72867-95-9Relevant academic research and scientific papers
THE PHOTOCHEMISTRY OF METHYL GERANATE, A MODEL CHROMOPHORE FOR INSECT JUVENILE HORMONE ANALOGS
Freeman, Peter K.,Siggel, Lorenz,Chamberlain, Paul H.,Clapp, Gary E.
, p. 5051 - 5064 (2007/10/02)
The irradiation of methyl geranate (3) in ether using 254 nm lamps produces methyl 5-methyl-2-isopropenyl-4-hexenoate (13), 1,6,6-trimethyl-endo-5-carbomethoxybicyclo-hexane (11), methyl 2-isopropenyl-5-methylcyclopentanecarboxylate (12) and methyl (3Z)-3,7-dimethyl-3,6-octadienoate (14).Photolysis run in water or in ether in the presence of base generates two additional dienes: methyl 3-methylene-7-methyl-6-octaenoate (16) and methyl (3E)-3,7-dimethyl-3,6-octadienoate (17).The photolysis of methyl (2E, 6E)-3,7-dimethyl-2,6-nonadienoate (4a) in ether procedures all Z/E isomers, 4a - 4d.
The Kinetics of Photochemical Deconjugation Reactions of Methyl Geranate
Freeman, Peter K.,Siggel, Lorenz
, p. 5065 - 5074 (2007/10/02)
The photochemical transformations of methyl geranate are analyzed in terms of the depedence of quantum yield upon base, 1,2-dimethylimidazole, concentration.The dependence of quantum yield of deconjugated esters methyl (3Z)-3,7-dimethyl-3,6-octadienoate (12), methyl 3-methylene-7-methyl-6-octenoate (13), and methyl (3E)-3,7-dimethyl-3,6-octadienoate (14) and the ratio of (13)/(12) and (13)/(14) upon base concentration, as well as the dependence of the ratios (methyl 2-isopropenyl-5-methylcyclopentanecarboxylate (15): deconjugated ester) (10)/(12), (10)/(13) and (10)/(14) upon the reciprocal of the base concentration, are consistent with relative rate constant ratios for (sigmatropic shift)/(dienol deprotonation) for photodienols 15, (precursor of 13), 17 (precursor of 12) and 19 (precursor of 14), of 72, 1.0 and 85.
