Triton-B-catalyzed, efficient, one-pot synthesis of dithiocarbazates through alcoholic tosylates

Article abstract of DOI:10.1080/00397910802519141

A quick, efficient, one-pot synthesis of dithiocarbazates was accomplished in high yields by the reaction of various tosylates of primary, secondary, and tertiary alcohols with a variety of substituted hydrazines using the benzyl-trimethylammonium hydroxi

Full text of DOI:10.1080/00397910802519141

This article was downloaded by: [East Carolina University]
On: 06 September 2013, At: 05:17
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Triton-B-Catalyzed, Efficient,
One-Pot Synthesis of
Dithiocarbazates Through
Alcoholic Tosylates
Devdutt Chaturvedi a , Nisha Mishra b , Amit K.
Chaturvedi b & Virendra Mishra b
a Bio-organic Chemistry Division, Indian Institute of
Integrative Medicine, Jammu-Tawi, India
b Synthetic Research Laboratory, Department of
Chemistry, B. S. A. College, Mathura, India
Published online: 04 Mar 2009.
To cite this article: Devdutt Chaturvedi , Nisha Mishra , Amit K. Chaturvedi
& Virendra Mishra (2009) Triton-B-Catalyzed, Efficient, One-Pot Synthesis of
Dithiocarbazates Through Alcoholic Tosylates, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 39:7,
1273-1281
To link to this article: http://dx.doi.org/10.1080/00397910802519141
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,

or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communications1, 39: 1273–1281, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802519141
Triton-B-Catalyzed, Efficient, One-Pot Synthesis
of Dithiocarbazates Through Alcoholic Tosylates
Devdutt Chaturvedi,1 Nisha Mishra,2 Amit K. Chaturvedi,2 and
Virendra Mishra2
1Bio-organic Chemistry Division, Indian Institute of Integrative Medicine,
Jammu-Tawi, India
2Synthetic Research Laboratory, Department of Chemistry,
B. S. A. College, Mathura, India
Abstract: A quick, efficient, one-pot synthesis of dithiocarbazates was accom-
plished in high yields by the reaction of various tosylates of primary, secondary,
and tertiary alcohols with a variety of substituted hydrazines using the benzyl–
trimethylammonium hydroxide (Triton-B)=CS2 system. The reaction conditions
are mild with simpler workup procedures than the reported methods.
Keywords: Alcoholic tosylates, benzyltrimethylammonium hydroxide, carbon
disulfide, dithiocarbazates, substituted hydrazines
INTRODUCTION
Organic dithiocarbazates have received much attention because of their
numerous remarkable medicinal, industrial, and synthetic applications.[1,2]
They have extensively been used as pharmaceuticals,[3] as agrochemicals,[4]
as intermediates in organic synthesis,[5] for protection of amino groups in
peptide synthesis,[6] as linkers in solid-phase organic synthesis,[7] and as
donor ligands in complexation reactions with transition metals.[8] To
satisfy the demand, their synthesis has changed from the use of costly
and toxic chemicals such as thiophosgene[9] and its derivatives,[10] directly
Received July 8, 2008.
Address correspondence to Devdutt Chaturvedi, Bio-organic Chemistry
Division, Indian Institute of Integrative Medicine, Canal Road, Jammu-Tawi
180001, J & K, India. E-mail: ddchaturvedi002@yahoo.co.in
1273

1274
D. Chaturvedi et al.
or indirectly, to abundantly available, cheap, and safe reagents such as like
CS2. However, their formation using CS2 employed harsh reaction condi-
tions, such as use of strong bases, high reaction temperatures, and long
reaction times.[11] Thus, we were prompted to improve procedures. Our
group[12] has been engaged during the past several years with the develop-
ment of new methodologies for the preparation of carbamates, dithio-
carbamates, and related compounds using cheap, abundantly available,
and safe reagents such as CO2 and CS2. Recently,[13] we found that
benzyltrimethyl ammonium hydroxide (Triton-B) is the best catalyst for
the synthesis of carbamates, dithiocarbamates, and dithiocarbonates
(xanthates). We report here an efficient, one-pot synthesis of dithiocarba-
zates from a variety of primary, secondary, and tertiary alcoholic tosylates
and substituted hydrazines using the Triton-B=CS2 system.
RESULTS AND DISCUSSION
A mixture of substituted hydrazine and CS2 was taken in dry dimethyl
sulfoxide (DMSO), and Triton-B was added to it. The reaction was
stirred for 30 min at room temperature, and then the corresponding alco-
holic tosylate was added. The reaction was continued until completion as
checked by thin-layer chromatography (TLC; see Table 1). We proposed
Table 1. Conversion of alcoholic tosylates into dithiocarbazates of formula 1–16
Entry
R1
R2
R3
R
Time (h)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
n-C3H7
PhCH2CH2
PhCH2
Ph
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
H
H
4-MeO-Ph
Ph
Ph
Bn
Bn
Ph-3-NO2
Ph-4-NO2
Ph-2,4-NO2
Naphthyl
Ph
Ph
n-C4H9
Ph
2
2
2.5
3
3
3
3
4
3
C2H5
Ph-4-MeO
C3H7
C3H7
C3H7
C4H9
C4H9
C5H11
C7H15
C9H19
C3H7
3
3
2.5
2.5
2
3
3.5
n-C4H9
Ph
Ph
C3H7
CH3
Ph
Note. All the products were characterized by IR, NMR, and mass
spectroscopic data.

One-Pot Synthesis of Dithiocarbazates
1275
Scheme 1.
that the Sꢀ of the dithiocarbazate ion produced will attack the electrophi-
lic 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 1. The reaction proved to be successful, and the desired products
were isolated. Their structures were confirmed by various spectroscopic
and analytical techniques. The alcoholic tosylates of primary, secondary,
and tertiary alcohols were prepared following the standard procedure.[14]
The whole reaction conditions are shown in Scheme 1.
We tried several solvents such as like n-heptane, n-hexane, acetoni-
trile, benzene, toluene, methanol, dichloromethane, chloroform, DMSO,
dimethylformamide, and hexamethylphosphoric triamide, of which dry
DMSO proved to be most suitable at room temperature.
In conclusion, we developed a convenient and efficient protocol for
the one-pot, three-component coupling of various amines with a variety
of primary, secondary, and tertiary alcoholic tosylates via the CS2 bridge
using Triton-B. This method generates the corresponding dithiocarba-
zates in good to excellent yields. Furthermore, this method exhibits sub-
strate versatility, mild reaction conditions, and experimental convenience.
This synthetic protocol is believed to offer a more general method for
the formation of carbon–sulfur bonds, which are essential to numerous
organic syntheses.
EXPERIMENTAL
General
Chemicals were procured from Merck, Aldrich, and Fluka chemical com-
panies. Reactions were carried out under an atmosphere of argon. IR
spectra (4000–200 cmꢀ1 were recorded on a Bomem MB-104 Fourier
transform infrared (FTIR) spectrophotometer using the neat technique,
where as NMR spectra were scanned on an AC-300 F NMR (300-
MHz) instrument using CDCl3 and some other deutrated solvents, with
tetra methylsilane (TMS) as internal standard. Elemental analyses were
conducted by means of a Carlo-Erba EA 1110-CNNO-S analyzer and
agreed favorably with calculated values.

1276
D. Chaturvedi et al.
Typical Experimental Procedure
Carbon disulfide (8 cm3) were slowly added and Triton-B (2 cm3) to a
stirred solution (under Ar) of 3 mmol substituted hydrazine in 5 cm3
anhyd. DMSO at room temperature. Then the mixture was stirred for
0.5 h, at which point 3 mmol of the required alcoholic tosylate were
added over a period of 5 min. The stirring was further continued until
the completion of reaction (Table 1). The reaction mixture was poured
into 20 cm3 distilled water, and the organic layer was extracted with
3ꢁ10 cm3 EtOAc. The organic layer was washed with 20 cm3 0.1
N HCl, 25 cm3 saturated solution of NaHCO3, and 30 cm3 brine; dried
(Na2SO4), and concentrated to get the desired compound.
Data
N0-(4-Methoxyphenyl)hydrazinecarbodithioc Acid Butyl Ester
(1, C12H18N2OS2)
1
Yield: 94%; yellow oil; IR (neat) t ¼ 675, 1210 cmꢀ1; H NMR (CDCl3)
€
d ¼ 0.85 (t, 3H, J ¼ 7.3 Hz), 1.33 (m, 2H), 1.85 (m, 2H), 2.0 (s, NH), 2.95
(t, 2H, J ¼ 6.3 Hz), 3.73 (s, 3H), 4.05 (m, NH), 6.75–7.60 (m, 4H);
13C NMR (CDCl3) d ¼ 13.5, 21.8, 32.4, 33.9, 43.7, 55.6, 112.5, 114.9,
134.5, 152.4, 222.5 (C ¼ S) ppm; MS (EI): m=z ¼ 270.
N0-Phenyl Hydrazine Carbodithioc Acid 3-Phenyl Propyl Ester
(2, C16H18N2S2)
1
Yield: 96%; yellow oil; IR (neat) t ¼ 676, 1205 cmꢀ1; H NMR (CDCl3)
€
d ¼ 2.05 (s, H, NH), 2.30 (m, 2H, Phꢂ CH2 ꢂ CH2 ꢂ CH2-S), 2.56 (t, 2H,
J¼ 7.2 Hz, Ph ꢂ CH2), 2.87 (t, 2H, Ph ꢂ CH2 ꢂ CH2 ꢂ CH2 ꢂ S), 4.03 (m, H,
Ph ꢂ NH), 6.66–7.12 (m, 10H, Ar-H); 13C NMR (CDCl3), d ¼ 32.2, 33.6,
34.4, 112.5, 119.2, 125.8, 128.6, 129.5, 138.6, 221.6 (C ¼ S) ppm; MS:
m=z ¼ 302.
N0-Phenyl-hydrazine Carbodithioc Acid Phenethyl Ester
(3, C15H16N2S2)
1
Yield: 87%; yellow oil; IR (neat) t ¼ 673, 1203 cmꢀ1; H NMR (CDCl3)
€
d ¼ 2.10 (s, H, NH), 3.20 (2H, t, J ¼ 6.5, Hz, Ph ꢂ CH2CH2S), 3.24
(m, 2H, J ¼ 7.2 Hz, PhCH2), 4.52 (m, H, PhNH), 6.69–7.15 (m, 10H,
Ar-H); 13C NMR (CDCl3) d ¼ 34.5, 37.3, 47.2, 49.9, 118.6, 192.7, 223.3
(C ¼ S) ppm; MS: m=z ¼ 288.

One-Pot Synthesis of Dithiocarbazates
1277
N0-Butyl Hydrazine Carbodithioc Acid Benzyl Ester (4, C12H18N2S2)
1
Yield: 92%; yellow oil; IR (neat) t ¼ 676, 1207 cmꢀ1; H NMR (CDCl3)
€
d ¼ 1.05 (t, 3H, CH3), 1.33 (m, 2H, CH2CH3), 1.56 (m, 2H,
CH2 ꢂ CH2CH3), 2.05 (br, NH), 2.65 (m, 2H, NHCH2), 4.13 (s, 2H,
PhCH2), 7.06–7.15 (m, 5H, Ar-H); 13C NMR (CDCl3) d ¼ 13.7, 20.2,
31.5, 38.5, 50.9, 126.8, 127.6, 128.5, 141.8, 223.5 ppm; MS: m=z ¼ 254.
N0-Butyl-hydrazine Carbodithioc Acid Sec-butyl Ester (5, C9H20N2S2)
1
Yield: 90%; IR (neat) t ¼ 682, 1214 cmꢀ1; H NMR (CDCl3) d ¼ 0.99
€
(t, 3H, CH3), 1.05 (t, 3H, CH3), 1.35 (m, 2H, CH2 ꢂ 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) d ¼ 10.2, 13.7, 20.2, 21.5, 31.2, 32.3, 40.1, 49.9, 223.4 ppm;
MS: m=z ¼ 220.
N0-(3-Nitrophenyl)-hydrazine Carbodithioc Acid 4-Methoxy Benzyl
Ester (6, C15H15N3O3S2)
1
Yield: 86%; yellow oil; IR (neat) t ¼ 678, 1211 cmꢀ1; H NMR (CDCl3)
€
d ¼ 2.05 (br, H, NHPh ꢂ OMe), 3.73 (s, 3H, OCH3), 4.06 (br, H,
NHPh ꢂ NO2), 6.65–7.66 (m, 8H, Ar-H); 13C NMR (CDCl3) d ¼ 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 ¼ 349.
N0-(4-Nitrophenyl)-hydrazine Carbodithioc Acid Butyl Ester
(7, C11H15N3O2S2)
1
Yield: 86%; yellow oil; IR (neat) t ¼ 666, 1203 cmꢀ1; H NMR (CDCl3)
€
d ¼ 0.96 (t, 3H, CH3), 1.33 (m, 2H, CH2CH3), 1.96 (m, 2H, SCH2 ꢂ 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) d ¼ 13.7, 21.6, 32.2, 33.7, 113.5,
124.6, 138.8, 143.3, 223.5 ppm; MS: m=z ¼ 285.
N0-(2,4-Dinitro-phenyl)hydrazinecarbodithioc Acid Butyl Ester
(8, C11H14N4O4S2)
1
Yield: 80%; yellow oil; IR (neat) t ¼ 670, 1212 cmꢀ1; H NMR (CDCl3)
€
d ¼ 0.94 (t, 3H, CH3), 1.32 (m, 2H, CH2CH3), 1.95 (m, 2H, SCH2 ꢂ CH2),

1278
D. Chaturvedi et al.
2.02 (br, H, NH), 2.83 (t, 2H, SCH2), 4.04 (br, N, NHArNO2), 7.19–9.50
(m, 3H, Ar-H); 13C NMR (CDCl3) d ¼ 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 ¼ 330.
N0-Naphthalen-2-yl Hydrazine Carbodithioc Acid Butyl Ester
(9, C15H18N2S2)
1
Yield: 83%, yellow oil; IR (neat) t ¼ 677, 1209 cmꢀ1; H NMR (CDCl3)
€
d ¼ 0.95 (t, 3H, CH3), 1.33 (m, 2H, CH2CH3), 1.97 (m, 2H,
SCH2 ꢂ CH2), 2.05 (br, H, NH), 2.84 (t, 2H, SCH2), 4.05 (br, N,
NHArNO2), 6.76–7.55 (m, 7H, Ar-H); 13C NMR (CDCl3) d ¼ 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 ¼ 290.
N0-Phenyl-hydrazine Carbodithioc Acid 1-Butyl Pentyl Ester
(10, C16H26N2S2)
1
Yield: 89%; yellow oil; IR (neat) t ¼ 677, 1212 cmꢀ1; H NMR (CDCl3)
€
d ¼ 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) d ¼ 14.2, 23.1,
28.5, 36.2, 41.4, 112.2, 119.3, 129.0, 142.4, 223.3 ppm; MS: m=z ¼ 310.
N0-Phenyl-hydrazine Carbodithioc Acid 1,1-Dibutyl Pentyl Ester
(11, C20H34N2S2)
1
Yield: 87%; yellow oil; IR (neat) t ¼ 669, 1210 cmꢀ1; H NMR (CDCl3)
€
d ¼ 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 (CDCl3) d ¼ 14.1, 23.4, 26.7, 39.6, 41.1,
112.5, 119.3, 129.6, 142.2, 223.5 ppm; MS: m=z ¼ 366.
N0-Butyl-hydrazine Carbodithioc Acid Hexyl Ester (12, C11H24N2S2)
1
Yield: 96%; yellow oil; IR (neat) t ¼ 674, 1208 cmꢀ1; H NMR (CDCl3)
€
d ¼ 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) d ¼ 13.7, 14.1, 20.2, 23.1, 28.6, 31.5, 32.6, 49.9, 223.1 ppm;
MS: m=z ¼ 248.

One-Pot Synthesis of Dithiocarbazates
1279
N0-Phenyl-hydrazine Carbodithioc Acid n-Octyl Ester
(13, C15H24N2S2)
1
Yield: 97%; yellow oil; IR (neat) t ¼ 679, 1211 cmꢀ1; H NMR (CDCl3)
d ¼ 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 ꢂ NH), 6.65–7.20 (m, 5H, Ar-H); 13C NMR (CDCl3) d ¼ 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=z¼ 296.
€
N0-Butyl Hydrazine Carbodithioc Acid Decyl Ester (14, C15H32N2S2)
1
Yield: 98%; yellow oil; IR (neat) t ¼ 673, 1220 cmꢀ1; H NMR (CDCl3),
€
d ¼ 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 ꢂ NH), 2.65 (m, 2H, NHCH2), 2.87 (t, 2H, SCH2); 13C NMR
(CDCl3) ꢂ d ¼ 13.7, 14.5, 20.3, 23.1, 28.9, 30.6, 30.9, 31.5, 32.5,
222.1 ppm; MS: m=z ¼ 304.
N0-Phenyl Hydrazine Carbodithioc Acid 1-Propyl Butyl Ester
(15, C14H22N2S2)
1
Yield: 86%; yellow oil; IR (neat) t ¼ 675, 1210 cmꢀ1; H NMR (CDCl3)
€
d ¼ 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) d ¼ 14.5, 20.1, 38.4, 40.8, 112.5, 118.3,
129.6, 143.3, 222.1 ppm; MS: m=z ¼ 282.
N0-Phenyl Hydrazine Carbodithioc Acid 1-Phenyl Ethyl Ester
(16, C15H16N2S2)
1
Yield: 83%; yellow oil; IR (neat) t ¼ 678, 1210 cmꢀ1; H NMR (CDCl3)
€
d ¼ 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), 13C NMR (CDCl3) d ¼ 23.4, 41.1,
112.5, 118.9, 126.5, 128.5, 129.7, 141.3, 142.5, 222.1 ppm; MS: m=z ¼ 288.
ACKNOWLEDGMENTS
Authors thank the Sophisticated Analytical Instrument Facility (SIAF)
division of Central Drug Research Institute (CDRI) for providing
spectroscopic and analytical data.

1280
D. Chaturvedi et al.
REFERENCES
1. Ragnarsson, U. Synthetic methodologies for alkyl substituted hydrazines.
Chem. Soc. Rev. 2001, 30, 205–213.
2. Schmidt, E. U. Hydrazine and Its Derivatives: Preparation, Properties,
Applications, 2nd ed.; Wiley-Interscience: New York, 2001; pp. 1–86.
3. (a) Bharti, N.; Maurya, M. R.; Naqvi, F.; Azam, A. Synthesis and anti-amoebic
activity of new cyclo-octadiene ruthenium (II) complexes with 2-acetylpyridine
and benzimidazole derivatives. Bio-Org. Med. Chem. Lett. 2000, 10, 2243–2245;
(b) Bharti, N.; Mannar, M. R.; Fehmida, N.; Bhattacharya, A.; Bhattacharya,
S.; Azam, A. Palladium (II) complexes of NS donor ligend derived from S-methyl
dithiocarbazate, S-benzyl dithiocarbazate, thiosemicarbazide as anti-amoebic
agents. Eur. J. Med. Chem. 2000, 35, 481–486.
4. Sengupta, S.; Pandey, O. P.; Rao, G. P. Sugarcane pathology: Fungal disease.
1999, 1, 279–302.
5. (a) Connolly, T. J.; Crittal, A. J.; Ebrahim, A. S.; Ji, G. Development and scale
up of a route to cyclohecylhydrazine dimethanesulfonate. Org. Process. Res.
Dev. 2000, 4, 526–529; (b) Gordan, M. S.; Krause, J. G.; Linneman-Mohr,
M. A.; Parchue, R. R. Hydrazides and hydrazones from carbazates. Synthesis
1980, 3, 244–246; (c) Hauser, M. J. The preparation and cyclization of some
chloroethyl carbazates: Some clarifications. J. Org. Chem. 1966, 31, 968–970.
6. Wuts, P. G. M.; Greene, T. W. Greene’s protective groups in organic
synthesis (John Wiley & Sons, New York, 2006), pp. 706–887.
7. (a) Huang, J. Y.; Choi, H. S.; Lee, D. H.; Yoo, S. E.; Gong, Y. D. Solid phase
synthesis of 5-amino-1-(substituted thiocarbomyl) pyrazole and 1, 2, 4-triazole
derivatives via dithiocarbazate linker. J. Comb. Chem. 2005, 7, 136–141; (b)
Hwang, J. Y.; Choi, H. S.; Lee, D. H.; Gong, Y. D. Solid phase synthesis of
1,3,4-oxadiazole and 1,3,4-thiadiazole derivatives via selective reagent based
cyclization of acyldithiocarbazate resins. J. Comb. Chem. 2005, 7, 816–819.
8. (a) Bolzati, C.; Benini, E.; Cavazza-Ceccato, M.; Cozzala, E.; Malago, E.;
Agostini, S.; Tisato, F.; Rofosco, F.; Bandoli, G. From symmetrical to assy-
metrical nitrido, phosphino-thiol complexes: A new class of neutral mixed
ligends 99mTC compounds as potential brain imaging agents. Bioconjugate
Chem. 2006, 17, 419–428; (b) Ali, M. A.; Mirza, A. H.; Butcher, R. J.;
Krause, K. A. The preparation, characterization and biological activity of
palladium (II) and platinum (II) complexes of tridentate NNS ligends derived
from S-methyl and S-benzyldithiocarbazates and x-ray crystal structure of the
[Pd(mpasme)cl] complexes. Transition Met. Chem. (N.Y.) 2006, 31, 79–87.
9. Dyker, H.; Scherkenbeck, J.; Gondol, D.; Goehrt, A.; Harder, A. Azadepsi-
petides: Synthesis and evaluation of a novel class of peptidomimetics. J. Org.
Chem. 2001, 66, 3760–3766.
10. Nara, S.; Sakamoto, T.; Miyazawa, E.; Kikugawa, Y. A convenient synthesis
of 1-alkyl 1-phenylhydrazines from 1-aminopthalimide. Synth. Commun.
2003, 33, 87–98.
11. Fox, D. L.; Ruxer, J. T.; Oliver, R. M.; Alford, K. L.; Salvatore, R. N. Mild
and efficient synthesis of carbazates and dithiocarbazates via a three compo-
nent coupling using Cs2CO3 and TBAI. Tetrahedron Lett. 2004, 45, 401–405.

One-Pot Synthesis of Dithiocarbazates
1281
12. For reviews, see (a) Chaturvedi, D.; Ray, S. Versatile use of carbon dioxide in
the synthesis of organic carbamates. Curr. Org. Chem. 2007, 11, 987–998; (b)
Chaturvedi, D.; Misra, N.; Mishra, V. Various approaches for the synthesis
of organic carbamates. Curr. Org. Synth. 2007, 3, 308–320; For our research
work, see (c) Chaturvedi, D.; Kumar, A.; Ray, S. An efficient, one-pot synth-
esis of carbamate esters through alcoholic tosylates. Synth. Commun. 2002, 32,
2651–2655; (d) Chaturvedi, D.; Kumar, A.; Ray, S. A high-yielding, one-pot
novel synthesis of carbamate esters from corresponding alcohols using Mitsu-
nobu’s reagent. Tetrahedron Lett. 2003, 44, 7637–7639; (e) Chaturvedi, D.;
Ray, S. An efficient, one-pot, basic resin catalyzed, novel synthesis of carba-
mate esters through alcoholic tosylayes. Lett. Org. Chem. 2005, 2, 742–744;
(f) Chaturvedi, D.; Ray, S. An efficient, basic resin mediated, one-pot synthesis
of dithiocarbamate esters through alcoholic tosylates. J. Sulfur Chem. 2005, 26,
365–371; (g) Chaturvedi, D.; Ray, S. An efficient, basic resin mediated, one-pot
synthesis of O-alkyl S-methyl dithiocarbonates from the corresponding
alcohols. J. Sulfur Chem. 2006, 27, 265–271; (h) Chaturvedi, D.; Ray, S. An
efficient, one-pot synthesis of dithiocarbamates from the corresponding alco-
hols using Mitsunobu’s reagent. Tetrahedron Lett. 2006, 47, 1307–1309; (i)
Chaturvedi, D.; Mishra, N.; Mishra, V. An efficient and novel synthesis of car-
bamate esters from the coupling of amines, halides, and carbon dioxide in the
presence of basic resin. Chin. Chem. Lett. 2006, 17, 1309–1312; (j) Chaturvedi,
D.; Ray, S. A high-yielding, one-pot synthesis of O,S-dialkyl dithiocarbonates
from alcohols using Mitsunobu’s reagent. Tetrahedron Lett. 2007, 48, 149–151;
(k) Chaturvedi, D.; Mishra, N.; Mishra, V. An efficient, basic resin mediated,
one-pot synthesis of dithiocarbamates by Michael addition of dithiocarbamate
to activated olefins. J. Sulfur Chem. 2007, 28, 39–44; (l) Chaturvedi, D.;
Mishra, N.; Mishra, V. A high-yielding, one-pot synthesis of dialkylcarbonates
from alcohols using Mitsunobu’s reagent. Tetrahedron Lett. 2007, 48,
5043–5045; (m) Chaturvedi, D.; Mishra, N.; Mishra, V. An efficient, one-pot
synthesis of S-alkyl thiocarbamates from the corresponding thiols using
Mitsunobu’s reagent. Synthesis 2008, 355–357.
13. (a) Chaturvedi, D.; Ray, S. A high-yielding, one-pot, Triton-B-catalyzed
expeditious synthesis of carbamate esters through four-component coupling
methodology. Monatsh. Chem. 2006, 137, 201–206; (b) Chaturvedi, D.;
Ray, S. Triton-B-catalyzed, efficient, one-pot synthesis of dithiocarbamate
esters. Monatsh. Chem. 2006, 137, 311–317; (c) Chaturvedi, D.; Ray, S.
Triton-B-catalyzed, efficient, one-pot synthesis of carbamate esters from
alcoholic tosylates. Monatsh. Chem. 2006, 137, 459–463; (d) Chaturvedi,
D.; Ray, S. A high yielding, one-pot synthesis of dithiocarbamates using
alcoholic tosylates. Monatsh. Chem. 2006, 137, 465–459; (e) Chaturvedi,
D.; Ray, S. An efficient, one-pot, Triton-B-catalyzed synthesis of O-alkyl
S-methyl dithiocarbonates. Monatsh. Chem. 2006, 137, 1219–1223.
14. Kabalka, G. W.; Varma, M.; Varma, R. S.; Srivastava, P. C.; Knapp, F. F.
Tosylation of alcohols. J. Org. Chem. 1986, 51, 2386–2388.