Granted Patent B2

US 8,367,859 · App. 12/816,742 · Granted Feb 5, 2013

Abstract

Claims (49)

1. A method for preparing a compound containing a cyclohexane ring, the compound having formula (I)

the method comprising:

(1) in a one-pot reaction, isomerizing one or more of cis,cis and cis,trans muconic acids or carboxylate derivatives thereof to form trans,trans muconic acid or carboxylate derivatives thereof, and contacting the trans,trans muconic acid or carboxylate derivatives thereof with a dienophile in a solvent under conditions such that one or more cyclohexene ring containing compounds having carboxylate groups at the 1 and 4 position are formed; and

(2) contacting the one or more cyclohexene ring containing compounds having carboxylate groups at the 1 and 4 position with hydrogen in the presence of one or more hydrogenation catalysts under conditions such that one or more compounds of formula (I) containing a cyclohexane ring having carboxylate groups at the 1 and 4 position are prepared,

wherein the cyclohexene ring containing compounds contain up to about 1 part per trillion of Carbon 14 as determined according to ASTM D6866-08, and 6 or more of the carbon atoms are derived from a muconate microbially synthesized from a biomass;

wherein said carboxylate derivatives contain group

wherein:

R 1 is independently in each occurrence hydrogen, a hydrocarbyl group optionally containing one or more heteroatoms or a cation wherein the hydrocarbyl group or cation do not interfere in the formation of the cyclohexene ring containing compounds;

R 2 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compounds; and

R 3 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compounds;

or R 2 and R 3 combine to form a cyclic ring that can contain heteroatoms;

Z is independently in each occurrence an anion, oxygen, nitrogen, sulfur, nitrile or a halogen; and

b is independently in each occurrence 0, 1 or 2 with the proviso that b is 0 when Z is an anion, halogen or nitrile; b is 1 when Z is oxygen or sulfur; and b is 2 when Z is nitrogen.

2. A method according to claim 1 wherein the one or more hydrogenation catalysts include one or more metals.

3. A method according to claim 1 wherein the cyclohexene ring containing compounds having carboxylate groups at the 1 and 4 position are contacted with hydrogen at ambient temperatures.

4. A method according to claim 1 wherein the cyclohexene ring containing compounds are contacted with hydrogen while being refluxed in one or more solvents.

5. A method according to claim 1 wherein the one or more hydrogenation catalysts contains one or more of nickel, platinum or palladium.

6. A method according to claim 1 wherein the contacting in step (2) occurs at a pressure from about 14.7 psi to about 200 psi.

7. A method according to claim 1 wherein the one or more cyclohexene ring containing compounds correspond to one or more of the following formulas:

8. A method according to claims 1 , further comprising producing one or more precursors to the one or more of cis, cis and cis,trans muconic acids or carboxylate derivatives thereof in a microbial synthesis based fermenter under controlled conditions from the biomass.

9. A method according to claim 1 wherein in step (1), the dienophile comprises one or more unsaturated cyclic compounds, one or more unsaturated esters or aromatic compounds having at least one unsaturated substituent.

10. A method according to claim 1 wherein in step (1), the isomerizing includes contacting the one or more of cis, cis and cis,trans muconic acids or carboxylate derivatives thereof, with one or more isomerization catalysts, or a source of ultraviolet radiation, or both, such that the one or more of cis, cis and cis,trans muconic acids or carboxylate derivatives thereof, isomerize to the trans,trans muconic acid or carboxylate derivatives thereof.

11. A method according to claim 1 wherein the trans,trans muconic acid carboxylate derivatives are esters of muconic acid and wherein the one or more cyclohexene ring containing compounds have alkyl carboxylate groups at the 1 and 4 positions and are prepared by

a) in said one-pot reaction, contacting the cis, cis or cis, trans muconic acid and one or more isomerization catalysts, or a source of ultraviolet radiation, or both, such that the cis,cis or cis,trans muconic acid isomerizes to the trans, trans muconic acid, and contacting the trans, trans muconic acid with the dienophile to form one or more cyclohexene compounds having carboxylic acid groups at the 1 and 4 positions;

b) removing the solvent; and

c) contacting the one or more cyclohexene compounds having carboxylic acid groups at the 1 and 4 positions with one or more esterifying agents in the presence of one or more strong acids under conditions that one or more cyclohexene ring containing compounds having alkyl carboxylate groups at the 1 and 4 positions are formed.

12. A method according to claim 1 , further comprising contacting the one or more compounds of formula (I) containing the cyclohexane ring having carboxylate groups at the 1 and 4 position with an acid such that the carboxylate groups are converted to methylol groups.

13. A method according to claim 1 , wherein Z is oxygen and the compound containing the cyclohexane ring corresponds to formula (II):

14. A method according to claim 13 wherein the compound containing the cyclohexane ring corresponds to one of the following formulas:

wherein:

R 4 is independently in each occurrence hydrogen, a hydrocarbyl group optionally containing a heteroatom containing functional group;

R 5 is independently in each occurrence a hydrocarbyl group optionally containing a heteroatom containing functional group; and

a is independently in each occurrence an integer of from 0 to 5.

15. A method according to claim 13 wherein R 2 is independently in each occurrence selected from chloro, bromo, C 1-8 alkyl, phenyl, or C 1-8 alkyl carboxylate, and R 3 is hydrogen.

16. A method according to claim 13 wherein R 2 is independently in each occurrence chloro, methyl, ethyl or phenyl, and R 3 is hydrogen.

17. A method according to claim 1 wherein the biomass includes a carbohydrate.

18. A method for preparing a compound containing a cyclohexane ring, the compound having formula (I)

the method comprising:

contacting one or more cyclohexene ring containing compounds having carboxylate groups at the 1 and 4 position with hydrogen in the presence of one or more hydrogenation catalysts under conditions such that one or more compounds of formula (I) containing a cyclohexane ring having carboxylate groups at the 1 and 4 position are prepared;

wherein said carboxylate derivatives contain group

wherein the cyclohexene compounds are derived from muconic acid prepared by microbial synthesis, in a one-pot reaction of (1) isomerizing one or more of cis,cis and cis,trans muconic acids prepared from said microbial synthesis, or carboxylate derivatives thereof, to form trans, trans muconic acid or carboxylate derivatives thereof, and (2) contacting the trans, trans muconic acid or carboxylate derivatives thereof with a dienophile under conditions such that the one or more cyclohexene compounds are formed;

wherein

R 1 is independently in each occurrence hydrogen, a hydrocarbyl group optionally containing one or more heteroatoms or a cation wherein the hydrocarbyl group or cation do not interfere in the formation of the cyclohexene ring containing compounds;

R 2 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compounds; and

R 3 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compounds;

or R 2 and R 3 combine to form a cyclic ring that can contain heteroatoms;

Z is independently in each occurrence an anion, oxygen, nitrogen, sulfur, nitrile or a halogen; and

b is independently in each occurrence 0, 1 or 2 with the proviso that b is 0 when Z is an anion, halogen or nitrile; b is 1 when Z is oxygen or sulfur; and b is 2 when Z is nitrogen.

19. A method according to claim 18 wherein the muconic acid is prepared by microbial synthesis from a biomass.

Assignments (12)