Silica chloride/NaNO2 as a novel heterogeneous system for the nitrosation of secondary amines under mild conditions

Article abstract of DOI:10.1081/SCC-120004060

Secondary amines can be readily converted to their corresponding nitroso derivatives with a combination of silica chloride (I), wet SiO₂ and sodium nitrite in dichloromethane at room temperature with moderate to excellent yields.

Full text of DOI:10.1081/SCC-120004060

This article was downloaded by: [University of Connecticut]
On: 19 May 2013, At: 21:40
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
SILICA CHLORIDE/NaNO AS A NOVEL HETEROGENEOUS
2
SYSTEM FOR THE NITROSATION OF SECONDARY AMINES
UNDER MILD CONDITIONS
a
b
a
Mohammad Ali Zolfigol , Farhad Shirini & Arash Ghorbani Choghamarani
a
Chemistry Department, College of Science, Bu-Ali Sina University, Post Box No. 4135,
Hamadan, 65174, Iran
b
Chemistry Department, College of Science, Gilan University, Rasht, Iran
Published online: 17 Oct 2011.
To cite this article: Mohammad Ali Zolfigol , Farhad Shirini & Arash Ghorbani Choghamarani (2002): SILICA CHLORIDE/NaNO2
AS A NOVEL HETEROGENEOUS SYSTEM FOR THE NITROSATION OF SECONDARY AMINES UNDER MILD CONDITIONS, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:12, 1809-1813
To link to this article: http://dx.doi.org/10.1081/SCC-120004060
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
©
2002 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.
SYNTHETIC COMMUNICATIONS, 32(12), 1809–1813 (2002)
SILICA CHLORIDE/NaNO AS A NOVEL
2
HETEROGENEOUS SYSTEM FOR THE
NITROSATION OF SECONDARY AMINES
UNDER MILD CONDITIONS
1
,
2
Mohammad Ali Zolfigol, * Farhad Shirini,
1
and Arash Ghorbani Choghamarani
1
Chemistry Department, College of Science,
Bu-Ali Sina University, Hamadan, Zip Code 65174,
Post Box No. 4135, Iran
2
Chemistry Department, College of Science,
Gilan University, Rasht, Iran
ABSTRACT
Secondary amines can be readily converted to their corre-
sponding nitroso derivatives with a combination of silica
chloride (I), wet SiO and sodium nitrite in dichloromethane
2
at room temperature with moderate to excellent yields.
N-Nitrosation chemistry of amines is an important and well-
[
1]
established reaction in organic synthesis. The most general reagent is
nitrous acid, generated from sodium nitrite and mineral acid in water or
[
in mixed alcohol–water solvents. Other nitrosating agents, such as
2]
[
3]
[4]
Fremy’s salt, bis(triphenylphosphine)nitrogen(1 þ )nitrite, N-haloamides
*
Corresponding author. Fax: (þ98) 811 8272404; E-mail: Zolfi@basu.ac.ir
809
1
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 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.
1
810
ZOLFIGOL, SHIRINI, AND GHORBANI CHOGHAMARANI
[
and sodium nitrite under phase-transfer conditions, oxyhyponitrite,
5]
[6]
[7]
[8]
dinitrogen tetroxide, solid acids (i.e. oxalic acid dihydrate, inorganic
[9]
[10]
acidic salts and hydrolyzable chloride salts ) and sodium nitrite have
also been used.
There is intense current research and general interest in heterogeneous
systems because of the perceived opportunities such systems present for
basic research and because of the unquestioned importance such systems
[
12,13]
have in industry and in developing technologies.
studies on the application of inorganic acidic salts we found that the silica
In continuation of our
[
11]
[14,15]
chloride (I) is an excellent source for generation of HCl. It is interesting
to note that the addition of wet SiO to the reaction mixture containing
2
silica chloride could generate HCl in situ. Therefore, we were interested in
using this reagent (I) for the nitrosation of secondary amines via in situ
þ
generation of HNO and NO respectively when used in conjunction with
2
NaNO , wet SiO in organic solvent (Scheme 1). We wish to report a simple
2
2
Scheme 1.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 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.
SILICA CHLORIDE/NaNO2
1811
Table 1. Nitrosation of Secondary Amines (1) to Their Corresponding
(II), and
Nitrosoamines (2) with a Combination of Silica Chloride (I), NaNO
Wet SiO (50% w/w) in Dichloromethane at Room Temperature
2
2
b
(
Reagent/Substrate)
c
Time
(h)
Yield
(%)
a
Entry
Substrate
Product
I (g)
II (mmol)
d
1
2
3
4
5
6
7
8
1
1
1
1
1
1
1
1
a
b
c
d
e
f
2 a0 .3
2 b0 .3
2 0c .3
2 d0 .3
2 0e .3
2 0f .3
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
0.75
0.75
1
100
90
95
98
95
95
98
92
1.5
0.75
0.75
1.5
g
h
2 g0 .3
2 0j .3
1.5
a
All of the isolated products are known and their spectra and physical data have
b
been reported in the literature; Wet SiO : substrate (0.2 g : 1 mmol); Isolated yields;
d
c
2
Conversion.
method for the effective nitrosation of secondary amines under mild and
heterogeneous conditions.
A range of secondary amines (1) was subjected to the nitrosation
reaction in the presence of silica chloride (I), NaNO (II) and wet SiO
2
2
(
50% w/w) in dichloromethane (Scheme 1). The nitrosation reactions were
performed under mild and completely heterogeneous conditions at room
temperature and proceeded in moderate to excellent yields (Table 1).
The nitrosation reaction did not occur in the absence of wet SiO . This
2
observation suggests that the water molecule is essential for such processes.
The presence of wet SiO thus provides an effective heterogeneous surface
2
[
10]
area for in situ generation of NOCl (Scheme 1). It also eases the reaction
work-up.
In conclusion, the cheapness and the availability of the reagents, easy
and clean work-up, make this method attractive for large-scale operations.
EXPERIMENTAL SECTION
General
Chemicals were purchased from Fluka, Merck and Aldrich chemical
companies. Yields refer to isolated pure products. The nitrosation products

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 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.
1
812
ZOLFIGOL, SHIRINI, AND GHORBANI CHOGHAMARANI
1
were characterized by comparison of their spectral (IR, H-NMR,
1
3
C-NMR), TLC and physical data with the authentic samples. Silica
15]
chloride was synthesized according to the reported procedure.
[
General Procedure for N-Nitrosation of Secondary Amines
A suspension of sodium nitrite, silica chloride (The molar ratio of
silica chloride and sodium nitrite to the substrate 1 was optimized Table),
amine (1, 5 mmol), silica chloride (1.5 g), NaNO (0.517 g, 7.5 mmol) and
2
wet SiO (50% w/w) in dichloromethane (10 ml) was vigorously stirred
2
magnetically at room temperature. The progress of the reaction was fol-
lowed by TLC. The reaction mixture was filtered after completion of the
reaction. The residue was washed with CH Cl (2 ꢀ 5 ml). Then anhydrous
2
2
Na SO (10 g) was added to the filtrate and filtered after 20 min. The solvent
2
4
was evaporated and the N-nitroso compound (2) were obtained (Table 1). If
further purification is needed, flash chromatography on silica gel [eluent:
acetone/petroleum ether (10 : 90)] provides highly pure 2.
REFERENCES
1. (a) Williams, D.L.H. Supplement F2: The Chemistry of Amino, Nitroso,
Nitro and Related Groups; John Wiley and Sons Ltd.: 1996; 665–682;
(b) Keefer, L.K.; Williams, D.L.H. Methods in Nitric Oxide Research;
John Wiley and Sons Ltd.: 1996; 509–519.
2
. (a) Vogels Text Book of Practical Organic Chemistry, 4th Ed.,
Longman: London and New York, 1986; (b) Sheriner, R.L.; Reynold,
T.L.; Fuson, C.; Curtin, D.Y.; Morrill, T.C. The Systematic Identifica-
tion of Organic Compounds, 6th Ed.; John Wiley and Sons, 1980;
2
20–223.
. Castedo, L.; Riguera, R.; Vezquez, M.P. J. Chem. Soc. Chem. Commun.
983, 301.
. Fanning, J.C.; Keefer, L.K.; Larry, K. J. Chem. Soc. Chem. Commun.
987, 955.
. Nakajima, M.; Warner, J.C.; Anselme, J.P. Tetrahedron Lett. 1984, 25,
619.
. Chang, S.K.; Hrrington, G.W.; Rothstein, M.; Shergalis, W.A.;
Swern, D.; Vohra, S.K. Cancer Res. 1979, 39, 3871.
. Makhova, N.N.; Karpov, G.A.; Mikhailyuk, A.N.; Bova, A.E.;
Khmel’nitskii, L.I.; Novikov, S.S. Izv. Akad. Nauk SSSR. Ser. Khim.
3
4
5
6
7
1
1
2
1978, 1, 226.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 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.
SILICA CHLORIDE/NaNO2
1813
8
9
. Zolfigol, M.A. Synth. Commun. 1999, 29, 905.
. Zolfigol, M.A.; Ghaemi, E.; Madrakian, E.; Kiany-Borazjani, M.
Synth. Commun. 2000, 30, 2057.
1
0. Zolfigol, M.A.; Shirini, F.; Ghorbani Choghamarani, A.; Taqian-
nasab, A.; Keypour, H.; Salehzadeh, S. J. Chem. Research (S) 2000, 420.
1. (a) Zolfigol, M.A.; Kiany-Borazjani, M.; Sadeghi, M.M.; Memarian,
H.R.; Mohammadpoor-Baltork, I. Synth. Commun. 2000, 30, 2945;
1
(
b) Zolfigol, M.A.; Kiany-Borazjani, M.; Sadeghi, M.M.; Memarian,
H.R.; Mohammadpoor-Baltork, I. J. Chem. Research (S) 2000, 197;
c) Zolfigol, M.A.; Nematollahi, D.; Mallakpour, S.E. Synth.
Commun. 1999, 29, 2277; (d) Zolfigol, M.A. Synth. Commun. 2000,
0, 1593; (e) Zolfigol, M.A.; Kiany-Borazjani, M.; Mallakpour, S.E.;
(
3
Nassr-Isfahani, H. Synth. Commun. 2000, 30, 2573; (f) Zolfigol, M.A.;
Madrakian, E.; Ghaemi, E. Indian J. Chem. 2000, 39B, 308;
(
g) Zolfigol, M.A.; Kiany-Borazjani, M.; Sadeghi, M.M.;
Mohammadpoor-Baltork, I.; Memarian, H.R. Synth. Commun.
000, 30, 3919.
2
12. Riego, J.M.; Sedin, Z.; Zaldivar, J.M.; Marziano, N.C.; Tortato, C.
Tetrahedron lett. 1996, 37, 513.
3. Turro, N.J. Tetrahedron 1987, 43, 1589.
4. Mohanazadeh, F.; Momeni, A.R.; Rangbar, Y. Tetrahedron lett. 1994,
1
1
3
3, 6127.
5. Firouzabadi, H.; Iranpoor, N.; Karimi, B.; Hazarkhani, H. Synlett
000, 263.
1
2
Received in the UK March 27, 2001