Chemical and Pharmaceutical Bulletin p. 1108 - 1114 (1999)
Update date:2022-08-05
Topics:
Yasuike, Shuji
Shiratori, Shin-Ichi
Kurita, Jyoji
Tsuchiya, Takashi
Fully unsaturated group 14 (Si, Ge, and Sn), group 15 (P, As, Sb, and Bi) and group 16 (S, Se, and Te) 2-trimethylsilyl-1-benzoheteroepines (16a- j), including the first isolated examples of bismepines, have been prepared by reaction of the corresponding electrophilic metal reagents (MX2 or MX4; M=group 14, 15, and 16 heavier elements) with the key 1,6-dilithium intermediate (9), generated from the common starting compound (Z,Z)-1-bromo- 4-(2-bromophenyl)-1-trimethylsilyl-1,3-butadiene (14) by treatment with tert- butyllithium. The trimethylsilyl group in 16b-j was readily removed by treatment with tetrabutylammonium fluoride to give the desired C- unsubstituted 1-benzoheteroepines (1b-j). Single crystal X-ray analyses of 1d (P) and 1f (Sb) revealed that the seven-membered rings exist in boat conformations with the heteroatoms at the bows. All obtained C-unsubstituted group 15 and 16 1-benzoheteroepines (1d-j) were thermolabile in solution towards heteroatom extrusion, while heteroepines (16d-j) having the bulky trimethylsilyl group at the 2-position were much more stable than 1d-j. The half-lives of 1d-j estimated from 1H-NMR spectral analysis indicate that the thermal stabilities of 1d-j decrease in the order 1f (Sb)>1d (P)>1e (As)>1g (Bi) in the group 15 heteroepines and 1j (Te)>1i (Se)>1h (S) in the group 16 heteroepines.
View MoreShanghai Rainbow Chemistry Co., Ltd.
Contact:+86-21-64968086-5815/5812
Address:3rd floor, Building 7, 251 Faladi Road, Zhangjiang Hi-Tech Park, Pudong District, Shanghai, P.R. China
Contact:+86-519-86339586,13584329896
Address:Changzhou Scientific and Education Park
website:http://www.easchem.com
Contact:+86-731-89722861 89722891
Address:2/F-4/Bld Colorful Palace, No.605 Changsha Ave, Yuhua Area Changsha Hunan China.
website:http://www.amadischem.com
Contact:86-571-89925085
Address:Watts Cosine.No.166.Xiangmao Road.
Chengdu Sino-Strong Pharmaceutical Co.,Ltd.
website:http://www.sino-strong.com.cn
Contact:+86-28-82666753
Address:459 West haike road,Cross-straits technological industry park, Wenjiang district,Chengdu, P.R.China
Doi:10.1039/c3ra44798g
(2014)Doi:10.1016/j.jorganchem.2013.06.028
(2014)Doi:10.1016/S0040-4039(00)61701-X
(1993)Doi:10.1016/S0040-4039(00)61344-8
(1993)Doi:10.1111/j.2042-7158.1994.tb03751.x
(1994)Doi:10.1016/j.tetlet.2013.12.110
(2014)