Journal of the Chemical Society. Perkin transactions I p. 1277 - 1286 (1996)
Update date:2022-08-03
Topics:
Ishii, Akihiko
Maeda, Kiyoto
Kodachi, Maki
Aoyagi, Noriko
Kato, Keiko
Maruta, Teruo
Hoshino, Masamatsu
Nakayama, Juzo
Synthesis of 8-hydroxy-4-methylthiophenetriptycene 1 was performed by treatment of the trilithium salt, prepared from 1,1,1-tris(2-bromo-4-methyl-3-thienyl)ethane 13, with diethyl carbonate. In a similar manner, the 8-hydroxy-4-ethylthiophenetriptycene 27 was prepared. The isomeric 4-hydroxy-8-methyl derivative 11 was also obtained by reaction of the trilithium salt, derived from 1,1,1-tris(3-bromo-5-methyl-2-thienyl)ethane 40, with dimethyl carbonate. Attempts to prepare 8-hydroxy-4-tert-butyl- 31 and 8-hydroxy-4-unsubstituted thiophenetriptycenes resulted in the formation of ketone 29 and hydroperoxide 32, respectively. The 8-hydroxy-4-methylthiophenetriptycene 1 decomposed to the corresponding ketone 26 on heating. Attempts to generate the carbocation at the bridgehead of compound 1 by dissolution in conc. H2SO4 or by acetolysis of methanesulfonate 44 were unsuccessful. 8-Acetoxy (45) and 8-methoxy (46) derivatives of compound 1 were prepared by treatment of compound 1 with acetic anhydride in triethylamine in the presence of DMAP and by methylation of the lithium salt of compound 1 with trimethyloxonium tetrafluoroborate, respectively. Comparison of IR spectra of regioisomers 1 and 11 indicated that hydrogen bonding of the bridgehead hydroxy group in compound 1 is somewhat hampered by the steric hindrance of the sulfur atoms of the three thiophene rings.
View MoreContact:+86-574- 87178138; 87297407
Address:No. 809, Liudingxingzuo, cangsong road, Ningbo, China
HAINAN JINYING IMPORT AND EXPORT CO. LTD
Contact:+86-898-32875423
Address:A SECTION 19TH FL, TIMES SQUARE, NO.2 GUO MAO AVENUE HAIKOU, HAINAN, P. R. OF CHINA
Hangzhou Hysen Pharma co.,Ltd.
website:http://www.hysenpharma.cn/
Contact:0086-571-88298791
Address:#701,Gudun Road Hangzhou
Shao Xing Empire Import&Export CO.,ltd
Contact:86-575-82127757
Address:11#, Weiwu Road, Shangyu Industrial Park, Hangzhou Bay, Hangzhou, Zhejiang Province, China
Shanghai Minstar Chemical Co., Ltd
website:http://www.minstargroup.com
Contact:86-21-18019205509
Address:BUILDING 8, NO.1098, CHUANSHA ROAD, SHANGHAI, CHINA
Doi:10.1039/d0dt03414b
(2020)Doi:10.1016/0040-4039(96)00874-X
(1996)Doi:10.1039/b201304e
(2002)Doi:10.1039/jr9570000137
(1957)Doi:10.1016/j.tetlet.2012.07.115
(2012)Doi:10.1016/0040-4039(96)01013-1
(1996)
