Job/Unit: O30402
/KAP1
Date: 01-07-13 18:34:27
Pages: 7
Vilsmeier Reagents in Situ: Synthesis of N-Sulfonylformamidines
4
4
29.1228. C20
.81, N 12.87; found C 55.52, H 4.70, N 12.52.
H
20
N
4
O
5
S·3/8H
2
O (428.5+6.8): calcd. C 55.19, H
Zampella, V. Russo, N. D. Bello, G. Nano, L. Nicolini, M. Lo-
cati, P. Fantucci, S. Florio, F. Colotta, J. Med. Chem. 2005, 48,
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Rappoport, in: The Chemistry of Sulphonic Acids, Esters and
Their Derivatives, Wiley, Chichester, UK, 1991.
436
441
446
451
456
461
466
471
476
481
486
491
496
4
N-[(E)-Pyrrolidin-1-ylmethylidene]benzenesulfonamide
81 Method B: reaction time 5 h, yield 94%, m.p. 132–133 °C (H
(3m):
O/
): δ = 1.95–1.99 (m, 4 H), 3.46–3.50 (m,
H), 3.58–3.62 (m, 2 H), 7.44–7.53 (m, 3 H), 7.89–7.91 (m, 2 H),
3
3
2
1
EtOH). H NMR (CDCl
3
2
8
1
.34 (s, 1 H) ppm. 1 C NMR (CDCl
26.5, 128.6, 131.7, 142.5, 155.9 ppm. IR: ν˜ = 2973, 1607, 1447,
3
3
): δ = 24.3, 25.0, 46.5, 50.0,
[
[
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–1
86 1346, 1307, 1278, 1188, 1143, 1087 cm . MS (ESI+): m/z = 239
+
15 2 2
H N O
S [M + H]+ 239.0849;
[
M + H] . HRMS calcd. for C11
found 239.0851. C11 S (238.30): calcd. C 55.44, H 5.92, N
1.76; found C 55.59, H 5.65, N 11.78.
14 2 2
H N O
2
3, 97–100; c) A. A. Bekhit, H. M. A. Ashour, Y. S. A. Ghany,
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1
4
Transformation of N-Sulfonylformamidines 3 into Sulfonamides 1:
Hydrazine monohydrate (500 mg, 10 mmol) was added at room
temperature to a stirred mixture of the appropriate N-sulfonyl-
formamidine 3 (1.0 mmol) in absolute ethanol (5 mL). The reaction
mixture was stirred for 1–2 h and the solvents were removed. Water
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3
3
4
91
96
01
[30 mL, in the case of the isolation of acid 1g a few drops of acetic
acid were added (pH around 5)] and ethyl acetate (30 mL) were
then added, the phases were separated, and the water phase was
additionally extracted with ethyl acetate (3ϫ 20 mL). The organic
phases were combined, dried with anhydrous Na SO and filtered,
2 4
and the solvents were removed to give very clean product 1 in good
3
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(
9
2E)-2-Phenyl-3-(4-sulfamoylphenyl)prop-2-enoic Acid (1g): Yield
0% from 3k, yield 84% from 3o, m.p. 169–171 °C (petroleum
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1
ether/EtOAc). H NMR ([D
7
(br. s, 1 H) ppm. C NMR ([D
1
6
]DMSO): δ = 7.16–7.21 (m, 4 H),
[
[
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13
4
06
11
6
]DMSO): δ = 125.4, 127.9, 128.6,
29.5, 130.3, 135.63, 135.64, 137.4, 137.9, 143.7, 168.0 ppm. IR: ν˜
3233, 3106, 2980, 1675, 1615, 1558, 1495, 1405, 1287, 1151 cm .
–
1
=
+
4
MS (ESI+): m/z = 304 [M + H] . HRMS calcd. for C15H14NO S
+
15 4 2
[M + H] 304.0638; found 304.0638. C H13NO S·1/5H O
1993, 58, 7022–7028; g) A. L. Silva, A. Covarrubias-Zúñiga,
4
(303.3+3.6): calcd. C 58.70, H 4.40, N 4.56; found C 58.94, H 4.00,
N 4.56.
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[
Supporting Information (see footnote on the first page of this arti-
cle): Characterization data that are not given in the main text. Cop-
ies of the H NMR and C NMR spectra are given for all new
compounds and also for known N-sulfonylformamidines 3.
2
878; Angew. Chem. Int. Ed. 2008, 47, 2836–2839; c) E. J. Yoo,
1
13
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16
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2
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[
Acknowledgments
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The Slovenian Research Agency is gratefully acknowledged for fin-
ancial support (project P1-0230). This work was supported within
the infrastructure of the EN-FIST Centre of Excellence, Ljubljana,
Slovenia. This study was partially supported by the Slovenian Re-
search Agency (Young Researcher grant to M. G.).
4
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Received: March 16, 2013
[
Bitondo, V. D. Cioccio, E. Galliera, V. Berdini, A. Topai, G.
Published Online:
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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