SYNTHESIS OF -AMINOPHOSPHONATES
485
Table 2. Yield, boiling and melting points, and some spectral data of compounds Ia g
bp,
C
31P NMR
Compd.
no.
Yield,
%
(p, mm Hg), spectrum,
mp,
1H NMR spectrum (CDCl3), , ppm
C
, ppm
29.05
Ia
Ib
Ic
80
77
74
79
76
108 110 (10)
70 (15)
124 (8)
90 91
0.98 s (3H, CH3CH2CH2), 1.1 m (11H, C6H11-cyclo), 1.24 t (6H,
CH3CH2O), 1.42 m (2H, CH3CH2CH2), 1.78 m (2H, CH3CH2CH2),
2.82 m (1H, CHP, J 17 Hz), 4.10 q (4H, CH3CH2O)
0.87 s (3H, CH3CH2CH2), 1.04 s [9H, C(CH3)3], 1.26 t (6H,
29.09
25.30
22.92
21.61
CH3CH2O), 1.45
m (2H, CH3CH2CH2), 1.68 m (2H,
CH3CH2CH2), 2.86 m (1H, CHP, J 17Hz), 4.06 q (4H, CH3CH2O)
1.12 m (11H, C6H11-cyclo), 1.28 t (6H, CH3CH2O), 4.14 q (4H,
CH3CH2O), 4.66 d (1H, CHP, J 17.9 Hz), 6.41, 7.18 m (5H,
CHC6H5)
1.22 t (6H, CH3CH2O), 3.92 q (4H, CH3CH2O), 4.68 d(1H, CHP,
J 17.9 Hz), 6.55, 7.30 m (5H, CHC6H5), 7.07, 7.43 m (5H,
NHC6H5)
1.04 s [9H, C(CH3)3], 1.24 t (6H, CH3CH2O), 3.98 q (4H,
CH3CH2O), 4.68 d (1H, CHP, J 17.9 Hz), 6.99, 7.57 m (3H,
C4H3æ)
1.22 t (6H, CH3CH2O), 4.08 q (4H, CH3CH2O), 4.54 d (1H, CHP,
J 16.4 Hz), 7.16 m (5H, NHC6H5), 7.60, 8.40 m (4H, C5H4N)
0.94 s(3H, CH3), 1.04 c (3H, CH3CH2), 1.12 m (11H, C6H11-cyclo),
1.28 t (6H, CH3CH2O), 1.51 m (2H, CH3CH2), 4.14 q (4H,
CH3CH2O)
Ida
Ie
86 (8)
Ifa
Ig
78
77
121 122
22.60
28.52
Oily
substance
a
Constants of compounds Id and If are identical to published data [4, 5].
Table 3. Elemental analyses of compounds Ia c, Ie, Ig
Found, %
Compd.
Calculated, %
H
Formula
no.
C
H
P
C
P
Ia
Ib
Ic
Ie
Ig
57.31
54.10
62.70
53.93
57.70
10.31
10.89
8.58
8.92
10.00
10.62
11.83
9.57
10.56
10.52
C14H30NO3P
C12H28NO3P
C17H28NO3P
C13H24NO4P
C14H30NO3P
57.73
54.34
62.77
53.97
57.73
10.31
10.57
8.61
8.30
10.31
10.65
11.70
9.54
10.72
10.65
EXPERIMENTAL
sium carbonate and 5 mol% TBAI. The mixture was
stirred for 15 min at room temperature, then
0.025 mol (3.8 g, 4.5 ml) of N-cyclohexylbutyral-
imine was added. The reaction mixture was heated to
40 45 C for 5 h. Then to the solution was added
15 ml of water, and the mixture was stirred till
K2CO3 dissolved. The organic layer was separated,
the water layer was extracted with chloroform (3
5 ml). The solvent was distilled off, the residue was
distilled in a vacuum. Yield of compound Ia 5.8 g
(80%).
1H NMR spectra were recorded on spectrometer
Tesla BS-147 with TMS as external reference.
31P NMR spectra were registered on Varian FT-80
instrument with TMS as internal reference, 85%
H3PO4 as external reference.
Reaction between O,O-diethyl phosphite and
N-cyclohexylbutyralimine (Ia) (general procedure).
To 0.025 mol (3.5 g, 3.2 ml) of O,O-diethyl phos-
phite in 10 ml of anhydrous benzene was added
0.05 mol (6.9 g) of freshly calcined powder of potas-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002