European Journal of Inorganic Chemistry
10.1002/ejic.201700209
2
H-1,2-azaphosphindole 9b
Yellow solid, 503 mg, 56 % yield. 31P NMR (121 MHz, CDCl
): δ 89.4 ppm; H NMR (300 MHz, CDCl
1
): δ 0.97 (t, J = 7.2 Hz,
3
3
3
H), 1.54-1.65 (m, 2H), 2.14-2.25 (m, 2H), 2.46 (s, 3H), 7.46 (dd, J = 3.9, 7.5 Hz, 1H), 7.52-7.63 (m, 4H), 7.80-7.91 (m, 3H);
): δ 15.16 (d, JCP = 16.5 Hz, CH ), 16.63 (d, JCP = 3.8 Hz, CH ), 21.82(d, JCP = 1.5 Hz, CH ), 36.04 (d,
), 127.02 (d, JCP = 12.8 Hz, CH), 128.52 (d, JCP =10.5 Hz, CH), 128.79 (s, 2CH), 129.04 (s, 2CH), 131.78 (s,
1
3C NMR (75 MHz, CDCl
CP = 61.5 Hz, CH
3
3
2
3
J
2
CH), 132.53 (d, JCP = 9.8 Hz, CH), 134.53 (d, JCP = 23.3 Hz, C), 139.22 (d, JCP = 75.8 Hz, C), 140.15 (d, JCP = 33.8 Hz, C),
+
1
43.00 (d, JCP = 2.3 Hz, C), 179.25 (d, JCP = 6.8 Hz, C). HRMS: m/z calcd for C17
H
19NPS [M+H] : 300.0976; found: 300.0974.
2
H-1,2-azaphosphindole 10a
Yellow solid, 280 mg, 28 % yield. 31P NMR (121 MHz, CDCl
): δ 86.4 ppm; H NMR (300 MHz, CDCl
1
): δ 3.74 (d, JPH = 15.0
3
3
Hz, 2H), 6.89-6.92 (m, 2H), 7.03-7.10 (m, 3H), 7.48-7.62 (m, 6H), 7.68-7.70 (m, 2H), 7.78-7.83 (m, 1H); 13C NMR (75 MHz,
CDCl ): δ 42.63 (d, JCP =55.5 Hz, CH ), 126.02 (d, JCP =13.5 Hz, CH), 127.11 (d, JCP =4.5 Hz, CH), 128.01 (d, JCP =3.0 Hz, 2CH),
28.70 (s, 2CH), 128.86 (s, 2CH), 129.00 (d, JCP =9.8 Hz, CH), 130.00 (d, JCP =5.3 Hz, 2CH), 130.60 (d, JCP =9.0 Hz, C), 131.49
3
2
1
(
1
d, JCP =9.8 Hz, CH), 131.79 (s, CH), 132.15 (d, JCP =2.3 Hz, CH), 134.21 (d, JCP =23.3 Hz, C), 140.05 (d, JCP =33.8 Hz, C),
+
40.90 (d, JCP =75.0 Hz, C), 179.85 (d, JCP =7.5 Hz, C). HRMS: m/z calcd for C20
H17NPS [M+H] : 334.0819; found: 334.0819.
2
H-1,2-azaphosphindole 10b
Yellow solid, 281 mg, 27 % yield. 31P NMR (121 MHz, CDCl
): δ 85.9 ppm; H NMR (300 MHz, CDCl
1
): δ 2.39 (s, 3H, Me),
3
3
3
.74 (d, JPH = 14.7 Hz, 2H, CH
2
), 6.91-6.93 (d, 2H), 7.07-7.09 (d, 3H), 7.37-7.42 (m, 2H), 7.48-7.59 (m, 3H), 7.64-7.69 (t, 3H);
), 42.70 (d, JCP = 55.5 Hz, CH ), 126.64 (d, JCP = 13.5 Hz, CH), 127.08 (d, JCP = 4.5
1
3C NMR (75 MHz, CDCl
3
): δ 21.82 (s, CH
3
2
Hz, CH), 128.01 (d, JCP = 3.8 Hz, 2CH), 128.69 (s, 2CH), 128.84 (2CH), 128.84 (d, JCP = 9.8 Hz, CH), 130.02 (d, JCP = 6.0 Hz,
2
7
C
CH), 130.74 (d, JCP = 8.3 Hz, C), 131.68 (s, CH), 132.36 (d, JCP = 9.8 Hz, CH), 134.33 (d, JCP = 23.3 Hz, C), 137.69 (d, JCP =
8.0 Hz, C), 140.58 (d, JCP = 33.8 Hz, C), 143.01 (d, JCP = 2.3 Hz, C), 179.94 (d, JCP = 6.8 Hz, C). HRMS: m/z calcd for
+
21
H
19NPS [M+H] : 348.0976; found: 348.0975. Anal. Calcd for C21
H18NPS: C 72.60, H 5.22, N 4.03; found: C 72.56, H 5.45,
N 3.87.
2
H-1,2-azaphosphindole 10c
Yellow solid, 404 mg, 37 % yield. 31P NMR (121 MHz, CDCl
): δ 84.7 ppm; H NMR (300 MHz, CDCl
1
): δ 3.69 (m, 2H, CH
),
3
3
2
3
.84 (s, 3H, OMe), 6.94-6.99 (m, 3H), 7.05-7.12 (m, 3H), 7.21 (dd, J = 2.4, 9.3 Hz, 1H), 7.45-7.57 (m, 4H), 7.66-7.69 (m, 2H);
): δ 42.64 (d, JCP = 55.5 Hz, CH ), 56.06 (s, OMe), 113.85 (d, JCP = 10.5 Hz, CH), 118.15 (d, JCP = 1.5
1
3C NMR (75 MHz, CDCl
3
2
Hz, CH), 127.15 (d, JCP = 3.8 Hz, CH), 127.45 (d, JCP = 15.8 Hz, CH), 128.02 (d, JCP = 3.8 Hz, 2CH), 128.64 (s, 2CH), 128.82 (s,
2
2
C
CH), 130.05 (d, JCP = 6.0 Hz, 2CH), 130.65 (d, JCP = 9.0 Hz, C), 131.67 (s, CH), 133.03 (d, JCP = 33.8 Hz, C), 134.44 (d, JCP =
4.0 Hz, C), 143.95 (d, JCP = 74.3 Hz, C), 162.59 (d, JCP = 12.8 Hz, C), 179.58 (d, JCP = 7.5 Hz, C). HRMS: m/z calcd for
+
21
H
19NOPS [M+H] : 364.0925; found: 364.0923.
2
H-1,2-azaphosphindoles 11a and 11a'
a yellow solid containing an inseparable mixture of two diastereoisomers, 479 mg, 62 % yield. 31P NMR (121 MHz, CDCl
): δ
3
1
8
7
8.01 (s, minor isomer) and 87.88 (s, major isomer) ppm; H NMR (300 MHz, CDCl
3
): δ 2.45-2.61 (m, 4H), 7.49-7.67 (m, 10H),
.85-7.98 (m, 8H); 13C NMR (75 MHz, CDCl
): δ 27.61 (m, CH
, mixture of two isomers), 126.82 (m, CH, mixture of two
3
2
isomers), 128.87(s, CH, minor isomer), 128.92(s, CH, major isomer), 129.01(s, CH, mixture of two isomers), 129.17(s, CH,
minor isomer), 129.22(s, CH, major isomer), 132.11 (t, J =4.5 Hz, CH, mixture of two isomers), 132.25 (d, J=2.3 Hz, CH,
mixture of two isomers), 132.74 (s, CH, mixture of two isomers), 134.06 (td, J =3.8, 11.3 Hz, C, mixture of two isomers), 139.62
(
t, J =17.3 Hz, C, mixture of two isomers), 141.21 (td, J =9.8, 38.3 Hz, C, mixture of two isomers), 180.12 (m, C=N, mixture of
+
two isomers). HRMS: m/z calcd for C26
H
23
N
2
P
2
S
2
[M+H] : 513.0778; found: 513.0780. Anal. Calcd for C28
H
22
N
2
P
2
S
2
: C 65.61,
H 4.33, N 5.47; found: C 65.36, H 4.65, N 5.27.
2
H-1,2-azaphosphindoles 11b and 11b'
a yellow solid containing an inseparable mixture of two diastereoisomers, 487 mg, 60 % yield. 31P NMR (121 MHz, CDCl
): δ
3
1
8
7
7.65 (s, minor isomer) and 87.47 (s, major isomer) ppm; H NMR (300 MHz, CDCl
3
): δ 2.34-2.53 (m, 10H), 7.46-7.67 (m, 10H),
.78-7.94 (m, 6H); 13C NMR (75 MHz, CDCl
): δ 21.86 (s, CH
, mixture of two isomers), 27.80 (td, J =3.8, 27.8 Hz, CH
3
3
2
,
mixture of two isomers), 127.36 (dd, J =6.8, 12.0 Hz, CH, mixture of two isomers), 128.73 (d, J =4.5 Hz, C, mixture of two
isomers), 128.82(s, C, minor isomer), 128.87(s, C, major isomer), 129.13(s, C, minor isomer), 129.18(s, C, major isomer),
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