KONDRASHOV et al.
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spectrum (DMSO-d6), δ, ppm, amide IVa: 5.19 d (1H,
CH, 3JCH–NH 10.5 Hz), 7.0–7.6 m (10H, 2C6H5), 9.14 d
(1H, NH, 3JCH–NH 10.5 Hz); amide VIa: 5.20 d (1H, CH,
3JCH–NH 10.5 Hz), 7.0–7.6 m (10H, 2C6H5), 9.09 d (1H,
NH, 3JCH–NH 10.5 Hz). 13C NMR spectrum (DMSO-d6),
δ, ppm, amide IVa: 68.24 (CBr2Cl), 72.60 (CH), 126.32,
127.22, 128.35, 128.42, 129.85, 132.01, 133.97, 140.39
(2C6H5); amide VIa: 49.94 (CBr3), 72.87 (CH), 126.36,
127.11, 128.26, 128.37, 129.92, 131.96, 134.20, 140.33
(2C6H5).
benzenesulfonic acid N-(1-tolyl-2,2-dibromo-2-chloro-
ethyl)amide (Vb) and N-(1-tolyl-2,2,2-tribromoethyl)-
1
amide (VIIb) in a ratio 4:3 (1H NMR data). H NMR
spectrum (DMSO-d6), δ, ppm, amide Vb: 2.20 s (3H, CH3),
5.11 d (1H, CH, 3JCH–NH 10.6 Hz), 6.91, 7.30, 7.52 m
3
(8H, 2C6H4), 9.10 d (1H, NH, JCH–NH 10.6 Hz);
amide VIIb: 2.20 s (3H, CH3), 5.11 d (1H, CH ,
3JCH–NH 10.6 Hz), 6.90, 7.30, 7.50 m (8H, 2C6H4),
9.05 d (1H, NH, 3JCH–NH 10.6 Hz). 13C NMR spectrum
(DMSO-d6), δ, ppm, amide Vb: 20.69 (CH3), 68.15
(CBr2Cl), 72.59 (CH), 127.95, 128.46, 128.61, 129.92,
131.01, 137.07, 137.98, 139.20 (2C6H4); amide VIIb:
20.69 (CH3), 49.80 (CBr3), 72.88 (CH), 127.86, 128.49,
128.56, 130.00, 131.25, 137.03, 137.90, 139.12 (2C6H4).
C-Amidoalkylation of toluene with a mixture of
imines IIa and IIIa was carried out similarly using
3.5 g of a mixture of imines IIa and IIIa and 10 ml of
toluene. We obtained 3.8 g of a mixture of benzene-
sulfonic acid N-(1-tolyl-2,2-dibromo-2-chloroethyl)-
amide (Va) and N-(1-tolyl-2,2,2-tribromoethyl)amide
(VIIa) in a ratio 4:3 (1H NMR data). 1H NMR spectrum
(DMSO-d6), δ, ppm, amide Va: 2.17 s (3H, CH3), 5.14 d
(1H, CH,3JCH–NH 10.5 Hz), 6.8–7.6 m (9H, C6H5+C6H4),
9.07 d (1H, NH, 3JCH–NH 10.5 Hz); amide VIIa: 2.16 s
(3H, CH3), 5.15 d (1H, CH, 3JCH–NH 10.5 Hz), 6.8–7.6 m
C-Amidoalkylation of benzene with imine IIc. To
a solution of imine IIc obtained as above described from
2.18 g of dichloroamide Ic and tribromoethylene was
added 12 ml of benzene and 0.5 ml of oleum. After
stirring for 3 h the solvent was removed in a vacuum,
the residue was washed with water, dried, and recrystal-
lized from hexane. Yield of trifluoromethanesulfonic acid
N-(1-phenyl-2,2-dibromo-2-chloroethyl)amide (IVc)
1.11 g (25%), mp 136–138°C. IR spectrum (KBr), ν, cm–1:
1130, 1200, 1230, 1375 (CF3SO2), 3275 (NH). 1H NMR
3
(9H, C6H5+C6H4), 9.02 d (1H, NH, JCH–NH 10.5 Hz).
13C NMR spectrum (DMSO-d6), δ, ppm, amide Va: 20.63
(CH3), 68.69 (CBr2Cl), 72.46 (CH), 126.33, 127.79,
128.42, 129.73, 131.15, 131.92, 137.71, 140.53
(C6H5+C6H4); amide VIIa: 21.03 (CH3), 50.49 (CBr3),
72.75 (CH), 126.36, 127.69, 128.37, 129.81, 131.37,
131.86, 137.61, 140.45 (C6H5+C6H4).
3
spectrum, δ, ppm: 5.29 d (1H, CH, JCH–NH 10.2 Hz),
3
6.39 d (1H, NH, JCH–NH 10.2 Hz), 7.35–7.55 m (5H,
C6H5). 13C NMR spectrum, δ, ppm: 65.45 (CBr2Cl),
1
73.20 (CH), 119.04 q (CF3, JC–F 321.7 Hz), 128.44,
129.29, 130.06, 133.51 (C6H5).
C-Amidoalkylation of benzene with a mixture of
imines IIb and IIIb was carried out similarly using
4.0 g of a mixture of imines IIb and IIIb and 12 ml of
benzene. We obtained 4.1 g of a mixture of 4-chloro-
benzenesulfonic acid N-(1-phenyl-2,2-dibromo-2-chloro-
ethyl)amide (IVb) and N-(1-phenyl-2,2,2-tribromoethyl)-
C-Amidoalkylation of toluene with a mixture of
imines IIc and IIIc was performed in the same way using
a mixture of imines IIc and IIIc prepared from 2.18 g of
dichloroamide Ic and tribromoethylene. Yield of
a mixture of trifluoromethanesulfonic acid N-(1-tolyl-
2,2-dibromo-2-chloroethyl)amide (Vc) and N-(1-tolyl-
2,2,2-tribromo-ethyl)amide (VIIc), 1:1, 0.8 g. IR
spectrum (KBr), ν, cm–1: 3250 (NH), 1420, 1370, 1220,
1
amide (VIb) in a ratio 4:3 (1H NMR data). H NMR
spectrum (DMSO-d6), δ, ppm, amide IVb: 5.18 d (1H,
3
CH, JCH–NH 10.8 Hz), 7.0–7.6 m (9H, C6H4+C6H5),
1
1180, 1120 (CF3SO2). H NMR spectrum (CDCl3), δ,
9.20 d (1H, NH, 3JCH–NH 10.8 Hz); amide VIb: 5.19 d
(1H, CH,3JCH–NH 10.8 Hz), 7.0–7.6 m (9H, C6H4+C6H5),
9.15 d (1H, NH, 3JCH–NH 10.8 Hz). 13C NMR spectrum
(DMSO-d6), δ, ppm, amide IVb: 68.36 (CBr2Cl), 73.16
(CH), 127.83, 128.87, 129.04, 130.43, 134.46, 137.53,
139.68 (C6H4+C6H5); amide VIb: 49.93 (CBr3), 73.43
(CH), 127.73, 128.89, 128.99, 130.51, 134.70, 137.50,
139.62 (C6H4+C6H5).
ppm, amide Vc: 2.36 s (3H, CH3), 5.24 d (1H, CH, 3JCH–
10.2 Hz), 6.17 d (1H, NH, 3JCH–NH 10.2 Hz), 7.20,
NH
7.42 AA'BB' (4H, C6H4); amide VIIc: 2.36 s (3H, CH3),
5.28 d (1H, CH, 3JCH–NH 10.2 Hz), 6.18 (1H, NH, 3JCH–
10.2 Hz), 7.20, 7.43 AA'BB' (4H, C6H4). 13C NMR
NH
spectrum (CDCl3), δ, ppm, amide Vc: 21.40 (CH3), 66.05
1
(CBr2Cl), 73.01 (CH), 119.01 q (CF3, JC–F 321.1 Hz),
129.06, 129.12, 130.77, 140.19 (C6H4); amide VIIc:
21.38 (CH3), 46.59 (CBr3), 73.21 (CH), 119.04 q (CF3,
1JC–F 321.0 Hz), 129.14, 129.24, 130.51, 140.22 (C6H4).
19F NMR spectrum, δ, ppm: –76.93 s, –76.89 c. 15N NMR
spectrum δ, ppm: –279.4 (Vc), –278.5 (VIIc). Mass
C-Amidoalkylation of toluene with a mixture of
imines IIb and IIIb was carried out similarly using
4.0 g of a mixture of imines IIb and IIIb and 12 ml of
toluene. We obtained 3.9 g of a mixture of 4-chloro-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007