Solid-phase synthesis of (E)-3-substituted acrylonitriles from polystyrene-supported α-selenoacetonitrile

Article abstract of DOI:10.1080/00397910802519158

A facile method for solid-phase organic synthesis of (E)-3-substituted acrylonitriles in good yields using polystyrene-supported α- selenoacetonitrile has been developed. The advantages of this method include straightforward operation, lack of odor, good

Full text of DOI:10.1080/00397910802519158

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Solid-Phase Synthesis of (E)-3-
Substituted Acrylonitriles from
Polystyrene-Supported α-
Selenoacetonitrile
Chao-Li Wang a , Yi-Xiang Huang a , Shou-Ri Sheng a
Wei Yang a & Ming-Zhong Cai a
,
a College of Chemistry and Chemical Engineering,
Jiangxi Normal University , Nanchang, China
Published online: 04 Mar 2009.
To cite this article: Chao-Li Wang , Yi-Xiang Huang , Shou-Ri Sheng , Wei Yang &
Ming-Zhong Cai (2009) Solid-Phase Synthesis of (E)-3-Substituted Acrylonitriles
from Polystyrene-Supported α-Selenoacetonitrile, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 39:7,
1282-1289
To link to this article: http://dx.doi.org/10.1080/00397910802519158
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Synthetic Communications1, 39: 1282–1289, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802519158
Solid-Phase Synthesis of (E)-3-Substituted
Acrylonitriles from Polystyrene-Supported
a-Selenoacetonitrile
Chao-Li Wang, Yi-Xiang Huang, Shou-Ri Sheng, Wei Yang,
and Ming-Zhong Cai
College of Chemistry and Chemical Engineering, Jiangxi Normal
University, Nanchang, China
Abstract: A facile method for solid-phase organic synthesis of (E)-3-substituted
acrylonitriles in good yields using polystyrene-supported a-selenoacetonitrile
has been developed. The advantages of this method include straightforward
operation, lack of odor, good stability, and high purity of the products.
Keywords: (E)-3-Substituted acrylonitrile, polystyrene-supported a-selenoaceto-
nitrile, solid-phase organic synthesis
Polymer-supported organic reagents have been applied to the rapid
preparation of small organic molecules because they can provide attrac-
tive and practical methods for combinatorial chemistry and solid-phase
organic synthesis (SPOS).[1] Organoselenium reagents have been increas-
ingly used as a powerful tool for introducing new functional groups
into organic substrates under extremely mild conditions.[2] For example,
the phenylseleno group is readily converted to a leaving group, giving
access to carbon–carbon double bond via oxidation followed by
b-elimination.[3] In addition, a selenium-stabilized carbanion has played
an important role in organic synthesis because of its easy availability
and particularly good nucleophile, which allows the formation of new
Received June 8, 2008.
Address correspondence to Shou-Ri Sheng, College of Chemistry and Chemical
Engineering, Jiangxi Normal University (Yaohu Campus), Nanchang, 330022,
China. E-mail: shengsr@jxnu.edu.cn
1282

SPOS of (E)-3-Substituted Acrylonitriles
1283
functionalized carbon–carbon bonds when it is used to react with com-
pounds bearing an electrophilic carbon atom.[2,4] Moreover, the poly-
meric selenium reagents[5] now have been developed for SPOS with a
combined advantage of decreased volatility and simplification of product
workup. 3-Substituted acrylonitriles[6] are versatile intermediates in
organic synthesis. The cyano group has broad synthetic applications in
organic and material chemistry.[7] Although methods for their prepara-
tions are well documented, efforts are continuing for the development
of more efficient methods with experimental simplicity. To our knowl-
edge, SPOS of 3-substituted acrylonitriles has not been reported. In con-
nection with our interest in solid-phase organoselenium chemistry,[8]
herein we report the preparation of a novel polymer-bound a-selenoace-
tonitrile reagent and its application for SPOS synthesis of 3-substituted
acrylonitriles, as shown in Scheme 1.
Polymer-supported a-selenoacetonitrile 3 was readily prepared by
treatment of a tetrohydrofuran (THF)–swollen suspension of cross-
linked (1%) polystyrene-bound selenium bromide 1[5a] with LiBH4, fol-
lowed by treatment with 2-bromoacetonitrile. Elemental analysis
revealed a loading of resin 3 (1.22 mmol N=g), and all its bromine was
found to be lost, indicating the performed bromine with a-methylnitrile
group exchange had gone to completion. Additionally, the Fourier trans-
form infrared (FT-IR) spectrum of the newly formed resin 3 showed a
strong stretching vibration of the cyano group at 2242 cmÀ1
.
As illustrated, the lithio derivative of resin 3 reacted smoothly with
various primary alkyl halides to furnish the new a-seleno alkylnitrile
resin 4, which could not be reliably analyzed with FT-IR. Hence, we
carried out next cleavage reaction directly after washing resin 4 using
solvents. Treatment of resin 4 with 30% hydrogen peroxide at 0ꢀC
and then at room temperature afforded the corresponding 3-substituted
acrylonitriles 5 in good yields (82–90%) and with good purities
(90–95%) (Table 1).
Scheme 1. Solid-phase synthesis of the route of (E)-3-substituted acrylonitriles.

1284
C.-L. Wang et al.
Table 1. Yields and purities of (E)-3-substituted acrylonitriles (5a–5h)
Entry
RCH2X
Product
Yielda (%)
Purityb (%)
1
2
C6H5CH2Cl
C6H5CH2Cl
C6H5CH2Cl
4-CH3C6H4CH2Br
4-CH3OC6H4CH2Br
2-CH3OC6H4CH2Br
4-ClC6H4CH2Br
4-NO2C6H4CH2Cl
2-Furylmethyl bromide
n-C6H13CH2Br
5a
5ac
5ad
5b
5c
90
86
82
90
88
90
88
84
85
82
95
94
90
95
93
95
92
93
93
92
3
4
5
6
5d
5e
7
8
5f
10
11
5g
5h
aYields were based on the functional loading of resin 3 (1.22 mmol N=g).
bPurities of crude products were determined by HPLC.
cObtained from the third regenerated resin 1.
dObtained from the fourth regenerated resin 1.
It should be noted that (E)-3-substituted acrylonitriles 5a–5 h are
formed exclusively, which was confirmed by the coupling constants
(J ¼ 16.5–16.8 Hz) between the two vinyl protons in their 1H NMR spec-
tra. The residual resin, polystyrene-supported phenylseleninic acid 6,
whose infrared data were identical to those previously reported,[9] showed
no residual cyano group absorption, which indicated the oxidative clea-
vage was complete. The resin 6 could be recyclized to selenium bromide
[10]
resin 1 by treatment with KI=Na2S2O3
followed by bromine.[5a] To
show the reactivity of the regenerated polymeric reagent, the conversion
of polymeric selenium bromide 1 to (E)-3-phenylacrylonitrile (5a) was
repeated four times in the same reaction. As seen from Table 1 (entries
2 and 3), compared with the result when the selenium bromide resin
was first used, the yield and purity of 5a decreased, which indicated that
recycling three to four times led to a gradual deterioration of the resin 1.
In summary, we have developed an efficient and convenient method
to synthesize (E)-3-substituted acrylonitriles through polymer-supported
a-selenoacetonitrile.
EXPERIMENTAL
1
Melting points were uncorrected. H NMR (400 MHz) and 13C NMR
(100 MHz) spectra were recorded on a Bruker Avance (400-MHz) spec-
trometer, using CDCl3 as the solvent and tetramethylsilane (TMS) as
internal standard. FT-IR spectra were taken on a Perkin-Elmer SP One

SPOS of (E)-3-Substituted Acrylonitriles
1285
FT-IR spectrophotometer. Microanalyses were performed with a Carlo
Erba 1106 Elemental Analyzer. High-performance liquid chromatogra-
phy (HPLC) analysis was performed on Agilent 1100 automated system
having a photodiode array (PDA) detector (kmax ¼ 254 nm used for this
study) using a gradient with CH3CN=H2O (1 mL=min) on an RP-18e col-
umn (150 ꢀ 4.6 mm). Polystyrene (H 1000, 100–200 mesh, cross-linked
with 1% divinylbenzene) for preparation of selenium bromide resin[5a]
was purchased from Nankai University, and the other starting materials
were purchased from commercial suppliers and used without further pur-
ification. THF was distilled from sodium-benzophenone immediately
prior to use.
Preparation of Polymer-Supported a-Selenoacetonitrile 3
Under a nitrogen atmosphere, 3.0 mmol LiBH4 was added to polystyrene-
supported selenium bromide 1 (1.0 g, 1.18 mmol Br=g, the loading of func-
tional Br was analyzed by elementary analysis) swelled in THF (10 mL)
for 30 min. After 1 h with shaking at room temperature, 2-bromoacetoni-
trile (3.0 mmol) in 2 mL of THF was added slowly, and the mixture was
shaken for 6 h. The resin was collected on a filter, washed successively with
H2O (2 ꢀ 20 mL), THF (3 ꢀ 5 mL), and CH2Cl2 (3 ꢀ 5 mL), and then dried
under vacuum overnight to afford 905 mg of resin 3 with a loading value
of 1.22 mmol N=g (theoretical loading of the resin 1.24 mmol N=g). IR
(KBr): n ¼ 3024, 2925, 2242, 1600, 1459, 1402, 1377, 1302, 1094, 1022,
1000, 737, 689, 671 cmꢁ1
.
General Procedure for the Preparation of (E)-3-Substituted
Acrylonitriles (5a–h)
Resin 3 (820 mg, 1.0 mmol) was added to a solution of 2.0 mmol of
lithium diisopropylamide (LDA) (2.2 mmol of diisopropylamine,
2.0 mmol of n-butyllithium) in anhydrous THF (10 mL) at –78ꢂC under
nitrogen atmosphere. After shaking at ꢁ78ꢂC for 1 h, the primary alkyl
halide (3.0 mmol in 5 mL THF) was added dropwise. Then the mixture
was warmed up gradually to room temperature and kept shaking for 8 h.
After neutralization with 1% hydrochloric acid, the resin 4a–h was col-
lected on a filter and washed successively with H2O (3 ꢀ 10 mL), THF
(3 ꢀ 5 mL), and Et2O (3 ꢀ 5 mL). To a suspension of the swollen resin
4a–h in THF (10 mL) was added 0.5 mL of 30% H2O2 (5.8 mmol) at 0ꢂC.
The suspension was shaken at 0ꢂC for 0.5 h and then at room temperature
for 1.0 h, the residual resin was collected by filtration and washed with

1286
C.-L. Wang et al.
CH2Cl2 (3 ꢀ 10 mL). The filtrate was washed with saturated NaHCO3
(20 mL) and with water, dried over magnesium sulfate, and evaporated
to give crude products 5a–h with 92–95% purity as determined by HPLC,
which were further purified by passing the crude product through a silica-
gel chromatographic column [ether–hexane as the eluent, 1:4–3:7 (v=v)],
affording the pure products for their structural analyses.
Data
(E)-3-Phenylacrylonitrile (5a)
Yellow oil (lit.[6d] oil); 1H NMR: d ¼ 7.41–7.32 (m, 6 H), 5.81 (d, J ¼ 16.8,
1 H); 13C NMR: d ¼ 150.5, 133.5, 131.1, 129.1, 127.3, 118.1, 96.3; IR
(neat): n ¼ 3029, 2218, 1619, 1495, 1449, 965 cmꢁ1; Anal. calcd. for
C9H7N: C, 83.69; H, 5.46; N, 10.84. Found: C, 83.78; H, 5.58; N, 10.92.
(E)-3-(4-Methylphenyl)acrylonitrile (5b)
Mp 70–71ꢂC (lit.[6e] mp 71–72ꢂC); 1H NMR: d ¼ 7.24–7.18 (m, 5 H), 5.74
(d, J ¼ 16.7 Hz, 1 H), 2.30 (s, 3 H); 13C NMR: d ¼ 150.6, 141.5, 130.2,
129.6, 127.1, 118.2, 95.1, 21.4; IR (KBr): n ¼ 3030, 2926, 2862, 2212,
1622, 1497, 1450, 1379, 967, 824 cmꢁ1. Anal. calcd. for C10H9N: C,
83.88; H, 6.34; N, 9.78. Found: C, 83.97; H, 6.41; N, 9.85.
(E)-3-(4-Methoxyphenyl)acrylonitrile (5c)
Yellow oil (lit.[6b] oil); 1H NMR: d ¼ 7.29–7.25 (m, 3 H), 6.84 (d, J ¼ 8.2 Hz,
2 H), 5.65 (d, J ¼ 16.5Hz, 1 H), 3.77 (s, 3 H); 13C NMR: d ¼ 162.06, 150.00,
129.05, 126.37, 118.64, 114.52, 93.40, 55.43; IR (neat): n ¼ 3035, 2928, 2867,
2214, 1620, 1500, 1383, 1180, 972, 831 cmꢁ1; Anal. calcd. for C10H9NO:
C, 75.45; H, 5.70; N, 8.80. Found: C, 75.56; H, 5.83; N, 8.90.
(E)-3-(2-Methoxyphenyl)acrylonitrile (5d)
Yellow oil (lit.[6m] oil); 1H NMR: d ¼ 7.57 (d, J ¼ 16.7 Hz, 1 H), 7.28–7.32
(m, 2 H), 6.90–6.93 (m, 2 H), 5.98 (d, J ¼ 16.7 Hz, 1 H), 3.82 (s, 3 H);
13C NMR: d ¼ 158.22, 146.39, 132.27, 128.89, 122.56, 120.81, 118.93,
111.29, 96.97, 55.52; IR (neat): n ¼ 3032, 2925, 2865, 2217, 1623, 1455,
1380, 1178, 972 cmꢁ1; Anal. calcd. for C10H9NO: C, 75.45; H, 5.70;
N, 8.80. Found: C, 75.55; H, 5.83; N, 8.87.

SPOS of (E)-3-Substituted Acrylonitriles
(E)-3-(4-Chlorophenyl)acrylonitrile (5e)
1287
Mp 85–86ꢂC (lit.[6c] mp 84–86ꢂC); 1H NMR: d ¼ 7.35–7.30 (m, 4 H), 7.26
(d, J ¼ 16.7 Hz, 1 H), 5.80 (d, J ¼ 16.7 Hz, 1 H); 13C NMR: d ¼ 149.2,
137.5, 132.1, 129.4, 128.4, 118.3, 97.1; IR (KBr): n ¼ 3038, 2219, 1625,
1499, 1456, 979, 832 cmꢁ1; Anal. calcd. for C9H6ClN: C, 66.07; H, 3.70;
N, 8.56. Found: C, 66.18; H, 3.82; N, 8.63.
(E)-3-(4-Nitrophenyl)acrylonitrile (5f)
1
Yellow solid; mp 203–204ꢂC (lit.[6d] mp 204–205ꢂC); H NMR: d ¼ 8.06
(d, J ¼ 8.7 Hz, 2 H), 7.57 (d, J ¼ 8.8 Hz, 2 H), 7.20 (d, J ¼ 16.8 Hz, 1 H),
5.84 (d, J ¼ 16.8 Hz, 1 H); 13C NMR: d ¼ 148.2, 147.1, 132.4, 127.6, 127.0,
118.7, 95.6; IR (KBr): n ¼ 3042, 2224, 1632, 1552, 1502, 985, 841 cmꢁ1
;
Anal. calcd. for C9H6N2O2: C, 62.07; H, 3.47; N, 16.09. Found:
C, 62.15; H, 3.56; N, 16.16.
(E)-3-(2-Furyl)acrylonitrile (5g)
Pale yellow oil (lit.[6e] yellow oil); 1H NMR: d ¼ 7.55 (dd, J ¼ 1.7, 0.8 Hz,
1 H), 7.18 (d, J ¼ 16.5 Hz, 1 H), 6.48 (dd, J ¼ 3.3, 1.7 Hz, 1 H), 6.43 (dd,
J ¼ 3.3, 0.8 Hz, 1 H), 5.78 (d, J ¼ 16.5 Hz, 1 H); 13C NMR: d ¼ 150.7,
143.1, 132.5, 118.6, 110.7, 108.9, 95.5; IR (neat): n ¼ 3015, 2219, 1605,
1504, 1340, 1230, 965 cmꢁ1; Anal. calcd. for C7H5NO: C, 70.58; H,
4.23; N, 11.76. Found: C, 70.66; H, 4.32; N, 11.84.
(E)-Non-2-enenitrile (5h)
Colorless oil (lit.[6j] colorless oil); 1H NMR: d ¼ 6.65 (dt, J ¼ 16.5, 7.1 Hz,
1 H), 5.22 (dt, J ¼ 16.5, 1.4 Hz, 1 H), 2.16–2.13 (m, 2 H), 1.41–1.13 (m,
8 H), 0.81 (t, J ¼ 6.9 Hz, 3H); 13C NMR: d ¼ 155.4, 117.0, 99.2, 32.8,
31.0, 28.2, 27.2, 21.8, 13.5; IR (neat): n ¼ 3031, 2960, 2863, 2218, 1616,
1385, 974, 723 cmꢁ1. Anal. calcd. for C9H15N: C, 78.77; H, 11.02;
N, 10.21. Found: C, 78.85; H, 11.13; N, 10.29.
ACKNOWLEDGMENT
We gratefully acknowledge financial support from the National Natural
Science Foundation (NSF) of China (No. 20562005) and NSF of Jiangxi
Province (Nos. 2008GZH0029 and 2007GZW0185) and the Research
Program of Jiangxi Province Department of Education (No. GJJ08165).

1288
C.-L. Wang et al.
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