ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 6, p. 1168. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © Yu.N. Mitrasov, D.A. Sosnov, O.V. Kondrat’yeva, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 6, p. 1038.
LETTERS
TO THE EDITOR
Reactions of Spiro[2.3]hexane-5-carbonyl Chloride
with Phosphorus(III) Acids Esters
Yu. N. Mitrasov, D. A. Sosnov, and O. V. Kondrat’yeva
Yakovlev Chuvash State Pedagogical University, ul. K. Marksa 38, Cheboksary, 428000 Russia
e-mail: sosnovd1987@mail.ru
Received February 14, 2013
DOI: 10.1134/S1070363213060303
We have previously shown that the reaction of
bicyclo[4.1.0]heptane-7-carbonyl chloride with
We found that spiro[2.3]hexane-5-carbonyl
chloride I reacts readily with phosphorous and aryl-
phosphonous acids esters. When an equimolar ratio of
reagents was used under mild conditions (0–20°C), the
attack of the P-nucleophiles occurs on the carbon atom
of the carbonyl group. As a result, the reaction
produces dialkyl spiro[2.3]hexane-5-carbonyl phos-
phonates IIa–IIc or alkylarylspiro[2.3]hexane-5-carbonyl
phosphinates IId–IIf.
medium esters of phosphorous and arylphosphonous
acids occurs with the retention of the small carbocycle
[1]. In continuation of this work it is interesting to
study the behavior of carbonyl compounds of
spirohexane series in the Arbuzov reaction [2]. Due to
the high energy strain of these spiranes one could
expect unusual reaction course affording new types of
organophosphorus compounds.
R1n
(OR2)2 n
R1nP(OR2)3−n
C
+ R2Cl
P
C
O
Cl
_
O
IIа_IIf
O
I
n = 0, R2 = C2H5 (а), C3H7 (b), С4H9 (c); n = 1, R1 = C6H5, R2 = C2H5 (d), C3H7 (e), С4H9 (f).
The structure of compounds IIa–IIf was confirmed
by the IR and H NMR spectroscopy. Thus, in the IR
Compound IIc. Yield 76%, bp 167–168°С (1 mm Hg),
1
dD20 1.1006 g cm–3, nD20 1.4752.
spectra there are low-intensive peaks of the stretching
vibrations of the C–H bonds of the three-membered
ring in the range of 3090–3095 cm–1 and the strong
absorption bands of carbonyl, phosphoryl, and ester
groups at 1700–1705, 1255–1260, 995–1050 cm–1,
respectively. The 1H NMR spectra the three-membered
ring protons resonate in a strong field (δ 0.61 ppm).
The four-membered ring protons were observed in a
weaker field as a doublet at δ 2.77 ppm (4Н, СН2, 3JHН
7.75 Hz) and a multiplet at 3.24 ppm (1H, CH). The
protons of alkoxy groups and aromatic ring appear in
characteristic areas.
Compound IId. Yield 81%, bp 182–183°С (1 mm Hg),
d420 1.1992 g cm–3, nD20 1.5456.
Compound IIe. Yield 78%, oily substance, d420
1.1792 g cm–3, nD20 1.5418.
Compound IIf. Yield 79%, oily substance, d420
1.1594 g cm–3, nD20 1.5378.
REFERENCES
1. Mitrasov, Yu.N., Sosnov, D.A., Lukicheva, N.A., and
Kondrat’yeva, O.V., Vestn. Chuvashck. Gos. Ped. Univ.
imeni I.Ya. Yakovleva, 2011, no. 2(70), p. 108.
2. Gazizov, T.Kh., Reaktsiya Arbuzova. Reaktsii efirov
kislot P(III) s galogensoderzhashchimi elektrofil’nymi
soedineniyami (Arbuzov Reaction. Reactions of P(III)
Acid Esters with Halogen Electrophilic Compounds),
Kazan: IOFKh imeni A.E. Arbuzova, 1991, pt. 1.
Compound IIa. Yield 75%, bp 151–153°С (5 mm Hg),
d420 1.1693 g cm–3, nD20 1.4774.
Compound IIb. Yield 82%, bp 161–162°С (2 mm
Hg), d420 1.1307 g cm–3, nD20 1.4765.
1168
Mitrasov
