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Yarovenko et al.
was ≤20 °C). The reaction mixture was stirred for 15 min and
then diluted with water (50 mL). The precipitate that formed
was filtered off and recrystallized from a 1 : 1 EtOH—H2O
mixture to obtain 2ꢀanilinoꢀ (2a), 2ꢀ(2,6ꢀdimethylanilino)ꢀ (2b),
2ꢀ(3,4ꢀdichloroanilino)ꢀ (2c), 2ꢀ(2ꢀnitroanilino)ꢀ (2d),
2ꢀ(3ꢀnitroanilino)ꢀ (2e), and 2ꢀ(4ꢀchloroanilino)ꢀ2ꢀoxoethaneꢀ
hydroxymoyl chloride (2f). Their spectroscopic and physicoꢀ
chemical characteristics are given in Table 1.
3,4ꢀBis(Nꢀphenylcarbamoyl)furoxane (3a). Freshly distilled
Et3N (0.69 mL, 0.50 g, 5 mmol) was added to a solution of
carbamoylformhydroxymoyl chloride 2a (1.0 g, 5 mmol) in
Et2O (5 mL). The solution was filtered off from the precipitate
and concentrated on a rotary evaporator. The residue was reꢀ
crystallized from EtOH. The yield was 0.81 g (50%). The specꢀ
troscopic and physicochemical characteristics of 3a are given
in Table 1.
Reactions of carbamoylformamide oximes 1a—c,f—k with
NaNO2 in the presence of H2SO4 (general procedure). The
reactions were carried out according to the aboveꢀmentioned
general procedure applied to the reactions of carbamoylamide
oximes 1a—f with NaNO2 with the use of 20% H2SO4 instead
of hydrochloric acid. Sodium nitrite was added upon cooling to
5—10 °C. Then the reaction mixture was diluted with H2O
(30 mL). The precipitate that formed was filtered off, dried,
and recrystallized from EtOH to obtain 3,4ꢀbis(Nꢀphenylꢀ
carbamoyl)ꢀ (3a), 3,4ꢀbis[Nꢀ(4ꢀmethoxyphenyl)carbamoyl]ꢀ (3b),
3,4ꢀbis[Nꢀ(3,4ꢀdichlorophenyl)carbamoyl]ꢀ (3c), 3,4ꢀbis[Nꢀ
(4ꢀnitrophenyl)carbamoyl]ꢀ (3d), 3,4ꢀbis[Nꢀ(2,3ꢀdimethylꢀ
phenyl)carbamoyl]ꢀ (3e), 3,4ꢀbis[Nꢀ(3ꢀmethoxyphenyl)carbaꢀ
moyl]ꢀ (3f), 3,4ꢀbis[Nꢀ(4ꢀchlorophenyl)carbamoyl]ꢀ (3g),
3,4ꢀbis[Nꢀ(4ꢀmethylphenyl)carbamoyl]ꢀ (3h), and 3,4ꢀbis[Nꢀ
(2,6ꢀdimethylphenyl)carbamoyl]furoxane (3i). Their spectroꢀ
scopic and physicochemical characteristics are given in Table 1.
2ꢀHydroxyiminoꢀ2ꢀmorpholinoꢀNꢀphenylacetamide (4d).
Morpholine (0.5 mL, 0.5 g, 5 mmol) was added to a solution of
hydroxymoyl chloride 2a (0.5 g, 2.5 mmol) in AcOEt (10 mL).
The precipitate that formed was filtered off and the filtrate was
concentrated on a rotary evaporator. The residue was recrystalꢀ
lized from a 1 : 1 EtOH—H2O mixture. The yield was 0.7 g.
The spectroscopic and physicochemical characteristics of 4d
are given in Table 1.
2ꢀAllylaminoꢀ2ꢀhydroxyiminoꢀ (4a), 2ꢀcyclopropylaminoꢀ
2ꢀhydroxyiminoꢀ (4b), 2ꢀdiallylaminoꢀ2ꢀhydroxyiminoꢀ (4c),
2ꢀhydroxyiminoꢀ2ꢀthiomorpholinoꢀNꢀphenylacetamide (4e), and
Nꢀ(4ꢀchlorophenyl)ꢀ2ꢀcyclopropylaminoꢀ2ꢀhydroxyiminoacetꢀ
amide (4f) were prepared analogously. Their spectroscopic and
physicochemical characteristics are given in Table 1.
SꢀBenzothiazolꢀ2ꢀyl 2ꢀanilinoꢀ2ꢀoxoethanehydroxyiminoꢀ
thioate (5). Sodium benzothiazoleꢀ2ꢀthiolate (0.1 g, 0.5 mmol)
was added to a solution of carbamoylhydroxymoyl chloride 2a
(0.1 g, 0.5 mmol) in EtOH (5 mL). The reaction mixture was
stirred for 24 h and filtered off from NaCl. The filtrate was
concentrated on a rotary evaporator. The residue was recrystalꢀ
lized from EtOH. The yield was 0.13 g (80%), m.p. 205 °C.
Found (%): C, 55.10; H, 3.50; N, 12.55. C15H11N3O2S2. Calꢀ
culated (%): C, 54.71; H, 3.34; N, 12.77. 1H NMR, δ: 7.20—7.90
(m, 9 H, H arom.); 11.15 (s, 1 H, NH). MS, m/z: 329 [M]+.
2ꢀHydroxyiminoꢀN(1)ꢀphenylacetamide (6). Sodium boroꢀ
hydride (0.3 g, 7.9 mmol) was added portionwise (0.1 g) with
stirring to a solution of hydroxymoyl chloride 2a (0.3 g,
1.5 mmol) in EtOH (5 mL) (upon the addition of the first
portion, the solution was clarified and gas evolution was obꢀ
served). Within 10 min after the addition of the last portion
(TLC control), the solution was filtered off and concentrated on
a rotary evaporator. The residue was recrystallized from EtOH.
The yield was 0.15 g (56%), m.p. 193—195 °C. Found (%):
C, 58.47; H, 4.59; N, 17.18. C8H8N2O2. Calculated (%):
C, 58.54; H, 4.88; N, 17.07. 1H NMR, δ: 7.05 (t, 1 H, H arom.,
J = 7.3 Hz); 7.30 (m, 2 H, H arom.); 7.65 (d, 2 H, H arom.,
J = 8.0 Hz); 7.50 (s, 1 H, CH); 10.00 (s, 1 H, NH); 12.05 (s,
1 H, OH). MS, m/z: 164 [M]+.
N(3),5ꢀDiphenylꢀ4,5ꢀdihydroisoxazoleꢀ3ꢀcarboxamide (7).
Triethylamine (∼10 drops) was added dropwise to a mixture of
carbamoylhydroxymoyl chloride 2a (0.20 g, 1 mmol) and styꢀ
rene (6.0 mL, 5.4 g, 52 mmol) until hydroxymoyl chloride was
completely dissolved. Then the liquid phase was distilled off on
a rotary evaporator. The residue was washed with water, dried,
and recrystallized from EtOH. The yield was 0.14 g (52%),
m.p. 123—126 °C. Found (%): C, 72.10; H, 5.20; N, 10.58.
C
16H14N2O2. Calculated (%): C, 72.18; H, 5.26; N, 10.53.
1H NMR, δ: 3.25 (m, 1 H, CH2); 3.80 (m, 1 H, CH2); 5.80 (m,
1 H, CH); 7.10 (m, 1 H, H arom.); 7.35 (m, 7 H, H arom.);
7.75 (m, 2 H, H arom.); 10.50 (s, 1 H, NH). MS, m/z: 266 [M]+,
249 [M – OH]+.
N(3),5ꢀDiphenylisoxazoleꢀ3ꢀcarboxamide (8a). Triethylꢀ
amine (0.2 mL, 0.15 g, 46 mmol) was added dropwise to a
suspension of carbamoylhydroxymoyl chloride 2a (0.10 g,
0.5 mmol) in freshly distilled phenylacetylene (5.0 mL, 4.65 g,
46 mmol). After 15 min, the solution was filtered off and conꢀ
centrated in vacuo on a rotary evaporator. The residue was
recrystallized from EtOH. The yield was 0.06 g (46%), m.p.
200—202.5 °C. Found (%): C, 72.60; H, 4.70; N, 10.75.
C
16H12N2O2. Calculated (%): C, 72.72; H, 4.58; N, 10.60.
1H NMR, δ: 7.15 (t, 1 H, H arom., J = 7.3 Hz); 7.35 (m, 2 H,
H arom.); 7.45 (s, 1 H, CH); 7.65 (m, 3 H, H arom.); 7.80 (m,
2 H, H arom.); 7.95 (m, 2 H, H arom.); 10.65 (s, 1 H, NH).
MS, m/z: 264 [M]+.
N(3)ꢀ(4ꢀChlorophenyl)ꢀ5ꢀphenylisoxazoleꢀ3ꢀcarboxamide 8b
was prepared analogously to compound 8a from carbamoylꢀ
hydroxymoyl chloride 2f. The yield was 0.04 g (33%), m.p.
217—219 °C. Found (%): C, 64.18; H, 3.67; Cl, 11.76; N, 9.45.
C
16H11ClN2O2. Calculated (%): C, 64.33; H, 3.71; Cl, 11.87;
1
N, 9.38. H NMR, δ: 7.40 (m, 3 H, H arom. + CH); 7.55 (m,
3 H, H arom.); 7.70 (m, 2 H, H arom.); 7.95 (m, 2 H, H arom.);
10.80 (s, 1 H, NH). MS, m/z: 298 [M]+.
2ꢀAzidoꢀ2ꢀhydroxyiminoꢀN(1)ꢀphenylacetamide (9a). Sodium
azide (0.10 g, 1.5 mmol) was added with stirring to a suspenꢀ
sion of carbamoylhydroxymoyl chloride 2a (0.10 g, 0.5 mmol)
in H2O (2 mL). The mixture was stirred for 30 min (TLC
control). The precipitate was filtered off and dried. The yield
was 0.92 g (90%), m.p. 138—140 °C (decomp.). IR, ν/cm–1
:
3300 (OH); 2920 (NH); 2860 (NH); 2150 (N3); 1670 (C=O).
MS, m/z: 253 [M+]. The compound was used for further transꢀ
formations without recrystallization.
2ꢀAzidoꢀN(1)ꢀ(4ꢀchlorophenyl)ꢀ2ꢀhydroxyiminoacetamide
(9b) was prepared analogously to compound 9a from carbamoylꢀ
hydroxymoyl chloride 2f. The yield was 0.90 g (85%), m.p.
129—133 °C (decomp.). MS, m/z: 239 [M]+.
1ꢀHydroxyꢀN(5)ꢀphenylꢀ1Hꢀ1,2,3,4ꢀtetrazoleꢀ5ꢀcarbꢀ
oxamide (10). Gaseous HCl was passed through a solution of
azide 9a (0.1 g, 0.5 mmol) in dioxane (5 mL) for 10 min. The
solution was kept at 0—5 °C for 24 h and then diluted with