May 1998
SYNTHESIS
737
1
3
6
C NMR: d = 20.7 (q), 84.8 [d, arom Cr(CO) ], 88.1 [d, arom Tricarbonyl[1-(h -3-chlorophenyl)-1H-indole]chromium (3m) : mp
3
Cr(CO) ], 89.5 [d, arom Cr(CO) ], 93.6 [d, arom Cr(CO) ], 105.6 (d, 96–98°C (pentane).
3
3
3
–1
C-3), 109.2 [s, arom Cr(CO) ], 110.8 (d), 118.2 [s, arom Cr(CO) ], IR (CHCl ): n = 1980, 1915 cm .
1
2
3
3
3
1
21.4 (d), 121.7 (d), 123.1 (d), 127.6 (d, C-2), 129.9 (s), 135.8 (s),
32.3 (s, 3C, CO).
H NMR: d = 5.3 [d, 1H, J = 6.4 Hz, arom Cr(CO) ], 5.5 [dd, 1H, J =
l.6, 6.4 Hz, arom Cr(CO) ], 5.7 [t, 1H, J = 6.4 Hz, arom Cr(CO) ], 5.9
3
3
3
Anal. Calcd for C H CrNO : C, 62.97; H, 3.82; N, 4.08. Found: C, [t, 1H, J = 1.6 Hz, arom Cr(CO) ], 6.7 (d, 1H, J = 3.5 Hz, H-3), 7.2–
18
13
3
3
6
2.90; H, 3.80; N, 4.07.
7.32 (m, 2H, arom), 7.35 (d, 1H, J = 3.5 Hz, H-2), 7.7 (m, 2H, arom).
Anal. Calcd for C H ClCrNO : C, 56.13; H, 2.77; N, 3.85. Found:
17
10
3
6
8
C, 56.22; H, 2.76; N, 3.84.
Tricarbonyl[1-(h -4-methylphenyl)-1H-indole]chromium (3d): mp
8
1
00–102°C (pentane), (lit. not reported). Spectroscopic data is in
8
6
Tricarbonyl[1,1¢-(h -1,2-phenylene)bis-1H-indole]chromium
(4):
agreement with that reported in the lit.
mp 198–200°C (pentane).
–1
IR (CHCl ): n = 1981, 1914 cm .
3
6
8
1
Tricarbonyl[1-(h -2-methoxyphenyl)-1H-indole]chromium (3e): mp
H NMR: d = 5.54 [m, 2H, arom Cr(CO) ], 5.92 [m, 2H, arom
3
8
1
20–121°C (pentane), (lit. not reported). Spectroscopic data is in Cr(CO) ], 6.4 [d, 2H, J = 3.4 Hz, H-3], 6.88 (d, 2H, J = 3.4 Hz, H-2),
3
8
agreement with that reported in the lit .
7.1–7.0 (m, 4H, arom), 7.28 (m, 2H, arom), 7.4–7.5 (m, 2H, arom).
+
EI-MS: m/z = 444 (M ).
6
Anal. Calcd for C25
H16CrN O : C, 67.57; H, 3.63; N, 6.3. Found: C,
2 3
Tricarbonyl[1-(h -2-(diethoxymethyl)phenyl)-1H-indole]chromium
6
7.65; H, 3.64; N, 6.26.
(
3f): mp 100–101°C (petroleum ether).
–1
IR (Nujol): n = 1972, 1904 cm .
6
1
Tricarbonyl[1,1¢-(h -1,3-phenylene)bis-1H-indole]chromium
(5):
H NMR: d = 0.6 (br s, 3H, Me), 1.3 (t, 3H, J = 7 Hz, Me), 2.9–3.2
mp 158–l60°C (pentane).
(
m, 2H, CH ), 3.6–3.8 (m, 2H, CH ), 5.1 (s, 1H, CH), 5.4 [t, 1H, J =
2
2
–1
IR (CHCl ): n = 1981, 1914 cm .
3
6
1
6
.3 Hz, arom Cr(CO) ], 5.5 [t, 1H, J = 5.9 Hz, arom Cr(CO) ], 5.6 [d,
3 3
H, J = 5.9 Hz, arom Cr(CO) ], 5.8 [d, 1H, J = 6.3 Hz, arom Cr(CO) ],
.6 (d, 1H, J = 3.3 Hz, H-3), 7.1–7.4 (m, 4H, arom+H-2), 7.6 (d, 1H,
J = 7.4 Hz, arom).
C NMR: d = 14.4 (q), 15.0 (q), 62.1 (t), 65.7 (t), 88.2, 89.8, 92.5,
2.54 [d, arom Cr(CO) ], 97.8 (d, CH), 103.8 (d, C-3), 109.4 [s, arom
Cr(CO) ], 110.1 (d), 11 1.7 [s, arom Cr(CO) ], 120.7, 121.2, 122.6 (d,
1
H NMR: d = 5.65 [dd, 2H, J = 1.6, 6.5 Hz, arom Cr(CO) ], 5.9 [t, 1H,
3
3
3
J = 6.5 Hz, arom Cr(CO) ], 6.15 [t, 1H, J = 1.6 Hz, arom Cr(CO) ],
3
3
6
.7 (d, 2H, J = 3.4 Hz, H-3), 7.2–7.35 (m, 4H, arom), 7.4 (d, 2H, J =
13
3.4 Hz, H-2), 7.65–7.75 (m, 2H, arom).
Anal. Calcd for C H CrN O : C, 67.57; H, 3.63; N, 6.3. Found: C,
25
16
2 3
9
3
6
7.60; H, 3.65; N, 6.31.
3
3
arom), 129 (s), 130.9 (d, C-2), 131.2 (s), 231.6 (s, 3C, CO).
EI-MS: m/z = 431 (M ).
6
+
Tricarbonyl[2-methyl-1-(h -phenyl)-1H-indole]chromium (8a): mp
58–160°C (petroleum ether).
1
–1
IR (Nujol): n = 1958, 1904, 1877 cm .
6
1
Tricarbonyl[1-(h -2-chlorophenyl)-1H-indole]chromium (3l): mp
H NMR: d = 2.55 (s, 3H, Me), 5.3 [dd, 1H, J = 6.0, 6.21 Hz, arom
1
09–110°C (petroleum ether).
Cr(CO) ], 5.46 [dd, 2H, J = 6.3, 6.5 Hz, arom Cr(CO) ], 5.58 [d, 2H,
3
3
–1
IR (CHCl ): n = 1986, 1923 cm .
J = 6.5 Hz, arom Cr(CO) ], 6.43 (s, 1H, H-3), 7.1–7.3 (m, 2H, arom),
3
3
1
H NMR: d = 5.2 [dd, 1H, J = 5.9, 6.4 Hz, arom Cr(CO) ], 5.5 [dd, 7.55 (d, 1H, J = 7.67 Hz, arom), 7.65 (d, 1H, J = 8.18 Hz, arom).
3
13
1
H, J = 5.9, 6.4 Hz, arom Cr(CO) ], 5.6 [d, 1H, J = 5.9 Hz, arom
C NMR: d = 14.6 (q), 90.66 [d, arom Cr(CO) ], 90.77 [d, 2C, arom
3
3
Cr(CO) ], 5.87 [d, 1H, J = 6.4 Hz, arom Cr(CO) ], 6.65 (d, 1H, J = Cr(CO) ], 91.28 [d, 2C, arom Cr(CO) ], 105.0 (d, C-3), 11 1.38 (d),
3
3
3
3
3
7
.3 Hz, H-3), 7.28–7.15 (m, 3H, arom), 7.32 (d, 1H, J = 3.3 Hz, H-2), 114.17 (s), 120.12 (d), 121.21 (d), 122.05 (d), 128.82 (s), 136.88 (s),
.65 (d, 1H, J = 7.3 Hz, arom).
137.27 (s), 231.98 (s, 3C, CO).
Anal. Calcd for C H ClCrNO : C, 56.13 ; H, 2.77; N, 3.85. Found: Anal. Calcd for C H CrNO : C, 62.97; H, 3.82; N, 4.08. Found: C,
17
10
3
18 13
3
C, 56.32; H, 2.80; N, 3.87.
63.02; H, 3.80; N, 4.05.
1
Table 2. Yields and H NMR Data of Compounds 6a–f, l, m, 9a,c
Producta R1
R
Yield (%)b
1H NMR (CDCl3)
d, J (Hz)
6
a
H
H15
96
6.7 (d, 1H, J = 3.3, H-3), 7.2–7.5 (m, 8H, arom.), 7.6 (d, 1H, J = 7.8, arom.),
.7 (d, 1H, J = 7.8, arom.)
7
6
6
b
c
H
H
2-Me2d
3-Me2d
95
97
2.1 (s, 3H, Me), 6.7 (d, 1H, J = 3.2, H-3), 7.0–7.4 (m, 8H, arom.), 7.8 (m, 1H, arom.)
2.5 (s, 3H, Me), 6.7 (d, 1H, J = 3.3, H-3), 7.1–7.4 (m, 7H, arom.),
7
.6 (d, 1H, J = 8.1), 7.7 (dd, 1H, J = 7.2, J = 1.4)
2.5 (s, 3H, Me), 6.7 (d, 1H, J = 3.2, H-3), 7.1–7.4 (m, 7H, arom.),
.6 (d, 1H, J = 6.0, arom.), 7.7 (d, 1H, J = 7.6, arom.)
6
d
H
4-Me2d
97
7
6
6
e
f
H
H
2-OMe
2-CH(OEt)2
93
90
3.8 (s, 3H, OMe), 6.7 (d, 1H, J = 2.7, H-3), 7.0–7.4 (m, 8H, arom.), 7.7 (m, 1H, arom.)
(C D ) 0.9 (br s, 3H, Me), 1.1 (br s, 3H, Me), 2.9–3.5 (m, 4H, CH ),
6
6
2
5
7
.1 (s, 1H, CH), 6.7 (d, 1H, J = 3.1, H-3), 7.0–7.25 (m, 7H, arom.),
.7 (d, 1H, J = 7.2, arom.), 8.0 (d, 1H, J = 7.7, arom.)
6
6
9
9
l
H
2-Cl
3-Cl
H
95
95
94
97
6.7 (d, 1H, J = 3.3, H-3), 7.1–7.6 (m, 9H, arom.)
m
a
c
H
CH3
CH3
6.7 (d, 1H, J = 3.3, H-3), 7.2–7.7 (m, 9H, arom.)
2.4 (s, 3H, Me), 6.4 (s, 1H, H-3), 7.1–7.6 (m, 9H, arom.)
3-Me
2.3 (s, 3H, Me), 2.5 (s, 3H, Me), 6.4 (s, 1H, H-3), 7.1–7.5 (m, 7H, arom.),
7
.58–7.62 (m, 1H, arom.)
a
Satisfactory microanalyses obtained: C ± 0.20, H ± 0.30, N ± 0.32.
Yield of isolated product.
b