C-Phosphorylated N-(Trichloroethylidene)sulfonamides
6.3 mmol) and triethyl phosphite (1.1 g, 6.3 mmol); white solid; N-[2,2,2-Trichloro-1-(diphenylphosphanyl)ethyl]-p-toluenesulfon-
FULL PAPER
m.p. 113 °C; yield: 2.42 g (92%). IR (KBr): ν˜ ϭ 1040 (POC), 1180,
amide (5f): This compound was prepared from sulfonamide 3b
1340 (SϭO), 1270 (PϭO), 3140 (NH) cmϪ1
.
1H NMR (CDCl3): (1.73 g, 5.1 mmol) and ethyl diphenylphosphinite (1.18 g,
3
3
δ ϭ 1.28 (t, JH,H ϭ 7 Hz, 3 H, CH3), 1.32 (t, JH,H ϭ 7 Hz, 3 H,
5.1 mmol); white solid; m.p. 191 °C; yield: 2.1 g (81%). IR (KBr):
2
3
1
CH3), 3.98Ϫ4.22 (m, 4 H, CH2O), 4.68 (dd, JH,P ϭ 19.2, JH,H
ϭ
ν˜ ϭ 1170, 1340 (SϭO), 1205 (PϭO), 3170 (NH) cmϪ1. H NMR
3
3
2
3
9.9 Hz, 1 H, CHP), 6.08 (dd, JH,H ϭ 9.9, JH,P ϭ 7.5 Hz, 1 H,
(CDCl3): δ ϭ 2.34 (s, 3 H, CH3), 5.27 (dd, JH,P ϭ 9.3, JH,H ϭ
3
3
3
3
NH), 7.49 (t, JH,H ϭ 8 Hz, 2 H, m-CϪH, Ph), 7.57 (t, JH,H
8 Hz, 1 H, p-CϪH, Ph), 7.92 (d, JH,H ϭ 8 Hz, 2 H, o-CϪH, Ph)
ϭ
6 Hz, 1 H, CHP), 6.41 (dd, JH,H ϭ 6, JH,H ϭ 6 Hz, 1 H, NH),
3
7.05 (d, 3JH,H ϭ 8 Hz, 2 H, Ar), 7.44Ϫ7.64 (m, 8 H, Ar), 7.82Ϫ7.91
ppm. 31P NMR (CDCl3):
δ
ϭ
14.4 ppm. C12H17Cl3NO5PS
(m, 4 δ ϭ 29.5 ppm.
H, Ar) ppm. 31P NMR (CDCl3):
(424.66): calcd. C 33.94, H 4.03, Cl 25.05, N 3.30, P 7.29; found C
33.81, H 3.92, Cl 25.20, N 3.34, P 7.23.
C21H19Cl3NO3PS (502.78): calcd. C 50.16, H 3.81, Cl 21.16, N
2.79, P 6.16, S 6.38; found C 50.24, H 3.87, Cl 21.20, N 2.75, P
6.14, S 6.41.
N-[2,2,2-Trichloro-1-(diethoxyphosphoryl)ethyl]-p-toluenesulfon-
amide (5b): This compound was prepared from sulfonamide 3b
(7.85 g, 23.3 mmol) and triethyl phosphite (3.9 g, 23.3 mmol); white
solid; m.p. 138 °C; yield: 8.3 g (96%). IR (KBr): ν˜ ϭ 1050 (POC),
General Procedure for Preparation of Diphosphorylated N-Ethenyl-
sulfonamides 8: An equimolar amount of the appropriate phosphite
or phosphinite was added to a cooled (ice) and stirred benzene
solution of imidoylphosphonate 1. After 1 h, the solvent was eva-
porated and the oily residue was washed with petroleum ether and
dried in vacuo.
1170, 1340 (SϭO), 1260 (PϭO), 3140 (NH) cmϪ1
.
1H NMR
3
(CDCl3): δ ϭ 1.31 (t, JH,H ϭ 7.2 Hz, 3 H, CH3CH2), 1.34 (t,
3JH,H ϭ 7.2 Hz, 3 H, CH3CH2), 2.42 (s, 3 H, CH3Ar), 4.04Ϫ4.25
2
3
(m, 4 H, CH2O), 4.68 (dd, JH,P ϭ 19.8, JH,H ϭ 9.8 Hz, 1 H,
N-[2,2-Dichloro-1-(diethoxyphosphoryl)ethenyl]-N-diethoxyphos-
phoryl-p-toluenesulfonamide (8a): This compound was prepared
from imidoylphosphonate 1b (0.19 g, 0.43 mmol) and triethyl phos-
phite (0.07 g, 0.43 mmol); colorless oil; yield: 0.2 g (87%). IR (film):
3
3
CHP), 5.7 (dd, JH,H ϭ 9.8, JH,P ϭ 9.8 Hz, 1 H, NH), 7.29 (d,
3JH,H ϭ 8 Hz, 2 H, Ar), 7.79 (d, JH,H ϭ 8 Hz, 2 H, Ar) ppm. 31P
3
NMR (CDCl3): δ ϭ 15.1 ppm. C13H19Cl3NO5PS (438.69): calcd.
C 35.59, H 4.37, Cl 24.24, N 3.19, P 7.06; found C 35.60, H 4.26,
Cl 24.45, N 3.35, P 6.89.
1
ν˜ ϭ 1050 (POC), 1180, 1380 (SϭO), 1280 (PϭO) cmϪ1. H NMR
(CDCl3): δ ϭ 1.30Ϫ1.39 (m, 12 H, CH3CH2), 2.44 (s, 3 H, CH3Ar),
3
4-Chloro-N-[2,2,2-trichloro-1-(diethoxyphosphoryl)ethyl]-
benzenesulfonamide (5c): This compound was prepared from ben-
zenesulfonamide 3c (6.8 g, 19.2 mmol) and triethyl phosphite
(3.8 g, 19.2 mmol); white solid; m.p. 117 °C; yield: 8.3 g (94%). IR
4.07Ϫ4.38 (m, 8 H, CH2O), 7.31 (d, JH,H ϭ 8 Hz, 2 H, Ar), 7.93
3
(d, JH,H ϭ 8 Hz, 2 H, Ar) ppm. NMR 31P (CDCl3): δ ϭ Ϫ3.9 (1
P, PN), 9.5 (1 P, PC) ppm. C17H27Cl2NO8P2S (538.32): calcd. C
37.93, H 5.06, Cl 13.17, N 2.60, P 11.51; found C 37.85, H 5.01,
Cl 13.28, N 2.63, P 11.48.
(KBr): ν˜ ϭ 1040 (POC), 1180, 1350 (SϭO), 1260 (PϭO), 3130
3
(NH) cmϪ1
.
1H NMR (CDCl3): δ ϭ 1.31 (t, JH,H ϭ 7 Hz, 3 H,
CH3), 1.34 (t, 3JH,H ϭ 7 Hz, 3 H, CH3), 4.04Ϫ4.29 (m, 4 H, CH2O),
N-[2,2-Dichloro-1-(diethoxyphosphoryl)ethenyl]-N-diisopropoxy-
phoslphorybenzenesulfonamide (8b): This compound was prepared
from imidoylphosphonate 1a (0.17 g, 0.39 mmol) and triisopropyl
phosphite (0.08 g, 0.39 mmol); colorless oil; yield: 0.2 g (91%). IR
4.68 (dd, 2JH,P ϭ 19, 3JH,H ϭ 10 Hz, 1 H, CHP), 6.40 (dd, 3JH,H ϭ
3
3
10, JH,P ϭ 7 Hz, 1 H, NH), 7.47 (d, JH,H ϭ 8 Hz, 2 H, Ar), 7.87
(d, 3JH,H ϭ 8 Hz, 2 H, Ar) ppm. 31P NMR (CDCl3): δ ϭ 14.3 ppm.
C12H16Cl4NO5PS (459.11): calcd. C 31.39, H 3.51, Cl 30.89, N
3.05, P 6.75, S 6.98; found C 31.36, H 3.50, Cl 30.73, N 3.15, P
6.90, S 7.00.
1
(film): ν˜ ϭ 1050 (POC), 1175, 1380 (SϭO), 1275 (PϭO) cmϪ1. H
NMR (CDCl3): δ ϭ 1.30Ϫ1.34 (m, 18 H, CH3), 4.19Ϫ4.31 (m, 4
H, CH2O), 4.78Ϫ4.89 (m, 1 H, CHO), 5.07Ϫ5.17 (m, 1 H, CHO),
3
3
7.51 (t, JH,H ϭ 8 Hz, 2 H, m-CϪH, Ph), 7.63 (t, JH,H ϭ 8 Hz, 1
N-[2,2,2-Trichloro-1-(diisopropoxyphosphoryl)ethyl]benzene-
sulfonamide (5d): This compound was prepared from sulfonamide
3a (3.2 g, 9.9 mmol) and triisopropyl phosphite (2.06 g, 9.9 mmol);
white solid; m.p. 119 °C; yield: 4 g (90%). IR (KBr): ν˜ ϭ 1020
H, p-CϪH, Ph), 8.05 (d, 3JH,H ϭ 8 Hz, 2 H, o-CϪH, Ph) ppm. 31
P
NMR (CDCl3): δ ϭ Ϫ6.9 (1 P, PN), 8.6 (1 P, PC) ppm.
C18H29Cl2NO8P2S (552.34): calcd. C 39.14, H 5.29, Cl 12.84, N
2.54, P 11.22; found C 39.08, H 5.25, Cl 12.91, N 2.53, P 11.19.
(POC), 1175, 1350 (SϭO), 1275 (PϭO), 3140 (NH) cmϪ1
.
1H
2
N-[2,2-Dichloro-1-(diisopropoxyphosphoryl)ethenyl]-N-diethoxy-
phosphoryl-p-toluenesulfonamide (8c): This compound was prepared
from imidoylphosphonate 1e (0.23 g, 0.49 mmol) and triethyl phos-
phite (0.08 g, 0.49 mmol); colorless oil; yield: 0.24 g (89%). IR
(CCl4): ν˜ ϭ 1040 (POC), 1185, 1390 (SϭO), 1280 (PϭO) cmϪ1. 1H
NMR (CDCl3): δ ϭ 1.27Ϫ1.39 (m, 18 H, CH3CH ϩ CH3CH2),
2.43 (s, 3 H, CH3Ar), 4.12Ϫ4.34 (m, 4 H, CH2O), 4.85Ϫ4.95 (m,
2 H, CHO), 7.30 (d, 3JH,H ϭ 8 Hz, 2 H, Ar), 7.94 (d, 3JH,H ϭ 8 Hz,
2 H, Ar) ppm. NMR 31P (CDCl3): δ ϭ Ϫ3.3 (1 P, PN), 7.7 (1 P,
PC) ppm. C19H31Cl2NO8P2S (566.37): calcd. C 40.29, H 5.52, Cl
12.52, N 2.47, P 10.94, S 5.66; found C 40.21, H 5.49, Cl 12.60, N
2.49, P 10.91, S 5.63.
NMR (CDCl3): δ ϭ 1.36 (m, 12 H, CH3), 4.66 (dd, JH,P ϭ 19.8,
3JH,H ϭ 9.6 Hz, 1 H, CHP), 4.76Ϫ4.88 (m, 2 H, CHO), 5.82 (dd,
3
3
3JH,H ϭ 9.6, JH,P ϭ 9.6 Hz, 1 H, NH), 7.50 (t, JH,H ϭ 8 Hz, 2
3
H, m-CϪH, Ph), 7.58 (t, JH,H ϭ 8 Hz, 1 H, p-CϪH, Ph), 7.92 (d,
3JH,H ϭ 8 Hz, 2 H, o-CϪH, Ph) ppm. 31P NMR (CDCl3): δ ϭ
12.2 ppm. C14H21Cl3NO5PS (452.72): calcd. C 37.14, H 4.68, Cl
23.49, N 3.09, P 6.84; found C 37.21, H 4.62, Cl 23.32, N 3.12,
P 6.79.
N-[2,2,2-Trichloro-1-(diisopropoxyphosphoryl)ethyl]-p-toluene-
sulfonamide (5e): This compound was prepared from sulfonamide
3b (3.1 g, 9.2 mmol) and triisopropyl phosphite (1.92 g, 9.2 mmol);
white solid; m.p. 133 °C; yield: 3.8 g (88%). IR (KBr): ν˜ ϭ 1010
(POC), 1175, 1350 (SϭO), 1255 (PϭO), 3150 (NH) cmϪ1
.
1H
N-[2,2-Dichloro-1-(diisopropoxyphosphoryl)ethenyl]-N-diisopro-
NMR (CDCl3): δ ϭ 1.37 (m, 12 H, CH3CH), 2.42 (s, 3 H, CH3Ar), poxyphosphorylbenzenesulfonamide (8d): This compound was pre-
3
4.65 (dd, 2JH,P ϭ 19.5, JH,H ϭ 9 Hz, 1 H, CHP), 4.76Ϫ4.88 (m, 2 pared from imidoylphosphonate 1d (0.095 g, 0.21 mmol) and triiso-
3
3
H, CHO), 5.67 (dd, JH,H ϭ 9, JH,P ϭ 9 Hz, 1 H, NH), 7.28 (d,
propyl phosphite (0.044 g, 0.21 mmol); white solid; m.p. 60 °C;
3JH,H ϭ 8 Hz, 2 H, Ar), 7.80 (d, JH,H ϭ 8 Hz, 2 H, Ar) ppm. 31P yield: 0.1 g (86%). IR (CCl4): ν˜ ϭ 1040 (POC), 1190, 1390 (SϭO),
NMR (CDCl3): δ ϭ 12.2 ppm. C15H23Cl3NO5PS (466.75): calcd.
1280 (PϭO) cmϪ1 1H NMR (CDCl3): δ ϭ 1.32Ϫ1.42 (m, 24 H,
C 38.60, H 4.97, Cl 22.79, N 3.00, P 6.64; found C 38.64, H 4.92, CH3), 4.78Ϫ4.99 (m, 3 H, CHO), 5.08Ϫ5.19 (m, 1 H, CHO), 7.50
3
.
3
Cl 22.67, N 3.12, P 6.71.
(t, 3JH,H ϭ 8 Hz, 2 H, m-CϪH, Ph), 7.62 (t, JH,H ϭ 8 Hz, 1 H, p-
Eur. J. Org. Chem. 2004, 3643Ϫ3649
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3647