Triton-B catalyzed, green and efficient method for the synthesis of dithiocarbazates

Article abstract of DOI:10.14233/ajchem.2019.21973

A novel, solvent free and high yielding method was accomplished for one-pot synthesis of dithiocarbazates by the reaction of various alkyl halides (primary, secondary and tertiary) with variety of substituted hydrazines using Triton-B (benzyl-trimethylammonium hydroxide) and carbon di sulphide. This new method of synthesizing dithiocarbazates involves mild conditions, simple procedures and high yields of the products as compared to previously used methods.

Full text of DOI:10.14233/ajchem.2019.21973

Asian Journal of Chemistry; Vol. 31, No. 7 (2019), 1581-1584
A
SIAN
J
OURNAL OF HEMISTRY
C
https://doi.org/10.14233/ajchem.2019.21973
Triton-B Catalyzed, Green and Efficient Method for the Synthesis of Dithiocarbazates
*
SADAF ZAIDI and MRIDULA SAXENA
Department of Applied Chemistry, Amity School of Applied Sciences, Amity University Uttar Pradesh, Lucknow Campus, Lucknow-226028,
India
*Corresponding author: E-mail: sadaf.zaidi00@gmail.com
Received: 1 February 2019;
Accepted: 30 March 2019;
Published online: 21 May 2019;
AJC-19418
A novel, solvent free and high yielding method was accomplished for one-pot synthesis of dithiocarbazates by the reaction of various
alkyl halides (primary, secondary and tertiary) with variety of substituted hydrazines using Triton-B (benzyl-trimethylammonium hydroxide)
and carbon di sulphide. This new method of synthesizing dithiocarbazates involves mild conditions, simple procedures and high yields of
the products as compared to previously used methods.
Keywords: Primary alkyl halides, Secondary alkyl halides, Tertiary alkyl halides, Triton-B, Carbon disulfide, Dithiocarbazates.
use of strong bases, higher reaction temperatures and longer
reaction times [30]. Thus, we became interested to introduce
the improved methodologies. Considering the high utility of
dithiocarbazates, we report here an efficient, green and solvent-
free synthesis of dithiocarbazates from the various alkyl halides
(primary, secondary and tertiary) with variety of substituted
hydrazines using Triton-B (benzyl-trimethylammonium hydro-
xide) and carbon disulphide.
INTRODUCTION
Organic dithiocarbazates have invited research attention
due to their impeccable chemistry and wild utility. They have
pivotal role in pharmaceutical, industrial applications and as
organic and inorganic synthon [1-5]. The thiocarbamoyl struc-
ture of dithiocarbazate shows various biological activities like
antibacterial, antifungal, anti-inflammatory and uncoupling
activity [6]. Their extensive use in pharmaceuticals [7-9],
agrochemicals [10], organic synthesis [11-13], coordination
chemistry [14-16] peptide synthesis [17], solid phase organic
synthesis [18] and complexation reactions with transition
metals [19,20] make them a unique hetero compound. The
donor ligand complexation reaction of dithiocarbazate with
transition metal is of considerable interest due to high biolo-
gical activity [21,22]. The unique hetero compound has shown
considerable biological activity in pharmaceutical and agricul-
tural industry [23,24]. They also show various activities like
antifungal, antiprotozoal, antibacterial and anticancer activity
[25].
EXPERIMENTAL
All the chemicals used were obtained from Merck,Aldrich
and Fluka chemical companies. Reactions were carried out in
nitrogen atmosphere. The structural analysis of compound was
done as IR spectra (4000-200 cm-1) on Bomem MB-104-FTIR
spectrophotometer where as NMRs were scanned onAC-300F,
NMR (300 MHz), instrument using CDCl3 and some other
deutrated solvents and TMS as internal standard. Elemental
analysis were made by Carlo-Erba EA 1110-CNNO-S analyzer
and the obtained values were in accordance with calculated
values.
General procedure: To a solution of substituted hydrazine
(3 mmol) and carbon disulfide (8 mmol) Triton-B (2 mmol)
were slowly added while stirring at room temperature. The
stirring was continued till 0.5 h after which required amount
of alkyl halide (3 mmol) was added (Scheme-I). The reaction
Keeping in view their high utility it is necessary to develop
a low-cost and high yielding method, hence, it is necessary to
change their synthesis from costly and toxic chemicals like
thiophosgene [26,27] and its derivatives [28,29] to the less
toxic, low-cost and safe reagents like CS2. Even, there were short-
comings with CS2 also like harsh reaction conditions such as
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1582 Zaidi et al.
Asian J. Chem.
S
R1
R3
R1
H
R
H
R
H
N
N
Triton-B/CS2
R2
N
H
N
R2
X
S
+
RT, 2-3 h, 82-98 %
R3
H
I
Scheme-I
was further continued until the completion of reaction (Table-1)
under argon. The obtained mixture was poured into water (20
mL) and the extraction of organic layer was done with EtOAc
(3 × 10 mL). The organic layer was washed with 0.1 N hydro-
chloric acid (20 mL), sodium bicarbonate solution (25 mL),
brine solution (30 mL) and dried sodium sulfate and concen-
trated to get the desired compound I. Later, the desired comp-
ounds were confirmed by IR, NMR and elemental analysis.
N′-Phenoxymethyl hydrazinecarbodithioic acid butyl
ester (1): Yellow solid, m.p. 115 ºC. 13C NMR (CDCl3) δ =
13.2, 21.6, 32.2, 33.7, 43.5, 55.2, 112.2, 114.6, 134.2, 152.1,
222.3 (C=S) ppm; MS (EI): m/z = 270; IR (KBr, νmax, cm-1) =
MHz, CDCl3) δ = 2.08 (s, H, NH), 3.17 (2H, t, J = 6.5 Hz,
Ph.CH2CH2S), 3.21 (m, 2H, J = 7.2 Hz, PhCH2), 4.50 (m, H,
PhNH), 6.66-7.12 (m, 10H, Ar-H); Elemental analysis of
C15H16N2S2 calcd. (found) %: C, 62.45 (62.71); H, 5.58 (6.63);
N, 9.70 (9.58); S, 22.22 (22.11).
N′-Phenethyl hydrazinecarbodithioic acid 3-phenyl-
propyl ester (4): Yellow solid, m.p. 115 ºC. 13C NMR (CDCl3),
δ = 13.4, 20.0, 31.2, 38.1, 50.6, 126.4, 127.2, 128.7, 141.6,
223.1 (C=S) ppm; MS: m/z = 254; IR (KBr, νmax,cm-1) = 675,
1208; 1H NMR (400 MHz, CDCl3) δ = 1.02 (t, 3H, CH3), 1.31
(m, 2H, CH2CH3), 1.52 (m, 2H, CH2.CH2CH3), 2.01 (br, NH),
2.62 (m, 2H, NHCH2), 4.10 (s, 2H, PhCH2), 7.02-7.12 (m,
5H, Ar-H); Elemental analysis of C12H18N2S2 calcd. (found) %:
56.64 (56.45); H, 7.12 (7.34); N, 11.00 (11.26); S, 25.20 (25.11).
N′-Butyl hydrazinecarbodithioic acid 1-methyl butyl
ester (5): Yellow solid, m.p. 122 ºC. 13C NMR (CDCl3) δ =
10.4, 13.5, 20.5, 21.1, 31.3, 32.5, 40.3, 49.7, 223.2 (C=S) ppm;
1
674, 1211; H NMR (400 MHz, CDCl3) δ = 0.83 (t, 3H, J=
7.3 Hz), 1.31 (m, 2H), 1.82 (m, 2H), 2.1 (s, NH), 2.92 (t, 2H,
J = 6.3 Hz), 3.70 (s, 3H), 4.02 (m, NH), 6.72-7.64 (m, 4H);
Elemental analysis of C12H18N2OS2 calcd. (found) %: C, 53.29
(53.23); H, 6.70 (6.64); N, 10.36 (10.32); S, 23.72 (23.57).
N′-Phenethyl hydrazinecarbodithioic acid 3-phenyl-
propyl ester (2):Yellow solid, m.p. 120 ºC.13C NMR (CDCl3),
δ = 32.4, 33.2, 34.0, 112.1, 119.5, 125.4, 128.2, 129.1, 138.2,
221.1 (C=S) ppm; MS: m/z = 302; IR ( (KBr, νmax,cm-1) = 674,
1208; 1H NMR (400 MHz, CDCl3) δ = 2.01 (s, H, NH), 2.28
(m, 2H, Ph.CH2.CH2.CH2-S), 2.50 (t, 2H, J = 7.2 Hz, Ph.CH2),
2.82 (t, 2H, Ph.CH2.CH2.CH2.S), 4.01 (m, H, Ph.NH), 6.64-
7.10 (m, 10H, Ar-H); Elemental analysis of C16H18N2S2 calcd.
(found) %: C, 63.53 (63.34); H, 6.00 (6.25); N, 9.25 (9.16); S,
21.21 (21.27).
1
MS: m/z = 220; IR (KBr, νmax, cm-1) = 681, 1212; H NMR
(400 MHz, CDCl3) δ = 0.97 (t, 3H, CH3), 1.03 (t, 3H, CH3),
1.31 (m, 2H, CH2.CH3), 1.39 (d, 3H, CHCH3), 1.51 (m, 2H,
CH3CH2CH2), 1.93 (m, 2H, CHCH2), 2.02 (br, H, NH), 2.61
(m, 2H, NHCH2), 2.73 (m, H, CH-S); Elemental analysis of
C9H20N2S2 calcd. (found) %: 49.04 (49.32); H, 9.14 (9.00); N,
12.70 (12.74); S, 29.11 (29.31).
N′-(3-Nitrophenyl)hydrazinecarbodithioic acid 4-
methoxybenzyl ester (6): Yellow solid, m.p. 118 ºC. 13C NMR
(CDCl3) δ = 38.1, 56.5, 107.3, 114.2, 118.2, 128.7, 129.7,
133.9, 143.9, 148.8, 160.8, 223.5 (C=S) ppm; MS: m/z = 349;
IR (KBr, νmax,cm-1) = 679, 1215; 1H NMR (400 MHz, CDCl3)
δ = 2.01 (br, H, NHPh.OMe), 3.76 (s, 3H, OCH3), 4.09 (br, H,
NHPh.NO2), 6.67-7.63 (m, 8H, Ar-H); Elemental analysis of
N′-Butyl hydrazinecarbodithioic acid 3-phenylpropyl
ester (3): Yellow solid, m.p. 124 ºC. 13C NMR (CDCl3), δ =
34.2, 37.1, 47.0, 49.5, 118.2, 192.3, 223.0 (C=S) ppm; MS:
1
m/z = 288; IR (KBr, νmax, cm-1) = 673, 1203; H NMR (400
TABLE-1
CONVERSION OF ALKYL HALIDES INTO PROTOTYPE OF GENERAL FORMULA I
Compd.
R1
R2
R3
X
R
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
n-C3H7
Phenyl ethyl
Phenyl methyl
Phenyl
C2H5
4-MeO.Ph
C3H7
C3H7
H
H
H
H
Me
H
H
H
H
C4H9
C4H9
H
H
H
H
H
H
H
H
H
H
H
H
H
C4H9
H
H
H
Br
Br
Cl
Cl
Br
Cl
Br
Br
Br
Br
Br
Cl
Cl
Cl
Br
Br
4-MeO-Ph
Phenyl
Phenyl
Butyl
2.0
2.0
2.5
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
2.5
2.5
2.0
3.0
3.0
93
96
86
91
89
84
85
82
82
88
86
95
95
98
85
82
Butyl
3-NO2.Ph
4-NO2.Ph
2,4-NO2.Ph
Naphthyl
Phenyl
Phenyl
Butyl
Phenyl
Butyl
Phenyl
Phenyl
C3H7
C4H9
C4H9
C5H11
C7H15
C9H19
C3H7
Phenyl
C3H7
CH3
H
H

Vol. 31, No. 7 (2019)
Triton-B Catalyzed, Green and Efficient Method for the Synthesis of Dithiocarbazates 1583
C15H15N3O3S2 calcd. (found) %: C, 51.55 (51.22); H, 4.32 (4.51);
N, 12.02 (12.23); S, 18.34 (18.02).
N′-Phenyl hydrazinecarbodithioic acid octyl ester (13):
Yellow solid, m.p. 120 ºC. 13C NMR (CDCl3) δ = 14.3, 23.12,
N′-(4-Nitrophenyl) hydrazinecarbodithioic acid butyl
ester (7): Yellow solid, m.p. 121 ºC. 13C NMR (CDCl3) δ =
13.5, 21.2, 32.4, 33.5, 113.9, 124.3, 138.7, 143.1, 223.3 (C=S)
28.7, 30.3, 31.3, 32.7, 112.4, 129.8, 118.7, 142.4, 223.8 ppm;
1
MS: m/z = 296; IR (KBr, νmax, cm-1) = 677, 1213; H NMR
(400 MHz, CDCl3) δ = 0.98 (t, 3H, CH3), 1.27 (m, 8H, CH2),
1.31 (m, 2H, CH2CH3), 1.98 (m, 2H, SCH2CH2), 2.04 (br, H,
NH), 2.86 (t, 2H, SCH2), 4.04 (br, H, Ph.NH), 6.63-7.24 (m,
5H, Ar-H); Elemental analysis of C15H24N2S2 calcd. (found) %:
C, 60.75 (60.54); H, 8.15 (8.32); N, 9.44 (9.31); S, 21.62 (21.76).
N′-Butyl hydrazinecarbodithioic acid decyl ester (14):
Yellow solid, m.p. 120 ºC. 13C NMR (CDCl3) δ = 13.5, 14.7,
20.6, 23.3, 28.7, 30.8, 30.7, 31.7, 32.3, 222.3 ppm; MS: m/z =
1
ppm; MS: m/z = 285; IR (KBr, νmax, cm-1) = 668, 1201; H
NMR (400 MHz, CDCl3) δ = 0.94 (t, 3H, CH3), 1.31 (m, 2H,
CH2CH3), 1.92 (m, 2H, SCH2.CH2), 2.09 (br, H, NH), 2.82 (t,
2H, SCH2), 4.01 (br, N, NHArNO2), 6.95-8.15 (m, 4H, Ar-H);
Elemental analysis of C11H15N3O2S2 calcd. (found) %: C, 46.28
(46.44); H, 5.31 (5.16); N, 14.71 (14.46); S, 22.46 (22.20).
N′-(2,4-Nitrophenyl) hydrazinecarbodithioic acid butyl
ester (8): Yellow solid, m.p. 108 ºC. 13C NMR (CDCl3) δ =
13.5, 21.7, 32.1, 33.9, 113.9, 119.1, 130.4, 132.6, 139.9, 143.1,
222.7 (C=S) ppm; MS: m/z = 330; IR (KBr, νmax, cm-1) = 671,
1214; 1H NMR (400 MHz, CDCl3) δ = 0.96 (t, 3H, CH3), 1.34
(m, 2H, CH2CH3), 1.97 (m, 2H, SCH2.CH2), 2.06 (br, H, NH),
2.86 (t, 2H, SCH2), 4.08 (br, N, NHArNO2), 7.16-9.52 (m, 3H,
Ar-H); Elemental analysis of C11H14N4O4S2 calcd. (found) %:
C, 39.98 (40.21); H, 4.26 (4.04); N, 16.95 (16.75); S, 19.40 (19.51).
N′-(1,4,4a,8a-Tetrahydronaphthalen-1-yl) hydrazine
carbodithioic acid butyl ester (9): Yellow solid, m.p. 120 ºC.
13C NMR (CDCl3) δ = 13.7, 22.5, 32.7, 33.7, 107.2, 117.4,
121.6, 124.7, 126.8, 127.6, 133.8, 142.8, 224.4 (C=S) ppm;
MS: m/z = 290; IR (KBr, νmax,cm-1) = 678, 1207; 1H NMR (400
MHz, CDCl3) δ = 0.93 (t, 3H, CH3), 1.31 (m, 2H, CH2CH3),
1.95 (m, 2H, SCH2.CH2), 2.04 (br, H, NH), 2.81 (t, 2H, SCH2),
4.07 (br, N, NHArNO2), 6.77-7.53 (m, 7H, Ar-H); Elemental
analysis of C15H18N2S2 calcd. (found) %: C, 62.02 (62.43); H,
6.24 (6.32); N, 9.63 (9.52); S, 22.07 (22.24).
1
304; IR (KBr, νmax, cm-1) = 676, 1224; H NMR (400 MHz,
CDCl3), δ = 0.95 (s, 3H, CH3), 0.97 (s, 3H, CH3), 1.27 (m,
12H, CH2), 1.32 (m, 4H, CH2CH3), 1.51 (m, 2H, CH2CH2CH3),
1.92 (m, 2H, SCH2CH2), 2.03 (br, 2H, NH.NH), 2.61 (m, 2H,
NHCH2), 2.85 (t, 2H, SCH2); Elemental analysis of C15H32N2S2
calcd. (found) %: C, 59.14 (59.31); H, 10.58 (10.33); N, 9.21
(9.20); S, 21.05 (21.23).
N′-Phenyl hydrazinecarbodithioic acid 1-propylbutyl
ester (15): Yellow solid, m.p. 123 ºC. 13C NMR (CDCl3) δ = 14.3,
20.11, 38.6, 40.6, 112.7, 118.6, 129.8, 143.6, 222.3 ppm; MS:
1
m/z = 282; IR (KBr, νmax, cm-1) = 674, 1212; H NMR (400
MHz, CDCl3) δ = 0.96 (s, 3H, CH3), 1.31 (m, 4H, CH2CH3),
1.90 (m, 4H, CHCH2), 2.01 (br, H, NH), 2.50 (m, H, CH-S),
4.13 (br, H, NH-Ar), 6.64-7.21 (m, 5H, Ar-H); Elemental
analysis of C14H22N2S2 calcd. (found) %: C, 59.52 (59.74); H,
7.84 (7.65); N, 9.91 (9.91); S, 22.71 (22.43).
N′-Phenyl hydrazinecarbodithioic acid 1-phenylethyl
ester (16):Yellow solid, m.p. 121 ºC. 13C NMR (CDCl3) δ = 23.6,
41.3, 112.7, 118.7, 126.7, 128.7, 129.5, 141.6, 142.4, 222.3 ppm;
MS: m/z = 288; IR (KBr, νmax,cm-1) = 677, 1212; 1H NMR (400
MHz, CDCl3) δ = 1.67 (d, 3H, CH3), 2.4 (br, H, NH), 3.97 (m,
H, CH-S), 4.4 (br, H, NH-Ar), 6.64-7.26 (m, 10H, Ar-H);
Elemental analysis of C15H16N2S2 calcd. (found) %: C, 62.45
(62.32); H, 5.58 (5.45); N, 9.70 (9.98); S, 22.22 (22.35).
N′-Phenyl hydrazinecarbodithioic acid 1-butylpentyl
ester (10): Yellow solid, m.p. 123 ºC. 13C NMR (CDCl3) δ =
14.4, 23.3, 28.7, 36.4, 41.6, 112.4, 119.5, 129.2, 142.6, 223.6
(C=S) ppm; MS: m/z = 310; IR (KBr, νmax,cm-1) = 675, 1210;
1H NMR (400 MHz, CDCl3) δ = 0.94 (t, 6H, CH3), 1.27 (m, 4H,
CH2CH2CH), 1.36 (m, 4H, CH2CH3), 1.94 (m, 4H, CHCH2),
2.07 (br, H, NH), 2.54 (t, H, SCH), 4.07 (br, H, NHAr), 6.64-
7.16 (m, 5H, Ar-H); Elemental analysis of C16H26N2S2 calcd.
(found) %: C, 61.88 (61.76); H, 8.43 (8.53); N, 9.01 (9.21); S,
20.64 (20.45).
RESULTS AND DISCUSSION
We are continuously working on the use of Triton-B for
the improved synthesis of sulphur compounds like carbamates,
dithiocarbamates and dithiocarbonates (xanthates). Here we
are reporting novel, solvent free and high yielding method
was accomplished for one-pot synthesis of dithiocarbazates
by the reaction of various alkyl halides (primary, secondary and
tertiary) with variety of substituted hydrazines using Triton-B
(benzyl-trimethylammonium hydroxide) and carbon disul-
phide. Thus, Triton-B was added to the mixture of substituted
hydrazine and carbon disulphide. After stirring the reaction
for 30 min at room temperature, corresponding alkyl halide
was added in it. The reaction was allowed to proceed and pro-
gress was checked by TLC (Table-1).
The synthesized compound was finally confirmed by IR
and NMR spectral analysis. The 13C NMR spectra of the synthe-
sized compounds seems to shows a peak between 222 ppm to
224 ppm for dithio-bonding (C=S) found in dithiocarbazate.
The presence of -CH3 group is thought to be shown by singlet
at δ = 0.96 and -CH2CH3 by multiplet at δ = 1.32 in the final
product. Compounds 2, 3, 4, 6, 7, 13, 15 and 16 show a sharp
N′-Phenyl hydrazinecarbodithioic acid 1,1-dibutylpentyl
ester (11): Yellow solid, m.p. 116 ºC. 13C NMR (CDCl3) δ =
14.2, 23.6, 26.9, 39.4, 41.3, 112.7, 119.5, 129.9, 142.4, 223.7
1
ppm; MS: m/z = 366; IR (KBr, νmax, cm-1) = 667, 1214; H
NMR (400 MHz, CDCl3) δ = 0.92 (t, 6H, CH3), 1.27 (m, 4H,
CH2CH2C), 1.31 (m, 4H, CH2CH3), 1.87 (m, 4H, CHCH2), 2.02
(br, H, NH), 4.2 (br, H, NH-Ar), 6.65-7.17 (m, 5H, Ar-H);
Elemental analysis of C20H34N2S2 calcd. (found) %: C, 65.51
(65.26); H, 9.34 (9.10); N, 7.63 (7.43); S, 17.48 (17.48).
N′-Butyl-hydrazinecarbodithioic acid hexyl ester (12):
Yellow solid, m.p. 118 ºC. 13C NMR (CDCl3) δ = 13.5, 14.2,
20.4, 23.3, 28.3, 31.7, 32.9, 49.7, 223.3 ppm; MS: m/z = 248;
IR (KBr, νmax,cm-1) = 676, 1206; 1H NMR (400 MHz, CDCl3)
δ = 0.94 (t, 6H, CH3), 1.27 (m, 4H, CH2CH2CH2CH3), 1.36 (t, 2H,
CH2CH3), 1.51 (m, 2H, NHCH2CH2), 1.92 (m, 2H, SCH2CH2),
2.1 (br, 2H, NH), 2.63 (t, 2H, NHCH2), 2.85 (t, 2H, SCH2);
Elemental analysis of C11H24N2S2 calcd. (found) %: C, 53.17
(53.32); H, 9.73 (9.53); N, 11.27 (11.38); S, 25.80 (25.63).

1584 Zaidi et al.
Asian J. Chem.
6. S. Kubota, M. Uda,Y. Mori, F. Kametani and H. Terada, J. Med. Chem.,
21, 591 (1978);
https://doi.org/10.1021/jm00204a018.
7. M.S.C. Pedras and M. Jha, Bioorg. Med. Chem., 14, 4958 (2006);
https://doi.org/10.1016/j.bmc.2006.03.014.
8. N. Bharti, M.R. Maurya, F. Naqvi and A. Azam, Bioorg. Med. Chem.
Lett., 10, 2243 (2000);
https://doi.org/10.1016/S0960-894X(00)00446-7.
9. B. Neelam, M. Mannar R, N. Fehmida, B. Alok, B. Sudha and A. Amir,
Eur. J. Med. Chem., 35, 481 (2000);
https://doi.org/10.1016/S0223-5234(00)00145-8.
10. H.S. Chen, Z.H. Li, Y.H. Han and Z.W. Wang, Chin. Chem. Lett., 10,
365 (1999).
11. T.J. Connolly, A.J. Crittall, A.S. Ebrahim and G. Ji, Org. Process Res.
Dev., 4, 526 (2000);
peak at (δ = 4 to 4.01) due to presence of aromatic ring in
alkyl halides. In compounds 1 and 2 the presence of multiplet
at δ = 4 seems to be due to presence of -NH group.
According to proposed reaction mechanism S– of the
dithiocarbazate ion produced attacks to the electrophilic carbon
of the corresponding alkyl halide to produce dithiocarbazates
in appreciable yields (82-98 %) at room temperature in 2-3 h
(Table-1). The progress of reaction was successful and the
isolated products were further confirmed by various spectro-
scopic and analytical techniques. The extraction procedures
of products were simple and obtained by concentration of
organic layer after filtration of basic resin from the reaction.
In order to get better results several solvents like n-heptane,
n-hexane, acetonitrile, benzene, toluene, methanol, dichloro-
methane, chloroform, DMSO, dimethylformamide and hexa-
methylphosphoric triamide were tried. Previously, the synthesis
of dithiocarbazates through the same mechanism has also been
reported but the procedure was not solvent free. In order to
enhance the efficiency of synthesis of dithiocarbamates we
tried the same reaction in the absence of solvent and found
that desired product can be isolated in higher yields.
https://doi.org/10.1021/op0002904.
12. M.J. Hauser, J. Org. Chem., 31, 968 (1966);
https://doi.org/10.1021/jo01341a514.
13. V. del Amo, A.P. McGlone, C. Foster and A.P. Davis, J. Comb. Chem.,
7, 1 (2005);
https://doi.org/10.1021/cc049875q.
14. M.T.H. Tarafder, M.A. Ali, N. Saravanan, W.Y. Weng, S. Kumar, N.
Umar-Tsafe and K.A. Crouse, Transition Met. Chem., 25, 3 (2000);
https://doi.org/10.1023/A:1007044910814.
15. S.-N. Li, Q.-G. Zhai, M.-C. Hu and Y.-C. Jiang, J. Chem. Crystallogr.,
41, 12 (2011);
https://doi.org/10.1007/s10870-010-9825-4.
16. F.N.-F. How, K.A. Crouse, M.I.M. Tahir, M.T.H. Tarafder and A.R.
Cowley, Polyhedron, 27, 3325 (2008);
Conclusion
In conclusion, we have accomplished a novel, solvent free
and high yielding method for one-pot synthesis of dithiocar-
bazates by the reaction of various alkyl halides (primary,
secondary and tertiary) with variety of substituted hydrazines
using Triton-B (benzyl-trimethylammonium hydroxide) and
carbon disulphide.. The high yields of corresponding dithio-
carbazates makes it a better method. Furthermore, this method
exhibits greener methodology, mild reaction conditions and
experimental convenience.
https://doi.org/10.1016/j.poly.2008.07.022.
17. M. Quibell, W.G. Turnell and T. Johnson, J. Chem. Soc. Perkin Trans.
I, 22, 2843 (1993);
https://doi.org/10.1039/p19930002843.
18. C.J. Gray, M. Quibell, N. Baggett and T. Hammerle, Int. J. Pept. Protein
Res., 40, 351 (1992);
https://doi.org/10.1111/j.1399-3011.1992.tb00311.x.
19. X. Huang, E. Tang, W.-M. Xu and J. Cao, J. Comb. Chem., 7, 802 (2005);
https://doi.org/10.1021/cc0498231.
20. J.Y. Hwang, H.S. Choi, D.H. Lee and Y.D. Gong, J. Comb. Chem., 7,
816 (2005);
https://doi.org/10.1021/cc0500957.
21. A. Monaci and F. Trali, J. Chem. Soc. Dalton Trans., 499 (1980);
https://doi.org/10.1039/DT9800000499.
22. S.B. Kalia, V. Sharma, K. Lumba, G. Kaushal and A. Sharma, Indian J.
Pharm. Sci., 69, 438 (2007);
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the fruitful discussions
with Dr. Devdutt Chaturvedi regarding the research andAmity
University Uttar Pradesh Lucknow Campus, India for providing
the infrastructure to conduct the research.
https://doi.org/10.4103/0250-474X.34558.
23. M.A. Ali and S.E. Livingstone, Coord. Chem. Rev., 13, 101 (1974);
https://doi.org/10.1016/S0010-8545(00)80253-2.
24. M.R. Maurya, S.S. Khurana, A. Azam, W. Zhang and D. Rheder, Eur.
J. Inorg. Chem., 2003, 1966 (2003);
CONFLICT OF INTEREST
https://doi.org/10.1002/ejic.200200642.
25. A. Saxena, J.K. Koacher and J.P.J. Tandon, Antibact. Antifung. Agent,
9, 435 (1981).
The authors declare that there is no conflict of interests
regarding the publication of this article.
26. C. Bolzati, E. Benini, M. Cavazza-Ceccato, E. Cazzola, E. Malagò, S.
Agostini, F. Tisato, F. Refosco and G. Bandoli, Bioconjug. Chem., 17,
419 (2006);
https://doi.org/10.1021/bc050358q.
27. M.A. Ali, A.H. Mirza, R.J. Butcher and K.A. Crouse, Transition Met.
Chem., 31, 79 (2006);
https://doi.org/10.1007/s11243-005-6305-3.
28. H. Dyker, J. Scherkenbeck, D. Gondol, A. Goehrt and A. Harder, J. Org.
Chem., 66, 3760 (2001);
https://doi.org/10.1021/jo001749v.
29. S. Nara, T. Sakamoto, E. Miyazawa andY. Kikugawa, Synth. Commun.,
33, 87 (2003);
REFERENCES
1. U. Ragnarsson, Chem. Soc. Rev., 30, 205 (2001);
https://doi.org/10.1039/b010091a.
2. B. Mishra, S. Reiling, D. Zarena and G. Wang, Curr. Opin. Chem. Biol.,
38, 87 (2017);
https://doi.org/10.1016/j.cbpa.2017.03.014.
3. F.R. Pavan, P.L. da S. Maia, S.R. Leite, V.M. Deflon, A.A. Batista,
D.N. Sato, S.G. Franzblau and C.Q. Leite, Eur. J. Med. Chem., 45,
1898 (2010);
https://doi.org/10.1016/j.ejmech.2010.01.028.
4. H. van der Goot, Eur. J. Chem., 35, 5 (2000);
https://doi.org/10.1016/S0223-5234(00)00101-X.
5. E.U. Schmidt, Hydrazine and its Derivatives Preparation, Properties,
Applications, Wiley-Interscience: New York, edn 2 (2001).
https://doi.org/10.1081/SCC-120015563.
30. D.L. Fox, J.T. Ruxer, J.M. Oliver, K.L. Alford and R.N. Salvatore,
Tetrahedron Lett., 45, 401 (2004);
https://doi.org/10.1016/j.tetlet.2003.10.144.