D. V. McGrath et al.
versity of Arizona. Flash column chromatography and TLC were per-
formed using silica gel 60 and Silica Gel 60 F254 plates respectively from
EMD.
4.7 mmol), triphenyl phosphine (4.4 g, 16.0 mmol), and DIAD (3.4 g,
16.0 mmol), after flash chromatography (SiO2, CH2Cl2), afforded 2d
(1.7 g, 69%) as a colorless solid: m.p. 118–1208C; 1H NMR (500 MHz,
CDCl3) d=7.46–7.44 (d, J=9.0 Hz, 4H), 7.01–6.99 (d, J=9 Hz, 4H), 6.85
(s, 2H), 4.07–4.05 (t, J=12.5 Hz, 4H), 2.31–2.29 (m, 4H), 1.98–1.95 (m,
6H), 1.77–1.75 ppm (m, 4H); 13C NMR (125 MHz, CDCl3) d=161.1,
144.5, 137.2, 128.74, 117.9, 116.6, 115.5, 111.0, 83.8, 68.7, 67.6, 28.1, 25.0,
18.1 ppm; MS (ESI, positive mode): m/z: 559.1 [M+Na]+;
C32H28N2O2S2Na requires 559.1; elemental analysis calcd for
C32H28N2O2S2: C 71.61, H 5.26, N 5.22; found: C 71.66, H 5.55, N 5.15.
4,5-Bis(4-hydroxyphenylthio)phthalonitrile (1): A mixture of 4-hydroxy-
thiophenol (9.6 g, 76 mmol), K2CO3 (35.0 g, 250 mmol), and DMSO
(200 mL) was stirred at room temperature under argon for 30 min. Di-
chlorophthalonitrile (5.0 g, 25 mmol) was then added and the reaction
mixture was maintained at 908C with stirring for 12 h. The reaction mix-
ture was allowed to cool to room temperature before being poured into
1m HCl (750 mL) to induce precipitation. The precipitate was filtered,
washed with water (1000 mL), and redissolved in ethyl acetate (350 mL).
The resulting solution was washed (H2O) until the aqueous layer became
neutral, dried (MgSO4), and the solvent was removed under reduced
pressure to obtain a yellow solid. The yellow solid was powdered using a
mortar and pestle, and then dispersed in CH2Cl2 (600 mL) with vigorous
stirring. The precipitate was filtered to obtain 1 (8.77 g, 91%) as a yellow
powder: m.p. 268–2708C; 1H NMR (500 MHz, [D6]DMSO) d=10.23 (s,
2H), 7.44–7.42 (d, J=9.0 Hz, 4H), 6.95 (s, 2H), 6.95–6.94 ppm (d, J=
9 Hz, 4H); 13C NMR (125 MHz, [D6]DMSO) d=159.7, 143.8, 137.3,
128.5, 117.6, 115.6, 115.2, 110.6 ppm; MS (ESI, negative mode): m/z:
412.7 [M+HCl]ꢀ; C20H13N2O2S2Cl requires 412.0. elemental analysis
calcd for C20H12N2O2S2: C 63.81, H 3.21, N 7.44; found: C 63.10, H 3.53,
N 7.29.
2,3,9,10,16,17,23,24-Octa(4-(prop-2-ynyloxy)phenthio)phthalocyanine
(3a): A mixture of phthalonitrile 2a (0.20 g, 0.44 mmol), DBU (0.06 g,
0.44 mmol), LiBr (3.8 mg, 0.04 mmol), and 1-pentanol (10 mL) was main-
tained at 1458C under argon for 48 h. The dark green reaction mixture
was allowed to cool to room temperature before precipitating into meth-
anol to obtain a green precipitate. The precipitate was insoluble in
CH2Cl2, chloroform, THF, ethyl acetate, methanol, acetone, NMP, and
hexanes. No characterization data was obtained on this material.
2,3,9,10,16,17,23,24-Octa(4-(but-3-ynyloxy)phenthio)phthalocyanine (3b):
Following the procedure for 3a, phthalonitrile 2b (0.20 g, 0.44 mmol),
DBU (0.06 g, 0.4 mmol), LiBr (3.8 mg, 0.04 mmol), and 1-pentanol
(10 mL), after flash chromatography (SiO2, EtOAc–hexanes, gradient
from 0:100 to 30:70, CH2Cl2, then THF), followed by precipitation in
hexanes afforded 3b (0.04 g, 43%) as a green solid: m.p. 3608C dec.; MS
(MALDI): m/z: 1986.0 [M+Cu]+; C112H82N8O8S8Cu requires 1986.3; ele-
mental analysis calcd for C112H82N8O8S8: C 69.90, H 4.29, N 5.82; found:
C 69.99, H 4.09, N 5.84.
4,5-Bis(4-(prop-2-ynyloxy)phenylthio)phthalonitrile (2a): A solution of 2-
propyn-1-ol (0.5, 9 mmol), phthalonitrile 1 (1.0 g, 2.6 mmol), triphenyl
phosphine (2.4 g, 9.3 mmol), and DIAD (1.9 g, 9.3 mmol) in THF
(20 mL) was sonicated at room temperature under argon for 3 h. The re-
action mixture was diluted with CH2Cl2 (300 mL), washed with water (3ꢂ
100 mL), and dried (MgSO4). The solvent was removed under reduced
pressure to obtain crude product as a yellow solid. The crude product
was powdered using a mortar and pestle, dispersed in hexanes (500 mL)
with vigorous stirring and then filtered to obtain a colorless solid that
was purified by flash chromatography (SiO2, 70% CH2Cl2 in hexanes) to
afford 2a (0.51 g, 42%) as a colorless solid: m.p. 176–1788C; 1H NMR
(500 MHz, CDCl3) d=7.49–7.48 (d, J=8.8 Hz, 4H), 7.11–7.10 (d, J=
8.8 Hz, 4H), 6.88 (s, 2H), 4.77–4.76 (d, J=2.5 Hz, 4H), 2.58–2.57 ppm (t,
J=4.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) d=160.0, 144.8, 137.6,
129.4, 119.7, 117.5, 115.9, 111.7, 78.1, 76.8, 56.4 ppm; MS (ESI, positive
mode): m/z: 475.1 [M+Na]+; C26H16N2O2S2Na requires 475.0; elemental
analysis calcd for C26H16N2O2S2: C 69.00, H 3.56, N 6.19; found: C 68.52,
H 3.80, N 6.09.
2,3,9,10,16,17,23,24-Octa(4-(pent-4-ynyloxy)phenthio)phthalocyanine
(3c): Following the procedure for 3a, phthalonitrile 2c (0.2 g, 0.4 mmol),
DBU (0.06 g, 0.4 mmol), and LiBr (3.4 mg, 0.04 mmol), after flash chro-
matography (SiO2, EtOAc–hexanes, gradient from 0:100 to 30:70,
CH2Cl2, then THF), followed by precipitation in hexanes afforded 3c
(0.05 g, 26%) as a green solid: m.p. 3508C dec.; 1H NMR (500 MHz,
CDCl3) d=8.84 (s, 8H), 7.64–7.62 (d, J=9.0 Hz, 16H), 7.07–7.05 (d, J=
9.0 Hz, 16H), 4.19–4.18 (t, J=12.0 Hz, 16H), 2.45–2.44 (m, 16H), 2.08–
2.03 (m, 8H), 1.97 ppm (m, 16H); MS (MALDI): m/z: 2035.5 [M]+;
C120H98N8O8S8 requires 2035.5; elemental analysis calcd for
C120H98N8O8S8: C 70.77, H 4.85, N 5.50; found: C 70.47, H 5.00, N 5.50.
2,3,9,10,16,17,23,24-Octa(4-(hex-5-ynyloxy)phenthio)phthalocyanine (3d):
Following the procedure for 3a, phthalonitrile 2d (1.77 g, 3.30 mmol),
DBU (0.50 g, 3.3 mmol), LiBr (0.02 g, 0.3 mmol), and 1-pentanol
(50 mL), after flash chromatography (SiO2, EtOAc–hexanes, gradient
from 0:100 to 30:70, CH2Cl2, then THF), followed by precipitation in
hexanes afforded (0.66 g, 37%) as a green solid: m.p. 3208C dec.;
1H NMR (500 MHz, CDCl3) d=8.72 (s, 8H), 7.62–7.60 (d, J=9.0 Hz,
16H), 7.04–7.02 (d, J=9 Hz, 16H), 4.09–4.06 (t, J=12.5 Hz, 16H), 2.29–
2.25 (m, 16H), 1.98–1.92 (m, 24H), 1.77–1.71 ppm (m, 16H); MS
(MALDI): m/z: 2147.7 [M]+; C127H114N8O8S8 requires 2147.6; elemental
analysis calcd for C128H114N8O8S8: C 71.54, H 5.35, N 5.21; found: C
71.67, H 5.70, N 5.47.
4,5-Bis(4-(but-3-ynyloxy)phenylthio)phthalonitrile (2b): Following the
procedure for 2a, 3-butyn-1-ol (0.6, 9 mmol), phthalonitrile 1 (1.0 g,
2.6 mmol), triphenyl phosphine (2.4 g, 9.3 mmol), and DIAD (1.9 g,
9.3 mmol), after flash chromatography (SiO2, CH2Cl2), afforded 2b
(0.34 g, 27%) as a colorless solid: m.p. 158–1608C; 1H NMR (500 MHz,
CDCl3) d=7.47–7.46 (d, J=8.5 Hz, 4H), 7.04–7.02 (d, J=8.5 Hz, 4H),
6.85 (s, 2H), 4.18–4.15 (t, J=13.5 Hz, 4H), 2.75–2.72 (t, J=16.5 Hz, 4H),
2.06 ppm (t, J=2.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) d=160.9,
144.9, 137.7, 129.3, 119.1, 117.2, 115.9, 111.9, 80.3, 70.6, 66.6, 20.0 ppm;
MS (ESI, positive mode) m/z: 503.0 [M+Na]+; C28H20N2O2S2Na requires
503.0; elemental analysis calcd for C28H20N2O2S2: C 69.97, H 4.19, N 5.83;
found: C 69.74, H 4.43, N 5.84.
Copper 2,3,9,10,16,17,23,24-Octa(4-(4-(1-dodecyl-1H-1,2,3-triazol-4-yl)-
butoxy)phenthio)phthalocyanine (4a):
A mixture of 3d (30.0 mg,
14.0 mmol), CuI (4.2 mg, 22 mmol), compound 5a (0.2 g, 1 mmol), DIPEA
(30.0 mg, 0.2 mmol), and dry THF (15 mL) was degassed and back filled
with argon three times and then stirred for 48 h under argon. The reac-
tion mixture was diluted with CH2Cl2 (100 mL), washed with EDTA
(0.1m, 4ꢂ100 mL), HCl (1n, 4ꢂ100 mL), dried (MgSO4), and filtered.
The solvent was evaporated and crude product was subjected to flash
chromatography (SiO2, MeOH–CH2Cl2, gradient from 0:100 to 4:96), fol-
lowed by precipitation in hexanes afforded 4a (43 mg, 79%) as a green
solid: m.p. 3208C dec.; 1H NMR (500 MHz, CDCl3) d 7.44–6.58 (m,
48H), 4.26 (brs, 16H), 4.03 (brs, 16H), 2.76 (brs, 16H), 1.84 (brs, 32H),
1.23–1.20 (m, 160H), 0.67 ppm (brs, 24H); MS (MALDI): m/z: 3898.8
[M+]; C224H312N32O8S8Cu requires 3898.2; elemental analysis calcd for
C224H312N32O8S8Cu: C 68.61, H 8.01, N 11.47; found: C 68.96, H 8.06, N
11.49.
4,5-Bis(4-(pent-4-ynyloxy)phenylthio)phthalonitrile (2c): Following the
procedure for 2a, 4-pentyn-1-ol (0.8, 9 mmol), phthalonitrile 1 (1.0 g,
2.6 mmol), triphenyl phosphine (2.4 g, 9.3 mmol), and DIAD (1.9 g,
9.3 mmol), after flash chromatography (SiO2, 70% CH2Cl2 in hexanes),
afforded 2c (0.61 g, 45%) as a colorless solid: m.p. 136–1388C; 1H NMR
(500 MHz, CDCl3) d=7.46–7.45 (d, J=11.5 Hz, 4H), 7.02–7.00 (d, J=
11.5 Hz, 4H), 6.85 (s, 2H), 4.14–4.12 (t, J=12 Hz, 4H), 2.45–2.41 (t, J=
16.5 Hz, 2H), 2.07–2.01 (m, 4H), 1.99 ppm (t, J=3 Hz, 4H); 13C NMR
(125 MHz, CDCl3) d=161.4, 144.9, 137.7, 129.2, 118.5, 117.1, 116.0,
111.5, 83.6, 69.6, 66.9, 28.5, 15.6 ppm; MS (ESI, positive mode): m/z:
531.1 [M+Na]+; C30H24N2O2S2Na requires 531.1; elemental analysis
calcd for C30H24N2O2S2: C 70.84, H 4.76, N 5.51; found: C 70.94, H 5.10,
N 5.60.
4,5-Bis(4-(hex-5-ynyloxy)phenylthio)phthalonitrile (2d): Following the
procedure for 2a, 5-hexyn-1-ol (1.6, 16 mmol), phthalonitrile 1 (1.8 g,
Copper 2,3,9,10,16,17,23,24-Octa(4-(4-(1-(3-phenylpropyl)-1H-1,2,3-tria-
zol-4-yl)butoxy)phenthio)phthalocyanine (4b): Following the procedure
8476
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 8472 – 8478