One-pot four-component synthesis of 2-aryl-3,3-dihaloacrylonitriles using potassium hexacyanoferrate(II) as environmentally benign cyanide source

Article abstract of DOI:10.1590/S0103-50532011000100020

An efficient route to one-pot four-component reactions of aroyl chlorides, potassium hexacyanoferrate(II), triphenylphosphine and carbon tetrahalides to synthesize 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3- dibromoacrylonitriles was described. This

Full text of DOI:10.1590/S0103-50532011000100020

J. Braz. Chem. Soc., Vol. 22, No. 1, 148-154, 2011.
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Article
A
One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles using
Potassium Hexacyanoferrate(II) as Environmentally Benign Cyanide Source
Zhouxing Zhao and Zheng Li*
Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical
Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, P. R. China
Foi descrita uma rota eficiente para reações em uma etapa com quatro componentes incluindo
cloretos de aroila, hexacianoferrato(II) de potássio, trifenilfosfina e tetrahaletos de carbono para
sintetizar 2-aril-3,3-dicloroacrilonitrilas e 2-aril-3,3-dibromoacrilonitrilas. Este protocolo tem
como vantagens o uso de uma fonte não-tóxica de cianeto, alto rendimento e procedimento
experimental simples.
An efficient route to one-pot four-component reactions of aroyl chlorides, potassium
hexacyanoferrate(II), triphenylphosphine and carbon tetrahalides to synthesize 2-aryl-3,3-
dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles was described. This protocol has
advantages of use of non-toxic cyanide source, high yield and simple work-up procedure.
Keywords: cyanation, four-component synthesis, potassium hexacyanoferrate(II), cyanide
source, triphenylphosphine, 2-aryl-3,3-dichloroacrylonitriles, 2-aryl-3,3-dibromoacrylonitriles
Introduction
is even cheaper than KCN. Very recently, K4[Fe(CN)6]
has been proved to be an efficient cyanide source for the
cyanation of halogenated arenes and aroyl chlorides to
prepare benzonitriles,8 and aroyl cyanides.9
Herein, we wish to report an efficient one-pot four-
component synthesis of 2-aryl-3,3-dichloroacrylonitriles
and 2-aryl-3,3-dibromoacrylonitriles using potassium
hexacyanoferrate(II) as an environmentally benign cyanide
source.
3,3-Dichloroacrylonitrilesand3,3-dibromoacrylonitriles
are well-known as the most important synthetic
intermediates.1 Although 2-aryl-3,3-dichloroacrylonitriles
and 2-aryl-3,3-dibromoacrylonitriles could be prepared
directly from phosphorus ylides with aroyl cyanides,2
the commercially available aroyl cyanides are limited
and comparatively expensive. Especially, synthesis of
aroyl cyanides had to utilize strong toxic reagents as
original cyanide sources, such as HgCN,3 NaCN,4 CuCN,5
KCN,6 and TMSCN,7 which render the cyanation of
aroyl chlorides unsafe and environmentally unfriendly.
In addition, the corresponding phosphorus ylides, which
are unstable to oxygen and moisture, also required to
synthesize by reactions of triphenylphosphine with
carbon tetrahalides prior to use. Therefore, there is a
need to explore environmentally benign cyanating agents
and simple procedure for the synthesis of 2-aryl-3,3-
dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles.
Potassium hexacyanoferrate(II), K4[Fe(CN)6], is
non-toxic and is even used in the food industry for
metal precipitation. In addition, it has been described
as an antiagglutinating auxiliary for table salt (NaCl).
K4[Fe(CN)6] is commercially available on a ton scale and
Results and Discussion
Initially, the reaction of benzoyl chloride, potassium
hexacyanoferrate(II), triphenylphosphine and carbon
tetrachloride was selected as a model reaction to examine
the feasibility of one-pot four-component synthesis of
2-phenyl-3,3-dichloroacrylonitrileunderdifferentconditions
(Scheme 1). It was found that the optimal mole ratio of
benzoyl chloride to potassium hexacyanoferrate(II) and
triphenylphosphine was 1:0.2:2 for the reaction, and the
excess carbon tetrachloride were required because it
acted both as a reactant and a solvent in this reaction. The
0.2 equivalent of potassium hexacyanoferrate(II) used in the
reaction indicated that a small excess of CN– was utilized in
the reaction. The best yield was obtained by the procedure
of first conducting the reaction of benzoyl chloride and
potassium hexacyanoferrate(II) at 160 oC for 3 h, then further
*e-mail: lizheng@nwnu.edu.cn

Vol. 22, No. 1, 2011
Zhao and Li
149
Table 1. One-pot four-component synthesis of various 2-aryl-3,3-
dichloroacrylonitriles
reacting the resulting mixture with triphenylphosphine and
carbon tetrachloride at 80 oC for 2 h.
O
Aroyl
chloride
Yielda mp (lit.)
(%)
Cl
Cl
Ar
Compd.
Product
5 h
(oC)
+
K4[Fe(CN)6] +
Ar
Cl
Ph3P + CCl4
NC
O
CCl2
CN
1a-n
Oil
(Oil)2
1a
Cl
75
Scheme 1. One-pot synthesis of 2-aryl-3,3-dichloroacrylonitriles.
O
CCl2
CN
Under the optimal conditions, various substituted aroyl
chlorides were examined for the one-pot four-component
reactions. The results are summarized in Table 1. It was
found that aroyl chlorides bearing electron-withdrawing
substituents such as chloro, iodo and nitro groups on the
aromatic ring gave the corresponding products in high
yield (1b-1d, 1i, 1j and 1m). In contrast, aroyl chlorides
bearing electron-donating substituents such as methyl, ethyl,
methoxy and ethoxy groups on the aromatic ring gave the
corresponding products in slightly lower yield under similar
conditions (1e-1h, 1k and 1l). For ortho-substituted aroyl
chlorides, the corresponding products were obtained in
slightly lower yield than para-substituted ones, presumably
due to the steric effect (1b, 1e and 1h). Heteroaroyl chloride,
furoyl chloride, was also very efficient for the one-pot four-
component reaction (1n).
Cl
1b
1c
1d
1e
1f
78
80
81
67
71
73
104-105
54-56
Cl
Cl
O
CCl2
CN
Cl
Cl
Cl
O
CCl2
CN
83-84
(84.5-85)2
Cl
Cl
Cl
O
CCl2
CN
CH3
CCl2
CN
Cl
Oil
CH3
O
Oil
(Oil)2
H3C
H3C
Cl
O
CCl2
CN
In addition, one-pot four-component reactions
of aroyl chlorides, potassium hexacyanoferrate(II),
triphenylphosphine and carbon tetrabromide to synthesize
various 2-aryl-3,3-dibromoacrylonitriles were also
investigated (Scheme 2). In comparison with carbon
tetrachloride, carbon tetrabromide is more active for the one-
pot four-component reaction. Therefore milder conditions
are required, such as lower reaction temperature and short
reaction time although solvent is needed because carbon
tetrabromide can not act as a solvent at low temperatures.
The optimal conditions for the selected four-component
reactionofbenzoylchloride, potassiumhexacyanoferrate(II),
triphenylphosphine and carbon tetrabromide were also
investigated. It was found that the optimal mole ratio
of benzoyl chloride to potassium hexacyanoferrate(II),
triphenylphosphine and carbon tetrabromide was 1:0.2:2:1
for the reaction, and the best yield was obtained by the
procedure of first conducting the reaction of benzoyl
Cl
1g
Oil
H3C
H3C
O
CCl2
CN
C2H5
CCl2
CN
Cl
1h
1i
68
79
80
Oil
C2H5
O
O2N
O2N
Cl
137-139
128-130
O
CCl2
CN
Cl
1j
O2N
C2H5O
H3CO
I
O2N
C2H5O
H3CO
I
O
CCl2
CN
Cl
1k
1l
75
72
102-104
O
CCl2
CN
106-108
(107.5-108)2
Cl
o
chloride and potassium hexacyanoferrate(II) at 160 C
for 3 h, then further reacting the resulting mixture with
triphenylphosphine and carbon tetrabromide in methylene
chloride at 10 oC for 0.5 h.
O
CCl2
CN
Cl
1m
1n
79
81
68-69
O
Br
Ar
CH2Cl2
3.5 h
+
O
CCl2
CN
K4[Fe(CN)6] +
Ar
Cl
Ph3P + CBr4
NC
Br
O
O
100-102
Cl
2a-n
a Isolated yields.
Scheme 2. One-pot synthesis of 2-aryl-3,3-dibromoacrylonitriles.

150
One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
Table 2. One-pot four-component synthesis of various 2-aryl-3,3-
dibromoacrylonitriles
Under the optimal conditions, various substituted
aroyl chlorides were examined for the reactions. The
results are summarized in Table 2. The various substituted
aroyl chlorides including electron-withdrawing groups
and electron-donating groups are effective for the
reactions, which have the similar effect on the yield to
carbon tetrachloride. It is noteworthy to mention that
4-phenylbenzoyl chloride and isophthaloyl dichloride
could also efficiently participate in the one-pot four-
component reactions of carbon tetrabromide, but not
for the reactions of carbon tetrachloride under the
studied conditions (2l and 2m). Heteroaroyl chloride,
furoyl chloride, was also very efficient for the one-pot
four-component reaction to obtain 2-(furan-2-yl)-3,3-
dibromoacrylonitrile (2n).
Yielda
(%)
mp
Compd. Aroyl chloride
Product
(oC)
O
CBr2
CN
2a
2b
2c
2d
75
78
80
82
62-64
84-86
Cl
O
CBr2
CN
Cl
Cl
Cl
O
CBr2
CN
Cl
Cl
Cl
78-80
O
CBr2
CN
Cl
103-104
Conclusions
Cl
Cl
O
CBr2
An efficient route to the one-pot four-component
reactions of aroyl chlorides, potassium hexacyanoferrate(II),
triphenylphosphine and carbon tetrahalides to
synthesize 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-
3,3-dibromoacrylonitriles has been developed. The
protocol has the advantages of using non-toxic potassium
hexacyanoferrate(II) as an environmentally benign cyanide
source instead of traditional strong toxic cyanating agents,
high yield and simple work-up procedure.
Cl
CN
2e
72
74-76
CH3
CH3
O
CBr2
CN
H3C
H3C
2f
Cl
75
77
80
40-41
74-76
O
CBr2
CN
Cl
Cl
Cl
2g
2h
H3C
H3C
O
CBr2
CN
Experimental
130-132
O2N
O2N
IR spectra were recorded using KBr pellets on an
O
CBr2
CN
1
Alpha Centauri FTIR spectrophotometer and H NMR
O2N
O2N
and 13C NMR spectra 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 hexacyanoferrate(II) dried at
80 oC under vacuum for 24 h and finely powdered prior to
use. All reactions were monitored by TLC. Flash column
chromatography was carried out using 200-300 mesh silica
gel at increased pressure.
2i
83
88-90
NO2
NO2
O
CBr2
CN
O2N
O2N
2j
Cl
78
77
158-160
136-138
CBr2
CN
O
Cl
2k
H3CO
H3CO
O
CBr2
CN
General procedure for the preparation of 2-aryl-3,3-
dichloroacrylonitriles
Cl
2l
68
74-76
The mixture of aroyl chloride (10 mmol) and potassium
hexacyanoferrate(II) (0.84 g, 2 mmol) was heated at
160 C for 3 h. After cooling to room temperature,
Ο
O
CBr2
CBr2
CN
2m
2n
84
82
156-158
52-53
Cl
Cl
NC
o
triphenylphosphine (5.24 g, 20 mmol) and carbon
tetrachloride (10 mL) were added. The resulting mixture
O
CBr2
CN
O
O
Cl
o
was further stirred at 80 C for 2 h. Then the solid was
a Isolated yields.
removed by filtration, and the filtrate was evaporated to

Vol. 22, No. 1, 2011
Zhao and Li
151
remove solvent under reduced pressure, and the residue
was subjected to silica gel flash column chromatography
(ethyl acetate, petroleum ether, 1:40, v/v) to obtain pure
product. The analytical and spectral data for products are
given below; melting poinst are given in Table 1.
931, 877, 791, 697. Found: C, 56.56; H, 3.34; N, 6.56. Calc.
for C10H7Cl2N: C, 56.63; H, 3.33; N, 6.60%.
2-(4-Methylphenyl)-3,3-dichloroacrylonitrile (1g)
Colorless oil; 1H NMR (CDCl3, 400 MHz): d 7.37 (d,
2H, J 8.4 Hz, Ar-H), 7.19 (d, 2H, J 8.4 Hz, Ar-H), 2.32
(s, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d 140.0, 135.7,
129.2, 128.2, 127.4, 115.3, 115.2, 20.9; IR (KBr) νmax/cm-1:
3031, 2923, 2222, 1573, 1509, 1258, 929, 815, 771. Found:
C, 56.70; H, 3.32; N, 6.57. Calc. for C10H7Cl2N: C, 56.63;
H, 3.33; N, 6.60%.
2-Phenyl-3,3-dichloroacrylonitrile (1a)
1
Colorless oil; H NMR (CDCl3, 400 MHz): d 7.52-
7.41 (m, 5H, Ar-H); 13C NMR (CDCl3, 100 MHz): d
137.1, 130.6, 130.0, 128.8, 128.6, 115.5, 108.2; IR (KBr)
ν
max/cm-1: 3061, 2922, 2223, 1563, 1445, 930, 824, 759,
695. Found: C, 54.65; H, 2.53; N, 7.10. Calc. for C9H5Cl2N:
C, 54.58; H, 2.54; N, 7.07%.
2-(2-Ethylphenyl)-3,3-dichloroacrylonitrile (1h)
Colorless oil; 1H NMR (CDCl3, 400 MHz): d 7.25-6.97
(m, 4H, Ar-H), 2.88 (q, 2H, J 6.4 Hz, CH2), 1.26 (t, 3H,
J 6.4 Hz, CH3); 13C NMR (CDCl3, 100 MHz): d 143.1,
129.1, 129.0, 128.8, 124.7, 124.1, 121.6, 120.3, 119.2, 25.6,
14.3; IR (KBr) νmax/cm-1: 3032, 2918, 2224, 1589, 1497,
1234, 942, 842. Found: C, 58.50; H, 3.99; N, 6.20. Calc.
for C11H9Cl2N: C, 58.43; H, 4.01; N, 6.19%.
2-(2-Chlorophenyl)-3,3-dichloroacrylonitrile (1b)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.60-7.31
(m, 4H, Ar-H), 13C NMR (CDCl3, 100 MHz): d 132.9,
132.4, 131.5, 130.4, 130.2, 127.4, 120.4, 115.6, 113.9; IR
(KBr) νmax/cm-1: 3042, 2999, 2219, 1604, 1510, 1256, 927,
825. Found: C, 46.55; H, 1.72; N, 6.04. Calc. for C9H4Cl3N:
C, 46.49; H, 1.73; N, 6.02%.
2-(3-Nitrophenyl)-3,3-dichloroacrylonitrile (1i)
2-(3-Chlorophenyl)-3,3-dichloroacrylonitrile (1c)
White solid; 1H NMR (CDCl3, 400 MHz): d 8.45 (s, 1H,
Ar-H), 8.33 (d, 1H, J 8.0 Hz,Ar-H), 7.87 (d, 1H, J 8.0 Hz,
Ar-H), 7.70 (t, 1H, J 8.0 Hz,Ar-H); 13C NMR (CDCl3, 100
MHz): d 148.2, 140.1, 134.6, 132.2, 130.2, 124.9, 123.9,
114.7, 113.4; IR (KBr) νmax/cm-1: 3081, 2924, 2223, 1614,
1532, 1348, 1263, 947. Found: C, 44.55; H, 1.67; N, 11.57.
Calc. for C9H4Cl2N2O2: C, 44.48; H, 1.66; N, 11.53%.
1
Light yellow solid; H NMR (CDCl3, 400 MHz): d
7.52 (s, 1H, Ar-H), 7.44-7.39 (m, 3H, Ar-H); 13C NMR
(CDCl3, 100 MHz): d 138.6, 134.9, 132.2, 130.3, 130.2,
128.8, 126.9, 115.1, 114.3; IR (KBr) νmax/cm-1: 3062, 2926,
2220, 1571, 1471, 1262, 943, 850. Found: C, 46.42; H, 1.73;
N, 5.99. Calc. for C9H4Cl3N: C, 46.49; H, 1.73; N, 6.02%.
2-(4-Chlorophenyl)-3,3-dichloroacrylonitrile (1d)
Light yellow solid; H NMR (CDCl3, 400 MHz): d
7.48-7.40 (m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz): d
2-(4-Nitrophenyl)-3,3-dichloroacrylonitrile (1j)
White solid; 1H NMR (CDCl3, 400 MHz): d 8.33 (d, J
9.2 Hz, 2H,Ar-H), 7.74 (d, 2H, J 9.2 Hz,Ar-H); 13C NMR
(CDCl3, 100 MHz): d 148.3, 140.2, 136.7, 130.0, 124.1,
114.7, 113.8; IR (KBr) νmax/cm-1: 3049, 2923, 2235, 1555,
1481, 1377, 1226, 1024, 939, 748. Found: C, 44.45; H,
1.66; N, 11.49. Calc. for C9H4Cl2N2O2: C, 44.48; H, 1.66;
N, 11.53%.
1
137.7, 136.2, 130.0, 129.1, 129.0, 115.2, 114.5; IR (KBr)
ν
max/cm-1: 3084, 2924, 2220, 1555, 1481, 1279, 927, 809.
Found: C, 46.45; H, 1.72; N, 6.01. Calc. for C9H4Cl3N: C,
46.49; H, 1.73; N, 6.02%.
2-(2-Methylphenyl)-3,3-dichloroacrylonitrile (1e)
Colorless oil; 1H NMR (CDCl3, 400 MHz): d 7.22-7.00
(m, 4H, Ar-H), 2.16 (s, 3H, CH3); 13C NMR (CDCl3, 100
MHz): d 138.5, 136.1, 130.4, 130.0, 129.9, 128.7, 126.2,
114.7, 114.2, 18.8; IR (KBr) νmax/cm-1: 3067, 2925, 2219,
1571, 1485, 1258, 930, 753. Found: C, 56.53; H, 3.32; N,
6.62. Calc. for C10H7Cl2N: C, 56.63; H, 3.33; N, 6.60%.
2-(4-Ethoxyphenyl)-3,3-dichloroacrylonitrile (1k)
1
White solid; H NMR (CDCl3, 400 MHz): d 7.46 (d,
2H, J 8.8 Hz,Ar-H), 6.93 (d, 2H, J 8.8 Hz,Ar-H), 4.06 (q,
2H, J 6.8 Hz, CH2), 1.43 (t, 3H, J 6.8 Hz, CH3); 13C NMR
(CDCl3, 100 MHz): d 160.0, 135.3, 130.2, 122.6, 115.8,
115.2, 114.6, 63.6, 14.6; IR (KBr) νmax/cm-1: 3059, 2988,
2218, 1606, 1510, 1265, 924. Found: C, 54.50; H, 3.77; N,
5.80. Calc. for C11H9Cl2NO: C, 54.57; H, 3.75; N, 5.79%.
2-(3-Methylphenyl)-3,3-dichloroacrylonitrile (1f)
Colorlessoil;1HNMR(CDCl3,400MHz):d7.28-7.20(m,
4H,Ar-H), 2.35(s, 3H, CH3);13CNMR(CDCl3, 100MHz):d
138.5, 136.6, 130.6, 130.4, 128.9, 128.5, 125.5, 115.5, 115.4,
21.0;IR(KBr)νmax/cm-1:3039, 2923, 2222, 1565, 1485, 1267,
2-(4-Methoxyphenyl)-3,3-dichloroacrylonitrile (1l)
White solid; H NMR (CDCl3, 400 MHz): d 7.48 (d,
2H, J 9.2 Hz, Ar-H), 6.95 (d, 2H, J 9.2 Hz, Ar-H), 3.84
1

152
One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
(s, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d 160.7, 135.4,
130.2, 122.8, 115.7, 115.2, 114.2, 55.3; IR (KBr) νmax/cm-1:
3067, 2988, 2218, 1589, 1465, 1287, 854, 765. Found: C,
52.59; H, 3.07; N, 6.17. Calc. for C10H7Cl2NO: C, 52.66;
H, 3.09; N, 6.14%.
132.4, 131.5, 130.4, 130.2, 127.4, 120.3, 115.5, 113.9; IR
(KBr) νmax/cm-1: 3069, 2924, 2218, 1554, 1467, 11435,
1287,1038, 853, 750. Found: C, 33.69; H, 1.25; N, 4.34.
Calc. for C9H4Br2ClN: C, 33.63; H, 1.25; N, 4.36%.
2-(3-Chlorophenyl)-3,3-dibromoacrylonitrile (2c)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.48-7.35
(m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz): d 134.9,
134.7, 130.3, 130.2, 128.6, 126.7, 121.2, 116.6, 111.1;
IR (KBr) νmax/cm-1: 3065, 2927, 2218, 1589, 1434, 1282,
981, 848, 751. Found: C, 33.59; H, 1.26; N, 4.35. Calc. for
C9H4Br2ClN: C, 33.63; H, 1.25; N, 4.36%.
2-(4-Iodophenyl)-3,3-dichloroacrylonitrile (1m)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.79 (d, 2H,
J 8.8 Hz, Ar-H), 7.26 (d, 2H, J 8.8 Hz, Ar-H); 13C NMR
(CDCl3, 100 MHz): d 138.1, 137.8, 130.3, 130.1, 115.2,
114.7, 96.6; IR (KBr) νmax/cm-1: 3065, 2220, 1572, 1481,
1288, 1276, 933, 834. Found: C, 33.41; H, 1.23; N, 4.31.
Calc. for C9H4Cl2IN: C, 33.37; H, 1.24; N, 4.32%.
2-(4-Chlorophenyl)-3,3-dibromoacrylonitrile (2d)
1
2-(Furan-2-yl)-3,3-dichloroacrylonitrile (1n)
White solid; H NMR (CDCl3, 400 MHz): d 7.43 (s,
White solid; 1H NMR (CDCl3, 400 MHz): d 7.76 (d,
1H, J 1.6 Hz, Fu-H), 7.04 (d, 1H, J 4.4 Hz, Fu-H), 6.41
(dd, 1H, J 3.6 Hz, J 1.6 Hz, Fu-H), 13C NMR (CDCl3, 100
MHz): d 148.3, 140.2, 136.6, 130.0, 124.1, 114.7, 113.8;
IR (KBr) νmax/cm-1: 3109, 2923, 2220, 1520, 1350, 931,
858, 817, 698. Found: C, 44.66; H, 1.62; N, 7.43. Calc. for
C7H3Cl2NO: C, 44.72; H, 1.61; N, 7.45%.
4H, Ar-H); 13C NMR (CDCl3, 100 MHz): d 136.2, 131.6,
129.9, 129.2, 121.5, 116.7, 110.4; IR (KBr) νmax/cm-1: 2922,
2213, 1590, 1482, 1095, 831. Found: C, 33.65; H, 1.25; N,
4.38. Calc. for C9H4Br2ClN: C, 33.63; H, 1.25; N, 4.36%.
2-(2-Methylphenyl)-3,3-dibromoacrylonitrile (2e)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.37-7.18
(m, 4H, Ar-H), 2.33 (s, 3H, CH3); 13C NMR (CDCl3, 100
MHz): d 136.1, 133.3, 130.8, 130.2, 128.8, 126.6, 122.4,
116.1, 111.9, 19.3; IR (KBr) νmax/cm-1: 3062, 2920, 2214,
1546, 1453, 1251, 852, 735. Found: C, 39.86; H, 2.35; N,
4.63. Calc. for C10H7Br2N: C, 39.91; H, 2.34; N, 4.65%.
General procedure for the preparation of 2-aryl-3,3-
dibromoacrylonitriles
The mixture of aroyl chloride (10 mmol) and
potassium hexacyanoferrate(II) (0.84 g, 2 mmol)
o
o
was heated at 160 C for 3 h. After cooling to 10 C,
triphenylphosphine (5.24 g, 20 mmol) and carbon
tetrabromide (3.31 g, 10 mmol) in 10 mL of methylene
chloride was slowly added dropwise with stirring.
2-(3-Methylphenyl)-3,3-dibromoacrylonitrile (2f)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.34-7.24
(m, 4H, Ar-H), 2.39 (s, 3H, CH3); 13C NMR (CDCl3, 100
MHz): d 138.8, 133.2, 130.8, 128.9, 128.8, 125.6, 122.7,
117.1, 109.4, 21.3; IR (KBr) νmax/cm-1: 3018, 2921, 2214,
1600, 1554, 1095, 850, 789. Found: C, 39.95; H, 2.34; N,
4.67. Calc. for C10H7Br2N: C, 39.91; H, 2.34; N, 4.65%.
o
The resulting mixture was further stirred at 10 C for
0.5 h. Then the solid was removed by filtration, and the
filtrate was evaporated to remove solvent under reduced
pressure, and the residue was subjected to silica gel
flash column chromatography (ethyl acetate, petroleum
ether, 1:40, v/v) to obtain pure product. The analytical
and spectral data for products are given below; melting
points are given in Table 2.
2-(4-Methylphenyl)-3,3-dibromoacrylonitrile (2g)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.39-7.23
(m, 4H, Ar-H), 2.38 (s, 3H, CH3); 13C NMR (CDCl3, 100
MHz): d 140.4, 130.4, 129.6, 128.4, 122.6, 117.1, 108.9,
21.4; IR (KBr) νmax/cm-1: 3028, 2917, 2220, 1613, 1551,
1505, 1260, 849, 823. Found: C, 39.96; H, 2.35; N, 4.66.
Calc. for C10H7Br2N: C, 39.91; H, 2.34; N, 4.65%.
2-Phenyl-3,3-dibromoacrylonitrile (2a)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.48-7.45
(m, 5H, Ar-H); 13C NMR (CDCl3, 100 MHz): d 133.3,
130.0, 128.9, 128.5, 122.6, 117.0, 109.7; IR (KBr) νmax/cm-1:
3062, 2923, 2216, 1443, 842. Found: C, 37.71; H, 1.77;
N, 4.86. Calc. for C9H5Br2N: C, 37.67; H, 1.76; N, 4.88%.
2-(4-Nitrophenyl)-3,3-dibromoacrylonitrile (2h)
White solid; 1H NMR (CDCl3, 400 MHz): d 8.32 (d, 2H,
J 7.2 Hz, Ar-H), 7.71 (d, 2H, J 7.2 Hz, Ar-H); 13C NMR
(CDCl3, 100 MHz): d 148.3, 139.1, 129.9, 124.2, 120.6,
116.2, 112.7; IR (KBr) νmax/cm-1: 3104, 2924, 2216, 1600,
1518, 1350, 1294, 858. Found: C, 32.49; H, 1.21; N, 8.41.
Calc. for C9H4Br2N2O2: C, 32.56; H, 1.21; N, 8.44%.
2-(2-Chlorophenyl)-3,3-dibromoacrylonitrile (2b)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.50-7.31
(m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz): d 132.8,

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2-(3,5-Dinitrophenyl)-3,3-dibromoacrylonitrile (2i)
Supplementary Information
White solid; 1H NMR (CDCl3, 400 MHz): d 9.13 (s, 1H,
Ar-H), 8.74 (s, 2H,Ar-H); 13C NMR (CDCl3, 100MHz): d
148.7, 136.3, 129.0, 128.9, 120.0, 118.4, 115.6; IR (KBr)
1
Full set of IR, H NMR and 13C NMR spectra are
available free of charge at http://jbcs.sbq.org.br, as pdf file.
ν
max/cm-1: 3094, 2983, 2224, 1627, 1543, 1344, 1279, 918,
853, 729. Found: C, 28.73; H, 0.80; N, 11.11. Calc. for
C9H3Br2N3O4: C, 28.68; H, 0.80; N, 11.15%.
Acknowledgments
The authors thank the National Natural Science
Foundation of China (20772096), and Key Laboratory of
Eco-Environment-Related Polymer Materials (Northwest
Normal University), Ministry of Education of China for
the financial support of this work.
2-(3-Nitrophenyl)-3,3-dibromoacrylonitrile (2j)
White solid; 1H NMR (CDCl3, 400 MHz): d 8.41 (s,
1H, Ar-H), 8.33 (d, 1H, J 8.4 Hz, Ar-H), 7.84 (d, 1H, J
8.4 Hz, Ar-H), 7.69 (t, 1H, J 8.4 Hz, Ar-H); 13C NMR
(CDCl3, 100 MHz): d 148.3, 134.7, 134.5, 130.3, 124.8,
123.8, 120.3, 116.2, 112.8; IR (KBr) νmax/cm-1: 3104,
2924, 2216, 1600, 1518, 1350, 1294, 858. Found: C,
32.61; H, 1.20; N, 8.46. Calc. for C9H4Br2N2O2: C, 32.56;
H, 1.21; N, 8.44%.
References
1. Shablykin, O. V.; Gakh, A. A.; Brovarets, V. S.; Rusanov, E.
B.; Drach, B. S.; Heteroat. Chem. 2008, 9, 506; Shablykin,
O. V.; Brovarets, V. S.; Drach, B. S.; Russ. J. Gen. Chem.
2007, 77, 1308; Brovarets, V. S.; Pilyo, S. G.; Chernega, A. N.;
Romanenko, E.A.; Drach, B. S.; Russ. J. Gen. Chem. 1999, 69,
1577; Popil’nichenko, S. V.; Brovarets, V. S.; Chernega, A. N.;
Poltorak, D. V.; Drach, B. S.; Heteroat. Chem. 2006, 17, 411;
Golovchenko, O. V.; Pilyo, S. G.; Brovarets, V. S.; Chernega,
A. N.; Drach, B. S.; Heteroat. Chem. 2004, 15, 454; Pilyo, S.
G.; Brovarets, V. S.; Vinogradova, T. K.; Golovchenko, A. V.;
Drach, B. S.; Russ. J. Gen. Chem. 2002, 72, 1714; Kozachenko,
A. P.; Shablykin, O.V.;Vasilenko,A. N.; Brovarets,V. S.; Russ.
J. Gen. Chem. 2010, 80, 127; Kozachenko,A. P.; Shablykin, O.
V.; Rusanov, E. B.; Vasilenko, A. N.; Brovarets, V. S.; Russ. J.
Gen. Chem. 2009, 79, 996.
2-(4-Methoxyphenyl)-3,3-dibromoacrylonitrile (2k)
1
IR H NMR (CDCl3, 400 MHz): d 7.44 (d, 2H, J 9.2
Hz, Ar-H), 6.94 (d, 2H, J 9.2 Hz, Ar-H), 3.84 (s, 3H,
CH3). 13C NMR (CDCl3, 100 MHz): d 160.6, 130.1, 125.4,
122.2, 117.1, 114.2, 108.0, 55.3. (KBr) νmax/cm-1: 2999,
2939, 2214, 1605, 1508, 1259, 1182, 1021, 829. Found: C,
37.95; H, 2.22; N, 4.41. Calc. for C10H7Br2NO: C, 37.89;
H, 2.23; N, 4.42%.
2-(4-Biphenyl)-3,3-dibromoacrylonitrile (2l)
Brown solid; 1H NMR (CDCl3, 400 MHz): d 7.74-7.42
(m, 9H, Ar-H); 13C NMR (CDCl3, 100 MHz): d 145.6,
139.1, 132.5, 129.0, 128.6, 127.9, 127.7, 127.2, 122.1,
118.9, 110.8; IR (KBr) νmax/cm-1: 3063, 2922, 2223, 1600,
1479, 1400, 842, 767. Found: C, 49.69; H, 2.49; N, 3.87.
Calc. for C15H9Br2N: C, 49.62; H, 2.50; N, 3.86%.
2. Soulen, R. L.; Carlson, S. C.; Lang, F.; J. Org. Chem. 1973, 38,
479; Clement, B.A.; Soulen, R. L.; J. Org. Chem. 1974, 39, 97;
Clement, B. A.; Soulen, R. L.; J. Org. Chem. 1976, 41, 556;
Sepiol, J. J.; Sepiol, J. A.; Soulen, R. L.; J. Org. Chem. 1984,
49, 1125.
1,3-bis(2,2-dibromo-1-cyanovinyl)benzene (2m)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.75-7.42
(m, 4H, Ar-H); 13C NMR (CDCl3, 100 MHz): d 133.3,
132.4, 132.3, 132.2, 131.5, 128.5, 128.4; IR (KBr) νmax/cm-1:
3055, 2923, 2200, 1636, 1479, 1433, 1102, 713, 514.
Found: C, 29.14; H, 0.81; N, 5.63. Calc. for C12H4Br4N2:
C, 29.07; H, 0.81; N, 5.65%.
3. Haase, K.; Hoffmann, H. M.; Angew. Chem., Int. Ed. 1982, 21,
83.
4. Kazuaki, S.; Bull. Chem. Soc. Jpn. 1987, 60, 1085.
5. Oakwood, T. S.; Weisgerber, C. A.; Org. Synth. 1955, 24, 14.
6. Patricinio, A. F.; Moran, P. J. S.; J. Braz. Chem. Soc. 2001, 12,
7; Cao,Y. Q.; Du,Y. F.; Chen, B. H.; Li, J. T.; Synth. Commum.
2004, 34, 2951.
7. Harle, H.; Jochims, J. C.; Chem. Ber. 1986, 119, 1400; Zeng,
W.;Yang, J.; Meng, B.; Zhang, B.; Jiang, M.; Chen, F. X.; Lett.
Org. Chem. 2009, 6, 637.
2-(Furan-2-yl)-3,3-dibromoacrylonitrile (2n)
White solid; 1H NMR (CDCl3, 400 MHz): d 7.58 (d,
1H, J 1.6 Hz, Fu-H), 7.08 (d, 1H, J 4.0 Hz, Fu-H), 6.54
(dd, 1H, J 3.6 Hz, J 1.6 Hz, Fu-H), 13C NMR (CDCl3, 100
MHz): d 145.9, 144.2, 115.3, 114.5, 113.5, 112.1, 103.7. IR
(KBr) νmax/cm-1: 3153, 2227, 1476, 1030, 850, 750. Found:
C, 30.29; H, 1.08; N, 5.08. Calc. for C7H3Br2NO: C, 30.36;
H, 1.09; N, 5.06%.
8. Schareina, T.; Zapf, A.; Beller, M.; J. Organomet. Chem. 2004,
689, 4576; Schareina, T.; Zapf, A.; Beller, M.; Chem. Commun.
2004, 1388; Schareina, T.; Zapf,A.; Beller, M.; Tetrahedron Lett.
2005, 46, 2585; Schareina, T.; Zapf, A.; Magerlein, W.; Muller,
N.;Beller, M.;TetrahedronLett. 2007, 48, 1087;Weissman, S.A.;
Zewge, D.; Chen, C.; J. Org. Chem. 2005, 70, 1508; Grossman,

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
O.; Gelman, D.; Org. Lett. 2006, 8, 1189; Li, L. H.; Pan, Z. L.;
Duan, X. H.; Liang, Y. M.; Synlett 2006, 2094; Velmathi, S.;
Leadbeater, N. E.; Tetrahedron Lett. 2008, 49, 4693; Chen, G.;
Weng, J.; Zheng, Z.; Zhu, X.; Cai,Y.; Cai, J.;Wan,Y.; Eur. J. Org.
Chem. 2008, 3524; Cheng, Y. N.; Duan, Z.; Yu, L. J.; Li, Z. X.;
Zhu,Y.; Wu,Y. J.; Org. Lett. 2008, 10, 901; Franz, A. W.; Popa,
L. N.; Muller, T. J. J.; Tetrahedron Lett. 2008, 49, 3300; Ren,Y.
L.; Liu, Z. F.; He, S. B.; Zhao, S.; Wang, J. J.; Niu, R. Q.; Yin,
W. P.; Org. Process Res. Dev. 2009, 13, 764.
9. Li, Z.; Shi, S. Y.; Yang, J. Y.; Synlett 2006, 2495.
Submitted: April 27, 2010
Published online: September 8, 2010

J. Braz. Chem. Soc., Vol. 22, No. 1, S1-S43, 2011.
Printed in Brazil - ©2011 Sociedade Brasileira de Química
0103 - 5053 $6.00+0.00
Supplementary Information
SI
One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles using
Potassium Hexacyanoferrate(II) as Environmentally Benign Cyanide Source
Zhouxing Zhao and Zheng Li*
Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical
Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, P. R. China
The IR, 1H MNR and 13C MNR spectra for products are given below:
2-Phenyl-3,3-dichloroacrylonitrile (1a)
IR (KBr) νmax/cm-1: 3061, 2922, 2223, 1563, 1445, 930, 824, 759, 695; 1H NMR (CDCl3, 400 MHz): d 7.52-7.41 (m,
5H, Ph-H), 13C NMR (CDCl3, 100MHz): d 137.1, 130.6, 130.0, 128.8, 128.6, 115.5, 108.2.
Figure S1. IR spectrum of 2-phenyl-3,3-dichloroacrylonitrile (1a).
*e-mail: lizheng@nwnu.edu.cn

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
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Figure S2 1H NMR spectrum of 2-phenyl-3,3-dichloroacrylonitrile (1a)
Figure S3. 13C NMR spectrum of 2-phenyl-3,3-dichloroacrylonitrile (1a).

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2-(2-Cholorophenyl)-3,3-dichloroacrylonitrile (1b)
IR (KBr) νmax/cm-1: 3042, 2999, 2219, 1604, 1510, 1256. 927, 825; 1H NMR (CDCl3, 400 MHz): d 7.60-7.31 (m, 4H,
Ph-H), 13C NMR (CDCl3, 100 MHz): d 132.9, 132.4, 131.5, 130.4, 130.2, 127.4, 120.4, 115.6, 113.9.
Figure S4. IR spectrum of 2-(2-cholorophenyl)-3,3-dichloroacrylonitrile (1b).
Figure S5. 1H NMR spectrum of 2-(2-cholorophenyl)-3,3-dichloroacrylonitrile (1b).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
Figure S6. 13C NMR spectrum of 2-(2-cholorophenyl)-3,3-dichloroacrylonitrile (1b).
2-(3-Cholorophenyl)-3,3-dichloroacrylonitrile (1c)
IR (KBr) νmax/cm-1: 3062, 2926, 2220, 1571, 1471, 1262. 943, 850; 1H NMR (CDCl3, 400 MHz): d 7.52 (s, 1H, Ph-H),
7.44-7.39 (m, 3H, Ph-H); 13C NMR (CDCl3, 100 MHz): d 138.6, 134.9, 132.2, 130.3, 130.2, 128.8, 126.9, 115.1, 114.3.
Figure S7. IR spectrum of 2-(3-cholorophenyl)-3,3-dichloroacrylonitrile (1c).

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Figure S8. 1H NMR spectrum of 2-(3-cholorophenyl)-3,3-dichloroacrylonitrile (1c).
Figure S9. 13C NMR spectrum of 2-(3-cholorophenyl)-3,3-dichloroacrylonitrile (1c).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
2-(4-Cholorophenyl)-3,3-dichloroacrylonitrile (1d)
IR (KBr) νmax/cm-1: 3084, 2924, 2220, 1555, 1481, 1279. 927, 809; 1H NMR (CDCl3, 400 MHz): d 7.48-7.40 (m, 4H,
Ph-H); 13C NMR (CDCl3, 100 MHz): d 137.7, 136.2, 130.0, 129.1, 129.0, 115.2, 114.5.
Figure S10. IR spectrum of 2-(4-cholorophenyl)-3,3-dichloroacrylonitrile (1d).
Figure S11. 1H NMR spectrum of 2-(4-cholorophenyl)-3,3-dichloroacrylonitrile (1d).

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Figure S12. 13C NMR spectrum of 2-(4-cholorophenyl)-3,3-dichloroacrylonitrile (1d).
2-(2-Methylphenyl)-3,3-dichloroacrylonitrile (1e)
IR (KBr) νmax/cm-1: 3067, 2925, 2219, 1571, 1485, 1258, 930, 753; 1H NMR (CDCl3, 400 MHz): d 7.22-7.00 (m, 4H,
Ph-H), 2.16 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d 138.5, 136.1, 130.4, 130.0, 129.9, 128.7, 126.2, 114.7, 114.2, 18.8.
Figure S13. IR spectrum of 2-(2-methylphenyl)-3,3-dichloroacrylonitrile (1e).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
Figure S14. 1H NMR spectrum of 2-(2-methylphenyl)-3,3-dichloroacrylonitrile (1e).
Figure S14. 13C NMR spectrum of 2-(2-methylphenyl)-3,3-dichloroacrylonitrile (1e).

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2-(3-Methylphenyl)-3,3-dichloroacrylonitrile (1f)
IR (KBr) νmax/cm-1: 3039, 2923, 2222, 1565, 1485, 1267, 931, 877, 791, 697; 1H NMR (CDCl3, 400 MHz): d 7.28-7.20
(m, 4H, Ar-H), 2.35 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d 138.5, 136.6, 130.6, 130.4, 128.9, 128.5, 125.5, 115.5,
115.4, 21.0.
Figure S16. IR spectrum of 2-(3-methylphenyl)-3,3-dichloroacrylonitrile (1f).
Figure S17. 1H NMR spectrum of 2-(3-methylphenyl)-3,3-dichloroacrylonitrile (1f).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
Figure S18. 13C NMR spectrum of 2-(3-methylphenyl)-3,3-dichloroacrylonitrile (1f).
2-(4-Methylphenyl)-3,3- dichloroacrylonitrile (1g)
IR (KBr) νmax/cm-1: 3031, 2923, 2222, 1573, 1509, 1258, 929, 815, 771; 1H NMR (CDCl3, 400 MHz): d 7.37 (d, 2H, J
8.4 Hz, Ar-H), 7.19 (d, 2H, J 8.4 Hz, Ar-H), 2.32 (s, 3H, CH3); 13C NMR (CDCl3, 100MHz): d 140.0, 135.7, 129.2, 128.2,
127.4, 115.3, 115.2, 20.9.
Figure S19. IR spectrum of 2-(4-methylphenyl)-3,3-dichloroacrylonitrile (1g).

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Figure S20. 1H NMR spectrum of 2-(4-methylphenyl)-3,3-dichloroacrylonitrile (1g).
Figure S21. 13C NMRspectrum of 2-(4-methylphenyl)-3,3-dichloroacrylonitrile (1g).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
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2-(2-Ethylphenyl)-3,3- dichloroacrylonitrile (1h)
IR (KBr) νmax/cm-1: 3032, 2918, 2224, 1589, 1497, 1234, 942, 842; H NMR (CDCl3, 400 MHz): d 7.25-6.97 (m, 4H,
Ar-H), 2.88 (q, 2H, J 6.4 Hz, CH2), 1.26 (t, 3H, J 6.4 Hz, CH3); 13C NMR (CDCl3, 100 MHz): d 143.1, 129.1, 129.0, 128.8,
124.7, 124.1, 121.6, 120.3, 119.2, 25.6, 14.3.
1
Figure S22. IR spectrum of 2-(2-ethylphenyl)-3,3-dichloroacrylonitrile (1h).
Figure S23. 1H NMR spectrum of 2-(2-ethylphenyl)-3,3-dichloroacrylonitrile (1h).

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Figure S24. 13C NMR spectrum of 2-(2-ethylphenyl)-3,3-dichloroacrylonitrile (1h).
2-(3-Nitrophenyl)-3,3-dichloroacrylonitrile (1i)
IR (KBr) νmax/cm-1: 3081, 2924, 2223, 1614, 1532, 1348, 1263, 947; 1H NMR (CDCl3, 400 MHz): d 8.45 (s, 1H, Ar-H),
8.33 (d, 1H, J 8.0 Hz, Ar-H), 7.87 (d, 1H, J 8.0 Hz, Ar-H), 7.70 (t, 1H, J 8.0 Hz, Ar-H); 13C NMR (CDCl3, 100 MHz): d
148.2, 140.1, 134.6, 132.2, 130.2, 124.9, 123.9, 114.7, 113.4.
Figure S25. IR spectrum of 2-(3-nitrophenyl)-3,3-dichloroacrylonitrile (1i).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
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Figure S26. 1H NMR spectrum of 2-(3-nitrophenyl)-3,3-dichloroacrylonitrile (1i).
Figure S27. 13C NMR spectrum of 2-(3-nitrophenyl)-3,3-dichloroacrylonitrile (1i).

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2-(4-Nitrophenyl)-3,3-dichloroacrylonitrile (1j)
IR (KBr) νmax/cm-1: 3049, 2923, 2235, 1555, 1481, 1377, 1226, 1024, 939, 748; 1H NMR (CDCl3, 400 MHz): d 8.33
(d, J 9.2 Hz, 2H, Ar-H), 7.74 (d, 2H, J 9.2 Hz, Ar-H); 13C NMR (CDCl3, 100 MHz): d 148.3, 140.2, 136.7, 130.0, 124.1,
114.7, 113.8.
Figure S28. IR spectrum of 2-(4-nitrophenyl)-3,3-dichloroacrylonitrile (1j).
Figure S29. 1H NMR spectrum of 2-(4-nitrophenyl)-3,3-dichloroacrylonitrile (1j).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
Figure S30. 13C NMR spectrum of 2-(4-nitrophenyl)-3,3-dichloroacrylonitrile (1j).
2-(4-Ethoxyphenyl)-3,3-dichloroacrylonitrile (1k)
IR (KBr) νmax/cm-1: 3059, 2988, 2218, 1606, 1510, 1265, 924; 1H NMR (CDCl3, 400 MHz): d 7.46 (d, 2H, J 8.8 Hz,
Ar-H), 6.93 (d, 2H, J 8.8 Hz, Ar-H), 4.06 (q, 2H, J 6.8 Hz, CH2), 1.43 (t, 3H, J 6.8 Hz, CH3); 13C NMR (CDCl3, 100 MHz):
d 160.0, 135.3, 130.2, 122.6, 115.8, 115.2, 114.6, 63.6, 14.6.
Figure S31. IR spectrum of 2-(4-ethoxyphenyl)-3,3-dichloroacrylonitrile (1k).

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Figure S32. 1H NMR spectrum of 2-(4-ethoxyphenyl)-3,3-dichloroacrylonitrile (1k).
Figure S33. 13C NMR spectrum of 2-(4-ethoxyphenyl)-3,3-dichloroacrylonitrile (1k).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
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2-(4-Methoxyphenyl)-3,3-dichloroacrylonitrile (1l)
IR (KBr) νmax/cm-1: 3067, 2988, 2218, 1589, 1465, 1287, 854, 765; 1H NMR (CDCl3, 400 MHz): d 7.48 (d, 2H, J 9.2
Hz, Ar-H), 6.95 (d, 2H, J 9.2 Hz, Ar-H), 3.84 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d 160.7, 135.4, 130.2, 122.8,
115.7, 115.2, 114.2, 55.3.
Figure S34.IR spectrum of 2-(4-methoxyphenyl)-3,3-dichloroacrylonitrile (1l).
Figure S35. 1H NMR spectrum of 2-(4-methoxyphenyl)-3,3-dichloroacrylonitrile (1l).

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Figure S36. 13C NMR spectrum of 2-(4-methoxyphenyl)-3,3-dichloroacrylonitrile (1l).
2-(4-Iodophenyl)-3,3-dichloroacrylonitrile (1m)
1
IR (KBr) νmax/cm-1: 3065, 2220, 1572, 1481, 1288, 1276, 933, 834; H NMR (CDCl3, 400 MHz): d 7.79 (d, 2H, J 8.8
Hz, Ar-H), 7.26 (d, 2H, J 8.8 Hz, Ar-H); 13C NMR (CDCl3, 100 MHz): d 138.1, 137.8, 130.3, 130.1, 115.2, 114.7, 96.6.
Figure S37. IR spectrum of 2-(4-iodophenyl)-3,3-dichloroacrylonitrile (1m).

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One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
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Figure S38. 1H NMR spectrum of 2-(4-iodophenyl)-3,3-dichloroacrylonitrile (1m).
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Figure S39. 13C NMR spectrum of 2-(4-iodophenyl)-3,3-dichloroacrylonitrile (1m).

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2-(Furan-2-yl)-3,3-dichloroacrylonitrile (1n)
IR (KBr) νmax/cm-1: 3109, 2923, 2220, 1520, 1350, 931, 858, 817, 698; 1H NMR (CDCl3, 400 MHz): d 7.76 (d, 1H, J 1.6
Hz, Fu-H), 7.04 (d, 1H, J 4.4 Hz, Fu-H), 6.41 (dd, 1H, J 3.6 Hz, J 1.6 Hz, Fu-H), 13C NMR (CDCl3, 100 MHz): d 148.3,
140.2, 136.6, 130.0, 124.1, 114.7, 113.8.
Figure S40. IR spectrum of 2-(furan-2-yl)-3,3-dichloroacrylonitrile (1n).
Figure S41. 1H NMR spectrum of 2-(furan-2-yl)-3,3-dichloroacrylonitrile (1n).

S22
One-Pot Four-Component Synthesis of 2-Aryl-3,3-Dihaloacrylonitriles
J. Braz. Chem. Soc.
Figure S42. 13C NMR spectrum of 2-(furan-2-yl)-3,3-dichloroacrylonitrile (1n).
2-Phenyl-3,3-dibromoacrylonitrile (2a)
IR (KBr) νmax/cm-1: 3062, 2923, 2216, 1579, 1487, 1247, 842, 752, 692; 1H NMR (400 MHz, CDCl3): d 7.45-7.48 (m,
5H, Ph-H); 13C NMR (CDCl3, 100 MHz): d 133.3, 130.0, 128.9, 128.5, 122.6, 117.0, 109.7.
Figure S43. IR spectrum of 2-phenyl-3,3-dibromoacrylonitrile (2a).

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Figure S44. 1H NMR spectrum of 2-phenyl-3,3-dibromoacrylonitrile (2a).
Figure S45. 13C NMR spectrum of 2-phenyl-3,3-dibromoacrylonitrile (2a).