Alkylation and acylation of C-phosphorylated acetamidines involving CH-acidic methylene group

Article abstract of DOI:10.1134/S1070363211040049

Reactions of sodium derivatives of C-phosphorylated acetamidines containing CH-acidic methylene group with alkyl and acyl halides were studied. The interaction occurs selectively to form the products of alkylation and acylation of methylene group, respect

Full text of DOI:10.1134/S1070363211040049

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 4, pp. 642–646. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.E. Shishkin, E.V. Mednikov, M.A. Shevchenko, O.V. Anishchenko, Yu.V. Popov, 2011, published in Zhurnal Obshchei Khimii,
2011, Vol. 81, No. 4, pp. 549–553.
Alkylation and Acylation of C-Phosphorylated Acetamidines
Involving CH-Acidic Methylene Group
V. E. Shishkin, E. V. Mednikov, M. A. Shevchenko, O. V. Anishchenko, and Yu. V. Popov
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
e-mail: tons@vstu.ru
Received April 22, 2010
Abstract—Reactions of sodium derivatives of C-phosphorylated acetamidines containing CH-acidic methylene
group with alkyl and acyl halides were studied. The interaction occurs selectively to form the products of
alkylation and acylation of methylene group, respectively. A convenient method for the synthesis of C-
alkylated and C-acylated derivatives of C-phosphorylated acetamidines was developed.
DOI: 10.1134/S1070363211040049
Alkylation and acylation of CH-acids are widely
used in the production of biologically active com-
pounds [1]. Previously, it was found that the C-phos-
phorylated acetamidines exhibit CH-acid properties,
and the reaction of these compounds with sodium
affords the corresponding monosodium derivatives [2].
In the course of studying these properties and synthesis
of new substances with biological activity, we
examined the alkylation and acylation of the sodium
derivatives of C-phosphorylated acetamidines.
Various alkyl halides: methyl iodide, ethyl bromide,
butyl iodide, benzyl chloride, chloroacetic acid ethyl
ester [3] were used as alkylating agents. The reactions
occur selectively via alkylation of methylene group to
form the corresponding products and sodium halide:
O
O
NCR1
O
O
NCR1
NR22
+ R3CH2X
(RO)2PCHC
(RO)2PCHNaC
−NaX
NR22
CH2
R3
I−IX
R = i-С3Н7, С4Н9; R1 = СН3, С6Н5; R2 = C2H5, C3H7, C4H9, i-C4H9; R3 = H (a), CH3 (b), C3H7 (c), C6H5 (d), COOC2H5 (e);
X = I (а, c), Br (b), Cl (d, e).
With 1,2-dichloroethane as alkylating agent at the
molar ratio of the reagents 2:1 formed bisamidines:
O
O
NCR1
O
(C4H9O)2PCHC
O
NCR1
N(C3H7)2
O
NCR1
CH2
+ ClCH2CH2Cl
2 (C4H9O)2PCHNaC
N(C3H7)2
−2 NaCl
H2C
(C4H9O)2PCHC
O
N(C3H7)2
X−XI
R1 = СН3, С6Н5.
642

ALKYLATION AND ACYLATION OF C-PHOSPHORYLATED ACETAMIDINES
643
The sodium derivatives of C-phosphorylated acet-
amidines were obtained as described in [2]. To the
freshly prepared sodium derivative in dioxane a
calculated amount of alkyl halide in dioxane was
added dropwise under vigorous stirring. In the case of
highly volatile halides 10–20% excess was used, while
the poorly volatile halides were used in equimolar
amount. To accelerate the alkylation process (espe-
cially with chlorinated alkanes) the temperature was
gradually increased to 40–50°C. In order to isolate the
target product the sodium halide was filtered off, and
the solvent was removed by distillation in a vacuum.
Yields of the alkylation products were 78–87%.
oxane, ether, acetone, and insoluble in water.
Purification of these compounds was carried out by
column chromatography on silica gel μLC 5/40,
eluting with chloroform–diethyl ether–acetone mixture
(1:2:1). Their individuality was monitored by TLC.
The physicochemical properties of the compounds
obtained I–IX are presented in Table 1.
In order to obtain the C-phosphorylated acet-
amidines with new structures and containing functional
groups, we studied the reaction of sodium derivatives
of C-phosphorylated acetamidines with accessible
carboxylic acid chlorides and bromides [4]. The
reactions proceed to form C-acylation products, the
organophosphorus ketones of complex structure:
The synthesized compounds are viscous yellow
liquids, well soluble in such organic solvents as di-
O
O
O
NCR1
O
NCR1
NR22
O
X
+ R3C
(RO)2PCHC
(RO)2PCHNaC
−NaX
NR22
C O
R3
XII−XVI
R = i-C3H7, C4H9; R1 = СН3, С6Н5; R2 = C2H5, C3H7; R3 = CH3 (a), C6H5 (b); Х = Br (a), Cl (а, b).
The reactions were performed at a molar ratio of
reagents 1:1–1.1 and a temperature of 50–60°C in the
anhydrous dioxane medium. The yield of salt is close
to quantitative. To isolate the target substance, sodium
halide was filtered off, and the solvent was removed by
distillation in a vacuum. The C-acylated derivatives
were obtained in yields 80–86%.
The acylation products are yellow liquids, well
soluble in organic solvents and insoluble in water.
Table 1. С-Alkylated derivatives of С-phosphorylated acetamidines
O
O
(RO)2PCHC
CH2
NCR1
NR22
R3
Calculated,
MRD
Found, %
Comp.
no.
Yield,
%
R
R1
R2
R3
nD20
d420
Formula
%
found calculated
N
P
N
P
i-C3H7 CH3 C3H7
H
H
87
85
84
81
83
80
83
78
79
1.4584 1.0114 97.72
1.4934 1.0449 125.96
1.4721 1.0044 120.46
1.4676 1.0739 104.64
1.4622 1.0653 104.81
1.4740 1.0645 122.12
1.5162 1.1159 141.88
1.5104 1.0751 121.93
1.5019 1.0561 130.59
98.10
126.88
121.34
105.34
104.50
123.09
142.57
122.23
131.31
7.64 8.41 С17Н35N2О4P 7.73 8.56
5.93 6.58 С24Н41N2О4P 6.19 6.84
6.21 7.30 С22Н45N2О4P 6.47 7.16
6.78 7.38 С20Н41N2О4P 6.92 7.66
7.08 7.43 С18Н35N2О6P 6.89 7.62
6.31 6.92 С22Н43N2О6P 6.06 6.69
5.08 5.83 С27Н45N2О6P 5.37 5.90
6.48 7.22 С23Н39N2О4P 6.39 7.06
6.27 6.82 С25Н43N2О4P 6.01 6.65
I
C4H9 C6H5 C3H7
II
C4H9 CH3 i-C4H9 CH3
III
IV
V
C4H9 CH3 C2H5 С3Н7
i-C3H7 CH3 C2H5 COOC2H5
C4H9 CH3 C3H7 COOC2H5
C4H9 C6H5 C3H7 COOC2H5
i-C3H7 CH3 C3H7 C6H5
C4H9 CH3 C3H7 C6H5
VI
VII
VIII
IX
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SHISHKIN et al.
Table 2. С-Acylated derivatives of С-phosphorylated acetamidines
O
O
NCR1
NR22
(RO)2PCHC
C O
R3
MRD
Found, %
Calculated, %
Comp.
no.
Yield,
%
R
R1
R2
R3
nD20
d420
Formula
found
calculated
N
P
N
P
C4H9 CH3 C2H5 CH3
C4H9 CH3 C3H7 CH3
C4H9 C6H5 C3H7 CH3
i-C3H7 CH3 C2H5 CH3
i-C3H7 CH3 C2H5 С6Н5
86
84
83
84
80
1.4624 1.1039 97.07
1.4697 1.0964 106.31
1.5028 1.0698 132.59
1.4678 1.0724 93.80
1.4987 1.0927 113.87
96.18
105.48
131.66
93.42
7.35
6.48
5.54
7.81
6.45
7.66 С18Н35N2О5P 7.18
7.30 С20Н39N2О5P 6.69
6.19 С25Н41N2О5P 5.83
8.33 С16Н31N2О5P 7.73
7.50 С21Н33N2О5P 6.60
7.95
7.41
6.46
8.56
7.31
XII
XIII
XIV
XV
XVI
112.90
These compounds were purified by column chro-
matography on silica gel μLC 5/40, eluting with
diethyl ether–acetone mixture (2:1). Their individuality
was monitored by TLC. The physicochemical pro-
perties of the compounds obtained XII–XVI are given
in Table 2.
sodium. To a solution of the resulting acetamidine sodium
derivative was dropwise added 1.26 g (0.0089 mol,
10 mol % excess) of methyl iodide in 3 ml of dioxane
under stirring at 20–30°C. The temperature was raised
to 40°C, and the stirring was continued for 3 h.
Sodium iodide was filtered off, the solvent was re-
moved by distillation in a vacuum at 15–20 hPa. The
residue was evacuated for 1 h at 50°C and 2–4 hPa.
Yield 2.55 g (87%). IR spectrum, ν, cm–1: 982–1070
The composition and structure of all synthesized
compounds were confirmed by the elemental analysis,
molecular refraction, IR and 1H NMR spectra.
1
(POC), 1245 (P=O), 1664 (C=N), 1732 (C=O). H
The computer screening for biological activity of
the obtained С-alkylated and C-acylated derivatives of
C-phosphorylated acetamidines was performed by
means of PASS program of the Orekhovich Insititute
of Biomedical Chemistry, which predicted a high
probability of inhibition of different enzymes (phos-
phatase carboxyesterase, cutinase, amidase, etc). These
compounds are characterized by activity against
psoriasis, osteoporosis, and immunomodulatory action.
NMR spectrum (CCl4), δ, ppm: 1.13 m (6H, CH3),
1.25 d (12H, CH3), 1.36 m (4H, CH2), 1.44 d.d (3Н,
СН3СР), 1.96 s [3Н, СН3С(О)], 2.98 m (1H, CHP),
3.10 m (4Н, NСН2), 4.59 m (2H, CHOP).
N1,N1-Dipropyl-N2-benzoyl(2-dibutoxyphos-
phoryl)propanamidine (II) was prepared similarly
from 1.93 g (0.0044 mol) of N1,N1-dipropyl-N2-
benzoyl(dibutoxyphosphoryl)acetamidine, 0.101
g
(0.0044 mol) of sodium and 0.68 g (0.0048 mol,
10 mol % excess) of methyl iodide. Yield 1.68 g
(85%). IR spectrum, ν, cm–1: 976-1060 (РОС), 1246
Thus, the convenient methods for synthesis of C-
alkylated and C-acylated derivatives of C-phos-
phorylated acetamidines were developed on the basis
of the CH-acid properties of the activated methylene
group of C-phosphorylated acetamidines.
1
(Р=О), 1600 (C–C), 1663 (С=N), 1735 (С=О). H
···
NMR spectrum (CCl4), δ, ppm: 0.76 t (12Н, СН3),
1.27 m (12Н, СН2), 1.53 d.d (3Н, СН3СР), 3.09 m
(1Н, СНР), 3.43 t (4Н, NСН2), 3.76 m (4Н, СН2ОР),
7.32 (5Н, С6Н5).
EXPERIMENTAL
N1,N1-Diisobutyl-N2-acetyl(2-dibutoxyphos-
phoryl)butanamidine (III) was prepared similarly
from 2.8 g (0.0069 mol) of N1,N1-diisobutyl-N2-acetyl-
(dibutoxyphosphoryl)acetamidine, 0.160 g (0.0069 mol)
of sodium and 0.82 g (0.0076 mol, 10 mol % excess)
of ethyl bromide. Reaction time 6 h. Yield 2.5 g
(84%). IR spectrum, ν, cm–1: 974–1065 (РОС), 1232
N1,N1-Dipropyl-N2-acetyl(2-diisopropoxyphos-
phoryl)propanamidine (I). To a solution of 2.83 g
(0.0081 mol) of N1,N1-dipropyl-N2-acetyl(diisopro-
poxyphosphoryl)acetamidine in 6 ml of anhydrous
dioxane was added by portions 0.187 g (0.0081 mol)
of sodium while stirring at 20–30°C. The reaction
mixture was stirred until complete disappearance of
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ALKYLATION AND ACYLATION OF C-PHOSPHORYLATED ACETAMIDINES
645
1
1
(Р=О), 1650 (С=N), 1730 (С=О). H NMR spectrum
1691, 1715 (С=О). H NMR spectrum (CCl4), δ, ppm:
0.75 t (12Н, СН3), 0.82 t (3Н, СН3), 1.26 m (12Н,
СН2), 3.11 d.d [2Н, СН2С(О)], 3.23 m (1Н, СНР),
3.46 t (4Н, NСН2), 3.70 q (2Н, ОСН2), 4.09 m (4Н,
СН2ОР), 7.33 m (5Н,С6Н5).
(CCl4), δ, ppm: 1.04 t (9Н, СН3), 1.15 d (12Н, СН3),
1.33 m (8Н, СН2), 1.54 m (2Н, СН), 1.76 m (2Н,
СН2СР), 1.95 s [3Н, СН3С(О)], 2.92 m (1Н, СНР),
3.44 d (4Н, NСН2), 3.92 m (4Н, СН2ОР).
N1,N1-Diethyl-N2-acetyl(2-dibutoxyphosphoryl)-
hexanamidine (IV) was prepared similarly from
2.66 g (0.0076 mol) of N1,N1-diethyl-N2-acetyl(dibut-
oxyphosphoryl)acetamidine, 0.175 g (0.0076 mol) of
sodium and 1.39 g (0.0076 mol) of butyl iodide.
Reaction time 6 h. Yield 2.46 g (81%). IR spectrum, ν,
cm–1: 978–1064 (РОС), 1244 (Р=О), 1673 (С=N),
1730 (С=О). 1H NMR spectrum (CCl4), δ, ppm: 0.95 t
(15Н, СН3), 1.34 m (12Н, СН2), 1.70 m (2Н, СН2СР),
1.96 s [3Н, СН3С(О)], 2.91 m (1Н, СНР), 3.43 q (4Н,
NСН2), 3.93 m (4Н, СН2ОР).
N1,N1-Dipropyl-N2-acetyl(2-diisopropoxyphos-
phoryl-3-phenyl)propanamidine (VIII) was prepared
similarly from 2.65 g (0.0076 mol) of N1,N1-dipropyl-
N2-acetyl(diisopropoxyphosphoryl)acetamidine, 0.178 g
(0.0076 mol) of sodium and 0.99 g (0.0078 mol) of
benzyl chloride. Reaction time 9 h, temperature 50°С.
Yield 2.58 g (78%). IR spectrum, ν, cm–1: 982–1072
(РОС), 1246 (Р=О), 1594 (C–C), 1664 (С=N), 1738
···
1
(С=О). H NMR spectrum (CCl4), δ, ppm: 1.08 t (6Н,
СН3), 1.25 d (12Н, СН3), 1.54 m (4Н, СН2), 1.97 s
[3Н, СН3С(О)], 2.20 m (2Н, СН2СР), 2.71 m (1Н,
СНР), 3.30 t (4Н, NСН2), 4.56 m (2Н, РОСН), 7.14 m
(5Н, С6Н5).
N1,N1-Diethyl-N2-acetyl(2-diisopropoxyphos-
phoryl-3-ethoxycarbonyl)propanamidine (V) was
prepared similarly from 2.60 g (0.0057 mol) of N1,N1-
diethyl-N2-acetyl(dibutoxyphosphoryl)acetamidine,
0.132 g (0.0057 mol) of sodium and 0.70 g (0.0057 mol)
of ethyl chloroacetate. Yield 2.05 g (83%). IR
spectrum, ν, cm–1: 988–1066 (РОС), 1240 (Р=О), 1660
N1,N1-Dipropyl-N2-acetyl(2-dibutoxyphosphoryl-
3-phenyl)propanamidine (IX) was prepared similarly
from 1.93 g (0.0051 mol) of N1,N1-dipropyl-N2-acetyl-
(dibutoxyphosphoryl)acetamidine, 0.118 g (0.0051 mol)
of sodium and 0.65 g (0.0051 mol) of benzyl chloride.
Reaction time 9 h, temperature 50°С. Yield 1.90 g (79 %).
1
(С=N), 1694, 1720 (С=О). H NMR spectrum (CCl4),
δ, ppm: 1.12 t (6Н, СН3), 1.24 d (12Н, СН3), 1.27 t
(3Н, СН3), 1.97 s [3Н, СН3С(О)], 2.68 d.d [2Н, СН2С
(О)], 2.96 m (1Н, СНР), 3.18 q (4Н, NСН2), 4.07 q
(2Н, ОСН2), 4.62 m (2Н, РОСН).
IR spectrum, ν, cm–1: 978–1067 (РОС), 1245 (Р=О),
1
1600 (C–C), 1668 (С=N), 1734 (С=О). H NMR
···
spectrum (CCl4), δ, ppm: 1.02 t (12Н, СН3), 1.31 m
(12Н, СН2), 1.96 s [3Н, СН3С(О)], 2.28 m (2Н,
СН2СР), 2.96 m (1Н, СНР), 3.31 t (4Н, NСН2), 3.94
m (4Н, РОСН2), 7.13 m (5Н, С6Н5).
N1,N1-Dipropyl-N2-acetyl(2-dibutoxyphosphoryl-
3-ethoxycarbonyl)-propanamidine (VI) was pre-
pared similarly from 2.12 g (0.0056 mol) N1,N1-
dipropyl-N2-acetyl(dibutoxyphosphoryl)acetamidine,
0.129 g (0.0056 mol) of sodium and 0.69 g (0.0056 mol)
of ethyl chloroacetate. Reaction time 4 h, temperature
50°С. Yield 2.07 g (80%). IR spectrum, ν, cm–1: 988–
1060 (РОС), 1246 (Р=О), 1668 (С=N), 1684, 1744
(С=О). 1H NMR spectrum (CCl4), δ, ppm: 0.88 t (12Н,
СН3), 1.18 t (3Н, СН3), 1.34 m (12Н, СН2), 1.96 s
[3Н, СН3С(О)], 2.67 d.d [2Н, СН2С(О)], 3.08 m (1Н,
СНР), 3.32 t (4Н, NСН2), 3.92 q (2Н, ОСН2), 4.08 m
(4Н, СН2ОР).
N1,N1-Dipropyl-N2-benzoyl(2-dibutoxyphosphoryl-
3-ethoxycarbonyl)propanamidine (VII) was prepared
similarly from 2.40 g (0.0055 mol) of N1,N1-dipropyl-
N2-benzoyl(2-dibutoxyphosphoryl)acetamidine, 0.12 g
(0.0055 mol) of sodium, and 0.67 g (0.0055 mol) of
ethyl chlororacetate. Reaction time 4 h, temperature
50°С. Yield 2.40 g (83%). IR spectrum, ν, cm–1: 980–
Ethane-1,2-bis[N1,N1-dipropyl-N2-acetyl(dibut-
oxyphosphoryl)acetamidine] (X) was prepared
similarly from 2.2 g (0.0060 mol) of N1,N1-dipropyl-
N2-acetyl(dibutoxyphosphoryl)acetamidine, 0.14
g
(0.0060 mol) of sodium and 0.29 g (0.0030 mol) of
1,2-dichloroethane. Reaction time 6 h, temperature 50°С.
Yield 1.9 g (85%), nD20 1.4838, d420 1.0417. MRD
213.59, calc. 212.74. IR spectrum, ν, cm–1: 974–1054
1
(РОС), 1240 (Р=О), 1665 (С=N), 1730 (С=О). H
NMR spectrum (CCl4), δ, ppm: 0.96 t (24Н, СН3),
1.32 m (24Н, СН2), 1.74 m (4Н, СН2), 1.96 s [6Н,
СН3С(О)], 2.93 m (2Н, СНР), 3.44 t (8Н, NСН2), 3.94
m (8Н, РОСН2). Found, %: N 7.46; P 7.70.
С38Н76N4О8P2. Calculated, %: N 7.19; P 7.97.
Ethane-1,2-bis[N1,N1-dipropyl-N2-benzoyl(dibut-
oxyphosphoryl)acetamidine] (XI) was prepared
similarly from 3.5 g (0.0082 mol) of N1,N1-dipropyl-
N2-benzoyl(dibutoxyphosphoryl)acetamidine, 0.19 g of
sodium and 0.41 g (0.0041 mol) of 1,2-dichloroethane.
1068 (РОС), 1238 (Р=О), 1600 (C–C), 1672 (С=N),
···
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SHISHKIN et al.
Reaction time 6 h, temperature 50°С. Yield 1.67 g
(83%), nD20 1.5178, d420 1.0795. MRD 250.88, calc.
(dibutoxyphosphoryl)acetamidine, 0.13 g (0.0057 mol)
of sodium, and 0.49 g (0.0063 mol, 10 mol% excess) of
acetyl chloride. Reaction time 2 h. Yield 2.3 g (83%).
IR spectrum, ν, cm–1: 982–1058 (РОС), 1246 (Р=О),
251.70. IR spectrum, ν, cm–1: 976–1066 (РОС), 1246
1
(Р=О), 1610 (C–C), 1678 (С=N), 1738 (С=О). H
···
NMR spectrum (CCl4), δ, ppm: 0.78 t (24Н, СН3),
1.26 m (24Н, СН2), 1.52 m (4Н, СН2), 3.08 m (2Н,
СНР), 3.44 t (8Н, NСН2), 3.92 m (8Н, РОСН2), 7.33
m (10Н, С6Н5). Found, %: N 6.13; P 6.61.
С48Н80N4О8P2. Calculated, %: N 6.02; P 6.87.
1600 (C–C), 1666 (С=N), 1725, 1730 (С=О). 1H NMR
···
spectrum (CCl4), δ, ppm: 0.76 t (12Н, СН3), 1.26 m
(12Н, СН2), 1.88 s [3Н, СН3С(О)], 2.77 d (1Н, СНР),
3.46 t (4Н, NСН2), 3.75 m (4Н, СН2ОР), 7.33 m (6Н,
С6Н5).
N1,N1-Diethyl-N2-acetyl(acetyldibutoxyphosphoryl)-
acetamidine (XII). To a solution of the sodium
derivative, obtained from 2.08 g (0.0060 mol) of N1,N1-
diethyl-N2-acetyl(dibutoxyphosphoryl)acetamidine and
0.14 g (0.0060 mol) of sodium was added dropwise
0.81 g (0.0066 mol, 10 mol% excess) of acetyl
bromide in 2 ml of dioxane at stirring. The temperature
was raised to 50°C, and the stirring was continued for
1 hours. Sodium bromide was filtered off; the solvent
was removed by distillation in a vacuum at 15–20 hPa.
The residue was evacuated for 1 h at 50°C and 2–
4 hPa. Yield 2.0 g (86%). IR spectrum, ν, cm–1: 986–
1061 (РОС), 1242 (Р=О), 1660 (С=N), 1723 (С=О).
1H NMR spectrum (CCl4), δ, ppm: 0.89 t (12Н, СН3),
1.28 m (8Н, СН2), 1.89 s [3Н, СН3С(О)], 1.96 s [3Н,
СН3С(О)], 2.83 d (1Н, СНР), 3.24 q (4Н, NСН2), 3.98
m (4Н, СН2ОР).
N1,N1-Diethyl-N2-acetyl(acetyldiisopropoxyphos-
phoryl)acetamidine (XV) was prepared similarly
from 1.96 g (0.0061 mol) of N1,N1-diethyl-N2-acetyl(di-
isopropoxyphosphoryl)acetamidine, 0.141 g (0.0061 mol)
of sodium and 0.48 g (0.0061 mol) of acetyl chloride.
Reaction time 2 h. Yield 1.63 g (84%). IR spectrum, ν,
cm–1: 988–1058 (РОС), 1240 (Р=О), 1672 (С=N),
1
1725, 1730 (С=О). H NMR spectrum (CCl4), δ, ppm:
1.13 t (6Н, СН3), 1.25 d (12Н, СН3), 1.89 s [3Н,
СН3С(О)], 1.97 s [3Н, СН3С(О)], 2.77 d (1Н, СНР),
3.25 q (4Н, NСН2), 4.65 m (2Н, СНОР).
N1,N1-Diethyl-N2-acetyl(benzoyldiisopropoxyphos-
phoryl)acetamidine (VI) was prepared similarly from
2.08 g (0.0065 mol) of N1,N1-diethyl-N2-acetyl(diiso-
propoxyphosphoryl)acetamidine, 0.15 g (0.0065 mol)
of sodium and 0.91 g (0.0065 mol) of benzoyl
chloride. Reaction time 4 h. Yield 2.3 g (80%). IR
N1,N1-Dipropyl-N2-acetyl(acetyldibutoxyphos-
phoryl)acetamidines (XIII) was prepared similarly
from 2.62 g (0.0069 mol) of N1,N1-dipropyl-N2-acetyl-
(dibutoxyphosphoryl)acetamidine, 0.16 g (0.0069 mol)
of sodium and 0.59 g (0.0076 mol, 10 mol% excess) of
acetyl chloride. Reaction time 2 h. Yield 2.42 g (84%).
IR spectrum, ν, cm–1: 982–1060 (РОС), 1248 (Р=О),
spectrum, ν, cm–1: 988–1060 (РОС), 1240 (Р=О), 1595
1
(C–C), 1668 (С=N), 1722, 1730 (С=О). H NMR
···
spectrum (CCl4), δ, ppm: 1.12 t (6Н, СН3), 1.24 d
(12Н, СН3), 1.96 s [3Н, СН3С(О)], 2.80 d (1Н, СНР),
3.23 q (4Н, NСН2), 4.67 m (2Н, РОСН), 7.35 m (5Н,
С6Н5).
1
1678 (С=N), 1720, 1730 (С=О). H NMR spectrum
REFERENCES
(CCl4), δ, ppm: 0.89 t (12Н, СН3), 1.38 m (12Н, СН2),
1.88 s [3Н, СН3С(О)], 1.93 s [3Н, СН3С(О)], 2.76 d
(1Н, СНР), 3.12 t (4Н, NСН2), 3.92 m (4Н, СН2ОР).
1. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: Novaya Volna, 2000, vols. 1–2.
N1,N1-Dipropyl-N2-benzoyl(acetyldibutoxyphos-
phoryl)acetamidine (XIV) was prepared similarly
from 2.50 g (0.0057 mol) N1,N1-dipropyl-N2-benzoyl-
2. RF Patent no. 2334753, IPC C 07 F9/40, 2008.
3. RF Patent no. 2334752, IPC C 07 F9/40, 2009.
4. RF Patent no. 2374258, IPC C 07 F9/40, 2009.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 4 2011