Oxidative cleavage with hydrogen peroxide: preparation of polycarboxylic acids from cyclic olefins.
Oxidative cleavage of carbon-carbon double bonds of cyclic olefins with hydrogen peroxide in the presence of heteropolyacids has been investigated as a clean and environmentally friendly preparation of polycarboxylic acids. In the presence of 12-tungstophospholic acid (H(3)PW(12)O(40)), adipic acid was obtained in 95% yield from cyclohexene in lipophilic phase and hydrogen peroxide in aqueous phase. In addition, 1,2,3,4-butanetetracarboxylic acid was also obtained in 87% yield from 1,2,3,6-tetrahydrophtharic acid anhydride, while endic acid anhydride did not afford corresponding 2,3,6-cyclopentanetetracarboxylic acid but only lactone compound was obtained. In this oxidation process, oxidative cleavage of carbon-carbon double bonds would proceed as the sequential reactions in which the rate determining step is oxidative cleavage of vicinal-diol compounds.
Fujitani
Kango
K
Environment Safety/Quality Assurance Department, New Japan Chemical Co., Ltd., Kyoto, Japan. fujitani-k@nj-chem.co.jp
Mizutani
Toshihiro
T
Oida
Tatsuo
T
Kawase
Tokuzo
T
D000272:Adipates / Q000138:chemical synthesis; D000812:Anhydrides / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D002264:Carboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D053138:Cyclohexenes / Q000737:chemistry; D003516:Cycloparaffins / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010772:Phosphotungstic Acid / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis*; D014867:Water / Q000737:chemistry
D000272:Adipates; D000812:Anhydrides; D002264:Carboxylic Acids; D053138:Cyclohexenes; D003516:Cycloparaffins; D007783:Lactones; D011108:Polymers; D014867:Water; D010772:Phosphotungstic Acid; C052568:cyclohexene; D002244:Carbon; C029900:adipic acid; D006861:Hydrogen Peroxide