Potassium Carboxylates by Direct Carbonylation of Potassium Alkoxides

Article abstract of DOI:10.1002/hlca.19870700312

Reaction of the K⁺ alkoxide of linalool (1) in benzene with CO at 425-440 bar and 120-130 degC for 12-30 h gave the K⁺ salt of 2,6-dimethyl-2-vinyl-5-heptenoic acid (4a) in a ca. 25percent yield based on ca. 65percent converted alkoxide.Reaction of the + <*> 18-crown-6> alkoxide of 1 with CO at 50-55 bar and 40 degC for 90-140 h gave a mixture containing mainly the + <*> 18-c-6> salts of 4a (ca. 62percent) and of the homogeranic acids 3a and 6a (together ca. 27percent of the mixture) in a ca. 35percent combined yield based on 50-60percent converted alkoxide.The uncomplexed or complexed K⁺ alkoxide of (S)-1 gave, with ca. 85percent net retention, the K⁺ salt of (S)-4a.Reaction of the + <*> 18-c-6> alkoxide of geraniol (2) with CO at 50 bar and 40 degC for 65-70 h gave myrcene (10) and geranyl formate (11) in a ca. 40-50percent yield each based on ca. 85percent converted alkoxide.Reaction of the + <*> 18-c-6> alkoxide of 3-pentyl-1,4-pentadien-3-ol (14) at 50 bar and r.t. for 70 h gave a mixture of the + <*> 18-c-6> salts of 2-pentyl-2-vinyl-3-butenoic acid (15a) (67percent) and the 4-pentyl-2,4-hexadienoic acids 18a and l9a (together 23percent of the mixture) in a ca. 90percent combined yield based on ca. 65percent converted alkoxide.