Homogeneous and stereoselective copper(II)-catalyzed monohydration of methylenemalononitriles to 2-cyanoacrylamides

Article abstract of DOI:10.1021/jo401997v

A facile and efficient route for the homogeneous and highly stereoselective monohydration of substituted methylenemalononitriles to (E)-2-cyanoacrylamides catalyzed by copper(II) acetate monohydrate in acetic acid containing 2% water is described, and a mechanism is proposed. The protocol has proved to be suitable for the monohydration of dicyanobenzenes and 2-substituted malononitriles.

Full text of DOI:10.1021/jo401997v

Article
pubs.acs.org/joc
Homogeneous and Stereoselective Copper(II)-Catalyzed
Monohydration of Methylenemalononitriles to 2‑Cyanoacrylamides
Xiaoqing Xin,† Dexuan Xiang,† Jiming Yang,† Qian Zhang,† Fenguo Zhou,† and Dewen Dong*,†,‡
†Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun,
130022 Jilin, People’s Republic of China
‡Changzhou Institute of Energy Storage Materials & Devices, Changzhou, 213000 Jiangsu, People’s Republic of China
S
* Supporting Information
ABSTRACT: A facile and efficient route for the homogeneous and highly stereoselective monohydration of substituted
methylenemalononitriles to (E)-2-cyanoacrylamides catalyzed by copper(II) acetate monohydrate in acetic acid containing 2%
water is described, and a mechanism is proposed. The protocol has proved to be suitable for the monohydration of
dicyanobenzenes and 2-substituted malononitriles.
regiospecific MnO2-catalyzed hydration process of methylene-
malononitriles with oximes into cyanoacrylamides was
reported.12 Actually, hydration of dinitriles is a matter of
importance as there are equal possibilities of mono- and
dihydration involving cooperative activation of nitrile and water
with two or more metallic centers.
During the course of our studies on malononitrile and its
derivatives, we achieved efficient one-pot synthesis of
polysubstituted benzenes13 and pyridines.14 In connection
with this previous work, we are interested in the hydration of
these substituted malononitriles under varied conditions. After
a series of research, we developed a facile and efficient approach
for the homogeneous and highly stereoselective monohydration
of substituted 2-methylenemalononitriles to 2-cyanoacryla-
mides catalyzed by copper(II) acetate monohydrate in acetic
acid. Herein, we report our results and the mechanism involved
in the process.
INTRODUCTION
■
The transformation based on hydration of nitriles to amides has
attracted considerable research attention in the past few
decades since functionalized amides not only can be used as
versatile building blocks in synthetic chemistry but also exhibit
pharmacological interest.1 The hydration of nitriles can
conventionally be achieved using strong acid or base catalysis.2
However, the reaction is mostly not possible to stop at the
amide stage, and further hydrolysis to the acid often occurs.
Meanwhile, the acid- or base-sensitive functionalities are usually
affected or lost during the harsh reaction conditions. To
overcome these intrinsic problems associated with the
hydration process, tremendous efforts have been made in the
catalytic hydration of nitriles.3 For instance, Yamada’s NHase
catalyst,4 Parkins’s platinum complexes,5 Murahashi’s ruthe-
nium system,6 and other transition-metal catalysts7 were
employed in hydration of nitriles and exhibited remarkable
activities in many cases.
Even though some significant advances have been achieved in
catalytic hydration, there are only a few reports on the
hydration of dinitriles. Breuilles and co-workers found that
treatment of β-hydroxyglutarodinitrile with MnO2/SiO2 for one
week at room temperature could result in the corresponding
monoamides in 55% yield (76% conversion).8 Grigg and co-
workers investigated the hydration of substituted malononitriles
using KF−Al2O3 in t-BuOH and obtained the monohydrated
products in 57−75% yields.9 A heterogeneous catalytic
hydration of dinitriles described by Kiss revealed that a mixture
of mono- and diamides was formed when adiponitrile and
acetaldoxime were treated with molecular sieves modified with
copper(II).10 Under microwave (MW) irradiation conditions in
aqueous media, dihydration of dicyano derivatives with
ruthenium nanocatalysts was achieved.11 Very recently, a
RESULTS AND DISCUSSION
■
The substrates, 2-methylenemalononitriles 1a−q, with two
cyano groups on the same sp2 carbon atom were prepared by
condensation of malononitrile with various aldehydes or
ketones according to the published procedure.15 We selected
2-benzylidenemalononitrile (1a) as the model compound to
examine its behavior under different conditions. Initially, the
substrate 1a and copper(II) acetate [Cu(OAc)2; 0.2 equiv]
were subjected to water in the presence of 10 mol %
tetrabutylammonium bromide (TBAB) at room temperature,
but no reaction was observed (Table 1, entry 1). When the
Received: September 9, 2013
Published: October 23, 2013
© 2013 American Chemical Society
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a
Under the conditions as for (E)-2a in Table 1, entry 15, a
series of reactions of 2-methylenemalononitriles 1b−q were
carried out, and some of the results are summarized in Table 2.
Table 1. Hydration of 1a under Different Conditions
Table 2. Monohydration of 2-Methylenemalononitriles 1 to
a
2-Cyanoacrylamides 2
catalyst
(concn, equiv)
temp
(°C)
time
(h)
entry
solvent
yield (%)
1
2
Cu(OAc)2 (0.2)
Cu(OAc)2 (0.2)
H2O
rt
8.0
8.0
nr
64
76
nr
nr
73
71
HOAc
80
80
reflux
80
80
80
80
80
80
80
80
100
60
80
80
3
Cu(OAc)2·H2O (0.2) HOAc
Cu(OAc)2·H2O (0.2) THF
Cu(OAc)2·H2O (0.2) toluene
CuCl2·2H2O (0.2)
CuCl2 (0.2)
8.0
4
8.0
entry
1
R1
R2
2
yield (%)
5
8.0
6
HOAc
HOAc
HOAc
HOAc
HOAc
8.0
1
2
1a
1b
1c
1d
1e
1f
Ph
H
H
H
H
H
H
H
H
H
H
H
H
H
(E)-2a16a
(E)-2b16a
(E)-2c16b
(E)-2d16a
(E)-2e16a
(E)-2f16a
(E)-2g16c
(E)-2h16a
(E)-2i16d
(E)-2j16b
(E)-2k16e
(E)-2l
81
89
84
83
92
86
93
90
87
91
79
82
86
54
7
12.0
12.0
6.0
4-ClC6H4
b
8
CuSO4·5H2O (0.2)
FeCl2·4H2O (0.2)
CuBr2 (0.2)
62 (25)
3
4-MeOC6H4
4-MeC6H4
9
nr
nr
4
10
11
12
13
14
15
16
6.0
5
3-MeOC6H4
3-MeC6H4
c
b
6
Cu(OAc)2·H2O (0.2) HOAc
Cu(OAc)2·H2O (0.2) HOAc
Cu(OAc)2·H2O (0.2) HOAc
Cu(OAc)2·H2O (0.2) HOAc
Cu(OAc)2·H2O (0.1) HOAc
8.0
67 (23)
d
d
d
d
d
6.0
82
80
7
1g
1h
1i
3-NO2C6H4
2-ClC6H4
5.0
8
b
12.0
6.0
55 (38)
9
2-NO2C6H4
2-thienyl
81
10
11
12
13
14
15
16
1j
b
Cu(OAc)2·H2O
(0.05)
HOAc
6.0
48 (43)
1k
1l
C6H5CHCH
4-ClC6H4CHCH
4-MeOC6H4CHCH
−(CH2)5−
d
17
HOAc
80
12.0
nr
1m
1n
1o
1p
(E)-2m
2n
a
Reagents and conditions: 1a (1.0 mmol), solvent (10.0 mL).
b
c
b
2o16b,17
(E)-2p
80(2:1)
Recovery of 1a in parentheses. Treated with acetic anhydride (v/v,
Ph
Me
Me
d
1:10) under reflux for 3.0 h. Containing 2% water.
4-ClC6H4
46
27
41
20
(Z)-2p17
(E)-2q
17
1q
4-NO2C6H4
Me
mixture was conducted at 80 °C for 8.0 h, retrocondensation
reaction of 1a took place to give back malononitrile and
benzaldehyde. To our delight, the reaction of 1a with
Cu(OAc)2 (0.2 equiv) could proceed in acetic acid at 80 °C
to afford (E)-2-cyano-3-phenylacrylamide [(E)-2a] (Table 1,
entry 2).16a
(Z)-2q
a
Reagents and conditions: (i) 1a−n (1.0 mmol), HOAc (10.0 mL),
H2O (0.2 mL), Cu(OAc)2·H2O (0.1 mmol), 80 °C, 6.0−10.0 h; (ii)
1o−q (1.0 mmol), HOAc (10.0 mL), H2O (0.2 mL), Cu(OAc)2·H2O
b
(0.1 mmol), 100 °C, 12.0 h. The ratio in parentheses is that of E to Z
isomers determined by H NMR.
1
The optimization of the reaction conditions, including
reaction solvents, catalysts, reaction temperature, and the feed
ratio of the catalysts, was then investigated. It was found that
(E)-2a could be obtained in 76% yield when copper(II) acetate
monohydrate, Cu(OAc)2·H2O, was employed in the reaction
system (Table 1, entry 3). However, no reaction occurred when
1a was treated with Cu(OAc)2·H2O (0.2 equiv) in tetrahy-
drofuran (THF) under reflux or toluene at 80 °C for 12.0 h
(Table 1, entries 4 and 5). Other divalent metal salts, such as
CuCl2·2H2O, CuCl2, CuSO4·5H2O, FeCl2·4H2O, and CuBr2,
were also attempted but were less active than Cu(OAc)2·H2O
(Table 1, entries 6−8) or inert to substrate 1a (Table 1, entries
9 and 10). It was interesting to note that use of the dried acetic
acid would result in a low conversion of 1a (Table 1, entry 11),
whereas in the acetic acid containing 2% water the yield of (E)-
2a reached 82% (Table 1, entry 12). Higher reaction
temperature had no significant influence on the reaction of
1a (Table 1, entry 13), but lower reaction temperature, for
example, at 60 °C, would result in low conversion and
prolonged reaction time (Table 1, entry 14). Upon a decrease
of the amount of Cu(OAc)2·H2O to 0.1 equiv, the reaction of
1a could furnish (E)-2a in 81% yield (Table 1, entry 15).
However, a further decrease of the amount of Cu(OAc)2·H2O
to 0.05 equiv would lead to the incomplete hydration of 1a
(Table 1, entry 16). Without any catalyst, the hydration of 1a
could not proceed in the acetic acid containing 2% water at 80
°C for even 12.0 h (Table 1, entry 17).
The substrates 1b−m bearing varied aryl, heteroaryl, or
cinnamenyl groups R1 could undergo hydration to afford the
corresponding (E)-2-cyanoacrylamides (E)-2b−m16 in high
yields (Table 2, entries 2−13). The structure of (E)-2d was
elucidated by means of X-ray single-crystal analysis (see Figure
S2, Supporting Information), and these data conveniently
revealed that the hydration precisely took place at the anti-
nitrile group with reference to the aryl group in (E)-2d. In
these cases, (E)-2-cyanoacrylamides (E)-2b−m were exclu-
sively obtained, which suggested that the catalytic hydration
proceeded in a highly stereoselective manner. 2-Cyclo-
hexylidenemalononitrile (1n) could also be hydrated to
monamide 2n in 54% yield under identical conditions (Table
2, entry 14). It was worth noting that the monohydration of
2,2-disubstituted methylenemalononitriles 1o−q could proceed
at 100 °C to give a mixture of (E)- and (Z)-2-cyanoacrylamides
2o−q with the E isomers as the predominant ones16b,17 (Table
2, entries 15−17). The structure of (E)-2p was established by
means of X-ray single-crystal analysis and its NMR spectra (see
Figure S1, Supporting Information). The above results
demonstrated the wide scope and synthetic utility of the
catalytic hydration of 2-methylenemalononitriles 1. In addition,
no overhydrolysis of the nitriles to carboxylic acids was
observed.
Next we intended to investigate the catalytic hydration of
dicyanobenzenes 1r−t bearing two cyano groups on the
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different sp2 carbon atoms. The experimental results revealed
that the reactions of 1r−t performed with Cu(OAc)2·H2O (0.1
equiv) in acetic acid containing 2% water at 100 °C could
furnish the corresponding monoamides 2r−t11a,b in high yields
(Scheme 1). Upon treatment with Cu(OAc)2·H2O (0.1 equiv)
To gain insight into the mechanism of hydration, the
reactions of 1a were performed with Cu(OAc)2 (0.1 equiv) in
HOAc-d4 containing 2% water at 80 °C for 6.0 h. No
1
deuterated product (E)-2a-d was obtained according to the H
NMR spectrum. The results demonstrated that the hydrogen
atom of amide does not originate from acetic acid, which is
different from the conventional hydration of nitriles catalyzed
by Brønsted acid or strong mineral acid.3f,20 Furthermore, the
monohydration of 1a could proceed under an atmosphere of
nitrogen, which indicated that the monohydration of nitrile
might not undergo a free radical process.
a
Scheme 1. Hydration of Dicyanobenzenes 1
On the basis of the above results obtained together with
those reported in the literature,7i,j,21 a mechanism for nitrile
hydration is proposed as depicted in Scheme 2. As reported by
Sharrock and co-workers, in the solution of Cu(OAc)2·H2O in
acetic acid containing 2% water, the copper complex A is
presumably formed.22 The hydration commences from the
coordination of methylenemalononitriles 1 to the divalent
copper center of A to give intermediate B. The anti-cyano
group of 1 with reference to the R1 group (R1 = aryl, R2 = alkyl,
H) is favored to coordinate to the copper center due to both
electronic and steric effects.23 The nucleophilic attack of H2O
on the carbon atom of the nitrile of B subsequently takes place
to afford intermediate C. The product, a monoamide of type 2,
was then formed by the tautomerization of an iminol, D, along
with the regeneration of the copper complex A.
a
̇
Reaction conditions: (i) 1r−t (1.0 mmol), Cu(OAc)2H2O (0.1
mmol), HOAc (10.0 mL), H2O (0.2 mL), 100 °C, 6.0−10.0 h; (ii)
1r−t (1.0 mmol), HOAc (10.0 mL), H2O (0.2 mL), Cu(OAc)2·H2O
(0.1 mmol), reflux, 10.0−12.0 h.
in acetic acid containing 2% water under reflux, terephthaloni-
trile (1r) and isophthalonitrile (1s) could be completely
converted into terephthalamide (3r)11a and isophthalamide
(3s)11b in 78% and 73% yields, respectively. However, in the
case of phthalonitrile (1t), the product phthalimide (4t)18
rather than phthalamide (3t) was exclusively obtained in 71%
yield. Notably, the selective mono- and dihydration of dicyano
derivatives could be conveniently achieved by controlling the
reaction temperature and time.
The catalytic hydration of 2-substituted malononitriles 1u−y
bearing two cyano groups on the same sp3 carbon atom was
further examined. By being subjected to acetic acid containing
2% water at 80 °C in the presence of Cu(OAc)2·H2O (0.1
equiv), the 2-monosubstituted malononitriles 1u−w could be
easily converted into the corresponding monoamides 2u−w in
good yields (Table 3, entries 1−3). The versatility of
CONCLUSION
■
In summary, we developed a facile and efficient route for the
homogeneous and stereoselective monohydration of 2-methyl-
enemalononitriles to 2-cyanoacrylamides catalyzed by copper-
(II) acetate monohydrate in acetic acid containing 2% water,
which was expanded to the monohydration of dicyanobenzenes
and 2-substituted malononitriles. In comparison to the prior
work on the hydration of dinitriles, this protocol is associated
with inexpensive and easily available copper(II) catalyst, simple
execution, mild conditions, good to high yields, and high
selectivity, which make it most attractive for academic research
and practical applications.
a
EXPERIMENTAL SECTION
Table 3. Monohydration of 2-Substituted Malononitriles 1
■
Materials and Methods. All reagents were purchased from
commercial sources and used without further treatment, unless
otherwise indicated. The products were purified by column
chromatography over silica gel. 1H NMR and 13C NMR spectra
were recorded at 300 MHz (or 400 MHz) and 100 MHz, respectively,
with TMS as the internal standard. IR spectra (KBr) were recorded on
an FTIR spectrophotometer in the range of 400−4000 cm−1. The
petroleum ether (PE) fraction used was that boiling in the 60−90 °C
range.
Synthesis. Typical Procedure for the Synthesis of Monoamides
2 (2a as an Example). A mixture of 2-benzylidenemalononitrile (1a)
(1.0 mmol, 154 mg) and Cu(OAc)2·H2O (20 mg, 0.1 mmol) H2O
(0.2 mL) in HOAc (10.0 mL) was stirred at 80 °C for 6.0 h and then
poured into saturated aqueous NaCl (50 mL), which was extracted
with dichloromethane (3 × 20 mL). The combined organic phase was
washed with water (3 × 20 mL), dried over MgSO4, filtered, and
concentrated in vacuo. The crude product was purified by flash
chromatography (silica gel, petroleum ether:ethyl acetate = 2:1) to
entry
1
R1
R2
2
yield (%)
1
2
3
4
5
1u
1v
1w
1x
1y
C6H5CO
4-ClC6H4CO
4-NO2C6H4CO
Ph
H
2u
76
77
72
89
88
H
2v
H
2w
2x19
2y
Bn
CO2Et
CH2CO2Et
a
Reagents and conditions: 1u−y (1.0 mmol), HOAc (10.0 mL), H2O
(0.2 mL), Cu(OAc)2·H2O (0.1 mmol), 80 °C, 2.0−12.0 h.
monoamide synthesis was also evaluated by studying the
reaction of 2,2-disubstituted malononitriles 1x and 1y under
identical conditions (Table 3, entries 4 and 5). It was observed
that some sensitive functionalities, such as benzoyl, ester, and
NO2 groups, could tolerate the catalytic hydration process and
the monohydration of dinitrile could be controlled to stop at
the amide stage.
1
give (E)-2a: yield 139 mg (81%); mp 120−122 °C; H NMR (300
MHz, DMSO) δ = 7.55−7.60 (m, 3H), 7.82 (s, 1H), 7.94−7.97 (m,
3H), 8.21 (s, 1H); 13C NMR (100 MHz, DMSO) δ = 106.7, 116.5,
129.2, 130.0, 131.9, 132.3, 150.7, 162.8; IR (KBr) 3398, 3313, 3161,
2218, 1670, 1597, 1371, 685 cm−1. Anal. Calcd for C10H8N2O: C,
69.76; H, 4.68; N, 16.27. Found: C, 69.53; H, 4.66; N, 16.20.
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Scheme 2. Plausible Mechanism for the Hydration of Nitriles Catalyzed by Cu(OAc)2·H2O in Acetic Acid Containing Water
(E)-2a−k, (E)-2o, (Z)-2o, (Z)-2p, 2r−t, and 2x are known
compounds. For the spectral and analytical data of (E)-2a−k and (E)-
2o, see ref 16, for those of (Z)-2o and (Z)-2p, see ref 17, for those of
2x, see ref 19, and for those of 2r−t, see ref 11.
Data for (E)-2b: yield 184 mg (89%); white solid; mp 198−200 °C;
1H NMR (400 MHz, DMSO) δ = 7.57−7.61 (m, 2H), 7.79 (s, 1H),
7.91−7.93 (m, 3H), 8.16 (s, 1H); 13C NMR (100 MHz, DMSO) δ =
107.1, 116.2, 129.2, 130.6, 131.5, 136.9, 149.2, 162.4. Anal. Calcd for
C10H7ClN2O: C, 58.13; H, 3.41; N, 13.56. Found: C, 58.29; H, 3.42;
N, 13.50.
Data for (E)-2c: yield 170 mg (84%); yellow solid; mp 207−209
°C; H NMR (300 MHz, DMSO) δ = 3.83 (s, 3H), 7.11 (d, J = 8.7 Hz,
2H), 7.70 (s, 1H), 7.82 (s, 1H), 7.95 (d, J = 8.7 Hz, 2H), 8.11 (s, 1H);
13C NMR (100 MHz, DMSO) δ = 55.5, 102.8, 114.7, 117.0, 124.4,
132.4, 150.1, 162.5, 163.1. Anal. Calcd for C11H10N2O2: C, 65.34; H,
4.98; N, 13.85. Found: C, 65.05; H, 4.96; N, 13.90.
Data for (E)-2d: yield 155 mg (83%); white solid; mp 154−156 °C;
1H NMR (300 MHz, CDCl3) δ = 2.43 (s, 3H), 6.31 (s, 1H), 6.38 (s,
1H), 7.30 (d, J = 8.1 Hz, 2H), 7.86 (d, J = 8.1 Hz, 2H), 8.30 (s, 1H);
13C NMR (100 MHz, DMSO) δ = 21.1, 105.1, 116.6, 129.1, 129.7,
130.1, 142.9, 150.5, 162.8; IR (KBr) 3387, 3317, 3157, 2218, 1695,
1591, 1373, 1182, 816, 608 cm−1. Anal. Calcd for C11H10N2O: C,
70.95; H, 5.41; N, 15.04. Found: C, 70.69; H, 5.44; N, 15.12.
Crystal data for (E)-2d: C11H10N2O, white crystal, M = 186.21,
monoclinic, P21/n, a = 13.4278(11) Å, b = 10.9087(9) Å, c =
13.4767(11) Å, α = 90.00°, β = 99.6090(10)°, γ = 90.00°, V =
1946.4(3) Å3, Z = 8, T = 293(2) K, F000 = 858. CCDC deposition
number 937685. These data can be obtained free of charge via www.
ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crys-
tallographic Data Centre, 12 Union Rd., Cambridge CB21EZ, U.K.;
fax (+44)1223-336-033; e-mail deposit@ccdc.cam.ac.uk).
Data for (E)-2e: yield 186 mg (92%); white solid; mp 146−148 °C;
1H NMR (300 MHz, DMSO) δ = 3.79 (s, 3H), 7.14 (d, J = 7.5 Hz,
1H), 7.43−7.51 (m, 3H), 7.82 (s, 1H), 7.94 (s, 1H), 8.15 (s, 1H); 13C
NMR (100 MHz, DMSO) δ = 55.2, 106.8, 114.7, 116.4, 118.1, 122.4,
130.3, 133.1, 150.5, 159.4, 162.6. Anal. Calcd for C11H10N2O2: C,
65.34; H, 4.98; N, 13.85. Found: C, 65.07; H, 5.01; N, 13.79.
Data for (E)-2f: yield 160 mg (86%); white solid; mp 104−105 °C;
1H NMR (300 MHz, DMSO) δ = 2.36 (s, 3H), 7.38−7.47 (m, 2H),
7.72−7.79 (m, 3H), 7.93 (s, 1H), 8.14 (s, 1H); 13C NMR (100 MHz,
DMSO) δ = 20.8, 106.4, 116.5, 127.0, 129.1, 130.6, 131.9, 133.0,
138.5, 150.6, 162.7; IR (KBr) 3472, 3298, 3148, 2218, 1707, 1603,
1385, 1373, 748 cm−1. Anal. Calcd for C11H10N2O: C, 70.95; H, 5.41;
N, 15.04. Found: C, 70.66; H, 5.38; N, 15.11.
7.90 (s, 1H), 8.23(s, 3H), 8.65 (s, 1H); 13C NMR (100 MHz, DMSO)
δ = 109.1, 115.7, 123.9, 126.0, 130.6, 132.3, 135.7, 147.8, 148.1, 162.0.
Anal. Calcd for C10H7N3O3: C, 55.30; H, 3.25; N, 19.35. Found: C,
55.15; H, 3.26; N, 19.27.
Data for (E)-2h: yield 186 mg (90%); white solid; mp 158−160 °C;
1H NMR (300 MHz, DMSO) δ = 7.52−7.67 (m, 3H), 7.93−8.08 (m,
3H), 8.37 (s, 1H); 13C NMR (100 MHz, DMSO) δ = 111.0, 115.5,
127.8, 129.7, 130.0, 130.5, 133.2, 134.0, 147.1, 161.8; IR (KBr) 3421,
3350, 3231, 2212, 1678, 1578, 1570, 1383, 1169, 989, 752, 692 cm−1.
Anal. Calcd for C10H7ClN2O: C, 58.13; H, 3.41; N, 13.56. Found: C,
58.24; H, 3.44; N, 13.61.
Data for (E)-2i: yield 189 mg (87%); white solid; mp 168−170 °C;
1H NMR (400 MHz, DMSO) δ = 7.77−7.80 (m, 1H), 7.84−7.95 (m,
4H), 8.26 (d, J = 8.8 Hz, 1H), 8.55 (s, 1H); 13C NMR (100 MHz,
DMSO) δ = 111.7, 115.4, 125.5, 128.9, 131.0, 132.3, 135.0, 147.4,
150.2, 161.8. Anal. Calcd for C10H7N3O3: C, 55.30; H, 3.25; N, 19.35.
Found: C, 55.51; H, 3.24; N, 19.44.
Data for(E)-2j: yield 162 mg (91%); yellow solid; mp 153−154 °C;
1H NMR (300 MHz, DMSO) δ = 7.30−7.33 (m, 1H), 7.72 (s, 1H),
7.83 (s, 1H), 7.87 (d, J = 3.6 Hz, 1H), 8.09 (d, J = 5.1 Hz, 1H), 8.41
(s, 1H); 13C NMR (100 MHz, DMSO) δ = 102.1, 116.7, 128.5, 134.9,
135.8, 137.7, 143.5, 162.6; IR (KBr) 3367, 3173, 1659, 1624, 1578,
1402, 1298, 793, 685 cm−1. Anal. Calcd for C8H6N2OS: C, 53.92; H,
3.39; N, 15.72. Found: C, 54.13; H, 3.37; N, 15.66.
Data for (E)-2k: yield 157 mg (79%); orange solid; mp 150−152
°C; 1H NMR (300 MHz, DMSO) δ = 7.17 (dd, J1 = 15.3 Hz, J2 = 11.4
Hz, 1H), 7.41−7.45 (m, 4H), 7.67−7.68 (m, 3H), 7.85 (s, 1H), 7.99
(d, J = 11.4 Hz, 1H); 13C NMR (100 MHz, DMSO) δ = 107.8, 115.4,
123.0, 128.2, 129.1, 130.6, 134.9, 146.8, 151.3, 162.5; IR (KBr) 3466,
3410, 3157, 2210, 1695, 1576, 1385, 978, 810 cm−1. Anal. Calcd for
C12H10N2O: C, 72.71; H, 5.08; N, 14.13. Found: C, 72.45; H, 5.12; N,
14.05
Data for (E)-2l: yield 191 mg (82%); yellow solid; mp 200−202 °C;
1H NMR (400 MHz, DMSO) δ = 7.17 (dd, J1 = 15.2 Hz, J2 = 11.2 Hz,
1H), 7.42 (dd, J = 15.2 Hz, 1H), 7.50 (d, J = 8.4 Hz, 2H), 7.65 (s, 1H),
7.72 (d, J = 8.4 Hz, 2H), 7.83 (s, 1H), 7.96 (d, J = 11.2 Hz, 1H); 13
C
NMR (100 MHz, DMSO) δ = 108.2, 115.3, 123.7, 129.1, 129.9, 133.8,
135.0, 145.2, 150.9, 162.4; IR (KBr) 3450, 3360, 3151, 2210, 1686,
1572, 1389, 1256, 822, 748 cm−1. Anal. Calcd for C12H9ClN2O: C,
61.95; H, 3.90; N, 12.04. Found: C, 62.22; H, 3.93; N, 11.99.
Data for (E)-2m: yield 196 mg (86%); yellow solid; mp 190−191
1
°C; H NMR (400 MHz, DMSO) δ = 3.81 (s, 3H), 7.00−7.06 (m,
3H), 7.38 (dd, J = 15.2 Hz, 1H), 7.06 (s, 1H), 7.65 (d, J = 8.8 Hz, 2H),
7.75 (s, 1H), 7.94 (d, J = 11.2 Hz, 1H); 13C NMR (100 MHz, DMSO)
δ = 55.4, 105.9, 114.6, 115.7, 120.7, 127.5, 130.2, 146.9, 151.8, 161.4,
162.8; IR (KBr) 3391, 3317, 3157, 2218, 1701, 1578, 1375, 1207, 754,
Data for (E)-2g: yield 202 mg (93%); white solid; mp 157−159 °C;
1H NMR (300 MHz, DMSO) δ = 7.73−7.78 (m, 1H), 7.84 (s, 1H),
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700 cm−1. Anal. Calcd for C13H12N2O2: C, 68.41; H, 5.30; N, 12.27.
Found: C, 68.18; H, 5.26; N, 12.34.
3.82 (dd, J1 = 18.3 Hz, J2 = 6.0 Hz, 1H), 4.04 (t, J = 6.0 Hz, 1H), 5.74
(s, 1H), 6.38 (s, 1H), 7.48−7.53 (m, 2H), 7.61−7.66 (m, 1H), 7.96−
7.98 (m, 2H); 13C NMR (100 MHz, DMSO) δ = 32.1, 37.7, 118.9,
128.1, 128.9, 133.8, 135.6, 165.9, 195.9; IR (KBr) 3412, 3325, 3196,
2206, 1645, 1566, 1400, 1173, 1065, 754 cm−1. Anal. Calcd for
C11H10N2O2: C, 65.34; H, 4.98; N, 13.85. Found: C, 65.52; H, 5.00;
N, 13.90.
Data for 2v: yield 182 mg (77%); yellow solid; mp 169−170 °C;
1H NMR (300 MHz, DMSO) δ = 3.59−3.78 (m, 2H), 4.07 (t, J = 6.9
Hz, 1H), 7.55 (s, 1H), 7.62 (d, J = 8.4 Hz, 2H), 7.93 (s, 1H), 8.02 (d, J
= 8.4 Hz, 2H); 13C NMR (100 MHz, DMSO) δ = 31.9, 37.6, 118.7,
128.9, 130.0, 134.2, 138.6, 165.7, 194.9. Anal. Calcd for C11H9ClN2O2:
C, 55.83; H, 3.83; N, 11.84. Found: C, 55.68; H, 3.85; N, 11.92.
Data for 2w: yield 178 mg (72%); yellow solid; mp 189−190 °C;
1H NMR (300 MHz, DMSO) δ = 3.69−3.86 (m, 2H), 4.10 (t, J = 6.6
Hz, 1H), 7.58 (s, 1H), 7.95 (s, 1H), 8.25 (d, J = 8.7 Hz, 2H), 8.35 (d, J
= 8.7 Hz, 2H); 13C NMR (100 MHz, DMSO) δ = 31.8, 37.8, 117.3,
122.8, 128.6, 140.1, 149.9, 164.8, 194.4. Anal. Calcd for C11H9N3O4:
C, 53.44; H, 3.67; N, 17.00. Found: C, 53.23; H, 3.66; N, 17.06.
Data for 2x: yield 235 mg (89%); white solid; mp 168−169 °C; 1H
NMR (300 MHz, DMSO) δ = 3.08 (d, J = 13.5 Hz, 2H), 3.39 (d, J =
7.8 Hz, 2H), 7.31 (s, 10H), 7.60 (s, 1H), 7.66 (s, 1H); 13C NMR (100
MHz, DMSO) δ = 41.9, 54.2, 119.7, 127.3, 128.2, 130.0, 135.3, 168.2.
Anal. Calcd for C17H16N2O: C, 77.25; H, 6.10; N, 10.60. Found: C,
77.01; H, 6.13; N, 10.64.
Data for 2n: yield 89 mg (54%); orange solid; mp 100−102 °C; 1H
NMR (300 MHz, CDCl3) δ = 1.64−1.82 (m, 6H), 2.60 (t, J = 6.0 Hz,
2H), 2.94 (t, J = 6.0 Hz, 2H), 6.08 (s, 1H), 6.17 (s, 1H); 13C NMR
(100 MHz, CDCl3) δ = 25.2, 27.7, 28.1, 31.0, 36.5, 102.1, 116.4, 162.9,
117.2; Anal. Calcd for C9H12N2O: C, 65.83; H, 7.37; N, 17.06. Found:
C, 65.47; H, 7.38; N, 16.97.
Data for a mixture of (E)-2o and (Z)-2o: E:Z = 2:1; yield 149 mg
1
(80%); orange solid; mp 125−129 °C; H NMR (Z isomer) (300
MHz, DMSO) δ = 2.40 (s, 3H), 7.39 (s, 5H), 7.51 (s, 1H), 7.74 (s,
1H); 1H NMR (E isomer) (300 MHz, DMSO) δ = 2.34 (s, 3H), 7.49
(s, 5H), 7.82 (s, 1H), 8.08 (s, 1H); 13C NMR (100 MHz, DMSO) δ =
22.0, 23.9, 108.5, 109.2, 116.7, 116.9, 127.1, 128.3, 128.6, 129.5, 129.7,
138.1, 139.3, 158.7, 160.8, 163.3, 163.5. Anal. Calcd for C11H10N2O:
C, 70.95; H, 5.41; N, 15.04. Found: C, 70.66; H, 5.44; N, 15.13.
Data for (E)-2p: yield 101 mg (46%); yellow solid; mp 161−163
1
°C; H NMR (300 MHz, DMSO) δ = 2.33 (s, 3H), 7.53 (d, J = 8.7
Hz, 2H), 7.57 (d, J = 8.7 Hz, 2H), 7.86 (s, 1H), 8.09 (s, 1H); 13C
NMR (100 MHz, DMSO) δ = 21.9, 109.0, 116.8, 128.7, 129.2, 134.5,
138.1, 159.7, 163.3. Anal. Calcd for C11H9ClN2O: C, 59.88; H, 4.11;
N, 12.70. Found: C, 59.67; H, 4.15; N, 12.75.
Crystal data for (E)-2p: C11H9ClN2O, white crystal, M = 220.65,
monoclinic, P21/n, a = 18.014 Å, b = 11.966 Å, c = 25.055 Å, α =
90.00°, β = 98.57°, γ = 90.00°, V = 5340.6 Å3, Z = 20, T = 273(2) K,
F000 = 2280. CCDC deposition number 938999. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the Cambridge Crystallographic Data Centre, 12 Union Rd.,
Cambridge CB21EZ, U.K.; fax (+44)1223−336−033; e-mail deposit@
ccdc.cam.ac.uk).
Data for (Z)-2p: yield 60 mg (27%); yellow solid; mp 135−136 °C;
1H NMR (300 MHz, DMSO) δ = 2.39 (s, 3H), 7.39 (d, J = 8.7 Hz,
2H), 7.49 (d, J = 8.7 Hz, 2H), 7.56 (s, 1H), 7.80 (s, 1H); 13C NMR
(100 MHz, DMSO) δ = 23.8, 109.6, 116.5, 128.4, 129.0, 134.3, 136.9,
157.7, 163.1. Anal. Calcd for C11H9ClN2O: C, 59.88; H, 4.11; N,
12.70. Found: C, 60.04; H, 4.14; N, 12.66.
Data for (E)-2q: yield 95 mg (41%); orange solid; mp 134−136 °C;
1H NMR (300 MHz, DMSO) δ = 2.37 (s, 3H), 7.77 (d, J = 8.7 Hz,
2H), 7.93 (s, 1H), 8.16 (s, 1H), 8.34 (d, J = 8.7 Hz, 2H); 13C NMR
(100 MHz, DMSO) δ = 21.8, 110.1, 116.2, 123.8, 128.7, 145.7, 147.9,
158.8, 162.8. C11H9N3O3: C, 57.14; H, 3.92; N, 18.17. Found: C,
57.38; H, 3.90; N, 18.09.
Data for 2y: yield 223 mg (88%); white solid; mp 104−106 °C; 1H
NMR (300 MHz, DMSO) δ = 1.18 (t, J = 7.2 Hz, 6H), 3.02 (s, 4H),
4.09 (q, J = 7.2 Hz, 4H), 7.66 (s, 1H), 7.68 (s, 1H); 13C NMR (100
MHz, DMSO) δ = 13.5, 38.7, 42.0, 60.2, 118.8, 166.7, 168.1. Anal.
Calcd for C11H16N2O5: C, 51.56; H, 6.29; N, 10.93. Found: C, 51.45;
H, 6.31; N, 10.90.
Typical Procedure for the Synthesis of 3 and 4 (3r as an
Example). To a solution of terephthalonitrile (1r) (1.0 mmol, 128
mg) and Cu(OAc)2·H2O (20 mg, 0.1 mmol) in HOAc (10.0 mL) was
added H2O (0.2 mL) in one portion. The mixture was stirred at reflux
for 12.0 h and then poured into saturated aqueous NaCl (50 mL). The
crude product was collected by filtration, washed with H2O, and dried
in vacuo to give pure product 3r: yield 128 mg (78%); mp 331−333
°C; 1H NMR (400 MHz, DMSO) δ = 7.48 (s, 2H), 7.93 (s, 4H), 8.06
(s, 2H); 13C NMR (100 MHz, DMSO) δ = 127.7, 136.9, 167.6. Anal.
Calcd for C8H8N2O2: C, 58.53; H, 4.91; N, 17.06. Found: C, 58.71; H,
4.89; N, 17.02.
3r, 3s, and 4t are known compounds. For the spectral and analytical
data of 3r and 3s, see ref 11, and for those of 4t, see ref 18.
Data for 3s: yield 120 mg (73%); white solid; mp 279−280 °C; 1H
NMR (400 MHz, DMSO) δ = 7.53 (s, 3H), 8.04 (s, 2H), 8.13 (s, 2H),
8.45 (s, 1H); 13C NMR (100 MHz, DMSO) δ = 127.0, 128.5, 130.4,
134.5, 168.0. Anal. Calcd for C8H8N2O2: C, 58.53; H, 4.91; N, 17.06.
Found: C, 58.45; H, 4.93; N, 17.11.
Data for (Z)-2q: yield 46 mg (20%); orange solid; mp 193−196 °C;
1H NMR (300 MHz, DMSO) δ = 2.43 (s, 3H), 7.60−7.63 (m, 3H),
7.87(s, 1H), 8.26 (d, J = 8.7 Hz, 2H); 13C NMR (100 MHz, DMSO) δ
= 24.0, 110.9, 116.1, 123.4, 128.5, 144.9, 147.7, 157.6, 162.5. Anal.
Calcd for C11H9N3O3: C, 57.14; H, 3.92; N, 18.17. Found: C, 57.40;
H, 3.93; N, 18.10.
Data for 2r: yield 124 mg (85%); white solid; mp 215−217 °C; 1H
NMR (300 MHz, DMSO) δ = 7.69 (s, 1H), 7.95 (d, J = 8.4 Hz, 2H),
8.02 (d, J = 8.4 Hz, 2H), 8.22 (s, 1H); 13C NMR (100 MHz, DMSO)
δ = 113.6, 118.3, 128.2, 132.3, 138.2, 166.4; IR (KBr) 3358, 3175,
2361, 1637, 1418, 1290, 748, 700 cm−1. Anal. Calcd for C8H6N2O: C,
65.75; H, 4.14; N, 19.17. Found: C, 65.58; H, 4.16; N, 19.11.
Data for 2s: yield 123 mg (84%); white solid; mp 228−230 °C; 1H
NMR (300 MHz, DMSO) δ = 7.67−7.72 (m, 2H), 8.01 (d, J = 7.8 Hz,
1H), 8.18 (d, J = 7.8 Hz, 2H), 8.28 (s, 1H); 13C NMR (100 MHz,
DMSO) δ = 111.4, 118.3, 129.7, 131.0, 132.2, 134.7, 135.3, 165.9; IR
(KBr) 3443, 3362, 3294, 3171, 2230, 1705, 1618, 1560, 1414, 1398,
860, 548 cm−1. Anal. Calcd for C8H6N2O: C, 65.75; H, 4.14; N, 19.17.
Found: C, 65.54; H, 4.16; N, 19.24.
Data for 4t: yield 104 mg (71%); white solid; mp 232−234 °C; 1H
NMR (400 MHz, DMSO) δ = 7.78 (s, 4H), 11.30 (s, 1H); 13C NMR
(100 MHz, DMSO) δ = 122.8, 132.6, 134.2, 169.1. Anal. Calcd for
C8H5NO2: C, 65.31; H, 3.43; N, 9.52. Found: C, 65.10; H, 3.41; N,
9.48.
ASSOCIATED CONTENT
* Supporting Information
■
S
X-ray single-crystal analysis of compounds (E)-2d and (E)-2p,
1H NMR and 13C NMR spectra for compounds 2−4, and CIF
files of crystallographic data for compounds (E)-2d and (E)-2p.
This material is available free of charge via the Internet at
http://pubs.acs.org.
Data for 2t: yield 120 mg (82%); white solid; mp 179−181 °C; 1H
NMR (300 MHz, DMSO) δ = 7.64−7.70 (m, 1H), 7.74−7.83 (m,
3H), 7.92 (d, J = 7.5 Hz, 1H), 8.18 (s, 1H); 13C NMR (100 MHz,
DMSO) δ = 110.2, 117.7, 128.1, 130.8, 132.7, 134.2., 138.7, 166.8; IR
(KBr) 3420, 3306, 3155, 2231, 1705, 1628, 1396, 906, 787, 673 cm−1.
Anal. Calcd for C8H6N2O: C, 65.75; H, 4.14; N, 19.17. Found: C,
65.63; H, 4.10; N, 19.11.
AUTHOR INFORMATION
Corresponding Author
*E-mail: dwdong@ciac.ac.cn.
■
Data for 2u: yield 154 mg (76%); white solid; mp 153−155 °C; 1H
NMR (300 MHz, CDCl3) δ = 3.64 (dd, J1 = 18.3 Hz, J2 = 6.0 Hz, 1H),
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
Financial support of this research by the National Natural
Science Foundation of China (Grants 51073150 and
21172211), the Department of Science and Technology of
Jilin Province (Grants 20111802 and 201205027), and the
“Hundred Talents Program” of the Chinese Academy of
Sciences is gratefully acknowledged.
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