Method for preparing carbene in solution, novel stable form of carbene obtained in particular by means of said method, and uses thereof in catalysis

Patent metadata

Field	Value
Publication number	US-9499643-B2
Application number	US-201113520834-A
Country	US
Kind code	B2
Filing date	Jan 7, 2011
Priority date	Jan 8, 2010
Publication date	Nov 22, 2016
Grant date	Nov 22, 2016

Abstract

The invention relates to a method for preparing carbene by means of deprotonation of a precursor salt using a strong base. A purpose of the invention is to enhance the synthesis of carbenes, i.e. to simplify same, to make said synthesis more economical and to obtain a liquid or solid, stable and pure form constituting a catalytic system that is easy to store and use and that has a higher efficiency, higher yield and higher selectivity than carbene catalysts of the prior art. In order to do so, the method comprises deprotonation in a solvent including an alcohol. The invention also relates to an alcohol-containing solution and carbene, and to a solid that can be obtained from the solution, e.g. by means of sublimation.

First claim

The invention claimed is:

1. A process for preparing a catalyst and/or a reactant, the reactant and catalyst comprising at least one carbene C in the form of a solution A that is stable at 20° C., wherein the solution A comprises at least one alcohol and the at least one carbene C,
wherein said process comprises:
reacting at least one strong base, optionally generated in situ, with at least one compound B, which is a precursor of the at least one carbene C,
wherein
the at least one strong base deprotonates an iminium functional group of structure (III) or (III′), and
wherein the deprotonating is carried out in an alcoholic medium, comprising the at least one alcohol, and said deprotonating produces a salt, which precipitates in and is separated from said solution A;

and wherein said compound B is selected from the group consisting of one or more compounds of formula (III) and (III′):

wherein
A and B are independently C or N, wherein
in formula (III), when A is N, then T 4 is not present and, when B is N, then T 3 is not present;
in formula (III′), when A is N, then T 4 or T 4′ is not present and, when B is N, then T 3 or T 3′ is not present; wherein

T 3 , T 3′ , T 4 and T 4′ are independently a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted by an alkyl or alkoxy group; an aryl group optionally substituted by an alkyl or alkoxy group; an alkenyl group; an alkynyl group; or an arylalkyl group, wherein the aryl part is optionally substituted by an alkyl or alkoxy group; or wherein
T 3 and T 4 form an aryl together with A and B, when A and B are each a carbon atom, provided that T 3′ and T 4′ are not present;
T 1 and T 2 are independently an alkyl group; an alkyl group is optionally substituted by an alkyl; an alkyl group, which is perfluorinated or optionally substituted by a perfluoroalkyl group; a cycloalkyl group is optionally substituted by an alkyl or alkoxy group; an aryl group is optionally substituted by an alkyl or alkoxy group; an alkenyl group; an alkynyl group; or an arylalkyl group, wherein the aryl part is optionally substituted by an alkyl or alkoxy group; or
T 1 and T 2 are independently a monovalent radical of formula (III):
—V1-V2  (III)

wherein
V1 is a saturated or an unsaturated divalent hydrocarbon group, which is optionally substituted,
V2 is a monovalent group selected from the group consisting of:
alkoxy, —OR a , with R a corresponding to hydrogen, alkyl or aryl;
silyl, —Si(OR b ) x (R c ) 3-x , with R b corresponding to hydrogen, alkyl, silyl or siloxanyl, R c corresponding to alkyl, aryl and x being an integer from 0 to 3; and
amine; or

the substituents T 1 , T 2 , T 3 , T 3′ , T 4 and T 4′ form a saturated or an unsaturated hydrocarbon chain, in pairs, when they are located on two adjacent ring members in the formulae (III) and (III′);

Z 1 is independently an anion derived from a Brönsted; and
collecting said at least one carbene C,
wherein said at least one carbene C has the formula (II) or (II′):

2. The process of claim 1 , wherein said at least one alcohol has the formula (I°) R°OH, wherein R° is an alkyl, cycloalkyl, aryl, alkenyl, alkynyl, arylalkyl, silyl or siloxane group.

3. The process of claim 1 , wherein said strong base is selected from the group consisting of alkali metal and alkaline earth metal hydroxides, alkoxides, hydrides and amides.

4. The process of claim 1 , wherein said alcoholic medium is sublimed so as to collect said carbene C in solid form.

5. The process of claim 1 , wherein said reacting is at a temperature of from 0° C. to 100° C.

6. The process of claim 1 , wherein compound B has said V2 group, and V2 is an amine which is —N(R a ) 2 , with R a corresponding to hydrogen, alkyl or aryl.

7. The process of claim 1 , wherein Z 1 is independently an anion derived from a Brönsted acid (protic acid) selected from the group consisting of:
carboxylic acids of formula G o -COOH, wherein G o is an a C 1 -C 22 alkyl; or a C 6 -C 18 aryl, substituted by one or more C 1 -C 6 alkyls;
sulfonic acids of formula G o -SO 3 H;
phosphoric acids of formula G o -PO 3 H;
the following inorganic acids: HF, HCl, HBr, HI, H 2 SO 4 , H 3 PO 4 , HClO 4 and HBF 4 , taken by themselves alone or in a combination thereof;
and mixtures thereof.

8. The process of claim 2 , wherein R° is selected from the group consisting of: methyl, ethyl, propyl and butyl.

9. The process of claim 1 , wherein said strong base is selected from the group consisting of CH 3 ONa, potassium tert-butoxide, KOH, NaOH, CH 3 CH 2 OMgOCH 2 CH 3 , and mixtures thereof.

10. The process of claim 1 , wherein compound B has said V1 group which is a linear or branched C 1 -C 10 alkylene.

11. The process of claim 1 , wherein said compound B is compound (III).

12. The process of claim 1 , wherein said compound B is compound (III′).

13. The process of claim 1 , wherein the at least one alcohol is isopropanol.

14. The process of claim 13 , wherein the mole ratio of the isopropanol to the compound B is greater than about 27.

15. The process of claim 1 , wherein the at least one alcohol is ethanol.

16. The process of claim 15 , wherein the mole ratio of the ethanol to the compound B is greater than about 27.

Assignees

• Maliverney Christian
• Saint-Jalmes Laurent
• Gojon Sophie
• Kato Tsuyoshi
• Baceiredo Antoine J
• Bluestar Silicones France
• Centre Nat Rech Scient

Inventors

• Maliverney Christian
• Saint-Jalmes Laurent
• Gojon Sophie
• Kato Tsuyoshi
• Baceiredo Antoine J

Classifications

• C08F4/00

  Polymerisation catalysts · CPC title

• C07D233/06 Primary

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms · CPC title

• C08F4/80 Primary

  selected from iron group metals or platinum group metals · CPC title

• C07D233/58 Primary

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms · CPC title

• B01J31/02

  containing organic compounds or metal hydrides · CPC title