ETHYNYLATION OF POLYUNSATURATED ALDEHYDES AND KETONES

Abstract

The present invention relates to a catalytic process for the ethynylation of specific polyunsaturated aldehydes and ketones.

Claims

1. A catalytic ethynylation process which comprises conducting a catalytic ethinylation reaction of a compound of formula (I): ##STR00017## wherein R.sup.1 signifies —H or —CH.sub.3, R.sup.2 signifies —H, and R.sup.3 signifies a moiety selected from the group consisting of: ##STR00018## with ethyne in NH.sub.3 as a solvent and in the presence of a catalyst of formula ROH, wherein R signifies K or Cs at a catalytic ethinylation reaction temperature between −40° C. to 10° C.

2. The catalytic ethynylation process according to claim 1, wherein the compound of formula (I) is a compound of formula (Ia): ##STR00019##

3. The catalytic ethynylation process according to claim 1, wherein the compound of formula (I) is a compound of formula (Ib): ##STR00020##

4. The catalytic ethynylation process according to claim 1, wherein the compound of formula (I) is a compound of formula (Ic): ##STR00021##

5. The catalytic ethynylation process according to claim 1, wherein the catalyst is added to the reaction mixture as an aqueous solution.

6. The catalytic ethynylation process according to claim 1, wherein R is K.

7. The catalytic ethynylation process according to claim 1, wherein the catalytic ethynylation reaction is carried out under pressure which is in a range from 2 bar to 15 bar.

8. The catalytic ethynylation process according to claim 1, wherein the catalytic ethynylation reaction temperature is between −30° to 5° C.

9. The catalytic ethinylation process according to claim 1, wherein the catalytic ethynylation reaction is carried out under pressure which is in a range of 5 bar to 12 bar.

10. The catalytic ethinylation process according to claim 1, wherein the catalytic ethynylation reaction is carried out under pressure which is in a range of 6 bar to 10 bar.

Description

EXAMPLES

Example 1: Ethynylation of Pseudo-Ionone (Compound of Formula (Ic))

[0053] The reaction was carried out in a 1 L-autoclave, which was washed with N2 before its use. Afterwards 150 g NH.sub.3 was added into the autoclave and cooled to −20° C. At this temperature acetylene (ethyne) was added so that the pressure was 5.6 bara.

[0054] Afterwards 1.68 g of KOH (as a 44 wt-% solution in H.sub.2O) was added followed by 354.45 g of the compound of formula (Ic). After 4 h reaction time, the reaction mixture was diluted with 100 ml n-heptane.

[0055] The obtained product (compound of formula (IIc)

##STR00015##

[0056] was purified and it was obtained in a yield of 32%.

Example 2: Ethynylation of Compound of Formula (Ia)

[0057] The reaction was carried out in a 1 L-autoclave, which was washed with N2 before its use. Afterwards 150 ml of NH.sub.3 was added and cooled to −20° C. At this temperature acetylene (ethyne) was added so that the pressure was 5.6 bara. 1.68 g of KOH (as a 44 wt-% solution in H.sub.2O) was added.

[0058] Afterwards 5 g of the compound of formula (Ia), dissolved in 5 g toluene, was added. After 6 h reaction time, the reaction mixture was diluted with 100 ml toluene.

[0059] The obtained product (compound of formula (IIa)

##STR00016##

[0060] was purified and it was obtained in a yield of 57%.