REACTION OF PHOSPHORIC (PHOSPHONIC) ACIDS AMIDES
1613
31P NMR spectrum (acetone): d 59.5, 0.5 ppm. Found,
%: P 18.21. C9H19ClN2O5P2. Calculated, %: P 18.65.
N-[O-phenyl(chloromethyl)phosphonyl]-N'-ethyl-
N'-[(O,O-diethyl)phosphoryl]urea (IIIc). Yield 89%,
1
nD20 1.4966. IR spectrum (KBr), n, cm : 1060 (POEt),
N-Ethylisouroniomethyl(hydroxy)phosphonate
(V). To a solution of 0.38 g (1 mmol) of phosphonate IVc
in 5 ml of anhydrous benzene was added 0.2 g (10 mmol)
of water, and the mixture was heated for 1 h at 80°C.
The separated precipitate was filtered off and washed
with benzene. Yield of compound V 0.13 g (87%),
1170, 1200 (POPh), 1270, 1295 (P=O), 1590 (Ph), 1695
(C=O), 3130 (NH). 1H NMR spectrum (CCl4), d, ppm:
1.17 m (9H, CH3CH2O, CH3CH2N), 3.4 m (2H, CH2N),
4.03 m (5H, OCH2, ClCH2), 7.2 m (5H, Ph), 9.63 br.s
(1H, NH). 31P NMR spectrum (acetone): d 13.9, 2.4 ppm.
Found, %: Cl 8.57; P 14.78. C14H23ClN2O6P2.Calculated,
%: Cl 8.59; P 15.01.
1
mp 191193°C. H NMR spectrum (D2O), d, ppm:
1.21 m (3H, CH3CH2), 3.2 m (2H, CH2N) 4.3 m (2H,
CH2P). 31P NMR spectrum (acetone): d 10.58 ppm.
Found, %: C 26.49; H 6.07; N 15.14; P 17.48.
C4H11N2O4P. Calculated, %: C 26.38; H 6.10; N 15.38;
P 17.00.
N-Bis(chloromethyl)phosphinyl-N'-ethyl-N'-
[(O,O-diethyl)phosphoryl]urea (IIId). Yield 63%, mp
1
4951°C. IR spectrum (KBr), n, cm : 1023 (POEt), 1238,
1
1252 (P=O), 1683 (C=O), 3169 (NH). H NMR spec-
Diethoxy[N-(4-thioxo-4-phenoxy-D21,3,4-thiaza-
phospholin-2-yl)-N-methyl]amidophosphate (VIII).
To a solution of 0.12 g (5.18 mmol) of NaH in 50 ml of
anhydrous ether under an atmosphere of dry argon was
added dropwise at stirring 0.7 g (5.18 mmol) of
amidophosphate IIa. The reaction mixture was stirred
for 4.5 h at 30°C, then 1.36 g (5.18 mmol) of isothio-
cyanatophosphonate VI was added dropwise. In 4 days
NaCl was separated, and solvent was removed. The resi-
due was subjected to chromatography on Al2O3 (neutral,
II grade Brockmann activity; eluent chloroform). Yield
trum (CCl4), d, ppm: 1.3 t (9H, CH3CH2), 3.4 m (2H,
CH2N), 4.1 m (8H, OCH2, ClCH2), 9.4 br.s (1H, NH).
31P NMR spectrum (acetone): d 27.0, 4.0 ppm. Found,
%: C 29.33; H 5.35; Cl 20.32; N 7.30; P 16.75.
C9H20Cl2N2O5P2. Calculated, %: C 29.28; H 5.49;
Cl 19.21; N 7.59; P 16.78.
Diethoxy[N-(4-oxo-4-chloromethyl-D21,3,4-
oxazaphospholin-2-yl)-N-methyl]amidophosphate
(IVb). To a solution of 0.5 g (1.41 mmol) of diphospho-
rylated urea IIIb in 5 ml of anhydrous benzene under an
atmosphere of dry argon was added dropwise at stirring
0.2 g (1.98 mmol) of triethylamine. In 20 days the triethy-
lamine hydrochloride was filtered off, and the solvent was
evaporated in a vacuum to obtain a residue as a viscous
transparent substance. Yield 0.4 g (89%). 1H NMR spec-
trum (C6D6), d , ppm (J, Hz): 1.14 m (6H, CH3CH2),
3.35 d (3H, CH3N, 3JPNCH 7.7), 3.58 d (2H, ClCH2, 2JPCH
9.4), 4.24 m (6H, CH2O, CH2P). 31P NMR spectrum: d
58.68, 0.49 ppm. Found, %: P 19.15. C8H17ClN2O5P2.
Calculated, %: P 19.47.
1.53 g (93%), nD20 1.5750. IR spectrum (KBr), n, cm :
1
695 (P=S), 1030 (POEt), 1165, 1200 (POPh), 1280 (P=O),
1530 (C=N), 1585 (Ph). 1H NMR spectrum (CDCl3), d,
3
ppm (J, Hz): 1.34 t (3H, CH3CH2, JHCCH 6.3), 1.36 t
(3H, CH3CH2, 3JHH 6.3), 3.29 d (3H, CH3N, 3JPNCH 7.0),
3.64 m (2H, CH2P), 4.15 m (4H, OCH2), 7.28 m (5H,
Ph). 13C NMR spectrum (CDCl3), ppm (J, Hz): 15.62
2
2
(C1), 15.75 (C1), 64.39 (C2, JPC 5.5), 64.22 (C2, JPC
5.5), 36.66 (C3, 1JCH 149, 2JPC 12), 171.0 (C4, 2JPC 13),
35.27 (C5, JPC 56), 150.55 (Ci, JPC 10), 121.23 (CO,
3JPC 5), 129.21 (Cm), 124.84 (Cp). 31P NMR spectrum
(acetone): d 112.38, 0.81 ppm. Found, %: P 15.38.
C13H20N2O4P2S2. Calculated, %: P 15.71.
2
2
Diethoxy[N-(4-oxo-4-phenoxy-D21,3,4-oxaza-
phospholin-2-yl)-N-ethyl]amidophosphate (IVc).
1
Yield 88%, mp 6264°C. IR spectrum (KBr), n, cm :
1026 (POEt), 1200, 1217 (POPh), 1267, 1282 (P=O), 1587
[N-(4-Thioxo-4-chloromethyl-D21,3,4-thiaza-
phospholin-2-yl)-N-phenyl]amidobis(chloromethyl)-
phosphinate (XIV). To a mixture of 0.54 g (2.27 mmol)
of amidophosphinate X and 0.23 g (2.27 mmol) of tri-
ethylamine in 10 ml of anhydrous benzene was added
0.50 g (2.27 mmol) of isothiocyanate IX. In 10 days the
triethylamine hydrochloride was removed, the solvent was
evaporated, and the viscous residue was kept in a vacuum
(0.01 mm Hg) to the constant weight. We obtained
0.85 g (88%) of compound XIII. IR spectrum (KBr), n,
1
(Ph), 1600 (C=N). H NMR spectrum (C6D6), d, ppm:
0.97 m (9H, CH3CH2), 3.82 m (8H, NCH2, OCH2, CH2P),
7.0 m (5H, Ph). 31P NMR spectrum (acetone): d 46.9,
1.8 ppm. Found, %: P 16.11. C14H22N2O6P2. Calculated,
%: P 16.49.
Diethoxy[N-(4-oxo-4-chloromethyl-D21,3,4-
oxazaphospholin-2-yl)-N-ethyl]amidophosphate
1
(IVd). Yield 92%. H NMR spectrum (C6D6), d, ppm
(J, Hz): 1.38 m (9H, CH3CH2), 2.66 m (2H, NCH2),
3.63 d (2H, ClCH2, 2JPCH 9.4), 4.07 m (6H, CH2O, CH2P).
1
cm : 690 (P=S), 1270 (P=O), 1570 (C=N), 1605 (Ph).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005