Efficient and convenient procedure for preparation of N-sulfonylimines catalyzed by montmorillonite K-10

Article abstract of DOI:10.1080/00397910600640073

A general and practical chemical route to the synthesis of N-sulfonylimines using montmorillonite K-10 as the catalyst is described. This method provides several advantages such as operational simplicity, short reaction time, using of inexpensive materials, noncorrosivity, lack of pollution, and high yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910600640073

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Efficient and Convenient Procedure for
Preparation of N‐Sulfonylimines Catalyzed by
Montmorillonite K‐10
Tong‐Shou Jin a , Mi‐Jun Yu a , Li‐Bin Liu a , Ying Zhao a & Tong‐Shuang Li a
a Department of Chemistry, College of Chemistry and Environmental
Science, Hebei University, Baoding, China
Version of record first published: 22 Sep 2006.
To cite this article: Tong‐Shou Jin , Mi‐Jun Yu , Li‐Bin Liu , Ying Zhao & Tong‐Shuang Li (2006): Efficient and
Convenient Procedure for Preparation of N‐Sulfonylimines Catalyzed by Montmorillonite K‐10, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:16,
2339-2344
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Synthetic Communicationsw, 36: 2339–2344, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600640073
Efficient and Convenient Procedure for
Preparation of N-Sulfonylimines Catalyzed
by Montmorillonite K-10
Tong-Shou Jin, Mi-Jun Yu, Li-Bin Liu, Ying Zhao,
and Tong-Shuang Li
Department of Chemistry, College of Chemistry and Environmental
Science, Hebei University, Baoding, China
Abstract: A general and practical chemical route to the synthesis of N-sulfonylimines
using montmorillonite K-10 as the catalyst is described. This method provides several
advantages such as operational simplicity, short reaction time, using of inexpensive
materials, noncorrosivity, lack of pollution, and high yields.
Keywords: Aldehydes, montmorillonite K-10, N-sulfonylimines, sulfonamides
INTRODUCTION
During the past several years, N-sulfonylimines have attracted strong interest
because of their broad uses: they can be used as powerful synthetic intermedi-
ates[1,2] and they can also be used in numerous reactions such as inverse
electron-demand Diels–Alder reactions,[3–5] addition reactions as carbonyl
equivalents,[6] and in ene reactions.[7] Various methods are available for
the construction of N-sulfonylimines involving the rearrangement of oxime
O-sulfinates,[8] Lewis acid- or solid acid-catalyzed reactions of sulfonamides
with aldehydes or acetals,[9–13] utilization of tellurium metal and chloramines
T,[14] addition of N-sulfinyl sulfonamides to aldehydes in the presence of
[15]
use of methyl orthosilicate,[16] halogen-mediated conversion
.
BF3 Et2O,
Received in Japan November 24, 2005
Address correspondence to Tong-Shou Jin, Department of Chemistry, College of
Chemistry and Environmental Science, Hebei University, No. 88 Hezuo Road,
Baoding 071002, Hebei Province, China. E-mail: jintongshou@yahoo.com.cn
2339

2340
T.-S. Jin et al.
of N-(trimethylsilyl)imines in the presence of corresponding sulfonyl
chloride,[17] and catalysis by HCOOH and NaHCO3.[18] Each of these
methods has its own merit, but some of these methods are plagued by the limit-
ation of long reaction times, expensive and hazardous reagents, cumbersome
experimental conditions, and requiring use of a microwave oven. Conse-
quently, there is scope for further renovation toward mild conditions,
increased of variation of the substituents in the components, and better yields.
Montmorillonite K-10 is a type of acidic stratified silicate mineral with a
three-layer structure with an ideal chemical formula of (Al2-yMgy)Si4O10
.
(OH)2 nH2O. In montmorillonite clay, one octahedral aluminate layer is
sandwiched between two octahedral silicate layers. The interlayer cations
are exchangeable, which allows alteration of the acidic nature of the
¨
material by a simple ion-exchange procedure. Both Bronsted and Lewis
acidic catalytic sites are available, and its natural occurrence as well as its
ion-exchange properties make it a useful catalyst. Up to now, montmorillonite
and in particular montmorillonite K-10 have been used as efficient acidic
catalysts for many organic transformations, such as substitution[19] and
acetalization.[20] This prompted us to initiate a systematic investigation on
montmorillonite K-10–catalyzed synthesis of N-sulfonylimines (Scheme 1),
and herein we disclose our results.
Montmorillonite K-10 was purchased from Aldrich. The catalyst has
surface area of 220–270 m2g21 and a bulk density of 300–370 g l21. The
montmorillonite K-10 was activated at 1208C over night prior to use.
In a typical general experimental procedure, a solution of aldehydes and
sulfonamide was heated in refluxing toluene in the presence of a catalytic
amount of montmorillonite K-10 for a certain period of time required to
complete the reaction, and the corresponding N-sulfonylimines were
obtained in good to excellent yields. The results are summarized in Table 1.
To study the generality of this process, several examples illustrating this
method for the synthesis of those N-sulfonylimines were studied. As shown in
Table 1, the effect of electrons and the nature of aldehydes on the aromatic
ring did not show strongly obvious effects in terms of yields under this
reaction condition. The reaction proceeded smoothly in refluxing toluene to
give the corresponding products 3 in high yields. Mention must be made
here that the conversion rate of p-toluenesulfonamide with aldehydes was a
little higher than benzenesulfonamide. For example, the reaction yield of
Scheme 1.

Table 1. Synthesis of N-sulfonylimines catalyzed by montmorillonite
Mp (8C)
Time
(min)
Yield
(%)a
Entry
R1
R2
Product
Found
Reported
110[17]
139–141[10]
116–118[13]
136[18]
128–129[14]
145[18]
125[18]
119–120[13]
114–116[14]
172–173[13]
127–130[10]
1
2
H
H
4-CH3
H
3a
3b
3c
3d
3e
3f
50
45
65
50
70
75
75
85
50
50
60
50
60
55
50
50
45
80
90
93
88
91
86
92
86
86
62
90
85
83
83
90
87
87
94
96
92
91
105–106
135
3
4-CH3
4-CH3
4-CH3O
4-CH3O
2-HO
4-CH3
H
114–116
133–135
127–128
140–142
120
4
5
4-CH3
H
6
7
4-CH3
H
3g
3h
3i
8
2-HO
117–119
117–118
172–173
190–192
98
9
3,4-(OCH2O)
4-Cl
4-Cl
4-CH3
4-CH3
H
10
11
12
13
14
15
16
17
18
19
3j
3k
3l
3-Cl
3-Cl
4-CH3
H
3m
3n
3o
3p
3q
3r
3s
103
110
102–104[13]
112–113[13]
2,4-Cl2
2,4-Cl2
2-Cl
4-CH3
H
113–115
129–130
180–182
143–145
134
4-CH3
4-CH3
4-CH3
H
128–129[10]
182–185[14]
143–145[10]
4-Br
3-NO2
3-NO2
aYield of pure isolated products.

2342
T.-S. Jin et al.
4-chlorobenzaldehyde (1.00 mmol) with C6H5SO2NH2 (1.00 mmol) was 83%
yield in refluxing toluene for 60 min, but it increased to 85% from 4-chloro-
benzaldehyde (1.00 mmol) with 4-CH3C6H4SO2NH2 (1.00 mmol) for
refluxing for 50 min.
We examined several experiments and found that the effect of the catalyst
and the molar ratio showed crucial effects on these conversions. As a model
reaction, the reaction of 2-chlorobenzaldehyde with p-toluenesulfonamide
catalyzed by montmorillonite K-10 in refluxing toluene was investigated.
The results are summarized in Table 2.
As shown in Table 2, the catalyst plays a crucial role in the success of the
reaction in terms of the rate and the yields. 2-Chlorobenzaldehyde reacted
with p-toluenesulfonamide in the presence of 50 mg of montmorillonite
K-10 to give the product 3p in modest yield (87%) in refluxing toluene
after 50 min of reaction time. Increasing the catalyst to 70, 80, and 90 mg
results in accelerating the reaction yields to 89%, 92%, and 94% respectively.
Higher amounts of the catalyst did not improve the results to a greater extent.
Thus, 90 mg of montmorillonite K-10 was chosen as a quantitative catalyst for
these reactions. In addition, the catalyst was easily regenerated by washing
with toluene followed by drying at 1208C for 2 h, and it could be reused
five times without significant loss of activity.
In conclusion, we have provided a facile and efficient method for the
synthesis of N-sulfonylimine catalyzed by montmorillonite K-10. This
method possesses these advantages of operational simplicity, short reaction
time, use of inexpensive materials, noncorrosivity, lack of pollution, and
high yields.
EXPERIMENTAL
Melting points are uncorrected. The new compounds prepared were character-
ized by 1H NMR, IR, and element analyses and are described in the
Table 2. Effect of catalyst on the
reaction of 2-chlorobenzaldehyde with
p-toluenesulfonamide
Montmorillonite
Yield (%)
50
70
87
89
92
94
91
85
83
80
90
100
120
150

Preparation of N-Sulfonylimines
2343
experimental section. Liquid aldehydes were purified by distillation before
use. IR spectra were recorded on a Bio-rad FIS-40 spectrometer (KBr).
1H NMR spectra were measured at 400 MHz on an Avance-400 spectrometer
using TMS as internal standard and CDCl3 as solvent.
General Procedure for the Preparation of N-Sulfonylimines
A mixture of aldehyde (1.00 mmol), sulfonamide (1.00 mmol), montmorillo-
nite K-10 (90 mg), and toluene (5 ml) was stirred under refluxing for 45–
90 min (Table 1) in a Dean-Stark apparatus. The reaction was monitored by
TLC. After completion of the reaction, the reaction mixture was cooled,
and montmorillonite K-10 was filtered off with toluene washing. The
solvent was evaporated under reduced pressure to provide the crude
product, and the crude product was purified by recrystallization with
hexane–ethyl acetate mixture or by flash chromatography on silica gel
(Et2O–hexane as eluent) to give the pure product.
The number of carbon atom in aryl is shown in Scheme 2.
Data
3l: IR (KBr), n (cm21) 3090, 1680, 1605, 1566, 1553, 1497, 1333, 1166, 805,
1
746, 694. H NMR (CDCl3) d (ppm) 9.00 (s, 1H, HC55N), 7.96 (s, 1H,
20-ArH), 7.90 (d, 2H, J ¼ 8.4 Hz, 2,6-SO2ArH), 7.79 (d, 1H, J ¼ 7.6 Hz,
60-ArH), 7.58 (d, 1H, J ¼ 8.0 Hz, 40-ArH), 7.46 (t, H, J ¼ 8.0 Hz, 50-ArH),
7.37 (d, 2H, J ¼ 8.0 Hz, 3,5-SO2ArH), 2.47 (s, 3H, CH3). Anal. calcd. for
C14H12NO2SCl: C, 57.24; H, 4.12; N, 4.77. Found: C, 57.11; H, 4.05; N, 4.92.
3o: IR (KBr), n (cm21) 3108, 2890, 1691, 1593, 1546, 1485, 1315, 1160, 820,
1
754, 694. H NMR (CDCl3) d (ppm) 9.47 (s, 1H, HC55N), 8.12 (d, 1H,
J ¼ 8.8 Hz, 60-ArH), 8.03 (d, 2H, J ¼ 8.0 Hz, 2,6-SO2ArH), 7.67 (d, 1H,
J ¼ 7.2 Hz 50-ArH), 7.58 (t, 2H, J ¼ 8.4 Hz, 3,5-SO2ArH), 7.53 (s, 1H, 30-
ArH), 7.34 (d, 1H, J ¼ 8.8 Hz, 4-SO2ArH). Anal. calcd. for C13H9NO2SCl2:
C, 49.70; H, 2.89; N, 4.46. Found: C, 49.89; H, 2.78; N, 4.35.
3s: IR (KBr),n (cm21) 3050, 1698, 1601, 1541, 1496, 1334, 1163, 806, 750,
1
696. H NMR (CDCl3) d (ppm) 9.16 (s, 1H, HC55N), 8.80 (s, 1H, 20-ArH),
8.47 (d, 1H, J ¼ 8.0 Hz, 60-ArH), 8.27 (d, 1H, J ¼ 7.6 Hz, 40-ArH), 8.05
Scheme 2.

2344
T.-S. Jin et al.
(d, 2H, J ¼ 7.6 Hz, 2,6-SO2ArH), 7.69 (m, 2H, 4-SO2ArH and 50-ArH), 7.60
(t, 2H, J ¼ 8.0 Hz, 3,5-SO2ArH). Anal. calcd. for C13H10N2O4S: C, 53.79; H,
3.47; N, 9.65. Found: C, 53.65; H, 3.53; N, 9.53.
ACKNOWLEDGMENT
The project was supported by the National Natural Science Foundation of
China (29872011), Educational Ministry of China, Educational Department
of Hebei Province (990104), and Science and Technology Commission of
Hebei Province (203107).
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