Synthesis of hexadecaalkyl-substituted metal phthalocyanines

Article abstract of DOI:10.1055/s-1998-2218

Hexadecaalkyl-substituted nickel phthalocyanines 11 and 12 and a bisaxially coordinated hexadecaalkyl-substituted ruthenium phthalocyanine 13 were synthesized from the corresponding tetraalkylphthalodinitriles 9 and 10, respectively, and metal chlorides.

Full text of DOI:10.1055/s-1998-2218

SYNTHESIS
Papers
1760
Synthesis of Hexadecaalkyl-Substituted Metal Phthalocyanines
Wolfgang Eberhardt, Michael Hanack*
Institut für Organische Chemie der Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen, Germany
Fax +49(7071)295244; E-mail: hanack@uni-tuebingen.de
Received 27 April 1998; revised 12 June 1998
Abstract: Hexadecaalkyl-substituted nickel phthalocyanines 11
and identical 10 alkyl groups and their conversion to
the hexadecaalkyl-substituted nickel phthalocyanines
PcNi(C7H15)8(CH3)8 11 and PcNi(C6H13)16 12 (Scheme
1). Full substitution of the phthalocyanine with long rather
than short chains as in 12 was preferred due to the expect-
ed higher solubility of this macrocycle, but due to the
bulkiness of the substituents we obtained 12 only in low
yield. Assuming that the electronic properties of the phth-
alocyanines are only little effected by the chain length of
the substituents, we synthesized the hexadecaalkyl-substi-
tuted phthalocyanine 11 with heptyl substituents in the 1,4-
positions and the smaller, methyl substituents in the 2,3-
positions, respectively. It was found that the lower steric
requirement of the methyl substituents facilitates phthalo-
cyanine formation in the case of phthalocyanine 11. The
synthesis and characterization of the hexadecaalkyl-substi-
tuted ruthenium phthalocyanine with bisaxial ligands
PcRu(C7H15)8(CH3)8(3-ClPy)2 13 is also described.
and 12 and a bisaxially coordinated hexadecaalkyl-substituted
ruthenium phthalocyanine 13 were synthesized from the corre-
sponding tetraalkylphthalodinitriles 9 and 10, respectively, and
metal chlorides. The obtained phthalocyanines show excellent sol-
ubility in aprotic organic solvents. Their spectral and electrochem-
ical properties are discussed.
Key words: hexadecaalkyl-substituted metal phthalocyanines, tet-
raalkylphthalodinitriles, UV/Vis spectroscopy, electrochemistry
Phthalocyanines are interesting compounds for various
applications in material science.1 Due to intermolecular
interactions between the macrocycles, peripherally un-
substituted phthalocyanines are practically insoluble in
common organic solvents. The introduction of bulky sub-
stituents in the peripheral positions of the macrocycle
drastically increases their solubility in organic solvents1
extending actual and potential fields of their technology.
Hence tetra- and octasubstituted phthalocyanines2 have
been intensively studied, among which tetrasubstituted
macrocycles exhibit usually a higher solubility than octa-
substituted derivatives.
The synthetic route for the hexadecaalkyl-substituted
nickel phthalocyanines 11 and 12 is shown in Scheme 1.
1,2-Dibromo-4,5-dimethylbenzene (1) was reacted with
iodine and periodic acid in concentrated sulfuric acid8 to
give the diiodo compound 3. The same procedure with
1,2-dibromo-4,5-dihexylbenzene (2) failed and so did
other common iodination procedures. Therefore, an un-
usual iodination method was used to give 1,2-dibromo-
3,6-diiodo-4,5-dihexylbenzene (4). 1,2-Dibromo-4,5-di-
hexylbenzene (2) was reacted with HgO in trifluoroacetic
acid9 forming a bis(trifluoroacetatomercury) intermediate
which was converted to 4 directly using I2/NaI as iodinat-
ing agent. The alkylbromoiodobenzenes 3 and 4 can be
selectively reacted at the iodo groups with alkynes by
Heck reaction10 leading to the dibromobenzenes 5 and 6
which were converted to the substituted phthalodinitriles
7 and 8 in a Rosenmund von Braun reaction with CuCN
in dimethylformamide. Catalytic hydrogenation of the
phthalodinitriles 7 and 8 with palladium as catalyst gave
the tetraalkylated phthalodinitriles 9 and 10. The hexade-
caalkyl-substituted nickel phthalocyanines 11 and 12
were prepared by reaction of the phthalodinitriles 9 and
10 with NiCl2 and a catalytic amount of DBU in octanol
at elevated temperature (Scheme 1). The yield of
PcNi(C6H13)16 12 was only about 1% even after pro-
longed reaction times due to the steric hindrance of the
long chain alkyl groups making phthalocyanine formation
more difficult. The unsymmetrically substituted
PcNi(C7H15)8(CH3)8 11 was obtained in moderate yield,
ca. 10%, emphasizing the fact that the sterically less de-
manding phthalodinitrile 9 facilitates phthalocyanine for-
mation compared to the phthalodinitrile 10.
Beside solubility, the spectral and electrochemical proper-
ties of phthalocyanines are also strongly influenced by pe-
ripheral substituents on the macrocycles. Hence the elec-
tronic structure of the phthalocyanine core is most affect-
ed in the case of fully substituted, i.e. hexadecasubstituted
phthalocyanines. Compared to tetra- and octasubstituted
metal phthalocyanines the substituent effects of hexade-
casubstituted phthalocyanines are relatively less well-
studied. Recently we reported the synthesis and character-
ization of hexadecaalkoxy-substituted metal phthalocy-
anines.3 We found that these fully substituted highly sol-
uble macrocycles show interesting optical and electro-
chemical properties.3,4 However, to the best of our
knowledge, hexadecaalkyl-substituted metal phthalocya-
nines R16PcM are unknown in the literature probably due
to the difficult accessibility of the tetraalkyl-substituted
phthalodinitriles5 as precursors.
Moreover, starting with tetraalkyl-substituted phthalodini-
triles the bulky alkyl substituents make the phthalocyanine
formation more difficult, especially when the substituents
are located in the 1,4-position of the phthalocyanine core as
shown in the case of octasubstituted derivatives.6,7 Com-
plete peripheral substitution of the phthalocyanine core
with alkoxy groups lowers the yield of phthalocyanine for-
mation but, nevertheless, these fully substituted phthalo-
cyanines were still obtained in a yield of up to 20%.3
We report here for the first time the synthesis and charac-
terization of tetraalkylphthalodinitriles with different (9)

SYNTHESIS
December 1998
1761
Scheme 1
The hexadecaalkyl-substituted ruthenium phthalocyanine
PcRu(C7H15)8(CH3)8(3-ClPy)2 13 with 3-chloropyridine
as axial ligands could be obtained by reaction of phthalo-
•
dinitrile 9 with RuCl3 3 H2O, a catalytic amount of DBU
and 3-chloropyridine in a mixture of octanol and 2-ethoxy-
ethanol (Scheme 2).11 The preparation of the correspond-
ing iron phthalocyanine PcFe(C7H15)8(CH3)8 14 by reac-
tion of phthalodinitrile 9 with Fe(OAc)2 or FeSO4, respec-
tively, by the same procedure as used for the preparation
of the nickel compound 11 was unsuccessful. Attempts to
stabilize the fully substituted iron phthalocyanine 14 in
the reaction mixture by bisaxial coordination with pyri-
dine failed. All prepared hexadecaalkyl-substituted phth-
alocyanines 11–13 exhibit a very high solubility in organ-
ic aprotic solvents.
UV/Vis spectra of the phthalocyanines 11–13 (Table 1) in
dichloromethane show the typical pattern, mainly the π–
π* transition of the heteroaromatic 18-π electron system:
a large intensive Q band in the visible region accompanied
by more or less resolved weak satellite bands. In the ultra-
violet region the characteristic Soret or B band is also ob-
served. Peripheral substitution of phthalocyanines by
alkyl chains gives a bathochromic shift of the Q band
compared to the unsubstituted macrocycle. For octasub-
Scheme 2
stituted macrocycles the Q band is more red shifted by cycles by alkyl chains gives a distinctly enhanced red shift
substituents at the 1,4-position than by those at the 2,3- of the Q band as shown in Table 1. The Q band of the
position (Table 1).12 Complete substitution of the macro- ruthenium phthalocyanine PcRu(C7H15)8(CH3)8(3-ClPy)2

SYNTHESIS
Papers
1762
(13) is less red shifted than those from the corresponding
nickel phthalocyanine 11 (Table 1).
Electrochemical studies of PcNi(C7H15)8(CH3)8 11 were
carried out to investigate the influence of the fully periph-
eral substitution on the electronic structure of the phthalo-
cyanine. Two oxidation steps as well as two reduction
steps were observed in the cyclic voltammogram of 11 in
dichloromethane/Bu4NPF6. The half-wave potentials E1/2
for the hexadecaalkyl-substituted nickel phthalocyanine
PcNi(C7H15)8(CH3)8 11 are slightly more negative than
for the 1,4-octasubstituted PcNi(C7H15)8 (Table 2) due to
the higher number of electron-donating alkyl substituents
in 11. The peak splittings of all half-wave potentials (∆Ep
= Epa – Epc) were in the range of 100 mV and nearly inde-
pendent of the scan rate in a range of 20 to 500 mV/s.
Therefore quasireversible one-electron transfers can be
assumed.
Figure. UV/Vis Spectra of 11: (a) 1st oxidation, (b) [0.6 V vs Ag/
Ag+] and 2nd oxidation, (c) [1.3 V vs. Ag/Ag+] in CH2Cl2/Bu4NPF6.
com-pared to absorption bands of the reduced species of
PcNi(C7H15)8.7 It was not possible to obtain a UV/Vis
spectrum of the second reduction of 11 due to experimen-
tal limitations of the potentiostate used.
The redox potentials obtained and shown in Table 2 were
supported by spectroelectrochemical investigations in
CH2Cl2/Bu4NPF6. As shown in the Figure for the first ox-
idation step of 11 we observed absorption bands in the
UV/Vis spectrum at 662, 783, 900 and 985 nm and for the
second oxidation step at 493 nm. According to similar ab-
sorption bands during oxidation of the octasubstituted
1
The H NMR spectra of the hexadecaalkyl-substituted
nickel phthalocyanines 11 and 12 (see experimental part)
show the resonances of the aliphatic protons at lower field
than the corresponding phthalodinitriles 9 and 10 due to
the aromatic ring current of the heteroaromatic system.13
The resonances of the protons close to the phthalocyanine
core are distinctly broadened since the mobility of the side
chains is reduced. We assume that these broad signals are
not caused by aggregation effects since the complete pe-
ripheral substitution of the macrocycles diminishes their
intermolecular interaction. The 1H NMR spectra of
the bisaxially coordinated ruthenium phthalocyanine
PcRu(C7H15)8(CH3)8(3-ClPy)2 13 differs mainly in the
additional signals of the bisaxial 3-chloropyridine ligand.
These signals show a diamagnetic ring current shift to
higher field compared to the free ligand. The 13C NMR
data of the hexadecaalkyl-substituted phthalocyanines
11–13 confirming the proposed structure are given in the
experimental part.
7
PcNi(C7H15)8 both oxidations were ascribed to the oxida-
tion of the macrocycle. Due to the complete peripheral
substitution of the macrocycle with electron donating
alkyl chains in 11 the absorption bands of the oxidized
species of 11 are slightly red shifted compared to the oxi-
dized species of the octasubstituted PcNi(C7H15)8.7 The
UV/Vis spectrum obtained for the first reduction of 11 is
characteristic for the reduction of the phthalocyanine
core. Absorption bands at 612, 654, 900 and 1002 nm
were observed. These bands are also slightly red shifted
Table 1. UV/Vis data of Phthalocyanines 11–13 in CH2Cl2
Compound
λmax (nm)
PcNi(C7H15)8(CH3)8 (11)
PcNi(C6H13)16 (12)
719 (Q), 647, 375, 342, 304
722 (Q),650, 370, 341, 305
707 (Q), 672sh, 638, 386sh, 346, 305
684 (Q), 651sh, 616, 374, 337, 300
In summary, for the first time the synthesis of hexade-
caalkyl-substituted metal phthalocyanines is described.
The highly soluble macrocycles were characterized by
spectroscopic methods. Complete peripheral substitution
of the phthalocyanines influences their optical and elec-
trochemical properties compared to less substituted sys-
tems.
a
1,4-PcNi(C7H15)8a
2,3-PcNi(C7H15)8
PcRu(C7H15)8(CH3)8(3-ClPy)2 675 (Q), 608, 430, 318
(13)
a In CHCl3, ref.7
Table 2. Half-Wave Potentials E1/2 (V vs. SCE) of 11 in CH2Cl2
(Scan Rate 100 mV/s, T = 20°C) in Comparison with 1,4-
PcNi(C7H15)8
IR spectra: Bruker IFS 48; NMR spectra: Bruker AC 250 (1H:
250 MHz; 13C: 62.9 MHz); MS: Finnigan MAT ISQ 70 (EI, 70 eV)
and Finnigan MAT 711A (FD, FAB); UV/Vis spectra: Shimadzu UV
2102 PC.
Compound
E1/2 (Ox1) E1/2 (Ox2) E1/2 (Red1) E1/2 (Red2)
Cyclic voltammetric measurements were carried out under argon by
using a three-electrode cell. They were performed with a E.G. & G
PAR potentiostate model 273. A platinum disc electrode and a plati-
num sheet were used as the working and counter electrode, a silver
wire and the ferrocene/ferrocene+ couple as the internal reference
electrode. The measurements were correlated vs. SCE.
PcNi(C7H15)8(CH3)8 0.45
1.15
1.27
–1.15
–1.05
–1.55
–1.47
(11)a
b
1,4-PcNi(C7H15)8
0.59
a c = 7.2 · 10–4 mol/L, 0.1 mol/LBu4NPF6.
b c = 3.0 · 10–4 mol/L, 0.1 mol/L Bu4NPF6, ref.7

SYNTHESIS
December 1998
1763
Spectroelectrochemical measurements were carried out under argon
by using a three-electrode cell. They were performed with a Jaissle
potentiostate model 1001 /T-NC and a Shimadzu UV/Vis/NIR spec-
trometer model UV-365. An ITO-glass, a platinum sheet and a silver
wire were used as working, counter and reference electrodes.
(50 mL) and hex-1-yne (8.2 g, 0.1 mol) was stirred for 24 h at 40°C
under N2. The further preparation is analogous to 5 (column chroma-
tography: silica gel, hexane; Rf 0.45); viscous oil; yield: 10.7 g (76%).
1H NMR (250 MHz, CDCl3): δ = 0.8–1.0 (m, 12H, CH3), 1.2–1.7 (m,
24H, CH2), 2.51 (t, 4H, J = 6.7 Hz, CH2), 2.77 (br t, 4H, CH2).
13C NMR (62.9 MHz, CDCl3): δ = 13.55, 14.04, 19.44, 22.04, 22.61,
29.78, 30.07, 30.65, 31.58, 32.54, 79.53, 99.83, 125.86, 126.55, 143.23.
IR (NaCl): ν = 725, 887, 912, 927, 1008, 1105, 1219, 1249, 1300,
1323, 1379, 1410, 1427, 1466, 2228, 2858, 2928, 2957 cm–1.
MS (FD, CH2Cl2): m/z = 564.1 [M+].
1,2-Dibromo-3,6-diiodo-4,5-dimethylbenzene (3):
To a solution of H5IO6 (16 g, 0.07 mol) in concd H2SO4 (200 mL) was
added finely powdered I2 (53.3 g, 0.21 mol) with vigorous stirring.
After 30 min the mixture was cooled to 0°C and 1,2-dibromo-4,5-
dimethylbenzene (1) (42 g, 0.16 mol) was added in small portions.
The mixture was allowed to warm up to r.t. and stirred for another
12 h. Subsequently the mixture was poured onto ice (1 kg). The pre-
cipitate was suction filtered, washed with water (500 mL) and MeOH
(500 mL) and finally dried; pale beige solid; yield: 35 g (42%).
1H NMR (250 MHz, DMSO-d6): δ = 2.65 (s, CH3).
C30H44Br2
(564.5)
calcd
found
C
63.83
63.59
H
7.86
7.60
Br
28.31
28.53
1,2-Dicyano-3,6-dihept-1-ynyl-4,5-dimethylbenzene (7):
A mixture of 1,2-dibromo-3,6-dihept-1-ynyl-4,5-dimethylbenzene
(5) (6.8 g, 15 mmol) and CuCN (5.4 g, 60 mmol) was refluxed in
DMF (40 mL) under N2 for 24 h After cooling the mixture was poured
into concd aq NH3 (200 mL) and a strong steam of air was bubbled
through the solution for 2 h. The crude product was suction filtered,
washed with water (200 mL) and dried (Na2SO4). Finally it was puri-
fied by column chromatography (silica gel, toluene; Rf 0.6); off-white
solid; yield: 4.0 g (77%); mp 45°C.
IR (KBr): ν = 1013, 1134, 1163, 1177, 1229, 1283, 1317, 1346, 1377,
1429, 2914, 2951 cm–1.
MS (EI): m/z = 515.7 [M+].
C8H6Br2I2
(515.8)
calcd
found
C
18.63
19.34
H
1.17
1.19
1,2-Dibromo-3,6-diiodo-4,5-dihexylbenzene (4):
1H NMR (250 MHz, CDCl3): δ = 0.90 (t, 6H, J = 7.2 Hz, CH3), 1.3–
1.7 (m, 12H, CH2), 2.44 (s, 6H, CH3), 2.52 (t, 4H, J = 7.0 Hz, CH2).
13C NMR (62.9 MHz, CDCl3): δ = 13.87, 18.91, 19.76, 22.11, 27.95,
31.04, 75.85, 104.49, 115.06, 116.17, 127.60, 144.14.
1,2-Dibromo-4,5-dihexylbenzene (2) (16.2 g, 0.04 mol) and HgO
(26 g, 0.12 mol) were dissolved in CF3CO2H (100 mL) and refluxed for
6 h. After cooling, water (300 mL), NaI (24 g, 0.16 mol) and I2 (40.6 g,
0.16 mol) were added. The mixture was stirred vigorously and heated
to 80°C for another 24 h. After cooling, under stirring 10% aq Na2S2O4
(300 mL) was added until the solution was pale yellow. The aqueous
phase was separated, the residue was washed with water (500 mL) and
finally dried (Na2SO4). The crude product was dissolved in hexane
(100 mL) and filtered through silica gel. Finally the product was recrys-
tallized (EtOH); white crystals; yield: 16.5 g (63%); mp 71°C.
1H NMR (250 MHz, CDCl3): δ = 0.90 (t, 6H, J = 6.9 Hz, CH3), 1.2–
1.6 (m, 16H, CH2), 2.99 (br t, 4H, CH2).
IR (KBr): ν = 663, 729, 837, 908, 1003, 1032, 1065, 1103, 1148,
1200, 1219, 1279, 1323, 1339, 1381, 1414, 1448, 1466, 1537, 1560,
2220, 2232, 2862, 2932, 2953 cm–1.
MS (EI): m/z = 344.3 [M+].
C24H28N2
(344.5)
calcd
found
C
83.68
84.04
H
8.19
8.27
N
8.13
7.88
1,2-Dicyano-4,5-dihexyl-3,6-dihex-1-ynylbenzene (8):
This compound was obtained from 1,2-dibromo-4,5-dihexyl-3,6-di-
hex-1-ynylbenzene (6) (8.5 g, 0.015 mol) and CuCN (5.4 g, 0.06 mol)
in DMF (40 mL) by the procedure used for the preparation of 7; pale
yellow viscous oil; yield: 4.8 g (70%).
13C NMR (62.9 MHz, CDCl3): δ = 14.05, 22.61, 29.18, 29.50, 31.38,
43.15, 110.90, 130.32, 145.36.
IR (KBr): ν = 723, 986, 1078, 1117, 1139, 1180, 1300, 1331, 1344,
1375, 1466, 2851, 2870, 2918, 2953 cm–1.
1H NMR (250 MHz, CDCl3): δ = 0.8–1.0 (m, 12H, CH3), 1.2–1.7 (m,
24H, CH2), 2.52 (t, 4H, J = 6.9 Hz, CH2), 2.80 (br t, 4H, CH2).
13C NMR (62.9 MHz, CDCl3): δ = 13.47, 13.97, 19.44, 21.99, 22.49,
29.64, 29.86, 30.29, 31.41, 32.16, 75.71, 103.56, 115.07, 116.46,
127.79, 148.40.
MS (EI): m/z = 655.8 [M+].
C18H26Br2I2 calcd
(656.0) found
C
32.96
33.18
H
3.99
4.00
1,2-Dibromo-3,6-dihept-1-ynyl-4,5-dimethylbenzene (5):
A mixture of 1,2-dibromo-3,6-diiodo-4,5-dimethylbenzene (3) (28.3 g,
55 mmol), (PPh3)2PdCl2 (1.54 g, 2.2 mmol) and CuI (100 mg) in NEt3
(40 mL), DMF (20 mL) and hept-1-yne (28.8 mL, 0.22 mol) was stirred
for 48 h at 40°C under N2. After cooling, the mixture was poured onto
ice (300 g) and acidified with 5% aq HCl (50 mL). The crude product
was extracted with CH2Cl2 (3 × 50 mL). The organic phase was washed
with water (100 mL) and dried (Na2SO4). The solvent was evaporated
and the dark residue was purified by column chromatography (silica
gel, hexane; Rf 0.35); waxy solid; yield: 7.0 g (28%).
IR (NaCl): ν = 727, 891, 928, 957, 995, 1009, 1115, 1250, 1300,
1323, 1342, 1354, 1366, 1379, 1425, 1466, 1527, 1558, 2230, 2235,
2860, 2930, 2959 cm–1.
MS (EI): m/z = 456.2 [M+].
C32H44N2
(456.7)
calcd
found
C
84.16
84.61
H
9.71
9.75
N
6.13
6.13
1,2-Dicyano-3,6-diheptyl-4,5-dimethylbenzene (9):
1,2-Dicyano-3,6-dihept-1-ynyl-4,5-dimethylbenzene (7) (3.4 g,
10 mmol) was dissolved in EtOAc (50 mL) and 10% Pd/C (1 g) was
added. The mixture was hydrogenated at r.t. for 48 h with a H2 pressure
of 1 bar. Subsequently the catalyst was separated and the solvent evap-
orated. The crude product was purified by column chromatography (sil-
ica gel, toluene; Rf 0.7); white crystals; yield: 3 g (85%); mp 82.5°C.
1H NMR (250 MHz, CDCl3): δ = 0.87 (t, 6H, J = 6.8 Hz, CH3), 1.2–
1.6 (m, 20H, CH2), 2.30 (s, 6H, CH3), 2.86 (t, 4H, J = 7.9 Hz, CH2).
13C NMR (62.9 MHz, CDCl3): δ = 13.99, 16.68, 22.52, 28.90, 29.54,
30.01, 31.63, 32.90, 113.51, 116.05, 141.61, 144.06.
1H NMR (250 MHz, CDCl3): δ = 0.90 (t, 6H, J = 7.2 Hz, CH3), 1.3–
1.7 (m, 12H, CH2), 2.37 (s, 6H, CH3), 2.51 (t, 4H, J = 7.0 Hz, CH2).
13C NMR (62.9 MHz, CDCl3): δ = 13.98, 19.21, 19.74, 22.18, 28.26,
31.11, 79.82, 100.79, 125.42, 126.56, 138.73.
IR (NaCl): ν = 646, 669, 737, 899, 920, 999, 1032, 1069, 1113, 1229,
1286, 1325, 1379, 1387, 1410, 1429, 1456, 1466, 2233, 2860, 2870,
2932, 2955 cm–1.
MS (EI): m/z = 452.0 [M+].
C22H28Br2
(452.3)
calcd
found
C
58.43
58.80
H
6.24
6.24
Br
35.33
35.25
IR (KBr): ν = 729, 1032, 1076, 1119, 1271, 1294, 1342, 1387, 1408,
1460, 1560, 2226, 2853, 2872, 2924, 2951 cm–1.
MS (EI): m/z = 352.4 [M+].
1,2-Dibromo-4,5-dihexyl-3,6-dihex-1-ynylbenzene (6):
C24H36N2
(352.6)
calcd
found
C
81.76
81.76
H
10.29
10.34
N
7.95
7.58
A mixture of 1,2-dibromo-3,6-diiodo-4,5-dihexylbenzene (4) (16.4 g,
0.025 mol), (PPh3)2PdCl2 (0.7 g, 1 mmol) and CuI (100 mg) in NEt3

SYNTHESIS
Bis(3-chloropyridine)-1,4,8,11,15,18,22,25-octaheptyl-
Papers
1764
1,2-Dicyano-3,4,5,6-tetrahexylbenzene (10):
1,2-Dicyano-4,5-dihexyl-3,6-dihex-1-ynylbenzene (8) (4.6 g,
10 mmol) was dissolved in a mixture of i-PrOH (30 mL) and HOAc
(3 mL) and Pd black (0.21 g) was added. The mixture was hydroge-
nated at r.t. for 24 h with a H2 pressure of 3 bar. The progress of the
reaction was monitored by TLC (silica gel, toluene; Rf 0.7). When the
reaction was complete, the catalyst was separated and the solvent
evaporated. The product was purified by column chromatography
(silica gel, toluene); viscous oil; yield: 1.1 g (23%).
2,3,9,10,16,17,23,24-octamethylphthalocyaninatoruthenium(II)
(13):
A mixture of 1,2-dicyano-3,6-diheptyl-4,5-dimethylbenzene (9)
•
(1.0 g, 2.8 mmol), RuCl3 3 H2O (0.18 g, 0.7 mmol), 3-chloropyridine
(0.5 mL) and DBU (0.5 mL) was refluxed in 2-ethoxyethanol (5 mL)
and octanol (5 mL) for 7 d under N2. The further preparation is anal-
ogous to compound 11; blue-green solid; yield: 36 mg (3%).
1H NMR (CDCl3): δ = 0.75 (t, 24H, J = 6.8 Hz, CH3), 1.0–1.5 (m,
48H, CH2), 1.6 (m, 16H, CH2), 1.9 (m, 16H, CH2), 2.4–2.5 (m, 4H, 3-
ClPy), 2.74 (s, 24H, CH3), 4.7 (br, 16H, CH2), 5.04 (m, 2H, 3-ClPy),
5.96 (m, 2H, 3-ClPy).
1H NMR (250 MHz, CDCl3): δ = 0.8–1.0 (m, 12H, CH3), 1.2–1.6 (m,
32H, CH2), 2.60 (br t, 4H, CH2), 2.79 (br t, 4H, CH2).
13C NMR (62.9 MHz, CDCl3): δ = 13.97, 22.49, 22.53, 29.56, 29.78,
29.88, 31.02, 31.11, 31.35, 32.29, 114.13, 116.00, 144.53, 145.50.
IR (NaCl): ν = 725, 800, 889, 928, 1015, 1113, 1177, 1219, 1281,
1352, 1379, 1420, 1466, 1558, 2226, 2858, 2928, 2957 cm–1.
MS (EI): m/z = 464.2 [M+].
13C NMR (CDCl3): δ = 14.05, 16.57, 22.67, 28.36, 29.53, 29.75,
31.31, 31.90, 121.88, 129.37, 132.46, 135.50, 136.02, 148.27, 149.17.
IR (KBr): ν = 690, 727, 745, 758, 798, 1047, 1103, 1121, 1148, 1221,
1302, 1373, 1416, 1466, 2853, 2922, 2953, 3051, 3096 cm–1.
MS (FAB): m/z = 1510.5 [M+– 2 3-ClPy].
C32H52N2
(464.8)
calcd
found
C
82.70
82.98
H
11.28
10.61
N
6.03
6.09
C106H152Cl2N10Ru calcd C 73.24
(1738.4) found 73.47
H
8.81 N 8.06 Cl 4.08
8.89 7.82 4.00
1,4,8,11,15,18,22,25-Octaheptyl-2,3,9,10,16,17,23,24-octameth-
ylphthalocyaninatonickel (11):
A mixture of 1,2-dicyano-3,6-diheptyl-4,5-dimethylbenzene (9)
(1.0 g, 2.8 mmol), NiCl2 (0.12 g, 0.9 mmol) and DBU (1 mL) was
refluxed in octanol (15 mL) for 7 d under N2. After cooling the crude
product was precipitated by adding MeOH (50 mL), washed and pu-
rified by column chromatography (silica gel, hexane/CH2Cl2 10:1).
For further purification the product was dissolved in CH2Cl2 (1 mL)
and precipitated by adding MeOH (30 mL). Finally, it was dried for 6
h at 50°C in vacuo; green solid; yield: 105 mg (10%); mp 222°C.
1H NMR (250 MHz, C6D6): δ = 0.8 (t, 24H, J = 6.8 Hz, CH3), 1.2 (m,
32H, CH2), 1.4 (m, 16H, CH2), 1.8 (m, 16H, CH2), 2.0 (m, 16H, CH2),
2.67 (s, 24H, CH3), 4.9 (br, 16H, CH2).
(1) Hanack, M.; Hees, M.; Stihler, P.; Winter, G.; Subramanian, L.
R. In Handbook of Conducting Polymers; Skotheim, T. A.; El-
senbaumer, R. L.; Reynolds, J. R., Ed.; Marcel Dekker, Inc.:
New York, 1998, pp 381–407.
Hanack, M.; Subramanian, L. R. In Handbook of Organic Con-
ductive Molecules and Polymers; Nalwa, H. S., Ed.; John Wi-
ley: Chichester, 1997; Vol. 1, pp 687–726.
Hanack, M.; Lang, M. Adv. Mater. 1994, 6, 819.
Leznoff, C. C.; Lever, A. BP Phthalocyanines: Properties and
Applications; VCH: Weinheim, 1989–1996; Vols. 1–4.
(2) Polley, R.; Heckmann, H.; Hanack, M. In Houben-Weyl; 4th
ed., Vol. E9; Thieme: Stuttgart, 1997, pp 718–742.
(3) Eberhardt, W.; Hanack, M. Synthesis 1997, 95.
(4) Eberhardt, W. Ph.D. Thesis, University of Tübingen, Germany,
1998.
(5) Suzuki, H.; Hanafusa, T. Synthesis 1974, 53.
(6) McKeown, N. B.; Chambrier, I.; Cook, M. J. J. Chem. Soc.,
Perkin Trans I 1990, 1169.
(7) Haisch, P.; Knecht, S.; Schlick, U.; Subramanian, L. R.; Ha-
nack, M. Mol. Cryst. Liq. Cryst. 1995, 270, 7.
(8) Mattern, L. M. J. Org. Chem. 1984, 49, 3051.
(9) Yagupolskii, L. M.; Popov, V. I.; Kondratenko, N. V. J. Org.
Chem. USSR 1976, 12, 923.
(10) Tao, W.; Nesbitt, S.; Heck, R. F. J. Org. Chem. 1990, 55, 63.
(11) Kobel, W.; Hanack, M. Inorg. Chem. 1986, 25, 103.
Hanack, M.; Osio-Barcina J.; Witke, E.; Pohmer, J. Synthesis
1992, 211.
Hanack, M.; Polley, R. Synthesis 1997, 295.
(12) Schmid, G.; Witke, E.; Schlick, U.; Knecht, S.; Hanack, M.
J. Mater. Chem. 1995, 5, 855.
13C NMR (62.9 MHz, C6D6): δ = 14.23, 16.95, 23.00, 29.19, 29.96,
30.33, 31.18, 32.26, 133.13, 136.17, 137.46, 147.34.
IR (KBr): ν = 931, 1101, 1138, 1170, 1223, 1275, 1306, 1331, 1369,
1458, 1506, 2854, 2924, 2955 cm–1.
MS (FD, CH2Cl2): m/z = 1468.2 [M+].
C96H144N8Ni calcd
(1468.9) found
C
78.50
78.45
H
9.88
9.27
N
7.63
7.71
1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-Hexadecahexylphthalo-
cyaninatonickel (12):
This compound was obtained from 1,2-dicyano-3,4,5,6-tetrahexyl-
benzene (10) (0.6 g, 1.3 mmol), NiCl2 (52 mg, 0.4 mmol) and DBU
(0.5 mL) in octanol (5 mL) by the procedure used for the preparation
of 11 (column chromatography: silica gel, hexane); green waxy solid;
yield: 4.5 mg (0.7%).
1H NMR (250 MHz, C6D6): δ = 0.87 (t, 24H, J = 7.0 Hz, CH3), 1.06
(t, 24H, J = 7.0 Hz, CH3), 1.2–1.6 (m, 64H, CH2), 1.7–2.0 (m, 32H,
CH2), 2.09 (br, 32H, CH2), 3.39 (br, 16H, CH2), 4.88 (br, 16H, CH2).
13C NMR (62.9 MHz, C6D6): δ = 14.22, 14.37, 23.16, 23.19, 29.27,
30.18, 30.47, 30.78, 30.85, 32.20, 32.35, 32.77, 133.63, 136.77,
141.60, 147.37.
(13) Keppeler, U.; Kobel, W.; Siehl, H.-U.; Hanack, M. Chem. Ber.
1985, 118, 2095.
Maskasky, J. E.; Mooney, J. R.; Kenney, M. E. J. Am. Chem.
Soc. 1972, 94, 2132.
IR (NaCl): ν = 723, 743, 762, 804, 829, 1015, 1092, 1140, 1175,
1217, 1227, 1283, 1323, 1377, 1466, 1506, 1576, 2855, 2924, 2957
cm–1.
MS (FD, CH2Cl2): m/z = 1916.2 [M+].
C128H208N8Ni calcd
(1917.8) found
C
80.17
80.18
H
10.93
11.05
N
5.84
5.26