Reactions of N-(2,2-dichloro-1-cyanoethenyl)-N′-methyl(phenyl)ureas with aliphatic amines

Article abstract of DOI:10.1134/S1070363217050164

Novel derivatives of 3,3-dichloroprop-2-enenitrile containing methylurea or phenylurea fragments have been synthesized. The obtained N-(2,2-dichloro-1-cyanoethenyl)-N′-methyl(phenyl)ureas undergo intramolecular cyclization in the presence of triethylamine

Full text of DOI:10.1134/S1070363217050164

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 5, pp. 985–990. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © S.A. Chumachenko, M.V. Kachaeva, O.V. Shablykin, E.B. Rusanov, V.S. Brovarets, 2017, published in Zhurnal Obshchei Khimii,
2017, Vol. 87, No. 5, pp. 795–800.
Reactions
of N-(2,2-Dichloro-1-cyanoethenyl)-N'-methyl(phenyl)ureas
with Aliphatic Amines
S. A. Chumachenkoa, M. V. Kachaevaa, O. V. Shablykina,
E. B. Rusanovb, and V. S. Brovaretsa*
a Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 1, Kiev, 02660 Ukraine
*e-mail: brovarets@bpci.kiev.ua
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received March 23, 2017
Abstract—Novel derivatives of 3,3-dichloroprop-2-enenitrile containing methylurea or phenylurea fragments
have been synthesized. The obtained N-(2,2-dichloro-1-cyanoethenyl)-N'-methyl(phenyl)ureas undergo
intramolecular cyclization in the presence of triethylamine to form 4-(dichloromethylidene)-5-imino-1-methyl
(phenyl)imidazolidin-2-ones. Reactions of N-(2,2-dichloro-1-cyanoethenyl)-N'-methylurea with aliphatic
amines have afforded 4-(alkylamino)-4-(dichloromethyl)-5-imino-1-methylimidazolidin-2-ones.
Keywords: cyclization, N-(2,2-dichloro-1-cyanoethenyl)-N'-methyl(phenyl)urea, 4-(alkylamino)-4-(dichloro-
methyl)-5-imino-1-methylimidazolidin-2-one, 4-(dichloromethylidene)-5-imino-1-phenylimidazolidin-2-one
DOI: 10.1134/S1070363217050164
It has been previously shown that alkyl (2,2-di-
chloro-1-cyanoethenyl)carbamates 1 react with primary
and secondary aliphatic amines to give 5-amino-2-
alkoxy-1,3-oxazole-4-carbonitrile 2 [1] or 5-amino-2-
oxo-2,3-dihydro-1H-imidazole-4-carbonitrile 3 deriva-
tives [2], depending on the reaction conditions
(Scheme 1).
(phenyl)ureas 5a and 5b, the analogs of compound 1,
with aliphatic amines. Compound 5b has been
described [3], however we failed to reproduce the
procedure of its preparation. Therefore, we proposed
other ways to synthesize compounds 5a and 5b. In
detail, N-(2,2-dichloro-1-cyanoethenyl)-N'-methylurea
5a was obtained starting from N-methyl-N'-(2,2,2-
trichloro-1-hydroxyethyl)urea 4 [4] via converting to
tetrachloride A, which was treated successively with
triethylamine, Me3SiCN, and again with triethylamine
Similar products could be expected when in the
reaction of N-(2,2-dichloro-1-cyanoethenyl)-N'-methyl-
Scheme 1.
CN
NR1R2
CN
NHR3
N
R1R2NH (excess)
AlkO
O
O
CN
O
2
Cl
AlkO
N
H
(1) R3NH2 (excess),
(2) KOH
HN
Cl
1
(3) HCl
N
R3
3
985

986
CHUMACHENKO et al.
Scheme 2.
O
Cl
O
OH
CCl3
O
SOCl2
Py
Et3N
Me
Me
Me
N
N
H
CCl3
N
N
H
N
N
CCl3
O
H
H
H
4
А
B
O
CN
O
N
CN
CN
H2O
Et3N
Me3SiCN Me
Me
Cl
Me
Cl
N
N
CCl3
N
H
N
N
H
H
H
Cl
Cl
SiMe3
SiMe3
C
D
5a
Scheme 3.
CN
O
CN
Ph
+ Ph
Cl
NCO
Cl
H2N
N
N
H
H
Cl
Cl
6
5b
without isolation, to give intermediates B, C, and D.
Hydrolysis of the latter gave N-(2,2-dichloro-1-cyano-
ethenyl)-N'-methylurea 5a in 52% yield (Scheme 2).
the formation of imidazole derivative in 76% yield.
The suggested reaction mechanism 5a→E→F→9 was
also confirmed by the fact that compounds 8a and 8b
did not react with aliphatic amines and the
transformation 8→9 did not occur. The indicated
direction of the reaction of N-(2,2-dichloro-1-cyano-
ethenyl)-N'-methylurea 5a and N-(2,2-dichloro-1-
cyanoethenyl)-N'-phenylurea 5b with aliphatic amines
in the presence of triethylamine was probably due to
the different rates of cyclization of intermediate E into
compounds 8a and 8b. In the case of R = Me, the
intermediate E quickly added the aliphatic amine to the
acylimine fragment, causing the E→8a transformation.
Further intramolecular cyclization of the intermediate
F afforded imidazolidines 9a–9e (Scheme 4).
N-(2,2-Dichloro-1-cyanoethenyl)-N'-phenylurea 5b
was prepared via the reaction of 2-amino-3,3-dichloro-
prop-2-enenitrile 6 [5] with phenyl isocyanate in a
DMF solution (Scheme 3). It should be noted that the
melting points of compounds 5b obtained by us and in
[3] were significantly different.
To prepare 2,5-diamino-1,3-oxazole derivatives, we
utilized the earlier developed [6] procedure for the
synthesis of 2-alkyl(aryl)-5-amino-1,3-oxazole-4-carbo-
nitrile, involving the treatment of compounds 5a and
5b with 2 eq. of Et3N and 1 eq. of an aliphatic amine in
methanol at 20–25°C. However, the expected oxazoles
7 were not formed under those conditions. The reac-
tions of N-(2,2-dichloro-1-cyanoethenyl)-N'-methyl-
urea 5a afforded 4-(alkylamino)-4-(dichloromethyl)-5-
imino-1-methylimidazolidin-2-ones 9a–9d in high
yields (Scheme 4). Their formation could be re-
presented in terms of a series of intermediate stages
5a→E→F→9a–9e. In the case of N-(2,2-dichloro-1-
cyanoethenyl)-N'-phenylurea 5b, 4-(dichloromethyl-
idene)-5-imino-1-phenylimidazolidin-2-one 8b was
obtained instead of the compounds 9. It should be
noted that conversion 5b→8b proceeded also in the
absence of an aliphatic amine, but only in the presence
of triethylamine. A similar transformation of com-
pound 5a in the presence of triethylamine resulted in
Structure and composition of the obtained
compounds were reliably confirmed by the spectral
methods and elemental analysis data. In the IR spectra
of compounds 5a and 5b, there was the signal of the
CN group (2230, 2233 cm–1), disappearing as a result
of the transformations 5→8 and 5→9. In the 13C NMR
spectra of acrylonitriles 5a and 5b, the signals of
carbonyl (154.1, 150.6 ppm) and nitrile groups were
found (for the compound 5a, it was identified at
123.9 ppm). In the case of compounds 8a, 9a–9e, the
13C NMR spectra contained the signals of carbonyl and
imino groups at 153.4–162.9 ppm. It was not possible
to record the high-resolution 13C NMR spectrum for
compound 8b.
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REACTIONS OF N-(2,2-DICHLORO-1-CYANOETHENYL)-N'-METHYL(PHENYL)UREAS
987
Scheme 4.
N
R
NH
R
O
O
CN
NH
C
N
Et3N
R
Cl
Cl
Cl
Cl
H
N
H
N
O
H
N
N
Cl
H
Cl
5a, 5b
R1R2NH
8а, 8b
E
R1R2NH
R1R2NH
R = Me
Et3N
N
CN
NR1R2
Me
NH
NH
C
NR1R2
CHCl2
N
NR1R2
CHCl2
Me
N
RHN
O
N
O
NH
9а_9e
H
O
F
7
R = Me (a), Ph (b); R1R2NH = MeNH2 (a), PhCH2NH2 (b), (Me)2NH (c), 4-Boc-N(CH2)4 (d), O(CH2)4NH (e).
Crystal structure of compounds 9 was confirmed by
X-ray diffraction using imidazolidin-2-one 9b as the
example. The general view of the molecule and its
basic geometry parameters are shown in Fig. 1.
EXPERIMENTAL
1H and 13C NMR spectra were recorded using a
Varian Mercury instrument (400 and 100 MHz) in
DMSO-d6 relative to internal TMS. IR spectra were
registered with a Vertex-70 spectrometer (KBr pellets).
Chromato–mass spectra were recorded using an
Agilent 1100 Series liquid chromatography–mass
spectrometry system equipped with a diode array and
an Agilent LC\MSD SL mass-selective detector.
Parameters of chromatography–mass spectral analysis:
column Zorbax SB-C18, 1.8 μm, 4.6 × 15 mm;
solvents: A, MeCN–H2O, 95 : 5, 0.1% CF3COOH; B,
Similarly to the earlier studied 5-imino-1,4,4-
triphenylimidazolidin-2-one [7], the imidazolidine ring
in the molecule of compound 9b was planar, the
deviation of the atoms from the plane was 0.0197 Å.
Most of the intracyclic bonds in the imidazolidine ring
(except for C2–C3 and C2–N2 bonds, which had the
usual values for single C–C and C–N bonds) exhibited
the parameters characteristic of conjugate systems,
being in the intermediate range of values for single and
double bonds (Fig. 1). The atoms N2 and N3 had planar-
trigonal environment: the sum of the bond angles for
those atoms was close to 360° because of the effective
coupling of their lone electron pairs with the
neighboring π-systems of the double bonds C=O and
C=N, while the sum of the bond angles for the
pyramidal nitrogen atom N3 isolated from such
interactions was 326(2)°.
In a crystal, the molecules formed a branched 2D
system of hydrogen bonds in which the layers of the
molecules combined via hydrogen bonds were in a
plane perpendicular to the axis ac. Parameters of the
hydrogen bonds are summarized in Table 1.
General view of the molecule of compound 9b in the
crystal. Some geometric parameters are as follows: N1–C1
1.384(3), N1–C3 1.376(3), C2–C3 1.525(4), N2–C2 1.451(3),
N2–C1 1.350(3), O1–C1 1.221(3), N4–C3 1.259(3), N3–C2
1.441(3), N3–C5 1.464(4), Cl1–C4 1.757(3), Cl2–C4 1.768(3) Ǻ;
N2C1N1 107.7(2)°, C3N1C1 111.5(2)°, N1C3C2 106.8(2)°,
N2C2C3 101.2(2)°, C1N2C2 112.6(2)°, C2N3C5 113.7(2)°.
In summary, the derivatives which are of interest as
potential biologically active compounds [8, 9] were
obtained starting from N-(2,2-dichloro-1-cyanoethenyl)-
N'-methyl(phenyl)urea novel (5-imino)imidazolidin-2-one.
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988
CHUMACHENKO et al.
Hydrogen bonding parameters in the crystal of 9b
D–H···A
N2–H(N2)···O1
D–H, Å
0.83(3)
H···A, Å
2.906(3)
∠D–H···A, deg
Symmetry operation
166(3)
1 – x, 1 – y, 1 – z
N3–H(N3)···N4
N4–H(N4)···O1
0.79(3)
0.75(3)
3.109(3)
3.110(3)
159(3)
155(3)
x + 0.5, 0.5 – y, z + 0.5
0.5 – x, y – 0.5, 0.5 – z
0.1% aqueous CF3COOH; flow of eluent 3 mL/min,
injected volume 1 μL; UV detectors 215, 254, 285 nm;
chemical ionization at atmospheric pressure. Elemental
analysis was performed at the Analytical Chemistry
Laboratory, Institute of Bioorganic Chemistry and
Petrochemistry, National Academy of Sciences of
Ukraine. The carbon and hydrogen content were
determined via the Pregl method; the nitrogen and
chlorine contents were determined via the Dumas
micromethod and Schöniger titration method,
respectively [10]. Melting points were measured with a
Fisher–Johns apparatus.
solution of compound 6 (10.0 g, 0.073 mol) [5] in di-
methylformamide (10 mL) with stirring at 20–25°C.
The mixture was kept for 4 days, then the precipitate
was filtered off and purified by recrystallization. Yield
45%, mp 215–217°C (propan-2-ol) (mp 184–186°C
[3]). IR spectrum, ν, cm–1: 1441, 1497, 1554, 1603,
1693, 2233 (CN), 3080–3354 (NH). 1Н NMR
3
spectrum, δ, ppm: 7.00 t (1Н, С6Н5, JHH = 7.2 Hz),
3
7.30 t (2Н, С6Н5, JHH = 8.0 Hz), 7.42 t (2Н, С6Н5,
3JHH = 8.0 Hz), 8.66 s (1Н, NH), 9.13 s (1Н, NH). 13C
NMR spectrum, δС, ppm: 111.6, 112.4, 118.5, 122.8,
125.3, 128.9, 138.5, 150.6 (С=О). Mass spectrum, m/z:
256 [M + H]+. Found, %: С 46.83; Н 2.84; Cl 27.61; N
16.60. С10Н7Сl2N3O. Calculated, %: С 46.90; Н 2.76;
Cl 27.69; N 16.41.
Commercially available reagents and solvents were
used. N-Methyl-N'-(2,2,2-trichloro-1-hydroxyethyl)urea
4 was synthesized as described elsewhere [4].
4-(Dichloromethylidene)-5-imino-1-methyl(phenyl)-
imidazolidin-2-ones (8a, 8b). Triethylamine (2.11 mL,
0.015 mol) was added to a suspension of compound 5
(1.0 g, 0.005 mol) in methanol (10 mL) at 20–25°C
with stirring. After 6 h, a clear solution was formed.
The solvent was removed under reduced pressure, and
the residue was treated with 10 mL of water. The
precipitate was filtered off and recrystallized from
propan-2-ol.
N-(2,2-Dichloro-1-cyanoethenyl)-N'-methylurea
(5a). Pyridine (4.36 mL, 0.054 mol) and SOCl2 (3.4 mL,
0.047 mol) were subsequently added to a suspension of
compound 4 (10.0 g, 0.045 mol) in dichloromethane
(100 mL) with stirring at 20–25°C. While stirring the
reaction mixture for 30–40 min, a clear solution was
formed. Triethylamine (13.1 mL, 0.095 mol) and then
(CH3)3SiCN (6.2 mL, 0.05 mol) were added to that
solution. The reaction mixture was stirred at 20–25°C
for 30 min, then triethylamine (13.1 mL, 0.095 mol)
was added. After stirring for 12 h, water (40–50 mL)
was added, and the organic layer was separated. The
extract was washed with water (4 × 5 mL), dried over
Na2SO4, evaporated, and purified by recrystallization.
Yield 52%, mp 166–168°C (benzene–hexane, 10 : 1).
IR spectrum, ν, cm–1: 1424, 1506, 1572, 1603, 1601,
4-(Dichloromethylidene)-5-imino-1-methylimida-
zolidin-2-one (8a). Yield 76%, mp 177–179°C. IR
spectrum, ν, cm–1: 1404, 1466, 1626, 1673, 1792 (C=O),
1
3029–3363 (NH). H NMR spectrum, δ, ppm: 2.93 s
(3Н, СН3), 8.56 s (0.8Н, NН), 8.73 s (0.2Н, NН),
10.65 s (1Н, NН). 13C NMR spectrum, δС, ppm: 25.5
(CH3), 102.7, 127.2, 153.4, 154.1. Mass spectrum, m/z:
194 [M + H]+. Found, %: С 30.80; Н 2.79; Cl 36.67; N
21.62. С5Н5Сl2N3O. Calculated, %: С 30.95; Н 2.60;
Cl 36.55; N 21.66.
1
1655, 2230 (CN), 3047–3362 (NH). Н NMR spec-
3
trum, δ, ppm: 2.61 d (3Н, СН3, JHH = 4.4 Hz), 6.51
br.s (1Н, NH), 8.57 s (1Н, NH). 13C NMR spectrum,
δС, ppm: 26.8 (CH3), 112.8, 113.1, 123.9 (CN), 154.1
(С=О). Mass spectrum, m/z: 194 [M + H]+. Found, %:
С 30.80; Н 2.79; Cl 36.67; N 21.62. С5Н5Сl2N3O.
Calculated, %: С 30.95; Н 2.60; Cl 36.55; N 21.66.
4-(Dichloromethylidene)-5-imino-1-phenylimida-
zolidin-2-one (8b). Yield 84%, mp 214–216°C. IR
spectrum, ν, cm–1: 1415, 1454, 1496, 1626, 1671, 1738
1
(C=O), 3092–3344 (NH). H NMR spectrum, δ, ppm:
N-(2,2-Dichloro-1-cyanoethenyl)-N'-phenylurea
(5b). PhNCO (8.7 g, 0.073 mol) was added to a
7.35–7.59 m (5Н, С6Н5), 8.58 br.s (1Н, NH), 10.85
br.s (1Н, NH). 13C NMR spectrum, δС, ppm: 103.0,
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REACTIONS OF N-(2,2-DICHLORO-1-CYANOETHENYL)-N'-METHYL(PHENYL)UREAS
989
128.6, 129.5, 132.2, 153.0 (С=О) (all the signals are
broadened). Mass spectrum, m/z: 256 [M + H]+. Found,
%: С 46.83; Н 2.84; Cl 27.61; N 16.60. С10Н7Сl2N3O.
Calculated, %: С 46.90; Н 2.76; Cl 27.69; N 16.41.
149°С. IR spectrum, ν, cm–1: 1476, 1674, 1752 (C=O),
2994–3297 (NH). Н NMR spectrum, δ, ppm: 2.15 s
1
(0.8×6Н, СН3), 2.30 s (0.2×6Н, СН3), 2.82 s (0.2×3Н,
СН3), 2.87 s (0.80×3Н, СН3), 6.62 s (0.8Н, СН), 6.66 s
(0.2Н, CН), 7.86 s (0.8Н, NH), 8.09 s (0.2Н, NН),
8.39 br.s (1Н, NН). 13C NMR spectrum, δC, ppm: 25.0
(CH3), 38.8 (CH3), 74.0, 82.3, 157.7, 161.4. Mass
spectrum, m/z: 239 [M + H]+. Found, %: С 35.27; Н
5.19; Cl 29.54; N 23.63. С7Н12Сl2N4O. Calculated, %:
С 35.16; Н 5.06; Cl 29.65; N 23.43.
4-(Dichloromethyl)-5-imino-1-methyl-4-(methyl-
amino)imidazolidin-2-one (9a). 20% solution (5 mL)
of methylamine in methanol was added with stirring at
20–25°C to a suspension of compound 5 (1.0 g,
0.005 mol) in methanol (5 mL). The mixture was
stirred for 12 h, and a clear solution was formed. The
solvent was removed under reduced pressure, and the
residue was treated with 10 mL of water. The
precipitate was filtered off and recrystallized from
propan-2-ol. Yield 62%, mp 146–148°C. IR spectrum,
ν, cm–1: 1461, 1662, 1737 (C=O), 3000–3321 (NH). 1Н
NMR spec-trum, δ, ppm: 2.05 s (3Н, СН3), 2.80 br.s
(1Н, NH), 2.85 s (3Н, CH3), 6.13 s (0.15Н, СН), 6.38 s
(0.85Н, CН), 8.10 s (1Н, NН), 8.29 s (1Н, NН). 13C
NMR spectrum, δС, ppm: 25.1 (CH3), 29.1 (CH3),
75.8, 80.8, 157.6, 162.5. Mass spectrum, m/z: 225
[M + H]+. Found, %: С 31.84; Н 4.27; Cl 31.47; N
24.93. С6Н10Сl2N4O. Calculated, %: С 32.02; Н 4.48;
Cl 31.50; N 24.89.
tert-Butyl-4-[4-(dichloromethyl)-5-imino-1-methyl-
2-oxoimidazolidin-4-yl]piperazine-1-carboxylate (9d).
Yield 51%, mp 154–156°С. IR spectrum, ν, cm–1:
1402, 1431, 1453, 1479, 1670, 1745 (C=O), 3087–
1
3307 (NH). Н NMR spectrum, δ, ppm: 1.37 s (9Н,
СН3), 2.23–2.51 m (2Н, СН2), 2.81 s (0.3×3Н, СН3),
2.86 s (0.7×3Н, СН3), 3.31 m (6Н, СН2), 6.70 s (1Н,
CН), 7.90 s (0.7H, NH), 8.14 s (0.3Н, NН), 8.45 s (1Н,
NН). 13C NMR spectrum, δC, ppm: 25.0 (CH3), 28.5
(CH3), 43.6, 46.3, 73.5, 79.5, 81.9, 154.0, 157.4, 160.8.
Mass spectrum, m/z: 380 [M + H]+. Found, %: С
44.28; Н 5.99; Cl 18.82; N 18.50. С14Н23Сl2N5O3.
Calculated, %: С 44.22; Н 6.10; Cl 18.65; N 18.42.
4-(Dichloromethyl)-5-imino-1-methyl-4-(morpholin-
4-yl)imidazolidin-2-one (9e). Yield 58%, mp 115–
117°С. IR spectrum, ν, cm–1: 1451, 1481, 1675, 1758
4-(Alkylamino)-4-(dichloromethyl)-5-imino-1-
methylimidazolidin-2-ones 9b–9e. Triethylamine
(2.11 mL, 0.015 mol) and the appropriate amine
(0.005 mol) were added in sequence at 20–25°C to a
stirred suspension of compound 5a (1.0 g, 0.005 mol)
in methanol (10 mL). The mixture was stirred for 12 h,
and a clear solution was formed. The solvent was
removed under reduced pressure, and the residue was
treated with 10 mL of water. The precipitate was
filtered off and recrystallized from propan-2-ol.
1
(C=O), 3077–3326 (NH). Н NMR spectrum, δ, ppm:
2.27–2.45 m (2Н, СН2), 2.82 s (0.3×3H, CH3), 2.86 s
(0.7×3Н, СН3), 3.30–3.40 m (2Н, СН2), 3.48–3.62 m
(4Н, СН2), 6.70 s (1Н, CН), 7.91 s (0.7H, NH), 8.18 s
(0.3Н, NН), 8.48 s (1Н, NН). 13C NMR spectrum, δC,
ppm: 25.0 (CH3), 46.7, 66.5, 73.4, 81.9, 157.5, 160.7.
Mass spectrum, m/z: 281 [M + H]+. Found, %: С
38.28; Н 5.16; Cl 25.08; N 19.99. С9Н14Сl2N4O2.
Calculated, %: С 38.45; Н 5.02; Cl 25.22; N 19.93.
4-(Benzylamino)-4-(dichloromethyl)-5-imino-1-
methylimidazolidin-2-one (9b). Yield 57%, mp 178–
180°С. IR spectrum, ν, cm–1: 1400, 1475, 1669, 1741
X-Ray diffraction study of a crystal of 9b (0.15 ×
0.18 × 0.28 mm) was carried out at room temperature
with a Bruker Smart Apex II diffractometer (MoKα-
radiation, graphite monochromator, θmax 26.42°, –12 ≤
h ≤ 11, –17 ≤ k ≤ 15, –13 ≤ l ≤ 13). In total, 15213
reflections were collected, of which 2908 were inde-
pendent (R-factor 0.0737). Absorption was corrected
for in SADABS software by the multiscanning method
(Tmin/Tmax = 0.8365/0.9349). Crystals of compound 9b
were monoclinic, the unit cell parameters: space group
Р21/n, а 9.8504(18), b 13.725(3), c 11.139(3) Å,
β 109.691(4)°, V 1417.9(5) Å3, Z 4, dcalc 1.411,
μ 0.455 mm–1, F(000) 624. The structure was solved
via the direct method and refined by the least squares
method in the full-matrix anisotropic approximation
1
(C=О), 3030–3274 (NH). Н NMR spectrum, δ, ppm:
3
2.87 s (3Н, СН3), 3.12 br. t (1H, NH, JHH = 7.2 Hz),
3
2
3.53 d. d (1H, CH2, JHH = 7.2, JHH = 12.8 Hz), 3.60
3
2
d. d (1H, CH2, JHH = 7.2, JHH = 12.8 Hz), 6.25 s
(0.15Н, СН), 6.40 s (0.85Н, CН), 7.24–7.33 m (5Н,
С6Н5), 8.25 br.s (1Н, NН), 8.47 s (1Н, NН). 13C NMR
spectrum, δС, ppm: 25.3 (CH3), 46.9 (CH2), 75.9, 80.3,
127.6, 128.7, 128.9, 139.8, 157.6, 162.9. Mass spec-
trum, m/z: 301 [M + H]+. Found, %: С 47.94; Н 4.47;
Cl 23.45; N 18.53. С12Н14Сl2N4O. Calculated, %: С
47.86; Н 4.69; Cl 23.54; N 18.60.
4-(Dimethylamino)-4-(dichloromethyl)-5-imino-
1-methylimidazolidin-2-one (9c). Yield 43%, mp 147–
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990
CHUMACHENKO et al.
2. Chumachenko, S.A., Shablykin, O.V., Kozachenko, A.P.,
Osadchuk, T.V., and Brovarets, V.S., Chem. Heterocycl.
Compd., 2011, vol. 47, no. 3, p. 336. doi 10.1007/
s10593-011-0762-8
using the SHELXTL software [11]. Positions of the
hydrogen CH atoms were geometrically calculated and
refined via a rider model. Positions of the hydrogen
NH atoms participating in the formation of hydrogen
bonds were detected from the differential Fourier
synthesis and refined isotropically. In the refinement,
2908 independent reflections were used, including
1669 reflections with I > 2σ(I), (184 refined param-
eters, the number of reflections per parameter 15.8,
weight ω = 1/[σ2(Fo2) + (0.0606P)2 + 0.2293P], where
Р = (Fo2 + 2Fc2)/3, the ratio of the maximum (mean)
shift to the error in the last cycle is 0.001 (0.000). Final
divergence factors: R1(F) 0.0485, wR2(F2) 0.1143 over
the reflections with I>2σ(I), R1(F) 0.1019, wR2(F2)
0.1417, GOF 1.071 over all independent reflections.
The residual electron density from the difference
Fourier series after the last refinement cycle was 0.36
and –0.32 e/Å3. Crystallographic data for compound
9b were deposited at the Cambridge Structural
Database (CCDC 1529645).
3. Dovlatyan, V.V. and Ambartsumyan, E.N., Arm. Khim.
Zh., 1969, vol. 22, no. 2, p. 135.
4. Ingrassia, L. and Mulliez, M., Synthesis, 1999, no. 10,
p. 1731. doi 10.1055/s-1999-3586
5. Matsumura, K., Saraie, T., and Hashimoto, N., Chem.
Pharm. Bull., 1976, vol. 24, no. 5, p. 912.
6. Matsumura, K., Saraie, T., and Hashimoto, N., Chem.
Pharm. Bull., 1976, vol. 24, no. 5, p. 924.
7. Kopf, J., Heuer, G.M., and Schweim, H.G., Acta
Crystallogr. (C), 1995, vol. 51, p. 1583. doi 10.1107/
S0108270195002630
8. Alker, D., Campbell, S.F., Cross, P.E., Burges, R.A.,
Carter, A.J., and Gardiner, D.G., J. Med. Chem., 1990,
vol. 33, no. 6, p. 1805. doi 10.1021/jm00168a041
9. Van Dort, M.E. and Jung, Y.-W., Bioorg. Med. Chem.
Lett., 2004, vol. 14, no. 21, p. 5285. doi 10.1016/
j.bmcl.2004.08.031
10. Klimova, V.A., Osnovnye mikrometody analiza orga-
nicheskikh soedinenii (Basic Micromethods for Analysis
of Organic Compounds), Moscow: Khimiya, 1975.
REFERENCES
1. Drach, B.S., Sviridov, E.P., Kisilenko, A.A., and
Kirsanov, A.V., Zh. Org. Chem., 1973, vol. 9, no. 9,
p. 1818.
11. Sheldrick, G.M., Acta Crystallogr. (A), 2008, vol. 64,
p. 112. doi 10.1107/S0108767307043930
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