03-11-2016 дата публикации
Номер: US20160318836A1
Disclosed is a process for the production of 2,6-dimethylhept-5-enal by Baeyer-Villiger oxidation of 3,7-dimethylocta-2,6-dienal in the presence of aqueous HOand SeO, followed by hydrolysis. 1. A process for the production of 2 ,6-dimethylhept-5-enal by Baeyer-Villiger oxidation of 3 ,7-dimethylocta-2 ,6-dienal in the presence of aqueous HOand SeO , resulting in 2 ,6-dimethylhepta-1 ,5-dien-1-yl formate , followed by hydrolysis.2. A process according to wherein the process is carried out in a protic or aprotic solvent.3. A process according to wherein the solvent is selected from water claim 2 , acetone claim 2 , tert-butanol claim 2 , and tert-amyl alcohol claim 2 , or mixtures thereof.4. A process according to claim 1 , wherein the process is carried out from 0° C. to 200° C.5. A process according to wherein claim 1 , 2 claim 1 ,6-dimethylhepta-1 claim 1 ,5-dien-1-yl formate is obtained which is essentially free of citral-6 claim 1 ,7-epoxid and citral-2 claim 1 ,3-epoxid.6. A process according to wherein the reaction is carried out at a conversion rate of citral from 10-100%. The present invention is concerned with a novel process for the production of 2,6-dimethylhept-5-enal, also known as Melonal, which is an important, aldehydic, melon-like odorant for the fragrance industry. In particular, the present invention relates to a process for the synthesis Melonal by selenium dioxide (SeO) catalyzed Bayer-Villiger reaction of (E/Z)-3,7-dimethylocta-2,6-dienal, also known as Citral, via the intermediate 2,6-dimethylhepta-1,5-dien-1-yl formate.Up to now 2,6-dimethyl-5-heptenal is industrially produced by Darzens reaction from 6-methyl-hept-5-en-2-one. This reaction requires alkylation with chloro acetic esters to glycidesters followed by hydrolysis and decarboxylation leading to the aldehyde. This approach is not atom economic as an alcohol (ROH), a chloride salt, as well as carbon dioxide is eliminated from the reactants.Some years ago Corma at al (J. Catal. 2005, ...
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