Sodium acetate-catalyzed regiospecific and high stereoselective aminobromination of β,β-dicyanostyrene derivatives with NBS as nitrogen/bromine source

Article abstract of DOI:10.1002/cjoc.201100346

An easy and efficient method for the aminobromination of β,β-dicyanostyrene derivatives with NBS as the aminobrominating reagent in CH₃CN catalyzed by NaOAc (10 mol%) is developed. This protocol provides convenient process to convert β,β-dicyanostyrene derivatives into the vicinal haloamines with full regiospecificity and high stereoselectivety in the ice-water bath in air. The reaction is high efficient in yielding the corresponding aminobrominated products in excellent yields (up to 95%) under these conditions. The outcome indicated that the reaction has an electrophilic addition feature. 12 Eexamples of β,β-dicyanostyrene derivatives have been investigated. An easy and efficient method for the aminobromination of β,β-dicyanostyrene derivatives with NBS as the aminobrominating reagent in CH₃CN catalyzed by NaOAc (10 mol%) is developed. The reaction is high efficient in yielding the corresponding aminobrominated products in excellent yields (up to 95%). Copyright

Full text of DOI:10.1002/cjoc.201100346

FULL PAPER
DOI: 10.1002/cjoc.201100346
Sodium Acetate-catalyzed Regiospecific and High Stereose-
lective Aminobromination of β,β-Dicyanostyrene Derivatives
with NBS as Nitrogen/Bromine Source
Li, Wenlia,b(李文丽)
Chen, Zhanguo*,a,b(陈战国)
Zhou, Jimeia,b(周继梅)
Hu, Junlia,b(胡均利)
Xia, Weia,b(夏伟)
a Key Laboratory for Macromolecular Science of Shaanxi Province, Xi'an, Shaanxi 710062, China
b School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, Shaanxi 710062, China
An easy and efficient method for the aminobromination of β,β-dicyanostyrene derivatives with NBS as the
aminobrominating reagent in CH3CN catalyzed by NaOAc (10 mol%) is developed. This protocol provides con-
venient process to convert β,β-dicyanostyrene derivatives into the vicinal haloamines with full regiospecificity and
high stereoselectivety in the ice-water bath in air. The reaction is high efficient in yielding the corresponding ami-
nobrominated products in excellent yields (up to 95%) under these conditions. The outcome indicated that the reac-
tion has an electrophilic addition feature. 12 Eexamples of β,β-dicyanostyrene derivatives have been investigated.
Keywords aminobromination, β,β-dicyanostyrene derivatives, regiospecificity, high stereoselectivity, NBS, so-
dium acetate
Introduction
tion of the electro-rich alkenes via the ionic reaction
catalyzed by BF3-etherate.[37] However, the reaction
provided corresponding products in low yield (no more
than 55% yield). Enlightened by the aminohalogenation
of β-nitrostyrenes with NCS and NBS,[33] we developed
the protocol of the aminobromination of the electro-
deficient olefins, β,β-dicyanostyrene derivatives, with
NBS as the nitrogen/bromine source. Herein, we wish to
disclose the very simple and efficient aminobromination
of β,β-dicyanostyrene derivatives with NBS catalyzed
by NaOAc. The reaction was performed handily in
MeCN in the ice-water bath without protection of the
inert gases. The products with regiospecificity and high
stereoselectivity as well as excellent yields (up to 95%)
can be achieved for a wide range of β,β-dicyanostyrene
derivatives.
The anminohalogenation reaction of olefins has at-
tracted many chemists and biologists’ attention since the
adductive products, the vicinal haloamine compounds,
are very important building blocks which can easily be
converted into numerous useful functional derivatives
by displacing the halogens with the nucleophile includ-
ing intramolecular and intermolecular reactions.[1-9]
Much work on the aminohalogenation of olefins has
been reported which mainly focused on the simple ole-
fins,]10-15]
α,β-unsaturated
ketones,[16-25]
cinna-
mates,[23,26-29] unsaturated mononitriles,[26,30] β-nitro-
styrene derivatives[26,31-33] and an array of nitrogen/
halogen
source
including
4-TsNCl2,[17,27,30]
2-NsNNaCl,[17,28,31] 4-TsNNaCl,[10,19] TsNBr2,[34] di-
chlorocarbamates,[2] TsNH2/NBS,[10-15,19,21-25] NBA[32] or
2-NsNCl2/2-NsNHNa.[18,24,29] The efficient catalysts
include Lewis acid,[13,31-33] Brønsted acid,[35] metal ele-
mental powders and nonmetallic elemental powders as
well as other catalysts.[10-15,21-25,32,36]
Results and discussion
The initial study was carried out on the reaction of
β,β-dicyanostyrene 1f with NBS under our previous
catalytic conditions.[32] The reaction was performed in
acetonitrile and catalyzed by using anhydrous K3PO4 to
give the corresponding aminobrominated product 3f in
87% yield (Entry 1, Table 1). Common solvents,
CH2Cl2, toluene, DMF, acetone, CHCl3, THF and DMF
were tested for the purpose of improving the reaction
yields (Entries 2—7, Table 1). Acetonitrile was found to
As an expansion of our interest in the aminobromina-
tion of α,β-unsaturated ketones, cinnamates and simple
olefins[21-25] as well as β-nitrostyrenes,[32] we are also
attracted recently by the aminobromination of β,β-di-
cyanostyrene derivatives which has not been found so
far. Early literature reported that N-bromosuccinimide
(NBS) was employed as reagent for the addition reac-
*
E-mail: chzhg@snnu.edu.cn; Tel.: 0086-029-85308442; Fax: 0086-029-85307776
Received September 15, 2011; accepted November 20, 2011; published online March 7, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201100346 or from the author.
830
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 830—836

Regiospecific and High Stereoselective Aminobromination of β,β-Dicyanostyrene Derivatives
be the efficient choice for this reaction because it helps
the reaction to be completed in such a short time of 10
min (Entry 1, Table 1). Although the reaction could af-
ford similar amounts of the corresponding vicinal
haloamino nitriles in other solvents, a longer reaction
time was needed (Entries 2—7, Table 1).
It is noteworthy that the reaction was sensitive to
temperature. The lower yields were observed when re-
action time was prolonged over 20 min at room tem-
perature because a part of desired product was decom-
pounded into unknown compound. However, when the
reaction was carried out in an ice-water bath, the de-
compounded product could not be observed even
though the reaction time was prolonged up to 3 h (Entry
15, Table 1). It was also found that the 1.1 equiv. of
NBS was necessary for ensuring the higher chemical
yield, because the chemical yield was decreased to 85%
when 1.0 equiv. of NBS was used under the above con-
ditions (Entry 16, Table 1).
93% (Entries 12—13, Table 1) within 20 min. The reac-
tion could also work well catalyzed by K2CO3, but the
desired aminobrominated product was in a slight lower
yield (Entry 9, 87%, Table 1). Surprisingly, when KOH
and NaOH, the stronger bases, were employed as the
catalyst, the lower yields of 87% and 67% of product 3f
were observed within the longer period (Entries 10, 11,
Table 1). The loadings of NaOAc were also investigated
(Entries 12—14, Table 1), 10 mol% NaOAc was found
to be necessary for this reaction. The control experiment
indicated that the reaction failed to give any aminobro-
minated product in the absence of the catalyst even
though the reaction time was prolonged up to 48 h (En-
try 8, Table 1). This result revealed that the catalyst
played a very important role in this reaction.
In exploring the scope and the limitations of the
NaOAc-catalyzed aminobromination of β,β-dicyano-
styrene and gaining an insight into the mechanism of the
reaction, various common β,β-dicyanostyrene deriva-
tives bearing the electron-donating groups (EDG) and/or
the electron-withdrawing groups (EWG) on the phenyl
rings were investigated under the optimized conditions.
The results are summarized in the Table 2.
In further optimizing the reaction conditions, a vari-
ety of other catalysts, such as K2CO3, KOH, NaOH, and
NaOAc, were then utilized for this reaction in acetoni-
trile. As indicated in Table 1(Entries 9—12), NaOAc
was found to be the most efficient catalyst for the reac-
tion in CH3CN and generated the vicinal haloamino
product 3f in a higher chemical yield range of 90%—
As shown in Table 2, the reactions of β,β-dicyano-
styrene derivatives with NBS were carried out success-
fully to obtain the corresponding aminobrominated
Table 1 Aminobromination of β,β-dicyanostyrene (1f) with NBS in various catalysts and solventsa
O
CN
O
O
N
catalyst
+
N
Br
CN
CN
CN
solvent, r.t. or ice bath
O
Br
(+) 3f
1f
2
−
Entry
1
Product
3f
1f/NBS
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.1
1∶1.0
Catalyst (mol%)
K3PO4 (20)
K3PO4 (20)
K3PO4 (20)
K3PO4 (20)
K3PO4 (20)
K3PO4 (20)
K3PO4 (20)
no
Solvent
MeCN
CH2Cl2
PhMe
Time, Temperature
10 min, r.t.
10 h, r.t.
Yieldb/%
87
2
86
3f
3
24 h, r.t.
75
3f
4
acetone
CHCl3
THF
30 min, r.t.
24 h, r.t.
79
3f
5
85
3f
6
45 min, r.t.
15 min, r.t.
48 h, r.t.
85
3f
7
DMF
70
3f
8
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
0
3f
9
K2CO3 (20)
KOH (20)
15 min, r.t.
35 min, r.t.
90 min, r.t.
15 min, r.t.
20 min, r.t.
20 min, r.t.
3 h, ice-water bath
3 h, ice-water bath
87
3f
10
11
12
13
14
15
16
80
3f
NaOH (20)
NaOAc (20)
NaOAc (10)
NaOAc (5)
NaOAc (10)
NaOAc (10)
67
3f
90
3f
93
3f
78
3f
93
3f
85
3f
a Conditions: substrate 1f (2.0 mmol), NBS (2.2 or 2.0 mmol), solvent (5 mL) at room temperature or in ice-water bath. b Isolated yield.
Chin. J. Chem. 2012, 30, 830—836
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Li et al.
FULL PAPER
Table 2 NaOAc-catalyzed aminobromination of various β,β-dicyanostyrene derivatives with NBSa
Entry
1
Substrate
Product
Time/h
Yieldb/%
O
O
CN
N
1a
1.0
92
92
95
94
91
93
87
87
CN
CN
CN
+
( ) 3a
−
O2N
Br
O2N
O
O
CN
N
2
3
4
5
6
7
8
1.5
1.5
1.2
1.7
3.0
2.0
1.0
1b
CN
CN
CN
+
( ) 3b
−
F
Br
F
O
O
CN
N
1c
1d
1e
CN
CN
CN
(+) 3c
−
Cl
Br
Cl
O
O
CN
CN
N
N
CN
CN
(+) 3d
−
Br
Br
Br
O
O
CN
CN
CN
CN
+
( ) 3e
−
Me
Br
O
Me
O
CN
N
1f
CN
CN
CN
+
( ) 3f
−
Br
O
O
CN
N
N
N
1g
CN
CN
CN
+
( ) 3g
−
MeO
MeO
Br
Br
Br
MeO
MeO
O
O
CN
1h
CN
CN
CN
(+) 3h
−
O
O
MeO
CN
1i
MeO
CN
CN
CN
9
1.0
1.2
94
89
+
( ) 3i
−
OMe
OMe
O
O
MeO
MeO
CN
N
1j
MeO
MeO
CN
CN
CN
10
+
( ) 3j
−
Br
OMe
OMe
832
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Chin. J. Chem. 2012, 30, 830—836

Regiospecific and High Stereoselective Aminobromination of β,β-Dicyanostyrene Derivatives
Continued
Yieldb/%
Entry
11
Substrate
Product
Time/h
2.0
CN
O
N
O
CN
1k
92
CN
(+) 3k
−
CN
Br
O
O
CN
N
12
24
0
1l
CN
CN
O
CN
(+) 3l
−
O
Br
a Conditions: substrate (2.0 mmol), NBS (2.2 mmol), NaOAc (0.2 mmol, 10 mol%), MeCN (5.0 mL) in ice-water bath. b Isolated yield.
products in excellent yields except for heterocycle
compound 1l. In deed, the heterocycle compound 1l has
been converted into an N-protected dehydroamino
compound under our reaction conditions (see Scheme 1,
and the data of analysis of N-protected dehydroamino
compound are shown in experimental section).
N-Chlorosuccinimide (NCS) can also be subjected to
this reaction. For the three cases which we examined,
the result indicated that the reaction could be performed
smoothly and the corresponding products were obtained
in excellent yields (up to 99%, as shown in Scheme 2).
Scheme 2
Scheme 1
O
O
O
CN
O
N
CN
NaOAc (10 mol%)
R
NaOAc (10 mol%)
CN
+
N Cl
O
R
+
N Br
CN
CH3CN, ice bath, 0.5 h
CN
O
CN
CH3CN, ice bath, 24 h
Cl
(+) 4
O
1
NCS
−
99% yield (4c)
98% yield (4f)
91% yield (4h)
(1c) R = 4-ClC6H4
(1f) R = C6H5
O
O
N
CN
CN
(1h) R = 3-CH3OC6H4
O
In order to seek the further evidences of regiospeci-
ficity of the reaction, the single crystal of one product,
N-[2-bromo-2,2-dicyano-1-phenylethyl]pyrrolidine-2,5-
dione (3f), was cultured. The regiospecificity and high
stereoselectivity of this addition product were confirmed
by X-ray crystallographic analysis (Figure 1). The result
shows that the bromine atom is added to the β-carbon
while the nitrogen atom is added to the α-carbon of
β,β-dicyanostyrene, and the reaction proceeds with
anti-stereochemistry.
N-[2,2-dicyano-1-furylvinyl]succinimide
The β,β-dicyanostyrenes bearing a strong electron-
withdrawing group on the 4-position of the benzene ring,
afforded a sole adductive product in nearly quantitative
yields from 92% to 94% (1a—1d, Table 2). For the sub-
strate 1g with a strong electron-donating group (OCH3)
on the 4-positon of the benzene ring, the slightly less
yield (Entry 7, 87% yield) than that of substrates with
strong electro-withdrawing group on the 4-position of
the benzene ring was observed. Other analogue sub-
strates, 1h and 1j, also gave slightly lower yields of the
products (Entries 8 and 10, 87% and 89%) except sub-
strate 1i. To our delight, the weak electron-donating
group /and no any substitute group bearing on the
4-position of the phenyl, the reactions also gave corre-
sponding products in excellent yields (Entries 5, 6 and
11, 91%—93% and 92%). The above outcome revealed
that the activity of substrates did not depend on the sub-
stitute group of benzene ring, especially those on the
4-position of the phenyl. Such experimental evidences
indicate that the aminobromination of β,β-dicyano-
styrene derivatives with NBS catalyzed by NaOAc pos-
sibly has an electrophilic addition feature.
The regioselectivity of other aminohalo products
was confirmed by their 1H NMR in accordance with the
chemical shifts of the protons on carbon atoms of ben-
zyl. The prominent fragmented ions of a part of prod-
ucts in their UHRMS spectra, ([4-MeC6H4C5H5O2N＋
Na] ＋ , 225.0758), ([4-MeOC6H4C5H5O2N ＋ Na] ＋
,
241.0699), ([3-MeOC6H4C5H5O2N＋Na]＋, 241.0691),
and ([3,5-(MeO)2C6H3C5H5O2N ＋ Na] ＋ , 271.0786)
were clearly observed which shows the aminobromina-
tion reaction has regiospecificity.
The mechanism of the NaOAc-catalyzed amino-
bromination of β,β-dicyanostyrene still remains unclear
at this stage. According to the regiospecificity of the
reaction and the fact that the substrates bearing an elec-
Chin. J. Chem. 2012, 30, 830—836
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833

Li et al.
FULL PAPER
charge related to its β-position because of the stabiliza-
tion effect from the phenyl ring. This pathway may be
possible to explain well the regiospecificity and high
stereoselectivity of the current system.
Conclusions
We have demonstrated an easy and efficient method
for the preparation of vicinal aminobrominated products
from a variety of β,β-dicyanostyrene derivatives with
NBS as aminobrominating reagent in CH3CN catalyzed
by NaOAc. The method can conveniently and effi-
ciently converts β,β-dicyanostyrene derivatives into
vicinal haloamines with the full regiospecificity and the
high stereoselectivity in ice-water bath. The excellent
yields were obtained under the mild conditions and
without the protection of inert gaseous atmosphere. As a
catalyst, NaOAc has the advantages of low cost, and no
toxicity. Additionally, it has the advantage of avoiding
any hazardous metals to be left in products. There is no
obvious difference of the activity of substrates between
the bearing of electron-donating and the electro-with-
drawing on the benzene ring. This outcome indicates
that the reaction has an electrophilic addition feature.
Figure 1 X-ray crystal structure of product (R)-3f.
tron-donating group and/or an electro-withdrawing
group exhibit similar reactivity, as well as the X-ray
crystallographic analysis of 3f, a possible pathway in-
volving an electrophilic addition fashion for this
base-catalyzed aminobromination was offered in
Scheme 3.
Experimental
Scheme 3 The possible pathway of NaOAc-catalyzed amino-
bromination of β,β-dicyanostyren with NBS
General information
O
O
O
Unless otherwise stated, all reagents were purchased
from the commercial sources and used without further
purification. The reaction progress was monitored by
TLC using Merck silica gel 60 F-254 with detection by
UV. The flash chromatography was performed using
Merck silica gel 60 with freshly distilled solvents. The
columns were typically packed as slurry and equili-
brated with the appropriate solvent system prior to use.
1H NMR (300 MHz) and 13C NMR (75 MHz) spectra
were recorded using CDCl3 or DMSO as a solvent.
Chemical shifts (δ) are reported relative to TMS as an
internal standard. UHRMS was recorded on a commer-
cial apparatus (ESI source). The crystal structure was
recorded on an X-ray diffraction spectrometer. Melting
point spectrometer was uncorrected.
-
N
C N
C N
CH3C ONa
C N
C N
+
Ar
Ar
O
N Br
(1)
+
+
Br
O
NBS
A
O
B
O
N
-
B
O
O
N
C N
C N
C N
(2)
+
Ar
Ar
Br
C N
Br
A
C
The literatures have reported that the N-halogen-
acidamide compound could be converted into an amide
group negative ion and a halogen positive ion via the
heterolytic cleavage of the N-halogen bond promoted by
catalyst.[38-41] Herein, we hypothesize that the first step
of the pathway is that the β,β-dicyanostyrene reacted
with NBS catalyzed by NaOAc to give an bromonium
ion intermediate A which is similar to our previous re-
ported aminohalogenation process (Scheme 3, Eq.
1).[23,25] The second step is an SN2 process in which the
three-membered ring (the bromonium ion) was opened
by the negative succinimide B to generate product C,
which accounts for the excellent anti-stereoselectivity
(Eq. 2). The regioselectivity can be explained by the fact
that the α-position of the bromonium ion intermediate
from β,β-dicyanostyrenes is loaded by more positive
Preparation of β,β-dicyanostyrene derivatives
According to the reported procedure[42] with the
slight modification, β,β-dicyanostyrene derivatives were
prepared as follows. Aromatic aldehyde (5.0 mmol),
malononitrile (5.0 mmol) and ammonium acetate (7.5
mmol) were mixed in an agate mortar. Then, the mixture
was ground at room temperature in air. The reaction
progress was monitored by TLC until the aromatic al-
dehyde disappeared. Upon the completion of the reac-
tion, the reaction mixture was dissolved in ethyl acetate
and washed by water (20 mL×3). The organic layer
was dried by anhydrous sodium sulfate and concen-
trated under reduced pressure to give the crude product
834
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Chin. J. Chem. 2012, 30, 830—836

Regiospecific and High Stereoselective Aminobromination of β,β-Dicyanostyrene Derivatives
which was recrystallized by ethanol to obtain the pure
13C NMR (CDCl3, 75 MHz) δ: 175.8(2), 141.4, 130.0(2),
product (yield＞95%).
129.9(2), 127.6, 111.4, 111.1, 62.55, 28.05(2), 27.77,
21.28; UHRMS (m/z) calcd for C15H12O2N3Br [M+Na]+
368.0005, found 368.0005. Prominent fragment calcd
for [4-MeC6H4C5H5O2N+Na]+ 225.0760, found
225.0758.
General procedure of aminobromination
Into a dry round-bottomed flask were added the sub-
strate (2 mmol), NBS (0.3916 g, 2.2 mmol), anhydrous
NaOAc (0.0164 g, 0.2 mmol, 10 mol%), and CH3CN (5
mL). The mixture was electromagnetically stirred in an
ice-water bath in air until the starting material was con-
sumed, or by-product could be detected by TLC. Then
the ethyl acetate (20 mL) was added to quench the reac-
tion. The combined organic phase was washed with
brine (10 mL×3) and water (10 mL×3). The organic
layer was dried over anhydrous sodium sulfate and con-
centrated under reduced pressure to give the crude
product which was purified by the column chromatog-
raphy packed with silica gel with petroleum ether and
EtOAc as the eluent to afford the pure product.
N-[2-Bromo-2,2-dicyano-1-(4-nitrophenyl)ethyl]-
pyrrolidine-2,5-dione (3a) White solid 0.6954 g
(92% yield). m.p. 154—156 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 8.31 (d, J＝8.3 Hz, 2H), 7.97 (d,
J＝8.2 Hz, 2H), 5.86 (s, 1H), 2.92 (s, 4H); 13C NMR
(CDCl3, 75 MHz) δ: 175.6(2), 149.3, 136.8, 131.4(2),
124.4(2), 110.8, 110.5, 61.81, 28.08(2), 26.56; UHRMS
(m/z) calcd for C14H9O4N4Br [M+Na]+ 398.9699, found
398.9641.
N-[2-Bromo-2,2-dicyano-1-phenylethyl]pyrrolidine-
2,5-dione (3f) Colorless crystal 0.6177 g (93% yield).
m.p. 142—143 ℃ (EtOH). 1H NMR (CDCl3, 300 MHz)
δ: 7.87—7.61 (m, 2H), 7.48 (t, J＝3.9 Hz, 3H), 5.74 (s,
1H), 2.86 (s, 4H); 13C NMR (CDCl3, 75 MHz) δ:
175.2(2), 130.5, 130.1, 129.6(2), 128.9(2), 110.8, 110.5,
62.27, 27.55(2), 27.08; UHRMS (m/z) calcd for
C14H10O2N3Br [M+Na]+ 355.9828, found 355.9791.
N-[2-Bromo-2,2-dicyano-1-(4-methoxyphenyl)ethyl]-
pyrrolidine-2,5-dione (3g) Colorless crystal 0.6307 g
(87% yield). m.p. 133—134 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.68 (d, J＝7.8 Hz, 2H), 6.94 (d,
J＝7.8 Hz, 2H), 5.69 (s, 1H), 3.83 (s, 3H), 2.84 (s, 4H);
13C NMR (CDCl3, 75 MHz) δ: 175.9(2), 161.5, 131.6(2),
122.4, 114.7(2), 111.5, 111.2, 62.26, 55.42, 28.05(3);
UHRMS (m/z) calcd for C15H12O3N3Br [M+Na]+
383.9954, found 383.9944. Prominent fragment calcd
for [4-MeOC6H4C5H5O2N+Na]+ 241.0709, found
241.0699.
N-[2-Bromo-2,2-dicyano-1-(3-methoxyphenyl)ethyl]-
pyrrolidine-2,5-dione (3h) Colorless crystal 0.6310 g
(87% yield). m.p. 143—145 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.42—7.17 (m, 3H), 7.02 (d, J＝
7.7 Hz, 1H), 5.71 (s, 1H), 3.83 (s, 3H), 2.86 (s, 4H); 13C
NMR (CDCl3, 75 MHz) δ: 175.8(2), 160.1, 131.7,
130.36, 122.2, 116.7, 115.4, 111.4, 111.1, 62.63, 55.44,
28.03(2), 27.45; UHRMS (m/z) calcd for C15H12O3N3Br
[M+Na]+ 383.9954, found 383.9937. Prominent
fragment calcd for [3-MeOC6H4C5H5O2N+Na]+
241.0709, found 241.0691.
N-[2-Bromo-2,2-dicyano-1-(4-fluorophenyl)ethyl]-
pyrrolidine-2,5-dione (3b) Colorless crystal 0.6438 g
(92% yield). m.p. 114—115 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.76 (t, J＝6.6 Hz, 2H), 7.13 (d,
J＝7.8 Hz, 2H), 5.74 (s, 1H), 2.87 (s, 4H); 13C NMR
(CDCl3, 75 MHz) δ: 175.7(2), 165.8, 132.4(2), 126.5,
116.7(2), 111.2, 110.9, 62.03, 28.05(2), 27.53; UHRMS
(m/z) calcd for C14H9O2N3BrF [M+Na]+ 371.9754,
found 371.9706.
N-[2-Bromo-1-(4-chlorophenyl)-2,2-dicyanoethyl]-
pyrrolidine-2,5-dione (3c) Colorless crystal 0.6939 g
(95% yield). m.p. 143—144 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.70 (d, J＝8.1 Hz, 2H), 7.43 (d,
J＝8.1 Hz, 2H), 5.72 (s, 1H), 2.87 (s, 4H); 13C NMR
(CDCl3, 75 MHz) δ: 175.7(2), 137.4, 131.5(2), 129.7 (2),
129.0, 111.1, 110.8, 62.08, 28.05(2), 27.28; UHRMS
(m/z) calcd for C14H9O2N3BrCl [M+Na]+ 389.9437,
found 389.9382.
N-[2-Bromo-1-(4-bromophenyl)-2,2-dicyanoethyl]-
pyrroli-dine-2,5-dione (3d) Colorless crystal 0.7731 g
(94% yield). m.p. 158—159 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.62 (d, J＝3.9 Hz, 4H), 5.71 (s,
1H), 2.87 (s, 4H); 13C NMR (CDCl3, 75 MHz) δ:
175.6(2), 132.7(2), 131.7(2), 129.5, 125.8, 111.1, 110.8,
62.19, 28.04(2), 27.16; UHRMS (m/z) calcd for
C14H9O2N3Br2 [M+Na]+ 433.8933, found 433.8930.
N-[2-Bromo-2,2-dicyano-1-(4-methylphenyl)ethyl]-
pyrrolidine-2,5-dione (3e) Colorless crystal 0.6287 g
(91% yield). m.p. 148—149 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.60 (d, J＝4.3 Hz, 2H), 7.25 (d,
J＝6.3 Hz, 2H), 5.69 (s, 1H), 2.83 (s, 4H), 2.37 (s, 3H);
N-[2-Bromo-2,2-dicyano-1-(3,5-dimethoxyphenyl)-
ethyl]pyrrolidine-2,5-dione (3i) Yellow solid 0.7348
g (94% yield). m.p. 88—89 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 6.90 (s, 2H), 6.54 (s, 1H), 5.64 (s,
1H), 3.80 (s, 6H), 2.86 (s, 4H); 13C NMR (CDCl3, 75
MHz) δ: 175.7(2), 161.2, 132.2, 111.4,111.1, 108.1(2),
102.8(2), 62.71, 55.55, 28.02 (2), 27.32; UHRMS (m/z)
calcd for C16H14O4N3Br [M+Na]+ 414.0059, found
414.0020.
Prominent
fragment
calcd
for
found
[3,5-(MeO)2C6H3C5H5O2N+Na]+
271.0786.
271.0815,
N-[2-Bromo-2,2-dicyano-1-(3,4,5-trimethoxyphenyl)-
ethyl]pyrrolidine-2,5-dione (3j) Wite soild 0.7498 g
(89% yield). m.p. 125—126 ℃ (EtOH). 1H NMR
(CDCl3, 300 MHz) δ: 7.04 (s, 2H), 5.64 (s, 1H), 3.88 (s,
9H), 2.88 (s, 4H); 13C NMR (CDCl3, 75 MHz) δ:
175.8(2), 153.6(2), 140.1, 125.4, 111.6,111.1, 107.7(2),
62.83, 60.84, 56.36(2), 28.00(2), 27.51; UHRMS (m/z)
calcd for C17H16O5N3Br [M+Na]+ 446.0145, found
446.0113.
N-[2-Bromo-2,2-dicyano-1-(1-naphthalene)]pyrroli-
dine-2,5-dione (3k) White soild 0.3531 g (92% yield).
Chin. J. Chem. 2012, 30, 830—836
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
835

Li et al.
FULL PAPER
m.p. 138—140 ℃ (EtOH). 1H NMR (CDCl3, 300 MHz)
δ: 8.52 (d, J＝7.3 Hz, 1H), 8.22 (d, J＝8.5 Hz, 1H),
7.95 (dd, J＝8.1, 7.8 Hz, 2H), 7.70—7.50 (m, 3H), 6.80
(s, 1H), 2.81 (s, 4H); 13C NMR (CDCl3, 75 MHz) δ:
175.8(2), 133.9, 131.7, 129.4, 128.9(2), 126.5, 126.5,
125.2, 122.0, 111.5, 111.4, 56.16, 28.00(2), 27.31;
UHRMS (m/z) calcd for C18H12O2N3Br [M+Na]+
405.9985, found 405.9975.
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N-[2,2-Dicyano-1-furylvinyl]succinimide
m.p.
1
188.7—188.9 ℃ (EtOH). H NMR (DMSO, 300 MHz)
δ: 8.39 (s, 1H), 7.85 (s, 1H), 7.01 (s, 1H), 3.03 (s, 4H);
13C NMR (DMSO, 75 MHz) δ: 175.03(2), 152.91,
146.18, 145.95, 126.43, 115.83, 112.24, 112.18, 77.87,
29.78(2). UHRMS (m/z) calcd for C12H7O3N3 [M+Na]+
264.0380, found 264.0352
N-[2-Chloro-2,2-dicyano-1-(4-chlorophenyl)ethyl]-
pyrrolidine-2,5-dione (4c) White soild 0.6376 g
(99% yield). m.p. 127.1—128.0 ℃ (EtOH). H NMR
(CDCl3, 300 MHz) δ: 7.67 (d, J＝8.2 Hz, 2H), 7.43 (d,
J＝8.2 Hz, 2H), 5.69 (s, 1H), 2.86 (s, 4H); 13C NMR
(CDCl3, 75 MHz) δ: 175.3, 136.9, 130.928(2), 129.2(2),
128.3, 110.3, 110.0, 61.8, 45.3, 27.6(2). UHRMS (m/z)
calcd for C14H9Cl2N3O2 ([M+Na]+) 343.9969, found
343.9958.
N-[2-Chloro-2,2-dicyano-1-phenylethyl]pyrrolidine-
2,5-dione (4f) White soild 0.5618 g (98% yield). m.p.
113.2—114.7 ℃ (EtOH). 1H NMR (CDCl3, 300 MHz) δ:
7.71 (d, J＝6.8 Hz, 2H), 7.47 (t, J＝7.5 Hz, 3H), 5.71 (s,
1H), 2.84 (s, 4H); 13C NMR (CDCl3, 75 MHz) δ: 175.4,
130.6, 129.9, 129.5(2), 128.9(2), 110.5, 110.2, 62.5,
45.5, 27.6(2). UHRMS (m/z) calcd for C14H10ClN3O2
[M+Na]+ 310.0359, found 310.0351.
1
N-[2-Chloro-2,2-dicyano-1-(3-methoxyphenyl)ethyl]-
pyrrolidine-2,5-dione (4h) White siold 0.5761 g
(91% yield). m.p. 126.8—127.7 ℃ (EtOH). H NMR
(CDCl3, 300 MHz) δ: 7.63—7.19 (m, 3H), 7.02 (d, J＝
7.5 Hz, 1H), 5.68 (s, 1H), 3.82 (s, 3H), 2.86 (s, 4H); 13C
NMR (CDCl3, 75 MHz) δ: 175.3, 159.6, 131.0,129.9,
121.6, 116.2, 114.9, 110.5, 110.2, 62.3, 54.9, 45.3,
27.6(2). UHRMS (m/z) calcd for C15H12ClN3O3
([M+Na]+) 340.0465, found 340.0459.
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1
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Acknowledgement
The authors are grateful to the Natural Science
Foundation of Shaanxi Province (No. 2009JM2011),
and the Innovation Foundation of Postgraduate Cultiva-
tion of Shaanxi Normal University (No. 2008CXB009).
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(Pan, B.)
836
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 830—836