23068-83-9Relevant academic research and scientific papers
Silyl Tosylate Precursors to Cyclohexyne, 1,2-Cyclohexadiene, and 1,2-Cycloheptadiene
McVeigh, Matthew S.,Kelleghan, Andrew V.,Yamano, Michael M.,Knapp, Rachel R.,Garg, Neil K.
, p. 4500 - 4504 (2020)
Transient strained cyclic intermediates have become valuable intermediates in modern synthetic chemistry. Although silyl triflate precursors to strained intermediates are most often employed, the instability of some silyl triflates warrants the developmen
7-Arylbicyclooct-1-enes - Synthesis by Cycloadditions of 1,2-Cyclohexadiene and 1-Methyl-1,2-cyclohexadiene and Thermal Equilibration of the exo/endo Isomers
Christl, Manfred,Schreck, Michael
, p. 915 - 920 (2007/10/02)
The exo/endo ratio of the isomers 3a, b formed in the known cycloaddition of styrene to 1,2-cyclohexadiene (2) has been found to depend on the temperature.The ultilization of (Z)-deuteriostyrene provided the proof of the stepwise nature of this reaction with the diradical 4 as the most probable intermediate.Heating of 3b at 140-170 deg C established the thermodynamic equilibrium between 3a and 3b (3a:3b = 93:7) and again 4 is assumed to be the intermediate.By means of kinetic measurements the activation parameters of the system 3a 3b have been determined. - From 2 and the trapping reagents p-methoxy-styrene, 1,1-diphenylethylene, and 1-phenylpropene the title compounds 6a, b, 7, and 8, respectively, were formed in low yields.In analogy to 2 its 1-methyl derivative 13 has been generated from 6,6-dibromo-1-methylbicyclohexane (9) with methyllithium.From the reaction in the presence of styrene the trapping products 14a, b were isolated in addition to the dimer 12 or 13. - The 1H NMR spectra of the title compounds support a rigid halfchair conformation of the cyclohexene moiety with the cyclobutane ring anellated equatorially.
