ETHYNYLATION OF POLYUNSATURATED ALDEHYDES AND KETONES

Abstract

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

Claims

1. A catalytic ethynylation of a compound of formula (I) ##STR00017## wherein R.sup.1 signifies —H, —CH.sub.3 or —CH.sub.2CH.sub.3, and R.sup.2 signifies —H, —CH.sub.3 or —CH.sub.2CH.sub.3, and R.sup.3 signifies a moiety ##STR00018## with ethyne in the presence of a catalyst of formula ROH, wherein R signifies K or Cs, and wherein NH.sub.3 is used as solvent.

2. Catalytic ethynylation according to claim 1, wherein R.sup.1 signifies —H or —CH.sub.3, and R.sup.2 signifies —H or —CH.sub.3, preferably —H.

3. Catalytic ethynylation according to claim 1, wherein the compound of formula (I) is the compound of formula (Ia) ##STR00019##

4. Catalytic ethynylation according to claim 1, wherein the compound of formula (I) compound of formula (Ib) ##STR00020##

5. Catalytic ethynylation according to claim 1, wherein the compound of formula (I) compound of formula (Ic) ##STR00021##

6. Catalytic ethynylation according to claim 1, wherein the catalyst is added to the reaction mixture as an aqueous solution.

7. Catalytic ethynylation according to claim 1, wherein R is K.

8. Catalytic ethynylation according to claim 1, wherein the catalytic ethynylation is carried out under pressure and wherein the pressure is in the range from 2 bar to 15 bar (preferably from 5 bar to 12 bar, more preferably from 6 bar to 10 bar).

9. Catalytic ethynylation according to claim 1, wherein the catalytic ethynylation is carried at a reaction temperature of between −40° C.-10° C. (preferably −30°-5° C.).

Description

EXAMPLES

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

[0052] The reaction was carried out in a 1 L-autoclave, which was washed with N.sub.2 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. 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.

[0053] The obtained product (compound of formula (IIc)

##STR00015##

[0054] was purified and it was obtained in a yield of 32%.

Example 2: Ethynylation of Compound of Formula (Ia)

[0055] The reaction was carried out in a 1 L-autoclave, which was washed with N.sub.2 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.

[0056] 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.

[0057] The obtained product (compound of formula (IIa)

##STR00016##

[0058] was purified and it was obtained in a yield of 57%.