Synthesis of monothiooxamides

Article abstract of DOI:10.1023/B:RUCB.0000030819.80699.6e

A convenient method for the synthesis of monothiooxamides by the reaction of chloroacetamides with a solution of elemental sulfur in amines was developed.

Full text of DOI:10.1023/B:RUCB.0000030819.80699.6e

Russian Chemical Bulletin, International Edition, Vol. 53, No. 2, pp. 415—419, February, 2004
415
Synthesis of monothiooxamides
I. V. Zavarzin,ꢀ V. N. Yarovenko, E. I. Chernoburova, and M. M. Krayushkin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation
Eꢀmail: zavi@ioc.ac.ru
A convenient method for the synthesis of monothiooxamides by the reaction of chloroꢀ
acetamides with a solution of elemental sulfur in amines was developed.
Key words: chloroacetamides, sulfur, amines, monothiooxamides.
Monothiooxamide fragments are present in natural
products.1 Currently, monothiooxamides are under inꢀ
tensive research as biologically active compounds.2,3 Of
particular interest is the use of monothiooxamides as
complexing structures.4 However, despite the high synꢀ
thetic potential, these compounds have been little studied
before the beginning of our works,5 mainly due to the lack
of convenient methods for their synthesis.
In our opinion, most promising is the synthesis of
monothiooxamides based on the reaction of chloroꢀ
acetamides with elemental sulfur and amines. Several exꢀ
amples of this reaction have been described in the literaꢀ
ture.6,7 However, this approach has a number of substanꢀ
tial drawbacks, including the necessity of longꢀterm heatꢀ
ing of the reaction mixture. It is known8 that on heating,
sulfur reacts with amines to give a mixture of products and
this can complicate the synthesis of monothiooxamides.
Previously,7 we showed that simultaneous addition of elꢀ
emental sulfur and amine to chloroacetamide 1а gives a
substantial amount of αꢀaminoacetamides 2а,b, which
then react with sulfur to give monothiooxamides 3a,b
only on longꢀterm heating (Scheme 1).
In this study, we showed that monothiooxamides can
be obtained in high yields under mild conditions by using
a specially prepared solution of sulfur in the required amine
(stirring of the components for 20—30 min). The effects
of the solvent, the nature of the substituent located in the
αꢀposition of the amide, and the substituents in the "acetꢀ
amide" and "amine" components were studied. It was
found that Sꢀfunctionalization of chloroacetamides proꢀ
ceeds most smoothly, the yield of monothiooxamide 3b
being 92%. In other cases, the product yield did not exꢀ
ceed 25% (Scheme 2).
Scheme 2
X = Cl (a), SPh (b), SCONH2 (c), S2CH2CONHPh (d)
The solvents of choice for this reaction are dimethylꢀ
formamide and an excess of the amine. We found that
only the mild reaction conditions (≈20 °C) enable the use
of DMF, because on heating, it reacts with chloroꢀ
acetamide 1a and sulfur to give the corresponding monoꢀ
thiooxamide 3с, which contains a dimethylamino group
in the thioamide fragment (Scheme 3).
Scheme 1
Scheme 3
R1 = H, R2 = Bun (a); R1R2 = —(CH2)2—O—(CH2)2— (b)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 398—401, February, 2004.
1066ꢀ5285/04/5302ꢀ0415 © 2004 Plenum Publishing Corporation

416
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Zavarzin et al.
Scheme 6
The nature of the substituent located in the acetamide
fragment does not affect significantly the sulfurization of
chloroacetamides. Compounds containing electronꢀwithꢀ
drawing or electronꢀreleasing substituents react almost
identically with a solution of elemental sulfur in an amine.
The synthesis of monothiooxamides 3d—i is shown in
Scheme 4.
1
R
6
R
R1
R2
Scheme 4
k
l
m
n
2ꢀCNC6H4
4ꢀMeOCOC6H4
4ꢀClC6H4
H
a
b
c
d
e
f
Ph
Ph
Ph
H
H
H
H
H
H
4ꢀMeOCO
4ꢀMeCONH
4ꢀEt2N
4ꢀMeO
4ꢀCl
2ꢀCNC6H4
4ꢀClC6H4
4ꢀMeOCOC6H4
H
H
g
2,3ꢀCH=CH—CH=CH—
Heteroaromatic amines also form monothiooxamides
Comꢀ
pound
R
3
d
R1
R2
when react with chloroacetamides in the presence of triꢀ
ethylamine. The synthesis of monothiooxamides 7a—d is
presented in Scheme 7.
1a, 3d
Ph
H
1f, 3e
1g, 3f
1h, 3g
3,5ꢀ(CF3)2C6H3
3ꢀ(NO2)C6H4
3,4ꢀCl2C6H3
e
f
g
Et
Et
Scheme 7
—(CH2)5—
—(CH2)5—
1i, 3h
1j, 3i
h
i
—(CH2)2—O—(CH2)2—
—(CH2)2—O—(CH2)2—
This method allows one to synthesize bisꢀmonothioꢀ
oxamides. Thus products 5а,b were prepared from chloroꢀ
acetamide 4 (Scheme 5).
R =
(a),
(b),
(c),
(d)
Scheme 5
The steric effects do not influence much the course of
the reaction and this allows one to use sterically hindered
chloroacetamides (1o,p) and amines (2,6ꢀdimethylaniline,
2,6ꢀdibromoꢀ4ꢀmethylaniline, 2ꢀbromoaniline, aminoꢀ
adamantane). Owing to mild reaction conditions, relaꢀ
tively unstable amines such as cyclopropylamine, allyꢀ
lamine, or aziridines can also be introduced in the reacꢀ
tion (Scheme 8).
One more advantage of the method is the possibility of
preparing monothiooxamide isomers. This is attained by
changing the positions of the "amine" and "acetamide"
reaction components (Scheme 9).
R1 = H, R2 = Ph (a); R1R2 = —(CH2)2—O—(CH2)2— (b)
The influence of substituents in the "amine" compoꢀ
nent proved to be more significant. In the reaction with
anilines, which are weaker bases than aliphatic amines,
triethylamine should be added to the reaction mixture as
the catalyst. The reaction gives diverse monothiooxamides
6a—g (Scheme 6).
Thus, we demonstrated that the use of a preliminarily
prepared solution of sulfur in amines is fairly convenient
for Sꢀfunctionalization of αꢀchloroacetamides, resulting
in the formation monothiooxamides.

Synthesis of monothiooxamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
417
Scheme 8
yield of thiooxamide 3b was 57%, m.p. 164—166 °C (cf.
Ref. 6: 166 °C).
Synthesis of N(S),N(S)ꢀdimethylꢀN(O)ꢀphenylthiooxamide
(3с). Chloroacetamide 1а (5.3 mmol) and sulfur (0.7 g) in 10 mL
of DMF were refluxed for 5 h. The mixture was cooled and
diluted with water and the precipitate was filtered off. The prodꢀ
uct was recrystallized from ethanol to give 0.2 g of thiooxamide
3с (62%), m.p. 142—143 °C. Found (%): C, 57.73; H, 5.64;
N, 13.57. C10H12N2OS. Calculated (%): C, 57.69; H, 5.77;
N, 13.46. 1H NMR, δ: 3.75 (s, 6 H, Me); 7.10 (m, 1 H, H
arom.); 7.30, 7.70 (both m, each 2 H, H arom.); 9.65 (s, 1 H,
NH). MS, m/z: 208 [M]+.
Synthesis of monothiooxamides (general procedure А).
Chloroacetamide 1 (5.0 mmol) was added to a solution of an
amine (5.5 mmol) and sulfur (0.7 g) in 10 mL of DMF prepared
beforehand. The reaction mixture was stirred at ≈20 °C for 8 h,
cooled, and diluted with water. The precipitate was filtered off,
washed with water, and dried. The product was dissolved in
acetone (10 mL) and the solution was filtered. The residue after
the removal of acetone was recrystallized from 95% ethanol to
give thiooxamide 3а, 88%, m.p. 58—60 °C (cf. Ref. 7: 58—60 °C)
and thiooxamide 3b, 92%, m.p. 165—166 °C (cf. Ref. 6: 166 °C).
N(S)ꢀ[2ꢀ(2ꢀChloroꢀ4ꢀnitrophenylamino)ethyl]ꢀN(O)ꢀ
phenylthiooxamide (3d). Yield 53%, m.p. 166—168 °C.
Found (%): C, 50.77; H, 3.89; Cl, 3.27; N, 14.86.
C16H15ClN4O3S. Calculated (%): C, 50.73; H, 3.99; Cl, 9.36;
N, 14.79. 1H NMR, δ: 3.65, 3.90 (both m, each 2 H, CH2); 7.00
(m, 2 H, H arom.); 7.15 (t, 1 H, H arom., J = 7.3 Hz); 7.40, 7.65
(both m, each 2 H, H arom.); 8.05 (m, 1 H, NH); 8.10 (s, 1 H,
H arom.); 10.35, 11.10 (both s, each 1 H, NH).
Compound
R
1a, 8b,d,e
1n, 8c,f
1o, 8a
1p, 8h
1q, 8g
PhNH—
NH2
2,6ꢀMe2C6H3NH—
2,6ꢀBr2ꢀ4ꢀMeC6H2NH—
4ꢀNO2C6H4NH—
8
a
R´
8
e
R´
CH2=CH—CH2—NH—
b
f
c
d
2ꢀBrC6H4NH—
g
h
2,6ꢀMe2C6H3NH—
PhCH2CH2NH—
Scheme 9
N(S),N(S)ꢀDiethylꢀN(O)ꢀ[3,5ꢀdi(trifluoromethyl)pheꢀ
nyl]thiooxamide (3e). Yield 86%, m.p. 100—101 °C. Found (%):
C, 45.29; H, 3.63; F, 30.56; N, 7.62. C14H14F6N2OS. Calcuꢀ
lated (%): C, 45.16; H, 3.76; F, 30.64; N, 7.53. 1H NMR, δ: 1.25
(m, 6 H, Me); 3.55, 3.95 (both m, each 2 H, CH2); 7.80 (m,
1 H, H arom.); 8.30 (m, 2 H, H arom.); 11.15 (s, 1 H, NH). MS,
m/z: 372 [M]+.
Nꢀ(3ꢀNitrophenyl)ꢀ2ꢀpiperidinoꢀ2ꢀthioxoacetamide (3f).
Yield 78%, m.p. 165—167 °C (cf. Ref. 10: 165—167 °C).
Nꢀ(3,4ꢀDichlorophenyl)ꢀ2ꢀpiperidinoꢀ2ꢀthioxoacetamide
(3g). Yield 73%, m.p. 186—187 °C (cf. Ref. 10: 185—187 °C).
Nꢀ(2ꢀChloropyridinꢀ3ꢀyl)ꢀ2ꢀmorpholinoꢀ2ꢀthioxoacetamide
(3h). Yield 68%, m.p. 157—159 °C. Found (%): C, 46.20;
H, 4.30; Cl, 12.36; N, 14.61. C11H12ClN3O2S. Calculated (%):
C, 46.24; H, 4.23; Cl, 12.41; N, 14.70. 1H NMR, δ: 3.78 (m,
6 H, H morphol.); 4.15 (m, 2 H, morphol.); 7.50 (m, 1 H, Py);
8.15 (d, 1 H, Py, J = 7.8 Hz); 8.30 (m, 1 H, Py); 11.50
(s, 1 H, NH).
Experimental
1
H NMR spectra were recorded on a Bruker WMꢀ250 inꢀ
strument (250 MHz) in DMSOꢀd6. Mass spectra were measured
on a Kratos MSꢀ30 instrument with direct sample injection into
the ion source and with 70 eV ionizing radiation. Melting points
were determined on a Boetius hot stage and were not corrected.
Column chromatography was carried out on silica gel (Merck 60,
70—230 mesh). Commercial chemicals (Aldrich) were used.
Chloroacetamides were synthesized by a known procedure.9
N(S)ꢀButylꢀN(O)ꢀphenylthiooxamide (3а) and 2ꢀmorpholinoꢀ
2ꢀthioxoacetanilide (3b) were prepared by a previously described
procedure.6 Chloroacetamide 1а (5.3 mmol), sulfur (0.7 g), and
an amine (10 mL) were mixed and refluxed for 1 h. Then the
mixture was cooled, diluted with water and extracted with
AcOEt. The organic layer was washed with water and dried over
MgSO4. After removal of the solvent, the product was recrystalꢀ
lized from ethanol. The yield of thiooxamide 3а was 28%, m.p.
58—60 °C (cf. Ref. 7: 58—60 °C). Under similar conditions, the
Nꢀ(3ꢀCyanoꢀ5,6ꢀdihydroꢀ4Hꢀcyclopenta[b]thienꢀ2ꢀyl)ꢀ
2ꢀmorpholinoꢀ2ꢀthioxoacetamide (3i). Yield 65%, m.p.
217—219 °C. Found (%): C, 61.17; H, 5.32; N, 10.22.
C
14H15N2O2S2. Calculated (%): C, 61.09; H, 5.45; N, 10.18.
1H NMR, δ: 2.35, 2.75, 2.85 (all m, each 2 H, CH2); 3.60, 3.70,
3.80, 4.15 (all m, each 2 H, H morphol.); 12.25 (s, 1 H, NH).
MS, m/z: 307 [M]+.
N,N´ꢀBis[(2ꢀmorpholinoꢀ1ꢀoxoꢀ2ꢀthioxo)ethyl]ꢀ1,2ꢀpheꢀ
nylenediamine (5b). Yield 72%, m.p. 229—231 °C. Found (%):
C, 51.17; H, 5.25; N, 13.26. C18H22N4O4S2. Calculated (%):
1
C, 51.04; H, 5.41; N, 13.29. H NMR, δ: 3.65—3.85 (m, 12 H,
H morphol.); 4.15 (m, 4 H, H morphol.); 7.30, 7.65 (both m,
each 2 H, H arom.); 9.95 (s, 2 H, NH). MS, m/z: 422 [M]+.

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Zavarzin et al.
N,N´ꢀBis[2ꢀ(2,6ꢀdimethylanilinoꢀ2ꢀoxoꢀ1ꢀthioxo)ethyl]piꢀ
N(O)ꢀ(2ꢀCyanophenyl)ꢀN(S)ꢀ(4ꢀmethoxyphenyl)thiooxamide
(6d). Yield 62%, m.p. 174—175 °C. Found (%): C, 61.51;
H, 4.27; N, 13.12. C16H13N3O2S. Calculated (%): C, 61.72;
H, 4.21; N, 13.50. 1H NMR, δ: 3.85 (s, 3 H, Me); 7.05 (d, 2 H,
H arom., J = 8.9 Hz); 7.45, 7.80 (both t, each 1 H, H arom., J =
7.7 Hz); 7.92 (m, 3 H, H arom.); 8.10 (d, 1 H, H arom., J =
8.3 Hz); 10.90, 12.33 (both s, each 1 H, NH).
perazine (8a). Yield 56%, m.p. 294—297 °C. Found (%):
C, 61.58; H, 6.09; N, 12.05. C24H28N4O2S2. Calculated (%):
C, 61.51; H, 6.02; N, 11.96. 1H NMR, δ: 2.25, 2.30 (both s,
each 6 H, Me); 4.05—4.18, 4.20—4.38 (both m, each 4 H,
CH2); 7.10 (m, 6 H, H arom.); 10.00 (s, 2 H, NH). MS,
m/z: 469 [M]+.
N(S)ꢀ(Adamantꢀ1ꢀyl)ꢀN(O)ꢀphenylthiooxamide (8b). Yield
64%, m.p. 135—139 °C. Found (%): C, 68.83; H, 6.95; N, 8.85.
N(O),N(S)ꢀBis(4ꢀchlorophenyl)thiooxamide (6e). Yield 73%,
m.p. 155—158 °C. Found (%): C, 51.98; H, 3.03; C1, 21.63;
N, 9.02. C14H10Cl2N2OS. Calculated (%): C, 51.71; H, 3.10;
Cl, 21.80; N, 8.61. 1H NMR, δ: 7.45, 7.55 (both d, each 2 H,
H arom., J = 8.8 Hz); 7.85, 8.00 (both d, each 2 H, H arom., J =
8.8 Hz); 10.60, 12.40 (both s, each 1 H, NH).
C
18H22N2OS. Calculated (%): C, 68.75; H, 7.05; N, 8.91.
1H NMR, δ: 1.51—1.75 (m, 7 H, Ad); 2.15 (m, 3 H, Ad); 2.35
(m, 5 H, Ad); 7.15 (t, 1 H, H arom., J = 7.5 Hz); 7.38 (d, 2 H,
H arom., J = 7.7 Hz); 7.72 (d, 2 H, H arom., J = 7.9 Hz); 9.78,
10.38 (both s, each 1 H, NH). MS, m/z: 314 [M]+.
N(O)ꢀ[4ꢀ(Methoxycarbonyl)phenyl]ꢀN(S)ꢀphenylthiooxamide
(6f). Yield 57%, m.p. 171—174 °C. Found (%): C, 61.42; H, 4.66;
N, 9.03. C16H14N2O3S. Calculated (%): C, 61.13; H, 4.49;
N(S)ꢀCyclopropylꢀN(O)ꢀphenylthiooxamide (8d). Yield 48%,
m.p. 93—95 °C (cf. Ref. 10: 93—95 °C).
1
N(S)ꢀAllylꢀN(O)ꢀphenylthiooxamide (8e). Yield 67%, m.p.
N, 8.91. H NMR, δ: 3.85 (s, 3 H, Me); 7.35 (t, 1 H, H arom.,
85—86 °C (cf. Ref. 10: 84—86 °C).
J = 8.1 Hz); 7.95 (m, 2 H, H arom.); 8.00 (m, 6 H, H arom.);
10.80, 12.40 (both s, each 1 H, NH). MS, m/z: 314 [M]+.
N(S)ꢀ(1ꢀNaphthyl)thiooxamide (6g). Yield 67%, m.p.
198—200 °C. Found (%): C, 62.78; H, 4.16; N, 12.38.
N(O)ꢀ(2,6ꢀdibromoꢀ4ꢀmethylphenyl)thiooxamide (8h). Yield
82%, m.p. 174—176 °C. Found (%): C, 44.69; H, 3.67; Br, 35.12;
N, 6.07. C17H16Br2N2OS. Calculated (%): C, 44.76; H, 3.54;
Br, 35.03; N, 6.14. 1H NMR, δ: 2.35 (s, 3 H, Me); 3.00, 3.85
(both m, each 2 H, CH2); 7.20—7.40 (m, 5 H, H arom.); 7.58 (s,
2 H, H arom.); 10.25, 10.90 (both s, each 1 H, NH).
Synthesis of monothiooxamide (general procedure В). Chloroꢀ
acetamide 1 (5.0 mmol) was added to a mixture, prepared beꢀ
forehand, consisting of an aromatic amine (5.5 mmol), sulfur
(0.7 g), and triethylamine (1 mL) in 5 mL of DMF. The mixture
was stirred at ≈20 °C for 8 h, cooled, and diluted with water. The
precipitate was filtered off, washed with water, and dried in air.
The product was dissolved in acetone, the solution was filtered,
and the residue remaining after removal of acetone from the
filtrate was recrystallized from 95% ethanol.
N,N´ꢀBis[(2ꢀanilinoꢀ1ꢀoxoꢀ2ꢀthioxo)ethyl]ꢀ1,2ꢀphenylenediꢀ
amine (5a). Yield 61%, m.p. 225—227 °C. Found (%): C, 60.87;
H, 4.07; N, 12.93. C22H18N4O2S2. Calculated (%): C, 60.81;
H, 4.18; N, 12.89. 1H NMR, δ: 7.35, 7.45 (both m, each 4 H,
H arom.); 7.75 (m, 2 H, H arom.); 7.95 (m, 4 H, H arom.);
10.60, 12.30 (both s, each 2 H, NH). MS, m/z: 434 [M]+.
N(S)ꢀ(4ꢀMethoxycarbonylphenyl)ꢀN(O)ꢀphenylthiooxamide
(6a). Yield 58%, m.p. 166—167 °C. Found (%): C, 61.42;
H, 4.66; N, 9.03. C16H14N2O3S. Calculated (%): C, 61.13;
H, 4.49; N, 8.91. 1H NMR, δ: 3.90 (s, 3 H, Me); 7.20 (m, 1 H,
H arom.); 7.40, 7.80, 8.05, 8.20 (all m, each 2 H, H arom.);
10.50, 12.50 (both s, each 1 H, NH). MS, m/z: 314 [M]+.
N(S)ꢀ[4ꢀ(Acetylamino)phenyl]ꢀN(O)ꢀphenylthiooxamide
(6b). Yield 68%, m.p. 205—208 °C. Found (%): C, 61.42;
H, 4.66; N, 14.01. C16H15N3O2S. Calculated (%): C, 61.32;
H, 4.82; N, 13.41. 1H NMR, δ: 2.10 (s, 3 H, Me); 7.20 (m, 1 H,
H arom.); 7.40 (d, 2 H, H arom., J = 7.1 Hz); 7.65 (d, 2 H,
H arom., J = 8.0 Hz); 7.80 (d, 2 H, H arom., J = 7.0 Hz); 7.95
(d, 2 H, H arom., J = 7.6 Hz); 10.00, 10.45, 12.50 (all s,
each 1 H, NH).
C
12H10N2OS. Calculated (%): C, 62.59; H, 4.38; N, 12.16.
1H NMR, δ: 7.55 (m, 4 H, H arom.); 7.72 (m, 1 H, H arom.);
8.00 (m, 2 H, H arom.); 8.15 (m, 2 H, NH2); 12.35 (s, 1 H,
NH). MS, m/z: 230 [M]+.
N(S)ꢀ(2ꢀPyridyl)thiooxamide (7a). Yield 77%, m.p.
160—162 °C. Found (%): C, 46.66; H, 3.76; N, 23.23.
C7H7N3OS. Calculated (%): C, 46.40; H, 3.89; N, 23.19.
1H NMR, δ: 7.40 (m, 1 H, Py); 8.00 (t, 1 H, Py, J = 7.7 Hz);
8.25 (s, 2 H, NH2); 8.55 (m, 1 H, Py); 8.82 (d, 1 H, Py, J =
8.2 Hz); 11.80 (s, 1 H, NH). MS, m/z: 181 [M]+.
N(S)ꢀ[2ꢀ(6ꢀBromopyridyl)]thiooxamide (7b). Yield 67%,
m.p. 195—198 °C. Found (%): C, 32.28; H, 2.36; Br, 30.84;
N, 16.07. C7H6BrN3OS. Calculated (%): C, 32.32; H, 2.33;
Br, 30.72; N, 16.15. 1H NMR, δ: 8.20 (m, 3 H, Py); 8.65 (m,
2 H, NH2); 11.95 (s, 1 H, NH).
N(S)ꢀ(4ꢀPyridyl)thiooxamide (7c). Yield 35%, m.p.
210—212 °C. Found (%): C, 46.37; H, 3.92; N, 23.23.
C7H7N3OS. Calculated (%): C, 46.40; H, 3.89; N, 23.19.
1H NMR, δ: 8.12 (m, 4 H, Py); 8.65 (m, 2 H, NH2); 12.25 (s,
1 H, NH). MS, m/z: 181 [M]+.
N(S)ꢀ(3ꢀCarbamoylꢀ4,5,6,7ꢀtetrahydroꢀ1ꢀbenzothiophenꢀ2ꢀ
yl)thiooxamide (7d). Yield 58%, m.p. 218—224 °C. Found (%):
C, 46.76; H, 4.06; N, 14.86. C11H13N3O2S2. Calculated (%):
C, 46.62; H, 4.62; N, 14.83. 1H NMR, δ: 2.80 (m, 4 H,
—CH2CH2—); 2.65—2.90 (m, 4 H, 2 CH2); 7.50, 8.10 (both m,
each 2 H, NH2); 14.5 (s, 1 H, NH). MS, m/z: 283 [M]+.
N(S)ꢀ(2ꢀBromophenyl)thiooxamide (8c). Yield 76%, m.p.
188—190 °C. Found (%): C, 37.02; H, 2.97; Br, 30.90; N, 10.73.
C8H7BrN2OS. Calculated (%): C, 37.08; H, 2.72; Br, 30.84;
1
N, 10.81. H NMR, δ: 7.30 (t, 1 H, H arom., J = 7.8 Hz); 7.45
(t, 1 H, H arom., J = 7.7 Hz); 7.75 (m, 2 H, H arom.); 8.15 (m,
2 H, NH2); 12.00 (s, 1 H, NH).
N(S)ꢀ[4ꢀ(Diethylamino)phenyl]ꢀN(O)ꢀphenylthiooxamide
(6c). Yield 53%, m.p. 108—109 °C. Found (%): C, 66.36;
H, 6.14; N, 12.96. C18H21N3OS. Calculated (%): C, 66.03;
H, 6.46; N, 12.83. 1H NMR, δ: 1.15 (m, 6 H, Me); 3.55 (m, 4 H,
CH2); 6.80 (m, 2 H, H arom.); 7.20 (m, 1 H, H arom.); 7.45,
7.80, 7.95 (all m, each 2 H, H arom.); 10.50, 12.05 (both s,
each 1 H, NH). MS, m/z: 327 [M]+.
2ꢀ(2ꢀBenzoylꢀ3ꢀphenylaziridino)ꢀ2ꢀthioxoacetamide (8f).
Yield 42%, m.p. 92—94 °C. Found (%): C, 65.82; H, 4.50;
N, 9.44. C17H14N2O2S. Calculated (%): C, 65.79; H, 4.55;
N, 9.03. 1H NMR, δ: 3.20, 3.75 (both m, each 1 H, CH);
7.25—7.75 (m, 10 H, H arom.); 8.05 (m, 2 H, NH2).
N(S)ꢀ(2,6ꢀDimethylphenyl)ꢀN(O)ꢀ(4ꢀnitrophenyl)thioxoꢀ
acetamide (8g). Yield 64%, m.p. 190—192 °C. Found (%):

Synthesis of monothiooxamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
419
C, 58.39; H, 4.56; N, 12.78. C16H15N3O3S. Calculated (%):
C, 58.35; H, 4.59; N, 12.67. 1H NMR, δ: 2.20 (s, 6 H, Me); 7.20
(m, 3 H, H arom.); 8.15, 8.35 (both d, each 2 H, H arom., J =
9.2 Hz); 11.00, 12.22 (both s, each 1 H, NH). MS, m/z: 329 [M]+.
6. B. Milligan and J. M. Swan, J. Chem. Soc., 1961, 1194.
7. M. M. Krayushkin, V. N. Yarovenko, L. G. Vorontsova,
M. G. Kurella, and I. V. Zavarzin, Izv. Akad. Nauk, Ser.
Khim., 1996, 485 [Russ. Chem. Bull., 1996, 45, 466 (Engl.
Transl.)].
8. K. Pzhevotskii, M. Voronkov, F. Pzhevotskaya, E. Malinskii,
and V. Usov, Zh. Organ. Khim., 1993, 29, 565 [Russ. J. Org.
Chem., 1993, 29 (Engl. Transl.)].
9. V. N. Yarovenko, S. A. Kosarev, I. V. Zavarzin, and M. M.
Krayushkin, Izv. Akad. Nauk, Ser. Khim., 1998, 2002 [Russ.
Chem. Bull., 1998, 47, 1947 (Engl. Transl.)].
10. V. N. Yarovenko, S. A. Kosarev, I. V. Zavarzin, and M. M.
Krayushkin, Izv. Akad. Nauk, Ser. Khim., 1999, 753 [Russ.
Chem. Bull., 1999, 48, 749 (Engl. Transl.)].
References
1. K.ꢀI. Kawai, K. Nozawa, H. Seya, N. Kawahara, S.ꢀI.
Udagawa, and S. Nakajima, Heterocycles, 1987, 26, 475.
2. Pat. JP 1999ꢀ297002 (Japan); Chem. Abstr., 2001, 134,
310987.
3. Pat. WO 2001/028991; Chem. Abstr., 2001, 134, 311228.
4. O. Mikhailov and M. Kazymova, Trans. Metal Chem.,
London, 1998, 23(2), 195.
5. V. N. Yarovenko, I. V. Zavarzin, A. Yu. Martynkin, and
M. M. Krayushkin, 18th Int. Symp. on the Organic Chemistry
of Sulfur, Book of Abstr., Florence (Italy), 1998, Pꢀ106, 104.
Received December 22 , 2003;
in revised form January 29, 2004