ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 12, pp. 2525–2526. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © Yu.N. Mitrasov, М.A. Frolova, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 12, pp. 2064–2065.
LETTERS
TO THE EDITOR
Phosphorus-Containing Small Rings:
XII.1 Reaction of 3-Phenyl-2,2-dichlorocyclobutanone
with Esters and Amidoesters of Phosphorus(III) Acids
Yu. N. Mitrasov and М. A. Frolova
Yakovlev Chuvash State Pedagogical University, ul. K. Marksa, 38, Cheboksary, Russia
е-mail: mariafrolova25@yandex.ru
Received March 11, 2010
DOI: 10.1134/S1070363210120224
The esters of phosphorus(III) acids are known to
react readily with α-halocarbonyl compounds to form
vinyl esters of the phosphorus(IV) acid [2, 3]. Ac-
cording to published data, halocyclobutanones have
not been used in this reaction. In this connection, aiming
to develop a synthetic approach to the phosphorus-con-
taining cyclobutanones, we studied the reaction of 3-
phenyl-2,2-dichlorocyclobutanone I with the esters and
amidoesters of phosphorus(III) acids. The reaction
progress was monitored by tracing the amount of
chloroalkanes released and also by means of TLC. It
was shown that depending on the nature of the phos-
phorus component the reaction temperature should be
varied within 80–130°С. Arylphosphonites are the
most active, and amidoesters, the least active. The
reaction products were purified by vacuum distillation
or by column chromatography. Their structure was
1
studied by IR, Н and 31Р NMR spectroscopy. By the
spectral data, this reaction proceeds as the Perkov reaction
[3] without the opening of the four-membered ring.
Ar
+ ArnP(OR)3−n
O
Ph
OP
Ph
−RCl
(OR)2−n
Cl
O
Cl
Cl
I
II
IIIа−IIIl
n
= 0, R = CH3 (
а
), C2H5 (
b
), C3H7 (
c
), C4H9 (
d
);
n
= 1, Ar = C6H5, R = CH3 (
).
e), C2H5 (f), C3H7 (g), C4H9 (h);
Ar = 4-CH3C6H4, R = CH3 (
i
), C2H5 (
j
), C3H7 (
k
), C4H9 (l
1
Compounds IIIа–IIIl are colorless liqiuds soluble in
culated, %: Cl 12.37; Р 11.03. Н NMR spectrum, δ,
3 4
organic solvents and poorly soluble in water.
ppm: 3.89 m (1Н, Н), 4.00 m (2Н, Н), 3.88 d (6Н,
OCH3, JНР 10.8 Hz), 6.72–7.57 m (5Н, С6Н5). 31Р
3
The growth-regulating activity of the phosphorus-
containing cyclobutanes IIIa–IIIl on the germinability
of the seeds of agricultural crops was revealed.
NMR spectrum: δP 4.0 ppm.
Compounds IIIb–IIIl were similarly prepared.
Dimethyl (3-phenyl-2-chloro-1-cyclobutenyl)phos-
phate (IIIа). A mixture of 2.2 g of ketone I and 1.7 g
of trimethyl phosphite was heated at 95–100°С under
argon for 6 h and then it was distilled. Yield 2.9 g
(76%), bp 128°С (1 mm Hg), d420 1.3144, nD20 1.5382.
Found, %: Cl 12.28; Р 10.93. С12Н14СlO4P. Cal-
Compound IIIb. Yield 68%, С14Н18СlO4P, bp 147
(1 mm Hg), d420 1.2544, nD20 1.5305.
Compound IIIc. Yield 72%, С16Н22СlO4P, bp 171
(1 mm Hg), 1.2115, 1.5254.
Compound IIId. Yield 68%, С18Н26СlO4P, bp 191
(1 mm Hg), d420 1.1755, nD20 1.5234.
1
For communication XXI, see [1].
2525
Mitrasov, Yu. N.
