1
620
EFIMOVA et al.
mixture of 10 ml of DMF and 30 ml of toluene and
kept at 20–30°C for 1 h. After that a solution of 2.9 g
of dimethyl-p-tert-butylaminomaleate in 10 ml of
toluene was gradually added and the mixture obtained
was refluxed for 2 h. Then the reaction mixture was
poured on ice and stirred for 30 min. The toluene layer
was removed, washed with water, and dried over
Na SO . After that toluene was removed, and dimethyl
character typical of tetraarenoporphyrazines. The
yields and characteristics of the metal complexes
obtained are presented in the table.
REFERENCES
1
. Mikhailenko, S.A., Barkanova, S.V., Lebedev, O.L.,
and Luk’yanets, E.A., Zh. Obshch. Khim., 1971, vol. 41,
no. 12, p. 2735.
2
4
6
-tert-butylquinoline-2,3-dicarboxylate was obtained
2. Kovshev, E.I. and Luk’yanets, E.A., Zh. Obshch. Khim.,
1972, vol. 42, no. 3, p. 696.
3. Marinina, L.E., Mikhailenko, S.A., and Luk’yanets E.A.,
Zh. Obshch. Khim., 1973, vol. 43, no. 9, p. 2025.
as light beige crystals. Yield 2.4 g (79%), mp 71–72°C.
1
H NMR spectrum, δ, ppm: 1.42 s (9H, t-Bu); 3.96–
7
4
.04 d (6H, Me); 7.84–7.86 d.d (1H, ArH ); 7.98–8.02
8
5
4
5
6
7
8
. Gal’pern, E.G., Luk’yanets, E.A., and Gal’pern, M.G.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1973, no. 9, p. 1976.
. Gal’pern, M.G. and Luk’yanets, E.A., Khim. Geterotsikl.
Soed., 1972, no. 6, p. 858.
. Efimova, S.V., Korzhenevskii, A.B., and Koifman, O.I.,
Zh. Obshch. Khim., 2008, vol. 78, no. 7, p. 1214.
. Kudrevich, S.V., Cand. Sci. (Chem.) Dissertation,
Moscow, 1993.
d (1H, ArH ); 8.10–8.12 d (1H, ArH ), 8.72 s (1H,
ArH ). Found, %: C 67.79, 67.81; H 6.29, 6.29; N
4
4
.67, 4.68. C H NO . Calculated, %: C 67.77; H
17 19 4
6.31; N 4.65.
-tert-Butylquinoline-2,3-dicarboxylic acid. A
6
mixture of 3 g of dimethyl 6-tert-butylquinoline-2,3-
dicarboxylate, 25 ml of 15% NaOH, and 30 ml of
toluene was refluxed for 8 h under intense stirring. The
reaction mixture was cooled to 55°C, diluted with
water, the water phase was separated and acidified
with 35% H SO . The precipitate formed was filtered
off and dried at 100°C. 6-tert-Butylquinoline-2,3-
dicarboxylic acid was obtained as a white powder,
yield 2.1 g (80%), mp 143–145°C. IR spectrum (KBr),
. Gal’pern M.G., Cand. Sci. (Chem.) Dissertation,
Moscow, 1974.
9. Kudrevich, S.V., Gal’pern, M.G., Luk’yanets, E.A., and
van Lier, J.E., Canad. J. Chem., 1996, vol. 74, p. 508.
10. Korzhenevskii, A.B., Markova, L.V., and Koifman O.I.,
Khim. Geterotsikl. Soed., 1992, no. 8, p. 1068.
2
4
1
1. Markova, L.V., Korzhenevskii, A.B., Koifman, O.I.,
–1
and Gal’pern M.G., Zh. Khim. Nevodnykh Rasyvorov,
ν, cm : 3425 (OH), 2960–2856 (C–H), 1726 (C=O).
Found, %: C 65.96, 65.95; H 5.48, 5.47; N 5.14, 5.16.
C H NO . Calculated, %: C 65.93; H 5.50; N 5.13.
1
992, vol. 1, no. 2, p. 207.
1
1
2 Grable, J. and Carro, S., Chem Ber., 1850, vol. 13, p. 99.
3. Lander D., US Patent no. 4459409, 1984, http: www.
freepatentsonline.com/4459409.html.
4. Reisch, J., Pharmazie, 1967, vol. 22, no. 8, p. 420.
5. Hozer, J. and Niementovski, S., J. Pr. Chem., 1927,
15
15
4
Metal complexes of tetra-(6-tert-butyl-2,3-
quinolino)porphyrazine (t-Bu -2,3-QicM, I-IV,
C H N M). A mixture of 1 mmol of 6-tert-butyl-
4
1
1
60
52 12
quinoline-2,3-dicarboxylic acid, 0.25 mmol of the
corresponding metal (copper, cobalt, zinc, or nickel)
acetate, and 0.04 mol of carbamide was thoroughly
ground and caked at 250°C for 3 h. The melt was taken
out of the test tube, ground, and purified by multiple
washing with hot water, diluted hydrochloric acid, and
diluted ammonium hydroxide. Metal complexes were
precipitated from the sulfuric acid solutions on ice, and
then subjected to chromatography on silica gel, elution
with chloroform. Green fraction was eluted, and the
eluate was evaporated to dryness.
vol. 116, p. 43.
1
6. Sintezy organicheskikh preparatov (Syntheses of
Organic Preparations), Kazanskii, B.A., Ed., Moscow:
Inostrannaya Literatura, vol. 4, 1953, p. 27.
7. Gabriel, S., Ber., 1882, vol. 15, p. 2004.
8. Gabriel, S., and Meyer, H., Ber., 1881, vol. 14, p. 2339.
9. Freundler, P., Bull. Soc. Chim., 1904, vol. 31, no. 3,
p. 876.
0. Friedlander, P. and Lenk, E., Ber., 1912, vol. 45, p. 2084.
1. Friedlander, P., Ber., 1882, vol. 15, p. 2573.
2. Friedlander, P. and Gohring, C.F., Ber., 1884, vol. 17,
1
1
1
2
2
2
Tetra-(6-tert-butyl-2,3-quinolino)porphyrazines are
dark green fine crystals with the metallic glance. They
do not melt up to 350°C and are well soluble in
organic solvents. Tetra-(6-tert-butyl-2,3-quinolino)por-
phyrazines obtained by us for the first time were
identified by the elemental analysis data and the
electron absorption spectra having the phthalocyanine
p. 456.
23. Bamberger, E., Ber., 1927, vol. 60, p. 319.
24. Ruggli, P. and Schmidt, A., Helv. Chim. Acta, 1935,
vol. 18, p. 1235.
25. Nord, F.F., Ber., 1919, vol. 52, p. 1711.
26. Bamberger, E. and Demuth, Ed., Ber., 1901, vol. 34,
p. 4015.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008