Heterocyclisation of substituted ylidenethiocarbonohydrazides using dimethyl acetylenedicarboxylate

Article abstract of DOI:10.1515/chempap-2015-0092

A facile and rapid procedure for the synthesis of dimethyl-2-[3-amino-5-(2-methoxy-2-oxoethylidene)- 4-oxothiazolidin-2-ylidenehydrazono]succinate, dimethyl {[2-alkylidenehydrazono)-5-(2-methoxy- 2-oxoethylidene)-4-oxothiazolidin-3-yl)amino]succinate and

Full text of DOI:10.1515/chempap-2015-0092

Chemical Papers 69 (7) 973–982 (2015)
DOI: 10.1515/chempap-2015-0092
ORIGINAL PAPER
Heterocyclisation of substituted ylidenethiocarbonohydrazides
using dimethyl acetylenedicarboxylate
a
b
aAlaa A. Hassan*, Fathy F. Abdel-Latif, Mohamed Abdel Aziz,
aSara M. Mostafa, Stefan Bräse, Martin Nieger
c
d
aChemistry Department, Faculty of Science, bDepartment of Medicinal Chemistry, Faculty of Pharmacy, El-Minia University,
El-Minia 61519, Egypt
cInstitute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
dLaboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki,
P.O. Box 55 (A. I. Virtasen aukio 1), 00014 Helsinki, Finland
Received 12 August 2014; Revised 5 December 2014; Accepted 8 December 2014
A facile and rapid procedure for the synthesis of dimethyl-2-[3-amino-5-(2-methoxy-2-oxoethyli-
dene)-4-oxothiazolidin-2-ylidenehydrazono]succinate, dimethyl {[2-alkylidenehydrazono)-5-(2-meth-
oxy-2-oxoethylidene)-4-oxothiazolidin-3-yl)amino]succinate
and
methyl
(4-amino-5-oxo-3-
thioxo-2,3,4,5-tetrahydro-1,2,4-triazine-6-yl)acetate affording yields of 61–54 %, 22–18 % and 14–
11 %, respectively, via a condensation reaction of dimethyl acetylenedicarboxylate (DMAD) with
(substituted ylidene)thiocarbonohydrazides. One of the products was conclusively confirmed by
single-crystal X-ray analysis. A mechanism for the formation of the products is presented.
c
ꢀ 2015 Institute of Chemistry, Slovak Academy of Sciences
Keywords: thiocarbonohydrazides, dimethyl acetylenedicarboxylate, hydrazonothiazolidinyl-suc-
cinates, aminothioxotriazinylacetate
Introduction
dimethyl acetylenedicarboxylate
(DMAD) has assumed an important role in modern
organic synthesis, not only because it is used as a
dienophile and a dipolarophile in cycloaddition reac-
tion, but also because of its use in combinatorial and
multi-component chemistry as well as in heterocyclic
synthesis (Sahoo, 2007; Heravi & Alishiri, 2014; Aly
et al., 2014).
It has been reported that DMAD can be used
as a Michael acceptor and reacts with various nu-
cleophiles containing sulphur and nitrogen atoms
such as thiourea derivatives leading to the forma-
tion of either 1,3-thiazolidin-4-ones or thiazine-4-ones
(Tomaščiková et al., 2008a; Ahmadi et al., 2009; B¨ohm
et al., 2009; Imrich et al., 2010). 1,3-Thiazolidin-4-ones
were observed as the sole product in the reaction of
thiosemicarbazide and thiosemicarbazone derivatives
with DMAD (Darehkordi et al., 2007; Tomaščiková et
al., 2008b; Alizadeh et al., 2010; Hassan et al., 2012a,
2013, 2014a, 2014b).
Recently,
Carbonothioic dihydrazide(aryl)methylene or (ary-
lylidene)thiocarbonohydrazides were added to the
triple bond and the carbonyl group of 1-benzoyl and
1-(2-thienoyl)-2-phenyl acetylenes to afford substi-
tuted dihydropyrazoles (Dvorko et al., 2006).
Benzylidene thiocarbonohydrazide was allowed to
react with 3-bromo-1-phenylprop-2-yn-1-one in the
presence of acetic acid to afford benzylidene-Nꢀ-(5-
benzoylmethyl-1,3,4-thiadiazolylhydrazone) (Glotova
et al., 2008).
In recent years, Schiff’s bases bearing aryl groups
or heterocyclic residues have attracted the attention of
many researchers due to their excellent biological ac-
tivity (Dimmock et al., 1997; Sengupta et al., 2001;
*Corresponding author, e-mail: alaahassan2001@mu.edu.eg
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A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
Fig. 1. The reactions on 1,5-bis(ylidene)thiocarbohydrazide Ia–Ie and DMAD (II).
Naik et al., 2002; Bacchi et al., 2005; Bekircan &
Bekats, 2006; Grangarapu et al., 2014).
Preparation of carbonothioic dihydrazide
2-(arylmethylene) (Va–Vj)
1,5-Bis(substituted methylidene)thiocarbonohy-
drazides Ia–Id was allowed to react with DMAD
(II ), to afford oxothiazolidine derivatives IIIa–IIId
as a single product (Fig. 1) (Hassan et al., 2012b).
Also, the DMAD-mediated cyclisation of 1,5-bis-
(ferrocenylmethylene)thiocarbonohydrazide led to the
formation of biologically heterocycles IIIe and IV
(Fig. 1) (Balázs et al., 2009).
To date, no analogous reactions with DMAD us-
ing (ylidene)thiocarbonohydrazides Va–Vj have been
described. This remarkable versatility in the reac-
tions of Ia–Id with DMAD warrants further inves-
tigation of the reactivity of Va–Vj and a compari-
son of the behaviour of Va–Vj towards DMAD. In
addition, this study sought to design and synthe-
sise new derivatives of oxothiazolidinylsuccinate and
(oxothioxo-1,2,4-triazinyl)acetate from Va–Vj.
The aromatic and aliphatic aldehyde (10 mmol) in
ethanol (40 mL) was added dropwise to the solution
of thiocarbohydrazide (15 mmol) in H2O (50 mL) and
acetic acid (1 mL) over a period of 1 h under reflux.
After the addition, the mixture was further refluxed
for 3 h. Then, the precipitate was collected by filtra-
tion and washed with water (3 × 10 mL). The re-
sulting solid was recrystallised from ethanol to give
the products Va–Vj, Va (Rhee, 1972; Shi et al., 2011);
Vb (Ferrari er al., 1999; Shi et al., 2011); Vc (Rhee,
1972); Ve (Rhee, 1972; Shi et al., 2011); Vf (Rajendran
& Jain, 1984; Kabashima et al., 1990); Vi (Nakar-
ishi & Solomon, 1977). The spectral and analytical
data for Vd, Vg, Vh and Vj are given in Tables 1 and
2. Dimethyl acetylenedicarboxylate (DMAD, II ) was
bought from Fluka (USA).
Experimental
Reaction of carbonothioic dihydrazide
2-(substituted methylene) Va–Vj with dimethyl
acetylene-dicarboxylate II
A Gallenkamp melting point apparatus was used
for determining the melting points (Weiss-Gallen-
kamp, Loughborough, UK); the results are uncor-
rected. The IR spectra (KBr discs technique) were
recorded on Alpha, Bruker FTIR (Germany) and
Shimadzu 408 instruments (Shimadzu, Japan). The
1H NMR (400.13 MHz) and 13C NMR (100.6 MHz)
spectra were determined on a Bruker AM 400 spec-
trometer (Bruker, Germany) with tetramethylsilane
as the internal standard; s = singlet, d = doublet,
t = triplet, m = multiplet, b = broad. The 13C
NMR signals were assigned on the basis of DEPT
135/90 spectra. Chemical shifts are expressed as δ in
parts per million (ppm). The mass spectra (70 eV,
electron impact mode) were recorded on a Finnigan
MAT 312 (Germany) instrument. The elemental anal-
yses for C, H, N and S were carried out at the Mi-
croanalytical Centre, Cairo University, Egypt using
an Elmyer 306, (Germany). Preparative layer chro-
matography (PLC) used air-dried 1.0 mm thick layers
of slurry-applied silica gel (Pf254, Merck, Germany)
on glass plates 48 cm × 20 cm using the solvents
listed.
A solution of Va–Vj (1 mmol) in absolute ethanol
(99.9 vol. %, 30 mL) was added to a 100 mL
round-bottom flask containing a stirred solution of
II (284 mg, 2 mmol) in absolute ethanol (10 mL)
with stirring. The mixture was gently refluxed while
stirring for 3h in the presence of air. The resulting
yellow precipitate was filtered, washed with ethanol
and recrystallised from the appropriate solvent to give
pure crystals of dimethyl {[2-alkylidenehydrazono)-5-
(2-methoxy-2-oxoethylidene)-4-oxothiazolidin-3-yl)-
amino]succinate VIIa–VIIi. The filtrate was concen-
trated and subjected to PLC using toluene–ethyl
acetate (10 : 2, vol.) as a developing solvent to
afford a number of zones. The two most intense
zones were extracted with acetone. The fastest-
migrating zone contained methyl (4-amino-5-oxo-3-
thioxo-2,3,4,5-tetrahydro-1,2,4-triazine-6-yl)acetate
(VIII ); the second zone contained dimethyl-2-[3-
amino-5-(2-methoxy-2-oxoethylidene)-4-oxo-thiazoli-
din-2-ylidenehydrazono]succinate VI (Heravi et al.,
2006).
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A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
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Table 1. Spectral data of newly prepared compounds Va–Vj, VI, VIIa–VIIj and VIII
Compounda
Spectral data
IR, ν˜/cm−1: 995, 1348 (C S and C—N), 1565 (NH def. and C—N str.), 1590 (Ar-C C), 3110–3190, 3305 (NH2
—
—
—
—
Vd
and NH)
1H NMR (DMSO-d6), δ: 3.70 (s, 3H, OCH3), 3.82 (s, 3H, OCH3), 3.89 (s, 3H, OCH3), 4.85 (br, 2H, NH2), 7.10 (s,
2H, Ar—CH), 7.91 (s, 1H, CH N), 9.84 (br, 1H, 4NH), 11.41 (br, 1H, 2NH)
—
—
13
—
—
C NMR (DMSO-d6), δ: 56.04, 56.06, 59.98 (OCH3), 129.51 (Ar—CH), 138.75 (Ar—C), 141.91 (CH N), 152.87
—
(Ar—C—O), 175.87 (C S)
—
MS, m/z (Ir/%): 284 (100) (M+), 258 (24), 210 (62), 195 (88), 136 (16)
—
—
Vg
Vh
Vj
IR, ν˜/cm−1: 990, 1358 (C S and C—N), 1560 (NH def. and C—N str.), 1585 (Ar—C C), 3120–3254, 3315 (NH2
—
—
and NH)
1H NMR (DMSO-d6), δ: 4.96 (br, 2H, NH2), 7.42–7.78 (m, 4H, Ar-CH), 7.90–8.15 (m, 3H, Ar-CH), 8.31 (s, 1H,
CH N), 9.83 (br, 1H, 4NH), 11.46 (br, 1H, 2NH)
—
—
13C NMR (DMSO-d6), δ: 127.07, 127.75, 128.55, 129.12, 129.78 (A-CH), 130.30, 133.13, 133.27 (Ar-C), 140.32
—
—
(CH N), 175.58 (C S)
—
—
MS, m/z (Ir/%): 244 (44) (M+), 169 (25), 154 (100), 127 (62)
IR, ν˜/cm−1: 996, 1348 (C S and C—N), 1565 (NH def. and C—N str.), 1590 (Ar-C C), 3140–3235, 3330 (NH2
—
—
—
—
and NH)
1H NMR (DMSO-d6), δ: 4.96 (br, 2H, NH2), 7.52–7.68 (m, 6H, Ar-CH), 8.15–8.22 (m, 3H, Ar-CH), 8.43 (s, 1H,
CH N), 9.72 (br, 1H, 4NH), 11.37 (br, 1H, 2NH)
—
—
13C NMR (DMSO-d6), δ: 125.14, 125.54, 127.16, 128.87, 129.25, 129.57 (Ar-CH), 130.26, 130.83, 133.95, 134.16
—
—
(Ar-C), 141.74 (CH N), 176.12 (C S)
—
—
MS, m/z (Ir/%): 294 (17) (M+), 219 (22), 203 (100), 177 (43)
IR, ν˜/cm−1: 995, 1343 (C S and C—N), 1568 (NH def. and C—N str.), 2946 (Ali-CH), 3195, 3437 (NH2 and NH)
1H NMR (DMSO-d6), δ: 0.86 (t, 3H, CH3, J = 7.62), 1.22–1.31 (m, 6H, 3 CH2), 1.39–1.43 (m, 2H, CH2), 4.75 (br,
—
—
2H, NH2), 7.18 (s, 1H, CH N), 9.23 (br, 1H, 4NH), 10.93 (br, 1H, 2NH)
—
—
13
—
—
—
—
C NMR (DMSO-d6), δ: 13.86 (CH3), 21.96, 24.78, 29.67, 31.12 (CH2), 66.12 (CH N), 172.53 (C S)
MS, m/z (Ir/%): 188 (81) (M+), 117 (100), 75 (93), 60 (98)
13C NMR (DMSO-d6), δ: 33.19 (CH2), 51.96, 52.55, 52.68 (OCH3), 116.38 (vinyl-CH), 138.75 (thiazolidine-C5),
VI
—
—
—
153.05 (acyclic C N), 161.68 (thiazolidine-C2), 162.69 (cyclic C O), 163.43, 165.43, 168.30 (ester-C O)
—
—
—
—
—
VIIa
IR, ν˜/cm−1: 1605 (Ar-C C), 1625 (C N), 1690, 1705, 1715, 1730 (CO)
—
—
1H NMR (CDCl3), δ: 3.64 (s, 2H, CH2), 3.83 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 3.88 (s, 3H, OCH3), 6.86 (s, 1H,
—
vinyl-CH), 7.46–7.53 (m, 2H, Ar-H), 7.73–7.78 (m, 2H, Ar-H), 8.33 (s, 1H, CH N)
—
13C NMR (CDCl3), δ: 33.16 (CH2), 52.11, 52.49, 52.61 (OCH3), 116.52 (vinyl-CH), 127.94, 128.76 (Ar-CH), 133.31,
—
—
135.86 (Ar-C), 139.12 (thiazolidine-C5), 141.81 (CH N), 152.12 (acyclic C N), 160.93 (thiazolidine-C2), 163.12
—
—
—
—
—
(cyclic C O), 163.84, 165.66, 167.86 (ester-C O).
—
MS, m/z (Ir/%): 480/482 (12) (M+), 449 (16), 390 (22), 287 (26), 193 (12), 153 (34), 125 (82), 59 (100)
—
—
VIIb
VIIc
VIId
IR, ν˜/cm−1: 1595 (Ar-C C), 1630 (C N), 1688,1695, 1715, 1725 (C O)
— —
— —
1H NMR (CDCl3), δ: 3.62 (s, 2H, CH2), 3.79 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), 3.88 (s, 3H,
—
OCH3), 6.85 (s, 1H, vinyl-CH), 7.40–7.55 (m, 2H, Ar-H), 7.70–7.84 (m, 2H, Ar-H), 8.28 (s, 1H, CH N)
—
13C NMR (CDCl3), δ: 33.11 (CH2), 51.89, 52.14, 52.59, 52.66 (OCH3), 116.46 (vinyl-CH), 125.72, 126.63 (Ar-
—
—
—
CH), 132.61 (Ar-C), 139.08 (thiazolidine-C5), 141.65 (CH N), 152.29 (acyclic C N), 153.44 (Ar-C—O) 159.87
—
—
—
—
(thiazolidine-C2), 163.31 (cyclic C O), 164.12, 165.66, 167.84 (ester-C O).
—
MS, m/z (Ir/%): 476 (12) (M+), 332 (16), 144 (17), 133 (100), 91 (53), 59 (22)
IR, ν˜/cm−1: 1604 (Ar-C C), 1626 (C N), 1700, 1690, 1710, 1728 (C O)
—
—
—
—
—
—
1H NMR (CDCl3), δ: 3.61 (s, 2H, CH2), 3.81 (s, 6H, 2OCH3), 3.83 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 3.89 (s, 3H,
—
OCH3), 6.87 (s, 1H, vinyl-CH), 7.14–7.49 (m, 3H, Ar-H), 8.34 (s, 1H, CH N)
—
13C NMR (CDCl3), δ: 32.41 (CH2), 51.86, 52.34, 52.39, 55.67, 57.63 (OCH3), 116.81 (vinyl-CH), 124.96, 125.32,
—
—
126.14 (Ar-CH), 132.16 (Ar-C), 139.28 (thiazolidine-C5), 141.96 (CH N), 151.84 (acyclic C N), 152.68 (Ar-C—O),
160.76 (thiazolidine-C2), 163.52 (cyclic C O), 164.12, 165.66, 168.14 (ester-C O)
MS, m/z (Ir/%): 506 (14) (M+), 475 (19), 413 (11), 351 (36), 164 (100), 148 (28), 120 (19), 92 (36), 59 (44)
—
—
—
—
—
—
IR, ν˜/cm−1: 1605 (Ar-C C), 1625 (C N), 1696,1700, 1715, 1728 (C O)
—
—
—
—
—
—
1H NMR (CDCl3), δ: 3.59 (s, 2H, CH2), 3.83 (s, 6H, 2OCH3), 3.84 (s, 3H, 2OCH3), 3.85 (s, 3H, OCH3), 3.87 (s,
—
3H, OCH3), 3.89 (s, 3H, OCH3), 6.85 (s, 1H, vinyl-CH), 7.10–7.12 (m, 2H, Ar-H), 8.38 (s, 1H, CH N)
—
13C NMR (CDCl3) δ: 33.88 (CH2), 51.93, 52.46, 52.59, 56.22, 56.34, 60.99 (OCH3), 116.78 (vinyl-CH), 127.60 (Ar-
—
—
CH), 129.96 (Ar-C), 140.12 (thiazolidine-C5), 141.16 (CH N), 153.48 (acyclic C N), 154.14 (Ar-C—O), 160.89
—
—
—
—
—
(thiazolidine-C2), 163.12 (cyclic C O), 165.39, 166.41, 167.92 (ester-C O)
MS, m/z (Ir/%): 536 (54) (M+), 359 (11), 218 (22), 180 (23), 91 (100), 59 (48)
—
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A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
Table 1. (continued)
Compounda
Spectral data
IR, ν˜/cm−1: 1567 (Ar-C C), 1613 (C N), 1697, 1710, 1718, 1735 (C O), 3457 (OH)
— —
— —
—
—
VIIe
1H NMR (CDCl3), δ: 3.61 (s, 2H, CH2), 3.83 (s, 3H, OCH3), 3.87 (s, 3H, OCH3), 3.90 (s, 3H, OCH3), 6.86 (s, 1H,
—
vinyl-CH), 7.36–7.49 (m, 2H, Ar-H), 7.73–7.75 (m, 1H, Ar-H), 7.85–7.87 (m, 1H, Ar-H), 8.62 (s, 1H, CH N), 9.41
—
(br, 1H, OH)
13C NMR (CDCl3), δ: 33.88 (CH2), 52.46, 52.51, 52.83 (OCH3), 116.77 (vinyl-CH), 118.50, 119.45, 128.30, 129.00
—
—
(Ar-CH), 134.12 (Ar-C), 138.47 (thiazolidine-C5), 141.66 (CH N), 155.90 (acyclic C N), 157.81 (Ar-C—O), 159.95
—
—
—
—
—
(thiazolidine-C2), 163.64 (cyclic C O), 164.48, 165.53, 167.92 (ester-C O)
MS, m/z (Ir/%): 462 (24) (M+), 344 (62), 285 (26), 134 (67), 106 (23), 78 (62), 59 (100).
—
—
—
VIIf
VIIg
VIIh
IR, ν˜/cm−1: 1606 (Ar-C C), 1623 (C N), 1690, 1700, 1708, 1721 (C O)
— —
— —
1H NMR (CDCl3), δ: 3.66 (s, 2H, CH2), 3.81 (s, 3H, OCH3), 3.83 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 6.48–6.52
—
(m, 1H, Ar-H), 6.89 (s, 1H, vinyl-CH), 7.01–7.19 (m, 1H, Ar-H), 7.54–7.61 (m, 1H, Ar-H), 8.35 (s, 1H, CH N)
—
13C NMR (CDCl3), δ: 32.22 (CH2), 51.90, 52.22, 52.58 (OCH3), 112.58 (furyl-CH), 115.97 (vinyl-CH), 121.06 (furyl-
—
—
—
C), 139.80 (thiazolidine-C5), 145.53 (CH N), 146.89 (furyl-CH), 149.58 (acyclic C N), 159.34 (thiazolidine-C2),
—
—
—
—
—
163.12 (cyclic C O), 164.42, 165.38, 167.81 (ester-C O)
MS, m/z (Ir/%): 436 (12) (M+), 374 (24), 342 (10), 284 (12), 278 (29), 186 (26), 94 (48), 80 (100), 59 (26)
IR, ν˜/cm−1: 1601 (Ar-C C), 1620 (C N), 1699, 1705, 1720, 1735 (C O)
—
—
—
—
—
—
1H NMR (CDCl3), δ: 3.68 (s, 2H, CH2), 3.82 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 3.89 (s, 3H, OCH3), 6.90 (s, 1H,
—
vinyl-CH), 7.40–7.60 (m, 2H, Ar-H), 7.72–8.00 (m, 4H, Ar-H), 8.15 (s, 1H, CH N), 8.55-8.65 (m, 1H, Ar-H)
—
13C NMR (CDCl3), δ: 32.33 (CH2), 51.77, 52.63, 53.89 (OCH3), 116.78 (vinyl-CH), 127.00, 127.70, 128.88, 129.57,
—
—
—
—
129.69 (Ar-CH), 131.33, 132.21, 133.75 (Ar-C), 139.71 (thiazolidine-C5), 140.29 (CH N), 152.76 (acyclic C N),
160.63 (thiazolidine-C2), 161.44 (cyclic C O), 164.50, 166.36, 168.59 (ester-C O)
MS, m/z (Ir/%): 496 (38) (M+), 437 (15), 328 (14), 168 (22), 154 (100). 140 (33), 127 (28)
—
—
—
—
IR, ν˜/cm−1: 1598 (Ar-C C), 1618 (C N), 1698, 1705, 1710, 1725 (C O)
—
—
—
—
—
—
1H NMR (CDCl3), δ: 3.58 (s, 2H, CH2), 3.84 (s, 3H, OCH3), 3.87 (s, 3H, OCH3), 3.91 (s, 3H, OCH3), 7.00 (s,
1H, vinyl-CH), 7.39–7.50 (m, 3H, Ar-H), 7.55–7.68 (m, 2H, Ar-H), 8.05–8.10 (m, 2H, Ar-H), 8.55 (s, 1H, CH=N),
8.68–8.72 (m, 2H, Ar-H)
13C NMR (CDCl3), δ: 33.56 (CH2), 52.36, 52.82, 53.17 (OCH3), 117.47 (vinyl-CH), 124.76, 125.74, 128.03, 128.19,
—
128.41, 129.16 (Ar-CH), 130.79, 131.19, 132.41 (Ar-C), 137.62 (thiazolidine-C5), 139.32 (CH N), 154.01 (acyclic
—
—
—
N), 161.02 (thiazolidine-C2), 164.42 (cyclic C O), 166.48, 168.00, 168.08 (ester-C O)
—
—
C
—
—
MS, m/z (Ir/%): 546 (14) (M+), 474 (10), 328 (16), 262 (22), 218 (32), 190 (54), 59 (100)
—
—
VIIi
VIII
IR, ν˜/cm−1: 1617 (C N), 1694, 1708, 1715, 1721 (C O), 2931-2965 (Ali-CH)
—
—
1H NMR (CDCl3), δ: 1.04 (d, 6H, 2CH3, J=6.76), 2.51 (m, 1H, CH), 3.62 (s, 2H, CH2), 3.81 (s, 3H, OCH3), 3.83
—
(s, 3H, OCH3), 3.86 (s, 3H, OCH3), 6.88 (s, 1H, vinyl-CH), 7.46 (s, 1H, CH N)
—
13C NMR (CDCl3), δ: 19.63 (CH3), 30.77 (CH), 33.12 (CH2), 51.87, 52.26, 52.89 (OCH3), 116.11 (vinyl-CH), 139.76
—
—
—
—
(thiazolidine-C5), 151.26 (acyclic C N), 152.12 (CH N), 160.23 (thiazolidine-C2), 162.35 (cyclic C O), 164.71,
—
—
—
165.62, 167.93 (ester-C O)
—
MS, m/z (Ir/%): 412 (9) (M+), 397 (24), 253 (83), 226 (58), 195 (44), 167 (7), 124 (16), 98 (29), 84 (100)
IR, ν˜/cm−1: 995, 1020 and 1360 (C S and C—N vibration), 1670, 1735 (C O), 3260, 3320 (NH2 and NH)
1H NMR (DMSO-d6), δ: 3.60 (s, 2H, CH2), 3.72 (s, 3H, OCH3), 6.55 (br, 2H, NH2), 10.69 (br, 1H, triazine-NH)
—
—
—
—
13
—
—
—
—
C NMR (DMSO-d6), δ: 36.01 (CH2), 52.12 (OCH3), 142.29 (triazine-C N), 148.27 (triazine-C O), 168.71 (ester-
—
—
C
O), 168.90 (C S)
—
—
MS, m/z (Ir/%): 216 (100) (M+), 188 (47), 185 (47), 156 (96), 100 99 (18), 59 (72)
a) Physical–chemical data of compounds: Va (Rhee, 1972; Shi et al., 2011); Vb (Ferrari er al., 1999; Shi et al., 2011); Vc (Rhee,
1972); Ve (Rhee, 1972; Shi et al., 2011); Vf (Rajendran & Jain, 1984; Kabashima et al., 1990); Vi (Nakarishi & Solomon, 1977)
and VI (Heravi et al., 2006).
Single-crystal X-ray structure determination
of VIII
absorption corrections were applied.
C6H8N4O3S, Mr = 216.22 g mol−1, colourless
plates, size 0.15 mm × 0.09 mm × 0.03 mm, tri-
˚
clinic, space group P – 1 (no. 2), a = 6.6803(8) A, b =
A single crystal X-ray diffraction study was carried
out on a Bruker-Nonius Kappa CCD diffractometer at
◦
˚
˚
6.8447(6)◦A, c = 10.34906(3) A, α = 94.209(4) , β =
◦
˚
90.834(6) , γ = 103.550(7) , V = 464.82(7) A , Z = 2,
3
˚
123 K using MoKα radiation (λ = 0.71073 A) (VIII ).
Direct Methods (SHELXS-98) (Sheldrick, 2008) were
used for the structure solution and refinement was car-
ried out using SHELXL-2013 (Sheldrick, 2008) (full-
matrix least-squares on F2). Hydrogen atoms were lo-
calised using a difference Fourier synthesis map and re-
fined using a riding model [H(N) free]. Semi-empirical
Dcalc = 1.544 mg m−3, F(000) = 224, = 0.34 mm−1
,
T = 123 K, 5801 measured reflections (2θmax = 50◦),
1617 independent reflections [Rint = 0.046], 137 pa-
rameters, 3 restraints, R1(for 1271I > 2σ(I )) = 0.043,
wR2 (for all data) = 0.096, S = 1.10, largest difference
of peak and hole = 0.230e−3/–0.315 e A−3
.
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A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
Table 2. Characterisation data of newly prepared compounds
977
wi(calc.)/%
wi(found)/%
Yield
M.p.
Compounda
Formula
Mr
C
H
N
S
Cl
%
◦C
Vd
Vg
C11H16N4O3S
C12H12N4S
284.33
244.32
294.37
188.29
480.88
476.47
506.49
536.51
462.43
436.40
496.49
546.55
412.42
216.22
46.47
46.34
58.99
59.12
65.28
65.37
44.65
44.42
47.46
47.61
50.42
50.33
49.80
49.66
49.25
49.09
49.35
49.51
46.79
46.82
53.68
53.52
59.33
59.48
46.60
46.76
33.33
33.46
5.67
5.74
4.95
5.03
4.79
4.68
8.46
8.64
3.56
3.48
4.23
4.28
4.38
4.46
5.51
5.62
3.92
4.06
3.70
3.61
4.06
3.97
4.06
3.98
4.89
4.79
3.73
3.61
19.70
19.81
22.93
22.81
19.03
18.87
29.75
29.59
11.65
11.81
11.76
11.84
11.06
10.92
10.44
10.58
12.12
11.98
12.84
13.01
11.28
11.41
10.25
10.14
13.58
13.45
25.91
26.07
11.28
11.14
13.12
13.19
10.89
11.02
17.03
16.87
6.67
6.54
6.73
6.91
6.33
6.24
5.98
6.11
6.93
7.08
7.35
7.22
6.46
6.32
5.87
6.02
7.77
7.91
14.83
14.98
–
–
–
–
–
–
–
–
7.37
7.52
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
96
205
94
92
75
56
57
58
59
57
55
61
60
54
14
215
208
206
222
230
233
210
248
201
222
224
230
135
Vh
C16H14N4S
Vj
C7H16N4S
VIIa
VIIb
VIIc
VIId
VIIe
VIIf
VIIg
VIIh
VIIi
VIII
C19H17ClN4O7S
C20H20N4O8S
C21H22N4O9S
C22H24N4O10
S
C19H18N4O8S
C17H16N4O8S
C23H20N4O7S
C27H22N4O7S
C16H20N4O7S
C6H8N4O3S
–
–
–
a) Physical–chemical data of compounds: Va (Rhee, 1972; Shi et al., 2011); Vb (Ferrari er al., 1999; Shi et al., 2011); Vc (Rhee,
1972); Ve (Rhee, 1972; Shi et al., 2011); Vf (Rajendran & Jain, 1984; Kabashima et al., 1990); Vi (Nakarishi & Solomon, 1977)
and VI (Heravi et al., 2006).
Results and discussion
(Ylidene)thiocarbonohydrazides Va–Vj were pre-
pared following the published procedures (Rhee, 1972;
Rajendran & Jain, 1984; Kabashima et al., 1990; Fer-
rari et al., 1999; Li et al., 2008; Dabholkar &Ravi,
2010; Shi et al., 2011). The structures of Va–Vj were
Fig. 2. Putative linear (confirmed by NMR) and tetrazine
confirmed by IR, 1H and 13C NMR spectra as well
thione structure of Va–Vj.
as by mass spectrometry. A comparison of the vari-
ous NH proton resonances shows that they appear as
three different signals in a 1 : 1 : 2 ratio in the region of
δH 11.46–10.93, 9.84–9.23 and 4.96–4.75 due to HN2,
HN4 and NH2, respectively. From these, and the shifts
in the CH proton resonances of groups attached to
for 3 h with the admission of air; a yellow precipitate
was formed with a 61–54 % yield except in the case
of the reaction between Vj and II when traces of VIIj
were formed (Fig. 3).
—
–CH N, it is clear that the structures of Va–Vj con-
This product was identified as dimethyl (hy-
drazonothiazolidinylamino)succinate VIIa–VIIi. The
residue of the filtrate was subjected to prepara-
tive layer chromatography (PLC). Separation of the
residue afforded a number of zones from which (hy-
drazonothiazolidinylamino)succinates VI and (amino-
thioxotriazinyl)acetate VIII could be isolated.
Compound VI was characterised as being dime-
thyl-2-[3-amino-5-(2-methoxy-2-oxoethylidene)-4-
—
firm a linear configuration not tetrazine thione deriva-
tives (Fig. 2) (Shi et al., 2011).
To examine their reactivity, (ylidene)thiocarbono-
hydrazides Va–Vj having aryl groups with different
types (with electron-donating and electron-withdraw-
ing on the benzene ring, naphthyl and anthryl groups),
aliphatic as well as heterocyclic rings were selected.
Ethanol solutions of DMAD, II and Va–Vj in a
molar ratio (2 : 1) were allowed to react under reflux
oxothiazolidin-2-ylidenehydrazono]succinate.
The
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978
A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
Fig. 3. Reaction products from Va–Vj and II.
structure of VI was determined by 1H NMR, 13C
NMR and mass spectrometry. For confirmation, the
compound was obtained as a single crystal for X-ray
diffraction, (Fig. S1 and Tables S1–S7 in supplemen-
tary data). It has been reported that the reaction of
thiocarbohydrazide with DMAD, II, in methanol af-
forded a single compound of VI (Heravi et al., 2006).
Compounds VIIa–VIIi were formed in the course of
the reaction of Va–Vj with DMAD, II. The molecular
structures of VIIa–VIIi are supported by the follow-
ing findings: for example VIId afforded the molecu-
lar formula of C22H24N4O5S. In the 1H NMR spec-
Fig. 4. Molecular structure of VIII in the crystal (displacement
parameters are drawn at 50 % probability level). The
crystallographic numbering does not reflect the system-
atic IUPAC numbering.
—
trum, the presence of azomethine CH N at 8.38,
—
vinyl-CH at 6.85, the methoxy groups at 3.89, 3.87,
3.85, 3.84 and 3.83 as well as CH2 signal at 3.59 with
the integral ratios of 3 : 3 : 3 : 6 : 2, in addition to
mula of C22H24N4O10S.
1
the aromatic protons at 7.10–7.12. The H NMR also
The IR spectrum of VIIf showed the characteristic
clearly indicated the absence of any signals assigned
to thiocarbonohydrazide-NHꢀs and NH2 protons. The
IR spectrum of VIId exhibited a characteristic strong
absorption at 1728 cm−1, 1715 cm−1, 1700 cm−1 and
1696 cm−1 due to carbonyl groups. These carbonyl
groups appeared in 13C NMR at 167.92, 166.41, 165.39
bands at 1623 cm−1 (C N), 1690 cm−1, 1700 cm−1
,
—
—
—
1708 cm−1 and 1721 cm−1 (C O). The 1H NMR
—
spectrum of VIIf showed one downfield singlet at 8.35
—
due to CH N, four different singlets in 2 : 3 : 3 : 3
—
ratio at 3.66 for (CH2) and three at 3.81, 3.83 and
3.86 due to (OCH3), as well as vinyl-CH at 6.89.
The 13C NMR spectrum revealed one signal at 32.22
due to CH2 and three methoxy groups at 51.90,
52.22 and 52.58, two furyl-CH at 112.58 and 121.06,
vinyl-CH at 115.97 and downfield signals at 139.80
—
and 163.12 for ester and thiazolidinone C O, respec-
—
—
—
tively. The presence of C N groups was confirmed
by the characteristic absorption bands at 1625 cm−1
The IR spectrum of VIId shows the absence of any
.
—
—
band assigned to the C S group. The thiazolinone-
—
(thiazolidine-C5), 145.53 (CH N), 146.89 (furyl-
—
C2, C5 resonate in 13C NMR at 160.89 and 140.12,
respectively. Furthermore, the 13C-DEPT-NMR spec-
trum exhibited positive signals at 116.78 (vinyl-CH),
60.99, 56.34, 56.22, 52.59, 52.46 and 51.93 (6 OCH3)
and a negative signal at 33.88 due to CH2. The mass
spectrum of VIId exhibited an intense molecular ion
peak at m/z = 536 consistent with the molecular for-
CH), 149.58 (acyclic C N), 159.34 (thiazolidine-C2),
—
163.12 (cyclic C O), 164.42, 165.38, 167.81 (ester
—
—
—
—
—
C
O).
The fastest migration zone which quenched all in-
dicator fluorescence upon exposure to 254 UV light
contained the triazine thione derivatives VIII. The IR
spectrum of VIII clearly showed two strong bands at
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A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
979
Fig. 5. Alternative intermediates (A–D) during reaction of Va–Vj and II.
Fig. 6. Isomeric products of A or B.
Fig. 7. Isomeric products of C or D.
1735 cm−1 and 1670 cm−1 assigned to the carbonyl
group. These carbonyl groups resonated in 13C NMR
at 168.71 and 148.27 (Li et al., 2008) due to ester
supplementary data; note that the crystallographic
numbering does not correspond to the symmetric
IUPAC numbering rules). The bond lengths C(1)–
˚
˚
—
and triazine C O, respectively. Another carbon sig-
N(6) (1.340(3) A), C(1)–N(2) (1.386(3) A), C(3)–N(2)
—
˚
nal at 168.90 was due to the triazine thione func-
tion. In the IR spectrum of VIII, intense bands at
1360 cm−1, 1020 cm−1 and 995 cm−1 were attributed
(1.376(3) A) suggest that these bonds have more of
a double bond character as they are comparable to
˚
C—N σ bond length of 1.47 A, reflecting a delo-
—
to strong coupling between the C S and C—N vi-
calised π-electron system for the six-membered ring.
The six-membered ring skeleton is planar (mean de-
viation from L.S. plane C(1), N(2), C(3), C(4), N(5)
—
brations (Nakarishi & Solomon, 1977; Socrates, 1980;
Schrader, 1989).
In addition, the structure of triazine derivatives
VIII was confirmed by single-crystal X-ray struc-
ture analysis (Fig. S3 and Tables S8–S14, in the
˚
and N(6) 0.007 A, see Fig. 4). The C(1)–S(1) bond
˚
length in VIII with 1.659(2) A is significant for the
double bond character.
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980
A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
Table 3. 13C-NMR shifts in products VIIa–VIIi (current work) and literature data related to XI structural alternatives
Compound
C-2
C-5
C-4
Vinyl-CH
Thiazinone(C-5)
VIIa–VIIi
159.87–161.02
166.80
137.62–140.12
–
161.44–164.92
164.00
115.97–117.47
–
–
XIa
121.60
a) Literature data related to XI substituted thiazin-4-one (Balázs et al., 2007).
Fig. 8. Rationale for formation of compounds VI–VIII.
The alternative intermediates A–D (Fig. 5) could
be proposed for the formation of products VI–VIII. If
the intermediate A or B could be formed, the isomeric
products IX or X may be formed (Fig. 6). Isomeric
products XI or VII may be formed if the reaction took
place through intermediate C or D (Fig. 7).
cially the 13C-chemical shifts for the ring carbonyl
atoms, (C-2), (C-5), (C-4) and vinyl-CH (see Table 3)
for comparison with all relevant alternatives.
Furthermore, products VI and VII entailed the for-
mation of intermediate XII (Fig. 8) which describes
the formation of the thiazolidinone ring. The struc-
ture of VII was elucidated on the basis of the previous
spectral data as well as the formation of compound
VI (Fig. S1 and Tables S1–S7, in the supplementary
data).
The ring C O resonances observed in 13C-NMR
—
—
precluded the thiazinone IX and thiazolidinone X
(which would be considerably downfield of those ob-
served). However, only the structures VIIa–VIIi ac-
commodate all the spectral data listed above, espe-
There follows a rationale for the formation of prod-
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A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
981
ucts VI–VIII as depicted in Fig. 8. Elimination of a
molecule of methanol from the intermediate C or D,
followed by the reaction with another molecule of II,
afforded products VIIa–VIIi. Compound VI could be
formed via the attached intermediate XII by moisture
(work up) and elimination of a molecule of the sub-
stituted aldehyde, followed by the reaction with an-
other molecule of II. On the other hand, intermediate
A abstracts a molecule of H2O from the air with the
elimination of a molecule of substituted aldehyde and
methanol to form the triazine thione derivatives VIII.
Antimicrobial and mutagenic properties of organotin(IV)
complexes with isatin and N-alkylisatin bisthiocarbonohy-
drazones. Journal of Inorganic Biochemistry, 99, 397–408.
DOI: 10.1016/j.jinorgbio.2004.10.008.
Balázs, F., Kudar, V., Csámpai, A., Nagy, T. Z., & Sohár, P.
(2007). Synthesis, IR-, NMR-, DFT and X-ray study of ferro-
cenyl heterocycles from thiosemicarbazones. Part 21: Study
on ferrocenes. Journal of Organometallic Chemistry, 692,
5621–5632. DOI: 10.1016/j.jorganchem.2007.09.017.
Balázs, F., Csámpai, A., Nagy, T. Z., Czugler, M., & So-
hár, P. (2009). Synthesis, ring transformations, IR-, NMR
and DFT study of heterocycles with two ferrocenyl units.
Journal of Organometallic Chemistry, 694, 3732–3741. DOI:
10.1016/j.jorganchem.2009.07.038.
Conclusions
Bekircan, O., & Bekats, H. (2006). Synthesis of new bis-1,2,4-
triazole derivatives. Molecules, 11, 469–477. DOI: 10.3390/
11060469.
A series of novel (thiazolidinylidenehydrazono)suc-
cinate derivatives and aminothioxo-triazinyl)acetate
were synthesised via the condensation reaction of
dimethyl acetylenedicarboxylate with (ylidene)thio-
carbonohydrazides, which has not been reported hith-
erto, and were chosen as easily accessible starting ma-
terials; the simple experimental procedure and the use
of substrates in the reaction without any prior activa-
tion as well as the relatively good yields are the ad-
vantages of the present method. The reactivity of (yli-
dene)thiocarbonohydrazides Va–Vj required the avail-
ability of azomethine-CH, thioamide-NHs as well as
NH2 as nucleophilic sites.
B¨ohm, S., Tomaščiková, J., Imrich, J., Danihel, I., Kristian,
P., Koch, A., Kleinpeter, E., & Klika, K. D. (2009). Com-
putational study to assign structure, tautomerism, E/Z
and s-cis/s-trans isomerism, π-delocalization, partial aro-
maticity and the ring size of 1,3-thiazolidin-4-ones and
1,3-thiazin-4-ones formed from thiosemicarbazides. Jour-
nal of Molecular Structure: Theochem, 916, 105–118. DOI:
10.1016/j.theochem.2009.09.019.
Dabholkar, V. V., & Ravi, T. D. (2010). Efficient synthesis of
some novel spiro heterocycles containing triazine nucleus and
their microbiological activity. Indian Journal of Chemistry,
49, 593–597.
Darehkordi, A., Saidi, K., & Islami, M. R. (2007). Preparation of
heterocyclic compounds by reaction of dimethyl and diethyl
acetylenedicarboxylate (DMAD, DEAD) with thiosemicar-
bazone derivatives. Arkivoc, 2007, 180–188.
Dimmock, J. R., Kumar, P., Allen, T. M., Kao, G. Y., Halleran,
S., Balzarini, J., & de Clercq, E. (1997). Synthesis and cyto-
toxic evaluation of some carbohydrazones and thiocarbohy-
drazones of various unsaturated ketones and related Mannich
bases. Die Pharmazie, 52, 182–186.
Dvorko, M., Y., Albanov, A. I., Chipanina, N. N., Sher-
styannikova, L. V., Samoilov, V. G., Komarova, T. N.,
& Glotova, T. E. (2006). New functionalized pyrazolines
from 1-aroyl-2-phenylacetylenes and thiocarbonohydrazides.
Chemistry of Heterocyclic Compounds, 42, 1421–1426. DOI:
10.1007/s10593-006-0258-0.
Ferrari, M. B., Capacchi, S., Pelosi, G., Reffo, G., Tarasconi,
P., Albertini, R., Pinelli, S., & Lunghi, P. (1999). Synthe-
sis, structural characterization and biological activity of he-
licin thiosemicarbazone monohydrate and a copper(II) com-
plex of salicylaldehyde thiosemicarbazone. Inorganica Chim-
ica Acta, 286, 134–141. DOI: 10.1016/s0020-1693(98)00383-
1.
Supplementary data
The supplementary data associated with this ar-
ticle (Heterocyclisation of substituted ylidenethiocar-
bonohydrazides using dimethyl acetylenedicarboxy-
late) can be found in the online version of this paper
(DOI: 10.1515/chempap-2015-0092).
Crystallographic data (excluding structure fac-
tors) for the structure reported in this work have
been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-
1003762 (VIII ). Copies of the data can be obtained
free of charge on application to the Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax:
+44(1223) 336 033: e-mail: deposit@ccdc.cam.ac.uk.
References
Glotova, T. E., Dvorko, M. Y., Samoilov, V. G., & Ushakov,
I. A. (2008). New 1,3,4-thiadiazole derivatives from 1-
benzylidenethiocarbonohydrazides and 3-bromo-1-phenyl-
prop-2-yn-1-one. Russian Journal of Organic Chemistry, 44,
866–869. DOI: 10.1134/s1070428008060158.
Grangarapu, K., Manda, S., Jallapally, A., Thota, S., Karki, S.
S., Balzarini, J., De Clercq, E., & Tokuda, H. (2014). Syn-
thesis of thiocarbohydrazide and carbohydrazide derivatives
as possible biologically active agents. Medicinal Chemistry
Research, 23, 1046–1056. DOI: 10.1007/s00044-013-0684-3.
Hassan, A. A., Ibrahim, Y. R., El-Sheref, E. M., Aly, A.
A., Bräse, S., & Brown, A. B. (2012a). Novel synthesis of
pyrazolyloxothiazolidine derivatives. Journal of Heterocyclic
Chemistry, 49, 1380–1385. DOI: 10.1002/jhet.1023.
Hassan, A. A., Ibrahim, Y. R., El-Sheref, E. M., & Brown, A.
B. (2012b). Novel synthesis of oxothiazolidine derivatives.
Ahmadi, A., Saidi, K., & Khabazzadeh, H. (2009). An efficient
synthesis of substituted 2-iminothiazolidin-4-one and thiadi-
azoloquinazolinone derivatives. Molecular Diversity, 13, 353–
356. DOI: 10.1007/s11030-009-9124-1.
Alizadeh, A., Noaparast, Z., Sabahano, H., & Zohreh, N.
(2010). One-pot, pseudo-five-component synthesis of bis[2-
(arylimino)-1,3-thiazolidin-4-ones]. Helvatica Chimica Acta,
93, 1401–1406. DOI: 10.1002/hlca.200900402.
Aly, A. A., Brown, A. B., & Hassan, A. A. (2014). Hetero-
cycles from the reaction of thione groups with acetylenic
bonds. Advances in Heterocyclic Chemistry, 113, 245–304.
DOI: 10.1016/b978-0-12-800170-7.00005-5.
Bacchi, A., Carcelli, M., Pelagatti, P., Pelizzi, G., Rodriguez-
Arguelles, M. C., Rogolino, D., Solinas, C., & Zani, F. (2005).
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 5/23/15 9:21 PM

982
A. A. Hassan et al./Chemical Papers 69 (7) 973–982 (2015)
Journal of Heterocyclic Chemistry, 49, 1054–1058. DOI:
10.1002/jhet.935.
Nakarishi, K., & Solomon, P. H. (1977). Infrared absorption
spectroscopy. San Francisco, CA, USA: Holden-Day.
Hassan, A. A., Ibrahim, Y. R., Aly, A. A., El-Sheref, E. M., &
Yamato, T. (2013). Reactions of dimethyl ethynedicarboxy-
late with (substituted ethylidene)hydrazinecarbothioamides.
Journal of Heterocyclic Chemistry, 50, 473–477. DOI: 10.
1002/jhet.712.
Hassan, A. A., Aly, A. A., Bedair, T. I. M., Brown, A. B.,
& El-Emary, T. I. (2014a). A facile method for the synthe-
sis of hydrazine-4-oxothiazolidine and imino-5-oxothiadiazine
derivatives from 1,4-disubstituted thiosemicarbazides. Jour-
nal of Heterocyclic Chemistry, 51, 44–49. DOI: 10.1002/jhet.
1655.
Hassan, A. A., Mohamed, N. K., Abd El-Haleem, L. E.,
Bräse, S., & Nieger, M. (2014b). Synthesis of some new
heteroylhydrazono-1,3-thiazolidin-4-ones. Journal of Hetero-
cyclic Chemistry, in press. DOI: 10.1002/jhet.2240.
Heravi, M. M., Nami, N., Neumu¨ller, B., Oskooie, H. A., &
Hekmatshoar, R. (2006). Synthesis of some trisubstituted
thiazolidin-4-ones. Journal of Chemical Research, 2006, 722–
724. DOI: 10.3184/030823406779173442.
Rajendran, G., & Jain, S. R. (1984). Structural assign-
ment of monothiocarbonohydrazones by 1H NMR spec-
troscopy. Organic Magnetic Resonance, 22, 6–10. DOI:
10.1002/mrc.1270220103.
Rhee, S. H. (1972). Synthesis and evaluation of antimicrobial-
antitumor activites of methylthiosemicarbazones and thio-
carbohydrazones. Journal of the Pharmaceutical Society of
Korea, 16, 162–175.
Sahoo, M. K. (2007). Dimethyl acetylene dicarboxylate. Synlett,
2007, 2142–2143. DOI: 10.1055/s-2007-984894.
Schrader, B. (1989). Raman/Infrared atlas of organic com-
pounds. Weinheim, Germany: Wiley.
Sengupta, P., Ghosh, S.,
& Mak, T. C. W. (2001). A
new route for the synthesis of bis(pyridine dicarboxy-
lato)bis(triphenylphosphine) complexes of ruthenium(II) and
X-ray structural characterisation of the biologically active
trans-[Ru(PPh3)2(L1H)2] (L1H2 = pyridine 2,3-dicarboxylic
acid). Polyhedron, 20, 975–980. DOI: 10.1016/s0277-5387(01)
00736-7.
Heravi, M. M., & Alishiri, T. (2014). Dimethyl acetylenedi-
Sheldrick, G. M. (2008). A short history of SHELX. Acta Crys-
tallographic Section A, 64, 112–122. DOI: 10.1107/s0108767
307043930.
Shi, Z. C., Zhao, Z. G., Liu, X. L., & Wu, L. L. (2011). Synthesis
of new deoxycholic acid bis thiocarbazones under solvent-free
conditions using microwave irradiation. Journal of Chemical
Research, 35, 198–201. DOI: 10.3184/174751911x129952679
48561.
carboxylate as
a building block in heterocyclic synthe-
sis. Advances in Heterocyclic Chemistry, 113, 1–66. DOI:
10.1016/b978-0-12-800170-7.00001-8.
Imrich, J., Tomaščiková, J., Danihel, I., Kristian, P., B¨ohm,
S., & Klika, K. D. (2010). Selective formation of 5- or 6-
membered rings, 1,3-thiazolidin-4-one vs. 1,3-thiazin-4-one,
from acridine thiosemicarbazides by the use of ethyne acid es-
ters. Heterocycles, 80, 489–503. DOI: 10.3987/com-09-s(s)56.
Socrates, G. (1980). Infrared characterization group frequen-
cies. New York, NY, USA: Wiley.
Kabashima, S., Okawara, T., Yamasaki, T.,
& Furukawa,
M. (1990). Synthesis of novel 1,3-thiazolidines and 1,3,4-
thiadiazolines from thiocarbohydrazines. Heterocycles, 31,
1129–1139. DOI: 10.3987/com-90-5380.
Tomaščiková, J., Imrich, J., Danihel, I., Bo¨hm, S., Kristian,
P., Pisarčíková, J., Sabol, M., & Klika, K. D. (2008a).
Regioselectivity and tautomerism of novel five-membered
ring nitrogen heterocycles formed via cyclocondensation
of acylthiosemicarbazides. Molecules, 13, 501–518. DOI:
10.3390/molecules13030501.
Tomaščiková, J., Danihel, I., B¨ohm, S., Imrich, J., Kristian,
P., Potačňák, I., Čejka, J., & Klika, K. D. (2008b). Molecu-
lar and solid-state structure of methyl [2-(acridin-9-ylimino)-
3-(tert-butylamino)-4-oxothiazolidin-5-ylidene]acetate. Jour-
nal of Molecular Structure, 875, 419–426. DOI: 10.1016/j.
molstruc.2007.05.030.
Li, Z., Feng, X.,
& Zhao, Y. L. (2008). Microwave in-
duced efficient synthesis of (un)substituted benzaldehyde (5-
aryl-1,3,4-thiadiazol-2-yl)hydrazones using silica-supported
dichlorophosphate as a recoverable dehydrant. Journal of
Heterocyclic Chemistry, 45, 1489–1492. DOI: 10.1002/jhet.
5570450540.
Naik, A. D., Annigeri, S. M., Gangadharmath, U. B., Revankar,
V. K., & Mahale, V. B. (2002). Thiocarbohydrazide as ”di-
amine” to construct macrocyclic and side-off compart-mental
ligands. Journal of Inclusion Phenomena and Macrocyclic
Chemistry, 43, 291–297. DOI: 10.1023/a:1021289104845.
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