N-SULFONYL- AND N-PHOSPHORYLBENZIMIDOYLPHOSPHONATES
1215
1
1
145 C (acetone). H NMR spectrum (CDCl3), , ppm:
254 Hz), 176.8 d (C=N, JCP 198 Hz). 19F NMR spec-
trum (CDCl3), F, ppm: 106.18. 31P NMR spectrum
(CDCl3), P, ppm: 4.0. Found, %: C 51.34; H 4.91; P
7.65; S 7.98. C17H19FNO5P. Calculated, %: C 51.13;
H 4.80; P 7.76; S 8.03.
3
3
1.09 t (3H, CH3, JHH 7.2 Hz), 1.20 t (3H, CH3, JHH
7.2 Hz), 3.7 3.8 m (1H, CH2O), 3.90 4.0 m (3H,
2
CH2O), 4.4 br.s (1H, NH), 4.94 d.d.d (1H, CH, JHP
23.7, JHP 3JHH 11 Hz), 6.8 7.5 m (14H, Ar). 19F
3
NMR spectrum (benzene), F, ppm: 113.7. 31P {1H}
Diethyl N-(phenylsulfonyl)-3-fluorobenzimido-
ylphosphonate IIIb. Yield 87%. IR spectrum (in thin
film), , cm : 1070 (POC), 1180, 1350 (S=O), 1260
(P=O), 1610 (C=N). H NMR spectrum (CDCl3), ,
ppm: 1.20 m (6H, CH3), 4.03 4.22 m (4H, CH2),
7.22 t (1H, Ar, JHH 8 Hz), 7.45 7.62 m (6H, Ar),
7.91 d (2H, Ar, JHH 8 Hz). 13C NMR spectrum
3
NMR spectrum (CDCl3), P, ppm: 8.6 d (1P, PN, JPP
1
42 Hz), 16.4 d.d (1P, PC, 3JPP 42, 6JPF 4.6 Hz). Found,
1
%: P 12.47. C23H26FNO6P2. Calculated, %: P 12.55.
Diphenyl -(diethoxyphosphorylamino)-3-
3
fluorobenzylphosphonate IId. Yield 75%, mp 167
3
1
169 C (acetone). H NMR spectrum (CDCl3), , ppm:
3
(CDCl3), C, ppm: 16.0 d (CH3, JCP 6.6 Hz), 64.7 d
3
3
1.08 t (3H, CH3, JHH 7.3 Hz), 1.21 t (3H, CH3, JHH
(CH2, JCP 6 Hz), 115.2 d.d (C2, ArF, JCF 24, JCP
2
2
3
7.2 Hz), 3.7 m (1H, CH2O), 4.0 m (3H, CH2O), 4.3
3.7 Hz), 118.6 d (C4, ArF, JCF 19 Hz), 124.0 t (C6,
2
2
2
br.s (1H, NH), 4.95 d.d.d (1H, CH, JHP 23.8, JHP
3JHH 11 Hz), 6.84 m (2H, Ar), 7.0 7.5 m (12H, Ar).
19F NMR spectrum (C6H6), F, ppm: 112.5. 31P
{1H} NMR spectrum (CDCl3), P, ppm: 8.4 d (1P,
PN, JPP 41 Hz), 16.0 d.d (1P, PC, JPP 41, JPF
1.5 Hz). Found, %: P 12.57. C23H26FNO6P2. Cal-
culated, %: P 12.55.
ArF, JCP = JCP 6 Hz), 127.5 s (C2, C6, ArSO2),
3
4
128.9 s (C3, C5, ArSO2), 130.0 d (C5, ArF, JCF
3
7.8 Hz), 133.5 s (C4, ArSO2), 135.3 d.d (CC=N, JCP
2
3
1
3
3
3
26, JCF 9 Hz), 139.5 s (C SO2), 161.8 d (C F, JCF
1
249 Hz), 176.8 d (C=N, JCP 201 Hz). 19F NMR spec-
trum (CDCl3), F, ppm: 111.54. 31P NMR spectrum
(CDCl3), P, ppm: 3.6. Found, %: C 50.88; H 4.76;
P 7.83; S 8.12. C17H19FNO5PS. Calculated, %: C
51.13; H 4.80; P 7.76; S 8.03.
N-[(Diphenylphosphinoyl)(3-fluorophenyl)me-
thyl]benzenesulfonamide was prepared similarly to
[7]; yield 54%, mp 225 C. 19F NMR spectrum
(CDCl3), F, ppm: 113.75. 31P NMR spectrum
(C6H6), P, ppm: 33.3. Found, %: C 64.82; H 4.47.
C25H21FNO3PS. Calculated, %: C 64.51; H 4.55.
Diethyl N-(diethoxyphosphoryl)benzimidoyl-
phosphonate IVa. Yield 89%, bp 175 180 C
(0.05 mm Hg). IR spectrum (in thin film), , cm :
1
1
1240, 1250 (P=O), 1650 (C=N). H NMR spectrum
(CDCl3), , ppm: 0.78 m (6H, CH3), 0.92 m (6H,
CH3), 3.64 m (4H, OCH2), 3.85 m (4H, OCH2), 7.09
m (3H, Ph), 7.7 m (2H, Ph). 13C NMR spectrum
Imidoylphosphonates III and IV. To a solution
of 0.02 mol of chlorine in 60 ml of carbon tetrachlo-
ride, 0.044 mol of anhydrous pyridine was added
dropwise with stirring and cooling to 0 C. The result-
ing mixture was stirred for an additional 30 min and
then was gradually warmed to room temperature.
After that, 0.02 mol of appropriate amide were added
in portions. The reaction mixture was stirred for 8
10 h at room temperature, pyridine hydrochloride was
filtered off, and the filtrate was evaporated in a
vacuum.
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(CDCl3), C, ppm: 15.1 d (CH3, JCP 6.4 Hz), 15.5 d
3
2
(CH3, JCP 5.8 Hz), 62.6 d (CH2, JCP 6.7 Hz), 63.3 d
2
(CH2, JCP 6.8 Hz), 127.2, 127.3 (C2, C3, Ph), 136.3
d.d (C1, Ph, 2JCP1 36 Hz, 3JCP 16 Hz), 130.6 s (C4, Ph),
181.0 d (C=N, JCP 195 Hz, JCP 6.5 Hz). 31P {1H}
2
NMR spectrum (CDCl3), P, ppm: 0.49 d (1P, PN,
3
3JPP 118 Hz), 3.81 d (1P, PC, JPP 118 Hz). Found,
%: P 16.29. C15H25HO6P2. Calculated, %: P 16.41.
Diethyl N-(phenylsulfonyl)-4-fluorobenzimido-
ylphosphonate IIIa. Yield 83%. IR spectrum (in thin
Diphenyl N-diethoxyphosphoryl-4-chlorobenz-
imidoylphosphonate IVb. Yield 80%. Viscous liquid.
1
film), , cm : 1070 (POC), 1180, 1350 (S=O), 1260
1
IR spectrum (in thin film), , cm : 1215 (POC),
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1
(P=O), 1610 (C=N). H NMR spectrum (CDCl3), ,
1220, 1285 (P=O), 1645 (C=N). H NMR spectrum
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4
ppm: 1.19 m (6H, CH3), 4.03 4.26 m (4H, CH2),
(CDCl3), , ppm: 1.09 d.t (6H, CH3, JHH 7.2, JPH
3
3
7.19 t (2H, Ar, JHH 8 Hz), 7.52 t (2H, Ar, JHH
0.9 Hz), 3.9 m (4H, OCH2), 7.1 7.4 m (10H, OPh),
3
3
3
8 Hz), 7.62 t (1H, Ar, JHH 8 Hz), 7.87 7.94 m (4H,
7.40 d (2H, Ar, JHH 8 Hz), 7.83 d (2H, Ar, JHH
Ar). 13C NMR spectrum (CDCl3), C, ppm: 15.8 d
8 Hz). 31P NMR spectrum (benzene), P, ppm: 5.2 d
(1P, PC, JPP 126 Hz), 0.5 d (1P, PN, JPP 126 Hz).
Found, %: P 12.09. C23H24ClNO6P2. Calculated, %:
P 12.20.
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2
1
3
(CH3, JCP2 7 Hz), 64.5 d (CH2, JCP 7 Hz), 115.3 d
(C3, ArF, JCF 23 Hz), 127.2 s (C2, C6, ArSO2), 128.8
s (C3, C5, ArSO2), 129.6 d.d (CC=N, JCP 25, JCF
2
2
3 Hz), 131.0 d.d (C2, ArF, JCF 9, JCP 4 Hz), 133.3 s
3
3
Diphenyl N-diethoxyphosphoryl-4-fluorobenz-
imidoylphosphonate IVc. Yield 84%. Viscous oil.
(C4, ArSO2), 139.6 s (C SO2), 164.5 d (C F, JCF
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006