Synthesis of C-phosphorylated acetamidines containing CH-acidic methylene group

Article abstract of DOI:10.1134/S1070363210010093

C-Phosphorylated acetamidines with the methylene group linked to dialkoxyphosphoryl and amidine groups possessing CH-acidic properties were obtained and characterized. At the reaction of these amidines with sodium one hydrogen atom is substituted to form sodium derivatives interesting as intermediates for the syntheses of the organophosphorus compounds of versatile nature. Based on the CH-acidity of C-phosphorylated acetamidines a convenient method is developed for the synthesis of C-phosphorylated bromoacetamidines.

Full text of DOI:10.1134/S1070363210010093

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 1, pp. 60–64. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.E. Shishkin, E.V. Mednikov, M.A. Shevchenko, O.V. Anishchenko, Yu.V. Popov, E.V. Gurba, Chau Nyat Bang, 2010, published in
Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 1, pp. 64–68.
Synthesis of C-Phosphorylated Acetamidines
Containing CH-Acidic Methylene Group
V. E. Shishkin, E. V. Mednikov, M. A. Shevchenko,
O. V. Anishchenko, Yu. V. Popov, E. V. Gurba, and Chau Nyat Bang
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400066 Russia
e-mail: tons@vstu.ru
Received May 2, 2009
Abstract―C-Phosphorylated acetamidines with the methylene group linked to dialkoxyphosphoryl and
amidine groups possessing CH-acidic properties were obtained and characterized. At the reaction of these
amidines with sodium one hydrogen atom is substituted to form sodium derivatives interesting as intermediates
for the syntheses of the organophosphorus compounds of versatile nature. Based on the CH-acidity of C-
phosphorylated acetamidines a convenient method is developed for the synthesis of C-phosphorylated
bromoacetamidines.
DOI: 10.1134/S1070363210010093
Reactions based on the CH-acid properties are
widely used in the synthesis of organophosphorus
compounds [1, 2]. The pesticide activity of the
phosphorus-containing amidines is also known [3]. In
this paper we synthesized C-phosphorylated acetami-
dines containing an active methylene group, in order to
use their CH-acidic properties for preparation of
biologically active substances.
Reactions of C-phosphorylated acetimidates with
amines and piperidine proceed without a solvent to a
completion at 50–60°C in 3 h. The rate of reaction
depends on the basicity of the amine, so at the use of
morpholine and dibenzylamine whose basicity is lower
than that of aliphatic amines the heating at 50–60°C
for 7 h is required to complete the process. The
syntheses were carried out with 1:1.5 molar ratio of N-
substituted C-phosphorylated imidate to the secondary
amine. To isolate the target substance the formed
ethanol and amine excess were removed in a vacuum.
To obtain chemically pure compounds column
adsorption chromatography on silica gel μL-5/40 was
used, eluent chloroform–diethyl ether–hexane in 1:2:1
ratio by volume. The individuality of compounds was
monitored by thin-layer chromatography on the Silufol
plates. The amidines I–XIV were synthesized with the
yield up to 97%.
For the synthesis we have chosen a method of
amidines preparation from the C-phosphorylated N-
substituted acetimidates by the reaction of the latter
with secondary amines or heterocyclic compounds
similar in the structure to the secondary amines.
O
NR1
+ HNR22
(RO)2PCH2C
− C2H5OH
NR22
O
NR1
I−IX
The synthesized C-phosphorylated acetamidines do
not contain in their molecules the NH-acidic reaction
centers, so nothing interferes with the study and
application of the CH-acidic properties of these
compounds. They are light yellow viscous liquids, well
soluble in organic solvents and poorly soluble in water.
At the reaction with hydrogen chloride the C-phos-
phorylated acetamidines form hydrochlorides. Under
the action of triethylamine the C-phosphorylated
amidines were quantitatively recovered from the
hydrochlorides.
(RO)2PCH2C
OC2H5
NR1
O
+ HN
X
(RO)2PCH2C
− C2H5OH
X
N
X−XIV
R = i-C3H7, C4H9; R1 = CH3C(O), C6H5C(O), Si(CH3)3,
C(C6H5)=NC6H5; R2
CH2C6H5; X = O, CH2.
= C2H5, C3H7, C4H9, i-C4H9,
60

SYNTHESIS OF C-PHOSPHORYLATED ACETAMIDINES
61
Physicochemical properties of compounds I–XIV
C-phosphorylated acetamidines is high enough to form
an appropriate sodium derivative at the action of
metallic sodium that can further be replaced by
different functional groups and halogen atoms.
are listed in Tables 1 and 2.
The synthesized acetamidines display CH-acidic
properties due to the mobility of hydrogen atoms of the
methylene group activated by the electron-withd-
rawing phosphonate and amidine groups. The lability
of the hydrogen atoms in the methylene group of the
The possibility of using the C-phosphorylated acet-
amidines as initial reagents for the synthesis of new
compounds is shown by the example of bromination:
O
O
NCR1
O
NCR1
O
(RO)2PCH2C
+ Na
(RO)2PCHNaC
−1/2 H2
NR22
NR22
O
O
NCR1
NCR1
O
O
(RO)2PCHC
Br
(RO)2PCHNaC
+ Br2
−NaBr
NR22
NR22
XV−XVII
R = i-C3H7, R1 = C6H5, R2 = C3H7 (XV); R = C4H9, R1 = C6H5, R2 = C4H9 (XVI); R = C4H9, R1 = CH3, R2 = C3H7 (XVII).
The C-phosphorylated acetamidines under the
action of metallic sodium form organometallic
compounds where the metal–carbon bond is of ionic
nature, as in all the compounds that form carbanions
with very electropositive alkali metals. The resulting
acetamidine carbanion has a high reactivity and an
ability to react readily with a molecule of bromine. The
bromination of the C-phosphorylated acetamidines
proceeds smoothly with a high yield of the bromo
derivatives.
In the process of bromination at 1:1 molar ratio of
reagents and temperature 50–60°C the bromoacet-
amidines are formed mono-substituted in the me-
thylene group. The reaction is carried out at vigorous
stirring in anhydrous dioxane. The purification of the
produced compounds was carried out using adsorption
column chromatography, eluent chloroform–diethyl
ether–hexane in the ratio 1:3:1 by volume. The
homogeneity of purified compounds was monitored by
thin-layer chromatography on Silufol plates.
Table 1. Physicochemical properties of C-phosphorylated acetamidines
NR1
O
(RO)2PCH2C
NR22
MRD
found calculated
Found, %
Calculated, %
Comp.
no.
Yield,
%
R
R1
R2
nD20
d420
Formula
N
P
N
P
i-C3H7 C(O)CH3 C2H5
C4H9 C(O)CH3 C2H5
i-C3H7 C(O)CH3 C3H7
C4H9 C(O)CH3 C3H7
C4H9 C(O)CH3 i-C4H9
i-C3H7 C(O)C6H5 C3H7
C4H9 C(O)C6H5 C3H7
C4H9 C(O)C6H5 C4H9
C4H9 C(O)C6H5 СН2С6Н5
92
96
93
97
94
95
94
93
96
1.4438 1.0042
1.4546 1.0074
1.4552 1.0106
1.4588 1.0081 101.92
1.4668 1.0064 111.34
1.4815 1.0336 112.98
1.4898 1.0399 121.88
1.4980 1.0445 130.85
1.5490 1.1117 152.50
84.61
93.65
93.46
85.51
93.45
93.45
102.75
112.05
112.70
122.23
131.53
151.89
8.42 9.50 C14H29N2O4P
7.91 8.62 C16H33N2O4P
8.20 8.73 C16H33N2O4P
7.70 8.51 C18H37N2O4P
7.09 7.91 C20H41N2O4P
6.57 7.34 C21H35N2O4P
6.52 7.28 C23H39N2O4P
5.88 6.42 C25H43N2O4P
5.03 5.61 C31H39N2O4P
8.67
8.05
8.05
7.48
6.96
6.83
6.38
6.00
5.25
9.68
8.89
8.89
8.21
7.67
7.56
7.06
6.64
5.79
I
II
III
IV
V
VI
VII
VIII
IX
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62
SHISHKIN et al.
Table 2. Physicochemical properties of C-phosphorylated acetamidines
NR1
O
(C4H9O)2PCH2C
X
N
MRD
Found, %
Calculated, %
Comp.
no.
Yield,
%
R1
Si(CH3)3
C6H5C(O)
C6H5C(O)
X
nD20
d420
Formula
found calculated
N
P
N
P
O
O
CH2
O
88
88
90
91
91
1.4820 1.0389 107.56
1.4948 1.0324 119.73
1.5058 1.0243 122.36
1.5218 1.086
1.5226 1.0619 142.88
106.77
119.43
123.29
139.18
142.04
7.32
6.85
6.52
8.60
8.71
8.01 С17Н37N2О4PSi 7.14 7.91
X
XI
XII
XIII
XIV
7.19 С21Н33N2О5P
7.19 С22Н35N2О4P
6.38 С27Н38N3О4P
6.35 С28Н40N3О3P
6.60 7.31
6.63 7.34
8.42 6.21
8.45 6.24
C(C6H5)=NC6H5
C(C6H5)=NC6H5 CH2
140.02
The synthesized compounds are viscous colored
liquids with a perfumed scent, well soluble in dioxane,
acetone, worse soluble in ether and unsaturated
hydrocarbons, and insoluble in water.
N1,N1-Diethyl-N2-acetyl(dibutoxyphosphoryl)acet-
amidine (II) was synthesized similarly from 7.9 g
(0.024 mol) of ethyl N-acetyl(dibutoxyphosphoryl)
acetimidate and 2.6 g (0.036 mol) of diethylamine,
1
yield 7.9 g (96%). H NMR spectrum (CCl4), δ, ppm:
Yield of C-phosphorylated bromoacetamidines XV–
XVII was 87–89%.
0.93 t (12H, CH3), 1.32 m (8H, CH2), 1.96 s (3H,
CH3C(O)), 2.74 d (2H, CH2P), 3.43 q (4H, NCH2),
3.96 m (4H, CH2OP). IR spectrum, ν, cm–1: 982–1054
(POC), 1250 (P=O), 1678 (C=N), 1738 (C=O).
Considering a wide range of the reactions, which
can be carried out with the participation of the ac-
tivated methylene group, we suggest that the C-
phosphorylated acetamidines are very promising
compounds for the synthesis of biologically active
substances.
N1,N1-Dipropyl-N2-acetyl(diisopropoxyphosphoryl)-
acetamidine (III was synthesized similarly from 12.0 g
(0.041 mol) of ethyl N-acetyl(diisopropoxyphos-
phoryl)acetimidate and 6.2 g (0.061 mol) of dipropyl-
amine. Yield 13.2 g (93%). 1H NMR spectrum (CCl4),
δ, ppm: 0.97 t (6Н, CH3), 1.26 d (12H, CH3), 1.96 s
(3H, CH3C(O)), 2.71 d (2H, CH2P), 3.34 q (4H,
NCH2), 4.62 m (2H, CH2OP). IR spectrum, ν, cm–1:
982–1058 (POC), 1246 (P=O), 1678 (C=N), 1732
(C=O).
N1,N1-Dipropyl-N2-acetyl(dibutoxyphosphoryl)-
acetamidine (IV was synthesized similarly from
13.8 g (0.0429 mol) of ethyl N-acetyl(dibutoxy-
phosphoryl)acetimidate and 6.5 g (0.0643 mol) of
dipropylamine. Yield 15.7 g (97%). 1H NMR spectrum
(CCl4), δ, ppm: 0.88 t (12H, CH3), 1.35 m (12H, CH2),
1.95 s (3H, CH3C(O)), 2.75 d (2H, CH2P), 3.32 t (4H,
NCH2), 3.92 m (4H, CH2OP). IR spectrum, ν, cm–1:
976–1048 (POC), 1243 (P=O), 1676 (C=N), 1738
(C=O).
EXPERIMENTAL
1
The H NMR spectra were registered on a Varian
Mercury 300 BB spectrometer, operating frequency
300 MHz, solvent carbon tetrachloride. Infrared
spectra were taken on a SPECORD M 82 instrument.
The spectra of liquids were taken from a thin layer.
N1,N1-Diethyl-N2-acetyl(diisopropoxyphosphoryl)-
acetamidine (I). In a flask equiped with a reflux con-
denser and a thermometer a mixture of 21.8 g
(0.074 mol) of ethyl N-acetyl(diisopropoxyphosphoryl)-
acetimidate with 8.1 g (0.111 mol) of diethylamine
was heated at 50–60°C for 3 h. Then the resulting
alcohol and amine excess were removed in a vacuum
(at 15–20 hPa) and the residue was evacuated for 1 h at
1
50°C and 2–4 hPa. Yield 21.8 g (92%). H NMR
N1,N1-Diisobutyl-N2-acetyl(dibutoxyphosphoryl)-
acetamidine (V) was synthesized similarly from
10.0 g (0.031 mol) of ethyl N-acetyl(dibutoxyphosphoryl)-
acetimidate and 6.0 g (0.046 mol) of diisobutylamine.
Yield 13.9 g (94%). 1H NMR spectrum (CCl4), δ, ppm:
spectrum (CCl4), δ, ppm: 1.12 t (6Н, CH3), 1.23 d
(12H, CH3), 1.96 s [3H, CH3C(O)], 2.75 d (2H, CH2P),
3.42 q (4H, NCH2), 4.61 m (2H, CH2OP). IR spectrum,
ν, cm–1 : 988–1048 (POC), 1246 (P=O), 1666 (C=N),
1732 (C=O).
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SYNTHESIS OF C-PHOSPHORYLATED ACETAMIDINES
63
1
0.91 t (6Н, CH3), 0.95 d (12H, CH3), 1.38 m (8H,
CH2), 1.59 m (2H, CH), 1.95 s (3H, CH3C(O)), 2.75 d
(2H, CH2P), 3.44 d (4H, NCH2), 3.96 m (4H, CH2OP).
IR spectrum, ν, cm–1 : 980–1062 (POC), 1249 (P=O),
1670 (C=N), 1720 (C=O).
N1,N1-Dipropyl-N2-benzoyl(diisopropoxyphos-
phoryl)acetamidine (VI) was synthesized similarly
from 10.5 g (0.029 mol) of ethyl N-benzoyl(diisopro-
poxyphosphoryl)acetimidate and 4.3 g (0.043 mol) of
dipropylamine. Yield 11.3 g (95%). 1H NMR spectrum
(CCl4), δ, ppm: 0.96 t (6Н, CH3), 1.25 d (12H, CH3),
2.72 d (2H, CH2P), 3.35 q (4H, NCH2) , 4.62 m (2H,
CH2OP), 7.3 m (5H, C6H5). IR spectrum, ν, cm–1: 976–
1062 (POC), 1245 (P=O), 1677 (C=N), 1738 (C=O),
1588 (C–Car).
N1,N1-Dipropyl-N2-benzoyl(dibutoxyphosphoryl)
acetamidine (VII) was synthesized similarly from
12.9 g (0.034 mol) of ethyl N-benzoyl(dibutoxy-
phosphoryl)acetimidate and 5.1 g (0.051 mol) of
dipropylamine. Yield 13.9 g (94%). 1H NMR spectrum
(CCl4), δ, ppm: 0.86 t (12H, CH3), 1.26 m (12H, CH2),
2.74 d (2H, CH2P), 3.46 t (4H, NCH2), 3.71 m (4H,
CH2OP), 7.28 m (5H, C6H5). IR spectrum, ν, cm–1:
980–1059 (POC), 1246 (P=O), 1678 (C=N), 1738
(C=O), 1600 (C–Car).
of morpholine. Duration 7 h. Yield 7.6 g (88%). H
NMR spectrum (CCl4) δ, ppm: 0 s (9H, CH3Si), 0.9 t
(6Н, CH3), 1.35 m (8H, CH2), 2.83 d (2H, CH2P ), 3.47 t
(4H, NCH2), 3.59 t (4H, CH2O), 3.93 m (4H, CH2 OP).
IR spectrum, ν, cm–1: 976–1057 (POC), 1246 (P=O),
1672 (C=N).
N1-Morpholido-N2-benzoyl(dibutoxyphosphoryl)-
acetamidine (XI) was synthesized similarly from 7.3 g
(0.019 mol) of ethyl N-benzoyl(dibutoxyphosphoryl)-
acetimidate and 2.4 g (0.028 mol) of morpholine.
1
Duration 7 h. Yield 7.1 g (88%). H NMR spectrum
(CCl4), δ, ppm: 0.9 t (6Н, CH3), 1.28 m (8H, CH2),
2.75 d (2H, CH2P), 3.46 t (4H, NCH2), 3.66 t (4H,
CH2O), 3.76 m (4H, CH2OP), 7.35 m (5H, C6H5). IR
spectrum, ν, cm–1: 980–1060 (POC), 1246 (P=O), 1678
(C=N), 1732 (C=O), 1600 (C–Car).
N1-Piperidido-N2-benzoyl(dibutoxyphosphoryl)-
acetamidine (XII) was synthesized similarly from
8.0 g (0.021 mol) of ethyl N-benzoyl(dibutoxy-
phosphoryl)acetimidate and 2.6 g (0.031 mol) of pi-
peridine. Yield 7.9 g (90%). 1H NMR spectrum (CCl4),
δ, ppm: 0.82 t (6Н, CH3), 1.24 m (14H, CH2), 2.75 d
(2H, CH2P), 3.42 t (4H, NCH2) , 3.76 m (4H, CH2OP),
7.26 m (5H, C6H5). IR spectrum, ν, cm–1: 976–1060
(POC), 1246 (P=O), 1678 (C=N), 1738 (C=O), 1600
(C–Car).
N1,N1-Dibutyl-N2-benzoyl(dibutoxyphosphoryl)-
acetamidine (VIII) was synthesized similarly from
9.0 g (0.023 mol) of ethyl N-benzoyl(dibutoxy-
phosphoryl ) acetimidate a and 4.4 g (0.034 mol) of
N1-Morpholido-N2-(N-phenylbenzimidoyl)(dibutoxy-
phosphoryl)acetamidine (XIII) was synthesized
similarly from 6.0 g (0.013 mol) of ethyl N-(N-phenyl-
benzimidoyl)(dibutoxyphosphoryl)acetimidate and
1.6 g (0.019 mol) of morpholine . Duration 7 h. Yield
1
dibutylamine. Yield 9.9 g (93%). H NMR spectrum
(CCl4), δ, ppm: 0.85 t (12H, CH3), 1.24 m (16H, CH2),
2.75 d (2H, CH2P), 3.45 t (4H, NCH2), 3.72 m (4H,
CH2OP), 7.3 m (5H, C6H5). IR spectrum, ν, cm–1: 978–
1062 (POC), 1239 (P=O), 1678 (C=N), 1738 (C=O),
1600 (C–Car).
1
5.9 g (91%). H NMR spectrum (CCl4), δ, ppm: 0.89 t
(6Н, CH3), 1.25 m (8H, CH2), 2.75 d (2H, CH2 P), 3.39 t
(4H, NCH2) , 3.57 t (4H, CH2 O), 3.92 m (4H, CH2
OP), 6.8 m (5H, C6H5), 7.35 m (5H, C6H5), IR spec-
trum, ν, cm–1: 988–1066 (POC), 1252 (P=O), 1679,
1738 (C=N); 1588, 1600 (C–Car).
N1,N1-Dibenzyl-N2-benzoyl(dibutoxyphosphoryl)-
acetamidine (IX) was synthesized similarly from 7.0 g
(0.018 mol) of ethyl N-benzoyl(dibutoxyphosphoryl)-
acetimidate and 3.9 g (0.020 mol) of dibenzylamine.
N1-Piperidido-N2-(N-phenylbenzimidoyl)(dibutoxy-
phosphoryl)acetamidine (XIV) was synthesized
similarly from 5.5 g (0.012 mol) of ethyl N-(N-phenyl-
benzimidoyl)(dibutoxyphosphoryl)acetimidate and
1.5 g (0.018 mol) of piperidine . Yield 5.6 g (91%). 1H
NMR spectrum (CCl4), δ, ppm: 0.87 t (6Н, CH3), 1.26 m
(14H, CH2), 2.74 d (2H, CH2P), 3.38 t (4H, NCH2),
3.89 m (4H, CH2OP), 6.82 m (5H, C6H5), 7.29 m (5H,
C6H5). IR spectrum, ν, cm–1: 988–1064 (POC), 1254
(P=O), 1666, 1738 (C=N), 1582, 1600 (C–Car).
1
Duration 7 h. Yield 9.2 g (96%). H NMR spectrum
(CCl4), δ, ppm: 0.82 t (6Н, CH3), 1.29 m (8H, CH2),
2.66 d (2H, CH2P), 3.36 t (4H, NCH2) , 3.93 m (4H,
CH2OP), 7.12 m (15N, C6H5). IR spectrum, ν, cm–1:
976–1066 (POC), 1246 (P=O), 1678 (C=N), 1720
(C=O), 1588, 1630 (C–Car).
N1-Morpholido-N2-trimethylsilyl(dibutoxyphos-
phoryl)-acetamidine (X) was synthesized similarly
from 7.7 g (0.022 mol) of ethyl N-trimethylsilyl(di-
butoxyphosphoryl)acetimidate and 2.9 g (0.033 mol)
N1,N1-Dipropyl-N2-benzoyl(diisopropoxyphos-
phoryl)bromoacetamidine (XV). To a 4-neck reactor
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 1 2010

64
SHISHKIN et al.
equipped with a stirrer, a thermometer, a reflux
condenser and and a dropping funnel was placed a
solution of 2.00 g (0.0048 mol) of N1,N1-dipropyl-N2-
benzoyl(diisopropoxyphosphoryl)acetamidine in 3 ml
of dioxane, and at stirring at 20–30°C was added in
small portions 0.11 g (0.0048 mol) of sodium. To the
resulting solution of the acetamidine sodium derivative
at stirring at 20–30°C was added dropwise 0.77 g
(0.0048 mol) of bromine. The sodium bromide salt
(0.49 g) was separated by filtration, the solvent was
removed by vacuum distillation (at 15–30 hPa), the
residue was evacuated for 1 h at 50–60°C and 2–
4 hPa. The substance formed was purified by
adsorption column chromatography on silica gel,
eluent chloroform–diethyl ether–hexane, 1:3:1 (Rf
0.70, Silufol, chloroform:hexane, 2:1 v/v, development
with iodine vapor). Yield 2.05 g (87%), nD20 1.5057,
d420 1.1972. MRD 121.29, calc. 120.41. Found, %: N
5.98, P 6.12. C21H34BrN2O4P. Calculated, %: N 5.72, P
1.1924, MRD 138.90, calc. 139.24. Found, %: N 5.44,
P 5.48. C25H42BrN2O4P. Calculated, %: N 5.14, P 5.69.
1H NMR spectrum (CCl4), δ, ppm: 0.75 t (12H, CH3),
1.22 m (16H, CH2), 2.8d (1H, CHP), 3.45 t (4H,
NCH2), 3.94 m (4H, CH2OP), 7.3 m (5H, C6H5), IR
spectrum, ν, cm–1: 982–1060 (POC), 1234 (P=O), 1678
(C=N) , 1738 (C=O), 1588 (C–C Ar), 745 (C–Br).
N1,N1-Dipropyl-N2-acetyl(dibutoxyphosphoryl)-
bromoacetamidine (XVII). Synthesized similarly to
compound XV of 2.30 g (0.0061 mol) of N1,N1-di-
propyl-N2-acetyl(dibutoxyphosphoryl)acetamidine,
0.14 g (0.0061 mol) of sodium and 0.97 g (0.0061 mol)
of bromine. Yield 2.47 g (89%). nD20 1.4835, d420
1.1821, MRD 110.02, calc. 110.46. Found, %: N 6.34,
P 6.58. C18H36BrN2O4P. Calculated, %: N 6.15, P 6.81.
1H NMR spectrum (CCl4), δ, ppm: 0.90 t (12H, CH3),
1.37 m (12H, CH2), 1.96 s [3H, CH3C(O)], 2.80 d (H
CHP), 3.35 t (4H, NCH2), 3.97 m (4H, CH2OP). IR
spectrum, ν, cm–1: 980–1072 (POC), 1248 (P=O), 1664
(C=N), 1736 (C=O), 746 (C–Br).
1
6.34. H NMR spectrum (CCl4), δ, ppm: 0.93 t (6Н,
CH3), 1.29 d (12H, CH3), 2.8 d (1H, CHP), to 3.50
(4H, NCH2), 4.78 m (2H, CH2OP), 7.35 m (5H, C6H5),
IR spectrum, ν, cm–1: 982–1070 (POC), 1245 (P=O),
1664 (C=N) , 1735 (C=O), 1600 (C–C Ar), 748 (C–Br).
N1,N1-Dibutyl-N2-benzoyl(dibutoxyphosphoryl)-
bromoacetamidine (XVI). Synthesized similarly to
compound XV from 1.60 g (0.0034 mol) of N1,N1-
dibutyl-N2-benzoyl(dibutoxyphosphoryl)acetamidine,
0.078 g (0.0034 mol) of sodium and 0.54 g (0.0034
mol) of bromine. Yield 1.58 g (88%). nD20 1.5192, d420
REFERENCES
1. Shishkin, V.E., Mednikov, E.V., Anishchenko, O.V.,
and No, B.I., Dokl. Akad. Nauk, 2001, vol. 380, no. 5,
p. 645.
2. Pudovik, A.N. and Yastrebova, G.E., Usp. Khim., 1970,
vol. 39, no. 5, p. 1190.
3. Shishkin, V.E., Doctorate Sci. (Chem.) Dissertation,
Kazan, 1988.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 1 2010