SYNTHESISAND SPECTRALCHARACTERISTICS OF UNSYMMETRICAL PORPHIRAZINES
727
1
607 (0.24), 423 sh, 356 (0.85). IR spectrum, n, cm : 2975
(12H), 0.42 s (2H). Found, %: Ñ 72.02; H 5.05; N 8.85.
Ñ74H58N8Î2S4. Calculated, %: Ñ 72.88; H 4.79; N 9.19.
(CH), 2886, 1458, 1385 (CÑ), 1221, 1096, 1048 (Ñ
Î), 882, 701, 614. H NMR spectrum, d, ppm: 8.307.90
m (20H), 7.657.41 m (6H), 7.407.25 m (38H), 0.41 s
(2H). Found, %: Ñ 83.45; H 5.12; N 10.35.
Ñ102H66N12Î2. Calculated, %: Ñ 82.13; H 4.59; N 11.27.
1
trans-Di[4-(p-triphenylmethylphenoxybenzo)]-
di[1,2-di(methylthio)]porphirazine (ABAB) (XI).
Violet powder, well soluble in benzene, chloroform, in-
soluble in acetone, DMF, water. Yield 0.03 g (14%). Elec-
tron absorption spectrum, lmax, nm (D/Dmax): 700 (0.63),
trans-Di[4-(p-triphenylmethylphenoxybenzo)]-
di(4,5-diphenylpyrazino)porphirazine (XII) (ABAB).
Blue powder, well soluble in benzene, chloroform, in-
soluble in acetone, DMF, water. Yield 0.09 g (5%). Elec-
tron absorption spectrum, lmax, nm (D/Dmax): 683 (1.00),
672 (0.92), 616 (0.25), 412 sh, 354 (0.67). IR spectrum,
1
622 (0.53), 347 (1.00). IR spectrum, n, cm : 2978 (C
H), 2924, 1648, 1471, 1380 (CÑ), 1235, 1161, 1047 (Ñ
1
Î), 881, 755, 679. H NMR spectrum, d, ppm: 7.45
7.40 m (6H), 7.357.25 m (38H), 2.49 m (12H), 0.31 s
(2H). Found, %: Ñ 73.90; H 5.15; N 8.70.
Ñ74H58N8Î2S4. Calculated, %: Ñ 72.88; H 4.79; N 9.19.
1
n, cm : 2978 (CH), 2889, 1457, 1381 (CÑ), 1229, 1091,
1041 (ÑÎ), 888, 711, 605. H NMR spectrum, d, ppm:
1
Condensation of 4-(p-triphenylmethylphenoxy)-
1,2-dicyanobenzene (I) with 2,3-dicyano-5,6-
diphenylpyrazine (III). Into a suspension of magnesium
1-butanolate prepared by boiling for 2 h 0.2 g of magne-
sium in 50 ml of anhydrous 1-butanol was charged a mix-
ture of 2.3 g (0.005 mol) of compound I, 0.7 g (0.002
mol) of compound III, and the reaction mixture was
heated at reflux for 4 h. Then the butanol was distilled off
to dryness, the residue was dissolved in 100 ml of concn.
sulfuric acid, and after keeping for 5 min the solution was
poured into 300 ml of water. The separated precipitate
was filtered off, washed with water till pH 7, then with
50 ml of acetone, and dried. Then the product was dis-
solved in benzene and subjected to chromatography on
aluminum oxide of II grade activity (eluent benzene-
acetone, 10:1 by volume). The product separated in the
column into 4 zones containing respectively porphirazines
of types A4, A3B, ABAB, and AABB that were isolated
by removing solvent from the corresponding fractions.
8.357.80 m (20H), 7.757.65 m (6H), 7.557.30 m (38H),
0.29 s (2H). Found, %: Ñ 83.15; H 4.08; N 10.86.
Ñ
102H68N12Î2. Calculated, %: Ñ 82.13; H 4.59; N 11.27.
REFERENCES
1. Phthalocyanines: Properties and Applications, Lez-
noff, C.C. and Lewer, A.B.P., Eds., New York: VCH
Publishers, 19891996, vol. 14.
2. The Porphyrins, Handbook, Kadish, K.M., Smith, K.M.,
and Guilard,R., Eds., New York: Academic Press, 2003,
vol. 1520.
3. de la Torre, G., Vazquez, P.,Agullo-Lopez, F., and Torres, T.,
J. Ma-ter. Chem., 1998, vol. 8, p. 1671.
4. Claessens, C.G., Blau, W.J., Cook, M., Hanack, M.,
Nolte, R.J.M., Torres, T., and Wohrle, D., Monatsh. Chem.,
2001, vol. 132, p. 3.
5. Metallomesogens. Synthesis, Properties, and Applications,
Serano, J.L., Ed., Weinheim: VCH, 1996, 498 p.
6. Cook, M.J., J. Mater. Chem., 1996, vol. 6, p. 677.
7.Vagin, S.I. and Hanack, M., Eur. J. Org. Chem., 2002, vol. 67,
p. 2859.
8. Montalban, A.G., Jarrell, W., Riguet, E., McCubbin, Q.J.,
Ander-son, M.E., White, A.J.P., Williams, D.J., Bar-
rett, A.G.M., and Hoffman, B.M., J. Org. Chem., 2000,
vol. 65, p. 2472.
9. Donazello, M.P., Ercolani, C., Gaberkorn,A.A., Kudrik, E.V.,
Meneghetti, M., Marcolongo, G., Rizolli, C., and Stu-
zhin, P.A., Chem. Eur. J., 2003, vol. 9, p. 4009.
10. Liu, Y., Xu, Y., Zhu, D., Vada, T., Sasabe, H., Liu, L., and
Wang, W., Thin Solid Films, 1994, 244, p. 943.
11. Cook, M.J. and Jafari-Fini,A., J. Mater. Chem., 1997, vol. 7,
p. 2327.
Tetra[4-(p-triphenylmethylphenoxy)]-phthalocya-
nine (A4) (VI). Yield 0.30 g (13%).
Tri[4-(p-triphenylmethylphenoxybenzo)](4,5-
diphenylpyrazino)porphirazine (VIII) (A3B). Dark-
green powder, well soluble in benzene, chloroform, in-
soluble in acetone, DMF, water. Yield 0.08 g (6%). Elec-
tron absorption spectrum, lmax, nm (D/Dmax): 683 (1.00),
1
616 (0.25), 402 sh, 350 (0.55). IR spectrum, n, cm : 2973
(CH), 2880, 1454, 1384 (CÑ), 1225, 1091, 1049 (Ñ
1
Î), 881, 706, 620. H NMR spectrum, d, ppm: 8.257.90
m (10H), 7.607.35 m (9H), 7.307.15 m (57H), 0.32 s
(2H). Found, %: Ñ 84.90; H 5.07; N 8.29. Ñ117H78N10Î3.
Calculated, %: Ñ 84.05; H 4.70; N 8.38.
cis-Di[4-(p-triphenylmethylphenoxybenzo)]di-
(4,5-diphenylpyrazino)porphirazine (X) (AABB).
Blue-green powder, well soluble in benzene, chloroform,
insoluble in acetone, DMF, water. Yield 0.14 g (8%). Elec-
tron absorption spectrum, lmax, nm (D/Dmax): 670 (1.00),
12. Kudrik, E.V., Nikolaev, I.Yu., and Shaposhnikov, G.P., Izv.
Akad. Nauk, Ser. Khim., 2000, no. 12, p. 2062.
13. Kobayashi, N., Kondo, R., Nakajima, S., and Osa, T., J. Am.
Chem. Soc., 1990, vol. 112, p. 9640.
14. Maizlish, V.E., Kulinich, V.P., Shishkina, O.V., Doroshi-
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004