Specific features of reaction of 2-R-benzo[e][1,3,2]dioxaphosphinin-4-ones with perfluorodiacetyl. Synthesis and steric structure of 4′,5′- bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-2λ 5-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2′-[1,3,2] dioxaphosphole]

Article abstract of DOI:10.1007/s11176-005-0270-6

2-R-benzo[e][1,3,2]dioxaphosphinin-4-ones react with perfluorodiacetyl under mild conditions to form relatively labile spirophosphoranes containing a 1,3,2-dioxaphosphole ring. These compounds gradually convert to more stable 2-R-4,5-bis(trifluoromethyl)-1,3,2λ⁵-dioxaphosphole 2-oxides and diastereometic 2-R-4-(trifluoroacetyl)-4-(trifluoromethyl)benzo[f][1,3, 2λ⁵]dioxaphosphepine 2-oxides, whose structure was confirmed by means of NMR and IR spectroscopy. The structure of 4′,5′ -bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-2λ ⁵-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2′-[1,3,2] dioxaphosphole] was confirmed by X-ray diffraction analysis. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11176-005-0270-6

Russian Journal of General Chemistry, Vol. 75, No. 4, 2005, pp. 549 560. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005,
pp. 587 599.
Original Russian Text Copyright
2005 by Konovalova, Mironov, Ivkova, Zagidullina, Gubaidullin, Litvinov, Kurykin.
Specific Features of Reaction
of 2-R-Benzo[e][1,3,2]dioxaphosphinin-4-ones
with Perfluorodiacetyl. Synthesis and Steric Structure
of 4 ,5 -Bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-
5
2 -spiro[benzo[e][1,3,2]dioxaphosphinine-
2,2 -[1,3,2]dioxaphosphole]
,
I. V. Konovalova,* V. F. Mironov,* ** G. A. Ivkova,* E. R. Zagidullina,*
A. T. Gubaidullin,** I. A. Litvinov,** and M. A. Kurykin***
*Kazan State University, Kazan, Tatarstan, Russia
**Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
***Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Received Ocrober 1, 2003
Abstract 2-R-benzo[e][1,3,2]dioxaphosphinin-4-ones react with perfluorodiacetyl under mild conditions to
form relatively labile spirophosphoranes containing a 1,3,2-dioxaphosphole ring. These compounds gradually
convert to more stable 2-R-4,5-bis(trifluoromethyl)-1,3,2 5-dioxaphosphole 2-oxides and diastereometic
2-R-4-(trifluoroacetyl)-4-(trifluoromethyl)benzo[f][1,3,2 5]dioxaphosphepine 2-oxides, whose structure was
confirmed by means of NMR and IR spectroscopy. The structure of 4 ,5 -bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-
tetrafluoropropoxy)-2 5-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2 -[1,3,2]dioxaphosphole] was confirmed by
X-ray diffraction analysis.
Fluorine-containing -dicarbonyl compounds, such
as perfluorodiacetyl, readily react with various P(III)
derivatives to form such P(V) compounds as 4,5-bis-
(trifluoromethyl)-1,3,2-dioxaphospholes (for reviews,
see [1, 2]). The latter compounds are important as
phosphorus-containing models of cyclic P(V) inter-
mediates of enzymatic reactions [3 7]. Recently first
representatives of stable phosphoranes in the series of
bicyclophosphorylated carbohydrates were prepared
by the reaction of perfluorodiacetyl with 1,2-O-iso-
propylidene- -D-glucofuranose 3,5,6-bicyclophosphite
functionalyzed derivatives of seven-membered hetero-
cycles, 6,7-benzo-1,3,2- and 6,7-benzo-1,4,2-dioxa-
phosphepines [10 12], in the present communication
we present the results of investigation of reactions of
2-R-benzo[e][1,3,2]dioxaphosphinin-4-ones
I
with
perfluorodiacetyl (for the preliminary report, see [13]).
The latter, unlike the compounds studied by Kadyrov
et al. [9], contains equivalent carbonyl groups, which
allows one to avoid formation of the mentioned regio-
isomers. However, it was found that the reactions with
perfluorodiacetyl occur under mild conditions ( 25 C,
CH2Cl2) and give rise not to ring enlargement prod-
ucts, benzophosphepines, but P(V) derivatives,
[8]. It is known that unsymmetrical perfluorinated
-
diketones, such as 4-(trifluoromethyl)perfluoropentane-
2,3-dione and perfluorinated hexane-2,3-dione, react
with 2-bis(2-chloroethyl)aminobenzo[e][1,3,2]dioxa-
phosphinin-4-one to form heteroring enlargement
5
1,3,2 -dioxaphospholes II containing the starting
benzophosphinine ring. The yields of these com-
pounds reach 90 95%. The structure of the products
was established by means of IR and NMR spec-
troscopy. The 31P NMR spectra of these compounds
in CH2Cl2 contain upfield signals in the range 54 to
57 ppm (IIa IId) and 33.1 ppm (IIe), characteristic
of pentaalkoxyspirophosphoranes with one five-
membered ring. The IR spectra contain strong bands
due to stretching vibrations of the C(O)O group
5
products, viz. 2-R-5-RFCO-5-RF-6,7-benzo-1,3,2 -
dioxaphosphepin-5-one 2-oxides [9]; therewith, the
reaction occurs with a relatively low selectivity, in-
volving both carbonyl groups of the -diketone [RF,
RF = CF3, C3F7; C3F7, CF3; CF3, CF(CF3)2; CF3,
CF(CF3)2; CF(CF3)2, CF3].
Continuing the cycle of works on the synthesis of
1070-3632/05/7504-0549 2005 Pleiades Publishing, Inc.

550
KONOVALOVA et al.
Table 1. 13C {1H} and 13C NMR spectral parameters of phosphoranes IIb IId (CDCl3 CH2Cl2 1: 1), C, ppm (J, Hz)
Atom
C1,2
C3
Compound IIb
Compound IIc
Compound IIda
129.36 br.q.m (br.q.m)b (45.6,
130.43 br.q.m (br.q.m) (45.3,
129.44 br.q.m (45.7, FCC1,2; 5.2,
FCC1,2; 4.0 4.1, POC1,2
)
FCC1,2; 4.0, POC1,2
)
POC1,2
)
158.87 d (d.d) (8.1, POC3; 4.1, 158.38 d (d.d) (8.5, POC3; 4.0, 157.44 d (8.5, POC3)
HC9CC3)
HC9CC3)
C4
114.19 d (m) (2.2, POCC4; 6.9 7.1, 153.69 d (m) (5.6, POC5)
HC6CC4; 6.9 7.1, HC8CC4)
113.23 d (2.2, POCC4)
152.74 d (5.7, POC5)
C5
153.68 d (m) (5.6, POC5) 114.11 113.23 d (2.2, POCC4)
d (m) (2.1, POCC4)
C6
119.52 d (d.d. d.d) (15.6, POCC6; 119.81 d (d.d.d) (166.1, HC6; 15.8, 118.89 d (15.8, POCC6)
166.1, HC6; 7.7, HC8CC6; 1.7,
HC7C8)
POCC6; 7.3, HC8CC6)
C7
C8
C9
137.50 d (d.d.d) (162.5, HC7; 8.9, 138.10 d (d.d.d) (162.2, HC7; 7.9, 137.13 s
HC9CC7; 1.6, POC5C6C7)
125.70 s (d.d) (164.4, HC8; 7.2, 126.36 s (d.d) (164.3, HC8; 6.8, 125.45 s
HC6CC8) HC6CC8)
130.94 s (br.d.d) (165.4, HC9; 7.4, 131.43 s (d.d) (165.4, HC9; 6.7, 130.59 s
HC7CC9) HC7CC9)
HC9CC7; 2.0, POC5C6C7)
C10,11 118.95 q.d (q.d) (270.0, FC10,11; 19.9, 118.91 q.d (q.d) (270.0, FC10,11
;
117.88 q.d (269.0, FC10,11; 19.9,
POCC10,11
69.12 d (t.d.q) (151.1, HC12; 11.7, 67.10 q.d (t.q.d) (154.0, HC12; 37.8, 65.65 t.d (30.5, FC13C12; 10.5,
POC12; 4.5, HC13C12) FC13C12; 10.3, POC12) POC12)
POCC10,11
)
20.0, POCC10,11
)
)
C12
C13
16.15 d (q.d.t) (127.4, HC13; 7.7, 22.93 q.d (q.d.t) (277.4, FC13; 11.4, 110.76 t.t.d (248.0, FC13; 37.5,
POCC13; 2.6, HC12C13)
POCC13; 4.4, HC12C13)
FC12C13; 13.0, POCC13)
a
14
14
13 14
b
13
C
, 109.90 t.t (250.0, FC ; 36.5, FC
C
).
Parenthesized are the signal multiplicities of the C NMR spectra.
1
2
2
5
(1750 1770 cm ) and OC=CO multiple bond
JPOC 8.1 8.5 and JPOC 5.6 5.7 Hz. The C4
1
3
4
(1660 1670 cm ). It should be noted that spirophos-
signal locates upfield (113.23 114.19 ppm, JPOCC
2.1 2.2 Hz). The C6 C9 signals were assigned con-
sidering the small difference in the ortho- and para-
shielding effects of the O1 atom, deshielding effect of
the COO substituent, and corresponding signal multi-
plicities. The dioxaphosphole C1 and C2 signals
phoranes IIa IIc and IIf (viscous oils) and IId (crys-
tals) are stable for some time in such solvents as
CH2Cl2 and CDCl3, which allowed their unambiguous
structural assessment by means of H and 19F (see
1
Experimental), as well as 13C NMR spectroscopy (see
Table 1). The 19F NMR spectra contain a broadened
singlet at 64 to 66 ppm from trifluoromethyl
fluorines.
appear at 129.3 130.4 ppm as a characteristic quartet
2
1,2
of doublets with the constants JFCC 45.3 45.7 and
2
1,2
JPOC
4.0 5.2 Hz. The trifluoromethyl carbon
signals, too, give a quartet of doublets (1JFC
270.0 and JPOCC
field region (117 119 ppm).
269.0
In the downfield region of the 13C NMR spectra,
there are C3 and C5 signals (157.4 158.8 and 152.7
153.7 ppm, respectively) with characteristic constants
10,11
3
10,12
19.9 20.0 Hz) in a fairly down-
+
P
R
R
O
O
O
CF3
C
P
C
CF3
+ CF3 C C CF3
O O
O
O
O
O
O
Ia Ie
A
7
9
6
CF3
R
+
P
O
O
5
11
CF3
10
R
8
2
1
O
O
CF3
O C
C
O
4
O
P
3
CF3
O
O
O
B
IIa IIe
R = OCH3 (a), O1C2H2CH133 (b), O1C2H2CF3 (c), O1C2H2CF2CHF2 (d), Ph (e).
13
13 14
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SPECIFIC FEATURES OF REACTION OF 2-R-BENZO[e][1,3,2]DIOXAPHOSPHININ-4-ONES
551
F9
F8
F10
C14
C13
F7
C12
F3
O5
C10
F1
O1
C1
O6
O3
C3
F4
C11
C9
F2
P2
C2
F6
C4
C7
C5
O2
O4
C8
C6
F5
Fig. 1. Molecular geometry of spirophosphorane IId in crystal (the base of the trigonal bipyramid is shown by thin lines).
The reaction evidently involves initial attack of the
phosphorus atom of phosphite I on the carbonyl
carbon atom of perfluorodiacetyl with intermediate
formation of dipolar ion A with a P+ C O fragment.
Ion A further rearranges into dipolar ion B containing
a P+ OC bond. The main direction of further stabili-
zation of ion B in which the negative charge is delo-
calized in the C(CF3) C(CF3) O triad is the attack of
the oxygen atom on phosphorus, leading to 5-phos-
phole II. It is hard to tell why perfluorodiacetyl, un-
like unsymmetrical perfluoro- -diketones [9], reacts
with benzophosphininones I in such a manner.
Probably, this is connected with peculiar features of
the electronic structure of this compound. Dibenzoyl
behaves similarly in reactions with compounds Ia and
Ic [14], but the related salicyl 5-phospholes, being
unstable, could only be detected by spectral methods.
By contrast, tetrachloro-o-benzoquinone forms a
The O2, O4, O5, and P2 atoms are situated in the base
of the bipyramid and form an ideal plane within
0.000(1) A. The sum of the O4P2O5, O2P2O4, and
O2P2O5 bond angles is 360.0(1) . The O1 and O3
atoms that occupy apical positions deviate from this
plane by slightly different distances, 1.712(1) and
1.641(1)
[the P2 O1 and P2 O3 bond lengths are
1.716(3) and 1.658(3) ]. The P2 O2, P2 O4, and
P2 O5 bonds lying in the base of the bipyramid are
correspondingly shorter [1.628(2), 1.589(3), and
1.580(3) ]. At the same time, the lengths of the exo-
and endocyclic P2 O5 and P2 O4 bonds are almost
the same. It is interesting to note that spirophos-
phorane III considered in [16] and structurally close
to spirophosphorane IId has a much smaller dif-
ference between axial and equatorial bond lengths. In
III, the axial P2 O1 and P2 O3 bonds are 1.691 and
1.693 , and the equatorial P2 O2, P2 O4, and P2 O5
stable salicyl P(V) derivative in reaction with benzo- bonds are 1.652, 1.636, and 1.588 , respectively.
phosphininone Ic [15].
The configuration of molecule III is more distorted
to a square pyramid, and the difference between the
P2 O1 and P2 O3 bond lengths in the 1,3,2-dioxa-
phosphole ring is smaller (0.039 ) than in IId
[0.088(3) ]. The asymmetry of this ring is stronger
in the latter molecule. The difference in the O2 C2
and O1 C1 bond lengths is 0.024(5) , while in
molecule III it is within the experimental error
(0.003 ). The axial equatorial arrangement of the
1,3,2-dioxaphosphole ring and the difference in the
lengths of in-pair equal bonds is notable even at a
longer distance from O1 and O2. The C2 C11 and
Tetrafluoropropoxy derivative IId well crystallizes
form methylene chloride as coarse crystals, and its
structure could also be confirmed by low-temperature
X-ray diffraction analysis. The steric structure of
compound IId in crystal is shown in Fig. 1, and the
atomic coordinates in and selected parameters of this
molecule (bond lengths and bond and torsion angles)
are listed in Tables 2 and 3.
The configuration of the phosphorus atom in phos-
phorane IId is close to a regular trigonal bipyramid.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

552
KONOVALOVA et al.
Table 2. Atomic coordinates, equivalent thermal parameters of non-hydrogen atoms B = 4/33 3(aiaj)B(i, j) ( 2), and
i=1 j=1
isotropic thermal parameters of hydrogen atoms Biso
(
2) in molecule IId
Atom
x
y
z
B or Biso Atom
x
y
z
B or Biso
P2
F1
F2
F3
F4
F5
F6
F7
F8
F9
F10
O1
O2
O3
O4
O5
O6
C1
C2
0.49113(8) 0.13279(7) 0.37310(8) 0.0121(3) C3
0.3794(3)
0.2976(3)
0.3284(3)
0.2601(3)
0.1530(3)
0.1172(3)
0.1887(3)
0.6823(3)
0.8604(3)
0.3367(3)
0.2171(3)
0.2436(4)
0.28516
0.10483
0.04453
0.16506
0.40260
0.31259
0.28083
0.1304(3)
0.2079(3)
0.2587(3)
0.3369(3)
0.3625(3)
0.3112(3)
0.2347(3)
0.1304(3)
0.0789(3)
0.0306(3)
0.0289(3)
0.1155(3)
0.37165
0.41441
0.32861
0.20108
0.00347
0.08467
0.10188
0.5621(3) 0.0150(13)
0.5107(3) 0.0147(9)
0.4199(3) 0.0147(9)
0.3771(3) 0.0176(13)
0.4231(4) 0.0213(9)
0.5117(4) 0.0213(9)
0.5564(3) 0.0197(13)
0.1166(3) 0.0163(9)
0.3799(4) 0.0215(10)
0.2090(3) 0.0162(13)
0.2092(3) 0.0182(13)
0.2790(4) 0.0234(14)
0.8086(2)
0.6575(3)
0.6122(3)
0.8871(2)
0.9452(2)
0.8827(3)
0.1268(2)
0.1617(2)
0.1316(3)
0.3288(3)
0.5240(2)
0.6468(2)
0.4825(2)
0.4302(2)
0.3852(2)
0.3678(3)
0.6499(3)
0.7207(3)
0.1117(2)
0.21062(19) 0.0626(2) 0.0332(9) C5
0.0679(2)
0.0457(2) 0.0371(10) C6
0.00233(19) 0.3272(3) 0.0392(10) C7
0.1237(2) 0.0319(9) C4
0.1404(2)
0.0612(4)
0.3593(4) 0.0595(13) C8
0.4924(3) 0.099(2)
C9
0.02083(19) 0.2516(2) 0.0299(9) C10
0.04915(19) 0.0960(2) 0.0294(8) C11
0.1647(2)
0.1670(2)
0.2681(3) 0.0421(10) C12
0.2317(3) 0.0426(10) C13
0.15064(19) 0.2371(2) 0.0155(5) C14
0.11297(19) 0.4226(2) 0.0155(5) H6
0.11153(19) 0.5106(2) 0.0155(5) H7
0.23321(19) 0.3650(2) 0.0155(5) H8
0.05597(19) 0.3286(2) 0.0151(8) H9
0.31879
0.39436
0.54100
0.61634
0.17913
0.16074
0.36146
0.0214
0.0256
0.0256
0.0235
0.0194
0.0194
0.0282
0.0870(2)
0.1298(3)
0.1084(3)
0.6464(2) 0.0218(9) H12A
0.2335(4) 0.0163(9) H12B
0.3378(4) 0.0215(10) H14
C1 C10 bond lengths, too, differ by 0.022(6) . Like
in III, the C F bond lengths in spirophosphorane IId
differ from each other and are within 1.312(6)
1.339(5) . The respective bond lengths in molecule
III span a slightly larger range (1.200 1.344 ).
The degree of distortion of the trigonal phosphorus
bipyramid in IId can also be judged about by the
deviations of the sums of bond angles from the ideal
value of 180 in three planes (O1O3O4P2, O1O3O2P2,
and O1O3O5P2) orthogonal to the bipyramid base
(O2O4O5P2). Hence, the sums of the OPO angles in
these three planes [each of them is planar within
0.065(1), 0.006(1), and 0.070(1) ] are 185.1(1),
3
5
O
C6H5
O
O4
1
O
O2
2
P
CF3
1
10CF3
11
III
Table 3. Selected bond lengths (d, ) and bond ( , deg) and torsion angles ( , deg) in molecule IId
Bond
P2 O1
d
Bond
d
Bond
d
1.716(3)
1.628(2)
1.658(3)
1.589(3)
1.580(3)
1.329(4)
1.327(5)
1.339(5)
1.331(5)
1.316(5)
1.312(6)
F7 C13
F8 C13
F9 C14
F10 C14
O1 C1
O2 C2
O3 C3
O4 C5
O5 C12
O6 C3
C1 C2
1.361(4)
1.359(4)
1.352(5)
1.365(5)
1.356(4)
1.380(5)
1.366(4)
1.401(4)
1.431(4)
1.198(5)
1.322(6)
C1 C10
C2 C11
C3 C4
C4 C5
C4 C9
C5 C6
C6 C7
C7 C8
C8 C9
C12 C13
C13 C14
1.475(6)
1.497(5)
1.464(6)
1.386(5)
1.408(5)
1.379(6)
1.388(5)
1.390(6)
1.380(6)
1.518(5)
1.495(6)
P2 O2
P2 O3
P2 O4
P2 O5
F1 C10
F2 C10
F3 C10
F4 C11
F5 C11
F6 C11
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SPECIFIC FEATURES OF REACTION OF 2-R-BENZO[e][1,3,2]DIOXAPHOSPHININ-4-ONES
Table 3. (Contd.)
553
Angle
O1P2O2
Angle
Angle
88.7(1)
171.6(1)
87.8(1)
93.7(1)
82.9(1)
122.7(1)
124.4(1)
97.3(1)
O1C1C10
C2C1C10
O2C2C1
O2C2C11
C1C2C11
O3C3O6
O3C3C4
O6C3C4
O4C5C4
O4C5C6
C7C8C9
C4C9C8
F1C10F2
F1C10F3
F1C10C1
F2C10F3
116.1(3)
131.6(3)
111.3(3)
115.4(4)
133.2(4)
118.8(4)
114.7(3)
126.3(3)
122.0(3)
115.8(3)
120.5(3)
119.6(3)
107.5(3)
107.6(3)
111.0(3)
106.1(3)
F2C10C1
F3C10C1
F4C11F5
112.7(3)
111.6(3)
105.7(3)
106.8(4)
111.8(3)
109.5(4)
112.9(4)
109.8(3)
105.4(3)
109.1(3)
108.2(3)
107.6(3)
109.9(3)
115.2(3)
109.8(3)
107.6(3)
O1P2O3
O1P2O4
O1P2O5
O2P2O3
O2P2O4
O2P2O5
O3P2O4
O3P2O5
O4P2O5
P2O1C1
P2O2C2
P2O3C3
P2O4C5
P2O5C12
O1C1C2
F4C11F6
F4C11C2
F5C11F6
F5C11C2
F6C11C2
O5C12C13
F7C13C12
F7C13C14
F8C13C12
F8C13C14
C12C13C14
F9C14C13
F10C14C13
90.5(1)
112.9(1)
112.3(2)
114.8(2)
126.8(2)
123.2(2)
125.6(2)
112.3(4)
Angle
Angle
Angle
O2P2O1C1
O4P2O1C1
O5P2O1C1
O1P2O2C2
O3P2O2C2
O4P2O2C2
O5P2O2C2
O2P2O3C3
O4P2O3C3
O5P2O3C3
O1P2O4C5
O2P2O4C5
7.4(3)
130.1(3)
117.0(3)
7.4(3)
171.9(3)
93.9(3)
86.2(3)
165.7(3)
43.5(3)
69.7(3)
150.1(3)
122.9(2)
O3P2O4C5
O5P2O4C5
O1P2O5C12
O2P2O5C12
O3P2O5C12
O4P2O5C12
P2O1C1C2
P2O2C2C1
P2O3C3C4
P2O3C3O6
P2O4C5C6
P2O4C5C4
36.6(3)
57.1(3)
6.9(3)
97.9(3)
179.6(3)
82.2(3)
5.6(5)
P2O5C12C13
O1C1C10F1
O1C1C10F3
O2C2C11F5
O2C2C11F6
O3C3C4C9
167.4(2)
178.2(3)
61.8(5)
121.2(4)
1.3(6)
179.6(3)
3.7(6)
O6C3C4C9
5.8(5)
O6C3C4C5
173.5(4)
61.6(4)
175.6(3)
176.8(3)
177.0(3)
27.4(5)
156.4(3)
160.9(3)
18.4(5)
O5C12C13C14
O5C12C13F8
F7C13C14F10
C12C13C14F9
171.6(1), and 184.3(1) . This result means that the
P2, O1, and O3 atoms fall roughly on the same axis.
20 . This is evidently connected with the steric repul-
sion of the electron-acceptor trifluoromethyl groups.
The second heteroring in molecule IId has a dis-
torted sofa conformation (Fig. 3). The pentaatomic
The conformation of the five-membered ring is a
strongly flattened envelope (Fig. 2). The phosphorus
atom deviates from the O1C1C2O2 plane [planar
within 0.001(2) ] only slightly [0.1516(5) ]. The
entire pentaatomic P2O1C1C2O2 fragment is planar
within 0.046(2) . The O4 and O5 atoms deviate from
this plane to opposite sides by 1.243(1) and
1.397(1) , while the deviation of O3 is insignificant
[0.136(1) ]. Endocyclic bond angles at O1, O2, C1,
and C2 [112.3 114.8(2) ] are significantly smaller
than respective endocyclic angles in the six-membered
heteroring in IId, as well as the exocyclic P2O5C12
angle. By contrast, the exocyclic C2C1C10 and C1C2C11
angles in structures IId and III are larger by about
O3C3C4C5O4 fragment is planar within 0.037(2)
.
The O6 atom deviates from the plane of this fragment
by only 0.0567(1) (the O6C3C4C5 and O3C3C4C5
dihedral angles are 173.5(4) and 2.3(5) ], and the
deviation of the phosphorus atom is more significant
[0.5822(5) ].
In the related cyclic P(III) derivative IV, the phos-
phinine heteroring has a sofa conformation with an
analogous planar fragment and a slightly greater
deviation of the phosphorus atom [0.5904(6) ].
The magnitudes of the O6C3C4C5 and O3C3C4C5
dihedral angles [178.3(3) and 0.2(4) , respectively]
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

554
KONOVALOVA et al.
O5
P2
O5
O3
O6
O1
O1
O2
O4
F3
F4
F1
F6
C8
C9
C4
C3
P2
C2
O3
O6
O2
F2
O4
F5 C11
Fig. 2. Envelope conformation of the 1,3,2-dioxaphos-
phole ring in phosphorane IId (side view).
Fig. 3. Sofa conformation of the 1,3,4-dioxaphosphinin-
4-one heteroring in phosphorane IId (side view).
suggest a stronger planarity of the O3C3C4C5O4
fragment [17] in molecule IV.
fragment planar within 0.011 (0.019)
to the same
side by 0.62 (0.69) and 0.23 (0.28) , respectively.
This molecule contains two more fragments [P2O3
C3(O6)C4 and P2 O3 C3 (O6 )C4 ] planar within
5
NCO
O
P
O3
0.02 and 0.009
(the corresponding dihedral angles
3
are 2.0 and 4.0 , respectively). The O4(O4 ) and
C5(5 ) deviate to the same side from them by 0.57
( 0.65) and 0.32 ( 0.38) , respectively. The boat
conformation of the molecule makes the carbonyl
4
O6
IV
Such flattening in both molecules is evidently con-
nected with the favorableness of conjugation of the
carbonyl group with the system of the benzene ring.
The O1, O2, and O5 atoms deviate from the above
plane by 1.085(1), 0,300(1), and 2.060(1) . Con-
trary to what is observed in structure IV, the C3 and
O4 atoms in structure IId deviate from the benzene
group to deviate from the C3C4C5O4 (C3 C4 C5 O4 )
plane at larger distances of 0.17 ( 0.24)
(the
O6C3C4C5 and O6 C3 C4 O5 dihedral angles are 164.9
and 169.1 ).
5
Cl
O
P
O3
3
ring plane to opposite sides by 0.110
and
4
O6
0.095(1) , which is probably connected with the
strong tension that appears in the phosphinine hetero-
ring with a trigonal bipyramidal phosphorus atom.
The change in the coordination of the phosphorus
atom produces certain changes in bond lengths and
angles in this heteroring. Hence, the difference in the
P2 O4 and P2 O3 bond lengths increases [0.069(3)
and 0.020(2) in structures IId and IV, respectively].
The same relates to the O4 C5 and O3 C3 bond
lengths [0.035(4) and 0.008(4) in structures IId and
IV, respectively]. As to bond angles, then some of
them (O3P2O4 and P2O4C5) in spirophosphorane IId
are also increased compared to those in IV, where
they are equal to 99.4(1), 121.4(2), and 124.1(2) ,
respectively.
4
O
Cl
5
P
3
O
4
O6
V
The tetrafluoropropoxy group in phosphorane IId
is equatorial. The C12 atom of this group is trans to
the axial P2 O3 bond [the O3P2O5C12 dihedral angle
is 179.6(3) ]. The P2 O3 and O5 C12 bonds are
almost eclipsed [the O1P2O5C12 dihedral angle is
6.9(3) ]. The pentaatomic O1O3P3O5C12 fragment is
planar within 0.071(2) . A conformation having P2
trans to C13 atoms is realized along the O5 C12 axis
[the P2O5C12C13 dihedral angle is 167.4(2) ]. It is
interesting to note that the more extended hexaatomic
Unlike structures IId and IV, both phosphinine
heterorings in diphosphorylated bicyclic pamoic acid
derivative V [18] have a distorted boat conformation,
which follows from by the deviations of the P2 (P2 )
and O3 (O3 ) from the C3C4C5O4 (C3 C4 C5 O4 )
O1O3P2O5C12C13
within 0.089(2)
fragment,
too,
is
planar
(W conformation of the O3P2O5
C12C13 fragment). Such location of the acyclic tetra-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SPECIFIC FEATURES OF REACTION OF 2-R-BENZO[e][1,3,2]DIOXAPHOSPHININ-4-ONES
555
fluoropropoxy group is evidently associated with its
tendency for minimum steric interactions with the
other substituents in the phosphorus bipyramid.
Almost ideal staggered conformations are realized
along the C12 C13 and C13 C14 bonds. As molecule
IId contains no labile hydrogen atoms, its crystal
lacks classical hydrogen bonds. The only interactions
H14
O2
found in its packing are of the C H O type: C14
H14 O2 (1 x, y, 1 z) and C6 H6 O6 (x, 1/2 y,
1/2 + z). The characteristics of these interactions are
the following: C14 H14 0.98 , H14 O2 2.48 , C14
3.433(5) , C14H14O2 163.5 ; C5 H6 0.93 , H6 O6
2.43 , C6 O6 3.3323(5) , and C6H6O6 161.3 .
The first interaction forms centrosymmetric dimers
and the second binds these dimers into zigzag tapes
running along the 0z axis (Fig. 4).
O2
O6
H14
Fig. 4. System of nonclassical interactions in the crystal
of compound IId.
Spirophosphoranes II are hydrolytically rather un-
stable and fairly rapidly decompose under the action
of air moisture. Note that the 1,3,2-dioxaphosphole
ring is hydrolyzed first to form diastereomeric phos-
phates VI in a 1:1 ratio, which can be further equally
readily hydrolyzed with cleavage of the phosphinine
ring. For this reason, we failed to isolate phosphates
VI pure, but could fairly easily identify them by spec-
tral methods.
Therewith, the upfield signals belonging to phos-
phoranes decrease in intensity, and signals charac-
teristic of four-coordinate phosphorus derivatives
appear ( P 9 12 and
10 to 14 ppm). Hence heating
P
of phosphorane IIa in chloroform for 6 h gives three
compounds. In 31P NMR spectrum (121.42 MHz,
P1
CHCl3) they are characterized by signals at
10
10.3 q (3JPOCH 12.2),
11.2 q (3JPOCH 11.0, and
2
CF3
13.3 ppm, q, (3JPOCHP11.0 Hz) in a 5:12:12 ratio.
6
5
O
O
O *
P
H2O
RH
P3
*
IIa IId
11
CF3
2
1
Heating of spirophosphorane IIb under analogous
3
O
4
conditions, too, leads to formation of three com-
O
9.1 t (3JPOCH 9.2),
10.5 t (3JPOCH
P2
O
P1
P3
pounds with
9.2 Hz), and
VI
12.2 ppm, t (3JPOCH 10.3 Hz) in a
1
1:2:2 ratio (conversion 72%). Heating of phospho-
rane IIb in toluene for 2 h results in its complete trans-
In the H NMR spectrum (400 MHz, CDCl3), the
proton at C1 appears as two doublets of quartets (
3
3
P1
formation to a mixture of compounds with
and
6.38, JPOCH 14.4 Hz, JFCCH 7.2 Hz; 5.99 ppm,
P2,3
3
in a 7:20 ratio. For spirophosphorane IIc to
3JPOCH 12.1 Hz, JFCCH 7.4 Hz). In the 13C {1H}
NMR spectrum, the C3 C6 signals are split into
doublets due to coupling with phosphorus, which
points to a cyclic structure of the phosphates. The 13C
NMR spectrum, too, exhibits additional multiplicity
completely transform into analogous compounds with
9.3 t (3JPOCH 12.1) and
12.9 ppm, t (3JPOCH
P2
1
1P0.3 Hz) (7:10 ratio) more prolonged heating in to-
luene (6 8 h) is needed. Note that heating of the same
phosphoranes (6 8 h) in the more polar acetonitrile
increases the fraction of the reaction products with
2,3
due to coupling with protons ( , ppm, J, Hz):
C
2
153.34 br.d.d and 154.28 br.d.d (C3, JCCCH 7.2 7.3),
chemical shifts
to 70 90% in the reaction mixture.
3
111.87 m and 111.90 m (C6, JPOCC 12.4. The acyclic
By vacuum distPillation we could only isolate com-
fluorinated substituent is also easily identified in the
1
pounds with P , viz. decomposition products of
phosphoranes IIa IIc. On the basis of the 31P, 19F,
spectrum ( , ppm; J, Hz): 75.16 d.q.d and
C
1
2
2
75.05 d.q.d (C1, JHC 155.4, JPCC 35.4, JPOC 4.8),
1H
and
NMR spectra and elemental analyses, these
117.66 q.d and 118.10 q.d (C10, JFC 270.0, JPOC
1
2
products were assigned the structure of phospholenes
VIIa VIIc.
19.8 and 20.7), 179.45 q.d.d and 179.20 q.d.d (C2,
2JFCC 38.8 and 39.0, JPOCC 5.6, JHCC 4.7 and 5.2),
3
2
120.01 q and 119.98 q (C11, JFC 282.9 283.0).
Hence, like spirophosphoranes containing
a
1
benzo[e][1,3,2]dioxaphosphinin-4-one fragment, we
studied previously [10, 14, 15, 19], compounds II can
split off oligomer VIII on thermolysis and form 1,3,2-
On prolonged handling or on heating spirophos-
phoranes gradually undergo some transformations.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

556
KONOVALOVA et al.
O
R
8
CF3
CF3
7
O
O
O
O
P
R
9
B
IIa IIe
P
+
O
13 O
6
10
5
4
O
n
C
CF3
14
11
CF3
O
O
12
IXa IXe
VIIa VIIe
VIII
R = OCH3 (a), OCH2CH3 (b), OCH2CF3 (c), OCH2CF2CHF2 (d), Ph (e).
P2,3
dioxaphospholes VII. Compounds with
were not
assigned on the basis of data in [19, 20].
isolated pure because of their tendency for hydrolysis
and lability under heating in the course of vacuum
distillation. Nevertheless, these compounds could
Thus, heating of spirophosphoranes II gives, along
with 1,3,2-dioxaphospholes VII, 1,3,2-dioxaphos-
phepines IX. As mentioned in [21], 4,5-bis(trifluoro-
1
sufficiently reliably identified by means of H, 13C,
19F, and 31P NMR and IR spectra, using the corres-
ponding enriched fractions obtained by vacuum dis-
tillation. Such analysis shows (see Experimental and
Table 1) that these compounds are 1,3,2-dioxaphos-
methyl)-1,3,2 -dioxaphospholes prepared from simple
5
phosphites can decompose to phosphates in the pre-
sence of pyridine. The unusual behavior of phospho-
ranes containing a benzo[e][1,3,2]dioxaphosphinin-4-
one fragment is observed for the first time and can be
considered as evidence to show either that the stage
of formation of spirophosphoranes II from dipolar ion
B is reversible or that both decomposition pathways
of phosphorane II begin with cleavage of the endo-
cyclic C(O) OP bond and involve formation of the
same intermediate. Such intermediate may, for ex-
ample, have structure C that comprises an acylium
cation and a phosphorane fragment having the alkoxide
ion as one of ligands. Such acylium cations can be
formed by hydrolysis of esters or under the action of
strong Lewis acids on carboxylic acid anhydrides or
chlorides [22]. In this case, the phosphorane fragment
of the molecule acts as a leaving group which then
very easily transforms into the phosphate substituent.
The negative charge during this process passes to the
more electron-acceptor dioxaphosphole ring, thus
inducing its opening (structure D). Intramolecular
attack of the carbanionic part of intermediate D on the
acylium ion leads to final phosphepine IX.
P2,3
phepines IX. Their chemical shifts (
) coincide
with those of benzophosphepines previously obtained
from methyl trifluoropyruvate [19] and hexafluoro-
acetone [20]. The CF3 and C(O)CF3 fluorine chemical
shifts fall in the range 61 67 ppm. The IR spectra
contain two types of absorption bands at 1700 1720
1
and 1660 1680 cm , characteristic of trifluoromethyl-
substituted and usual keto groups. The 13C NMR
spectrum of diastereomeric phosphepines IXb (see
Experimental) significantly enriched with one dia-
stereomer (8:1) contains signals of key carbon atoms
of the phosphepine ring with expected multiplicities.
Hence, in the downfield region of the spectrum, a
singlet at 185.26 ppm and a quartet of doublets at
181.13 ppm, belonging respectively to the C5 and C13
atoms of the endo- and exocyclic carbonyl groups, are
present. In the upfield region of the spectrum, a signal
of the quaternary C4 atom with the corresponding
multiplicity (broadened quartet of doublets) is ob-
served. The signals of the rest carbon atoms were
O
R
P
R
CF3
CF3
O
O
O
P
II
|
IX
>
O
+
O
O
+
O
|
O
O
C CF3
F3C
C
D
This proposed scheme of the transformation of
phosphorane II to phosphepine IX may evidently also
explain the transformation of phosphorane X to diaza-
phosphole XI [23].
In the latter case, too, an acylium cation containing
an alkoxide phosphorane fragment (structure E) is
initially formed. Further on, a phosphoryl group is
formed, with the pentafluorophenoxide anion playing
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SPECIFIC FEATURES OF REACTION OF 2-R-BENZO[e][1,3,2]DIOXAPHOSPHININ-4-ONES
557
Bu
N
Bu
N
<
C6F5O
O
C6F5O
O
Me
Me
Me
Me
P
P
>
+
N
O
N
O
O
O
Bu
Bu
X
E
Bu
Bu
N
O
P
O
P
N
Me
Me
Me
Me
O
O
N
N
+
OC6F5 Bu
Bu
OC6F5
O
O
F
XI
the role of a group leaving the phosphorus atom
(structure E).
the SIR program [26] and refined by the SHELXL-97
program [27] first isotropically and then anisotro-
pically. Hydrogen atoms were revealed by difference
synthesis and included in structure amplitudes with
fixed thermal and positional parameters. The final
divergence factors were R 0.068 and RW 0.185 on
2500 reflections with F2 > 2 . The drawings of the
molecule and crystal packing, as well as calculation
of intra- and intermolecular interactions were per-
formed using the PLATON program [28].
Hence, in this work we showed for the first time
that cyclic salicyl derivatives of phosphorous acid
react with perfluorodiacetyl by the way of formation
of spiriphosphorane structures containing a 1,3,2-di-
oxaphosphole fragment. At elevated temperatures, the
products undergo further thansformations mainly in
two directions, viz. via formation of 4-1,3,2-dioxa-
phospholes and a salicylic acid oligomer and via
formation of benzo[f][1,3,2]dioxaphosphepines.
Reaction of 2-methoxybenzo[e][1,3,2]dioxaphos-
phinin-4-one (Ia) with perfluorodiacetyl. To a
mixture of 3.96 g of methyl phosphite Ia and 10 ml
of CH2Cl2, a solution of 3.95 g of perfluorodiacetyl
in 4 ml of CH2Cl2 was slowly added dropwise with
stirring at 25 C. The reaction mixture was let to
warm up to 20 C over the course of 30 min, and the
solvent was removed in a vacuum (12 mm Hg) at a
temperature of no higher than 15 20 C to obtain 4 ,5 -
bis(trifluoromethyl)-2-methoxy-4-oxo-2 5-spiro-
[benzo[e][1,3,2]dioxaphosphinine-2,2 -[1,3,2]dioxa-
phosphole] (IIa), viscous colorless oil, yield 94%.
EXPERIMENTAL
The NMR spectra were recorded on Bruker MSL-
400 (13C, 100.6 MHz; 31P 162.0 MHz), Bruker WM-
1
250 (13C 62.5 MHz, H, 250 MHz, 31P, 101.6 MHz),
and Varian Unity-300 (1H, 300 MHz; 19F 282.2 MHz)
spectrometers. The spectra were measured against
internal HMDS and external 85% phosphoric acid.
The 19F NMR spectra were obtained for solutions
containing 10% of C6F6, and then
were recalcu-
lated against CFCl3. The IR spectra wFere recorded on
a Specord M-80 spectrometer for films or suspensions
in mineral oil between KBr plates. Compounds I were
obtained as described in [20, 24, 25].
IR spectrum, , cm : 2990, 2930, 2885 (CH), 1784
1
(C=O), 1741, 1712, 1682, 1614, 1594, 1481, 1465,
1454, 1442, 1375, 1310, 1225 1240, 1175 1180,
1122, 1060, 1020, 970, 875. 19F NMR spectrum
(CH2Cl2):
65.05 ppm (br.s). 31P NMR spectrum
F
X-ray diffraction analysis of compound IId was
carried out on an Enraf Nonius CAD-4 automatic four-
curcle diffractometer. Crystals of compound IId
are monoclinic; at 20 C, a 10.420, b 14.560(5), c
(121.42 MHz, CH2Cl2, , ppm, J, Hz):
54.6 q
(3JPOCH 16.1). Found, %: C 36.53; H 2.09.PC12H7F6
O6P. Calculated, %: C 36.73; H 1.78. Compound IIa
was further heated for 1 h at 65 68 C in CHCl3 to
5
11.690(5)
,
102.22(2) , V 1733(1) 3, Z 4, dcalc
form 2-methoxy-4,5-bis(trifluoromethyl)-1,3,2 -di-
3
1.89 g cm , space group P21/c. The cell parameters
and the intensities of 2732 reflections, among which
2500 were with I > 2 (I), were measured at 150 C,
oxaphosphole 2-oxide (VIIa) and diastereomeric
2-methoxy-4-(trifluoroacetyl)-4-(trifluoromethyl)-4,5-
dihydrobenzo[f][1,3,2 5]dioxaphosphepin-5-one-2-
oxides IXa in the ratio 0.5 IIa:1.71 VIIa:1.0 (IXa).
Upon heating for 6 h at 65-68 C in CHCl3, the signal
CuK radiation, graphite monochromator,
/2
scanning, < 74.45 . No intensity decay of three
control reflections was observed during measurements. of the starting phosphorane disappeared, and a 5:24
The structures were solved by the direct method using mixture of compounds VIIa and IXa formed. The
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

558
KONOVALOVA et al.
3JH CCH 7.4, JH CCCH 1.0) (d1), 7.35 d.d.d (H10,
4
diastereomeric ratio in phosphepine IXa was 1:1.
Methoxyphosphole VIIa was isolated by vacuum
distillation, yield 16%, bp 80 C (0.2 mm). 31P NMR
spectrum (121.43 MHz, CH2Cl2), P, ppm (J, Hz):
13.0 q (3JPOCH 12.2). Found, %: C 22.17; H 1.22.
C5H3F6O4P. Calculated, %: C 22.06; H 1.10.
9
10
8
10
7.23 d.d.d.d (H8, JH CCH 8.4, 4JH
1.0,
8
CCCH
3
9
8
10
5
4JPOCCH 0.9, JH
0.4) (d1), 7.26 d.d.d.d (H8,
8
CCCCH
8
11
3JH CCH
8.4, 4JH
1.1, 4JPOCCH
1.1,
9
8
10
8
8
CCCH
3
5JH
0.5) (d2); 4.37 4.39 m (CH2, JHCCH 7.1,
11
8
CCCCH
3
3JPOCH 10.6) (d1, d2); 1.47 t.d (CH3, JHCCH 7.1,
Reaction of 2-ethoxybenzo[e][1,3,2]dioxaphos-
phinin-4-one (Ib) with perfluorodiacetyl was carried
out by an analogous procedure. 4 ,5 -Bis(trifluoro-
methyl)-2-ethoxy-4-oxo-2 5-spiro[benzo[e][1,3,2]di-
oxaphosphinine-2,2 -[1,3,2]dioxaphosphole] (IIb) was
obtained as a colorless viscous oil, yield 95%. IR
3
4
4JPOCCH 1.1) (d1), 1.44 t.d (CH3, JHCCH 7.1, JPOCCH
1.4) (d2). Phosphole VIIb was isolated by vacuum
distillation, yield 35%, bp 90 C (0.2 mm Hg). 31P
NMR spectrum (121.43 MHz, CH2Cl2), P, ppm: 9.1 t
(3JPOCC 9.2 Hz). 19F NMR spectrum (CH2Cl2),
ppm: 65.43 br.s. Found, %: C 24.93; H 2.11. C6H5F
,
,
F
1
ppm: 65.22 br.s. 19F NMR spectrum (CDCl3),
spectrum, cm : 1780, 1750, 1716, 1695, 1680, 1644,
1610, 1590 (C=O, OC=C, C=Carom); 1470, 1450,
1390, 1350 ( CH); 1310, 1305, 1290 (CF, O C);
1230, 1140 1150, 1095 1100, 1020 1030, 1000, 982,
F6O4P. Calculated, %: C 25.17, H 1,75. One of the
fractions, enriched (88%) with one of the diastereo-
mers of dioxaphosphepine IXb was also isolated by
vacuum distillation, yield 27%, bp 120 123 C (0.1
1
960, 850 860, 768. H NMR spectrum (300 MHz,
CDCl3, , ppm, J, Hz): 8.03 d.d.d (H9*, JH CCH 7.8,
3
8
9
1
4JH CCCH 0.5), 7.66 d.d.d.d (H7, JH CCH 8.3,
3
mm Hg). IR spectrum, , cm : 1721, 1712, 1680
7
9
6
7
3JH CCH
7.4, JPOCCCH 2.0, JH CCCH 1.8),
5
4
(C=O), 1620, 1590, 1495, 1410 (C=Car, CH), 1360,
1320, 1310 (POC, CF, CH), 1295 (P=O). 13C {1H}
NMR spectrum (the multiplicities of signals in the 13C
NMR spectrum are given in parentheses), , ppm
8
7
7 9 7
7.30 d.d.d.d (H8, JH CCH 7.4, JH CCCH 1.1,
3
4
9
8
6
8
6JPOCCCCH 0.1), 7.20 d.d.d.d (H6, JH CCH 8.3,
3
8
7
6
4JH CCCH 1.1, JPOCCH 1.1, JH CCCCH 0.5), 4.18 m
4
5
2
(J, Hz): 87.93 br.q.d (br.q,d) (C4, JFCC 29.0 32.0),
8
6
6
9
6
185.26 br.s (br.s) (C5); 125.55 br.s (br.m) (C6);
and 4.25 m (POCH2, AB part of the ABMX3 spectrum,
2
1
148.48 d (m) (C7, JPOC 9.0); 121.52 d (d.d) (C8, JHC
3JAX = JBX 7.0, JAM = JBM 12.3, JAB 5.5), 1.25 d.t
3
3
3
3
3
3
(CH3, JAX = JBX 7.0, J(POCCX) 2.1). 19F NMR
spectrum (CH2Cl2), F, ppm: 64.77 br.s. 19F NMR
spectrum (CDCl3), F, ppm: 64.98 br.s. 31P {1H}
NMR spectrum (162.0 MHz, CH2Cl2), P, ppm (J,
Hz): 55.6 t (3JPOCH 12.2). Found, %: C 38.71; H
2.49. C13H9F6O6P. Calculated, %: C 38.42; H 2.22.
Phosphorane IIb was heated in toluene for 2 h at
110 C, after which the solvent was distilled off in a
vacuum to leave a viscous slightly yellowish oil com-
prising a 7:20 mixture of 4,5-bis(trifluoromethyl)-2-
3
3
4
167.6, JPOC 7.8, JHCCC 7.8 8.0); 138.50 s (d.d)
(C9, JH3C 163.6, JHCCC 9.0); 126.30 s (d.d) (C10, 1JCH
1
3
166.4, JHCCC 7.8); 131.89 d (d.d.d.d) (C11, JHC
1
3
4
2
168.0, JHCCC 8.6, JPOCCC 2.4, JHCC 1.7); 118.10 q.d
(q.d) (C12, JPC 270.4, JPOCC 20.7); 181.13 q.d (q.d)
1
3
(C13, JFCC 29.0 32.0, JPOCC 5.9 6.4); 120.30 q (q)
2
3
(C14, JPC 282.9), 69.18 d (t.d.q) (CH2, JPOC 6.9,
1
1
2JHCC 4.2); 15.47 d (q.d.t) (CH3, JCH 127.8, JHCC
1
2
2.5). 19F NMR spectrum (CH2Cl2),
, ppm:
61.37 br.s (COCF3), 67.11 br.s (CF3). 19FF NMR
spectrum (CDCl3), F, ppm: 61.68 br.s (COCF3),
67.26 br.s (CF3). 13P NMR spectrum (162.0 MHz,
CH2Cl3), P, ppm: 11.9 br.t (3JPOCH 10.6 Hz).
5
ethoxy-1,3,2 -dioxaphosphole 2-oxide (VIIb) and
diastereomeric 2-ethoxy-4-(trifluoroacetyl)-4-(trifluo-
romethyl)-4,5-dihydrobenzo[f][1,3,2 5]dioxaphos-
phepin-5-one 2-oxides IXb. 1H NMR spectrum
(300 MHz, CDCl3 + 20% of CH2Cl2) of isomeric
phosphepines (d1, d2), , ppm (J, Hz): 8.08 d.d.d
Reaction of 2-(2,2,2-trifluoroethoxy)benzo[e]-
[1,3,2]dioxaphosphinin-4-one (Ic) with perfluoro-
diacetyl was carried out by an analogous procedure,
using 10.65 g of compound Ic, 25 ml of CH2Cl2, and
7.76 g of perfluorodiacetyl in 10 ml of CH2Cl2. The
solvent was distilled off in a vacuum (12 mm Hg) at
a temperature of no higher than 15 20 C to obtain
4 ,5 -Bis(trifluoromethyl)-4-oxo-2-(2,2,2-trifluoro-
ethoxy)-2 5-spiro[benzo[e][1,3,2]dioxaphosphinine-
(H11, JH
7.9, J
1.8, J
0.4)
1.8)
7.4,
3
4
5
10
11
9
1
9
11
CCH
H CCCH1
H CCCCH
(d1), 7.84 br.d.d (H11, JH
7.8, J
3
4
10
11
9
H CCCH
11
CCH
(d2); 7.73 d.d.d.d (H9, JH CCH 8.4, JH
3
3
8
9
10
9
CCH
4JH
1.8, JPOCCCH 1.2) (d1), 7.66 d.d.d.d (H9,
5
11
9
9
CCCH
3JH CCH
8.4, 3JH
7.6, 4JH
1.8,
8
9
10
9
11
9
CCH
CCCH
5JPOCCCH 1.2) (d2); 7.37 d.d.d.d (H10, J
7.9,
3
2,2 -[1,3,2]dioxaphosphole] (IIc) as
viscous oil, yield 96%. H NMR spectrum (300 MHz,
a
colorless
9
11
10
CCH
H
1
3JH
7.8, JH CCH 7.6, JH CCCH 1.1) (d2);
3
4
11
10
9 10 8 10
CCH
CDCl3 + 10% of CH2Cl2), , ppm (J, Hz): 8.04 d.d.d
3
(H9, 1H, JH CCH9 7.9, 4J
9 1.8, 5JH CCCCH9 0.4);
*
8
7
6
H CCCH
Here and hereinafter, the atom numbering is that used in the
corresponding structures in the text.
7.69 d.d.d.d (H7, 1H, JH CCH 8.4, JH CCH 7.4,
3
3
6
7
8
7
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SPECIFIC FEATURES OF REACTION OF 2-R-BENZO[e][1,3,2]DIOXAPHOSPHININ-4-ONES
559
3
5JPOCCCH 1.8); 7.33 d.d.d (H8, 1H, JH CCH 7.9,
Reaction of 2-phenylbenzo[e][1,3,2]dioxaphos-
7
9
8
3JH CCH 7.4, JH CCCH 0.9); 7.22 d.d.d.d (H6, 1H,
4
phinin-4-one (Ie) with perfluorodiacetyl. To a solu-
tion of 6.27 g of phosphinine Ie in 20 ml of CH2Cl2,
4.98 g of perfluorodiacetyl in 5 ml of methylene
chloride was slowly added at 25 C under argon. The
reaction mixture was let to warm up to 15 20 C, and
the solvent was removed in a vacuum (12 mm Hg) at
a temperature of no higher than 15 C. The resulting
viscous colorless oil, 4 ,5 -bis(trifluoromethyl)-4-oxo-
2-phenyl-2 5-spiro[benzo[e][1,3,2]dioxaphosphinine-
2,2 -[1,3,2]dioxaphosphole] (yield 90%) is thermally
7
8
6
8
4
4
5
3JH CCH 8.4, J
0.9, J
0.9, J
7
6
8
6
6
9
6
H CCCH
POCCH
H CCCCH
3
3
0.4); 4.49 d.q (OCH2, 2H, JPOCH 12.1, JFCDCH 7.7).
19F NMR spectrum (CDCl3), F, ppm (J, Hz):
75.79 br.t.m (CH2CF3, 3JHCCF 7.8), 64.93 br.s (CF3,
6F). 31P NMR spectrum (162.0 MHz, CH2Cl3),
,
P
ppm (J, Hz): 54.5 t (3JPOCH 12.2). Found, %: C
34.17; H 1.53. C13H6F9O6P. Calculated, %: C 33.91;
H 1.30. Compound IIc was heated in toluene (110 C)
for 8 h, after which the solvent was removed in a
vacuum (12 mm), and the residue was distilled in a
vacuum to obtain 4,5-bis(trifluoromethyl)-2-(2,2,2-
trifluoroethoxy)-1,3,2 5-dioxaphosphole 2-oxide
1
and hydrolytically unstable. IR spectrum, , cm :
1784, 1747 sh., 1682, 1614, 1594, 1481, 1465, 1453,
1355, 1219, 1171, 1132, 11.06, 995, 934, 774, 751,
691. 19F NMR spectrum (CH2Cl2),
, ppm:
F
64.93 br.s. 31P {1H} NMR spectrum (121.42 MHz,
CDCl3), P, ppm: 34.1 ppm. After heating in CHCl3
for 6 days at 68 C, the content of phosphorane IIe
decreases to 61.2%. Under these conditions, 27% of
2-phenyl-4-(trifluoroacetyl)-4-(trifluoromethyl)-4,5-
dihydrobenzo[f][1,3,2 5]dioxaphosphepin-5-one 2-
oxides (IXe) formed. 31P NMR spectrum of com-
pound VIIe (CH2Cl2), , ppm (J, Hz): 19.1 br.t
(3JFCCH 14.8). 31P NMR spectrum of compound IXe,
P, ppm (J, Hz): 15.1 and 12.8 br.m (7:6). 19F NMR
spectrum (CH2Cl2) of compound IXe, F, ppm:
61.26 br.s, 67.43 br.s. Attempted distillation of the
mixture of compounds VIIe and IXe failed because
of tarring.
1
VIIc, yield 27%, bp 80 C (0.2 mm Hg). H NMR
spectrum (300 MHz, CDCl3 + 10% CH2Cl2), , ppm
(J, Hz): 4.69 d.q (3JPOCH 12.1, JFCCH 7.8). 19F NMR
3
spectrum (CDCl3), F, ppm (J, Hz): 64.93 br.s (CF3),
75.78
t
(3JFCCH 7.8). 31P NMR spectrum
(121.43 MHz, CH2Cl2), P, ppm: 9.7 br.t (3JPOCH
12.1 Hz). Found, %: C 21.33; H 1.03. C6H2F9O4P.
Calculated, %: C 21.18; H 0.59.
Reaction of 2-(2,2,3,3-tetrafluoropropoxy)benzo-
[e][1,3,2]dioxaphosphinin-4-one (Id) with perfluo-
rodiacetyl. To a solution of 7.4 g of phosphinine Id
in 15 ml of CH2Cl2, a solution of 4.81 g of perfluoro-
diacetyl in 6 ml of CH2Cl2 was slowly added drop-
wise with stirring at 25 C under argon. The reaction
mixture was allowed to stand for 1 day at room
temperature. The crystals that formed were filtered off
and dried in a vacuum (12 mm Hg) to obtain 4 ,5 -bis-
(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoroprop-
oxy)-2 -spiro[benzo[e][1,3,2]dioxaphosphinine-2,2 -
[1,3,2]dioxaphosphole] (IId), yield 95%, mp 78 C.
IR spectrum, , cm : 1756, 1732 sh., 1700, 1668,
1620, 1595, 1323, 1308, 1212, 1075, 1060, 1030,
ACKNOWLEDGMENTS
The work was financially supported by the Univer-
sities of Russia Basic Research Program (project
no. UR.05.01.016), Program for Support of Leading
Scientific Schools of the Russian Federation (project
no. 750.2003.3), and Basic Research and Higher
Education Collaborative Program of CRDF and the
Ministry of Education of the Russian Federation
(project no. REC-007).
5
1
1
1000, 975, 950, 900. H NMR spectrum (300 MHz),
3
, ppm (J, Hz): 8.05 d.d (H9, 1H, JH CCH 7.8,
8
9
3
4JH CCCH 1.7); 7.72 d.d.d.d (H7, 1H, JH CCH 8.4,
7
9
6
7
3JH CCH 7.8, JH CCCH 1.7, JPOCCCH 2.2);
4
5
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7
9
7
7
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