Recyclization of 2,6-diamino-4-aryl(cyclohexyl)-3,5-dicyano-4H-thio(seleno) pyrans

Article abstract of DOI:10.1007/s11176-005-0475-8

Recyclization of 2,6-diamino-4-aryl(cyclohexyl)-3,5-dicyano-4H-thio(seleno) pyrans in the presence of an equimolar amount of an α-bromo carbonyl compound, ethyl iodide, 1,2-dibromoethane, or 3-chlorophenyl isocyanate yields, respectively, 3-aryl(cyclohexy

Full text of DOI:10.1007/s11176-005-0475-8

Russian Journal of General Chemistry, Vol. 75, No. 10, 2005, pp. 1610 1617. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 10, 2005,
pp. 1688 1694.
Original Russian Text Copyright
2005 by Dyachenko, Chernega, Garasevich.
Recyclization of 2,6-Diamino-4-aryl(cyclohexyl)-3,5-dicyano-
4H-thio(seleno)pyrans
V. D. Dyachenko*, A. N. Chernega**, and S. G. Garasevich***
* Shevchenko National Pedagogical University, Lugansk, Ukraine
** Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
*** Shevchenko National University, Kiev, Ukraine
Received September 21, 2004
Abstract Recyclization of 2,6-diamino-4-aryl(cyclohexyl)-3,5-dicyano-4H-thio(seleno)pyrans in the
presence of an equimolar amount of an -bromo carbonyl compound, ethyl iodide, 1,2-dibromoethane, or
3-chlorophenyl isocyanate yields, respectively, 3-aryl(cyclohexyl)-2-[thiazol(selenazol)-2-yl]acrylonitriles,
6-amino-4-phenyl-2-ethylsulfanyl-1,4-dihydropyridine-3,5-dicarbonitrile, 5-amino-7-phenyl-2,3,4,7-tetrahydro-
thiazolo[3,2-a]pyridine-6,8-dicarbonitrile, or N,N -bis(3-chlorophenyl)urea.
It was shown previously [1 3] that recyclization
of 2,6-diamino-4-alkyl(aryl, heteryl)-3,5-dicyano-4H-
thio(seleno)pyrans in refluxing ethanol in the presence
of N-methylmorpholine yields N-methylmorpholinium
6-amino-4-alkyl(aryl, heteryl)-3,5-dicyano-2-thio(sele-
no)lates. With hydrazine or aniline used as the base
in the reaction, 2,6-dihydrazino-4-phenyl-3,5-dicyano-
pyridine or 6-amino-2-phenylamino-4-phenyl-3,5-di-
cyanopyridine, respectively, is formed [4]. At the
same time, with pyridinium ylides or aliphatic ketones
used as CH acids in this recyclization, 3-(1-pyridinio)-
5-cyano-3,4-trans-1,2,3,4-tetrahydro-6-pyridinethio-
late [5] or 5,6-dialkyl-4-aryl-3-cyanopyridine-2(1H)-
thiones [6], respectively, are formed as a result of
interchange of the methylene components.
involves regioselective S-alkylation of A with ethyl
iodide to the corresponding 1,4-dihydropyridine IV.
Replacement of ethyl iodide in this reaction by
1,2-dibromoethane led to the formation of 5-amino-7-
phenyl-2,3,4,7-tetrahydrothiazolo[3,2-a]pyridine-6,8-
dicarbonitrile V. Thus, in this case the reaction goes
beyond formation of sulfide D and involves subse-
quent chemoselective intramolecular alkylation of the
nitrogen atom of the dihydropyridine ring with the
bromoethyl group, yielding heterocyclic system V.
The spectral characteristics confirm the structures
of III V. In particular, their IR spectra contain charac-
teristic absorption bands of stretching vibrations of a
conjugated cyano group (see Experimental, Tables 1,
1
Here we report on the recyclization of 2,6-diamino-
4-aryl(cyclohexyl)-3,5-dicyano-4H-thio(seleno)pyrans
Ia Ii in the presence of an equimolar amount of an
-bromo carbonyl compound IIa IIm, ethyl iodide,
1,2-dibromoethane, or 3-chlorophenyl isocyanate. The
reactions of Ia Ii with -bromo ketones IIa IIm in
refluxing ethanol yield substituted acrylonitriles IIIa
IIIz and III . This reaction pathway involves opening
of the thio(seleno)pyran ring with the formation of
unstable thio(seleno)amides of aryl(cycloalkyl)methyl-
enecyanoacetic acid A and malonodinitrile. This is
followed by the Hantzsch reaction yielding 2-aryl(cy-
clohexyl)-2-[thiazol(selenazol)-2-yl]acrylonitriles
IIIa IIIz and III , which are potentially bioactive
compounds [7, 8]. Recyclization of thiopyran Ih with
an equimolar amount of ethyl iodide yields 6-amino-4-
phenyl-2-ethylsulfanyl-1,4-dihydropyridine-3,5-dicar-
bonitrile IV. The scheme of its formation apparently
2). The H NMR spectra of dihydropyridines IV and
V contain, along with the proton signals of the sub-
stituents in the expected regions, a singlet of the C4H
proton of the dihydropyridine ring at
4.24 and
4.27 ppm, respectively (see Experimental), in agree-
ment with data from [9 11].
The reaction of thiopyran Ia with 3-chlorophenyl
isocyanate in refluxing toluene yielded N,N -bis(3-
chlorophenyl)urea VI. Apparently, its formation be-
came possible owing to the presence of 2-chloroaniline
E in the reaction mixture. Compound E, in turn, could
be formed by decomposition of hypothetical unstable
3-chlorophenylthiocarbamic acid F formed by the
reaction of 3-chlorophenyl isocyanate with H2S re-
leased in the course of transformation of A into aryl-
methylenemalonodinitrile G. Note that the addition of
H2S to the nitrile group is reversible [12].
1070-3632/05/7510-1610 2005 Pleiades Publishing, Inc.

RECYCLIZATION OF 2,6-DIAMINO-4-ARYL(CYCLOHEXYL)-3,5-DICYANO-..
1611
R
R
CN
X
R
CN
NC
N
CN
R
NH2
H2N
X
CN
IIIa III
Ia Ij
G
R
3-ClC6H4NCO
H2X
Br
IIa IIm
O
O
Ph
R
[3-ClC6H4NHCSH]
EtI
CN
SEt
CN
F
H2N
COS
H2N
X
B
A
[3-ClC6H4NH2]
CH2(CN)2,
Br(CH2)2Br
CH2(CN)2
F
Ph
3-ClC6H4NCO
Ph
CN
SEt
NC
CN
NC
O
C
>N
HN
SCH2CH2Br
H2N
N
H
D
NH
HN
C
Cl
Cl
VI
Ph
Ph
CN
S
NC
CN
SEt
NC
H2N
H2N
N
N
H
IV
V
I, X = S (a f, h j), Se (g); R = 4-EtC6H4 (a), 3-PhOC6H4 (b), 4-NO-3-MeOC6H3 (c), 4-PhC6H4 (d), cyclohexyl (e),
1-naphthyl (f), Ph (g, h), 4-ClC6H4 (i), 2,4-(EtO)2C6H3 (k). II, R = 4-PhC6H4 (a), 3-coumarinyl (b), Ph (c), 4-FC6H4 (d),
cyclopropyl (e), 4-BuC6H4 (f), 4-MeOC6H4 (g), 4-MeC6H4 (h), 4-ClC6H4 (i), 2-HOC6H4 (j), 8-bromocoumarin-3-yl (k),
6-methyl-3-cyano-2-ethylsulfanylpyridin-5-yl (l), 4-cyclohexylphenyl (m). III, X = S (a h, j z, ), Se (i); R = 4-EtC6H4
(a), 1-naphthyl (b e), 2,4-(EtO)2C6H3 (f, g), 3-PhOC6H4 (h, q u), Ph (i l), 4-NO-3-MeOC6H3 (m p), 4-ClC6H4 (v, x, y),
cyclohexyl (w, z), 4-PhC6H4 ( ); R = 3-coumarinyl (a, p, s), 4-PhC6H4 (b, f, h, l, n), Ph (c, o, t), 4-FC6H4 (d), cyclo-
propyl (e), 4-BuC6H4 (g, m, x), 4-MeOC6H4 (i, k, u, ), 4-MeC6H4 (j), 4-cyclohexylphenyl (q), 4-ClC6H4 (r, z),
6-methyl-2-ethylsulfanyl-3-cyanopyridin-5-yl (v), 8-bromocoumarin-3-yl (w), 2-HOC6H4 (y).
The structure of VI was unambiguously confirmed
by single crystal X-ray diffraction. The general view
of the molecule of VI and its main geometric param-
eters are shown in Fig. 1. The main bond lengths ( )
and bond angles (deg) are as follows: N1 C1 1.348(3),
the bond angles at this atom is 359.9 . The very effi-
cient n(N1) (C1=O1) conjugation causes shortening
of the N1 C1 bond to 1.348(3)
(typical Nsp Csp
2
2
bond length is 1.43 1.45
[13, 14]). Note that the
bond lengths and bond angles in VI are relatively
close to those found in the previously studied diaryl
derivatives of urea [15]. The molecules of VI in the
crystal are linked in infinite chains (Fig. 2) through
bifurcate hydrogen bonds N1 H1 O1 of medium
strength [16] [N1 O1 2.856(3), H1 O1 2.12(4),
N1 C2 1.412(3), O1 C1 1.238(5), C1 N1 1.348(3),
C1N1C2 123.9(2), O1C1N1 122.3(2), O1C1N1 122.3(2),
N1C1N1 115.4(3). The central group C2N1C1O1N1C2
is approximatley planar: The deviations of atoms from
the least-squares plane do not exceed 0.054 , and the
torsion angles C2N1C1O1 and C2N1C1N1 are 6.8
and 173.2 , respectively. The benzene rings C2 7 and
N1 H1 0.80(4)
,
N1H1O1 154(3) ].
Urea is one of a few presently known organic crys-
tals with large birefringence and high nonlinear coeffi-
cients in combination with good transparence (down
to 200 nm) and radiation resistance, which makes it
7
C2 are turned relative to this plane by 51.4 , form-
ing with each other a dihedral angle of 85.6 . The N1
atom has a trigonal planar configuration: the sum of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005

1612
DYACHENKO et al.
Table 1. Yields, constants, and elemental analyses of substituted acrylonitriles IIIa IIIz and III
Found, %
H
Calculated, %
Comp. Yield,
mp,
C
Formula
no.
%
C
N
C
H
N
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
85
81
76
79
82
90
72
79
77
72
88
68
84
70
81
92
94
84
91
75
80
84
70
84
88
80
77
170 172
195 197
129 131
143 145
100 102
174 176
94 95
132 133
120 121
144 145
122 123
188 190
100 101
185 186
149 150
178 180
150 151
157 158
161 163
108 109
118 119
200 202
193 195
88 89
71.75
80.95
77.95
73.97
75.32
74.22
72.02
78.81
64.30
75.29
71.52
78.85
70.61
72.95
68.13
65.48
77.72
69.22
72.18
75.60
72.98
59.51
57.99
69.64
63.69
65.60
75.94
4.12
4.14
3.99
3.50
4.50
5.16
6.44
4.13
3.71
4.58
4.35
4.19
5.49
4.30
4.05
3.39
5.48
3.49
3.48
4.12
4.37
3.42
3.75
4.88
3.12
5.02
4.49
7.06
6.59
8.13
7.71
9.09
6.07
6.31
6.02
7.52
9.14
8.68
7.48
7.12
6.77
8.19
7.15
5.89
6.60
6.14
7.23
6.71
13.09
6.21
7.19
8.05
8.43
6.97
C23H16N2O2S
C28H18N2S
C22H14N2S
C22H13FN2S
C19H14N2S
C28H24N2O2S
C26H28N2O2S
C30H20N2OS
C19H14N2OSe
C19H14N2S
71.86
81.13
78.08
74.14
75.47
74.31
72.19
78.92
62.47
75.47
71.68
79.09
70.74
73.15
68.25
65.66
77.89
69.48
72.31
75.77
73.15
59.64
57.15
69.74
63.81
65.74
76.12
4.20
4.38
4.17
3.68
4.67
5.35
6.52
4.42
3.86
4.67
4.43
4.43
5.68
4.42
4.22
3.51
5.67
3.64
3.60
4.24
4.42
3.58
3.88
5.05
3.27
5.21
4.60
7.29
6.76
8.28
7.86
9.26
6.19
6.48
6.14
7.67
9.26
8.80
7.69
7.17
6.82
8.38
6.96
6.06
6.75
6.25
7.36
6.82
13.25
6.35
7.39
8.27
8.52
7.10
IIIj
IIIk
IIIl
C19H14N2OS
C24H16N2S
IIIm
IIIn
IIIo
IIIp
IIIq
IIIr
IIIs
IIIt
IIIu
IIIv
IIIw
IIIx
IIIy
IIIz
III
C23H22N2O2S
C25H18N2O2S
C19H14N2O2S
C22H14N2O4S
C30H26N2OS
C24H15ClN2OS
C27H16N2O3S
C24H16N2OS
C25H18N2O2S
C21H15ClN4S2
C21H17BrN2O2S
C22H19ClN2S
C18H11ClN2OS
C18H17ClN2S
C25H18N2OS
179 180
98 100
160 162
a
Fluorescence is observed under UV irradiation.
Table 2. IR and 1H NMR spectra of substituted acrylonitriles IIIa IIIz and III
1H NMR spectrum, , ppm (J, Hz)
Comp. IR spectrum,a
C3H (s),
C5H (s)
1
no.
cm ,
other signals
of thiazole
IIIa
2218, 1738
(C=O)
8.49, 8.31
1.32 t (3H, Me, J 6.24), 2.73 q (2H, CH2), 7.39 m (4H, H arom.), 7.62 m (1H,
H arom.), 7.78 d (1H, H arom., J 6.81), 7.97 d (2H, H arom., J 7.14), 8.88 s
(1H, C4H of coumarin)
IIIb
IIIc
IIId
2217
2214
2219
9.05, 8.40
9.07, 8.39
9.01, 8.30
7.36 7.88 m (12H, H arom.), 8.01 8.29 m (4H, H arom.)
7.41 7.82 m (7H, H arom.), 8.06 8.29 m (5H, H arom.)
7.19 7.40 m (2H, H arom.), 7.51 7.78 m (4H, H arom.), 7.99 8.23 m (5H,
H arom.)
IIIe
2218
8.86, 7.52
7.61 7.80 m (3H, H arom.), 8.02 8.17 m (4H, H arom.), 0.82 1.13 m (4H,
2CH2), 2.10 2.33 m (1H, C1H of cyclopropane)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005

RECYCLIZATION OF 2,6-DIAMINO-4-ARYL(CYCLOHEXYL)-3,5-DICYANO-..
Table 2. (Contd.)
1613
1H NMR spectrum, , ppm (J, Hz)
Comp. IR spectrum,a
C3H (s),
C5H (s)
1
no.
cm
other signals
of thiazole
IIIf
2215
2205
8.45, 8.21
8.40, 8.06
1.12 1.52 m (6H, 2Me), 4.02 4.35 m (4H, 2CH2), 6.67 d (2H, H arom., J 8.34),
7.46 m (3H, H arom.), 7.75 m (5H, H arom.), 8.11 d (2H, H arom., J 7.06)
0.89 t (3H, Me, J 7.11), 1.12 1.73 m (10H, 2Me and 2CH2), 2.59 t (2H, CH2,
J 7.54), 4.14 m (4H, 2CH2), 6.63 s (1H, C6H3), 6.78 d (1H, C6H3, J 8.05),
7.26 d (2H, C6H4, J 8.79), 7.88 d (2H, C6H4), 8.13 d (1H, C6H3)
7.02 7.28 m (5H, H arom.), 7.39 7.64 m (5H, H arom.), 7.72 7.89 m (6H,
H arom.), 8.13 d (2H, H arom., J 8.41)
3.81 s (3H, Me), 7.05 d and 7.50 d (2H each, C6H4, J 8.84), 7.58 m (3H, Ph),
8.07 m (2H, Ph)
2.38 s (3H, Me), 7.30 d and 7.93 d (2H each, C6H4, J 7.72), 7.59 m (3H, Ph),
8.02 m (2H, Ph)
IIIg
IIIh
IIIi
2220
2217
2219
2222
8.39, 8.31
8.59, 8.33
8.32, 8.15
8.26, 7.98
IIIj
IIIk
3.83 s (3H, Me), 6.94 d and 7.92 d (2H each, C6H4, J 8.84), 7.52 m (3H, Ph),
7.99 m (2H, Ph)
IIIl
IIIm
2214
2208,
3612 (OH)
8.31, 8.12
8.16, 8.11
7.33 7.71 m (7H, H arom.), 8.01 8.08 m (7H, H arom.)
0.91 t (3H, Me, J 6.25), 1.14 1.78 m (4H, 2CH2), 2.61 t (2H, CH2, J 6.18),
3.87 s (3H, MeO), 6.96 d and 7.62 d (1H each, C6H3, J 7.11), 7.29 d and
7.92 d (2H each, C6H4, J 7.05), 7.48 s (1H, C6H3), 10.22 br.s (1H, OH)
3.88 s (3H, Me), 6.98 d and 7.76 d (1H each, C6H3, J 7.07), 7.39 7.65 m (9H,
H arom.), 8.11 s (1H, C6H3), 10.22 br.s (1H, OH)
IIIn
IIIo
IIIp
2216,
3622 (OH)
2214,
3610 (OH)
2220, 3598
(OH),
8.25, 7.89
8.19, 8.08
8.45, 8.21
3.86 s (3H, Me), 6.96 d (1H, C6H3, J 7.04), 7.35 7.81 m (5H, H arom.),
8.01 d (2H, Ph, J 7.13), 10.21 br.s (1H, OH)
3.92 s (3H, Me), 6.94 d and 7.86 d (1H each, C6H3, J 7.12), 7.36 7.68 m (4H,
H arom.), 6.74 s (1H, C6H3), 8.87 s (1H, C4H of coumarin), 9.92 br.s (1H, OH)
1718 (C=O)
2215
IIIq
8.25, 7.98
1.21 1.59 m (6H, 3CH2), 1.63 1.98 m (5H, CH2CHCH2), 7.07 t (2H, Ph,
J 7.62), 7.11 m (2H, H arom.), 7.23 d and 7.88 d (2H each, C6H4, J 8.10),
7.36 m (2H, H arom.), 7.51 t (1H, Ph, J 7.98), 7.63 s (1H, H arom.), 7.76 d
(1H, H arom., J 6.72)
IIIr
IIIs
2219
8.27, 8.15
8.52, 8.34
7.03 7.19 m (4H, H arom.), 7.35 7.48 m (4H, H arom.), 7.52 t (1H, H arom.,
J 7.90), 7.62 m (1H, H arom.), 7.76 d (1H, H arom., J 7.82), 8.02 d (2H,
H arom., J 8.50)
7.08 d (2H, H arom., J 7.15), 7.18 d (2H, H arom., J 6.94), 7.41 m (4H,
H arom.), 7.58 m (2H, H arom.), 7.69 s (1H, C6H4), 7.83 t (2H Ph, J 7.45),
8.88 s (1H, C4H of coumarin)
2218,
1720 (C=O)
IIIt
IIIu
2214
2222
8.31, 8.25
8.34, 8.12
7.02 7.84 m (12H, H arom.), 8.03 d (2H, H arom., J 7.02)
3.81 s (3H, Me), 7.07 d and 7.97 d (2H each, C6H4, J 8.85), 7.12 7.82 m (9H,
H arom.)
IIIv
2217, 2224
8.41, 8.35
1.39 t (3H, Me, J 7.23), 2.80 s (3H, Me), 3.29 q (2H, CH2), 7.52 d and 8.01 d
(2H each, C6H4), 8.07 s (1H, C4H of pyridine)
IIIw
2212,
8.04 d (J 2.24), 1.05 1.48 m (6H, 3CH2), 1.64 1.87 m (4H, 2CH2), 1.63 m (1H, C1H of cyclo-
1728 (C=O)
8.45
hexane), 7.33 d (1H, C7H of coumarin, J 2.18), 7.38 d (1H, C5H of coumarin,
J 3.62), 7.68 d. d (1H, C6H of coumarin, J 8.64 and 2.23), 8.77 s (1H, C4H of
coumarin)
IIIx
2220
8.26, 7.93
0.94 t (3H, Me, J 7.02), 1.39 m (2H, CH2), 1.62 m (2H, CH2), 2.61 t (2H, CH2,
J 7.12), 7.20 d and 7.88 d (2H each, C6H4, J 7.62), 7.52 d and 8.01 d (2H
each, 4-ClC6H4, J 7.26)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005

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DYACHENKO et al.
Table 2. (Contd.)
1H NMR spectrum, , ppm (J, Hz)
Comp. IR spectrum,a
C3H (s),
C5H (s)
1
no.
cm
other signals
of thiazole
IIIy
IIIz
III
2218,
3614 (OH)
2223
8.27, 8.24
6.88 m (2H, H arom.), 7.10 m (1H, H arom.), 7.54 d (2H, 4-ClC6H4, J 8.50),
8.07 m (3H, H arom.), 10.31 br.s (1H, OH)
7.35 d, (J 2.19), 1.18 1.54 m (6H, 3CH2), 1.69 1.95 m (4H, 2CH2), 2.71 m (1H, C1H of cyclo-
8.11
8.35, 8.21
hexane), 7.46 d and 7.99 d (2H each, C6H4, J 8.49)
3.82 s (3H, Me), 7.05 d and 7.50 d (2H each, C6H4, J 8.39), 7.72 8.12 m (9H,
H arom.)
2219
a
(C N) unless otherwise indicated.
a valuable material for nonlinear conversion of the
laser radiation frequency from the IR to UV range
[17]. Therefore, the known and newly synthesized
urea derivatives are very interesting and promising
from the viewpoint of manifestation of nonlinear
optical properties (e.g., quadratic nonlinear suscepti-
bility). Therefore, we measured for VI the intensity
of the generation of the second harmonic in polycrys-
talline samples by the Kurtz Perry method. We found
that the intensity of the second harmonic generation
for powders of VI is about 80% of that for unsubsti-
tuted urea.
C6
C5
O1
C7
C4
N1
N1
C2
C1
C2
C3
Cl1
Fig. 1. General view of the molecule of N,N -bis(3-chlorophenyl)urea VI with the atom numbering. Atoms symmetry-related
(twofold axis) to the basis (symmetrically independent) atoms are marked with primes.
b
0
a
c
Fig. 2. Crystal packing of VI. Dotted lines denote intermolecular hydrogen bonds; a, b, and c are unit cell parameters.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005

RECYCLIZATION OF 2,6-DIAMINO-4-ARYL(CYCLOHEXYL)-3,5-DICYANO-..
1615
EXPERIMENTAL
nopyran Ig was described in [21]. Compound If was
characterized in [2]; Ih and Ii, in [1]; and Ij, in [3].
The IR spectra were recorded on an IKS-29 spec-
trometer (mulls in mineral oil). The H NMR spectra
2,6-Diamino-3,5-dicyano-4-(4-ethylphenyl)-4H-
thiopyran Ia: yield 88%, mp 181 183 C (from
1
were taken on Bruker WP-100SY (100 MHz) (Ia, Ic
Ie, IIIb IIIi, IIIm IIIo, IIIt, IIIu, III , VI), Gemini-
200 (199.975 MHz) (IIIr, IIIw, IIIx), Bruker AC-200
(200.13 MHz) (IIIa, IIIp, IIIs), Bruker WM-250
(250.13 MHz) (IIIz), Bruker AM-300 (300.13 MHz)
(Ib), and Bruker DR-500 (500.13 MHz) (IIIv, IIIy,
IV, V) spectrometers in DMSO-d6, internal reference
TMS. The mass spectra were measured on a Kratos
MS-890 spectrometer (electron impact, 70 eV) with
direct sample inlet.
1
EtOH). IR spectrum, , cm : 3445, 3341, 3198
(NH2), 2194 sh (C N), 1645 [ (NH2)]. 1H NMR spec-
trum, , ppm: 1.19 t (3H, Me, J 6.23 Hz), 2.58 q (2H,
CH2), 4.23 s (1H, C4H), 6.90 br.s (4H, 2NH2), 7.18 s
(4H, C6H4). Found, %: C 63.70; H 4.84; N 19.72.
C15H14N4S. Calculated, %: C 63.81; H 5.00; N 19.84.
2,6-Diamino-4-(3-phenoxy)-3,5-dicyano-4H-thio-
pyran Ib: yield 80%, mp 196 198 C (from EtOH).
1
IR spectrum, , cm : 3455, 3333, 3202 (NH2),
1
2185 sh (C N), 1648 [ (NH2)]. H NMR spectrum,
The melting points were determined with a Koefler
unit.
, ppm: 4.32 s (1H, C4H), 6.99 br.s (4H, 2NH2),
7.07 s (1H, H arom.), 7.12 7.58 m (8H, H arom.).
Found, %: C 65.71; H 3.90; N 16.14. C19H14N4OS.
Calculated, %: C 65.88; H 4.07; N 16.17.
The reaction progress was monitored on Silufol
UV-254 plates, eluent acetone hexane, 3 : 5 by vol-
ume, development with iodine vapor.
4-(4-Hydroxy-3-methoxyphenyl)-2,6-diamino-
3,5-dicyano-4H-thiopyran Ic: yield 71%, mp 140
142 C (from EtOH). IR spectrum, , cm : 3590 (OH),
The intensity of the second harmonic generation
for VI was measured with a pulse YAG:Nd3+ laser
(1064 nm) in the modulated Q-factor mode. The re-
cording system consisted of a monochromator with a
series of photoreceivers.
1
3440, 3302, 3195 (NH2), 2176 sh (C N), 1640
1
[ (NH2)]. H NMR spectrum, , ppm: 3.73 s (3H,
MeO), 4.16 s (1H, C4H), 6.48 6.95 m (7H, C6H3 and
2NH2), 8.92 br.s (1H, OH). Found, %: C 55.80; H
3.89; N 18.58. C14H12N4O2S. Calculated, %: C 55.99;
H 4.03; N 18.65.
X-ray diffraction study of VI was performed with
a 0.28 0.30 0.59-mm single crystal at room tem-
perature on an Enraf-Nonius CAD-4 automatic four-
circle diffractometer (MoK radiation, 0.71069 A,
2,6-Diamino-4-(biphenyl-4-yl)-3,5-dicyano-4H-
thiopyran Id: yield 72%, mp 218 220 C (from
scanning rate ratio 2 / 1.2, 25 , sphere seg-
ment 0 11, 0 l 5, 696 reflec-
h
k
17, 0max
1
EtOH). IR spectrum, , cm : 3450, 3312, 2197
(NH2), 2179 sh (C N), 1640 [ (NH2)]. 1H NMR spec-
trum, , ppm: 4.35 s (1H, C4H), 6.47 br.s (4H, 2NH2),
7.32 7.71 m (9H, H arom.). Found, %: C 68.92; H
4.11; N 16.78. C19H14N4S. Calculated, %: C 69.07;
H 4.27; N 16.96.
tions). Crystal data: rhombic system, a 9.707(1), b
14.358(2), c 4.577(2) ; V 637.9(2) 3, M 281.1,
3
1
Z 2,
1.46 g cm ,
4.96 cm , F(000) 288,
space gcraolcup P21212. The structure was solved by the
direct method and refined by the least-squares method
in the full-matrix anisotropic approximation using
SHELXS and SHELXL-93 programs [18, 19]. In the
refinement we used 627 reflections with I > 2 (I) (103
refined parameters, 6.1 reflections per parameter). All
the hydrogen atoms were revealed from the differen-
tial electron density synthesis and were refined iso-
2,6-Diamino-3,5-dicyano-4-cyclohexyl-4H-thio-
pyran Ie was prepared according to [22]; yield 86%,
1
mp 215 217 C (from EtOH). IR spectrum, , cm :
3450, 3390, 3300 (NH2), 2190 sh (C N), 1640
1
[ (NH2)]. H NMR spectrum, , ppm: 1.10 m (5H,
CH2CHCH2), 1.69 m (6H, 3CH2), 2.71 d (1H, C4H,
J 3.18 Hz), 6.80 br.s (4H, 2NH2). Found, %: C 59.78;
H 6.04; N 21.52. C13H16N4S. Calculated, %: C 59.97;
H 6.19; N 21.52.
tropically. In the refinement we used the weight
= 1/[ (F20) + (0.046P)2 + 0.137], where
2
scheme
R = (F20 + 2F2c)/3. The final divergence factors are
R(F) 0.033 and RW(F2) 0.041, GOF 1.054. The resid-
ual electron density from the differential Fourier series
was 0.13 and 0.20 e/ 3. We made the correction for
anomalous absorption and did not make absorption
corrections. The absolute configuration of VI was
determined by Flack’s method [20]: p = 0.3(2).
3-Aryl-2-[4-R -thiazol(selenazol)-2-yl]acryloni-
triles IIIa IIIz and III . A mixture of 10 mmol of
thio(seleno)pyran I and 10 mmol of -bromo ketone
II in 40 ml of absolute ethanol was refluxed for 8 h.
The precipitate that formed on cooling was filtered off
and washed with ethanol and hexane. The resulting
compounds IIIa IIIz and III were recrystallized
from BuOH (Tables 1, 2). Mass spectrum of IIIr, m/z
4-Aryl-2,6-diamino-3,5-dicyano-4H-thiopyrans
Ia If and Ih Ij were prepared according to [1]; sele-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005

1616
DYACHENKO et al.
1
(Irel, %): 417 (11) [M + 2]+, 416 (33) [M + 1]+, 415
(58) [M]+, 414 (98) [M 1]+, 413 (100) [M 2]+, 388
(22), 321 (13), 207 (24), 168 (85), 133 (79), 89 (52),
77 (49) [Ph]+, 51 (24), 39 (6). Mass spectrum of IIIv,
m/z (Irel, %): 425 (4) [M + 2]+, 424 (12) [M + 1]+,
423 (45) [M]+, 422 (100) [M 1]+, 421 (10) [M 2]+,
407 (29), 389 (71), 206 (25), 173 (28), 146 (21), 120
(32), 82 (10), 69 (17), 51 (8), 45 (23). Mass spectrum
of IIIw, m/z (Irel, %): 443 (25) [M + 2]+, 442 (100)
[M + 1]+, 441 (92) [M]+, 440 (9) [M 1]+, 361 (39),
223 (18), 174 (22), 145 (57), 113 (14), 101 (22), 87
(9), 67 (28), 55 (19), 41 (68). Mass spectrum of IIIy,
m/z (Irel, %): 341 (13) [M + 2]+, 340 (38) [M + 1]+,
339 (46) [M]+, 338 (100) [M 1]+, 337 (65) [M 2]+,
206 (10), 150 (14), 121 (72), 89 (24), 78 (19), 63 (9),
51 (12), 39 (7).
1658 (CONH). H NMR spectrum, , ppm: 7.05 7.72
m (6H, H arom.), 7.72 s (2H, H arom.), 8.97 br.s (2H,
2NH). Found, %: C 55.31; H 3.40; N 10.12. C13H10
Cl2N2O. Calculated, %: C 55.54; H 3.59; N 9.96.
REFERENCES
1. Sharanin, Yu.A., Shestopalov, A.M., Nesterov, V.N.,
Melenchuk, S.N., Promonenkov, V.K., Shklover, V.E.,
Struchkov, Yu.T., and Litvinov, V.P., Zh. Org. Khim.,
1989, vol. 25, no. 6, p. 1323.
2. Dyachenko, V.D., Krivokolysko, S.G., Shara-
nin, Yu.A., and Litvinov, V.P., Khim. Geterotsikl.
Soedin., 1997, no. 7, p. 909.
3. Dyachenko, V.D., Krivokolysko, S.G., Shara-
nin, Yu.A., and Litvinov, V.P., Zh. Org. Khim., 1997,
vol. 33, no. 7, p. 1084.
6-Amino-4-phenyl-2-ethylsulfanyl-1,4-dihydro-
pyridine-3,5-dicarbonitrile IV. A mixture of 2.5 g of
thiopyran Ih and 0.8 ml of ethyl iodide in 20 ml of
absolute ethanol was refluxed for 5 h and filtered
while hot; the filtrate was allowed to stand for 2 days
at room temperature. The resulting precipitate was
separated and washed with ethanol and hexane. Yield
1.7 g (60%), mp 151 153 C (from EtOH). IR spec-
4. Shams, H.Z., Elkholy, Y.M., Ibrahim, N.S., and El-
nagdi, M.N., J. Pr. Chem., 1988, vol. 330, no. 5,
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1
trum, , cm : 3400, 3372, 3330 (NH2), 2177 sh
6. Sharanin, Yu.A. and Shestopalov, A.M., Zh. Org.
Khim., 1989, vol. 25, no. 6, p. 1331.
1
(C N), 1638 [ (NH2)]. H NMR spectrum, , ppm:
1.26 t (3H, Me, J 6.23 Hz), 2.98 m (2H, CH2), 4.24 s
(1H, C4H), 5.81 br.s (2H, 2NH2), 7.19 7.38 m (5H,
Ph), 9.04 br.s (1H, NH). Found, %: C 63.75; H 4.82;
N 19.71. C15H14N4S. Calculated, %: C 63.81; H 5.00;
N 19.84.
7. US Patent 5658375, 1997, Ref. Zh. Khim., 1999,
3O566P.
8. Koketsu, M. and Ishihara, H., EPW Application
1323714, 2003, Ref. Zh. Khim., 2003, 03.22-
19O359P.
5-Amino-7-phenyl-2,3,4,7-tetrahydrothiazolo-
[3,2-a]pyridine-6,8-dicarbonitrile V was prepared
similarly to IV, with ethyl iodide replaced by 0.9 ml
of 1,2-dibromoethane, yield 1.5 g (53%), mp 181
9. Dyachenko, V.D., Krivokolysko, S.G., and Shara-
nin, Yu.A., Zh. Obshch. Khim., 1995, vol. 65, no. 6,
p. 1042.
1
183 C (from EtOH). IR spectrum, , cm : 4122,
10. Krauze, A. and Duburs, G., Khim. Geterotsikl. Soedin.,
3354, 3193 (NH2), 2190 sh (C N), 1650 [ (NH2)].
1H NMR spectrum, , ppm: 3.43 t (2H, SCH2, J
6.64 Hz), 4.14 t (2H, NCH2), 4.27 s (1H, C7H),
6.28 br.s (2H, NH2), 7.19 7.38 m (5H, Ph). Mass
spectrum, m/z (Irel, %): 282 (4) [M + 2]+, 281 (6) [M +
1]+, 280 (29) [M]+, 213 (16), 203 (100) [M Ph]+,
176 (10), 140 (13), 77 (12) [Ph]+, 51 (9), 39 (5).
Found, %: C 64.14; H 4.20; N 19.87. C15H12N4S.
Calculated, %: C 64.26; H 4.32; N 19.98.
2000, no. 6, p. 794.
11. Dyachenko, V.D., Krivokolysko, S.G., and Litvi-
nov, V.P., Zh. Org. Khim., 1998, vol. 34, no. 6, p. 927.
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Nitriles), Moscow: Khimiya, 1972.
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Orpen, A.G., and Tailor, R., J. Chem. Soc., Perkin
Trans. 2, 1987, no. 12, p. S1.
N,N -Bis(3-chlorophenyl)urea VI. A mixture
of 2.5 g of thiopyran Ih and 1.2 ml of 3-chlorophenyl
isocyanate in 30 ml of absolute toluene was refluxed
for 2 h with protection from atmospheric moisture,
filtered while hot, and allowed to stand for 24 h at
20 C. The resulting precipitate was separated and
washed with toluene and hexane. Yield 1.0 g (36%),
14. Burke-Laing, M. and Laing, M., Acta Crystalogr.,
Sect. B, 1976, vol. 32, no. 12, p. 3216.
15. Kuleshova, L.N. and Zorkii, P.M., Acta Crystallogr.,
Sect. B, 1981, vol. 37, no. 7, p. 1363.
16. Etter, M.C., Urbanczyk-Lipkowska, Z., Zia-Ebra-
himi, M., and Panunto, T.W., J. Am. Chem. Soc.,
1990, vol. 112, no. 23, p. 8415.
1
mp 238 240 C (from i-PrOH). IR spectrum, , cm :
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RECYCLIZATION OF 2,6-DIAMINO-4-ARYL(CYCLOHEXYL)-3,5-DICYANO-..
1617
17. Shemla, D. and Ziss, Zh., Nonlinear Optical Properties
of Organic Molecules and Crystals, New York:
Academic, 1987.
18. Sheldrick, G.M., SHELXS-86. Program for the Solu-
tion of Crystal Structures, Gottingen: Univ. of Gottin-
gen, 1986.
20. Flack, H.D., Acta Crystallogr., Sect. A, 1983, vol. 39,
no. 3, p. 876.
21. Dyachenko, V.D., Nesterov, V.N., Struchkov, V.E.,
Sharanin, Yu.A., and Shklover, V.E., Zh. Obshch.
Khim., 1989, vol. 59, no. 4, p. 881.
19. Sheldrick, G.M., SHELXL-93. Program for the Re-
finement of Crystal Structures, Gottingen: Univ. of
Gottingen, 1993.
22. Dyachenko, V.D., Krivokolysko, S.G., Nesterov, V.N.,
and Litvinov, V.P., Khim. Geterotsikl. Soedin., 1997,
no. 12, p. 1655.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 10 2005