Catalytic ester decarbonylation

Patent metadata

Field	Value
Publication number	US-9718763-B2
Application number	US-201614990308-A
Country	US
Kind code	B2
Filing date	Jan 7, 2016
Priority date	Jan 7, 2015
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

A process of preparing olefins of the formula (I) is described herein:

with R 1 being a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, and R 2 being a substituted or unsubstituted (C 1 -C 20 )hydrocarbyl. The process includes reacting a compound of formula (II)

wherein Ar is chosen from

in the presence of a palladium-based catalyst and an organic solvent.

A process of preparing olefins of the formula (III) is also described:

with R 3 being a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, R 4 being a substituted or unsubstituted (C 1 -C 20 )hydrocarbyl, and R 5 being a substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl. The process includes reacting a compound of formula (IV)

wherein Ar is chosen from

with a compound of formula (V)

wherein Ar is chosen from

in the presence of a palladium-based catalyst and an organic solvent.

First claim

What is claimed is:

1. A process of preparing an olefin of formula (I):

wherein:

R 1 is chosen from a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl;
R 2 is chosen from a substituted or unsubstituted (C 1 -C 20 )hydrocarbyl;
the process comprising:

reacting a compound of formula (II)

wherein Ar is chosen from

in the presence of a palladium-based catalyst and an organic solvent, to provide the compound of the formula (I).

2. The process of claim 1 , wherein the reacting of the compound of the formula (II) is also conducted in the presence of one or more ligands, wherein the preparation of the olefin of the formula (I) in the presence of the one or more ligands has a selectivity to α-olefins of at least about 60%.

3. The process of claim 2 , wherein the one or more ligands comprise one or more of: one or more phenylphosphine-based ligands or one or more heterocyclic carbene ligands.

4. The process of claim 1 , wherein the reacting of the compound of the formula (II) further occurs in the presence a salt.

5. The process of claim 4 , wherein the salt is chosen from an alkali metal halide, an alkaline-earth metal halide, tetrabutylammonium bromide, or combinations thereof.

6. The process of claim 1 , wherein R 1 is chosen from (C 1 -C 20 )alkyl, (C 3 -C 8 )cycloalkyl, (C 2 -C 12 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 10 )aryl, (C 7 -C 27 )alkylaryl, (C 7 -C 27 )alkylaryl, (C 2 -C 20 )alkylcarbonyloxy, (C 6 -C 27 )arylcarbonyloxy, (C 2 -C 20 )alkoxycarbonyl, or (C 6 -C 27 )aryloxycarbonyl groups.

7. The process of claim 6 , wherein one or more of the (C 1 -C 20 )alkyl, the (C 3 -C 8 )cycloalkyl, the (C 2 -C 12 )alkenyl, the (C 2 -C 20 )alkynyl, the (C 6 -C 10 )aryl, the (C 7 -C 27 )arylalkyl, the (C 7 -C 27 )alkylaryl, the (C 2 -C 20 )alkylcarbonyloxy, the (C 6 -C 27 )arylcarbonyloxy, the (C 2 -C 20 )alkoxycarbonyl, or the (C 6 -C 27 )aryloxycarbonyl groups of R 1 are substituted by one or more groups chosen from Cl, F, Br, I, R′, OR′, SR′, NR′ 2 , SiR′ 3 , COOR′, (C═O)R′, CN, or CONR 2 ′, wherein R′ is chosen from H or a (C 1 -C 12 )alkyl.

8. The process of claim 1 , wherein in R 2 is chosen from H, a (C 1 -C 20 )alkyl, a (C 6 -C 8 )aryl, or a phenyl group.

9. The process of claim 1 , wherein the preparation of the olefin of the formula (I) occurs in the absence of a phosphine ligand.

10. A process of preparing an olefin of formula (III):

wherein:
R 3 is chosen from a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl;
R 4 is chosen from a substituted or unsubstituted (C 1 -C 20 )hydrocarbyl;
R 5 is chosen from a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl;

the process comprising:
reacting a compound of formula (IV)

wherein Ar is chosen from

with a compound of formula (V)

wherein Ar is chosen from

in the presence of a palladium-based catalyst, and an organic solvent.

11. The process of claim 10 , wherein the reacting of the compound of the formula (IV) with the compound of the formula (V) is also conducted in the presence of one or more ligands.

12. The process of claim 11 , wherein the one or more ligands comprise one or more of: one or more phenylphosphine-based ligands or one or more heterocyclic carbene ligands.

13. The process of claim 10 , wherein the reacting of the compound of the formula (IV) with the compound of formula (V) occurs in the presence of a salt.

14. The process of claim 13 , wherein the salt comprises at least one of: an alkali metal halide, an alkaline-earth metal halide, tetrabutylammonium bromide or combinations thereof.

15. The process of claim 10 , wherein R 3 is chosen from (C 1 -C 20 )alkyl, (C 3 -C 8 )cycloalkyl, (C 2 -C 12 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 10 )aryl, (C 7 -C 27 )arylalkyl, (C 7 -C 27 )alkylaryl, (C 2 -C 20 )alkylcarbonyloxy, (C 6 -C 27 )arylcarbonyloxy, (C 2 -C 20 )alkoxylcarbonyl, and (C 6 -C 27 )aryloxycarbonyl groups.

16. The process of claim 15 , wherein one or more of the (C 1 -C 20 )alkyl, the (C 3 -C 8 )cycloalkyl, the (C 2 -C 12 )alkenyl, the (C 2 -C 20 )alkynyl, the (C 6 -C 10 )aryl, the (C 7 -C 27 )arylalkyl, the (C 7 -C 27 )alkylaryl, the (C 2 -C 20 )alkylcarbonyloxy, the (C 6 -C 27 )arylcarbonyloxy, the (C 2 -C 20 )alkoxycarbonyl, or the (C 6 -C 27 )aryloxycarbonyl groups of R 3 are substituted by one or more groups chosen from Cl, F, Br, I, R′, OR′, SR′, NR′ 2 , SiR′ 3 , COOR′, (C═O)R′, CN, and CONR 2 ′, wherein R′ is chosen from H and (C 1 -C 12 )alkyl.

17. The process of claim 10 , wherein R 4 is chosen from H, a (C 1 -C 20 )alkyl, a (C 6 -C 8 )aryl, or a phenyl group.

18. The process of claim 10 , wherein R 5 is chosen from (C 1 -C 20 )alkyl, (C 3 -C 8 )cycloalkyl, (C 2 -C 12 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 10 )aryl, (C 7 -C 27 )arylalkyl, (C 7 -C 27 )alkylaryl, (C 7 -C 27 )alkenylaryl, (C 2 -C 20 )alkylcarbonyloxy, (C 6 -C 27 )arylcarbonyloxy, (C 2 -C 20 )alkoxycarbonyl, and (C 6 -C 27 )aryloxycarbonyl groups.

19. The process of claim 18 , wherein one or more of the (C 1 -C 20 )alkyl, the (C 3 -C 8 )cycloalkyl, the (C 2 -C 12 )alkenyl, the (C 2 -C 20 )alkynyl, the (C 6 -C 10 )aryl, the (C 7 -C 27 )arylalkyl, the (C 7 -C 27 )alkylaryl, the (C 7 -C 27 )alkenylaryl, the (C 2 -C 20 )alkylcarbonyloxy, the (C 6 -C 27 )arylcarbonyloxy, the (C 2 -C 20 )alkoxycarbonyl, or the (C 6 -C 27 )aryloxycarbonyl groups of R 5 are substituted by one or more groups chosen from Cl, F, Br, I, R′, OR′, SR′, NR′ 2 , SiR' 3 , COOR′, (C═O)R′, CN, and CONR 2 ′, wherein R′ is chosen from H and a (C 1 -C 12 )alkyl group.

20. The process of claim 10 , wherein R 5 is chosen from

wherein R 6 , R 7 , R 8 , and R 9 are each independently chosen from H, Cl, Br, F, NO 2 , OH, OR′ and a (C 1 -C 5 )alkyl, and wherein R′ is a (C 1 -C 5 )alkyl group.

21. The process of claim 10 , wherein the preparation of the olefin of the formula (III) occurs in the absence of a phosphine ligand.

Assignees

• Univ Minnesota

Inventors

• Tolman William Baker
• Hillmyer Marc A
• John Alex
• Hogan Levi Thomas

Classifications

• C07C255/08

  Acrylonitrile; Methacrylonitrile · CPC title

• C07C15/50

  polycyclic non-condensed · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C07C11/02

  Alkenes · CPC title