MULTISUBSTITUTED PHTHALONITRILES, NAPHTHALENEDICARBONITRILES, AND PHENANTHRENETETRACARBONITRILES AS PRECURSORS FOR PHTHALOCYANINE SYNTHESES

Electrophilic aromatic nitration under mild conditions of 4-hydroxypht halonitrile gave 4-hydroxy-3-nitroptlthalonitrile and 4-hydroxy-5-nitr ophthalonitrile, while bromination yielded 3-bromo-4-hydroxyphthalonit rile, 4-bromo-5-hydroxyphthalonitrile, and 3,5-dibromo-4-hydroxyphthal onitrile. Iodination gave 4-hydroxy-5-iodophthalonitrile and 4-hydroxy -3,5-diidophthalonitrile. Coupling of 4-iodophthalonitrile, 3-iodophth alonitrile, and 5-iodo-2,3-dicyanonaphthalene with trans-1,2-bis(tri-n -butylstannyl)ethene gave trans-1,2-bis(3 ,4-dicyanophenyl)ethene, tra ns-1,2-bis(2,3-dicyanophenyl)ethene, and trans-1,2-bis(6,7-dicyanonaph thyl)ethene. Photocyclization of a dilute solution of cis- or trans-1, 2-bis(3,4-dicyanophenyl)ethene in dioxane gave a 1:1 mixture of 2,3,6, 7- and 2,3,5,6-tetracyanophenanthrenes separable by chromatography.