Preparation of naphthalocyanines

Details Preparation of naphthalocyanines Preparation of naphthalocyanines

1995-09-28

1997-08-12

Shah, Mukund J.

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

540122, 540139, 540142, C09B 4704

Patent

active

056567529

DESCRIPTION:

BRIEF SUMMARY
This application is a 317 of PCT/EP94/00863 Mar. 18, 1994.
The present invention relates to a novel process for preparing alkoxy-octasubstituted metal-free or metal-containing naphthalocyanines by etherification of 1,4-dihydroxy-2,3-dicyanonaphthalene and formation of the metal-free naphthalocyanine with or without subsequent metallization.
EP-A-433 220 describes the preparation of metal-free and metal-containing naphthalocyanines starting from 1,4-dihydroxy-2,3-dicyanonaphthalenes. Furthermore, GB-A-2 200 650 discloses the preparation of these naphthalocyanines starting from 1,4-dialkoxy-2,3-dicyanonaphthalenes. Finally, individual steps are described in J. Org. Chem. 29 (1964), 3591, and in J. Chem. Soc., Perkin Trans. I (1988), 2453. However, it has been found that the prior art methods give the naphthalocyanines only in unsatisfactory yield and purity.
It is an object of the present invention to provide a novel process for preparing naphthalocyanines, which can be carried out in a simple manner and by means of which the target products can be obtained in high yield and purity.
We have found that this object is achieved by a process for preparing naphthalocyanines of the formula I ##STR1## where Me is twice hydrogen or a bivalent metal-containing radical with or without further ligands, and from 1 to 3 oxygen atoms in ether function, or C.sub.4 -C.sub.20 -alkenyl, the metal-free naphthalocyanine with or without subsequent metallization, which comprises an alkylating agent of the formula II defined above, in a molar ratio of from 1:2 to 1:3 in the presence of a diluent and of a base, pouring the reaction mixture onto water, filtering the precipitated dicyanonaphthalene of the formula III ##STR2## where R is in each case as defined above, off with suction, and washing and drying it, with an alkali metal alkoxide into the naphthalocyanine of the formula I where Me is twice hydrogen in the presence of an alcohol, the molar ratio of alkali metal alkoxide:dicyanonaphthalene. III being from 1:2.5 to 2.5:1, and optionally then reaction with a metal salt in the presence of an alcohol into the metal-containing naphthalocyanine of the formula I where Me is a metal-containing ligand, the naphthalocyanine and the metal salt being reacted with each other in a molar ratio of from 1:1 to 1:10.
All alkyl and alkenyl groups appearing in the abovementioned formulae may be straight-chain or branched.
The radicals R can be identical or different. sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial names derived from the oxo process alcohols--cf. Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 7, pages 215 to 217, and also Volume 11, pages 435 and 436), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl, butenyl, but-3-en-1-yl, pentenyl, pent-4-en-1-yl, 3-methyl-but-3-en-1-yl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, undec-10-en-1-yl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl or eicosenyl.
A suitable bivalent metal-containing radical is in particular copper.
Preference is given to a procedure for preparing naphthalocyanines of the formula I where Me is twice hydrogen or copper.
Preference is further given to a procedure for preparing naphthalocyanines of the formula I where R is in each case C.sub.2 -C.sub.13 -alkyl or C.sub.4 -C.sub.11 -alkenyl or

REFERENCES:
J. Org. Chem. 29 (1964) 3591.
Cook et al., J. Chem Soc., Perkin I 1988 pp. 2453-2458.
Reynolds et al. J. Org. Chem., 1964 p. 3591.

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