A.M. Sevim et al. / Dyes and Pigments 89 (2011) 162e168
163
metal-free and metallo-phthalocyanines (M ¼ Ni(II), Zn(II), Cu(II),
2.2.2. 2,9,16,23-Tetrakis(4-carboxymethylsulfanyl)-
phthalocyanine (2)
Co(II)) carrying thioglycolic acid substituents on the periphery
were synthesized. Spectral results such as FT-IR, UVeVis, EI-MS,
13C-NMR and 1H-NMR for the newly synthesized compounds are in
good agreement with the proposed structures. Last part of this
work dealt with the cotton fabric which was modified with
a cationic auxiliary and converted to cationic cotton fabric for
dyeing process. The cationic cotton fabric was then dyed with the
metallo-phthalocyanines (2aed) in the presence of sodium
carbonate. Finally, washing and water fastness tests were per-
formed and evaluated according to ISO criteria.
4-(Carboxymethylsulfanyl)phthalonitrile (1) (0.50 g, 2.291 mmol)
was dissolved in 6 mL of dry 1-pentanol and heated at 140 ꢀC under
N2. After addition of elemental lithium (0.122 g, 16.05 mmol) a green
colour appeared in a few seconds. The suspension was stirred under
reflux for 1 h. Then the mixture was cooled to room temperature,
acidified with HCl and the resulting precipitate was centrifuged and
the supernatant discarded. The precipitated blue-green solid was
filtered and washed first with water, then successively with cold
methanol, hexane and diethyl ether, and finally dried in vacuo. This
compound is soluble in polar solvents especially DMF, THF, DMSO
and pyridine. Yield: 0.165 g, 32.9%. M.p. > 200 ꢀC. IR ymax/(cmꢁ1):
3600e2500 (carboxylic acid OH), 3281 (NeH), 3058 (Ar-H),
2920e2855 (aliphatic CH),1703 (C]O),1598,1500,1448,1385,1298,
2. Experimental
2.1. Materials
1134, 1010, 895, 816, 736, 663. 1H NMR (d-DMSO,
4H, COOH), 8.32e7.41 (m,12H, Ar-H), 4.18 (s, 8H, CH2), ꢁ6.54 (br s, 2H,
NeH); UVeVis lmax (nm) (log ) in THF: 708 (4.41), 676 (4.43), 340
d ppm): 13.21 (br s,
All reactions were carried out under nitrogen atmosphere in
dried solvents. All reagents and solvents were of reagent grade
quality obtained from commercial suppliers. Rucogen FWS from
Rudolf was used as wetting and degreasing agent. Slipper from
Mega-Teknoloji, Inc. was used for fracture-prevention purposes.
Catalase was used under Sera Zyme C-SX brand name from Dystar.
Cationizing chemical used was Mordiente DEL from Asutex. The
homogeneity of the synthesized products was tested in each step
by TLC. Analytical thin-layer chromatography (TLC) was performed
using Merck 60 F 254 silica gel (precoated sheets, 0.2 mm thick). All
solvents were dried and purified as described by Perrin and
Armarego [27]. The solvents were stored over molecular sieves.
4-Nitrophthalonitrile [28] was synthesized according to published
methods.
UV measurements were done with Scinco SD-1000 double beam
UV-visible spectrophotometer. A PerkineElmer Spectrum One FTIR
spectrophotometer with ATR sampling accessory was used for IR
data collection. 1H NMR and 13C NMR spectra were recorded with
a Bruker 200 MHz FT-NMR spectrometer. Mass spectra were
obtained with a Perkin Elmer Clarus 500 GC/MS in EIþ mode.
Dyeing of the fabrics was performed in Ahiba sample dyeing
apparatus.
3
(4.39); Anal. Calc. for C40H26N8O8S4: C, 54.91; H, 3.00; N, 12.81; S,
14.66%. Found: C, 54.90; H, 2.99; N, 12.80; S, 14.61%.
2.2.3. General procedure for the 2,9,16,23-Tetrakis(4-
carboxymethylsulfanyl)- phthalocyaninatometal derivatives (2aed)
4-(Carboxymethylsulfanyl)phthalonitrile (1) (0.50 g, 2.291 mmol)
was dissolved in 6 mL of dry 1-pentanol and anhydrous metal salt [Zn
(AcO)2 2,5 g (13.6 mmol), CoCl2 1.75 g (13.48 mmol), NiCl2 1.75 g
(13.50 mmol) or CuCl2 1.80 g (13.40 mmol)] and heated at 140 ꢀC
under N2. The suspension was stirred under reflux for 48 h. Then, the
mixture was cooled to ambient temperature. The reaction mixture
was acidified with HCl and the resulting precipitate was centrifuged
and the supernatant discarded. The precipitated green coloured solid
was filtered and washed first with water, thenwith methanol, hexane
and diethyl ether, finally dried in vacuo.
2.2.3.1. 2,9,16,23-Tetrakis(4-carboxymethylsulfanyl)-phthalocyanina-
tozinc(II) (2a). This is soluble in polar solvents especially DMF, THF,
DMSO and pyridine. Yield: 0.145 g, 27%. M.p. > 200 ꢀC. IR ymax
/
(cmꢁ1): 3600e2500 (carboxylic acid OH), 3058 (Ar-H), 2926e2861
(aliphatic CH), 1714 (C]O), 1598, 1485, 1455, 1380, 1259, 1132, 1037,
975, 908, 885, 822, 761, 741, 681. 1H NMR (d-DMSO,
d
ppm):
7.73e7.25 (m, 12H, Ar-H), 4.10 (s, 8H, CH2); UVeVis lmax (nm) (log
3
)
2.2. Synthesis of phthalocyanine derivatives (2, 2aed)
in THF: 684 (4.53), 345 (4.56); Anal. Calc. for C40H26N8O8S4Zn: C,
51.20; H, 2.58; N, 11.94. Found: C, 51.19; H, 2.56; N, 11.93%.
2.2.1. 4-(Carboxymethylsulfanyl)phthalonitrile (1)
4-Nitrophthalonitrile (0.5 g, 2.89 mmol) and an excess thio-
glycolic acid (0.5 mL, 5.8 mmol) were dissolved in 15 mL of dry
DMF. Anhydrous K2CO3 (1.59 g, 11.56 mmol) was added in small
portions over 2 h and the mixture was stirred vigorously at room
temperature under N2 stream for 1 h. The reaction mixture was
poured into ice-water mixture (100 mL) and the pH of the solution
was adjusted to 1 by addition of 1:1 HCl solution. The precipitate
was filtered, washed with water until the filtrate was neutral, then
washed with successively with hexane and diethyl ether, and
dried. Finally, a pale beige product was crystallized from aceto-
neehexane. Yield: 0.396 g, 62.9 %, MA ¼ 218.2 g/mol, M.p. ¼132 ꢀC.
IR ymax/(cmꢁ1): 3500 (carboxylic acid OH), 3096e3028 (Ar-H), 2935
(Aliphatic CH), 2229 (C^N), 1709 (C]O), 1584e1479 (Ar C]C),
2.2.3.2. 2,9,16,23-Tetrakis(4-carboxymethylsulfanyl)-phthalocyani-
natocobalt(II) (2b). This is soluble in polar solvents especially DMF,
THF, DMSO and pyridine. Yield: 0.181 g, 34%. M.p. > 200 ꢀC. IR ymax
/
(cmꢁ1): 3600e2500 (carboxylic acid OH), 3053 (Ar-H), 2956e2861
(aliphatic CH), 1717 (C]O), 1600, 1521, 1381, 1296, 1133, 1069, 1042,
932, 892, 819, 742,685 ; UVeVis lmax (nm) (log 3) in THF: 679 (4.36),
325 (4.25); Anal. Calc. for C40H26N8O8S4Co: C, 51.56; H, 2.60; N,
12.02; Found: C, 51.54; H, 2.62; N, 12.04%.
2.2.3.3. 2,9,16,23-Tetrakis(4-carboxymethylsulfanyl)- phthalocyani-
natonickel(II) (2c). This is soluble in polar solvents especially DMF,
THF, DMSO and pyridine. Yield: 0.168 g, 31.5%. M.p. > 200 ꢀC. IR
ymax/(cmꢁ1): 3600e2500 (carboxylic acid OH), 3058 (Ar-H),
2921e2850 (aliphatic CH),1709 (C]O),1601,1531,1454,1399,1262,
1213, 1171, 1067, 902, 872, 830, 717, 675. 1H NMR (CO(CD3)2
,
d
ppm): 8.01 (s, 1H, Ar-H),7.97 (d,1H Ar-H), 7.85 (d, 1H Ar-H), 4.12 (s,
1086, 1039, 934, 893, 816, 765, 747, 690; 1H NMR (d-DMSO,
d
ppm):
2H, CH2); 13C NMR (d-DMSO,
d
ppm): 169.91 (C]O), 116.27 (C^N),
7.51e7.25 (m, 12H, Ar-H), 4.06 (s, 8H, CH2) UVeVis lmax (nm) (log 3)
115.05 (C^N), 146.06 (Ar-C), 135.22 (Ar-C), 132.47 (Ar-C), 131.87
(Ar-C), 129.18 (Ar-C), 110.11 (Ar-C), 33.54 (Aliphatic C). MS (GC-MS,
Scan EIþ): m/z: 218 [Mþ]. For C10H6N2O2S Anal. Calc.: C, 55.04; H,
2.77; N, 12.84; S, 14.69%. Found: C, 55.02; H, 2.75; N, 12.83; S,
14.67%.
in THF: 680 (4.62), 360 (4.53); Anal. Calc. for C40H26N8O8S4Ni: C,
51.57; H, 2.60; N, 12.03. Found: C, 51.55; H, 2.61; N, 12.05%.
2.2.3.4. 2,9,16,23-Tetrakis(4-carboxymethylsulfanyl)- phthalocyani-
natocopper(II) (2d). This is soluble in polar solvents especially DMF,