Methods of converting polyols

Patent metadata

Field	Value
Publication number	US-9260367-B2
Application number	US-201414475300-A
Country	US
Kind code	B2
Filing date	Sep 2, 2014
Priority date	Mar 2, 2012
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

Methods for converting polyols are provided. The methods provided can include using a metal pincer catalyst (e.g., an iridium pincer catalyst) to remove at least one alcohol group from a polyol. The methods provided can include converting glycerol to 1,3-propanediol.

First claim

What is claimed is:

1. A method for removing at least one alcohol group from a polyol, the method comprising:
reacting the polyol, hydrogen (H 2 ) gas, an acid, an organic solvent, and a metal pincer catalyst to form a reaction product, the polyol having at least two alcohol groups before the reacting, and the reaction product including the polyol having at least one fewer alcohol groups after the reacting,
wherein the metal pincer catalyst has the general formula (I):

wherein M 1 is iridium or rhodium,
wherein each of X 1 and X 3 are independently selected from —CH 2 — or —O—,
wherein X 2 is C or N, and
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from the group consisting of hydrogen, a halide, —OH, —NH 2 , —CN, —SH, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl,
or general formula (II):

wherein M 2 is iridium or rhodium,
wherein each of X 4 , X 5 and X 6 are independently selected from C or N, and
wherein each of R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from the group consisting of hydrogen, a halide, —OH, —NH 2 , —CN, —SH, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
or general formula (III):

wherein M 3 is iridium or rhodium, and
wherein each of R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are independently selected from the group consisting of hydrogen, a halide, —OH, —NH 2 , —CN, —SH, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
or general formula (IV):

 wherein each of R 31 , R 32 , R 33 , R 34 , R 35 , R 38 , R 39 , R 40 , R 41 , and R 42 are independently selected from the group consisting of hydrogen, a halide, —OH, —NH 2 , —CN, —SH, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
wherein is a single or double bond; and
wherein each of R 36 and R 37 are independently selected from the group consisting of hydrogen, a halide, —OH, —NH 2 , —CN, —SH, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, or wherein R 36 and R 37 are joined together to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

2. The method of claim 1 , wherein the polyol comprises a linear or cyclic C 1 -C 6 alkane molecule substituted with the at least two alcohol groups before the reacting.

3. The method of claim 1 , wherein the acid comprises a homogeneous or heterogeneous proton donor.

4. The method of claim 1 , wherein the acid is selected from the group consisting of sulfuric acid, tungstic acid, phosphoric acid, hydrochloric acid and trifluoromethanesulfonic acid.

5. The method of claim 3 , wherein the homogeneous acid is used at a concentration range of about 0.03M to about 0.1M.

6. The method of claim 1 , wherein the organic solvent includes dioxane, sulfolane, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidone, 1-methyl-2-piperidone, bis(2-methoxyethyl)ether, or a combination thereof.

7. The method of claim 1 , wherein X 1 and X 3 are —O—.

8. The method of claim 1 , wherein X 2 is C.

9. The method of claim 1 , wherein R 1 , R 2 , R 6 , and R 7 are the same.

10. The method of claim 1 , wherein R 8 , R 9 , R 17 , and R 18 are the same.

11. The method of claim 1 , wherein R 19 , R 20 , R 29 , and R 30 are the same.

12. The method of claim 1 , wherein R 31 , R 32 , R 41 and R 42 are the same.

13. The method of claim 1 , wherein the metal pincer catalyst is coupled to a solid support.

14. The method of claim 1 , wherein the reacting is carried out at a temperature selected from:
a temperature greater than about 160° C.;
a temperature between about 160° C. to about 220° C.; or
a temperature between about 170° C. to about 200° C.

15. The method of claim 1 , wherein the polyol comprises glycerol, erythritol, xylitol, sorbitol, mannitol, glucose, fructose, or sucrose before the reacting.

16. The method of claim 1 , wherein the polyol is glycerol before the reacting and the reaction product comprises 1,3-propanediol.

17. The method of claim 1 , wherein the polyol is glycerol before the reacting and greater than about 60% of the glycerol is converted to 1,3-propanediol.

18. The method of claim 1 , wherein the reaction product further comprises 1-propanol.

19. The method of claim 1 , wherein the polyol is 1,2-propanediol before the reacting and the reaction product comprises 1-propanol.

20. The method of claim 1 , wherein the metal pincer catalyst is present at about 0.05 to about 1 mole % with respect to the polyol.

21. The method of claim 1 , wherein the polyol is glycerol before the reacting and, before the reacting, the method further includes combining a crude glycerol byproduct from transesterification of triglycerides with an acid to form a separated mixture comprising a crude product separated from a solution including glycerol, methanol, and methyl ester.

Assignees

• Univ Washington Ct Commerciali
• Univesity Of Washington Through Its Ct For Comm

Inventors

• Goldberg Karen I
• Heinekey D Michael
• Weliange Nandita Malathi
• Ahmed Foskey Takiya J
• Camp Eric R
• Wong Gene
• Lao David

Classifications

• B01J31/18

  containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)} · CPC title

• C07C29/60 Primary

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title

• B01J2531/822

  Rhodium · CPC title

• B01J2531/0244

  Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds · CPC title

• B01J31/1875

  Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof) · CPC title