Methods, Syntheses and Characterization of Diaryl, Aryl Benzyl, and Dibenzyl Sulfides

Article abstract of DOI:10.1007/s10870-020-00859-w

Twenty-four aryl benzyl sulfides, diaryl sulfides and dibenzyl sulfides were synthesized by four methods and characterized by ¹H NMR, FT-IR and Gas chromatography. The reaction conditions of different synthesis methods were studied from the aspects of time, solvent, base and dispersant. The molecular structures of benzylphenyl sulfide (2S), (4-tert-butylbenzyl)(4-methylphenyl) sulfide (4S), (4-methylbenzyl)(4-methylphenyl) sulfide (9S), di(4-methylphenyl) sulfide (11S), (3,5-dimethylphenyl)(4-methyl phenyl) sulfide (15S), and dibenzyl sulfide (19S) [22] have been determined by single-crystal X-ray crystallography. Compounds 2S and 15S crystallize in the monoclinic space group P2₁/c, with a = 12.278(3), b = 15.894(3), c = 5.6056(11) ?, β = 94.532(2)°, and Z = 4 for 2S, and a = 9.800(9), b = 7.950(7), c = 16.690(15) ?, β = 100.890(12)°, and Z = 4 for 15S. The unit cell of 4S has a triclinic Pī symmetry with the cell parameters a = 6.0436(10), b = 8.7871(14), c = 15.535(2) ?, α = 81.921(2)°, β = 81.977(2)°, γ = 80.889(2)°, and Z = 2. Compounds 9S and 11S both crystallize in the orthorhombic space group P2₁2₁2₁, with a = 6.188(3), b = 8.041(4), c = 26.005(14) ?, and Z = 4 for 9S, and a = 5.835(2), b = 8.010(3), c = 25.131(9) ?, and Z = 4 for 11S. Graphic Abstract: Twenty-four aryl sulfide compounds with different substituents were synthesized and characterized, and the molecular structures of six different sulfide compounds have been determined by single-crystal X-ray crystallography.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-020-00859-w

Journal of Chemical Crystallography
https://doi.org/10.1007/s10870-020-00859-w
ORIGINAL PAPER
Methods, Syntheses and Characterization of Diaryl, Aryl Benzyl,
and Dibenzyl Sulfdes
Wen‑Yan Zhou1 · Min Chen1 · Pei‑Zhi Zhang1 · Ai‑Quan Jia1 · Qian‑Feng Zhang1
Received: 7 May 2020 / Accepted: 25 August 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
Twenty-four aryl benzyl sulfdes, diaryl sulfdes and dibenzyl sulfdes were synthesized by four methods and characterized
by 1H NMR, FT-IR and Gas chromatography. The reaction conditions of diferent synthesis methods were studied from the
aspects of time, solvent, base and dispersant. The molecular structures of benzylphenyl sulfde (2S), (4-tert-butylbenzyl)
(4-methylphenyl) sulfde (4S), (4-methylbenzyl)(4-methylphenyl) sulfde (9S), di(4-methylphenyl) sulfde (11S), (3,5-dimeth-
ylphenyl)(4-methyl phenyl) sulfde (15S), and dibenzyl sulfde (19S) [22] have been determined by single-crystal X-ray
crystallography. Compounds 2S and 15S crystallize in the monoclinic space group P21/c, with a=12.278(3), b=15.894(3),
c = 5.6056(11) Å, β = 94.532(2)°, and Z = 4 for 2S, and a = 9.800(9), b = 7.950(7), c = 16.690(15) Å, β = 100.890(12)°,
and Z=4 for 15S. The unit cell of 4S has a triclinic Pī symmetry with the cell parameters a=6.0436(10), b=8.7871(14),
c=15.535(2) Å, α=81.921(2)°, β=81.977(2)°, γ=80.889(2)°, and Z=2. Compounds 9S and 11S both crystallize in the
orthorhombic space group P212121, with a=6.188(3), b=8.041(4), c=26.005(14) Å, and Z=4 for 9S, and a=5.835(2),
b=8.010(3), c=25.131(9) Å, and Z=4 for 11S.
Graphic Abstract
Twenty-four aryl sulfde compounds with diferent substituents were synthesized and characterized, and the molecular struc-
tures of six diferent sulfde compounds have been determined by single-crystal X-ray crystallography.
Extended author information available on the last page of the article
Vol.:(0123456789)
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Journal of Chemical Crystallography
Keywords Aryl benzyl sulfde · Diaryl sulfde · Dibenzyl sulfde · Synthesis · Characterization · Crystal structure
Introduction
Experimental
Sulfdes (R-S-R), the R group can be various functional
groups, such as alkyl, alkenyl, alkynyl, aryl and benzyl.
They are useful starting materials for the synthesis of many
organic compounds [1, 2]. Typically, they can be oxidized
into sulfoxides or sulfones, which have received extensive
attention as essentially synthetic intermediates in some
important organic molecule syntheses, such as lansopra-
zole and omeprazole [3–5]. Due to the diversity of its own
functional groups and the substitution of diferent functional
groups, such as nitro, amino, chloro and alkyl, the free com-
bination makes a wide range of sulfdes, accordingly their
synthetic methods are diferent. However, traditional meth-
ods for formation of C–S bond have some problems such as
tedious reaction operation, unfriendly ecological environ-
ment, excessive raw materials, high toxicity and expensive
catalysts [6]. Recently, several new synthetic methods of
sulfdes have been explored [7, 8]. Herein, we report four
methods for the syntheses of twenty-four diaryl sulfdes,
aryl benzyl sulfdes, and dibenzyl sulfdes based on litera-
ture methods [9–12]. And the reaction conditions of dif-
ferent synthesis methods were studied from the aspects of
time, solvent, base and dispersant to improve the reaction
yield. It is found that thirteen diaryl sulfdes and dibenzyl
sulfdes could be synthesized in a quantitative yield by the
following method: 5 mol% CuI as a catalyst, PEG400 as a
reaction medium, iodobenzene/benzyl bromide and tolthiol/
benzylthiol as the reactant at a molar ratio of 1:1 at 120 °C.
This method is simple, environment friendly, and economi-
cal. The synthesized twenty-four diaryl sulfdes, aryl ben-
zyl sulfdes, and dibenzyl sulfdes were characterized by 1H
NMR, FT-IR and Gas chromatography, of which the struc-
tures of six sulfdes were established by X–ray crystallog-
raphy in this paper.
General Considerations
All syntheses were carried out under nitrogen by stand-
ard Schlenk techniques. Iodobenzene, 2-iodotoluene,
3-iodotoluene, 4-iodotoluene, 2,4-dimethyliodobenzene,
3,5-dimethyliodobenzene, benzyl bromide, 2-bromoben-
zyl bromide, 2-methylbenzyl bromide, 3-methylbenzyl
bromide, 4-methylbenzyl bromide, 4-tert-butylbenzyl bro-
mide, (1-bromoethyl)benzene, bromobenzene, 4-bromotol-
uene, p-toluenethiol, benzylthiol, 1-ethyl-4-iodobenzene,
4-iodoanisole, CuI, Pd(PPh3)4 and PEG400 were purchased
from Alfa Aesar Ltd. and used without further purifcation.
1H NMR spectra were recorded on a Bruker ALX 400 spec-
1
trometer. The HNMR measurements were performed at
room temperature. Chemical shifts (δ, ppm) were reported
with reference to SiMe4 (1H). Infrared spectra were recorded
on a Perkin-Elmer 16 PC FT-IR spectrophotometer using
KBr pellets. Gas chromatography analyses were performed
with an FID detector on a Shimadzu GC-2010 Plus spec-
trometer using the RTX-5 column (15 m× 0.25 mm, flm
thickness 0.25 µm). The initial temperature of the column
was 110 °C and increased to 260 °C with a rate of 20 °C
min−1.
Synthesis by Method A (See Scheme 1) [9]
Phenyl(1‑Phenylethyl) Sulfde (1S)
A solution of CS2 (0.92 g, 12 mmol), NaOH (10% aq. solu-
tion, 10 mL) and diethylamine (1.2 mL, 12 mmol) were
stirred for 1 h at room temperature. CuI (0.19 g, 0.99 mmol,
10% mol), iodobenzene (2.0 g, 10 mmol) and PEG400
(20 mL) were added, and the reaction mixture was stirred
Scheme 1 Synthesis of aryl benzyl sulfdes 1S–3S
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Journal of Chemical Crystallography
at refux. After 15 h, KOH (2.2 g, 40 mmol) was added and
the mixture was stirred at 110 °C for 4 h. After cooling,
(1-bromoethyl)benzene (2.8 g, 15 mmol) was added to the
solution, which was stirred at room temperature for 1 h, and
the reaction solution was diluted with water (20 mL) and
further extracted with ethyl acetate (10 mL × 2). The sol-
vent was removed in vacuo, and the residue was washed
by cool diethyl ether (8 mL × 3). Yield: 50%. GC: purity
93.4%, tR = 4.708 min. IR (cm−1): 1175 v(–S–Ar), 836
for X-ray difraction were obtained by slow evaporation of
its dichloromethane/methanol solution (v:v=1:3) at room
temperature in three days. Yield: 75%. GC: purity 100%,
tR =6.347 min. IR (cm−1): 1173 v(–S–Ar), 831 v(–CH2–S–).
1H NMR (400 MHz, CDCl3) δ (ppm): 1.30 (s, 9H, (CH3)3),
2.31 (s, 3H, CH3), 4.06 (s, 2H, CH2), 7.06–7.31 (m, 8H,
Ar–H).
Benzyl(4‑Methylphenyl) Sulfde (5S)
1
v(–CH(CH3)–S–). H NMR (400 MHz, CDCl3) δ (ppm):
1.61 (d, J=7.2 Hz, 3H, CH3), 4.35 (q, J=21 Hz, 1H, CH),
7.05 (d, J=8.0 Hz, 2H, Ar–H), 7.19–7.27 (m, 8H, Ar–H).
The method was similar to that used for 4S, employing ben-
zyl bromide (0.86 g, 5.0 mmol) instead of 4-tert-butylben-
zyl bromide. Yield: 70%. GC: purity 100%, tR =8.401 min.
1
Benzylphenyl Sulfde (2S)
IR (cm−1): 1179 v(–S–Ar), 835 v(–CH2–S–). H NMR
(400 MHz, CDCl3) δ (ppm): 2.31 (s, 3H, CH3), 4.16 (s, 2H,
CH2), 7.08–7.25 (m, 9H, Ar–H).
The method was similar to that used for 1S, employing ben-
zyl bromide (2.6 g, 15 mmol) instead of (1-bromoethyl)ben-
zene. Colorless crystals suitable for X-ray difraction were
obtained by slow evaporation of its dichloromethane/metha-
nol solution (v:v = 2:5) at room temperature in fve days.
Yield: 67%. GC: purity 96.0%, tR =4.161 min. IR (cm−1):
(2‑Bromobenzyl)(4‑Methylphenyl) Sulfde (6S)
The method was similar to that used for 4S, employ-
ing 2-bromobenzyl bromide (1.3 g, 5.0 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 78%. GC: purity 98.4%,
tR =7.472 min. IR (cm−1): 1175 v(–S–Ar), 837 v(–CH2–S–).
1H NMR (400 MHz, CDCl3) δ (ppm): 2.33 (s, 3H, CH3),
4.07 (s, 2H, CH2), 7.08–7.26 (m, 8H, Ar–H).
1
1171 v(–S–Ar), 839 v(–CH2–S–). H NMR (400 MHz,
CDCl3) δ (ppm): 4.10 (s, 2H, CH2), 7.16–7.30 (m, 10H,
Ar–H).
(2‑Bromobenzyl)phenyl Sulfde (3S)
(2‑Methylbenzyl)(4‑Methylphenyl) Sulfde (7S)
The method was similar to that used for 1S, employ-
ing 2-bromobenzyl bromide (3.8 g, 15 mmol) instead of
(1-bromoethyl)benzene. Yield: 60%. GC: purity 93.5%,
tR =8.263 min. IR (cm−1): 1180 v(–S–Ar), 835 v(–CH2–S–).
1H NMR (400 MHz, CDCl3) δ (ppm): 4.21 (s, 2H, CH2),
7.09–7.34 (m, 8H, Ar–H), 7.54 (d, J=8.0 Hz, 1H, Ar–H).
The method was similar to that used for 4S, employ-
ing 2-methylbenzyl bromide (0.93 g, 5.0 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 65%. GC: purity 100%,
tR =7.398 min. IR (cm−1): 1172 v(–S–Ar), 840 v(–CH2–S–).
1H NMR (400 MHz, CDCl3) δ (ppm): 2.38 (s, 3H, CH3),
2.40 (s, 3H, CH3), 4.00 (s, 2H, CH2), 7.05–7.22 (m, 8H,
Ar–H).
Synthesis by Method B (See Scheme 2) [10]
(3‑Methylbenzyl)(4‑Methylphenyl) Sulfde (8S)
(4‑Tert‑Butylbenzyl)(4‑Methylphenyl) Sulfde (4S)
The method was similar to that used for 4S, employ-
ing 3-methylbenzyl bromide (0.93 g, 5.0 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 87%. GC: purity 99.4%,
tR =7.410 min. IR (cm−1): 1176 v(–S–Ar), 833 v(–CH2–S–).
1H NMR (400 MHz, CDCl3) δ (ppm): 2.32 (s, 3H, Ar–CH3),
2.37 (s, 3H, CH3), 4.05 (s, 2H, CH2), 7.04–7.24 (m, 8H,
Ar–H).
To a solution of THF (30 mL) was added sodium p-tol-
ylthiolate (0.90 g, 6.0 mmol) and 4-tert-butylbenzyl bro-
mide (1.1 g, 5.0 mmol), which was then stirred at refux
for 6 h. After cooling and extraction with dichloromethane
(10 mL × 2), the solvent was removed in vacuo, and the
residue was washed with cool methanol. Crystals suitable
Scheme 2 Synthesis of aryl benzyl sulfdes 4S–9S
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Journal of Chemical Crystallography
(4‑Methylbenzyl)(4‑Methylphenyl) Sulfde (9S)
Di(4‑Methylphenyl) Sulfde (11S)
The method was similar to that used for 4S, employ-
ing 4-methylbenzyl bromide (0.93 g, 5.0 mmol) instead
of 4-tert-butylbenzyl bromide. Crystals suitable for X-ray
diffraction were obtained by slow evaporation of its
dichloromethane/methanol solution (v:v = 1:3) at room
temperature in three days. Yield: 73%. GC: purity 99.5%,
tR =7.403 min. IR (cm−1): 1173 v(–S–Ar), 835 v(–CH2–S–).
1H NMR (400 MHz, CDCl3) δ (ppm): 2.35 (s, 3H, Ar–CH3),
2.30 (s, 3H, CH3), 4.03 (s, 2H, CH2), 7.05–7.29 (m, 8H,
Ar–H).
The method was similar to that used for 10S, employ-
ing 4-bromotoluene (1.7 g, 10 mmol) instead of bromoben-
zene. Crystals suitable for X-ray difraction were obtained by
slow evaporation of its dichloromethane/methanol solution
(v:v=1:3) at room temperature in fve days. Yield: 60%. GC:
purity 90.0%, tR = 4.796 min. IR (cm−1): 1179 v(–S–Ar).
1H NMR (400 MHz, CDCl3) δ (ppm): 2.32 (s, 6H, CH3),
7.09–7.26 (m, 8H, Ar–H).
Synthesis by Method D (See Scheme 4) [12]
Synthesis by Method C (See Scheme 3) [11]
(2‑Methylphenyl)(4‑Methylphenyl) Sulfde (12S)
Phenyl(4‑Methylphenyl) Sulfde (10S)
A mixture of p-toluenethiol (1.2 g, 10 mmol), KOH (2.2 g,
40 mmol), PEG400 (20 mL) were stirred in methanol at 70 °C
for 15 min. Then 2-iodotoluene (2.2 g, 10 mmol) and CuI
(0.10 g, 5% mol) were added, and the reaction mixture was
stirred at 110 °C for 12 h. After cooling and extraction with
hexane (10 mL×6), the solvent was removed in vacuo and
the desired product was obtained. Yield: 100%. GC: purity
97.8%, tR =6.839 min. IR (cm−1): 1183 v(–S–Ar). 1H NMR
(400 MHz, CDCl3) δ (ppm): 2.33 (s, 3H, CH3), 2.38 (s, 3H,
CH3), 7.10–7.23 (m, 8H, Ar–H).
A mixture of Pd(PPh3)4 (0.46 g, 0.40 mmol), bromoben-
zene (1.6 g, 10 mmol) and tolthiol (0.70 g, 6.0 mmol)
were stirred in methanol for 6 h at refux. After cooling,
the solution was fltered, and the fltrate was washed with
water (10 mL × 2) and further extracted with dichlo-
romethane (10 mL × 3). After removal of solvents in
vacuo, a white powder was obtained. Yield: 65%. GC:
purity 95.4%, tR = 6.382 min. IR (cm−1): 1180 v(–S–Ar).
1H NMR (400 MHz, CDCl3) δ (ppm): 2.33 (s, 3H, CH3),
7.12–7.30 (m, 9H, Ar–H).
(3‑Methylphenyl)(4‑Methylphenyl) Sulfde (13S)
The method was similar to that used for 12S, employ-
ing 3-iodotoluene (2.2 g, 10 mmol) instead of 2-iodotoluene.
Yield: 100%. GC: purity 97.3%, tR =6.927 min. IR (cm−1):
Scheme 3 Synthesis of diaryl sulfdes 10S and 11S
Scheme 4 Synthesis of diaryl sulfdes 12S–17S and dibenzyl sulfdes 18S–24S
1 3

Journal of Chemical Crystallography
1178 v(–S–Ar). 1H NMR (400 MHz, CDCl3) δ (ppm): 2.22
(s, 3H, CH3), 2.27 (s, 3H, CH3), 6.89–7.23 (m, 8H, Ar–H).
Dibenzyl Sulfde (19S)
The method was similar to that used for 18S, employing ben-
zyl bromide (1.7 g, 10 mmol) instead of 4-tert-butylben-
zyl bromide. Crystals suitable for X-ray difraction were
obtained by slow evaporation of its dichloromethane/meth-
anol solution (v:v=1:3) at room temperature in four days.
Yield: 100%. GC: purity 100%, tR =4.837 min. IR (cm−1):
835 v(–CH2–S–). 1H NMR (400 MHz, CDCl3) δ (ppm): 3.60
(s, 4H, CH2), 7.22–7.37 (m, 10H, Ar–H).
(2,4‑Dimethylphenyl)(4‑Methylphenyl) Sulfde (14S)
The method was similar to that used for 12S, employ-
ing 2,4-dimethyliodobenzene (2.3 g, 10 mmol) instead
of 2-iodotoluene. Yield: 100%. GC: purity 94.5%,
1
tR = 7.424 min. IR (cm−1): 1180 v(–S–Ar). H NMR
(400 MHz, CDCl3) δ (ppm): 2.31 (s, 6H, CH3), 2.34 (s, 3H,
CH3), 6.94–7.26 (m, 7H, Ar–H).
(2‑Bromobenzyl)Benzyl Sulfde (20S)
(3,5‑Dimethylphenyl)(4‑Methylphenyl) Sulfde (15S)
The method was similar to that used for 18S, employ-
ing 2-bromobenzyl bromide (2.5 g, 10 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 99.0%. GC: purity
The method was similar to that used for 12S, employ-
ing 3,5-dimethyliodobenzene (2.3 g, 10 mmol) instead of
2-iodotoluene. Crystals suitable for X-ray difraction were
obtained by slow evaporation of its dichloromethane/metha-
nol solution (v:v= 1:3) at room temperature in four days.
Yield: 100%. GC: purity 100%, tR =5.168 min. IR (cm−1):
1175 v(–S–Ar). 1H NMR (400 MHz, CDCl3) δ (ppm): 2.25
(s, 6H, CH3), 2.34 (s, 3H, CH3), 6.84–7.28 (m, 7H, Ar–H).
1
99.0%, tR = 6.973 min. IR (cm−1): 839 v(–CH2–S–). H
NMR (400 MHz, CDCl3) δ (ppm): 3.69 (s, 2H, CH2), 3.74
(s, 2H, CH2), 7.11–7.33 (m, 8H, Ar–H), 7.56 (d, J=8.0 Hz,
1H, Ar–H).
(2‑Methylbenzyl)Benzyl Sulfde (21S)
(4‑Ethylphenyl)(4‑Methylphenyl) Sulfde (16S)
The method was similar to that used for 18S, employ-
ing 2-methylbenzyl bromide (1.9 g, 10 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 93.2%. GC: purity 93.2%,
The method was similar to that used for 12S, employ-
ing 1-ethyl-4-iodobenzene (2.3 g, 10 mmol) instead
of 2-iodotoluene. Yield: 100%. GC: purity 99.4%,
1
tR = 5.398 min. IR (cm−1): 833 v(–CH2–S–). H NMR
(400 MHz, CDCl3) δ (ppm): 2.30 (s, 3H, CH3), 3.60 (s, 2H,
CH2), 3.66 (s, 2H, CH2), 7.14–7.32 (m, 9H, Ar–H).
tR = 7.567 min. IR (cm−1): 1181 v(–S–Ar). H NMR
1
(400 MHz, CDCl3) δ (ppm): 1.22 (t, J = 15 Hz,
3H,–CH2CH3), 2.32 (s, 3H, Ar–CH3), 2.65 (q, J = 22 Hz,
2H,–CH2CH3), 7.10–7.13 (m, 4H, Ar–H), 7.23–7.24 (m,
4H, Ar–H).
(3‑Methylbenzyl)Benzyl Sulfde (22S)
The method was similar to that used for 18S, employ-
ing 3-methylbenzyl bromide (1.9 g, 10 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 94.5%. GC: purity 94.5%,
(4‑Methoxyphenyl)(4‑Methylphenyl) Sulfde (17S)
1
tR = 5.304 min. IR (cm−1): 836 v(–CH2–S–). H NMR
The method was similar to that used for 12S, employ-
ing 4-iodoanisole (2.3 g, 10 mmol) instead of 2-iodotoluene.
Yield: 100%. GC: purity 94.7%, tR =5.644 min. IR (cm−1):
(400 MHz, CDCl3) δ (ppm): 2.35 (s, 3H, CH3), 3.58 (s, 2H,
CH2), 3.62 (s, 2H, CH2), 7.13–7.32 (m, 9H, Ar–H).
1
1179 v(–S–Ar), 1253 v(–O–CH3). H NMR (400 MHz,
(4‑Methylbenzyl)Benzyl Sulfde (23S)
CDCl3) δ (ppm): 2.22 (s, 3H, Ar–CH3), 3.73 (s, 3H,–OCH3),
6.78–7.29 (m, 8H, Ar–H).
The method was similar to that used for 18S, employ-
ing 4-methylbenzyl bromide (1.9 g, 10 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 93.5%. GC: purity 93.5%,
(4‑Tert‑Butylbenzyl)Benzyl Sulfde (18S)
1
tR = 5.401 min. IR (cm−1): 835 v(–CH2–S–). H NMR
The method was similar to that used for 12S, employing ben-
zylthiol (1.2 g, 10 mmol) instead of p-toluenethiol, 4-tert-
butylbenzyl bromide (2.3 g, 10 mmol) instead of 2-iodo-
toluene. Yield: 97.5%. GC: purity 97.5%, tR = 6.507 min.
IR (cm−1): 837 v(–CH2–S–). 1H NMR (400 MHz, CDCl3)
δ (ppm): 1.32 (s, 9H, CH3), 3.58 (s, 2H, CH2), 3.61 (s, 2H,
CH2), 7.13–7.32 (m, 9H, Ar–H).
(400 MHz, CDCl3) δ (ppm): 2.36 (s, 3H, CH3), 3.58 (s, 2H,
CH2), 3.61 (s, 2H, CH2), 7.13–7.33 (m, 9H, Ar–H).
Benzyl(1‑Phenylethyl) Sulfde (24S)
The method was similar to that used for 18S, employ-
ing (1-bromoethyl)benzene (1.9 g, 10 mmol) instead of
4-tert-butylbenzyl bromide. Yield: 100%. GC: purity 100%,
1 3

Journal of Chemical Crystallography
tR =4.848 min. IR (cm−1): 835 v(–CH(CH3)–S–). 1H NMR
(400 MHz, CDCl3) δ (ppm): 1.54 (d, J=18 Hz, 3H, CH3),
3.50 (s, 2H, CH2), 3.81 (q, J=14 Hz, 1H, CH), 7.21–7.32
(m, 10H, Ar–H).
thermal parameters, and allowed to ride on their respective
parent carbon atoms before the fnal cycle of least-squares
refnement.
X‑Ray Crystallography
Results and Discussion
A summary of crystallographic data and experimental
details for compounds 2S, 4S, 9S, 11S, 15S, and 19S is
summarized in Table 1. Intensity data were collected on
a Bruker SMART APEX 2000 CCD difractometer using
graphite-monochromated Mo–Kα radiation (λ=0.71073 Å)
at 296(2) K. The collected frames were processed with the
software SAINT [13]. The data was corrected for absorption
using the program SADABS [14]. Structures were solved by
the direct methods and refned by full-matrix least-squares
on F2 using the SHELXTL software package [15, 16]. All
non-hydrogen atoms were refned anisotropically. The posi-
tions of all hydrogen atoms were generated geometrically
(Csp3–H=0.96 Å and Csp2–H=0.93 Å), assigned isotropic
Firouzabadi and coworkers [9] presented a one-pot prepara-
tion of aryl benzyl sulfdes employing CS2 as the sulfur sur-
rogate, and CuI as the catalyst in PEG200. However, PEG200
was expensive and products were difcult to extract from
it. In this paper, PEG400 was used as the dispersant, which
was cheaper and easier to separate than PEG200. Method A:
as shown in Scheme 1, the reaction of diferent substituted
benzyl bromide and iodobenzene in the presence of CS2 at
refux aforded aryl benzyl sulfdes 1S–3S, after repeated
several times, the experiment results showed that the yield
could achieve 67%, comparable to the yields reported by
Firouzabadi (70%). O’Mahony [10] reported the synthesis
of aryl benzyl sulfdes by reacting sodium p-tolylthiolate
Table 1 Crystallographic data and experimental details for complexes
Complex
2S
4S
9S
11S
15S
19S
Empirical formula
Formula weight
Crystal system
a (Å)
C13H12S
200.29
Monoclinic
12.278(3)
15.894(3)
5.6056(11)
C18H22S
270.42
Triclinic
6.0436(10)
8.7871(14)
C15H16S
228.34
Orthorhombic
6.188(3)
8.041(4)
C14H14S
214.31
Orthorhombic
5.835(2)
8.010(3)
25.131(9)
C15H16S
228.34
Monoclinic
9.800(9)
7.950(7)
16.690(15)
C14H14S
214.31
Orthorhombic
14.169(13)
11.476(10)
7.300(7)
b (Å)
c (Å)
15.352(2)
26.005(14)
α (°)
81.921(2)
β(°)
γ (°)
94.532(2)
81.977(2)
80.889(2)
791.2(2)
Pī
100.890(12)
V (Å3)
1090.5(4)
P21/c
4
1.220
296(2)
424
1293.9(12)
P212121
4
1.172
296(2)
488
1174.6(8)
P212121
4
1.212
296(2)
456
1277(2)
P21/c
4
1.188
296(2)
488
1187.0(18)
Pbcn
4
1.199
296(2)
456
Space group
Z
2
Dcalc (g cm−3
)
1.135
296(2)
292
0.190
4922
Temperature (K)
F(000)
μ(Mo-Kα) (mm−1
Total refn
)
0.253
6659
0.221
7761
0.239
7215
0.224
7673
0.236
6327
Independent refn
Rint
2469
0.0233
0.0364, 0.0926
3486
0.0174
0.0408, 0.1047
2931
0.0322
0.0469, 0.1116
2642
0.0232
0.0333, 0.0845
2945
0.0287
0.0486, 0.1389
1336
0.0350
0.0398, 0.1039
R1a,wR2b(I>2σ(I))
R1, wR2 (all data)
0.0486, 0.1006
0.0517, 0.1143
0.0979, 0.1376
0.0399, 0.0892
0.0783, 0.1608
0.0664, 0.1157
GoFc
1.026
1.033
1.024
1.039
1.023
1.021
Flack parameter
–
–
− 0.10(14)
0.04(8)
–
-
/
∑
∑
aR1 =
Fo − F
Fo
��
�
�
��
��
�
�
�
c
��
�
�
�
[
/
]
1∕2
(
)
2
∑
∑
2
�
�
bwR2 =
w
F
− F
2
o
2
2
o
�
�
�
�
�
w F
�
�
�
�
�
�
c
�
[
/
]
1∕2
(
)
∑
2
cGoF =
W
Fo − F
N
− N
�
�
c
param
�
�
obs
1 3

Journal of Chemical Crystallography
with substituted benzyl bromide, the reaction time was 16 h,
and the highest yield was only 50%. We changed the sol-
vent, as shown in Method B (Scheme 2), THF was used as
the solvent, the reaction time shortened to be 8 h, and the
yield of compounds 4S–9S was up to 87%. Migita and cow-
orkers [11] reported a traditional palladium-based catalytic
reaction, and a series of diaryl sulfdes were synthesized
(11%–59%). However, the solvent they used were DMSO
and DMF, which was difcult to remove. In Method C, we
selected methanol as the solvent, which was easy to remove
and much cheaper. As shown in Scheme 3, bromobenzene
and tolthiol were reacted in methanol at refux for 6 h cata-
lyzed by Pd(PPh3)4 aforded diaryl sulfdes 10S and 11S
(60%–65%). Wang and coworkers [12] reported the synthe-
sis of diaryl and dibenzyl sulfdes catalyzed by CuI, PEG1000
was used as the dispersant and K3PO4 was used as the base.
Although PEG1000 was cheaper than PEG400, it also has a
higher viscosity and hard to process. Besides, we found that
when KOH was used as the base, the catalytic efciency
of the reaction was higher. So in Method D, we selected
PEG400 as the dispersant and KOH as the base, as shown in
Scheme 4, reaction of substituted iodobenzene/benzyl bro-
mide and tolthiol/benzylthiol gave diaryl sulfdes 12S–17S
(100%) and dibenzyl sulfdes 18S–24S (93.2%–100%) in
high yields. In addition, the manipulations of Method D
were simple, and the product could be obtained in a one-pot
reaction, which was obviously economical and applicable.
The infrared spectra of aryl benzyl sulfdes 1S–9S and
diaryl sulfides 10S–17S showed–S–Ar peaks at around
1176 cm−1. The aryl benzyl sulfdes 1S–9S and dibenzyl
sulfdes 18S–24S showed–CH2–S–or–CH(CH3)–S–peaks
at about 835 cm−1 [17, 18]. The 1H NMR spectra of com-
pounds 2S–9S, 18S–24S all showed -CH2–S- protons as a
single peak ranging from 4.00–4.21 ppm, which are compa-
rable to those in the related compounds [19]. The signal of
a -CH(CH3)–S- proton in compound 1S showed a doublet
at 1.61 ppm with J=7.2 Hz, while the –CH(CH3)–S- pro-
tons in dibenzyl sulfde 24S showed a doublet at 1.54 ppm
with J=14 Hz. GC analysis showed that the average reten-
tion time of aryl benzyl sulfde compounds (6.840 min) was
normally longer than those of diaryl sulfde compounds
(6.343 min) and dibenzyl sulfde compounds (5.610 min),
and the isomers of 21S, 22S and 23S have almost the same
retention time: 5.398, 5.304 and 5.401 min, respectively,
indicating that o-, m-, or p-positions of a methyl group have
little efect on the retention time of similar compounds.
Molecular structures and packing views of compounds
2S, 4S, 9S, 11S, 15S, and 19S were further confrmed by
single crystal X-ray crystallography, as shown in Figs. 1,
2, 3, 4, 5, 6, respectively. Selected bond lengths and angles
are given in Tables 2, 3, 4, 5, 6, 7. The C(sp2)–S bond
lengths in aryl benzyl sulfdes 2S, 4S and 9S are 1.7606(15),
1.7640(15), 1.752(4) Å, respectively, which are similar to
Fig. 1 a Molecular structure of benzylphenyl sulfde 2S, showing the
atom labeling scheme and 40% thermal ellipsoids. b Packing mode of
compound 2S projected along with bc plane
Fig. 2 a Molecular structure of (4-tert-butylbenzyl)(4-methylphenyl)
sulfde 4S, showing the atom labeling scheme and 40% thermal ellip-
soids. b Packing mode of compound 4S projected along with bc plane
1 3

Journal of Chemical Crystallography
Fig. 3 a Molecular structure of (4-methylbenzyl)(4-methylphenyl)
sulfde 9S, showing the atom labeling scheme and 40% thermal ellip-
soids. b Packing mode of compound 9S projected along with bc plane
Fig. 5 a Molecular structure of (3,5-dimethylphenyl)(4-methylphe-
nyl) sulfde 15S, showing the atom labeling scheme and 40% thermal
ellipsoids. b Packing mode of compound 15S projected along with ac
plane
compared to those in aryl benzyl sulfdes 2S, 4S and 9S. In
dibenzyl sulfde compound 19S, the C(sp3)–S bond length is
1.798(2) Å, which is similar to the same structure reported
by Hansson (1.8098(12) Å) [22]. The C(sp3)–S–C(sp3)
bond angle is 101.67(14)° in dibenzyl sulfde 19S, which
agrees well to those in related dibenzyl sulfdes (101.23(8)o)
[20] and di-4-cyanobenzyl sulfde (101.64°) [23], smaller
than those in aryl benzyl sulfides 2S (103.94(7)°), 4S
(104.58(7)°), 9S (104.84(14)°), and diaryl sulfides 11S
(104.65(8)°), and 15S (104.58(9)°), which may be due to
the steric hindrance of the two benzyl rings.
In summary, twenty-four sulfides were synthesized
1
based on four synthetic methods and characterized by H
NMR, FT-IR and Gas chromatography. Six of the sulfdes
involving diaryl sulfde, aryl benzyl sulfde, and dibenzyl
sulfde compounds were characterized by the single crys-
tal X–ray difraction analysis. Method A employing PEG400
as the dispersant to replace PEG200 could synthesize aryl
benzyl sulfdes 1S–3S in a cheaper and easier way without
decreasing the yields [9]. Method B using the solvent THF
to replace dichloromethane-H2O (v:v=1:1) led to isolation
of aryl benzyl sulfdes 4S–9S with improved yields (87%
vs. 50%) [10]. Method C could be used to synthesize dia-
ryl sulfdes 10S and 11S in better yields by using methanol
Fig. 4 a Molecular structure of di(4-methylphenyl) sulfde 11S,
showing the atom labeling scheme and 40% thermal ellipsoids. b
Packing mode of compound 11S projected along with bc plane
those in analogous compounds [20, 21], and a little shorter
than the corresponding C(sp3)–S bond lengths (1.8039(15)
Å for 2S, 1.8108(16) Å for 4S, 1.760(3) Å for 9S). The aver-
age C(sp2)–S bond lengths are 1.7768(16) Å and 1.768(2)
Å in diaryl sulfdes 11S and 15S, respectively, which are
1 3

Journal of Chemical Crystallography
Table 5 Selected bond lengths (Å) and angles (°) for di(4-methylphe-
nyl) sulfde 11S
S(1)–C(1)
S(1)–C(8)
C(4)–C(7)
C(11)–C(14)
1.7749(17)
1.7786(16)
1.509(2)
C(1)–S(1)–C(8)
C(5)–C(4)–C(7)
C(10)–C(11)–C(14)
104.65(8)
121.93(17)
121.26(16)
1.512(2)
Table 6 Selected bond lengths (Å) and angles (°) for (3,5-dimethyl-
phenyl)(4-methylphenyl) sulfde 15S
S(1)–C(1)
S(1)–C(7)
C(3)–C(14)
C(5)–C(13)
C(10)–C(15)
1.770(2)
1.765(3)
1.504(3)
1.504(3)
1.498(3)
C(7)–S(1)–C(1)
C(4)–C(3)–C(14)
C(6)–C(5)–C(13)
C(9)–C(10)–C(15)
104.58(9)
120.32(19)
121.1(2)
121.3(2)
Table 7 Selected bond lengths (Å) and angles (°) for dibenzyl sulfde
19S
S(1)–C(1)
S(1)–C(1A)
C(1)–C(2)
1.798(2)
1.798(2)
1.507(2)
C(1)–S(1)–C(1A)
C(2)–C(1)–S(1)
101.67(14)
114.87(11)
as the solvent [11]. Method D using PEG400 and KOH to
replace PEG1000 and K3PO4 is an efcient method to synthe-
size diaryl sulfdes 12S–17S and dibenzyl sulfdes 18S–24S
due to its quantitative yield and environment friendly [12].
Fig. 6 a Molecular structure of dibenzyl sulfde 19S, showing the
atom labeling scheme and 40% thermal ellipsoids. b Packing mode of
compound 19S projected along with ac plane
Table 2 Selected bond lengths (Å) and angles (°) for benzylphenyl
sulfde 2S
Supplementary Material
S(1)–C(1)
S(1)–C(8)
C(1)–C(2)
1.8039(15)
1.7606(15)
1.507(2)
C(8)–S(1)–C(1)
C(2)–C(1)–S(1)
103.94(7)
108.92(10)
Crystallographic data for a summary of crystallographic
data and experimental details for benzylphenyl sulfde (2S),
(4-tert-butylbenzyl)(4-methylphenyl) sulfde (4S), (4-meth-
ylbenzyl)(4-methylphenyl) sulfde (9S), di(4-methylphenyl)
sulfde (11S), (3,5-dimethylphenyl)(4-methylphenyl) sulfde
(15S) and dibenzyl sulfde (19S) have been deposited with
the Cambridge Crystallographic Data Centre as supplemen-
tary publication nos. CCDC 2001056-2001061, respectively.
Copies of the data can be obtained free of charge on applica-
tion to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
[fax: (+44)1233-336-033; e-mail: deposit@ccdc.cam.ac.uk].
Table 3 Selected bond lengths (Å) and angles (°) for (4-tert-butylb-
enzyl)(4-methylphenyl) sulfde 4S
S(1)–C(1)
S(1)–C(12)
C(1)–C(2)
C(5)–C(8)
C(8)-C(9)
C(14)-C(15)
1.8108(16)
1.7640(15)
1.502(2)
1.528(2)
1.535(2)
1.387(2)
C(12)–S(1)–C(1)
C(2)–C(1)–S(1)
C(4)–C(5)–C(8)
C(10)–C(8)–C(9)
C(14)–C(15)–C(18)
104.58(7)
107.57(11)
119.67(13)
109.20(15)
121.10(16)
Acknowledgements This project was supported by the National Natu-
Table 4 Selected bond lengths (Å) and angles (°) for (4-methylben-
zyl)(4-methylphenyl) sulfde 9S
ral Science Foundation of China (21372007).
S(1)–C(1)
S(1)–C(8)
C(4)–C(7)
C(8)–C(9)
C(12)–C(15)
1.752(4)
1.760(3)
1.524(4)
1.499(4)
1.517(4)
C(8)–S(1)–C(1)
C(2)–C(1)–S(1)
C(3)–C4)–C(7)
C(9)–C(8)–S(1)
C(11)–C(12)–C(15)
104.84(14)
117.1(2)
120.4(3)
110.2(2)
122.2(3)
Compliance with Ethical Standards
Conflict of Interests The authors declare that they have no confict of
interests.
1 3

Journal of Chemical Crystallography
14. Sheldrick GM (1996) Sadabs. University of Göttingen, Göttingen,
Germany
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Afliations
Wen‑Yan Zhou1 · Min Chen1 · Pei‑Zhi Zhang1 · Ai‑Quan Jia1 · Qian‑Feng Zhang1
1
* Qian-Feng Zhang
Institute of Molecular Engineering and Applied Chemistry,
ahutchang@yahoo.com; zhangqf@ahut.edu.cn
Anhui University of Technology, Ma’anshan, Anhui 243002,
People’s Republic of China
1 3