Novel [4 + 2] cycloaddition reaction of aryl-methylidenemalononitriles to unsaturated chalcogen amides. Synthesis, structure, and properties of triethylammonium 3,5,5-tricyano-1,4,5,6-tetrahydropyridine-2-selenolates and -thiolates

Article abstract of DOI:10.1007/s10593-013-1378-y

Reaction of arylmethylidenemalononitriles with 3-aryl-2-cyanoprop-2- eneselenoamides in the presence of Et₃N gave triethylammonium 4,6-diaryl-3,5,5-tricyano-1,4,5,6-tetrahydropyridine-2-selenolates. A similar reaction with cyclohexylidenecyanothioacetamide yields triethylammonium 4-aryl-1,5,5-tri-cyano-3-azaspiro[5.5]undec-1-ene-2-thiolate. Alkylation of the obtained selenolates and thiolates gives 6-(alkylseleno)-2,4-diaryl-1,4- dihydropyridine-3,3,5(2H)-tricarbonitriles and 4-(alkylthio)-2-aryl-3-aza- spiro[5.5]undec-4-ene-1,1,5-tricarbonitriles, respectivelly. The structure of 2,4-di(2-furyl)-6-{[2-(4-methylphenyl)-2-oxoethyl]seleno}-1,4-dihydropyridine-3, 3,5(2H)-tricarbonitrile has been confirmed by the X-ray structural analysis.

Full text of DOI:10.1007/s10593-013-1378-y

Chemistry of Heterocyclic Compounds, Vol. 49, No. 9, December, 2013 (Russian Original Vol. 49, No. 9, September, 2013)
NOVEL [4+2] CYCLOADDITION REACTION OF ARYL-
METHYLIDENEMALONONITRILES TO UNSATURATED
CHALCOGEN AMIDES. SYNTHESIS, STRUCTURE, AND
PROPERTIES OF TRIETHYLAMMONIUM 3,5,5-TRICYANO-
1,4,5,6-TETRAHYDROPYRIDINE-2-SELENOLATES AND -THIOLATES
K. A. Frolov1, V. V. Dotsenko1*, S. G. Krivokolysko1, and E. O. Kostyrko2
Reaction of arylmethylidenemalononitriles with 3-aryl-2-cyanoprop-2-eneselenoamides in the presence
of Et3N gave triethylammonium 4,6-diaryl-3,5,5-tricyano-1,4,5,6-tetrahydropyridine-2-selenolates. A
similar reaction with cyclohexylidenecyanothioacetamide yields triethylammonium 4-aryl-1,5,5-tri-
cyano-3-azaspiro[5.5]undec-1-ene-2-thiolate. Alkylation of the obtained selenolates and thiolates gives
6-(alkylseleno)-2,4-diaryl-1,4-dihydropyridine-3,3,5(2H)-tricarbonitriles and 4-(alkylthio)-2-aryl-3-aza-
spiro[5.5]undec-4-ene-1,1,5-tricarbonitriles, respectivelly. The structure of 2,4-di(2-furyl)-6-{[2-(4-
methylphenyl)-2-oxoethyl]seleno}-1,4-dihydropyridine-3,3,5(2H)-tricarbonitrile has been confirmed by
the X-ray structural analysis.
Keywords: arylmethylidenemalononitriles, cyanoselenoacetamide, cyanothioacetamide, prop-2-ene-
selenoamides, prop-2-enethioamides, 1,4,5,6-tetrahydropyridines, [4+2] cycloaddition, X-ray structural
analysis.
Due to their availability and unusual chemical properties, ,-unsaturated thioamides [1-3] and
selenoamides [4] continue to attract the attention of investigators and are widely used in the synthesis of
heterocyclic compounds. One of the most successful examples which demonstrates the unique synthetic
potential of unsaturated thioamides is the preparation of 3,4-dihydro-2H-thiopyran and 4H-thiopyran derivatives
through their reaction with electron deficient alkenes and alkynes [5-10].
Similar reaction has been discussed in the studies [11, 12] where a spontaneous dimerization of 3-aryl-
2-cyanoprop-2-enethioamides 1 takes place through a [4+2] cycloaddition to give the thiopyrans 2. There are
known a series of examples of the cycloaddition of maleic anhydride to ,-unsaturated selenoamides to
_______
*To whom correspondence should be addressed, e-mail: victor_dotsenko@bigmir.net.
1"ChemEx" Laboratory, Vladimir Dal' East Ukrainian National University, 20-A Molodyozhnyi Kv., Luhansk
91034, Ukraine.
2A. A. Bogomolets National Medical University, 13 T. Shevchenka Blvd., Kyiv 01601, Ukraine; e-mail:
lenakostirko@ukr.net.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1384-1396, September, 2013.
Original article submitted July 19, 2013.
0009-3122/13/4909-1289©2013 Springer Science+Business Media New York
1289

Ar
Ar
S
X
Y
X
Y
R
R
[5–7, 9, 10]
+
NHR1
NHR1
S
Ar
Ar
S
CO2Me
MeO2C
R2
CN
R3
CN
[8, 10]
+
NHR3
S
N
R2
H
S
Ar
Ar
NH2
NC
CN
S
2
CN
Ar
[11, 12]
S
H2N
H2N
1
2
X = NO2, CN, CO2Me, CO2Et; Y = H, Ph, CO2Me, or X + Y = CONRCO;
R = H, CN; R1 = H, alkyl, acyl; R2 = H, CO2Me; R3 = H, Me, cycloalkyl
form condensed 4H-selenopyrans [13, 14]. We have recently found that 3-(2-thienyl)-2-cyanoacrylselenoamide
(3a) reacts readily with (2-thienyl)methylidenemalononitrile (4a) in the presence of Et3N to form
triethylammonium 3,5,5-tricyano-4,6-di(2-thienyl)-1,4,5,6-tetrahydropyridine-2-selenolate (5a) [15]. To the
best of our knowledge this is the first example of a reaction in which an unsaturated selenoamide behaves as a
C=C–C=N synthon/dienophile in a formal [4+2] cycloaddition.
Se
Et3NH+
NC
Et3N, acetone
3–4°С, 24 h
Se
CN
NC
NC
X
NH
X
X
+
NH2
53–71%
3a,b
4a,b
NC CN
X
5a,b
SeCH2R
NH
RCH2Hal
EtOH, H2O
NC
, 1–3 min
25 °C, 24 h
NC CN
X
X
33–56%
6a–e
3–5 a X = S, b X = O; 6 a X = S, R = PhNHCO; b X = S, R = 4-MeC6H4NHCO;
с X = O, R = PhCO; d X = O, R = 4-MeC6H4CO; e X = O, R = 4-MeC6H4NHCO
In continuation of our studies, we have decided to examine the scope and limitations of the novel
reaction. It was found that this reaction is general for the use of ,-unsaturated selenoamides 3. Hence, the
selenolate 5b was obtained in 53% yield in the reaction of the selenoamide 3b with furfurylidenemalononitrile
(4b). The selenolates 5a,b are readily alkylated by alkyl halides to give the 6-(alkylseleno)-2,4-diaryl-1,4-di-
hydropyridine-3,3,5(2H)-tricarbonitriles 6a-e in 33-56% yields.
The structure of the 2,4-di(2-furyl)-6-{[2-(4-methylphenyl)-2-oxoethyl]seleno}-1,4-dihydropyridine-3,3,5(2H)-
tricarbonitrile (6d) was studied by X-ray structural analysis (Fig. 1). The tetrahydropyridine ring exists in a "half chair"
type conformation with a little twisted endocyclic C(1)–C(2) double bond (torsional angle N(1)–C(1)–C(2)–C(3)
-8.1(2)º). The deviations of atoms C(4) and C(5) from the mean plane of the remaining atoms are -0.515(3) and
1290

0.377(3) Å, respectively. The furan substituents and the cyano group C(21)–N(4) have an equatorial orientation
(torsional angles C(1)–C(2)–C(3)–C(16) -142.16(14)º, C(1)–N(1)–C(5)–C(22) 176.39(13)º, and C(21)–C(4)–C(5)–
N(1) 170.89(11)º), but the cyano group C(20)–N(3) is axial (torsional angle C(20)–C(4)–C(5)–N(1) 52.80(14)º). The
furan substituent at the atom C(3) is disordered into the two positions A and B with relative population 0.485(10):
0.515(10) due to rotation around the C(3)–C(16) bond. In position A the oxygen atom of the furan ring has a syn
orientation relative to the hydrogen atom at the C(3) atom (torsional angle O(2A)–C(16)–C(3)–H(3) -21º), but
in position B (together with the furan substituent at the C(5) atom) it has the anti orientation (torsional angles
O(2B)–C(16)–C(3)–H(3) 173º and O(3)–C(22)–C(5)–H(5) 163º). The Se(1)–C(6) bond deviates a little from the
plane of the C(1)–C(2) double bond (torsional angle C(2)–C(1)–Se(1)–C(6) 161.97(12)º) which, along with the
gauche-gauche conformation of the substituents at the methylene group (torsional angles C(1)–Se(1)–C(6)–C(7)
84.02(11)º and Se(1)–C(6)–C(7)–O(1) -88.78(18)º), sets up the conditions for formation of the intramolecular
hydrogen bond N(1)–H(1)···O(1) (H···O 2.01 Å, N–H···O 159º). The tolyl substituent is coplanar with the carbonyl
group (torsional angle O(1)–C(7)–C(8)–C(13) -0.6(3)º) despite the formation in such a conformation of the
shortened intramolecular contact H(9)···H(6a) of 2.13 Å (sum of van der Waals radii 2.32 Å [16]). The molecules
are bound as centrosymmetric dimers in the crystal via intermolecular hydrogen bonds C(23)–H(23)···O(1)i [i:
1-x, -y, -z] (H···O 2.27 Å, C–H···O 153º).
1
The H NMR spectra of compounds 6a-e show signals for 4-CH protons as singlets at 5.06-5.24 ppm and
6-CH protons as doublets or broadened singlets with JCH–NH = 1.0-2.0 Hz at 5.45-5.74 ppm. The NH protons of the
tetrahydropyridine ring appear as broadened singlets or as doublets at 8.16-9.06 ppm with JCH–NH = 1.0-2.0 Hz. It
should be noted that the 1H NMR spectra of compounds 5a,b and 6a-e are not doubled in signals, characteristic
for a mixture of diastereomers, and this indicates the stereoselectivity of the cycloaddition process. Based on the
X-ray analytical results the obtained compounds can be represented as a racemic mixture with a (2S,4S) and
(2R,4R) configuration of the C-2 and C-4 optically active centers as indicated in the case of compounds 6a-e
(Fig 2). This result agrees well with the stereochemical configuration of the analogous thiopyran 2 cycloaddition
product (Ar = 3-MeOC6H4) elucidated by the X-ray structural analysis [17].
Fig. 1. Molecular structure of compound 6d with representation of atoms with thermal vibration ellipsoids of
50% probability.
S
SeCH2R
NH
SeCH2R
NH
Ar
H
NC
NC
CN
H2N
NC
Ar
X
X
X
X
S
NH2
H
NC CN
(2S,4S)
NC CN
(2R,4R)
2
(Ar = 3-MeOC6H4)
6a–e
Fig. 2. Stereoisomers of compounds 6a-e and 2.
1291

The IR spectra of pyridines 5b and 6a-e are characterized by the presence of strong absorption band at
2173-2198 cm-1 (3-C≡N) and a weak intensity absorption at 2231-2276 cm-1 (5-C≡N).
To further expand scope of the reaction, the reaction of arylmethylidenemalononitriles 4 with other
cyanothioacetamide derivatives has been studied.
It was found that the reaction of the thioacrylamide 7 with unsaturated dinitriles 4b,c in cold acetone in
the presence of Et3N (1.5 equiv.) gave the cycloaddition products 8a,b in 68-72% yields. The obtained thiolates
8a,b were readily alkylated in aqueous alcohol as shown in the scheme below to form S-alkylation products
9a-c. Compounds 8a,b are beige, amorphous powders, poorly soluble in acetone and ether but soluble in DMSO
and hot aqueous EtOH. The 1H NMR spectra of the 4-aryl-1,5,5-tricyano-3-azaspiro[5.5]undec-1-ene-
2-thiolates 8a,b show 4-CH protons at 4.85-4.96 ppm and signals for the NH protons at high field in the region
5.80-5.84 ppm. In the spectra of the alkylation products 9a-c a downfield shift is seen for the 4-CH protons
observed at 5.14-5.34 ppm and for the NH protons at 8.83-9.08 ppm. The structure of the triethylammonium
1,5,5-tricyano-4-phenyl-3-azaspiro[5.5]undec-1-ene-2-thiolate (8b) is also confirmed by 13C NMR
spectroscopic results with the use of the attached proton test (APT).
S
NC
1.5 equiv. Et3N
Me2CO
NH2
NC
NC
Ar
CN
CN
+
NC
Ar
5–10°C, 24 h
N
S
H
Et3NH+
4b,c
7
8a,b
ClCH2CONHR
70% EtOH
NC
CN
NC
Ar
, 1–2 min
25°C, 2–3 h
NHR
N
S
H
O
9a–c
4b, 8a Ar = 2-furyl, 4c, 8b Ar = Ph; 9 a Ar = 2-furyl, R = 4-MeC6H4;
b Ar = Ph, R = 4-MeC6H4; c Ar = Ph, R = 3-Cl-4-MeC6H3
It is interesting to note that the literature data [18] proposes that the Et3N-catalyzed reaction of the
thioacrylamide 7 with the unsaturated nitriles 4 takes place differently, and depending on the conditions
produces either the isoquinolinethiones 10 or the 3,4,5,6,7,8-hexahydronaphthalenes 11.
4
+
7
Ar
CN
NH2
CN
Et3N, EtOH
Et3N, EtOH
NH
[18]
, 2 h
room temp., 24 h
S
CN
CN
Ar
10
11
Upon reproduction of the reported method it was found that the reaction of thioamide 7 with unsaturated
nitriles 4d,e at 25ºC in alcohol in the presence of catalytic amounts of Et3N gives products which
physicochemical and spectroscopic parameters proved to be identical to the hexahydronaphthalenes 11 as
reported in the work [18]. However, the yields after purification (20-22%) proved to be markedly lower than
reported (55-76%). The first compounds of this type 11 were reported by Gewald and Schill [19] as the products
of a three-component condensation of cyclohexanone with malononitrile and benzaldehyde and also as
1292

the products of cross dimerization of cyclohexylidenemalononitrile with the unsaturated dinitriles 4. However in
later work [20-25] it was shown (including the involvement of the X-ray structural analysis [26, 27]) that the
structure 11 were assigned wrong and that these compounds should be assigned the structure of the isomeric
1
heteroannular 2-amino-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitriles 12. Analysis of the H NMR
and 13C NMR (APT) spectroscopic data confirmed that the products of the reaction of thioamide 7 with
dinitriles 4d,e under the conditions reported above are compounds 12a,b. We also were unable to reproduce the
method for synthesis of the isoquinolines 10. Refluxing thioamide 7 with one equivalent of unsaturated dinitrile
4d in the presence of catalytic amounts of Et3N gave the tetrahydronaphthalene 13 as the known product of
aromatization of compounds 12 [20, 21].
CN
+
7
CN
4d,e
Ar
CN
Ar
CN
Ar
(from 4d)
Et3N, EtOH
NH2
CN
NH2
CN
Et3N, EtOH
25°C, 24 h
, 2 h
CN
12a,b
13
4d, 12a, 13 Ar = 4-MeOC6H4; 4e, 12b Ar = 4-MeC6H4
Such major differences in the reaction course were due to the amount of base used, which allowed us to
make several proposals regarding the mechanism for the formation of compound 8. The key intermediate
necessary for the cycloaddition reaction is likely the 1-azabutadiene-2-thiolate 14. In the case of insufficient
base an alternative Michael addition/carbocyclization process becomes possible for the thioamide 7 and leads to
the naphthalenes 12.
Et3NH+
S
S
H
S
N
Ar
1.5 equiv.
Et3N
ArCH=C(CN)2
NC
NC
NH2
NH
CN
CN
4
NC
8
7
14
cat. Et3N
CN
S
NC CN
HN
CN
NC
C
CN
Ar
H2N
NH2
NC
NC
S
Ar
Ar
NH2
CH –
4
–SH–
NC
NC
12
Treatment of the cyclopentylidenecyanothioacetamide (15) with dinitriles 4b,c (acetone, 1.5 equiv.
Et3N, 25ºC) causes tarring of the reaction mixture. However, using the excess of piperidine in alcohol the
thioamide 15 and benzylidenemalononitrile (4c) gave the indane derivative 16 in 47% yield.
The 3-aryl-2-cyanothioacrylamides 1 react readily with the unsaturated nitriles 4 in the presence of
1.5 equiv. of Et3N to give white or light-yellow, finely crystalline powders insoluble in acetone. However, in
contrast to thioamide 7 and selenoamides 3a,b reaction products were complex mixtures. We propose
1293

CN
Ph
S
Piperidine
EtOH
NH2
CN
4c
+
NH2
25°C, 24 h
CN
15
16
that, along with the expected triethylammonium 3,5,5-tricyano-1,4,5,6-tetrahydropyridine-2-thiolates 17 there
are side products of a concurrent process of dimerization of thioamides 1 are being formed. A detailed analysis
on the course of the reaction of thioacrylamides 1 with the arylmethylidenemalononitriles 4 will be the subject
of our further research.
R
NC
NC
R1
1.5 equiv. Et3N
acetone, 25°C
CN
S
Et3NH+
+
product mixture
1
+
4
N
H
17
An attempt to synthesize compounds of type 11 by reacting isobutyral, cyanothioacetamide (18), and
benzylidenemalononitrile (4c) was unsuccessful, the product being a 69% yield of the 4H-thiopyran 19
(a known product of the reaction of thioamide 18 with the dinitrile 4c [28, 29]).
Ph
NMM, acetone
25°C, 24 h
S
NC
CN
NC
4c
+
Me2CHCHO
+
69%
NH2
H2N
S
NH2
18
19
NMM = N-methylmorpholine
Treatment of the penta-2,4-dienethioamide 20 with benzylidenemalononitrile (4c) in acetone in the
presence of excess Et3N led to tarring of the reaction mixture. It was also impossible to utilize cyanoacetamide
derivatives in the reaction, the starting acrylamide 21 being isolated in 40 and 21% yields after reaction with the
unsaturated dinitriles 4b,c.
1.5 equiv. Et3N
acetone, 25°C
S
Tarring
4c
+
Ph
NH2
CN
20
1.5 equiv. Et3N
acetone, 25°C
CN
4b,c
+
NH2
Cl
O
21
However, it was possible to identify several limitations in relation to the structure of the dienophile
reaction component. The unsaturated dinitriles 22 and 23 did not react with the thioacrylamide 7, likely as a
result of steric hindrance.
In conclusion, the reaction of 3-aryl-2-cyanoselenoacrylamides with arylmethylidenemalononitriles in
the presence of a excess of Et3N in acetone occurs as a formal [4+2] cycloaddition to yield the corresponding
1294

NC
NC
CN
CN
O
1.5 equiv. Et3N
acetone, 25°C
or
7
+
N
H
22
23
triethylammonium 3,5,5-tricyano-1,4,5,6-tetrahydropyridine-2-selenolates. Under the similar conditions the
cyclohexylidenecyanothioacetamide gives triethylammonium 4-aryl-1,5,5-tricyano-3-azaspiro[5.5]undec-1-ene-
2-thiolates. However, in the presence of catalytic amounts of Et3N, a carbocyclization occurs to yield 2-amino-
4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitriles. It was possible to establish several limitations of this
novel reaction which were determined by the structure of the starting reagents. The structure of 2,4-di(2-furyl)-
6-{[2-(4-methylphenyl)-2-oxoethyl]seleno}-1,4-dihydropyridine-3,3,5(2H)-tricarbonitrile was studied using
X-ray structural analysis.
EXPERIMENTAL
IR spectra were recorded on an IRS-29 (LOMO) spectrophotometer using vaseline oil. 1H NMR spectra
were recorded on Bruker DPX-400 (400 MHz, compounds 5b, 6a-e, 8a,b, 9a-c, 19) or Bruker Avance 500
(500 MHz, compounds 12a,b, 13, 16) spectrometers using DMSO-d6 with TMS as internal standard. APT 13C
NMR spectra were recorded on a Bruker Avance 500 spectrometer (125 MHz) using DMSO-d6 with TMS as
internal standard. HPLC-MS was performed on a Agilent 1100 liquid chromatograph with a diode array detector
(215, 254, and 265 nm) and an Agilent LC/MSD SL mass selective detector. Column Zorbax SB-C18, solvents:
A – MeCN–H2O, 95:5 + 0.1% CF3COOH, B – H2O + 0.1% CF3COOH, flow rate 3 ml/sec, electrospray
ionization at atmospheric pressure. Elemental analysis was carried out on a Carlo-Erba 1106 Elemental
Analyzer. Melting points were determined on a Kofler heating stage and are not corrected. Monitoring of the
purity of the products was carried out by TLC on Silufol UV-254 plates in the system acetonehexane (1:1) and
visualized using iodine vapor and a UV detector. 2-Cyano-3-(2-thienyl)-selenoacrylamide (3a) and 2-cyano-3-
(2-furyl)acrylselenoamide (3b) were prepared by condensation of cyanoselenoacetamide with the corresponding
aldehydes [30]. Triethylammonium 3,5,5-tricyano-4,6-di-(2-thienyl)-1,4,5,6-tetrahydropyridine-2-selenolate
(5a) [15], cyclohexylidenecyanothioacetamide (7) [31], cyclopentylidenecyanothioacetamide (15) [31], and
cyanothioacetamide (18) [32] were prepared by a known methods.
Triethylammonium 3,5,5-Tricyano-4,6-di(2-furyl)-1,4,5,6-tetrahydropyridine-2-selenolate (5b). A
mixture of 2-cyano-3-(2-furyl)acrylselenoamide (3b) (450 mg, 2.0 mmol), (2-furyl)methylidenemalononitrile
(4b) (290 mg, 2.0 mmol), and an excess of Et3N (0.41 ml, 3.0 mmol) in acetone (3 ml) was stirred under an
argon stream with cooling in an ice bath (3-4ºC) to dissolution of the starting reagents (2-3 min), and left for
24 h at the indicated temperature under an argon atmosphere. The precipitate formed was filtered off and
washed with acetone and hexane. Yield 500 mg (53%), beige powder, mp 129-131ºC. IR spectrum, ν, cm-1:
1
3
3431, 3212 (N–H), 2260 (5-C≡N), 2173 (3-C≡N). Н NMR spectrum, δ, ppm (J, Hz): 1.13 (9Н, t, J = 7.1,
3
N(СН2CH3)3); 2.79 (6Н, q, J = 7.1, N(СН2CH3)3); 4.98 (1Н, s, 4-СН); 5.37 (1Н, br. s, 6-СН); 6.48-6.52 (2Н,
m, Н-3,4 Fur); 6.59 (1Н, d, J = 3.2, Н-3' Fur); 6.72-6.73 (1Н, m, Н-4' Fur); 7.63-7.64 (1Н, m, Н-5 Fur);
3
7.69-7.70 (1Н, m, Н-5' Fur). The signals for the NH and NH+ protons were not observed as a result of deuterium
exchange. Found, %: С 56.27; Н 5.41; N 15.02. C22H25N5О2Se. Calculated, %: С 56.17; Н 5.36; N 14.89.
6-(Alkylseleno)-2,4-diaryl-1,4-dihydropyridine-3,3,5(2H)-tricarbonitriles 6a-e (General Method).
A mixture of the selenolate 5a,b (0.30 mmol) and the corresponding alkyl halide (0.30 mmol) in 70% EtOH
(20 ml) was refluxed under an argon stream to full dissolution of the starting reagents (1-3 min), rapidly filtered
through a paper filter, and left for 24 h at 25ºC in an argon atmosphere. The precipitate formed was filtered off
and washed with EtOH and hexane to give the selenides 6a-e, samples of which were purified from a suitable
solvent for analytical purposes.
1295

2-{[3,5,5-Tricyano-4,6-di(2-thienyl)-1,4,5,6-tetrahydropyridin-2-yl]seleno}-N-phenylacetamide
(6a). Yield 90 mg (56%), colorless crystals, mp 205-207ºC (EtOH–AcOH, 1:1). IR spectrum, ν, cm-1: 3411,
3302, 3210 (N–H), 2231, 2190 (C≡N), 1708 (С=О). 1Н NMR spectrum, δ, ppm (J, Hz): 3.85 (1Н, d, 2J = 13.5)
and 3.90 (1Н, d, 2J = 13.5, SeCH2); 5.24 (1Н, s, 4-CН); 5.74 (1Н, d, 3J = 1.0, 6-CН); 7.05 (1Н, t, 3J = 7.5, H-4 Ph);
7.10-7.11 (1H, m, Н-4 thienyl); 7.17-7.18 (1H, m, Н-4' thienyl); 7.25-7.29 (3H, m, H Ar); 7.49-7.59 (5H, m, H Ar);
8.99 (1Н, d, 3J = 1.0, NH); 10.34 (1Н, s, CONH). Found, %: С 53.72; Н 3.24; N 13.21. C24H17N5ОS2Se. Calculated,
%: С 53.93; Н 3.21; N 13.10.
2-{[3,5,5-Tricyano-4,6-di(2-thienyl)-1,4,5,6-tetrahydropyridin-2-yl]seleno}-N-(4-methylphenyl)acet-
amide (6b). Yield 55 mg (33%), beige powder, mp 212-214ºC (EtOH–AcOH, 1:1). IR spectrum, ν, cm-1: 3476,
1
3391, 3300 (N–H), 2249, 2194 (C≡N), 1710 (С=О). Н NMR spectrum, δ, ppm (J, Hz): 2.29 (3Н, s, ArСН3);
2
2
3
3.81 (1Н, d, J = 13.5) and 3.86 (1Н, d, J = 13.5, SeCH2); 5.22 (1Н, s, 4-СН); 5.73 (1Н, d, J = 1.0, 6-СН);
7.05 (2H, d, 3J = 8.3, H Ar); 7.10 (1H, dd, 3J = 5.1, 3J = 3.4, Н-4 thienyl); 7.15-7.16 (1H, m, Н-4' thienyl); 7.27
(1Н, d, 3J = 3.4, Н-3 thienyl); 7.38 (2H, d, 3J = 8.3, H Ar); 7.47-7.49 (2Н, m, H Ar); 7.56 (1Н, d, 3J = 5.1, Н-5
3
thienyl); 9.07 (1Н, d, J = 1.0, NH); 10.25 (1Н, s, CONH). Found, %: С 54.72; Н 3.53; N 12.91.
C25H19N5ОS2Se. Calculated, %: С 54.74; Н 3.49; N 12.77.
2,4-Di(2-furyl)-6-{[2-oxo-2-phenylethyl]seleno}-1,4-dihydropyridine-3,3,5(2H)-tricarbonitrile (6c).
Yield 75 mg (51%), colorless crystals, mp 185-187ºC (EtOH). IR spectrum, ν, cm-1: 3379, 3273 (NH), 2252,
2192 (C≡N), 1660 (С=О). 1Н NMR spectrum, δ, ppm (J, Hz): 4.70 (2Н, br. s, SeCH2); 5.08 (1Н, s, 4-СН); 5.45
(1Н, br. s, 6-СН); 6.49-6.50 (1Н, m, Н-4 Fur); 6.53-6.55 (1Н, m, Н-4' Fur); 6.60 (1Н, d, 3J = 3.2, Н-3 Fur); 6.80
(1Н, d, 3J = 3.2, Н-3' Fur); 7.49-7.53 (2H, m, H Ar); 7.60-7.63 (2H, m, H Ar); 7.70-7.72 (1Н, m, Н-5 Fur); 8.00
(2H, d, 3J = 8.1, H Ar); 8.16 (1Н, br. s, NH). Found, %: С 58.86; Н 3.39; N 11.63. C24H16N4О3Se. Calculated, %:
С 59.15; Н 3.31; N 11.50.
2,4-Di(2-furyl)-6-{[2-(4-methylphenyl)-2-oxoethyl]seleno}-1,4-dihydropyridine-3,3,5(2H)-tricarbo-
nitrile (6d). Yield 75 mg (50%), colorless crystals, mp 201-203ºC (AcOH). IR spectrum, ν, cm-1: 3212, 3131
(NH), 2276, 2193 (C≡N), 1660 (С=О). 1Н NMR spectrum, δ, ppm (J, Hz): 2.44 (3Н, s, ArCH3); 4.67 (2Н, br. s,
3
SeCH2); 5.09 (1Н, s, 4-CН); 5.46 (1Н, d, J = 2.0, 6-CН); 6.50-6.51 (1Н, m, Н-4 Fur); 6.54-6.56 (1Н, m, Н-4'
3
3
3
Fur); 6.60 (1H, d, J = 3.0, Н-3 Fur); 6.81 (1H, d, J = 3.0, Н-3' Fur); 7.31 (2Н, d, J = 8.1, H Ar); 7.64-7.65
(1Н, m, Н-5 Fur); 7.73-7.74 (1Н, m, Н-5' Fur); 7.89 (2Н, d, 3J = 8.1, H Ar); 8.17 (1Н, d, 3J = 2.0, NH). Found,
%: С 59.61; Н 3.66; N 11.24. C25H18N4О3Se. Calculated, %: С 59.89; Н 3.62; N 11.17.
3,5,5-Tricyano-2-{[4,6-di(2-furyl)-1,4,5,6-tetrahydropyridin-2-yl]seleno}-N-(4-methylphenyl)acet-
amide (6e). Yield 56 mg (36%), beige powder, mp 211-213ºC (AcOH). IR spectrum, ν, cm-1: 3432, 3301, 3180
(NH), 2251, 2198 (C≡N), 1650 (С=О, С=С). 1Н NMR spectrum, δ, ppm (J, Hz): 2.30 (3Н, s, ArCH3); 3.80 (1Н, d,
3J = 13.5) and 3.87 (1Н, d, 3J = 13.5, SeCH2); 5.07 (1Н, s, 4-CН); 5.53 (1Н, d, 3J = 1.7, 6-CН); 6.48-6.49 (1Н, m,
Н-4 Fur); 6.54-6.55 (1Н, m, Н-4' Fur); 6.58 (1Н, d, 3J = 3.4, Н-3 Fur); 6.84 (1Н, d, 3J = 3.4, Н-3' Fur); 7.06 (2Н, d,
3J = 8.3, H Ar); 7.41 (2Н, d, 3J = 8.3, H Ar); 7.61 (1Н, d, 3J = 1.0, Н-5 Fur); 7.68 (1Н, d, 3J = 1.2, Н-5' Fur); 8.93
(1Н, d, 3J = 1.7, NH); 10.24 (1Н, s, CONH). Found, %: С 57.91; Н 3.79; N 13.68. C25H19N5О3Se. Calculated, %:
С 58.15; Н 3.71; N 13.56.
Triethylammonium 4-Aryl-1,5,5-tricyano-3-azaspiro[5.5]undec-1-ene-2-thiolates 8a,b (General
Method). Et3N (0.35 ml, 2.5 mmol) was added to a mixture of the cyclohexylidenecyanothioacetamide 7
(300 mg, 1.66 mmol) and the corresponding arylmethylidenemalononitrile 4a,b (1.70 mmol) in a minimum
volume of cold acetone (1.5-2.0 ml). The solution obtained was stirred at 5ºC, and formation of a precipitate
began after 3-5 min. The reaction mixture was stirred for a further 2 h and left for 24 h in a fridge. The
precipitate was filtered off and washed successively with acetone and ether.
Triethylammonium 1,5,5-Tricyano-4-(2-furyl)-3-azaspiro[5.5]undec-1-ene-2-thiolate (8a). Yield
480 mg (68%), beige powder, mp 108-110ºC. IR spectrum, ν, cm-1: 3160 (NH), 2250 (5-C≡N), 2168 (1-C≡N).
3
1Н NMR spectrum, δ, ppm (J, Hz): 1.20 (9Н, t, J = 7.1, N(СН2CH3)3); 1.50-2.37 (10Н, m, (СН2)5); 2.99-3.02
(6Н, m, N(СН2CH3)3); 4.96 (1Н, br. s, 4-СН); 5.80 (1Н, br. s, 1-NН); 6.48-6.49 (1Н, m, Н-4 Fur);
1296

6.64-6.65 (1Н, m, Н-3 Fur); 7.63-7.64 (1Н, m, Н-5 Fur). The signals for the NH+ proton were not observed
likely as a result of deuterium exchange. Found, %: С 65.16; Н 7.46; N 16.44. C23H31N5ОS. Calculated, %:
С 64.91; Н 7.34; N 16.46.
Triethylammonium 1,5,5-Tricyano-4-phenyl-3-azaspiro[5.5]undec-1-ene-2-thiolate (8b). Yield
521 mg (72%), beige powder, mp 126-128ºC. IR spectrum, ν, cm-1: 3180 (NH), 2248 (5-C≡N), 2160 (1-C≡N).
1Н NMR spectrum, δ, ppm (J, Hz): 1.19 (9Н, t, 3J = 7.3, N(СН2CH3)3); 1.56-1.79 (8Н, m) and 2.33-2.47 (2Н, m,
3
(СН2)5); 3.02 (6Н, q, J = 7.3, N(СН2CH3)3); 4.85 (1Н, br. s, 4-СН); 5.84 (1Н, br. s, NН); 7.44-7.45 (2Н, m,
Н Ph); 7.54-7.57 (3Н, m, Н Ph). The signals for the NH+ proton were not observed likely as a result of
13
deuterium exchange. C NMR spectrum, δ, ppm: 8.8 (N(CH2CH3)3); 21.1*, 21.7* (C-3,5 cyclohexylidene); 24.9*
(C-4 cyclohexylidene); 33.4*, 35.0* (C-2,6 cyclohexylidene); 43.2* (С-4); 45.7* (N(CH2CH3)3); 51.7* (C-5); 57.8
(C-6); 70.7* (C-3); 113.2* (5-C≡N); 114.7* (5-C≡N); 126.7* (3-C≡N); 128.1 (C-2,3,5,6 Ph); 129.3 (C-4 Ph);
136.5* (C-1 Ph); 173.5 (C-2). Mass spectrum, m/z: 102.2 [Et3NH+]+, 352.0 [M-Et3N+H2O]+. Found, %: С 69.13;
Н 7.76; N 16.10. C25H33N5S. Calculated, %: С 68.93; Н 7.64; N 16.08.
4-(Alkylthio)-2-aryl-3-azaspiro[5.5]undec-4-ene-1,1,5-tricarbonitriles 9a-c (General Method). The
starting thiolate 8a,b (0.35 mmol) was dissolved with heating in 70% EtOH (5-7 ml), and a solution of the
corresponding N-substituted chloroacetamide (0.35 mmol) in EtOH (2-3 ml) was added. The mixture was
refluxed with vigorous stirring for 1-2 min (precipitation of the product usually began) and then stirred for 2-3 h
at 25ºC. After 24 h, the precipitate was filtered off and washed with 70% EtOH, Et2O, and petroleum ether to
give compounds 9a-c in an analytically pure state.
2-{[1,5,5-Tricyano-4-(2-furyl)-3-azaspiro[5.5]undec-1-en-2-yl]thio}-N-(4-methylphenyl)acetamide
(9a). Yield 99 mg (60%), fine, yellow-pink crystals, mp 234-236ºC. IR spectrum, ν, cm-1: 3300-3270 (NH),
1
2242 (5-C≡N), 2190 (1-C≡N), 1660 (С=О, С=С). Н NMR spectrum, δ, ppm (J, Hz): 1.22-2.11 (10Н, m,
(СН2)5); 2.29 (3Н, s, ArCH3); 3.87 (2H, br. s, SCH2); 5.34 (1Н, br. s, 4-CН); 6.53-6.54 (1Н, m, Н-4 Fur);
3
3
6.81-6.82 (1Н, m, Н-3 Fur); 7.07 (2H, d, J = 7.8, H Ar); 7.41 (2H, d, J = 7.8, H Ar); 7.71-7.72 (1Н, m, Н-5
Fur); 9.08 (1H, br. s, NH); 10.31 (1H, s, CONH). Found, %: С 66.18; Н 5.46; N 14.90. C26H25N5O2S.
Calculated, %: С 66.22; Н 5.34; N 14.85.
2-{[1,5,5-Tricyano-4-phenyl-3-azaspiro[5.5]undec-1-en-2-yl]thio}-N-(4-methylphenyl)acetamide (9b).
Yield 111 mg (66%), white powder, mp 262-264ºC. IR spectrum, ν, cm-1: 3280-3255 (NH), 2250 (5-C≡N), 2190
(1-C≡N), 1640 (С=О, С=С). 1Н NMR spectrum, δ, ppm (J, Hz): 1.22-2.10 (10Н, m, (СН2)5); 2.28 (3Н, s, ArCH3);
3.92 (1Н, d, 2J = 15.0) and 3.99 (1Н, d, 2J = 15.0, SCH2); 5.24 (1Н, br. s, 4-CН); 7.09 (2Н, d, 3J = 8.5, H Ar); 7.41
3
(2Н, d, J = 8.5, H Ar); 7.45-7.50 (3Н, m, H Ph); 7.63-7.65 (2H, m, H Ph); 8.96 (1H, br. s, NH); 10.30 (1H, s,
CONH). Found, %: С 69.98; Н 5.70; N 14.50. C28H27N5OS. Calculated, %: С 69.83; Н 5.65; N 14.54.
N-(3-Chlorophenyl-4-methyl-)-2-{[1,5,5-tricyano-4-phenyl-3-azaspiro[5.5]undec-1-en-2-yl]thio}acet-
amide (9c). Yield 112 mg (62%), fine, colorless needles, mp 245-247ºC. IR spectrum, ν, cm-1: 3240 (NH), 2250
1
(5-C≡N), 2193 (1-C≡N), 1655 (С=О, С=С). Н NMR spectrum, δ, ppm (J, Hz): 1.22-2.10 (10Н, m, (СН2)5);
2.30 (3Н, s, ArCH3); 3.89 (1Н, d, 2J = 15.1) and 3.95 (1Н, d, 2J = 15.1, SCH2); 5.14 (1Н, br. s, 4-CН); 7.16 (1Н,
d, 3J = 8.2, H Ar); 7.29 (1Н, d, 3J = 8.2, H Ar); 7.46-7.47 (3Н, m, H Ph); 7.60-7.62 (2H, m, H Ph); 7.67 (1Н, s,
H Ar); 8.83 (1H, br. s, NH); 10.42 (1H, s, CONH). Found, %: С 65.26; Н 5.11; N 13.60. C28H26ClN5OS.
Calculated, %: С 65.17; Н 5.08; N 13.57.
2-Amino-4-acyl-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitriles 12a,b were prepared by
the reported method [18] for the synthesis of the isomeric compounds 11. A mixture of the
cyclohexylidenecyanothioacetamide 7 (300 mg, 1.66 mmol), the corresponding arylmethylidenemalononitrile
4d,e (1.66 mmol), and Et3N (0.2 ml) in abs. EtOH (5 ml) was stirred for 24 h at 25ºC. An equal volume of iced
water was added, and the product was stirred. The resinous precipitate was separated and recrystallized from
EtOH. The obtained products were spectroscopically identical to the compounds prepared by Gewald and Schill
[19] and have a tetrahydronapthalene structure 12.
_______
*Asterisks indicate out of phase signals here and subsequently in the Experimental.
1297

2-Amino-4-(4-methoxyphenyl)-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitrile
(12a).
Yield 111 mg (20%), pale-yellow crystals, mp 248-250ºC (sublimes, mp 229ºC) [18], 253-254ºC [21], 239
1
(22)). Н NMR spectrum, δ, ppm (J, Hz): 0.80-0.87 (1Н, m), 1.40-1.48 (2Н, m), 1.63-1.70 (1Н, m), 2.05-2.20
(2Н, m) and 2.71-2.79 (1Н, m, 4a-СН, 5,6,7-CH2); 3.45 (1Н, d, 3J = 12.5, 4-СH); 3.78 (3H, s, OСН3); 5.70 (1H,
s, 8-CH); 6.98-7.05 (2Н, m, H Ar); 7.32-7.49 (4H, m, NH2, H Ar). 13С NMR spectrum, δ, ppm: 21.0 (CH2); 24.9
(CH2); 27.0 (CH2); 34.0* (C-4a); 43.1 (С-3); 50.1* (С-4); 55.1* (ОСН3); 81.6 (С-1); 112.5 (3-C≡N); 112.6
(3-C≡N); 113.6*, 114.3* (С-3,5 Ar); 116.1 (1-C≡N); 120.2* (C-8); 126.3 (C-8a); 128.0*, 133.5* (C-2,6 Ar);
128.9 (C-i Ar); 143.5 (C-2); 159.5 (C-4 Ar). Mass spectrum, m/z: 331.2 [M+H]+. Found, %: С 72.78; Н 5.50;
N 16.90. C20H18N4O. Calculated, %: С 72.71; Н 5.49; N 16.96.
2-Amino-4-(4-methylphenyl)-4a,5,6,7-tetrahydronaphthalene-1,3,3(4H)-tricarbonitrile
(12b).
1
Yield 114 mg (22%), white powder, mp 268-270ºC (sublimes, mp 278-280ºC [18], 245-247ºC [33]). Н NMR
spectrum, δ, ppm (J, Hz): 0.79-0.87 (1Н, m), 1.40-1.48 (2Н, m), 1.63-1.68 (1Н, m), 2.04-2.19 (2Н, m), and
3
2.73-2.78 (1Н, m, 4a-СН, 5,6,7-CH2); 2.33 (3H, s, ArСН3); 3.45 (1Н, d, J = 12.5, 4-СH); 5.71 (1H, s, 8-СН);
7.21-7.45 (6Н, m, NH2, H Ar). 13С NMR spectrum, δ, ppm: 20.7* (ArСН3); 21.0 (CH2); 24.8 (CH2); 27.0 (CH2);
33.9* (C-4a); 43.0 (С-3); 50.4* (С-4); 81.6 (С-1); 112.4 (3-C≡N); 112.5 (3-C≡N); 116.1 (1-C≡N); 120.3*
(C-8); 126.7*, 129.0*, 129.1*, 132.2* (С Ar); 128.9 (C-8a); 131.5 (C-4 Ar); 138.3 (C-i Ar); 143.6 (C-2). Mass
spectrum, m/z: 315.1 [M+H]+. Found, %: С 76.48; Н 5.80; N 17.72. C20H18N4. Calculated, %: С 76.41; Н 5.77;
N 17.82.
2-Amino-4-(4-methoxyphenyl)-5,6,7,8-tetrahydronapthalene-1,3-dicarbonitrile (13) was prepared
according to the reported method [18] for the synthesis of the isoquinolinethiones 10. A mixture of
cyclohexylidenecyanothienoacetamide 7 (300 mg, 1.66 mmol), 4-(methoxyphenyl)methylidenemalononitrile 4d
(306 mg, 1.66 mmol) and Et3N (0.2 ml) in 96% EtOH (8 ml) was refluxed for 2 h and left overnight (in the case
of the isoquinolinethione 10 it did not form a precipitate). The solution was diluted with iced water, held for 1
day at 0ºC, and the mother liquor was decanted, and the resinous precipitate was triturated with ether. The
obtained product was filtered off and recrystallized from EtOH. Yield 166 mg (33%), dark-yellow powder, mp
1
170-175ºC (decomp.) which was about 89% pure according to HPLC data. Н NMR spectrum, δ, ppm (J, Hz):
1.55-1.59 (2Н, m) and 1.70-1.75 (2Н, m, 6,7-СН2); 2.18-2.21 (2Н, m, 5-СН2); 2.83-2.86 (2Н, m, 8-СН2); 3.83
(3Н, s, OСН3); 6.36 (2H, br. s, NH2); 7.05 (2H, d, 3J = 8.3, H Ar); 7.21 (2H, d, 3J = 8.3, H Ar). Mass spectrum,
m/z: 304.2 [M+H]+.
5-Amino-7-phenylindane-4,6-dicarbonitrile (16). Piperidine (0.27 ml, 2.7 mmol) was added to a
suspension of the cyclopentylidenecyanothioacetamide (15) (300 mg, 1.8 mmol), benzylidenemalononitrile 4c
(278 mg, 1.8 mmol), and 96% EtOH (3 ml), and the mixture was stirred for 0.5 h and left for 24 h at 25ºC. The
precipitated crystals were filtered off and washed with EtOH. Yield 220 mg (47%), bright-yellow crystals, mp
1
211-213ºC (mp 220ºC [34], 226-228ºC [35], 148-149ºC [36]). Н NMR spectrum, δ, ppm: 1.96-1.99 (2Н, m,
2-СН2); 2.58-2.61 (2Н, m, 1-СН2); 2.99-3.02 (2Н, m, 3-СН2); 6.52 (2H, br. s, NH2); 7.39-7.51 (5H, m, Н Ph).
13С NMR spectrum, δ, ppm: 24.0 (C-2); 31.3 (C-1); 33.5 (C-3); 92.2, 94.1 (C-4,6); 115.4 (C≡N); 116.2 (C≡N);
128.3*, 128.4* (C-2,3,5,6 Ph); 128.8* (C-4 Ph); 130.9 (C-7a); 136.7 (C-i Ph); 145.7 (C-3a); 152.3 (C-7); 154.8
(C-5). Mass spectrum, m/z: 260.1 [M+H]+. Found, %: С 78.68; Н 5.10; N 16.22. C17H13N3. Calculated, %:
С 78.74; Н 5.05; N 16.20.
Reaction of Cyanothioacetamide (18) with Isobutyral and Benzylidenemalononitrile (4c). A
mixture of the cyanothioacetamide (18) (200 mg, 2.0 mmol), isobutyral (0.18 ml, 2.0 mmol), and
N-methylmorpholine (1 drop) was stirred in acetone (4 ml). After 5 min, the unsaturated nitrile 4c (308 mg,
2.0 mmol) and N-methylmorpholine (0.33 ml, 3.0 mmol) were added, and the mixture was stirred for 1 h at
25ºC. The precipitate formed was filtered off after 24 h to give the pure 2,6-diamino-4-phenyl-4H-thiopyran-
1
3,5-dicarbonitrile (19). Yield 351 mg (69%), pale-yellow powder, mp 183-185ºC (mp 184ºC [28]). H NMR
spectrum, , ppm: 4.25 (1H, s, 4-CH); 6.90 (4H, br. s, 2NH2), 7.22-7.27 (3H, m, H Ar); 7.32-7.36 (2H, m,
H Ar).
1298

X-ray Structural Analysis of Compound 6d. Crystals of compound 6d are triclinic (C25H18N4O3Se,
M 501.39). At 298 K: a 8.6829(2), b 10.6183(2), c 13.2165(3) Å;  110.158(2),  92,622(2),  92.0710(18)º;
–
V 1140.95(5) Å3; Z 2; space group P1, dcalc 1.46 g/cm3, (MoK) 1.68 mm-1; F(000) 508. The unit cell
parameters and intensities of 38694 reflections (7759 independent, Rint 0.027) were measured on an Xcalibur 3
automatic, four-circle diffractometer (MoK, graphite monochromator, CCD detector, -scanning, 2max
65.34º). The structure was solved by the direct method using the SHELX-97 program package [37]. The
positions of the hydrogen atoms were calculated geometrically and refined using the "rider" model with
Uiso = nUeq for the attached atom (n = 1.5 for a methyl group and n = 1.2 for remaining hydrogen atoms). The
structure was refined using F2 full-matrix least-squares analysis in the anisotropic approximation for non-
hydrogen atoms to wR2 = 0.082 for 7759 reflections (R1 0.032 for 6150 reflections with F > 4(F), S 1.02). For
refinement of the structure, limits were placed on the bond lengths in the disordered furan ring as follows: C–O
1.37(1), C(–C)=C(–H) 1.34(1), C(–H)=C(–H) 1.32(1), and C–C 1.42(1). The full crystallographic data for the
structure of compound 6d has been placed at the Cambridge Crystallographic Data Center (deposit CCDC
948637).
The authors are grateful to Prof. O. V. Shishkina (Scientific-Technological Complex "Institute of
Monocrystals", National Academy of Sciences of Ukraine, Kharkov) for carrying out the X-ray structural
analysis.
REFERENCES
1.
C. P. Dell, in: C. J. Moody (editor), Comprehensive Organic Functional Group Transformations, Vol.
5, Pergamon, Oxford (1995), p. 613.
2.
3.
4.
T. Murai, Top. Curr. Chem., 251, 247 (2005).
V. P. Litvinov, Usp. Khim., 68, 817 (1999).
V. V. Dotsenko, K. A. Frolov, and S. G. Krivokolysko, Khim. Geterotsikl. Soedin., 705 (2013). [Chem.
Heterocycl. Compd., 49, 657 (2013)].
5.
6.
B. Y. Riad, S. E. Abdou, F. A. Attaby, and S. A. Mansour, Sulfur Lett., 6, 105 (1987).
S. A. El-Sharabasy, S. M. Hussain, S. M. A. Gawad, and H. A. Daboun, Indian J. Chem., Sect. B: Org.
Chem. Incl. Med. Chem., 27B, 472 (1988).
7.
8.
9.
I. T. Barnish, C. W. G. Fishwick, D. R. Hill, and C. Szantay, Tetrahedron, 45, 7879 (1989).
J. Bloxham and C. P. Dell, J. Chem. Soc., Perkin Trans. 1, 989 (1994).
M. A. A. Elneairy, S. M. Eldin, F. A. Attaby, and A. K. K. El-Louh, Phosphorus, Sulfur Silicon Relat.
Elem., 167, 289 (2000).
10.
T. G. Deryabina, M. A. Demina, N. P. Bel'skaya, and V. A. Bakulev, Izv. Akad. Nauk, Ser. Khim., 2784
(2005). [Russ. Chem. Bull., Int. Ed., 54, 2880 (2005)].
11.
12.
13.
J. S. A. Brunskill, A. De, and D. F. Ewing, J. Chem. Soc., Perkin Trans. 1, 629 (1978).
J. S. A. Brunskill, A. De, and D. F. Ewing, J. Chem. Soc., Perkin Trans. 2, 4 (1980).
G. K. Lebedeva, I. Ya. Kvitko, and A. V. El'tsov, Khim. Geterotsikl. Soedin., 527 (1979). [Chem.
Heterocycl. Compd., 15, 429 (1979)].
14.
15.
I. I. Potapochkina, I. Ya. Kvitko, and G. I. Koldobskii, Zh. Org. Khim., 22, 2367 (1986). [J. Org. Chem.
USSR, 22, 2126 (1986)].
K. A. Frolov and S. G. Krivokolysko, Khim. Geterotsikl. Soedin., 1104 (2011). [Chem. Heterocycl.
Compd., 47, 909 (2011)].
16.
17.
Yu. V. Zefirov and P. M. Zorkii, Usp. Khim., 58, 713 (1989).
J. S. A. Brunskill, A. De, D. F. Ewing, and A. J. Welch, Acta Crystallogr., Sect. C: Cryst. Struct.
Commun., C40, 493 (1984).
1299

18.
19.
20.
G. E. H. Elgemeie, H. A. Regaila, and N. Shehata, J. Chem. Soc., Perkin Trans. 1, 1267 (1990).
K. Gewald and W. Schill, J. Prakt. Chem., 313, 678 (1971).
Yu. A. Sharanin, V. K. Promonenkov, and V. P. Litvinov, in: M.-G. A. Shvekhgeimer (editor),
Summaries of Science and Technology. Organic Chemistry [in Russian], Vol. 20 (I), VINITI, Moscow
(1995), p. 148.
21.
Yu. A. Sharanin, Yu. A. Baskakov, Yu. T. Abramenko, Yu. G. Putsykin, A. F. Vasil'ev, and E. B.
Nazarova, Zh. Org. Khim., 16, 2192 (1980). [J. Org. Chem. USSR, 16, 1870 (1980)].
I. A. El-Sakka, S. M. El-Kousy, and Z. E. Kandil, J. Prakt. Chem., 333, 345 (1991).
A. M. Shestopalov, Yu. M. Emel'yanova, and V. N. Nesterov, Izv. Akad. Nauk, Ser. Khim., 1103
(2003)]. [Russ. Chem. Bull., Int. Ed., 52, 1164 (2003)].
22.
23.
24.
E. S. Kurbatov, V. V. Krasnikov, and V. V. Mezheritskii, Zh. Org. Khim., 42, 472 (2006). [Russ. J. Org.
Chem., 42, 460 (2006)].
25.
26.
H. M. Al-Matar, K. D. Khalil, H. Meier, H. Kolshorn, and M. H. Elnagdi, ARKIVOC, xvi, 288 (2008).
V. A. Tafeenko, T. V. Bogdan, and L. A. Aslanov, Zh. Strukt. Khim., 35, No. 3, 78 (1994). [J. Struct.
Chem., 35, 345 (1994)].
27.
28.
29.
L. Rong, H. Han, H. Jiang, and S. Tu, Synth. Commun., 38, 3530 (2008).
G. E. H. Elgemeie, M. M. M. Sallam, S. M. Sherif, and M. H. Elnagdi, Heterocycles, 23, 3107 (1985).
Yu. A. Sharanin, A. M. Shestopalov, V. P. Litvinov, V. Yu. Mortikov, L. A. Rodinovskaya, M. P.
Goncharenko, and V. K. Promonenkov, Zh. Org. Khim., 22, 1962 (1986). [J. Org. Chem. USSR, 22,
1986)].
30.
V. P. Litvinov and V. Dyachenko, Zh. Org. Khim., 35, 1406 (1999). [Russ. J. Org. Chem., 35, 1377
(1999)].
31.
32.
V. V. Dotsenko, S. G. Krivokolysko, and V. P. Litvinov, J. Heterocycl. Chem., 48, 162 (2011).
V. V. Dotsenko, S. G. Krivokolysko, V. V. Polovinko, and V. P. Litvinov, Khim. Geterotsikl. Soedin.,
328 (2012). [Chem. Heterocycl. Compd., 48, 309 (2012)].
33.
34.
35.
36.
37.
F. F. Abdel-Latif and R. M. Shaker, J. Chem. Res. (Synop.), No. 4, 146 (1995).
G. E. H. Elgemeie, A. M. Elzanate, and A. K. Mansour, J. Chem. Soc., Perkin Trans. 1, 1073 (1992).
J. Mirek and P. Milart, Z. Naturforsch., B: Anorg. Chem., Org. Chem., 41, 1471 (1986).
K. Komorowski, DE Pat. Appl. 2340569; Chem. Abstr., 82, 29862 (1975).
G. Sheldrick, Acta Cryst., Sect. A: Found. Crystallogr., 64, 112 (2008).
1300