Method for synthesising esters

Patent metadata

Field	Value
Publication number	US-9701615-B2
Application number	US-201415035447-A
Country	US
Kind code	B2
Filing date	Nov 6, 2014
Priority date	Nov 8, 2013
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

A method for synthesising a second ester from a first ester, the method including the following steps: a) placing a first ester and a catalyst in the presence of dihydrogen such as to obtain a first alcohol and a second alcohol; b) extracting the second alcohol from the reaction medium; c) reacting the first alcohol with the catalyst of step a) in order to obtain a second ester and dihydrogen; and d) recirculating the dihydrogen obtained in step c) by injecting same into step a).

First claim

The invention claimed is:

1. A method for synthesizing a second ester from a first ester which comprises the following steps:
a) bringing a first ester and a catalyst of formula 1 and dihydrogen into contact in order to obtain a first alcohol and a second alcohol;
b) separating said second alcohol from the reaction medium;
c) reacting said first alcohol with the catalyst of formula 1 from step a) in order to obtain a second ester and dihydrogen; and
d) recycling the dihydrogen obtained in step c) by introducing it into step a);
said formula 1 being:

where R are groups, which may be identical or different, selected from the group consisting of cyclohexyl, phenyl, isopropyl and ethyl;
where Y is a PR′ 3 phosphine, a CO radical or a hydrogen atom, R′, which are identical or different, being C 1 -C 12 alkyl groups or C 6 -C 12 aryl groups; and
where Z is a hydrogen atom, a HBH 3 group or a halogen atom.

2. The method as claimed in claim 1 , wherein step c) of the method is carried out without addition of a hydrogen acceptor.

3. The method as claimed in claim 1 , wherein the step(s) a) and/or c) of the method is/are carried out without addition of solvent.

4. The method as claimed in claim 3 , wherein the step(s) a) and/or c) of the method is/are carried out without addition of base.

5. The method as claimed in claim 1 , wherein Z is not a halogen atom.

6. The method as claimed in claim 1 , wherein the R′ group is a methyl, ethyl, isopropyl or phenyl group.

7. The method as claimed in claim 1 , wherein R is a cyclohexyl or isopropyl group.

8. The method as claimed in claim 1 , wherein said first ester has the following formula:

where R 1 is a C 2 to C 32 alkyl group, and R 2 is a C 1 to C 6 alkyl group.

9. The method as claimed in claim 1 , wherein said first ester has the following formula:

where R 3 are identical or different C 2 to C 32 alkyl groups.

10. The method as claimed in claim 1 , wherein the loading of said catalyst of formula 1 used in step b) is selected from a range extending from 500 ppm to 1 ppm.

11. The method as claimed in claim 1 , wherein step a) is carried out under reaction conditions comprising:
i) a temperature ranging from 5° C. to 150° C.
ii) a pressure of dihydrogen ranging from 1 bar to 50 bar.

12. The method as claimed in claim 1 , wherein step c) is carried out under reaction conditions comprising:
i) a temperature ranging from 5° C. to 200° C.;
ii) a pressure that allows the concomitant release of hydrogen.

13. The method as claimed in claim 12 , wherein said pressure that allows the release of hydrogen is a pressure equal to or below atmospheric pressure.

14. A method of catalytic synthesis, comprising the use of a catalyst of formula 1:

where R are groups, which may be identical or different, selected from the group consisting of cyclohexyl, phenyl, isopropyl and ethyl;
where Y is a PR′ 3 phosphine, a CO radical or a hydrogen atom, R′, which are identical or different, being C 1 -C 12 alkyl groups or C 6 -C 12 aryl groups; and
where Z is a hydrogen atom, a HBH 3 group or a halogen atom, in order to carry out a catalytic synthesis, said synthesis comprising the following steps:
a) bringing a first ester and a catalyst of formula 1 and dihydrogen into contact in order to obtain a first alcohol and a second alcohol;
b) separating said second alcohol from the reaction medium.

15. The method as claimed in claim 14 , wherein said first ester is a fatty acid methyl ester.

16. The method as claimed in claim 11 , wherein step a) is carried out under reaction conditions comprising:
i) a temperature ranging from 75° C. to 125° C.;
ii) a pressure of dihydrogen ranging from 1 bar to 50 bar.

17. The method as claimed in claim 11 , wherein step a) is carried out under reaction conditions comprising:
i) a temperature ranging from 5° C. to 150° C.; and
ii) a pressure of dihydrogen ranging 10 to 30 bar.

18. The method as claimed in claim 11 , wherein step a) is carried out under reaction conditions comprising:
i) a temperature ranging from 75° C. to 125° C.; and
ii) a pressure of dihydrogen ranging 10 to 30 bar.

19. The method as claimed in claim 10 , wherein the loading of said catalyst of formula 1 used in step b) is selected from a range extending from 200 ppm to 20 ppm.

20. The method as claimed in claim 12 , wherein step c) is carried out under reaction conditions comprising:
i) a temperature ranging from 100° C. to 150° C.;
ii) a pressure that allows the concomitant release of hydrogen.

Assignees

• Pivert
• Centre Nat De La Rech Scient (Cnrs)
• Université Des Sciences Et Tech De Lille 1
• Lille Ecole Centrale
• Centre Nat De La Rech Scient (Cnrs

Inventors

• Dumeignil Franck
• Desset Simon
• Paul Sébastien
• Raffa Guillaume
• Zhang Lei

Classifications

• C07C29/149 Primary

  with hydrogen or hydrogen-containing gases · CPC title

• C07C67/40 Primary

  by oxidation of primary alcohols · CPC title

• C07C67/00

  Preparation of carboxylic acid esters · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C07C69/58

  Esters of straight chain acids with eighteen carbon atoms in the acid moiety · CPC title