Synthesis of Some New Polyfunctionalized Pyridines

Article abstract of DOI:10.1002/jhet.3049

5-Methyl-2,4-dihydro-3H-pyrazol-3-one and/or 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one was reacted with arylidenemalononitrile in the presence of sodium alkoxide to give 2-amino-6-alkoxy-4-arylpyridine-3,5-dicarbonitrile 4a–e instead of the reported pyrazolo[3,4-b]pyridine-5-carbonitriles. The same products 4a–e were prepared via reaction of arylidenemalononitrile with sodium alkoxide in an appropriative alcohol. However, the new synthetic route for preparation of their positional isomer 4-amino-6-alkoxy-2-arylpyridine-3,5-dicarbonitrile 7a–j has been achieved via reaction of 2-aminoprop-1-ene-1,1,3-tricarbonitrile with different aromatic aldehydes under the same conditions.

Full text of DOI:10.1002/jhet.3049

Month 2017
Synthesis of Some New Polyfunctionalized Pyridines
*
A. A Amer
Department of Chemistry, Faculty of Science, Sohag University, Sohag 82524, Egypt
*
E-mail: amer_chem@yahoo.com
Received June 26, 2017
DOI 10.1002/jhet.3049
Published online 00 Month 2017 in Wiley Online Library (wileyonlinelibrary.com).
5-Methyl-2,4-dihydro-3H-pyrazol-3-one and/or 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one was
reacted with arylidenemalononitrile in the presence of sodium alkoxide to give 2-amino-6-alkoxy-4-
arylpyridine-3,5-dicarbonitrile 4a–e instead of the reported pyrazolo[3,4-b]pyridine-5-carbonitriles. The
same products 4a–e were prepared via reaction of arylidenemalononitrile with sodium alkoxide in an
appropriative alcohol. However, the new synthetic route for preparation of their positional isomer
4-amino-6-alkoxy-2-arylpyridine-3,5-dicarbonitrile 7a–j has been achieved via reaction of 2-aminoprop-1-
ene-1,1,3-tricarbonitrile with different aromatic aldehydes under the same conditions.
J. Heterocyclic Chem., 00, 00 (2017).
INTRODUCTION
in presence of sufficient amount of alkoxide anion
afforded pyrazolo[3,4-b]pyridine-5-carbonitrile deriva-
tives 3 [16]. While herein, we found that reaction of
5-methyl-2,4-dihydro-3H-pyrazol-3-one 1a and/or 5-
methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one 1b with
arylidenemalononitrile 2 in the presence of sodium
The pyridine ring is fundamental heterocyclic fragment
of naturally occurring biomolecules and synthetic
compounds. Within the last few decades, many efforts
have been made to design diverse synthetic approaches
for pyridine derivatives [1]. Among a wide range of
pyridines, cyanopyridines acquired a special attention due
to their great therapeutic importance. They act as
anticonvulsant [2], antihypertensive [3], anti-inflammatory
[4], antimicrobial [5], antiviral [6], antibacterial [7], anti-
alzaheimer [8], antihistamine [9], and antitumor [10]
drugs. Therefore, synthesis of cyanopyridine derivatives
is the current interest owing to their enormous occurrence
in diverse biologically active compounds. On the other
hand, 2-aminoprop-1-ene-1,1,3-tricarbonitrile is a versa-
tile synthon, and hence it was extensively used in many
reactions to prepare the many heterocyclic compounds
that have diverse pharmaceutical activities [11–15].
alkoxide
gave
2-amino-6-alkoxy-4-arylpyridine-3,5-
dicarbonitrile 4a–e instead of pyrazolo[3,4-b]pyridine-
5-carbonitriles 3 [16]. Furthermore, the same product
4-amino-2-alkoxy-6-arylpyridine-3,5-dicarbonitrile 4 was
prepared by refluxing arylidenemalononitrile 2 with
sodium alkoxide in the appropriative alcohol for 3 h, this
result shows that the pyrazolone 1a,b do not have any
role in this reaction (Scheme 1).
The chemical structures of the synthesized 2-amino-6-
alkoxy-4-arylpyridine-3,5-dicarbonitrile
4a–e
were
confirmed by their spectral (IR, 1H, 13C NMR) and
elemental analyses data. For example, the IR spectrum of
4b showed absorption bands at 3334 and 3232 cmÀ1
characteristic for NH2 group beside the nitrile stretching
Looking to these multifold properties exhibited by
cyanopyridines, we report herein the uses of the
2-aminoprop-1-ene-1,1,3-tricarbonitrile as a convenient
synthon for preparation of new polyfunctionalized
4-amino-6-alkoxy-2-arylpyridine-3,5-dicarbonitrile in the
hope that they may possess different biological activities.
1
vibration bands at 2215 cmÀ1. H NMR spectrum of 4b
exhibited two singlet signals at δ 3.01 and 3.98, which
are characteristic for N(CH3)2 and OCH3 protons, in
addition to two doublet signals at δ 6.83 and 7.39 with
coupling constant J = 8 Hz corresponding to aromatic
protons, also, it exhibited broad singlet signal at δ
7.69 ppm for the amino group. Its 13C NMR spectrum
exhibited data consistent with the established structure in
which the methoxide carbon atom appeared at δ 55.03:
carbons of N(CH3)2 group at δ 40.15; the nitrile carbons
at δ 111.76, 116.04, while the pyridine C-3 and C-5
RESULTS AND DISCUSSION
It has been reported that reaction of 5-methyl-2,4-
dihydro-3H-pyrazol-3-one 1a with arylidenemalononitrile
© 2017 Wiley Periodicals, Inc.

A. A. Amer
Vol 000
Scheme 1. Synthesis of 2-amino-6-alkoxy-4-arylpyridine-3,5-dicarbonitrile 4a–e.
appeared at δ 83.11, 83.32, finally, the other aromatic
carbons are characterized by peaks at δ 116.57, 120.82,
130.20, 152.00, 161.19, 161.94, and 166.60 ppm.
aromatic aldehydes under the same reaction conditions
(Method B, Scheme 2).
The chemical structures of the new products 7a–j were
established by their spectral (IR, 1H, 13C NMR) and
elemental analyses data. The IR spectrum of 7a
contains bands assignable for the amino stretching
vibration absorption appeared at 3336, 3238 cmÀ1
beside the nitrile stretching vibration bands at
There are many reported procedures for the synthesis of
2-amino-6-alkoxy-4-arylpyridine-3,5-dicarbonitrile 4 via
multi-components reaction between aldehyde and two
equivalent moles of malononitrile [17–20], but there is
not anyone for synthesis of their positional isomer 4-
amino-6-alkoxy-2-arylpyridine-3,5-dicarbonitrile 7. While
searching for possible synthesis of 4-amino-6-alkoxy-2-
arylpyridine-3,5-dicarbonitrile 7, we found out that 2-
2204 cmÀ1 1H NMR spectrum of 7a showed the
.
presence of two singlet signals at δ 3.03 and δ 4.02
characteristic of N(CH3)2 and OCH3 groups,
respectively, also, it exhibited singlet signal at δ 7.30
for the amino group and two doublet signals at δ 7.81
and 7.89 ppm for aromatic protons. 13C NMR spectrum
of 7a exhibited data consistent with the established
structure in which the methoxy carbon is characterized
by peak at δ 54.84, in addition to the N(CH3)2 at δ
40.13, while nitrile carbons appears at δ114.28, 111.55.
Finally, the pyridine C-3 and C-5 appeared at δ 75.19
and 84.78, while the other aromatic carbon are
aminoprop-1-ene-1,1,3-tricarbonitrile
5 has not been
previously studied in such reactions. However, it was
found that stirring of malononitrile dimer 5 with aromatic
aldehyde at room temperature in presence of sodium
alkoxide afforded 2-amino-4-arylbuta-1,3-diene-1,1,3-
tricarbonitrile 6, which was refluxed with sodium
alkoxide to give the targeted products 7a–j (Method A,
Scheme 2). Also, the same products 7a–j were directly
prepared via refluxing of malononitrile dimer 5 with
Scheme 2. Synthesis of 4-amino-6-alkoxy-2-arylpyridine-3,5-dicarbonitrile 7a–j.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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Polyfunctionalized Pyridines
Scheme 3. Plausible mechanism for the formation of 4 and 7.
characterized by peaks at δ 116.99, 123.72, 130.69,
152.61, 160.35, 163.16, and 165.94 ppm.
respectively. Elemental analyses were obtained on a
Perkin-Elmer CHN-analyzer model.
The formation of 4 was assumed to take place through
hydrolysis of arylidenemalononitrile 2 giving aromatic
General procedure for the synthesis of compounds 4a–e.
Method A: Pyrazolone 1a,b (3 mmol) was added to a
aldehyde and malononitrile, then
a
Knoevenagel
freshly prepared sodium alkoxide solution (4 mmol of
sodium in 50 mL of each of absolute ethanol or
methanol). Arylidenemalononitrile 2 (2 mmol) was then
added and the reaction mixture was heated under reflux
for about 3 h. After completion of reaction (monitored
with TLC), the reaction mixture was cooled to RT and
poured in ice-cold water. The solid deposited was then
collected by filtration, washed several times with water,
and recrystallized from suitable solvent.
condensation and Michael addition between aromatic
aldehyde and two equivalent malononitrile afforded a
tetracyano intermediate A. Subsequently, cyclization took
place due to alkoxide nucleophilic attack at one of the
nitrile groups through path I to give 2-amino-6-alkoxy-
4-arylpyridine-3,5-dicarbonitrile 4. While the formation
of their positional isomer 7 was assumed to take place
through dimerization of malononitrile giving malononitrile
dimer 5, which was condensed with aromatic aldehydes
to afford 6 followed by alkoxide addition to nitrile
group and cyclization to dihydropyridine E, which
underwent aromatization by air oxidation to produce 4-
amino-6-alkoxy-2-arylpyridine-3,5-dicarbonitrile 7 (Path
II, Scheme 3).
Method B: A mixture of arylidenemalononitrile 2
(2 mmol) and sodium alkoxide (3 mmol of sodium in
50 mL of each of absolute ethanol or methanol) was
heated under reflux for about 3 h. After completion of
reaction (monitored with TLC), the reaction mixture was
cooled to RT and poured in ice-cold water. The solid
precipitate was then collected by filtration, washed
several times with water, and recrystallized from suitable
solvent.
EXPERIMENTAL
2-Amino-6-methoxy-4-phenylpyridine-3,5-dicarbonitrile
Melting points were detected with a Kofler melting
points apparatus and uncorrected. Infrared spectra were
recorded with a FT-IR-ALPHBROKER-Platinum-ATR
spectrometer and are given as cmÀ1using the attenuated
(4a).
Yield (Method A, 53%; Method B, 61%); mp
263°C (reported 259–261)[17]; FTIR (cmÀ1) 3408,
3329, 3187, 2970, 2911, 2214, 1647;1H NMR
(400 MHz, DMSO-d6) δ 7.92 (s. br., 2H, NH2), 7.57 (s,
3H, 3CHarom.), 7.53 (s, 2H, 2CH arom.), 3.99 (s, 3H,
OCH3); 13C NMR (100 MHz, DMSO-d6) δ 166.25,
1
total reflection method. H NMR and 13C NMR spectra
for all compounds were recorded in DMSO-d6on a
Bruker Bio Spin AG spectrometer at 400 and 100 MHz,
Journal of Heterocyclic Chemistry
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A. A. Amer
Vol 000
161.66, 161.24, 134.64, 130.69, 129.10, 128.78, 115.83,
115,36, 84.03, 83.82, 55.19; Anal. Calcd. for
C14H10N4O (250): C, 67.19; H, 4.03; N, 22.39. Found:
C, 67.31; H, 3.91; N, 22.07.
2-Amino-6-methoxy-4-[4-(dimethylamino)phenyl]-pyridine-
3,5-dicarbonitrile (4b). Yield (Method A, 49%; Method B,
methoxide for
3
h. After completion of reaction
(monitored with TLC), the reaction mixture was cooled
to RT and poured in ice-cold water. The solid deposited
was then collected by filtration, washed several times
with water, and recrystallized from suitable solvent.
Method B: Equimolar amounts (2 mmol) of aromatic
aldehydes, 2-aminoprop-1-ene-1,1,3-tricarbonitrile (0.4 g),
and sodium alkoxide solution (4 mmol of sodium in
50 mL of each of absolute ethanol or methanol) were
heated at reflux for about 3 h. After completion of
reaction (monitored with TLC), the reaction mixture was
cooled to RT and poured in ice-cold water. The solid
deposited was then collected by filtration, washed
several times with water, and recrystallized from suitable
55%); mp 281°C; FTIR (cmÀ1) 3471, 3421, 3334, 3232,
2948, 2215, 1642;1H NMR (400 MHz, DMSO-d6) δ 7.69
(s. br., 2H, NH2), 7.39 (d, j = 8 Hz, 2H, 2CHarom.), 6.83
(d, j = 8 Hz, 2H, 2CHarom.), 3.98 (s, 3H, OCH3), 3.01 (s,
6H, N(CH3)2); 13C NMR (100 MHz, DMSO-d6) δ
166.60, 161.94, 161.19,152.00, 130.20, 120.82, 116.57,
116.04, 111.76, 83.32, 83.11, 55.03, 40.15; Anal. Calcd.
for C16H15N5O (293): C, 65.52; H, 5.15; N, 23.88.
Found: C, 65.60; H, 5.01; N, 23. 56.
2-Amino-6-methoxy-4-(4-methoxyphenyl)pyridine-3,5-
solvent.
4-Amino-2-[4-(dimethylamino)phenyl]-6-methoxypyridine-
dicarbonitrile (4c).
Yield (Method A, 51%; Method B,
3,5-dicarbonitrile (7a). Yield (Method A, 71%; Method
B, 63%); mp 291°C; FTIR (cmÀ1) 3336, 3238, 3018,
2898, 2858, 2204, 1648;1H NMR (400 MHz,
DMSO-d6) δ 7.89 (d, j = 8 Hz, 2H, 2CHarom.), 7.30 (s,
br, 2H, NH2), 7.81(d, j = 8 Hz, 2H, 2CHarom.), 4.02 (s,
3H, OCH3), 3.03 (s, 6H, N(CH3)2); 13C NMR
59%); mp 298°C; FTIR (cmÀ1) 3422, 3327, 3229, 3031,
2985, 2940, 2210, 1634;1H NMR (400 MHz, DMSO-d6)
δ 7.96 (s. br., 2H, NH2), 7.49 (d, j = 9 Hz, 2H,
2CHarom.), 7.12 (d, j = 9 Hz, 2H, 2CHarom.), 3.97 (s, 3H,
OCH3), 3.85 (s, 3H, OCH3); 13C NMR (100 MHz,
DMSO-d6) δ 166.34, 161.72, 161.23,160.90, 130.60,
126.50, 116.17, 115.73, 114.51, 83.78, 83.62, 55.81,
55.16; Anal. Calcd. for C15H12N4O2 (280): C, 64.28; H,
(100 MHz, DMSO-d6)
δ 165.94, 163.16, 160.35,
152.61, 130.69, 123.72, 116.99, 114.28, 111.55, 84.78,
75.19, 54.84, 40.13; Anal. Calcd. for C16H15N5O (293):
C, 65.52; H, 5.15; N, 23.88. Found: C, 65.49; H, 5.01;
4.32; N, 19.99. Found: C, 64.31; H, 4.19; N, 19.62.
2-Amino-6-ethoxy-4-phenylpyridine-3,5-dicarbonitrile
(4d). Yield (Method A, 49%; Method B, 54%); mp 239–
N, 23.53.
4-Amino-2-methoxy-6-(4-methoxyphenyl)pyridine-3,5-
240°C (reported 238–239)[17]; FTIR (cmÀ1) 3459, 3316,
3214, 2978, 2918, 2213, 1620;1H NMR (400 MHz,
DMSO-d6) δ 7.96 (s. br., 2H, NH2), 7.57 (s, 3H,
3CHarom.), 7.53 (s, 2H, 2CHarom.), 4.45 (q, j = 7 Hz,
2H, CH2), 1.35 (t, j = 7 Hz, 3H, CH3); 13C NMR
dicarbonitrile (7b). Yield (Method A 69%; Method B 59);
mp 291°C; FTIR (cmÀ1) 3351, 3236, 3008, 3031, 2960,
2916, 2220, 1672;1H NMR (400 MHz, DMSO-d6) δ 7.88
(s. br, 2H, NH2), 7.47 (s, 2H, 2CHarom.), 7.11(s, 2H,
2CHarom.), 4.02 (s, 3H, OCH3), 3.86 (s, 3H, OCH3); 13C
(100 MHz, DMSO-d6)
δ 165.82, 161.63, 161.26,
NMR (100 MHz, DMSO-d6)
δ
166.25, 163.33,
134.65, 130.69, 129.11, 128.80, 115.93, 115,48, 84.98,
83.60, 63.83, 14.70; Anal. Calcd. for C15H12N4O (264):
C, 68.17; H, 4.58; N, 21.20. Found: C, 68.09; H, 4.29;
162.00,160.07, 131.01, 129.53, 116.31, 114.35, 113.87,
86.57, 76.29, 55.94, 55.09; Anal. Calcd. for C15H12N4O2
(280): C, 64.28; H, 4.32; N, 19.99. Found: C, 64.38; H,
N, 21.11.
4.21; N, 19.72.
2-Amino-6-ethoxy-4-(4-methoxyphenyl)pyridine-3,5-
4-Amino-2-methoxy-6-(3-methylphenyl)pyridine-3,5-
dicarbonitrile (4e).
Yield (Method A, 50%; Method B,
dicarbonitrile (7c). Yield (Method A, 62%; Method B,
57%); mp 268–270°C; FTIR (cmÀ1) 3412, 3336, 3234,
3011, 2944, 2213, 1653;1H NMR (400 MHz, DMSO-d6)
δ 7.97 (br, 2H, NH2), 7.48 (t, j = 8 Hz, 1H, 1CHarom.),
56%); mp 200–202°C (reported 199–200)[17]; FTIR
(cmÀ1) 3412, 3338, 3238, 2967, 2935, 2212, 1650;1H
NMR (400 MHz, DMSO-d6) δ 7.90 (s. br., 2H, NH2),
7.49 (d, j = 8 Hz, 2H, 2CHarom.), 7.12 (d, j = 8 Hz, 2H,
2CHarom.), 4.44 (q, j = 8 Hz, 2H, CH2), 3.85 (s, 3H,
OCH3), 1.35 (t, j = 8 Hz, 3H, CH3); 13C NMR
(100 MHz, DMSO-d6) δ 165.96, 161.74, 161.25,160.95,
130.56, 126.64, 116.13, 115.63, 114.54, 84.04, 83.61,
63.75, 55.83, 14.70; Anal. Calcd. for C16H14N4O2 (294):
C, 65.30; H, 4.79; N, 19.04. Found: C, 65.53; H, 4.59;
N, 18.82.
7.14 (d, j = 8 Hz, 1H, 1CHarom.), 7.08 (m, 2H, 2CHphenyl
)
3.98 (s, 3H, OCH3), 3.82 (s, 3H, OCH3); 13C NMR
(100 MHz, DMSO-d6) δ 166.20, 161.64, 160.97, 159.56,
135.87, 130.29, 120.91, 115.82, 115.17, 115.35, 114.55,
83.97, 79.20, 55.83, 55.17; Anal. Calcd. for C15H12N4O2
(280): C, 64.28; H, 4.32; N, 19.99. Found: C, 64.09; H,
4.19; N, 19.56.
4-Amino-2-(4-chlorophenyl)-6-methoxypyridine-3,5-
dicarbonitrile (7d). Yield (Method A, 70%; Method B,
59%); mp 245–246°C; FTIR (cmÀ1) 3519, 3382, 3326,
3219, 2953, 2221, 1650; 1H NMR (400 MHz,
DMSO-d6) δ 8.05 (br, 2H, NH2), 7.66 (d, j = 8 Hz,
General procedure for the synthesis of compounds 7a–j.
Method A: 0.4 g (1.6 mmol) of 2-amino-4-(aryl)buta-1,3-
diene-1,1,3-tricarbonitrile (6) was refluxed in 35 mL
methanol containing 0.11 g (2.0 mmol) of sodium
Journal of Heterocyclic Chemistry
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Polyfunctionalized Pyridines
2H, 2CHarom.), 7.57 (d, j = 8 Hz, 2H, 2CHarom.), 3.98 (s,
3H, OCH3); Anal. Calcd. for C14H9ClN4O (284.5): C,
59.06; H, 3.19; N, 19.68. Found: C, 59.16; H, 3.25; N,
4-Amino-2-ethoxy-6-(4-hydroxyphenyl)pyridine-3,5-
dicarbonitrile (7j).
Yield (Method A, 58%; Method B,
51%); mp 198°C dec.; FTIR (cmÀ1) 3454, 3329, 3227,
2994, 2953, 2217, 1657;1H NMR (400 MHz, DMSO-d6)
δ 9.97 (br, 1H, OH), 7.76 (br, 2H, NH2), 7.36 (d,
j = 8 Hz, 2H, 2CHphenyl), 6.92 (d, j = 8 Hz, 2H,
2CHphenyl), 4.44 (q, j = 7 Hz, 2H, CH2), 1.35 (t, j = 7 Hz,
3H, CH3); 13C NMR (100 MHz, DMSO-d6) δ 166.00,
161.77, 161.25, 159.79, 130.59, 124.97, 116.24, 115.83,
115.72, 83.91, 77.48, 63.72, 14.69; Anal. Calcd. for
C15H12N4O2 (280): C, 64.28; H, 4.32; N, 19.99. Found:
C, 63.11; H, 3.80; N, 19.71.
19.38.
4-Amino-2-(4-hydroxyphenyl)-6-methoxypyridine-3,5-
dicarbonitrile (7e).
Yield (Method A, 60%; Method B,
51%); mp 228–230°C dec.; FTIR (cmÀ1) 3444, 3327,
3222, 2954, 2918, 2214, 1644;1H NMR (400 MHz,
DMSO-d6) δ 9.90 (br, 1H, OH), 7.76 (s. br, 2H, NH2),
7.36 (d, j = 7 Hz, 2H, 2CHphenyl), 6.92 (d, j = 7 Hz, 2H,
2CHphenyl), 3.98 (s, 3H, OCH3); Anal. Calcd. for
C14H10N4O2 (266): C, 63.15; H, 3.79; N, 21.04. Found:
C, 63.01; H, 3.57; N, 20.81.
4-Amino-2-(furan-2-yl)-6-methoxypyridine-3,5-
dicarbonitrile (7f). Yield (Method A, 68%; Method B,
REFERENCES AND NOTES
57%); mp 268°C; FTIR (cmÀ1) 3330, 3221, 3007,
2982, 2214, 1651;1H NMR (400 MHz, DMSO-d6) δ
8.02 (s, 1H, CHfuryl) 7.44 (s. br, 3H, NH2 + CHfuryl),
6.771(s, 1H, CHfuryl), 4.02 (s, 3H, OCH3); 13C NMR
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δ 166.38, 160.16, 151.44,
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23.07.
4-Amino-2-(4-chlorophenyl)-6-ethoxypyridine-3,5-
dicarbonitrile (7 g). Yield (Method A, 68%; Method B,
55%); mp 193°C; FTIR (cmÀ1) 3465, 3327, 3220, 2980,
2928, 2215, 1620; 1H NMR (400 MHz, DMSO-d6) δ
7.98 (br, 2H, NH2), 7.66 (d, j = 9 Hz, 2H, 2CHarom.),
7.56 (d, j = 9 Hz, 2H, 2CHarom.), 4.45 (q, j = 7 Hz, 2H,
CH2), 1.36 (t, j = 7 Hz, 3H, CH3); 13C NMR (100 MHz,
DMSO-d6) δ 165.75, 161.57, 160.09, 135.64, 133.51,
130.81, 129.29, 115.78, 115,34, 84.01, 80.62, 63.89,
14.68; Anal. Calcd. for C15H11ClN4O (298.5): C, 60.31;
H, 3.71; N, 18.76. Found: C, 59.83; H, 3.19; N, 18.07.
4-amino-2-[4-(dimethylamino)phenyl]-6-ethoxypyridine-3,5-
dicarbonitrile (7 h). Yield (Method A, 66%; Method B,
50%); mp 239–241°C; FTIR (cmÀ1) 3430, 3334, 3230,
3001, 2968, 2213, 1637;1H NMR (400 MHz, DMSO-d6)
δ 7.77 (s br, 2H, NH2), 7.39 (d, j = 8 Hz, 2H,
2CHarom.), 6.83 (d, j = 8 Hz, 2H, 2CHarom.), 4.43 (q,
j = 7 Hz, 2H, CH2), 301 (s, 6H, N(CH3)2), 1.35 (t,
j = 7 Hz, 3H, CH3); Anal. Calcd. for C17H17N5O (307):
C, 66.43; H, 5.58; N, 22.79. Found: C, 66.57; H, 5.41;
N, 22.61.
4-Amino-2-ethoxy-6-(3-methoxyphenyl)pyridine-3,5-
dicarbonitrile (7i). Yield (Method A, 62%; Method B,
51%); mp 211°C; FTIR (cmÀ1) 3425, 3336, 3234,
3064, 2983, 2941, 2214, 1644;1H NMR (400 MHz,
DMSO-d6) δ 7.93 (br, 2H, NH2), 7.48 (t, j = 7 Hz,
1H, 1CHarom), 7.10 (m, 3H, 3CHarom), 4.44 (q,
j = 7 Hz, 2H, CH2) 3.82 (s, 3H, OCH3), 1.35 (t,
j = 7 Hz, 3H, CH3); Anal. Calcd. for C16H14N4O2
(294): C, 65.30; H, 4.79; N, 19.04. Found: C, 65.07;
H, 4.52; N, 18.86.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet