Synthesis and properties of 2-chloro-1,3,2-dioxaarsolane and 1,2-bis(1,3,2-dioxaarsolan-2-yloxy)ethane

Full text of DOI:10.1134/S1070428012060206

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 6, pp. 864–866. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.V. Kutkin, V.A. Semenova, I.I. Sizov, S.A. Sukhotskaya, S.M. Kondratenko, N.A. Kostikova, M. V. Korol'kov, 2012, published in
Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 6, pp. 866–868.
SHORT
COMMUNICATIONS
Synthesis and Properties of 2-Chloro-1,3,2-dioxaarsolane
and 1,2-Bis(1,3,2-dioxaarsolan-2-yloxy)ethane
A. V. Kutkin, V. A. Semenova, I. I. Sizov, S. A. Sukhotskaya, S. M. Kondratenko,
N. A. Kostikova, and M. V. Korol'kov
State Research Institute of Organic Chemistry and Technology, sh. Entuziastov 23, Moscow, 111024 Russia
e-mail: dir@gosniiokht.ru
Received October 22, 2011
DOI: 10.1134/S1070428012060206
Arsoric and arsorous acid esters are traditionally
classed with organoarsenic compounds and are used as
antioxidants, doping agents, antiseptics, insecticides,
drugs, and bioactive food components [1]; therefore,
development of preparative procedures for their syn-
thesis remain an important problem. 2-Chloro-1,3,2-
dioxaarsolane (I), 1,2-bis(1,3,2-dioxaarsolan-2-yloxy)-
ethane (II), and their hydrolysis products are con-
venient starting materials for the synthesis of a number
of arsenic-containing compounds. It is known that
phosphorus(III) and arsenic(III) chlorides react with
ethylene glycol in inert solvents to give, respectively,
1,3,2-dioxaphospholane and 1,3,2-dioxaarsolane deriv-
atives [2, 3]. The reaction with AsCl3 is much less
selective, and it leads to a mixture of products, the
major being 1,3,2-dioxaarsolane derivatives [3].
selectivity by reaction of arsorous anhydride with
ethylene glycol (yield 89–92%) [3, 4]; however, this
reaction requires severe conditions (140–150°C, re-
duced pressure to remove water, and double distillation
of the reaction mixture) [4].
We found that dioxaarsolanes I and II can be
selectively synthesized in good yields without using
HCl acceptor and that the synthesis of II may be
performed under solvent-free conditions. The reaction
of AsCl3 with ethylene glycol at a ratio of 1:(1.0–1.1)
in carbon tetrachloride gave 57% of I, whereas in the
presence of 3 equiv of ethylene glycol compound II
was formed as the only product in 66% yield. At
an AsCl3-to-ethylene glycol ratio of 1.0:(1.5–2.5) or
1:3.5 several other 1,3,2-dioxaarsolane derivatives
were formed, among which 2-(1,3,2-dioxaarsolan-2-yl-
oxy)ethanol (III), 2-(1,3,2-dioxaarsolan-2-yloxy)ethyl
2-hydroxyethyl hydrogen arsorite (IV), and 2-(1,3,2-
dioxaarsolan-2-yloxy)ethyl bis(2-hydroxyethyl)
arsorite (V) were identified by GC–MS.
The reaction of AsCl3 with an equimolar amount of
ethylene glycol in anhydrous diethyl ether in the
presence of pyridine as hydrogen chloride acceptor
produced 2-chloro-1,3,2-dioxaarsolane (I) and bis-
arsorous ester II. Compound I can be converted into II
in excess ethylene ethylene glycol, whereas ester II
reacts with excess AsCl3 to afford chlorodioxaarsolane
I [3, 4] (Scheme 1). Ester II can be obtained with high
OH
O
O
OH
O
As
O
As
As
O
O
OH
O
O
III
IV
OH
O
O
O
Scheme 1.
As
As
O
O
OH
O
O
OH
+
AsCl3
As
V
HO
Cl
O
I
Arsolanes I and II are sensitive to moisture. Com-
pound II at room temperature is converted in 2 days
into 2-(1,3,2-dioxaarsolan-2-yloxy)ethanol (III), and
hydrolysis of the latter in excess water yields 1,3,2-di-
oxaarsolan-2-ol.
O
O
HOCH2CH2OH
AsCl3
O
As
As
O
O
O
II
864

SYNTHESIS AND PROPERTIES OF 2-CHLORO-1,3,2-DIOXAARSOLANE
865
Compound I was also synthesized in quantitative
yield by treatment of dichloro(2-chlorovinyl)arsane
(VI) or chlorobis(2-chlorovinyl)arsane (VII) (α- and
β-lewisites) with excess ethylene glycol (Scheme 2).
Cl 20.71. C2H4AsClO2. Calculated, %: C 14.09;
H 8.08; As 43.96; Cl 20.80.
1,2-Bis(1,3,2-dioxaarsolan-2-yloxy)ethane (II).
Arsenic(III) chloride, 181.5 g (1 mol), was added over
a period of 1 h under stirring to 186 g (3 mol) of
ethylene glycol heated to 40–45°C. The mixture was
stirred for 1 h at 65–70°C, 200 ml of ethanol was
added, and the mixture was neutralized with NaHCO3
and filtered. The solvent was distilled off from the
filtrate, and the residue was distilled under reduced
pressure. Yield 11.2 g (66%), light yellow oily liquid,
bp 160–163°C (0.1 mm); published data: bp 114.5–
115°C (0.02 mm) [6], 150°C (0.03 mm) [7], 154–
Scheme 2.
R
OH
+
I
As
HO
Cl
Cl
VI, VII
VI, R = Cl; VII, R = ClCH=CH.
The process is accompanied by liberation of tri-
chloroethane, and it can be used for degassing of
lewisite-based chemical weapons with ethylene glycol-
containing reagents [5]. Compound II can be prepared
in quantitative yield by transesterification of triisobutyl
and tripropyl arsorites VIII and IX (Scheme 3). The
reverse transesterification does not occur.
1
157°C (1 mm) [8], 166–167°C (4 mm) [4]. H NMR
spectrum, δ, ppm: 3.66–4.01 m (8H, 4-H, 5-H), 3.94 s
(4H, CH2). 13C NMR spectrum, δC, ppm: 57.80 (CH2),
67.71 (4-H, 5-H). Mass spectrum, m/z (Irel, %): 329 (1),
300 (1), 271 (2), 270 (44), 182 (3), 165 (8), 136 (4),
135 (100), 133 (3), 117 (9), 106 (3), 105 (5), 93 (2), 92
(2), 91 (26), 77 (2), 75 (2), 61(1). Found, %: C 22.02;
H 3.81; As 44.98. C6H12As2O6. Calculated, %:
C 21.84; H 3.67; As 45.41.
Scheme 3.
OR
As
HOCH2CH2OH
II
2-(1,3,2-Dioxaarsolan-2-yloxy)ethanol (III).
1H NMR spectrum, δ, ppm: 3.42 t (2H, CH2OH),
3.59 t (2H, CH2O), 3.66 m (4H, OCH2CH2O), 4.08–
3.81 m (AsOCH2), 3.61 s (OH). Mass spectrum of
silylated derivative C2H4O2AsOCH2CH2OSiMe3, m/z
(Irel, %): 253 (6), 210 (2), 209 (5), 208 (33), 193 (1),
165 (19), 164 (10), 135 (100), 133 (2), 117 (8), 106
(2), 105 (6), 104 (6), 103 (50), 91 (13), 89 (3), 77 (11),
75 (11), 73 (67), 59 (8), 58 (5), 45 (13), 43 (12).
i-BuOH or PrOH
RO
OR
VIII, IX
VIII, R = i-Bu; IX, R = Pr.
The acute toxicity of compound II in white mice
after intragastric administration was estimated at
LD50 70.7 mg/kg, which corresponds to the IInd class
of hazard according to GOST 12.1.007-76. Chlorodi-
oxaarsolane I exhibited pronounced skin irritating
The mass spectra (electron impact) were obtained
on an HP 5973 mass-selective detector coupled with
an HP 6890 gas chromatograph [HP-5MS quartz capil-
lary column, 30 m×0.25 mm, film thickness 0.25 μm;
injector temperature 250°C, oven temperature pro-
gramming from 40°C (2 min) at a rate of 10 deg/min to
200°C (2 min), then at a rate of 30 deg/min to 260°C
(2 min); carrier gas flow rate 1.0 cm3/min; interface
effect leading to edema and ulceration [LD50
100.0 mg/kg (intragastric administration), LD50
38.7 mg/kg (cutaneous administration); Ist class of
hazard according to GOST 12.1.007-76].
=
=
2-Chloro-1,3,2-dioxaarsolane (I). Arsenic(III)
chloride, 20 g (0.11 mol), was added over a period of
1 h under stirring to a solution of 6.2 g (0.1 mol) of
ethylene glycol in 160 ml of carbon tetrachloride, the
mixture was stirred for 1 h at 15–20°C, the solvent was
distilled off under reduced pressure, and the residue
was distilled at 57.0–57.5°C (8 mm); published data:
bp 70–71°C (10 mm) [8], 66–67°C (9 mm) [4]. The
colorless oily product crystallized in 24 h. Yield 9.7 g
(57%), colorless crystals, mp 44–45°C [4, 8]. 1H NMR
1
temperature 280°C]. The H and 13C NMR spectra
were measured from solutions in CDCl3 on a Bruker
AM-300 spectrometer at 300.13 and 75.47 MHz,
respectively; the chemical shifts are given relative to
tetramethylsilane. Commercial AsCl3, NaHCO3, EtOH,
i-BuOH, PrOH, N,O-bis(trimethylsilyl)trifluoroacet-
amide, and ethylene glycol were used without addi-
tional purification. Triisobutyl arsorite (VIII) and tri-
propyl arsorite (IX) were synthesized from AsCl3 and
the corresponding sodium alkoxide in isobutyl or
propyl alcohol and isolated by distillation [9]. Carbon
tetrachloride was purified as described in [10].
13
spectrum: δ 4.30 ppm, br.s (4H, CH2). C NMR spec-
trum: δC 68.84 ppm (CH2). Mass spectrum, m/z
(Irel, %): 170 (3), 142 (36), 140 (100), 135 (62), 117
(9), 112 (33), 110 (46), 105 (7), 91 (42), 77 (4), 76 (6),
75 (27), 43 (20). Found, %: C 14.19; H 8.22; As 43.82;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012

KUTKIN et al.
866
5. Utkin, A.Yu., Kholodova, V.A., Chebotaev, V.V., Kut-
This study was performed under financial support
by the Ministry of Industry and Trade of the Russian
Federation (contract no. 109/1/4, Dec 31, 2010).
kin, A.V., and Kostikova, N.A., Ros. Khim. Zh., 2007,
vol. 51, no. 2, p. 19.
6. Chadaeva, N.A., Kamai, G.Kh., and Mamakov, K.A.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1971, p. 1726.
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