10092 J. Am. Chem. Soc., Vol. 118, No. 42, 1996
Sommerauer et al.
8.91 (br, 4H), 9.03-9.31 (m, 4H); 13C-NMR (CDCl3/CS2, 62.89 MHz)
δ 25.30, 25.48, 29.49, 34.72, 44.15, 44.21, 118,92, 119.20, 122.41 (m),
128.63, 135.80 (m), 137.80 (m), 144.64, 144.73, 145.24, 145.99, 185.75;
IR (KBr disk) ν 3068 (w), 2924 (s), 2854 (m), 1612 (s), 1485 (m),
1468 (s), 1352 (m), 1242 (s), 1123 (m), 1097 (s), 750 (m) cm-1; UV
(CH2Cl2) λ (ꢀ) 670.0 (1.082), 643.0 (0.179) sh, 604.0 (0.171), 365.0
(0.162) sh, 336.0 (0.259), 297.5 (0.287), 274.0 (0.260), 246.5 (0.350)
nm. Anal. Calcd for C92H104N8O4Ni: C, 76.52; H, 7.26; N, 7.76.
Found: C, 75.74; H, 7.22; N, 7.47.
zation from acetone gave (p-nitrophenyl)quinoline-4-carboxylic acid
(17): yield 3g (63.8%) as yellow powder, decomposes at 200 °C (CO2
evolution).
For 16: yield 1.2 g; MS m/z (relative intensity) 294.1 (M+), 249.0,
1
204.0 (100), 176.0, 124.5, 101.0, 87.9, 74.9; H-NMR (DMSO, 250
MHz) δ 7.75 (t, 1H), 7.88 (t, 1H), 8.19 (d, 1H), 8.36 (d, 2H), 8.53 (d,
2H), 8.56 (s, 1H), 8.64 (d, 1H), 14.01 (s, br, 1H); 13C-NMR (DMSO,
62.89 MHz) δ 119.46, 123.83, 124.01, 125.43, 128.43, 128.62, 129.98,
130.56, 138.02, 143.67, 148.16, 148.31, 153.53, 167.35; IR (KBr disk)
ν 3093 s, 2921 s, 2530 s, 1717 (s), 1595 (m), 1531 (s), 1348 (s), 1244
(m), 1200 (m), 798 (m), 762 (m), 696 (m) cm-1. Anal. Calcd for
C16H10N2O4: C, 65.31; H, 3.43; N, 9.52. Found: C, 65.33; H, 3.63;
N, 9.60.
Tetrakis[(cyclohexylthio)phthalocyaninato]nickel(II) (11): dark
blue powder; MS (FD) m/e 1026.2 (M+), 513.0 (M2+); 1H-NMR
(CDCl3, 250 MHz) δ 1.7 (br), 1.9 (br), 2.1 (br), 2.3 (br), 3.5 (br, 4H),
6.9-7.7 (br, 12H); 13C-NMR (CDCl3, 62.89 MHz) δ 26.18 (2 peaks),
33.49, 45.78, 46.11, 46.47, 120.02 (m), 121.70 (m), 122.60 (m), 129.43
(m), 130.08 (m), 131.48 (m), 133.79 (m), 136.11 (m); IR (KBr disk) ν
2928 (s), 2853 (m), 1605 (s), 1533 (w), 1448 (m), 1400 (m), 1313
(m), 1261 (m), 1144 (m), 1099 (m), 1087 (m), 1043 (w), 997 (w), 935
(m), 818 (w), 750 (m) cm-1; UV (CH2Cl2) λ (ꢀ) 683.0 (0.735), 650.5
(0.364) sh, 622.5 (0.308) sh, 412.5 (0.145) sh, 364.0 (0.188) sh, 334.0
(0.325), 301.5 (0.571), 261.5 (0.401) nm. Anal. Calcd for C56H56N8-
NiS4: C, 65.43; H, 5.49; N, 10.89; S, 12.47. Found: C, 64.06; H,
5.39; N, 10.66; S, 12.40.
For 17: yield 0.55 g; MS m/z (relative intensity) 294.1 (M+), 249.0,
1
204.0 (100), 176.0, 124.5, 101.0, 87.9, 74.9; H-NMR (DMSO, 250
MHz) δ 7.76 (t, J ) 7.0 Hz, 1H), 7.85 (t, J ) 8.0 Hz, 1H), 7.92, (dd,
J ) 7.0, 2.2 Hz, 1H), 8.19 (d, J ) 8 Hz, 1H), 8.34 (dd, J ) 7.5, 2.2
Hz, 1H), 8.56 (s, 1H), 8.65 (d, J ) 8.4 Hz, 1H), 8.72 (d, J ) 7.6 Hz,
1H), 9.05 (t, J ) 1.8 Hz, 1H), 14.10 (s, br, 1H); 13C-NMR (DMSO,
62.89 MHz) δ 119.04, 121.51, 123.79, 124.30, 125.39, 128.34, 129.85,
130.49 (2C), 133.36, 138.03, 139.36, 148.22, 148.44, 153.35, 167.38;
IR (KBr disk) ν 3001 (w), 2932 (w), 2850 (w), 2642 (w), 1699 (s),
1514 (s), 1416 (m), 1348 (s), 1319 (m), 1277 (m), 1259 (m), 860 (m),
847 (m), 762 (m) cm-1. Anal. Calcd for C16H10N2O4: C, 65.31; H,
3.43; N, 9.52. Found: C, 64.63; H, 3.51; N, 9.31.
Tetrakis((1S)-endo-(-)-bornyloxy)phthalocyanine (12). 5-[((1S)-
endo-(-)-bornyloxy)-1,3-dihydro-1,3-diiminoisoindoline (0.5 g, 1.68
mmol) was dissolved in 10 mL of DMF and heated under reflux for
60 h. The solvent was evaporated to dryness, and the residue was
dissolved in chloroform and purified by column chromatography (silica
gel, CHCl3). The product was dissolved in a small amount of DCM
and precipitated with methanol to provide 85 mg (18.1%) of 12 as a
N-[(2-Phenyl-4-quinolyl)carbonyl]-4-(dimethylmethoxysilyl)bu-
tanamide (24). Triethylamine (1.9 mL, 13.6 mmol) and 14 (1.2 mL,
6.2 mmol) were dissolved in 20 mL of DCM under cooling in an ice
bath. To this solution was added 2-phenylquinoline-4-carboxylic acid
chloride (20) (1.9 g, 6.2 mmol) in 20 mL of DCM. The cooling bath
was removed and the solution stirred at room temperature for 1 h. The
reaction mixture was evaporated to dryness, and the residue was
dissolved in DCM/acetonitrile (10:1). The crude product was purified
with flash chromatography (silica gel 40-63 µm) in DCM/acetonitrile
(10:1): yield 1.3 g (53.4%) as colorless oil; MS m/z (relative intensity)
392.3 (M+), 363.2, 349.2, 317.1, 261.1, 232.1, 204.1 (100), 176.0, 149.0,
89.0; 1H-NMR (CDCl3, 250 MHz) δ 0.0 (s, 6H, SiCH3), 0.56 (m, 2H,
SiCH2), 1.37 (m, 2H, CH2), 1.60 (qi, 2H, J ) 7.3 Hz, CH2), 3.30 (s,
3H, OCH3), 3.39 (q, 2H, J ) 6.22 Hz, NCH3), 6.5 (s, 1H, NH), 7.30
(m, 4H, ArH), 7.57 (m, 2H, ArH), 7.93 (m, 4H, ArH); 13C-NMR
(CDCl3, 62.89 MHz) δ -2.6, 15.6, 20.7, 33.0, 39.8, 50.2, 116.3, 123.3,
125.0, 127.2, 127.4 (2C), 128.8 (2C), 129.7, 129.9, 130.1, 138.7, 143.2,
148.5, 156.6, 167.6; 29Si-NMR (CDCl3, 49.69 MHz) δ 11.2; IR (KBr
disk) ν 3273 (m), 3062 s, 2932 s, 1643 (s), 1591 (m), 1549 (s), 1495
s, 1350 (m), 1288 s, 1252 (m), 1088 (s), 841 (m), 771 (m), 694 (w)
cm-1. Anal. Calcd for C23H28N2O2Si: C, 70.37; H, 7.19; N, 7.14.
Found: C, 70.82; H, 6.83; N, 6.92.
1
blue powder: MS (FD) m/e 1123.0 (M+ + 1); H-NMR (CDCl3, 250
MHz) δ -1.59 (br, 2H), 1.09 (s, 12H), 1.22, 1.27 (s, 24H), 1.6 (br,
12H), 1.99 (br, 8H), 2.59 (br, 4H), 2.83 (br, 4H), 4.94 (br, 4H), 7.48-
7.65 (m, 4H), 8.35-8.50 (m, 4H), 8.80-9.12 (m, 4H); 13C-NMR
(CDCl3, 62.89 MHz) δ 13.54, 14.07, 19.10, 19.28, 19.50, 19.84, 26.72,
27.18, 27.87, 28.26, 36.43, 37.19, 45.54, 49.71, 49.79, 83.55, 84.02,
106.38, 106.70, 108.98, 118.86, 121.25, 123.47, 128.78, 137.91, 148.78
(m), 160.73, 160.95; IR (KBr disk) ν 3290 (w), 3068 (w), 2951 (s),
2873 (m), 1614 (s), 1475 (s), 1391 (w), 1366 (w), 1258 (s), 1115 (m),
1096 (s), 1053 (m), 1008 (w), 824 (w), 748 (m), 716 (w) cm-1; UV
(CH2Cl2) λ (ꢀ) 707.0 (0.952), 671.5 (0.828), 645.5 (0.312), 610.5
(0.200), 395.0 (0.249), 343.0 (0.483), 292.0 (0.273), 256.0 (0.207) nm.
Anal. Calcd for C72H82N8O4: C, 76.96; H, 7.36; N, 9.98. Found: C,
75.41; H, 7.35; N, 9.83.
Tetrakis(cyclooctyloxy)phthalocyanine (13). 1,2-Dicyano-4-(oc-
tyloxy)benzene (0.45 g, 1.77 mmol) was dissolved in 5 mL of DMAE
and heated under reflux for 40 h. The solvent was distilled, and the
residue was purified by column chromatography (silica gel, CHCl3).
The product was dissolved in THF/diethyl ether (1:1) and precipitated
with methanol to provide 80 mg (17.6%) of 13 as a blue powder: MS
N-[(2-(o-Nitrophenyl)-4-quinolyl)carbonyl]-4-(dimethylmeth-
oxysilyl)butanamide (25). (a) 16 (1.2 g, 4.1 mmol) was suspended
in 30 mL of DCM. Under cooling with ice water, 1,1′-carbonyldiimi-
dazole (0.67 g, 4.13 mmol) in 30 mL of DCM was added, and the
mixture was stirred for 2 h. During the reaction, a clear yellow solution
containing 21 was obtained. (b) Without further purification, this
solution was slowly added to an equimolar solution of 14 in 20 mL of
DCM, and the mixture was stirred overnight. The mixture was
evaporated to dryness and the residue dissolved in DCM/acetonitrile
(10:1). The crude product was purified by flash chromatography (silica
gel 40-63 µm) in DCM/acetonitrile (10:1) (Rf ) 0.29): yield 1.08 g
(60.3%) as yellow powder; mp 144-146 °C; MS m/z (relative intensity)
436.4 (M+), 422.3, 405.3, 362.3, 332.3, 306.2, 277.2, 249.2, 203.2,
1
(FD) m/e 1019.3 (M+ + 1), 2038.9; H-NMR (CDCl3, 250 MHz) δ
-4.2 (br, 2H), 1.87-2.34 (m, br, 60H), 4.84 (br, 4H), 7.11-7.27 (m,
4H), 7.74 -7.83 (m, 4H), 8.09-8.28 (m, 4H); 13C-NMR (CDCl3, 62.89
MHz) δ 23.34, 23.46, 25.93, 26.01, 27.55, 27.60, 31.75, 31.91, 78.42,
78.47, 78.55, 78.61, 106.36, 106.40, 106.45, 106.51, 106.59, 106.62,
118.79, 118.85, 118.91, 122.88, 122.92, 123.00, 123.05, 128.30, 128.35,
137.29, 127.32, 137.36, 137.46, 147.5 (br), 159.21, 159.26; IR (KBr
disk) ν 3292 (w), 3068 (w), 2920 (s), 2852 (m), 1612 (s), 1477 (s),
1340 (m), 1257 (m), 1236 (s), 1096 (s), 1049 (m), 1011 (s), 973 (m),
822 (w), 748 (m) cm-1; UV (CH2Cl2) λ (ꢀ) 707.0 (1.203), 672.0 (1.032),
644.0 (0.400), 610.5 (0.265), 394.5 (0.330), 344.0 (0.644), 291.0 (0.402)
nm. Anal. Calcd for C64H74N8O4: C, 75.40; H, 7.32; N, 11.00.
Found: C, 74.25; H, 7.09; N, 11.00.
1
176.9, 89.0 (100), 59.0; H-NMR (CDCl3, 400 MHz) δ 0.09 (s, 6H,
SiCH3), 0.67 (m, 2H, SiCH2), 1.51 (m, 2H, CH2), 1.72 (qi, 2H, J )
7.3 Hz, CH2), 3.37 (s, 3H, OCH3), 3.56 (q, 2H, J ) 6.22 Hz, NCH3),
6.31 (s, 1H, NH), 7.56 (2d, 1H, J ) 7.7 Hz, ArH), 7.63 (2d, 2H, J )
7.7 Hz, ArH), 7.75 (2d, 1H, J ) 7.7 Hz, ArH), 7.86 (s, 1H, ArH), 8.14
(dd, 2H, J ) 7.7, 8.2 Hz, ArH), 8.27 (m, 2H, ArH), 8.47 (d, 1H, J )
7.7 Hz, ArH), 8.96 (s, 1H); 13C-NMR (CDCl3, 100.61 MHz) δ -2.7,
15.6, 20.7, 32.9, 39.9, 50.2, 115.7, 122.2, 123.7, 124.2, 125.0, 128.0,
129.8, 130.2, 130.6, 133.1, 140.4, 143.8, 148.7, 148.9, 153.8, 167.1;
29Si-NMR (CDCl3, 49.69 MHz) δ 19.44; IR (KBr disk) ν 3277 (m),
3073 (w), 2930 (m), 1641 (s), 1589 (m), 1547 (s), 1527 (s), 1346 (s),
1288 (w), 1252 (m), 1088 (m), 845 (m), 762 (w), 689 (w) cm-1. Anal.
(Mononitrophenyl)quinolinecarboxylic acids (16, 17). 2-Phen-
ylquinoline-4-carboxylic acid (15, 4 g, 16 mmol) was slowly added to
a cold solution of 5 mL of 65% HNO3 and 7 mL of 100% H2SO4. The
cooling bath was removed, and the mixture stirred for 2 h at room
temperature. The mixture was heated to 50 °C and stirred again for 2
h. The solution was cooled and poured into ice water. The obtained
residue was washed with water until pH 7, dried at 60 °C, and
recrystallized from ethanol. The first fraction contained pure (o-
nitrophenyl)quinoline-4-carboxylic acid (16), and all other fractions
contained both possible products 16 and 17. Fractionated recrystalli-