The Synthesis of 2,11-Diamino-4,9-diphenyl-4,9-dihydrobenzo [f] pyrano[3,2-h]chromene-3,10-dicarbonitrile Derivatives using Triethanolammonium Acetate as a Green Ionic Liquid

Article abstract of DOI:10.1002/jccs.201700019

Triethanolammonium acetate [TEA][HOAc] was used as a green ionic liquid and successfully utilized for the multi-component synthesis of 2,11-diamino-4,9-diphenyl-4,9-dihydrobenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile derivatives as new compounds by the reaction of 2,3-naphthalenediol with malononitrile and various aldehydes. Mild reaction conditions and high yields are some of the advantages of this method. These compounds were identified by IR, NMR spectroscopy and mass analysis.

Full text of DOI:10.1002/jccs.201700019

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
The Synthesis of 2,11-Diamino-4,9-diphenyl-4,9-dihydrobenzo [f] pyrano[3,2-h]
chromene-3,10-dicarbonitrile Derivatives using Triethanolammonium Acetate as a
Green Ionic Liquid
a
a
a
a
*
Ardeshir Khazaei , Ehsan Bashirian, Azam Ranjbaran, Marzieh Khazaei and
Ahmad Reza Moosavi-Zareb
*
aFaculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran
bDepartment of Chemistry, Sayyed Jamaleddin Asadabadi University, Asadabad 6541835583, Iran
(Received: January 15, 2017; Accepted: March 29, 2017; DOI: 10.1002/jccs.201700019)
Triethanolammonium acetate [TEA][HOAc] was used as a green ionic liquid and successfully uti-
lized for the multi-component synthesis of 2,11-diamino-4,9-diphenyl-4,9-dihydrobenzo[f]pyrano
[3,2-h]chromene-3,10-dicarbonitrile derivatives as new compounds by the reaction of 2,3-
naphthalenediol with malononitrile and various aldehydes. Mild reaction conditions and high
yields are some of the advantages of this method. These compounds were identified by IR, NMR
spectroscopy and mass analysis.
Keywords: Ionic liquid; Triethanolammonium acetate; 2,11-Diamino-4,9-diphenyl-4,9-
dihydrobenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile; One-pot synthesis.
INTRODUCTION
Ionic liquids (ILs) find increasing applications in
many fields of chemistry and industry due to their
chemical and thermal stability, low vapor pressure, and
high ionic conductivity.1
their use as drugs, pesticides, analogs of natural com-
pounds, dyes, and other materials with practical
importance.27–32
Previously, these derivatives were synthesized in
two steps. The first step consisted in preparing and iso-
lating arylmethylene malononitrile, and the second step
involved the reaction of this compound with the corre-
sponding phenol or naphthol.33–35
In this paper, we report the use of triethanolam-
monium acetate [TEA][HOAc] as a green IL and cata-
lyst (Scheme 1) for the synthesis of 2,11-diamino-4,
9-diphenyl-4,9-dihydrobenzo[f]pyrano[3,2-h]chromene-3,
10-dicarbonitrile derivatives by the reaction of 2,3-
naphthalenediol with malononitrile and aldehydes
(Scheme 2) with excellent yields.36
In the past few years, ILs have been popularly
used for organic synthesis as environmentally friendly
solvents, for catalysis, and also as media for extraction
processes.2–10 Perhaps the best way in which an IL can
be used in catalysis is as a combined catalyst and sol-
vent. Since the melting points of ILs are low, they can
act as solvents for diverse reactions. Such reactions
often give selectivity and reactivity different from those
with conventional organic solvents. Therefore, ILs have
been classified as “green solvents”.11 Reports indicate
that a variety of reactions can be performed in ILs ran-
ging from electrophilic reactions,12,13 hydrogenation,14
Wittig reaction,15 heterocyclic synthesis,16,17 and nucle-
ophilic substitution reactions.18,19 The early use of ILs
as catalysts was merely based on their role as polar
media to facilitate organic reactions.20–26
RESULTS AND DISCUSSION
This IL contains hydroxyl and ammonium groups,
which could be coordinated with the hydrogens on the
active methylene group of malononitrile and the car-
bonyl group of the aromatic aldehydes (Scheme 3).
At first, the reaction of naphthalene-2,3-diol with
benzaldehyde and malononitrile was selected as a
model reaction. Then, in order to optimize the reaction
2,11-Diamino-4,9-diphenyl-4,9-dihydrobenzo[f]pyr
ano[3,2-h]chromene-3,10-dicarbonitrile derivatives are
an important class of organic compounds because of
*Corresponding authors. Email: khazaei_1326@yahoo.com; moosavizare@yahoo.com
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Khazaei et al.
Table 2. Effect of amount of the catalyst on the synthesis of
2,11-diamino-4,9-diphenyl-4,9-dihydrobenzo[f]pyra
no[3,2-h]chromene-3,10-dicarbonitrile
Entry
Catalyst (mol %)
Time (h)
Yielda (%)
1
2
3
0.047
0.095
0.143
1
1
1
80
80
95
Scheme 1. Synthesis of triethanolammonium acetate
[TEA][HOAc].
a Isolated yield.
ethanol, H2O and PEG, ethanol was found to be the
best solvent in this reaction (Table 1, entry 3). As
shown in Tables 2 and 3, the best reaction conditions
were obtained in ethanol under reflux conditions in the
presence of 0.143% of the catalyst. The model reaction
was also tested under solvent-free conditions; but the
yield of product was low in comparison with that with
the solvent.
To show the generality of the catalyst, various
aromatic aldehydes containing electron-withdrawing
and electron-donating groups and halogens were tested
under these reaction conditions (Table 4). Electron-
withdrawing substituents (such as NO2) on the aldehyde
increase the reaction time, and electron-donating substi-
tuents (such as OMe) on the aldehyde decrease the reac-
tion time (Table 4, entries 5 and 6).
Scheme 2. Synthesis of 2,11-diamino-4,9-diphenyl-
4,9-dihydrobenzo[f]pyrano[3,2-h]chromene
-3,10-dicarbonitrile
derivatives
using
triethanolammonium acetate.
Various catalysts were tested in the synthesis of
2,11-diamino-4,9-diphenyl-4,9-dihydrobenzo[f]pyrano[3,
2-h]chromene-3,10-dicarbonitrile under optimal condi-
tions in ethanol as solvent in comparison with [TEA]
[HOAc]. As shown in Table 5, [TEA][HOAc] was the
best catalyst in the synthesis of the products under these
reaction conditions.
In a possible mechanism that is supported by the
literature37 and shown in Scheme 4, at first malononi-
trile reacts with the carbonyl group of the aldehyde
which is activated by the tri-ethanol ammonium acetate
Scheme 3. Triethanolammonium acetate [TEA]
[HOAc] coordinated with malononitrile
and aldehydes.
conditions, the effect of temperature, amount of cata-
lyst, and kinds of solvent on the model reaction was
studied. The obtained results are summarized in
Tables 1–3. Among the solvents H2O/ethanol (1:1),
Table 1. Effect of various solvents on the synthesis of 2,11-
diamino-4,9-diphenyl-4,9-dihydrobenzo[f] pyrano
[3,2-h]chromene-3,10-dicarbonitrile using [TEA]
[HOAc] (0.143 mol%)
Table 3. Effect of temperature on the synthesis of 2,11-
diamino-4,9-diphenyl-4,9-dihydrobenzo [f] pyrano
[3,2-h]chromene-3,10-dicarbonitrile
Entry
Solvent
Time (h)
Yielda (%)
Entry
Temperature (ꢀC)
Time (h)
Yielda (%)
1
2
3
4
5
Solvent-free
H2O–ethanol (1:1)
Ethanol
H2O
PEG (300)
2
2
1
2
2
30
85
95
40
90
1
2
3
4
r.t.
60
70
Reflux
6.5
3
1
60
85
90
95
1
a Isolated yield.
a Isolated yield.
2
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Triethanolammonium Acetate as Green Ionic Liquid
Table 4. Synthesis of 2,11-diamino-4,9-diphenyl-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile deriv-
atives using [TEA][HOAc] as a green ionic liquid catalyst
Table 4. Continued
Time
(min)
Yielda
(%)
M.p.
Entry
8
Product
ꢀC (Lit.)
Time
(min)
Yielda
(%)
M.p.
390
73
244–248
(241 [36])
Entry
1
Product
ꢀC (Lit.)
60
95
315 (dec.)
(>300
[33])
9
60
72
317
2
3
360
70
279–281
321–323
10
360
76
69
338–341
150
90
11
60
314
4
5
6
60
20
95
85
67
332
337–342
12
13
240
180
84
74
327–330
120
306
316
7
390
85
316–319
14
150
76
311–313
a Isolated yield.
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Khazaei et al.
Table 5. Effect of various catalysts on the synthesis of 2,11-
diamino-4,9-diphenyl-4,9-dihydrobenzo [f] pyrano
[3,2-h]chromene-3,10-dicarbonitrile
temperature within 2 h to give [TEA][HOAc] as a light
yellow viscous liquid.
Catalyst (mol %)
Time (h) Yielda (%)
Typical procedure for the preparation of 2,11-diamino-
4,9-diphenyl-4,9-dihydrobenzo[f]pyrano[3,2-h] chromene-
3,10-dicarbonitrile derivatives
Fe2O3 nanoparticle
ZnFe2O3 nanoparticle
Al2O3 nanoparticle
2.5
2.5
3
40
45
10
95
49
64
32
20
To a mixture of 2,3-naphthalenediol (1 mmol),
malononitrile (2 mmol), aldehydes (2 mmol), and etha-
nol (3 mL) in a round-bottom flask, 0.143 mol % of
triethanolammonium acetate [TEA][HOAc] as a green
IL catalyst was added. The resulting mixture was first
stirred magnetically in ethanol as solvent under reflux
conditions for an appropriate time (Table 4). After
completion of the reaction as observed by thin-layer
chromatography (TLC; n-hexane/ethyl acetate: 2/1), the
solid was washed three times with a 5% aqueous solu-
tion of alcohol and recrystallized from 95% aqueous
ethanol. The spectra of compounds have been reported
in supporting information.
IL [HN+(CH2CH2OH)3][CH3COO−]
1
IL [HN+(CH2CH2OH)3][HSO4
IL[HN+(Et)3][CH3COO−]
TCCA
]
2.5
1
−
3
3
PBNS
a Isolated yield.
as an acidic IL to give intermediate I after removing one
molecule of H2O. 2,3-Naphthalenediol attacks the cyanoo-
lefin compound (I) as a Michael acceptor to give II, which
converts to III. Finally, intramolecular cyclocondensation
reaction of III affords the desired product (Scheme 4).
EXPERIMENTAL
Spectral data of the compounds
Typical procedure for the preparation of
triethanolammonium acetate [TEA][HOAc]
To a 250-mL flask was added triethanolamine
(1 mmol) and acetic acid (1 mmol) at room
2,11-Diamino-4,9-diphenyl-4,9-dihydrobenzo[f]pyra-
no[3,2-h]chromene-3,10-dicarbonitrile (Table 4, entry 1):
m.p: 315ꢀC (dec.). FT-IR ν (cm−1): 3488, 3377, 3249
(NH2) 2188 (CN); 1HNMR (DMSO-d6, 90 MHz): δ
(ppm): 5.23 (s, 2H), 6.88–7.62 (m, 14H), 10.28 (s, 4H).
2,11-Diamino-4,9-di(naphthalen-2-yl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 2): m.p: 279–281ꢀC (dec.). FT-IR ν (cm−1): 3466,
3374 (NH2), 2197 (CN). 1HNMR (DMSO-d6,
400 MHz): δ (ppm): 5.45 (s, 2H), 6.96 (s, 2H), 7.17 (s,
2H), 7.27 (s, 4H), 7.46 (s, 2H), 7.67 (s, 2H), 7.81 (s, 6H),
10.33 (s, 4H). 13CNMR (DMSO-d6, 100 MHz): δ
(ppm): 38.6, 57.6, 109.9, 116.8, 120.4, 123.3, 124.3,
124.9, 125.7, 126.3, 127.4, 128.6, 131.2, 131.8, 132.8,
139.0, 142.9, 145.0, 159.6; MS: m/z = 568 [M+].
2,11-Diamino-4,9-bis(3-bromophenyl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 3): m.p: 321–323ꢀC (dec.). FT-IR ν (cm−1): 3454,
3331, 3196 (NH2), 2197 (CN). 1HNMR (acetone,
500 MHz): δ (ppm): 5.47 (s, 2H), 6.23 (s, 2H), 6.31 (s,
1H), 7.25–7.30 (m, 2H), 7.36–7.42 (m, 6H), 7.51 (s, 1H)
7.55 (s, 2H), 7.91–7.93 (m, 2H); 13C NMR (DMSO-d6,
125 MHz): δ (ppm): 38.4, 59.2, 117.3, 120.6, 122.9,
124.9, 126.9, 127.0, 127.7, 130.4, 130.7, 131.9, 137.7,
148.5, 160.1; MS: m/z = 626 [M+].
Scheme 4. Proposed mechanism for the synthesis of
2,11-diamino-4,9-diphenyl-4,9-dihydroben
zo [f] pyrano [3,2-h]chromene-3,10-
dicarbonitrile derivatives using Triethano-
lammonium acetate.
4
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Triethanolammonium Acetate as Green Ionic Liquid
2,11-Diamino-4,9-bis(4-bromophenyl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 4): m.p: 332ꢀC (dec.). FT-IR ν (cm−1): 3448, 3331,
3190 (NH2), 2194 (CN). 1HNMR (DMSO-d6,
500 MHz): δ (ppm): 5.35 (s, 2H), 6.86 (s, 1H), 7.17 (d,
J = 8.5 Hz, 4H), 7.30–7.31 (m, 2H), 7.42 (d, J = 8.5 Hz,
4H), 7.74–7.78 (m, 2H); 13CNMR (DMSO-d6,
125 MHz): δ (ppm): 38.3, 59.0, 115.8, 117.4, 120.6,
120.8, 124.9, 126.9, 127.5, 127.7, 130.1, 132.6, 137.6,
145.2, 159.9; MS: m/z = 626 [M+].
2,11-Diamino-4,9-bis(4-nitrophenyl)-4,9-dihydroben-
zo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 5): m.p: 337–342ꢀC (dec.). FT-IR ν (cm−1): 3445,
3365, 3191 (NH2), 2190 (CN); 1HNMR (DMSO,
500 MHz): δ (ppm): 5.59 (s, 2H), 7.00 (s, 1H), 7.31 (d,
J = 3.0 Hz, 2H), 7.56 (d, J = 8.5 Hz, 4H), 7.74–7.75 (m,
2H), 8.11 (d, J = 8.5 Hz, 4H); 13CNMR (DMSO-d6,
125 MHz): δ (ppm): 31.4, 57.6, 116.7, 120.6, 124.6,
124.9, 125.0, 125.0, 127.5, 129.0, 137.6, 147.0, 152.9,
160.1; MS: m/z = 558 [M+].
2,11-Diamino-4,9-bis(3-methoxyphenyl)-4,9-dihydr-
obenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 6): m.p: 306ꢀC (dec.); FT-IR ν (cm−1): 3451,
3335, 3191 (NH2), 2193 (CN); 1HNMR (DMSO,
500 MHz): δ (ppm): 3.66 (s, 6H), 5.33 (s, 2H), 6.76
(m, 8H), 7.19 (m, 2H), 7.35 (m, 2H), 7.83 (m, 2H);
13CNMR (DMSO-d6, 125 MHz): δ (ppm): 38.9, 55.7,
59.6, 112.5, 113.9, 117.6, 119.9, 120.8, 124.8, 126.7,
127.8, 130.8, 137.5, 147.4, 160.1, 160.2; MS: m/z
= 528 [M+].
32.8, 51.1, 95.9, 99.5, 114.2, 115.8, 116.7, 122.1, 130.0,
131.3, 145.7, 151.3, 152.6; MS: m/z = 504 [M+].
2,11-Diamino-4,9-bis(2-chlorophenyl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 9): m.p: 317ꢀC (dec.); FT-IR ν (cm−1): 3471, 3439,
3375, 3187 (NH2), 2193 (CN); 1HNMR (DMSO-d6,
500 MHz): δ (ppm): 5.72 (s, 2H), 6.84 (s, 3H), 6.94 (s,
1H), 7.21 (m, 6H), 7.35 (d, J = 3 Hz, 2H), 7.43 (s, 2H),
7.60 (s, 2H); 13CNMR (DMSO-d6, 125 MHz): δ (ppm):
36.5, 58.0, 116.8, 120.1, 124.2, 127.0, 127.7, 129.1,
129.6, 130.6, 131.2, 132.0, 137.9, 142.6, 160.0; MS: m/z
= 538 [M+].
2,11-Diamino-4,9-bis(3-chlorophenyl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 10): m.p: 338–341ꢀC (dec.); FT-IR ν (cm−1): 3451,
3329, 3193 (NH2), 2199 (CN). 1HNMR (DMSO-d6,
500 MHz): δ (ppm): 5.41 (s, 2H), 6.81 (m, 3H),
7.19–7.35 (m, 9H), 5.41 (s, 2H), 7.81 (s, 2H); 13CNMR
(DMSO-d6, 125 MHz): δ (ppm): 38.4, 59.2, 117.3,
120.5, 124.9, 126.6, 127.0, 127.5, 127.6, 127.8, 131.6,
134.2, 137.8, 148.3, 160.1; MS: m/z = 536 [M+].
2,11-Diamino-4,9-bis(2,3-dichlorophenyl)-4,9-dihy-
drobenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile
(Table 4, entry 11): m.p: 314ꢀC (dec.). FT-IR ν (cm−1):
1
3472, 3327, 3190 (NH2), 2196 (CN). HNMR (DMSO-
d6, 500 MHz): δ (ppm): 5.79 (s, 2H), 6.87 (s, 2H), 6.96-
7.02 (m, 1H), 7.21 (m, 3H), 7.31 (m, 2H), 7.45 (m, 2H),
7.52 (m, 2H); 13CNMR (DMSO-d6, 125 MHz): δ
(ppm): 37.3, 57.4, 116.4, 120.0, 123.9, 127.1, 127.5,
129.8, 130.0, 130.1, 130.2, 133.0, 137.8, 145.1, 160.0;
MS: m/z = 606 [M+].
2,11-Diamino-4,9-bis(3-fluorophenyl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 7): m.p: 316–319ꢀC (dec.). FT-IR ν (cm−1): 3460,
2,11-Diamino-4,9-bis(2,4-dichlorophenyl)-4,9-dihy-
drobenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile
(Table 4, entry 12): m.p: 320–330ꢀC (dec.). FT-IR ν
1
3388, 3332, 3199 (NH2), 2197 (CN); HNMR (DMSO-
1
d6, 500 MHz): δ (ppm): 5.39 (s, 2H), 6.81 (m, 3H), 6.96
(m, 1H), 7.07 (m, 2H), 7.21 (m, 3H), 7.33 (m, 3H), 7.42
(s, 1H), 7.80 (m, 2H); 13CNMR (DMSO-d6, 125 MHz):
δ (ppm): 37.6, 58.3, 66.3, 113.7, 116.4, 119.7, 123.1,
124.0, 126.0, 126.9, 130.9, 136.9, 147.8, 159.2, 161.0,
163.4; MS: m/z = 504 [M+].
(cm−1): 3471, 3333, 3187 (NH2), 2194 (CN); HNMR
(DMSO-d6, 500 MHz): δ (ppm): 5.73 (s, 2H), 6.93 (s,
1H), 7.23-7.30 (m, 5H), 7.38 (d, J = 3Hz, 2H),
7.54–7.55 (m, 2H), 7.61 (m, 2H); 13CNMR (DMSO-
d6, 125 MHz): δ (ppm): 31.5, 57.4, 116.3, 120.0,
124.0, 127.0, 127.4, 129.3, 129.9, 132.6, 132.9, 133.2,
137.8, 141.7, 159.8; MS: m/z = 606 [M+].
2,11-Diamino-4,9-bis(2,6-dichlorophenyl)-4,9-dihy-
drobenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile
(Table 4, entry 13): m.p: 316ꢀC (dec.). FT-IR ν
(cm−1): 3473, 3382 (NH2), 2178 (CN); 1HNMR
(Aceton, 500 MHz): δ (ppm): 6.21 (s, 2H), 6.30 (s,
2H), 7.23–7.34 (m, 7H), 7.56–7.61 (m, 3H), 7.70 (d,
2,11-Diamino-4,9-bis(4-fluorophenyl)-4,9-dihydrobe-
nzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 8): m.p: 243–248ꢀC (dec.). FT-IR ν (cm−1): 3476,
1
3385, 3333, 3241, (NH2), 2219 (CN). HNMR (DMSO-
d6, 500 MHz): δ (ppm): 5.27 (s, 2H), 6.51 (s, 1H), 6.51
(s, 1H), 6.82–6.94 (m, 7H), 7.24 (s, 1H), 7.36 (s, 4H),
7.63 (s, 2H); 13CNMR (DMSO-d6, 125 MHz): δ (ppm):
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Khazaei et al.
J = 8 Hz, 2H); 13CNMR (DMSO-d6, 125 MHz): δ
(ppm): 36.2, 53.6, 111.3, 114.5, 120.3, 123.1, 124.7,
125.2, 125.7, 127.6, 129.7, 130.3, 131.7, 135.2, 138.3,
141.1, 145.4, 161.0; MS: m/z = 606 [M+].
2,11-Diamino-4,9-bis(2-methoxyphenyl)-4,9-dihydr-
obenzo[f]pyrano[3,2-h]chromene-3,10-dicarbonitrile (Table 4,
entry 14): m.p: 311–313ꢀC (dec.); FT-IR ν (cm−1): 3470,
3330, 3189 (NH2), 2192 (CN); 1HNMR (DMSO-d6,
400 MHz): δ (ppm): 3.83 (s, 6H), 5.63 (s, 2H), 6.76 (s,
3H), 6.87 (m, 2H), 7.04–7.06 (m, 4H), 7.19 (m, 2H),
7.35–7.37 (m, 2H), 7.77 (m, 2H); 13CNMR (DMSO-d6,
100 MHz): δ (ppm): 32.4, 55.8, 66.3, 111.8, 116.6, 120.0,
121.0, 123.4, 125.7, 126.9, 128.2, 128.6, 132.7, 137.0,
155.8, 159.6; MS: m/z = 528 [M+].
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CONCLUSION
In this work, we reported the catalytic application
of triethanolammonium acetate [TEA][HOAc] as a
green IL and catalyst in the synthesis of 2,11-diamino-
4,9-diphenyl-4,9-dihydrobenzo[f]pyrano[3,2-h]chromene-
3,10-dicarbonitrile derivatives by the one-pot three-
component condensation reaction of 2,3-naphthalenediol,
malononitrile, and various aldehydes with good to excel-
lent yields and in short reaction times in ethanol under
reflux conditions.
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ACKNOWLEDGMENTS
We sincerely acknowledge the financial support
from the Bu-Ali Sina University Research Councils and
the Center of Excellence in Development of Chemistry
Methods (CEDCM).
Supporting information
Additional supporting information is available in
the online version of this article.
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