CATALYTIC ETHYNYLATION

Abstract

The present invention relates to the catalytic ethynlation of αβ-unsaturated ketones for producing tertiary acetylenic alcohols.

Claims

1. A process for the production of compounds of formula (III) ##STR00008## wherein R is hydrogen or an aliphatic, cyclo-aliphatic or aromatic hydrocarbon which can be unsubstituted or substituted with lower alkoxy or lower alkyl groups and R.sub.1 is CH.sub.3 or CH.sub.2CH.sub.3, wherein a compound of formula (I) ##STR00009## wherein the substituents have the same meanings as defined for the compound of formula (III) is reacted with a compound of formula (II)
≡  (II) in NH.sub.3 as a solvent and in the presence of KOH, characterized in that KOH is added to reaction mixture in solid form, and wherein the process is carried without any addition of water.

2. Process according to claim 1, wherein R is an aliphatic or aromatic hydrocarbon which is substituted with lower alkoxy or lower alkyl groups and R.sub.1 is CH.sub.3.

3. Process according to claim 1, wherein the compound of formula (I) is the compound of formula (I′) ##STR00010## and the compound of formula (III) is the compound of formula (III′) ##STR00011##

4. Process according to claim 1, wherein the process is carried out at a temperature below +5° C.

5. Process according to claim 1, wherein the process is carried out at a temperature of from −60° C. to 5° C.

6. Process according to claim 1, wherein the process is carried out at atmospheric conditions.

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

8. Process according to claim 1, herein the process is carried without any addition of water.

Description

EXAMPLES

Example 1

[0054] 66 mMol β-ionone were added to a mixture of 16 mMol KOH and 23 w % C.sub.2H.sub.2 in NH.sub.3 and agitated for 1 h, at −10° C. at a pressure of 4.2 bar.

[0055] Afterwards 200 ml n-hexane were added slowly to the reaction mixture and the reaction mixture was degassed for about 2 h.

[0056] The inorganic phase was separated from the organic phase, neutralized with AcOH and extracted with 150 ml n-hexane.

[0057] The combined organic phases were washed with 150 ml water, dried on Na.sub.2SO.sub.4, filtered and concentrated under vacuum.

[0058] The yield was 77%.

Example 2

[0059] The same reaction conditions as in Example 1 was chosen for Example 2. In addition, 10 ml water were added after 1 hour.

[0060] The yield was 81%.