SYNTHESIS OF 4-ARYL-2-HYDROXY-4-OXO-2-BUTENOIC (AROYLPYRUVIC) ACIDS
631
a solution of 0.01 mol of sodium 4-aminobenzene-
sulfonylacetamide in 15 mL of glacial acetic acid was
added a solution of 0.01 mol of methyl 4-chloro-
benzoylpyruvate in 10 mL of glacial acetic acid. The
reaction mixture was refluxed for 5–10 min. After
cooling, the precipitate formed was filtered off and
recrystallized from an acetic acid–dioxane mixture
(1 : 2). Yield 3.34 g (79%), mp 248–250°С. IR
spectrum, ν, cm–1: 3264 (СONH), 3125 (ОН), 1724,
2-Hydroxy-4-(2,4-dichlorophenyl)-4-oxo-2-bu-
tenoic acid N-(4-acetylaminosulfonylphenyl)amide
(V) was obtained similarly. Yield 3.79 g (83%), mp
206–208°С. IR spectrum, ν, cm–1: 3568, 3500, 3344
(СONH), 3120 (ОН), 1696 (СОNH), 1620 (С=О),
1
1376, 1160 (SO2). H NMR spectrum, δ, ppm: 1.90 s
(3Н, СН3 СО), 4.60 s (2Н, COCH2CO), 6.76 s (1Н, СН=),
7.43–7.99 m (7Н, СНAr), 10.83 s (1Н, СONHC6H4),
11.87 s (1H, SO2NHCO). Found, %: С 47.39, 47.17; H
3.04, 3.15; N 6.04, 6.21; S 6.92, 7.11. C18H14Cl2·
N2O6S. Calculated, %: С 47.28; H 3.09; N 6.13; S 7.01.
1
1696 (СОNH), 1610 (С=О), 1376, 1152 (SO2). H
NMR spectrum, δ, ppm: 1.92 s (3Н, CH3CO), 4.61 s
(2Н, COCH2CO), 7.13 s (1Н, СН=), 7.48–8.01 m (8Н,
СНAr), 10.91 s (1Н, СONHC6H4), 11.90 s (1H,
SO2NHCO). Found, %: С 51.24, 51.01; H 3.65, 3.51;
N 6.54, 6.71; S 7.49, 7.66. C18H15ClN2O6S. Calculated,
%: С 51.13; H 3.58; N 6.62; S 7.58.
5-Phenylpyrazole-3-carboxylic acid N-(4-acetyl-
aminosulfonylphenyl)amide (VI). To a suspension of
0.005 mol of compound II in 35 mL of glacial acetic
acid was added 0.006 mol of hydrazine hydrate (20%
excess). The reaction mixture was refluxed for 2 h.
After cooling, the precipitate formed was filtered off
and recrystallized from ethanol. Yield 1.25 g (65%),
mp 283–285°С. IR spectrum, ν, cm–1: 3344, 3190,
2-Hydroxy-4-oxo-4-phenyl-2-butenoic acid N-(4-
acetylaminosulfonylphenyl)amide (II) was obtained
similarly. Yield 2.95 g (76%), mp 232–234°С. IR
spectrum, ν, cm–1: 3240 (СONH), 3150 (ОН), 1720,
1
3128 (NH), 1724, 1664 (CОN), 1376, 1160 (SO2). H
1
NMR spectrum, δ, ppm: 1.91 s (3Н, CH3CO), 7.19 s
(1Н, СH-4), 7.34–8.03 m (9Н, СНAr), 10.44 s (1Н,
СОNНС6 Н4), 11.80 s (1Н, SО2NНСО), 13.69 s (1Н,
NН-1). Found, %: С 56.09, 56.38; H 4.15, 4.26; N
14.47, 14.66; S 8.43, 8.26. C18H16N4O4S. Calculated,
%: С 56.24; H 4.20; N 14.57; S 8.34.
1696 (СОNH), 1610 (С=О), 1376, 1156 (SO2). H
NMR spectrum, δ, ppm: 1.90 s (3Н, CH3CO), 4.61 s
(2Н, COCH2CO), 7.15 s (1Н, СН=), 7.43–8.03 m (9Н,
СНAr), 10.94 s (1Н, CONHC6H4), 11.80 s (1H,
SO2NHCO). Found, %: С 55.52, 55.79; H 4.09, 4.22;
N 7.12, 7.29; S 8.18, 8.34. C18H16N2O6S. Calculated,
%: С 55.66; H 4.15; N 7.21; S 8.26.
REFERENCES
2-Hydroxy-4-oxo-4-(4-fluorophenyl)-2-butenoic
acid N-(4-acetylaminosulfonylphenyl)amide (III)
was obtained similarly. Yield 3.86 g (95%), mp 258–
260°С. IR spectrum, ν, cm–1: 3240 (СONH), 3120
(ОН), 1724, 1688 (СОNH), 1620 (С=О), 1368, 1160
(SO2). 1H NMR spectrum, δ, ppm: 1.90 s (3Н,
CH3CO), 4.60 s (2Н, COCH2CO), 7.13 s (1Н, СН=),
7.23–8.15 m (8Н, СНAr), 10.91 s (1Н, CONHC6H4),
11.89 s (1H, SO2NHCO). Found, %: С 53.08, 53.33; H
3.65, 3.77; N 6.81, 6.97; S 7.98, 7.80. C18H15FN2O6S.
Calculated, %: С 53.20; H 3.72; N 6.89; S 7.89.
1. Maslivets, А.N., Tarasova, O.P., and Andreichikov, Yu.S.,
Zh. Org. Khim., 1992, vol. 28, no. 6, p. 1287.
2. Andreichikov, Yu.S., Kozlov, A.P., and Kurdina, L.N.,
Zh. Org. Khim., 1984, vol. 20, no. 4, p. 826.
3. Andreichikov, Yu.S., Milyutin, A.V., Krylova, I.V.,
Saraeva, R.F., Dormidontova, E.V., Drovosekova, M.P.,
Nazmetdinov, F.Ya., and Kolla, V.E., Pharm. Chem. J.,
1990, vol. 24, no. 7, p. 33.
4. Andreichikov, Yu.S., Nalimova, Yu.A., Tandryakova, S.P.,
and Vilenchik, Ya.M., Zh. Org. Khim., 1978, vol. 14,
no. 1, p. 160.
5. Kozlov, A.P., Sazhnev, S.S., Kozlova, G.A., and
Andreichikov, Yu.S., Zh. Org. Khim., 1996, vol. 32,
no. 10, p. 1573.
6. Kozlov, A.P., Ryabova, V.V., and Varkentin, L.I., Book
of Abstracts, Conference Dedicated to A. Butlerov
“Chemistry of Unsaturated Compounds,” Kazan, 1986,
p. 120.
7. Kozlov, A.P., Varkentin, L.I., and Andreichikov, Yu.S.,
Zh. Org. Khim., 1984, vol. 20, no. 10, p. 2198.
8. Kozlov, A.P., Varkentin, L.I., and Andreichikov, Yu.S.,
Zh. Org. Khim., 1989, vol. 25, no. 9, p. 1991.
9. Andreichikov, Yu.S., Gein V.L., and Anikina I.N., Zh.
Org. Khim., 1986, vol. 22, no. 8, p. 1749.
2-Hydroxy-4-(3-methoxyphenyl)-4-oxo-2-butenoic
acid N-(4-acetylaminosulfonylphenyl)amide (IV)
was obtained similarly. Yield 3.39 g (81%), mp 218–
220°С. IR spectrum, ν, cm–1: 3360, 3256 (СONH), 3130
(ОН), 1728, 1710 (СОNH), 1620 (С=О), 1380, 1160 (SO2).
1H NMR spectrum, δ, ppm: 1.90 s (3Н, СН3СО), 3.79 s
(3Н, 3-CH3O), 4.60 s (2Н, COCH2CO), 7.13 s (1Н,
СН=), 7.20–8.02 m (8Н, СНAr), 10.89 s (1Н, СONH·
C6H4), 11.85 s (1H, SO2NHCO). Found, %: С 54.41,
54.68; H 4.28, 4.41; N 6.61, 6.78; S 7.56, 7.74. C19H18N2·
O7S. Calculated, %: С 54.54; H 4.34; N 6.69; S 7.66.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014