A green preparation of N-chloro- and N-bromosaccharin

Article abstract of DOI:10.1081/SCC-120016353

The reaction of the sodium salt of saccharin, potassium chloride or bromide and oxone in water at room temperature for 24h produced pure N-chloro- and N-bromosaccharin in 58% and 64% yield, respectively.

Full text of DOI:10.1081/SCC-120016353

This article was downloaded by: [University of Arizona]
On: 24 December 2012, At: 02:01
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
A Green Preparation of N -Chloro- and N -
Bromosaccharin
a
a
a
Soraia P. L. de Souza , Joaquim F. M. da Silva & Marcio C. S. de Mattos
a
Instituto de Química, Departamento de Química Orgânica, Universidade Federal do Rio de
Janeiro, Rio de Janeiro, Brazil
Version of record first published: 17 Aug 2006.
To cite this article: Soraia P. L. de Souza , Joaquim F. M. da Silva & Marcio C. S. de Mattos (2003): A Green Preparation of N
Chloro- and N -Bromosaccharin, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
-
Organic Chemistry, 33:6, 935-939
To link to this article: http://dx.doi.org/10.1081/SCC-120016353
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to
anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 6, pp. 935–939, 2003
A Green Preparation of
N-Chloro- and N-Bromosaccharin
Soraia P. L. de Souza, Joaquim F. M. da Silva, and
Marcio C. S. de Mattos*
Instituto de Quımica, Departamento de Quımica
´ ´
Organica, Universidade Federal do Rio de Janeiro,
Rio de Janeiro, Brazil
ˆ
ABSTRACT
The reaction of the sodium salt of saccharin, potassium chloride or
Õ
bromide and oxone in water at room temperature for 24 h produced
pure N-chloro- and N-bromosaccharin in 58% and64% yiel,d
respectively.
Key Words: Green chemistry; Saccharin; N-Halosaccharin.
*
´
Correspondence: Marcio C. S. de Mattos, Instituto de Quımica, Departamento
de Quımica Organica, Universidade Federal do Rio de Janeiro, Caixa Postal
´
ˆ
68545 21945-970, Rio de Janeiro, Brazil; Fax: þ55-21-25627133; E-mail:
mmattos@iq.ufrj.br.
9
35
DOI: 10.1081/SCC-120016353
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
9
36
de Souza, da Silva, and de Mattos
INTRODUCTION
Although N-halosaccharins are more electrophilic than the structur-
[
1]
ally analogue N-haloimides, they have foundlittle attention in the lit-
[3]
erature. Whereas N-iodo-
mentioned, N-chloro- and N-bromosaccharin are mostly described as
analytical
oxidants of aldehydes,
a-hydroxyacids, etc, andtheir application as halogenating reagent for
aromatic compounds
a-carbonylic
With few exceptions,
[
1,2]
and N-fluorosaccharin
are scarcely
[4,5]
and/or oxidizing reagents. These compounds are mild
[6,7]
[8,9]
[9]
[10]
alcohols,
glycols,
a-amino-
and
and
procedure for preparation
[9]
[
11,12]
[13]
[13,14]
andallylic,
positions is very useful.
benzylic,
[
14,15]
[16,17]
[18]
the classical
of N-chloro- and N-bromosaccharin is reaction of sodium salt of
saccharin with the halogen. However, the handling and manipulation
of the toxic andcorrosive halogens is problematic at multigram-scale.
Recently, Curini publishedthe
carbamates by the reaction with sodium chloride and oxone
2 KHSO ꢀ KHSO ꢀ K SO ) in a suspension of wet alumina in
N-chlorination of amides and
Õ
(
5
4
[19]
2
4
ꢁ
Õ
chloroform at 45 C. The role of oxone in these reactions is to oxidize
[
20]
the chloride anion and generate chlorine in situ.
The utilization of environmentally acceptable, healthy, safe, and
readily available materials in a simple process is very attractive nowadays
andconsistent with green chemistry challenges.
precedent we present here our results on an alternate and safe route to
[
21]
Basedon this
N-chloro and N-bromosaccharin.
RESULTS
The reaction of the sodium salt of saccharin with potassium halide
Õ
(
1 equiv. mol) andoxone (1 equiv. mol) was performedin water at room
temperature for 24 h. Using these conditions on a 10 mmol scale, the
corresponding N-halosaccharin precipitates at the endof the reaction.
The products were obtained in high purity (no need of recrystallization),
albeit in moderate yield after washing with cold water (Sch. 1 and Table 1).
The purity of the N-halosaccharins obtainedwas edt erminedby
[1]
iodometric titration andthey were characterizedby spectroscopic
methods and their melting point. The reaction was performed at
50-mmol scale andthe products were obtainedin similar yieldandpurity.
In summary we propose a new preparation of N-chloro- and
N-bromosaccharin that does not use or handle toxic and corrosive
halogens. The reaction conditions are mild, the yield is moderate and

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
N-Chloro- and N-Bromosaccharin
937
Scheme 1.
Table 1. Preparation of N-halosaccharin.
a
Yield/% Purity/% M.p. [lit.]/ C
ꢁ
ꢂ1
KBr/cm
X
ꢀ
Cl
58
64
>96
>99
145–148
[
3094; 1739 (C¼O); 1361 (SO ); 1235
2
2
18]
[152
165–167
]
(N-Cl); 1194 (SO
3094; 1709 (C¼O); 1352 (SO
(N-Br); 1191 (SO ); 949; 748; 574
); 955, 748; 757
Br
2
); 1231
[
17]
[170–172
]
2
a
[1]
Determinedby io do metric titration.
the isolation of the products in high purity is simple. Our methodology is
easier andsafer than the pre de cessors, the reaction can be scaledup and
water is the reaction solvent, all of which is in accordance with the green
[22]
chemistry philosophy.
EXPERIMENTAL
Typical procedure for the preparation of N-halosaccharin: To a well-
stirredsolution of so di um saccharin (10.25 g, 50 mmol), Na 2CO (2.65 g,
3
25 mmol) andKCl or KBr (3.78 g or 6.00 g, respectively—50 mmol) in
water (250 mL), a solution of oxone (30.75 g, 50 mmol) in water (30 mL)
Õ
ꢁ
was added slowly at 0 C. After stirring for 24 h at room temperature, the
solidwas filteredoff, washedwith coldwater and dr iedto give the pure
N-halosaccharin. The results obtainedare shown in Table 1.
ACKNOWLEDGMENTS
SPLS thanks CNPq for a fellowship. We thank Prof. W. Bruce
Kover andJoel Jones Jr. for helpful i ds cussions. We also thank
Prof. Carlos A.S. Riehl for technical assistance in the N-halosaccharin
titration.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
9
38
de Souza, da Silva, and de Mattos
REFERENCES
1
2
3
. Dolenc, D. N-Iodosaccharin—A new reagent for iodination of
alkenes andactivatedaromatics. Synlett 2000, (4), 544–546.
. Fairbanks, A.J.; Aloui, M. N-Iodosaccharin: A potent new
activator of thiophenylglycosides. Synlett 2001, (6), 797–799.
. Gakh, A.A.; Romaniko, S.V.; Ugrak, B.I.; Fainzilberg, A.A.
N-Fluorination with cesium fluoroxysulfate. Tetrahedron 1991,
47 (35), 7447–7458.
4
. Chauhan, R.P.S.; Ahmed, I.; Kumar, A. Determination of milli-
gram amounts of thiourea, allylthiourea andphenylthiourea using
N-chlorosaccharin in acetic-acidme di a. Asian J. Chem. 1995, 7 (3),
667–668. (Chem. Abstr. 1995, 123, 245771p)
5. Das, C.M. Determination of some sulfur-compounds with N-bro-
moimides. Talanta 1991, 38 (3), 347–350. (Chem. Abstr. 1991, 114,
258834a)
6
. Khan, M.U.; Verma, J.K.; Nigam, S.K.; Parihar, S.S.; Dwiverdi,
H.P. Kinetics andmechanistic approach on N-chlorosaccharin oxi-
dation of some aliphatic aldehydes. Oxid. Commun. 1998, 21 (3),
362–368.
7
. Sharma, V.K.; Sharma, K.; Gupta, H.D.; Gupta, P.P. Kinetics of
oxidation of benzaldehyde and substituted benzaldehydes by N-bro-
mosaccharin in aqueous acetic acid-perchloric acid medium. Oxid.
Commun. 1995, 18 (4), 395–406.
8
. Manoharan, V.; Venkatasubramanian, N. Kinetics of oxidation of
aliphatic secondary alcohols by N-bromosaccharin. J. Indian Chem.
Soc. 1986, 63 (6), 613–615.
9
. Bachhawat, J.M.; Mathur, N.K. Oxidation of secondary alcohols,
glycols, a-hydroxy acids, amino acids and hydrocarbons by
N-bromosaccharin. Indian J. Chem. 1971, 9 (12), 1335–1336.
10. Manikyamba P.; Sundaram, E.V. Kinetics of oxidation of amino-
acids by N-bromosaccharin. Indian J. Chem. 1980, 19A (11),
1122–1124.
1
1. Zajc, B. Synthesis of (þ/ꢀ)-trans-7,8-Dihydrodiol of 6-fluoro-
benzo[a] pyrene via hydroxyl-directed regioselective function-
alization of SubstitutedPyrene. J. Org. Chem. 1999, 64 (6),
1902–1907.
1
2. Mozek, I.; Sket, B. Chlorination andbromination of molecules by
an N-halosaccharin/pyridinium poly(hydrogen fluoride) system.
Synth. Commun. 1992, 22 (17), 2513–2520.
13. Bachhawat, J.M.; Koul, A.K.; Prashad, B.; Ramegowd, N.S.;
Narang, C.K.; Mathur, N.K. Allylic andBenzylic chlorination

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
N-Chloro- and N-Bromosaccharin
939
and oxidation of organic substrate using N-chlorosaccharin. Indian
J. Chem. 1973, 11 (6), 609–610.
1
4. Sanchez, E.I.; Fumarola, M.J. N-Bromosaccharin: Benzylic and
a-carbonylic bromination. J. Org. Chem. 1982, 47 (8), 1588–1590.
5. Panchatsharam, V.S.; Sundaram, S.; Venkatasubramanian, N.
Chlorination of ketones with N-chlorosaccharin. Indian J. Chem.
1
1981, 20A (5), 469–472.
16. Zajc, B. A convenient preparation of N-bromosaccharin, source of
electrophilic bromine. Synth. Commun. 1999, 29 (10), 1779–1784.
1
7. Sanchez, E.I.; Fumarola, M.J.
N-bromosaccharin using bromine chloride. Synthesis 1976, (11),
36–737.
A
new synthesis of
7
18. Chattaway, F.D. A contribution to the chemistry of o-Benzoic
Sulphinida. J. Chem. Soc. 1905, 87 (2), 1882–1887.
1
9. Curini, M.; Epifani, F.; Marcotullio, M.C.; Rosati, O.; Tsadjout, A.
Õ
N-chlorination of amides and carbamates by oxone andso di um
chloride. Synlett 2000, (6), 813–814.
20. Dieter, R.K.; Nice, L.E.; Velu, S.E. Oxidation of a,b-enones and
alkenes with oxone and sodium halides: A convenient laboratory
preparation of chlorine andbromine. Tetrahe rd on Lett.
7 (14), 2377–2380.
1996,
3
21. Clark, J.H. Green chemistry: Challenges andopportunities. Green
Chem. 1999, 1 (1), 1–8.
22. Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Practice;
OxfordUniversity Press: Oxfor d, 2000.
Receivedin the USA April 3, 2002

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.