeI in 100 cc. abs. MeOH refluxed 48 hrs. with stirring with 4 g. Na2CO3, acidified with 48% HI, and evapd. to dryness in vacuo yielded 9.25 g. XVI.2MeI, m. 289-94° (decompn.). XVI.2MeI in 100 cc. dry 1-methylmorpholine treated slowly with 2 g. LiAlH4 in 20 cc. 1-methylmorpholine with stirring and cooling, the mixt. heated 48 hrs. at 90-5°, treated with cooling with EtOAc, and centrifuged, the ppt. dissolved in 10% NaOH and extd. with Et2O, and the combined ext. and 1-methylmorpholine soln. fractionated gave 2.73 g. XV, m. 51.5-3.5°. XV (1.0 g.) warmed 15 min. on the steam bath with 2.0 g. p-MeC6H4SO2Cl in 20 cc. 10% aq. NaOH gave only 135 mg. pure XV, m. 54.3-5.3°. XII (0.72 g.) in 10 cc. 98% HCO2H and 6 cc. 37% CH2O refluxed 18 hrs. gave 0.72 g. XIII, m. 52-4°. XII (0.320 g.) and 5 g. MeI in 20 cc. abs. MeOH refluxed 65 hrs. with 0.85 g. NaHCO3 and worked up in the usual manner yielded 0.667 g. XIII.2MeI, prisms, m. 225-8° (decompn.) (from aq. EtOH). XII (0.72 g.) and 3 cc. concd. HCl in 30 cc. glacial AcOH treated slowly with cooling and stirring with 2.0 g. BuONO, the soln. kept 0.5 hr. at 0° and 18 hrs. at room temp., concd. in vacuo, dild. with H2O, and extd. with CHCl3, the ext. worked up, the residual sirup distd., the resulting oil chromatographed on 10 g. Al2O3 with 5:1 petr. ether-Et2O, and the 1st 60 cc. effluent worked up gave 103 g. XVII (R = R' = Cl), m. 67° XVI (0.72 g.) deaminated in the same manner yielded 87 mg. XVII. On the basis of these results D-isomannide has 2 endo-OH groups, isosorbide has 1 endo at C-5 and 1 exo at C-2, and L-isoidide has 2 exo-OH groups. Revised configurations are suggested for a no. of dianhydrohexitol derivs. and other compds. contg. bicyclic ring systems with 2 cisfused 5-membered rings on the basis of the steric effects observed (previous configuration and revised configuration given): 5-chloro-5-deoxy(?)-1,4:3,6-dianhydro-D-glucitol (W. G. Overend, et al., C.A. 43, 2939f), 5-chloro-5-deoxy-1,4:3,6-dianhydro-L-iditol; x-iodo-x'-O-p-toluenesulfonyl-1,4:3,6-dianhydro-D-glucitol (Hockett, et al., C.A. 40, 4677.3), 5-iodo-5-deoxy-2-O-p-toluenesulfonyl-1,4:3,6-dianhydro-L-iditol; 2,5-dichloro-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol (Wiggins, C.A. 39, 2736.9), 2,5-dichloro-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol; 2-chloro-2-deoxy-5-O-methanesulfonyl-1,4:3,6-dianhydro-D-mannitol (Montgomery and Wiggins, C.A. 43, 2940a), 2-chloro-2-deoxy-5-O-methanesulfonyl-1,4:3,6-dianhydro-D-glucitol; 2-chloro-2-deoxy-5-phenylcarbamyl(?)-1,4:3,6-dianhydro-D-mannitol (Carr´e and Mauclere, C.A. 25, 4526), 2-chloro-2-deoxy-5-phenylcarbamyl-1,4:3,6-dianhydro-D-glucitol; 2,5-diiodo-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol (Hockett, et al., C.A. 40, 4677.8), 2,5-diiodo-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol; 2,5-diamino-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol and derivs. (Montgomery and Wiggins, C.A. 40, 5016.4), 2,5-diamino-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol and derivs.; 2,5-dithio-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol and derivs. (Bladon and Owen, C.A. 44, 6811h), 2,5-dithio-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol and derivs.
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    Brimacombe, J.; Foster, A. B.; Stacey, M.; Whiffen, D. H. Aspects of stereochemistry – I: Properties and reactions of some diols. Tetrahedron 1958, 4, 351– 360,  DOI: 10.1016/0040-4020(58)80056-3
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    Aspects of stereochemistry. I. Properties and reactions of diols
    Brimacombe, J. S.; Foster, A. B.; Stacey, M.; Whiffen, D. H.
    Tetrahedron (1958), 4 (), 351-60CODEN: TETRAB; ISSN:0040-4020.
    The extent of intramol. H-bonding, as detd. by infrared spectroscopy in the HO stretching region in certain vicinal diols provided evidence for the stabilities of certain conformations. With the exception of cyclohexane-trans-1,2-diol (I), the carbocyclic trans diols were prepd. by bromination of the corresponding olefins, solvolysis of the trans bromides with AcOH and AgOAc and sapon. of the trans diacetates (Winstein and Roberts, C.A. 48, 5812f). The carbocyclic cis diols were obtained by hydroxylation of the appropriate olefins with KMnO4 (Clarke and Owen, C.A. 43, 7434h). Cycloheptene (12 g.) in 40 ml. Et2O at 0° brominated in Et2O, the colored soln. washed successively with 0.01N NaOH and water, the dried (MgSO4) soln. evapd. and the residue distd. gave 25.4 g. trans-1,2-dibromocycloheptane b20-5 138-40°, n23.5D 1.5532; this added to 40 g. AgOAc in 80 ml. AcOH and 25 ml. Ac2O (previously kept 2 hrs. at 110°), the mixt. kept 15 hrs. at 110° and the filtered soln. evapd. gave 8.2 g. trans-1,2-diacetoxycycloheptane b0.5 99-101°, n23D 1.4530. The diacetate (4 g.) boiled 2 hrs. in 8 ml. alc. and 8 ml. 35% aq. NaOH, the mixt. dild. with 8 ml. water and extd. 1 day with Et2O yielded 74% cycloheptane-trans-1,2-diol (II), b0.5 100°, m. 60-2°. Similarly were prepd. indan-trans-1,2-diol (III), m. 156-7°, and cyclopentane-trans-1,2-diol (IV), b15-20 131°. I, m. 102-3°, was prepd. according to Roebuck and Adkins [Org. Syntheses, Collective Vol. III, 217(1955)]. The cis-1,2-diols of cyclohexane (V), m. 93-4°, cycloheptane (VI), m. 45-6°, cyclopentane (VII), b29 133°, and indan (VIII), m. 96-8°, were obtained in 14, 11, 11, and 10.8-14.5% yields, resp. 3,4-Di-O-acetyl-D-xylal [3 g., m. 36-8°, [α]20D -288° (c 1.0, H2O)] prepd. according to Overend, et al. (C.A. 44, 6819f) in 100 ml. 1:1 alc.-H2O hydrogenated 30 min. with 100 mg. PtO2, the filtered soln. evapd. and the product distd. gave 1.3 g. 3,4-di-O-acetyl-1,5-anhydro-2-deoxy-D-threopentitol (IX), b0.5 102°, [α]20D -38° (c 0.85, CHCl2), [M]D -77°. IX (1.4 g.) refluxed 2 hrs. in 8 ml. 6N NaOH and 8 ml. alc., the soln. filtered through Amberlite IR-120 (H+) and the filtrate evapd. yielded 60.7% 1,5-anhydro-2-deoxy-D-threopentitol (X), b0.5 75-80°, m. 69°, [α]20D -29.6° (c 2.5, H2O), [M]D -35°. Hydrogenation of 3.2 g. 3,4-di-O-acetyl-L-arabinal (b0.01 110-40°, [α]20D -236° (c 1.12, CHCl3), prepd. according to Deriaz, et al. (C.A. 44, 2453a), and worked up similarly to X gave 2.2 g. 3,4-di-O-acetyl-1,5-anhydro-2-deoxy-L-erythropentitol (XI), b0.2 86-90°, [α]20D 75° (c 1.0, H2O), [M]D 151°. XI (1.4 g.) sapond. as for IX yielded 60.7% 1,5-anhydro-2-deoxy-L-erythropentitol (XII), b0.2-0.3 120°, [α]20D 64° (c 1.5, H2O), [M]D 75°. L-Arabinal (0.8 g., m. 80-2°, [α]20D -202° (c 3.0, H2O) prepd. according to D., et al.) in 20 ml. 1:1 alc.-H2O hydrogenated 1 hr. with 50 mg. PtO2 and the filtered soln. evapd. yielded 70.4% XII. DiBu L-tartrate (10 g., n16.5D 1.4450, [α]20D 10.2°) in 50 ml. tetrahydrofuran added slowly with stirring to 6 g. LiAlH4 in 150 ml. tetrahydrofuran and 75 ml. Et2O, the mixt. refluxed 1.5 hrs. and decompd. with 200 ml. H2O, the mixt. centrifuged and the solid residue washed with water, the combined centrifugates evapd. and the residue taken up in 200 ml. 1:1 H2O-MeOH, the soln. neutralized with CO2 and the filtered soln. evapd., the glassy solid taken up in 20 ml. 1:1 H2SO4-H2O and shaken 1 hr. with 15 ml. BzH, the mixt. dild. with water and filtered, the ppt. washed (water) and crystd. (PhMe) yielded 2.2 g. 1,2,3,4-di-O-benzylidene-L-threitol (Klosterman and Smith, C.A. 48, 2585f), m. 216-17°, [α]25D 81° (c 0.5, CHCl3), hydrolyzed 30 min. in 40 ml. 1:3 N H2SO4-alc., the hydrolyzate concd. and extd. with Et2O, the ext. filtered through Amberlite IRA-400 (HO-), the filtrate evapd. and the residue recrystd. to give 0.5 g. L-threitol (XIII), m. 88-9°, [α]20D -4° (c 8.0, H2O). XIII (2.17 g.) in 2.2 g. H2O and 2.2 g. H2SO4 heated 24 hrs. at 120° in a sealed tube, the hydrolyzate dild. with water, the soln. filtered through Amberlite IRA-400 (HO-) and the filtrate concd. gave 1.1 g. 1,4-anhydro-L-threitol (XIV), b15-17 120°, m. 63-4°, [α]20D -4° (c 7.2, H2O). Erythritol (3 g.) in 3 g. H2O and 3 g. H2SO4 heated 2 days at 120° and in a sealed tube and the hydrolyzate worked up as for XIII gave 1,4-anhydroerythritol (XV), b2-3 144°, n20D 1.4767. The zone electrophoretic (ionophoretic) mobility of the diols were detd. using the app. and technique of Foster, et al. (C.A. 50, 4584g), with a borate buffer (pH 10). The mobility, MG is defined as that mobility relative to D-glucose under standard conditions. The diols (0.43 millimole) in 5 ml. H2O were treated with 15 ml. 0.05M NaIO4 and the vol. rapidly adjusted to 100 ml. at 0°, aliquots withdrawn periodically titrated for unchanged NaIO4 by the standard arsenite method and where possible the times of half oxidation (t0.5) were recorded. The diols (26 mg.) in AcOH at 20° were treated with 49 ml. 0.1315N Pb(OAc)4 in AcOH at 20°, the vol. adjusted to 50 ml. and the unconsumed oxidant detd. on 5-ml. aliquots according to Hockett and McClenahan (C.A. 33, 68034). Methylation of 1,3-O-methylidene glyceritol (XVI), b11 82°, n20D 1.4533, according to Hibbert and Carter (C.A. 23, 98) gave 5-O-methyl-1,3-dioxan-5-ol, b. 147°, n25D 1.4230, converted by acid hydrolysis to 2-O-methyl-1,3-O-methylidene glyceritol, b13 120°, n23D 1.4476, completely resistant to attack by Pb(OAc)4 under the above conditions. Infrared spectra were measured in 2-cm. layers in CCl4 according to Spedding and Whiffen (C.A. 51, 15275b) with concns. of less than 0.005M diol. The results are tabulated (compd., ν for free and bonded OH in cm.-1, arithmetical difference between frequencies, arithmetical difference between standard secondary (3629 cm.-1) and bonded OH group frequencies, t0.5 for NaIO4 oxidation, t0.5 for Pb(OAc)4 oxidation and MG given): I, 3633, 3602, 31, 27, rapid, 1.9 hrs., 0.00; X, 3633, 3608, 25, 21, 20 min., 5 hrs., 0.00; V, 3632, 3592, 40, 37, rapid, 5 min., 0.07; XII, 3633, 3583, 50, 46, rapid, 9 min., 0.23; IV, 3624, -, -, -, 5 min., 10 min., 0.00; XIV, 3624, -, -, -, -, 11 hrs., 0.00; VII, 3624, 3579, 45, 50, rapid, rapid, 0.69; XV, 3624, 3585, 39, 44, -, rapid, 0.88; 1,4,3,6-dianhydro-D-glucitol, 3624, 3540, 84, 89, -, -, -; 1,4,3,6-dianhydro-D-glucitol, 3624, 3540, 84, 89, -, -, -; 1,4,3,6-dianhydro-D-glucitol, 3624, 3540, 84, 89, -, -, -; 1,4,3,6-dianhydro-D-mannitol, -, 3540, -, 89, -, -, -; 1,4,3,6-dianhydro-L-iditol, 3624, -, -, -, -, -, -; III, 3624, -, -, -, 60 min., -, 0.00; VII, 3620, 3579, 41, 50, rapid, -, 0.72; II, 3626, 3589, 37, 40, rapid, -, 0.53; VI, 3632, 3588, 44, 41, rapid, -, 0.69; XVI, 3625, 3593, 42, 36, -, -, -. In certain compds. the stabilities of different conformations can be affected by H-bonding from a substituent HO group to a ring O. Using the parameters evaluated by Whiffen (C.A. 51, 4261i) [M]D in aq. soln. were calcd. for the possible chair conformations of certain pyran derivs. (diol, conformation, [M]D calcd., and [M]D observed given): X, HO groups axial, -43°, -35°, HO groups equatorial, -45°, -; XII, C-3 HO group axial, -45°, -, C-4 HO group axial, 88°, 75°. The rate of reaction of the vicinal diols of these cyclic systems with glycol splitting reagents, and their zone electrophoretic mobility in an alk. borate buffer is influenced by the presence of a ring O atom.
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    Montgomery, R.; Wiggins, L. F. 78. The anhydrides of polyhydric alcohols. Part V. 2 : 5-Diamino 1 : 4–3 : 6-dianhydro mannitol and sorbitol and their sulphanilamide derivatives. J. Chem. Soc. 1946, 0, 393– 396,  DOI: 10.1039/jr9460000393
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    Anhydrides of polyhydric alcohols. V. 2,5-Diamino-1,4,3,6-dianhydromannitol and -sorbitol and their sulfanilamide derivatives
    Montgomery, R.; Wiggins, L. F.
    Journal of the Chemical Society (1946), (), 393-6CODEN: JCSOA9; ISSN:0368-1769.
    1,4,3,6-Dianhydromannitol (59 g.) in 300 cc. dry C5H5N, treated at 0° with 155 g. p-MeC6H4SO2Cl in portions and allowed to warm to and stand at room temp. for 24 h., gives 162 g. of the 2,5-ditosyl deriv. (I), m. 93-4°, [α]D20 92.2° (CHCl3, c 2.582). I (50 g.) in 1500 cc. MeOH-NH3 (satd. at 0°), heated at 170-80° for 30 h., the residue heated with 42 g. Ba(OH)2 in 400 cc. H2O for 1 h., the residue from this operation freed from H2O by repeated distn. with C6H6, and extd. 6 times with 250-cc. portions of CHCl3, gives 12.8 g. of 2,5-diamino-1,4,3,6-dianhydromannitol (II), a sirup, b0.01 150° (bath), m. 59-62°, [α]D20 33.6° (CHCl3, c 2.322), which could be kept in cryst. condition only under N in sealed tubes; oxalate, m. 246-7° (decompn.); adipate, m. 189°; picrate, m. 227-8° (decompn.); sulfate, decomps. above 310°; dimethylenemucate, m. 246-7° (decompn.). II did not inhibit the growth of Staphylococcus aureus in vitro. II yields a disalicylidene deriv., yellow, m. 188-9°. The bis(p-acetamidophenylsulfonyl) deriv. (III), m. 278-9°, was prepd. from II and p-AcNHC6H4SO2Cl in dil. Me2CO contg. NaOH or NaHCO3 on stirring at room temp. for 45 min. or in C5H5N at room temp. for 2 days; it is optically inactive. Hydrolysis of 10 g. of III in 100 cc. Me2CO and 200 cc. 2 N HCl (refluxing 6 h.), or by heating 1 g. with 10 cc. 10% NaOH at 100° for 2 h., gives 2,5-disulfanilamido-1,4,3,6-dianhydromannitol (IV), m. 227-8°; it is optically inactive and does not form salts in aq. soln.; dry HCl in Me2CO-C6H6 (1:1) yields a di-HCl salt which effervesces between 180° and 215°, and yields IV with cold H2O. Reacetylation of IV (AcOH-Ac2O) gives III. II (3 g.) and p-O2NC6H4SO2Cl in C5H5N yield 9.3 g. of the bis(p-nitrophenylsulfonyl) deriv. (V), m. 213-14°, [α]D20 7.5° (Me2CO, c 2.65); redn. with Sn and HCl, or over Raney Ni, gives IV. Dianhydrosorbitol (58 g.) yields 190 g. of the 2,5-ditosyl deriv. (V), m. 101-2°, [α]D23 57.8° (CHCl3, c 4.945); treated as in the case of I, 50 g. of V yields 8.5 g. (54%) of 2,5-diamino-1,4,3,6-dianhydrosorbitol (VI), b0.01 105-10° (bath), nD18 1.5165, [α]D 43.6° (H2O, c 1.538); oxalate, m. 253-4° (decompn.); picrate, m. 200° (decompn.); HCl salt, does not m. 320°; sulfate, does not m. 330°; dimethylenemucate, m. 235-6° (decompn.); dimethylenesaccharate, m. 220-1° (decompn.). The salts did not inhibit the growth of S. aureus in vitro. The disalicylidene deriv. of VI m. 186-7°; bis(p-acetamidophenylsulfonyl) deriv., m. 263-4°, [α]D 51.4° (Me2CO-H2O (1:1), c 0.6); 2,5-disulfanilamido-1,4,3,6-dianhydrosorbitol (VII), m. 239-40°, [α]D 49.2° (Me2CO, c 0.406); the di-HCl salt, prepd. under anhyd. conditions, effervesces about 130° and is completely hydrolyzed by cold H2O. Bis(p-nitrophenylsulfonyl) deriv., m. 216-17°, [α]D20 56.8° (Me2CO, c 2.138); catalytic redn. over Raney Ni at room temp. and atm. pressure yields VII. IV and VII were only slightly sol. in H2O (0.02 g./100 cc.) but were fairly sol. in dil. HCl; they are inferior in bacteriostatic activity to sulfathiazole.
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  22. 22
    Bashford, V. G.; Wiggins, L. F. 82. Anhydrides of polyhydric alcohols. Part XIII. The amino-derivatives of 1 : 4–3 : 6-dianhydro-mannitol, -sorbitol, and -L-iditol, and their behaviour towards nitrous acid. J. Chem. Soc. 1950, 0, 371– 374,  DOI: 10.1039/jr9500000371
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    Anhydrides of polyhydric alcohols. XIII. The amino derivatives of 1, 4:3, 6-dianhydromannitol, -sorbitol, and L-iditol and their behavior towards nitrous acid
    Bashford, V. G.; Wiggins, L. F.
    Journal of the Chemical Society (1950), (), 371-4CODEN: JCSOA9; ISSN:0368-1769.
    cf. C.A. 43, 2939f; 44, 1O24d. 2, 5-Diamino-1, 4:3, 6-dianhydro-2, 5-didesoxysorbitol (I) (3.95 g.) in 25 cc. H2O, acidified with dil. HCl and treated with 4.5 g. NaNO2 in 25 cc. H2O, gives 1.27 g. 1,4:3,6-dianhydro-L-iditol (II), b0.05 115-30° (bath), [α]D 46.7° (Me2CO, c 1.9), characterized as the 2,5-bis(methylsulfonyl) deriv., m. 156.5° the small yield indicates that II was not the only product; the 2, 5-didesoxymannitol analog (III) of I also gives II; in the formation of II, deamination is accompanied by Walden inversion at C5 in the case of I and at both C2 and C5 in the case of III; 2,5-bis(p-tolylsulfonyl) deriv. (IV) of II, m. 90°, [α]D38.2°(CHCl3, c 2). IV(42g.) in 900 cc. MeOH, satd. at 0° with NH3, heated 30 hrs. at 160-70°, and the residue heated at 100° with 50 g. Ba(OH)2 in 400 cc. H2O, gives 2 g. 2,5-imino-1,4:3,6-dianhydro-2,5-didesoxy-D-mannitol (?) (V), m. 99-100°, [α]D 90.5° (CHCl3, c 2.65) [picrate, yellow, m. 219-20° (decompn.); HCl salt, m. 280-90° (decompn.); oxalate, m. 243°]; with NaNO2 in dil. AcOH, V forms an N-NO deriv., m. 121.5°, [α]D -323° (CHCl3, c 2.43). The conversion of I and III into II is paralleled by the epimerization of 2,4:3,5-dimethylene-D-manno- and -D-glucosaccharic acids (C.A. 38, 2631.8).
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  23. 23
    Thiyagarajan, S.; Gootjes, L.; Vogelzang, W.; Wu, J.; van Haveren, J.; van Es, D. S. Chiral building blocks from biomass: 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol. Tetrahedron 2011, 67, 383– 389,  DOI: 10.1016/j.tet.2010.11.031
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    23
    Chiral building blocks from biomass: 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol
    Thiyagarajan, Shanmugam; Gootjes, Linda; Vogelzang, Willem; Wu, Jing; van Haveren, Jacco; van Es, Daan S.
    Tetrahedron (2011), 67 (2), 383-389CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)
    An efficient route towards the synthesis of 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol 4 has been developed resulting in significant improvements in both isolated yields and purity when compared to literature procedures. As a consequence, resin-grade 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol 4 has become available for lab. scale step-growth polymer synthesis. Addnl., an interesting renewable chiral 2-amino-2-deoxy-1,4-3,6-dianhydroiditol, has been isolated.
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  24. 24
    Thiyagarajan, S.; Gootjes, L.; Vogelzang, W.; van Haveren, J.; Lutz, M.; van Es, D. S. Renewable rigid diamines: efficient, stereospecific synthesis of high purity isohexide diamines. ChemSusChem 2011, 4, 1823– 1829,  DOI: 10.1002/cssc.201100398
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    Renewable Rigid Diamines: Efficient, Stereospecific Synthesis of High Purity Isohexide Diamines
    Thiyagarajan, Shanmugam; Gootjes, Linda; Vogelzang, Willem; van Haveren, Jacco; Lutz, Martin; van Es, Daan S.
    ChemSusChem (2011), 4 (12), 1823-1829CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    We report an efficient three-step strategy for synthesizing rigid, chiral isohexide diamines derived from 1,4:3,6-dianhydrohexitols. These biobased chiral building blocks are presently the subject of several investigations (in our and several other groups) because of their application in high-performance biobased polymers, such as polyamides and polyurethanes. Among the three possible stereo-isomers, dideoxy-diamino isoidide and dideoxy-diamino isosorbide can be synthesized from isomannide and isosorbide resp. in high yield with abs. stereo control. Furthermore, by using this methodol. dideoxy-amino isomannide - a tricyclic adduct - was obtained starting from isoidide in high yield. Our improved synthetic route is a valuable advance towards meeting scale and purity demands for evaluating the properties of new biobased performance materials, which will benefit the development of these plastics.
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    Kuszmann, J.; Medgyes, G. Synthesis and biological activity of 1,4:3,6-dianhydro-2,5-diazido-2,5-dideoxyhexitols. Carbohydr. Res. 1980, 85, 259– 269,  DOI: 10.1016/s0008-6215(00)84675-3
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    25
    Synthesis and biological activity of 1,4:3,6-dianhydro-2,5-diazido-2,5-dideoxyhexitols
    Kuszmann, Janos; Medgyes, Gabor
    Carbohydrate Research (1980), 85 (2), 259-69CODEN: CRBRAT; ISSN:0008-6215.
    Reaction of 1,4:3,6-dianhydro-2,5-di-O-mesyl- and -tosyl-D-mannitol with NaN3 afforded the 2,5-diazido-L-iditol deriv. The analogous D-glucitol isomer was obtained in a similar reaction starting from the corresponding D-glucitol derivs., and showed significant, hypnotic activity (no data). For establishing the structure-activity relationship, 1,4:3,6-dianhydro-2,5-diazido-2,5-dideoxy-L-mannitol (I), as well as its antipode (II), was synthesized, starting from D-mannitol. I was as effective as Doriden (3-ethyl-3-phenylglutarimide), a well known hypnotic drug. II and the bioisosteric 1(4),3(6)-dithio deriv. were, however, inactive.
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    Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.; Beller, M. The catalytic amination of alcohols. ChemCatChem 2011, 3, 1853– 1864,  DOI: 10.1002/cctc.201100255
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    Pera-Titus, M.; Shi, F. Catalytic amination of biomass-based alcohols. ChemSusChem 2014, 7, 720– 722,  DOI: 10.1002/cssc.201301095
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    Catalytic Amination of Biomass-Based Alcohols
    Pera-Titus, Marc; Shi, Feng
    ChemSusChem (2014), 7 (3), 720-722CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Although alc. amination reactions were extensively studied since the early decades of the last century, the realization of sustainable development in the amine industry by implementing biomass-based alcs. as starting materials is still in its infancy. Catalytic systems based on Ru and Ir operating by means of the BH mechanism are currently available for performing such reactions. However, to reduce the prodn. costs, homogeneous systems based on cheaper metals operating by nucleophilic substitution, as well as supported metal nanoparticles (Ni, Co, Cu, Pd, Au) on low- alk. supports, are highly desired and new developments are expected to occur soon. With these catalysts in hand, new research areas for amination involving biomass-based alcs. with market opportunities are expected to be developed during this decade.
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    Pingen, D.; Diebolt, O.; Vogt, D. Direct amination of bio-alcohols using ammonia. ChemCatChem 2013, 5, 2905– 2912,  DOI: 10.1002/cctc.201300407
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    Direct Amination of Bio-Alcohols Using Ammonia
    Pingen, Dennis; Diebolt, Olivier; Vogt, Dieter
    ChemCatChem (2013), 5 (10), 2905-2912CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A slightly adapted catalyst system has been successfully applied in the direct amination of primary and secondary alcs. Moreover, the applicability to diols has been shown, giving high selectivity towards the primary diamines. It was found that the Ru/P ratio as well as the amt. of ammonia used are highly important in this system, esp. for higher substrate loadings. The catalyst was employed on a larger batch scale for the conversion of isomannide to the corresponding diamine. Addnl., it was shown that the catalyst is stable for at least six consecutive runs. No significant loss of activity and selectivity was obsd.
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  29. 29
    Wright, L. W.; Brandner, J. D. Catalytic Isomerization of Polyhydric Alcohols.1 II. The Isomerization of Isosorbide to Isomannide and Isoidide. J. Org. Chem. 1964, 29, 2979– 2982,  DOI: 10.1021/jo01033a043
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    Catalytic isomerization of polyhydric alcohols. II. The isomerization of isosorbide to isomannide and isoidide
    Wright, L. W.; Brandner, J. D.
    Journal of Organic Chemistry (1964), 29 (10), 2979-82CODEN: JOCEAH; ISSN:0022-3263.
    At 220-240° and 150 atm. H pressure the reversible interconversion of the 1,4:3,6-dianhydrohexitols of D-glucitol, D-mannitol, and L-iditol reaches a steady state after 2-6 h. in the presence of Ni-kieselguhr catalyst. At this time the approx. concns. are 57 % 1,4:3,6-dianhydro-L-iditol, 36% 1,4:3,6-dianhydro-D-glucitol; and 7% 1,4:3,6-dianhydro-D-mannitol. These figures are shown to be consistent with probability considerations, i.e., the relative amts. of the dianhydrohexitols are related to the probability of a given OH group being either exo or endo. Taking the steady-state mole fraction of 1,4:3,6-dianhydro-L-iditol as 0.57, it is calcd. that the probability of a OH being exo is 3 times the probability of its being endo. Calcn. of the mole fraction of the other 2 anhydrohexitols on the basis of these relative probabilities yields values in close agreement with those found exptl. The isomerization is strongly accelerated by increasing alky. of the catalyst-dianhydrohexitol slurry. Cf. CA 56, 11677c.
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    Brandner, D.; Wright, L. W. Process for producing isoidide. U.S. Patent no. 3,023,223 A, 1962.
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    Schelwies, M.; Brinks, M.; Schaub, T.; Melder, J.-P.; Paciello, R.; Merger, M. Process for the homogeneously catalyzed amination of alcohols with ammonia in the presence of a complex catalyst which comprises nonanionic ligands. Patent no. WO 2014016241 A1 2014
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    Bahé, F.; Grand, L.; Cartier, E.; Jacolot, M.; Moebs-Sanchez, S.; Portinha, D.; Fleury, E.; Popowycz, F. Direct amination of isohexides via borrowing hydrogen methodology: regio- and stereoselective issues. Eur. J. Org. Chem. 2020, 2020, 599– 608,  DOI: 10.1002/ejoc.201901661
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    Direct Amination of Isohexides via Borrowing Hydrogen Methodology: Regio- and Stereoselective Issues
    Bahe, Florian; Grand, Lucie; Cartier, Elise; Jacolot, Maiwenn; Moebs-Sanchez, Sylvie; Portinha, Daniel; Fleury, Etienne; Popowycz, Florence
    European Journal of Organic Chemistry (2020), 2020 (5), 599-608CODEN: EJOCFK; ISSN:1099-0690. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The regio and diastereoselective direct mono or diamination of bio-based isohexides (isosorbide and isomannide) has been developed through borrowing hydrogen (BH) methodol. using a cooperative catalysis between an iridium complex and a Bronsted acid. The access to chiral amino-alc. (NH2-OH) and diamine (NH2-NH2), interesting optically pure bio-based monomers, was also proposed using BH strategy.
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    Pfützenreuter, R.; Rose, M. Aqueous-phase amination of biogenic isohexides by using Ru/C as a solid catalyst. ChemCatChem 2016, 8, 251– 255,  DOI: 10.1002/cctc.201501077
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    Aqueous-Phase Amination of Biogenic Isohexides by using Ru/C as a Solid Catalyst
    Pfuetzenreuter, Rebecca; Rose, Marcus
    ChemCatChem (2016), 8 (1), 251-255CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
    An aq. phase process for the amination of biogenic isohexides with ammonia using Ru/C as solid catalyst is reported. The products possess great potential for the prodn. of biogenic polyamides. From the diol substrates amino alcs. and diamines are derived as main products with significantly varying product selectivity depending on the substrates' stereochem. The catalytic reaction is performed at temps. of 140-180 °C. The Ru/C catalyst shows a high activity in the aq. phase, which is beneficial for the transformation of the polar biogenic substrates. Despite the basic conditions, the metal leaching is negligible and the catalyst can be recycled easily in batch operation and, thus, enables further process development due to the mild and scalable reaction conditions.
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    Niemeier, J.; Engel, R. V.; Rose, M. Is water a suitable solvent for the catalytic amination of alcohols?. Green Chem. 2017, 19, 2839– 2845,  DOI: 10.1039/c7gc00422b
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    Is water a suitable solvent for the catalytic amination of alcohols?
    Niemeier, Johannes; Engel, Rebecca V.; Rose, Marcus
    Green Chemistry (2017), 19 (12), 2839-2845CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)
    The catalytic conversion of biomass and biogenic platform chems. typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aq. phase mainly for energetic reasons by avoiding the initial water sepn. Herein, we report the amination of biogenic alcs. in aq. solns. using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcs. is successfully proved. Hence, water appears to be a suitable solvent for the sustainable prodn. of biogenic amines and offers great potential for further process development.
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    Hu, H.; Ramzan, A.; Wischert, R.; Jerôme, F.; Michel, C.; de Olivera Vigier, K.; Pera-Titus, M. Pivotal role of H2 in the isomerisation of isosorbide over a Ru/C catalyst. Catal. Sci. Technol. 2021, 11, 7973– 7981,  DOI: 10.1039/d1cy01709h
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    Pivotal role of H2 in the isomerization of isosorbide over a Ru/C catalyst
    Hu, H.; Ramzan, A.; Wischert, R.; Jerome, F.; Michel, C.; de Olivera Vigier, K.; Pera-Titus, M.
    Catalysis Science & Technology (2021), 11 (24), 7973-7981CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
    Isosorbide isomerisation is a known reaction that can proceed over Ru and Ni-based heterogeneous catalysts. As a rule, an exogenous H2 pressure (40-100 bar) is required, even though H2 does not participate stoichiometrically in the reaction. By marrying expts. with DFT computations, we ascribe the role of H2 in isosorbide isomerisation to a coverage effect on the catalyst surface. We demonstrate the possibility of conducting the reaction at a low H2 pressure either in the presence of an inert gas to increase H2 soly. in an underlying solvent or using 2-propanol as a hydrogen donor. This might benefit the economy and safety of a potential industrial process.
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    Hausoul, P. J. C.; Negahdar, L.; Schute, K.; Palkovits, R. Unravelling the Ru-catalyzed hydrogenolysis of biomass-based polyols under neutral and acidic conditions. ChemSusChem 2015, 8, 3323– 3330,  DOI: 10.1002/cssc.201500493
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    Unravelling the Ru-Catalyzed Hydrogenolysis of Biomass-Based Polyols under Neutral and Acidic Conditions
    Hausoul, Peter J. C.; Negahdar, Leila; Schute, Kai; Palkovits, Regina
    ChemSusChem (2015), 8 (19), 3323-3330CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The aq. Ru/C-catalyzed hydrogenolysis of biomass-based polyols such as erythritol, xylitol, sorbitol, and cellobitol is studied under neutral and acidic conditions. For the first time, the complete product spectrum of C2-C6 polyols is identified and, based on a thorough anal. of the reaction mixts., a comprehensive reaction mechanism is proposed, which consists of (de)hydrogenation, epimerization, decarbonylation, and deoxygenation reactions. The data reveal that the Ru-catalyzed deoxygenation reaction is highly selective for the cleavage of terminal hydroxyl groups. Changing from neutral to acidic conditions suppresses decarbonylation, consequently increasing the selectivity towards deoxygenation.
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    Wang, T.; Ibañez, J.; Wang, K.; Fang, L.; Sabbe, M.; Michel, C.; Paul, S.; Pera-Titus, M.; Sautet, P. Rational design of selective metal catalysts for alcohol amination with ammonia. Nat. Catal. 2019, 2, 773– 779,  DOI: 10.1038/s41929-019-0327-2
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    Rational design of selective metal catalysts for alcohol amination with ammonia
    Wang, Tao; Ibanez, Javier; Wang, Kang; Fang, Lin; Sabbe, Maarten; Michel, Carine; Paul, Sebastien; Pera-Titus, Marc; Sautet, Philippe
    Nature Catalysis (2019), 2 (9), 773-779CODEN: NCAACP; ISSN:2520-1158. (Nature Research)
    The lack of selectivity for the direct amination of alcs. with ammonia (a modern and clean route for the synthesis of primary amines) is an unsolved problem. Here, we combine first-principles calcns., scaling relations, kinetic simulations and catalysis expts. to det. the key factors that govern the activity and selectivity of metal catalysts for this reaction. We show that the loss of selectivity towards primary amines is linked to a surface-mediated C-N bond coupling between two N-contg. intermediates: CH3NH and CH2NH. The barrier for this step is low enough to compete with the main surface hydrogenation reactions and it can be used as a descriptor for selectivity. The activity and selectivity maps (using the C and O adsorption energies as descriptors) were combined for the computational screening of 348 dil. bimetallic catalysts. Among the best theor. candidates, Co98.5Ag1.5 and Co98.5Ru1.5 (5 wt% Co) were identified exptl. to be the most promising catalysts.
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    Honkala, K.; Hellman, A.; Remediakis, I. N.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Nørskov, J. K. Ammonia synthesis from first-principles calculations. Science 2005, 307, 555– 558,  DOI: 10.1126/science.1106435
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    Ammonia Synthesis from First-Principles Calculations
    Honkala, K.; Hellman, A.; Remediakis, I. N.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Norskov, J. K.
    Science (Washington, DC, United States) (2005), 307 (5709), 555-558CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    The rate of ammonia synthesis over a nanoparticle ruthenium catalyst can be calcd. directly on the basis of a quantum chem. treatment of the problem using d. functional theory. We compared the results to measured rates over a ruthenium catalyst supported on magnesium aluminum spinel. When the size distribution of ruthenium particles measured by transmission electron microscopy was used as the link between the catalyst material and the theor. treatment, the calcd. rate was within a factor of 3 to 20 of the exptl. rate. This offers hope for computer-based methods in the search for catalysts.
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    Lu, X.; Zhang, J.; Chen, W.-K.; Roldan, A. Kinetic and mechanistic analysis of NH3 decomposition on Ru(0001), Ru(111) and Ir(111) surfaces. Nanoscale Adv 2021, 3, 1624– 1632,  DOI: 10.1039/d1na00015b
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    Kinetic and mechanistic analysis of NH3 decomposition on Ru(0001), Ru(111) and Ir(111) surfaces
    Lu, Xiuyuan; Zhang, Jing; Chen, Wen-Kai; Roldan, Alberto
    Nanoscale Advances (2021), 3 (6), 1624-1632CODEN: NAADAI; ISSN:2516-0230. (Royal Society of Chemistry)
    We investigated the catalytic NH3 decompn. on Ru and Ir metal surfaces using d. functional theory. The reaction mechanisms were unraveled on both metals, considering that, on the nano-scale, Ru particles may also present an fcc structure, hence, leading to three energy profiles. We implemented thermodn. and kinetic parameters obtained from DFT into microkinetic simulations. Batch reactor simulations suggest that hydrogen generation starts at 400 K, 425 K and 600 K on Ru(111), Ru(0001) and Ir(111) surfaces, resp., in excellent agreement with expts. During the reaction, the main surface species on Ru are NH, N and H, whereas on Ir(111), it is mainly NH. The rate-detg. step for all surfaces is the formation of mol. nitrogen. We also performed temp.-programmed reaction simulations and inspected the desorption spectra of N2 and H2 as a function of temp., which highlighted the importance of N coverage on the desorption rate.
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    Benndorf, C.; Madey, T. E. Adsorption and orientation of NH3 on Ru(001). Surf. Sci. 1983, 135, 164– 183,  DOI: 10.1016/0039-6028(83)90217-0
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    Adsorption and orientation of ammonia on ruthenium(001)
    Benndorf, Carsten; Madey, Theodore E.
    Surface Science (1983), 135 (1-3), 164-83CODEN: SUSCAS; ISSN:0039-6028.
    The interaction of NH3 with clean Ru(001) surfaces was studied by using LEED ESDIAD (electron stimulated desorption ion angular distribution), TDS (thermal desorption spectroscopy), and work function changes (Δ.vphi.). Four different binding states (denoted as α1, α2, β, and γ) were detected with TDS. At low coverages, NH3 desorbs from the α1 state with a TDS peak max. at ∼310 K. The broadening of the TDS peaks and their shift to lower temp. with increasing NH3 coverage are related to repulsive lateral interactions between neighboring NH3 mols. At higher NH3 coverages (θNH3 ⪆ 0.15), a 2nd desorption peak (α2) develops at 180 K, accompanied by a (2 × 2) LEED structure. With further increase of NH3 exposure a sharp desorption peak (β state) is found at 140 K, an is interpreted as due to NH3 species desorbing from a 2nd adsorption layer. Finally a desorption peak due to multilayer adsorption (γ state) is found at 115 K. At low NH3 coverages (α1 state), a halo-like H+ ESDIAD pattern gives evidence of randomly oriented or freely rotating NH3 monomers, bounded via the N atoms to the surface with the H atoms pointing away from the surface. This orientation of NH3 is supported by work function measurements showing a linear decrease of Δ.vphi. in the α1 state. Structural information concerning the adsorption geometry of NH3 in the β state was obtained from LEED and ESDIAD. During the formation of the 2nd NH3 layer (β) a (2√3 × 2√3)R30° LEED pattern is obsd. and is accompanied by an ESDIAD pattern with a hexagonal outline. A structural model of the β-state bonding, in which 2nd layer NH3 mols. are bonded via 3-fold H bonds to the 1st layer NH3, is proposed.
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    Selective oxidation of ammonia over Ru(0 0 0 1)
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    Surface Science (2004), 555 (1-3), 83-93CODEN: SUSCAS; ISSN:0039-6028. (Elsevier Science B.V.)
    The decompn. and oxidn. of NH3 were studied on the Ru(0 0 0 1) surface in the temp. range from 150 up to 800 K. The results were compared to those found for Ir(1 1 0) and Ir(5 1 0). TDS results showed that most of the NH3 is dissociatively adsorbed between 150 and 300 K, with formation of H2 around 300 K and N2 between 600 and 800 K. N2 desorption shifts to lower temps. with increasing surface O coverage. The products of NH3 oxidn. obsd. were N2, H2O, and N2O. Formation of NO was not found. Inhibition of the reaction presumably by N species was obsd. until 450 and 670 K, depending on the NH3/O2 ratios. Above those temps. the reaction started as manifested by a decrease in the NH3 and O2 pressures and a simultaneous increase in the H2O, N2 and N2O pressures.
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    Theoretical Chemistry Accounts (2008), 120 (1-3), 215-241CODEN: TCACFW; ISSN:1432-881X. (Springer GmbH)
    We present two new hybrid meta exchange-correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amt. of nonlocal exchange (2X), and it is parametrized only for nonmetals. The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree-Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree-Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochem., four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for mol. excitation energies. We also illustrate the performance of these 17 methods for three databases contg. 40 bond lengths and for databases contg. 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochem., kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chem. and for noncovalent interactions.
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    A series of auxiliary basis sets to fit Coulomb potentials for the elements H to Rn (except lanthanides) is presented. For each element only one auxiliary basis set is needed to approx. Coulomb energies in conjunction with orbital basis sets of split valence, triple zeta valence and quadruple zeta valence quality with errors of typically below ca. 0.15 kJ mol-1 per atom; this was demonstrated in conjunction with the recently developed orbital basis sets of types def2-SV(P), def2-TZVP and def2-QZVPP for a large set of small mols. representing (nearly) each element in all of its common oxidn. states. These auxiliary bases are slightly more than three times larger than orbital bases of split valence quality. Compared to non-approximated treatments, computation times for the Coulomb part are reduced by a factor of ca. 8 for def2-SV(P) orbital bases, ca. 25 for def2-TZVP and ca. 100 for def2-QZVPP orbital bases.
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    Optimized scale factors for calcg. vibrational harmonic and fundamental frequencies and zero-point energies have been detd. for 145 electronic model chemistries, including 119 based on approx. functionals depending on occupied orbitals, 19 based on single-level wave function theory, three based on the neglect-of-diat.-differential-overlap, two based on doubly hybrid d. functional theory, and two based on multicoefficient correlation methods. Forty of the scale factors are obtained from large databases, which are also used to derive two universal scale factor ratios that can be used to interconvert between scale factors optimized for various properties, enabling the derivation of three key scale factors at the effort of optimizing only one of them. A reduced scale factor optimization model is formulated in order to further reduce the cost of optimizing scale factors, and the reduced model is illustrated by using it to obtain 105 addnl. scale factors. Using root-mean-square errors from the values in the large databases, we find that scaling reduces errors in zero-point energies by a factor of 2.3 and errors in fundamental vibrational frequencies by a factor of 3.0, but it reduces errors in harmonic vibrational frequencies by only a factor of 1.3. It is shown that, upon scaling, the balanced multicoefficient correlation method based on coupled cluster theory with single and double excitations (BMC-CCSD) can lead to very accurate predictions of vibrational frequencies. With a polarized, minimally augmented basis set, the d. functionals with zero-point energy scale factors closest to unity are MPWLYP1M (1.009), τHCTHhyb (0.989), BB95 (1.012), BLYP (1.013), BP86 (1.014), B3LYP (0.986), MPW3LYP (0.986), and VSXC (0.986).
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    Quantum mechanics/mol. mechanics (QM/MM) simulations provide an efficient avenue for studying reactions catalyzed in zeolite systems; however, the accuracy of such calcns. is highly dependent on the zeolite MM parameters used. Previously reported parameters (P1), which were chosen to minimize the root mean square (RMS) deviations of adsorption energies compared with full QM ωB97X-D/6-31+G** adsorption energies, are shown to overestimate binding energies compared with exptl. values, particularly for larger substrates. To address this issue, a new parameter set (P2) is derived by rescaling the previously reported characteristic energies of the Lennard-Jones potential in P1. The accuracy of the thermal correction for adsorption enthalpies detd. by the rigid rotor-harmonic oscillator approxn. (RRHO) is examd. and shown to be improved by treating low-lying vibrational modes as free translational and rotational modes via a quasi-RRHO model. With P2 and quasi-RRHO, adsorption energies calcd. with QM/MM agree with exptl. values with an RMS error of 1.8 kcal/mol for both nonpolar and polar mols. adsorbed in MFI, H-MFI, and H-BEA. By contrast, the RMS error for the same test sets obtained using parameter set P1 is 8.3 kcal/mol. Glucose-fructose isomerization catalyzed by Sn-BEA is taken as an example to demonstrate that improved values for apparent activation energies can be obtained using the methodol. reported here. With parameter set P2, the apparent activation energy calcd. with QM/MM reproduces the exptl. value to within 1 kcal/mol. By contrast, using parameter set P1, the error is -12.9 kcal/mol.
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    We have developed a flexible, general-purpose microkinetic modeling code, Micki, to analyze complex, heterogeneously catalyzed chem. reactions based upon first-principles calcns. This Python-based code is modular and object oriented, framing the development of microkinetic models in familiar chem. terms. We also present novel approaches, incorporated into Micki, to describe diffusion limited reactions, multidentate bindings, thermodynamically consistent lateral interactions, and Bronsted-Evans-Polanyi ests. of changes in barrier heights. Micki has built-in modules for subsequent anal. of microkinetic models, including degree of rate control and rate order. As a demonstration of the power and flexibility of the code, we build a microkinetic model for the water-gas shift reaction and compare to previously published exptl. results and microkinetic models, showing that Micki can quant. reproduce exptl. turnover frequencies with minimal empirical optimization. (c) 2019 American Institute of Physics.
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  • Abstract

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    Scheme 1

    Scheme 1. Products Obtained from the Direct Amination of Isohexides with NH3 over Ru/Ca
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    a(A) isohexide isomers, (B) isohexide monoamines, and (C) isohexide diamines.

    Figure 1

    Figure 1. Kinetic profiles for the direct amination of (a) isosorbide IS, (b) isomannide IM, and (c) isoidide II, with NH3. Reaction conditions: 1 g isohexide, 15 mL NH3·H2O (25 wt %), pH = 13.5, 0.2 g Ru/C (5 wt %), 10 bar H2, and 180 °C.

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    Figure 2

    Figure 2. Mass spectra of (a) initial isomannide IM solution and reaction mixture obtained from the amination of IM after (b) 18, (c) 72, and (d) 168 h. Reaction conditions: 1 g IM, 15 mL NH3·H2O (25 wt %), 0.2 g Ru/C (5 wt %), 10 bar H2, and 180 °C. A higher concentration was used for the injected solution to obtain the mass spectrum (d) (0.5 mg/mL vs 0.1 mg/mL).

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    Figure 3

    Figure 3. Proposed reaction routes for the formation of detected byproducts during the amination of IM.

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    Figure 4

    Figure 4. Conversion of isomannide IM and product distribution in the amination of IM without (left) and with (right) addition of 0.15 g AS2 (15 wt % to IM) to the starting solution. Reaction conditions: 1 g IM, 15 mL NH3·H2O (25 wt %), 0.2 g Ru/C (5 wt %), 10 bar H2, 180 °C, and 18 h.

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    Figure 5

    Figure 5. (a) Conversion of isomannide IM and product distribution, as a function of the amount of NH3, in the direction of amination of IM. Reaction conditions: 1 g IM, 15 mL solvent, 15 to 2.2 mL NH3·H2O (25 wt %), 0.2 g Ru/C (5 wt %), 10 bar H2, 180 °C, and 18 h. (b) Molar ratio of aminoalcohols-to-diamine products as a function of the amount of NH3.

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    Figure 6

    Figure 6. Conversion of isomannide IM and product distribution under different H2 pressures. Reaction conditions: 1 g IM, 15 mL NH3·H2O (25 wt %) (pH = 13), 0.2 g Ru/C (5 wt %), 180 °C, and 18 h.

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    Figure 7

    Figure 7. Conversion of isomannide IM and product distribution at 1 and 0.5 g IM under (a) 5 bar and (b) 10 bar H2. Other reaction conditions: 15 mL NH3·H2O (25 wt %) (pH = 12), 0.2 g Ru/C catalyst, 180 °C, and 18 h.

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    Figure 8

    Figure 8. Product distribution and mass loss in the isomerization reaction of isomannide IM in the presence of NaOH (pH = 10) (left) and NH3·H2O (25 wt %, 1 mL) (pH = 8) (right). Reaction conditions: 1 g IM, 15 mL solvent, 0.05 g Ru/C (5 wt %), 30 bar H2, 200 °C, and 2 h.

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    Figure 9

    Figure 9. Product distribution in consecutive isomerization–amination tests. Step A reaction conditions: 15 mL mixture, 0.05 g Ru/C (5 wt %), 30 bar H2, 200 °C, and 2 h. Step B reaction conditions: 15 mL mixture, 9 g NH3, pH > 13, 0.2 g Ru/C (5 wt %), 10 bar H2, 180 °C, and 18 h.

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    Figure 10

    Figure 10. (a) Gibbs free energy profiles, including adsorption and O–H scission (TSOH) of IM and the four aminoalcohol intermediates (AS1, AS2, AM1, and AM2) found in the amination reaction of isohexides. The entropic and enthalpic contributions were calculated at 200 °C and 1 atm using a harmonic ideal gas approximation. Reference energy is the pristine Ru(0001) slab, IM in the gas phase, and NH3 in the gas phase. When considering the aminoalcohols, the water molecule generated by the amination of IM is set in the gas phase. (b) Optimized structures of AM1 on Ru(0001). N in blue, O in red, C in gray, H in white, and Ru in green. Only selected top-most atoms of the Ru slabs are shown. The distance between the H of the −OH and the average height of the topmost layer of Ru is indicated with a black dash and given in Å. *OH and *NH2 stand for adsorption configuration through OH and NH2 functional groups, respectively.

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    Figure 11

    Figure 11. Predicted coverage obtained from microkinetics in combination with the energy barriers computed at the DFT level (Figure S6) as a function of (a) temperature at a H2/NH3 ratio of 1.0 and (b) H2/NH3 ratio at a temperature of 200 °C. The adsorbed species *OH, H2O*, NH2*, N2*, and H* have negligible coverage at H2/NH3 = 1.0 with increasing temperature; N* and O* become negligible with the increasing H2/NH3 ratio. The evolution of free sites is shown on the twin axis in cyan color.

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    Figure 12

    Figure 12. Proposed reaction pathways for the amination of IM with NH3 over Ru/C in the presence of H2. (a) Direct amination of IM and (b) IM isomerization to IS, followed by direct amination.

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    Scheme 2

    Scheme 2. Possible Products Obtained from the Dehydrogenation of Isohexides and Reductive Amination of Isohexide Monoketones
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      Amines are key-intermediates in chem. industry due to their nucleophilic characteristic which confers a high reactivity to them. Thus, they are key-monomers for the synthesis of polyamides, polyureas, polyepoxydes···which are all of growing interest in automotive, aerospace, building or health applications. Despite a growing interest for biobased monomers and polymers, and particularly polyamides, it should be noticed that very few natural amines are available. Actually, there is only chitosan and poly(lysine). In this review, we present both fundamental and applied research on the synthesis of biobased primary and secondary amines with current available biobased resources. Their use is described as building block for material chem. Hence, we first recall some background on the synthesis of amines, including the reactivity of amines. Second we focus on the synthesis of biobased amines from all sorts of biomass, from carbohydrate, from terpenes, or from oleochem. sources. Third, because they need optimization and technol. developments, we discuss some examples of their use for the creation of biobased polymers. We conclude on the future of the synthesis of biobased amines and their use in different applications.
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      Mannitol (I) (20 g.) in 70 cc. dichloroglycerol, ClCH2CH(OH)CH2Cl heated at 140-50° while HCl is passed through the suspension for 3.5 hrs., gives 5.4 g. of 1,4,3,6-dianhydromannitol (isomannide) (II), m. 87-8°, [α]D 91° (H2O, c 2.28). I (500 g.) in 3 l. fuming HCl, boiled 72 hrs., gives 140 g. of II. 1,6-Dichloromannitol, ClCH2[CH(OH)]4CH2Cl (III) (C.A. 38, 2628.6) (2 g.), heated in vacuo at 180°, gives 0.95 g. of II. II (4 g.) in 5.6 g. C5H5N, treated with SOCl2 at 0° and heated 0.5 hr. at 100°, gives 70% of the 2,5-di-Cl compd. (IV), m. 67°, [α]D 93.5° (CHCl3, c 2.054); this is unchanged on distn. with fused KOH. II (1 g.), treated 4 times with MeI and Ag2O at 45°, gives 0.9 g. of the 2,5-di-Me ether (IVA), m. 75-6°, [α]D18 175° (CHCl3, c 2.287). II (1 g.) in 20 cc. fuming HCl, heated 24 hrs. in a sealed tube, gives 0.25 g. of III; thus positions 1 and 6 are involved in the anhydro rings. II (1 g.), heated at 120° for 29 hrs. with 50 cc. MeOH satd. with NH3 at 0°, gives 0.8 g. unchanged II; it is also unaffected with 10% MeOH-MeONa under the same conditions. II is not oxidized by HNO3 (d. 1.14) on heating at 100° for 4 hrs. Pb(OAc)4 in AcOH is without action on II in 48 hrs., indicating that the 2 OH groups are not on adjacent C atoms. IV (7.2 g.) in 200 cc. fuming HCl, heated in a sealed tube for 72 hrs. at 110°, gives 1.6 g. of unchanged IV and 3.4 g. of 1,2,5,6-tetrachloromannitol (V), m. 69-70°, [α]D 28.3° (CHCl3, c 3.107); 3,4-di-Bz deriv., m. 109-10°, [α]D17 -95.4° (CHCl3, c 1.048). V and PCl5 at 130° for 1 hr. give hexachloromannitol; thus V possesses the configuration of I. With MeONa at room temp. for 4 hrs. 1 g. of V gives 0.5 g. of IV. V (0.3 g.), shaken overnight with 25 cc. Me2CO contg. 0.1 cc. H2SO4, gives 0.33 g. of the 3,4-acetone deriv. (VI), b0.05 115° (bath temp.), nD16 1.4954, [α]D 56.8° (CHCl3, c 2.405); VI results also in 0.4-g. yield from 1 g. of 1,6-dichloro-3,4-acetonemannitol (VII)(Micheel, C.A. 26, 4304) and SOCl2 in C5H5N (1 hr. at 100°). VII (5 g.), treated 5 times with MeI and Ag2O at 45° for 9 hrs., gives 1.6 g. of the 2,5-di-Me ether (VIII), m. 56°, [α]D 11.5° (CHCl3, c 2.253); 0.503 g. of VIII in 40 cc. of 75% EtOH contg. 5% H2SO4, kept at room temp. for 550 hrs. (change in [α]D from 9.5° to -35°), gives 0.21 g. of 1,6-dichloro-2,5-dimethylmannitol, m. 131°; with MeONa in MeOH 0.17 g. gives 0.09 g. of IVA; this shows that the HO groups of II are located at C2 and C5. Mannitan (IX) distils at 10 mm. practically without decompn.; distn. of 2 g. of IX with 2 drops of concd. H2SO4 at 10 mm. gives 1.1 g. of II. IX (5 g.) in 50 cc. C5H5N, treated at 0° with 6 g. p-MeC6H4SO2Cl and kept at room temp. for 96 hrs. (with addn. of 25 cc. Ac2O after 48 hrs.), gives 10.5 g. of 1-tosyl-2,4,5-triacetylmannitan (X), a liquid. Reaction of X with MeONa gives II. That the tosyl group is on a primary alc. group is shown by treatment of X with NaI in Me2CO to give 80% of p-MeC6H4SO3Na. The above facts prove that the rings are hydrofuranol in type.
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      Isosorbide as a Renewable Platform chemical for Versatile Applications-Quo Vadis?
      Rose, Marcus; Palkovits, Regina
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      A review. Isosorbide is a platform chem. of considerable importance for the future replacement of fossil resource-based products. Applications as monomers and building blocks for new polymers and functional materials, are conceivable. This minireview deals with all aspects of isosorbide chem., which includes its prodn., special properties, and chem. transformations for its utilization in biogenic polymers and other applications of interest.
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      Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): A review
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      A review. The use of the 1,4:3,6-dianhydrohexitols isosorbide, isomannide, and isoidide in polymers is reviewed. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. In the field of polymeric materials, these diols are essentially employed to synthesize or modify polycondensates. Their attractive features as monomers are linked to their rigidity, chirality, non-toxicity, and the fact that they are not derived from petroleum. First, the synthesis of high glass transition temp. polymers with good thermomech. resistance is possible. Second, the chiral nature of 1,4:3,6-dianhydrohexitols may lead to specific optical properties. Finally, biodegradable polymers can be obtained. The prodn. of isosorbide on an industrial scale with a purity satisfying the requirements for polymer synthesis suggests that isosorbide will soon emerge in industrial polymer applications. However, a deciding factor will be the redn. of polymn. time of these low-reactivity monomers to values compatible with economically viable prodn. processes to give polyesters, polyamides, poly(amide esters), poly(ester imides), polycarbonates, polyurethanes, and polyethers.
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      Wu, J.; Jasinska-Walc, L.; Dudenko, D.; Rozanski, A.; Hansen, M. R.; van Es, D.; Koning, C. E. An investigation of polyamides based on isoidide-2,5-dimethyleneamine as a green rigid building block with enhanced reactivity. Macromolecules 2012, 45, 9333– 9346,  DOI: 10.1021/ma302126b
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      An Investigation of Polyamides Based on Isoidide-2,5-dimethyleneamine as a Green Rigid Building Block with Enhanced Reactivity
      Wu, Jing; Jasinska-Walc, Lidia; Dudenko, Dmytro; Rozanski, Artur; Hansen, Michael Ryan; van Es, Daan; Koning, Cor E.
      Macromolecules (Washington, DC, United States) (2012), 45 (23), 9333-9346CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      Novel, semicryst. polyamides and copolyamides were synthesized from a new carbohydrate-based diamine, namely isoidide-2,5-dimethyleneamine (IIDMA). In combination with 1,6-hexamethylene diamine (1,6-HDA) as well as the biobased sebacic acid (SA) or brassylic acid (BrA), the desired copolyamides were obtained via melt polymn. of the nylon salts followed by a solid-state polycondensation (SSPC) process. Depending on the chem. compns., the no. av. mol. wts. (Mn) of the polyamides were in the range of 4000-49000 g/mol. With increasing IIDMA content in the synthesized copolyamides, their corresponding glass transition temps. (Tg) increased from 50 °C to approx. 60-67 °C while the melting temps. (Tm) decreased from 220 to 160 °C. The chem. structures of the polyamides were analyzed by NMR and FT-IR spectroscopy. Both differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analyses revealed the semicryst. character of these novel copolyamides. Variable-temp. (VT) 13C{1H} cross-polarization/magic-angle spinning (CP/MAS) NMR and FT-IR techniques were employed to study the crystal structures as well as the distribution of IIDMA moieties over the cryst. and amorphous phases of the copolyamides. The performed ab initio calcns. reveal that the stability of the IIDMA moieties is due to a pronounced "boat" conformation of the bicyclic rings. The incorporation of methylene segments in between the isohexide group and the amide groups enables the hydrogen bonds formation and organization of the polymer chain fragments. Given the sufficiently high Tm values (∼200 °C) of the copolyamides contg. less than 50% of IIDMA, these biobased semicryst. copolyamides can be useful for engineering plastic applications.
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    16. 16
      Montgomery, R.; Wiggins, L. F. 77. The anhydrides of polyhydric alcohols. Part IV. The constitution of dianhydro sorbitol. J. Chem. Soc. 1946, 390– 393,  DOI: 10.1039/jr9460000390
      16
      Anhydrides of polyhydric alcohols. IV. Constitution of dianhydrosorbitol
      Montgomery, R.; Wiggins, L. F.
      Journal of the Chemical Society (1946), (), 390-3CODEN: JCSOA9; ISSN:0368-1769.
      cf. Hockett, et al., C.A. 40, 4677.3. Sorbitol (500 g.) and concd. HCl, refluxed 24 hrs., give 265 g. (66%) of 1,4,3,6-dianhydrosorbitol (I), b10 160-5°, m. 61-3°, [α]D 43.9° (H2O, c 0.8). I does not react with Pb(OAc)4 in AcOH or with BzH in the presence of ZnCl2. I (100 g.) in 200 cc. H2O at 40°, treated with 258 g. Me2SO4 and 360 cc. 30% NaOH in 10 portions during 2 hrs., gives 92 g. of the 2,5-di-Me deriv. (II), b0.1 93-5° (bath), nD19 1.4622, [α]D21 92.9° (CHCl3, c 1.51). I does not react with 5% MeONa in MeOH (20 hrs. at 120°) or with MeOH-NH3 (satd. at 0°) at 120° for 30 hrs. I (5 g.) and 50 cc. fuming HCl, heated at 100-10° for 24 hrs., give 5 g. of a dark brown sirup which, with (HCHO)3 and concd. H2SO4, yields 1,6-dichloro-2,4,3,5-dimethylenesorbitol, m. 116° (C.A. 38, 2628.6). 1,2-Acetoneglucose (40 g.) yields 30 g. of the 5,6-ditosyl deriv. (III) and 18.2 g. of the 3,5,6-tritosyl deriv., m. 129-30°, [α]D17 -3.4° (CHCl3, c 4.14), which results also on further tosylation of III (cf., however, Ohle, et al., C.A. 23, 103, who describe a 3,5,6-deriv. m. 95-6°, [α]D -5.2°). Reduction of 3,6-anhydro-glucose over Raney Ni at 110-20°/100 atm. gives 3,6-anhydrosorbitol (IV); distn. of 0.2 g. with a trace of H2SO4 gives 25 mg. of I. IV (1 g.) and 1.28 g. p-MeC6H4-SO2Cl in 10 cc. C5H5N, mixed at 0° and kept at room temp. for 60 hrs., Ac2O being added at 0° after the 1st 16 hrs., give 1.63 g. of 1-tosyl-2,4,5-triacetyl-3,6-anhydrosorbitol (V); 1.2 g. of V and 0.25 g. Na in 20 cc. MeOH and 10 cc. CHCl3, on standing overnight, give 73% of I. V (0.4 g.) and 0.29 g. NaI in 15 cc. Me2CO, heated at 110°, give 80% of p-MeC6H4SO3Na; the other product could not be crystd. Catalytic reduction of 1 g. of 2,5-dimethyl-3,6-anhydroglucose in H2O over 1 g. Raney Ni at 110-20°/100 atm. for 6 hrs., gives 1 g. of 2,5-dimethyl-3,6-anhydrosorbitol, m. 70-1°, [α]D22 -15.6° (CHCl3, c 0.173); treated as above with p-MeC6H4SO2Cl and Ac2O in C5H5N, 0.3 g. yields 0.23 g. of 1-tosyl-4-acetyl-2,5-dimethyl-3,6-anhydrosorbitol which, with MeONa in MeOH-CHCl3, gives 0.07 g. of II.
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    17. 17
      Fletcher, H. G., Jr; Goepp, R. M., Jr Hexitol Anhydrides.1 1,4,3,6-Dianhydro-L-iditol and the Structures of Isomannide and Isosorbide. J. Am. Chem. Soc. 1946, 68, 939– 941,  DOI: 10.1021/ja01210a007
      17
      1,4,3,6-Dianhydro-L-iditol and the structure of isomannide and isosorbide
      Fletcher, Hewitt G., Jr.; Goepp, R. Max, Jr.
      Journal of the American Chemical Society (1946), 68 (), 939-41CODEN: JACSAT; ISSN:0002-7863.
      1,4,3,6-Dianhydrosorbitol (isosorbide) (I) (50 g.) and 10 g. Raney Ni in abs. EtOH, freed of EtOH in vacuo, heated 10 min. at 135-40°/2 mm., and then subjected to a pressure of 3750 lb./sq. in. of H at 190-200° for 2 hrs., gave a sirup which could not be crystd. Distn. of 46.1 g. at 140° (bath)/2 mm. gave 27.2 g. of distillate, [α]D25 44.2° in AcOH, and 18.1 g. of a residue (II), [α]D25 27.4° in AcOH. II (18.1 g.) in 50 ml. C5H5N at 0°, treated with 32 ml. BzCl, allowed to stand overnight at room temp., poured into 726 ml. ice water, and crystd. from EtOH, gave 31 g. of a product, m. 81.8-90°; the CHCl3, soln., shaken with aq. NaHCO3 to remove the BzOH and the product crystd. from EtOH and BuOH, gave 16.1 g. of the 2,5-di-Bz deriv. (III), m. 111-11.3° (m. ps. cor.), [α]D23.4 140.3° (CHCl3, c 2.03), [α]D28.2 110.5° (C5H5N, c 2.07), of 1,4,3,6-dianhydro-L-iditol (L-isoidide) (IV), m. 63.8-4.4°, [α]D24.5 20.8° (CHCl3, c 2.02), [α]D28.2 33.3° (C5H5N, c 2.24°). By the same method, 50 g. of isomannide (V) gives 0.92 g. of III. L-Iditol (0.97 g.) and 2 drops concd. H2SO4, heated at 140-5° (bath)/4 cm. for 1.25 hrs. and the product treated with BzCl in C5H5N, gave 31.4% of III. III (10 g.) in 40 ml. CHCl3 at 0°, treated with a chilled soln. of 0.1 g. Na in 40 ml. MeOH and kept at 0° for 23 hrs., gave 90.4% of IV, which is sparingly sol. in CHCl3. The prepn. of IV is best explained by the assumption that Raney Ni exerts a dehydrogenating action on the secondary alcs., converting 1 or both of the free HO groups to sym. CO groups, which are subsequently reduced with the formation of a mixt. of diastereoisomers. The isolation of IV from I and V proves the structure of IV and confirms those of I and V.
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    18. 18
      Fletcher, H. G., Jr; Goepp, R. M., Jr 1,4;3,6-Hexitol dianhydride L-isoidide. J. Am. Chem. Soc. 1945, 67, 1042– 1043,  DOI: 10.1021/ja01222a513
      18
      1,4,3,6-Hexitol dianhydride. L-Isoidide
      Fletcher, Hewitt G., Jr.; Goepp, R. Max, Jr.
      Journal of the American Chemical Society (1945), 67 (), 1042-3CODEN: JACSAT; ISSN:0002-7863.
      Reduction of D-isomannide or D-isosorbide at 200° over Raney Ni at 250 atms. gives a mixt. of hexitol dianhydrides from which, by benzoylation and fractional crystn., there is sepd. 1,4,3,6-dianhydro-L-iditol (L-isoidide) (I), m. 63.7-4.5°, [α]D24.5 20.8° (H2O, c 2.02), [α]D28.2 33.27° (C5H5N, c 2.24); dibenzoate, m. 111-11.3°, [α]D25.2 141.9° (CHCl3, c 2.15), [α]D28.2 110.5° (C5H5N, c 2.07). Similar data are given for the D-sorbitol and D-mannitol derivs. I also results by the direct acid-catalyzed anhydrization of L-iditol.
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    19. 19
      Cope, C.; Shen, T. Y. The stereochemistry of 1,4: 3,6-dianhydrohexitol derivatives. J. Am. Chem. Soc. 1956, 78, 3177– 3182,  DOI: 10.1021/ja01594a055
      19
      Stereochemistry of 1,4:3,6-dianhydrohexitol derivatives
      Cope, Arthur C.; Shen, T. Y.
      Journal of the American Chemical Society (1956), 78 (), 3177-82CODEN: JACSAT; ISSN:0002-7863.
      Ditosylate (I) (35 g.) of D-isomannide (II) and 40 g. Et4NOAc.H2O (III) refluxed 70 hrs. on the steam bath in 400 cc. Me2CO, concd. to 100 cc., dild. with 400 cc. H2O, and extd. with CHCl3, the extd. evapd., the residue distd., and the distillate (b0.7 120-50° bath) cooled gave 14.1 g. diacetate (IV) of 1,4:3,6-dianhydro-L-iditol (V), b0.5 100-10°, m. 57-7.6°, [α]D25 89.6° (c 1.5, CHCl3); all m.ps. are cor. II (4.0 g.) treated 2 days at 0-5° with 12 cc. Ac2O and 15 cc. pyridine, dild. with H2O, and extd. with CHCl3 gave 5.63 g. diacetate (VI) of 1,4:3,6-dianhydro-D-mannitol (VII), b0.5 118°, nD25 1.4680, [α]D25 194.5° (c 6.7, CHCl3). IV (12.5 g.) in 90 cc. abs. MeOH treated at 0° with 10 cc. N Ba(OMe)2 in MeOH, kept 18 hrs. at 5°, treated with powd. Dry Ice, and centrifuged, and the supernatant liquid worked up yielded 7.1 g. V, m. 43-3.5°, [α]D25 18.7° (c 2, H2O). IV (350 mg.) in 5 cc. 20% KOH shaken 20 min. with 1 cc. BzCl yielded 386 mg. dibenzoate of V, flakes, m. 110.6-11.4° (from aq. EtOH), [α]D26 134.2° (c 3, CHCl3). V (1.46 g.) treated 18 hrs. at 0-5° with 4.5 g. p-MeC6H4SO2Cl in 15 cc. pyridine and dild. with ice water yielded 3.96 g. di-p-toluene-sulfonate (VIII) of V, m. 105.5-106° (from MeOH), [α]D25 33.2° (c 2.5, CHCl3). Ditosylate (IX) (9.0 g.) of isosorbide refluxed 72 hrs. with 5.0 g. III in Me2CO, concd., dild. with H2O, and extd. with CHCl3 yielded 4.54 g. 5-O-acetyl-2-O-p-toluenesulfonyl-1,4:3,6-dianhydro-L-iditol (X), m. 95.5-6.3° (from MeOH), [α]D25 50.5° (c 4.7, CHCl3). X (1.0 g.) in 10 cc. abs. MeOH treated at 0° with 10 cc. 0.1N Ba(OMe)2 in MeOH, neutralized after 18 hrs. with powd. Dry Ice, centrifuged, and evapd. in vacuo, the oily residue treated 18 hrs. with 1.0 g. p-MeC6H4SO2Cl in 10 cc. pyridine at 5°, and the mixt. poured into ice water and filtered yielded 0.67 g. VIII, m. 105-6°. VIII (3.8 g.) and 1.75 g. III in 50 cc. Me2CO refluxed 72 hrs., concd. to 20 cc. and dild. with H2O gave 2.19 g. unchanged VIII, m. 104.5-5.3°. I (22.6 g.), 20 g. K phthalimide, and 300 cc. HCONMe2 heated 40 hrs. at 110° and dild. with 1.5 l. H2O, and the pptd. solid extd. with 300 cc. boiling EtOH left 6.9 g. 2,5-diphthalimido-2,5-dideoxy deriv. (XI) of V, prisms, m. 243.4-3.6° (from EtOAc-EtOH), [α]D25 168° (c 1, CHCl3). XI (8.08 g.), 1.51 g. 85% N2H4.H2O, and 200 cc. EtOH refluxed 2 days, treated with 20 cc. 4N HCl, refluxed 1 hr., and filtered, the filtrate evapd. to dryness in vacuo, the residue dissolved in 30 cc. H2O, filtered, treated with Darco, acidified to pH about 4.5 with aq. (CO2H)2, and dild. with EtOH to ppt. 2.1 g. oxalate, m. 242-3°, and the oxalate dissolved in H2O, treated with 0.7 g. NaOH in H2O, and distd. yielded 0.97 g. 2,5-di-NH2 analog (XII) of XI, b0.2 110°, m. 59-60°; picrate, m. 227.8-28.1°. I (39 g.) and 70 g. Me2NH shaken 72 hrs. at 120° in 500 cc. tetrahydrofuran in a steel bomb, the mixt. concd., treated with 100 cc. 20% aq. NaOH and extd. with Et2O, the ext. evapd., and the sirupy residue distd. yielded 7.5 g. 2,5-di-(Me2NCH2) analog (XIII) of XI, b0.2 80-100°, m. 57.5-8.5° (sublimed at 40° and 0.2 mm.), [α]D26 30.0° (c 2.1, H2O). XIII treated with excess MeI in boiling MeOH and recrystd. from aq. EtOH gave XIII.2MeI.H2O, m. 260° (decompn.), [α]D26 33.3° (c 2.2, H2O). XIII gave a dipicrate, m. 222° (decompn.) (from aq. EtOH). IX (45.2 g.) and 100 g. Me2NH in 600 cc. tetrahydrofuran heated at 120-30° with shaking in a bomb, cooled, concd., treated with 150 cc. 20% NaOH, and extd. with Et2O, and the ext. worked up gave 0.68 g. crude low boiling fraction, b0.3 41°, and 14.5 g. residue; the distillate treated with MeI in MeOH yielded 1.13 g. 5-dimethylamino-5-deoxy-1,4:3,6-dianhydro-1,2-L-iditoleen methiodide, plates, m. 202-3° (decompn.), [α]D31 33.1° (c 2.5, H2O); the nonvolatile residue in Et2O washed with H2O, dried over KOH, and concd. gave a brown sirup, which treated with picric acid yielded the picrate of 2-O-p-toluenesulfonyl-5-dimethylamino-5-deoxy-1,4:3,6-dianhydro-L-iditol (XIV), m. 179.4-80.8°. The sirup treated with MeI in MeOH gave XIV.MeI, prisms, m. 177.6-8.6° (from EtOH). IX (45.2 g.) and 100 g. Me2NH in 600 cc. tetrahydrofuran shaken 48 hrs. at 165°, concd., treated with 150 cc. 20% aq. NaOH, and extd. with Et2O, and the ext. worked up yielded 13.4 g. 2,5-bis(dimethylamino)-2,5-dideoxy-1,4:3,6-dianhydro-D-glucitol (XV), white prisms, m. 54.6-5.4° (sublimed at 80° and 0.5 mm.), [α]D25 106.3° (c 1.6, H2O). Cryst. oxalate (1.17 g.) of 2,5-di-NH2 analog (XVI) of XV in 10 cc. 98% HCO2H and 8 cc. 37% CH2O refluxed 18 hrs., treated with 10 cc. 4N HCl and evapd. to dryness in vacuo, the residue dissolved in 30 cc. N NaOH and extd. with Et2O, the ext. worked up, and the residue sublimed at 80° and 0.5 mm. gave 0.67 g. XV, m. 54-4.5°, which gave XV.2MeI.H2O, m. 292-5° (decompn.). XVI (3.0 g.) and 25 g. MeI in 100 cc. abs. MeOH refluxed 48 hrs. with stirring with 4 g. Na2CO3, acidified with 48% HI, and evapd. to dryness in vacuo yielded 9.25 g. XVI.2MeI, m. 289-94° (decompn.). XVI.2MeI in 100 cc. dry 1-methylmorpholine treated slowly with 2 g. LiAlH4 in 20 cc. 1-methylmorpholine with stirring and cooling, the mixt. heated 48 hrs. at 90-5°, treated with cooling with EtOAc, and centrifuged, the ppt. dissolved in 10% NaOH and extd. with Et2O, and the combined ext. and 1-methylmorpholine soln. fractionated gave 2.73 g. XV, m. 51.5-3.5°. XV (1.0 g.) warmed 15 min. on the steam bath with 2.0 g. p-MeC6H4SO2Cl in 20 cc. 10% aq. NaOH gave only 135 mg. pure XV, m. 54.3-5.3°. XII (0.72 g.) in 10 cc. 98% HCO2H and 6 cc. 37% CH2O refluxed 18 hrs. gave 0.72 g. XIII, m. 52-4°. XII (0.320 g.) and 5 g. MeI in 20 cc. abs. MeOH refluxed 65 hrs. with 0.85 g. NaHCO3 and worked up in the usual manner yielded 0.667 g. XIII.2MeI, prisms, m. 225-8° (decompn.) (from aq. EtOH). XII (0.72 g.) and 3 cc. concd. HCl in 30 cc. glacial AcOH treated slowly with cooling and stirring with 2.0 g. BuONO, the soln. kept 0.5 hr. at 0° and 18 hrs. at room temp., concd. in vacuo, dild. with H2O, and extd. with CHCl3, the ext. worked up, the residual sirup distd., the resulting oil chromatographed on 10 g. Al2O3 with 5:1 petr. ether-Et2O, and the 1st 60 cc. effluent worked up gave 103 g. XVII (R = R' = Cl), m. 67° XVI (0.72 g.) deaminated in the same manner yielded 87 mg. XVII. On the basis of these results D-isomannide has 2 endo-OH groups, isosorbide has 1 endo at C-5 and 1 exo at C-2, and L-isoidide has 2 exo-OH groups. Revised configurations are suggested for a no. of dianhydrohexitol derivs. and other compds. contg. bicyclic ring systems with 2 cisfused 5-membered rings on the basis of the steric effects observed (previous configuration and revised configuration given): 5-chloro-5-deoxy(?)-1,4:3,6-dianhydro-D-glucitol (W. G. Overend, et al., C.A. 43, 2939f), 5-chloro-5-deoxy-1,4:3,6-dianhydro-L-iditol; x-iodo-x'-O-p-toluenesulfonyl-1,4:3,6-dianhydro-D-glucitol (Hockett, et al., C.A. 40, 4677.3), 5-iodo-5-deoxy-2-O-p-toluenesulfonyl-1,4:3,6-dianhydro-L-iditol; 2,5-dichloro-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol (Wiggins, C.A. 39, 2736.9), 2,5-dichloro-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol; 2-chloro-2-deoxy-5-O-methanesulfonyl-1,4:3,6-dianhydro-D-mannitol (Montgomery and Wiggins, C.A. 43, 2940a), 2-chloro-2-deoxy-5-O-methanesulfonyl-1,4:3,6-dianhydro-D-glucitol; 2-chloro-2-deoxy-5-phenylcarbamyl(?)-1,4:3,6-dianhydro-D-mannitol (Carr´e and Mauclere, C.A. 25, 4526), 2-chloro-2-deoxy-5-phenylcarbamyl-1,4:3,6-dianhydro-D-glucitol; 2,5-diiodo-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol (Hockett, et al., C.A. 40, 4677.8), 2,5-diiodo-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol; 2,5-diamino-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol and derivs. (Montgomery and Wiggins, C.A. 40, 5016.4), 2,5-diamino-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol and derivs.; 2,5-dithio-2,5-dideoxy-1,4:3,6-dianhydro-D-mannitol and derivs. (Bladon and Owen, C.A. 44, 6811h), 2,5-dithio-2,5-dideoxy-1,4:3,6-dianhydro-L-iditol and derivs.
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    20. 20
      Brimacombe, J.; Foster, A. B.; Stacey, M.; Whiffen, D. H. Aspects of stereochemistry – I: Properties and reactions of some diols. Tetrahedron 1958, 4, 351– 360,  DOI: 10.1016/0040-4020(58)80056-3
      20
      Aspects of stereochemistry. I. Properties and reactions of diols
      Brimacombe, J. S.; Foster, A. B.; Stacey, M.; Whiffen, D. H.
      Tetrahedron (1958), 4 (), 351-60CODEN: TETRAB; ISSN:0040-4020.
      The extent of intramol. H-bonding, as detd. by infrared spectroscopy in the HO stretching region in certain vicinal diols provided evidence for the stabilities of certain conformations. With the exception of cyclohexane-trans-1,2-diol (I), the carbocyclic trans diols were prepd. by bromination of the corresponding olefins, solvolysis of the trans bromides with AcOH and AgOAc and sapon. of the trans diacetates (Winstein and Roberts, C.A. 48, 5812f). The carbocyclic cis diols were obtained by hydroxylation of the appropriate olefins with KMnO4 (Clarke and Owen, C.A. 43, 7434h). Cycloheptene (12 g.) in 40 ml. Et2O at 0° brominated in Et2O, the colored soln. washed successively with 0.01N NaOH and water, the dried (MgSO4) soln. evapd. and the residue distd. gave 25.4 g. trans-1,2-dibromocycloheptane b20-5 138-40°, n23.5D 1.5532; this added to 40 g. AgOAc in 80 ml. AcOH and 25 ml. Ac2O (previously kept 2 hrs. at 110°), the mixt. kept 15 hrs. at 110° and the filtered soln. evapd. gave 8.2 g. trans-1,2-diacetoxycycloheptane b0.5 99-101°, n23D 1.4530. The diacetate (4 g.) boiled 2 hrs. in 8 ml. alc. and 8 ml. 35% aq. NaOH, the mixt. dild. with 8 ml. water and extd. 1 day with Et2O yielded 74% cycloheptane-trans-1,2-diol (II), b0.5 100°, m. 60-2°. Similarly were prepd. indan-trans-1,2-diol (III), m. 156-7°, and cyclopentane-trans-1,2-diol (IV), b15-20 131°. I, m. 102-3°, was prepd. according to Roebuck and Adkins [Org. Syntheses, Collective Vol. III, 217(1955)]. The cis-1,2-diols of cyclohexane (V), m. 93-4°, cycloheptane (VI), m. 45-6°, cyclopentane (VII), b29 133°, and indan (VIII), m. 96-8°, were obtained in 14, 11, 11, and 10.8-14.5% yields, resp. 3,4-Di-O-acetyl-D-xylal [3 g., m. 36-8°, [α]20D -288° (c 1.0, H2O)] prepd. according to Overend, et al. (C.A. 44, 6819f) in 100 ml. 1:1 alc.-H2O hydrogenated 30 min. with 100 mg. PtO2, the filtered soln. evapd. and the product distd. gave 1.3 g. 3,4-di-O-acetyl-1,5-anhydro-2-deoxy-D-threopentitol (IX), b0.5 102°, [α]20D -38° (c 0.85, CHCl2), [M]D -77°. IX (1.4 g.) refluxed 2 hrs. in 8 ml. 6N NaOH and 8 ml. alc., the soln. filtered through Amberlite IR-120 (H+) and the filtrate evapd. yielded 60.7% 1,5-anhydro-2-deoxy-D-threopentitol (X), b0.5 75-80°, m. 69°, [α]20D -29.6° (c 2.5, H2O), [M]D -35°. Hydrogenation of 3.2 g. 3,4-di-O-acetyl-L-arabinal (b0.01 110-40°, [α]20D -236° (c 1.12, CHCl3), prepd. according to Deriaz, et al. (C.A. 44, 2453a), and worked up similarly to X gave 2.2 g. 3,4-di-O-acetyl-1,5-anhydro-2-deoxy-L-erythropentitol (XI), b0.2 86-90°, [α]20D 75° (c 1.0, H2O), [M]D 151°. XI (1.4 g.) sapond. as for IX yielded 60.7% 1,5-anhydro-2-deoxy-L-erythropentitol (XII), b0.2-0.3 120°, [α]20D 64° (c 1.5, H2O), [M]D 75°. L-Arabinal (0.8 g., m. 80-2°, [α]20D -202° (c 3.0, H2O) prepd. according to D., et al.) in 20 ml. 1:1 alc.-H2O hydrogenated 1 hr. with 50 mg. PtO2 and the filtered soln. evapd. yielded 70.4% XII. DiBu L-tartrate (10 g., n16.5D 1.4450, [α]20D 10.2°) in 50 ml. tetrahydrofuran added slowly with stirring to 6 g. LiAlH4 in 150 ml. tetrahydrofuran and 75 ml. Et2O, the mixt. refluxed 1.5 hrs. and decompd. with 200 ml. H2O, the mixt. centrifuged and the solid residue washed with water, the combined centrifugates evapd. and the residue taken up in 200 ml. 1:1 H2O-MeOH, the soln. neutralized with CO2 and the filtered soln. evapd., the glassy solid taken up in 20 ml. 1:1 H2SO4-H2O and shaken 1 hr. with 15 ml. BzH, the mixt. dild. with water and filtered, the ppt. washed (water) and crystd. (PhMe) yielded 2.2 g. 1,2,3,4-di-O-benzylidene-L-threitol (Klosterman and Smith, C.A. 48, 2585f), m. 216-17°, [α]25D 81° (c 0.5, CHCl3), hydrolyzed 30 min. in 40 ml. 1:3 N H2SO4-alc., the hydrolyzate concd. and extd. with Et2O, the ext. filtered through Amberlite IRA-400 (HO-), the filtrate evapd. and the residue recrystd. to give 0.5 g. L-threitol (XIII), m. 88-9°, [α]20D -4° (c 8.0, H2O). XIII (2.17 g.) in 2.2 g. H2O and 2.2 g. H2SO4 heated 24 hrs. at 120° in a sealed tube, the hydrolyzate dild. with water, the soln. filtered through Amberlite IRA-400 (HO-) and the filtrate concd. gave 1.1 g. 1,4-anhydro-L-threitol (XIV), b15-17 120°, m. 63-4°, [α]20D -4° (c 7.2, H2O). Erythritol (3 g.) in 3 g. H2O and 3 g. H2SO4 heated 2 days at 120° and in a sealed tube and the hydrolyzate worked up as for XIII gave 1,4-anhydroerythritol (XV), b2-3 144°, n20D 1.4767. The zone electrophoretic (ionophoretic) mobility of the diols were detd. using the app. and technique of Foster, et al. (C.A. 50, 4584g), with a borate buffer (pH 10). The mobility, MG is defined as that mobility relative to D-glucose under standard conditions. The diols (0.43 millimole) in 5 ml. H2O were treated with 15 ml. 0.05M NaIO4 and the vol. rapidly adjusted to 100 ml. at 0°, aliquots withdrawn periodically titrated for unchanged NaIO4 by the standard arsenite method and where possible the times of half oxidation (t0.5) were recorded. The diols (26 mg.) in AcOH at 20° were treated with 49 ml. 0.1315N Pb(OAc)4 in AcOH at 20°, the vol. adjusted to 50 ml. and the unconsumed oxidant detd. on 5-ml. aliquots according to Hockett and McClenahan (C.A. 33, 68034). Methylation of 1,3-O-methylidene glyceritol (XVI), b11 82°, n20D 1.4533, according to Hibbert and Carter (C.A. 23, 98) gave 5-O-methyl-1,3-dioxan-5-ol, b. 147°, n25D 1.4230, converted by acid hydrolysis to 2-O-methyl-1,3-O-methylidene glyceritol, b13 120°, n23D 1.4476, completely resistant to attack by Pb(OAc)4 under the above conditions. Infrared spectra were measured in 2-cm. layers in CCl4 according to Spedding and Whiffen (C.A. 51, 15275b) with concns. of less than 0.005M diol. The results are tabulated (compd., ν for free and bonded OH in cm.-1, arithmetical difference between frequencies, arithmetical difference between standard secondary (3629 cm.-1) and bonded OH group frequencies, t0.5 for NaIO4 oxidation, t0.5 for Pb(OAc)4 oxidation and MG given): I, 3633, 3602, 31, 27, rapid, 1.9 hrs., 0.00; X, 3633, 3608, 25, 21, 20 min., 5 hrs., 0.00; V, 3632, 3592, 40, 37, rapid, 5 min., 0.07; XII, 3633, 3583, 50, 46, rapid, 9 min., 0.23; IV, 3624, -, -, -, 5 min., 10 min., 0.00; XIV, 3624, -, -, -, -, 11 hrs., 0.00; VII, 3624, 3579, 45, 50, rapid, rapid, 0.69; XV, 3624, 3585, 39, 44, -, rapid, 0.88; 1,4,3,6-dianhydro-D-glucitol, 3624, 3540, 84, 89, -, -, -; 1,4,3,6-dianhydro-D-glucitol, 3624, 3540, 84, 89, -, -, -; 1,4,3,6-dianhydro-D-glucitol, 3624, 3540, 84, 89, -, -, -; 1,4,3,6-dianhydro-D-mannitol, -, 3540, -, 89, -, -, -; 1,4,3,6-dianhydro-L-iditol, 3624, -, -, -, -, -, -; III, 3624, -, -, -, 60 min., -, 0.00; VII, 3620, 3579, 41, 50, rapid, -, 0.72; II, 3626, 3589, 37, 40, rapid, -, 0.53; VI, 3632, 3588, 44, 41, rapid, -, 0.69; XVI, 3625, 3593, 42, 36, -, -, -. In certain compds. the stabilities of different conformations can be affected by H-bonding from a substituent HO group to a ring O. Using the parameters evaluated by Whiffen (C.A. 51, 4261i) [M]D in aq. soln. were calcd. for the possible chair conformations of certain pyran derivs. (diol, conformation, [M]D calcd., and [M]D observed given): X, HO groups axial, -43°, -35°, HO groups equatorial, -45°, -; XII, C-3 HO group axial, -45°, -, C-4 HO group axial, 88°, 75°. The rate of reaction of the vicinal diols of these cyclic systems with glycol splitting reagents, and their zone electrophoretic mobility in an alk. borate buffer is influenced by the presence of a ring O atom.
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    21. 21
      Montgomery, R.; Wiggins, L. F. 78. The anhydrides of polyhydric alcohols. Part V. 2 : 5-Diamino 1 : 4–3 : 6-dianhydro mannitol and sorbitol and their sulphanilamide derivatives. J. Chem. Soc. 1946, 0, 393– 396,  DOI: 10.1039/jr9460000393
      21
      Anhydrides of polyhydric alcohols. V. 2,5-Diamino-1,4,3,6-dianhydromannitol and -sorbitol and their sulfanilamide derivatives
      Montgomery, R.; Wiggins, L. F.
      Journal of the Chemical Society (1946), (), 393-6CODEN: JCSOA9; ISSN:0368-1769.
      1,4,3,6-Dianhydromannitol (59 g.) in 300 cc. dry C5H5N, treated at 0° with 155 g. p-MeC6H4SO2Cl in portions and allowed to warm to and stand at room temp. for 24 h., gives 162 g. of the 2,5-ditosyl deriv. (I), m. 93-4°, [α]D20 92.2° (CHCl3, c 2.582). I (50 g.) in 1500 cc. MeOH-NH3 (satd. at 0°), heated at 170-80° for 30 h., the residue heated with 42 g. Ba(OH)2 in 400 cc. H2O for 1 h., the residue from this operation freed from H2O by repeated distn. with C6H6, and extd. 6 times with 250-cc. portions of CHCl3, gives 12.8 g. of 2,5-diamino-1,4,3,6-dianhydromannitol (II), a sirup, b0.01 150° (bath), m. 59-62°, [α]D20 33.6° (CHCl3, c 2.322), which could be kept in cryst. condition only under N in sealed tubes; oxalate, m. 246-7° (decompn.); adipate, m. 189°; picrate, m. 227-8° (decompn.); sulfate, decomps. above 310°; dimethylenemucate, m. 246-7° (decompn.). II did not inhibit the growth of Staphylococcus aureus in vitro. II yields a disalicylidene deriv., yellow, m. 188-9°. The bis(p-acetamidophenylsulfonyl) deriv. (III), m. 278-9°, was prepd. from II and p-AcNHC6H4SO2Cl in dil. Me2CO contg. NaOH or NaHCO3 on stirring at room temp. for 45 min. or in C5H5N at room temp. for 2 days; it is optically inactive. Hydrolysis of 10 g. of III in 100 cc. Me2CO and 200 cc. 2 N HCl (refluxing 6 h.), or by heating 1 g. with 10 cc. 10% NaOH at 100° for 2 h., gives 2,5-disulfanilamido-1,4,3,6-dianhydromannitol (IV), m. 227-8°; it is optically inactive and does not form salts in aq. soln.; dry HCl in Me2CO-C6H6 (1:1) yields a di-HCl salt which effervesces between 180° and 215°, and yields IV with cold H2O. Reacetylation of IV (AcOH-Ac2O) gives III. II (3 g.) and p-O2NC6H4SO2Cl in C5H5N yield 9.3 g. of the bis(p-nitrophenylsulfonyl) deriv. (V), m. 213-14°, [α]D20 7.5° (Me2CO, c 2.65); redn. with Sn and HCl, or over Raney Ni, gives IV. Dianhydrosorbitol (58 g.) yields 190 g. of the 2,5-ditosyl deriv. (V), m. 101-2°, [α]D23 57.8° (CHCl3, c 4.945); treated as in the case of I, 50 g. of V yields 8.5 g. (54%) of 2,5-diamino-1,4,3,6-dianhydrosorbitol (VI), b0.01 105-10° (bath), nD18 1.5165, [α]D 43.6° (H2O, c 1.538); oxalate, m. 253-4° (decompn.); picrate, m. 200° (decompn.); HCl salt, does not m. 320°; sulfate, does not m. 330°; dimethylenemucate, m. 235-6° (decompn.); dimethylenesaccharate, m. 220-1° (decompn.). The salts did not inhibit the growth of S. aureus in vitro. The disalicylidene deriv. of VI m. 186-7°; bis(p-acetamidophenylsulfonyl) deriv., m. 263-4°, [α]D 51.4° (Me2CO-H2O (1:1), c 0.6); 2,5-disulfanilamido-1,4,3,6-dianhydrosorbitol (VII), m. 239-40°, [α]D 49.2° (Me2CO, c 0.406); the di-HCl salt, prepd. under anhyd. conditions, effervesces about 130° and is completely hydrolyzed by cold H2O. Bis(p-nitrophenylsulfonyl) deriv., m. 216-17°, [α]D20 56.8° (Me2CO, c 2.138); catalytic redn. over Raney Ni at room temp. and atm. pressure yields VII. IV and VII were only slightly sol. in H2O (0.02 g./100 cc.) but were fairly sol. in dil. HCl; they are inferior in bacteriostatic activity to sulfathiazole.
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    22. 22
      Bashford, V. G.; Wiggins, L. F. 82. Anhydrides of polyhydric alcohols. Part XIII. The amino-derivatives of 1 : 4–3 : 6-dianhydro-mannitol, -sorbitol, and -L-iditol, and their behaviour towards nitrous acid. J. Chem. Soc. 1950, 0, 371– 374,  DOI: 10.1039/jr9500000371
      22
      Anhydrides of polyhydric alcohols. XIII. The amino derivatives of 1, 4:3, 6-dianhydromannitol, -sorbitol, and L-iditol and their behavior towards nitrous acid
      Bashford, V. G.; Wiggins, L. F.
      Journal of the Chemical Society (1950), (), 371-4CODEN: JCSOA9; ISSN:0368-1769.
      cf. C.A. 43, 2939f; 44, 1O24d. 2, 5-Diamino-1, 4:3, 6-dianhydro-2, 5-didesoxysorbitol (I) (3.95 g.) in 25 cc. H2O, acidified with dil. HCl and treated with 4.5 g. NaNO2 in 25 cc. H2O, gives 1.27 g. 1,4:3,6-dianhydro-L-iditol (II), b0.05 115-30° (bath), [α]D 46.7° (Me2CO, c 1.9), characterized as the 2,5-bis(methylsulfonyl) deriv., m. 156.5° the small yield indicates that II was not the only product; the 2, 5-didesoxymannitol analog (III) of I also gives II; in the formation of II, deamination is accompanied by Walden inversion at C5 in the case of I and at both C2 and C5 in the case of III; 2,5-bis(p-tolylsulfonyl) deriv. (IV) of II, m. 90°, [α]D38.2°(CHCl3, c 2). IV(42g.) in 900 cc. MeOH, satd. at 0° with NH3, heated 30 hrs. at 160-70°, and the residue heated at 100° with 50 g. Ba(OH)2 in 400 cc. H2O, gives 2 g. 2,5-imino-1,4:3,6-dianhydro-2,5-didesoxy-D-mannitol (?) (V), m. 99-100°, [α]D 90.5° (CHCl3, c 2.65) [picrate, yellow, m. 219-20° (decompn.); HCl salt, m. 280-90° (decompn.); oxalate, m. 243°]; with NaNO2 in dil. AcOH, V forms an N-NO deriv., m. 121.5°, [α]D -323° (CHCl3, c 2.43). The conversion of I and III into II is paralleled by the epimerization of 2,4:3,5-dimethylene-D-manno- and -D-glucosaccharic acids (C.A. 38, 2631.8).
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    23. 23
      Thiyagarajan, S.; Gootjes, L.; Vogelzang, W.; Wu, J.; van Haveren, J.; van Es, D. S. Chiral building blocks from biomass: 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol. Tetrahedron 2011, 67, 383– 389,  DOI: 10.1016/j.tet.2010.11.031
      23
      Chiral building blocks from biomass: 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol
      Thiyagarajan, Shanmugam; Gootjes, Linda; Vogelzang, Willem; Wu, Jing; van Haveren, Jacco; van Es, Daan S.
      Tetrahedron (2011), 67 (2), 383-389CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)
      An efficient route towards the synthesis of 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol 4 has been developed resulting in significant improvements in both isolated yields and purity when compared to literature procedures. As a consequence, resin-grade 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol 4 has become available for lab. scale step-growth polymer synthesis. Addnl., an interesting renewable chiral 2-amino-2-deoxy-1,4-3,6-dianhydroiditol, has been isolated.
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    24. 24
      Thiyagarajan, S.; Gootjes, L.; Vogelzang, W.; van Haveren, J.; Lutz, M.; van Es, D. S. Renewable rigid diamines: efficient, stereospecific synthesis of high purity isohexide diamines. ChemSusChem 2011, 4, 1823– 1829,  DOI: 10.1002/cssc.201100398
      24
      Renewable Rigid Diamines: Efficient, Stereospecific Synthesis of High Purity Isohexide Diamines
      Thiyagarajan, Shanmugam; Gootjes, Linda; Vogelzang, Willem; van Haveren, Jacco; Lutz, Martin; van Es, Daan S.
      ChemSusChem (2011), 4 (12), 1823-1829CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      We report an efficient three-step strategy for synthesizing rigid, chiral isohexide diamines derived from 1,4:3,6-dianhydrohexitols. These biobased chiral building blocks are presently the subject of several investigations (in our and several other groups) because of their application in high-performance biobased polymers, such as polyamides and polyurethanes. Among the three possible stereo-isomers, dideoxy-diamino isoidide and dideoxy-diamino isosorbide can be synthesized from isomannide and isosorbide resp. in high yield with abs. stereo control. Furthermore, by using this methodol. dideoxy-amino isomannide - a tricyclic adduct - was obtained starting from isoidide in high yield. Our improved synthetic route is a valuable advance towards meeting scale and purity demands for evaluating the properties of new biobased performance materials, which will benefit the development of these plastics.
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    25. 25
      Kuszmann, J.; Medgyes, G. Synthesis and biological activity of 1,4:3,6-dianhydro-2,5-diazido-2,5-dideoxyhexitols. Carbohydr. Res. 1980, 85, 259– 269,  DOI: 10.1016/s0008-6215(00)84675-3
      25
      Synthesis and biological activity of 1,4:3,6-dianhydro-2,5-diazido-2,5-dideoxyhexitols
      Kuszmann, Janos; Medgyes, Gabor
      Carbohydrate Research (1980), 85 (2), 259-69CODEN: CRBRAT; ISSN:0008-6215.
      Reaction of 1,4:3,6-dianhydro-2,5-di-O-mesyl- and -tosyl-D-mannitol with NaN3 afforded the 2,5-diazido-L-iditol deriv. The analogous D-glucitol isomer was obtained in a similar reaction starting from the corresponding D-glucitol derivs., and showed significant, hypnotic activity (no data). For establishing the structure-activity relationship, 1,4:3,6-dianhydro-2,5-diazido-2,5-dideoxy-L-mannitol (I), as well as its antipode (II), was synthesized, starting from D-mannitol. I was as effective as Doriden (3-ethyl-3-phenylglutarimide), a well known hypnotic drug. II and the bioisosteric 1(4),3(6)-dithio deriv. were, however, inactive.
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    26. 26
      Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.; Beller, M. The catalytic amination of alcohols. ChemCatChem 2011, 3, 1853– 1864,  DOI: 10.1002/cctc.201100255
      There is no corresponding record for this reference.
    27. 27
      Pera-Titus, M.; Shi, F. Catalytic amination of biomass-based alcohols. ChemSusChem 2014, 7, 720– 722,  DOI: 10.1002/cssc.201301095
      27
      Catalytic Amination of Biomass-Based Alcohols
      Pera-Titus, Marc; Shi, Feng
      ChemSusChem (2014), 7 (3), 720-722CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Although alc. amination reactions were extensively studied since the early decades of the last century, the realization of sustainable development in the amine industry by implementing biomass-based alcs. as starting materials is still in its infancy. Catalytic systems based on Ru and Ir operating by means of the BH mechanism are currently available for performing such reactions. However, to reduce the prodn. costs, homogeneous systems based on cheaper metals operating by nucleophilic substitution, as well as supported metal nanoparticles (Ni, Co, Cu, Pd, Au) on low- alk. supports, are highly desired and new developments are expected to occur soon. With these catalysts in hand, new research areas for amination involving biomass-based alcs. with market opportunities are expected to be developed during this decade.
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    28. 28
      Pingen, D.; Diebolt, O.; Vogt, D. Direct amination of bio-alcohols using ammonia. ChemCatChem 2013, 5, 2905– 2912,  DOI: 10.1002/cctc.201300407
      28
      Direct Amination of Bio-Alcohols Using Ammonia
      Pingen, Dennis; Diebolt, Olivier; Vogt, Dieter
      ChemCatChem (2013), 5 (10), 2905-2912CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A slightly adapted catalyst system has been successfully applied in the direct amination of primary and secondary alcs. Moreover, the applicability to diols has been shown, giving high selectivity towards the primary diamines. It was found that the Ru/P ratio as well as the amt. of ammonia used are highly important in this system, esp. for higher substrate loadings. The catalyst was employed on a larger batch scale for the conversion of isomannide to the corresponding diamine. Addnl., it was shown that the catalyst is stable for at least six consecutive runs. No significant loss of activity and selectivity was obsd.
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    29. 29
      Wright, L. W.; Brandner, J. D. Catalytic Isomerization of Polyhydric Alcohols.1 II. The Isomerization of Isosorbide to Isomannide and Isoidide. J. Org. Chem. 1964, 29, 2979– 2982,  DOI: 10.1021/jo01033a043
      29
      Catalytic isomerization of polyhydric alcohols. II. The isomerization of isosorbide to isomannide and isoidide
      Wright, L. W.; Brandner, J. D.
      Journal of Organic Chemistry (1964), 29 (10), 2979-82CODEN: JOCEAH; ISSN:0022-3263.
      At 220-240° and 150 atm. H pressure the reversible interconversion of the 1,4:3,6-dianhydrohexitols of D-glucitol, D-mannitol, and L-iditol reaches a steady state after 2-6 h. in the presence of Ni-kieselguhr catalyst. At this time the approx. concns. are 57 % 1,4:3,6-dianhydro-L-iditol, 36% 1,4:3,6-dianhydro-D-glucitol; and 7% 1,4:3,6-dianhydro-D-mannitol. These figures are shown to be consistent with probability considerations, i.e., the relative amts. of the dianhydrohexitols are related to the probability of a given OH group being either exo or endo. Taking the steady-state mole fraction of 1,4:3,6-dianhydro-L-iditol as 0.57, it is calcd. that the probability of a OH being exo is 3 times the probability of its being endo. Calcn. of the mole fraction of the other 2 anhydrohexitols on the basis of these relative probabilities yields values in close agreement with those found exptl. The isomerization is strongly accelerated by increasing alky. of the catalyst-dianhydrohexitol slurry. Cf. CA 56, 11677c.
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    30. 30
      Brandner, D.; Wright, L. W. Process for producing isoidide. U.S. Patent no. 3,023,223 A, 1962.
      There is no corresponding record for this reference.
    31. 31
      Schelwies, M.; Brinks, M.; Schaub, T.; Melder, J.-P.; Paciello, R.; Merger, M. Process for the homogeneously catalyzed amination of alcohols with ammonia in the presence of a complex catalyst which comprises nonanionic ligands. Patent no. WO 2014016241 A1 2014
      There is no corresponding record for this reference.
    32. 32
      Bahé, F.; Grand, L.; Cartier, E.; Jacolot, M.; Moebs-Sanchez, S.; Portinha, D.; Fleury, E.; Popowycz, F. Direct amination of isohexides via borrowing hydrogen methodology: regio- and stereoselective issues. Eur. J. Org. Chem. 2020, 2020, 599– 608,  DOI: 10.1002/ejoc.201901661
      32
      Direct Amination of Isohexides via Borrowing Hydrogen Methodology: Regio- and Stereoselective Issues
      Bahe, Florian; Grand, Lucie; Cartier, Elise; Jacolot, Maiwenn; Moebs-Sanchez, Sylvie; Portinha, Daniel; Fleury, Etienne; Popowycz, Florence
      European Journal of Organic Chemistry (2020), 2020 (5), 599-608CODEN: EJOCFK; ISSN:1099-0690. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The regio and diastereoselective direct mono or diamination of bio-based isohexides (isosorbide and isomannide) has been developed through borrowing hydrogen (BH) methodol. using a cooperative catalysis between an iridium complex and a Bronsted acid. The access to chiral amino-alc. (NH2-OH) and diamine (NH2-NH2), interesting optically pure bio-based monomers, was also proposed using BH strategy.
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    33. 33
      Pfützenreuter, R.; Rose, M. Aqueous-phase amination of biogenic isohexides by using Ru/C as a solid catalyst. ChemCatChem 2016, 8, 251– 255,  DOI: 10.1002/cctc.201501077
      33
      Aqueous-Phase Amination of Biogenic Isohexides by using Ru/C as a Solid Catalyst
      Pfuetzenreuter, Rebecca; Rose, Marcus
      ChemCatChem (2016), 8 (1), 251-255CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
      An aq. phase process for the amination of biogenic isohexides with ammonia using Ru/C as solid catalyst is reported. The products possess great potential for the prodn. of biogenic polyamides. From the diol substrates amino alcs. and diamines are derived as main products with significantly varying product selectivity depending on the substrates' stereochem. The catalytic reaction is performed at temps. of 140-180 °C. The Ru/C catalyst shows a high activity in the aq. phase, which is beneficial for the transformation of the polar biogenic substrates. Despite the basic conditions, the metal leaching is negligible and the catalyst can be recycled easily in batch operation and, thus, enables further process development due to the mild and scalable reaction conditions.
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    34. 34
      Niemeier, J.; Engel, R. V.; Rose, M. Is water a suitable solvent for the catalytic amination of alcohols?. Green Chem. 2017, 19, 2839– 2845,  DOI: 10.1039/c7gc00422b
      34
      Is water a suitable solvent for the catalytic amination of alcohols?
      Niemeier, Johannes; Engel, Rebecca V.; Rose, Marcus
      Green Chemistry (2017), 19 (12), 2839-2845CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)
      The catalytic conversion of biomass and biogenic platform chems. typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aq. phase mainly for energetic reasons by avoiding the initial water sepn. Herein, we report the amination of biogenic alcs. in aq. solns. using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcs. is successfully proved. Hence, water appears to be a suitable solvent for the sustainable prodn. of biogenic amines and offers great potential for further process development.
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    35. 35
      Hu, H.; Ramzan, A.; Wischert, R.; Jerôme, F.; Michel, C.; de Olivera Vigier, K.; Pera-Titus, M. Pivotal role of H2 in the isomerisation of isosorbide over a Ru/C catalyst. Catal. Sci. Technol. 2021, 11, 7973– 7981,  DOI: 10.1039/d1cy01709h
      35
      Pivotal role of H2 in the isomerization of isosorbide over a Ru/C catalyst
      Hu, H.; Ramzan, A.; Wischert, R.; Jerome, F.; Michel, C.; de Olivera Vigier, K.; Pera-Titus, M.
      Catalysis Science & Technology (2021), 11 (24), 7973-7981CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      Isosorbide isomerisation is a known reaction that can proceed over Ru and Ni-based heterogeneous catalysts. As a rule, an exogenous H2 pressure (40-100 bar) is required, even though H2 does not participate stoichiometrically in the reaction. By marrying expts. with DFT computations, we ascribe the role of H2 in isosorbide isomerisation to a coverage effect on the catalyst surface. We demonstrate the possibility of conducting the reaction at a low H2 pressure either in the presence of an inert gas to increase H2 soly. in an underlying solvent or using 2-propanol as a hydrogen donor. This might benefit the economy and safety of a potential industrial process.
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    36. 36
      Hausoul, P. J. C.; Negahdar, L.; Schute, K.; Palkovits, R. Unravelling the Ru-catalyzed hydrogenolysis of biomass-based polyols under neutral and acidic conditions. ChemSusChem 2015, 8, 3323– 3330,  DOI: 10.1002/cssc.201500493
      36
      Unravelling the Ru-Catalyzed Hydrogenolysis of Biomass-Based Polyols under Neutral and Acidic Conditions
      Hausoul, Peter J. C.; Negahdar, Leila; Schute, Kai; Palkovits, Regina
      ChemSusChem (2015), 8 (19), 3323-3330CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The aq. Ru/C-catalyzed hydrogenolysis of biomass-based polyols such as erythritol, xylitol, sorbitol, and cellobitol is studied under neutral and acidic conditions. For the first time, the complete product spectrum of C2-C6 polyols is identified and, based on a thorough anal. of the reaction mixts., a comprehensive reaction mechanism is proposed, which consists of (de)hydrogenation, epimerization, decarbonylation, and deoxygenation reactions. The data reveal that the Ru-catalyzed deoxygenation reaction is highly selective for the cleavage of terminal hydroxyl groups. Changing from neutral to acidic conditions suppresses decarbonylation, consequently increasing the selectivity towards deoxygenation.
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    37. 37
      Wang, T.; Ibañez, J.; Wang, K.; Fang, L.; Sabbe, M.; Michel, C.; Paul, S.; Pera-Titus, M.; Sautet, P. Rational design of selective metal catalysts for alcohol amination with ammonia. Nat. Catal. 2019, 2, 773– 779,  DOI: 10.1038/s41929-019-0327-2
      37
      Rational design of selective metal catalysts for alcohol amination with ammonia
      Wang, Tao; Ibanez, Javier; Wang, Kang; Fang, Lin; Sabbe, Maarten; Michel, Carine; Paul, Sebastien; Pera-Titus, Marc; Sautet, Philippe
      Nature Catalysis (2019), 2 (9), 773-779CODEN: NCAACP; ISSN:2520-1158. (Nature Research)
      The lack of selectivity for the direct amination of alcs. with ammonia (a modern and clean route for the synthesis of primary amines) is an unsolved problem. Here, we combine first-principles calcns., scaling relations, kinetic simulations and catalysis expts. to det. the key factors that govern the activity and selectivity of metal catalysts for this reaction. We show that the loss of selectivity towards primary amines is linked to a surface-mediated C-N bond coupling between two N-contg. intermediates: CH3NH and CH2NH. The barrier for this step is low enough to compete with the main surface hydrogenation reactions and it can be used as a descriptor for selectivity. The activity and selectivity maps (using the C and O adsorption energies as descriptors) were combined for the computational screening of 348 dil. bimetallic catalysts. Among the best theor. candidates, Co98.5Ag1.5 and Co98.5Ru1.5 (5 wt% Co) were identified exptl. to be the most promising catalysts.
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    38. 38
      Honkala, K.; Hellman, A.; Remediakis, I. N.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Nørskov, J. K. Ammonia synthesis from first-principles calculations. Science 2005, 307, 555– 558,  DOI: 10.1126/science.1106435
      38
      Ammonia Synthesis from First-Principles Calculations
      Honkala, K.; Hellman, A.; Remediakis, I. N.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Norskov, J. K.
      Science (Washington, DC, United States) (2005), 307 (5709), 555-558CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      The rate of ammonia synthesis over a nanoparticle ruthenium catalyst can be calcd. directly on the basis of a quantum chem. treatment of the problem using d. functional theory. We compared the results to measured rates over a ruthenium catalyst supported on magnesium aluminum spinel. When the size distribution of ruthenium particles measured by transmission electron microscopy was used as the link between the catalyst material and the theor. treatment, the calcd. rate was within a factor of 3 to 20 of the exptl. rate. This offers hope for computer-based methods in the search for catalysts.
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    39. 39
      Lu, X.; Zhang, J.; Chen, W.-K.; Roldan, A. Kinetic and mechanistic analysis of NH3 decomposition on Ru(0001), Ru(111) and Ir(111) surfaces. Nanoscale Adv 2021, 3, 1624– 1632,  DOI: 10.1039/d1na00015b
      39
      Kinetic and mechanistic analysis of NH3 decomposition on Ru(0001), Ru(111) and Ir(111) surfaces
      Lu, Xiuyuan; Zhang, Jing; Chen, Wen-Kai; Roldan, Alberto
      Nanoscale Advances (2021), 3 (6), 1624-1632CODEN: NAADAI; ISSN:2516-0230. (Royal Society of Chemistry)
      We investigated the catalytic NH3 decompn. on Ru and Ir metal surfaces using d. functional theory. The reaction mechanisms were unraveled on both metals, considering that, on the nano-scale, Ru particles may also present an fcc structure, hence, leading to three energy profiles. We implemented thermodn. and kinetic parameters obtained from DFT into microkinetic simulations. Batch reactor simulations suggest that hydrogen generation starts at 400 K, 425 K and 600 K on Ru(111), Ru(0001) and Ir(111) surfaces, resp., in excellent agreement with expts. During the reaction, the main surface species on Ru are NH, N and H, whereas on Ir(111), it is mainly NH. The rate-detg. step for all surfaces is the formation of mol. nitrogen. We also performed temp.-programmed reaction simulations and inspected the desorption spectra of N2 and H2 as a function of temp., which highlighted the importance of N coverage on the desorption rate.
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    40. 40
      Benndorf, C.; Madey, T. E. Adsorption and orientation of NH3 on Ru(001). Surf. Sci. 1983, 135, 164– 183,  DOI: 10.1016/0039-6028(83)90217-0
      40
      Adsorption and orientation of ammonia on ruthenium(001)
      Benndorf, Carsten; Madey, Theodore E.
      Surface Science (1983), 135 (1-3), 164-83CODEN: SUSCAS; ISSN:0039-6028.
      The interaction of NH3 with clean Ru(001) surfaces was studied by using LEED ESDIAD (electron stimulated desorption ion angular distribution), TDS (thermal desorption spectroscopy), and work function changes (Δ.vphi.). Four different binding states (denoted as α1, α2, β, and γ) were detected with TDS. At low coverages, NH3 desorbs from the α1 state with a TDS peak max. at ∼310 K. The broadening of the TDS peaks and their shift to lower temp. with increasing NH3 coverage are related to repulsive lateral interactions between neighboring NH3 mols. At higher NH3 coverages (θNH3 ⪆ 0.15), a 2nd desorption peak (α2) develops at 180 K, accompanied by a (2 × 2) LEED structure. With further increase of NH3 exposure a sharp desorption peak (β state) is found at 140 K, an is interpreted as due to NH3 species desorbing from a 2nd adsorption layer. Finally a desorption peak due to multilayer adsorption (γ state) is found at 115 K. At low NH3 coverages (α1 state), a halo-like H+ ESDIAD pattern gives evidence of randomly oriented or freely rotating NH3 monomers, bounded via the N atoms to the surface with the H atoms pointing away from the surface. This orientation of NH3 is supported by work function measurements showing a linear decrease of Δ.vphi. in the α1 state. Structural information concerning the adsorption geometry of NH3 in the β state was obtained from LEED and ESDIAD. During the formation of the 2nd NH3 layer (β) a (2√3 × 2√3)R30° LEED pattern is obsd. and is accompanied by an ESDIAD pattern with a hexagonal outline. A structural model of the β-state bonding, in which 2nd layer NH3 mols. are bonded via 3-fold H bonds to the 1st layer NH3, is proposed.
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    41. 41
      Carabineiro, S. A. C.; Matveev, A. V.; Gorodetskii, V. V.; Nieuwenhuys, B. E. Selective oxidation of ammonia over Ru(0001). Surf. Sci. 2004, 555, 83– 93,  DOI: 10.1016/j.susc.2004.02.022
      41
      Selective oxidation of ammonia over Ru(0 0 0 1)
      Carabineiro, S. A. C.; Matveev, A. V.; Gorodetskii, V. V.; Nieuwenhuys, B. E.
      Surface Science (2004), 555 (1-3), 83-93CODEN: SUSCAS; ISSN:0039-6028. (Elsevier Science B.V.)
      The decompn. and oxidn. of NH3 were studied on the Ru(0 0 0 1) surface in the temp. range from 150 up to 800 K. The results were compared to those found for Ir(1 1 0) and Ir(5 1 0). TDS results showed that most of the NH3 is dissociatively adsorbed between 150 and 300 K, with formation of H2 around 300 K and N2 between 600 and 800 K. N2 desorption shifts to lower temps. with increasing surface O coverage. The products of NH3 oxidn. obsd. were N2, H2O, and N2O. Formation of NO was not found. Inhibition of the reaction presumably by N species was obsd. until 450 and 670 K, depending on the NH3/O2 ratios. Above those temps. the reaction started as manifested by a decrease in the NH3 and O2 pressures and a simultaneous increase in the H2O, N2 and N2O pressures.
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    42. 42
      Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O. ̈.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09; Gaussian, Inc.: Wallingford, CT, 2016.
      There is no corresponding record for this reference.
    43. 43
      Zhao, Y.; Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 2008, 120, 215– 241,  DOI: 10.1007/s00214-007-0310-x
      43
      The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
      Zhao, Yan; Truhlar, Donald G.
      Theoretical Chemistry Accounts (2008), 120 (1-3), 215-241CODEN: TCACFW; ISSN:1432-881X. (Springer GmbH)
      We present two new hybrid meta exchange-correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amt. of nonlocal exchange (2X), and it is parametrized only for nonmetals. The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree-Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree-Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochem., four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for mol. excitation energies. We also illustrate the performance of these 17 methods for three databases contg. 40 bond lengths and for databases contg. 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochem., kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chem. and for noncovalent interactions.
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    44. 44
      Weigend, F.; Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297– 3305,  DOI: 10.1039/b508541a
      44
      Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
      Weigend, Florian; Ahlrichs, Reinhart
      Physical Chemistry Chemical Physics (2005), 7 (18), 3297-3305CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 mols. representing (nearly) all elements-except lanthanides-in their common oxidn. states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, d. functional theory and correlated methods, for which we had chosen Moller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
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    45. 45
      Weigend, F.; Ahlrichs, R. Accurate Coulomb-fitting basis sets for H to Rn. Phys. Chem. Chem. Phys. 2006, 8, 1057– 1065,  DOI: 10.1039/b515623h
      45
      Accurate Coulomb-fitting basis sets for H to Rn
      Weigend, Florian
      Physical Chemistry Chemical Physics (2006), 8 (9), 1057-1065CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      A series of auxiliary basis sets to fit Coulomb potentials for the elements H to Rn (except lanthanides) is presented. For each element only one auxiliary basis set is needed to approx. Coulomb energies in conjunction with orbital basis sets of split valence, triple zeta valence and quadruple zeta valence quality with errors of typically below ca. 0.15 kJ mol-1 per atom; this was demonstrated in conjunction with the recently developed orbital basis sets of types def2-SV(P), def2-TZVP and def2-QZVPP for a large set of small mols. representing (nearly) each element in all of its common oxidn. states. These auxiliary bases are slightly more than three times larger than orbital bases of split valence quality. Compared to non-approximated treatments, computation times for the Coulomb part are reduced by a factor of ca. 8 for def2-SV(P) orbital bases, ca. 25 for def2-TZVP and ca. 100 for def2-QZVPP orbital bases.
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    46. 46
      Luchini, G.; Alegre-Requena, J. V.; Funes-Ardoiz, I.; Paton, R. S. GoodVibes: automated thermochemistry for heterogeneous computational chemistry data; F1000 Research Ltd, 2020, Vol 9.
      There is no corresponding record for this reference.
    47. 47
      Alecu, I. M.; Zheng, J.; Zhao, Y.; Truhlar, D. G. Computational thermochemistry: scale factor databases and scale factors for vibrational frequencies obtained from electronic model chemistries. J. Chem. Theory Comput. 2010, 6, 2872– 2887,  DOI: 10.1021/ct100326h
      47
      Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries
      Alecu, I. M.; Zheng, Jingjing; Zhao, Yan; Truhlar, Donald G.
      Journal of Chemical Theory and Computation (2010), 6 (9), 2872-2887CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)
      Optimized scale factors for calcg. vibrational harmonic and fundamental frequencies and zero-point energies have been detd. for 145 electronic model chemistries, including 119 based on approx. functionals depending on occupied orbitals, 19 based on single-level wave function theory, three based on the neglect-of-diat.-differential-overlap, two based on doubly hybrid d. functional theory, and two based on multicoefficient correlation methods. Forty of the scale factors are obtained from large databases, which are also used to derive two universal scale factor ratios that can be used to interconvert between scale factors optimized for various properties, enabling the derivation of three key scale factors at the effort of optimizing only one of them. A reduced scale factor optimization model is formulated in order to further reduce the cost of optimizing scale factors, and the reduced model is illustrated by using it to obtain 105 addnl. scale factors. Using root-mean-square errors from the values in the large databases, we find that scaling reduces errors in zero-point energies by a factor of 2.3 and errors in fundamental vibrational frequencies by a factor of 3.0, but it reduces errors in harmonic vibrational frequencies by only a factor of 1.3. It is shown that, upon scaling, the balanced multicoefficient correlation method based on coupled cluster theory with single and double excitations (BMC-CCSD) can lead to very accurate predictions of vibrational frequencies. With a polarized, minimally augmented basis set, the d. functionals with zero-point energy scale factors closest to unity are MPWLYP1M (1.009), τHCTHhyb (0.989), BB95 (1.012), BLYP (1.013), BP86 (1.014), B3LYP (0.986), MPW3LYP (0.986), and VSXC (0.986).
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    48. 48
      Ribeiro, R. F.; Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Use of solution-phase vibrational frequencies in continuum models for the free energy of solvation. J. Phys. Chem. B 2011, 115, 14556– 14562,  DOI: 10.1021/jp205508z
      48
      Use of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation
      Ribeiro, Raphael F.; Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
      Journal of Physical Chemistry B (2011), 115 (49), 14556-14562CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
      We find that vibrational contributions to a solute's free energy are in general insensitive to whether the solute vibrational frequencies are computed in the gas phase or in soln. In most cases, the difference is smaller than the intrinsic error in solvation free energies assocd. with the continuum approxn. to solvation modeling, although care must be taken to avoid spurious results assocd. with limitations in the quantum-mech. harmonic-oscillator approxn. for very low-frequency mol. vibrations. We compute solute vibrational partition functions in aq. and carbon tetrachloride soln. and compare them to gas-phase mol. partition functions computed with the same level of theory and the same quasiharmonic approxn. for the diverse and extensive set of mols. and ions included in the training set of the SMD continuum solvation model, and we find mean unsigned differences in vibrational contributions to the solute free energy of only about 0.2 kcal/mol. On the basis of these results and a review of the theory, we conclude, in contrast to previous work, that using partition functions computed for mols. optimized in soln. is a correct and useful approach for averaging over solute degrees of freedom when computing free energies of solutes in soln., and it is moreover recommended for cases where liq. and gas-phase solute structures differ appreciably or when stationary points present in liq. soln. do not exist in the gas phase, for which we provide some examples. When gas-phase and soln.-phase geometries and frequencies are similar, the use of gas-phase geometries and frequencies is a useful approxn.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFSjtr3O&md5=3a164fbab7255d92e1099064e7f72261
    49. 49
      Li, Y.-P.; Gomes, J.; Mallikarjun Sharada, S.; Bell, A. T.; Head-Gordon, M. Improved force-field parameters for QM/MM simulations of the energies of adsorption for molecules in zeolites and a free rotor correction to the rigid rotor harmonic oscillator model for adsorption enthalpies. J. Phys. Chem. C 2015, 119, 1840– 1850,  DOI: 10.1021/jp509921r
      49
      Improved Force-Field Parameters for QM/MM Simulations of the Energies of Adsorption for Molecules in Zeolites and a Free Rotor Correction to the Rigid Rotor Harmonic Oscillator Model for Adsorption Enthalpies
      Li, Yi-Pei; Gomes, Joseph; Mallikarjun Sharada, Shaama; Bell, Alexis T.; Head-Gordon, Martin
      Journal of Physical Chemistry C (2015), 119 (4), 1840-1850CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Quantum mechanics/mol. mechanics (QM/MM) simulations provide an efficient avenue for studying reactions catalyzed in zeolite systems; however, the accuracy of such calcns. is highly dependent on the zeolite MM parameters used. Previously reported parameters (P1), which were chosen to minimize the root mean square (RMS) deviations of adsorption energies compared with full QM ωB97X-D/6-31+G** adsorption energies, are shown to overestimate binding energies compared with exptl. values, particularly for larger substrates. To address this issue, a new parameter set (P2) is derived by rescaling the previously reported characteristic energies of the Lennard-Jones potential in P1. The accuracy of the thermal correction for adsorption enthalpies detd. by the rigid rotor-harmonic oscillator approxn. (RRHO) is examd. and shown to be improved by treating low-lying vibrational modes as free translational and rotational modes via a quasi-RRHO model. With P2 and quasi-RRHO, adsorption energies calcd. with QM/MM agree with exptl. values with an RMS error of 1.8 kcal/mol for both nonpolar and polar mols. adsorbed in MFI, H-MFI, and H-BEA. By contrast, the RMS error for the same test sets obtained using parameter set P1 is 8.3 kcal/mol. Glucose-fructose isomerization catalyzed by Sn-BEA is taken as an example to demonstrate that improved values for apparent activation energies can be obtained using the methodol. reported here. With parameter set P2, the apparent activation energy calcd. with QM/MM reproduces the exptl. value to within 1 kcal/mol. By contrast, using parameter set P1, the error is -12.9 kcal/mol.
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    50. 50
      Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. J. Phys. Rev. B 1996, 54, 11169– 11186,  DOI: 10.1103/physrevb.54.11169
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      Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
      Kresse, G.; Furthmueller, J.
      Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
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      Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865– 3868,  DOI: 10.1103/physrevlett.77.3865
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      Generalized gradient approximation made simple
      Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
      Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
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      Steinmann, S.; Corminboeuf, C. A generalized-gradient approximation exchange hole model for dispersion coefficients. J. Chem. Phys. 2011, 134, 044117,  DOI: 10.1063/1.3545985
      52
      A generalized-gradient approximation exchange hole model for dispersion coefficients
      Steinmann, Stephan N.; Corminboeuf, Clemence
      Journal of Chemical Physics (2011), 134 (4), 044117/1-044117/5CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      A simple method for computing accurate d.-dependent dispersion coeffs. is presented. The dispersion coeffs. are modeled by a generalized gradient-type approxn. to Becke and Johnson's exchange hole dipole moment formalism. Our most cost-effective variant, based on a disjoint description of atoms in a mol., gives mean abs. errors in the C6 coeffs. for 90 complexes below 10%. The inclusion of the missing long-range van der Waals interactions in d. functionals using the derived coeffs. in a pair wise correction leads to highly accurate typical noncovalent interaction energies. (c) 2011 American Institute of Physics.
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      Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953– 17979,  DOI: 10.1103/physrevb.50.17953
      53
      Projector augmented-wave method
      Blochl
      Physical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.
      There is no expanded citation for this reference.
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    54. 54
      Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758– 1775,  DOI: 10.1103/physrevb.59.1758
      54
      From ultrasoft pseudopotentials to the projector augmented-wave method
      Kresse, G.; Joubert, D.
      Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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    55. 55
      Hermes, E. D.; Janes, A. N.; Schmidt, J. R. M. Micki: A python-based object-oriented microkinetic modeling code. J. Chem. Phys. 2019, 151, 014112,  DOI: 10.1063/1.5109116
      55
      Micki: A python-based object-oriented microkinetic modeling code
      Hermes, Eric D.; Janes, Aurora N.; Schmidt, J. R.
      Journal of Chemical Physics (2019), 151 (1), 014112/1-014112/13CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      We have developed a flexible, general-purpose microkinetic modeling code, Micki, to analyze complex, heterogeneously catalyzed chem. reactions based upon first-principles calcns. This Python-based code is modular and object oriented, framing the development of microkinetic models in familiar chem. terms. We also present novel approaches, incorporated into Micki, to describe diffusion limited reactions, multidentate bindings, thermodynamically consistent lateral interactions, and Bronsted-Evans-Polanyi ests. of changes in barrier heights. Micki has built-in modules for subsequent anal. of microkinetic models, including degree of rate control and rate order. As a demonstration of the power and flexibility of the code, we build a microkinetic model for the water-gas shift reaction and compare to previously published exptl. results and microkinetic models, showing that Micki can quant. reproduce exptl. turnover frequencies with minimal empirical optimization. (c) 2019 American Institute of Physics.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c07501.

    • Coordinates for DFT calculations (ZIP)

    • Blank mass spectra of the MS system; mass spectra of AS2 and DAS; mass spectra of the reaction mixture after amination of isomannide IM under 30 bar H2; possible byproducts from IM amination; reductive amination of endo-OH ketone mixtures; optimized structures for different adsorption modes of aminoalcohols through either −OH or −NH2 functional groups; reaction profile corresponding to the dehydrogenation of NH3 to form NHx species on Ru(0001); GC methods A and B used for the analysis of product mixtures in the amination of IM; representative GC chromatograms obtained for reactant and product analysis using GC methods A and B; GC method C used for the analysis of product mixtures in the oxidation of IM and IS; representative GC chromatograms obtained for reactant and product analysis using GC methods A and C; steady-state coverage of surface species and empty catalytic sites as a function of temperature at a H2/NH3 ratio of 1.0; evolution of N2 gas as a function of temperature for H2/NH3 molar ratio of 1.0; and a table listing substrate conversion and product yield for figures in the main text (PDF)


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