School of Chemistry, EaStCHEM, University of St Andrews, St Andrews, Fife, UK KY16 9ST.
Dalton Trans. 2010 Jan 7(1):85-92. doi: 10.1039/b916425a. Epub 2009 Nov 5.
Syntheses of heteroleptic 1,8-bis(phosphino)naphthalenes and 5,6-bis(phosphino)acenaphthenes were attempted using several synthetic strategies. Reaction of aryllithium with triphenylphosphite gave ArP(OPh)(2) (Ar = substituted naphthalene or acenaphthene), which was transformed into ArP(CF(3))(2), using a nucleophilic trifluoromethylation reaction with Me(3)SiCF(3)/CsF. The importance of the correct choice of solvent for the trifluoromethylation reactions is discussed. The incompatibility of ArP(CF(3))(2) with organolithium hampered the attachment of the second phosphine functionality to the organic backbone. Tetraphenoxyethylene was obtained in a small amount as a side product in the trifluoromethylation reaction. Selected new compounds were characterized by single-crystal X-ray diffraction.
尝试使用了几种合成策略来合成杂双（膦）萘和 5,6-双（膦）苊。芳基锂与三苯基氧膦反应得到 ArP(OPh)(2)（Ar = 取代的萘或苊），然后通过与 Me(3)SiCF(3)/CsF 的亲核三氟甲基化反应将其转化为 ArP(CF(3))(2)。讨论了正确选择三氟甲基化反应溶剂的重要性。ArP(CF(3))(2)与有机锂不相容，这阻碍了第二个膦官能团与有机主链的连接。在三氟甲基化反应中，少量的四苯氧基乙烯作为副产物得到。所选的新化合物通过单晶 X 射线衍射进行了表征。
