One-Pot Copper-Catalysed Thioetherification of Aryl Halides Using Alcohols and Lawesson's Reagent in Diglyme

Article abstract of DOI:10.1002/ejoc.201500256

A new protocol for the thioetherification of structurally varied alcohols with aryl halides using Lawesson's reagent, catalysed by copper(I) iodide, and using diglyme as a safe solvent was developed. Using this method, the reactions of aryl halides proceeded efficiently, and the desired sulfides were obtained in high to excellent yields. The method uses alcohols as starting materials, which is a significant advantage over methods that start from thiols. Alcohols are widely commercially available in a much greater structural diversity than thiols, and they are also nontoxic and not foul-smelling. A reaction mechanism was proposed. A copper-catalysed method for the thioetherification of alcohols with aryl halides using Lawesson's reagent was developed.

Full text of DOI:10.1002/ejoc.201500256

FULL PAPER
DOI: 10.1002/ejoc.201500256
One-Pot Copper-Catalysed Thioetherification of Aryl Halides Using Alcohols
and Lawesson’s Reagent in Diglyme
Mohammad Gholinejad*[a]
Dedicated to Professor Nasser Iranpoor on the occasion of his retirement
Keywords: Homogeneous catalysis / Arylation / Alcohols / Copper / Sulfur / Thioethers
A new protocol for the thioetherification of structurally varied
as starting materials, which is a significant advantage over
alcohols with aryl halides using Lawesson’s reagent, cata- methods that start from thiols. Alcohols are widely commer-
lysed by copper(I) iodide, and using diglyme as a safe solvent
was developed. Using this method, the reactions of aryl hal-
cially available in a much greater structural diversity than
thiols, and they are also nontoxic and not foul-smelling. A
ides proceeded efficiently, and the desired sulfides were ob- reaction mechanism was proposed.
tained in high to excellent yields. The method uses alcohols
through the in situ generation of S-alkylisothiouronium
Introduction
salts from the reaction of alkyl halides and thiourea,[8] were
reported by Firouzabadi and coworkers. Subsequently,
these odourless methods were developed using other sulfur
surrogates[9] such as xanthogenate,[10] thioacetamide,[11]
thiourea,[12] potassium thiocyanate,[13] thioacetate,[14] so-
dium hydrosulfide,[15] sodium sulfide,[16] elemental sulfur,[17]
sulfonyl hydrazides,[18] Na2S2O3,[19] potassium 5-methyl-
1,3,4-oxadiazole-2-thiolate,[20] aminothiourea,[21] sulfonyl
hydrazide,[22] and phosphorothioic acids and related com-
pounds.[23] However, the challenge of designing new syn-
thetic and catalytic systems for C–S bond formation under
mild and greener reaction conditions remains.
Aryl sulfides are important compounds, and their
number includes anti-HIV and anti-inflammatory drugs, as
well as drugs used for the treatment of Alzheimer’s disease,
Parkinson’s disease, and diabetes.[1] For a long time, aryl
sulfides were prepared using traditional methods such as
Ullmann-type reactions of arenethiols with aryl halides.[2]
However, this method requires harsh reaction conditions
such as elevated temperatures (Ͼ200 °C). Another method
for the preparation of aryl sulfides is the treatment of aryl-
lithium or Grignard reagents with sulfur-based electro-
philes. But this approach is not suitable for molecules con-
taining sensitive functional groups.[3]
Lawesson’s reagent (Figure 1) is one of the most widely
used reagents for the transformation of a carbonyl func-
tional group into a thiocarbonyl group, as well as for the
synthesis of a wide range of heterocyclic compounds con-
taining sulfur atoms.[24] In 1993, an article by Nishio, re-
vealed that alcohols could be directly converted into the
corresponding thiols in the presence of Lawesson’s rea-
gent.[25] In this paper, a new protocol for the thio-
etherification of structurally different alcohols in the pres-
ence of commercially available Lawesson’s reagent as a sul-
fur surrogate and copper(I) iodide as a catalyst in diglyme
as a safe solvent is described. Compared to the bad-smell-
ing thiols, alcohols are very common compounds that are
easy to prepare by hydration of alkenes, or by reduction
The development in recent years of transition-metal cata-
lysts,[4] including copper[5] or palladium[6] catalysts, for C–
S bond formation through the reaction of aryl halides and
thiols means that reactions can now proceed under mild
reaction conditions. But although the fact that harsh reac-
tion conditions can now be avoided represents an important
achievement, these methods still suffer from a disadvantage.
They rely on the direct use of volatile, foul smelling, envi-
ronmentally unfriendly low-molecular-weight thiols. This
problem becomes more serious for larger-scale operations.
To solve the problem, two new odourless methods for C–S
bond formation, including one-pot thia-Michael addition
reactions[7] and one-pot thioetherification of aryl halides
[a] Institute for Advanced Studies in Basic Sciences IASBS,
Zanjan, Iran (Islamic Republic of)
E-mail: gholinejad@iasbs.ac.ir
http://iasbs.ac.ir/chemistry/dep=3&ef=en&page=
personalpage.php&id=889
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500256.
Figure 1. Lawesson’s reagent.
4162
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Thioetherification of Aryl Halides
of aldehydes, ketones, acids, or esters. In addition, many 1-propanol, an optically active alcohol, with 4-iodotoluene
structurally different alcohols are commercially available.
under the optimized reaction conditions was also studied.
However, determination of the enantiomeric excess values
by polarimetry showed that the product was almost racemic
(Table 2, entry 36). All attempts to carry out the reaction
of the tertiary alcohol tBuOH with iodobenzene under the
optimized reaction conditions were unsuccessful. The reac-
Results and Discussion
In initial experiments, the reaction of iodobenzene with
benzyl alcohol and Lawesson’s reagent was investigated,
using copper(I) iodide as a catalyst, and with different bases
and solvents (Table 1).
Table 2. Aryl halides and alcohols tested in the copper-catalysed
thioarylation reaction using Lawesson’s reagent.[a]
Table 1. Optimization of the reaction conditions (DMA = N,N-
dimethylacetamide).[a]
Entry
Solvent
Base
Yield [%][b]
1
2
3
4
5
6
7
8
DMF
K2CO3
K2CO3
Na2CO3
tBuOK
Et3N
tBuOK
K2CO3
Et3N
74
96
76
71
10
28
22
8
54
diglyme
diglyme
diglyme
diglyme
xylene
xylene
xylene
DMA
9
10
11
K2CO3
K2CO3
K2CO3
DMSO
H2O
68
trace
[a] Reactions carried out on a 0.5 mmol scale. [b] Yields determined
by GC analysis.
The results indicated that the use of K2CO3 as a base and
dry diglyme as a solvent at 120 °C were the most effective
conditions for the reaction of iodobenzene with benzyl
alcohol. Having established these optimized reaction condi-
tions (Table 1, entry 2), the scope of the procedure was
evaluated by varying the alcohols and aryl halides (Table 2).
Structurally different alcohols, including benzyl alcohol,
4-nitrobenzyl alcohol, 2-phenylethanol, 3-phenylethanol,
cinnamyl alcohol, 1-hexanol, 1-octanol, and cyclohexanol,
were treated in the presence of Lawesson’s reagent and CuI
with aryl iodides. The reactions proceeded smoothly to give
the desired sulfides in high to excellent yields. In addition,
the reactions of alcohols with aryl bromides progressed well
to give the desired sulfide products in high yields. The reac-
tion of a heterocyclic alcohol, pyridin-3-ylmethanol, with
aryl halides was also studied, and the desired sulfide prod-
ucts were obtained in 81 and 84% yields (Table 2, entries 15
and 16). In addition, the reactions of the heterocyclic aryl
halides 2-bromo- and 5-bromopyrimidine with alcohols
proceeded well to give the corresponding sulfides in 80–
84% yields (Table 2, entries 21–23). However, the reactions
of aryl chlorides with alcohols under the optimized reaction
conditions were sluggish. A low yield was obtained for the
reaction of chlorobenzene with benzyl alcohol, and moder-
ate yields for the reactions of 1-hexanol and benzyl alcohol
with the more reactive active 1-chloro-4-nitrobenzene
(Table 2, entries 33–35). The reaction of (R)-(+)-1-phenyl-
Eur. J. Org. Chem. 2015, 4162–4167
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M. Gholinejad
FULL PAPER
Table 2. (Continued)
ditions. The reaction proceeded well, and desired sulfide
product was obtained in 87% isolated yield.
The CuI catalyst is soluble under the reaction conditions,
and reactions proceeded under homogeneous conditions. A
proposed mechanism for this reaction is presented in
Scheme 1. In the first step, nucleophilic attack of the
alcohol onto a dipolar species of Lawesson’s reagent pro-
duces an O-alkyl phosphonodithioic acid intermediate,[24b]
which is then deprotonated by the base. Based on the fact
that an optically active alcohol led to a racemic product
(Table 2, entry 36), the resulting phosphonodithioic anion
may be in equilibrium with an ion-pair intermediate. Next,
the phosphonodithioic anion adds to carbon of alcohol
(–OCHR1R2) to generate a thiolate ion. The resulting thio-
late then reacts according to the well-known copper-cata-
lysed coupling of thiols with aryl halides.[5b]
Scheme 1. Proposed mechanism for the reaction.
Conclusions
In conclusion, a new method for copper-catalysed car-
bon–sulfur bond formation based on the reaction of aryl
halides, Lawesson’s reagent, and alcohols has been devel-
oped. Using this protocol, primary and secondary alcohols
reacted efficiently with aryl bromides and iodides. Reac-
tions proceeded through the one-pot conversion of the
alcohol into a thiolate by reaction with Lawesson’s reagent.
One of the important features of this protocol is the variety
of commercially available alcohols that can be used, which
makes this approach much easier than alternative methods
that use the corresponding thiols. This strategy was success-
fully used for a large-scale reaction.
[a] Reaction conditions: ROH (1.3 mmol), Lawesson’s reagent
(0.78 mmol), ArX (1 mmol), K2CO3 (1.5 mmol), CuI (10 mol-%),
and diglyme (2 mL). [b] Isolated yields. [c] 5% styrene as a by-prod-
uct was detected by GC. [d] Reaction conditions: 1,3-propanediol
(1 mmol), Lawesson’s reagent (1.5 mmol), iodobenzene (2 mmol),
K2CO3 (3 mmol), CuI (10 mol-%), and diglyme (2 mL).
tion of 1,3-propanediol was also studied; both hydroxyl
groups participated in the reaction, and the desired sulfide
product was obtained in 71% isolated yield (Table 2, en-
try 37).
To demonstrate this reaction on a larger scale, the reac-
tion of iodobenzene (10 mmol) with Lawesson’s reagent
(6 mmol) and benzyl alcohol (13 mmol) in the presence of
Experimental Section
General Remarks: All chemicals were purchased from Acros,
catalyst (1 mmol) was studied under similar optimized con- Sigma–Aldrich, and Merck. Alcohols were distilled before use, and
4164 Eur. J. Org. Chem. 2015, 4162–4167
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Thioetherification of Aryl Halides
were stored under dry argon gas. Reactions were monitored by
thin-layer chromatography (silica gel 254 analytical sheets obtained
from Fluka) or gas chromatography (Varian, cp-3800). Column
chromatography was carried out on silica gel 60 Merck (230–
240 mesh) in glass columns (2 or 3 cm diameter). 1H and 13C NMR
spectra were recorded with a Bruker Avance (400 MHz) spectrome-
ter, and chemical shifts are reported in ppm. Spectra were cal-
ibrated using residual nondeuterated solvent as an internal refer-
ence (CDCl3: δ = 7.29 ppm). FTIR spectra were recorded with a
Bruker Vector 22 instrument. CHN analysis was carried out with
a vario EL instrument. Optical rotations were determined with a
Perkin–Elmer 241 polarimeter.
1469, 1338, 1092, 802, 477 cm–1. C13H10BrNO2S (324.19): calcd. C
48.16, H 3.11, N 4.32, S 9.89; found C 49.08, H 3.25, N 4.19, S
9.78.
1
1f: Yellow solid, m.p. 66–69 °C. H NMR (400 MHz, CDCl3): δ =
8.13 (d, J = 8.4 Hz, 2 H), 7.37 (d, J = 8.8 Hz, 2 H), 7.20 (d, J =
8 Hz, 2 H), 7.09 (d, J = 7.6 Hz, 2 H), 4.11 (s, 2 H), 2.34 (s, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 146.97, 145.92, 137.71,
131.90, 130.59, 129.89, 129.60, 123.66, 39.65, 21.13 ppm. IR
(CH Cl ): ν = 3412, 2924, 2855, 1607, 1516, 1340, 1093, 856,
˜
2
2
483 cm–1. C14H13NO2S (259.32): calcd. C 64.74, H 5.05, N 5.40, S
12.36; found C 64.77, H 4.96, N 5.47, S 12.43.
1
1g: Pale yellow oil. H NMR (400 MHz, CDCl3): δ = 7.43 (d, J =
General Procedure for Thioetherification of Aryl Halides Using
Alcohols and Lawesson’s Reagent: Alcohol (1.3 mmol), Lawesson’s
reagent (0.78 mmol), aryl halide (1 mmol), K2CO3 (1.5 mmol,
207 mg), CuI (10 mol-%, 19 mg), and diglyme (2 mL) were added
to a 5 mL flask, and the mixture was magnetically stirred and
heated under argon at 120 °C for the appropriate reaction time.
The progress of the reaction was monitored by GC or TLC analy-
sis. After the reaction was complete, the product was isolated using
column chromatography on silica gel (EtOAc/n-hexane).
7.6 Hz, 2 H), 7.38–7.34 (m, 4 H), 7.30–7.23 (m, 4 H), 3.24 (t, J =
7.6 Hz, 2 H), 2.99 (t, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 140.27, 136.42, 129.25, 129.02, 128.59, 126.53, 126.05,
35.69, 35.14 ppm. IR (CH Cl ): ν = 3064, 3027, 2924, 2853, 1585,
˜
2
2
1483, 1444, 1083, 739, 697, 485 cm–1. C14H14S (214.32): calcd. C
78.46, H 6.58, S 14.96; found C 78.38, H 6.61, S 15.01.
1h: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.39–7.34
(m, 4 H), 7.27–7.24 (m, 3 H), 7.19–7.17 (m, 2 H), 3.19 (t, J =
7.2 Hz, 2 H), 2.96 (t, J = 7.2 Hz, 2 H), 2.39 (s, 3 H) ppm. 1H NMR
(400 MHz, CDCl3): δ = 140.38, 136.25, 132.49, 130.14, 129.78,
Typical Procedure for Thioetherification of Iodobenzene Using
Benzyl Alcohol and Lawesson’s reagent: Lawesson’s reagent
(6 mmol), benzyl alcohol (13 mmol), iodobenzene (10 mmol),
K2CO3 (15 mmol, 2 g), CuI (1 mmol-%, 190 mg) and diglyme
(20 mL) were added to a 25 mL flask, and the mixture was magnet-
ically stirred and heated under argon at 120 °C for 12 h. Then the
corresponding sulfide product was isolated by column chromatog-
raphy on silica gel using n-hexane/EtOAc (5:1) as the eluent.
128.56, 128.53, 126.44, 35.86, 35.80, 21.08 ppm. IR (CH Cl ): ν =
˜
2
2
3066, 3025, 2923, 2857, 1598, 1492, 1448, 1090, 1024, 804, 704,
494 cm–1. C15H16S (228.35): calcd. C 78.90, H 7.06, S 14.04; found
C 79.14, H 6.89, S 13.97.
1i: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.38–7.31 (m,
6 H), 7.28–7.21 (m, 4 H), 2.98 (t, J = 7.6 Hz, 2 H), 2.82 (t, J =
7.6 Hz, 2 H), 2.07–2.0 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 141.35, 136.61, 129.15, 128.93, 128.58, 128.48, 126.05,
1
1a: White solid, m.p. 44–46 °C. H NMR (400 MHz, CDCl3): δ =
7.36–7.22 (m, 10 H), 4.18 (s, 2 H) ppm. 13C NMR (100 MHz,
125.88, 34.74, 32.91, 30.68 ppm. IR (CH Cl ): ν = 3413, 3064,
˜
2
2
CDCl3): δ = 137.97, 136.91, 130.31, 129.39, 129.38, 129.04, 127.72,
3025, 2927, 1584, 1483, 1444, 1083, 1024, 739, 695, 483 cm–1.
C15H16S (228.35): calcd. C 78.90, H 7.06, S 14.04; found C 78.79,
H 7.11, S 14.10.
126.87, 39.54 ppm. IR (KBr): ν = 3046, 2356, 1625, 1480, 1466,
˜
1171, 1075, 723, 685, 474 cm–1. C13H12S (200.30): calcd. C 77.95,
H 6.04, S 16.01; found C 78.04, H 6.01, S 15.95.
1j: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.43–7.40 (m,
2 H), 7.36–7.21 (m, 10 H), 6.47 (d, J = 15.6 Hz, 1 H), 6.29 (dd, J
= 7.2, 15.6 Hz, 1 H), 3.75 (d, J = 7.6 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 136.76, 135.84, 132.81, 130.30, 128.87,
1
1b: Yellow oil. H NMR (400 MHz, CDCl3): δ = 7.34–7.24 (m, 7
H), 7.10 (d, J = 8 Hz, 2 H), 4.11 (s, 2 H), 2.35 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 137.81, 136.61, 132.47, 130.72,
129.65, 128.87, 128.47, 127.11, 39.80, 21.10 ppm. IR (CH Cl ): ν =
˜
2
2
3025, 2921, 2859, 1492, 1450, 1087, 1025, 803, 704, 492 cm–1.
C14H14S (214.32): calcd. C 78.46, H 6.58, S 14.96; found C 78.35,
H 6.64, S 15.01.
128.55, 127.60, 126.45, 126.36, 125.08, 37.16 ppm. IR (CH Cl ): ν
˜
2
2
= 3414, 3065, 2922, 1612, 1490, 1446, 1089, 1024, 803, 700,
493 cm–1. C15H14S (226.34): calcd. C 79.60, H 6.23, S 14.17; found
C 79.46, H 6.28, S 14.26.
1
1c: Colourless oil. H NMR (400 MHz, CDCl3): δ = 7.32–7.23 (m,
1k: Pale yellow solid, m.p. 70–74 °C. 1H NMR (400 MHz, CDCl3):
δ = 7.36–7.25 (m, 7 H), 7.13 (d, J = 8 Hz, 2 H), 6.42 (d, J = 15.6 Hz,
1 H), 6.28 (dd, J = 7.2, 15.6 Hz, 1 H), 3.69 (d, J = 7.2 Hz, 2 H),
2.35 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 136.85,
136.69, 132.59, 131.95, 131.15, 129.66, 128.54, 127.54, 126.36,
7 H), 7.0–6.95 (m, 2 H), 4.06 (s, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 163.82, 161.37, 138.01, 133.97, 133.89, 131.23, 131.20,
129.34, 128.96, 127.69, 116.52, 116.30, 40.95 ppm. 19F NMR
(376 MHz, CDCl ): δ = –114.84 ppm. IR (CH Cl ): ν = 2920, 2856,
˜
3
2
2
1489, 1082, 965, 806, 546 cm–1. C13H11FS (218.29): calcd. C 71.53,
125.39, 37.88, 21.10 ppm. IR (KBr): ν = 2919, 2857, 1631, 1487,
˜
H 5.08, S 14.69; found C 70.43, H 5.16, S 14.63.
1022, 800, 753, 685, 489 cm–1. C16H16S (240.36): calcd. C 79.95, H
6.71, S 13.34; found C 79.83, H 6.65, S 13.52.
1d: Pale yellow solid, m.p. 79–81 °C. 1H NMR (400 MHz, CDCl3):
δ = 8.15 (d, J = 8.4 Hz, 2 H), 7.41 (d, J = 8.8 Hz, 2 H), 7.30–7.24
(m, 5 H), 4.14 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
147.05, 145.57, 134.49, 131.07, 129.59, 129.11, 127.35, 123.72,
1l: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.51 (s, 2 H),
7.69 (d, J = 7.6 Hz, 2 H), 7.33–7.23 (m, 6 H), 4.11 (m, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 148.75, 147.34, 137.36, 134.57,
38.99 ppm. IR (CH Cl ): ν = 3069, 2926, 2845, 1643, 1512, 1091,
˜
2
2
901, 735, 470 cm–1. C13H11NO2S (245.30): calcd. C 63.65, H 4.52,
130.98, 129.13, 127.29, 123.83, 36.56 ppm. IR (CH Cl ): ν = 3413,
˜
2
2
3050, 2022, 2574, 1579, 1474, 1428, 1258, 1089, 1026, 803, 743,
697, 480 cm–1. C12H11NS (201.29): calcd. C 71.60, H 5.51, N 6.96,
S 15.93; found C 71.42, H 5.43, N 7.10, S 16.05.
N 5.71, S 13.07; found C 63.78, H 4.61, N 5.64, S 12.97.
1e: Pale yellow solid, m.p. 104–106 °C. 1H NMR (400 MHz,
CDCl3): δ = 8.16 (d, J = 8.8 Hz, 2 H), 7.42–7.38 (m, 4 H), 7.17–
7.14 (m, 2 H), 4.14 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ 1m: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.50–8.49
= 147.15, 145.06, 133.65, 132.53, 132.20, 129.59, 123.81, 121.48,
(m, 1 H), 8.43 (s, 1 H), 7.65 (d, J = 8 Hz, 2 H), 7.30–7.10 (m, 3
38.94 ppm. IR (KBr): ν = 3073, 2919, 2848, 1634, 16.01, 1511, H), 7.09 (d, J = 8 Hz, 2 H), 4.05 (s, 2 H), 2.33 (s, 3 H) ppm. 13C
˜
Eur. J. Org. Chem. 2015, 4162–4167
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M. Gholinejad
NMR (100 MHz, CDCl3): δ = 148.96, 147.46, 137.62, 137.19, 131.84, 128.73, 126.56, 46.54, 33.33, 26.05, 25.76 ppm. IR
FULL PAPER
134.43, 131.84, 130.69, 129.89, 123.67, 37.25, 21.11 ppm. IR (CH Cl ): ν = 3060, 2927, 2854, 1727, 1578, 1473, 1441, 1027, 742,
˜
2
2
(CH Cl ): ν = 3024, 2922, 2859, 1578, 1486, 1425, 1093, 1027, 805,
690 cm–1. C12H16S (192.32): calcd. C 74.94, H 8.39, S 16.67; found
C 74.75, H 8.47, S 16.78.
˜
2
2
711, 494 cm–1. C13H13NS (215.31): calcd. C 72.52, H 6.09, N 6.51,
S 14.89; found C 72.68, H 6.13, N 6.46, S 14.73.
1v: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.35 (d, J = 8 Hz,
2 H), 7.13 (d, J = 7.6 Hz, 2 H), 3.07–3.02 (m, 1 H), 2.36 (s, 3 H),
2.01–1.98 (m, 2 H), 1.80–1.64 (m, 3 H), 1.41–1.24 (m, 5 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 136.90, 132.81, 131.18, 129.82,
129.55, 128.54, 47.11, 33.39, 26.13, 25.80, 21.12 ppm. IR (CH2Cl2):
1n: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.39 (d, J = 8 Hz,
2 H), 7.34 (d, J = 7.6 Hz, 2 H), 7.23–7.20 (m, 1 H), 2.98 (t, J =
7.4 Hz, 2 H), 1.75–1.68 (m, 2 H), 1.53–1.49 (m, 2 H), 1.46–1.36 (m,
3 H), 0.96 (t, J = 6.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 137.17, 128.86, 125.64, 33.61, 31.45, 29.19, 28.61, 22.63,
ν = 3022, 2928, 2853, 1491, 1448, 806, 501 cm–1. C H S (206.35):
˜
13 18
calcd. C 75.67, H 8.79, S 15.54; found C 75.61, H 8.80, S 15.59.
14.11 ppm. IR (CH Cl ): ν = 2924, 2858, 1582, 1470, 1449, 1091,
˜
2
2
1023, 799, 736 cm–1. C12H18S (194.33): calcd. C 74.16, H 9.34, S
1
1w: Pale yellow oil. H NMR (400 MHz, CDCl3): δ = 7.42 (d, J =
16.50; found C 74.25, H 9.20, S 16.55.
8.8 Hz, 2 H), 6.87 (d, J = 8.4 Hz, 2 H), 3.82 (s, 3 H), 2.96–2.91 (m,
1 H), 1.97–1.95 (m, 2 H), 1.79–1.63 (m, 2 H), 1.63–1.61 (m, 1 H),
1.38–1.22 (m, 5 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 159.33,
135.64, 124.96, 114.30, 55.30, 47.92, 33.41, 26.16, 25.81 ppm. IR
1
1o: Yellow oil. H NMR (400 MHz, CDCl3): δ = 7.37–7.31 (m, 4
H), 7.22–7.18 (m, 1 H), 2.96 (t, J = 7.2 Hz, 2 H), 1.73–1.65 (m, 2
H), 1.48–1.31 (m, 10 H), 0.93 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 137.10, 128.84, 128.82, 125.63, 33.58,
(CH Cl ): ν = 2929, 2848, 1588, 1490, 1451, 1285, 1245, 1177, 1033,
˜
2
2
825, 636, 527 cm–1. C13H18OS (222.34): calcd. C 70.22, H 8.16, S
31.85, 29.23, 29.19, 29.18, 28.91, 22.70, 14.16 ppm. IR (CH Cl ): ν
˜
2
2
= 2924, 2856, 1582, 1469, 1450, 1089, 1024, 802, 736 cm–1. C14H22S
(222.39): calcd. C 75.61, H 9.97, S 14.42; found C 75.53, H 10.02,
S 14.45.
14.42; found C 70.53, H 8.07, S 14.35.
1x: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.42 (s, 1 H),
7.27 (d, J = 8 Hz, 2 H), 7.16–7.12 (m, 4 H), 4.15 (s, 2 H), 2.37 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.36, 134.72, 134.38,
133.50, 131.86, 131.48, 131.37, 129.83, 129.45, 127.0, 37.26,
1p: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.14 (d, J =
8.4 Hz, 2 H), 7.33 (d, J = 8.4 Hz, 2 H), 3.04 (t, J = 7.6 Hz, 2 H),
1.78–1.70 (m, 2 H), 1.48–1.28 (m, 13 H), 0.90 (t, J = 6 Hz, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 148.25, 125.94, 125.94,
123.95, 31.92, 31.79, 29.16, 29.11, 28.92, 28.48, 22.67, 14.13 ppm.
21.20 ppm. IR (CH Cl ): ν = 3024.3, 2924.8, 2862.3, 1587.4,
˜
2
2
1478.2, 1096.8, 1048.2, 808.2, 498.2 cm–1. C14H12Cl2S (283.21):
calcd. C 59.37, H 4.27, S 11.32; found C 59.58, H 4.16, S 11.02.
MS (EI, 70 eV): m/z = 282.1 [M]+.
IR (CH Cl ): ν = 2924, 2856, 1643, 1583, 1336, 1090, 843, 738,
˜
2
2
532 cm–1. C14H21NO2S (267.39): calcd. C 62.89, H 7.92, N 5.24, S
1y: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.40 (s, 1 H),
7.40–7.30 (m, 2 H), 7.14–6.97 (m, 4 H), 4.10 (s, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 163.75, 161.29, 134.69, 134.61,
134.06, 133.65, 131.45, 129.69, 129.65, 129.52, 126.98, 116.23,
11.99; found C 62.72, H 7.87, N 5.31, S 12.02.
1q: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.14 (d, J =
8.8 Hz, 2 H), 7.33 (d, J = 8.8 Hz, 2 H), 3.04 (t, J = 7.6 Hz, 2 H),
1.78–1.71 (m, 2 H), 1.51–1.44 (m, 2 H), 1.36–1.28 (m, 4 H), 0.92
(t, J = 6.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 148.21,
144.83, 125.98, 123.94, 31.95, 31.30, 28.57, 28.46, 22.51, 14.01 ppm.
C12H17NO2S (239.33): calcd. C 60.22, H 7.16, N 5.85, S 13.40;
found C 59.94, H 7.01, N 5.78, S 13.21.
116.01, 37.86 ppm. IR (CH Cl ): ν = 3065.3, 2925.7, 2855.9,
˜
2
2
1587.6, 1480.4, 1227.1, 1094.9, 828.1, 554.2 cm–1. C13H9Cl2FS
(287.18): calcd. C 54.37, H 3.16, S 11.17; found C 54.11, H 3.01, S
11.39. MS (EI, 70 eV): m/z = 285.8 [M]+.
1z: Pale yellow solid, m.p. 88–91 °C. 1H NMR (400 MHz, CDCl3):
δ = 7.35–7.21 (m, 7 H), 6.86 (d, J = 8.4 Hz, 2 H), 4.12 (s, 2 H),
3.82 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.77,
136.57, 129.97, 129.76, 129.38, 128.86, 126.28, 113.92, 55.30,
1r: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.57 (d, J =
4.8 Hz, 2 H), 7.47–7.23 (m, 5 H), 7.02–6.99 (m, 1 H), 6.69 (d, J =
15.6 Hz, 2 H), 6.39 (dd, J = 7.2, 15.6 Hz, 1 H), 4.03 (dd, J = 1.2,
7.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 127.01,
157.29, 136.83, 133.04, 128.55, 127.60, 126.40, 124.77, 116.58,
38.45 ppm. IR (CH Cl ): ν = 2955.5, 2913.6, 2355.4, 1510.1,
˜
2
2
1303.1, 1096.4, 1029.8, 825.3, 740.4, 515.1 cm–1. C14H14OS
(230.32): calcd. C 73.01, H 6.13, S 13.92; found C 73.34, H 6.26, S
13.67.
33.48 ppm. IR (CH Cl ): ν = 3030, 2925, 1556, 1380, 1193, 966,
˜
2
2
755, 696 cm–1. C13H12N2S (228.31): calcd. C 68.39, H 5.30, N
1aa: Pale yellow solid, m.p. 65–67 °C. 1H NMR (400 MHz,
CDCl3): δ = 7.33–7.26 (m, 3 H), 7.21–7.13 (m, 3 H), 6.88 (d, J =
8.8 Hz, 2 H), 4.09 (s, 2 H), 3.83 (s, 3 H), 2.37 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 158.82, 137.74, 136.06, 130.06,
130.04, 129.16, 128.69, 126.44, 125.99, 113.95, 55.31, 37.66,
12.27, S 14.04; found C 68.52, H 5.38, N 12.16, S 13.94.
1s: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.53 (d, J =
4.8 Hz, 2 H), 6.98–6.96 (m, 1 H), 3.17 (t, J = 7.2 Hz, 2 H), 1.79–
1.71 (m, 2 H), 1.51–1.44 (m, 2 H), 1.34–1.29 (m, 8 H), 0.90 (t, J =
6.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 172.85,
157.16, 116.25, 31.84, 30.92, 29.19, 29.18, 29.10, 28.94, 22.67,
20.36 ppm. IR (CH Cl ): ν = 3060.1, 2925.3, 2841.8, 1596.5,
˜
2
2
1506.4, 1304.2, 1029.3, 833.7, 745.05, 689.7 cm–1. C15H16OS
(244.35): calcd. C 73.73, H 6.60, S 13.12; found C 73.48, H 6.72, S
13.32.
14.13 ppm. IR (CH Cl ): ν = 2924, 2856, 1556, 1458, 1380, 1194,
˜
2
2
761 cm–1. C12H20N2S (224.36): calcd. C 64.24, H 8.98, N 12.49, S
14.29; found C 64.11, H 9.04, N 12.53, S 14.32.
1bb: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.47 (d, J =
8 Hz, 2 H), 7.17 (d, J = 8 Hz, 2 H), 3.76–3.72 (m, 1 H), 2.38–2.36
(m, 4 H), 2.36–1.74 (m, 4 H), 1.64–1.58 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 138.06, 133.56, 130.0, 129.66, 84.01, 38.90,
1t: Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 9.04 (s, 1 H), 8.58
(s, 1 H), 7.32–7.24 (m, 6 H), 4.12 (s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 158.35, 156.58, 136.08, 129.01, 128.87,
128.83, 127.85, 39.03 ppm. C11H10N2S (202.27): calcd. C 65.32, H
4.98, N 13.85, S 15.85; found C 65.44, H 4.94, N 13.83, S 15.79.
34.93, 31.29, 26.81, 22.54, 21.23, 14.06 ppm. IR (CH Cl ): ν =
˜
2
2
3298.1, 2928.4, 2861.1, 1492.6, 1455.8, 1098.9, 1022.7, 806.7, 636.9,
1
1u: Yellow oil. H NMR (400 MHz, CDCl3): δ = 7.43–7.19 (m, 5 500.5 cm–1. C15H20S (232.38): calcd. C 77.53, H 8.67, S 13.80;
H), 3.14–3.06 (m, 2 H), 2.01–1.97 (m, 2 H), 1.77–1.63 (m, 3 H),
found C 77.81, H 8.55, S 13.64. MS (EI, 70 eV): m/z = 232.3
1.40–1.26 (m, 5 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 135.15, [M]+.
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Eur. J. Org. Chem. 2015, 4162–4167

Thioetherification of Aryl Halides
1cc: Pale yellow solid, m.p. 79–81 °C. 1H NMR (400 MHz, CDCl3):
δ = 8.12 (d, J = 8.6 Hz, 2 H), 7.43–7.32 (m, 7 H), 4.28 (s, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 147.31, 145.22, 135.46,
128.88, 128.75, 127.84, 126.61, 123.95, 37.02 ppm. C13H11NO2S
(245.30): calcd. C 63.65, H 4.52, N 5.71, S 13.07; found C 63.74,
H 4.402, N 5.84, S 13.19.
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1
1dd: Yellow oil. H NMR (400 MHz, CDCl3): δ = 7.31–7.22 (m, 5
H), 7.21–7.17 (m, 2 H), 7.04 (d, J = 8 Hz, 2 H), 4.02–3.98 (m, 1
H), 2.31 (s, 1 H), 2.04–1.92 (m, 2 H), 0.93 (t, J = 7.6 Hz, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 142.10, 137.19, 133.06, 131.29,
129.43, 128.27, 127.91, 126.97, 55.75, 29.22, 21.13, 12.32 ppm. IR
(CH Cl ): ν = 3024.9, 2963.5, 2924.9, 1490.9, 1451.6, 1091.3,
˜
2
2
1023.2, 804.6, 701.8 cm–1. C16H18S (242.38): calcd. C 79.29, H 7.49,
S 13.22; found C 79.53, H 7.29, S 13.18.
1ee: Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.37–7.21
(m, 8 H), 7.23–7.20 (m, 2 H), 3.09 (t, J = 7.2 Hz, 4 H), 2.03–1.96
(m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 136.04, 129.38,
128.98, 126.11, 32.42, 28.31 ppm. IR (CH Cl ): ν = 3416, 3062,
˜
2
2
2955, 2920, 1581, 1475, 1434, 1257, 1087, 1022, 799, 738, 691, 621,
482 cm–1. C15H16S2: C 69.18, H 6.19, S 24.63; found C 69.31, H
6.15, S 24.54.
Acknowledgments
The author is grateful to the Research Council of the Institute for
Advanced Studies in Basic Sciences (IASBS) and the Iran National
Science Foundation (INSF) (grant number 93020713) for their sup-
port of this work.
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Received: February 23, 2015
Published Online: May 27, 2015
Eur. J. Org. Chem. 2015, 4162–4167
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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