ORGANIC TERTIARY OR QUATERNARY AMMONIUM SALTS AS CATALYSTS IN THE FORMATION OF GAMMA, DELTA-UNSATURATED KETONES

Abstract

The present invention relates to the manufacture of gamma, delta-unsaturated ketones from tertiary vinyl carbinols and vinylic ethers or ketals using an organic tertiary or quaternary ammonium salt as catalyst.

Claims

1. A process for the manufacture of gamma, delta-unsaturated ketones of the formula (I) ##STR00010## by reaction of a compound of the formula (II) with a compound of the formula (IIIa) or (IIIb) ##STR00011## in the presence of an organic tertiary or quaternary ammonium salt as catalyst; wherein R.sup.1 represents a methyl or ethyl group; R.sup.2 represents a saturated or unsaturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms; R.sup.3 represents a methyl or an ethyl group; R.sup.4 represents H or methyl or an ethyl group; R.sup.5 represents a linear or branched C.sub.1-10-alkyl group, particularly a methyl or an ethyl group; R.sup.5 and R.sup.5 represent either a linear or branched C.sub.1-10-alkyl group, particularly a methyl or an ethyl group; or R.sup.5 and R.sup.5 form together a linear or branched C.sub.1-10-alkylene group, particularly an ethylene or propylene group; and wherein the wavy line represents a carbon-carbon bond and which when linked to the carbon-carbon double bond is either in the Z or in the E-configuration.

2. The process according to claim 1, wherein the catalyst is an organic tertiary ammonium salt and has a cation of the formula (IV) ##STR00012## wherein R.sup.20, R.sup.21 and R.sub.22 represent independently from each other a linear or branched C.sub.1-18-alkyl or cycloalkyl group.

3. The process according to claim 2, wherein R.sup.20 ?R.sup.21?R.sup.22.

4. The process according to claim 2, characterized in R.sup.20 ?R.sup.21?R.sup.22?methyl or ethyl.

5. The process according to claim 1, wherein the catalyst is a an organic tertiary ammonium salt and has a cation of the formula (V) ##STR00013## wherein R.sup.30, R.sup.31, R.sup.32, R.sup.33 and R.sup.34 represent independently from each other either H or a linear or branched C.sub.1-12-alkyl or C.sub.5-12-cycloalkyl group.

6. The process according to claim 5, wherein R.sup.30?R.sup.31?R.sup.32?R.sup.33, preferably R.sup.30?R.sup.31?R.sup.32?R.sup.33?H.

7. The process according to claim 5, wherein R.sup.34 represents a methyl group or H, preferably H.

8. The process according to claim 1, wherein the catalyst is a an organic quaternary ammonium salt and has a cation of the formula (VI) ##STR00014## wherein R.sup.20, R.sup.21, R.sup.22 and R.sup.23 represent independently from each other a linear or branched C.sub.1-18-alkyl or cycloalkyl group.

9. The process according to claim 8, wherein R.sup.20 ?R.sup.21?R.sup.22?R.sup.23.

10. The process according to claim 8, characterized in R.sup.20 ?R.sup.21?R.sup.22?R.sup.23?ethyl or butyl, preferably butyl.

11. The process according to claim 1, wherein the anion of the organic tertiary or quaternary ammonium salt comprises a phosphor atom which is bound to at least one oxygen atom, preferably selected from the group consisting of PO.sub.4.sup.3?, HPO.sub.4.sup.2?, H.sub.2PO.sub.4.sup.?, P.sub.2O.sub.7.sup.3?, HP.sub.2O.sub.7.sup.2? and H.sub.3P.sub.2O.sup.7?.

12. The process according to claim 1, wherein R.sup.1 represents a methyl group.

13. The process according to claim 1, wherein the molar ratio of the compound of the formula (II) to the compound of the formula (IIIa) or (IIIb) is ranging from 1:15 to 1:1, and in case of using the compound of the formula (IIIa) said ratio is more preferred in the range from 1:5 to 1:2, more preferably ranging from 1:3.5 to 1:2, most preferably ranging from 1:3 to 1:2, particularly ranging from 1:2.5 to 1:2; or in case of using the compound of the formula (IIIa) said ratio is more preferred in the range from 1:10 to 1:2, more preferably ranging from 1:8 to 1:3, most preferably ranging from 1:8 to 1:5.

14. The process according to claim 1, wherein the amount of the organic tertiary or quaternary ammonium salt is ranging from 0.01-0.3 mol-%, preferably ranging from 0.02-0.1 mol-%, more preferably ranging from 0.02-0.07 mol-%, based on the amount of the compound of the formula (II).

15. The process according to claim 1, wherein R.sup.2 is selected from the group consisting of the formula (R.sup.2-I), (R.sup.2-II), (R.sup.2-III) and (R.sup.2-IV), ##STR00015## wherein the dotted line represents the bond by which the substituent of the formula (R.sup.2-I), (R.sup.2-II), (R.sup.2-III) or (R.sup.2-IV) is bound to the rest of the compound of the formula (I) or formula (II); and wherein any double bond having dotted line () represents independently from each other either a single carbon-carbon bond or a double carbon-carbon bond; and wherein any wavy line represents independently from each other a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z or in the E-configuration; and wherein n represents 1, 2, 3 or 4, particularly 1 or 2.

16. The process claim 1, wherein the compound of the general formula (I) is selected from the group consisting of 6-methyl-5-hepten-2-one, 6-methyl-5-octen-2-one, 6,10-dimethyl-5,9-undecadien-2-one, 6,10-dimethyl-5-undecen-2-one, 6,10,14-trimethylpentadeca-5,9-dien-2-one, 6,10,14-trimethylpentadeca-5,13-dien-2-one and 6,10,14-trimethyl-5,9,13-pentadeca-trien-2-one, preferably 6-methyl-5-hepten-2-one or 6,10-dimethyl-5,9-undecadien-2-one.

17. A reaction mixture comprising a compound of the formula (II), ##STR00016## a compound of the formula (IIIa) or (IIIb) ##STR00017## and a catalyst being an organic tertiary or quaternary ammonium salt wherein R.sup.1 represents a methyl or ethyl group; R.sup.2 represents a saturated or unsaturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms; R.sup.3 represents a methyl or an ethyl group; R.sup.4 represents H or methyl or an ethyl group; R.sup.5 represents a linear or branched C.sub.1-10-alkyl group, particularly a methyl or an ethyl group; R.sup.5 and R.sup.5 represent either a linear or branched C.sub.1-10-alkyl group, particularly a methyl or an ethyl group; or R.sup.5 and R.sup.5 form together a linear or branched C.sub.1-10-alkylene group, particularly an ethylene or propylene group.

Description

EXAMPLES

[0098] The present invention is further illustrated by the following non-limiting experiments.

Experimental Series 1

[0099] 2-methyl-3-buten-2-ol (MBE) was mixed with 2.1 equivalents of isopropenyl methyl ether (IPM) in the presence of the respective catalyst, and stirred at a temperature of 150? C. during reaction time as given in table 1. The respective product, i.e. 6-methyl-5-hepten-2-one, was obtained in the yield and selectivity as indicated in table 1 (see FIG. 1).

TABLE-US-00001 TABLE 1 Formation of 6-methyl-5-hepten-2-one from 2-methyl-3-buten- 2-ol and isopropenyl methyl ether (2.1 equivalent) using ammonium salts at 150? C. and a pressure of 8.5 bara Amount.sup.3 Reaction Yield Selectivity Example Ammonium salt.sup.1 Type.sup.2 [mol %] time [h] [%] [%] 1 (Et.sub.3NH)H.sub.2PO.sub.4 tert. 0.18 24 92 93 2 (Et.sub.3NH).sub.2HPO.sub.4 tert. 0.15 24 91 94 3 (pyH)H.sub.2PO.sub.4 quat. 0.10 16 91 92 4 (pyH)H.sub.3P.sub.2O.sub.7 quat. 0.1 16 89 89 5 (Et.sub.3NH)HSO.sub.4 tert. 0.01 16 43 43 6 (Bu.sub.4N)HSO.sub.4 quat. 0.1 16 41 43 .sup.1(Et.sub.3NH) = triethylammonium; (pyH) = pyridinium; (Bu.sub.4N) = tetrabutylammonium .sup.2tert. = tertiary ammonium salt; quat. = quaternary ammonium salt .sup.3amount of catalyst relative to 2-methyl-3-buten-2-ol

Experimental Series 2

[0100] 3,7-dimethylocta-1,6-dien-3-ol (LL) was mixed with the number of equivalents given in table 2 of isopropenyl methyl ether (IPM) in the presence of respective catalyst in the amount as given in table 2, and stirred at a temperature of 150? during 16 hours. The respective product, i.e. 6,10-dimethyl undeca-5,9-dien-2-one, was obtained in the yield and selectivity as indicated in table 2 (see FIG. 2).

TABLE-US-00002 TABLE 2 Formation of 6,10-dimethyl-5,9-undecadien-2-one from 3,7-dimethyl-1,6-octadien- 3-ol and isopropenyl methyl ether (IPM) using ammonium salt at 150? C. and a pressure of 8.5 bara during a reaction time of 16 hours. Amount Amount.sup.4 Yield Selectivity Example Ammonium salt.sup.1 Type.sup.2 IPM.sup.3 [eq] [mol %] [%] [%] 7 (pyH)H.sub.3P.sub.2O.sub.7 quat. 2.1 0.2 72.8 73 8 (pyH)H.sub.3P.sub.2O.sub.7 quat. 2.5 0.2 82.7 83 9 (pyH)H.sub.2PO.sub.4 quat. 2.1 0.2 81.1 84 10 (pyH)H.sub.2PO.sub.4 quat. 2.5 0.2 86.0 87 11 (Et.sub.3NH)H.sub.2PO.sub.4 tert. 2.1 0.2 74.37 91.4 12 (Et.sub.3NH)H.sub.2PO.sub.4 tert. 2.5 0.2 77.24 93.2 13 (Et.sub.3NH).sub.2HPO.sub.4 tert. 2.1 0.2 71.61 93.7 14 (Et.sub.3NH).sub.2HPO.sub.4 tert. 2.5 0.2 76.05 94.3 Ref. 1 (NH.sub.4)HSO.sub.4 inorg. 2.1 0.2 11.3 11 Ref. 2 (NH.sub.4)HSO.sub.4 inorg. 2.5 0.2 14.2 14 Ref. 3 (NH.sub.4).sub.2HPO.sub.4 inorg. 2.1 0.2 48.5 96 Ref. 4 (NH.sub.4).sub.2HPO.sub.4 inorg. 2.5 0.2 32.2 97 .sup.1(pyH) = pyridinium; (Et.sub.3NH) = triethylammonium .sup.2tert. = tertiary ammonium salt; quat. = quaternary ammonium salt; inorg. = inorganic ammonium salt .sup.3amount of IPM relative to 3,7-dimethyl-1,6-octadien-3-ol .sup.4amount of catalyst relative to 3,7-dimethyl-1,6-octadien-3-ol