Metal complexes of tetra(6-tert-butyl-2,3-quinolino)porphyrazine: I. Synthesis

Article abstract of DOI:10.1134/S1070363208080252

Complexes of tetra(6-tert-butyl-2,3-quinolino)porphyrazine with Cu, Co, Zn, and Ni soluble in hydrophobic liquids were synthesized for the first time by template tetramerization of derivatives of 6-tert-butylquinoline-2,3- dicarboxylic acid formed from the corresponding acid in the course of carbamide synthesis in presence of the bivalent metal ions.

Full text of DOI:10.1134/S1070363208080252

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 8, pp. 1614–1621. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © S.V. Efimova, A.B. Korzhenevskii, O.I. Koifman, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 8, pp. 1379–1386.
Metal Complexes of Tetra(6-tert-butyl-2,3-quinolino)porphyrazine:
I. Synthesis
a
b
b
S. V. Efimova , A. B. Korzhenevskii , and O. I. Koifman
a
Ivanovo State University of Chemical Engineering
pr. F. Engels avenue 7, Ivanovo, 153000 Russia
e-mail: sef@isuct.ru
b
Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Received January 11, 2008
Abstract—Complexes of tetra(6-tert-butyl-2,3-quinolino)porphyrazine with Cu, Co, Zn, and Ni soluble in
hydrophobic liquids were synthesized for the first time by template tetramerization of derivatives of 6-tert-
butylquinoline-2,3-dicarboxylic acid formed from the corresponding acid in the course of carbamide synthesis
in presence of the bivalent metal ions.
DOI: 10.1134/S1070363208080252
Aza-substitution and peripheral benzannelation of
phthalocyanine molecule leading to the increase in
stability, in the catalytic activity, in the semi-
conduction properties and some other characteristics of
their metal complexes is one of the ways for obtaining
fundamentally new functional materials. At the same
time the complication of the aromaric peripheral frag-
ments fused to the porphyrazine skeleton causes a decrease
in solubility of such compounds in organic solvents.
characterised by us [10, 11], but their low solubility in
–4
the majority of solvents not exceeding 10
M
significantly restrained their investigation and use, and
in some cases made it practically impossible.
Synthesis of tetraheteroarenoporphyrazine metal
complexes as a rule is a template cyclotetramerization
of aromatic o-dinitriles in the polar form in presence of
the corresponding metal ions (the nitrile method).
When o-dicarboxylic acids are used as the synthons,
the nitrogen source is necessary, and carbamide is
added to the reaction mixture (the carbamide method).
The latter decomposes with the evolution of ammonia,
and o-dinitriles are formed.
With the purpose of improving the solubility of
tetraarenoporphyrazines various lipophilic substituents
are introduced in the peripheral groups of the macro-
cyclic ligand. For instance, the introduction of tert-
butyl groups in the molecule of phthalocyanine [1],
Hence, the main problem in the synthesis of new tetra-
heteroarenoporphyrazines is obtaining of the corres-
ponding reactive synthons. We suggested to use tert-
butylacridinic acid or its nitrogen-containing deriva-
tives like diamide and dinitrile as the starting substances.
2
,3-naphthalocyanine [2], tetra-(9,10-phenanthro)-
porphyrazine [3], tetra-3,4-pyridinoporphyrazine [4],
pyrazinoporphyrazine [5], tetra-2,3- and tetra-6,7-
quinoxalinoporphyrazines [6–8], and tetra-2,3-(benzo-
[
f]quinoxalino)porphyrazine [9] significantly increased
the solubility of macrocycle as well as of its metal
complexes in organic solvents. Therefore not only their
investigation is facilitated, but also the area of their
application is significantly broadened.
Analysis of the reported data concerning the
synthesis of unsubstituted quinoline-2,3-dicarboxylic
acid and its derivatives showed that the existing
synthetic procedures were time-consuming, and their
laboratory implementation was complicated [12, 13].
Besides, the starting substances are difficultly
available [14]. The Niementowski–Hozer method [15]
seemed to be the most convenient. This procedure
permits to prepare unsubstituted dialkyl quinoline-2,3-
dicarboxylates in quantitative yield by condensation of
o-aminobenzaldehyde with dialkyl oxalylacetates.
The work presented deals with the development of
a synthetic procedure for preparation of tetra(6-tert-
butyl-2,3-quinolino)porphyrazine complexes with bi-
valent metals.
Unsubstituted tetra-2,3-quinolinoporphyrazines were
for the first time synthesized and spectroscopically
1614

METAL COMPLEXES OF TETRA(6-tert-BUTYL-2,3-QUINOLINO)PORPHYRAZINE: I.
1615
Therefore the synthesis of tert-butylsubstituted dialkyl
quinolinodicarboxylates should be carried out along
one of two modifications of the Niementowski-Hozer
method presented in Scheme 1.
Scheme 1.
COH
NH2
COOR
+
+
ROC
O
C
O
CH2 COR
COOR
t-Bu
t-Bu
N
N
O
t-Bu
NH2
COH
COOR
COOR
ROC
O
C
O
CH2 COR
O
t-Bu
3 2 5
R = CH , C H .
But numerous attempts to prepare tert-butyl-
substituted o-aminobenzaldehydes presented in Sche-
me 2 failed.
Though 2-amino-4-tert-butyl- and 2-amino-5-tert-
butylbenzaldehydes were not described before, several
preparative methods for unsubstituted 2-amino-
Scheme 2.
CH3
CH3
CH3
NO2
Zn, HCl
NH2 (CH
3
CO)
2
O
NHCOCH3
HNO , H SO
3
2
4
CH3
t-Bu
t-Bu
t-Bu
CrO , CH COOH
CrO ,CH COOH
3 3
CrO , CH COOH
3
3
3
3
t-Bu
COH
COH
NO2
COH
NH2
FeSO , HCl
4
HNO , H SO
4
3
2
t-Bu
t-Bu
t-Bu
(
CH ) N , CF COOH
2 6 4 3
CH3
HNO , H SO
4
3
2
NO2
NH2
NHCOCH3
(
CH CO) O
3 2
Fe, HCl
t-Bu
t-Bu
t-Bu
t-Bu
DMFA, POCl3
(
CH ) N , CF COOH
2
6
4
3
NO2
NH2
FeSO , HCl
4
COH
COH
t-Bu
t-Bu
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008

1
616
EFIMOVA et al.
benzaldehyde are known [16–25]. Most effective
among them is the reduction of o-nitrobenzaldehyde
with ferrous sulfate–ammonium hydroxide mixture
were tert-butylsubstituted anthranils resulting from the
intramolecular cyclodehydratation of the initially
formed tert-butylsubstituted o-formyl-N-phenylhyd-
roxylamines extremely unstable due to the destab-
ilizing effect of the tert-butyl group. Reaction pro-
ceeds analogously to formation of anthranil [26].
[
16]. But our numerous attempts to use this system for
the synthesis of tert-butyl-substituted o-aminobenz-
aldehydes failed. The only products reliably identified
Scheme 3.
NHOH
COH
NO2
_
COH
[H]
H O
2
t-Bu
O
slow
fast
N
t-Bu
t-Bu
An attempt of formylation of tert-acetanilide with
subsequent removing the protective group also failed
because the aldehyde formed evidently enters into a
reaction with amino. groups to form intractable tar-like
polymeric Schiff bases.
tert-butylaniline followed by the closure of heteroring
and the hydrolysis of dialkyl dicarboxylate [27–29].
Synthesis of the previously unknown 6-tert-butyl-
2
,3-quinolinedicarboxylic acid and the compounds I–
IV was carried out as shown in Scheme 4 according to
one of the alternative pathways A and B.
That is why for preparation of 6-tert-butyl-
quinoline-2,3-dicarboxylic acid, the key product in the
synthesis of metal complexes of the lipophilic tetra-
Though the pathway A was longer and required the
isolation of the intermediate product it proved to be
more attractive because it provided the target product
in a higher purity and yield.
2
,3-quinolinoporphyrazines, we developed a modified
method of introducing the formyl group in N-alkylated
Scheme 4.
CH COOR
C
COOR
CH CH2
Hal CH COOR
Hal CH COOR
CH CH2
3
3
PhMe
NH +
N
CH CH2
CH CH2
3
3
+
NH2
A
NH2
Hal CH COOR
Hal CH COOR
+
t-Bu
t-Bu
Bu NCl, NaOH
PhMe, CH COOH
4
3
B
Hal = Br, Cl
R = CH , C H
CH COOR
3
2 5
t-Bu
NH
C
COOR
DMF, POCl3
N
N
COOH
COOH
COOR
COOR
NaOH
t-Bu
t-Bu
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008

METAL COMPLEXES OF TETRA(6-tert-BUTYL-2,3-QUINOLINO)PORPHYRAZINE: I.
Scheme 4. (Contd.)
1617
M(CH COO) , (NH ) CO, (NH ) MoO
4
3
2
2 2
4 2
t-Bu
t-Bu
N
N
N
N
N
N
M
N
N
N
N
N
N
t-Bu
t-Bu
I–IV, M = Cu, Co, Zn, Ni.
For the synthesis of dialkyl p-tert-butylanilino-
maleic acid various starting compounds including
dimethyl and dialkyl dichloro- and dibromosuccinates
were used. In the course of optimization of the reaction
conditions it was found that using dimethyl
dibromosuccinate was preferred because of higher
yields of intermediate products, and the compounds
obtained could be used without further purification.
after numerous washings with hot water, diluted
hydrochloric acid, and ammonia. The fine purification
of metal complexes was carried out by precipitation
from sulfuric acid solutions onto ice followed by
chromatography on silica gel.
Similarly to the case of the other unsymmetrical
synthons the cyclotetramerization of functional
derivatives of 6-tert-butylquinoline-2,3-dicarboxylic
acid leads evidently to formation of atropisomers V–
VIII.
The metal complexes were obtained by the car-
bamide method, and the target products were isolated
t-Bu
t-Bu
t-Bu
t-Bu
N
N
N
N
N
N
N
N
N
N
N
M
N
N
N
M
N
N
N
N
N
N
N
N
N
N
t-Bu
t-Bu
t-Bu
t-Bu
V
VI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008

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618
EFIMOVA et al.
t-Bu
t-Bu
t-Bu
t-Bu
N
N
N
N
N
N
N
N
N
N
N
M
N
N
N
M
N
N
N
N
N
N
N
N
N
N
t-Bu
t-Bu
t-Bu
t-Bu
VII
VIII
Tetra(6-tert-butyl-2,3-quinolineo)porphyrazines syn-
metal complexes of tetra(heteroareno)porphyrazines.
The characteristic property of tetra (azaareno)por-
phyrazine metal complexes is the formation of
hydrated forms [31]. Metal complexes of tetra(6-tert-
butyl-2,3-quinolino)porphyrazine I–IV were also ob-
tained in the hydrated forms. Formation of such forms
may be caused by the existence of strong interaction
between the molecules of water and the heteroaromatic
fragments or by the specific structure of the crystalline
lattice of the macrocyclic compound including the
molecule of water. We believe that the second
assumption is more probable because water is removed
only by the prolonged heating of tetra(6-tert-butyl-2,3-
quinolino)porphyrazine metal complexes in a vacuum
at 250–300°C. The crystallization water content was
evaluated gravimetrically. The comparison of the
electron absorption spectra of tetra(6-tert-butyl-2,3-
quinolino)porphyrazine metal complexes in the
hydrated and the anhydrous form showed that in both
cases positions of the maxima of the absorption bands
practically coincide.
thesized although well soluble and purified by column
chromatography cannot be separated into pure
atropisomers. On the other hand, from the atro-
pisomeric mixtures of analogous compounds, for
example, of the copper and zinc complexes of N-
methylated tetra(2,3-pyridino)porphyrazine, the indi-
vidual isomers were isolated, and it was demonstrated
that the majority of their properties was practically
identical [30].
Compounds I–IV prepared by us for the first time
were identified by the elemental analysis data and the
electron absorption spectra (see the table). They are
dark green powders not melting up to 350°C and much
more soluble in DMF and DMSO compared to the
unsubstituted analogs. Besides, they became soluble in
chloroform, benzene, and ethanol, what permitted to
purify them by column chromatography on silica gel.
All the solutions have intense bluish-green color, and
their electron absorption spectra are typical of the
Physicochemical characteristics of the metal complexes of tetra(6-tert-butyl-2,3-quinolineo)porphyrazines
Elemental analysis data
Electron absorption spectra in CHCl3
Absorption bands λmax, nm (log ε)
II III IV
Compound
C, %
H, %
N, %
60 52 2
C H N12M·nH O
found/calculated found/calculated found/calculated
I
t-Bu
t-Bu
4
4
-2,3-QlcCu·4H
2
O
O
O
66
57
66
54
66.62 / 66.94
67.45 / 67.23
66.28 / 66.83
65.74 / 69.59
5.42 / 5.57
5.38 / 5.60
5.41 / 5.57
5.48 / 5.41
15.95 / 15.62
15.74 / 15.69
15.57 / 15.59
16.85 / 16.24
724 (4.58) 686 (4.27) 652 (4.32) 355 (4.62)
716 (4.64) 684 (4.21) 662 (4.27) 351 (4.75)
-2,3-QlcCo·4H
2
t-Bu
4
-2,3-QlcZn·4H
-2,3-QlcNi·2H
2
725 (4.59) 684 (4.41)
–
367 (4.81)
t-Bu
4
2
O
721 (4.65) 691 (4.37) 648 (4.32) 362 (4.85)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 8 2008

METAL COMPLEXES OF TETRA(6-tert-BUTYL-2,3-QUINOLINO)PORPHYRAZINE: I.
1619
EXPERIMENTAL
standard procedure. Yield 67%, mp 167°C (published
mp 166–168°C [37]). Found, %: C 75.46, 75.42; H
8.78, 8.89; N 7.32, 7.35. C H NO. Calculated, %: C
1
H NMR spectra were taken on a Bruker spec-
1
2
17
trometer from CDCl solutions against 0.1% internal
75.39, H 8.90, N 7.33.
3
TMS. The IR spectra were recorded on an Avatar 360
FT-IR ESP spectrometer in KBr pellets. The electron
absorption spectra were measured on a Perkin–Elmer
Lambda 20 spectrophotometer in quartz rectangular
2
-Nitro-5-tert.-butylbenzaldehyde was obtained
by the consecutive nitration [36] and formylation [33]
of tert-butylbenzene. Yield 32%, mp 35–37°C. H
1
–
4
–6
NMR spectrum, δ, ppm: 1.25 s (9H, t-Bu), 7.71 s (1H,
0
.1–1 cm cells from 10 –10 M solutions. All the
3
2
6
ArH ), 7.87 s (1H, ArH ), 8.05 s (1H, ArH ), 10.22 s
1H, CHO). Found, %: C 75.28, 75.23; H 5.30, 5.24; N
solvents used were of the “chemically pure” grade, and
the sulfuric acid of the “superfine” grade. The
elemental analyses of the compounds obtained were
carried out on a Flash EATM 1112 elemental analyzer.
Purity of the compounds obtained was controlled by
TLC on Merk Silica Gel 60 plates. Column chroma-
tography was carried out on a Merk 0.040–0.063 mm
silica gel. Metal acetates were kept in a vacuum dryer
for 10 h at 110°C before use. All the solutions used
were purified by the standard procedures directly
before use.
(
5
5
.92, 5.89. C H O N. Calculated, %: C 75.31; H
15 13 2
.44; N 5.86.
Dimethyl diethylaminomaleate. To a solution of
3.04 g of dimethyl dibromosuccinate in toluene 1.46 g
of diethylamine was gradually added. The mixture
obtained was kept for 8 h at 80–85°C and then
refluxed for 3 h. On cooling the reaction mixture was
washed with water, and toluene was distilled off.
Dimethyl diethylaminomaleate is a light yellow syrup-
1
like fluid. Yield 2 g (93%). H NMR spectrum, δ, ppm:
.16 t (6H, Me), 3.19–3.21 q (4H, CH ), 3.99 s (6H,
Me), 4.60 s (1H, CH).
3
-(tert-Butyl)-6-methylaniline was prepared by the
1
2
consecutive nitration and reduction of 4-tert-butyl-
toluene [32]. Yield 58%, bp 121°C (20 mm Hg)
1
(
published data bp 118–121°C (20 mm Hg) [32]). H
Dimethyl p-tert-butylanilinomaleate. a. To a
solution of 2.15 g of dimethyl diethylaminomaleate in
20 ml of toluene 1.49 g of p-tert-butylaniline and 3 g
of glacial acetic acid were added. The mixture obtained
was heated for 4 h at 80–85°C, cooled to 20°C, and
washed with a mixture of 10 ml of water and 2 ml of
NMR spectrum, δ, ppm: 1.29 s (9H, t-Bu). 2.43 s (3H,
2
Me), 3.28 br.s (2H, NH ), 6.63 s (1H, ArH ), 6.98–
2
5
4
7.02 d (1H, ArH ), 7.08–7.12 d (1H, ArH ).
3
-(tert-Butyl)-6-methylacetanilide was prepared
by acetylation of 3-(tert-butyl)-6-methylaniline with
acetic anhydride according to the standard procedure.
Yield 98%, mp 112°C (published mp 112°C [32]).
Found, %: C 76.02, 76.08; H 9.25, 9.26; N 6.82, 6.80.
C H NO. Calculated, %: C 76.10; H 9.27; N 6.83.
1
2% HCl. After that toluene was distilled off. Yield of
the target product 2.5 g (85%).
b. To a solution of 3.04 g of dimethyl dibromo-
succinate in chlorobenzene 1.49 g of p-tert-
butylaniline, 3.6 g of 33% water solution of NaOH,
and 1.35 g of tetrabutylammonium chloride were
added. The mixture obtained was heated for 2.5 h at
13
19
2
-Nitro-4-tert-butylbenzaldehyde. a. It was
prepared by consecutive formylation [33] and nitration
[
34] of 4-tert-butylbenzene. Yield 37%.
7
5–80°C, cooled, and washed with water. After that
b. It was prepared by oxidation of 2-nitro-4-tert-
chlorobenzene was removed. Yield of the target
butyltoluene [35]. Yield 48%.
product 1.5 g (52%).
2
-Nitro-4-tert-butylbenzaldehyde is a light yellow
Dimethyl p-tert-butylanilinomaleate is a yellow
fine crystalline powder well soluble in alcohols,
chloroform, toluene, and insoluble in water, mp 62–
1
crystallizing substance, mp 35–37°C. H NMR
spectrum, δ, ppm: 1.20 s (9H, t-Bu), 7.65 s (1H, ArH ),
.72 s (1H, ArH ), 8.10 s (1H, ArH ), 9.98 s (1H,
5
3
6
1
7
63°C. H NMR spectrum, δ, ppm: 1.27 s (9H, t-Bu),
CHO). Found, %: C 75.21, 75.25; H 5.32, 5.38; N
3.68–3.70 d (6H, me), 5.31 s (1H, CH=), 6.75-6.86 d
(2H, ArH ), 7.33–7.22 d (2H, ArH ), 9.63 br.s (1H,
NH). Found, %: C 66.00, 65.98; H 7.20, 7.21; N 4.82,
2
3
5
5
.98, 5.94. C H O N. Calculated, %: C 75.31; H
.44; N 5.86.
15
13
2
4.81. Calculated, %: C 65.97; H 7.22; N 4.81.
4-tert-Butylacetanilide was synthesized by the
consecutive nitration and reduction of tert-butyl-
benzene [36] and acetylation of tert-butylaniline by the
Dimethyl 6-tert-butylquinoline-2,3-dicarboxylate.
Phosphorus oxychloride, 15 ml, was added to a
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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.
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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.
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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.
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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
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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.
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METAL COMPLEXES OF TETRA(6-tert-BUTYL-2,3-QUINOLINO)PORPHYRAZINE: I.
1621
2
2
2
3
3
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3
7. Sintezy organicheskikh soedinenii (Syntheses of Or-
ganic Compounds), Nesmeyanov, A.N., Ed., Moscow:
Izd. Akad. Nauk SSSR, vol. 1, 1950, p. 48.
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