Dianhydrohexitols

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Dianhydrohexitols (isohexides) are bicyclic oxygen-containing heterocycles formed from two fused tetrahydrofuran rings , which are formed by double dehydration from the sugar alcohols sorbitol (also known as sorbitol or glucitol), mannitol (mannitol) or iditol. Isohexides, especially isosorbide, are promising dialcohols made from biogenic raw materials and are used as precursors for solvents and drugs against angina pectoris , and as building blocks for bio-based and biodegradable polymers, such as. B. Poly (isosorbide succinate) PIS.

Structures

Dianhydrohexitols are optically active secondary diols and show endo-exo isomerism .

Isosorbide Isoidid Isomannid
Isosorbide.svg Isoidide.svg Isomannide.svg
1,4: 3,6-dianhydro-D-glucidol 1,4: 3,6-dianhydro-L-iditol 1,4: 3,6-dianhydro-D-mannitol

The presence of 1.4: 3.6 fused rings in all three epimeric isohexides was clarified in the 1940s.

The hydroxy group in the 2-position of isosorbide (1,4: 3,6-dianhydro-D-glucidol or 1,4: 3,6-dianhydro-D-sorbitol) is in the exo - configuration before, during the 5-position endo - is configured. In isoidide (1,4: 3,6-dianhydro-L-iditol) both OH groups are exo - exo , in isomannide (1,4: 3,6-dianhydro-D-mannitol) endo - endo are oriented.

In isomannide, the two endo -hydroxy groups form intramolecular hydrogen bonds , while in isosorbide only the endo -OH group in the 5-position is capable of intramolecular hydrogen bonding.

Isohexides with hydrogen bonds

The cis or V-shaped arrangement of the bicyclic system of 1,4: 3,6-dianhydrohexitols at an angle of 120 ° causes different steric influences on the hydroxyl groups and thus also different reactivity. While the endo -OH group in the isosorbide is activated by the intramolecular hydrogen bond and thus has a higher nucleophilicity and reactivity, the exo -OH group is more easily accessible to sterically demanding substituents.

Occurrence and representation

When mannitol was heated with hydrochloric acid for 24 hours, isomannide was obtained for the first time in 1884.

Double dehydration of mannitol to isomannide

The precursor sorbitol for isosorbide is now produced in megatons by hydrogenating D- glucose - from starch or biomass such as cellulose .

Isosorbide synthesis based on polysaccharides

and acid-catalyzed dehydrated to isosorbide. The process was first described in a patent in 1927.

The synthesis of isomannide requires an additional step to the primary starting material D- fructose either by isomerization of glucose or by cleavage of sucrose . Fructose is converted into mannitol by catalytic hydrogenation or biotechnologically with lactic acid bacteria . From the alditol mannitol z. B. by means of dehydration with solid acids (acidic zeolites ) in yields of up to 63% the dianhydrohexitol isomannide.

Recently, the dehydration of sorbitol and mannitol with dimethyl carbonate as a dehydrating agent under catalysis with strong nitrogen bases, such as. B. Diazabicycloundecen DBU to isosorbide or isomannide described.

The precursor for the third isohexide, isoidide , is the non-natural aldose L-idose or the sugar alcohol L-iditol derived from it. Therefore, isoidide has to be obtained by the isomerization of isomannide and isosorbide.

Isomerization of isohexides by dehydration / rehydration

At temperatures above 200 ° C. and hydrogen pressures of 100-250 bar in the presence of Raney nickel , an equilibrium mixture of the exemplary composition 55: 45: 5 for isoidide, isosorbide and isomannide is established - probably via a dehydrogenation / hydrogenation mechanism . B. can be broken down into the individual isohexides by distillation .

properties

The different arrangement of the two hydroxyl groups of the dianhydrohexitole causes differences in the physical properties, such as melting points and dipole moments or polarities or distribution behavior between the mobile and stationary phase in thin layer chromatography , as well as in the chemical properties such. B. Reactivities

Dianhydrohexitols Melting point ° C Dipole moment D R f value (silica gel, EtOH)
Isomannid 86.7-89.5 3.17 0.42
Isosorbide 61.9-64.0 1.65 0.52
Isoidid 63.7-64.5 1.91 0.60

The endo -hydroxy group (in the 5-position) in the isosorbide is more reactive, but the exo -hydroxy group (in the 2-position) is more easily attacked by bulky reactants. The endo -secondary hydroxyl groups can also easily be oxidized to ketones with platinum as a catalyst, with isomannide forming 2,5-diketone and isosorbide forming 5-monoketone, while under these conditions isoidide is not attacked.

Oxidation of isohexides

Like isosorbide and isomannide, isoidide can be purified by recrystallization from ethyl acetate and, in contrast to the other two isohexides, is only sparingly soluble in chloroform . The taste of isosorbide and isomannide is described as sweet with a hint of bitterness.

Applications

Due to its relatively simple synthetic accessibility, isosorbide is now also available on an industrial scale - e.g. B. The company Roquette Frères in Lestem , France has been operating a plant with an annual capacity of 20,000 tons since 2015.

Because of their limited availability, their high price and - in the case of isomannide - lower activity in polymerization reactions, isomannide and especially isoidide have so far not achieved the importance of isosorbide.

The to a platform chemical explained isosorbide from renewable raw materials is in the form of Isosorbidmononitrats and isosorbide dinitrate use as a drug for angina pectoris and as a raw material for polymers from renewable raw materials , such. B. as a diol component for polyurethanes and epoxy resins , as a replacement for bisphenol A in polycarbonates and as a comonomer in polyesters such as poly (ethylene-co-isosorbide) terephthalate PEIT. Isosorbide diesters with long-chain (C 8 and C 12 ) carboxylic acids are proposed as plasticizers for polyvinyl chloride PVC.

Individual evidence

  1. ↑ D. Braun, M. Bergmann: 1,4: 3,6-Dianhydrohexite as building blocks for polymers . In: Adv. Synth. Catal. tape 334 , no. 4 , 1992, pp. 298-310 , doi : 10.1002 / prac.19923340403 .
  2. ↑ M. Lomeli-Rodriguez, JR Corpas-Martinez, S. Willis, R. Mulholland, JA Lopez-Sanchez: Synthesis and characterization of renewable polyester coil coatings from biomass-derived isosorbide, FDCA, 1,5-pentanediol, succinic acid, and 1,3-propanediol . In: Polymers . tape 10 , no. 6 , 2018, p. 600 , doi : 10.3390 / polym10060600 .
  3. ^ R. Montgomery, LF Wiggins: 77. The anhydrides of polyhydric alcohols. Part IV. The constitution of dianhydro sorbitol . In: J. Chem. Soc. 1946, p. 390-393 , doi : 10.1039 / JR460000390 .
  4. ↑ a b H.G. Fletcher, Jr., RM Goepp, Jr .: Hexitol anhydrides. 1,4,3,6-dianhydro-L-iditol and the structures of isomannide and isosorbide . In: J. Amer. Chem. Soc. tape 68 , no. 6 , 1946, pp. 939-941 , doi : 10.1021 / ja01210a007 .
  5. ↑ a b c K. Heyns, W.-P. Trautwein, H. Paulsen: About catalytic oxidations, XX. Selective catalytic oxidation of 1.4; 3.6-dianhydrohexites . In: Chem. Ber. tape 96 , no. 12 , 1963, pp. 3195-3199 , doi : 10.1002 / cber.19630961214 .
  6. ↑ G. Flèche, M. Huchette: Isosorbide. Preparation, Properties and Chemistry . In: Starch . tape 38 , no. 1 , 1986, pp. 26–30 , doi : 10.1002 / star.19860380107 .
  7. ^ AC Cope, TY Shen: The stereochemistry of 1,4: 3,6-dianhydrohexitol derivatives . In: J. Amer. Chem. Soc. tape 78 , no. 13 , 1956, pp. 3177-3182 , doi : 10.1021 / ja01594a055 .
  8. ↑ A. Fauconnier: Anhydride de la mannite . In: Bull. Soc. Chim. France . tape 2 , no. 41 , 1884, p. 119-125 ( bnf.fr ).
  9. ↑ a b M. Rose, R. Palkovits: Isosorbide as a renewable platform chemical for versatile applications - quo vadis? In: ChemSusChem . tape 5 , no. 1 , 2012, p. 167-176 , doi : 10.1002 / cssc.201100580 .
  10. ↑ Patent DE488602 : Process for the production of valuable products from sorbitol. Registered on June 8, 1927 , published on December 12, 1929 , applicant: IG Farbenindustrie AG, inventor: J. Müller, U. Hoffmann. ‌
  11. ↑ B. Toukoniitty, J. Kuusisto, J.-P. Mikkola, T. Salmi, DY Murzin: Effect of ultrasound on catalytic hydrogenation of D-fructose to D-mannitol . In: Ind. Eng. Chem. Res. Volume 44 , no. 25 , 2005, pp. 9370-9375 , doi : 10.1021 / ie050190s .
  12. ^ SH Song, C. vielle: Recent advances in the biological production of mannitol . In: Appl. Microbiol. Biotechnol. tape 84 , no. 1 , 2009, p. 55-62 , doi : 10.1007 / s00253-009-2086-5 .
  13. ↑ H. Yokoyama, H. Kobayashi, J. Hasegawa, A. Fukuoka: Selective dehydration of mannitol to isomannide over Hβ zeolite . In: ACS Catal. tape 7 , no. 7 , 2017, p. 4828-4834 , doi : 10.1021 / acscatal.7b01295 .
  14. ↑ F. Aricò, S. Evaristo, P. Tundo: Synthesis of five- and six-membered heterocycles by dimethyl carbonate with catalytic amounts of nitrogen bases . In: Green Chem. Band 17 , no. 2 , 2015, p. 1176-1185 , doi : 10.1039 / C4GC01822B .
  15. ↑ a b H.G. Fletcher, RM Goepp: 1,4: 3,6-Hexitol dianhydride L-Isoidide . In: J. Amer. Chem. Soc. tape 67 , no. 6 , 1945, p. 1042-1043 , doi : 10.1021 / ja01222a513 .
  16. ↑ a b c Rebecca V. Engel: Heterogeneously catalysed amination and isomerization of isohexides . Ed .: RWTH Aachen , dissertation. Aachen 2016 ( rwth-aachen.de ).
  17. ↑ Patent EP2817314B1 : Method of making isoidide. Registered on February 19, 2013 , published on April 19, 2017 , applicant: Stichting Wageningen Research, Archer-Daniels-Midland Co., inventors: E. Hagberg, K. Martin, JH van Ee, JEL Le Nôtre, DS van Es, J. van Haveren. ‌
  18. ↑ CK Lee, GG Birch: Structural functions of taste in the sugar series: gustatory properties of anhydro sugars . In: J. Food Sci. tape 40 , no. 4 , 1975, p. 784-787 , doi : 10.1111 / j.1365-2621.1975.tb00556 .
  19. ↑ NN: Roquette launches 'world's largest' isosorbide production unit . In: Additives for Polymers . tape 2015 , no. 6 , 2015, p. 8-9 , doi : 10.1016 / S0306-3747 (15) 30073-7 .
  20. ↑ F. Fenouillot, A. Rousseau, G. Colomines, R. Saint-Loup, J.-P. Pascault: Polymers from renewable 1,4: 3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): a review . In: Progress Polym. Sci. tape 35 , no. 5 , 2010, p. 578-622 , doi : 10.1016 / progpolymsci.2009.10.001 .
  21. ↑ JC Bersot, N. Jacquel, R. Saint-Loup, P. Fuertes: Efficiency increase of poly (ethylene terephthalate-co-isosorbide terephthalate) synthesis using bimetallic catalytic systems . In: Macromol. Chem. Phys. tape 212 , no. 19 , 2011, p. 2114–2120 , doi : 10.1002 / macp.201100146 .
  22. ↑ Y. Yang, J. Huang, R. Zhang, J. Zhu: Designing bio-based plasticizers: Effect of alkyl chain length on plasticization properties of isosorbide diesters in PVC blends . In: Mater. Design . tape 126 , 2017, p. 29-36 , doi : 10.1016 / j.matdes.2017.04.005 .