Process for the dimerization of activated olefins

Patent metadata

Field	Value
Publication number	US-2017107168-A1
Application number	US-201515312033-A
Country	US
Kind code	A1
Filing date	May 19, 2015
Priority date	May 20, 2014
Publication date	Apr 20, 2017
Grant date	—

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

1 .- 15 . (canceled)

16 . 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 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,
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, where 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 -haloalkyl, 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, where 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 of C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and halogen, and where the N-heterocycle is mono-, bi- or tricyclic, and where 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, where 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 where 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.

17 . The process of claim 16 , where 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.

18 . The process of claim 16 , where the radical R 1 in formulae I.a, I.b and II is selected from unsubstituted C 1 -C 4 -alkyl, in particular methyl.

19 . The process of claim 16 , where R 2 is selected from unsubstituted C 1 -C 6 -alkyl.

20 . The process of claim 16 , where in formulae I.a, I.b and II both R 2 are identical.

21 . The process of claim 16 , where the compound of formula II is selected from the group consisting of methyl methacrylate, ethyl methacrylate and n-butyl methacrylate.

22 . The process of claim 16 , where the proton-donating functional group has a pKa-value in water at 25° C. in the range of from 7 to 13.

23 . The process of claim 16 , where the additive is selected from the group consisting of aromatic alcohols, halogenated aliphatic alcohols, protonated aliphatic amines and thiols.

24 . The process of claim 16 , where the additive is an aromatic alcohol.

25 . The process of claim 16 , where 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.

26 . The process of claim 16 , where the additive is selected from the group consisting of phenol, 4-methoxyphenol, 1,4-dihydroxybenzene and naphthalen-2-ol.

27 . The process of claim 16 , where 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.

28 . The process of claim 27 , where the N-heterocyclic carbene catalyst is generated in-situ from a suitable precursor.

29 . The process of claim 16 , where 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.

30 . The process of claim 16 , where 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.

31 . The process of claim 16 , where 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.

Assignees

• Basf Se

Inventors

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

Classifications

• 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