An Efficient, basic resin-mediated, one-pot synthesis of dithiocarbazates through alcoholic tosylates

Article abstract of DOI:10.1080/10426500802203137

A quick and efficient, one-pot synthesis of dithiocarbazates was accomplished in high yields by the reaction of various alcoholic tosylates of primary, secondary, and tertiary alcohols, with substituted hydrazines using an Amberlite IRA 400 (basic resin)/

Full text of DOI:10.1080/10426500802203137

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Phosphorus, Sulfur, and Silicon
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An Efficient, Basic Resin-
Mediated, One-Pot Synthesis
of Dithiocarbazates Through
Alcoholic Tosylates
Devdutt Chaturvedi a , Nisha Mishra b , Amit K.
Chaturvdi b & Virendra Mishra b
a Bio-Organic Chemistry Division , Indian Institute of
Integrative Medicine , Jammu-Tawi, J. & K, India
b Synthetic Research Laboratory, Department of
Chemistry , B. S. A. College , Mathura, U. P., India
Published online: 19 Feb 2009.
To cite this article: Devdutt Chaturvedi , Nisha Mishra , Amit K. Chaturvdi &
Virendra Mishra (2009) An Efficient, Basic Resin-Mediated, One-Pot Synthesis of
Dithiocarbazates Through Alcoholic Tosylates, Phosphorus, Sulfur, and Silicon and the
Related Elements, 184:3, 550-558, DOI: 10.1080/10426500802203137
To link to this article: http://dx.doi.org/10.1080/10426500802203137
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Phosphorus, Sulfur, and Silicon, 184:550–558, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802203137
An Efficient, Basic Resin-Mediated, One-Pot Synthesis
of Dithiocarbazates Through Alcoholic Tosylates
Devdutt Chaturvedi,1 Nisha Mishra,2 Amit K. Chaturvdi,2
and Virendra Mishra2
1Bio-Organic Chemistry Division, Indian Institute of Integrative
Medicine, Jammu-Tawi, J. & K., India
2Synthetic Research Laboratory, Department of Chemistry, B. S. A.
College, Mathura, U. P., India
A quick and efficient, one-pot synthesis of dithiocarbazates was accomplished in
high yields by the reaction of various alcoholic tosylates of primary, secondary,
and tertiary alcohols, with substituted hydrazines using an Amberlite IRA 400
(basic resin)/CS2 system. The reaction conditions are mild with simpler work-up
procedures than previously reported methods.
Keywords Alcoholic tosylates; Amberlite IRA 400; carbon disulfide; dithiocarbazates;
substituted hydrazines
INTRODUCTION
Organic dithiocarbazates have attracted much attention due to
their numerous remarkable medicinal, industrial, and synthetic
applications.1,2 They have been extensively used as pharmaceuti-
cals,3–6 agrochemicals,7–10 intermediates in organic synthesis,11–13 for
the protection of amino groups in peptide synthesis,14–17 as linkers in
solid phase organic synthesis,18,19and as donor ligands in complexation
reactions with transition metals.20–22 To satisfy demand, their synthe-
sis has been changed from the use of costly and toxic chemicals such as
thiophosgene23 and its derivatives,24,25directly or indirectly, to the more
abundantly available, cheap, and safe reagents such as CS2. However,
their formation using CS2 employed harsh reaction conditions such
Received 16 April 2008; accepted 14 May 2008.
The authors wish to thank SIAF division of CDRI for providing spectroscopic and
analytical data.
Address correspondence to Devdutt Chaturvedi, Natural Products Chemistry Divi-
sion, North-East Institute of Science and Technology (NEIST), Jorhat-785006, Assam,
India. E-mail: ddchaturvedi002@yahoo.co.in
550

One-Pot Synthesis of Dithiocarbazates
551
as the use of strong bases, higher reaction temperatures, and longer
reaction times.26,27 Thus, we were prompted to embark on developing
improved procedures. Our group28–40 has been engaged in the past sev-
eral years in the development of new methodologies for the preparation
of carbamates, dithiocarbamates, and related compounds using cheap,
abundantly available, and safe reagents such as CO2 and CS2. More
recently41–47we found that Amberlite IRA 400 (basic resin) is the best
reagent for the synthesis of carbamates, dithiocarbamates, and dithio-
carbonates (xanthates). Furthermore, use of basic resin has also been
reported48 for the tetrahydropyranylation of alcohols and phenols. In
the present communication, we report here an efficient, one-pot synthe-
sis of dithiocarbazates from variety of primary, secondary, and tertiary
alcoholic tosylates and substituted hydrazines using basic resin/CS2
system.
RESULTS AND DISCUSSION
In connection with our ongoing interest pertaining to the use of
Amberlite IRA 400 (basic resin) for the synthesis of carbamates, dithio-
carbamates, and dithiocarbonates (xanthates),41–47 we now wish to re-
port a simple and effective one-pot procedure for the preparation of
dithiocarbazates from a variety of primary, secondary, and tertiary al-
coholic tosylates and substituted hydrazines using a basic resin/CS2
system. Thus, a mixture of substituted hydrazine and CS2 were taken
in dry DMSO, and Amberlite IRA 400 (basic resin) was added. The
reaction was stirred for 30 min at room temperature and then the
corresponding alcoholic tosylate was added. The reaction was further
continued until the completion as determined by TLC (see Table I). It
–
is proposed that the S of the dithiocarbazate ion produced will attach
to the electrophilic carbon of the respective alcoholic tosylates to afford
dithiocarbazates in high yields (80–98%) at room temperature in 2–4 h,
as mentioned in Table I. The reaction proved to be successful, and the
desired products were isolated and their identities confirmed by vari-
ous spectroscopic and analytical techniques. Since the products were
simply obtained by concentration of the organic layer after filtration
of the basic resin from the reaction mixture, this indicates the nov-
elty of the method among the reported procedures. Reactions have also
been attempted without using Amberlite resin, but no products could
be observed, which indicates the necessity of basic resin in carrying
out the reaction. Alcoholic tosylates of primary, secondary, and tertiary
alcohols were prepared following the standard procedure.49 The whole
reaction conditions are shown in Scheme 1.

552
D. Chaturvedi et al.
S
R1
R3
R
H
R1
R3
H
R
Amberlite IRA 400
N
N
N
H
N
R2
S
R2
OTos
+
CS2, dry DMSO, rt, 2-4h
H
H
I
SCHEME 1
We tried several solvents such as n-heptane, n-hexane, acetoni-
trile, benzene, toluene, methanol, dichloromethane, chloroform, DMSO,
dimethylformamide, and hexamethylphosphoric triamide, of which dry
DMSO at room temperature proved to be the most suitable.
In conclusion, we have developed a convenient and efficient protocol
for one-pot, three-component coupling of various amines with a variety
of alcoholic tosylates of primary, secondary, and tertiary alcohols via
a CS2 bridge using basic resin (Amberlite IRA 400). This method gen-
erates the corresponding dithiocarbazates in good to excellent yields.
Furthermore, this method exhibits substrate versatility, mild reaction
conditions, and experimental convenience. This synthetic protocol de-
veloped in our laboratory is believed to offer a more general method
for the formation of carbon–sulfur bonds essential to numerous organic
syntheses.
TABLE I Conversion of Alcoholic Tosylates into Dithiocarbazates of
General Formula I
Entry
R1
R2
R3
R
Time (h)
Isolated Yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14.
15.
16.
n-C3H7
PhCH2CH2
PhCH2
Ph
C2H5
4-MeOPh
C3H7
C3H7
C3H7
C4H9
C4H9
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
4-MeOPh
Ph
Ph
Bn
Bn
3-NO2Ph
4-NO2Ph
2,4-NO2Ph
Naphthyl
Ph
Ph
Bn
Ph
Bn
Ph.
Ph
2
2
2.5
3
3
3
3
4
3
3
3
2.5
2.5
2
93
96
86
91
89
84
85
80
84
91
88
95
92
98
86
83
C5H11
C7H15
C9H19
C3H7
C3H7
CH3
H
H
3
3.5
Ph
Note: All the products were characterized by IR, NMR, and mass spectroscopic data.

One-Pot Synthesis of Dithiocarbazates
553
EXPERIMENTAL
Chemicals were procured from Merck, Aldrich, and Fluka chemical
companies. Amberlite IRA 400 (basic resin) was also purchased from
Merck. Reactions were carried out under an atmosphere of nitrogen.
IR spectra (4000–200 cm−1) were recorded on Bomem MB-104–FTIR
spectrophotometer, whereas NMRs were scanned on an AC-300F NMR
(300 MHz) instrument using CDCl3 and TMS as internal standard.
Elemental analysis were made on a Carlo-Erba EA 1110-CNNO-S an-
alyzer and agreed favorably with the calculated values.
Typical Experimental Procedure
To a stirred solution of substituted hydrazine (3 mmol) in anhyd. DMSO
(5 mL), carbon disulfide (8 mmol) and basic resin (5 mmol) were slowly
added at room temperature. Then the mixture was stirred for 0.5 h, at
which point the required alcoholic tosylates (3 mmol) was added over a
period of 5 min. The reaction mixture was further continued until the
completion of reaction (cf Table I) under argon. The reaction mixture
was filtered to remove the resin. The filtrate was poured into water
(20 mL), and the organic layer was extracted with EtOAc (3 × 10 mL).
The organic layer was washed with 0.1 N HCl (20 mL), a saturated
solution of sodium bicarbonate (25 mL), and brine (30 mL), and was
dried (Na2SO4) and concentrated to get the desired compound.
Data for Dithiocarbazates
N’-(4-Methoxyphenyl) Hydrazine Carbodithioc Acid Butyl
Ester (1, C12H18N2OS2)
1
IR υ ( cm−1) = 675, 1210; H NMR (CDCl3) δ = 0.85(t, 3H, J= 7.3
Hz), 1.33(m, 2H ), 1.85(m, 2H), 2.0 (s, NH), 2.95 (t, 2H, J= 6.3 Hz),
3.73 (s, 3H), 4.05(m, NH), 6.75–7.60(m, 4H); 13CNMR (CDCl3) δ = 13.5,
21.8, 32.4, 33.9, 43.7, 55.6, 112.5, 114.9, 134.5, 152.4, 222.5 (C=S) ppm;
MS (EI): m/z = 270; Analysis: C12H18N2OS2, Calcd: C, 53.30; H, 6.71;
N, 10.36; S, 23.72; Found: C, 53.24; H, 6.65; N, 10.33; S, 23.58.
N’-Phenyl Hydrazine Carbodithioc Acid 3-Phenyl Propyl Ester
(2, C16H18N2S2)
IR υ (cm−1) = 676, 1205; H1NMR (CDCl3) δ = 2.05 (s, H, NH), 2.30
(m, 2H, Ph.CH2. CH2.CH2-S)), 2.56 (t, 2H, J = 7.2 Hz, Ph.CH2), 2.87(t,
2H, Ph.CH2.CH2. CH2.S), 4.03 (m, H, Ph.NH), 6.66–7.12 (m, 10H,
Ar-H); 13C NMR (CDCl3), δ = 32.2, 33.6, 34.4, 112.5, 119.2, 125.8, 128.6,
129.5, 138.6, 221.6 (C S) ppm; MS: m/z = 302; Analysis: C16H18N2S2,

554
D. Chaturvedi et al.
Calcd: C, 63.54; H, 6.00; N, 9.26; S, 21.20; Found: C, 63.35; H, 6.26; N,
9.17; S, 21.28.
N’-Phenyl-hydrazine Carbodithioc Acid Phenethyl Ester
(3, C15H16N2S2)
IR υ (cm−1) = 673, 1203; H1NMR (CDCl3) δ = 2.10 (s, H, NH), 3.20
(2H, t, J = 6.5, Hz, Ph.CH2CH2S), 3.24 (m, 2H, J = 7.2 Hz, PhCH2),
4.52 (m, H, PhNH), 6.69–7.15 (m, 10H, Ar-H); 13CNMR (CDCl3), δ =
34.5, 37.3, 47.2, 49.9, 118.6, 192.7, 223.3 (C=S) ppm; MS: m/z = 288;
Analysis: C15H16N2S2, Calcd: C, 62.46; H, 5.59; N, 9.71; S, 22.23; Found:
C, 62.70; H, 6.64; N, 9.59; S, 22.10.
N’-Butyl Hydrazine Carbodithioc Acid Benzyl Ester
(4, C12H18N2S2)
IR υ (cm−1) = 676, 1207; H1NMR (CDCl3) δ = 1.05 (t, 3H, CH3), 1.33
(m,2H, CH2CH3), 1.56 (m, 2H, CH2.CH2CH3), 2.05( br, NH), 2.65 (m,
2H, NHCH2), 4.13 (s, 2H, PhCH2), 7.06–7.15 (m, 5H, Ar-H)); 13CNMR
(CDCl3), δ = 13.7, 20.2, 31.5, 38.5, 50.9, 126.8, 127.6, 128.5, 141.8, 223.5
ppm; MS: m/z = 254; Analysis: C12H18N2S2, Calcd: C, 56.65; H, 7.13;
N, 11.01; S, 25.21; Found: C, 56.46; H, 7.35; N, 11.27; S, 25.12.
N’-Butyl-hydrazine Carbodithioc Acid Sec-butyl Ester
(5, C9H20N2S2)
IR υ (cm−1) = 682, 1214; H1NMR (CDCl3) δ = 0.99 (t, 3H, CH3), 1.05
(t, 3H, CH3), 1.35 (m, 2H, CH2.CH3), 1.41(d, 3H, CHCH3), 1.55 (m,
2H, CH3CH2CH2), 1.96 (m, 2H, CHCH2), 2.0 (br, H, NH), 2.65 (m, 2H,
NHCH2), 2.70 (m, H, CH-S), 13C NMR (CDCl3) δ = 10.2, 13.7, 20.2, 21.5,
31.2, 32.3, 40.1, 49.9, 223.4 ppm; MS: m/z = 220; Analysis: C9H20N2S2,
Calcd: C,49.05; H, 9.15; N, 12.71; S, 29.10; Found: C, 49.33; H, 9.01; N,
12.75; S, 29.32.
N’-(3-Nitrophenyl)-hydrazine Carbodithioc Acid 4-Methoxy
Benzyl Ester (6, C15H15N3O3S2)
IR υ (cm−1) = 678, 1211; H1NMR (CDCl3) δ = 2.05 (br, H,
NHPh.OMe), 3.73( s, 3H, OCH3), 4.06 (br, H, NHPh.NO2), 6.65–7.66(m,
8H, Ar-H); 13C NMR (CDCl3) δ = 38.3, 56.7, 107.5, 114.6, 118.4, 128.5,
129.9, 133.6, 143.6, 148.7, 160.6, 223.2 ppm; MS: m/z = 349; Analysis:
C15H15N3O3S2, Calcd: C, 51.56; H, 4.33; N, 12.03; S, 18.35; Found: C,
51.23; H, 4.50; N, 12.24; S, 18.03.

One-Pot Synthesis of Dithiocarbazates
555
N’-(4-Nitrophenyl)-hydrazine Carbodithioc Acid Butyl Ester
(7, C11H15N3O2S2)
IR υ (cm−1) = 666, 1203; H1NMR (CDCl3) δ = 0.96 (t, 3H, CH3), 1.33
(m, 2H, CH2CH3), 1.96 (m, 2H, SCH2.CH2), 2.05 (br, H, NH), 2.87 (t,
2H, SCH2), 4.04 (br, N, NHArNO2), 6.92-8.15 (m, 4H, Ar-H); 13C NMR
(CDCl3) δ = 13.7, 21.6, 32.2, 33.7, 113.5, 124.6, 138.8, 143.3, 223.5
ppm; MS: m/z = 285; Analysis: C11H15N3O2S2,Calcd: C, 46.29; H, 5.30;
N, 14.72; S, 22.47; Found: C, 46.45; H, 5.17; N, 14.47; S, 22.21.
N’-(2,4-Dinitro-phenyl)hydrazinecarbodithioc Acid Butyl Ester
(8, C11H14N4O4S2)
IR υ (cm−1) = 670, 1212; H1NMR (CDCl3) δ = 0.94 (t, 3H, CH3), 1.32
(m, 2H, CH2CH3), 1.95(m, 2H, SCH2. CH2), 2.02 (br, H, NH), 2.83 (t,
2H, SCH2), 4.04 (br, N, NHArNO2), 7.19–9.50 (m, 3H, Ar-H); 13CNMR
(CDCl3) δ = 13.8, 21.9, 32.3, 33.8, 113.6, 119.2, 130.2, 132.8, 139.7,
143.3, 222.5 ppm; MS: m/z = 330; Analysis: C11H14N4O4S2, Calcd: C,
39.99; H, 4.27; N, 16.96; S, 19.41; Found: C, 40.22; H, 4.05; N, 16.76, S,
19.50.
N’-Naphthalen-2-yl Hydrazine Carbodithioc Acid Butyl Ester
(9, C15H18N2S2)
IR υ (cm−1) = 677, 1209; 1H NMR (CDCl3) δ = 0.95 (t, 3H, CH3), 1.33
(m, 2H, CH2CH3), 1.97 (m, 2H, SCH2.CH2), 2.05 (br, H, NH), 2.84 (t,
2H, SCH2), 4.05 (br, N, NHArNO2), 6.76–7.55 (m, 7H, Ar-H); 13CNMR
(CDCl3) δ = 13.9, 22.1, 32.5, 33.9, 107.4, 117.2, 121.3, 124.5, 126.6,
127.2, 133.5, 142.6, 224.1 ppm; MS: m/z = 290; Analysis: C15H18N2S2,
Calcd: C, 62.03; H, 6.25; N, 9.64; S, 22.08; Found: C, 62.44; H, 6.33; N,
9.53; S, 22.25.
N’-Phenyl-hydrazine Carbodithioc Acid 1-Butyl Pentyl Ester
(10, C16H26N2S2)
IR υ (cm−1) = 677, 1212; 1H NMR (CDCl3) δ = 0.96 (t, 6H, CH3), 1.29
(m, 4H, CH2CH2CH), 1.33 (m, 4H, CH2CH3), 1.92 (m, 4H, CHCH2),
2.05 (br, H, NH), 2.52 (t, H, SCH), 4.05 (br, H, NHAr), 6.66-7.18 (m, 5H,
Ar-H); 13C NMR (CDCl3) δ = 14.2, 23.1, 28.5, 36.2, 41.4, 112.2, 119.3,
129.0, 142.4, 223.3 ppm; MS: m/z = 310; Analysis: C16H26N2S2, Calcd:
C, 61.89; H, 8.44; N, 9.02; S, 20.65; Found: C, 61.77; H, 8.54; N, 9.22; S,
20.46.
N’-Phenyl-hydrazine Carbodithioc Acid 1,1-Dibutyl Pentyl
Ester (11, C20H34N2S2)
1
IR υ (cm−1) = 669, 1210; H NMR (CDCl3) δ = 0.96 (t, 6H, CH3),
1.29 (m, 4H, CH2CH2C), 1.33 (m, 4H, CH2CH3), 1.88 (m, 4H, CHCH2),
2.04 (br, H, NH), 4.0 (br, H, NH-Ar), 6.67-7.19 (m, 5H, Ar-H); 13C NMR

556
D. Chaturvedi et al.
(CDCl3) δ = 14.1, 23.4, 26.7, 39.6, 41.1, 112.5, 119.3, 129.6, 142.2, 223.5
ppm; MS: m/z = 366; Analysis: C20H34N2S2, Calcd: C, 65.52; H, 9.35;
N, 7.64; S, 17.49; Found: C, 65.27; H, 9.11; N, 7.44; S, 17.49.
N’-Butyl-hydrazine Carbodithioc Acid Hexyl Ester
(12, C11H24N2S2)
1
IR υ (cm−1) = 674, 1208; H NMR (CDCl3) δ = 0.96 (t, 6H, CH3),
1.29 (m, 4H, CH2CH2CH2CH3), 1.33 (t, 2H, CH2CH3), 1.55 (m, 2H,
NHCH2CH2), 1.96 (m, 2H, SCH2CH2), 2.0 (br, 2H, NH), 2.65 (t, 2H,
NHCH2), 2.87 (t, 2H, SCH2), 13C NMR (CDCl3) δ = 13.7, 14.1, 20.2, 23.1,
28.6, 31.5, 32.6, 49.9, 223.1 ppm; MS: m/z = 248; Analysis: C11H24N2S2,
Calcd: C, 53.18; H, 9.74; N, 11.28; S, 25.81; Found: C, 53.33; H, 9.54; N,
11.39; S, 25.64.
N’-Phenyl-hydrazine Carbodithioc Acid N-octyl Ester
(13, C15H24N2S2)
IR υ (cm−1) = 679, 1211; 1H NMR (CDCl3) δ = 0.96 (t, 3H, CH3), 1.29
(m, 8H, CH2), 1.33 (m, 2H, CH2CH3), 1.96 (m, 2H, SCH2CH2), 2.0 (br,
H, NH), 2.88 (t, 2H, SCH2), 4.0 (br, H, Ph.NH), 6.65-7.20 (m, 5H, Ar-H),
13C NMR ( CDCl3) δ = 14.5, 23.10, 28.9, 30.5, 31.5, 32.5, 112.2, 129.6,
118.9, 142.2, 223.6 ppm; MS: m/z = 296; Analysis: C15H24N2S2, Calcd:
C, 60.76; H, 8.16; N, 9.45; S, 21.63; Found: 60.55; H, 8.33 N, 9.30; S,
21.77.
N’-Butyl Hydrazine Carbodithioc Acid Decyl Ester
(14, C15H32N2S2)
IR υ (cm−1) = 673, 1220; 1HNMR (CDCl3), δ = 0.97 (s, 3H, CH3), 0.99
(s, 3H, CH3), 1.29 (m, 12H, CH2), 1.34 (m, 4H, CH2CH3), 1.55 (m, 2H,
CH2CH2CH3), 1.96 (m, 2H, SCH2CH2), 2.0 (br, 2H, NH.NH), 2.65 (m,
2H, NHCH2), 2.87 (t, 2H, SCH2), 13CNMR (CDCl3) δ = 13.7, 14.5, 20.3,
23.1, 28.9, 30.6, 30.9, 31.5, 32.5, 222.1 ppm; MS: m/z = 304; Analysis:
C15H32N2S2, Calcd: C, 59.15; H, 10.59; N, 9.20; S, 21.06; Found: C,
59.30; H, 10.34; N, 9.21; S, 21.24.
N’-Phenyl Hydrazine Carbodithioc Acid 1-Propyl Butyl Ester
(15, C14H22N2S2)
IR υ (cm−1) = 675, 1210; 1H NMR (CDCl3) δ = 0.97 (s, 3H, CH3), 1.33
(m, 4H, CH2CH3), 1.92 (m, 4H, CHCH2), 2.0 (br, H, NH), 2.52 (m, H,
CH-S), 4.1 (br, H, NH-Ar), 6.66–7.22 (m, 5H, Ar-H); 13C NMR (CDCl3)
δ = 14.5, 20.1, 38.4, 40.8, 112.5, 118.3, 129.6, 143.3, 222.1 ppm; MS:
m/z = 282; Analysis: C14H22N2S2, Calcd: C, 59.53; H, 7.85; N, 9.92; S,
22.70; Found: C, 59.75; H, 7.66; N, 9.92; S, 22.44.

One-Pot Synthesis of Dithiocarbazates
557
N’-Phenyl Hydrazine Carbodithioc Acid 1-Phenyl Ethyl Ester
(16, C15H16N2S2)
1
IR υ (cm−1) = 678, 1210; H NMR (CDCl3) δ = 1.69 (d, 3H, CH3),
2.2(br, H, NH), 3.98 (m, H, CH-S), 4.2 (br, H, NH-Ar), 6.66–7.22 (m,
10H, Ar-H), 13CNMR (CDCl3) δ = 23.4, 41.1, 112.5, 118.9, 126.5, 128.5,
129.7, 141.3, 142.5, 222.1 ppm; MS: m/z = 288; Analysis: C15H16N2S2,
Calcd: C, 62.46; H, 5.59; N, 9.71; S, 22.23; Found: C, 62.33; H, 5.46; N,
9.99; S, 22.36.
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