Synthesis of phthalonitriles containing ω-alkenyl, ω-(alkylsulfanyl)alkyl, and ω-(alkylsulfonyl)alkyl substituents and phthalocyanine derivatives based thereon

Article abstract of DOI:10.1134/S1070428013010235

Alkylation of phthalonitrile radical anion sodium salt with terminal alkenyl bromides (4-bromobut-1-ene, 5-bromopent-1-ene, and 6-bromohex-1-ene) gave the corresponding 4-alkenylphthalonitriles which reacted with alkanethiols (BuSH and n-C₁₀H

Full text of DOI:10.1134/S1070428013010235

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 1, pp. 138–144. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © E.V. Panteleeva, A.S. Kondrat’ev, L.I. Goryunov, V.V. Koval’, E.A. Luk’yanets, V.D. Shteingarts, 2013, published in Zhurnal
Organicheskoi Khimii, 2013, Vol. 49, No. 1, pp. 142–148.
Synthesis of Phthalonitriles Containing ω-Alkenyl,
ω-(Alkylsulfanyl)alkyl, and ω-(Alkylsulfonyl)alkyl Substituents
and Phthalocyanine Derivatives Based Thereon
E. V. Panteleevaa, b, A. S. Kondrat’eva, L. I. Goryunov†a, V. V. Koval’c,
E. A. Luk’yanetsd, and V. D. Shteingartsa
a Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: shtein@nioch.nsc.ru
b Novosibirsk State University, Novosibirsk, Russia
c Institute of Chemical Biology and Fundamental Medicine, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, Russia
d State Research Center “Research Institute of Organic Intermediate Products and Dyes,” Moscow, Russia
Received December 11, 2011
Abstract—Alkylation of phthalonitrile radical anion sodium salt with terminal alkenyl bromides (4-bromobut-
1-ene, 5-bromopent-1-ene, and 6-bromohex-1-ene) gave the corresponding 4-alkenylphthalonitriles which
reacted with alkanethiols (BuSH and n-C10H21SH) to produce 4-(ω-alkylsulfanylalkyl)phthalonitriles. Oxida-
tion of the latter with hydrogen peroxide afforded 4-(ω-alkylsulfonylalkyl)phthtalonitriles. 4-Alkenyl- and
4-(ω-alkylsulfonylalkyl)phthalonitriles were brought into condensation with zinc(II) acetate to obtain the
corresponding zinc phthalocyanines.
DOI: 10.1134/S1070428013010235
One-electron reduction of phthalonitrile (I) with
further functionalization via transformations involving
the terminal double bond. By analogy with the data of
[4–6], it seemed possible to accomplish radical addi-
tion of alkanethiols across the double bond of II with
formation of 4-(ω-alkylsulfanylalkyl)phthalonitriles as
potential precursors of phthalocyanines with sulfur-
containing functional groups, which may attract
interest from the practical viewpoint. For example, the
presence of AlkSO2(CH2)n groups should improve the
solubility of phthalocyanines in cellular aqueous–lipid
medium and thus enhance their efficiency in the
diagnostics and therapy of cancer [7, 8].
alkali metals in liquid ammonia generates radical anion
·
salts M+ I– whose transformations provide the shortest
routes to difficultly accessible benzonitrile and phthalo-
nitrile derivatives [1, 2] that are base compounds in
fine organic synthesis. In particular, modified phthalo-
nitriles obtained in such a way can be used as building
blocks for assembling phthalocyanines. For instance,
the reduction of phthalonitrile (I) with lithium in liquid
·
ammonia yields radical anion salt Li+ I− which under-
goes dimerization to form biphenyl-2,3′,4′-tricarbo-
nitrile [1]; the latter, as well as a number of its deriva-
tives, was used to synthesize functionalized tetraaryl-
phthalocyanines [3]. Reaction of radical anion I–· salts
with alkyl bromides gives 4-alkylphthalonitriles, and
the formation of 4-(hex-5-en-1-yl)phthalonitrile in
analogous reaction [1] suggests the possibility for
synthesizing in this way 4-(ω-alkenyl)phthalonitriles
II. Compounds II and phthalocyanines that could be
obtained therefrom are promising as substrates for
In view of the above stated, the goal of the present
work was to develop a short and general synthetic
approach to phthalonitriles containing terminal alkenyl
groups and synthesize on their base ω-(alkylsulfanyl)-
alkyl- and ω-(alkylsulfonyl)alkyl-substituted phthalo-
nitriles as building blocks for assembling the corre-
sponding phthalocyanines. The key step is alkenylation
·
of radical anion salt Na+ I− generated by reduction of
†
phthalonitrile (I) with sodium in liquid ammonia.
Deceased.
138

SYNTHESIS OF PHTHALONITRILES
139
Scheme 1.
CN
CN
CN
CN
CN
NH3 (liq.), –33°C
Na+
+
H2C=CH(CH2)nBr
+
·
( )n
IIa–IIc
( )n
H2C
CH2
·
I
Na+
VIIa–VIIc
( )n
H2C
CN
+
( )n
CH2
VIIIb, VIIIc
CN
CN
CN
CN
H2O2
RSH, AIBN
IIa–IIc
RS
RSO2
( )n
( )n
IIIa–IIId
IVa–IVc
X
X
N
N
N
N
N
NC
Zn(OAc)2
Zn(OAc)2
RSH, AIBN
IIa–IIc
IVa–IVc
Zn
N
VIIa–VIIc
N
N
RS
( )n
IXa–IXc
X
X
Va–Vc, VIa–VIc
IIIa, IIIc, IVb, VIb, IXa, IXb, R = Bu; IIIb, IIId, IVa, IVc, VIa, VIc, IXc, R = n-C10H21; IIa, IIIa, IIIb, IVa, Va, VIa, VIIa, IXa,
n = 2; IIb, n = 3; IIc, IIIc, IIId, IVb, IVc, Vb, Vc, VIb, VIc, VIIb, VIIc, VIIIb, VIIIc, IXb, IXc, n = 4; V, X = CH2=CH(CH2)n;
VI, X = RSO2(CH2)n + 2
.
4-Alkenylphthalonitriles IIa–IIc thus obtained were
subjected to functionalization via addition of alkane-
thiols at the terminal double bond with formation of
4-(ω-alkylsulfanylalkyl)phthalonitriles IIIa–IIId, and
the latter were oxidized with hydrogen peroxide to
4-(ω-alkylsulfonylalkyl)phthalonitriles IVa–IVc
(Scheme 1). Dinitriles II and IV were then brought
into condensation in the presence of Zn(OAc)2 to obtain
the corresponding zinc phthalocyanines V and VI.
ing 4-substituted derivatives IIa–IIc (14−32%, accord-
ing to the H NMR data) and ipso-substitution prod-
1
ucts, 2-alkenylbenzonitriles VIIa–VIIc (17−39%). In
addition, small amounts (2−12%) of double alkenyla-
tion products, 2,5-dialkenylbenzonitriles VIIIb and
VIIIc were formed (Scheme 1). Apart from the alkeny-
lation products, the reaction mixtures contained up to
50% of initial nitrile I (in keeping with the reaction
mechanism, 2 equiv of radical anion with respect to
electrophile is required [1, 2]), biphenyl-2,3′,4′-tricar-
bonitrile (up to 5%), benzonitrile (formed as a result of
We selected sodium in the first step, taking into
·
account that Na+ I− is less prone to dimerization in
·
liquid ammonia than Li+ I− and that metallic potassium
·
protonation of I−), and products of reductive alkenyla-
is less convenient to handle with than sodium, though
tion of the latter, alkenylbenzenes (~5–10%). 4-(But-3-
en-1-yl)phthalonitrile (IIa), 4-(pent-4-en-1-yl)phthalo-
nitrile (IIb), 2-(pent-4-en-1-yl)benzonitrile (VIIb), and
2,5-bis(pent-4-en-1-yl)benzonitrile (VIIIb) were
isolated for the first time, whereas 4-(hex-5-en-1-yl)-
phthalonitrile (IIc), 2-(hex-5-en-1-yl)benzonitrile
·
the alkylation of K+ I− gives analogous results [1, 2].
Among alkenyl halides, just alkenyl bromides ensured
the best yields of alkylphthalonitriles [2].
·
Under the given conditions, the reaction of Na+ I−
with alkenyl bromides afforded mainly the correspond-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013

PANTELEEVA et al.
140
Reaction of alkenylphthalonitriles IIa and IIc and alkenylbenzonitriles VIIa and VIIc with butane-1-thiol and decane-1-thiol
Amounts of reactants, mmol
Concentration of sulfide in the product
mixture, mmol (mol %),a yield, %
II, VII
alkanethiol
azobis(isobutyronitrile)
IIa, 1.08
IIa, 0.72
IIc, 1.03
IIc, 1.36
VIIa, 0.79
VIIc, 0.83
VIIc, 0.94
BuSH, 2.77
DecSH, 1.70
BuSH, 1.50
DecSH, 2.04
BuSH, 1.58
BuSH, 1.84
DecSH, 1.13
0.13
0.09
0.19
0.13
0.08
0.08
0.09
IIIa, 0.77 (71), 49
IIIb, 0.61 (85), 82
IIIc, 0.90 (88), 87
IIId, 1.16 (85), 29
IXa, 0.32 (41), 17
IXb, 0.54 (65), 39
IXc, 0.83 (88), 60
a
According to the 1H NMR and GC–MS data.
in the allylic position. Previously unknown sulfides
IIIa–IIId and IXa–IXc were isolated by preparative
thin-layer chromatography; they contained 90–97% of
the main substances, and the major impurities were
their isomers. The structure of the isolated compounds
was determined on the basis of their 1H NMR, IR, and
mass spectra (including high-resolution mass spectra)
and elemental analyses.
(VIIc), 2,5-bis(hex-5-en-1-yl)benzonitrile (VIIIc), and
2-(but-3-en-1-yl)benzonitrile (VIIa) were described
previously [1, 9].
·
Thus the reaction of Na+ I− with terminal alkenyl
bromides in liquid ammonia gives 4-alkenylphthalo-
nitriles II in 13−25% yield. While estimating this
result, it should be taken into account that the proposed
procedure ensures one-pot synthesis of compounds II
from accessible phthalonitrile. Alternative approaches
are generally multistep, and they require less acces-
sible starting compounds and expensive catalysts for
cross coupling. Alkenylbenzonitriles VII and VIII
isolated in addition to the target products may also be
useful as potential versatile building blocks that are
difficult to obtain by other methods, and unreacted
phthalonitrile (I) may be recycled.
By oxidation of compounds IIIb–IIId with hydro-
gen peroxide in acetic acid we obtained the corre-
sponding sulfones, 4-[4-(decylsulfonyl)butyl]phthalo-
nitrile (IVa), 4-[6-(butylsulfonyl)hexyl]phthalonitrile
(IVb), and 4-[6-(decylsulfonyl)hexyl]phthalonitrile
(IVc) in 46, 54, and 68% yield, respectively.
We tried to synthesize phthalocyanines from dini-
triles II–IV. By reaction of alkenylnitriles IIa–IIc with
zinc(II) acetate we obtained the corresponding tetraal-
kenyl-substituted zinc phthalocyanines Va–Vc, and
ω-(alkylsulfonyl)alkyl derivatives IVa–IVc gave rise
to zinc complexes VIa–VIc; the yields ranged from 52
to 71%. Our attempts to synthesize phthalocyanines
from sulfides III were unsuccessful; as a result, com-
plex mixtures were formed, and we failed to isolate
target compounds. Zinc complexes Va–Vc and VIa–
VIc were characterized by 1H NMR, electronic absorp-
tion, and MALDI-TOF mass spectra. Their electronic
absorption spectra were typical of phthalocyanines;
they contained a Q band in the region λ 675–722 nm
and Soret band in the region λ 346–375 nm.
As a probable way of further functionalization of
alkenyl-substituted benzonitriles and phthalonitriles,
we converted them into ω-(alkylsulfanyl)alkyl deriva-
tives by reaction with alkanethiols (BuSH and
C10H21SH) in the presence of azobis(isobutyronitrile)
according to the procedure used previously for analo-
gous transformation of phenolic compounds [4–6]. The
major products were the corresponding sulfides, 4-[4-
(butylsulfanyl)butyl]phthalonitrile (IIIa), 4-[4-(decyl-
sulfanyl)butyl]phthalonitrile (IIIb), 4-[6-(butylsul-
fanyl)hexyl]phthalonitrile (IIIc), 4-[6-(decylsulfanyl)-
hexyl]phthalonitrile (IIId), 2-[4-(butylsulfanyl)butyl]-
benzonitrile (IXa), 2-[6-butylsulfanyl)hexyl]benzo-
nitrile (IXb), and 2-[6-(decylsulfanyl)hexyl]benzo-
nitrile (IXc) (Scheme 1; see table). According to the
1H NMR data, the reaction mixtures also contained
small amounts of isomeric Markovnikov adducts and
alkenyl-substituted nitriles with an alkylsulfanyl group
To conclude, we have synthesized 4-(ω-alkenyl)-,
4-(ω-alkylsulfanylalkyl)-, and 4-(ω-alkylsulfonylal-
kyl)phthalonitriles and demonstrated the possibility for
preparation therefrom of zinc phthalocyanines bearing
ω-alkenyl and ω-(alkylsulfonyl)alkyl substituents.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013

SYNTHESIS OF PHTHALONITRILES
141
0.230 g (10.0 mmol) of metallic sodium was added in
EXPERIMENTAL
several portions in a stream of ammonia. The resulting
The 1H NMR spectra were recorded on Bruker AM-
400 (400.133 MHz) and Bruker AV-300 spectrometers
(300.132 MHz) from 10–15% solutions in CDCl3 or
(CD3)2CO relative to the residual proton signal of the
solvent. The IR spectra were measured on a Bruker
V-22 instrument from thin films. The electronic ab-
sorption spectra were recorded on an HP Agilent 8453
spectrophotometer from 10–5–10–4 M solutions in
CHCl3. The precise molecular weights were deter-
mined from the high-resolution mass spectra recorded
on a DFS instrument. The reaction mixtures were
·
dark brown suspension of Na+ I− was stirred for 5 min,
0.510 ml (5.0 mmol) of 4-bromobut-1-ene was added
dropwise under stirring at –33°C, and the mixture was
stirred until ammonia evaporated to a half of the initial
volume. The mixture was then exposed to atmospheric
air, ~50 ml of diethyl ether was added, the mixture was
stirred until ammonia no longer evaporated, 50 ml of
water was added, and the mixture was extracted with
diethyl ether (3×50 ml). The extracts were combined,
washed with water until neutral reaction, dried over
MgSO4, and evaporated. The residue was analyzed by
analyzed by GC–MS using a Hewlett Packard G1081A 1H NMR and GC–MS. Individual products were isolat-
ed by TLC. Fractions containing compounds VIIa
(Rf 0.6) and IIa (Rf 0.2) were washed off from the
sorbent with diethyl ether and analyzed by H NMR
instrument. The MALDI-TOF mass spectra were re-
corded on a Bruker Daltonics Autoflex III mass spec-
trometer (Germany) in reflection mode with positive
ion generation ([M + H]+). Nitrogen laser (λ 337.1 nm)
with a frequency of 25 Hz and a power of 3–4 mW
(150–200 μJ per pulse) was used as ionization source,
and a saturated solution of 2,5-dihydroxybenzoic acid
in acetonitrile was used as matrix. The mass spectrom-
eter was calibrated against external standard consisting
of Angiotensin II (1046.5420), Angiotensin I
(1296.6853), Substance P (1347.7361), Bombesin
(1619.8230), and ACTH clip 1-17 (2093.0868). In all
cases, both in the calibration and while recording the
spectra, single-isotope ion weights were used. Prepar-
ative thin-layer chromatography was performed on
glass plates with a fixed layer of silica gel LSL254 (5–
40 μm) containing 13 wt % of gypsum and a lumines-
cent indicator). Alkenyl nitriles II, VII, and VIII were
separated by double elution with hexane–diethyl ether
(9:1 by volume). Compounds III and IX were isolated
by six-fold elution with hexane–methylene chloride
(7:3 by volume). The separation process was moni-
tored visually by UV irradiation of a dried plate.
1
and GC–MS. Yield of IIa 0.230 g (25%). Colorless
oily substance. IR spectrum: ν 2235 cm–1 (C≡N).
3
1H NMR spectrum, δ, ppm: 2.38 q (2H, CH2, J =
7.6 Hz), 2.81 t (2H, CH2, 3J = 7.6 Hz), 4.95–5.01 (2H,
=CH2), 5.69–5.79 (1H, =CH–), 7.53 d.d (5-H, 3J = 8.0,
4
4J = 1.5 Hz), 7.59 d (3-H, J = 1.5 Hz), 7.69 d (6-H,
3J = 8.0 Hz). Found: m/z 182.0840 [M]+. C12H10N2.
Calculated: M 182.0844. Yield of VIIa 0.129 g (16%).
Its spectral parameters were consistent with those
reported in [1, 9].
Following a similar procedure, from 1.280 g
(10.0 mmol) of phthalonitrile, 0.228 g (9.9 mmol) of
metallic sodium, and 0.573 ml (5.0 mmol) of 5-bromo-
pent-1-ene we obtained nitriles IIb, VIIb, and VIIIb.
4-(Pent-4-en-1-yl)phthalonitrile (IIb). Yield
0.145 g (15%), colorless oily substance. IR spectrum:
1
ν 2234 cm–1 (C≡N). H NMR spectrum, δ, ppm:
3
1.77 quint (2H, CH2, J = 7.8 Hz), 2.10 q (2H, CH2,
3
3J = 7.8 Hz), 2.81 t (2H, CH2, J = 7.8 Hz), 4.95 d.m
3
(1H, =CH2, Jcis = 10.0 Hz), 5.02 d.m (1H, =CH2,
3Jtrans = 17.0 Hz), 5.83 d.d.t (1H, =CH–, 3J = 7.8, 3Jcis =
Liquid ammonia was purified by dissolving metal-
lic sodium therein and subsequent distillation directly
into a reaction flask cooled to –70°C. Commercial
alkenyl bromides, alkanethiols, AIBN (Alfa Aesar),
zinc(II) acetate dihydrate (98%, ABCR), and Whatman
GB 005 (Schleicher & Schuell) were used. Phthalo-
nitrile of pure grade was purified by sublimation,
mp 141°C [10].
3
3
10.0, Jtrans = 17.0 Hz), 7.78 d.d (1H, 5-H, J = 8.0,
4J = 1.6 Hz), 7.90 d (1H, 3-H, 4J = 1.6 Hz), 7.93 d (1H,
3
6-H, J = 8.0 Hz). Found: m/z 196.1025 [M]+.
C13H12N2. Calculated: M 196.1000.
2-(Pent-4-en-1-yl)benzonitrile (VIIb). Yield
0.304 g (36%), colorless oily substance. IR spectrum:
1
ν 2224 cm–1 (C≡N). H NMR spectrum, δ, ppm:
3
4-(But-3-en-1-yl)phthalonitrile (IIa) and 2-(but-
3-en-1-yl)benzonitrile (VIIa). A 250-ml three-necked
flask equipped with a stirrer and gas-inlet and outlet
tubes was charged with 1.344 g (10.5 mmol) of
phthalonitrile, and 100 ml of liquid ammonia was
distilled thereinto. The cooling bath was removed, and
1.76 quint (2H, CH2, J = 7.8 Hz), 2.12 q (2H, CH2,
3
3J = 7.8 Hz), 2.83 t (2H, CH2, J = 7.8 Hz), 4.98 d.m
3
(1H, =CH2, Jcis = 11.0 Hz), 5.03 d.m (1H, =CH2,
3Jtrans = 17.0 Hz), 5.81 d.d.t (1H, =CH–, 3J = 7.8, 3Jcis =
3
3
4
11.0, Jtrans = 17.0 Hz), 7.25 t.d (5-H, J = 8, J =
3
3
1.6 Hz), 7.29 d.m (3-H, J = 8.0), 7.47 t.d (4-H, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013

PANTELEEVA et al.
142
8.0, 4J = 1.6 Hz), 7.57 d.d (6-H, 3J = 8.0, 4J = 1.6 Hz).
Found: m/z 171.1046 [M]+. C12H13N. Calculated:
M 171.1048.
IXa–IXc were synthesized in a similar way (the
amounts of the reactants are given in table).
4-[4-(Butylsulfanyl)butyl]phthalonitrile (IIIa).
Yield 0.166 g (49%), yellow oily substance which
solidified at ~8°C. IR spectrum: ν 2234 cm–1 (C≡N).
2,5-Bis(pent-4-en-1-yl)benzonitrile (VIIIb). Yield
0.073 g (5%), colorless oily substance. IR spectrum:
3
1H NMR spectrum, δ, ppm: 0.87 t (3H, CH3, J =
1
ν 2224 cm–1 (C≡N). H NMR spectrum, δ, ppm: 1.65–
7.2 Hz), 1.31–1.43 (2H, CH2), 1.48–1.58 (2H, CH2),
1.58–1.65 (2H, CH2), 1.69–1.79 (2H, CH2), 2.47 t (2H,
1.79 (4H, CH2), 2.03–2.14 (4H, CH2), 2.59 t (2H, CH2,
3
3J = 7.6 Hz), 2.79 t (2H, CH2, J = 7.6 Hz), 4.95–5.05
3
3
3
SCH2, J = 7.2 Hz), 2.52 t (2H, SCH2, J = 7.2 Hz),
(4H, =CH2), 5.73–5.86 (2H, =CH–), 7.19 d (3-H, J =
3
3
3
4
2.84 t (2H, ArCH2, J = 7.5 Hz), 7.54 d.d (5-H, J =
8.0 Hz), 7.29 d.d (4-H, J = 8.0, J = 1.6 Hz), 7.39 d
8.0, 4J = 1.8 Hz), 7.60 d.d (3-H, 4J = 1.8, 5J = 0.6 Hz),
4
(6-H, J = 1.6 Hz). Found: m/z 293.1673 [M]+.
4
7.70 br.d (6-H, J = 8.0 Hz). Mass spectrum, m/z
C17H21N. Calculated: M 293.1674.
(Irel, %): 272 (67) [M]+, 217 (25), 211 (25), 183 (71),
169 (11), 154 (52), 141 (88), 114 (25), 104 (16), 90
(21), 61 (88), 56 (100), 41 (38). Found, %: C 71.52;
H 7.27; S 11.79. C16H20N2S. Calculated, %: C 70.55;
H 7.40; S 11.77. M 272.13.
4-(Hex-5-en-1-yl)phthalonitrile (IIc) and 2-(hex-
5-en-1-yl)benzonitrile (VIIc) were obtained from
1.344 g (10.5 mmol) of phthalonitrile, 0.237 g
(10.3 mmol) of metallic sodium, and 0.560 ml
(5.0 mmol) of 6-bromohex-1-ene. We isolated 0.261 g
(24%) of IIc and 0.313 g (33%) of VIIc as colorless
oily substances. Their spectral parameters were con-
sistent with those given in [1].
4-[4-(Decylsulfanyl)butyl]phthalonitrile (IIIb).
Yield 0.225 g (82%), colorless oily substance which
solidified at ~8°C. IR spectrum: ν 2234 cm–1 (C≡N).
1H NMR spectrum (300 MHz, CDCl3), δ, ppm: 0.85 t
3
4-[6-(Butylsulfanyl)hexyl]phthalonitrile (IIIc).
A mixture of 0.222 g (1.03 mmol) of nitrile IIc and
0.032 g (0.19 mmol) of AIBN was heated to 60°C
under stirring in a stream of argon. Butane-1-thiol,
0.163 ml (1.50 mmol), was added over a period of
0.5 h, and the mixture was stirred for 9 h at 55–80°C.
The mixture was then cooled to room temperature,
3 ml of 20% aqueous sodium hydroxide was added,
and the mixture was extracted with diethyl ether (3×
5 ml). The extract was washed with water until neutral
reaction and dried over Na2SO4, and the solvent was
distilled off. The product was isolated by TLC. A frac-
tion with Rf ~0.30 was washed off from the sorbent
with diethyl ether, and the solvent was distilled off.
Yield 0.290 g (87%), colorless oily substance which
solidified at ~8°C. IR spectrum: ν 2234 cm–1 (C≡N).
(3H, CH3, J = 7.2 Hz), 1.20–1.37 (14H, CH2), 1.49–
1.69 (4H, CH2), 1.69–1.80 (2H, CH2), 2.46 t (2H,
3
3
CH2S, J = 7.2 Hz), 2.52 t (2H, CH2S, J = 7.2 Hz),
3
3
2.73 t (2H, ArCH2, J = 7.2 Hz), 7.53 d.d (5-H, J =
7.8, J = 1.5 Hz), 7.61 d (3-H, J = 1.5 Hz), 7.70 d
4
4
3
(6-H, J = 7.8 Hz). Mass spectrum, m/z (Irel, %): 356
(38) [M]+, 295 (6), 271 (13), 282 (4), 229 (5), 217 (28),
187 (6), 183 (19), 173 (100), 155 (15), 141 (48), 114
(8), 97 (8), 83 (10), 69 (8), 61 (6), 55 (10), 43 (9), 41
(8). Found: m/z 356.2290 [M]+. C22H32N2S. Calculated:
M 356.2281.
4-[6-(Decylsulfanyl)hexyl]phthalonitrile (IIId).
Yield 0.166 g (29%), colorless waxy material,
mp ~34°C. IR spectrum: ν 2234 cm–1 (C≡N). 1H NMR
spectrum, δ, ppm: 0.86 t (3H, CH3, 3J = 7.2 Hz), 1.24–
1.30 (12H, CH2), 1.31–1.46 (6H, CH2), 1.50–1.66 (6H,
3
1H NMR spectrum, δ, ppm: 0.88 t (3H, CH3, J =
3
CH2), 2.48 t (2H, CH2S, J = 7.5 Hz), 2.49 t (2H,
3
3
7.5 Hz), 1.22–1.41 (6H, CH2), 1.48–1.58 (4H, CH2),
CH2S, J = 7.2 Hz), 2.71 t (2H, ArCH2, J = 7.5 Hz),
7.52 d.d (5-H, 3J = 8.0, 4J = 1.5 Hz), 7.60 d (3-H, 4J =
1.5 Hz), 7.70 d (6-H, 3J = 8.0 Hz). Mass spectrum, m/z
(Irel, %): 384 (17) [M]+, 351 (3), 299 (5), 282 (4), 245
(8), 243 (8), 211 (12), 187 (4), 173 (100), 155 (27),
141 (25), 129 (3), 111 (6), 97 (14), 83 (25), 69 (29), 61
(25), 55 (49), 43 (39), 41 (39). Found, %: C 74.84;
H 9.66; S 8.08. C24H36N2S. Calculated, %: C 74.95;
H 9.43; S 8.34. M 384.26.
3
1.58–1.67 (2H, CH2), 2.47 t (4H, CH2SCH2, J =
3
7.5 Hz), 2.70 t (2H, ArCH2, J = 7.5 Hz), 7.51 d.d
3
4
4
(5-H, J = 8.0, J = 1.8 Hz), 7.60 d.d (3-H, J = 1.8,
5J = 0.4 Hz), 7.69 br.d (6-H, J = 8.0 Hz). Mass spec-
3
trum, m/z (Irel, %): 300 (43) [M]+, 267 (8), 257 (5), 255
(18), 243 (23), 211 (49), 198 (29), 183 (8), 169 (16),
167 (20), 159 (18), 155 (59), 141 (59), 128 (6), 114
(22), 103 (29), 89 (35), 75 (4), 69 (18), 61 (100), 56
(80), 47 (16), 41 (61). Found, %: C 71.02; H 8.44.
C18H24N2S. Calculated, %: C 71.95; H 8.05. M 300.17.
2-[4-(Butylsulfanyl)butyl]benzonitrile (IXa).
Yield 0.035 g (17%), colorless oily substance. IR spec-
1
4-[ω-(Alkylsulfanyl)alkyl]phthalonitriles IIIa, IIIb,
and IIId and 2-[ω-(alkylsulfanyl)alkyl]benzonitriles
trum: ν 2224 cm–1 (C≡N). H NMR spectrum, δ, ppm:
3
0.88 t (3H, CH3, J = 7.5 Hz), 1.37 m (2H, CH2),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013

SYNTHESIS OF PHTHALONITRILES
143
1.53 m (2H, CH2), 1.64 m (2H, CH2), 1.77 m (2H,
pound IIIb. Yield 0.005 g (46%), colorless crystals,
3
1
CH2), 2.47 t (2H, SCH2, J = 7.5 Hz), 2.52 t (2H,
mp 58–59°C. H NMR spectrum, δ, ppm: 0.88 t (3H,
3
3
3
SCH2, J = 7.5 Hz), 2.84 t (2H, ArCH2, J = 7.5 Hz),
CH3, J = 7.2 Hz), 1.15–1.37 (12H, CH2), 1.38–1.50
7.26 t.d (5-H, 3J = 7.8, 4J = 1.5 Hz), 7.30 d.d (3-H, 3J =
7.8, J = 1.5 Hz), 7.48 t.d (4-H, J = 7.8, J = 1.5 Hz),
(2H, CH2), 1.74–1.98 (6H, CH2), 2.78 t (2H, ArCH2,
4
3
4
3J = 7.3 Hz), 2.92 m (4H, CH2SO2CH2), 7.54 d (5-H,
3
4
3
7.58 d.d (6-H, J = 7.8, J = 1.5 Hz). Mass spectrum,
m/z (Irel, %): 247 (3) [M]+, 190 (4), 158 (6), 156 (8),
144 (19), 131 (100), 116 (25), 103 (3), 89 (10), 77 (2),
61 (23), 56 (6), 41 (10), 30 (2). Found, %: C 72.74;
H 8.54; S 13.39. C15H21NS. Calculated, %: C 72.82;
H 8.56; S 12.96. M 247.40.
3J = 8.0 Hz), 7.62 s (3-H), 7.73 d (6-H, J = 8.0 Hz).
Found, %: C 68.14; H 8.37; S 7.72. C22H32O2N2S. Cal-
culated, %: C 68.00; H 8.30; S 8.25.
4-[6-(Butylsulfonyl)hexyl]phthalonitrile (IVb)
was synthesized from 0.050 g (0.167 mmol) of com-
pound IIIc. Yield 0.030 g (54%), colorless crystals,
1
2-[6-(Butylsulfanyl)hexyl]benzonitrile (IXb).
mp 95–96°C. H NMR spectrum, δ, ppm: 0.93 t (3H,
3
Yield 0.092 g (39%), colorless oily substance. IR spec-
CH3, J = 7.2 Hz), 1.30–1.55 (6H, CH2), 1.56–1.70
1
trum: ν 2224 cm–1 (C≡N). H NMR spectrum, δ, ppm:
(2H, CH2), 1.71–1.89 (4H, CH2), 2.70 t (2H, ArCH2,
3
3
0.89 t (3H, CH3, J = 7.5 Hz), 1.32–1.44 (6H, CH2),
3J = 7.4 Hz), 2.92 t (4H, CH2SO2CH2, J = 7.1 Hz),
3
1.49–1.58 (4H, CH2), 1.68 m (2H, CH2), 2.47 t (4H,
7.52 d (5-H, J = 7.9 Hz), 7.60 s (3-H), 7.70 d (6-H,
3
3
CH2SCH2, J = 7.5 Hz), 2.81 t (2H, ArCH2, J =
3J = 8.0 Hz). Found, %: C 65.24; H 7.03; S 9.44.
3
4
7.5 Hz), 7.25 t.d (5-H, J = 7.8, J = 1.5 Hz), 7.29 d.d
C18H24O2N2S. Calculated, %: C 65.03; H 7.28; S 9.64.
(3-H, 3J = 7.8, 4J = 1.5 Hz), 7.48 t.d (4-H, 3J = 7.8, 4J =
4-[6-(Decylsulfonyl)hexyl]phthalonitrile (IVc)
was synthesized from 0.086 g (0.224 mmol) of com-
pound IIId. Yield 0.063 g (68%), colorless crystals,
mp 84–85°C. 1H NMR spectrum, δ, ppm: 0.83 t (3H,
3
4
1.5 Hz), 7.57 d.d (6-H, J = 7.8, J = 1.5 Hz). Mass
spectrum, m/z (Irel, %): 275 (7) [M]+, 218 (27), 186
(38), 170 (4), 167 (4), 158 (20), 144 (100), 131 (31),
116 (44), 103 (9), 89 (15), 77 (2), 69 (7), 61 (38), 55
(15), 47 (7), 41 (24). Found, %: C 74.64; H 9.82;
N 5.03; S 12.21. C17H25NS. Calculated, %: C 74.13;
H 9.15; N 5.08; S 11.64. M 275.17.
3
CH3, J = 7.2 Hz), 1.09–1.30 (12H, CH2), 1.31–1.46
(6H, CH2), 1.56–1.70 (2H, CH2), 1.71–2.00 (4H, CH2),
3
2.71 t (2H, ArCH2, J = 7.5 Hz), 2.90 t (4H,
3
3
CH2SO2CH2, J = 7.5 Hz), 7.52 d (5-H, J = 7.5 Hz),
3
2-[6-(Decylsulfanyl)hexyl]benzonitrile (IXc).
7.60 s (3-H), 7.70d (6-H, J = 7.5 Hz). Found, %:
Yield 0.211 g (60%), colorless oily substance. IR spec-
C 74.84; H 9.66; S 8.08. C24H36O2N2S. Calculated, %:
C 74.95; H 9.43; S 8.34.
1
trum: ν 2224 cm–1 (C≡N). H NMR spectrum, δ, ppm:
3
0.85 t (3H, CH3, J = 6.9 Hz), 1.24–1.30 (12H, CH2),
Zinc complexes of tetraalkenyl- and tetra[ω-(al-
kylsulfonyl)alkyl]phthalocyanines Va–Vc and VIa–
VIc (general procedure). A glass ampule was charged
with compound IIa–IIc or IVa–IVc and finely pow-
dered zinc(II) acetate dihydrate at a molar ratio of 2:1,
the mixture was thoroughly stirred, and the ampule
was evacuated to a residual pressure of ~15 mm,
sealed, and heated for 2 h at 225°C. The ampule was
cooled and opened, and the mixture was dissolved in
0.5–1 ml of chloroform and subjected to paper chro-
matography on Whatman GB 005 using in succession
hexane, hexane–chloroform (10:1, 5:1, 3:1, 1:1 by
volume), and chloroform (3 times) as eluents. Com-
plexes V and VI were isolated as blue–green crystals
soluble in chloroform, benzene, and 1,4-dioxane.
1.35–1.46 (6H, CH2), 1.47–1.57 (4H, CH2), 1.59–1.66
3
(2H, CH2), 2.47 t (4H, CH2SCH2, J = 7.2 Hz), 2.81 t
3
3
4
(2H, ArCH2, J = 7.8 Hz), 7.25 t.d (5-H, J = 7.5, J =
3
4
1.5 Hz), 7.29 d.d (3-H, J = 7.8, J = 1.5 Hz), 7.48 t.d
3
4
3
(4-H, J = 7.8, J = 1.5 Hz), 7.58 d.d (6-H, J = 7.8,
3J = 1.5 Hz). Mass spectrum, m/z (Irel, %): 359 (5)
[M]+, 218 (36), 181 (61), 173 (15), 158 (20), 144
(100), 131 (27), 116 (27), 103 (3), 97 (3), 83 (6), 69
(10), 61 (10), 55 (18), 43 (16), 41 (18). Found, %:
C 76.71; H 11.05; N 3.65; S 10.17. C23H37NS. Calcu-
lated, %: C 76.82; H 10.37; N 3.89; S 8.92. M 359.27.
4-[ω-(Alkylsulfonyl)alkyl]phthalonitriles IVa–IVc
(general procedure). Compound IIIb–IIId, 1 mmol,
was dissolved in 0.75 ml of acetic acid, 10 mmol of
50% aqueous H2O2 was added, and the mixture was
heated for 20 h at 70°C, diluted with a 0.2–0.5 volume
of water, heated to the boiling point, and cooled to
20°C. The precipitate was filtered off and dried first in
air and then under reduced pressure (~15 mm).
[2,9(10),16(17),23(24)-Tetrakis(but-3-en-1-yl)-
phthalocyaninato]zinc(II) (Va) was synthesized from
0.018 g (0.099 mmol) of compound IIa and 0.01 g of
Zn(OAc)2·2H2O. Yield 0.011 g (58%). Electronic ab-
sorption spectrum (DMSO), λmax, nm (logε): 287
1
4-[6-(Decylsulfonyl)butyl]phthalonitrile (IVa)
(3.95), 352 (4.28), 613 (4.04), 679 (4.81). H NMR
was synthesized from 0.010 g (0.028 mmol) of com-
spectrum, δ, ppm: 2.32–2.48 (2H, CH2), 2.81 t (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013

PANTELEEVA et al.
144
3
CH2, J = 7 Hz), 4.90–5.07 (2H, =CH2), 5.69–5.84
{2,9(10),16(17),23(24)-Tetrakis[6-(decylsulfonyl)-
hexyl]phthalocyaninato}zinc(II) (VIc) was synthe-
sized from 0.015 g (0.036 mmol) of compound IVc
and 0.003 g of Zn(OAc)2·2H2O. Yield 0.010 g (66%).
Electronic absorption spectrum (DMSO), λmax, nm
(logε): 295 (3.96), 349 (3.83), 612 (3.31), 679 (4.34).
Mass spectrum, m/z: 1732.58 [M + H]+. Calculated for
C96H145N8O8S4Zn: M 1732.89.
3
(1H, =CH–), 7.42 d (1H, J = 7.5 Hz), 7.54 s (1H),
7.62 d (1H, J = 7.4 Hz). Found: m/z 795.41 [M + H]+
3
(MALDI-TOF). Calculated for C48H41N8Zn: M 795.29.
Found, %: C 71.78; H 6.01. C48H40N8Zn. Calculated,
%: C 72.58; H 5.08. M 794.27.
[2,9(10),16(17),23(24)-Tetrakis(pent-4-en-1-yl)-
phthalocyaninato]zinc(II) (Vb) was synthesized from
0.0294 g (0.148 mmol) of compound IIb and 0.016 g
of Zn(OAc)2·2H2O. Yield 0.0215 g (68%). Electronic
absorption spectrum (DMSO), λmax, nm (logε): 351
1
The H NMR spectra of complexes VIa–VIc were
essentially similar, δ, ppm: 0.75–1.90 [(CH2)4], 2.71 t
(ArCH2, J = 7.3 Hz), 2.84–2.94 (CH2SO2CH2), 7.40 d
(J = 7.5 Hz), 7.55 s, 7.64 d (J = 7.5 Hz).
1
(4.37), 612 (4.05), 679 (4.85). H NMR spectrum
(300 MHz, CCl4), δ, ppm: 1.66–1.79 (2H, CH2), 2.00–
This study was performed under financial support
by the Government of Moscow, by the Chemistry and
Materials Science Department of the Russian Academy
of Sciences (project no. 5.1.7), and by the Siberian
Division of the Russian Academy of Sciences (inter-
disciplinary integration project no. 67).
3
2.11 (2H, CH2), 2.7 t (2H, CH2, J = 7.8 Hz), 4.94 s
(1H, =CH2), 4.98 d (1H, =CH2, 3J = 7.6 Hz), 5.64–5.80
3
(1H, =CH–), 7.40 d (1H, J = 8.5 Hz), 7.53 s (1H),
7.60 d (1H, J = 7.6 Hz). Found: m/z 851.46 [M + H]+
3
(MALDI-TOF). Calculated for C52H49N8Zn: M 851.40.
Found, %: C 72.54; H 6.49. C52H48N8Zn. Calculated,
%: C 73.44; H 5.69. M 850.38.
REFERENCES
[2,9(10),16(17),23(24)-Tetrakis(hex-5-en-1-yl)-
phthalocyaninato]zinc(II) (Vc) was synthesized from
0.023 g (0.109 mmol) of nitrile IIc and 0.011 g of
Zn(OAc)2·2H2O. Yield 0.017 g (71%). Electronic ab-
sorption spectrum (CHCl3), λmax, nm (log ε): 242
1. Panteleeva, E.V., Vaganova, T.A., Luk’yanets, E.A., and
Shteingarts, V.D., Russ. J. Org. Chem., 2006, vol. 42,
p. 1280.
2. Bil’kis, I.I., Panteleeva, E.V., and Shteingarts, V.D.,
1
Russ. J. Org. Chem., 1998, vol. 34, p. 1632.
(4.36), 299 (4.01), 375 (3.89), 682 (4.45). H NMR
3. Selivanova, G.A., Amosov, E.V., Goryunov, L.I., Bali-
na, S.V, Vasil’ev, V.G., Sal’nikov, G.E., Luk’yanets, E.A.,
and Shteingarts, V.D., Russ. J. Org. Chem., 2011,
vol. 47, p. 1240; Selivanova, G.A., Vasil’ev, V.G., Shtein-
garts, V.D., Vorozhtsov, G.N., Luk’yanets, E.A., Goryu-
nov, L.I., and Balina, S.V., Russian Patent no. 2398763,
2010; Chem. Abstr., 2010, vol. 153, no. 422154.
spectrum, δ, ppm: 1.33–1.50 (2H, CH2), 1.55–1.74
(2H, CH2), 1.95–2.14 (2H, CH2), 2.69 t (2H, CH2, 3J =
7.3 Hz), 4.85–5.03 (2H, =CH2), 5.61–5.78 (1H, =CH–),
3
7.40 d (1H, J = 7.5 Hz), 7.55 s (1H), 7.64 d (1H,
3J = 7.5 Hz). Found: m/z 907.36 [M + H]+ (MALDI-
TOF). Calculated for C56H57N8Zn: M 907.51. Found,
%: C 72.16; H 6.75. C56H56N8Zn. Calculated, %:
C 74.20; H 6.23. M 906.49.
4. Markov, A.F., Cand. Sci. (Chem.) Dissertation, Novo-
sibirsk, 2006.
5. Yusubov, N.N. and Bairamov, M.R., Russ. J. Org.
Chem., 1999, vol. 35, p. 951.
6. Lind, H., US Patent no. 4021468, 1977; Chem. Abstr.,
{2,9(10),16(17),23(24)-Tetrakis[4-(decylsulfonyl)-
butyl]phthalocyaninato}zinc(II) (VIa) was synthe-
sized from 0.010 g (0.026 mmol) of nitrile IVa and
0.003 g of Zn(OAc)2·2H2O. Yield 0.005 g (52%).
Electronic absorption spectrum (CHCl3), λmax, nm
(logε): 201 (4.96), 223 (4.69), 346 (3.97), 675 (4.18).
Mass spectrum, m/z: 1620.83 [M + H]+. Calculated for
C88H129N8O8S4Zn: M 1620.68.
1977, vol. 89, no. 27167j.
7. Wieder, M.E., Hone, D.C., Cook, M.J., Handsley, M.M.,
Gavrilovic, J., and Russell, D.A., Photochem.
Photobiol. Sci., 2006, vol. 5, p. 727; Garcia Vior, M.C.,
Cobice, D., Dicelio, L.E., and Awruch, J., Tetrahedron
Lett., 2009, vol. 50, p. 2467.
{2,9(10),16(17),23(24)-Tetrakis[6-(butylsulfonyl)-
hexyl]phthalocyaninato}zinc(II) (VIb) was synthe-
sized from 0.008 g (0.024 mmol) of nitrile IVb and
0.002 g of Zn(OAc)2·2H2O. Yield 0.005 g (66%).
Electronic absorption spectrum (DMSO), λmax, nm
(logε): 352 (4.40), 612 (4.08), 679 (4.85). Mass spec-
trum, m/z: 1396.64 [M + H]+). Calculated for
C72H97N8O8S4Zn: M 1396.25.
8. Vol’pin, M.E., Krainova, N.Yu., Moskaleva, I.V.,
Novodarova, G.N., Vorozhtsov, G.N., Gal’pern, M.G.,
Kaliya, O.L., Luk’yanets, E.A., and Mikhalenko, S.A.,
Izv. Akad. Nauk, Ser. Khim., 1996, p. 2105.
9. Bunce, R.A. and Lara, L.B., Org. Prep. Proced. Int.,
1999, vol. 31, p. 407.
10. Beilsteins Handbuch der organischen Chemie, 1926,
EIV, vol. 9B, p. 815.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013