21328-74-5Relevant articles and documents
Novel and mild route to phthalocyanines and 3-iminoisoindolin1-ones via N,N-diethylhydroxylamine-promoted conversion of phthalonitriles and a dramatic solvent-dependence of the reaction
Luzyanin, Konstantin V.,Kukushkin, Vadim Yu.,Kopylovich, Maximilian N.,Nazarov, Alexey A.,Galanski, Markus,Pombeiro, Armando J. L.
scheme or table, p. 135 - 142 (2009/04/07)
Refluxing a mixture of phthalonitrile C6R1R 2R3R4(CN)2 1 (R1-R 4 = H), or its substituted derivatives 2 (R1, R 3, R4 = H, R2 = Me), or 3 (R1, R4 = H, R2, R3 = Cl) (lequiv.) and N,N-diethylhy-droxylamine, Et2NOH, (4 equivs.) in methanol for 4 h results (Route A) in precipitation of the symmetrical (6 and 8) and an isomeric mixture of unsymmetrical (7) phthalocyanines, isolated in good (55-65 % ) yields. The reaction of phthalonitriles 1, 2, or 4 (R1, R 3, R4 = H, R2 = NO2) (4 equivs.) with Et2NOH (8 equivs.) in the presence of a metal salt MCl 2 (M = Zn, Cd, Co, Ni) (1 equiv.) in n-BuOH or without solvent results in the formation of metallated phthalocyanine species (9-17). Upon refluxing in freshlydistilled dry chloroform, phthalonitrile 1 or its substituted analogues 2, 3 or 5 (R1-R4 = F) (1 equiv.) react with N,N-diethylhydroxylamine (2 equivs.) affording 3-iminoisoindolin-1- ones 18-21 (Route B) isolated in good yields (55-80%). All the prepared compounds were characterized with C, H, and N elemental analyses, ESI-MS, IR, and compounds 18-21 also by ID (1H, 13C(1H]), and 2D (1H,15N-HMBC and 1H,13CHMQC, 1H,13C-HMBC) NMR spectroscopy.
Low-temperature synthesis of phthalocyanine and its metal complexes
Kharisov,Ortiz Mendez,Rivera De La Rosa
, p. 617 - 631 (2008/10/09)
Conditions for synthesizing unsubstituted phthalocyanine and its metal complexes from phthalonitrile at low temperatures (0-50°C) are optimized. Phthalocyanine and phthalocyaninates are produced under these conditions using activated Rieke metals, metals on inert substrate, sources of soluble metals in the form of unstable metal complexes, zeolites, solid-phase electrosynthesis of phthalonitrile, and UV irradiation. The use of pyrophoric metals is found to be the most efficient due to a large number of defects in their structure favoring the initial stage of phthalonitrile cyclization on a metal matrix. The suggested mechanism of formation of phthalocyanine macrocycle assumes participation of metal agglomerates occurring in activated metals. Pleiades Publishing, Inc., 2006.
Use of elemental metals in different grade of activation for phthalocyanine preparation
Kharisov,Coronado, C.E. Cantú,Cerda, K.P. Coronado,Méndez, U. Ortiz,Guzmán, J.A. Jacobo,Patlán, L.A. Ramírez
, p. 1269 - 1272 (2008/10/09)
Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various non-aqueous solvents in presence of a series of elemental metals in different grade of activation is described. Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various non-aqueous solvents in presence of a series of elemental metals in different grade of activation is described. Special attention is paid to phthalocyanine formation at relatively low temperatures (0-50°C). In case of use of various forms of activated and non-active nickel, it is shown that its most active form causes rapid PcNi formation at 0-25°C without addition of CH 3ONa.
High-pressure Conditions for Improved Synthesis of Phthalocyanines
Edmondson, Stephen J.,Hill, Jon S.,Isaacs, Neil S.,Mitchell, Philip C. H.
, p. 1115 - 1118 (2007/10/02)
Improved rates of formation and yields of phthalocyanines are observed when the reaction between phthalonitrile and a metal salt is carried out at pressures around 10 kbar.The reaction also benefits from the presence of a superbase, 1,5-diazabicyclonon-5-ene or 1,8-diazabicycloundec-7-ene, and a reducing agent, hydroquinone.In addition to providing superior yields of metallophthalocyanoines from a variety of metal salts, these improvements permit the synthesis of phthalocyanines otherwise difficult to obtain.High pressure combinated with a reducing agent is particularly advantageous.In the absence of a metal salt, good yields of metal-free phthalocyanine were obtained.
SYNTHESIS OF METALLOPHTHALOCYANINES FROM PHTALONITRILE WITH STRONG ORGANIC BASES
Tomoda, Haruhiko,Saito, Shojiro,Shiraishi, Shinsaku
, p. 313 - 316 (2007/10/02)
Several metallophthalocyanines (MPc: M=Ni(II), Co(II), Zn(II), Pb(II), Fe(II), Sn(II), Cd(II), Mg(II), and Mn(III)) were obtained by heating phthalonitrile with metal salts in alcohols in the presence of 1,8-diazabicycloundec-7-ene.Metal acetylacet
Phthalocyanization of Cadmium Sulfide and Zinc Oxide. Effects on the Photochemistry in Aqueous Dispersion
Harbour, John R.,Dietelbach, Bonita,Duff, James
, p. 5456 - 5460 (2007/10/02)
A novel method for the synthesis of metal phthalocyanines on inorganic semiconductive powders is described.Coverage roughly equivalent to a monolayer is achieved for cadmium phthalocyanine on CdS and zinc phthalocyanine on ZnO.This surface modification increases the quantum efficiency, Φ, for H2O2 generation in CdPC/CdS up to a factor of 3 while reducing Φ by a factor of 2 in the ZnPC/ZnO.These results are discussed in relation to surface states and O2 adsorption.In the donor-free cases, photodissolution is still observed with the phthalocyanized powders.Although the phthalocyanines do not sensitize H2O2 formation, ESR results reveal that charge transfer does occur between ZnPC and ZnO.
