A convenient synthesis of phosphorodithioates and novel conversion of epoxides to thiiranes

Article abstract of DOI:10.1055/s-2004-829176

Alumina-supported ammonium acetate under microwave irradiation was found to be an efficient reagent for the preparation of phosphorodithioates from phosphorus pentasulfide under solvent-free condition. A simple, efficient, and new method has been developed for the synthesis of thiiranes from epoxides through a one-pot reaction of epoxides with the mixture of phosphorus pentasulfide in the presence of ammonium acetate and acidic alumina under reflux in EtOH or solvent-free conditions under microwave irradiation. These methods are easy, rapid, and good-yielding reactions for the synthesis of phosphorodithioates and thiiranes.

Full text of DOI:10.1055/s-2004-829176

PAPER
2035
A Convenient Synthesis of Phosphorodithioates and Novel Conversion of
Epoxides to Thiiranes
One-Pot Synthes
a
b
orodithioate
a
s
a
nd Conv
k
ersion of Epoxide
s
K
to Thiiranes aboudin,* Hamid Norouzi
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Gava Zang, Zanjan 45195-159, Iran
Fax +98(241)4249023; E-mail: kaboudin@iasbs.ac.ir
Received 29 March 2004; revised 27 April 2004
tion time in the first method leads to a competitive
reaction as shown in Scheme 1.14
Abstract: Alumina-supported ammonium acetate under micro-
wave irradiation was found to be an efficient reagent for the prepa-
ration of phosphorodithioates from phosphorus pentasulfide under
solvent-free condition. A simple, efficient, and new method has
been developed for the synthesis of thiiranes from epoxides through
a one-pot reaction of epoxides with the mixture of phosphorus pen-
tasulfide in the presence of ammonium acetate and acidic alumina
under reflux in EtOH or solvent-free conditions under microwave
irradiation. These methods are easy, rapid, and good-yielding reac-
tions for the synthesis of phosphorodithioates and thiiranes.
In the recent years the use of reagents and catalysts immo-
bilized on solid supports has received considerable atten-
tion. Such reagents not only simplify purification
processes but also help prevent release of reaction resi-
dues into the environment.15
S
S
P
S
P
+M-S
OR
OR
HS
P OR
+
RS
OR
OR
Key words: phosphorodithioates, alumina, epoxides, thiiranes,
microwave
OR
I
Scheme 1
Organophosphorus compounds have found a wide range
of application in the areas of industrial, agricultural, and
medicinal chemistry owing to their biological and physi-
cal properties as well as their utility as synthetic interme-
diates.1 The synthesis of phosphate esters is an important
objective in organic synthesis, since they have found use
in the preparation of biologically active molecules, and
are also versatile intermediate in synthesis of amides and
esters.2 Among the phosphate esters, phosphorodithioate
derivatives are of interest as effective pesticides.3 Phos-
phorodithioates have been the subject of a number of pat-
ents and publications involving various uses including
antiviral compounds,4 plant growth regulators,5 inhibitors
of a number different enzymes,6 and as lubricants,7 among
others. In recent years a number of phosphorodithioates
have been introduced as thionating agent.8,9 Despite their
wide range of pharmacological activity, industrial and
synthetic applications, the synthesis of phosphorodithio-
ates has received little attention. The following methods,
not generally applicable, have been reported in the litera-
ture: (i) reaction of alkali salts of dialkyl phosphorodithio-
ic acids with alkyl halides or their addition to double
bonds10 (ii) reaction of thiol salts with dialkyl
phosphorochlorododithioate11 (iii) reaction of disulfides
of dialkyl phosphorodithioic acids with Grignard reagents
or alkyl or aryl lithium reagents12 and (iv) oxidative cou-
pling of H-phophonodithioates with alcohols in the pres-
ence iodine in pyridine.13 However, all of these methods
have problems as include drastic reaction conditions, ex-
pensive reagents and starting materials, and a longer reac-
The application of microwave energy to accelerate organ-
ic reactions is of increasing interest and offers several ad-
vantages over conventional techniques.16 Synthesis of
molecules that normally require long periods can be
achieved conveniently and very rapidly in a microwave
oven. As a part of our efforts to explore the utility of sur-
face-mediated reactions for the synthesis of organophos-
phorus compounds,17–19 we report here a new method for
the preparation of phosphorodithioates by reaction of
phosphorus pentasulfide with EtOH in the presence of
alumina supported ammonium acetate followed by the re-
action with alkyl halides under solvent-free conditions us-
ing microwave irradiation producing high yields of
phosphorodithioates. On the other hand, reaction of ep-
oxides under above conditions gave thiiranes as major
product (Scheme 2).
S
Al2O3(a)/NH4OAc
P2S5 C H OH
+NH4-S
P
OCH2CH3
OCH2CH3
+
2
5
MW/1 min
1
O
R
RX
S
S
R
RS
P
OCH2CH3
OCH2CH3
2
3
Scheme 2
Recently we reported that a mixture of alumina/ammoni-
um acetate/sulfur in the presence of diethylphosphite un-
der microwave irradiation is a suitable reagent for the
synthesis of phosphorothioates of alkyl halides and con-
version of epoxides to thiiranes.19a,c Further investigation
SYNTHESIS 2004, No. 12, pp 2035–2039
x
x.
x
x
.
2
0
0
4
Advanced online publication: 21.07.2004
DOI: 10.1055/s-2004-829176; Art ID: Z06604SS
© Georg Thieme Verlag Stuttgart · New York

2036
B. Kaboudin, H. Norouzi
PAPER
of the application of alumina supported ammonium ace- ganic thiocyanates or related compounds.22 Thiiranes
tate in organophosphorus synthesis showed that the mix- could not be prepared from some of the alkene oxides
ture of phosphorus pentasulfide in EtOH reacts in the such as styrene oxide, stilbene oxide, and cycloalkene ox-
presence of alumina supported ammonium acetate under ide by means of thiourea and thiocyanates.23 Recently use
microwave irradiation and gives O,O¢-diethyl ammoni- of recyclable ionic liquid for conversion of oxiranes to ep-
umdithiophosphate (1) quantitatively.
oxides has been reported.24
Here we report a new procedure for conversion of ep-
oxides to thiiranes using of a mixture of phosphorus pen-
tasulfide in EtOH in the presence of alumina supported
ammonium acetate under reflux in EtOH or solvent-free
conditions under microwave irradiation. Initially, we car-
ried out the experiment with 2-phenoxymethyloxirane in
the presence of phosphorus pentasulfide in EtOH after 24
hours, which afforded the corresponding episulfide in
46% yield. When this reaction was carried out under mi-
crowave irradiation in the presence of alumina for two
minutes the corresponding thiirane was obtained in 55%
yield. The use of alumina supported ammonium salts
(NH4OAc, NH4HCO3, NH4Br, NH4PF6 and NH4I) in
place of alumina give good results under reflux in EtOH
or microwave irradiation. The best results were obtained
with ammonium acetate. We also report here a new proce-
dure for conversion of epoxides to thiiranes using a mix-
ture of alumina/ammonium acetate in the presence of
phosphorus pentasulfide under reflux in EtOH or solvent-
free conditions under microwave irradiation (Table 2).
These results prompted us to extend this process for vari-
ous epoxides. Interestingly, aryl, alkyl, and sterically hin-
dered epoxides reacted smoothly under this reaction
condition to produce corresponding thiiranes in good to
excellent yields (Table 2). As shown in Table 2, epoxides
in the presence ammonium acetate/alumina were reacted
with phosphorus pentasulfide, giving the required prod-
ucts in good to excellent yields. Similarly, cyclohexyl ox-
ide was converted into the corresponding thiirane in good
yield.
Scheme 3
Table 1 Reaction of O,O¢-Diethyl Ammoniumdithiophosphate (1)
with Alkyl Halides under Solvent-Free Conditions Using Microwave
Irradiation
Product 2
R
X
Reaction Time Yield
(min)
(%)a
82
88
80
93
90
80
85
75
a
a
b
c
d
e
f
PhCH2
Br
Cl
Br
Br
Cl
Cl
Cl
Br
2
2
2
2
2
4
3
2
PhCH2
PhCH2CH2
p-NO2C6H4CH2
p-MeC6H4CH2
o-MeC6H4CH2
1-C10H7CH2
1-C10H7CH2
f
a Isolated yields.
The reaction of alkyl halides with this mixture under mi-
crowave irradiation for 2–4 minutes gave phospho-
rodithioates (2) in 75–93% yield (Table 1 and Scheme 3).
As shown in Table 1, a wide range of alkyl halides were
reacted with O,O¢-diethyl ammoniumdithiophosphate (1),
giving the required products 2 in excellent yields. The re-
actions were clean with no tar formation.
The reaction of cyclooctene oxide and epoxy cyclodode-
cane in the presence ammonium acetate/alumina with
phosphorus pentasulfide, gave low yields (15–20%
yields) after 30 hours under reflux in EtOH. Styrene oxide
reacted with phosphorus pentasulfide in the presence am-
monium acetate/alumina, giving the corresponding thi-
irane in excellent yield.
Thiiranes are the simplest sulfur heterocycles and occur in
nature. These are an important class of compounds with
applications in the pharmaceutical, polymer, pesticide and
herbicide industries.20 Extensive investigations over the
last twenty years have shown they are of particular impor-
tance in biological and medicinal research. Although there
are many classical methods for synthesizing thiiranes,
these involve long reaction times, the use of strongly acid-
ic or oxidizing conditions, high-temperature reaction con-
ditions, expensive reagents, poor yields, formation of
several by-products due to the rearrangement or polymer-
ization of oxiranes, and use of moisture sensitive, and foul
smelling reagents which must be handled with care.21 The
most important method for the synthesis of thiiranes is the
conversion of alkene oxides (epoxides) to thiiranes with
thiourea, thioamides, phosphine sulfide, dimethylthiofor-
mamide in the presence of trifluoroacetic acid, and inor-
In summary, a simple work-up, low consumption of sol-
vent, fast reaction rates, mild reaction conditions, good to
excellent yields, relatively clean reactions with no tar for-
mation make these methods as attractive and a useful con-
tribution to the present methodologies for the preparation
of phosphorodithioates and thiiranes.
All chemicals were commercial products and distilled or recrystal-
lized before use. All melting points were obtained on a Buchi 510
apparatus and are uncorrected. A commercially available pulse mi-
crowave at operating at 2450 MHz (600 W) was used in all experi-
ments. The IR spectra were determined using a FT-IR Brucker-
Vector 22 spectrometer. NMR spectra were taken with a DMX-500
Brucker Avance instrument with the chemical shifts reported as d
ppm and scalar couplings expressed in Hz. Silica gel column chro-
Synthesis 2004, No. 12, 2035–2039 © Thieme Stuttgart · New York

PAPER
One-Pot Synthesis of Phosphorodithioates and Conversion of Epoxides to Thiiranes
2037
Table 2 Conversion of Epoxides to Thiiranes Using di-Phosphorus Pentasulfide in EtOH in the Presence of Ammonium Acetate/Alumina
with or without Microwave Irradiationa
Entry
Epoxide
Al2O3–NH4OAc–MW
Yield (%)b
Al2O3–NH4OAc–Reflux
Time (min)
Time (min)
Yield (%)b
O
a
2
83
0.5
91
Ph
O
b
c
180c
4d
30
25
–
–
–
–
Ph
O
Ph
d
e
3
2
72
82
2
2
75
92
O
O
PhO
H2C
O
O
f
4
76
1
83
O
CH3
CH3
h
i
3
4
55
10
3
2
50
76
O
H3C
O
O
H3C(CH2)11
a Conversions were monitored by GC analysis.
b Yields refers to the isolated pure products after column chromatography.
c Shaking without microwave irradiation.
d Reaction without the use of ammonium acetate.
matography was carried out with Silica gel 100 (Merck No. 10184).
Merck Silica-gel 60 F254 plates (No. 5744) were used for the pre-
parative TLC.
Anal. Calcd for C4H14NPS2O2: C, 23.64; H, 6.90; N, 6.89. Found:
C, 23.53; H, 6.84; N, 6.73.
S-Benzyl O,O-Diethyl Phosphorodithioate (2a)10
Synthesis of Dithiophosphates Using of Phosphorus Pentasul-
fide in EtOH on the Alumina-Supported Ammonium Acetate
under Microwave Irradiation; General Procedure
Colorless oil.
1H NMR (500 MHz, CDCl3–TMS): d = 1.31 (t, J = 7.1 Hz, 6 H),
3.95–4.03 (m, 2 H), 4.05 (d, J = 15.5 Hz, 2 H), 4.09–4.18 (m, 2 H),
7.25–7.34 (m, 5 H).
13C NMR (125.7 MHz, CDCl3–TMS): d = 15.6 (d, JPC = 8.2 Hz),
37.5 (d, JPC = 3.8 Hz), 63.8 (d, JPC = 5.8 Hz), 127.5, 128.5, 128.8,
137 (d, JPC = 5.5 Hz).
The reagent (10 mmol) was prepared by the combination of ammo-
nium acetate (10 mmol, finely ground) and alumina (Al2O3, acidic,
2.5 g) in a mortar and pestle by grinding them together until a fine,
homogeneous, powder was obtained (5–10 min). Phosphorus pen-
tasulfide (10 mmol) was reacted with EtOH (5 mL) for 1 h and alu-
mina supported ammonium acetate was added to this mixture. The
mixture was irradiated with microwave for 1 min. The alkyl halide
(9 mmol) was added to this reagent (solid alkyl halides need to be
31P NMR (202.4 MHz, CDCl3–H3PO4): d = 93.59.
O,O-Diethyl S-(2-Phenyl)ethyl Phosphorodithioate (2b)
grinded) and subjected to microwave irradiation for 2–4 min using
720 W power (a kitchen-type microwave was used in all experi-
ments). Chromatography through a plug of silica gel with EtOAc–
n-hexane (1:9) as eluent and evaporation of the solvent under re-
duced pressure gave the pure products as oils in 75–93% yields. All
products gave satisfactory spectral data in accord with the assigned
structures.
Colorless oil.
1H NMR (500 MHz, CDCl3–TMS): d = 1.35 (t, J = 7.1 Hz, 6 H),
2.96 (m, 2 H), 3.11 (m, 2 H), 3.95–4.21 (m, 4 H), 7.19–7.35 (m, 5
H).
13C NMR (125.7 MHz, CDCl3–TMS): d = 15.7 (d, JPC = 8.3 Hz),
29.6, 36.7 (d, JPC = 5.1 Hz), 63.8 (d, JPC = 5.9Hz).
31P NMR (202.4 MHz, CDCl3–H3PO4): d = 95.26.
Ammonium O,O-Diethyl Phosphorodithioate (1)
White crystals (EtOH); mp 165–166 °C.
1H NMR (500 MHz, D2O–TMS): d = 1.21 (t, J = 7.1 Hz, 6 H), 3.91–
4.03 (m, 4 H).
Anal. Calcd for C12H19PS2O2: C, 49.63; H, 6.59. Found: C, 50.65;
H, 6.56.
O,O-Diethyl S-(p-Nitrophenyl)methyl Phosphorodithioate (2c)
Colorless oil.
31P NMR (202.4 MHz, D2O–H3PO4): d = 111.22.
Synthesis 2004, No. 12, 2035–2039 © Thieme Stuttgart · New York

2038
B. Kaboudin, H. Norouzi
PAPER
1H NMR (500 MHz, CDCl3–TMS): d = 1.10 (t, J = 7.1 Hz, 6 H),
3.82–3.90 (m, 2 H), 3.93–3.98 (m, 2 H), 4.02 (d, J = 16.2 Hz, 2 H),
7.41 (d, J = 8.2 Hz, 2 H), 7.98 (d, J = 8.2 Hz, 2 H).
13C NMR (125.7 MHz, CDCl3–TMS): d = 15.6 (d, JPC = 8.0 Hz),
36.6 (d, JPC = 3.3 Hz), 63.9 (d, JPC = 5.8 Hz), 123.5, 129.8, 145.0 (d,
salts were removed by washing with an aq solution of Na2CO3 and
then with water. Chromatography through a plug of silica gel with
EtOAc–n-hexane (1:9) as eluent and evaporation of the solvent un-
der reduced pressure gave the pure products in 10–92% yields. All
products gave satisfactory spectral data in accord with the assigned
structures according with literature reports.21c
JPC = 3.8 Hz), 146.9.
31P NMR (202.4 MHz, CDCl3–H3PO4): d = 92.40.
Acknowledgement
Anal. Calcd for C11H16NPS2O4: C, 41.11; H, 5.02; N, 4.35. Found:
C, 41.63; H, 5.35; N, 4.45.
The Institute for Advanced Studies in Basic Sciences (IASBS) is
thanked for supporting this work.
O,O-Diethyl S-(p-Methylphenyl)methyl Phosphorodithioate
(2d)
Colorless oil.
References
1H NMR (500 MHz, CDCl3–TMS): d = 1.29 (t, J = 7.1 Hz, 6 H),
2.33 (s, 3 H), 3.97–4.07 (m, 4 H), 4.11–4.20 (m, 2 H), 7.11 (d, J =
7.7 Hz, 2 H), 7.23 (d, J = 7.7 Hz, 2 H).
13C NMR (125.7 MHz, CDCl3–TMS): d = 15.7 (d, JPC = 8.5 Hz),
21.1, 37.4 (d, JPC = 3.8 Hz), 63.7 (d, JPC = 5.7 Hz), 128.8, 129.3,
134.0 (d, JPC = 5.7 Hz), 137.2.
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31P NMR (202.4 MHz, CDCl3–H3PO4): d = 93.65.
Anal. Calcd for C12H19PS2O2: C, 49.63; H, 6.59. Found: C, 51.36;
H, 6.66.
O,O-Diethyl S-(o-Methylphenyl)methyl Phosphorodithioate
(2e)
Colorless oil.
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1H NMR (500 MHz, CDCl3–TMS): d = 1.30 (t, J = 7.1 Hz, 6 H),
2.38 (s, 3 H), 3.90–4.08 (m, 4 H), 4.11–4.20 (m, 2 H), 7.11–7.19 (m,
3 H), 7.29 (d, J = 3.9 Hz, 1 H).
13C NMR (125.7 MHz, CDCl3–TMS): d = 15.7 (d, JPC = 8.1 Hz),
19.2, 35.7 (d, JPC = 3.3 Hz), 63.7 (d, JPC = 5.9 Hz), 123.3, 125.4,
126.0, 126.4, 127.7, 128.8, 128.9, 131.2, 132.5 (d, JPC = 6.2 Hz),
133.9.
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31P NMR (202.4 MHz, CDCl3–H3PO4): d = 93.17.
Anal. Calcd for C12H19PS2O2: C, 49.63; H, 6.59. Found: C, 51.16;
H, 6.66.
O,O-Diethyl S-(1-Naphthyl)methyl Phosphorodithioate (2f)
Colorless oil.
1H NMR (500 MHz, CDCl3–TMS): d = 1.31 (t, J = 7.1 Hz, 6 H),
4.03–4.12 (m, 2 H), 4.15–4.25 (m, 2 H), 4.56 (d, J = 13.3 Hz, 2 H),
7.41 (t, J = 7.2 Hz, 1 H), 7.47–7.64 (m, 3 H), 7.81 (d, J = 8.3 Hz, 1
H), 7.88 (d, J = 8.1 Hz, 1 H), 8.10 (d, J = 8.1 Hz, 1 H).
13C NMR (125.7 MHz, CDCl3–TMS): d = 15.8 (d, JPC = 8.1 Hz),
35.6 (d, JPC = 3.5 Hz), 63.9 (d, JPC = 5.9 Hz), 126.1, 127.9, 129.95,
130.5, 134.7 (d, JPC = 6.5 Hz), 136.6.
31P NMR (202.4 MHz, CDCl3–H3PO4): d = 93.43.
Anal. Calcd for C15H19PS2O2: C, 55.22; H, 5.87. Found: C, 57.45;
H, 5.96.
Synthesis of Thiiranes of Epoxides; General Procedure
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The reagent (10 mmol) was prepared by the combination of ammo-
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2.5 g) in a mortar and pestle by grinding them together until a fine,
homogeneous, powder was obtained (5–10 min). Phosphorus pen-
tasulfide (10 mmol) was reacted with EtOH (5 mL) for 1 h and alu-
mina supported ammonium acetate was added to this mixture. The
mixture was subjected to microwave irradiation for 1 min. Epoxide
(9 mmol) was added to mixture and was irradiated with microwave
for 2–4 min using 300–450 W (a kitchen-type microwave was used
in all experiments) or refluxed in EtOH (20 mL) for 0.5–3 h. The
mixture was then washed with CHCl3 (200 mL). All of ammonium
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Synthesis 2004, No. 12, 2035–2039 © Thieme Stuttgart · New York

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One-Pot Synthesis of Phosphorodithioates and Conversion of Epoxides to Thiiranes
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