67437-47-2Relevant academic research and scientific papers
Temperature-dependent photochemistry of 1,3-diphenylpropenes. The di-π-methane reaction revisited
Lewis,Zuo,Kalgutkar,Wagner-Brennan,Miranda,Font-Sanchis,Perez-Prieto
, p. 11883 - 11889 (2007/10/03)
The temperature-dependent photochemical behavior of 1,3-diphenylpropene and several of its 3-substituted derivatives has been investigated over a wide temperature range. The singlet state is found to decay via two unactivated processes, fluorescence and intersystem crossing, and two activated processes, trans,-cis isomerization and phenyl-vinyl bridging. The latter activated process yields a diradical intermediate which partitions between ground-state reactant and formation of the di-π-methane rearrangement product. Kinetic modeling of temperature-dependent singlet decay times and quantum yields of fluorescence, isomerization, di-π-methane rearrangement, and nonradiative decay provides rate constants and activation parameters for each of the primary and secondary processes. Substituents at the 3-position are found to have little effect on the electronic spectra or unactivated fluorescence and intersystem crossing pathways. However, they do effect the activated primary and secondary processes. Thus, the product ratios are highly temperature dependent.
ELECTRON TRANSFER ON CIS- AND TRANS-1,2-DIPHENYLCYCLOPROPANE: STEREOISOMERIZATION AND FORMATION OF 1,3-DIPHENYLPROPENE AND 1,3-DIPHENYLPROPANE
Boche, Gernot,Schneider, Dieter R.,Wernicke, Klaus
, p. 2961 - 2964 (2007/10/02)
Reaction of cis- or trans-1,2-diphenylcyclopropane with Na/K leads to stereoisomerization and (after protonation) to 1,3-diphenylpropane and 1,3-diphenylpropene, the latter not being formed by H-migration.
OLEFIN REACTIONS WITH HMn(CO)5: PRODUCT SELECTIVITY BY MICELLE SEQUESTERING
Matsui, Yasushi,Orchin, Milton
, p. 369 - 374 (2007/10/02)
The reaction of HMn(CO)5 with certain cyclopropenes, when carried out in a detergent medium gives a different mixture of hydroformylated and hydrogenated products than is obtained when the same reaction is carried out in a homogeneous medium.These results are consistent with the intermediacy of caged geminate radical pairs whose escape from the cage is retarded by micelle sequestering.
The Preparation and Photolysis of (E)-1-Aryl-3-methyl-3-phenylbut-1-enes
Blunt, John W.,Coxon, James M.,Robinson, Ward T.,Schuyt, Helen A.
, p. 565 - 579 (2007/10/02)
Reaction of 2-methyl-2-phenylpropylmagnesium chloride with benzaldehyde in tetrahydrofuran gave, 2,7-dimethyl-2,4,5,7-tetraphenyloctane-4,5-diol as a 1:2 mixture of clear transparent crystalline plates (meso) and needles (+/-), 3-methyl-1,3-diphenylbutan-1-one, benzyl alcohol, 2-methyl-2-phenyl-propane and a low yield of 3-methyl-1,3-diphenylbutan-1-ol.The distinction between the meso- and the (+/-)-diols was unequivocal because the unique space group of the former requires the dimeric molecules to lie about a crystallographic centre of symmetry.The mechanism involved in the formation of the products of the Grignard reaction is examined.By careful choice of reaction conditions a series of 1-aryl-3-methyl-3-phenylbutan-1-ols were prepared.Dehydration of the 1-aryl-3-methyl-3-phenylbutan-1-ols with p-toluenesulfonic acid and a short reaction time gives (E)-1-aryl-3-methyl-3-phenylbut-1-enes but longer reaction times afford 3-aryl-1,1-dimethylindanes.Photolysis of the (E)-1-aryl-3-methyl-3-phenylbut-1-enes affords (Z)-1-aryl-3-methyl-3-phenylbut-1-enes and trans-1-aryl- 3,3-dimethyl-2-phenylcyclopropanes.Extended photolysis gives 4-aryl-2-methyl-3-phenylbut-1-enes via trans-1-aryl-3,3-dimethyl-2-phenylcyclopropane by rupture of the cyclopropyl bond adjacent to the aryl substituent.
STOICHIOMETRIC HYDROFORMYLATION WITH HMn(CO)5
Nalesnik, Theodore E.,Orchin, Milton
, p. C5 - C8 (2007/10/02)
We report here the first example of a stoichiometric hydroformylation using HMn(CO)5.Treatment of a hexane solution of 1,2-diphenyl-3,3-dimethylcyclopropene with HMn(CO)5 at 55 deg C gave after 5 h a 27percent yield of aldehydes, 87percent cis and 13perce
