SYNTHESIS OF 3-(4-OXO-4H-3,1-BENZOXAZIN-2-YL)-. . .
89
Scheme 4.
for 3 h under reflux. Excess thionyl chloride was
distilled off under reduced pressure, and the residue
2-(3-Phenylaminosulfonylphenyl)-4H-3,1-benz-
oxazin-4-one (VIII). Yield 2.91 g (77%), mp 190
192 C. H NMR spectrum (DMSO-d6), , ppm: 7.00
8.65 m (13H, Harom), 10.25 s (1H, SO2NH). Found,
%: C 63.22; H 3.57; N 7.52; S 8.78. C20H14N2O4S.
Calculated, %: C 63.48; H 3.73; N 7.40; S 8.47.
1
was recrystallized from toluene. Yield 2.8 g (87%),
1
mp 135 137 C. H NMR spectrum (DMSO-d6),
,
ppm: 7.65 8.60 m (8H, Harom). Found, %: C 52.20;
H 2.42; Cl 11.37; N 4.42; S 10.17. C14H8ClNO4S.
Calculated, %: C 52.26; H 2.51; Cl 11.02; N 4.35;
S 9.96.
Sulfonamides V and VI (general procedure).
A mixture of 0.03 mol of piperidine or aniline and
3.22 g of sulfonyl chloride IV in 10 ml of acetonitrile
was heated for 2 h under reflux. The mixture was
poured into water, and the precipitate was filtered off
and recrystallized from acetic acid.
N-(2-Piperidinocarbonylphenyl)-3-(phenyl-
aminosulfonyl)benzamide (IX). A mixture of 3.78 g
of benzoxazinone VIII and 0.01 mol of piperidine in
10 ml of acetonitrile was heated for 1 h under reflux.
It was then poured into water, and the precipitate was
filtered off and recrystallized from acetic acid. Yield
1
4.03 g (87%), mp 147 150 C. H NMR spectrum
(DMSO-d6), , ppm: 7.00 8.35 m (13H, Harom),
1.60 m [6H, (CH2)3], 3.40 m (4H, NCH2), 10.45 s
(CONH), 10.25 s (1H, SO2NH). Found, %: C 64.25;
H 5.23; N 9.17; S 6.92. C25H25N3O4S. Calculated, %:
C 64.77; H 5.44; N 9.06; S 6.92.
N-(2-Piperidinocarbonylphenyl)-3-(piperidino-
sulfonyl)benzamide (V). Yield 4.2 g (92%), mp 180
1
182 C. H NMR spectrum (DMSO-d6), , ppm: 7.20
8.25 m (8H, Harom), 1.55 m [12H, (CH2)3], 3.30 m
(8H, NCH2), 10.45 s (CONH). Found, %: C 63.15;
H 6.21; N 9.17; S 6.92. C24H29N3O4S. Calculated, %:
C 63.27; H 6.42; N 9.22; S 7.03.
REFERENCES
1. Timoshenko, G.N., Grigorichev, A.K., Moskvi-
chev, Yu.A., and Mironov, G.S., Izv. Vyssh. Uchebn.
Zaved., Ser. Khim. Khim. Tekhnol., 1986, vol. 29,
no. 5, pp. 23 26.
N-(2-Phenylaminocarbonylphenyl)-3-(phenyl-
aminosulfonyl)benzamide (VI). Yield 4.38 g (93%),
1
mp 231 233 C. H NMR spectrum (DMSO-d6),
,
ppm: 7.00 8.60 m (18H, Harom), 10.45 s (1H, CONH),
10.25 s (1H, SO2NH), 12.10 s (1H, CONH). Found,
%: C 66.11; H 4.23; N 8.72; S 6.88. C26H21N3O4S.
Calculated, %: C 66.22; H 4.49; N 8.91; S 6.80.
Benzoxazines VII and VIII (general procedure).
Piperidine or aniline, 0.01 mol, was added with stir-
ring to a solution of 3.22 g of sulfonyl chloride IV
in 10 ml of acetonitrile. Pyridine, 0.01 mol, was then
added, and the mixture was kept for 1 h at 20 C and
poured into water. The precipitate was dried and
recrystallized from toluene.
2. Moskvichev, Yu.A., Timoshenko, G.N., Grigori-
chev, A.K., Tarasov, A.V., Smirnova, T.M., and
Frolova, O.B., Izv. Vyssh. Uchebn. Zaved., Ser. Khim.
Khim. Tekhnol., 1996, vol. 39, no. 3, pp. 82 84.
3. Tarasov, A.V., Moskvichev, Yu.A., Timoshenko, G.N.,
Frolova, O.B., and Kozlova, O.S., Russ. J. Org. Chem.,
2000, vol. 36, no. 1, pp. 69 71.
4. Buhler, K.-U., Spezialplaste, Berlin: Akademie, 1978.
5. Comprehensive Organic Chemistry, Barton, D. and
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 5.
6. FRG Patent no. 4140303, 1993; Ref. Zh., Khim.,
2-(3-Piperidinosulfonylphenyl)-4H-3,1-benzoxa-
zin-4-one (VII). Yield 2.92 g (79%), mp 174 176 C.
1H NMR spectrum (DMSO-d6), , ppm: 7.65 8.50 m
(8H, Harom), 1.55 m [6H, (CH2)3], 3.20 m (4H,
NCH2). Found, %: C 61.72; H 4.82; N 7.61; S 8.77.
C19H18N2O4S. Calculated, %: C 61.61; H 4.90;
N 7.56; S 8.65.
1993, no. 7N104P.
7. Krasovitskii, B.M. and Bolotin, B.M., Organicheskie
lyuminofory (Organic Luminophores), Leningrad:
Khimiya, 1976.
8. Suter, C.M., The Organic Chemistry of Sulfur: Tetra-
covalent Sulfur Compounds, New York: Wiley, 1944.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002