Synthesis of sec-butyl disulfide by phase transfer catalysis

Article abstract of DOI:10.14233/ajchem.2015.18395

Sec-Butyl disulfide was synthesized from sulfur?sodium hydroxide and sec-butyl chloride using tetrabutyl ammonium bromide as the phase transfer catalyst. The optimal experiment condition obtained by orthogonal design and the average product yield was 84.95 %. The samples synthesized under optical conditions were characterized by infrared spectrometry?gas chromatography-mass spectrometer.

Full text of DOI:10.14233/ajchem.2015.18395

Asian Journal of Chemistry; Vol. 27, No. 9 (2015), 3208-3210
A
SIAN
J
OURNAL OF HEMISTRY
C
http://dx.doi.org/10.14233/ajchem.2015.18395
Synthesis of sec-Butyl Disulfide by Phase Transfer Catalysis
1
2
3
2,*
XINQI LIU , JIA WANG , SONGFANG ZHAO and GUOQIN HU
1
2
3
Henan Vocational College of Chemical Technology, Zhengzhou 450042, Henan Province, P.R. China
College of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, Henan Province, P.R. China
Henan Province Engineering Technology Research Center of sulfhydryl compounds, Sanmenxia 472100, Henan Province, P.R. China
*
Corresponding author: Tel/Fax: +86 371 67781712; E-mail: huguoqin@zzu.edu.cn
Received: 2 July 2014; Accepted: 15 September 2014; Published online: 26 May 2015;
AJC-17225
sec-Butyl disulfide was synthesized from sulfur, sodium hydroxide and sec-butyl chloride using tetrabutyl ammonium bromide as the
phase transfer catalyst. The optimal experiment condition obtained by orthogonal design and the average product yield was 84.95 %. The
samples synthesized under optical conditions were characterized by infrared spectrometry, gas chromatography-mass spectrometer.
Keywords: Phase transfer catalysis, Alkyl halide, sec-Butyl disulfide, Orthogonal experiment.
Jiangsu Zhongda Instrument Factory) ; RE-52AA rotary
evaporator (Haiya Wing instrument); SHB-III type multi-
purpose water circulating pump (Zhengzhou GreatWall Industry
and Trade Co., Ltd.); WQF-510 infrared spectrometer (Beijing
Rayleigh Analytical instrument Corporation); GPC-GCMS
type GC-MS (Shimadzu Corporation); 202 electric oven
INTRODUCTION
sec-Butyl disulfide is an important fine chemical inter-
mediates used in thiosulfinates sulfur and oxygen compounds
synthesized simultaneously with pesticides, biology, materials,
petrochemicals, dyes and food science wide range of uses. In
recent years, with the expansion of downstream products, di-
sec-disulfide market demand is increasing year by year, attracted
wide attention at home and abroad.
(
Shanghai electro-optical instrument Factory).
Chlorinated secondary butane (99 %), nine water sulfide,
1-7
sulfur sublimation, chloroform, anhydrous sodium sulfate,
tetrabutylammonium bromide were of analytical grade.
Synthesis: In 100 mL three-necked flask equipped with
a thermometer and a stirring motor, the measurement was
added sodium sulfide, sulfur powder and distilled water, 50 °C
water bath with stirring 40 min, the mixture became a red-
brown solution is sodium bisulfite solution (easily oxidized
should now with the current).
In the above measurement was added a freshly prepared
solution of sodium sulfide and chlorinated butane secondary
phase transfer catalyst, the reaction was refluxed under constant
stirring, the reaction is followed by gas chromatography.
The reaction was allowed to stand stratification, the upper
organic phase was yellow, orange lower aqueous phase. The
aqueous phase was extracted three times with a small amount
of chloroform and the combined organic phase was washed
three times with distilled water and removal of inorganic salts,
plus a certain amount of anhydrous sodium sulfate and left
for 5 h, filtered to give a pale yellow or colourless two-butyl
disulfide The crude product. After distillation under reduced
pressure, followed by a two-butyl sulfide, disulfide and trisulfide.
Combination of all the literature , di-sec-disulfide synthesis
of different materials are divided into: thiol method, 1,3-buta-
diene method, Grignard reagent and halogenated hydrocarbons
law. Currently, the largest reported in the literature is the
mercaptan as raw materials, but especially in low-carbon chain
thiol mercaptan fetid, volatile, pollution, corrosive, so the
industry is generally not used for this synthesis.
The authors focus on research halogenated hydrocarbons
as raw material, phase transfer catalysis synthesis of butyl
disulfide. Pre-emphasis to the sec-bromine as raw materials
8,9
to carry out research work . Butyl bromide activity is high,
but the price is expensive and difficult byproduct sodium
bromide recovery. Therefore, the authors focused on readily
available and inexpensive raw material of butyl chloride as
raw materials, tetrabutylammonium bromide as a phase transfer
catalyst synthesis of butyl disulfide.
EXPERIMENTAL
AB204-N-type electronic analytical balance (Mettler-
Toledo Instruments Co., Ltd.); JJ-1 electric blender (Jiangsu-
jintan Shuangjie Instrument); HH-type water bath (Jintan City,

Vol. 27, No. 9 (2015)
Synthesis of sec-Butyl Disulfide by Phase Transfer Catalysis 3209
RESULTS AND DISCUSSION
Orthogonal test results: Impact of n(Na
temperature, reaction time on the yield of di-sec-disulfide: The
experimental study focused on the amount of catalyst, water
2
S), reaction
8
0
0
0
790
usage, n(S): n(C
4
9
H Cl), n(S). Therefore, the present study L25
1
280
377
458
6
(
5 ) orthogonal arrangement to the yield of di-sec-disulfide
measure. The results are shown in Table-1.
As can be seen from the size range R, R larger the value
the greater the impact on the experiment, so the impact of
factors affecting the order of the experiment: the amount of
1
1
4
2874
2924
catalyst > time > n (S): n(C
of water > reaction temperature, the best combination of the
experiment is A
4 9
H Cl) > n(S ): n(Na
2
S) > amount
2964
B
5 2
4 2
C D E
3 4
F .
Experimental results under optimized conditions:
Obtained by orthogonal experiment optimum synthesis condi-
tions, in accordance with 1 optimization in the experimental
program was repeated twice, yields were 84.9 and 85 %. The
results showed that under the optimal combination of process
scheme for the synthesis target product, the average yield of
the product reached 84.95 %. Orthogonal table above yields a
set of experiments yield either to verify the correctness and
accuracy of the experimental results.
4
000
3500
3000
2500
Wavenumber (cm )
Fig. 1. FT-IR spectrum of sec-butyl disulfide
2000
1500
1000
500
–1
-
1
stretching vibration; 2924 and 790 cm , respectively for
methylene base in CH bond asymmetric stretching vibration
peak and peak plane rocking; 1280 as bending vibration of
methylene CH bond. This is consistent with the standard
10
second-butyl disulfide pattern .
Infrared spectroscopy: Fig. 1 shows bands at 2964,
-1
Gas chromatography-mass spectrometry: The reaction
product obtained was diluted with methanol in a volume ratio
of 50 times, for the GC-MS analysis. Gas chromatographic
2
874, 1458 and 1377 cm , respectively for methyl CH bond
asymmetric stretching vibration peak, symmetric stretching
vibration, bending vibration of antisymmetric and symmetric
TABLE-1
RESULTS OF ORTHOGONAL DESIGN (L25 5 )
6
Entry
A
2.5
2.5
2.5
2.5
2.5
3
3
3
3
3
3.5
3.5
3.5
3.5
3.5
4
4
4
4
4
4.5
4.5
4.5
4.5
4.5
69..3
75.46
77.62
77.68
81.5
12.2
B
4
5
6
7
8
4
5
6
7
8
4
5
6
7
8
4
5
6
7
8
4
5
6
7
C
D
E
43
46
49
52
55
52
55
43
46
49
46
49
52
55
43
55
43
46
49
52
49
52
55
43
F
7.5
8.5
9.5
10.5
11.5
11.5
7.5
8.5
9.5
10.5
10.5
11.5
7.5
8.5
9.5
Yield (%)
66.7
68.7
73.8
77.6
59.71
68.7
77.7
68.0
78.1
84.8
75.8
84.7
74.4
76.0
77.4
82.4
80.8
78.3
69.2
77.7
75.2
81.7
84.8
84.4
81.4
-
1
2
3
4
5
6
7
8
9
0.725:1
0.75:1
0.775:1
0.8:1
0.825:1
0.75:1
0.775:1
0.8:1
0.825:1
0.725:1
0.775:1
0.8:1
0.825:1
0.725:1
0.75:1
0.8:1
0.825:1
0.725:1
0.75:1
0.775:1
0.825:1
0.725:1
0.75:1
0.775:1
0.8:1
0.51:1
0.53:1
0.55:1
0.57:1
0.59:1
0.55:1
0.57:1
0.59:1
0.51:1
0.53:1
0.59:1
0.51:1
0.53:1
0.55:1
0.57:1
0.53:1
0.55:1
0.57:1
0.59:1
0.51:1
0.57:1
0.59:1
0.51:1
0.53:1
0.55:1
78.4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
9.5
10.5
11.5
7.5
8.5
8.5
9.5
10.5
11.5
7.5
73.86
71.98
78.5
80.76
75.16
8.78
8
46
Mean value 1
Mean value 2
Mean value 3
Mean value 4
Mean value 5
Range R
73.76
78.72
75.84
77.06
76.18
4.96
77.5
73.74
77.88
78.82
73.62
5.2
75.44
76.46
77.54
76
76.12
2.1
78.92
76.14
77.22
70.88
8.04
-
-
-
-
-
A
B
C
D
E
F
Amount of catalyst used (%); Amount of water (g); n(S):n(Na S); n(S):n(C H Cl); Reaction temperature (°C); Reaction time/h
2
4
9

3
210 Liu et al.
Asian J. Chem.
%
61
100
117
50
41
146
55
75
89
131
147
150.0
9
6
207
200.0
281
0
50.0
75.0
100.0
125.0
175.0
225.0
250.0
275.0
%
57
100
50
122
41
178
39
61
88 93
180
175.0
7
3
107
117
135
149
150.0
207
0
50.0
75.0
100.0
125.0
200.0
%
57
100
89
50
41
210
9
8
154
39
61
7
3
105
117 122
125.0
145
0
50.0
75.0
100.0
150.0
175.0
200.0
Fig. 2. GC-MS spectrum of sec-butyl disulfide
conditions described above, the MS conditions: Ion source
EI, the ionization voltage of 70 eV, ion source temperature
was 200 °C, scan range of 30-300 m/z.
Fig. 2 followed by retention time in the gas phase spectra
from short to long sequence of spectra of each peak, the system
searches through the mass of data, were recognized as two
sec-sulfide, di-sec-butyl disulfide and two three sulfide.
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2
S) = 0.775:1, n(S ): n(C
4 9
H Cl) =
3
0.53:1, temperature 49 °C, reaction time of 10.5 h. The experi-
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was 84.95 %. The product of infrared spectroscopy, gas-mass
spectrometry to characterize the experimental results agree
with the standard.
(
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