Multisubstituted phthalonitriles, naphthalenedicarbonitriles, and phenanthrenetetracarbonitriles as precursors for phthalocyanine syntheses

Abstract

Electrophilic aromatic nitration under mild conditions of 4-hydroxyphthalonitrile gave 4-hydroxy-3-nitrophthalonitrile and 4-hydroxy-5-nitrophthalonitrile, while bromination yielded 3-bromo-4-hydroxyphthalonitrile, 4-bromo-5-hydroxyphthalonitrile, and 3,5-dibromo-4-hydroxyphthalonitrile. Iodination gave 4-hydroxy-5-iodophthalonitrile and 4-hydroxy-3.5-diidophthalonitrile. Coupling of 4-iodophthalonitrile, 3-iodophthalonitrile, and 5-iodo-2,3-dicyanonaphthalene with trans-1.2-bis(tri-n-buty1stannyl)ethene gave trans-1,2-bis(3,4-dicyanophenyl)ethene, trans-I ,2-bis(2,3-dicyanophenyl)ethene, and trans-l,2-bis(6,7-dicyanonaphthy1)ethene. Photocyclization of a dilute solution of cis-or trans-I,2-bis(3,4-dicyanopheny1)ethene in dioxane gave a 1: 1 mixture of 2,3,6,7-and 2,3,5,6-tetracyanophenanthrenes separable by chromatography.Key words: phthalonitriles, naphthalenedicarbonitriles, phenanthrenetetracarbonitriles, electrophilic substitution.Resume : La nitration Clectrophile aromatique du 4-hydroxyphtalonitrile, dans des conditions douces, conduit au 4-hydroxy-3-nitrophtalonitrile et au 4-hydroxy-5-nitrophtalonitrile alors que sa bromation fournit du 3-bromo-4-hydroxyphtalonitrile, du 4-bromo-5-hydroxyphtalonitrile, etdu3,5-dibromo-4-hydroxyphtalonitrile. L'iodation foumit du 4-hydroxy-5-iodophtalonitrile et du 4-hydroxy-3.5-diiodophtalonitrile. Le couplage des 4-iodophtalonitrile 3-iodophtalonitrile et 5-iodo-2,3-dicyanonaphtalkne avec du trans-l,2-bis(tri-11-butylstannyl)Cthkne fournit du trans-l,2-bis(3,4-dicyanophCnyl)6thkne, du trans-I ,2-bis(2,3-dicyanophCny1)Cthkne et du trans-1.2-bis(6,7-dicyanonaphty1)Cthkne. La photocyclisation d'une solution diluCe des isomkres cis-et trans-l,2-bis(3,4-dicyanophCny1)tthkne dans le dioxane fournit un melange I : 1 des 2,3,6.7-et 2.3.5.6-tCtracyanophCnanthrknes que l'on peut separer par chromatographie.

Use of palladium catalysis in the synthesis of novel porphyrins and phthalocyanines

“…For instance, multisubstituted phthalonitriles, naphthalenedicarbonitriles and phenanthrene tetracarbonitriles were synthesized using multistep reaction procedures involving palladium-catalyzed coupling reactions [76]. Ethyne-and ethene-linked phthalonitriles were synthesized via the Heck and Stille coupling of 3-iodophthalonitrile with either acetylene with Pd(Ph 3 P) 2 Cl 2 and triethylamine or trans-1,2-bis(tri-n-butylstannyl)ethene with Pd(Ph 3 P) 4 .…”

The use of bisphthalonitriles in the synthesis of side-strapped 1,11,15,25-tetrasubstituted phthalocyanines

“…In a manner similar to that previously described in the preparation of 4-hydroxyphthalonitrile (lo), 865 mg (5.00 mmol) of 3-nitrophthalonitrile (1) (8,9) was dissolved in 5 mL of DMSO. K2C03 (760 mg, 5.51 mmol) and NaN02 (345 mg, For personal use only.…”

Synthesis, Structure Peculiarities and Acid-Basic Behaviour of Triazoleporphyrazines

“…In this connection, significant attention has been paid to the synthesis of substituted phthalonitriles and their functional derivatives used as phthalocyanines precursors. [11][12][13] The second way to gain access to noncentrosymmetric macrocycles is a modification of a central core by formal substitution of one of pyrrole or isoindole rings by another cycle. Azoles seem to be the most attractive heterocycles for core modification since they are heteroanalogues of pyrrole.…”