Oxidation of dialkyl arylethynylphosphonates in a system CF 3CO2H-CH2Cl2-PbO2

Full text of DOI:10.1134/S1070428006050228

ISSN 1070-4280 Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 5, pp. 770-771. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó S.A. Aristov, A.V. Vasil’ev, A.P. Rudenko, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No.5,
pp. 785-786.
SHORT
COMMUNICATIONS
Oxidation of Dialkyl Arylethynylphosphonates in a System
CF3CO2H-CH2Cl2-PbO2
S.A. Aristov,A.V. Vasil’ev, andA.P. Rudenko
St. Petersburg Academy of Forestry Engineering, St. Petersburg, 194021 Russia
e-mail: aleksvasil@mail.ru
Received November11, 2005
DOI: 10.1134/S1070428006050228
a,b-Unsaturated phosphonates and versatile com-
pounds synthesized therefrom find wide practical applica-
tions as incombustible polymers, antibiotics, various bio-
logically active substances, and convenient intermediates
in the synthesis of 1-arylethylphosphonates possessing
immunosuppressor properties with the central type
action [1].
and other difficultly available carbonyl derivatives of the
unsaturated series [3, 4]. This communication reports on
the preparative opportunities provided by oxidation of
dialkyl arylethynylphosphonates Ia and Ib in a system
CF3CO2H–CH2Cl2–PbO2 via intermediate formation of
cation-radicals of compounds Ia and Ib to afford
dicarbonyl diphosphonates IIa and IIb. Polyfunctional
compounds IIa and IIb belong to a new class of
substances which can be valuable synthons for
preparation of carbo- and heterocyclic derivatives.
We formerly demonstrated that the one-electron
oxidation of acetylene compounds resulted in products of
the oxidative dimerization, 1,1,2,2-tetraaroylethenes [2]
2
2
2
2
&
3ꢀ2(Wꢁ
&
&) &2 +ꢃꢃꢃꢃ&+ &O ꢃꢃꢃꢃ3E2
ꢂ
5
& &
5
& & 3ꢀ2(Wꢁ
ꢃB
& & 3ꢀ2(Wꢁ
H
ꢀ(W2ꢁ 3
5
5
2
2
,, ꢀꢁ,,E
, ꢀꢁ,E
R = 4-MeO (a), 2,4,6-Me3 (b).
pounds of trans-(E-) configuration in the similar cation-
radical reactions of arylpropynone derivatives
ArCºCCOR [2–4].
Initial diethyl arylethynylphosphonates Ia and Ib were
prepared by the Michaelis-Becker reaction [5] treating
sodium diethyl phosphate with 1-bromo-2-arylethynes
prepared by procedure [6]. Diethyl phenylethynyl-
phosphonate was obtained by method [7].
Substrates Ia and Ib containing electron-donor groups
R were oxidized into final products IIa and IIb within
3.5 and 21 h in 62 and 15% yields respectively. Under
similar conditions at 20°C within 30 h the attempt failed
to oxidize diethyl phenylethynylphosphonate possessing
higher oxidation potential than compounds Ia and Ib: The
unreacted initial compound was quantitatively recovered
from the reaction mixture.
The structure of compounds IIa and IIb was
established from IR, 1H, 13C,31P NMR, and mass spectra.
We assigned to compounds IIa and IIb the trans-(E-)
configuration based on the formation of related com-
Diethyl 4-methoxyphenylethynylphosphonate
–1
(Ia). Yield 32%, oily substance. IR spectrum, n, Cm :
1
2185 (CºC), 1250 (P=O). H NMR spectrum, d, ppm:
1.38 t (6H, 2Me, J 7.3 Hz), 3.82 s (3H, MeO), 4.20 quintet
770

OXIDATION OF DIALKYL ARYLETHYNYLPHOSPHONATES
771
409 (32), 335 (16), 297 (24), 147 (100), 119 (42), 91 (18).
Found, %: C 60.86; H 7.08. C30H42O8P2. Calculated, %:
C 60.80; H 7.14. M 592.24.
(4H, 2CH2, J 7.3 Hz), 6.86 d (2Harom, J 8.8 Hz), 7.49 d
(2Harom, J 8.8 Hz). Found, %: C 57.97; H 6.02. C13H17O4P.
Calculated, %: C 58.21; H 6.39 .
1H, 13C, and 31P NMR spectra were registered on
a spectrometer Bruker AM-500 (operating frequencies
500, 125.76, and 202.5 MHz respectively) in CDCl3. As
internal references served the residual signal of CHCl3
(d 7.25 ppm) for 1H, the signal of CDCl3 (d 77.0 ppm)
for 13C, and the signal of H3PO4 (85% water solution)
was used as external reference (d 0.0 ppm) for 31P. IR
spectra of solutions of compounds in chloroform were
recorded on a spectrophotometer Specord 75 IR. Mass
spectra were measured on an MKh-1321 instrument,
ionizing voltage 70 eV, direct admission of the sample
into the ion source at the temperature 100–120°C.
Diethyl 2,4,6-trimethylphenylethynylphosphonate
–1
(Ib). Yield 34%, oily substance. IR spectrum, n, cm :
1
2185 (CºC), 1250 (P=O). H NMR spectrum, d, ppm:
1.38 t (6H, 2Me, J 7.3 Hz), 2.27 s (3H, Me), 2.40 s (6H,
2Me), 4.21 quintet (4H, 2CH2, J 7.3 Hz), 6.86 s (2Harom).
Found, %: C 64.38; H 7.80. C15H21O3P. Calculated, %:
C 64.27; H 7.55.
Tetraethyl [1,2-bis(4-methoxyphenylcarbonyl)]-
ethene-1,2-diyl-1,2-diphosphonate (IIa). To a solution
of 0.14 ml of CF3CO2H in 3 ml of CH2Cl2 at 0°C while
vigorous stirring was added 100 mg (0.37 mmol) of
compound Ia, then 88 mg (0.37 mmol) of PbO2, and the
stirring of the reaction mixture was continued for 3.5 h.
On completion of the reaction the mixture was poured
into 50 ml of chloroform. The chloroform solution was
washed with water, with a saturated solution of NaHCO3,
again with water, dried over Na2SO4, and the solvent
was distilled off. The residue was subjected to column
chromatography on silica gel. Eluent petroleum ether (bp
40–70°C)–ethyl acetate. Yield 65 mg (62%), mp 162–
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–1
163°C. IR spectrum, n, cm :1670 (C=O), 1250 (P=O).
1H NMR spectrum, d, ppm: 1.10 br.s (12H, 4Me), 3.88 s
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(6H, 2MeO), 3.94 br.s (8H, 4CH2), 6.98 d (4Harom
,
J 8.5 Hz), 8.04 d (4Harom, J 8.5 Hz). 13C NMR spectrum,
d, ppm: 15.9 (Me), 55.5 (OMe), 63.4 (OCH2), 113.7,
129.3, 132.3, 146.8 d (C=C, JCP 162.9 Hz), 164.1, 190.8 t
(C=O, JCP 9.7 Hz). 31P NMR spectrum, d, ppm: 7.31 s.
Mass spectrum, m/z (Irel, %): 568 (3) [M]+, 433 (10), 135
(100), 107 (5), 92 (5), 77 (9). Found, %: C 55.11; H 5.99.
C26H34O10P2. Calculated, %: C 54.93; H 6.03. M 568.16.
Tetraethyl [1,2-bis(2,4,6-trimethylphenyl-
carbonyl)]ethene-1,2-diyl-1,2-diphosphonate (IIb)
was prepared by the same procedure as compound IIa
from 100 mg (0.36 mmol) of substrate Ib by oxidation
with 85 mg (0.36 mmol) of PbO2 in a mixture of 0.14 ml
of CF3CO2H and 3 ml of CH2Cl2 at 20°C within 21 h.
–1
Yield 16 mg (15%), mp 184–185°C. IR spectrum, n, cm :
1
1670 (C=O), 1250 (P=O). H NMR spectrum, d, ppm:
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1.11 br.s (12H, 4Me, J 7.1 Hz), 2.27 s (6H, 2Me), 2.53 s
(12H, 4Me), 3.96 m (8H, 4CH2), 6.85 s (4Harom). Mass
spectrum, m/z (Irel, %): 592 (6) [M]+, 455 (20), 438 (11),
vol. 32, p. 2387.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 5 2006