Bis(pentafluorophenyl)phosphinous acid in the synthesis of P,P-bis(pentafluorophenyl)phosphorylalkanones and -alkanediones

Article abstract of DOI:10.1007/s11172-014-0741-1

Addition of bis(pentafluorophenyl)phosphinous acid to α,β-alkenones and α,β,β'-alkene-diones in anhydrous Et₂O (the solvent, in which the P-OH tautomeric form predominates) proceeds rapidly and regiospecifically at the C=C bond of the substrate

Full text of DOI:10.1007/s11172-014-0741-1

Russian Chemical Bulletin, International Edition, Vol. 63, No. 10, pp. 2317—2324, October, 2014
2317
Bis(pentafluorophenyl)phosphinous acid in the synthesis
of P,Pꢀbis(pentafluorophenyl)phosphorylalkanones and ꢀalkanediones*
E. I. Goryunov, I. B. Goryunova, Yu. V. Nelyubina, N. G. Frolova, E. D. Savin,
T. V. Strelkova, M. P. Pasechnik, and V. K. Brel
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
2
8 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: phoc@ineos.ac.ru
Addition of bis(pentafluorophenyl)phosphinous acid to ,ꢀalkenones and ,,´ꢀalkeneꢀ
diones in anhydrous Et O (the solvent, in which the P—OH tautomeric form predominates)
2
proceeds rapidly and regiospecifically at the C=C bond of the substrate at room temperature in
the absence of catalysts. The reaction leads to bis(pentafluorophenyl)phosphorylated alkanones
and alkanediones, as a rule, in the yields close to quantitative and can be considered as a highly
efficient method for the synthesis of the corresponding functionalized phosphine oxides. The
structures of obtained compounds were established by IR and NMR spectroscopy and Xꢀray
diffraction analysis.
Key words: phosphinous acid P,Pꢀbis(pentafluorophenyl)ꢀsubstituted, addition to C=C
bonds, ylidenealkanones(alkanediones), phosphorylalkanones(alkanediones), P,Pꢀbis(pentaꢀ
fluorophenyl)ꢀsubstituted, synthesis, IR spectroscopy, NMR spectroscopy, Xꢀray diffraction
studies.
Though the first representatives of ꢀdiphenylphosꢀ
to nonfluorinated analogues. Finally, it is well known that
replacement of hydrogen atoms with fluorine atoms is
a powerful modificator influencing the character of bioꢀ
logical activity of organic compounds (see, for example,
Ref. 10 and references cited therein).
phorylalkanones were synthesized already at the beginꢀ
1
ning of 20th century, this type of functionalized phosꢀ
phine oxides became of special interest relatively recently.
It was found that such phosphorylated ketones can
extract actinides and lanthanides from acidic solutions
more efficiently than known organophosphorus monoꢀ
and bidentate extractants.2 Besides, phosphorylꢀcontainꢀ
ing compounds of this type, as it was demonstrated
for 4ꢀmethylꢀ4ꢀ(diphenylphosphoryl)pentanꢀ2ꢀone as an
By now, only one compound of this type,
(C F ) P(O)CHPhCH C(O)C H OMeꢀp, is described in
6
5 2
2
6
4
,3
the literature, which was obtained by the reaction of
bis(pentafluorophenyl)phosphinous acid (1) with the corꢀ
1
1
responding substituted chalcone in refluxing chloroform.
4
example, are antipyrenes for poly(vinyl chloride). Phosꢀ
The purpose of the present study is to determine to which
extent the reaction of acid 1 with ,ꢀenones can be conꢀ
sidered as a general method for the synthesis of such phosꢀ
phoryl ketones and develop a possibly simple and efficient
process for their preparation, i.e., to achieve the objecꢀ
phorylated alkanones can be used in the design of various
organophosphorus heterocyclic systems,5 in which the
presence of the phosphoryl fragment can be a factor inꢀ
creasing biological activity of corresponding compounds.9
From the practical point of view, it seemed potentially
very promising to modify the named phosphoryl ketones
by the replacement of the phenyl groups at the phosphorus
atom with the pentafluorophenyl fragments. In fact, the
perfluorination of the phenyl rings in the diphenylphosꢀ
phoryl substituent of phosphorylalkanones can provide
a high degree of affinity with fluorineꢀcontaining diluents
—8
1
1
tives, which could not be achieved in the work because
of its preliminary character.
It should be noted that acid 1 is a diarylhydrophosphoꢀ
ryl compound, which according to NMR spectroscopy
can exist in solutions either as a P(O)H form (which is
observed for the overwhelming majority of this type of
1
2
compounds ), or as a mixture of P(O)H and P—OH
forms. Since the P—OH form of hydrophosphoryl comꢀ
(
for example, with mꢀnitrobenzotrifluoride used in modern
extraction technologies), as well as considerably enhance
the antipyrene properties of such compounds as compared
1
3
pounds is the most active toward electrophiles, comꢀ
pound 1 potentially gives a golden opportunity for inꢀ
creasing reactivity only via the variation of the nature of
organic solvents used as a medium in the reactions with
,ꢀenones.
*
Dedicated to Academician of the Russian Academy of Sciences
Yu. N. Bubnov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2317—2324, October, 2014.
066ꢀ5285/14/6310ꢀ2317 © 2014 Springer Science+Business Media, Inc.
1

2318
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
Goryunov et al.
However, it turned out that the literature data on the
behavior of compound 1 in solutions are contradictory.
Since in the cases of DMSO and Nꢀmethylpyrroliꢀ
done, there would be, undoubtedly, certain difficulties in
the step of the isolation of target products in the individual
state, diethyl ether is a preferable choice for the reactions
of acid 1 with ,ꢀenones.
Thus, in the work1 it was indicated that the H NMR
spectra in deuterochloroform showed that this acid exists
as a mixture of P(O)H and P—OH tautomers, whereas in
hexadeuterodimethylsulfoxide only the P—OH form is
present. On the contrary, the latest studies15 allowed one
to draw a conclusion that a solution of 1 in chloroform
contains only the P(O)H isomer, whereas in dimethylsulfꢀ
oxide both tautomers were present, though the P—OH
tautomer was a predominant one (76%). It was also
shown1 that in such solvents, as toluene, CH Cl , and
4
1
The studies of the synthetic potential of the reacꢀ
tions of bis(pentafluorophenyl)phosphinous acid with
,ꢀenones started from the simplest representative of this
class of compounds, methyl vinyl ketone (MVK).
It was found that the reaction of acid 1 with MVK (the
ratio 1 : 1.05, respectively) in anhydrous diethyl ether proꢀ
ceeded at very high rate even at room temperature,** and,
5
2
2
31
acetonitrile, acid 1 exists as a P(O)H tautomer, whereas in
the case of MeOH, THF, DMF, dimethoxyethane, and
diethyl ether both the P(O)H and the P—OH forms are
present in solutions, though, the concentrations of acid 1
in these experiments were not specified. In this connecꢀ
tion, in order to obtain the correct data on the behavior of
acid 1 in the listed organic solvents we determined the
position of tautomeric equilibrium of this hydrophosphorꢀ
yl compound in the 0.05 M solutions in CDCl , CD Cl ,
according to the P NMR spectroscopy, already after 1 h
the signals of the starting hydrophosphoryl compound are
absent in the reaction mixture (Scheme 1, a).
Scheme 1
3
2
2
CD CN, (CD ) SO, MeOH, and diethyl ether and, if it
3
3 2
3
1
was possible by a simultaneous use of both P and
H NMR spectroscopy. In the case of first five solvents,
1
our results turned out to be very similar to those given in
the work,1 that can indicate the absence of noticeable
influence of the concentration factor on the position of tautoꢀ
meric equilibrium in these solvents. Conversely, the conꢀ
tent of the P—OH form in 0.05 M solution of 1 in diethyl
ether (71%) turned out to be considerably higher than that
reported in the work15 (60%) and became actually the
5
a. 20 C, 1 h, anhydrous Et O; b. 20 C, 8 h, anhydrous CHCl .
2
3
The reaction was not accompanied by the formation of
any side products, and the earlier unknown 4ꢀ[bis(pentaꢀ
fluorophenyl)phosphoryl]butanꢀ2ꢀone (2) was isolated in
almost quantitative yield.
same as the content of this form in DMSO/DMSOꢀd .*
6
Besides, we determined the position of tautomeric equiꢀ
librium in 0.05 M solutions of acid 1 in a number of other
A control experiment (see Scheme 1, b), in which the
reaction of acid 1 and MVK was carried out in anhydrous
chloroform (where the named phosphinous acid exists exꢀ
clusively as a P(O)H form), rather than in diethyl ether
showed a sharp decrease in the rate of the process (the
synthetically important solvents (CCl , C D , and
4
6
6
CD NO ), which were not studied earlier. We found that
3
1
2
31
the H and P NMR spectra of solutions of acid 1 exhibit
only one doublet each in the regions  8.23—8.95 and
–
(18.97—23.57), respectively, which have the spinꢀspin
31
P NMR spectroscopy showed that the signals of the
coupling constants in the range 567—583 Hz virtually idenꢀ
starting organophosphorus compound disappear only
after 8 h), which is in full agreement with the concluꢀ
tical for each solvent, i.e., the spinꢀspin coupling constant
1
values characteristic of the JH,P. The results obtained unꢀ
13
sions on the relative reactivities of the P(O)H and the
ambiguously indicate that compound 1 in these three solꢀ
vents is present exclusively as the P(O)H tautomer.
To sum up, based on the available data a grounded
suggestion can be made that among studied organic solꢀ
vents diethyl ether, dimethylsulfoxide, and Nꢀmethylꢀ
pyrrolidone are the most promising for the use as a mediꢀ
um to carry out the reactions of acid 1 with ,ꢀenones,
since in these solvents the highest content of the POH
form of this acid is observed.
P—OH forms of hydrophosphoryl compounds.
The phosphorylalkanone 2 is a lowꢀmelting white crysꢀ
talline compound stable in air in both the solid state and in
solution. The composition of this compound was conꢀ
firmed by elemental analysis, its structure was confirmed
1
1
31
by IR spectroscopy and NMR spectroscopy ( H, H{ P},
13
1
19
1
31
1
C{ H}, F{ H}, and P{ H}) (see Experimental), as
well as by Xꢀray diffraction studies (Fig. 1).
*
* In the case of nonfluorinated analog 1, diphenylphosphinous
*
As it was recently demonstrated,16 yet higher content of the
acid, the reaction with MVK proceeds at a comparable rate unꢀ
der much more drastic conditions: at 95 C and under influence
of microwave irradiation.
P—OH tautomer (90%) is observed in solution of 1 in Nꢀmethylꢀ
pyrrolidone (for the concentration of ~0.56 mol L–1).
17

[
Bis(pentafluorophenyl)phosphoryl]alkanones
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
2319
F(8)
F(7)
is not virtually accompanied by the formation of any noticeꢀ
able amounts of side products either* and leads to the
desired 4ꢀ[bis(pentafluorophenyl)phosphoryl]ꢀ4ꢀphenylꢀ
butanꢀ2ꢀone (5) in the yield close to quantitative (Scheme 2).
C(9)
F(6)
C(8)
C(10)
C(11)
O(1)
O(2)
C(12)
C(7)
C(13)
C(14)
F(9)
P(1)
C(1)
C(15)
Scheme 2
C(16)
F(10)
F(5)
F(1)
C(2)
C(6)
C(3)
O(5)
F(4)
F(2)
C(4)
F(3)
i. 20 C, 2 h, anhydrous Et O.
2
Fig. 1. General view of the structure of 4ꢀ[bis(pentafluoroꢀ
phenyl)phosphoryl]butanꢀ2ꢀone (2) in representation of atoms
by ellipsoids of thermal vibrations (p = 50%).
The structure of phosphoryl ketone 5 was confirmed
by IR spectroscopy and NMR spectroscopy ( H, H{ P},
1
1
31
1
3
1
19
1
31
1
C{ H}, F{ H}, and P{ H}). Note that a 10 ppm difꢀ
ference in the chemical shifts of the singlet signals in
A comparison of the IR spectroscopy data for ketone 2
31
1
the P{ H} NMR spectra of ketone 5 ( = 23.6) and
and its nonfluorinated analog Ph P(O)CH CH C(O)Me
P
2
2
2
its nonfluorinated analog Ph P(O)CHPhCH C(O)Me
(
3) indicates that in the series of ꢀ(diarylphosphoryl)ꢀ
2
2
2
2
(
P = 33.6) is slightly less than in the case of the pair of
alkanones a replacement of Pꢀphenyl fragments with the
pentafluorophenyl substituents possessing a pronounced
electronꢀwithdrawing effect, causes a considerable shift of
the P=O group vibrational frequency: from 1180 for 3 (see
phosphoryl ketones 2—3. Due to the presence in the molꢀ
ecule of ketone 5 of the asymmetric benzyl carbon atom,
the hydrogen atoms of the neighboring methylene fragꢀ
ment become diastereotopic and, as a consequence, anisoꢀ
chronic (i.e., having different chemical shifts) in the achiral
medium. For a similar reason, both pentafluorophenyl
fragments attached to the phosphorus atom are anisoꢀ
chronic, that is indicated by the doubling of the signals for
–
1
Ref. 5) to 1219 cm for 2, while for the C=O groups such
a replacement expectedly results in much less changes and
–
1
the corresponding  value is only 8 cm
.
Similarly to the IR spectra, a total replacement of hyꢀ
drogen atoms with the fluorine atoms in the diphenylphosꢀ
phoryl fragment of ketone 3 (see Ref. 17) results in a conꢀ
siderable (~12 ppm) upfield shift of the signal in the
13
1
the corresponding indicative nuclei in the C{ H} and
1
9
1
F{ H} NMR spectra (see Experimental).
3
1
1
1
The studies of the reaction of acid 1 with mesityl oxide
P{ H} NMR spectrum. In the H NMR spectrum, the
signals for the methylene fragments are found as the douꢀ
(
6) in anhydrous diethyl ether at ~20 C (Scheme 3)
1
31
blets of triplets, which in the H{ P} NMR spectrum are
transformed to triplets. To correctly assign the signals for
the protons of the CH P and the CH C(O) groups with
close positions in the H NMR spectrum, we used the
corresponding H— Cꢀcorrelation (HMQC). The signals
Scheme 3
2
1
2
1
13
13
19
19
for the nuclei of C (see Ref. 18) and F atoms were
assigned based on the data published earlier. In the
13
1
C{ H} NMR spectrum of phosphoryl ketone 2, the sigꢀ
nal for the carbonyl carbon atom was found as a doublet
3
with a spinꢀspin coupling constant J
= 12.9 Hz, that
C,P
indicates20 the transꢀarrangement of the C=O and the P=O
groups. It should be emphasized that this conclusion, obꢀ
tained based on the results of spectral studies, is in full
agreement with the results of Xꢀray diffraction studies for
phosphoryl ketone 2.
The reaction of acid 1 with 4ꢀphenylbutꢀ3ꢀenꢀ2ꢀone (4)
in anhydrous ether at ~20 C proceeds at a slightly lower
rate than in the case of MVK, which, most likely, is caused
by an increase of sterical hindrance. However, this reaction
i. 20 C, 48 h, anhydrous Et O.
2
*
It should be noted that, as it has been shown earlier,21 the
reaction of benzylideneacetone 4 with a number of diorganꢀ
ylphosphinous acids, including diphenylphosphinous acid, in
Et O at room temperature leads to the products of addition of
2
hydrophosphoryl compounds exclusively at the C=O bond of
the starting enone.

2320
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
Goryunov et al.
F(3)
F(2)
as a reliable instrument for finding a mutual arrangement
of the P=O and the C=O groups in the molecule of phosꢀ
phorylated ketone independent of the nature of the orgꢀ
anyl substituent at the phosphorus atom.
C(3)
F(1)
C(4)
C(5)
C(2)
C(6)
The reaction of acid 1 with the corresponding ,ꢀ
unsaturated alkenediones in anhydrous Et O at ~20 C
2
F(4)
C(1)
O(1)
can be successfully used for the preparation of bis(pentaꢀ
fluorophenyl)phosphorylated alkanediones.
F(10)
Thus, according to the 31P NMR spectroscopy data,
the reaction of acid 1 with 3ꢀbenzylidenepentaneꢀ2,4ꢀdiꢀ
one (8) under these conditions comes to completion withꢀ
in 24 h in the absence of any initiators or catalysts,**
which results in the isolation of 3ꢀ{ꢀ[bis(pentafluoroꢀ
phenyl)phosphoryl]benzyl}pentaneꢀ2,4ꢀdione (9) in high
yield (Scheme 4).
F(9)
P(1)
C(15)
C(14)
C(16)
F(5)
C(11)
C(13)
C(12)
C(18)
C(7)
C(8)
C(10)
O(2)
C(17)
C(9)
F(7)
F(6)
F(8)
Scheme 4
Fig. 2. General view of the structure of 4ꢀ[bis(pentafluoroꢀ
phenyl)phosphoryl]ꢀ4ꢀmethylpentanꢀ2ꢀone (7) in representation
of atoms by ellipsoids of thermal vibrations (p = 50%).
showed that the presence of two substituents at the termiꢀ
nal atom of the C=C bond of ,ꢀenone leads to a further,
though noncritical, decrease in the rate of the reaction,
thus confirming our suggestion on the sterical character of
such an effect.
This reaction, like in the case of ,ꢀenones studied
earlier, retains its regioselectivity,* which results in the
isolation of 4ꢀ[bis(pentafluorophenyl)phosphoryl]ꢀ4ꢀ
methylpentanꢀ2ꢀone (7) in 92.2% yield.
i. 20 C, 24 h, anhydrous Et O.
2
The structure of phosphoryl ketone 7 was confirmed
1
1
31
by IR spectroscopy, NMR spectroscopy ( H, H{ P},
The structure of compound 9 was confirmed by IR
13
1
19
1
31
1
1
1
31
19
1
C{ H}, F{ H}, and P{ H}) (see Experimental), and
spectroscopy, NMR spectroscopy ( H, H{ P}, F{ H},
13
1
31
1
Xꢀray diffraction studies (Fig. 2). In this case, it is noticeꢀ
able that the chemical shifts of the signals in the 31P{ H}
NMR spectra of the fluorineꢀcontaining phosphoryl
ketone 7 (P = 34.9) and its nonfluorinated analog
C{ H}, P{ H}), and Xꢀray diffraction studies (Fig. 3).
1
In the IR spectrum of diketone 9, two vibrational bands
–
1
for the carbonyl groups are found at 1712 and 1732 cm
.
2
2
Earlier, a similar effect was also observed in the case of
nonfluorinated diketone Ph P(O)CHPhCH[C(O)Me] . In
5
Ph P(O)CMe CH C(O)Me ( = 37.2) are already virꢀ
2
2
2
P
2
2
tually the same. Like in the case of the simplest ꢀ[bisꢀ
pentafluorophenyl)phosphoryl]alkanone 2, a suggestion
on the transoid arrangement of the P=O and the C=O
fragments in the molecule of fluorophosphorusꢀcontainꢀ
this case, the quantum chemical calculations of the vibraꢀ
tional frequencies in the conformation of the global miniꢀ
mum showed that the vibrations of the C=O groups of
compound under consideration are bound both inꢀphase
and inꢀantiphase. It is possible that similar situation is
also in place in the case of decafluorinated phosphoryl
diketone 9.
In the molecule of diketone 9, there are present an
asymmetric benzyl carbon atom, included in the compoꢀ
sition of the P(O)CH fragment, and two prochiral centers: the
phosphorus atom and the methine carbon atom bonded to
(
ing ketone 7, made based on the spinꢀspin coupling conꢀ
3
stant J
(17.6 Hz) of the carbon atom of the carbonyl
C,P
group of this compound, is confirmed by the Xꢀray difꢀ
fraction data. The results obtained indicate that in the
series of ꢀdiorganylphosphorylalkanones parameters of
the corresponding spinꢀspin coupling constant can serve
*
According to the literature data,23 the addition of diorganꢀ
7
ylphosphinous acids containing no fluorine atoms to mesityl
oxide 6 at room temperature, like in the case of another nonterꢀ
minal ,ꢀenone 4, proceeds exclusively at the C=O bond of the
starting unsaturated ketone.
** Earlier we have shown, that an efficient addition of dipheꢀ
nylphosphinous acid (nonfluorinated analog of 1) at ~20 C to
enedione 8 becomes feasible only in the presence of 1,5,7ꢀ
triazabicyclo[4.4.0]decꢀ5ꢀene as a catalyst.

[
Bis(pentafluorophenyl)phosphoryl]alkanones
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
2321
phosphoryl diketone 9 is a cause of the effect observed in
1
13
19
F(9)
the H, C and F NMR spectra of this compound (see
Experimental): the signals for a number of the correspondꢀ
C(22)
C(23)
ing nuclei which compose the Ph and one of the C F
substituents are found as the broad signals, rather than as
expected multiplets.
In conclusion, the addition of bis(pentafluorophenyl)ꢀ
phosphinous acid to ,ꢀalkenones and ,,´ꢀalkeneꢀ
C(11)
C(21)
F(10)
6 5
F(8)
C(10)
C(9)
C(24)
C(20)
C(12)
C(7)
C(19)
C(13)
C(18)
diones in anhydrous Et O proceeds regiospecifically at the
O(1)
2
F(7)
C(8)
F(6)
C=C bond of the substrate at high rate at ~20 C in the
absence of any catalysts and usually in the yields close to
quantitative and leads to bis(pentafluorophenyl)phosꢀ
phorylated alkanones and alkanediones, which allows one
to consider this process as a highly efficient method for
the synthesis of the corresponding functionalized phosꢀ
phine oxides.
To increase the practical importance of this method,
we suggested a new simple and efficient version for the
synthesis of the starting acid 1, consisting in the aqueous
hydrolysis of bromobis(pentafluorophenyl)phosphine (10)
(Scheme 5).
C(17)
O(3)
F(1)
C(2)
P(1)
C(14)
O(2)
C(1)
C(6)
C(15)
C(16)
F(2)
F(5)
C(3)
C(5)
C(4)
F(4)
F(3)
Fig. 3. General view of the structure of 3ꢀ{ꢀ[bis(pentafluoroꢀ
phenyl)phosphoryl]benzyl}pentaneꢀ2,4ꢀdione (9) in represenꢀ
tation of atoms by ellipsoids of thermal vibrations (p = 50%).
Scheme 5
the acyl groups. In this connection, both the Pꢀpentaꢀ
fluorophenyl substituents and the COMe groups are diaꢀ
stereotopic and magnetically nonequivalent in achiral meꢀ
This approach is favorably distinguished from the
1
1
31
19
1
dium, which can be seen in the H/ H{ P}, F{ H}, and
classic14 method for the preparation of acid 1: the starting
13
1
C{ H} NMR spectra as a doubling of signals of the corꢀ
organophosphorus compound is not bis(pentafluoroꢀ
phenyl)chlorophosphine (11), but synthetically more
available** analog 10.
responding indicative nuclei.* In particular, the signals
for the carbon atoms of the C=O groups are found as two
3
doublets at  = 200.74 ( J
(
= 14.7 Hz) and 201.74
P
C,P
3
JC,P = 1.5 Hz). Taking into account a high reliability of
Experimental
the correlation between the corresponding spinꢀspin coupꢀ
ling constant and a mutual arrangement of the carbonyl
and the phosphoryl fragments confirmed for diorganꢀ
ylphosphorylated monoketones, the highꢀfield signal can
be assigned to the C=O fragment of the phosphoryl diꢀ
ketone molecule 9, which is in the transoid position with
respect to the phosphoryl group, whereas the lowꢀfield
signal can be assigned to the cisoid C=O fragment. Note
that according to the Xꢀray diffraction data, the phenyl
substituent at the C(13) atom is cisꢀoriented relative to the
phosphoryl group and in close proximity to the perfluoroꢀ
phenyl substituent C(7)—C(12) (C(7)...C(19) 2.955(1) Å).
By all accounts, this specific feature of the structure of
1
1
31
13
1
19
1
31
1
H, H{ P}, C{ H}, F{ H}, and P{ H} NMR spectra
1
1
31
were recorded on Bruker AVꢀ400 ( 400.13 ( H and H{ P}),
00.61 ( C{ H}), 376.49 ( F{ H}), and 161.98 MHz ( P{ H}))
and Bruker AVꢀ600 (in the case of H and C{ H} NMR spectra
of compound 2) (600.22 ( H) and 150.925 MHz ( C)). The
signals for the residual protons of the deuterated solvent (in the
case of CCl , the signals for the residual protons of D O (capilꢀ
lary)) were used as a reference for the H and H{ P} NMR
spectra, for C{ H} NMR spectra the reference was the signals
for the carbon atom nuclei of the deuterated solvent, external
13
1
19
1
31
1
1
1
13
1
1
13
4
2
31
1
1
13
1
19
1
31
1
standards for F{ H} and P{ H} NMR spectra were CFCl
and 85% H PO , respectively.
3
3
4
In this case, if in the 13C{ H} NMR spectrum such a doubling
1
** According to the recent data,24 bromophosphine 10 can be
*
is observed for the signals of all four types of nuclei of carbon
easily synthesized in one step by the reaction of C F MgBr with
6
5
atoms (orthoꢀ, metaꢀ, paraꢀ, and ipsoꢀ) of pentafluorophenyl fragꢀ
PCl , whereas a twoꢀstep process remains the only method for
3
19
1
ments, in the F{ H} NMR spectrum such an effect is observed
only for the nuclei of the fluorine atoms located at orthoꢀ and
paraꢀpositions of these substituents.
the synthesis of chlorophosphine 11, reliably leading to the indiꢀ
vidual product: C F MgX  (C F ) PNRR´  11 (see, for
6
5
6 5 2
example, Ref. 18).

2322
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
Goryunov et al.
IR spectra were recorded on a Bruker Tensor 37 Fourꢀ
by the FGUP Russian Scientific Center of Applied Chemistry,
Saint Petersburg) were used without additional purification.
Reaction progress of addition of 1 to unsaturated carbonyl
compounds was monitored by 3 P NMR spectroscopy.
Elemental analysis was performed in the Laboratory of
Microanalysis of A. N. Nesmeyanov Institute of Organoelement
Compounds of the Russian Academy of Sciences.
–
1
ierꢀtransform spectrometer (resolution 2 cm ) in the region of
–
1
4
00—4000 cm . Samples were prepared in KBr pellets.
The crystals of bis(pentafluorophenyl)phosphorylalkanones
, 7, and 9 suitable for Xꢀray diffraction studies were obtained by
1
2
evaporation of solutions of the corresponding compounds in anꢀ
hydrous diethyl ether at ~20 C.
Xꢀray diffraction studies of compounds 2 and 7 were carried
out on a Smart APEX2 DUO CCD diffractometer, compound 9
was studies on a Smart APEX2 CCD diffractometer (MoꢀK
radiation, graphite monochromator, ꢀscan technique). The
structures were solved by direct method and refined by least
Bromobis(pentafluorophenyl)phosphine (10). The Grignard
reagent was obtained by a standard method from bromopentaꢀ
fluorobenzene (60 g, 0.243 mol) and magnesium turnings (6.1 g,
0.251 mol) in anhydrous diethyl ether (210 mL) and was filtered
through a porous glass filter under argon. The ethereal solution
of the Grignard reagent was placed into a 500ꢀmL roundꢀbottom
threeꢀneck glass flask equipped with a mechanical stirrer, dropꢀ
ping funnel, and an alcohol thermometer, cooled to –50 C,
followed by a dropwise addition of a solution of freshly distilled
phosphorus trichloride (14.5 g, 0.106 mol) in anhydrous diethyl
ether (10 mL) at this temperature over 0.5 h. The reaction mixꢀ
ture was stirred for 2 h, gradually raising temperature to ~20 C,
allowed to stand for 3 days, filtered through a porous glass filter
under argon. A precipitate was washed with anhydrous diethyl
ether (2×50 mL), the ether from the combined filtrates was evapꢀ
orated, the residue was distilled in vacuo, collecting a fraction
with b.p. 80—130 C (~1 Torr), the fraction obtained was redisꢀ
tilled in vacuo. The yield was 28.4 g (67%), b.p. 119—121 C
squares method in anisotropic fullꢀmatrix approximation on
2
F
hkl. Positions of hydrogen atoms were calculated geometricalꢀ
ly and refined in isotropic approximation using a riding model.
Principal crystallographic data and parameters of refinement
are given in Table 1. All the calculations were carried out using
the SHELXTL PLUS software.
The starting bromopentafluorobenzene (Acros) was dried
with anhydrous CaCl and distilled before the reaction; phosꢀ
2
phorus trichloride, methyl vinyl ketone, and mesityl oxide 6
(
Acros) were distilled before the reaction; 4ꢀphenylbutꢀ3ꢀenꢀ2ꢀ
one 4 (Acros) and 3ꢀbenzylidenepentaneꢀ2,4ꢀdione 8 (Alfa Aeꢀ
sar) were used without additional purification. The basic Brockꢀ
mann I Al O (50—200 m, Acros) was used.
2
3
31
Organic solvents used in the work were purified according to
the standard procedures.2
(0.5 Torr) (cf. Ref. 26: b.p. 100—104 C (0.1 Torr)). P NMR
5
3
(MeCN (anhydrous)), : 12.81 (quint, J = 37.1 Hz).
P,F
Deuterated solvents for the recording NMR spectra (CDCl3,
CD Cl , C D , CD CN, CD NO , and DMSOꢀd ) produced
Bis(pentafluorophenyl)phosphinous acid (1). Bromobis(pentaꢀ
fluorophenyl)phosphine (10) (10 g, 22.5 mmol) was added dropꢀ
2
2
6
6
3
3
2
6
Table 1. Principal crystallographic data and parameters refinement for compounds 2, 7, and 9
Parameter
2
7
9
Molecular formula
C H F O P
C H F O P
C H F O P
1
6
7
10
2
18 11 10
2
24 13 10
3
Molecular weight
T/K
Crystal system
Space group
452.19
120
Monoclinic
480.24
100
Monoclinic
570.31
120
Triclinic
Pꢀ1
P2 /c
P2 /c
1
1
Z
4
10.4562(19)
15.837(3)
10.3974(19)
90.00
100.499(3)
90.00
1692.9(5)
1.774
4
9.9196(4)
11.4783(4)
15.9353(6)
90.00
99.4720(10)
90.00
1789.66(12)
1.782
2
a/Å
b/Å
c/Å
10.2732(17)
10.4596(18)
11.5429(19)
87.627(3)
69.131(3)
78.278(3)
1134.1(3)
1.670

/deg
/deg
/deg


3
V/Å
dcalc/g cm–3

/cm–1
2.78
2.69
2.3
F(000)
896
960
572
2
max/deg
58
60
56
Reflections collected
Number of independent reflections
Number of reflections with I > 2(I)
Number of refined parameters
R1
12024
4479
3763
263
0.0339
0.0907
1.013
19667
5216
4601
283
0.0304
0.0839
1.031
12426
5448
4344
345
0.0493
0.1444
1.018
wR2
GOOF
Residual electron
density/e Å–3, max/min
0.443/–0.343
0.422/–0.363
1.201/–0.637

[
Bis(pentafluorophenyl)phosphoryl]alkanones
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
2323
wise to an iceꢀcold water (50 mL) with vigorous stirring using
a magnetic stirrer and cooling by ice, the mixture was stirred for
itate formed was separated, sequentially washed on the filter
with a mixture of hexane—ether (2 : 1) (3×3 mL) and hexane
(5 mL), and dried in air. The yield was 1.502 g (94.8%), m.p.
168.5—169.5 C. Found (%): C, 49.69; H, 2.01; F, 35.31;
P, 6.17. C H F O P. Calculated (%): C, 50.02; H, 2.10; F, 35.96;
3
h with external cooling in an iceꢀwater bath. A precipitate
formed was separated, washed with iceꢀcold water (15 mL), thorꢀ
oughly wrung out, dried in air for 1 h, kept over P O in vacuo
2
5
22 11 10 2
–
1
31
1
(
~1 Torr) at 30 C until the weight was constant, and recrystalꢀ
P, 5.86. IR, /cm : 1219 (P=O), 1715 (C=O). P{ H} NMR
–
1
1
lized from hexane. The yield was 7.2 g (84%), m.p. 97—99 C
(CDCl , c = 0.1 mol L ), : 23.62 (s). H NMR (CDCl3,
3
1
–1
–1
(

=
1
cf. Ref. 14: m.p. 97—98 C). H NMR (CCl , c = 0.05 mol L ),
c = 0.1 mol L ), : 2.16 (s, 3 H, Me); 3.32 (dd, CH H , 1 H,
4
A
В
1
31
2
3
: 8.66 (d, P(O)H, J
= 569.2 Hz). P NMR (CCl , c =
0.05 mol L–1), : –22.93 (d, P(O)H, JP,H = 571.9 Hz).
H NMR (C D , c = 0.05 mol L ), : 8.23 (d, P(O)H, J =
J
= 18.2 Hz, J
= 12.4 Hz); 3.53 (ddd, CH H , 1 H,
H ,P A В
H,P
4
H ,H
A
B
A
1
2J
3
3
= 18.0 Hz, J
= 9.8 Hz, J
= 6.4 Hz); 4.47—4.54
H ,P
H ,H
H ,H
B
A
B
B
–1
1
(m, 1 H, CHP); 7.18—7.27 (m, 3 H, mꢀPh, pꢀPh); 7.40—7.44
6
3
6
H,P
1
–1
1
31
–1
=
566.7 Hz). P NMR (C D , c = 0.05 mol L ), : –23.57 (d,
(m, 2 H, oꢀPh). H{ P} NMR (CDCl , c = 0.1 mol L ), : 2.16
6
1
6
3
2
1
–1
P(O)H, J = 566.7 Hz). H NMR (CD NO , c = 0.05 mol L ),
: 8.95 (d, P(O)H, JH,P = 583.1 Hz). P NMR (CD NO ,
c = 0.05 mol L ), : –18.97 (d, P(O)H, J
(s, 3 H, Me); 3.32 (d, CH H , 1 H, J
= 17.7 Hz); 3.53
= 10.2 Hz); 4.51
P,H
3
2
A
В
H ,H
A
B
1
31
2
3

(dd, CH H , 1 H, J
= 17.9 Hz, J
H ,H H ,H
A B
3
2
A
В
B
–
1
1
3
= 583.0 Hz).
(d, 1 H, CHP, J
= 9.2 Hz); 7.18—7.27 (m, 3 H, mꢀPh,
H,HB
P,H
3
13
1
4
ꢀ[Bis(pentafluorophenyl)phosphoryl]butanꢀ2ꢀone (2). A. In
pꢀPh); 7.42 (d, 2 H, oꢀPh, J
c = 0.1 mol L ), : 30.26 (s, Me); 43.67 (s, CH ); 44.50 (d, CHP,
JC,P = 76.3 Hz); 106.16 (dm, ipsoꢀC F , JC,P = 93.9 Hz);
108.40 (dm, ipsoꢀC F , JC,P = 85.8 Hz); 128.57 (d, pꢀPh,
JC,P = 2.2 Hz); 129.04 (d, mꢀPh, J
oꢀPh, J = 7.3 Hz); 134.54 (d, ipsoꢀPh, J = 5.9 Hz); 137.32
= 6.9 Hz). C{ H} NMR (CDCl ,
H,H 3
–
1
diethyl ether. A solution of acid 1 (2.292 g, 6 mmol) in anhydrous
diethyl ether (24 mL) was added dropwise to a solution of freshly
distilled MVK (0.44 g, 6.3 mmol) in anhydrous ether (6 mL).
The reaction mixture was allowed to stand for 1 h at ~20 C,
concentrated to dryness, and kept in vacuo (~ 1 Torr) at 75 C for
2
1
1
6
5
1
6
5
5
4
= 1.5 Hz); 129.16 (d,
C,P
3
2
C,P
C,P
1
1
3
.5 h. The yield was 2.675 g (98.6%), m.p. 87.5—89 C (hexꢀ
(dm, mꢀC F , J
= 250.2 Hz); 137.93 (dm, mꢀC F , J
=
6
5
C,F
6
5
C,F
1
ane—CCl ). Found (%): C, 42.23; H, 1.47; F, 42.02; P, 6.71.
= 256.0 Hz); 143.98 (dm, pꢀC F , J
= 260.4 Hz); 144.43
C,F
4
6
5
1
1
C H F O P. Calculated (%): C, 42.50; H, 1.56; F, 42.01;
(dm, pꢀC F , J
= 246.5 Hz); 146.53 (dm, oꢀC F , J
=
1
6
7
10
2
6
5
C,F
6
5
C,F
–
1
31
1
1
P, 6.85. IR, /cm : 1219 (P=O), 1728 (C=O). P{ H} NMR
CDCl , c = 0.1 mol L ), : 19.97 (s). H NMR (Bruker AVꢀ400,
CDCl , c = 0.1 mol L ), : 2.23 (s, 3 H, Me); 2.87 (dt, 2 H,
CH P,
= 251.6 Hz); 146.90 (dm, oꢀC F , J
C=O, J = 16.1 Hz). F{ H} NMR (CDCl , c = 0.1 mol L ),
: –130.33 (d, 2 F, oꢀC F , J
oꢀC F , J = 16.5 Hz); –143.78 (t, 1 F, pꢀC F , J = 20.6 Hz);
= 251.6 Hz); 203.33 (d,
C,F
6
5
–
1
1
3
19
1
–1
(
3
C,P
3
–
1
3
= 16.5 Hz); –132.30 (d, 2 F,
3
6
5
F,F
3
= 7.2 Hz, 2
3
3
J
J
3
= 11.2 Hz); 3.02 (dt, 2 H,
= 13.4 Hz). H NMR (Bruker
2
H,H
3
H,P
6
5
F,F
6
5
F,F
1
3
CH CH P, J
= 7.2 Hz, J
–144.23 (t, 1 F, pꢀC F , J
= 20.6 Hz); –(157.43—157.70)
F,F
2
2
H,H
H,P
6
5
–
1
AVꢀ600, CDCl , c = 0.1 mol L ), : 2.23 (s, 3 H, Me); 2.87 (dt,
(m, 2 F, mꢀC F ); –(158.70—158.93) (m, 2 F, mꢀC F ).
3
6 5 6 5
3
H, CH P, J
2
2
2
= 7.6 Hz, J
= 11.5 Hz); 3.01 (dt, 2 H,
4ꢀ[Bis(pentafluorophenyl)phosphoryl]ꢀ4ꢀmethylpentanꢀ2ꢀone
(7). A solution of acid 1 (1.146 g, 3 mmol) in anhydrous diethyl
ether (12 mL) was added dropwise to a solution of mesityl oxide (6)
(0.31 g, 3.15 mmol) in anhydrous ether (3 mL). The reaction
mixture was allowed to stand for 48 h at ~20 C and concentratꢀ
ed to dryness, the residue was dissolved in anhydrous CH Cl
H,H
H,P
3
3
1
31
CH CH P, J
= 7.4 Hz, J
= 13.4 Hz). H{ P} NMR
2
2
H,H
H,P
–
1
(
CDCl , c = 0.1 mol L ), : 2.23 (s, 3 H, Me); 2.88 (t, 2 H,
CH P, J
C{ H} NMR (Bruker AVꢀ600, CDCl , c = 0.1 mol L ),
: 27.33 (d, CH P, J
3
3
3
= 7.2 Hz); 3.02 (t, 2 H, CH CH P, J
= 7.3 Hz).
H,H
2
1
H,H
2
2
1
3
–1
3
1

= 81.8 Hz); 29.63 (s, Me); 34.58 (d,
C,P
2
2
2
2
1
CH CH P, J
= 4.4 Hz); 107.38 (dtm, ipsoꢀC F , J
= 21.0 Hz); 137.89 (dm, mꢀC F , JC,F
C,F 6 5
=
=
(5 mL). The solution obtained was filtered through a layer of
basic Al O3 (0.57 g), the Al O3 was washed with anhydrous
2
2
C,P
6
5
C,P
1
=
=
95.1 Hz, 2J
2
2
1
263.1 Hz); 144.59 (dm, pꢀC F , J
dm, oꢀC F , J = 256.5 Hz); 204.52 (d, C=O, J = 13.3 Hz).
F{ H} NMR (CDCl , c = 0.1 mol L ), : –131.63 (d, 4 F,
oꢀC F , JF,F = 21.3 Hz); –143.64 (t, 2 F, pꢀC F , JF,F
= 263.1 Hz); 147.11
CH Cl2 (6 mL), the combined filtrates were concentrated to
6
5
C,F
2
1
3
(
dryness and dried in vacuo (~1 Torr) at 50 C over 1 h. The yield
6
5
C,F
C,P
1
9
1
–1
was 1.328 g (92.2%), m.p. 126—127.5 C (hexane—CCl ).
3
4
3
3
=
Found (%): C, 44.97; H, 2.26; F, 39.43; P, 6.32. C H F O P.
6
5
6
5
18 21 10
2
–
1
=
21.3 Hz); –(157.73—157.93) (m, 4 F, mꢀC F ).
Calculated (%): C, 45.02; H, 2.31; F, 39.56; P, 6.45. IR, /cm :
1212 (P=O), 1724 (C=O). P{ H} NMR (CDCl , c = 0.1 mol L ),
: 34.87 (s). H NMR (CDCl , c = 0.1 mol L ), : 1.57 (d, 6 H,
6
5
3
1
1
–1
B. In chloroform. A solution of acid 1 (2.292 g, 6 mmol) in
3
–1
1
anhydrous chloroform (10 mL) was added dropwise to a solution
of freshly distilled MVK (0.44 g, 6.3 mmol) in anhydrous chloroꢀ
form (20 mL), kept for 8 h at ~20 C, and treated afterwards as in the
preceding case. The yield was 2.695 g (99.3%), m.p. 88—89 C
3
3
MeCP, J
= 21.1 Hz); 2.23 (s, 3 H, MeC(O)); 2.99 (d, 2 H,
= 9.5 Hz). H{ P} NMR (CDCl , c = 0.1 mol L ),
3
H,P
3
1
31
–1
CH , J
2
H,P
: 1.58 (s, 6 H, MeCP); 2.23 (s, 3 H, MeC(O)), 3.00 (s, 2 H,
1
3
1
–1
(
hexane—CCl ). The spectral characteristics of compound obꢀ
CH ). C{ H} NMR (CDCl , c = 0.1 mol L ), : 19.34
4
2
3
4
tained are identical to the corresponding parameters of phosꢀ
phoryl ketone 2 obtained by method A.
(s, CH CP); 32.25 (d, CH C(O), J = 2.2 Hz); 40.79 (d, MeCP,
JC,P = 74.8 Hz); 44.85 (s, CH ); 107.48 (dtm, ipsoꢀC F ,
= 82.9 Hz, J
= 253.8 Hz); 144.29 (dm, pꢀC F , J
(dm, oꢀC F , J = 256.0 Hz); 205.04 (d, C=O, J = 17.6 Hz).
F{ H} NMR (CDCl , c = 0.1 mol L ), : –(126.79—127.01)
(m, 4 F, oꢀC F ); –144.00 (t, 2 F, pꢀC F , J
–157.72 (t, 4 F, mꢀC F , J = 19.3 Hz).
3
3
C,P
1
2
6
5
=
1J
2
= 20.9 Hz); 137.94 (dm, mꢀC F , J
1
4
ꢀ[Bis(pentafluorophenyl)phosphoryl]ꢀ4ꢀphenylbutanꢀ2ꢀone
5). A solution of acid 1 (1.146 g, 3 mmol) in anhydrous diethyl
ether (12 mL) was added dropwise to a solution of 4ꢀphenylbutꢀ
ꢀenꢀ2ꢀone (4) (0.46 g, 3.15 mmol) in anhydrous ether (3 mL),
C,P
C,F 6 5 C,F
1
(
= 263.4 Hz); 146.87
6
5
C,F
1
3
6
5
C,F
C,P
19
1
–1
3
3
3
The reaction mixture was kept for 2 h at ~20 C and concentratꢀ
= 20.6 Hz);
6
5
6
5
F,F
3
ed to dryness, the residue was dissolved in anhydrous CH Cl2
2
6 5 F,F
(
5 mL). The solution obtained was filtered through a layer of basic
Al O (0.57 g), the Al O was washed with anhydrous CH Cl
2
6 mL). The combined filtrates were concentrated to dryness,
3ꢀ{ꢀ[Bis(pentafluorophenyl)phosphoryl]benzyl}pentaneꢀ2,4ꢀ
dione (9). A solution of acid 1 (1.146 g, 3 mmol) in anhydrous
diethyl ether (12 mL) was added dropwise to a solution of
3ꢀbenzylidenepentaneꢀ2,4ꢀdione (8) (0.59 g, 3.15 mmol) in anꢀ
2
3
2
3
2
(
triturated with a 2 : 1 mixture of hexane—ether (3 mL), a precipꢀ

2324
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 10, October, 2014
Goryunov et al.
hydrous ether (3 mL). The reaction mixture was allowed to stand
for 24 h at ~20 C and concentrated to dryness, the residue was
dissolved in anhydrous CH Cl (10 mL). The solution obtained
from June 30, 2008, Published 27.11.2009; Byul. isobret. [Inꢀ
vention Bull.], 2009, No. 33 (in Russian).
5. P. S. Lemport, G. V. Bodrin, M. P. Pasechnik, A. G. Matveꢀ
eva, P. V. Petrovskii, A. V. Vologzhanina, E. E. Nifant´ev,
Russ. Chem. Bull. (Int. Ed.), 2007, 56, 1911 [Izv. Akad. Nauk,
Ser. Khim., 2007, 1846].
6. P. S. Lemport, G. V. Bodrin, A. I. Belyakov, P. V. Petroꢀ
vskii, A. V. Vologzhanina, E. E. Nifant´ev, Mendeleev Comꢀ
mun., 2009, 19, 303.
7. A. A. Ambartsumyan, L. A. Sviridova, N. I. Vorozhtsov, E. I.
Goryunov, G. V. Bodrin, I. B. Goryunova, A. B. Uryupin,
T. T. Vasil´eva, O. V. Chakhovskaya, K. A. Kochetkov, E. E.
Nifant´ev, Dokl. Akad. Nauk, 2013, 448, 413 [Dokl. Chem.
(Engl. Transl.), 2013].
8. J. P. Haelters, B. Corbel, G. Sturtz, Phosphorus and Sulfur,
1988, 37, 41.
9. F. Palacios, A. M. Ochoa de Retana, J. Oyarzabal, Tetraheꢀ
dron, 1999, 55, 5947.
10. N. Houllier, J. Gopisetti, P. Lestage, M.ꢀC. Lasne, J. Rouꢀ
den, Bioorg. Med. Chem. Lett., 2010, 20, 6667.
11. N. G. Frolova, E. D. Savin, E. I. Goryunov, K. A. Lysenko,
Yu. V. Nelyubina, P. V. Petrovskii, E. E. Nifant´ev, Dokl.
Akad. Nauk, 2010, 430, 202 [Dokl. Chem. (Engl. Transl.), 2010].
12. E. E. Nifant´ev, Khimiya gidrofosforyl´nykh soedinenii [Chemꢀ
istry of Hydrophosphoryl Compounds], Nauka, Moscow, 1983,
264 pp. (in Russian).
2
2
was filtered through a layer of basic Al O (1.14 g), the Al O
3
2
3
2
was washed with anhydrous CH Cl2 (10 mL), the combined
2
filtrates were concentrated to dryness, the residue was triturated
with a 2 : 1 mixture of hexane—ether (6 mL). A precipitate
formed was separated, sequentially washed on the filter with
a 2 : 1 mixture of hexane—ether (2×3 mL) and hexane (5 mL),
and dried in air. The yield was 1.52 g (88.9%), m.p. 165—167 C
(
hexane—CCl ). Found (%): C, 50.49; H, 2.28; F, 33.17; P, 5.49.
4
C H F O P. Calculated (%): C, 50.54; H, 2.30; F, 33.31;
2
4
13 10
3
–
1
31
1
P, 5.43. IR, /cm : 1219 (P=O); 1712, 1732 (C=O). P{ H} NMR
(
CDCl , c = 0.1 mol L ), : 26.04 (s). 1H NMR (CDCl3,
–
1
3
–
1
c = 0.1 mol L ), : 2.05 (s, 3 H, Me); 2.34 (s, 3 H, Me); 4.98
dd, 1 H, CHP, J
CHCHP, J
mꢀPh, pꢀPh); 7.31 (br.s, 2 H, oꢀPh). H{ P} NMR (CDCl ,
c = 0.1 mol L ), : 2.05 (s, 3 H, Me); 2.35 (s, 3 H, Me); 4.98 (d,
H, CHP, J
3
2
(
= 11.0 Hz, J
= 6.0 Hz); 5.08 (dd, 1 H,
= 10.2 Hz); 7.15—7.26 (m, 3 H,
H,P
H,H
H,P
3
3
= 10.6 Hz, J
H,H
1
31
3
–
1
3
3
1
= 11.2 Hz); 5.08 (d, 1 H, CHCHP, J
=
H,H
H,H
=
11.1 Hz); 7.16—7.26 (m, 3 H, mꢀPh, pꢀPh); 7.31 (br.s, 2 H,
13
1
–1
oꢀPh). C{ H} NMR (CDCl , c = 0.1 mol L ), : 29.62 (s, Me);
3
1
4
3
1
1
1
0.88 (s, Me); 49.41 (dt, CHP, J = 76.3 Hz, J
07.15 (dtm, ipsoꢀC F , JC,P = 100.5 Hz, JC,F = 17.4 Hz);
10.03 (dtm, ipsoꢀC F , JC,P = 88.8 Hz, 2JC,F = 17.8 Hz);
= 5.5 Hz);
C,P
C,F
1
2
6
5
1
6
5
5
29.04 (d, pꢀC H , J
= 3.7 Hz); 129.15 (br.s, oꢀPh); 129.27
6
5
C,P
4
2
(
d, mꢀPh, J
= 2.2 Hz); 133.37 (d, ipsoꢀPh, J
= 4.4 Hz);
13. J. A. Miller, G. M. Stevenson, B. C. Williams, J. Chem. Soc.
C., 1971, 2714.
14. D. D. Magnelli, G. Tesi, J. U. Lowe, Jr., W. E. McQuistion,
Inorg. Chem., 1966, 5, 457.
15. B. Hoge, S. Neufeind, S. Hettel, W. Wiebe, C. Thösen,
J. Organomet. Chem., 2005, 690, 2382.
16. B. Kurscheid, W. Wiebe, B. Neumann, H.ꢀG. Stammler,
B. Hoge, Eur. J. Inorg. Chem., 2011, 5523.
C,P
C,P
1
1
37.07 (dm, mꢀC F , J
= 256.0 Hz); 137.64 (dm, mꢀC F ,
6
5
C,F 6 5
1
1
JC,F = 250.1 Hz); 143.71 (dm, pꢀC F , J = 260.2 Hz); 144.18
6
5
C,F
1
1
(
dm, pꢀC F , J
= 261.9 Hz); 146.06 (dm, oꢀC F , J
250.9 Hz); 147.16 (dm, oꢀC F , J = 250.9 Hz); 200.74 (d,
C,F
=
6
5
C,F
6
5
C,F
1
=
6
5
3
3
19
1
C=O, J = 14.7 Hz); 201.74 (d, C=O, J = 1.5 Hz). F{ H}
C,P
C,P
–
1
NMR (CDCl , c = 0.1 mol L ), : –128.97 (dm, 2 F, oꢀC F ,
3
6 5
3
JF,F = 14.3 Hz); –131.40 (br.s, 2 F, oꢀC F ); –144.79 (tm, 1 F,
6
5
3
3
pꢀC F , J = 20.3 Hz); –145.41 (tt, 1 F, pꢀC F , J = 20.3 Hz,
17. G. Keglevich, M. Sipos, D. Takacs, I. Greiner, Heteroatom
Chem., 2007, 18, 226.
6
5
F,F
6
5
F,F
4
JF,F = 6.5 Hz); –(159.08—159.33) (m, 4 F, mꢀC F ).
6
5
1
8. M. V. Jimenez, J. J. PerezꢀTorrente, M. I. Bartolome, L. A.
Oro, Synthesis, 2009, 1916.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 14ꢀ03ꢀ00695ꢀa)
and the Russian Academy of Sciences (Program for Funꢀ
damental Studies of the Presidium of the Russian Acadeꢀ
my of Sciences Pꢀ8 "Development of Methods for Prepaꢀ
ration of Chemical Compounds and Development of New
Materials").
19. M. G. Hogben, W. A. Graham, J. Am. Chem. Soc., 1969,
91, 283.
2
2
0. C. A. Kingsbury, D. Thoennes, Tetrahedron Lett., 1976, 3037.
1. A. N. Pudovik, A. A. Sobanov, I. V. Bakhtiyarova, M. G.
Zimin, Zh. Obshch. Khim., 1983, 53, 2456 [J. Gen. Chem.
USSR (Engl. Transl.), 1983, 53].
2
2
2. E. I. Goryunov, G. V. Bodrin, I. B. Goryunova, Yu. V. Neꢀ
lyubina, P. V. Petrovskii, T. V. Strelkova, A. S. Peregudov,
A. G. Matveeva, M. P. Pasechnik, S. V. Matveev, E. E. Nifanꢀ
t´ev, Russ. Chem. Bull. (Int. Ed.), 2013, 62, 780 [Izv. Akad.
Nauk, Ser. Khim., 2013, 779].
3. A. A. Sobanov, I. V. Bakhtiyarova, M. G. Zimin, A. N.
Pudovik, Zh. Obshch. Khim., 1986, 56, 711 [J. Gen. Chem.
USSR (Engl. Transl.), 1986, 56].
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Received June 3, 2014;
in revised form September 16, 2014