One-pot direct synthesis of thiocarbamates from aniline, carbon monoxide, and thiols catalyzed by selenium

Article abstract of DOI:10.1080/00397910701483506

Catalyzed by selenium, oxidative carbonylation of aniline and thiols with carbon monoxide and oxygen affords the corresponding thiocarbamates mostly in moderate to good yields under solvent-free conditions at ambient temperature. Copyright Taylor & Franci

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One‐Pot Direct Synthesis of Thiocarbamates
from Aniline, Carbon Monoxide, and Thiols
Catalyzed by Selenium
Xiaopeng Zhang a b & Shiwei Lu b
a College of Chemistry and Environmental Science, Henan Normal University,
Xinxiang, China
b National Engineering Research Center for Catalysis, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian, China
Published online: 05 Oct 2007.
To cite this article: Xiaopeng Zhang & Shiwei Lu (2007): One‐Pot Direct Synthesis of Thiocarbamates from
Aniline, Carbon Monoxide, and Thiols Catalyzed by Selenium, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 37:19, 3291-3299
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Synthetic Communicationsw, 37: 3291–3299, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701483506
One-Pot Direct Synthesis of Thiocarbamates
from Aniline, Carbon Monoxide, and Thiols
Catalyzed by Selenium
Xiaopeng Zhang
College of Chemistry and Environmental Science, Henan Normal
University, Xinxiang, China and National Engineering Research Center
for Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, Dalian, China
Shiwei Lu
National Engineering Research Center for Catalysis, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian, China
Abstract: Catalyzed by selenium, oxidative carbonylation of aniline and thiols with
carbon monoxide and oxygen affords the corresponding thiocarbamates mostly in
moderate to good yields under solvent-free conditions at ambient temperature.
Keywords: carbon monoxide, oxidative carbonylation, selenium, thiocarbamates
INTRODUCTION
Thiocarbamates are compounds of great interest because they find many
important applications in medicine as bactericides[1] and antivirals,[2] in
biology as bioregulators[3] and enzyme inhibitors,[4] and in agriculture as pes-
ticides[5] and herbicides.[6] Various routes to generate thiocarbamates are
available in the literature. Most frequently used approaches include 1) carbo-
nylation of amine and element sulfur with carbon monoxide, followed by
Received in Japan November 16, 2006
Address correspondence to Shiwei Lu, National Engineering Research Center for
Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian, China. E-mail: lusw@dicp.ac.cn
3291

3292
X. Zhang and S. Lu
alkylation with alkyl halides,[6c,6e,7] which is a multistep approach; 2) intramo-
lecular rearrangements of various derivatives, which is extremely limited in
starting materials;[8] 3) treatment of thiols with isocyanates, carbamoyl
chlorides, or carbamoylimidazolium salts or treatment of chlorothioformates
with amines (unfortunately, the necessary intermediates are typically
prepared directly or indirectly from phosgene);[9] and 4) oxidative coupling
of aryl thiols with amines and carbon monoxide catalyzed by noble
metal.[10] In addition, thiocarbamate synthesis has also been accomplished
by selenium-catalyzed carbonylation of amine and disulfide[11] and by the
reaction of trichloroacetyl chloride with thiols and amines.[12] Cyclic thio-
carbamates can be obtained from the reaction of amino thiols with carbon
monoxide in the presence of selenium.[13]
Recently, we reported a new and facile route for the synthesis of thio-
carbamates from aniline, carbon monoxide, and thiols mediated by stoichio-
metric selenium in two steps.[14] From the viewpoint of industrial
production, fewer reaction steps and less catalyst make a method more attrac-
tive than alternatives. Therefore, we explored a direct approach to thiocarba-
mates. Catalyzed by selenium, oxidative carbonylation of aniline and thiols
with carbon monoxide and oxygen in the presence of triethylamine
proceeds smoothly at ambient temperature in one pot under solvent-free con-
ditions to afford the corresponding thiocarbamates (Scheme 1).
RESULTS AND DISCUSSION
To evaluate which factors markedly affect the reaction, we investigated the
reaction of aniline with propane-1-thiol under various conditions (Table 1).
The reaction failed to give the corresponding thiocarbamate in the absence
of selenium or base (Table 1, entries 1 and 7), indicating that both these
reagents are necessary in the reaction system. The reaction gave no product
in the presence of commonly used bases such as pyridine, sodium
hydroxide, potassium hydroxide, and sodium acetate (Table 1, entries 3–6),
and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was not very effective
(Table 1, entry 2). Triethylamine was found to be the best base in the one-
pot catalytic system (Table 1, entry 9). The effect of amount of triethylamine
was also tested, and two molar equivalents were optimal; yield decreased
when equal molar equivalents of triethylamine were used (Table 1, entries 8
and 9). The ratio of carbon monoxide and oxygen affects the reaction. The
more the oxygen used, the more side product diphenylurea was produced,
Scheme 1.

One-Pot Synthesis of Thiocarbamates
3293
Table 1. Selenium-catalyzed carbonylation of aniline with propane-1-thiol under
various reaction conditionsa
Entry
Base
Temp.
n(co)/n(O2)
Yieldb (%)
1
None
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
308C
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
9 : 1
4 : 2
2 : 1
0
19
2
DBU
Pyridine
NaOH
KOH
NaOAc
Et3N
3
0
0
4c
5c
6c
7d
8e
9
0
0
0
Et3N
Et3N
75
86(11)f
66(26)f
28(60)f
72(23)f
47(43)f
10
11
12
13
Et3N
Et3N
708C
Ambient
Ambient
Et3N
Et3N
aReaction conditions: aniline, 5 mmol; propane-1-thiol, 5 mmol; Se, 0.15 mmol;
base, 10 mmol; 10 h; P(co þ O2), 1.0 MPa.
bIsolated yield.
c0.4 mL of H2O, 2 mL of acetone.
dNone of Se.
e5 mmol of Et3N.
fDiphenylurea.
and accordingly, the less desired thiocarbamate was obtained (Table 1, entries
12 and 13). We adopted a 9:1 ratio of carbon monoxide to oxygen in the
reaction system. The reaction was conducted at ambient temperature; the
higher the temperature, the more side product (Table 1, entries 9–11). The
reaction proceeded smoothly without solvent, reaching completion within
10 h. After the reaction, catalyst selenium can be easily recovered from the
reaction mixture by simple filtration. The desired thiocarbamate can be
purified either by column chromatography or by recrystallization from light
petroleum ether.
The generality of the present method is evident from the reaction of a
variety of thiols with aniline under the optimal reaction conditions to give a
series of phenyl-thiocarbamic acid ester. As shown in Table 2, the reaction
proceeded smoothly with a range of thiols. The reaction seemed highly
sensitive to both steric and electronic factors. Thus, for those minor impedi-
ment thiols with a straight chain, the reaction proceeded well to give the cor-
responding products in high yields (Table 2, entries 1, 2, 4, 6, and 7), whereas
for the thiols with branch components, low yields of the corresponding thio-
carbamates were obtained because of their bulkiness (Table 2, entries 3, 5,
and 8). Phenyl-thiocarbamic acid S-benzyl ester (2i) was also obtained in
good yields mostly because of the high reactivity of the benzyl thiol

3294
X. Zhang and S. Lu
Table 2. Selenium-catalyzed carbonylation of aniline with a series of thiols to
thiocarbamatesa
Yieldb
(%)
Entry
Thiol
R
Product
1
1a
1b
1c
1d
1e
1f
Ethyl
Propyl
2a
2b
2c
2d
2e
2f
84
86
62
83
0
2
3
iso-Propyl
Butyl
4
5
tert-Butyl
Pentyl
Hexyl
6
83
81
72
86
35
23
38
48
7
1g
1h
1i
2g
2h
2i
8
Cyclohexyl
Benzyl
Phenyl
9
10
11c
12
13
1j
2j
1k
1l
4-Chlorophenyl
4-Methylphenyl
4-Methoxyphenyl
2k
2l
1m
2m
aReaction conditions: aniline, 5 mmol; thiol, 5 mmol; Se, 0.15 mmol; Et3N,
10 mmol; 10 h; ambient temperature; n(co)/n(o2) ¼ 9:1, P (co þ o2) ¼ 1.0 MPa.
bIsolated yield.
(Table 2, entry 9). When aryl thiols were used instead of alkyl thiols in the
reactions, poor product yields were obtained. This is mostly due to the weak
nucleophilicity of aryl thiols. The aryl thiol containing electron-withdrawing
group (Table 2, entry 11) is less reactive than that with electron-donating
group (Table 2, entry 13), resulting in product yield lower with the former
than with the latter.
Compared to other catalytic systems, the present catalytic system has a
remarkable advantage. Namely, it has phase-transfer catalysis function in
the reaction process,[15] which is very interesting and useful. Before the
reaction, the catalyst selenium is solid in the selenium-catalyzed system.
During the reaction process, solid selenium reacts with carbon monoxide to
form SeCO, which can dissolve in the reaction mixtures to form a homo-
geneous catalytic system. Then SeCO reacts with aniline and thiol,
affording the corresponding thiocarbamate and hydrogen selenide. The
resulting hydrogen selenide is then oxidized to solid selenium by oxygen.
After the reaction, the catalyst selenium can easily be separated from the
reaction mixtures by simple phase separation. The recovered selenium can
be reused. In addition, this catalytic system is simple and stable, and the
catalyst selenium is cheap and easily available.
A possible route to thiocarbamates is presented in Scheme 2. First, the
reaction was initiated by the formation of carbonyl selenide 1,[16] which
generated in situ from carbon monoxide and selenium in the presence of

One-Pot Synthesis of Thiocarbamates
3295
Scheme 2.
triethylamine. Next 1 underwent nucleophilic addition of aniline to form
phenylcarbamoselenoic Se-acid salt 2.[13] Then, the nucleophilic attack of
thiol on 2 produced the desired thiocarbamate 3,[13] accompanied by the
formation of hydrogen selenide 4. Hydrogen selenide was then oxidized to
selenium by oxygen for the coming catalytic cycle.
CONCLUSION
In conclusion, a one-pot direct synthetic method for thiocarbamates has been
developed. Using straight or less hindered alkyl thiols as thiol reactant, this
reaction can proceed well with aniline to thiocarbamates in high yields.
From the viewpoint of application, the present method is very significant: it
is a one-pot, solvent-free synthesis with high atom economy, simple starting
materials, cheap and reusable catalyst, mild reaction conditions, simple
operation, and simple purification of the products.
EXPERIMENTAL
Elemental selenium (99.99%), carbon monoxide (99.9%), and oxygen
(99.9%) were used as purchased. Aniline, thiols, and triethylamine were
reagent grade and used without further purification. Melting points were deter-
mined on a Taike X-4 apparatus (Beijing, China) and are uncorrected. 1H and
13C NMR spectra were recorded on a Bruker DRX 400 spectrometer with
CDCl3 as solvent and Me4Si as internal standard.

3296
X. Zhang and S. Lu
Typical Procedure
To a 100-mL stainless steel autoclave, selenium (0.15 mmol), aniline
(5 mmol), propane-1-thiol (5 mmol), and triethylamine (10 mmol) were
added. The reactor was sealed and flushed three times with the mixed gas
of carbon monoxide and oxygen (9:1). Then the mixed gas was introduced
to the autoclave (1.0 MPa). The reaction proceeded at ambient temperature
with stirring. After 10 h, the apparatus was degassed. The crude product
was dissolved in THF. Selenium was then recovered by simple filtration.
The filtrate was concentrated. The pure phenyl-thiocarbamic acid S-propyl
ester (2b) was obtained either by column chromatography (silica gel, chloro-
form/petroleum ether, 2/1) in 86% yield or by recrystallization from light
petroleum ether in 71% yield as colorless needles. Mp 83–848C (lit.[17]
848C); 1H NMR (400 MHz, CDCl3)
d 7.42–7.07 (m, 6H), 2.95
(t, J ¼ 8.0 Hz, 2H), 1.68 (sextet, J ¼ 8.0 Hz, 2H), 0.99 (t, J ¼ 8.0 Hz, 3H).
Data
Phenyl-thiocarbamic acid S-ethyl ester (2a): Mp 67–688C (lit.[18] 69.5–
1
708C); H NMR (400 MHz, CDCl3) d 7.43–7.09 (m, 6H), 2.99 (q, 2H),
1.35 (t, 3H).
Phenyl-thiocarbamic acid S-iso-propyl ester (2c): Mp 112–1138C (lit.[19]
112.5–1138C); 1H NMR (400 MHz, CDCl3) d 7.43–7.09 (m, 6H), 3.72
(m, 1H), 1.39 (d, 6H).
Phenyl-thiocarbamic acid S-butyl ester (2d): Mp 73–748C (lit.[17] 73–
1
748C); H NMR (400 MHz, CDCl3) d 7.42–7.08 (m, 6H), 2.98 (t, 2H), 1.64
(m, 2H), 1.42 (m, 2H), 0.93 (t, 3H).
Phenyl-thiocarbamic acid S-pentyl ester (2f): Mp 47–488C (lit.[14] 47–
1
488C); H NMR (400 MHz, CDCl3) d 7.59 (brs, 1H), 7.41–7.05 (m, 5H),
2.95 (t, 2H), 1.64 (m, 2H), 1.33 (m, 4H), 0.87 (t, 3H).
1
Phenyl-thiocarbamic acid S-hexyl ester (2g): Mp 698C (lit.[14] 698C); H
NMR (400 MHz, CDCl3) d 7.41–7.08 (m, 6H), 2.96 (t, 2H), 1.65 (m, 2H),
1.38 (m, 2H), 1.29 (m, 4H), 0.88 (t, 3H).
Phenyl-thiocarbamic acid S-cyclohexyl ester (2h): Mp 115–1168C (lit.[18]
115–115.58C); 1H NMR (400 MHz, CDCl3) d 7.42–7.03 (m, 6H), 3.54
(t, 1H), 1.88 (dt, 4H), 1.47 (m, 6H).
Phenyl-thiocarbamic acid S-benzyl ester (2i): Mp 97–988C (lit.[20] 96–
1
978C); H NMR (400 MHz, CDCl3) d 7.31–6.99 (m, 11H), 4.13 (s, 2H).

One-Pot Synthesis of Thiocarbamates
3297
Phenyl-thiocarbamic acid S-phenyl ester (2j): Mp 122–1238C (lit.[9b]
1238C); 1H NMR (400 MHz, CDCl3) d 7.63–7.08 (m, 11H).
Phenyl-thiocarbamic acid S-4-chlorophenyl ester (2k): Mp 147–1488C
1
(lit.[21] 152.5–1558C); H NMR (400 MHz, CDCl3) d 7.52–7.10 (m, 10H).
Phenyl-thiocarbamic acid S-4-methylphenyl ester (2l): Mp 131–1328C
1
(lit.[22] 1328C); H NMR (400 MHz, CDCl3) d 7.50–7.08 (m, 10H), 2.38
(s, 3H).
Phenyl-thiocarbamic acid S-4-methoxylphenyl ester (2m): Mp 109–1108C
(lit.[23] 1108C); 1H NMR (400 MHz, CDCl3) d 7.52–6.93 (m, 10H), 3.81 (s, 3H).
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