Process for the dimerization of activated olefins

Patent metadata

Field	Value
Publication number	US-9796654-B2
Application number	US-201515312033-A
Country	US
Kind code	B2
Filing date	May 19, 2015
Priority date	May 20, 2014
Publication date	Oct 24, 2017
Grant date	Oct 24, 2017

Abstract

The present invention relates to a process for the preparation of compounds or a mixture of compounds of the general formulae I.a or I.b

wherein
R 1 is selected from C 1 -C 12 -alkyl, C 3 -C 6 -cycloalkyl, —C(═O)OR 2 , —PO(OR 2a ) 2 , aryl and hetaryl, R 2 , R 2a are independently of each other selected from the group consisting of hydrogen, C 1 -C 12 -alkyl, C 1 -C 12 -alkenyl, where the last two radicals mentioned are unsubstituted, partly or completely halogenated or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C 1 -C 6 -alkoxy and CN, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, aryl and aryl-C 1 -C 4 -alkyl, where the last four radicals mentioned are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, —CN, and halogen, which comprises dimerizing olefin compound of the general formula II,

in the presence of at least one N-heterocyclic carbene catalyst.

First claim

The invention claimed is:

1. A process for preparing a compound or a mixture of compounds of the general formulae I.a or I.b

wherein
R 1 is selected from the group consisting of C 1 -C 12 -alkyl, C 3 -C 6 -cycloalkyl, —C(═O)OR 2 , —PO(OR 2a ) 2 , aryl and hetaryl,
R 2 , R 2a are independently of each other selected from the group consisting of hydrogen, C 1 -C 12 -alkyl, —C 2 -C 12 alkenyl-, wherein the last two radicals mentioned are unsubstituted, partly or completely halogenated or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C 1 -C 6 -alkoxy and CN, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, aryl and aryl-C 1 -C 4 -alkyl, wherein the last four radicals mentioned are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, —CN, and halogen,
the process comprising dimerizing olefin compound of the general formula II,

in the presence of at least one N-heterocyclic carbene catalyst selected from compounds of the general formula V

in which
R 4 and R 5 are independently selected from the group consisting of C 1 -C 6 -alkyl, aryl and heteroaryl, wherein aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and halogen;
R 6 is selected from the group consisting of C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy, C 1 -C 6 -haloalkyl, —NR 7 R 8 , halogen, aryloxy, aryl and heteroaryl, wherein aryloxy, aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and halogen;
R 7 is selected from the group consisting of hydrogen, C 1 -C 12 -alkyl and aryl;
R 8 is selected from the group consisting of C 1 -C 12 -alkyl and aryl;
or R 5 together with R 6 and the atoms to which they are bound form a fused, unsaturated N-heterocycle, which is unsubstituted or substituted by 1, 2 or 3 radicals selected from the group consisting C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and halogen, and wherein the N-heterocycle is mono-, bi- or tricyclic, and wherein the N-heterocycle optionally has 1, 2 or 3 further heteroatoms as ring members, which are selected from O, S and N, and in the presence of at least one additive having at least one proton donating functional group, wherein the additive is used in an amount of from 0.005 to 4 mol-%, based on the total amount of compound (II) in the reaction mixture, and wherein the proton-donating functional group has a pKa-value in water at 25° C. in the range of from 4 to 14, to yield a compound of the general formulae I.a or I.b or a mixture thereof.

2. The process of claim 1 , wherein the additive is used in an amount of from 0.005 to 1.5 mol-%, based on the total amount of compound (II) in the reaction mixture.

3. The process of claim 1 , wherein the radical R 1 in formulae I.a, I.b and II is selected from unsubstituted C 1 -C 4 -alkyl.

4. The process of claim 1 , wherein R 2 is selected from unsubstituted C 1 -C 6 -alkyl.

5. The process of claim 1 , wherein in formulae I.a, I.b and II, both R 2 are identical.

6. The process of claim 1 , wherein the compound of formula II is selected from the group consisting of methyl methacrylate, ethyl methacrylate and n-butyl methacrylate.

7. The process of claim 1 , wherein the proton-donating functional group has a pKa-value in water at 25° C. in the range of from 7 to 13.

8. The process of claim 1 , wherein the additive is selected from the group consisting of aromatic alcohols, halogenated aliphatic alcohols, protonated aliphatic amines and thiols.

9. The process of claim 1 , wherein the additive is an aromatic alcohol.

10. The process of claim 1 , wherein the additive is selected from the group consisting of phenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 4-(trifluoromethyl)phenol, 4-hydroxybenzonitril, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and naphthalen-2-ol.

11. The process of claim 1 , wherein the additive is selected from the group consisting of phenol, 4-methoxyphenol, 1,4-dihydroxybenzene and naphthalen-2-ol.

12. The process of claim 1 , wherein in formula V, R 4 , R 5 and R 6 are independently selected from phenyl which is optionally substituted by 1, 2, or 3 radicals selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and halogen.

13. The process of claim 12 , wherein the N-heterocyclic carbene catalyst is generated in-situ from a compound of the general formulae

wherein R 4 , R 5 and R 6 are as defined in claim 1 .

14. The process of claim 1 , wherein the N-heterocyclic carbene catalyst is used in an amount of from 0.1 to 10 mol-%, based on the total amount of compound II.

15. The process of claim 1 , wherein the dimerization reaction is performed in the presence of less than 10 weight-%, based on the total amount of compound II, of an inert organic solvent.

16. The process of claim 1 , wherein the dimerization reaction is performed in the presence of 0.005 to 1.5 mol % of additive and 0.5 to 5 mol % of N-heterocyclic carbene catalyst, based on the total amount of compound II.

17. The process of claim 1 , wherein the radical R 1 in formulae I.a, I.b and II is methyl.

Assignees

• Basf Se

Inventors

• Vautravers Nicolas
• Teles Joaquim H
• Berkessel Albrecht
• Paul Mathias
• Yatham Veera R

Classifications

• C07C69/593

  Dicarboxylic acid esters having only one carbon-to-carbon double bond · CPC title

• B01J31/0244

  with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• C07C67/347 Primary

  by addition to unsaturated carbon-to-carbon bonds · CPC title