Arylthiolation of arylamine derivatives with (arylthio)-pyrrolidine-2,5-diones

Article abstract of DOI:10.1002/adsc.201400929

A simple and efficient method for arylthiolation of arylamines has been developed. The protocol uses (arylthio)pyrrolidine-2,5-diones as the arylthiolating reagents, acetonitrile as the solvent, and no catalyst and additive are required, which avoids contamination from the transition metal catalysts in the target products. Therefore, the present method should provide a convenient, efficient and practical strategy for the synthesis of other aryl sulfides.

Full text of DOI:10.1002/adsc.201400929

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DOI: 10.1002/adsc.201400929
Arylthiolation of Arylamine Derivatives with (Arylthio)-
pyrrolidine-2,5-diones
Hua Tian,a,b Haijun Yang,a Changjin Zhu,b and Hua Fua,b,*
a
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of
Chemistry, Tsinghua University, Beijing 100084, Peopleꢀs Republic of China
Fax : (+86)-10-6278-1695; e-mail: fuhua@mail.tsinghua.edu.cn
Department of Applied Chemistry, Beijing Institute of Technology, Beijing 100081, Peopleꢀs Republic of China
b
Received: September 22, 2014; Revised: November 4, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400929.
Abstract: A simple and efficient method for arylthio- should provide a convenient, efficient and practical
lation of arylamines has been developed. The proto- strategy for the synthesis of other aryl sulfides.
col uses (arylthio)pyrrolidine-2,5-diones as the ar-
ylthiolating reagents, acetonitrile as the solvent, and
no catalyst and additive are required, which avoids Keywords: arylamine derivatives; aryl sulfides; ar-
contamination from the transition metal catalysts in ylthiolation; Friedel–Crafts reaction; synthetic meth-
the target products. Therefore, the present method ods
Introduction
Cheng and co-workers reported a copper-catalyzed
aerobic oxidative C H bond thiolation of the di- or
À
Aryl sulfides widely occur in various fields,[1] and they trimethoxybenzene species with disulfides.[19] In 2011,
are often found in biologically and pharmaceutically Bellerꢀs research group developed the palladium-cata-
active molecules.[2] The traditional methods for the lyzed direct arylthiolation of electron-rich arenes with
synthesis of aryl sulfides are through the coupling of arylsulfonyl cyanides.[20] Liu and co-workers reported
thiols or disulfides with aryl halides or pseudohalides the copper-mediated aerobic synthesis of aryl- or
catalyzed by transition metals[3] such as palladium,[4] alkyl-substituted 2-mercaptobenzothiazoles by the
copper,[5] iron,[6] gold,[7] rhodium,[8] cobalt,[9] indium,[10] direct thiolation of benzothiazoles with aryl or alkyl
and nickel.[11] Other alternative methods include the thiols in the presence of stoichiometric CuI, 2,2’-bi-
transition metal-catalyzed reactions of arylmagnesium pyridine and Na2CO3.[21a] Liꢀs group described FeCl3/
halides[12] or arylboronic acid derivatives[13] with suita- I2-catalyzed synthesis of 4-chalcogen-substituted aryl-
ble electrophilic arylsulfur reagents. Obviously, direct amines with disulfides.[21b] In 2012, Bolm reported
À
arylthiolation of the aryl C H bond is attractive. a transition metal-free direct thiolation of 1,3,4-oxa-
However, the examples using this strategy are scarce. diazoles and related heteroarenes in the presence of
In 2006, Tudge and co-workers reported the halide- Cs2CO3.[22] The AlCl3-mediated[23a] or palladium-cata-
catalyzed sulfenylation of indoles.[14a] Recently, lyzed[23b] aryl(alkyl)thiolation of arenes was also de-
a CeCl3-catalyzed sulfenylation of indoles with N-(ar- scribed. Very recently, we have developed the iron- or
ylthio)phthalimides has been developed.[14b] Yuꢀs boron-catalyzed C H arylthiolation of substituted
À
group developed a copper-catalyzed aerobic oxidative phenols at room temperature.[24] Herein, we report
thiolation of 2-phenylpyridine with PhSH and a simply and efficient arylthiolation of arylamines
MeSSMe.[15] Later, Doi and Batey reported an intra- without addition of any catalyst and additive.
À
molecular C S bond formation of 2-substituted ben-
[16]
À
zothiazoles via C H functionalization, respectively.
Fukuzawa and co-workers investigated the copper- Results and Discussion
catalyzed direct thiolation of benzoxazole with diaryl
disulfides and aryl thiols using the CuI/2,2’-bipyridine As shown in Table 1, the reaction of aniline (1a) with
complex as catalyst.[17] In 2010, Qingꢀs research group 1-(phenylthio)pyrrolidine-2,5-dione (2a) leading to 4-
demonstrated the direct use of DMSO as the reagent (phenylthio)benzenamine (3a) was applied as the
[18]
À
for Cu(II)-mediated C H bond methylthiolation.
model to optimize the reaction conditions including
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Table 1. Optimization of the conditions for the reaction of aniline (1a) with 1-(phenylthio)pyrrolidine-2,5-dione (2a).[a]
Entry
Catalyst
Solvent
Temperature [oC]
Time [h]
Yield of 3a [%][b]
Yield of 3a’ [%][b]
1
2
3
4
5
6
7
8
DCE
DMF
DMSO
dioxane
THF
100
100
100
100
100
100
100
100
100
80
24
24
24
24
24
24
24
12
18
24
24
24
24
24
24
24
24
24
24
72
8
21
0
4
0
0
0
0
4
6
0
CHCl3
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
70
83
49
67
58
22
53
67
64
0
Trace
3
trace
0
9
10
11
12
13
14
15
16
17
18
19
60
FeCl3
BF3·OEt2
CuCl2
Pd(OAc)2
ZnCl2
AlCl3
100
100
100
100
100
100
100
100
trace
3
3
0
0
4
4
0
12
70
77
29
TFA
H2SO4
[a]
Reaction conditions: without exclusion of air, aniline (1a) (0.3 mmol), 1-(phenylthio)pyrrolidine-2,5-dione (2a)
(0.33 mmol), catalyst (0.03 mmol), anhydrous solvent (2 mL), temperature (60–1008C), reaction time (12–24 h).
Isolated yield.
[b]
the catalysts, solvents and temperature. Seven sol- son with that of 1a, which is not favorable for the
vents were screened (entries 1–7) in the absence of electrophilic substitution.
catalyst at 1008C for 24 h, and MeCN gave the high-
After obtaining the optimized conditions, we inves-
est yield of 3a while a small amount of the diarylthio- tigated the scope of the arylthiolation of arylamine
lated product (3a’) was observed (entry 7). Yields de- derivatives with (arylthio)pyrrolidine-2,5-diones. As
creased when reaction temperature or time was re- shown in Table 2, all the tested substrates provided
duced (compare entries 7–11). We tested various good to excellent yields, and the reaction efficiency
Lewis acids (entries 12–19), and the results showed was related to electronic and steric effects. For substi-
that their addition did not promote reactivity. As tuted arylamines, the substrates with electron-donat-
shown in Figure 1, the addition of transition metal ing groups provided higher reactivity than those with
salt could lead to the formation of complex Ia (en- electron-withdrawing groups. The site of arylthiola-
tries 12–17), and reaction of an inorganic acid with tion depended on the electron density of the carbon
aniline provided the corresponding ammonium spe- on the phenyl ring and steric hindrance. For example,
cies (I’a) (entries 18 and 19). The electron density of arylthiolation of aniline (1a) mainly occurred at the
the phenyl ring in Ia and I’a is decreased in compari- para-site to the amino function because of the low
steric hindrance of the para-site, and ortho-substituted
products were obtained when the para-site of the
amino function was occupied by a substituent (en-
tries 2, 5–7). For b-aminonaphthalene (1s), the aryl-
AHCTUNGTREGtNNUN hiolation occurred at the a-site because of the higher
electron density of the a-carbon (entry 21). The site
of arylthiolation of 3-methylaniline (1w) was depen-
dent on both electronic and steric effects (entry 22).
N-Substitued arylamines also were good substrates
(entries 13, 22 and 28). For (arylthio)pyrrolidine-2,5-
Figure 1. Treatment of aniline with Lewis acids.
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Arylthiolation of Arylamine Derivatives with (Arylthio)pyrrolidine-2,5-diones
Table 2. Arylthiolation of arylamine derivatives (1) with (arylthio)pyrrolidine-2,5-diones (2) leading to 3.[a]
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Table 2. (Continued)
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Arylthiolation of Arylamine Derivatives with (Arylthio)pyrrolidine-2,5-diones
Table 2. (Continued)
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Table 2. (Continued)
[a]
Reaction conditions: substituted arylamine (1) (0.3 mmol), 1-(arylthio)pyrrolidine-2,5-dione (2) (0.33 mmol),
dry CH3CN (2 mL), temperature (1008C), reaction time (21–30 h).
Isolated yield.
[b]
diones, the substrates with electron-withdrawing
groups on the aromatic rings gave higher yields than
those with electron-donating groups. Arylthiolation of
3-aminophenol (1d) afforded two products 3d and 3d’’
because of the higher electronic density of the phenyl
ring (entry 4). In addition, diarylthiolation of sub-
strates 1a and 1b was found to occur (entries 1 and 2).
For substrates containing halo and electron-withdraw-
ing groups, some unknown by-products were observed
by thin layer chromatography. The arylthiolation of
arylamine derivatives could tolerate various function-
al groups including ethers (entries 3, 16 and 23), hy-
Scheme 1. Application of synthesized 3b in the synthesis of
a sulfur heterocycle.
À
À
droxy (entry 4), C F bond (entry 5), C Cl bond (en-
À
À
tries 6, 18–22), C Br bond (entries 7, 17 and 23), C I
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Arylthiolation of Arylamine Derivatives with (Arylthio)pyrrolidine-2,5-diones
Scheme 2. Possible mechanism for the arylthiolation of arylamines with (arylthio)pyrrolidine-2,5-diones.
dichloromethane/hexane or dichloromethane/MeOH/AcOH
bond (entry 8), acetyl (entry 9), carboxyl (entry 10),
trifluoromethyl (entry 11), nitro (entries 12, 24-28),
and cyano (entry 20) groups.
as the eluent to give the desired target product (3).
Three representative examples are given below.
4-Bromo-2-(phenylthio)aniline (3g): Eluent: dichlorome-
Furthermore, we examined applications of the syn-
thesized products. First, the reaction of 4-methyl-2-
(phenylthio)benzenamine (3b) with 2 equiv. of tert-
butyl nitrite at 08C provided the corresponding aryl-
diazonium salt (4), and then treatment of 4 in the
presence of 2 equiv. of copper powder gave the corre-
sponding S-heterocyle (3-methyldibenzo[b,d]thio-
phene) in 66% yield (Scheme 1).
A possible mechanism for the arylthiolation of sub-
stituted arylamines with (arylthio)pyrrolidine-2,5-
diones is proposed in Scheme 2. Reaction of (aryl-
ACHTUNGTRENNUNGthio)pyrrolidine-2,5-dione (2) with arylamine (1) gives
II, freeing I, and treatment of II with I affords the
target product (3) leaving succinimide.
1
thane/hexane (1:5); yield: 55 mg (66%); brown oil; H NMR
(CDCl3, 400 MHz): d=7.56 (d, J=2.3 Hz, 1H), 7.30 (dd, J=
8.7 Hz, 2.3 Hz, 1H), 7.24 (t, J=7.8 Hz, 2H), 7.10–7.16 (m,
3H), 6.68 (d, J=8.7 Hz, 1H), 3.87 (br.s, 2H); 13C NMR
(CDCl3, 100 MHz): d=147.5, 139.0, 135.8, 133.8, 129.3,
127.2, 126.1, 117.1, 117.0, 109.7; EI-MS: m/z=279.3, 281.3
(M+).
1-(2-Amino-5-(phenylthio)phenyl)ethanone (3i): Eluent:
dichloromethane/hexane (1:8); yield: 53 mg (73%); yellow
oil; 1H NMR (CDCl3, 400 MHz): d=7.92 (d, J=1.4 Hz,
1H), 7.37 (dd, J=8.7 Hz, 1.4 Hz, 1H), 7.22 (t, J=7.3 Hz,
2H), 7.09–7.13 (m, 3H), 6.65 (d, J=8.7 Hz, 1H), 6.48 (br. s,
2H), 2.54 (s, 3H); 13C NMR (CDCl3, 100 MHz): d=200.3,
150.7, 140.9, 139.3, 139.2, 129.1, 127.2, 125.6, 118.9, 118.7,
117.5, 27.9; EI-MS: m/z=243.3 (M+).
4-(Phenylthio)-2-(trifluoromethyl)aniline (3k): Eluent: di-
chloromethane/hexane (1:3); yield: 54 mg (67%); yellow oil;
1H NMR (CDCl3, 400 MHz): d=7.60 (d, J=1.8 Hz, 1H),
7.39 (dd, J=8.7 Hz, 1.8 Hz, 1H), 7.21–7.25 (m, 2H), 7.12–
7.16 (m, 3H), 6.70 (d, J=8.7 Hz, 1H), 4.29 (br.s, 2H);
13C NMR (CDCl3, 100 MHz): d=144.9, 139.0, 138.4, 132.8
(q, J=4.8 Hz), 129.1, 128.2, 126.1, 124.6 (q, J=273.2 Hz),
120.9, 118.3, 114.5 (q, J=29.7 Hz); EI-MS: m/z=269.1
(M+).
Conclusions
We have developed a simple, efficient and practical
method for the arylthiolation of arylamines. The pro-
tocol uses (arylthio)pyrrolidine-2,5-diones as the ar-
ylthiolation reagents for arylamine derivatives, aceto-
nitrile as the solvent, and catalyst, additive and exclu-
sion of air were not required, which avoided contami-
nation by transition metal catalysts of the target prod-
ucts. Furthermore, applications of the synthesized
arylthiolation products emphasise the great value of
the present method. We believe that this environmen-
tally friendly method will find wide applications.
Acknowledgements
The authors wish to thank the National Natural Science
Foundation of China (Grant Nos. 21172128, 21372139 and
21221062), and the Ministry of Science and Technology of
China (Grant No. 2012CB722605) for financial support.
Experimental Section
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Hua Tian, Haijun Yang, Changjin Zhu, Hua Fu*
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
9
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These are not the final page numbers!