Tandem synthesis of bicyclic ortho-aminocarbonitrile derivatives in ionic liquids

Article abstract of DOI:10.1002/jhet.2088

An efficient synthesis of 2-amino-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitriles via the tandem four-component condensation of one equivalent of aromatic aldehyde, cyclohexanone, and two equivalents of malononitrile in ionic liquids was underta

Full text of DOI:10.1002/jhet.2088

Month 2014
Tandem Synthesis of Bicyclic ortho-Aminocarbonitrile Derivatives in
Ionic Liquids
Y. Wan,a X-X. Zhang,b L-L. Zhao,b C. Wang,b L-F. Chen,b G-X. Liu,b S-Y. Huang,b S-N. Yue,b W-L. Zhang,b
a
*
and H. Wu
aKey Laboratory of Biotechnology on Medical Plant of Jiangsu Province, Xuzhou, 221116, People’s Republic of China
bSchool of Chemistry and Chemical Engineering, Jiangsu Normal University, Xuzhou, 221116, People’s Republic of
China
*
E-mail:wuhui72@126.com
Received April 25, 2013
DOI 10.1002/jhet.2088
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com).
An efficient synthesis of 2-amino-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitriles via the
tandem four-component condensation of one equivalent of aromatic aldehyde, cyclohexanone, and two
equivalents of malononitrile in ionic liquids was undertaken. Up to four new bonds and one new ring were
formed in one-pot with water as the only by-product in this multi-component procedure.
J. Heterocyclic Chem., 00, 00 (2014).
INTRODUCTION
RESULTS AND DISCUSSION
Creation of molecular functionality and diversity[1]
from common starting materials while combining eco-
nomic[2,3] and environmental[4] aspects constitutes a
great challenge in modern organic chemistry[5]. In these
contexts, multi-component reactions (MCRs) in ionic
liquids must be competent to come close to reaching this
ideal goal. MCRs meet the economic desires, for they can
avoid time-consuming and costly processes for purifica-
tion of various precursors and tedious steps of protection
and deprotection of functional groups[6].
Malononitrile is one of the most versatile reagents to be
used in MCRs because of the high reactivity of both the
methylene and the cyano groups[15]. Traditionally, it is a
very useful method to extend carbon chains and to prepare
heterocyclic compounds that have medical and industrial
utility[16]. From this perspective, we used malononitrile
(2, 2.0 mmol) as the active reagent to react with aromatic
aldehyde (1e, 1.0 mmol) and cyclohexanone (3, 1.0 mmol)
to optimize the reaction conditions at first. A summary of
the optimization experiment is provided in Table 1.
Ionic liquids are regarded as substitutes for traditional
solvent in syntheses because of their non-volatility, non-
flammability, stability, and ease of recyclability[7].
Therefore, MCRs in ionic liquids have emerged as a
powerful tool in organic chemistry[8].
It was found that the reaction could not run smoothly in
organic solvent and water except in the presence of ionic
liquid (Table 1, Entries 1–8). No reaction was carried out
in lower polar CHCl3 (Table 1, Entry 1). In the solvents
with higher polarity, the reaction cannot afford expected
product (Table 1, DMF entry 2, and H2O entry 3). In the
medium polar solvent such as EtOH (Table 1, entry 4),
the reaction can be carried out, but the yield of product
was lower than that in ionic liquid (Table 1, Entries 4–7).
It showed that the polarity of solvent has great effect on
the reaction process and yield. The importance of ionic
liquids may be attributed to its appropriate dissolution
and excellent ionic conductivity. The influence of different
cations or anions on the yield was further studied. As
revealed in Table 1, [BPy]BF4 appeared to be the best
media for this reaction (Table 1, Entries 5–8). Finally,
it was also realized that the process was efficiently
facilitated at 60°C (Table 1, Entries 10–13). However,
elevating the temperature did not enhance the yields of
ortho-aminocarbonitriles are widely used in organic
synthesis for the preparation of various heterocyclic
compounds[9]. Numerous preparations of them have been
investigated during the past few years[10–13]. However,
most methods have their limitations such as requirement
of organic solvents (MeOH, HOAc)[10,11,14], using
catalyst (Et3N[10], morpholine[11], 1,2-diamine[14]), and
complex substrate[10–13]. To obtain these potential units of
ortho-aminocarbonitriles in high yields as well as in a green
media, we would like to report an efficient and green method
to synthesize 2-amino-4a,5,6,7-tetrahydronaphthalene-1,3,3
(4H)-tricarbonitriles via four-component of one equivalents
of aromatic aldehyde, cyclohexanone, and two equivalents
of malononitrile in ionic liquids [BPy]BF4 (Scheme 1).
© 2014 HeteroCorporation

Y. Wan, X-X. Zhang, L-L. Zhao, C. Wang, L-F. Chen,G-X. Liu,
S-Y. Huang, S-N. Yue, W-L. Zhang, and H. Wu
Vol 000
Scheme 1
intermediate IV, followed by intramolecular cyclization to
form V. The isomerization of V gives the final product 4.
In summary, an efficient method is exploited for the syn-
thesis of 2-amino-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-
tricarbonitriles from four-component condensation in [BPy]
BF4. The features of this multi-component procedure include
mild reaction conditions, high yields, one-pot, operational
simplicity, and the formation of up to four new bonds and
one new ring in one-pot with water as the only by-product.
In addition, there are several modifiable and coordinate sites
in this interesting type of framework, so the subsequent step
of the combinatorial development process, namely, structural
optimization, should be possible.
Table 1
Synthesis of 4e under different conditions.a
Temperature
Yield
(%)d
Entry
Solvent
CHCl3
DMF
H2O
(°C)
Time (h)
1
2
3
4
5
6
7
8
60
60
60
60
60
60
60
60
60
60
RT
40
50
70
12
12
12
12
12
12
12
12
8
4
4
4
4
Nre
Npf
Npf
30
60
56
62
95
92
EtOH
[BMIM]Brb
[BMIM]BF4
[BPy]Brc
[BPy]BF4
[BPy]BF4
[BPy]BF4
[BPy]BF4
[BPy]BF4
[BPy]BF4
[BPy]BF4
9
10
11
12
13
14
92
Nre
45
72
91
EXPERIMENTAL
4
aReactions were performed in 1:2:1 (4-cyanobenzaldehyde: malononitrile:
benzaldehyde: cyclohexanone) in different conditions.
bBMIM = 1-butyl-3-methylimidazolium.
cBPy = 1-butylpyridiniumtetra.
General Information. IR spectra were recorded with a Bruker
Varian FTIR-Tensor-27 spectrophotometer (Germany) using
KBr optics. 1H-NMR spectra were recorded at 400 MHz on a
Bruker DPX 400 spectrometer using TMS as an internal standard
and DMSO-d6 as solvent. Mass was determined by using a
Bruker TOF-MS high resolution mass spectrometer (Germany).
Ionic liquid [BPy]BF4 was prepared in our lab.
dIsolated yields.
eNo reaction.
fNot product 4e.
General procedure for the preparation of 2-amino-4a,5,6,7-
tetrahydronaphthalene-1,3,3(4H)-tricarbonitriles 4. A mixture
of aromatic aldehyde (1.0 mmol), malononitrile (2.0 mmol) and
cyclohexanone (1.0 mmol), and ionic liquid of [BPy]BF4 (2 mL)
was stirred at 60°C until complete consumption of the starting
material as monitored by TLC. After completion of the reaction, the
mixture was cooled down to RT and added water (40 mL), then the
crude solid was filtered and washed with 95% EtOH. The solid
residue was then recrystallized (95% EtOH/DMF, 1:4) to provide
the pure product 4.
4e (Table 1, Entry 14). Therefore, reaction temperature
of 60°C in ionic liquid [BPy]BF4 were identified as the
optimum condition.
To explore the application of this method, the scope of
the substrates was evaluated with a variety of aromatic
aldehydes under the optimal condition (Table 2). It
showed that this reaction can afford moderate to high
yield, and the product can be separated easily. However,
the yields of 4 were not sensitive to the electronic
properties of the aromatic rings in the presence of
electron-withdrawing groups (such as halide, cyano) or
electron-donating groups (such as alkyl group).
The possible reaction mechanism was proposed in
Scheme 2. We presume that the reaction proceeds via initial
formation of I through Knoevenagel condensation of aryl
aldehyde and malononitrile. Meanwhile, cyclohexanone
condensed with another malononitrile to give the other
product of Knoevenagel condensation II. Then, II lost a
hydrogen atom under the action of ionic liquids. Subse-
quently, the Michael addition between III and I produces
The spectral data of new products are given in the
succeeding text. 2-amino-4-(4-chlorophenyl)-4a,5,6,7-tetrahy
dronaphthalene-1,3,3(4H)-tricarbonitrile (4a).
Melting point
288–289°C; IR (KBr) ν: 3421, 3343, 3252, 3229, 3034, 2946, 2865,
2212, 1645, 1605, 1493, 1447, 1430, 1414, 1391, 1350, 1339, 1278,
1212, 1162, 1094, 1037, 1015, 956, 918, 882, 838, 805, 782,
1
753, and 727 cmÀ1; H-NMR (400 MHz, DMSO-d6) (δ, ppm):
0.81–0.90 (m, 1H, CH2), 1.44–1.47 (m, 2H, CH2), 1.68–1.70
(m, 1H, CH2), 2.05–2.21 (m, 2H, CH2), 2.77–2.83 (m, 1H, CH2),
3.66 (d, J= 12.8 Hz, 1H, CH), 5.73 (s, 1H, CH═), 7.40 (s, 2H,
NH2), and 7.48–7.62 (m, 4H, ArH); 13C-NMR (100 MHz, DMSO-
d6): δ 143.3, 133.8, 133.6, 128.6, 120.5, 116.1, 112.4, 112.2, 81.6,
49.7, 42.5, 33.7, 26.9, 24.8, and 20.9; HRMS: Calcd for
C19H15ClN4 [M + Na]+ found (expected): 357.0914 (357.0883).
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Tandem Synthesis of Bicyclic ortho-Aminocarbonitrile Derivatives in Ionic Liquids
Table 2
Synthesis of 4 under optimum different conditions.a
Mp/°C
Entry
R
Products
Time/h
Yield/% b
Found
Report
1
2
3
4
5
6
7
8
4-Cl
4-Br
4-I
H
4-CN
4-F
3-Br
3-F
3,4,5-(CH3O)3
4-CH3O
2-Br
3,4-(CH3O)2
2,4-(Cl)2
2-Cl
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4
4
4
5
4
4
5
5
4
4
5
5
5
5
5
89
87
91
83
92
85
88
82
83
89
87
85
84
89
88
248–250
265–268
212–214
255–257
239–241
265–267
250–253
260–262
234–236
261–262
245–248
254–255
257–260
271–272
264–265
273–274[12]
254–255[11]
270–272[13]
261–263[12]
9
10
11
12
13
14
15
265–268[13]
2-CH3O
aAll reactions were performed in 2 mL [BPy]BF4, 2 (2.0 mmol) and 3 (1.0 mmol) at 60°C.
bIsolated yields.
Scheme 2
2-amino-4a,5,6,7-tetrahydro-4-(4-iodophenyl)naphthalene-1,3,3
(4H)-tricarbonitrile (4c). Melting point 268–269°C; IR (KBr) ν:
3425, 3345, 3250, 3005, 2922, 2863, 2830, 2209, 1645, 1597,
1485, 1447, 1431, 1407, 1392, 1349, 1302, 1277, 1211, 1162,
2-amino-4-(3-bromophenyl)-4a,5,6,7-tetrahydronaphthalene-1,3,3
(4H)-tricarbonitrile (4g). Melting point 250–253°C; IR (KBr) ν:
3447, 3357, 3204, 3035, 2948, 2918, 2854, 2840, 2217, 1632, 1619,
1594, 1568, 1473, 1433, 1390, 1269, 1212, 1201, 1164, 1097, 1023,
1
1102, 1041, 1007, 953, 917, 864, 831, 804, 779, and 750 cmÀ1
;
950, 922, 868, 813, 777, 746, and 686 cmÀ1; H-NMR (400 MHz,
1H-NMR (400 MHz, DMSO-d6) (δ, ppm): 0.80–0.90 (m, 1H,
CH2), 1.41–1.49 (m, 2H, CH2), 1.65–1.71 (m, 1H, CH2), 2.09–2.23
(m, 2H, CH2), 2.75–2.82 (m, 1H, CH2), 3.60 (d, J= 12.4 Hz, 1H,
CH), 5.72 (s, 1H, CH═), 7.23 (d, J= 8.0 Hz, 1H, ArH), 7.39–7.41
(m, 3H, NH2 + ArH) and 7.82–7.88 (m, 2H, ArH); 13C-NMR
(100 MHz, DMSO-d6): δ 143.3, 137.4, 134.4, 131.1, 128.6, 120.5,
116.1, 112.4, 112.2, 95.7, 81.6, 49.9, 42.6, 33.6, 26.9, 24.8, and
20.9; HRMS: Calcd for C19H15IN4 [M + Na]+ found (expected):
449.0263 (449.0239).
DMSO-d6) (δ, ppm): 0.82–0.92 (m, 1H, CH2), 1.40–1.54 (m, 2H,
CH2), 1.66–1.70 (m, 1H, CH2), 1.99–2.06 (m, 1H, CH2), 2.17–2.23
(m, 1H, CH2), 2.81–2.84 (m, 1H, CH2), 3.65 (d, J = 12.8 Hz,
1H, CH), 5.73 (s, 1H, CH═), 7.41 (s, 2H, NH2), 7.45–7.50
(m, 1H, ArH), and 762–7.79 (m, 3H, ArH); 13C-NMR
(100 MHz, DMSO-d6): δ 143.3, 137.4, 134.7, 130.7, 128.5,
126.2, 120.5, 116.1, 112.7, 112.3, 112.2, 81.6, 49.9, 42.6,
33.7, 26.9, 24.8, and 20.9; HRMS: Calcd for C19H15BrN4
[M + H]+ found (expected): 379.0543 (379.0559).
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Y. Wan, X-X. Zhang, L-L. Zhao, C. Wang, L-F. Chen,G-X. Liu,
S-Y. Huang, S-N. Yue, W-L. Zhang, and H. Wu
Vol 000
2-amino-4-(3-fluorophenyl)-4a,5,6,7-tetrahydronaphthalene-
1,3,3(4H)-tricarbonitrile (4h). Melting point 273–275°C; IR
CH2), 3.88 (d, J = 12.4 Hz, 1H, CH), 5.77 (s, 1H, CH═), 7.46
(s, 2H, NH2), and 7.58–7.87 (m, 3H, ArH); 13C-NMR
(100 MHz, DMSO-d6): δ 143.0, 134.6, 133.9, 132.6, 131.7,
129.6, 129.2, 128.1, 121.1, 115.9, 112.0, 111.4, 81.6, 46.5,
41.4, 34.1, 26.7, 24.7, and 20.7; HRMS: Calcd for
C19H14Cl2N4 [M + Na]+ found (expected): 391.0522 (391.0494).
2-amino-4-(2-chlorophenyl)-4a,5,6,7-tetrahydronaphthalene-1,3,3
(4H)-tricarbonitrile (4n). Melting point 281–283°C; IR (KBr) ν:
3448, 3358, 3204, 3073, 2949, 2921, 2856, 2839, 2217, 1632, 1597,
1478, 1447, 1434, 1391, 1340, 1270, 1243, 1212, 1201, 1165, 1056,
(KBr) ν: 3420, 3341, 3255, 3232, 3031, 2935, 2866, 2830,
2211, 1650, 1601, 1498, 1454, 1430, 1392, 1350, 1339, 1274,
1212, 1160, 1103, 1038, 954, 882, 866, 838, 808, 787, 731,
714, and 698 cmÀ1 1H-NMR (400 MHz, DMSO-d6) (δ, ppm):
;
0.80–0.90 (m, 1H, CH2), 1.40–1.51 (m, 2H, CH2), 1.66–1.70
(m, 1H, CH2), 2.00–2.21 (m, 2H, CH2), 2.78–2.84 (m, 1H,
CH2), 3.54 (d, J = 12.8 Hz, 1H, CH), 5.73 (s, 1H, CH═), 7.38
(s, 2H, NH2), 7.43 (s, 2H, ArH), and 7.49–7.61 (m, 2H, ArH);
13C-NMR (100 MHz, DMSO-d6): δ 143.3, 128.6, 123.1, 120.5,
116.1, 112.4, 112.2, 81.6, 49.9, 42.6, 33.5, 26.9, 24.8, and 20.9.
2-amino-4a,5,6,7-tetrahydro-4-(3,4,5-trimethoxyphenyl)
1
1041, 951, 813, 776, and 749 cmÀ1; H-NMR (400 MHz, DMSO-
d6) (δ, ppm): 0.77–0.87 (m, 1H, CH2), 1.35–1.50 (m, 2H, CH2),
1.65–1.69 (m, 1H, CH2), 2.04–2.22 (m, 2H, CH2), 2.84–2.89 (m,
1H, CH2), 3.89 (d, J= 12.4 Hz, 1H, CH), 5.77 (s, 1H, CH═), 7.45
(s, 2H, NH2), 7.47–7.54 (m, 2H, ArH), 7.63 (d, J=8.0Hz, 1H,
ArH), and 7.78 (d, J= 7.6 Hz, 1H, ArH); 13C-NMR (100 MHz,
DMSO-d6): δ 143.4, 135.1, 131.8, 130.6, 130.1, 129.1, 128.4, 127.8,
120.9, 115.9, 112.2, 111.5, 81.5, 46.5, 41.6, 34.5, 26.7, 24.7, and
20.8; HRMS: Calcd for C19H15ClN4 [M + H]+ found (expected):
335.1059 (335.1064).
naphthalene-1,3,3(4H)-tricarbonitrile (4i).
Melting point
245–256°C; IR (KBr) ν: 3447, 3358, 3253, 3005, 2939, 2872,
2836, 2201, 1640, 1593, 1509, 1469, 1456, 1429, 1349, 1334,
1306, 1275, 1253, 1130, 1008, 967, 845, 804, 756, and 698 cmÀ1
;
1H-NMR (400 MHz, DMSO-d6) (δ, ppm): 0.85–0.95 (m, 1H,
CH2), 1.47–1.59 (m, 2H, CH2), 1.68–1.72 (m, 1H, CH2), 2.01–2.23
(m, 2H, CH2), 2.78–2.85 (m, 1H, CH2), 3.45 (d, J= 12.4 Hz, 1H,
CH), 3.71 (s, 3H, OCH3), 3.76 (s, 3H, OCH3), 3.81 (s, 3H, OCH3),
5.73 (s, 1H, CH), 6.83 (s, 1H, ArH), 6.89 (s, 1H, ArH), and 7.34 (s,
2H, NH2); 13C-NMR (100 MHz, DMSO-d6): δ 153.1, 152.4, 143.6,
137.8, 130.2, 128.9, 120.3, 116.2, 112.9, 112.4, 104.2, 81.5, 60.1,
56.0, 51.1, 42.9, 34.0, 26.9, 24.9, and 21.0; HRMS: Calcd for
C22H22N4O3 [M + H]+ found (expected): 391.1822 (391.1771).
2-amino-4a,5,6,7-tetrahydro-4-(4-dimethoxyphenyl)naphthalene-
1,3,3(4H)-tricarbonitrile (4j). Melting point 261–262°C; IR (KBr) ν:
3420, 3341, 3252, 3015, 2947, 2868, 2832, 2213, 1650, 1599, 1516,
1474, 1458, 1431, 1391, 1339, 1309, 1287, 1255, 1213, 1181, 1120,
2-amino-4a,5,6,7-tetrahydro-4-(2-methoxyphenyl)naphthalene-
1,3,3(4H)-tricarbonitrile (4o).
Melting point 280–282°C; IR
(KBr) ν: 3418, 3341, 3258, 3235, 2941, 2924, 2859, 2832, 2211,
1650, 1604, 1569, 1477, 1454, 1429, 1394, 1337, 1299, 1279, 1212,
1159, 1091, 1077, 1038, 996, 888, 846, 796, 745, and 687 cmÀ1; 1H-
NMR (400 MHz, DMSO-d6) (δ, ppm): 0.72–0.81 (m, 1H, CH2),
1.38–1.52 (m, 2H, CH2), 1.64–1.68 (m, 1H, CH2), 2.02–2.20
(m, 2H, CH2), 2.73–2.80 (m, 1H, CH2), 3.78 (s, 3H, OCH3), 3.85
(d, J= 12.4 Hz, 1H, CH), 5.73 (s, 1H, CH═), 7.07–7.15 (m, 2H,
ArH), 7.37(s, 2H, NH2), 7.40–7.44 (m, 1H, ArH), and 7.53
(d, J= 7.2 Hz, 1H, ArH); 13C-NMR (100 MHz, DMSO-d6): δ 157.8,
143.8, 130.1, 128.0, 122.2, 120.6, 120.6, 116.0, 112.6, 112.0, 111.8,
81.5, 55.8, 42.3, 42.0, 33.9, 26.8, 24.8, and 20.9; HRMS: Calcd for
C20H18N4O [M+H]+ found (expected): 331.1582 (331.1560).
1029, 953, 917, 882, 839, 806, 795, 765, and 729 cmÀ1; H-NMR
1
(400 MHz, DMSO-d6) (δ, ppm): 0.79–0.89 (m, 1H, CH2), 1.44–1.50
(m, 2H, CH2), 1.66–1.70 (m, 1H, CH2), 2.04–2.22 (m, 2H, CH2),
2.72–2.79 (m, 1H, CH2), 3.47 (d, J= 12.4 Hz, 1H, CH), 3.79 (s, 3H,
OCH3), 5.71 (s, 1H, CH═), 6.96–7.07 (m, 2H, ArH), 7.35(s, 3H,
NH2 +ArH), and 7.50 (d, J= 8.0 Hz, 1H, ArH); 13C-NMR (100 MHz,
DMSO-d6): δ 159.5, 155.5, 143.6, 133.6, 129.0, 126.4, 120.2, 118.6,
115.4, 112.6, 112.5, 81.6, 55.1, 50.0, 43.2, 34.0, 27.0, 24.9, 21.0;
HRMS: Calcd for C20H18N4O [M+H]+ found (expected): 331.1506
(331.1560).
Acknowledgments. We are grateful to the foundation of the
“Priority Academic Program Development of Jiangsu Higher
Education Institutions”, “Key Basic Research Project in Jiangsu
University” (No. 10KJA430050), the “Graduate Innovation Project in
Jiangsu Province” (No. CXLX13_972, 2013YYB121), “The Project
of Outstanding Scientific and Technological Innovation Team for
Higher Education Institutions in Jiangsu Province (Pre-development
of medicinal microbial resources)” for financial support.
2-amino-4-(2-bromophenyl)-4a,5,6,7-tetrahydronaphthalene-1,3,3
(4H)-tricarbonitrile (4k).
Melting point 294–296°C; IR (KBr) ν:
3425, 3346, 3251, 3224, 3005, 2922, 2863, 2830, 2209, 1645, 1603,
1486, 1447, 1431, 1407, 1392, 1349, 1302, 1277, 1211, 1162, 1121,
1062, 1041, 1007, 953, 917, 831, 804, 779, and 750 cmÀ1; 1H-NMR
(400 MHz, DMSO-d6) (δ, ppm): 0.77–0.87 (m, 1H, CH2), 1.34–1.46
(m, 2H, CH2), 1.65–1.69 (m, 1H, CH2), 2.09–2.21 (m, 2H, CH2),
2.85–2.91 (m, 1H, CH2), 3.87 (d, J= 12.4 Hz, 1H, CH), 5.77 (s, 1H,
CH═), 7.41–7.43 (m, 1H, ArH), 7.47 (s, 2H, NH2), 7.58 (t, J=7.6Hz,
1H, ArH), and 7.75–7.81 (m, 2H, ArH); 13C-NMR (100 MHz, DMSO-
d6): δ 143.5, 133.5, 133.4, 130.9, 129.2, 128.5, 128.4, 126.5, 120.9,
115.9, 112.2, 111.5, 81.5, 49.3, 41.6, 34.7, 26.8, 24.7, and 20.8;
HRMS: Calcd for C19H15BrN4 [M + H]+ found (expected): 379.0594
(379.0559).
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2-amino-4-(2,4-dichlorophenyl)-4a,5,6,7-tetrahydronaphthalene-
1,3,3(4H)-tricarbonitrile (4m).
Melting point 280–282°C; IR
(KBr) ν: 3448, 3361, 3072, 3032, 2949, 2921, 2861, 2836, 2217,
1632, 1592, 1561, 1470, 1453, 1433, 1389, 1350, 1301, 1269,
1211, 1197, 1167, 1099, 1045, 971, 952, 907, 885, 846, 824, 812,
1
794, and 763 cmÀ1; H-NMR (400 MHz, DMSO-d6) (δ, ppm):
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0.77–0.86 (m, 1H, CH2), 1.35–1.53 (m, 2H, CH2), 1.66–1.70
(m, 1H, CH2), 2.09–2.23 (m, 2H, CH2), 2.84–2.97 (m, 1H,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Tandem Synthesis of Bicyclic ortho-Aminocarbonitrile Derivatives in Ionic Liquids
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet