Journal of Organic Chemistry p. 973 - 980 (1980)
Update date:2022-07-29
Topics:
Duerr, Heinz
Nickels, Helmut
Pacala, Luba A.
Jones, Maitland
EHT and CNDO/2 calculations on benzocyclobutenylidene (6) are described.Flash pyrolysis of the tosylhydrazone salt 7 affords benzocyclobutene and o-xylene in low yield, along with the formal syn and anti carbene dimers 13 and 14.Condensed-phase reactions were achieved by photolysis of the salt 15.Benzocyclobutenylidene (6) gave rise to the formal carbene dimers 17 and 18.Insertion of carbene 6 into the carbon-hydrogen bonds of 2,3-dimethylbutane produced the benzocyclobutenes 20 and 21 (insertion ratio tertiary:primary = 9:1).Cycloaddition of 6 to olefins gave only spiro<3.2>hexene derivatives 22.Multiplicity studies of 6 with cis or trans olefins indicated that 6 undergoes <1+2> cycloaddition in a stereospecific manner.Competition experiments using dienes and monoolefins implicate an equilibrium between singlet and triplet 6.Further competition experiments with styrene/para-substituted styrene pairs demonstrated that 6 reacts faster with electron-poor styrenes.Possible explanations for this apparent anomaly are discussed.
View MoreDezhou Longteng Chemical Co., Ltd.
website:http://www.sodium-methoxide.cn/
Contact:0086-18866052283
Address:Xinhua Industrial Zone, Dezhou City, Shandong Province, China
Zhejiang Chemicals Import & Export Corporation (ZHECHEM)
Contact:+86-571-87046953
Address:No. 37, Qingchun Road
SHIFANG SUHONG CHEMICAL CO.,LTD
Contact:+86-838-2224563
Address:Room 1207 Zongchen Sunshine No.128 Taishan South Road,Deyang City,Sichuan China
Contact:13813902930 025-52714267
Address:20 Fengji Road, Yuhua Economic Development Zone, Nanjing, Jiangsu, P. R. China
Shanghai Chemchallenger Biotech Co., Ltd.
Contact:0086-21-68110815
Address:Room 2056, Building 1, No. 1065, Jiaxin Road Shanghai China (Mainland) 201800
Doi:10.1021/jo01296a037
(1980)Doi:10.1002/jps.2600681132
(1979)Doi:10.1002/hlca.19790620828
(1979)Doi:10.1002/jhet.5570160733
(1979)Doi:10.1016/j.bmc.2004.04.035
(2004)Doi:10.1021/jo00422a033
(1977)