H. Kantekin et al. / Journal of Organometallic Chemistry 693 (2008) 1353–1358
1357
for 46 h. The mixture was cooled to room temperature and
then poured into aqueous ammonia (20 mL, %25). After
stirring for 4 h, the mixture was extracted with
(2 ꢁ 50 mL) chloroform. The combined organic layers
were washed with water, dried over anhydrous sodium sul-
fate and filtered and the concentrated. After this reaction,
the desired compound 6 was purified by column chroma-
tography on silica gel using chloroform as eluent. Yield:
0.545 g (76%). Anal. Calc. for C33H38N4O6S4: C, 55.44;
H, 5.36; N, 7.84; S, 17.94. Found: C, 55.80; H, 5.41; N,
7.81; S, 17.92%. IR(NaCl disk) mmax/cmꢀ1: 3060 (Ar–H),
2925–2855 (Aliph. C–H), 2229 (C„N), 1591, 1564, 1514,
DBU, gently heated, and subsequently heated at 198 °C
for 5 h. After cooling to room temperature, the dark green
solid product was precipitated by EtOH. The resulting
dark green precipitate was washed with hot EtOH then
MeOH. The green product was chromatographed on a sil-
ica gel with CHCl3/EtOH (3:7, volume ratio) as eluent.
Yield: 0.057 g (37%). Anal. Calc. for C132H152N16NiO24S16:
C, 54.32; H, 5.25; N, 7.68; S, 17.58. Found: C, 54.35; H,
5.29; N, 7.70; S, 17.56%. IR(NaCl disk) mmax/cmꢀ1: 3072
(Ar–H), 2927–2856 (Aliph. C–H), 1592, 1454, 1323, 1206,
1
1159, 1107, 984, 898. H NMR (CDCl3): (d: ppm): 7.68
(m, 16H, Ar–H), 7.45 (s, 8H, Ar–H), 4.16 (t, 16H,
O–CH2), 3.43 (t, 16H, N–CH2), 3.21 (t, 16H, N–CH2), 2.74
(t, 16H, S–CH2), 2.49 (t, 16H, S–CH2), 2.12 (s, 24H,
CH3), 1.21 (m, 24H, CH2). UV–Vis [(in chloroform)
[(10ꢀ5 e dm3 molꢀ1 cmꢀ1)]: 674 (5.23), 629 (5.01), 395 (4.5),
278 (5.26). MS; m/z: 2918 [M]+.
1
1456, 1287, 1153, 1088, 814. H NMR (CDCl3), (d: ppm):
7.71 (d, 4H, Ar–H), 7.67 (d, 4H, Ar–H), 7.26 (s, 2H,
Ar–H), 4.28 (t, 4H, O–CH2), 3.57 (t, 4H, N–CH2), 3.40
(t, 4H, N–CH2), 2.74 (t, 4H, S–CH2), 2.58 (t, 4H,
S–CH2), 2.42 (s, 6H, CH3), 1.24 (m, 2H, CH2). 13C NMR
(CDCl3), (d: ppm): 151.29 (Ar–C), 144.11 (Ar–C), 130.91
(Ar–CH), 130.032 (Ar–CH), 129.54(Ar–CH), 127.15
(Ar–CH), 122.78 (Ar–CH), 115.85 (C„N), 68.53 (O–
CH2), 50.49 (N–CH2), 48.21 (N–CH2), 31.93 (S–CH2),
30.16 (S–CH2), 29.37 (CH2), 22.71 (CH3). MS, (m/z) =
714 [M]+.
3.6. Tetrakis [N,N0-(2,20-(propane-1,3-diylbis
(sulfanediyl))bis(ethane-2,1-diyl))bis
(4-methylbenzenesulfonamide)-phthalocyaninato]
cobalt(II) (9)
A mixture of dicyano compound 6 (0.15 g, 0.21 mmol)
and anhydrous CoCl2 (0.0067 g, 0.053 mmol),was placed
in a tube. The solid was then irradiated under microwaves
(350 W power) for five to fifteen minutes. The dark green
product was obtained. After cooling to room temperature,
the dark green solid product was precipitated by EtOH.
The resulting dark green precipitate was washed several
times with hot EtOH–MeOH. The green product was chro-
matographed on a silica gel with CHCl3/EtOH (3:7,
volume ratio) as eluent. Yield: 0.047 g (31%), m.p.:
274–276 °C. Anal. Calc. for C132H152CoN16O24S16: C,
54.32; H, 5.25; N, 7.68; S, 17.58. Found: C, 54.40; H,
3.4. Tetrakis [N,N0-(2,20-(propane-1,3-diylbis
(sulfanediyl))bis(ethane-2,1-diyl))bis
(4-methylbenzenesulfonamide)-phthalocyanine] (7)
A mixture of dicyano compound 6 (0.2 g, 0.28 mmol)
were placed in a Schlenk tube under nitrogen in the pres-
ence of DBU, gently heated, and subsequently heated at
198 °C for 5 h. After cooling to room temperature, the
dark green solid product was precipitated by EtOH. The
resulting dark green precipitate was washed with hot EtOH
then MeOH. The green product was chromatographed on
a silica gel with CHCl3/EtOH (3:7, volume ratio) as eluent.
Yield: 0.05 g (25%), m.p.: 210–213 °C. Anal. Calc. for
5.27; N, 7.70, S, 17.54%. IR(KBr pellets): mmax/cmꢀ1
:
3075 (Ar–H), 2924–2858 (Aliph. C–H), 1594, 1462, 1339,
1156, 1075, 948, 897, 782. UV–Vis [(in chloroform) [(10ꢀ5
e dm3 molꢀ1 cmꢀ1)]: 677 (5.21), 614 (4.92), 284 (5.24).
MS; m/z: 2955 [M+2H2O+1]+.
C
132H154N16O24S16: C, 55.40; H, 5.42; N, 7.83; S, 17.93.
Found: C, 55.22; H, 5.45; N, 7.58; S, 17.91%. IR(KBr pel-
lets) mmax/cmꢀ1: 3335 (N–H), 3072 (Ar–H), 2921–2851
(Aliph. C–H), 1597, 1458, 1377, 1284, 1156, 1089, 814.
1H NMR (DMSO): (d: ppm): 7.68 (m, 16H, Ar–H), 7.26
(s, 8H, Ar–H), 4.28 (t, 16H, O–CH2), 3.40 (t, 16H,
N–CH2), 3.36 (t, 16H, N–CH2), 2.86 (t, 16H, S–CH2),
2.63 (t, 16H, S–CH2), 2.41 (s, 24H, CH3), 1.24 (m, 24H,
4. Conclusion
We have presented new dicyano starting materials
(ligands) and their conversion to metallophthalocyanines
that are soluble in a number of solvents. For this,
N,N0-(2,20-(propane-1,3-diylbis(sulfanediyl))bis(ethane-2, 1-
diyl))bis(4-methylbenzenesulfonamide) (3) was reacted with
1,2-bis(2-iodoethoxy)-4,5-dibromobenzene (4) in dry aceto-
nitrile containing finely ground anhydrous Cs2CO3 as a
template agent to give the Synthesis of 19,20-dibromo-
4,14-ditosyl-3,4,5,6,8,9,10,12,13,14,15,16-dodecahydro-2H-
benzo[b][1,4,10,14,7,17]dioxadithiadi azacyclononadecine
(5). The dicyano compound (6) is obtained from the dibromo
derivative by refluxing in DMF with three equivalents of
CuCN. Starting from 6, metal-free 7, nickel(II) phthalocya-
nines 8 and cobalt(II) phthalocyanines were prepared.
CH2). UV–Vis [(in chloroform)
k
max/nm 10ꢀ5
e
(molꢀ1 cmꢀ1)]: 683 (4.28), 632 (5.10), 338 (5.03), 278
(5.21). MS; m/z = 2862 [M+1]+.
3.5. Tetrakis [N,N0-(2,20-(propane-1,3-diylbis
(sulfanediyl))bis(ethane-2,1-diyl))bis
(4-methylbenzenesulfonamide)-phthalocyaninato]
nickel(II) (8)
A mixture of dicyano compound 6 (0.15 g, 0.21 mmol)
and anhydrous NiCl2 (0.0067 g, 0.052 mmol),was placed
in a Schlenk tube under nitrogen in the presence of