Liquid ammonia as a medium in the convenient preparation of ammonium O,O-dialkyl phosphorothioate and ammonium O,O-dialkyl phosphoroselenoate

Article abstract of DOI:10.1081/SCC-100107016

Ammonium O,O-dialkyl phosphorothioate and O,O-dialkyl phosphoroselenoate were conveniently synthesized from dialkyl phosphites and elemental sulfur and selenium in liquid ammonia in good yields.

Full text of DOI:10.1081/SCC-100107016

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LIQUID AMMONIA AS A MEDIUM IN THE CONVENIENT
PREPARATION OF AMMONIUM O,O-DIALKYL
PHOSPHOROTHIOATE AND AMMONIUM O,O-DIALKYL
PHOSPHOROSELENOATE
a
b
Grażyna Mielniczak & Andrzej Łopusiński
a
Center of Molecular and Macromolecular Studies, Polish Academy of Sciences ,
Sienkiewiczaz 112, Łódź, PL 90-362, Poland
b
Center of Molecular and Macromolecular Studies, Polish Academy of Sciences ,
Sienkiewicza 112, Łódź, PL 90-362, Poland
Published online: 16 Aug 2006.
To cite this article: Grażyna Mielniczak & Andrzej Łopusiński (2001) LIQUID AMMONIA AS A MEDIUM IN THE CONVENIENT
PREPARATION OF AMMONIUM O,O-DIALKYL PHOSPHOROTHIOATE AND AMMONIUM O,O-DIALKYL PHOSPHOROSELENOATE,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:23,
3659-3664, DOI: 10.1081/SCC-100107016
To link to this article: http://dx.doi.org/10.1081/SCC-100107016
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SYNTHETIC COMMUNICATIONS, 31(23), 3659–3664 (2001)
LIQUID AMMONIA AS A
MEDIUM IN THE CONVENIENT
PREPARATION OF AMMONIUM
O,O-DIALKYL PHOSPHOROTHIOATE
AND AMMONIUM O,O-DIALKYL
PHOSPHOROSELENOATE
Gra z_ yna Mielniczak and Andrzej Bopusin
´
ski*
Center of Molecular and Macromolecular Studies,
Polish Academy of Sciences, Sienkiewicza 112,
PL 90-362 Lodz´ , Poland
´
ABSTRACT
Ammonium O,O-dialkyl phosphorothioate and O,O-dialkyl
phosphoroselenoate were conveniently synthesized from dia-
lkyl phosphites and elemental sulfur and selenium in liquid
ammonia in good yields.
The monothioacids of phosphorus and their salts are crucial com-
1
–3
pounds in organophosphorus chemistry
and play an important role as
a starting materials in the, synthesis of several products with practical appli-
4
cations. Numerous methods for the synthesis of organic monothioacids of
*
Corresponding author.
3
659
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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´
3
660
MIELNICZAK AND BOPUSINSKI
phosphorus are existed. The simplest one based on the reaction of addition
of elemental sulfur into dialkyl phosphites and their structural analogs.
The reaction is performed in the presence of stoichiometric amount of
5
–7
8–11
alkali metal
or amines.
The further reaction of the salts formed
with mineral acids provide access to the free acids which generally are
stable compounds, and can be easily isolated and purified by distillation
or crystallization techniques.
Usually free organic monoselenoacids of phosphorus, obtained
5
,12–21
by decomposition of their sodium or potassium salts
with mineral
acids, are thermolabile compounds. Some of them were isolated by distilla-
1
5
tion, however, they show relatively low purity and stability during storage.
The sodium or potassium salts of monoselenoacids precipitated from their
solutions shown relatively good stability. In some cases they can be purified
by recrystallization from suitable solvents. Only few examples of the
synthesis of alkyl-or/and arylammonium salts of organic selenophosphorus
1
8,21–24
acids have been reported.
We wish to report herein a new procedure for the oxidative addition
of elemental sulfur, or selenium to the O,O-dialkyl phosphites, performed in
the liquid ammonia used as the reagent and solvent (eg. 1).
This method is useful for the synthesis of ammonium O,O-dialkyl
phosphorothioate and O,O-dialkyl phosphoroselenoate respectively, under
mild conditions. The straight forward isolation of pure products in excellent
yield by simple filtration and evaporation of the solvent, is important advan-
tage for the provided method.
EXPERIMENTAL
1
The H NMR were recorded on the 200.13 MHz with a Bruker
3
1
AC 200 MHz instrument using TMS as an internal standard. P NMR
spectra were taken on the same spectrometer at 81 MHz. Positive shifts

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LIQUID AMMONIA
3661
are downfield from 85% H PO used as a external reference. LSIMS spectra
3
4
were recorded on Finnigan MAT 95 spectrometer. Melting points were
determined with a Boetius apparatus and are uncorrected.
General Procedure for the Preparation
of Salts 2a–e and 3a–e
The reaction flask containing of finely powdered elemental sulfur or
selenium (10–12 mmol) suspended in 15–25 mL of dry liquid ammonia was
ꢀ
cooled to À 35 C in dry ice bath. The suspension was magnetically stirred
for the 20 min, and freshly prepared O,O-dialkyl phosphite (10 mmol)
dissolved in 0.5 mL and dry diethyl ether was added at once to the reaction
solution. The stirring was continued for 6–8 h at the temperature of
ꢀ
ꢀ
the cooling bath between À 33 C and À 35 C. Then, the cooling bath was
removed and the reaction mixture was stirred until the all amount of ammo-
nia was distilled off. The remaining crude product was dissolved in
dry chloroform (10–15 mL). The solution was filtered through Cellite. The
evaporation of solvent in vacuo and drying of the remaining solid for 2 h
under reduced pressure (0.01–1.00 mmHg) at room temperature, gave
practically analytically pure, in most cases, ammonium salts of acids. If
necessary they can be recrystallized from the suitable anhydrous solvents.
The analytical data characteristic for the synthesized salts 2a–e and 3a–e are
presented in Table 1.
Table 1. Synthesis of Compounds 2a–e and 3a–e
Yield
i
(%)
M.P.
ꢀ
MS FAB
m/z
31
Product
R
X
( C)
P NMR
2a
2b
2c
2d
2e
3a
3b
3c
3d
3e
C H
2
S
S
S
S
100 (95)
100 (92)
100 (90)
100 (84)
100 (96)
87 (78)
80 (75)
80 (70)
77 (69)
83 (75)
141–142
140–141
143–144
147–148
152–154
135–137
131–132
137–139
127–129
151–152
57.77
57.57
55.32
57.68
57.95
169
197
197
225
253
217
244
244
5
n-C
3
H
7
i-C
n-C H
3
H
7
4
9
t
BuCH
2
S
C
n-C H
H
2 5
Se
Se
Se
Se
Se
51.19; JP-Se 775.8
51.84; JP-Se 775.4
47.54; JP-Se 765.4
48.14; JP-Se 744.9
51.33; JP-Se 766.3
3
7
i-C
n-C
BuCH
3
H
7
ii
4
H
9
273
t
ii
2
310
i
31
yields calculated from P spectra, in brackets yields after isolation; calculated for
ii
8
0
Se.

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MIELNICZAK AND BOPUSINSKI
CONCLUDING REMARKS
In conclusion, the use of liquid ammonia as a medium of the reaction
of O,O-dialkyl phosphites with elemental sulfur or selenium provides a
remarkably simple and mild synthetic route to the ammonium salts of
monothio- 2a–e and monoselenoacids 3a–e of phosphorus.
The ammonium O,O-dialkyl phosphorothioates were synthesized
1
0
previously by Pesin and Khaletskij by the procedure, in which the dry
gaseous ammonia was passed through the boiling reaction solution
ꢀ
(75–80 C) containing sulfur to which the corresponding O,O-dialkyl phos-
phite was added gradually.
The procedure demonstrated herein, offers a milder reaction con-
ditions which are especially important for the preparation of salts of organic
monoselenium phosphorus acids. The salts 3a–e obtained according to this
procedure, show high purity and good stability. If necessary, they can be
recrystallized from the suitable anhydrous solvents without decomposition.
According to the known concept, in ‘‘elemental sulfur’’ (S ) the sulfur
8
atoms react first as electrophilic centers. They are susceptible towards a
nucleophilic attack, which results in a stepwise degradation of sulfur-
sulfur bonds. This degradation of cyclooctasulfur is demonstrated by
action of sodium nitrite, sulfite sulfur atom, sulfate or cyanide anions and
2
5
tricoordinated phosphorus compounds and other nucleophiles.
The observed successful addition of elemental sulfur and selenium to
the O,O-dialkyl phosphites performed in liquid ammonia at relatively low
temperature, seems to be an unexpected result. It is very probably that the
degradation of cyclooctasulfur and cyclooctaselenium rings by ammonia
takes place under the reaction conditions. The subsequent attack of the
III
nucleophilic P phosphorus atom of the phosphite on the electrophilic
center of such activated sulfur or selenium atoms, is resulted in the forma-
tion of the observed ammonium salts.
Similar reactions of the opening of cyclic S by aqueous ammonia in
8
2
6
27
the presence of mercury oxide as well by aliphatic amines with formation
2
of heptasulfurimide have been reported. The analogous mechanism for the
well known Willgerodt carbonyl transformations is postulated.
8
2
9
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Received in the Netherlands February 5, 2001

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