Green synthesis of thiiranes from oxiranes under solvent- and catalyst-free conditions

Article abstract of DOI:10.1080/17415993.2012.678495

A simple and efficient method for the conversion of oxiranes to thiiranes using ammonium thiocyanate (NH₄SCN) under solvent- and catalyst-free conditions is described. These conditions enable clean and fast conversion of oxiranes to the corresponding thiirane.

Full text of DOI:10.1080/17415993.2012.678495

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Green synthesis of thiiranes from
oxiranes under solvent- and catalyst-
free conditions
Batool Akhlaghinia a , Mohammad Rahimizadeh a , Hosein Eshghi a
Sara Zhaleh a & Soodabeh Rezazadeh a
,
a Department of Chemistry, Faculty of Sciences, Ferdowsi
University of Mashhad, Mashhad, 9177948974, Iran
Version of record first published: 04 May 2012.
To cite this article: Batool Akhlaghinia , Mohammad Rahimizadeh , Hosein Eshghi , Sara Zhaleh &
Soodabeh Rezazadeh (2012): Green synthesis of thiiranes from oxiranes under solvent- and catalyst-
free conditions, Journal of Sulfur Chemistry, 33:3, 351-361
To link to this article: http://dx.doi.org/10.1080/17415993.2012.678495
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Journal of Sulfur Chemistry
Vol. 33, No. 3, June 2012, 351–361
Green synthesis of thiiranes from oxiranes under solvent- and
catalyst-free conditions
Batool Akhlaghinia*, Mohammad Rahimizadeh, Hosein Eshghi, Sara Zhaleh and Soodabeh
Rezazadeh
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad 9177948974,
Iran
(Received 13 December 2011; final version received 18 March 2012)
A simple and efficient method for the conversion of oxiranes to thiiranes using ammonium thiocyanate
(NH4SCN) under solvent- and catalyst-free conditions is described. These conditions enable clean and fast
conversion of oxiranes to the corresponding thiirane.
S
60-90 oC
O
R2
R3
R2
R3
H
H
+ NH4SCN
+ H4NOCN
R1
R1
1-20
Keywords: oxirane; thiirane; catalyst-free; solvent-free; ammonium thiocyanate
1. Introduction
Organic sulfur compounds have become increasingly useful and important in organic synthesis.
Thiiranes, which are the simplest sulfur heterocycles, are important and useful building blocks
for the synthesis of polymers, pharmaceuticals, pesticides, and herbicides (1, 2). Various methods
have been developed for the synthesis of thiiranes. The most general procedure for the synthesis of
thiiranes is the conversion of epoxides by an oxygen–sulfur exchange reaction with thiourea (3),
inorganic thiocyanates (4), Dowex-50WX8-supported thiourea (5), and polymer-supported thio-
cyanates (6). Along with each of these sulfur transfer reagents, a protic acid such as Mg(HSO4)2
(3g), etidronic acid (7), oxalic acid (4k), SiO2-HBF4 (4d) or a Lewis acid such as NH4Cl (3a),
Al(DS)3 · 3H2O (3b), SiO2-AlCl3 (3c), LiBF4 (3h), RuCl3 (3i), SbCl3 (3j), montmorillonite K-10
(3k), I2 (4a), LiClO4 (4b), SnIV (TPP)(BF4)2 (4c), 2,4,6-trichloro-1,3,5-triazine (4f ), TiO2 (4g),
SnIV (TPP)(OTf)2 (4h), InBr3 (4l), Bi(TFA)3 (4m), Bi(OTf)3 (4m), BiCl3 (4n), TiO(CF3CO2)2
*Corresponding author. Email: akhlaghinia@um.ac.ir
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2012 Taylor & Francis
http://dx.doi.org/10.1080/17415993.2012.678495
http://www.tandfonline.com

352 B. Akhlaghinia et al.
(4o), TiCl3(CF3SO3) (4o), ceric ammonium nitrate (4p), metalloporphyrins, (4q, 4r, 4s), SiO2-Cl
(4t) and ionic liquid (8) is employed.
However, some of these methods suffer from drawbacks such as long reaction times, high
temperatures, low yields of the products, use of organic solvents, the need to use aqueous and/or
alcoholic media, use of highly acidic catalysts, rapid increase of pH during the reaction, difficulties
in the separation of the product from the original reactant and catalyst, formation of polymeric
byproducts, high catalytic loading, and, in most of the cases, the use of an expensive (4g, 9)
and unrecoverable catalyst. Also the toxicity and volatility of many organic solvents, particularly
chlorinated hydrocarbons that are widely used in organic synthesis, have posed a serious threat to
the environment. Consequently, methods that successfully minimize use of catalysts and solvents
are the focus of much attention. In this paper, we wish to report an improved, efficient, and easy
synthesis of thiiranes from oxiranes that is environmental-friendly and more economical than
previously reported procedures. This new method produces thiiranes in high yields under solvent-
and catalyst-free conditions from the reaction of oxiranes with ammonium thiocyanate.
2. Results and discussion
Herein, we report a novel and simple solvent- and catalyst-free method for conversion of oxiranes
to thiiranes (Scheme 1).
The optimum reaction parameters, shown in Scheme 1, were chosen after examining a variety
of reaction factors. In a set of experiments, the reaction of styrene oxide as a model substrate with
ammonium thiocyanate was studied in different solvents in the absence of any catalyst. 2-Phenyl
thiirane was not obtained when the reaction was performed in dichloromethane, chloroform,
nitromethane, and1,4-dioxaneatroomtemperature(Table 1, Entries1–4). Underthesamereaction
S
60-90 oC
O
R2
R3
R2
R3
H
H
+ NH4SCN
+ H4NOCN
R1
R1
1-20
1-17 :
R1 = Ph, PhOCH2, 4-CNC6H4OCH2, 4-NO2C6H4OCH2, 4-FC6H4OCH2, 4-ClC6H4OCH2,
4-BrC6H4OCH2, 4-tert-BuC6H4OCH2, 2-tert-Bu-4-MeC6H4OCH2,2-Me-4-tert-BuC6H4OCH2,
1-naphthylOCH2 , 2-naphthylOCH2 , CH3(CH2)3., ClCH2 ,CH2CHCH2OCH2, (CH3)2CHOCH2,
CH2CH(CH3)CO(CH2)2
R2 = R3 = H
18-20 :
cyclohexeneoxide , 1-methylcyclohexeneoxide , trans-stilbeneoxide
Scheme 1. Conversion of oxiranes to thiiranes under solvent- and catalyst-free condition.

Journal of Sulfur Chemistry 353
Table 1. Conversion of styrene oxide to 2-phenyl thiirane in various solvents, different molar ratios of H4NSCN/styrene
oxide, and different temperatures.
Molar ratio of
NH4SCN/ styrene oxide
Entry
Solvent
Temp. (◦C)
Time
Conversion %a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Nitromethane
Dichloromethane
Chloroform
1,4-Dioxane
Acetone
Acetonitrile
Tetrahydrofuran
–
Dichloromethane
Chloroform
1,4-Dioxane
Acetone
Acetonitrile
Tetrahydrofuran
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
Nitromethane
–
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1.5/1
1.2/1
1.5/1
2/1
2/1
3/1
4/1
1/1
1/1
2/1
1/1
1/1
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
90
80
90
80
80
24 h
24 h
24 h
24 h
24 h
24 h
24 h
6.5 h
24 h
24 h
24 h
24 h
24 h
20 h
20 min
30 min
45 min
10 min
30 min
25 min
5 min
17 min
17 min
15 min
4 h
0
0
0
0
20
40
50
100
0
0
0
60
90
100
100
100
100
100
100
100
100
100
100
100
100
0
90
80
80
80
65
55
90
90
24 h
15 min
15 min
60 min
100
100
100
–
–
75
conditions when the reaction was performed in acetone, acetonitrile, and tetrahydrofuran, 20–50%
of 2-phenyl thiirane was produced (Table 1, Entries 5–7). At room temperature and under solvent-
free conditions, styrene oxide was completely converted to 2-phenyl thiirane after 6.5 h (Table 1,
Entry 8).
To improve styrene oxide conversion, the effect of temperature was examined in all of
the solvents mentioned above. No product was obtained in dichloromethane, chloroform, and
1,4-dioxane after 24 h even at reflux (Table 1, Entries 9–11). However, in refluxing acetone, ace-
tonitrile, and tetrahydrofuran, conversion of styrene oxide to 2-phenyl thiirane was improved
significantly (Table 1, Entries 12–14).
Refluxing nitromethane surprisingly provides an efficient medium for conversion of styrene
oxide to 2-phenyl thiirane in a short reaction time (Table 1, Entry 15). Consequently, the effect
of temperature and of the molar ratio of H4NSCN/styrene oxide was studied in nitromethane
(Table 1, Entries 16–26). Lowering the temperature increased the reaction time (e.g. compare
Entry 16 with 17), which when the molar ratios of H4NSCN/styrene oxide were increased (e.g.
compare Entry 16 with 21), the reaction was completed in a shorter reaction time. The best result
was obtained at 90◦C with a 2/1 molar ratio of H4NSCN/styrene oxide in nitromethane (Table 1,
Entry 21). Finally, the optimized conditions (90◦C and 2/1 molar ratio of H4NSCN/styrene
oxide) were used with our new solvent-free reaction conditions (Table 1, Entry 27). Styrene
oxide in the presence of H4NSCN was completely converted to 2-phenyl thiirane with a 2/1
molar ratio of H4NSCN/styrene oxide at 90◦C under these solvent- and catalyst-free conditions.
Decreasing the molar ratio of H4NSCN/styrene oxide at the same temperature has no effect on

354 B. Akhlaghinia et al.
Table 2. Conversion of different oxiranes to thiiranes under solvent- and catalyst-free conditions.
Entry
1
Substrate
Producta
Temp (◦C)
90
Time
Isolated yield%
98
O
S
15 min
S
O
O
O
2
3
90
90
15 min
9 min
96
97
S
O
O
O
NC
NC
O
S
O
O
4
5
6
7
8
90
90
90
90
90
7 min
10 min
11 min
13 min
15 min
98
98
94
96
93
O2N
O2N
O
S
O
O
F
F
O
O
S
S
O
O
O
O
Cl
Br
Cl
Br
O
O
S
O
O
S
O
O
9
10
11
90
90
90
18 min
17 min
10 min
95
95
O
S
O
O
O
S
O
O
98
(Continued)

Journal of Sulfur Chemistry 355
Table 2. Continued
Entry
12
Substrate
Producta
Temp (◦C)
90
Time
8 min
Isolated yield%
95
S
O
O
O
S
O
13
14
60
65
22 min
15 min
97
96
O
S
Cl
Cl
O
S
15
16
65
65
14 min
20 min
98
95
O
O
O
O
S
O
O
O
17
65
12 min
96
O
S
18
19
60
60
25 min
2 h
93
90
O
S
Ph
Ph
O
S
Ph
Ph
O
S
20
60
40 min
98
aThe products were identified by the comparison of its physical constants, IR and NMR spectral data with those of an authentic sample
(see Supplementary material).
the reaction time (compare Entries 27 and 28). On the basis of these data, the best molar ratio
of H4NSCN/styrene oxide is 1/1 at 90◦C, under solvent- and catalyst-free conditions, for the
formation of 2-phenyl thiirane (Table 1, Entry 28). According to the data in Table 1, it seems that
conversion of styrene oxide to 2-phenyl thiiranes under solvent- and catalyst-free conditions is
very sensitive to temperature (e.g. compare Entries 28 and 29).
The reaction of different oxiranes with ammonium thiocyanate was also studied under solvent-
and catalyst-free conditions at 90◦C (Table 2). As a result of the low boiling points of the aliphatic
oxiranes, the reaction temperatures were lowered to 60–65◦C (Table 2, Entries 13–20).
With these optimized solvent- and catalyst-free conditions, a wide variety of different aryl
and alkyl oxiranes react with ammonium thiocyanate to provide an efficient conversion to the
corresponding thiiranes with 100% conversions. According to the data in Table 2, this method
is efficient in conversion of monosubstituted, disubstituted, and trisubstituted oxiranes to the
corresponding thiiranes.
Although various methods for the preparation of thiiranes have been extensively reported, this
type of results for reactions on optical active epoxides is very rare (14, 15). The conversion of

356 B. Akhlaghinia et al.
optically active styrene oxide to 2-phenyl thiirane using NH4SCN is studied under solvent- and
catalyst-free conditions. When we reacted optically active (R) - (+) styrene oxide with ammonium
thiocyanate by applying a 1/1 molar ratio of NH4SCN/styrene oxide at 90◦C, 2-phenyl thiirane
(styrene episulfide) was obtained in 98% yield with 0% optical purity (Scheme 2).
The mechanism of these transformations is not clear. We believe that nucleophilic attack of
thiocyanate ions opens the epoxide ring and leads to formation of I. Subsequently, intramolecular
nucleophilic attack of oxygen at the nitrile carbon will give a five-membered ring interme-
diate II which then opens to III. Finally, intramolecular nucleophilic substitution with the
negatively charged sulfur leads to the formation of thiirane and cyanate ions (Scheme 3). The
result of Scheme 2 suggests that the nucleophilic attack is performed on two equally stable con-
formers of intermediate III. However, further mechanistic studies are required to confirm this
mechanism.
The present method has the following advantages: the procedure is simple, the reaction times are
short, the workup is easy, and the yield of thiiranes is high. Most importantly, it can be performed
with a wide range of oxiranes with any kind of functional groups under solvent- and catalyst-free
conditions.
Ph
H
Ph
H
+
H4NSCN
S
O
racemic mixture
( R ) - ( + )
Scheme 2. Conversion of optically active (R) - (+) styrene oxide to a racemic mixture of styrene
episulfide.
NH4
O
O
NH4 SCN
S
C N
R
R
I
OCN
CH
R
N
O
CH
S
S
NCO
R
S
R
II
III
III
S
+ H4N OCN
R
Scheme 3. The proposed mechanism of the conversion of oxiranes to thiiranes.

Journal of Sulfur Chemistry 357
3. Experimental
3.1. General
The products were purified by column chromatography. The purity determinations of the products
were accomplished by TLC on silica gel polygram STL G/UV 254 plates. The melting points of
the products were determined with an Electrothermal Type 9100 melting point apparatus. The FT-
IR spectra were recorded on anAvatar 370 FT-IR Therma Nicolet spectrometer. The NMR spectra
were provided on Brucker Avance 100 and 400 MHz instruments in CDCl3. All of the products
1
were known compounds and characterized by the IR and H NMR spectra and comparison of
their melting points (or those of the derivatives) with known compounds. Different structurally
oxiranes were prepared and purified by the method described previously (10). Elemental analyses
were performed using a Elementar, Vario EL III instrument. Mass spectra were recorded with a
Shimadzu GC-17A&MS-QP5050instrument at 70 eV; in m/z (rel.%). The optical rotation was
determined using a Atabo AP300 polarimeter.
3.2. Typical procedure for conversion of styrene oxide to 2-phenyl thiirane
Ammonium thiocyanate (0.0761 g, 1 mmol) was added to styrene oxide (0.1202 g, 1 mmol) in a
round-bottomed flask equipped with a condenser. The reaction mixture was stirred magnetically
at 90◦C. The progress of the reaction was followed by TLC. Upon completion of the reaction, the
viscousmasswassubjectedto silicagel flashcolumnchromatographyusing n-hexane/ethylacetate
(20/1) as an eluent. 2-Phenyl thiirane was obtained in 98% yield (0.1334 g) after removing the
solvent under reduced pressure.
2-phenyl thiirane (Table 2, Entry 1)
1
Oil (4n). IR (neat, cm−1) ν: 3060, 3027, 2963, 1490, 1454, 1261, 1073, 801, 761, 695, 610. H
NMR (400 MHz CDCl3, 25◦C, ppm) δ: 7.35 (m, 5H), 3.95 (t, 1H, J = 6.0 Hz), 2.92 (dd, 1H,
J = 6.4 Hz, J = 1.2 Hz), 2.71 (dd, 1H, J = 5.2 Hz, J = 1.2 Hz). 13C NMR (100 MHz, CDCl3,
25◦C, ppm) δ: 139.2, 128.7, 127.7, 126.8, 36.2, 27.5.
2-(Phenoxymethyl)thiirane (Table 2, Entry 2)
Oil (4n). IR (neat, cm−1) ν: 3060, 3039, 2921, 2872, 1599, 1496, 1243, 1034, 754, 691. 1H NMR
(400 MHz, CDCl3, 25◦C, ppm) δ: 7.36 (t, 2H, J = 8.0 Hz), 7.04 (t, 1H, J = 8.0 Hz), 6.98 (dd, 2H,
1H, J = 8.8 Hz, J = 0.8 Hz), 4.26 (dd, 1H, J = 10.0 Hz, J = 5.6 Hz), 395 (dd, 1H, J = 10.0 Hz,
J = 6.8 Hz), 3.33(q, 1H, J = 5.6 Hz), 2.66 (d, 1H, J = 6 Hz), 2.38 (dd, 1H, J = 5.2 Hz, J =
1.2 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 158.5, 129.6, 121.3, 114.8, 72.6, 31.5, 24.1.
2-((4-Cyanophenoxy)methyl)thiirane (Table 2, Entry 3)
1
IR (KBr, cm−1) ν: 3096, 2982, 2932, 2217, 1605, 1509, 1300, 1259, 1177, 1024, 843. H NMR
(400 MHz, CDCl3, 25◦C, ppm) δ: 7.60 (d, 2H, J = 8.8 Hz), 6.97 (d, 2H, J = 8.8 Hz), 4.21 (dd,
1H, J = 10 Hz, J = 6 Hz), 4.04 (dd, 1H, J = 10 Hz, J = 6.8 Hz), 3.29 (q, 1H, J = 6 Hz), 2.65 (d,
1H, J = 6 Hz), 2.36 (dd, 1H, J = 4.80 Hz, J = 1.2 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm)
δ: 161.6, 134.1, 119.1, 115.3, 104.5, 72.8, 30.9, 23.7. EI-MS: m/z 192 (M+); Elemental analysis
data: C%: 62.90 (calc. 62.8); H%: 4.60 (calc. 4.74); N%: 7.36 (calc. 7.32); S%: 16.5 (calc. 16.70).

358 B. Akhlaghinia et al.
2-((4-Nitrophenoxy)methyl)thiirane (Table 2, Entry 4)
m.p. 93.5◦C, Lit. (11): 93◦C. IR (KBr, cm−1) ν: 3113, 3076, 2917, 1597, 1511, 1343, 1262, 1180,
1021, 849, 755. 1H NMR (400 MHz, CDCl3, 25◦C, ppm) δ: 8.22 (dd, 2H, J = 10.4 Hz,
J = 3.2 Hz), 6.99 (d, 2H, J = 8 Hz),4.27 (dd, 1H, J = 10.0 Hz, J = 5.6 Hz), 4.09 (dd,
1H, J = 10.0 Hz, J = 6.8 Hz), 3.31 (q, 1H, J = 6.0 Hz), 2.67 (d, 1H, J = 6.4 Hz),
2.38 (dd, 1H, J = 5.2 Hz, J = 1.6 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ:
163.3, 141.8, 126.0, 114.6, 73.1, 30.8, 23.7.
2-((4-Fluorophenoxy)methyl)thiirane (Table 2, Entry 5)
IR (neat, cm−1) ν: 3053, 2992, 2926, 2871, 1505, 1467, 1208, 1097, 1049, 1033, 827, 763. 1H
NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 7.04–6.98 (m, 2H), 6.91–6.86 (m, 2H), 4.17 (dd, 1H,
J = 10.0 Hz, J = 6.0 Hz), 3.92 (dd, 1H, J = 10.4 Hz, J = 7.2 Hz), 3.28 (q, 1H, J = 6.0 Hz),
2.63 (d, 1H, J = 6 Hz), 2.34 (t, 1H, J = 4 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ:
154.59, 154.57, 116.1, 115.9, 73.4, 31.4, 23.8. EI-MS: m/z 184 (M+); Elemental analysis data:
C%: 58.28 (calc. 58.62); H%: 4.73 (calc. 4.92); S%: 17.28 (calc. 17.40).
2-((4-Chlorophenoxy)methyl)thiirane (Table 2, Entry 6)
Oil (11). IR (neat, cm−1) ν: 3068, 2986, 2925, 1597, 1589, 1491, 1245, 1098, 1012, 820. 1H NMR
(400 MHz, CDCl3, 25◦C, ppm) δ: 7.28 (t, 2H, J = 8.8 Hz), 6.87 (d, 2H, J = 8.8 Hz), 4.18 (dd,
1H, J = 10.0 Hz, J = 5.6 Hz), 3.93 (dd, 1H, J = 10.0 Hz, J = 6.8 Hz), 3.28 (q, 1H, J = 6.0 Hz),
2.64 (d, 1H, J = 6.0 Hz), 2.35 (d, 1H, J = 5.2 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ:
157.0, 129.5, 126.2, 116.0, 72.9, 31.2, 23.9.
2-((4-Bromophenoxy)methyl)thiirane (Table 2, Entry 7)
Oil (11). IR (neat, cm−1) ν: 3072, 2990, 2925, 1588, 1488, 1284, 1243, 1173, 1030, 821. 1H NMR
(100 MHz, CDCl3, 25◦C, ppm) δ: 7.44 (d, 1H, J = 5 Hz), 7.38 (d, 1H, J = 5 Hz), 6.85 (d, 1H,
J = 4 Hz), 6.77 (d, 1H, J = 4 Hz), 4.15 (dd, 1H, J = 10 Hz, J = 5 Hz), 3.90 (dd, 1H, J = 10 Hz,
J = 5 Hz), 3.28 (q, 1H, J = 5 Hz), 2.61 (dd, 1H, J = 5 Hz, J = 2.5 Hz), 2.32 (dd, 1H, J = 5 Hz,
J = 2.5 Hz).
2-((4-tert-Butylphenoxy)methyl)thiirane (Table 2, Entry 8)
Oil (4b). IR (neat, cm−1) ν: 3039, 2962, 2900, 2868, 1513, 1245, 1185, 1033, 1013, 829. 1H NMR
(400 MHz, CDCl3, 25◦C, ppm) δ: 7.36 (d, 2H, J = 8.8 Hz), 6.91 (d, 2H, J = 8.4 Hz), 4.27 (dd,
1H, J = 10.0 Hz, J = 5.2 Hz), 3.93 (dd, 1H, J = 10.0 Hz, J = 7.6 Hz), 3.32 (q, 1H, J = 5.2 Hz),
2.65 (d, 1H, J = 6.0 Hz), 2.36 (d, 1H, J = 5.2 Hz), 1.36 (s, 9H). 13C NMR (100 MHz, CDCl3,
25◦C, ppm) δ: 156.2, 144.0, 126.4, 114.2, 72.7, 34.1, 31.6, 31.5, 24.1.
2-((2-tert-Butyl-4-methylphenoxy)methyl)thiirane (Table 2, Entry 9)
IR (neat, cm−1) ν: 3031, 2954, 2867, 1497, 1221, 1095, 1033, 1013, 804, 774. 1H NMR (400 MHz,
CDCl3, 25◦C, ppm) δ: 7.15 (d, 1H, J = 1.6 Hz), 7.01 (d, 1H, J = 8.4 Hz), 6.76 (d,
1H, J = 8.4 Hz), 4.23 (dd, 1H, J = 10.0 Hz, J = 5.6 Hz), 4.01 (dd, 1H, J = 10.0 Hz,
J = 6.8 Hz), 3.38 (q, 1H, J = 6.0 Hz), 2.67 (d, 1H, J = 6.0 Hz), 2.39 (d, 1H, J =
5.2 Hz), 2.34 (s, 3H), 1.46 (s, 9H). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ:

Journal of Sulfur Chemistry 359
155.1, 137.9, 129.8, 127.7, 127.2, 112.1, 72.6, 34.8, 31.7, 29.9, 23.9, 20.8. EI-MS: m/z 236 (M+).
Elemental analysis data: C%: 71.07 (calc. 71.14); H%: 8.22 (calc. 8.35); S%: 13.43 (calc. 13.57).
2-((4-tert-Butyl-2-methylphenoxy)methyl)thiirane (Table 2, Entry 10)
IR (neat, cm−1) ν: 3027, 2962, 2867, 1508, 1469, 1302, 1269, 1246, 1142, 1034, 807, 619, 611.
1H NMR (400 MHz, CDCl3, 25◦C, ppm) δ: 7.28 (s, 1H), 7.21 (dd, 1H, J = 8.4 Hz, J =
2.0 Hz), 6.82 (d, 1H, J = 8.4 Hz), 4.28 (dd, 1H, J = 10.4 Hz, J = 5.6 Hz), 3.98 (dd, 1H,
J = 10.4 Hz, J = 7.2 Hz), 3.36 (q, 1H, J = 5.6 Hz), 2.67 (d, 1H, J = 6.0 Hz), 2.40 (d,
1H, J = 5.2 Hz), 2.35 (s, 3H), 1.38 (s, 9H). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ:
154.5, 143.7, 128.1, 126.4, 123.3, 111.2, 72.9, 34.1, 31.8, 31.6, 24.0, 16.6. EI-MS: m/z 236 (M+);
Elemental analysis data: C%: 71.07 (calc. 71.14); H%: 8.22 (calc. 8.35); S%: 13.43 (calc.13.57).
2-((Naphthalen-4-yloxy)methyl)thiirane (Table 2, Entry 11)
Oil (4b). IR (neat, cm−1) ν: 3051, 2929, 2864, 1634, 1580, 1462, 1392, 1274, 1102, 910, 751, 624.
1H NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 8.32 (dd, 1H, J = 8 Hz, J = 4 Hz), 7.77 (dd, 1H, J =
8 Hz, J = 4 Hz), 7.66–7.1 (m, 4 H), 6.78 (dd, 1H, J = 8 Hz, J = 4 Hz), 4.33 (dd, 1H, J = 10 Hz,
J = 5 Hz), 4.07 (dd, 1H, J = 10 Hz, J = 5 Hz), 3.40 (q, 1H, J = 5 Hz), 2.66 (d, 1H, J = 5 Hz),
2.42 (d, 1H, J = 5 Hz)
2-((Naphthalen-3-yloxy)methyl)thiirane (Table 2, Entry 12)
m.p. 74◦C, Lit (12): 74◦C. IR (KBr, cm−1) ν: 3059, 2928, 2855, 1629, 1599, 1469, 1389, 1260,
1
1220, 1186, 840, 742. H NMR (400 MHz, CDCl3, 25◦C, ppm) δ: 7.78 (m, 3H) 7.48 (t, 1H,
J = 7.6 Hz), 7.39 (t, 1H, J = 7.2 Hz), 7.21 (d, 1H, J = 8.8 Hz), 7.17 (s, 1H), 4.37 (dd, 1H,
J = 10.0 Hz, J = 5.2 Hz), 4.06 (dd, 1H, J = 10.0 Hz, J = 7.2 Hz), 3.38 (q, 1H, J = 6.0 Hz),
2.69 (d, 1H, J = 6.0 Hz), 2.42 (d, 1H, J = 5.2 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ:
156.4, 134.5, 129.6, 129.2, 127.7, 126.8, 126.5, 123.9, 118.8, 107.0, 72.6, 31.4, 24.1.
2-Butyl thiirane (Table 2, Entry 13)
Oil (3a).IR (neat, cm−1) ν: 2921, 1435, 1259, 1108, 798, 612. 1H NMR (400 MHz, CDCl3, 25◦C,
ppm) δ: 2.16 (m, 3H), 1.84 (m, 2H), 1.53 (m, 2H), 1.41 (m, 2H), 1.28 (t, 3H).
2-(Chloromethyl)thiirane (Table 2, Entry 14)
Oil (4n). IR (neat, cm−1) ν: 2955, 2925, 2853, 1721, 1678, 1527, 1422, 1347, 1218, 920, 747. H
1
NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 3.70–3.5 (d, J = 5 Hz, 2H), 3.10–3.00 (m, 1H), 2.50 (t,
J = 5 Hz, 1H), 2.20 (dd, J = 7.5 Hz, 1H).
2-((Allyloxy)methyl)thiirane (Table 2, Entry 15)
Oil (4n). IR (neat, cm−1) ν: 2990, 2958, 2929, 1716, 1637, 1452, 1333, 1313, 1293, 1158, 1046,
1
942, 813, 657, 618. H NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 5.91 (m, 1H), 5.35 (dd, 1H,
J = 10 Hz, J = 4 Hz), 5.16 (dd, 1H, J = 5 Hz, J = 1.1 Hz), 4.10 (d, 2H, J = 5 Hz), 3.58 (dd, 2H,
J = 10 Hz, J = 5 Hz), 3.11 (q, 1H, J = 5 Hz), 2.56 (d, 1H, J = 5 Hz), 2.25 (d, 1H, J = 5 Hz).

360 B. Akhlaghinia et al.
2-(Isopropoxymethyl)thiirane (Table 2, Entry16)
Oil (4n). IR (KBr, cm−1) ν: 2963, 2923, 2858, 1714, 1454, 1373, 1266, 1119, 1082, 739, 611, 457.
1H NMR (400 MHz, CDCl3, 25◦C, ppm) δ: 3.67 (m, 2H), 3.41 (dd, 1H, J = 10.4 Hz, J = 7.2 Hz),
3.09 (q, 1H, J = 5.6 Hz), 2.55 (d, 1H, J = 6.4 Hz), 2.23 (d, 1H, J = 4.8 Hz), 1.20 (t, 6H, J =
4.8 Hz). 13C NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 72.9, 72.0, 32.7, 24.2, 22.2, 22.1.
2-Methyl-6-(thiiran-2-yl)hex-1-en-3-one (Table 2, Entry 17)
Oil(3c). IR(KBr, cm−1)ν:2994, 2958, 2933, 1720, 1637, 1452, 1313, 1293, 1159, 1046, 942, 813,
618. 1HNMR(100 MHz, CDCl3, 25◦C, ppm)δ:6.10(q, 1H, J = 1.1 Hz), 5.58(q, 1H, J = 1.1 Hz),
4.28 (d, 1H, J = 5 Hz), 4.17 (d, 1H, J = 5 Hz), 3.16 (q, 1H, J = 5 Hz), 2.57 (d, 1H, J = 5 Hz),
2.32 (d, 1H, J = 5 Hz), 1.93 (t,3H, J = 1.1 Hz).
Cyclohexene episulfide (Table 2, Entry 18)
Oil (4n). IR (KBr, cm−1) ν: 2935, 2855, 1728, 1444, 1351, 1275, 1194, 1002, 754. 1H NMR
(100 MHz, CDCl3, 25◦C, ppm) δ: 2.80 (m, 2H), 1.89 (m, 2H), 1.64 (m, 2H), 1.49 (m, 2H),
1.20 (m, 2H).
trans-Stilben episulfide (Table 2, Entry 19)
m.p. 51–53◦C, Lit (3a): 53–54◦C. IR (KBr, cm−1) ν: 3077, 3057, 3031, 3020, 2990, 1597, 1495,
1451, 1282, 1221, 1071, 963, 855, 765, 744, 692, 615, 526. 1H NMR (100 MHz, CDCl3, 25◦C,
ppm) δ: 7.38 (s, 10H), 3.90 (s, 2H).
1-Methylcyclohexene episulfide (Table 2, Entry 20)
Oil (16). IR (neat, cm−1) ν: 2966, 2935, 2871, 1739, 1642, 1618, 1544, 1464, 1378, 1227, 1136,
1086, 912, 747, 650. 1H NMR (100 MHz, CDCl3, 25◦C, ppm) δ: 2.50 (t, 1H), 1.50–1.30 (m, 4H),
1.10–0.90 (m, 4H), 1.00 (s, 3H).
Acknowledgement
We gratefully acknowledge the partial support of this study by Ferdowsi University of Mashhad Research Council (grant
no. p/3/18322).
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