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4,15‐Diamino[2.2]paracyclophane, a Reusable Template for Topochemical Reaction Control in Solution
Author(s) -
Zitt Holger,
Dix Ina,
Hopf Henning,
Jones Peter G.
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200207)2002:14<2298::aid-ejoc2298>3.0.co;2-e
Subject(s) - chemistry , saponification , amide , hydrolysis , lithium aluminium hydride , urea , cyclophane , yield (engineering) , organic chemistry , diamine , lithium (medication) , medicinal chemistry , crystal structure , materials science , metallurgy , medicine , endocrinology
An efficient synthesis of [2.2]paracyclophane‐4,15‐dicarboxylic acid ( 11 ) from [2.2]paracyclophane ( 8 ) has been developed. The diacid was converted via the diazide 14 into the 4,15‐diisocyanato[2.2]paracyclophane ( 15 ), a versatile intermediate that could be transformed into many new pseudo ‐geminally substituted derivatives of 8 . For example, treatment of 15 with alcohols provided the carbamates 16 and 17 . On treatment of 15 with diisopropylamine, the urea 18 was obtained, whereas reduction with lithium aluminium hydride afforded the cyclic urea 20 . Hydrolysis of 15 furnished the diamine 19 , which was used as a reusable spacer in a [2+2]photoaddition experiment. Thus, treatment of 19 with trans ‐cinnamoyl chloride ( 25 ) provided the bis(amide) 26 , which on irradiation in acetone ring‐closed to give the cyclobutane 28 . Saponification of this yielded 3,4‐diphenyl‐1,2‐cyclobutanedicarboxylic acid ( 27 , β‐truxinic acid) and returned the spacer system 19 , both in quantitative yield. The X‐ray structures of 15 and 20 are reported. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)