Synthesis of N-acylarenesulfonamides

Full text of DOI:10.1023/B:RUJO.0000034956.41855.46

Russian Journal of Organic Chemistry, Vol. 40, No. 2, 2004, pp. 282-283. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 2, 2004,
pp. 310-311.
Original Russian Text Copyright Ó 2004 by Utkina, Michurin, Shishulina.
SHORT
COMMUNICATIONS
Synthesis of N-Acylarenesulfonamides
E. N. Utkina,A.A. Michurin, andA. V. Shishulina
Nizhegorodskii State Technical University, Nizhni Novgorod, 603600 Russia
Received April 4, 2003
$
&
O 2 ꢀ+ 2
&O &22+
2
,6-Disubstituted 1,4,3,5-oxathiadiazine-4,4-dioxides of
,,D
62 1+
type I are known to be used for preparation of N-sulfonyl-
substituted ureas, guanidines, amidines and other acyclic
and cyclic compounds containing N-sulfonyl group, some
of which possess high biological activity [1–3].
6
,,,
N-Trichloroacetyl-2-thiophenesulfonamide (IIa).
We demonstrated that dioxides I readily and
selectively reacted with aromatic and heteroaromatic
compounds affording the corresponding N-acylarene-
sulfonamides II.
To a solution of 0.23 g (0.66 mmol) of 6-methyl-2-
trichloromethyl-1,4,3,5-oxathiadiazine-4,4-dioxide Iain
9
ml of benzene was added 0.06 ã (0.77 mmol) of thiophene,
and the mixture was heated to 50°C for 6 h. Then the
solvent was distilled off, and the residue was neutralized
2
1
&
2
1
&
with Na CO solution, 0.20 ml of concn. hydrochloric acid
6
2
2
3
5 ꢁꢀ +
H& 1
was added, and 0.27 g (98%) of N-trichloroacetyl-2-
thiophenesulfonamide IIa was isolated, mp 154°C (from
5
ꢁ62 1+ 5&
0
5
2
0H
–
1
ethanol). IR spectrum, n, cm : 3310 (NH), 1745 (C=O),
,Dꢀꢁ,E
,,D ,,H
1360, 1150 (SO ). Found, %: N 4.43. Neutralization
2
equivalent 306.40. C H Cl NO S . Calculated, %: N 4.54.
Neutralization equivalent 306.86.
R = CCl (Ià, IIà–d), CBr (Ib, IIe); R’ = 2-thienyl (IIa),
6
4
3
3 2
3
3
4
-MeC H (IIb), 4-Me NC H (IIc), 4-MeOC H (IId, e).
6 4 2 6 4 6 4
N-Trichloroacetyl-4-methylbenzenesulfonamide
(
IIb). Asolution of 0.15 g (0.57 mmol) of dioxide Ia in 5
This reaction is a convenient procedure for building
up an amidosulfonyl group in arene (hetarene).
ml of toluene was heated to 110°C for 5 h. The residue
after evacuation was neutralized with Na CO solution,
2
3
It is presumable that one among possible paths of
arenes (hetarenes) amidosulfonylation is a route involving
generation from dioxides I of reactive species, N-
sulfonylamides (A) [4] followed by their reaction with
arenes (hetarenes).
0
.10 ml of concn. HCl was added, and 0.16 g (89%) of
sulfonamide IIb was filtered off, mp 141°C (from ethanol)
–1
(
(
publ.: mp 140–142°C [7]). IR spectrum, n, cm : 3350
NH), 1755 (C=O), 1400, 1185 (SO ). Found, %: N 4.39.
2
Neutralization equivalent 315.80. C H Cl NO S.
9
8
3
3
Calculated, %: N 4.43. Neutralization equivalent 316.50.
5
'
5ꢀ+
,
& 1
$
N-Trichloroacetyl-4-dimethylaminebenzene-
sulfonamide (IIc). A solution of 0.20 g (0.75 mmol) of
dioxide Ia and 0.14 g (1.13 mmol) N,N-dimethylaniline in
,,
ꢀ
0
H&1
2
62
7
ml of benzene was heated to 110°C for 5 h. From the
The composition and structure of sulfonamides II were
confirmed by elemental analyses, values of neutralization
equivalents, and IR spectra.
reaction mixture was filterd off 0.22 g (85%) of
sulfonamide IIc, mp (decomp.) 230°C (from ethanol).
IR spectrum, n, cm : 3280 (NH), 1735 (C=O), 1360,
1135 (SO ). Found, %: N 8.02. Neutralization equivalent
–1
The structure of sulfonamide IIa was also proved by
2
its selective hydrolysis on Al O [5] to afford 2-thio-
348.06. C H Cl N O S. Calculated, %: N 8.10.
2
3
10 11
3
2
3
phenesulfonamide III.
Neutralization equivalent 348.67.
1070-4280/04/4002-0282Ó2004 MAIK “Nauka/Interperiodica”

SYNTHESIS OF N-ACYLARENESULFONAMIDES
283
–
1
N-Trichloroacetyl-4-methoxybenzenesulfon-
amide (IId). Asolution of 0.10 g(0.38 mol) of dioxide Ia
in 3 ml of anisole was heated to 100°C for 5 h. The
ethanol), mp 142°C [6]. IR spectrum, í, cm : 3335 (NH),
1590 (C=C), 1360, 1170 (SO ). The aluminum oxide was
2
washed with 25% water solution of ammonia and filtered
off. The water filtrate was evaporated to give 0.12 g
(99%) of ammonium trichloroacetate IR spectra were
recorded on spectrophotometer UR-20 from solutions in
CH Cl .
residue after evacuation was neutralized with Na CO3
2
solution, 0.10 ml of concn. HCl was added, and 0.11 g of
sulfonamide IId was filtered off, mp 168°C (from
–
1
ethanol). IR spectrum, n, cm : 3390 (NH), 1785 (C=O),
380, 1174 (SO ). Found, %: N 4.30. Neutralization
2
2
1
2
equivalent 334.31. C H Cl NO S. Calculated, %: N 4.21.
Neutralization equivalent 332.50.
9
8
3
4
REFERENCES
The reaction of dioxide Ib with anisole under similar
conditions afforded N-tribromoacetyl-4-methoxy-
benzenesulfonamide (IIe) (93%), mp 153°C (from
1
. Michurin, A.A., Utkina, E.I., Zakharov, L.N., Fukin, G.K., and
Shishulina, A.V., Zh. Org. Khim., 2000, vol. 36, p. 1559.
.Abramova, L.I., Titova, O.M., Michurin,A.A., and Zil’berman,
2
–
1
ethanol). IR spectrum, n, cm : 3390 (NH), 1750 (C=O),
380< 1150 (SO ). Found, %: N 3.03. Neutralization
E.N., Vysokomol. Soed. , 1994, vol. 36, p. 2084.
3. US Patent 4830663, 1987; Ref. Zh. Khim., 1990, 14O423P.
4. Burgess, E.M. and Williams, W.M., J. Org. Shem., 1973,
vol. 38, p. 1244.
5. Utkina, E.N., Michurin,A.A., and Shishulina,A.V., Zh. Org.
Khim., 2000, vol. 36, p. 1263.
1
2
equivalent 465.51. C H Br NO S. Calculated, %: N 3.01.
9
8
3
4
Neutralization equivalent 465.70.
-Thiophenesulfonamide (III). A solution of 0.20 g
0.64 mol) of sulfonamide IIa in 15 ml methylene chloride
2
(
was maintained at stirring for 48 h at 15°C with 1.00 g of
Al O . The precipitate of Al O was filtered off and
6. Spravochnik khimika (Handbook of Chemist), Moscow:
Khimiya, 1964, vol. 2, p. 982.
2
3
2
3
washed with acetone. The solvent was distilled off to
afford 0.11 g (99%) of sulfonamide III, mp 142°C (from
7. Kretov, A.E. and Kremlev, M.M., Ukr. Khim. Zh., 1959,
vol. 25, p. 482.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004