ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 12, pp. 2523–2524. © 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. 2062–2063.
LETTERS
TO THE EDITOR
Phosphorus-Containing Small Rings:
1
XI. Reaction of 3-Phenyl-2,2-dichlorocyclobutanone
with Dialkyl Phosphites
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/S1070363210120212
Cyclobutane derivatives containing carbonyl group
have been studied in detail [2]. However the data on
the reactions of ketones of the cyclobutane series with
hydrophosphoryl compounds are absent in the
literature. In this connection we studied for the first
time the reaction of 3-phenyl-2,2-dichlorocyclobutanone
I with dialkyl phosphites. The selection of the initial
phosphorylation objects was due both to their ac-
cessibility [3] and to the presence of aromatic ring and
chlorine atoms along with the strained four-membered
ring providing a possibility to further modification of
the phosphorylation products into organophosphorus
compounds of new types.
Dimethyl (1-hydroxy-3-phenyl-2,2-dichlorocyclo-
butyl)phosphonate (IIа). To a solution of 2.2 g of
ketone I and 1.1 g of dimethyl phosphite in 5 ml of
benzene was added 20 drops of the saturated alcohol
solution of sodium methoxide while stirring at 25°С.
After completion of the weak self-heating (temperature
rise up to 40°С) the mixture was stirred for 1 h at 40–
50°С and washed with water. The organic layer was
dried with anhydrous sodium sulfite and subjected to
chromatography on aluminum oxide. Yield 2 g (66%),
20
20
colorless oil, d 1.4121, n 1.5553. Found, %: Сl
4
D
21.81; P 9.53. С Н Cl O Р. Calculated, %: Сl 21.92;
1
2
15
2
4
1
3
P 9.61. Н NMR spectrum, δ, ppm: 4.73 m (1Н, Н ),
4
3
3
7
.64 m (2Н, Н ), 3.74 d (6Н, OCH , J 10.35 Hz),
3
НР
The reactions were carried out using equimolar rea-
gent ratio in the presence of a catalytic amount of
saturated alcohol solutions of sodium alkoxylate. The
formed products were purified by the column chro-
matography, and their structure was investigated by the
31
.21–7.37 m (5Н, С Н ), 4.61 s (1Н, ОН). Р NMR
6
5
spectrum: δ 20 ppm.
P
Compounds IIb-IId were similarly prepared.
1
31
20
4
methods of IR, Н and Р NMR spectroscopy. The
Compound IIb. Yield 76%, С Н Cl O Р, d
1
4
19
2
4
20
spectral data showed that dialkyl (1-hydroxy-3-phenyl-
,2-dichlorocyclobutyl)phosphonates IIa–IId formed.
1.3424, nD 1.5463.
2
2
4
0
Compound IIc. Yield 81%, С Н Cl O Р, d
1
6
23
2
4
This is consistent with the scheme proposed for ali-
phatic aldehydes and ketones [4]. The reaction of ketone
I with O-alkylarylphosphonites proceeds analogously.
20
1
.2916, n 1.5392.
D
20
4
Compound IId. Yield 75%, С Н Cl O Р, d
1
8
27
2
4
20
O
1.2401, nD 1.5332.
HO
O
RONa
P(OR)2
Cl
+
(RO) PH
The growth-regulating activity of the phosphorus-
containing cyclobutanes IIa–IId on the germinability
of the seeds of agricultural crops was revealed.
2
Cl
Ph
Ph
Cl
Cl
O
I
IIа−IId
).
The IR spectra were registered on an IR Fourier-
R = CH
3
(
а), C
2
H
5
(
b
), C
3
H
7
(
c
), C
4
H (d
9
3
1
spectrometer FSМ 1202 (KBr, film). The Р NMR
spectrum was taken on a Bruker WP-80 instrument
(32.44 MHz) with external reference 85% H PO . The
1
For communication X, see [1].
3
4
2
523