PROCESS OF PRODUCTION OF 1-(5,5-DIMETHYLCYCLOHEX-1-EN-1-YL)ETHANONE AND 1-(5,5-DIMETHYLCYCLOHEX-6-EN-1-YL )ETHANONE

Abstract

The present invention relates to an improved method for producing of 1-(5,5-dimethylcyclohex-1-en-1-yl)ethanone and 1-(5,5-dimethylcyclohex-6-en-1-yl)ethanone.

Claims

1. A process of production of compounds of formula (I) ##STR00022## by a rearrangement reaction of the compound of formula (II) ##STR00023## wherein the rearrangement reaction is catalyzed by at least one Au(I)-complex.

2. Process according to claim 1, wherein at least one Au(I) complex of the following compound of formula (III)
Y—Au(I)—Z  (III), wherein Z is an anion, which is selected from the group consisting of [BX.sub.4].sup.−, [PX.sub.6].sup.−, [SbF.sub.6].sup.−, [ClO.sub.4].sup.−, CF.sub.3COO.sup.−, sulfonates, tetra(3,5-bis(trifluoromethyl)phenyl)borate (BAr.sub.F.sup.−), tetraphenylborate, and z the anion of formula (IV) ##STR00024## wherein Q represents a phenyl or a C.sub.1-8-alkyl which preferably is substituted by at least one substituent chosen from the group consisting of F, Cl, NO.sub.2 and X is a halogen atom, especially F and Cl, and Y is an organic ligand, is used

3. Process according to claim 1, wherein the organic ligand Y of Au(I) complex of formula (III) is selected from the group consisting of ##STR00025## ##STR00026##

4. Process according to claim 1, wherein the anion Z of Au(I) complex of formula (III) selected from the group consisting of following anions [BF.sub.4].sup.−, [PF.sub.6].sup.−, [SbF.sub.6].sup.−, [ClO.sub.4].sup.−, CF.sub.3COO.sup.−, sulfonates (such as triflate CF.sub.3SO.sub.3.sup.−), tetra(3,5-bis(trifluoromethyl)phenyl)borate (BAr.sub.F.sup.−), tetraphenylborate, and the anion of formula (IV′) ##STR00027##

5. Process according to claim 1, wherein the process is carried out in a solvent or a mixture of solvents.

6. Process according to claim 5, wherein the solvent is chosen from the group consisting of methanol, ethanol, 2-butanol and tert-butanol.

7. Process according to claim 1, wherein the process is carried out at elevated temperature.

8. Process according to claim 7, wherein the process is carried out at a temperature from 30° C. to 120° C.

9. Process according to claim 1, wherein the substrate (compound of formula (II)) to catalyst ratio is 2:1 to 10000:1, preferably 10:1 to 3000:1.

Description

EXAMPLES

Example 1: Rearrangement of 1-ethynyl-3,3-dimethylcyclohexanol

[0046] ##STR00017##

[0047] 118.8 mg (0.2 mmol, 0.1 equiv.) of dicyclohexylphosphine biphenyl gold(I)-chloride and 56.88 mg (0.2 mmol, 0.1 equiv.) of silver triflate were dissolved under argon at 23° C. in 5.0 ml of tert.-butanol in a septum bottle. 362.6 μl (90%, 2 mmol, 1 equiv.) of 1-ethynyl-3,3-dimethylcyclohexanol (90%, 2 mmol, 1 equiv.) were added. The reaction mixture was stirred for 105 min at 80° C. Afterwards the reaction mixture was cooled to 23° C. A sample was taken out and analyzed by GC and NMR.

[0048] The conversion of this reaction was 98.9%. The products of formulae (I′ and I″) were obtained in a yield of 89.6 wt-%.

[0049] It is possible to separate the two isomers if desired.

Examples 2-6

[0050] The following examples were carried out under the same reaction condition as in example 1.

[0051] The ligands are defined as above and the ligands are added in the chloride form and the anions in the form of the Ag(I) salt.

TABLE-US-00001 conversion yield Exp. ligand anion [%] [%] 2 Y.sup.2 SbF.sub.6.sup.− 98.6 78.3 3 Y.sup.2 [00018] 95.4 88.9 4 Y.sup.2 [00019] 98.7 89.1 5 Y.sup.3 BF.sub.4.sup.− 78.5 40.8 6 Y.sup.3 [00020] 75.6 41.9

Comparative Examples (Examples 7-11)

[0052] The same reaction as described in Example 1 was repeated, but Au catalysts, which do not fall under the scope of the claims were used.

[0053] Example 7 and 8 are carried out without any organic ligands. AuCl was used in combination with the silver salt

TABLE-US-00002 conversion yield Exp. ligand anion [%] [%] 7 — BF4—.sup.− 16.8 0 8 — [00021] 5.3 3.1

[0054] Example 9, 10 and 11 and 8 are carried out with catalysts where Au(0) is adsorbed on a carrier.

TABLE-US-00003 conversion yield Exp. Cat [%] [%] 9 Au/TiO.sub.2 2.9 0 10 Au/Al.sub.2O.sub.3 4.8 0 11 Au/C 4.6 0

[0055] Therefore it can be seen that the choice of the suitable (claimed) catalyst is essential.