Reactivity of N,N″-1,ω-alkanediyl-bis-[N′-organylthiourea] Derivatives Towards Isatylidene Malononitrile

Article abstract of DOI:10.1002/jhet.2524

(Z)-2-(2-Oxoindolin-3-ylidene)-2-(substituted amino)acetonitriles, 2-thioxoimidazolidine-1-carbothioamides, and 2-thioxotetrahydropyrimidine-1(2H)-carbothioamides were synthesized via conventional thermal or microwave-assisted reaction of isatylidene malo

Full text of DOI:10.1002/jhet.2524

Month 2015
Reactivity of N,N″-1,ω-alkanediyl-bis-[N′-organylthiourea] Derivatives
Towards Isatylidene Malononitrile
a
a
a
b
c
*
Alaa A. Hassan, Kamal M. A. El-Shaieb, Amal S. Abd El-Aal, Stefan Bräse, and Martin Nieger
aChemistry Department, Faculty of Science, Minia University, El-Minia 61519, Egypt
bInstitute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg6, Karlsruhe 76131, Germany
cLaboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, A. I. Virtasen aukio I,
Helsinki 00014, Finland
*
E-mail: alaahassan2001@mu.edu.eg
Additional Supporting Information may be found in the online version of this article.
Received May 16, 2015
DOI 10.1002/jhet.2524
Published online 00 Month 2015 in Wiley Online Library (wileyonlinelibrary.com).
(Z)-2-(2-Oxoindolin-3-ylidene)-2-(substituted amino)acetonitriles, 2-thioxoimidazolidine-1-carbothioamides,
and 2-thioxotetrahydropyrimidine-1(2H)-carbothioamides were synthesized via conventional thermal or
microwave-assisted reaction of isatylidene malononitrile with N,N″-1,ω-alkanediyl-bis-[N′-organylthiourea] de-
rivatives. Rationale for these conversations involving the nucleophilic addition on the dicyanomethylene carbon
atom and intramolecular heterocyclization of the title compounds is presented. The structure of the (Z)-2-(2-
oxoindolin-3-ylidene)-2-(phenylamino)acetonitrile has been confirmed by the X-ray analysis.
J. Heterocyclic Chem., 00, 00 (2015).
INTRODUCTION
RESULTS AND DISCUSSION
Isatylidene malononitrile is an especially important
starting material or intermediate for the synthesis of various
heterocyclic [1–3], noncyclic [4–8], and spiro compounds
as a Michael acceptor or an activating double bond [9–20].
Literature surveys reveal that various derivatives of isatin
possess diverse activities such as antibacterial [21], antifun-
gal [22], antiviral [23], anti-HIV [24], anticancer [25], and
anticonvulsant activities [26].
3-Substituted indoles had been used as starting materials
for the synthesis of a number of alkaloids, agrochemicals,
and pharmaceuticals [27].
It has been reported that 1-acetyl-3-dicyanomethylene
isatin reacted with aniline in nonpolar solvents, leading to
cyanoenamines [28]. Multicomponent reaction of ninhy-
drin, malononitrile, and sodium azide in H2O, the desired
2-(1,3-dioxo-1H-inden-2-(3H)-ylidene)-2-(1H-tetrazol-5-
yl)acetonitrile, was obtained [3].
However, those methods for synthesis of (substituted
amino-2-oxoindolin-3-ylidene)acetonitriles still have some
disadvantages including long-reaction times, expensive re-
agents, and unavailable catalyst for activation, water sensi-
tivity, drastic conditions, and low yields.
On the other hand, recently, we have reported the reac-
tion of N,N″-1,ω-alkanediyl-bis[N′-organylthiourea] deriv-
atives 1a–h with dimethyl acetylenedicarboxylate 2 to give
bis(thiazolidin-4-ones) 3a–h (Scheme 1) [29]. Also, bis-
oxathiaaza[3.3.3]propellane derivatives were synthesized
by the reaction of bithioureas 1 with (1,3-dioxo-2,3-
dihydro-1H-inden-2-ylidene)propanedinitrile [30].
In this article, when we carried out the reaction of N,N″-
1,ω-alkanediyl-bis[N′-organylthiourea] derivatives 1a–d
with isatylidene malononitrile 4 [the analogues of
(dioxoindenylidene)propanedinitrile] under conventional
thermal or microwave (MW) assisted in EtOH/pip./DMF
as a solvent, we observed an unexpected process leading
of the functionalized (substituted amino-2-oxoindolin-3-
ylidene)acetonitriles
5a–d,
2-thioxoimidazolidine-1-
carbothioamides 6a–d, or 2-thioxoperhydropyrimidine-1-
carbothioamides 7, instead of the anticipated spiro
indolone derivatives 8a–d and 9a–d (Scheme 2).
Considering the advantage of MW irradiation, we have de-
veloped a simple and efficient method for the synthesis of
substituted amino-2-oxoindolin-3-ylidene)acetonitriles 5a–d.
Different solvents, such as acetic acid, ethanol/pyridine, and
DMF, were explored; the best result was obtained when the re-
action was observed in EtOH/DMF mixture, and one drop of
piperidine was employed.
When either conventionally heated (method A) or MW irra-
diation (method B) in the presence of EtOH/DMF and piperi-
dine (see Table 1 for details), a sticky residue was always
obtained. Chromatographic separation gave numerous zones,
from the most intense of which the (substituted amino-2-
oxoindolin-3-ylidene)acetonitriles 5a–d and the cyclization
products 6a–d or 7 could be isolated (Table 1 and
Scheme 2).
Earlier, it has been reported that aniline reacted with 4 to
give green crystals of 5a; the structure of the isolated prod-
uct was assigned on the IR and elemental analysis [31].
© 2015 HeteroCorporation

A. A. Hassan, K. M. A. El-Shaieb, A. S. Abd El-Aal, S. Bräse, and M. Nieger
Vol 000
Table 1
Scheme 1. Reaction of 1a–h with 2.
Reactions of 1a–d and 4 by conventional heating
(A) and microwave irradiation (B).
Yields of products
in milligram (%)
Starting
materials
(mmol)
Reaction
conditions
Method A Method B
1a + 4
(1.0 + 1.0)
1b + 4
(1.0 + 1.0)
1c + 4
(1.0 + 1.0)
1d + 4
A = reflux for 13 h
5a; 60 (31)
5a;115 (59)
6a; 89 (28)
5b; 107 (55)
6b; 97 (27)
5c; 109 (56)
6c; 67 (28)
5d; 111 (57)
6d; 66 (28)
7; 114 (33)
B = 700 power, 8 min 6a; 63 (19)
A = reflux for 15 h 5b; 53 (27)
B = 700 power, 1 min 6b; 54 (15)
A = reflux for 14 h 5c; 49 (25)
B = 700 power, 9 min 6c; 46 (18)
A = reflux for 11 h 5d; 55 (28)
B = 700 power, 7 min 6d; 51 (22)
(1.0 + 1.0)
1e + 4
A = reflux for 12 h
7; 72 (21)
(1.0 + 1.0)
B = 700 power, 6 min
Scheme 2
(around 9.46 for R = Ph, 7.82 for R = Bn, 7.47 for R = al-
lyl, and 7.41 for R = ethyl). The downfield shift of NHR
was attributed to intramolecular hydrogen bond between
NHR and indolone-CO.
1
The H NMR of allyl clearly shows three multiples at
4.10–4.25, 5.16–5.21, and 5.72-5.85 due to (allyl-CH2N),
(allyl-CH2=), and (allyl-CH=), respectively. Another four
protons because of aromatic protons were observed.
The decoupled carbon spectra of 5c showed signals
at 118.12 and 168.32 assigned to cyano group and
indolone-CO, respectively. The 13C-DEPT-NMR spec-
trum of 5c showed negative signals at 44.65 and
118.31 ppm, confirming the presence of allyl-CH2N
and allyl-CH2=, whereas 13C-DEPT-NMR spectrum of
5c showed positive signal at δc = 134.25 due to allyl-
CH=.
Moreover, structure of compound 5a was confirmed
unambiguously by single crystal X-ray structure
analysis (Fig. 1 and Tables S1–S7 in Supplementary
Information).
In the title compound C16H11N3O (Fig. 1), the nine-
membered 1H-indole ring system is essentially planar with
a mean deviation of 0.011 Ǻ from the N1/C3A–C7A/C2/
C3 l.s.-plane.
In the crystal, an intramolecular hydrogen bonding be-
tween Ph(NH) and indolone-CO confirms a cisoid geome-
try with respect to C3–C8 (note that the crystallographic
numbering does not correspond to IUPAC numbering
rules) (Fig. 1).
The formation of 2-(2-oxoindolin-3-ylidene)-2-(substituted
amino)acetonitriles 5a–d and imidazolidine as well as
dihydropyrimidine derivatives (6a–d and 7) can be rational-
ized as depicted in Scheme 3. An initial attack by HN-R of
1a–e on the C=C double bond of 4 afforded the intermediate
10, because the cyclization to 6a–d and 7 involves intramo-
lecular nucleophile attack of the thioamide-NH on the
In our hands, the structure of 5a–d was determined on
the basis of their IR, NMR, and mass spectrometry.
The IR spectrum of 5c as an example contained absorption
bands belonging to the stretching vibration of conjugated cy-
ano group at 2217 cmÀ1, sharp band for indolone-CO at
1672 cmÀ1, broad bands at 3258–3288 cmÀ1 because of
1
NH’s. The H NMR spectra of all derivatives 5a–d show
two NH proton signals each, one at 10.59–10.98 due to
indolone-NH. The δH values for the exocyclic NHR
groups (in 5a–d) are dependent on the nature of R
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2015
N,N′-1,ω-Alkanediyl-bis-[N′-organylthiourea] and Isatylidene Malononitrile
EXPERIMENTAL
Gallenkamp melting point apparatus were used for the
determination of the melting points (Weiss-Gallenkamp,
Loughborough, UK), and uncorrected. The IR spectra
(KBr) discs were recorded on
a
Bruker FT-IR
(BrukerBioSpin, Karlsruhe, Germany) and Shimadzu 408
instruments (Shimadzu Corporation, Kyoto, Japan);
1
400-MHz H NMR and 100-MHz 13C NMR spectra were
determined on a Bruker AM 400 spectrometer with
tetramethylsilane as the internal standard, s =singlet,
t =triplet, q = quartet, m =multiplet, and b= broad. The
13C NMR signals were assigned on the basis of DEPT
135/90 spectra. Chemical shifts are expressed as δ (ppm).
The mass spectra (70 eV, electron impact mode) were
recorded on Finnigan MAT 312 (Germany) instrument
and 8430 instrument. The elemental analysis for C, H,
and N was carried out at the Micro Analytical Center,
Cairo University, Egypt (Elmyer 306 analyzer).
Preparative layer chromatography (plc) used air-dried
1.0-mm-thick layers of slurry applied silica gel (Merck Pf
254) on 48-cm-wide and 20-cm-high glass plates using
the solvents listed. MW irradiation were made using
START Lab station for MW-enhanced chemistry oven.
Figure 1. Molecular structure of 5a in the crystal (displacement parame-
ters are drawn at 50% probability level). The crystallographic numbering
does not reflect the systematic IUPAC numbering.
Scheme 3
STARTING MATERIALS
N,N′′-(1,ω-alkanediyl)bis(N′-organylthiourea) derivatives
1a–e were prepared by the reaction of the diamine
(1,2-diaminoethane, 1,3-diaminopropane) with ethyl-,
phenyl-, benzyl-, or allylisothiocyanate in DMF according
to published procedures in literature: (1a) [32], (1b) [33],
(1c) [34], (1d) [35], and (1e) [36]. 1,3-dihydro-3-
dicyanoethylene-2H-indol-2-one (4) was prepared according
to the procedure [37].
Reactions of 1,3-dihydro-3-dicyanoethylene-2H-indol-2-
one (4) with Organylthiourea Derivatives 1a–e. Method A:
By Conventional Heating.
Substituted organylthioureas
1a–e (1.0 mmol) were dissolved in 20-mL absolute
ethanol with two drops of piperidine and 2-mL DMF.
The mixture was added to indolone 4 (1.0 mmol) in
10-mL absolute ethanol and heated in an oil bath for
11–15h. Colorless crystals from compound 2-thioxoimi
dazolidine-1-carbothioamides 6a–d or 2-thioxotetrahydro
pyrimidine-1-carbothioamide 7 were precipitated, filtered,
and washed with a small amount of cold ethanol. The
filtrate was concentrated and subjected to plc using
toluene/ethyl acetate (10:2) as developing solvent to give
numerous zones from which the most intense orange
zone was extracted to give (substituted amino-2-
oxoindolin-3-ylidene)acetonitriles, recrystallization from
listed solvents.
thiocarbonyl group with elimination (oxoindolin-3-yli-
dene)-2-(substituted amino)acetonitriles 5a–d (Scheme 3).
CONCLUSION
Reaction of easily accessible neat title compounds with
isatylidene malononitrile allows a clean, fast, and conve-
nient method for the preparation of five-membered and
six-membered diaza-heterocyclic thiones along with
(oxoindolin-3-ylidene)-2-(substituted amino)acetonitriles.
Yields may be moderately enhanced by MW application
instead of conventional heating.
Method B: By Microwave Irradiation.
Equimolar
amounts of 1a–e (1.0 mmol) and 4 (195mg, 1.0 mmol)
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

A. A. Hassan, K. M. A. El-Shaieb, A. S. Abd El-Aal, S. Bräse, and M. Nieger
Vol 000
were well mixed in 10-mL absolute ethanol with two drops
of piperidine and 2-mL DMF. The mixture was irradiated
via MW oven under reflux condenser (the time of
irradiation as monitored in Table 1). After completion of
the reaction, the residue was separated as reported earlier.
(E)-2-(2-Oxoindolin-3-ylidene)-2-(phenylamino)acetonitrile
(5a). Orange crystals (heptane), mp 178–180°C; IR (KBr):
7.38–7.41 (m, 1H, Ar-H), 7.41 (br, s, 1H, NH-C2H5), 10.59
(br, s, 1H, indole-NH); 13C NMR (DMSO-d6): δc 15.78
(CH3), 49.14 (CH2), 117.98 (CN), 120.95 (=C-CN), 127.25
(indolone-C3), 121.70, 121.87, 122.19, 122.78 (Ar-CH),
136.13, 138.24 (Ar-C), 168.01 (indolone-CO); ms: m/z (%)
213 (M+, 81), 184 (19), 169 (23), 119 (54), 76 (100), 68
(72). Anal. Calcd. for C12H11N3O (213.24): C, 67.72; H,
5.20; N, 19.71. Found: C, 67.90; H, 5.26; N, 19.55.
υ = 3262–3290 (NH), 2230 (CN), 1671 (CO), 1615 (Ar-
1
C=C). H NMR (DMSO-d6): δH 7.24–7.28 (m, 1H, Ar-H),
N-Phenyl-2-thioximidazolidine-1-carbothioamide (6a). mp 176–177
6.95–6.97 (m, 1H, Ar-H), 7.09–7.14 (m, 1H, Ar-H), 7.35–
7.38 (m, 1H, Ar-H), 7.41–7.46 (m, 2H, Ar-H), 7.96–7.98 (m,
2H, Ar-H), 7.20–7.23 (m, 1H, Ar-H), 9.46 (br, s, 1H, NH-
Ph), 10.98 (br, s, 1H, indole-NH); 13C NMR (DMSO-d6): δc
118.71 (CN), 121.14 (=C–CN), 127.55 (indolone-C3),
121.61, 122.24, 125.40, 126.04, 127.03, 129.07, 129.73 (Ar-
CH), 136.50, 138.86, 139.81 (Ar-C), 168.98 (indolone-CO);
ms: m/z (%) 261 (M+, 78), 234 (100), 206 (28), 45 (19), 77
(67). Anal. Calcd. for C16H11N3O (261.28): C, 73.55; H,
(lit. 176–177) °C [38].
2-Thioxoimidazolidine-1-carbothioicbenzylamide (6b). mp 137–139
(lit. 135–136) °C [39].
N-Allyl-2-thioxoimidazolidine-1-carbothioamide (6c). mp 123–125
(lit. 126–128) °C [33].
N-Ethyl-2-thioxoimidazolidine-1-carbothioamide (6d). mp 168–170
(lit. 166–167) °C [40].
N-Phenyl-2-thioxotetrahydropyrimidine-1(2H)-carbothio-amide
(7). mp 155–156 (lit. 150–152) °C [41].
4.24; N, 16.08. Found: C, 73.64; H, 4.30; N, 16.23.
(E)-2-(Benzylamino)-2-(2-oxoindolin-3-ylidene)acetonitrile
(5b). Orange crystals (heptane), mp 168–170°C; IR (KBr):
SINGLE CRYSTAL X-RAY STRUCTURE
DETERMINATION OF 5A
υ =3265–3298 (NH), 2235 (CN), 1676 (CO), 1617 (Ar-
C=C); 1H NMR (DMSO-d6): δH 4.72 (s, 2H, CH2Ph),
6.79–6.83 (m, 1H, Ar-H), 7.15–7.22 (m, 1H, Ar-H), 7.25–
7.28 (m, 1H, Ar-H), 7.29–7.33 (m, 1H, Ar-H), 7.39–7.44
(m, 2H, Ar-H), 7.46–7.51 (m, 2H, Ar-H), 7.00–7.12 (m,
1H, Ar-H), 7.82 (br, s, 1H, NH-CH2Ph), 10.67 (br, s, 1H,
indole-NH); 13C NMR (DMSO-d6): δc 58.27 (CH2),
118.81 (CN), 122.30 (=C-CN), 128.18 (indolone-C3),
121.24, 122.14, 122.28, 123.22, 126.16, 128.18, 129.02
(Ar-CH), 136.45, 138.35, 139.50 (Ar-C), 168.66 (indolone-
CO); ms: m/z (%) 275 (M+, 80), 248 (100), 157 (32), 106
(44), 91 (70). Anal. Calcd. for C17H13N3O (275.11): C,
Single crystals were obtained by recrystallization from hep-
tane. The single crystal X-ray diffraction study was carried out
on a Bruker-Nonius Kappa CCD diffractometer at 123K using
MoKα radiation (λ = 0.71073 Ǻ). Direct methods (SHELXS-
97 [42]) were used for structure solution and refinement using
SHELXL-2013 [42] (full-matrix least-squares on F2). Hydro-
gen atoms were localized by different electron density determi-
nation and refined using a riding model (H(N)) free. Refined as
1 2-component pseudo-merohedral twin (twin-matrix (À1 0 0,
0 À1 0, 1 0 1), BASF 0.373(1)). A semi-empirical absorption
correction was applied.
Compound 5a. C16H11N3O, Mr = 261.28 gmolÀ1, orange
plates, crystal size 0.36× 0.15 ×0.03 mm, monoclinic space
group, P21/c (no. 14), a=7.601(1) Å, b=6.430(1) Å,
c=25.602 (4) Å, β =98.46(1)°, V=1237.7(3) Å3, Z=4,
74.17; H, 4.76; N, 15.26. Found: C, 74.24; H, 4.60; N, 15.35.
(E)-2-(Allylamino)-2-(2-oxoindolin-3-ylidene)acetonitrile
(5c). Yellowish orange crystals (heptane), mp 110–111°C;
IR (KBr): υ= 3258–3288 (NH), 2217 (CN), 1672 (CO),
1
Dcalcd =1.402Mg/m3,
F(000)=544,
μ =0.091mmÀ1
,
1616 (Ar-C=C); H NMR (DMSO-d6): δH 4.10–4.25 (m,
2H, allyl-CH2N), 5.16–5.21 (m, 2H, allyl-CH2=), 5.72–5.85
(m, 1H, allyl-CH=), 7.06–7.15 (m, 1H, Ar-H), 7.21–7.30 (m,
1H, Ar-H), 7.34–7.36 (m, 1H, Ar-H), 7.38–7.40 (m, 1H, Ar-
H), 7.47 (br, s, 1H, NH-allyl), 10.63 (br, s, 1H, indole-NH);
13C NMR (DMSO-d6): δc 118.31 (allyl-CH2), 134.25 (allyl-
CH=), 44.65 (allyl-CH2N), 118.12 (CN), 121.21 (=C-CN),
127.43 (indolone-C3), 121.71, 121.95, 122.29, 122.82 (Ar-
CH), 136.01, 138.31 (Ar-C), 168.32 (indolone-CO); ms: m/z
(%) 225 (M+, 82), 169 (24), 119 (31), 91 (100), 57 (55), 41
(59). Anal. Calcd. for C13H11N3O (225.25): C, 69.32; H,
4.92; N, 18.66. Found: C, 69.19; H, 5.03; N, 18.72.
(E)-2-(Ethylamino)-2-(2-oxoindolin-3-ylidene)acetonitrile
(5d). Yellowish orange crystals (heptane), mp 158–160°C;
IR (KBr): υ =3252–3278 (NH), 2223 (CN), 1672 (CO), 1612
(Ar-C=C); 1H NMR (DMSO-d6): δH 1.22 (t, 3H, CH3,
J= 7.21), 3.28 (q, 2H, CH2, J=7.21), 6.98–7.01 (m, 1H, Ar-H),
7.06–7.25 (m, 1H, Ar-H), 7.32–7.37 (m, 1H, Ar-H),
T=123K, 13,799 measured reflections (2θmax =55°), 2963
independent reflections [Rint =0.061], 188 parameters, two
restraints, R1 [for 2646 reflections with I> 2σ(I)]=0.044,
wR2 (for all data )=0.106, S=1.05, largest difference
peak and hole=0.241/À0.238eÅÀ3
.
REFERENCES AND NOTES
[1] Shanthi, G.; Perumal, P. T. Tetrahedron Lett 2008, 49, 7139.
[2] Lashgari, N.; Ziarani, G. M. Arkivoc 2012, (i), 277.
[3] Tisseh, Z. N.; Dabiri, M.; Nobahar, M.; Khavasi, H. R.;
Bazgir, A. Tetrahedron 2012, 68, 1769.
[4] Liu, L.; Wu, D.; Li, X.; Wang, S.; Li, H.; Li, J.; Wang, W.
Chem Commun 2012, 48, 1692.
[5] Zhao, H.; Lan, Y.- B.; Liu, Z.- M.; Wang, Y.; Wang, X.- W.;
Tao, J.- C. Eur J Org Chem 2012, 2012, 1935.
[6] Hosseini-Sarvari, M.; Tavakolian, M. New J Chem 2012, 36,
1014.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2015
N,N′-1,ω-Alkanediyl-bis-[N′-organylthiourea] and Isatylidene Malononitrile
[7] Liu, Z.- M.; Li, N.- K.; Huang, X.- F.; Wu, B.; Li, N.; Kwok,
[24] Sriram, D.; Yogeeswari, P.; Myneedu, N. S.; Saraswat, V.
Bioorg Med Chem Lett 2006, 16, 2127.
[25] Gürsoy, A.; Karali, N. Eur J Med Chem 2003, 38, 633.
[26] Verma, M.; Pandeya, S. N.; Singh, K. N.; Stables, J. P. Acta
Pharm 2004, 54, 49.
[27] Süzen, S.; Buyukbingol, E. II Farmaco 1998, 53, 525.
[28] Younes, M. I. Liebigs Ann Chem 1990, 703.
[29] Hassan, A. A.; El-Shaieb, K. M. A.; Abd El-Aal, A. S.;
Bräse, S.; Nieger, M. Z Naturforsh (B) 2015, 70, 243.
[30] Hassan, A. A.; El-Shaieb, K. M. A.; Abd El-Aal, A. S.;
Bräse, S.; Nieger, M. Aust J Chem 2015 (In Press).
[31] Sadek, K. U.; Selim, M. A.; Ali, M.; Elnagdi, M. H. Hetero-
atom Chem 1995, 6, 597.
C.- Y.; Wang, Y.; Wang, X.- W. Tetrahedron 2014, 70, 2406.
[8] Kumar, A.; Chimni, S. S. Beilstein J Org Chem 2014, 10, 929.
[9] Redkin, R. G.; Shemchuk, L. A.; Chernykh, V. P.; Shishkin,
O. V.; Shishkina, S. V. Tetrahedron 2007, 63, 11444.
[10] Chen, W.- B.; Wu, Z.- J.; Pei, Q.- L.; Cun, L.- F.; Zhang,
X.- M.; Ynan, W.- C. Org Lett 2010, 12, 3132.
[11] Wang, J.; Li, J.; Liu, H.; Xu, Z.; Zhu, S. Lett Org Chem 2015,
12, 62.
[12] El-Ossaily, Y. A.; Zaki, R. M.; Metwally, S. A. J Sci Res 2014,
6, 293.
[13] Cheng, D.; Ishihara, Y.; Tan, B.; Barbas, C. F. ACS Catal
2014, 4, 743.
[14] Chen, N.- Y.; Ren, L.- P.; Zou, M.- M.; Xu, Z.- P.; Shao, X.- S.;
Xu, X.- Y.; Li, Z. Chin Chem Lett 2014, 25, 197.
[32] D’ Angeli, F.; Bandel, A.; Giormani, V. J Org Chem 1963, 28,
1596.
[15] Tisseh, Z. N.; Ahmadi, F.; Dabiri, M.; Khavasi, H. R.;
Bazgir, A. Tetrahedron Lett 2012, 53, 3603.
[16] Hassan, A. A.; Abdel-Latif, F. F.; Nour El-Din, A. M.; Abdel-
Aziz, M.; Mostafa, S. M.; Br se, S. J Heterocyclic Chem 2011, 48, 1050.
[17] Yin, X.- G.; Liu, X.- Y.; Hu, Z.- P.; Yan, M. Org Biomol
Chem 2012, 10, 1506.
[18] Huang, X.- F.; Zhang, Y.- F.; Qi, Z.- H.; Li, N.- K.;
Geng, Z.- C.; Li, K.; Wang, X.- W. Org Biomol Chem 2014, 12, 4372.
[19] Jiang, X.; Sun, Y.; Yao, J.; Cao, Y.; Kai, M.; He, N.; Zhang, X.;
Wang, Y.; Wang, R. Synth Catal 2012, 354, 917.
[33] Hassan, A. A.; Mourad, A. E.; El-Shaieb, K. M. A.; Abou-
Zied, A. H.; Döpp, D. Heteroatom Chem 2003, 14, 535.
[34] Mizrakh, L. T.; Polonskaya, L. Y.; Gvozdetskii, A. N.;
Vosil’ev, A. M.; Ivanova, T. M.; Lisina, N. I. Khim-Farm Zn 1987, 12,
322; Chem Abstr 1988, 108, 21771r.
[35] Müller, K.- D.; N gele, H. Monatsh Chem 1912, 33, 941.
[36] Müller, K.- D.; Gerwarth, U. W. J Organomet Chem 1976,
110, 15.
[37] Dandia, A.; Singh, R.; Schdeva, H.; Gupta, R.; Paul, S. J Chin
Chem Soc 2003, 50, 273.
[20] Lan, Y.- B.; Zhao, H.; Liu, Z.- M.; Liu, G.- G.; Tao, J.- C.;
Wang, X.- W. Org Lett 2011, 13, 4866.
[38] Matsumura, N.; Kusamiya, M.; Inoue, H.; Iwasaki, F.
J Heterocyclic Chem 1995, 32, 1269.
[21] Kassab, S.; Hegazy, G.; Eid, N.; Amin, K.; El-Gendy, A.
Nucleosides Nucleotides Nucleic Acids 2010, 29, 72.
[22] Dandia, A.; Singh, R.; Khaturia, S.; M rienne, C.; Morgant, G.;
Loupy, A. Bioorg Med Chem 2006, 14, 2409.
[39] Di Bello, C.; Veronese, C. A.; Tonrolo, C.; Filira, F.;
D’Angeli, F. Gazz Chim Ital 1970, 100, 86.
[40] D’Angeli, F.; Bandel, A. Tetrahedron Lett 1961, 1, 5.
[41] Hassan, A. A.; Döpp, D. J Heterocycl Chem 2006, 43, 593.
[42] Sheldrick, G. M. Acta Crystallogr 2008, A64, 112.
[23] Quenelle, D.; Keith, K.; Kern, E. Antiviral Res 2006, 71, 24.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet