Synthesis of isohexide dicarbamates and derivatives thereof

Patent metadata

Field	Value
Publication number	US-9487537-B2
Application number	US-201414781364-A
Country	US
Kind code	B2
Filing date	May 7, 2014
Priority date	Jun 12, 2013
Publication date	Nov 8, 2016
Grant date	Nov 8, 2016

Abstract

Dicarbamates of the reduction products of 2-hydroxymethyl-5-furfural (HMF) and a method of preparing the same are described. The method involves reacting a mixture of an isohexide and a cynate salt in a non-aqueous solvent, with a miscible acid having a pKa of about 3.7 or less. The dicarbamates of HMF-reduction products can serve as precursor materials from which various derivative compounds can be synthesized.

First claim

We claim:

1. A process for preparing dicarbamates of reduction products of HMF, the process comprising: providing a mixture of a HMF-reduction product with a cyanate salt in an inert organic solvent, reacting said mixture with an acid having a pK a ≦3.7.

2. The process according to claim 1 , wherein said acid is added to said reaction mixture of HMF-reduction products at a rate of about 0.03-0.1 stoichiometric equivalents per minute.

3. The process according to claim 1 , wherein said HMF-reduction product is at least: a) FDM and b) THF-diols.

4. The process according to claim 1 , wherein said organic solvent is at least: methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, xylenes, linear and/or branched alkanes, tetrahydrofuran, 1,4-dioxane, dimethylsulfoxide, acetonitrile, dimethylformamide, acetic acid, HMPT, nitromethane, pyridine, N-methyl pyrolidinone, dimethylacetamide, ethyl acetate, acetone, methyl tert-butyl ether, and diethyl ether.

5. The process according to claim 1 , wherein said cyanate salt having a cationic counter-ion selected from the group consisting of: Na, K, Li, Ag, Hg, Al, Ca, Mg, Pb, Sn, Ti, Ni, Cs, Rb, Cu, Zn, Cd, In, Co, Ga, Ba, Pd, Pt, Tl, Fr, Sb, Ge, Sr, Be, V, Bi, Mo, Mn, Fe, Nb, Cr, Eu, organic cations of ammonium, pyridinium, and a combination of the foregoing.

6. The process according to claim 1 , wherein said acid is either an organic acid or a mineral acid.

7. The process according to claim 6 , wherein when said acid is an organic acid, said acid is at least: trifluoro-acetic acid (TFA) trichloro-acetic acid, oxalic acid, pyruvic acid, malonic acid, furamic acid, maleic acid, malic acid, tartaric acid, picric acid, electron deficient benzoic acids (mono, di, and tri-nitro, cyano, trifluoro), terephthalic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethylsulfonic acid.

8. The process according to claim 6 , wherein when said acid is a mineral acid, said acid is at least: sulfuric acid, hydrogen halide, perchloric acid, phosphoric acid, and boric acid.

9. The process according to claim 1 , wherein said reaction is conducted at a temperature in a range from about 0° C. to about 55° C.

10. The process according to claim 1 , further comprising purifying said dicarbamates of HMF-reduction products, according to a protocol involving a simple filtration, washing, and drying under high vacuum.

11. The process according to claim 1 , wherein said process results in at least a 55% yield of corresponding dicarbamates of HMF-reduction products.

12. The process according to claim 11 , wherein said process results in about a 70% or greater yield of corresponding dicarbamates of HMF-reduction products.

13. The process according to claim 8 , wherein said hydrogen halide is selected from: HCl, HBr, and HI.

Assignees

• Archer Daniels Midland Co
• Archer Daniels Midland Co

Inventors

• Stensrud Kenneth

Classifications

• A61K31/428

  condensed with carbocyclic rings · CPC title

• C08G73/00

  Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00 {(polycarbodiimides prepared from isocyanates C08G18/025, C08G18/797)} · CPC title

• C07D307/42 Primary

  Singly bound oxygen atoms · CPC title

• C08G12/26

  with heterocyclic compounds · CPC title

• C07D307/12

  Radicals substituted by oxygen atoms · CPC title