Journal of Organometallic Chemistry p. 295 - 312 (1985)
Update date:2022-08-05
Topics: THERMOLYSE
Dubac, Jaques
Laporterie, Andre
Iloughmane, Hafida
Thermolysis of esters of silacyclopent-4-ene-3-ols Me2<*>CH=CR-CR'(X)<*>H2 (R,R'=H or Me; X=OC(O)NHPh, OC(S)SMe) leads to 1,1-dimethylsilole (1), 1,1,3-trimethylsilole (2) or 1,1,3,4-tetramethylsilole (3).The thermally unstable S-methylxanthates decompose involving both competitive β-C-H and β-C-Si eliminations.With N-phenylcarbamates a regioselective C-H elimination on an endocyclic carbon, leads to the expected siloles 1-3, is mainly observed.A one pot synthesis of 3, the first methylsilole stable as a monomer, from the corresponding alcohol (X=OH, R=R'=Me) and phenyl isocyanate is described. 1,1,3,4-Tetramethylgermole (4) is similarly obtained.The relative stability of the methylsiloles, their ability to form Diels-Alder dimers and to isomerize into a transoid diene, is discussed.In this respect, the strong influence of C-methyl groups on the stabilization of the tetramethylsilole, as in the case of the 1,1,3,4-tetramethylphospholium ion, is made possible.The principal characteristisc of NMR and mass spectra of methylsiloles 1-3 and those of their stable tricarbonyliron complexes are studied.
View MoreFusilin chemical science & technology co., ltd.
Contact:532-80698166/86057573, +86-400-669-7885
Address:School of Material Science & Engineering, Shandong Uinversity of Science & Technology, Huangdao Zone, Qindao, Shandong
website:http://www.NEM.COM.CN
Contact:+86-393-4411771
Address:The west section of shengli Road,Puyang,Henan Province,China
Contact:Tel:+86-29-88764861 Fax:+86-29-88764861
Address:Rm#2107, Block A, Epin Meidao Building, Gaoxin Rd, Hi-Tech Zone, Xi’an, China
suzhou BetterBioChem Co., Ltd.
website:http://www.betterbiochem.com
Contact:+86-18013506594
Address:No. 8 Building, 18 nong, Xi Yingnan Road, Pudong, Shanghai,China
Tianjin Ingenochem Technology Co.,Ltd
Contact:+86-22-23677060
Address:Hitech Green Industry Park K2-9-602, Nankai district
Doi:10.1039/jr9350001591
(1935)Doi:10.1002/anie.200500480
(2005)Doi:10.1021/ol051234w
(2005)Doi:10.1021/ja01158a509
(1950)Doi:10.1016/j.tet.2005.04.022
(2005)Doi:10.1016/j.bmcl.2007.04.065
(2007)