699-42-3Relevant academic research and scientific papers
THE SYNTHESIS OF 1-BENZYLDIMETHYLSILYL-4-PHENYLTHIO-1,3-BUTADIENE: A NEW DIENE-REGENERABLE DIELS-ALDER SYNTHON
Pegram, J. J.,Anderson, C. B.
, p. 6719 - 6720 (2007/10/02)
1-Benzyldimethylsilyl-4-phenylthio-1,3-butadiene (1), prepared by hydrosilation of propargyl alcohol, oxidation and followed by Wittig-Horner reaction, underwent Diels-Alder reaction with methyl methacrylate.The adduct after oxidation to the sulfone when
Uncatalyzed Sigmatropic 1,5-Shift of Acyl Groups in the Thermolysis of 5-Acyl-5-methyl-1,3-cyclohexadienes
Schiess, Peter,Dinkel, Rolf,Fuenfschilling, Peter
, p. 787 - 800 (2007/10/02)
Four different 5-acyl-5-methyl-1,3-cyclohexadienes 1a-d (R=COOCH3, COCH3, COC6H5, CHO) have been shown to yield mixtures of 1,3-disubstituted cyclohexadienes 2-7 and 1,3-disubstituted aromatic product 8 upon thermolysis at 150-300 deg C in solution and at 350-500 deg C in the gas phase in a flow system.Two reaction pathways are considered for the rearrangement of the C-Skeleton.For the ester 1a 13C-isotopic substitution shows that products arise to 75-86percent through a 1,5-sigmatropic shift of the methoxycarbonyl group and to 14-25percent through a sequence of reaction steps involving a 1,7-H-shift reaction in an acyclic intermediate.For the more reactive compounds 1b-d isomerization is assumed to follow the 1,5-sigmatropic pathway exclusively.A kinetic study yields the following sequence for the migration tendency of acyl groups toward sigmatropic 1,5-shift: COOCH3 COCH3 COC6H5 CHO.
