Reaction of 2-R-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinanes with perfluorodiacetyl [2]

Full text of DOI:10.1023/A:1015462710700

Russian Journal of General Chemistry, Vol. 72, No. 2, 2002, pp. 321 322. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 2, 2002,
pp. 346 347.
Original Russian Text Copyright
2002 by Ivkova, Zagidullina, Mironov, Konovalova, Kurykin.
LETTERS
TO THE EDITOR
Reaction of 2-R-4-Oxo-5,6-benzo-1,3,2-dioxaphosphorinanes
with Perfluorodiacetyl
G. A. Ivkova, E. R. Zagidullina, V. F. Mironov, I. V. Konovalova, and M. A. Kurykin
Kazan State University, Kazan, Tatarstan, Russia
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Received March 7, 2001
It is known that the reaction of perfluorinated -di-
ketones such as 4-trifluoromethylperfluoropentane-2,3-
dione and perfluorohexane-2,3-dione with 2-R-4-oxo-
5,6-benzo-1,3,2-dioxaphosphorinanes I yields the prod-
ucts of extension of the starting heterocycle, 2-R-2,5-
dioxo-5-RF CO-5-RF -6,7-benzo-1,3,2-dioxaphosphep-
ins [1]. Both carbonyl groups of -diketone with
equal probability take part in the process with the rel-
atively low regioselectivity [RF, RF = CF3, C3F7;
C3F7, CF3; CF3, CF(CF3)2; CF(CF3)2, CF3].
tioned regioisomers is avoided. However, we found
that perfluoroacetyl under mild conditions ( 20 C,
CH2Cl2), instead of benzophosphepins, the products
of ring extension, gives in high yields (90 95%) five-
5
coordinate phosphorus derivatives,
1,3,2-dioxa-
phospholines II, containing the initial benzophos-
phorinane ring. The 31P NMR spectra of these com-
pounds (IIa IId) contain the upfield signals at 54
to 57 ppm, characteristic of pentaalkoxyspirophos-
phoranes with one five-membered ring. Their IR spec-
tra contain the absorption bands of stretching vibra-
1
Proceeding with studies on preparation of functional
derivatives of seven-membered heterocycles, 6,7-ben-
zo-1,3,2- and 6,7-benzo-1,4,2-dioxaphosphepins [2, 3],
we examined in this work the reactions of phosphor-
inanes I with perfluorodiacetyl, which, contrary to
the previously used compounds [1], contains similar
carbonyl groups, so that formation of the above-men-
tions of the C(O)O group (1750 1770 cm ) and
1
of the OC=CO multiple bond (1660 1670 cm ).
Note that spirophosphoranes IIa IIc (viscous oils)
and IId (crystals melting at 76 78 C with decom-
position) are relatively stable in such solvents as
CH2Cl2 and CDCl3, which allowed us to confirm
their structure by 13C NMR spectroscopy.
R
P
5
3
R
O
O
O
O
O
CF3
P
+ CF3 C C CF3
O O
4
2
O
CF3
1
O
O
Ia Ie
IIa IIe
O
P
R
O
O
O
CF3
O
R
O
+
+
P
O
CF3
C(O)CF3
n
O
O
CF3
III
IVa IVe
Va Ve
R = OMe (a), OEt (b), OCH2CF3 (c), OCH2CF2CHF2 (d), Ph (e).
1070-3632/02/7202-0321$27.00 2002 MAIK Nauka/Interperiodica

322
IVKOVA et al.
The 13C NMR spectra (CDCl3, 62.5 MHz) of IIb
The NMR spectra were measured on a Bruker
WM-250 spectrometer. The experimental details and
spectral characteristics of the products will be pub-
lished later.
IId contain the following signals proving the forma-
tion of dioxaphospholine ring and the preservation of
the dioxaphosphorinane ring, C, ppm (J, Hz): C1,
128.89 (IIb), 129.42 (IIc), 129.44 (IId), all multi-
2
plets (2JFCC 45 50, JPOC 5 6); C2, 117.94, 117.91,
ACKNOWLEDGMENTS
3
117.88, all q.d (1JFC 268.4 269.0, JPOCC 19.2 19.9);
C3, 157.87, 157.38, 157.44, all d (2JPOC 8.2 8.5);
C4, 113.20, 113.12, 113.23, all d (3JPOCC 1.6 2.8);
C5, 152.68, 152.79, 152.74, all d (2JPOC 5.5 5.7).
The reaction of phosphorinane Ie with perfluorodiace-
The study was financially supported by the prog-
ram Universities of Russia Basic Research (project
no. 015-05-01-17), the program of support of leading
scientific schools in Russia (project no. 00-15-97424),
and the joint program of CRDF and the Ministry of
Education of Russia Basic Research and Higher Ed-
ucation (grant REC-007).
tyl yields, along with phosphorane IIe ( 33.1 ppm,
P
62.1%), also phospholene IVe ( 19.1 ppm, 27.3%)
P
and isomeric phosphepins Ve ( 15.1 and 12.8 ppm,
P
10.6%).
REFERENCES
Heating of phosphoranes II yields four-coordinate
phosphorus derivatives, phospholines IV, formed by
elimination of salicylic oligomer III, and 6,7-benzo-
1,3,2-dioxaphosphepins V. The ratio of these prod-
ucts depends on substituent R. Heating of the same
phosphoranes in dry acetonitrile yields phosphepins V.
Their content in the reaction mixture is 70 90%. The
31P NMR spectra of phospholines IV contain the
signals at 9 11 ppm, while diastereomeric phos-
phepins V are characterized by more upfield signals
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from 10 to 12 ppm.
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 2 2002