Synthesis of Phenyl Dithiocarbamates Starting from Sodium Dialkyldithiocarbamates and Aryl Boronic Acids: a Copper Catalyzed S-Arylation

Article abstract of DOI:10.1002/ejoc.201801271

A convenient and efficient protocol for the S-arylation of sodium dialkyldithiocarbamates was developed. With the catalysis of copper(I) bromide, sodium dialkyldithiocarbamates coupled with aryl boronic acids giving the C-S coupling products smoothly in g

Full text of DOI:10.1002/ejoc.201801271

A Journal of
Accepted Article
Title: Synthesis of Phenyl Dithiocarbamates Starting from Sodium
Dialkyldithiocarbamates and Aryl Boronic Acids: a Copper
Catalyzed S-Arylation
Authors: Ming-Yuan Gao, Wan Xu, Shi-Bo Zhang, Yue-Sheng Li, and
Zhi-Bing Dong
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801271
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801271
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10.1002/ejoc.201801271
European Journal of Organic Chemistry
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Synthesis of Phenyl Dithiocarbamates Starting from Sodium
Dialkyldithiocarbamates and Aryl Boronic Acids: a Copper
Catalyzed S-Arylation
Ming-Yuan Gao,[a][‡] Wan Xu,[a][‡] Shi-Bo Zhang,[a] Yue-Sheng Li,[c] and Zhi-Bing Dong*[a][b]
Abstract: A convenient and efficient protocol for the S-arylation of
sodium dialkyldithiocarbamates was developed. With the catalysis of
copper(I) bromide, sodium dialkyldithiocarbamates coupled with aryl
boronic acids giving the C-S coupling products smoothly in good to
excellent yields. This protocol features easily available starting
materials, easy performance, short reaction time, broad substrate
scope and nice yields, showing its potential synthetic value for the
convenient preparation of some potentially biologically active
compounds.
reaction of amines with thiophosgene and its substituted
derivatives,[11] which is not attractive for environmental concerns.
Besides, a couple of procedures involving the reactions of
sodium dithiocarbamates with diazonium chlorides,[12] diaryl
diazonium salts in the presence of hypervalent iodines,[13] as
well as the cross-coupling by using organometallic reagents with
tetramethyllithium disulfides[14] have also been achieved.
Although effective, these methods still suffer from environmental
issues, difficulty in preparing the reagents, high reaction
temperatures, or multiple reaction steps which limit their
applications (Figure 2).
Introduction
Sodium dialkyldithiocarbamates are a class of cheap and
common compounds as industrial products, which are used in a
wide range of fields such as medicine,[1] pesticide[2] and
vulcanization accelerators.[3] They can also be ideal reagents for
the development of completely new synthetic transformations.[4]
On the other hand, organic dithiocarbamates (especially phenyl
dithiocarbamates) play very important roles in biologically active
compounds,[5] agriculture[6] and versatile synthetic intermediates
in organic synthesis.[7] This fragment is also very useful in the
pharmaceutical field[8] as anti-infective agents (a, b) and nervous
system agents (c) (Figure 1). Moreover, they can be used as
protecting groups in peptide synthesis,[9] and have recently been
used in the synthesis of ionic liquids.[10]
Figure 2. Previously reported synthetic methods of phenyl dithiocarbamates.
Recently, our group has reported alternative methods for the
synthesis of these important compounds starting from
tetraalkylthiuram disulfides with aryliodides[15] or aryl boronic
acids,[16] while most of these protocols involve the use of base.
As part of our longstanding interests in organosulfur chemistry[17]
and to further extend our work, we would like to report herein an
efficacious, mild and base-free method for the synthesis of S-
aryl dithiocarbamates through C-S coupling starting from sodium
dialkyldithiocarbamates and aryl boronic acids (Scheme 1),
which could be attractive and alternative approach for the
construction of these important compounds.
Figure 1. Representative drugs containing phenyl dithiocarbamates skeletons.
On the basis of their important natures, phenyl dithiocarbamates
have been paid extensive attention by the synthetic and
medicinal chemists. The most commonly used method is the
Scheme 1. Synthesis of S-aryl dithiocarbamates (this work).
Results and Discussion
[a]
School of Chemistry and Environmental Engineering, Wuhan
Institute of Technology, Wuhan 430205, China.
E-mail: dzb04982@wit.edu.cn
http://cee.wit.edu.cn/info/1052/1538.htm
Department of Chemistry, Ludwig-Maximilians-Universität,
Butenandtstrasse 5-13, 81377 München, Germany.
Nonpower Nuclear Technology Collaborative Innovation Center,
Hubei University of Science & Technology, Xianning 437100, China.
We began our investigation using phenyl boronic acid (1a) and
sodium dimethyldithiocarbamates (2a) to optimize the reaction
conditions (Table 1). In the initial investigations, a series of
copper catalysts were screened (Table 1, entries 1-6), only trace
(or none) of the product was obtained. To our delight, the
desired product 3a could be obtained in moderate yield (55%,
[b]
[c]
[‡]
These authors contributed equally to this work.
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10.1002/ejoc.201801271
European Journal of Organic Chemistry
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59%) by using CuI or CuBr (10 mol%) as catalyst (Table 1,
entries 7-8). Encouraged by this result, various ligands were
screened (Table 1, entries 8-15) and 1,10-phenanthroline (Table
1, entry 8) was chosen as the best one. Subsequently, the
loading of the catalyst and ligand were examined (entries 8, 16-
18), and the optimal loading is 10 mol% of CuBr and 10 mol% of
1,10-phenanthroline. The examination of reaction temperature
(Table 1, entries 19-23) and solvents (Table 1, entries 22, 24-27)
showed that N, N-dimethylformamide (DMF) was the best
solvent, and 80°C was the optimal reaction temperature. In the
end, the substrate ratio of 1a to 2a was screened (Table 1,
entries 28-33), and it turned out that the equivalent ratio (1a : 2a)
is 2:1 (entry 32). The optimal reaction conditions are
summarized in entry 32, Table 1.
With the optimal reaction conditions in hand, the scope of the
reaction was examined by checking the diverse substituted aryl
boronic acids and sodium dialkyldithiocarbamates. The results
are summarized in Table 2. In general, the substituted aryl
boronic acids reacted well with sodium dialkyldithio-carbamates,
furnishing the C-S coupling products (aryl dithio-carbamates) in
good to excellent yields. Aryl boronic acids bearing electron-
donating groups, such as Me- and MeO- (1b, 1i) promoted the
reaction slightly, and weak electron-withdrawing groups, such as
F, Cl and Br (1d, 1e, 1f) deactivated the aryl boronic acids,
providing the desired products in slightly lower yields (entries 4,
5 and 6). However, aryl boronic acid bearing a strong electron-
withdrawing group such as CN (1h) gave the product in a
moderate yield (entry 8). Ortho steric hindrance also influenced
the reaction and slightly decreased the yields (entries 3, 7 and
10). In addition, general good yields were achieved when
naphthalen-2-yl boronic acid was surveyed (entries 11 and 12),
and sodium diethyldithiocarbamates reacted with phenyl boronic
acids giving the desired products in also good yields (entries 13-
15).
Table 1. Optimization of the reaction conditions [a]
Entry
Catalyst
(mol%)
Ligand
(mol%)
Solvent
T (°C)
Yield (%)[b]
Cu(OAc)2
1,10-Phen
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
DMAc
THF
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
r.t.
<5
<5
Table 2. Synthesis of phenyl dithiocarbamates [a]
1
2
CuO
Cu(OTf)2
CuSO4
NiBr2
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
PPh3
3
N.R.
<5
4
5
N.R.
N.R.
55
6
NiCl2
7
CuI
8
CuBr
59
Entry
Substrate 1
Substrate 2
Product 3
9
CuBr
43
Yield[b]
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
CuBr
Py
N.R.
<5
CuBr
bipy
CuBr
glycine
<5
1
CuBr
L-proline
<5
CuBr
DEMDA
N.R.
N.R.
34
1a
3a: 86%
3b: 91%
3c: 73%
CuBr
TEMDA
2a
2a
2a
CuBr (5%)
CuBr (15%)
CuBr (20%)
CuBr
1,10-Phen (5%)
1,10-Phen (15%)
1,10-Phen (20%)
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
60
60
N.R.
35
2
3
CuBr
40
1b
1c
CuBr
CuBr
60
80
51
61
CuBr
CuBr
CuBr
CuBr
CuBr
120
80
80
80
80
54
51
43
31
PhMe
54
28[c]
29[d]
30[e]
31[f]
32[g]
33[h]
34
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr
-
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
-
DMF
DMF
DMF
DMF
DMF
DMF
DMF
80
80
80
80
80
80
80
54
72
70
77
4
5
86
71
N.R.
1d
1e
2a
2a
3d: 72%
3e: 80%
[a] Reaction conditions: 1a (1 mmol), 2a (1.2 mmol), CuBr (10 mol%), solvent
(3 mL), stirred for 4 hours. [b] Isolated yield. [c] 1a (1 mmol), 2a (1 mmol). [d]
1a (1 mmol), 2a (1.5 mmol). [e] 1a (1 mmol), 2a (2 mmol). [f] 1a (1.5 mmol), 2a
(1 mmol). [g] 1a (2 mmol), 2a (1 mmol). [h] 1a (2.5 mmol), 2a (1 mmol).
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10.1002/ejoc.201801271
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[a] Reaction conditions: 1 (2.0 mmol), 2 (1.0 mmol), CuBr (10 mol%), 1,10-
Phenantroline (10 mol%), DMF (3 mL), stirred at 80 oC for 4-6 h. [b] Isolated
yields based on 2.
6
A control experiment in the nitrogen atmosphere was conducted
and trace of the product was obtained (Scheme 2), indicating the
oxygen is crucial for the model reaction.
1f
2a
2a
2a
2a
2a
2a
3f: 84%
7
8
1g
3g: 77%
Scheme 2. Control experiment under nitrogen atmosphere.
Based on the reaction results and the control experiment, the
mechanism of this reaction is proposed (Scheme 3). Firstly, CuI
catalyst reacts with sodium dialkyldithiocarbamate to generate
intermediate A. Secondly, A is oxidized by oxygen in the air to
give intermediate B which is ready for the transmetallation with
aryl boronic acid, furnishing intermediate C, and C is oxidized
1h
3h: 66%
again to produce the Cu(III) intermediate D. Finally,
D
undergoes reductive elimination easily, giving the desired
product E along with recyclable CuI catalyst.
9
1i
3i: 94%
10
11
1j
3j: 84%
1k
3k: 82%
Scheme 3. Proposed reaction mechanism.
12
Conclusions
1l
2a
2b
2b
2b
3l: 83%
3m: 83%
3n: 86%
3o: 89%
In summary, we have developed a copper-catalyzed efficient
and useful method for the synthesis of various substituted S-aryl
dithiocarbamates. In the presence of CuBr/1,10-Phenantroline,
aryl boronic acids reacts with sodium dialkyldithiocarbamates
which are a class of common and stable industrial products,
furnishing a series of 15 desired phenyl dithiocarbamates in
good to excellent yields. This protocol features easily available
starting materials, easy operations, short reaction time, broad
substrate scope and nice yields, illustrating its potential synthetic
value for the convenient preparation for some potentially
bioactive compounds.
13
14
15
1a
1b
Experimental Section
1i
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10.1002/ejoc.201801271
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13C NMR (100 MHz, CDCl3): δ = 197.4, 165.2, 162.7, 139.1 (d, JC-F = 8
Hz), 127.15 (d, JC-F = 3 Hz), 116.36 (d, JC-F = 22 Hz), 45.8, 41.9 ppm.
HRMS (ESI) m/z [M+H]+ Calcd for C9H11FNS2 (216.0312), found
216.0308.
General remarks: All starting materials were purchased from
commercial suppliers and used without further purification unless
otherwise stated. Yields refer to isolated compounds estimated to be
95% pure as determined by 1H NMR and capillary GC analysis. NMR
spectra were recorded on a Bruker AM400 NMR instrument in CDCl3
using TMS as an internal standard. Chemical shifts are given in ppm and
coupling constants (J) are given in Hz. All melting points were
determined on a RY-1G melting point instrument without correction.
High-resolution mass spectra (HRMS) were recorded on a Finnigan MAT
95Q or Finnigan 90 mass instrument (ESI). TLC was performed using
aluminum plates coated with SiO2 (Merck 60, F-254) and visualized with
UV light at 254 nm. Column chromatography was performed on silica gel
(200-300 mesh) with PE-EtOAc as eluent.
4-Chlorophenyl dimethylcarbamodithioate (3e): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3e 184 mg (yield:
80 %), a white solid. M.p.: 101-102 °C. 1H NMR (400 MHz, CDCl3): δ =
7.42-7.37 (m, 4 H), 3.54 (s, 3 H), 3.48 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 196.7, 138.2, 136.6, 130.1, 129.4, 45.7, 42.0, 43.0 ppm.
HRMS (ESI) m/z [M+H]+ Calcd for C9H11ClNS2 (232.0007), found
232.0010.
Typical procedure (TP): To a dried tube equipped with a magnetic
stirrer and a septum were added phenyl boronic acid (2.0 mmol) and
sodium dialkyldithiocarbamates (1.0 mmol) dissolved in DMF (3.0 mL).
The mixture was stirred for 5 min, and then 1,10-Phenantroline (10 mol%)
and CuBr (10 mol%) were added. The reaction mixture was heated at
80 °C and monitored by TLC until the starting material was finished. The
mixture was cooled down to room temperature, and the reaction was
quenched with sat. NH4Cl solution (10 mL), after the mixture was
extracted with ethyl acetate, dried with anhydrous Na2SO4, and then
concentrated under vacuum. The residue was purified by flash column
chromatography to afford the desired product.
4-Bromophenyl dimethylcarbamodithioate (3f): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3f 231 mg (yield:
84 %), a white solid. M.p.: 120-122 °C. 1H NMR (400 MHz, CDCl3): δ =
7.58 (s, 1 H), 7.55 (s, 1 H), 7.33 (s, 1 H), 7.31 (s, 1 H), 3.54 (s, 3 H), 3.49
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.5, 138.4, 132.4, 130.8,
125.0, 45.8, 42.0 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C9H11BrNS2
(275.9511), found 275.9503.
Phenyl dimethylcarbamodithioate (3a): According to TP, the residue
was purified by flash chromatography on silica gel (petroleum ether/ethyl
acetate = 5:1) to give the target compound 3a 169 mg (yield: 86 %), a
white solid. M.p.: 90-92 °C, 1H NMR (400 MHz, CDCl3): δ = 7.49-7.45(m,
5 H), 3.56 (s, 3 H), 3.50 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
197.6, 137.0, 131.7, 130.0, 129.1, 45.7, 42.0 ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C9H12NS2 (198.0406), found 198.0411.
2-Bromophenyl dimethylcarbamodithioate (3g): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3g 210 mg (yield:
77 %), a white solid. M.p.: 90-92 °C. 1H NMR (400 MHz, CDCl3): δ = 7.69
(d, J=8.0 Hz, 1H), 7.55 (d, J=8.0 Hz, 1H), 7.31-7.22 (m, 2H), 3.52 (s, 3H),
3.48 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 194.9, 139.7, 133.5,
133.1, 131.8, 131.6, 128.1, 45.5, 42.1 ppm. HRMS (ESI) m/z [M+H]+
Calcd for C9H11BrNS2 (275.9511), found 275.9514.
4-Methylphenyl dimethylcarbamodithioate (3b): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 7:1) to give the target compound 3b 192 mg (yield:
91 %), a white solid. M.p.: 110-112 °C. 1H NMR (400 MHz, CDCl3): δ =
7.35 (t, J = 6.0 Hz, 2 H), 7.26 (t, J = 6.0 Hz, 2 H), 3.56 (s, 3 H), 3.49 (s, 3
H), 2.40 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 198.2, 140.4,
136.8, 130.0, 128.3, 45.7, 41.9, 21.5 ppm. HRMS (ESI) m/z [M+H]+ Calcd
for C10H14NS2 (212.0562), found 212.0559.
4-Cyanophenyl dimethylcarbamodithioate (3h): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3h 146 mg (yield:
66 %), a white solid. M.p.: 125-126 °C. 1H NMR (400 MHz, CDCl3): δ =
7.72-7.68 (m, 2H), 7.60-7.57 (m, 2H), 3.55 (s, 3H), 3.51 (s, 3H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 194.9, 137.5, 137.4, 132.4, 118.2, 113.6,
45.6, 42.1 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C10H11N2S2
(223.0358), found 223.0360.
2-Methylphenyl dimethylcarbamodithioate (3c): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 7:1) to give the target compound 3c 154 mg (yield:
73 %), a white solid. M.p.: 83-85 °C. 1H NMR (400 MHz, CDCl3): δ =
7.43–7.32 (m, 3 H), 7.27–7.23 (m, 2 H), 3.54 (s, 3 H), 3.50 (s, 3 H), 2.40
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.5, 143.8, 137.7, 131.1,
130.7, 130.7, 126.7, 45.7, 42.0 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C10H14NS2 (212.0562), found 212.0569.
4-Methoxyphenyl dimethylcarbamodithioate (3i): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3i 213 mg (yield:
94 %), a white solid. M.p.: 97-99 °C. 1H NMR (400 MHz, CDCl3): δ = 7.37
(d, J = 4.0 HZ, 2 H), 6.96 (d, J = 4.0 Hz, 2 H), 3.83 (s, 3 H), 3.54 (s, 3H),
3.48 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 198.7, 161.1, 138.4,
122.6, 114.7, 55.3, 45.8, 41.9 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C10H14NOS2 (228.0512), found 228.0509.
4-Fluorophenyl dimethylcarbamodithioate (3d): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3d 154 mg (yield:
72 %), a white solid. M.p.: 92-93 °C. 1H NMR (400 MHz, CDCl3): δ =
7.44-7.39 (m, 2 H), 7.14–7.09 (m, 2 H), 3.53 (s, 3 H), 3.48 (s, 3 H) ppm.
2-Methoxyphenyl dimethylcarbamodithioate (3j): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3j 190 mg (yield:
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10.1002/ejoc.201801271
European Journal of Organic Chemistry
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84 %), a white solid. M.p.: 89-90 °C. 1H NMR (400 MHz, CDCl3): δ =
7.52-7.40 (m, 2H), 7.05-6.99 m, 2H), 3,86 (s, 3H), 3.54 (s, 3H), 3.52 (s,
3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.8, 160.5, 138.8, 132.5,
121.2, 119.9, 111.9, 66.2, 45.7, 42.1 ppm. HRMS (ESI) m/z [M+H]+ Calcd
for C10H14NOS2 (228.0512), found 228.0512.
Acknowledgements
We thank the foundation support from National Natural Science
Foundation of China (21302150), foundation of Chen-Guang
program from Hubei Association for Science and Technology,
foundation of Chutian distinguished fellow from Hubei Provincial
Department of Education, foundation of High-end Talent
Cultivation Program from Wuhan Institute of Technology. Z.-B. D.
acknowledges the Humboldt Foundation and China Scholarship
Council for a fellowship.
Naphthalene-2-yl dimethylcarbamodithioate (3k): According to TP,
the residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3k 202 mg (yield:
82 %), a colorless oil. 1H NMR(400 MHz, CDCl3): δ = 8.24 (d, J = 8 Hz, 1
H), 7.98 (d, J = 8.0 Hz, 1 H), 7.87 (d, J = 8.0 Hz, 1 H), 7.74 (d, J = 8.0 Hz,
1 H), 7.52 (q, 3 H), 3.54 (s, 3 H), 3.51 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 196.6, 137.0, 135.1, 134.2, 131.5, 129.0, 128.6, 127.2, 126.3,
125.7, 45.6, 42.1 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C13H14NS2
(248.0562), found 248.0566.
Keywords: Dialkyldithiocarbamates • Boronic acid • Arylation •
C-S Coupling • Synthesis
[1]
a) D. Geneviève, Z. Jennifer, M. W. John, S. C. Nicolas, AIDS. 2013, 27,
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Ackers, J. Antimicrob. Chemoth. 1998, 42, 817-820.
Naphthalene-1-yl dimethylcarbamodithioate (3l): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 5:1) to give the target compound 3l 205 mg (yield:
83%), a yellow solid. M.p.: 150.8-152.8 °C. 1H NMR (400 MHz, CDCl3): δ
= 8.24 (m, 1H), 7.99 (d, J = 8Hz, 1H), 7.88 (m, 1H), 7.74 (m, 1H), 8.24 (m,
1H), 7.56-7.49 (m, 3H), 3.61 (s, 3H), 3.55 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3): δ = 196.5, 137.0, 135.0, 134.1, 131.4, 128.9, 128.6, 127.1,
126.2, 125.7, 125.7, 45.5, 42.1 ppm; HRMS (ESI) m/z [M+H]+ Calcd for
C13H14NS2 (248.0562), found 248.0570.
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Nakagawa, Antimicrob. Agents Chemother. 1997, 41, 2278-2281; e) N.
G. Urlyapova, A. A. Yushchenko, A. D. Daudova, V. A. Makarov, Bull.
Exp. Biol. Med, Springer, 2006, 143, 327-329.
Phenyl diethylcarbamodithioate (3m): According to TP, the residue
was purified by flash chromatography on silica gel (petroleum ether/ethyl
acetate = 5:1) to give the target compound 3m 186 mg (yield: 83 %), pale
yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.48 (d, J = 12.0 Hz, 5 H), 4.02
(d, J = 4.0 Hz, 2 H), 3.84 (d, J = 8.0 Hz, 2 H), 1.39 (t, J = 4.0 Hz, 3 H),
1.29 (d, J = 4.0 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.9,
137.2, 131.6, 130.0, 129.0, 49.9, 47.3, 12.8, 11.6 ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C11H16NS2 (226.0677), found 226.0673.
[6]
[7]
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a) C. Len, D. Postel, G. Ronco, P. Villa, J. Agric. Food Chem. 1997, 45,
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Raghubir, M. P.Dubey, Indian Drugs 1999, 36, 50-54.
4-Methylphenyl diethylcarbamodithioate (3n): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 7:1) to give the target compound 3n 203 mg (yield:
85 %), a white solid, M.p.: 75-76 °C. 1H NMR (400 MHz, CDCl3): δ =
7.28 (d, J = 8.0 Hz, 2 H), 7.16 (d, J = 4.0 Hz, 2 H), 3.94 (d, J = 8.0 Hz, 2
H), 3.76 (d, J = 4.0 Hz, 2 H), 2.32 (s, 3 H), 1.31 (t, J = 4.0 Hz, 3 H), 1.20
(t, J = 4.0 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.5, 140.2,
137.0, 129.9, 128.1, 49.9, 47.2, 21.5, 12.7, 11.6 ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C12H18NS2 (240.0875), found 240.0877.
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T. W. Greene, P. G. M. Wuts in Protecting Groups in Organic Synthesis,
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4-Methoxyphenyl diethylcarbamodithioate (3o): According to TP, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 7:1) to give the target compound 3o 226 mg (yield:
89%), a white solid. M.p.: 73-75 °C. 1H NMR (400 MHz, CDCl3): δ = 7.23
(d, J = 8.0 Hz, 2 H), 6.80 (d, J = 8.0 Hz, 2 H), 3.87 (d, J = 8.0 Hz, 2 H),
3.68 (s, 5 H), 1.24 (t, J = 6.4 Hz, 3 H), 1.13 (t, J = 6.4 Hz, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 197.1, 161.0, 138.6, 122.4, 114.6, 55.3,
50.0, 47.1, 12.7, 11.6 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C12H18NOS2 (256.0825), found 256.0830.
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4352-4356; d) W. Xu, M. T. Zeng, S. S. Liu, Y. S. Li, Z. B. Dong,
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10.1002/ejoc.201801271
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Tetrahedron Lett. 2017, 58, 4289-4292; e) X. Liu, M. Liu, W. Xu, M. T.
Zeng, H. Zhu, C. Z. Chang, Z. B. Dong, Green Chem. 2017, 19, 5591-
5598; f) X. Liu, S. B. Zhang, Z. B. Dong, Eur. J. Org. Chem. 2018, DOI:
10.1002/ejoc.201800993; g) X. Liu, S. B. Zhang, H. Zhu, Z. B. Dong, J.
Org. Chem. 2018, DOI: 10.1021/acs.joc.8b01644.
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10.1002/ejoc.201801271
European Journal of Organic Chemistry
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Key Topic*: C-S Coupling
Ming-Yuan Gao, Wan Xu, Shi-Bo Zhang,
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Synthesis
Dithiocarbamates
of
Starting
Phenyl
from
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Sodium Dialkyldithiocarbamates and
Aryl Boronic Acids:
Catalyzed S-Arylation
a
Copper
*one or two words that highlight the emphasis of the paper or the field of the study
A convenient and efficient protocol for S-arylation of sodium dialkyldithiocarbamates was developed. The desired aryl
dithiocarbamates were synthesized in good to excellent yields in the presence of CuBr as catalyst and 1,10-phenantroline as
ligand, a variety of functional groups on aryl boronic acids could be tolerated. The method features easily available starting
materials, easy performance, short reaction time, broad substrate scope and nice yields, illustrating its potential synthetic
value for the convenient preparation of some potentially biologically active compounds.
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