Hydrocyanation of sulfonylimines using potassium hexacyanoferrate(II) as an eco-friendly cyanide source

Article abstract of DOI:10.5935/0103-5053.20130218

An efficient and eco-friendly method for hydrocyanation of sulfonylimines via one-pot two-step procedure using potassium hexacyanoferrate(II) as a cyanide source, benzoyl chloride as a promoter, and potassium carbonate as a base is described. This protocol has the features of using nontoxic, nonvolatile and inexpensive cyanide source, high yield, and simple work-up procedure.

Full text of DOI:10.5935/0103-5053.20130218

http://dx.doi.org/10.5935/0103-5053.20130218
J. Braz. Chem. Soc., Vol. 24, No. 11, 1739-1743, 2013.
Printed in Brazil - ©2013 Sociedade Brasileira de Química
0103 - 5053 $6.00+0.00
Article
A
Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an
Eco-Friendly Cyanide Source
Zheng Li,* Rongzhi Li, Huanhuan Zheng, Fei Wen, Hongbo Li, Junjun Yin and Jingya Yang
Key Laboratory of Eco-Environment-Related Polymer Materials for Ministry of Education, College of Chemistry
and Chemical Engineering, Northwest Normal University, 730070 Lanzhou, Gansu, P. R. China
Um método eficiente e ecologicamente amigável de hidrocianação de sulfoniliminas por um
procedimento de duas etapas em uma única operação usando hexacianoferrato(II) de potássio
como fonte de cianeto, cloreto de benzoíla como promotor e carbonato de potássio como uma
base é descrito. Este método tem como característica o uso de fonte de cianeto atóxica, não volátil
e barata, alto rendimento e um procedimento simples.
An efficient and eco-friendly method for hydrocyanation of sulfonylimines via one-pot two-
step procedure using potassium hexacyanoferrate(II) as a cyanide source, benzoyl chloride as a
promoter, and potassium carbonate as a base is described. This protocol has the features of using
nontoxic, nonvolatile and inexpensive cyanide source, high yield, and simple work-up procedure.
Keywords: sulfonylimine, hydrocyanation, potassium hexacyanoferrate(II), Strecker-type
reaction, green chemistry
Introduction
To overcome these problems, attention has been given to
the development of alternative cyanide sources that are
relative cheap, less toxic, and easier to handle.
The Strecker reaction, nucleophilic addition of
cyanide ion to imines, is of great importance to modern
organic chemistry as it offers one of the most direct and
viable methods for the synthesis of α-aminonitriles.1
α-Aminonitriles are significantly important intermediates
for the synthesis of a wide variety of amino acids, amides,
diamines, and nitrogen-containing heterocycles.2 The recent
advance of Strecker reaction has been reviewed by Feng
and coworkers.3 The hydrocyanation of sulfonylimines
to synthesize α-sulfonylimidonitriles is one of the
most important Strecker-type reactions. Ooi4 reported
the Strecker reaction of sulfonylimines using aqueous
potassium cyanide as a cyanide source. Kim5 studied the
hydrocyanation of sulfonylimines using ethyl cyanoformate
as a cyanide source. Nakamura,6 Feng7 and Kantam8
investigated the Strecker-type reaction of sulfonylimines
using trimethylsilane cyanide as a cyanide source. In
addition, the reported Strecker reactions also utilize HCN,9
Zn(CN)2,10 (EtO)2P(O)CN,11 Et2AlCN,12 Bu3SnCN,13
MeCOCN,14 and acetone cyanohydrin15 as cyanide sources.
However, some problems including toxicity, volatility or
high cost are still associated with these cyanating agents.
Potassium hexacyanoferrate(II), K4[Fe(CN)6], is mainly
used as carburizing agent in the iron and steel industry.And
it is also used in the food industry for metal precipitation.
In addition, it has been described as an anti-agglutinating
auxiliary for table salt (NaCl). K4[Fe(CN)6] is a by-product
of the coal chemical industry and commercially available
on a ton scale, and it is even cheaper than KCN. Recently,
K4[Fe(CN)6] has been used as a cyanide source for some
substitution reactions to synthesize benzonitriles,16
aroyl cyanides,17 benzyl cyanides,18 cinnamonitriles,19
dihaloacrylonitriles20 and cyano substituted heterocycles.21
Our recent research interests focused on the cyanation of
unsaturated compounds by nucleophilic addition reactions
using K4[Fe(CN)6] as an eco-friendly cyanide source,
which included the cyanation of aldehydes and ketones to
cyanohydrins,22 the cyanation of aldimines and ketimines
to α-aminonitriles,23 and the cyanation of α,β-unsaturated
ketones to β-cyano ketones.24 In this work, we report an
efficient method for the hydrocyanation of sulfonylimines
to α-sulfonylimidonitriles using K4[Fe(CN)6] as an
eco-friendly cyanide source.
*e-mail: lizheng@nwnu.edu.cn

1740
Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
J. Braz. Chem. Soc.
Results and Discussion
cyanide source, benzoyl chloride as a promoter, and
potassium carbonate as a base (Table 2).A set of anhydrous
solvents was tested for the reaction. Polar solvents such as
MeOH, EtOH, MeCN, THF, and CH2Cl2 gave the desired
product 2a in moderate to high yields (Table 2, entries 1-5).
Especially the reaction in EtOH afforded 2a in the highest
yield (Table 2, entry 2). However, it was found that the
reaction in polar aprotic solvents such as DMSO and DMF
gave unidentified by-products (Table 2, entries 6-7). In
addition, no product was observed in nonpolar solvents
such as toluene and n-hexane.
Initially, N-benzylidene-4-methylbenzenesulfonamide
(1a) was selected as a substrate to investigate the feasibility
of hydrocyanation of sulfonylimines using K4[Fe(CN)6] as
an eco-friendly cyanide source (Scheme 1). The reaction
was attempted under different conditions such as using
Lewis acids, Lewis bases, and organometallic compounds
as catalysts at different temperature in various solvents.
However, no product could be obtained for this reaction, the
possible reason is that K4[Fe(CN)6] is too stable to release
cyanide ions in the studied conditions. In the later study, it
was found that benzoyl chloride could efficiently promote
the reaction to yield corresponding hydrocyanation product
through an intermediate, benzoyl cyanide, which could be
isolated and identified from the reaction system. Actually,
the hydrocyanation reaction for 1a directly utilized benzoyl
cyanide as a cyanating agent could effectively give the
same product by a similar way in high yield. This further
demonstrated the fact of benzoyl cyanide as a reaction
intermediate. It was also found that only 0.2 equiv of
K4[Fe(CN)6] was needed for 1 equiv of 1a, which indicated
that six CN– of K4[Fe(CN)6] could be fully utilized in this
reaction. In addition, no by-products were observed in
this reaction, which implied the high chemoselectivity of
the reaction.
Table 2. The effect of solvents on the yield of hydrocyanation of 1a
using K4[Fe(CN)6]a
Entry
Solvent
MeOH
EtOH
Reaction time / h
Yield / %b
1
2
3
4
5
6
7
5
1
80
93
50
30
55
0c
CH3CN
THF
12
3.5
12
24
24
CH2Cl2
DMSO
DMF
0c
aReaction condition: 1a (0.5 mmol), potassium hexacyanoferrate(II)
(0.1 mmol), benzoyl chloride (0.6 mmol) and potassium carbonate
(0.1 mmol) in solvent (8 mL); bisolated yields; cunidentified by-products
were observed.
It was found that bases played a key role in the studied
reaction. The reaction gave very low yield in the absence
of a base (Table 1, entry 1). However, the reaction could
be proceeded smoothly in the presence of some bases,
such as Et3N, DMAP, K2CO3, KOH, and NaOH (Table 1,
entries 2-6). Among them, K2CO3 gave the highest yield
within the shortest reaction time (Table 1, entry 4).
Based on the above promising findings, a series of
sulfonylimines formed from aldehydes and sulfonamides
were examined for the hydrocyanation in EtOH using
K4[Fe(CN)6] as a cyanating agent, benzoyl chloride as a
promoter, and K2CO3 as a base (Table 3, Scheme 1). It
was found that sulfonylimines including electron-donating
groups on aromatic rings of R2 gave the corresponding
products in very high yields (Table 3, entries 1-5). In
contrast, sulfonylimines including electron-withdrawing
groups on aromatic rings of R2 gave slightly lower yields
(Table 3, entries 6-10). In addition, ortho-substituted
sulfonylimines exhibited large sterical hindrance and gave
lower yields than the para-ones (Table 3, entries 7-8).
Sulfonylimines with aliphatic R2, such as ethyl and
isopropyl, could also participate in the hydrocyanation
reactions to give the corresponding products in high
yields although they needed more reaction time
(Table 3, entries 12-13). Sulfonylimines including
heterocycle, such as furan-2-yl, could also smoothly
react with K4[Fe(CN)6] (Table 3, entry 11). R1 groups
on sulfonylimines had no obvious effect on the yields of
products. In addition, the sulfonylimines formed from
Table 1. The effect of bases on the yield of hydrocyanation of 1a using
K4[Fe(CN)6]a
Entry
Base
none
Reaction time / h
Yield / %b
1
2
3
4
5
6
24
24
1
10
90
91
93
92
75
Et3N
DMAP
K2CO3
KOH
1
2
NaOH
10
aReaction condition: 1a (0.5 mmol), potassium hexacyanoferrate(II)
(0.1 mmol), benzoyl chloride (0.6 mmol) and base (0.1 mmol) in ethanol
(8 mL); bisolated yields.
The solvents also played an important role in the
hydrocyanation of 1a using K4[Fe(CN)6] as an eco-friendly

Vol. 24, No. 11, 2013
Li et al.
1741
Scheme 1. The hydrocyanation of sulfonylimines using K4[Fe(CN)6].
Table 3. Optimized hydrocyanation of sulfonylimines using K4[Fe(CN)6]a
Entry
R1
R2
Product
2a
time / h
1
Yield / %b
mp (lit.) / oC
152-154 (152-154)26
149-150 (155-156)27
124-125 (128-129)26
158-160
1
2
3
4
4-CH3
4-CH3
4-CH3
4-CH3
C6H5
93
95
96
82
4-CH3C6H4
4-CH3OC6H4
4-(CH3)2NC6H4
2b
0.5
2c
0.5
2d
1.5
5
4-CH3
2e
1
90
166-168 (124-126)28
6
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3
4-FC6H4
2-ClC6H4
4-ClC6H4
2,4-2ClC6H3
4-BrC6H4
2f
2g
2h
2i
1
1
1
1
1
60
65
74
54
66
122-124 (100-104)28
112-114 (118-119)27
130-132 (134-135)27
136-137
7
8
9
10
2j
150-151 (150-151)27
11
4-CH3
2k
3
63
98-100 (98-100)26
12
13
14
15
16
17
4-CH3
4-CH3
H
CH3CH2
(CH3)2CH
C6H5
2l
2m
2n
2o
2p
2q
4
4
1
1
1
1
86
65
93
95
90
72
52-54
78-79 (74-76)28
98-100 (100-102)28
100-102
H
4-CH3C6H4
4-ClC6H4
4-BrC6H4
H
122-124
H
130-132
aReaction condition: sulfonylimines (0.5 mmol), potassium hexacyanoferrate(II) (0.1 mmol), benzoyl chloride (0.6 mmol) and potassium carbonate
(0.1 mmol) in ethanol (8 mL); bisolated yields.
ketones and p-toluenesulfonamide were also attempted
for the hydrocyanation reactions using K4[Fe(CN)6].
However, very low isolated yields were obtained under
the similar conditions. The possible reason is the large
sterical hindrance of the substrates.
Then the nucleophilic additions of hydrogen cyanide to
sulfonylimines 1 yield α-sulfonylimidonitriles 2 as products.
Conclusions
A plausible mechanism for the hydrocyanation of
sulfonylimines to synthesize α-sulfonylimidonitriles using
K4[Fe(CN)6] as a cyanide source, according to Hunig’s
review,25 is shown in Scheme 2. Firstly K4[Fe(CN)6] reacts
with benzoyl chloride to form benzoyl cyanide as an
intermediate. Then benzoyl cyanide is attacked by ethanol
in the presence of potassium carbonate to yield nucleophilic
additional intermediate A. Intermediate A undergoes the
loss of ethyl benzoate to produce hydrogen cyanide in situ.
In summary, an efficient method has been developed
for the hydrocyanation of sulfonylimines to synthesize
α-sulfonylimidonitriles by one-pot two-step procedure
using K4[Fe(CN)]6 as an original eco-friendly cyanide
source, benzoyl chloride as a promoter, and potassium
carbonate as a base. The protocol compared with literature
methods has advantages of using non-toxic, nonvolatile
and inexpensive cyanide source, high yield, and simple
work-up procedure.

1742
Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
J. Braz. Chem. Soc.
Scheme 2. The proposed mechanism for hydrocyanation of sulfonylimines using K4[Fe(CN)]6.
Experimental
Supplementary Information
IR spectra were recorded using KBr pellets on an
Alpha Centauri FTIR spectrophotometer. H NMR and
Full set of characterization data (IR, 1H and 13C NMR
spectra) are available free of charge at http://jbcs.sbq.org.br
as PDF file.
1
13C NMR spectra were recorded on a Mercury-400BB
instrument using CDCl3 as solvent and Me4Si as
internal standard. Melting points were observed in
an electrothermal melting point apparatus. Potassium
Acknowledgements
o
hexacyanoferrate(II) was dried at 80 C under vacuum
The authors thank the National Natural Science
Foundation of China (21162024) and Provincial Natural
Science Foundation of Gansu (1107RJZA189) for the
financial support of this work.
for 24 h and finely powdered prior to use. Sulfonylimines
were generally prepared according to modified literature
methods by refluxing of 4-methylbenzenesulfonamide or
benzenesulfonamide with various aldehydes in toluene
using anhydrous magnesium sulfate as a dehydrating
agent and acetic acid as a catalyst.29
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Submitted: July 5, 2013
Published online: September 4, 2013

J. Braz. Chem. Soc., Vol. 24, No. 11, S1-S29, 2013.
Printed in Brazil - ©2013 Sociedade Brasileira de Química
0103 - 5053 $6.00+0.00
Supplementary Information
SI
Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an
Eco-Friendly Cyanide Source
Zheng Li,* Rongzhi Li, Huanhuan Zheng, Fei Wen, Hongbo Li, Junjun Yin and Jingya Yang
Key Laboratory of Eco-Environment-Related Polymer Materials for Ministry of Education, College of Chemistry
and Chemical Engineering, Northwest Normal University, 730070 Lanzhou, Gansu, P. R. China
13
The general procedure for the preparation of
sulfonylimines
Ar-H), 8.90 (s, 1H, CH). C NMR (100 MHz, CDCl3) d
22.3, 56.7, 115.4, 125.8, 128.6, 130.3, 134.4, 136.5, 145.1,
166.1, 170.0.
The mixture of 4-methylbenzenesulfonamide or
benzenesulfonamide (20 mmol), aldehyde (22 mmol),
anhydrous magnesium sulfate (5 mmol) and acetic acid
(4 mmol) in 20 mL of toluene was refluxed at 110 oC for
15 h. The progress of the reaction was monitored by TLC.
After the completion, the system was cooled to room
temperature, and the solvent was removed under reduced
pressure. The resulting solid was recrystallized from
diethyl ether to give pure product. The analytical data for
representative products are given below.
N-(2-Chlorobenzylidene)-4-methylbenzenesulfonamide (1g)
White solid; mp: 115-116 oC (lit. 114-116 oC).3 1H NMR
(400 MHz, CDCl3) d 2.44 (s, 3H, CH3), 7.28-7.91 (m, 8H,
Ar-H), 9.12 (s, 1H, CH). 13C NMR (100 MHz, CDCl3)
d 22.7, 126.8, 128.6, 129.2, 129.6, 131.3, 131.8, 134.4,
137.2, 168.2.
N-(Furan-2-ylmethylene)-4-methylbenzenesulfonamide (1k)
o
o
Brown solid; mp: 100-102 C (lit. 101-102 C).3
1H NMR (400 MHz, CDCl3) d 2.34 (s, 1H, CH3), 6.78–7.77
(m, 7H, Ar-H), 8.85 (s, 1H, CH). 13C NMR (100 MHz,
CDCl3) d 22.7, 112.8, 115.6, 126.8, 128.8, 131.1, 148.6,
151.8, 154.5, 157.2.
N-Benzylidene-4-methylbenzenesulfonamide (1a)
White solid; mp: 109-110 oC (lit. 112-113 oC).1 1H NMR
(400 MHz, CDCl3) d 2.32 (s, 3H, CH3), 7.24 (d, 2H,
J 8.4 Hz, Ar-H), 7.48 (t, 2H, J 7.8 Hz, Ar-H), 7.50 (t, 1H,
J 6.4 Hz,Ar-H), 7.80-7.83 (m, 4H,Ar-H), 8.98 (s, 1H, CH).
13C NMR (100 MHz, CDCl3) d 21.8, 128.3, 129.8, 130.2,
131.5, 135.3, 140.1, 145.1, 170.6.
The general procedure for the hydrocyanation
of sulfonylimines
The mixture of K4[Fe(CN)6] (0.1 mmol) and benzoyl
o
N-(4-Methylbenzylidene)-4-methylbenzenesulfonamide (1b)
White solid; mp: 111-113 oC (lit. 112-114 oC).2 1H NMR
(400 MHz, CDCl3) d 2.43 (s, 6H, CH3), 7.27 (d, 2H,
J 7.6 Hz, Ar-H), 7.35 (d, 2H, J 7.8 Hz, Ar-H), 7.83 (d, 2H,
J 7.6 Hz, Ar-H), 7.91 (d, 2H, J 7.6 Hz, Ar-H), 8.97 (s, 1H,
chloride (0.6 mmol) was stirred at 160 C for 3 h, then
the reaction system was cooled to room temperature,
and sulfonylimines (0.5 mmol) and potassium carbonate
(0.1 mmol) in ethanol (8 mL) were added. The mixture
was further stirred at room temperature for appropriate
time indicated in Table 3. After completion of the reaction
monitored by TLC, the resulting mixture was filtered to
remove the solids. The liquor was concentrated, and the
residues were isolated by column chromatography using
petroleum ether and ethyl acetate (6:1) as eluent to give pure
product. The analytical data for products are given below.
13
CH). C NMR (100 MHz, CDCl3) d 22.1, 126.9, 128.5,
129.9, 130.3, 130.4, 131.9, 135.8, 144.9, 170.5.
N-(4-Methoxybenzylidene)-4-methylbenzenesulfonamide
(1c)
White solid; mp: 128-130 oC (lit. 128-129 oC).3 1H NMR
(400 MHz, CDCl3) d 2.35 (s, 3H, CH3), 3.77 (s, 3H, OCH3),
6.92 (d, 2H, J 8.6 Hz, Ar-H), 7.28 (d, 2H, J 7.8 Hz, Ar-
H), 7.80 (d, 2H, J 7.6 Hz, Ar-H), 7.84 (d, 2H, J 7.6 Hz,
N-(Cyanophenylmethyl)-4-methylbenzenesulfonamide (2a)
White solid; mp 152-154 oC; IR (KBr) νmax/cm-1 3254
(NH), 2245 (CN), 1334 (S=O asym), 1157 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.46 (s, 3H, CH3), 5.10 (d,
*e-mail: lizheng@nwnu.edu.cn

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J. Braz. Chem. Soc.
1H, J 8.4 Hz, NH), 5.48 (d, 1H, J 8.4 Hz, CH), 7.36-7.46 (m,
7H,ArH), 7.82 (t, 2H, J 8.4 Hz,ArH); 13C NMR (100 MHz,
CDCl3) d 21.6, 48.2, 116.2, 127.0, 127.3, 129.4, 129.9,
130.0, 132.0, 135.9, 144.7.Anal. calcd. for C15H14N2O2S: C,
62.92; H, 4.93; N, 9.78; found: C, 62.81; H, 4.95; N, 9.81.
ArH), 7.83 (d, 2H, J 7.6 Hz, ArH); 13C NMR (100 MHz,
CDCl3) d 21.7, 48.0, 101.8, 107.5, 108.7, 116.3, 121.0,
125.6, 126.5, 127.3, 129.7, 130.1, 136.0, 144.7, 148.6,
149.0. Anal. calcd. for C16H14N2O4S: C, 58.17; H, 4.27; N,
8.48; found: C, 58.09; H, 4.26; N, 8.50.
N-[Cyano(4-tolyl)methyl]-4-methylbenzenesulfonamide (2b)
White solid; mp 149-150 oC; IR (KBr) νmax/cm-1 3270
(NH), 2248 (CN), 1336 (S=O asym), 1160 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.28 (s, 3H, CH3 ), 2.38 (s,
3H, CH3), 5.09 (d, 1H, J 8.4 Hz, NH), 5.34 (d, 1H, J 8.4 Hz,
CH), 7.12 (d, 2H, J 8.0 Hz, ArH), 7.23 (d, 2H, J 8.0 Hz,
ArH), 7.28 (d, 2H, J 8.0 Hz, ArH), 7.72 (d, 2H, J 8.0 Hz,
ArH); 13C NMR (100 MHz, CDCl3) d 21.1, 21.6, 47.9,
116.4, 127.0, 127.3, 129.1, 130.0, 136.1, 140.0, 144.6.
Anal. calcd. for C16H16N2O2S: C, 63.98; H, 5.37; N, 9.33;
found: C, 64.09; H, 5.36; N, 9.35.
N-[Cyano(4-fluorophenyl)methyl]-4-methylbenzene-
sulfonamide (2f)
White solid; mp 122-124 oC; IR (KBr) νmax/cm-1 3256
(NH), 2243 (CN), 1332 (S=O asym), 1156 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.45 (s, 3H, CH3), 5.43 (d,
1H, J 9.6 Hz, CH), 5.59 (bs, 1H, NH), 7.03-7.07 (m, 2H,
ArH), 7.33-7.42 (m, 4H,ArH), 7.76 (d, 2H, J 8.0 Hz,ArH);
13C NMR (100 MHz, CDCl3) d 21.6, 47.5, 116.3, 127.2,
128.0, 129.1, 129.2, 130.0, 135.9, 144.8, 162.1, 164.6.Anal.
calcd. for C15H13FN2O2S: C, 59.20; H, 4.31; N, 9.20; found:
C, 59.14; H, 4.30; N, 9.16.
N-[Cyano(4-methoxyphenyl)methyl]-4-methylbenzene-
sulfonamide (2c)
N-[(2-Chlorophenyl)(cyano)methyl]-4-methylbenzene-
sulfonamide (2g)
White solid; mp 124-125 oC; IR (KBr) νmax/cm-1 3271
(NH), 2248 (CN), 1337 (S=O asym), 1160 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.37 (s, 3H, CH3), 3.71
(s, 3H, OCH3), 5.25 (d, 1H, J 8.4 Hz, NH), 5.32 (d, 1H,
J 8.4 Hz, CH), 6.77-6.82 (m, 2H, ArH), 7.18-7.28 (m,
4H, ArH), 7.68-7.73 (m, 2H, ArH); 13C NMR (100 MHz,
CDCl3) d 22.0, 48.0, 55.8, 115.0, 116.8, 124.4, 127.5, 128.8,
130.3, 136.4, 144.9, 160.9.Anal. calcd. for C16H16N2O3S: C,
60.74; H, 5.10; N, 8.85; found: C, 60.83; H, 5.09; N, 8.82.
White solid; mp 112-114 oC; IR (KBr) νmax/cm-1 3248
(NH), 2241 (CN), 1340 (S=O asym), 1159 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.41 (s, 3H, CH3), 5.67-
5.70 (m, 2H, NH and CH), 7.24-7.34 (m, 5H, ArH), 7.49
(d, 1H, J 7.2 Hz, ArH), 7.72-7.74 (m, 2H, ArH); 13C NMR
(100 MHz, CDCl3) d 21.5, 46.3, 115.8, 127.4, 127.9, 129.4,
130.0, 130.3, 130.7, 131.4, 133.1, 135.9, 144.6.Anal. calcd.
for C15H13ClN2O2S: C, 56.16; H, 4.08; N, 8.73; found: C,
56.00; H, 4.09; N, 8.75.
N-{Cyano[4-(dimethylamino)phenyl]methyl}-4-methyl-
benzenesulfonamide (2d)
N-[4-Chlorophenyl(cyano)methyl]-4-methylbenzene-
sulfonamide (2h)
White solid; mp 158-160 oC; IR (KBr) νmax/cm-1 3297
(NH), 2247 (CN), 1335 (S=O asym), 1164 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.48 (s, 3H, CH3), 2.99 (s,
6H, N(CH3)2), 4.95 (d, 1H, J 8.0 MHz, NH), 5.37 (d, 1H,
J 8.0 Hz, CH), 6.69 (d, 2H, J 8.0 Hz, ArH), 7.27 (d, 2H,
J 8.0 Hz, ArH), 7.38 (d, 2H, J 8.0 Hz, ArH), 7.84 (d, 2H,
J 8.0 Hz, ArH); 13C NMR (100 MHz, CDCl3) d 22.0, 40.3,
47.9, 112.6, 117.0, 127.2, 128.3, 129.9, 136.2, 144.9.Anal.
calcd. for C17H19N3O2S: C, 61.98; H, 5.81; N, 12.76; found:
C, 62.21; H, 5.83; N, 12.73.
White solid; mp 130-132 oC; IR (KBr) νmax/cm-1 3262
(NH), 2249 (CN), 1342 (S=O asym), 1160 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.46 (s, 3H, CH3), 5.30 (d,
1H, J 9.2 Hz, NH), 5.45 (d, 1H, J 9.2 Hz, CH), 7.35-7.39
(m, 6H, ArH), 7.77 (d, 2H, J 8.4 Hz, ArH); 13C NMR
(100 MHz, CDCl3) d 21.6, 47.5, 116.0, 127.2, 128.5,
129.5, 130.0, 130.6, 135.8, 136.0, 144.8. Anal. calcd. for
C15H13ClN2O2S: C, 56.16; H, 4.08; N, 8.73; found: C, 56.22;
H, 4.08; N, 8.72.
N-[Cyano(2,4-dichlorophenyl)methyl]-4-methylbenzene-
sulfonamide (2i)
N-{Benzo[d][1,3]dioxol-5-yl(cyano)methyl}-4-methyl-
benzenesulfonamide (2e)
White solid; mp 136-137 oC; IR (KBr) νmax/cm-1 3248
(NH), 2248 (CN), 1343 (S=O asym), 1158 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.44 (s, 3H, CH3), 5.51 (bs,
1H, NH), 5.64 (d, 1H, J 8.8 Hz, CH), 7.28-7.32 (m, 3H,
ArH), 7.37 (s, 1H, ArH), 7.44 (d, 1H, J 8.4 Hz, ArH), 7.72
(d, 2H, J 8.0 Hz,ArH); 13C NMR (100 MHz, CDCl3) d 21.7,
45.7, 115.5, 127.3, 128.1, 128.4, 130.0, 130.3, 130.4, 133.9,
White solid; mp 166-168 oC; IR (KBr) νmax/cm-1 3212
(NH), 2244 (CN), 1338 (S=O asym), 1159 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.48 (s, 3H, CH3), 5.10 (d,
1H, J 8.4 Hz, NH), 5.39 (d, 1H, J 8.4 Hz, CH), 6.03 (s,
2H, CH2), 6.81 (d, 1H, J 8.4 Hz, ArH), 6.89 (s, 1H, CH,
ArH), 6.95 (d, 1H, J 8.4 Hz, ArH), 7.39 (d, 2H, J 7.6 Hz,

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135.7, 137.0, 144.8. Anal. calcd. for C15H12Cl2N2O2S: C,
50.72; H, 3.41; N, 7.89; found: C, 50.64; H, 3.42; N, 7.91.
N-[Cyano(phenyl)methyl]benzenesulfonamide (2n)
White solid; mp 98-100 C; IR (KBr) νmax/cm-1 3261
(NH), 2248 (CN), 1341 (S=O asym), 1169 (S=O sym);
1H NMR (400 MHz, CDCl3) d 5.47 (d, 1H, J 9.2 Hz, NH),
5.79 (d, 1H, J 9.2 Hz, CH), 7.28-7.91 (m, 10H, ArH);
13C NMR (100 MHz, CDCl3) d 48.2, 116.3, 127.1, 127.3,
129.4, 129.5, 129.9, 132.0, 133.7, 138.9. Anal. calcd. for
C14H12N2O2S: C, 61.75; H, 4.44; N, 10.29; found: C, 61.66;
H, 4.45; N, 10.25.
o
N-[4-(Bromophenyl)(cyano)methyl]-4-methylbenzene-
sulfonamide (2j)
White solid; mp 150-151 oC; IR (KBr) νmax/cm-1 3262
(NH), 2248 (CN), 1343 (S=O asym), 1160 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.45 (s, 3H, CH3), 5.40 (d,
1H, J 9.6 Hz, NH), 5.51 (d, 1H, J 9.6 Hz, CH), 7.29 (d,
2H, J 8.4 Hz, ArH), 7.34 (d, 2H, J 8.4 Hz, ArH), 7.50 (d,
2H, J 8.4 Hz, ArH), 7.75 (d, 2H, J 8.4 Hz, ArH); 13C NMR
(100 MHz, CDCl3) d 21.7, 47.7, 115.9, 124.2, 127.3, 127.8,
128.8, 130.1, 130.6, 131.2, 132.6, 135.8, 144.9.Anal. calcd.
for C15H13BrN2O2S: C, 49.33; H, 3.59; N, 7.67; found: C,
49.26; H, 3.60; N, 7.70.
N-[Cyano(4-tolyl)methyl]benzenesulfonamide (2o)
White solid; mp 100-102 oC; IR (KBr) νmax/cm-1 3278
(NH), 2245 (CN), 1336 (S=O asym), 1163(S=O sym);
1H NMR (400 MHz, CDCl3) d 2.36 (s, 3H, CH3), 5.43 (d,
1H, J 8.0 Hz, NH), 5.59 (d, 1H, J 8.0 Hz, CH), 7.18-7.31 (m,
4H, ArH), 7.55-7.93 (m, 5H, ArH); 13C NMR (100 MHz,
CDCl3) d 21.2, 48.0, 116.4, 127.0, 127.3, 129.0, 129.5,
130.0, 133.7, 139.0, 140.1.Anal. calcd. for C15H14N2O2S: C,
62.92; H, 4.93; N, 9.78; found: C, 62.99; H, 4.92; N, 9.76.
N-[Cyano(furan-2-yl)methyl]-4-methylbenzenesulfonamide
(2k)
o
White solid; mp 98-100 C; IR (KBr) νmax/cm-1 3277
(NH), 2251 (CN), 1337 (S=O asym), 1161 (S=O sym);
1H NMR (400 MHz, CDCl3) d 2.44 (s, 3H, CH3), 5.37 (d,
1H, J 9.2 Hz, NH), 5.53 (d, 1H, J 9.2 Hz, CH), 6.34-6.35
(m, 1H, Fu-H), 6.47 (d, 1H, J 3.6 Hz, Fu-H), 7.34 (d, 2H,
J 8.4 Hz, ArH), 7.38 (s, 1H, Fu-H), 7.77 (d, 2H, J 8.4 Hz,
N-[(4-Chlorophenyl)(cyano)methyl]benzenesulfonamide
(2p)
White solid; mp 122-124 oC; IR (KBr) νmax/cm-1 3229
(NH), 2238 (CN), 1333 (S=O asym), 1170 (S=O sym);
1H NMR (400 MHz, CDCl3) d 5.44 (bs, 1H, NH), 5.50
(d, 1H, J 8.0 Hz, CH), 7.40 (s, 4H, ArH), 7.58-7.62 (m,
2H, ArH), 7.68-7.72 (m, 1H, ArH), 7.93 (d, 2H, J 8.0 Hz,
ArH); 13C NMR (100 MHz, CDCl3) d 47.7, 115.8, 127.3,
128.5, 129.6, 129.6, 130.5, 133.9, 136.2, 138.8.Anal. calcd.
for C14H11ClN2O2S: C, 54.82; H, 3.61; N, 9.13; found: C,
54.77; H, 3.60; N, 9.16.
13
ArH); C NMR (100 MHz, CDCl3) d 21.9, 42.4, 110.6,
111.0, 114.7, 127.3, 131.2, 135.9, 143.9, 144.5, 144.8.Anal.
calcd. for C13H12N2O3S: C, 56.51; H, 4.38; N, 10.14; found:
C, 56.66; H, 4.39; N, 10.13.
N-(1-Cyanopropyl)-4-methylbenzenesulfonamide (2l)
o
White solid; mp 52-54 C; IR (KBr) νmax/cm-1 3283
(NH), 2249 (CN), 1333 (S=O asym), 1161 (S=O sym);
1H NMR (400 MHz, CDCl3) d 0.95-0.96 (m, 3H, CH3),
2.01-2.04 (m, 2H, CH2), 2.44 (s, 3H, CH3), 4.69 (d, 1H,
J 9.2 Hz, CH), 5.12 (bs, 1H, NH), 7.26-7.36 (m, 2H, ArH),
N-[(4-Bromophenyl)(cyano)methyl]benzenesulfonamide
(2q)
White solid; mp 130-132 oC; IR (KBr) νmax/cm-1 3233
(NH), 2239 (CN), 1332 (S=O asym), 1169 (S=O sym);
1H NMR (400 MHz, CDCl3) d 5.28 (d, 1H, J 9.2 Hz,
NH), 5.50 (d, 1H, J 9.2 Hz, CH), 7.33-7.55 (m, 2H,
ArH), 7.56-7.74 (m, 5H, ArH), 7.92-7.96 (m, 2H, ArH);
13C NMR (100 MHz, CDCl3) d 47.7, 115.7, 124.4, 127.2,
128.7, 129.6, 130.9, 132.6, 133.9, 138.8. Anal. calcd. for
C14H11BrN2O2S: C, 47.88; H, 3.16; N, 7.98; found: C, 47.74;
H, 3.17; N, 7.95.
13
7.77-7.79 (m, 2H, ArH); C NMR (100 MHz, CDCl3) d
13.3, 21.3, 21.6, 51.2, 116.0, 126.0, 127.3, 129.9, 134.2,
136.2, 144.5. Anal. calcd. for C11H14N2O2S: C, 55.44; H,
5.92; N, 11.76; found: C, 55.58; H, 5.94; N, 11.80.
N-(1-Cyano-2-methylpropyl)-4-methylbenzenesulfonamide
(2m)
o
White solid; mp 78-79 C; IR (KBr) νmax/cm-1 3281
(NH), 2240 (CN), 1339 (S=O asym), 1162 (S=O sym);
1H NMR (400 MHz, CDCl3) d 1.04 (d, 6H, J 6.8 Hz, CH3),
1.99-2.07 (m, 1H, CH), 2.44 (s, 3H, CH3), 4.01-4.05 (m,
1H, CH), 5.53 (bs, 1H, NH), 7.35 (d, 2H, J 7.6 Hz, ArH),
7.78 (d, 2H, J 7.6 Hz, ArH); 13C NMR (100 MHz, CDCl3)
d 17.8, 18.5, 21.7, 32.4, 50.6, 116.8, 127.2, 130.1, 136.0,
144.6. Anal. calcd. for C12H16N2O2S: C, 57.12; H, 6.39; N,
11.10; found: C, 57.04; H, 6.41; N, 11.06.
References
1. Lu, K.; Kwon, O.; Brummond, K. M.; Davis, M. M.; Org. Synth.
2009, 86, 212.
2. Hasaninejad, A.; Zare, A.; J. Sulfur Chem. 2007, 28, 357.
3. Trost, B. M.; Marrs, C.; J. Org. Chem. 1991, 56, 6468.

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Figure S1. 1H NMR spectrum (400 MHz, CDCl3) of N-(cyanophenylmethyl)-4-methylbenzenesulfonamide (2a).
Figure S2. 13C NMR spectrum (100 MHz, CDCl3) of N-(cyanophenylmethyl)-4-methylbenzenesulfonamide (2a).

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Figure S3. IR of N-(cyanophenylmethyl)-4-methylbenzenesulfonamide (2a).
Figure S4. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(4-tolyl)methyl]-4-methylbenzenesulfonamide (2b).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S5. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(4-tolyl)methyl]-4-methylbenzenesulfonamide (2b).
Figure S6. IR of N-[cyano(4-tolyl)methyl]-4-methylbenzenesulfonamide (2b).

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Figure S7. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(4-methoxyphenyl)methyl]-4-methylbenzenesulfonamide (2c).
Figure S8. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(4-methoxyphenyl)methyl]-4-methylbenzenesulfonamide (2c).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S9. IR of N-[cyano(4-methoxyphenyl)methyl]-4-methylbenzenesulfonamide (2c).
Figure S10. 1H NMR spectrum (400 MHz, CDCl3) of N-{cyano[4-(dimethylamino)phenyl]methyl}-4-methylbenzenesulfonamide (2d).

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Figure S11. 13C NMR spectrum (100 MHz, CDCl3) of N-{cyano[4-(dimethylamino)phenyl]methyl}-4-methylbenzenesulfonamide (2d).
Figure S12. IR of N-{cyano[4-(dimethylamino)phenyl]methyl}-4-methylbenzenesulfonamide (2d).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S13. 1H NMR spectrum (400 MHz, CDCl3) of N-{benzo[d][1,3]dioxol-5-yl(cyano)methyl}-4-methylbenzenesulfonamide (2e).
Figure S14. 13C NMR spectrum (100 MHz, CDCl3) of N-{benzo[d][1,3]dioxol-5-yl(cyano)methyl}-4-methylbenzenesulfonamide (2e).

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Figure S15. IR of N-{benzo[d][1,3]dioxol-5-yl(cyano)methyl}-4-methylbenzenesulfonamide (2e).
Figure S16. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(4-fluorophenyl)methyl]-4-methylbenzenesulfonamide (2f).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S17. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(4-fluorophenyl)methyl]-4-methylbenzenesulfonamide (2f).
Figure S18. IR of N-[cyano(4-fluorophenyl)methyl]-4-methylbenzenesulfonamide (2f).

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Figure S19. 1H NMR spectrum (400 MHz, CDCl3) of N-[(2-chlorophenyl)(cyano)methyl]-4-methylbenzenesulfonamide (2g).
Figure S20. 13C NMR spectrum (100 MHz, CDCl3) of N-[(2-chlorophenyl)(cyano)methyl]-4-methylbenzenesulfonamide (2g).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S21. IR of N-[(2-chlorophenyl)(cyano)methyl]-4-methylbenzenesulfonamide (2g).
Figure S22. 1H NMR spectrum (400 MHz, CDCl3) of N-[4-chlorophenyl(cyano)methyl]-4-methylbenzenesulfonamide (2h).

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Figure S23. 13C NMR spectrum (100 MHz, CDCl3) of N-[4-chlorophenyl(cyano)methyl]-4-methylbenzenesulfonamide (2h).
Figure S24. IR of N-[4-chlorophenyl(cyano)methyl]-4-methylbenzenesulfonamide (2h).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S25. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(2,4-dichlorophenyl)methyl]-4-methylbenzenesulfonamide (2i).
Figure S26. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(2,4-dichlorophenyl)methyl]-4-methylbenzenesulfonamide (2i).

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Figure S27. IR of N-[cyano(2,4-dichlorophenyl)methyl]-4-methylbenzenesulfonamide (2i).
Figure S28. 1H NMR spectrum (400 MHz, CDCl3) of N-[4-(bromophenyl)(cyano)methyl]-4-methylbenzenesulfonamide (2j).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S29. 13C NMR spectrum (100 MHz, CDCl3) of N-[4-(bromophenyl)(cyano)methyl]-4-methylbenzenesulfonamide (2j).
Figure S30. IR of N-[4-(bromophenyl)(cyano)methyl]-4-methylbenzenesulfonamide (2j).

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Figure S31. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(furan-2-yl)methyl]-4-methylbenzenesulfonamide (2k).
Figure S32. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(furan-2-yl)methyl]-4-methylbenzenesulfonamide (2k).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
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Figure S33. IR of N-[cyano(furan-2-yl)methyl]-4-methylbenzenesulfonamide (2k).
Figure S34. 1H NMR spectrum (400 MHz, CDCl3) N-(1-cyanopropyl)-4-methylbenzenesulfonamide (2l).

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Figure S35. 13C NMR spectrum (100 MHz, CDCl3) of N-(1-cyanopropyl)-4-methylbenzenesulfonamide (2l).
Figure S36. IR of N-(1-cyanopropyl)-4-methylbenzenesulfonamide (2l).

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Figure S37. 1H NMR spectrum (400 MHz, CDCl3) of N-(1-cyano-2-methylpropyl)-4-methylbenzenesulfonamide (2m).
Figure S38. 13C NMR spectrum (100 MHz, CDCl3) of N-(1-cyano-2-methylpropyl)-4-methylbenzenesulfonamide (2m).

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Figure S39. IR of N-(1-cyano-2-methylpropyl)-4-methylbenzenesulfonamide (2m).
Figure S40. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(phenyl)methyl]benzenesulfonamide (2n).

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Hydrocyanation of Sulfonylimines Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source
J. Braz. Chem. Soc.
Figure S41. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(phenyl)methyl]benzenesulfonamide (2n).
Figure S42. IR of N-[cyano(phenyl)methyl]benzenesulfonamide (2n).

Vol. 24, No. 11, 2013
Li et al.
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Figure S43. 1H NMR spectrum (400 MHz, CDCl3) of N-[cyano(4-tolyl)methyl]benzenesulfonamide (2o).
Figure S44. 13C NMR spectrum (100 MHz, CDCl3) of N-[cyano(4-tolyl)methyl]benzenesulfonamide (2o).