An efficient synthesis of sulfonylhydrazides and sulfonylsemicarbazides by utilizing alumina as a catalyst

Article abstract of DOI:10.1002/jccs.200700220

Sulfonyl hydrazides and sulfonyl semicarbazides are readily prepared by the reacting of hydrazine derivatives with sulfonyl chlorides in the presence of basic alumina under solvent-free conditions. Reaction of a sulfonyl chloride with t-butylcarbazate, followed by hydrolysis provides the corresponding sulfonyl hydrazides in higher yield and shorter time than previously reported.

Full text of DOI:10.1002/jccs.200700220

Journal of the Chinese Chemical Society, 2007, 54, 1561-1563
1561
An Efficient Synthesis of Sulfonylhydrazides and Sulfonylsemicarbazides
by Utilizing Alumina as a Catalyst
Javad Safaei-Ghomi
Department of Chemistry, Faculty of Science, University of Kashan, 51167 Kashan, I. R. Iran
Sulfonyl hydrazides and sulfonyl semicarbazides are readily prepared by the reacting of hydrazine de-
rivatives with sulfonyl chlorides in the presence of basic alumina under solvent-free conditions. Reaction
of a sulfonyl chloride with t-butylcarbazate, followed by hydrolysis provides the corresponding sulfonyl
hydrazides in higher yield and shorter time than previously reported.
Keywords: Basic alumina; Sulfonyl hydrazide; Sulfonyl semicarbazide; t-Butylcarbazate.
INTRODUCTION
RESULTS AND DISCUSSION
Sulfonyl hydrazide and sulfonyl semicarbazide de-
rivatives exhibit a variety of bacteriostatic activity and also
are important compounds as blowing agents in cellular rub-
ber and plastics.1-4 The b-aromatic sulfonyl hydrazides are
particularly useful in the production of azo dyestuffs.5
Different methods for the preparation of these com-
pounds have been reported.6-10 In some of these methods
the yields of products are not high,6,7 the solvent is toxic
(pyridine),6 the reaction times are longer,6,9 and also the
starting materials (sulfinic acid salt) are not commercially
available.10 Recently, considerable attention has been paid
to solvent-free reaction conditions.11-15 These reactions are
not only of interest from an environmental point of view,
but in many cases also offer considerable synthetic advan-
tages in terms of yield, selectivity, simplicity of the reaction
procedure and associated ease of manipulation. Alumina is
a highly porous and granular form of aluminum oxide. It is
available in three pH ranges (basic, neutral, and acidic) for
use in chromatographic cleanup procedures. Basic alumina
has a pH of 9-10. It is used to separate basic and neutral
compounds that are stable to alkali, alcohols, hydrocar-
bons, steroids, alkaloids, and natural pigments. Its advan-
tages are that it can be used as supporting reagent for or-
ganic synthesis under solvent-free conditions.16,17
Treatment of hydrazine derivatives with sulfonyl
chlorides in the presence of basic alumina in a mortar with
grinding by a pestle afforded the corresponding sulfonyl-
hydrazides and sulfonylsemecarbazides (Scheme I). After
a few minutes of reaction time, addition of a few drops of
liquid such as ethanol or water in the reaction media is es-
sential. The products were extracted by a solvent such as
hot water, ethanol or THF. The yields of these reactions
were higher (70-95%) and the reaction times were shorter
(5-20 min) than conventional methods6-10 (Table 1).
Scheme I
Basic Alumina
R-SO2-Cl + H2NR'
R-SO2NHR'
2
1
3
The preparation of some sulfonyl hydrazides by reac-
tion of sulfonyl chloride with hydrazine is often compli-
cated by the production of a considerable amount of 1,2-
disulfonylhydrazides.18-21 We have developed the use of
protected hydrazines, which allow preparation of hydra
-
zides without concomitant formation of undesirable side
products under solvent-free conditions. In this method we
used t-butyl carbazate instead of hydrazine that reacted
with sulfonylchloride in the presence of basic alumina to
produce intermediate 5. Hydrolysis of the intermediate
carbazate 5 gives direct in situ formation of the hydrazide 6
under mild conditions (Scheme II).
We now wish to report that basic alumina could effi-
ciently catalyze the preparation of sulfonylhydrazides and
sulfonylsemecarbazides from corresponding sulfonyl chlo-
rides with hydrazine derivatives in a simple and extremely
convenient one-step method.

1562 J. Chin. Chem. Soc., Vol. 54, No. 6, 2007
Safaei-Ghomi
Table 1. Preparation of R-SO2NHR' 3 from sulfonyl chlorides 1
3
R
R'
Times (min) Yield (%)
Mp (oC)
a
b
c
d
e
f
Me
NHPh
NHPh
NHPh
NHPh
NHPh
5
5
97
95
92
95
93
90
90
83
87
80
75
120-122 (121-123)23
136-138 (137-138)22
150-152 (151)22
165-167 (166-168)23
158-160 (157-159)6
190-192 (192)10
224-226 (225-226)10
235-237 (237-238)10
222-224 (222)10
Ph
4-MeC6H4
5
4-ClSO2C6H4OC6H4
4-MeCONHC6H4
Me
8
7
NHCONH2
NHCONH2
NHCONH2
NHCONH2
NHCONH2
NHCSNH2
15
10
15
10
20
15
g
h
i
Ph
4-MeC6H4
4-ClSO2C6H4OC6H4
4-MeCONHC6H4
4-MeCONHC6H4
j
225-226 (227) 6
194-195 (193-194)6
k
Scheme II
Basic Alumina
R-SO2-Cl + H2NNHCOOtBu
R-SO2NHNHCOOtBu
5
4
1
CF3COOH
R-SO2NHNH2
6
The advantages of this new method over previously
reported methods (solvent conditions) are that it provides
enhanced reaction rates, cleaner products, manipulative
simplicity and higher yields18,21 (Table 2).
shorter time than previously reported.
EXPERIMENTAL
General
In conclusion, we have provided a convenient and ef-
ficient procedure for the preparation of sulfonylhydrazides
and sulfonylsemecarbazides from corresponding sulfonyl
chlorides with hydrazine derivatives in the presence of ba-
sic alumina under solvent-free conditions. In a simple and
extremely convenient method, sulfonyl chloride reacted
with t-butylcarbazate followed by hydrolysis to provide the
corresponding sulfonyl hydrazides in higher yield and a
All yields refer to isolated products that were charac-
terized by mp data, and IR and NMR spectral analysis.
Melting points were determined on a Kofler block and are
uncorrected. FT-IR spectra were recorded on a Nicolet
Magna 550 spectrometer (KBr). 1H NMR spectra were de-
termined on a Bruker DRX-400 AVANCE (400 MHz)
Table 2. Synthesis of R-SO2NHNH2 6 from sulfonyl chlorides 1 and t-butyl carbazates 4
Times (min) Overal yield (%)
Mp 6 (oC)
10 84
102-104 (102-103)20
6
R
a
Ph
b
c
4-MeC6H4
15
15
78
75
108-110 (110)18
181-182 (181-183)6
4-MeCONHC6H4

Synthesis of Sulfonylhydrazides and Sulfonylsemicarbazides Using Alumina J. Chin. Chem. Soc., Vol. 54, No. 6, 2007 1563
Received March 16, 2007.
spectrometer using CDCl3 or [D6] DMSO as solvents and
TMS as internal standard.
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General Procedure for the Preparation of b-aromatic
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A mixture of sulfonyl chloride (1 mmol), hydrazine
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specified in Table 1. Addition of a few drops of ethanol or
water in the reaction media was essential. On completion of
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poured into 10 mL of ethanol or hot water. The solid alu-
mina separated on a suction funnel and the solvent evapo-
rated by rotary evaporation to give the crude product. The
solid sulfonylhydrazides or sulfonylsemicarbazides, which
are separated, are washed with water and recrystallized
from aqueous ethanol or hot water.
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