Coupling of 4,5-diiodophthalonitrile with rerr-butyldimethylsilylacetylene and a palladium catalyst gave 4,5-bis(rerr-butyldimethylsilylethynyl)phthalonitrile. Cleavage of the silyl moiety with tetftibutylammonium fluoride gave 4,5-diethynylphthalonitrile, while condensation in 2-N,N-dimethylaminoethanol without or with Zn(OAc)2 gave metal-free 2, 3,8,9,16,17,23,24-wtakis(tert-butyldimethylsilylethynyl)phthalocyanine or its zinc derivative. Cleavage of the silyl groups of the zinc derivative gave an insoluble product whose tH NMR spectrum was indicative of 2,3,9,10,16,17,23,?A.-octaettrynylphthalocyaninato zinc(Il). Bromination of phthalonitrile withN,lV{ibromoisocyanuric acid gave a separable mixture of 3,6-,3,21and 4,S-dibromophthalonitrile along with the monobromophthalonitrites. Coupling of 3,4dibromophalonitrile with ren-butylacetylene gave 3,4-bis(ren-butylethynyl)phthalonitrile, which on condensation with lithium lpentanolate gave 1,2,8,9,15,16,22,23-octzkjs(3,3-dimethyl-l-butynyl)phthalocyanins as a single isomer, the first known 1,2,8,9,15.16,22,23-octasubstituted phthalocyanine.

Lithium metal added to a solution of 4-neopentoxyphthalonitrile in 1-octanol or other long-chain primary alcohols at room temperature resulted in phthalocyanine formation at a reasonable rate in good yield, while preformed lithium l-octanolate under the same conditions gave 2,9,16,23-tetraneopentoxyphthalocyanine, but in lower yield at a slower rate. The use of lower-molecular-weight alcohols slowly gave a phthalocyanine in lower yields. Reverse micelle formation when using long-chain alcohols is proposed as a possibility for enhanced phthalocyanine formation at room temperatue. 2,9,16,23-Tetasubstituted phthalocyanines and metallated phthalocyanines were prepared at room temperature from 4-neopentoxyphthalonitrile, 4-bis(4-methoxyphenyl)methoxyphthalonitdle, 4-[-(4-ethoxy-3-methoxyphenyl)-l-phenyl]methoxyphthalonitrile and phthalonitrile using lithium l-octanolate in l-octanol or by the addition, to a solution of the phthalonitrile in ethanol, of calcium turnings or, to a solution of the phthalonitrile in methanol, of magnesium, zinc, iron or copper powder. The tetrasubstituted phthalocyanines produced exhibited a nonstatistical distribution of regioisomers, indicating that electronic effects become important in room-temperature cyclotetramerization of phthalonitriles to phthalocyanines. Copyright O 2000 John Wiley & Sons, Ltd. KBYWORDSz 2,9,16,23-tetrakis[bis(4-methoxyphenyl)methoxy]phthalocyaninato zinc(Il); 2,9,16,23-tetrakis[ 1-(4-ethoxy-3-methoxyphenyl)-I-phenyl]methoxyphthalocyaninato zinc(Il); metal catalysis

The fundamental vibrational modes of a series of six halophthalonitriles have been studied using Raman and inlrared spectroscopy. The vibrational assignment of experimental wave numbers obtained from solid samples was aided using quantum chemical computations. Semi-empirical

Coupling of 4,5-diiodophthalonitrile with tert-butyldimethylsilylacetylene and a palladium catalyst gave 4,5-bis(tert-butyldimethylsilylethynyl)phthalonitrile. Cleavage of the silyl moiety with tetrabutylammonium fluoride gave 4,5-diethynylphthalonitrile, while condensation in 2-N,N-dimethylaminoethanol without or with Zn ( OAc )2 gave metal-free 2,3,8,9,16,17,23,24-octakis(tert-butyldimethylsilylethynyl)phthalocyanine or its zinc derivative. Cleavage of the silyl groups of the zinc derivative gave an insoluble product whose 1 H NMR spectrum was indicative of 2,3,9,10,16,17,23,24-octaethynylphthalocyaninato zinc(II). Bromination of phthalonitrile with N,N-dibromoisocyanuric acid gave a separable mixture of 3,6-, 3,4- and 4,5-dibromophthalonitrile along with the monobromophthalonitriles. Coupling of 3,4-dibromophalonitrile with tert-butylacetylene gave 3,4-bis(tert-butylethynyl)phthalonitrile, which on condensation with lithium 1-pentanolate gave 1,2,8,9,15,16,22,23-octakis(3,3-dimethyl-1-butynyl)phthalocyanine as a single isomer, the first known 1,2,8,9,15,16,22,23-octasubstituted phthalocyanine.

Lithium metal added to a solution of 4-neopentoxyphthalonitrile in 1-octanol or other long-chain primary alcohols at room temperature resulted in phthalocyanine formation at a reasonable rate in good yield, while preformed lithium 1-octanolate under the same conditions gave 2,9,16,23-tetraneopentoxyphthalocyanine, but in lower yield at a slower rate. The use of lower-molecular-weight alcohols slowly gave a phthalocyanine in lower yields. Reverse micelle formation when using long-chain alcohols is proposed as a possibility for enhanced phthalocyanine formation at room temperature. 2,9,16,23-Tetrasubstituted phthalocyanines and metallated phthalocyanines were prepared at room temperature from 4-neopentoxyphthalonitrile, 4-bis(4-methoxyphenyl)methoxyphthalonitrile, 4-[1-(4-ethoxy-3-methoxyphenyl)-1-phenyl]methoxyphthalonitrile and phthalonitrile using lithium 1-octanolate in 1-octanol or by the addition, to a solution of the phthalonitrile in ethanol, of calcium turnings or, to a solution of the phthalonitrile in methanol, of magnesium, zinc, iron or copper powder. The tetrasubstituted phthalocyanines produced exhibited a non-statistical distribution of regioisomers, indicating that electronic effects become important in room-temperature cyclotetramerization of phthalonitriles to phthalocyanines.