The photochemical reactions of 9,10-anthracenedicarbonitrile and 1,4-naphthalenedicarbonitrile in acetonitrile in the presence of bases
作者:Mauro Freccero、Mariella Mella、Angelo Albini
DOI:10.1016/s0040-4020(01)85074-2
日期:1994.2
the observed products is supplied. The key steps are protonation to yield the radical DCAH. and addition of the latter to acetonitrile, or to better nucleophiles when these are present. 1,4-Naphthalenedicarbonitrile is similarly transformed to the 4-amino-1-carbonitrile.
在含有氢氧化物或甲醇盐的MeCN-MeOH或MeCN-H 2 O中辐照9,10-蒽二甲腈(DCA)会生成9-甲基亚氨基-10-蒽乙腈(已分离,但很容易水解为相应的胺)。次要产物是多氰胺和9-羟基-10-蒽腈。在纯甲醇中照射会导致脱氰。在这两种情况下,第一步都是还原为DCA- 。,在这种情况下会持续几个小时。提供了从自由基阴离子到所观察到的产物的机理的证据。关键步骤是质子化以产生DCAH自由基。并将后者添加到乙腈中,或在存在更好的亲核试剂时添加。类似地,将1,4-萘二甲腈转化为4-氨基-1-甲腈。