TOPOCHEMISTRY .31. FORMATION OF CYCLO-OCTA-1,5-CIS,CIS-DIENES FROM 1,4-DISUBSTITUTED S-TRANS-BUTADIENES IN SOLID STATE - CONTRIBUTION TO PROBLEM OF C4-VERSUS C8-CYCLODIMERISATION
TOPOCHEMISTRY .31. FORMATION OF CYCLO-OCTA-1,5-CIS,CIS-DIENES FROM 1,4-DISUBSTITUTED S-TRANS-BUTADIENES IN SOLID STATE - CONTRIBUTION TO PROBLEM OF C4-VERSUS C8-CYCLODIMERISATION
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DOI：
10.1039/j29710001552
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发表时间：
1971-01-01
期刊：
影响因子：
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通讯作者：
SCHMIDT, GMJ
中科院分区：
文献类型：
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作者：
GREEN, BS;LAHAV, M;SCHMIDT, GMJ
固体五-1，3-二烯-1-羧酸(4)、五-1，3-二烯-1-甲酰胺(5)、丁二烯-1，4-二碳腈(6)、苯丙基丙烯酸(10)、其甲酯(46)和酰胺(49)(均为反式，反式构型)，都在光照(λ>；290 nm)下发生二聚反应，得到二乙烯基环丁烷(C4)衍生物。(4)、(5)、(6)和(49)的完全表征的光产物的结构和(N-苯基)苯基丙烯酰胺(53)的光稳定性可以从它们单体的已知或假定的堆积排列中预测出来。环-八-1，5-反式-二烯，尽管在拓扑化学和对称性上允许来自具有平行丁二烯链的单体[(4)，(5)，(6)，和可能的(10)]，但没有观察到。虽然不能严格排除C8-环二聚体的形成，但我们的结果既不支持也不需要它们的存在。在(4)，(5)和(10)的照射下形成的(全AX)-环-八-1，5-顺，顺-二烯(C8)衍生物不是主要的光产物，而是由光化学产生的顺-1，2-二乙烯基环丁烷的热(COPE)重排产生的。
Solid penta-1,3-diene-1-carboxylic acid (4), penta-1,3-diene-1-carboxamide (5), buta-1,3-diene-1,4-dicarbonitrile (6), styrylacrylic acid (10), its methyl ester (46), and amide (49)(all trans,trans-configurated), all photodimerise on irradiation (λ > 290 nm), to divinylcyclobutane (C4) derivatives. The structures of the fully characterised photoproducts from (4), (5), (6), and (49) and the light-stability of (N-phenyl)styrylacrylamide (53), are predictable from the known or postulated packing arrangements of their monomers.Cyclo-octa-1,5-trans,trans-dienes, although topochemically and symmetry-allowed from monomers which crystallise with parallel butadiene chains [(4), (5), (6), and possibly (10)], are not observed. Although the formation of C8-cyclodimers cannot be rigorously excluded our results neither support nor require their presence.The (all-ax)-cyclo-octa-1,5-cis,cis-diene (C8) derivatives formed during irradiation of (4), (5), and (10) are not primary photoproducts but arise from thermal (Cope) rearrangements of photochemically produced cis-1,2-divinylcyclobutanes.