Bulletin of the Chemical Society of Japan p. 1144 - 1152 (1982)
Update date:2022-08-03
Topics:
Morita, Tadayoshi
Takase, Kahei
Four kinds of biazulenes, 1,1'- (1a), 2,2'- (2a), 1,2'- (3a), and 2,6'-biazulenes (4a), and their derivatives were synthesized by utilizing Ullmann-type coupling of haloazulene derivatives.Ullmann reaction of ethyl 3-iodo- (5a) and 2-iodoazulene-1-carboxylates (6b) gave diethyl 1,1'-biazulene-3,3-dicarboxylate (1b) and diethyl 2,2'-biazulene-1,1'-dicarboxylate (2b), respectively, in excellent yields.The reaction of 2-iodoazulene gave 2a directly.Diethyl 2-chloroazulene-1,3-dicarboxylate (7a) and 5-alkyl derivatives also reacted to give tetraethyl 2,2'-biazulene-1,1',3,3'- tetracarboxylate (2d) and its 5,5'-dialkyl derivatives, respectively.A mixed Ullmann reaction of 5a and 6b afforded a mixture of 1b, 2b, and diethyl 1,2'-biazulene-1',3-dicarboxylate (3b).Similarly, a mixed Ullmann reaction of 7a and diethyl 6-iodoazulene-1,3-dicarboxylate gave a mixture of 2d and tetraethyl 2,6'-biazulene-1,1',3,3'-tetracarboxylate (4b).The parent hydrocarbons of biazulenes, 1a, 2a, 3a, and 4a, could be derived from the corresponding ethoxycarbonyl derivatives, 1b, 2b, 2d, 3b, and 4b, respectively, by decarboxylation.The planarity of biazulenes and their ester derivatives is also discussed on the basis of the spectral data.
View MoreJintan Jinnuo Chemical Co., Ltd.
Contact:+86-519-80199901
Address:Room 1804, Building 1, Huacheng Business Plaza, Jintan, Jiangsu, China
Contact:+86-511-88790000
Address:338 North Yushan Rd, Zhenjiang, Jiangsu 212016
QINGDAO TAOSIGN INTERNATIONAL TRADE CO.,LIMITED
Contact:+86-0532-82683616
Address:RM1402, Doublestar Seacoase 7#, No. 5 Guizhou Road, Qingdao, Shandong, China
JIN TAN CHENG'EN CHEMICAL CO.,LTD.
Contact:86-519-82116250
Address:NO.102,village Dongfang,conomic development zone
Shanghai HengXun Pharmaceutical Tech. Co., Ltd.
Contact:86-86-52730756
Address:Room 603, No. 240, Tianmuzhong Road, Zhabei, Shanghai, China
Doi:10.1007/s11243-009-9316-7
(2010)Doi:10.1039/c5dt00704f
(2015)Doi:10.1039/c39950000833
(1995)Doi:10.1016/0223-5234(96)88248-1
(1995)Doi:10.1016/0040-4039(95)00955-C
(1995)Doi:10.1016/S0022-328X(00)00755-5
(2001)