Development of an improved method for conversion of thiuram disulfides into N,N-dialkylcarbamoyl halides and derivatives

Article abstract of DOI:10.1080/00397910903537331

A convenient procedure for preparing N,N-disubstituted carbamoyl halides is reported. It consists of two steps: (1) reaction of carbon disulfide and a secondary amine in the presence of a polar organic solvent and oxygen to produce the corresponding tetraalkyl thiuram disulfides and (2) reaction of tetraalkyl thiuram disulfide with a halide in the presence of an aprotic organic solvent to produce the corresponding N,N-disubstituted carbamoyl halide. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910903537331

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Development of an Improved Method
for Conversion of Thiuram Disulfides
into N,N-Dialkylcarbamoyl Halides and
Derivatives
a
a
b
K. Adeppa , D. C. Rupainwar & Krishna Misra
a
U.P. Technical University, Lucknow, U.P., India
b
Indian Institute of Information Technology, Jhalwa Campus,
Allahabad, U.P., India
Published online: 15 Dec 2010.
To cite this article: K. Adeppa , D. C. Rupainwar & Krishna Misra (2010): Development of an Improved
Method for Conversion of Thiuram Disulfides into N,N-Dialkylcarbamoyl Halides and Derivatives,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 41:2, 285-290
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Synthetic Communications , 41: 285–290, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903537331
DEVELOPMENT OF AN IMPROVED METHOD FOR
CONVERSION OF THIURAM DISULFIDES INTO
N,N-DIALKYLCARBAMOYL HALIDES AND
DERIVATIVES
1
K. Adeppa, D. C. Rupainwar, and Krishna Misra
1
2
1
U.P. Technical University, Lucknow, U.P., India
2
Indian Institute of Information Technology, Jhalwa Campus,
Allahabad, U.P., India
A convenient procedure for preparing N,N-disubstituted carbamoyl halides is reported. It
consists of two steps: (1) reaction of carbon disulfide and a secondary amine in the presence
of a polar organic solvent and oxygen to produce the corresponding tetraalkyl thiuram
disulfides and (2) reaction of tetraalkyl thiuram disulfide with a halide in the presence of
an aprotic organic solvent to produce the corresponding N,N-disubstituted carbamoyl halide.
Keywords: Carbon disulfide; N,N-disubstituted carbamoyl halide; secondary amine; tetraalkyl thiuram
disulfide
INTRODUCTION
[1]
Carbamoyl halides are an important class of commercially available chemi-
cals. These are useful intermediates in the preparation of thiocarbamate herbicides
via their reaction with thiols (e.g., sodium alkylmercaptides). Carbamoyl halides,
particularly chlorides, are useful in the preparation of 1,4-disubstituted-5(4H)-
[
2]
[3]
[4]
[5]
tetrazolinones, imidazole derivatives, Reissert analogs, phenyl carbamates,
[
6]
[7]
unsymmetrical ureas, pyrrole-N-carbonyl compounds, O-b-oxoalkylcarbamates,
O-allylic urethanes and carbonates, synthesis of carbamates, phthalides, prep-
aration of arylisocyanates,
and N,N-dialkyl carbamate esters. Carbamoyl chlorides are also used for Friedel–
[8]
[9]
[10]
[11]
[12]
N,N-dimethylcarbamoyloxy-3-thiadiazoles-1,2,4,
[
13]
Crafts acylation followed with treatment of ammonia or amines to produce aro-
matic amides or substituted amides, which on hydrolysis yield corresponding acids.
[
14]
Triphosgene is also being used in the synthesis of carbamoyl chloride. In this com-
munication, we describe a novel method of N,N-disubstituted carbamoyl chloride by
reaction of tetraalkyl thiuramdisulfide and chlorine gas.
Received July 25, 2009.
Address correspondence to Krishna Misra, Indian Institute of Information Technology, Jhalwa
Campus, Allahabad, U.P. 211002, India. E-mail: krishnamisra@hotmail.com; kkmisra@yahoo.com
2
85

286
K. ADEPPA, D. C. RUPAINWAR, AND K. MISRA
RESULTS AND DISCUSSION
The tetraalkyl thiuramdisulfides were prepared by reacting secondary amines
with carbon disulfide in the presence of manganese acetate. The yields of thiurams
were more than 98%. The tetrasubstituted thiuramdisulfides were fully characterized
and are summarized in Table 1. The next step was chlorination of thiurams. For
this purpose, chlorine gas was passed in the solution of tetraalkylthiuram in dichlo-
romethane. Subsequent hydrolysis of the intermediate with saturated sodium
bicarbonate solution gave carbamoyl chloride.
EXPERIMENTAL
All chemicals (dimethylamine, diethylamine, di-n-propylamine, diisopropyl
amine, N,N-ethyl, methylamine, di-n-butylamine, piperidine, isopropyl alcohol, and
dichloromethane) were purchased from Merck, India. All the products gave satisfac-
tory, melting and boiling points. Gas chromatographic (GC) analysis was performed
on a Thermo Fisher model 1000 gas chromatograph.
Preparation of Tetraalkyl Thiuram Disulfide
In a 500-ml autoclave-type reaction flask equipped with a double jacket for the
circulation of heating liquid, thermometer, pressure gauge, reflux condenser, and
stirrer, a solution of secondary amine (300 mmol) and 24.4 mg manganese acetate
was dissolved in isopropanol (250 ml), and carbondisulfide (19 ml) was added to
the solution. The reflux condenser was replaced with a stopper. The reaction mixture
ꢀ
was heated at 50 C and stirred vigorously, and oxygen gas was introduced up to a
pressure of 1.7 bar. Under these conditions, the reaction was complete after 1–3 h.
Tetraalkyl thiuram disulfide was obtained in 98–99% yield.
Preparation of N,N’-Dialkylcarbamoylchloride
In a 1-L reaction flask equipped with a reflux condenser and stirrer, a solution
of tetraalkyl thiuram disulfide (0.47 mol) in dichloromethane (800 ml) and chlorine
gas (130 g) were bubbled into the resulting suspension over a period of 6–8 h, main-
ꢀ
taining the reaction mass at a temperature of 24–26 C in an ice bath. After half of
the chlorine had been added, the tetraalkyl thiuram disulfide dissolved to a clear
reddish brown solution. After three quarters of the chlorine had been added, the
solution became cloudy because of the formation of free sulfur. At the completion
of chlorination, the reaction mass became a thick slurry because of the formation
of phosgenimonium salt (N,N-dialkyldichloro methanium chloride). After stirring
for 20 min more, saturated sodium bicarbonate solution (2 g in 15 ml water) was
added during a period of 2–3 h. At the completion of addition of sodium bicarbon-
ate, the precipitate disappeared and sulfur was separated from the mass as a sticky
paste. The dichloromethane layer was separated and distilled at atmospheric press-
ure. The residual material was transferred to a 100-ml distillation flask and distilled
0
under reduced pressure (10 mm Hg). The total yield of N,N -dialkylcarbamoylchlor-
ides varied from 85 to 90%.

CARBAMOYL HALIDES FROM THIURAM DISULFIDES
287
Table 1. Reaction conditions for step 1, conversion of secondary amines to tetraalkyl thiuram disulfides
by reaction with carbon disulfide
ꢀ
ꢀ
Reaction Yield Mp ( C) Mp ( C)
lit.
No.
1
Starting amine
Tetraalkyl thiuramdisulfide
time
(%)
observed
[15]
67–69
2 h
98.6
66–68
1
0 min
h,
[15]
2
3
98.2
98.5
150–151
68–70
151
5
3
1 h,
0 min
[15]
70
1 h,
5 min
[16]
48
4
99.2 47.5–48.0
2
[17]
69
5
1 h
98.3
68–69
[18]
117
6
7
3 h
95.5
94.2
115–117
115–116
[19]
115
30 min
2 h,
0 min
[20]
87
8
93.8
88–89
3

288
K. ADEPPA, D. C. RUPAINWAR, AND K. MISRA
Table 2. Reaction conditions for step 2, conversion of tetraalkyl thiuram disulfides to N,N-disubstituted
carbamoyl chlorides
ꢀ
Starting tetraalkyl thiuram
disulfide
N,N-disubstituted
carbamoyl chloride
Reaction Yield Boiling point ( C)
time
No.
1
(%)
at mm Hg
6 h
92.00
bp40: 88–89
2
3
6 h
86.20
90.30
bp775: 167–168
bp15: 60–62
6 h,
0 min
4
3
6 h,
0 min
4
92.65
bp10: 115–116
7 h,
5 min
5
87.00
bp10: 110–112
1
6
0 min
h,
6
7
88.65
85.60
5
3
7 h,
0 min
bp10: 108–109
7 h,
5 min
8
88.10
bp0.2: 165–167
1

CARBAMOYL HALIDES FROM THIURAM DISULFIDES
289
CONCLUSION
The present method describes a simple and efficient method for the synthesis of
0
commercially important N,N -substituted carbamoylchlorides from the correspond-
ing tetraalkyl thiuram disulfides, prepared from secondary alkyl amines and carbon
disulfide. The notable feature of this two-step preparation is that the process is econ-
omically viable (i.e., enhanced rate of reaction and negligible by-products), with a
cleaner reaction profile, which makes it a useful and attractive process for synthesis.
The generality and simple experimental and product isolation procedures are
expected to play an important role in the development of this new method. It is
an important step in the development of a greener and more efficient commercial
synthesis. This will certainly prove to be an important improvement over the
phosgenation method being used at present.
ACKNOWLEDGMENTS
The authors gratefully acknowledge CBMR, SGPGI, Lucknow, for NMR
spectra and CDRI, Lucknow, for IR spectra and elemental analysis. One of the
authors (K. Adeppa) wishes to convey his grateful feelings to India Pesticides Lim-
ited, Lucknow, India, for providing all laboratory facilities and financial support,
which made it possible to complete the present work successfully.
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