Belarmino Cabral Marília Gabriela, Pereira de Oliveira Santos Deise Maria, Cristiano Rodrigo, Gallardo Hugo, Bentaleb Ahmed, Hillard Elizabeth A, Durola Fabien, Bock Harald
Centre de Recherche Paul Pascal, CNRS & Université de Bordeaux, 115, av. Schweitzer, 33600, Pessac, France.
Departamento de Química, Universidade Federal da Paraíba, CEP 58051-900, João Pessoa, Paraíba, Brazil.
Chempluschem. 2017 Mar;82(3):342-346. doi: 10.1002/cplu.201600566. Epub 2016 Dec 28.
The photocyclization of tetraethyl 1,4-phenylenebis(phenylmaleate) in the presence of iodine and oxygen predominantly yields tetraethyl [5]helicene-5,6,9,10-tetracarboxylate, together with small amounts of tetraethyl dibenz[a,h]anthracene-5,6,12,13-tetracarboxylate and tetraethyl benzo[ghi]perylene-3,4,11,12-tetracarboxylate. The helicene tetraester is planarized to the benzoperylene tetraester by Scholl reaction with AlCl followed by reesterification of the partially hydrolyzed crude product. Subsequent treatment with a branched alkylamine yields a columnar liquid-crystalline benzoperylene diimide whose mesophase is stable at room temperature despite its limited and non-centrosymmetric alkyl periphery. Its absorption spectrum is markedly red-shifted compared to that of a similar benzoperylene triimide.
在碘和氧气存在下，1,4 - 亚苯基双（苯基马来酸酯）四乙酯的光环化反应主要生成[5]螺旋烯 - 5,6,9,10 - 四羧酸四乙酯，同时伴有少量的二苯并[a,h]蒽 - 5,6,12,13 - 四羧酸四乙酯和苯并[ghi]苝 - 3,4,11,12 - 四羧酸四乙酯。通过与氯化铝进行肖尔反应，然后对部分水解的粗产物进行再酯化，将螺旋烯四酯平面化为苝四酯。随后用支链烷基胺处理，得到一种柱状液晶苝二酰亚胺，尽管其烷基周边有限且非中心对称，但在室温下其介晶相是稳定的。与类似的苝三酰亚胺相比，其吸收光谱明显红移。
