Synthesis and characterization of some dithiocarbohydrazones

Article abstract of DOI:10.1081/SCC-120015405

Three bisthiocarbohydrazones had been synthesized and characterized. The structures of the three compounds were determined by elemental analysis, IR, MS, ¹HNMR and ¹³CNMR. The crystal structure of one of the compounds was determined

Full text of DOI:10.1081/SCC-120015405

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SYNTHESIS AND CHARACTERIZATION OF SOME
DITHIOCARBOHYDRAZONES
Anjiang Zhang a , Yunlong Hou a , Lixue Zhang a & Yi Xiong b
a Department of Chemistry , Wenzhou Teachers College , Wenzhou, 325027, P.R. China
b Department of Chemistry , Zhejiang University , Hangzhou, 310027, P.R. China
Published online: 23 Aug 2006.
To cite this article: Anjiang Zhang , Yunlong Hou , Lixue Zhang & Yi Xiong (2002) SYNTHESIS AND CHARACTERIZATION OF
SOME DITHIOCARBOHYDRAZONES, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 32:24, 3865-3869, DOI: 10.1081/SCC-120015405
To link to this article: http://dx.doi.org/10.1081/SCC-120015405
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SYNTHETIC COMMUNICATIONS
Vol.32, No.24, pp.3865–3869, 2002
SYNTHESIS AND CHARACTERIZATION
OF SOME DITHIOCARBOHYDRAZONES
Anjiang Zhang,1, Yunlong Hou,1 Lixue Zhang,1
*
and Yi Xiong1,2
1Department of Chemistry, Wenzhou Teachers College,
Wenzhou, 325027, P.R. China
2Department of Chemistry, Zhejiang University,
Hangzhou, 310027, P.R. China
ABSTRACT
Three bisthiocarbohydrazones had been synthesized and
characterized.The structures of the three compounds were
determined by elemental analysis, IR, MS, 1H NMR and
13C NMR.The crystal structure of one of the compounds
was determined by X-ray single crystal diffraction techniques.
Key Words: Bisthiocarbohydrazone; Synthesis; Crystal
structure
Carbohydrazones and thiocarbohydrazones of various unsaturated
ketones and related Mannich bases were evaluated for their cytotoxic proper-
ties.[1] A series of 2-acetyl pyridine thiocarbohydrazones were synthesized and
tested as inactivater of HSV-1 ribonucleotide reductase[2] with better results
than the analogous 2-acetyl pyridine thiosemicarbohydrazone derivatives.
*Corresponding author.E-mail: anjiangzhang@hotmailc.om
3865
DOI: 10.1081/SCC-120015405
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3866
ZHANG ET AL.
Scheme 1.
These compounds and their metal complexes exhibit antimicrobial and
mutagenic activity,[3] especially as bacteriostatic, antitumor and antiviral
agents, and have received special attention and have been extensively
investigated in several research fields.[4,5] In order to study the complexes
of 1,5-bisthiocarbohydrazone with metal ions, we synthesized firstly the
three new thiocarbohydrazones under mild conditions (Scheme 1).
EXPERIMENTAL SECTION
Apparatus
The contents of carbon, hydrogen and nitrogen were carried out on an
Flash-1112 elemental analyzer.The IR spectra were recorded on a Nicolet-
360 FT-IR spectrophotometer using KBr discs in the range 4000–400 cmꢀ1
.
1H NMR and 13C NMR spectra were performed on a Bruker Avance-300
NMR spectrometer in DMSO-d6 solution using TMS as an internal refer-
ence.MS spectra were recorded on an HP5989A apparatus.Melting points
were determined on an XT-4 melting point apparatus and are uncorrected.
X-ray diffraction data of compound 1 were collected on a Nicolet R3M/E
four-circle diffractometer with MoKa (ꢀ ¼ 0.71073 A) radiation.Scan rang
was 2.17ꢁ ꢂ ꢁ ꢂ 25.00ꢁ.
Reagents
Thiocarbohydrazide was prepared by the literature method.[6] All
other chemicals and solvents used were of AR grade.
Experimental Procedure
Preparation of 1,5-bis(4-methoxybenzaldehyde)dithiocarbohydrazone:
In a 250 mL round bottom flask provided with an electromagnetic stirrer

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DITHIOCARBOHYDRAZONES
3867
and a reflux condenser were placed water (40 mL), thiocarbohydrazide
(0.025 mol). The flask was then heated on a water bath until the solid
compounds dissolved, 0.06 mol p-anisaldehyde in EtOH (30 mL) was
added using a constant pressure funnel with stirring.The solution
was refluxed with continuous stirring at 70–80ꢁC for 3 h.The mixture was
then cooled to room temperature and the yellow precipitate, which formed,
was filtered off, washed with EtOH (40%) three times and recrystallized
from EtOH to give yellow pure product.Single crystals were obtained by
slow evaporation of the mixture of ethanol and dioxane (1 : 1).
Preparation of 1,5-bis( p-dimethylaminobenzaldehyde)dithiocarbohydra-
zone: To the hot solution of thiocarbohydrazide (0.025 mol) in water
(50 mL) was added p-dimethylaminobenzaldehyde (0.06 mol) in ethanol
ꢁ
(30 mL).The mixture was stirred at 90–100 C for 3 h.After the mixture
was cooled to room temperature, the yellow precipitate was filtered off
and washed with EtOH (50%) three times.The crude product was recrys-
tallized from EtOH to give yellow pure product and dried under reduced
pressure.
Preparation of 1,5-bis(2-furaldehyde)dithiocarbohydrazone: To the hot
solution of thiocarbohydrazide (0.025 mol) in water (50 mL) was added a
solution of furfural (5 mL) in water (50 mL), the mixture was refluxed at
60–70ꢁC for 1.5 h. The yellow precipitate was washed with hot water three
times and dried under reduced pressure.
Characterization Data for Products
1,5-bis(4-Methoxybenzaldehyde)dithiocarbohydrazone 1: Yellow powder,
yield 97%, m.p. 201–203ꢁC.Anal.Calcd.for C 17H18N4O2S: C, 59.62; H,
5.30; N, 16.37. Found: C, 59.36; H, 5.05; N, 15.99. IR (cmꢀ1): 3128 (N-H);
1604 (C¼N); 1541 (¼C-N); 1253 (C¼S); 1303, 1029 (CH3-O); 821 (aromatic
ring). 1H-NMR (ꢂ: ppm): 11.67 (s, 1H, –NH–); 11.40 (s, 1H, –NH–); 8.50 (s,
1H, –CH¼); 8.07 (s, 1H, –CH¼); 6.99–7.78 (m, 8H, aromatic ring protons),
3.79 (–OCH3). 13C-NMR (ꢂ: ppm): 174.54 (–C¼S); 143.43 (–HC¼N–);
161.11, 129.19, 126.99, 114.54 (–CH¼CH–); 55.59 (–OCH3).MS ( m/z): 342
(Mþ), 268, 192, 150, 134, 133, 92, 91, 90, 77 (100%).
1,5-bis( p-Dimethylaminobenzaldehyde)dithiocarbohydrazone 2: Yellow
powder, yield 75%, m.p. 245–247ꢁC.Anal.calcd.for C 19H24N6S: C, 61.92;
H, 6.56; N, 22.81. Found: C, 61.64; H, 6.30; N, 22.52. IR (cmꢀ1): 3127 (N-
H); 1601 (C¼N); 1362 (¼C-N); 1230 (C¼S); 1229, 946 (CH3-N); 812 (aro-
1
matic ring). H-NMR (ꢂ: ppm): 11.43 (s, 1H, –NH–); 11.15 (s, 1H, –NH–);
8.48 (s, 1H, –CH¼); 8.40 (s, 1H, –CH¼); 6.72–7.64 (m, 8H, aromatic ring
protons), 2.96 (–NCH3). 13C-NMR (ꢂ: ppm): 173.55 (–C¼S); 129.75

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3868
ZHANG ET AL.
(–CH¼N–); 151.75, 128.95, 121.85, 112.00 (–CH¼CH–); 40.67 (–NCH3).
MS (m/z): 368 (Mþ), 294, 266, 251, 174, 147, 106 (100%), 91, 77.
1,5-bis(2-Furaldehyde)dithiocarbohydrazone 3: Yellow powder, yield
81%, m.p. 194–196ꢁC.Anal.calcd.for C 11H10N4O2S: C, 50.37; H, 3.84;
N, 21.36. Found: C, 50.00; H, 3.57; N, 21.11. IR (cmꢀ1): 3128 (N-H); 1619
(C¼N); 1016 (C-O); 753 (fural ring). 1H-NMR (ꢂ: ppm): 11.25 (s, 2H, –NH–);
8.00 (s, –CH¼); 6.67–7.84 (m, 6H, aromatic ring protons), 13C-NMR (ꢂ:
ppm): 174.70 (–C¼S); 133.15 (–HC¼N–); 148.08, 145.43, 113.87, 112.56
(–CH¼CH–).MS ( m/z): 262 (Mþ), 188, 167, 152, 110, 94, 80, 52 (100%), 43.
X-Ray Diffraction Study of
1,5-bis(4-Methoxybenzaldehyde)dithiocarbohydrazone
A transparent colorless crystal (0.44 Â 0.44 Â 0.20 mm) was mounted
on a Nicolet R3M/E diffractometer with Mo-Ka radiation (0.71073 A).The
unit cell was measured by centering 35 reflections and refined by full-matrix
least-squares on F2.Details of the data collection and processing are pre-
sented as: empirical formula C17H18N4O2S Á 1/2 C4H8O2 (1,4-dioxane); for-
mula weight 386.47; crystal system, monoclinic; space group, p21/c.The unit
cell dimensions are: a ¼ 14.363(3) A, b ¼ 12.622(2) A, c ¼ 10.970(2) A,
b ¼ 101.730ꢁ, V ¼ 1947.2(6) A3, Z ¼ 4, Dcalc. ¼ 1.318 Mg/m3, ꢃ ¼ 0.193 mmꢀ1
,
T ¼ 295(2) K, F(000) ¼ 816.No.of reflections collected were 3622, No.of
Independent reflections were 3425 (Rint ¼ 0.0173), R1 ¼ 0.056, wR2 ¼ 0.1496
for final R indices [I>2ꢄ(I)], wR2 ¼ 0.1675 on all data. The crystal structure
of the compound is showed as below (Fig.1).
Figure 1. The crystal structure of compound 1.

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DITHIOCARBOHYDRAZONES
3869
The compound 1 exists as dimer containing one solvent molecule (1,4-
dioxane), due to weak intermolecular hydrogen bonds N2ꢀH2N Á Á Á S
ðH2N Á Á Á S ¼ 2:58 A, N2 Á Á Á S ¼ 3:424 A, N2ꢀH2N Á Á Á S ¼ 165:8ꢁÞ formed in
the crystals as shown in Figure 1.Supplementary material includes atom
coordinates, bond angles, detailed data on hydrogen bonds and other
relevant data.The X-ray data were deposited at the Cambridge
Crystallographic Data Center No.172140.
It has been found that the three compounds also have strong inhibi-
tory and killing effect on human leukemia cell (HL-60) and human liver
cancer cell (BEL-7402) etc., the results will be reported later.
ACKNOWLEDGMENTS
We are grateful to the Project of Supporting the University Backbone
Teachers Foundation of the Education Ministry of China and the NSF of
Zhejiang province, China (project No.297003).
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Received in Japan October 23, 2001

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