Journal of the American Chemical Society p. 5674 - 5678 (1994)
Update date:2022-07-30
Adam, Waldemar
Andler, Simone
The formation of the rearrangement ketone 3-phenyl-1-(phenylmethoxy)-2-propanone (3) in the thermolysis of 3,3-bis(phenylmethyl)-1,2-dioxetane (1) was rigorously probed for radical-induced chain decomposition. The latter mechanism appears to operate on the basis of the following experimental facts: (a) thermolysis of a mixture of the dioxetanes 1-h4 and 1-d4, afforded significant amounts of the crossover β-keto ethers 3-h2 and 3-d2, (b) decomposition in toluene-d8 in the presence of tert-butyl peroxalate (4) resulted in substantial incorporation of externally generated phenylmethyl-d7 radicals in the form of the β-keto ether 3-d7, and (c) in the presence of the triplet quenchers dibromomethane and 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH) the formation of the β-keto ether 3 was suppressed. Clearly, in the thermolysis of dioxetane 1, free phenylmethyl radicals are generated through Norrish type I cleavage of triplet-excited 1,3-diphenyl-2-propanone (2). Attack on the dioxetane peroxide bond leads to the β-keto ether 3 by β cleavage of the resulting alkoxy radical with regeneration of the chain-carrying phenylmethyl radical.
View MoreContact:+8613400661290
Address:No 908,Kangwan Rd, Liuyang Economic
Chengdu Green technology Co.,Ltd.
Contact:86-28-82608355
Address:C9 ,Economic Headquarters, Economic Development Zone, Chengdu.
Sichuan Highlight Fine Chemicals Co., Ltd.
Contact:+86-28-8525 1605
Address:A5-102 Airport base,388 West Airport Huang He Zhong Lu,2 Section
NINGBO PANGS CHEM INT’L CO., LTD.
Contact:+86-0574-27666801
Address:Floor 21, Building 11, Xintiandi, No. 689, Shijiroad, Ningbo, Zhejiang, China
Reliable Pharmatech (Tianjin) Co., Ltd.
Contact:86-22-28567687
Address:Zuoanmingdi, Xianshuigu, Jinnan District
Doi:10.1021/jo00094a046
(1994)Doi:10.1016/0040-4039(94)88023-9
(1994)Doi:10.1021/ja00100a070
(1994)Doi:10.1002/chem.201303468
(2014)Doi:10.1039/jr9310001771
(1931)Doi:10.1016/j.poly.2018.05.058
(2018)