Interaction of α,α-difluoroazides with trivalent phosphorus compounds and triphenylantimony

Article abstract of DOI:10.1134/S1070363210080141

α,α-Difluoroazides react with triphenylantimony and various compounds of trivalent phosphorus according to the oxidative fluorination scheme. In the case of trivalent phosphorus compound the primary products are phosphazenes, phosphazides or difluorophosphoranes that may undergo further transformations to the corresponding fluorine derivatives of pentavalent phosphorus. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210080141

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 8, pp. 1646–1651. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.A. Lermontov, A.G. Polivanova, S.B. Shkavrov, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 8, pp. 1335–
1340.
Interaction of α,α-Difluoroazides with Trivalent Phosphorus
Compounds and Triphenylantimony
S. A. Lermontova, A. G. Polivanovab, and S. B. Shkavrovc
aInstitute of Physiologically Active Substances, Russian Academy of Sciences,
Severnyi proezd 1, Chernogolovka, Moscow oblast, 142432 Russia
e-mail: lermon@ipac.ac.ru
bMendeleev Chemical Technology University, Moscow, Russia
e-mail: zagchem@mail.ru
cChemical Diversity Research Institute, Khimki, Moscow oblast, Russia
e-mail: shsv69@mail.ru
Received October 22, 2009
Abstract—α,α-Difluoroazides react with triphenylantimony and various compounds of trivalent phosphorus
according to the oxidative fluorination scheme. In the case of trivalent phosphorus compound the primary
products are phosphazenes, phosphazides or difluorophosphoranes that may undergo further transformations to
the corresponding fluorine derivatives of pentavalent phosphorus.
DOI: 10.1134/S1070363210080141
Earlier we have demonstrated for the azides A-1and
A-2 that α,α-difluoroazides react with trivalent
phosphorus compounds by a general mechanism [1]
presented in Scheme 1.
azides A-5 and A-6 (Scheme 2).
Azides A-5 and A-6 were obtained by the reaction
of azide A-2 with the corresponding amines. Azides
A-3 and A-4 were obtained from ethyl bromo(difluoro)-
acetate according to Scheme 3.
Azide A-2, proved to be an active oxidative
fluorinating reagent, contains the ester functional
group that allows its modification. For this reason we
were interested to explore how the conversion of the
ester group into amide one would affect the reactivity
of the azide molecule in general. It was also interesting
to investigate how the reducing of the fluorinated chain
of the azide A-2 by one СF2-group would affect the
reaction properties of fluorinated azides. With this
purpose we have synthesized new α,α-difluoroazides
A-3 and A-4 and two amide derivatives of azide A-2,
First, ethyl bromodifluoroacetate was aminated by
primary or secondary amine and the resulting
bromodifluoroacetamide I was treated with sodium
azide, affording the target azidodifluoroacetamides.
When trying to obtain ethyl azidodifluoroacetate by
interaction of ethyl bromo(difluoro)acetate with
sodium azide according to [2] azidoetan and sodium
bromodifluoroacetate were obtained as products
(Scheme 3). At the changed the reaction conditions
Scheme 1.
F
F
F
N3
N3
O
CH3
R3P
CF3
F
F
F
F
O
A-2
A-1
F
F
F
F
F
−N2
N3
R'
+
N
F
R3P N N
N
+ R3P
+ CN R'
R3P
R3P
N
F
F
F
R'
R'
R'
1646

INTERACTION OF α,α-DIFLUOROAZIDES
1647
Scheme 2.
O
F
F
R1
R2
R1
R2
N3
N
N3
N
F
F
F
F
O
A-5, A-6
A-3, A-4
H
N
R1
R2
(A-3, A-5),
(A-4, A-6).
N
=
N
(temperature, solvent) also these products were
obtained.
compounds containing in addition to the products III–
VII, phosphazenes II, which are completely
decomposed at boiling in benzene for three hours. 31Р
NMR spectra of the phosphazenes II contain
characteristic signals with δР 0–4 ppm, (triplet of
triplets, JP–F = 14–17 Hz, JP–F = 4–6 Hz). When
azides A-4 and A-6 containing the NH-fragment in
their structure were used, 31Р NMR spectrum of the
reaction mixture, along with the signals of compounds
III–VII, contained a large number of the signals of by-
products that probably form when the main products
react with NH bonds at elevated temperatures. The
ratio of organophosphorus products in the reaction
mixture are given in Table 1.
We performed the reaction of azides A-3–A-6 with
some trivalent phosphorus substances and found that
they proceed essentially in the same way as with
azides A-1and A-2.
3
4
It turned out that trimethyl- and triethylphosphites
react with the azides A-3–A-6 already at room
temperature. In the case of azide A-3 at room
temperature a mixture of pentavalent phosphorus
compounds III–VII (Scheme 4) is formed. Azide A-5
at room temperature gives a mixture of phosphorus(V)
Scheme 3.
R1 R2
R1
N
F
F
F
F
THF
O
CH3
+
troom
N
H
Br
Br
R2
O
O
I
R1
R1
N
NaN3
DMSO
F
F
F
F
N
50oC
R2
Br
R2
N3
O
O
H2N
R1
R2
HN
,
=
N
H
F
F
F
F
O−Na+
O
CH3
+ NaN3
+ N3
CH3
Br
Br
O
O
Scheme 4.
O
(RO)3PF2 + (RO)3P O + (RO)
+ (RO)4PPF6−
2 P
O
F
+
+ (RO)
2P
(RO)3P
(RO)3P + N3CF2R'
N
CF2R'
R'
+ NC
R
III
IV
V
II
VI
VII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1648
LERMONTOV et al.
Scheme 5.
[(C2H5)2N]3P + N3CF2R'
[(C2H5)2N]3P
N
N
N
CF2R'
+ NC
VIII
O
F
F
F
O
F
Et2N
110oC
[(C2H5)2N]
2 P
+
R'
+
P
P
F
[(C2H5)2N]3
XI
IX
X
The reaction of hexaethyltriamidophosphite with
azides A-3–A-6 at room temperature leads to the
formation of phosphazides VIII. These are
distinguished by a high thermal stability: they only
begin to decompose after boiling in toluene for three
hours. 31Р NMR spectra of VIII contain characteristic
signals with δР 42–43 ppm [1]. After boiling in toluene
in the spectrum of the reaction mixture the signals
corresponding to compounds IX–XI with P–F bond
appear (Scheme 5). The ratio of organophosphorus
products in the reaction mixture are given in Table 2.
mixture are given in Table 2. For the identification of
difluoro(tri-o-tolyl)phosphorane we synthesized it by
the reaction of tri-o-tolylphosphine with xenon
difluoride. 31Р NMR spectrum of the substance
obtained in this case was fully consistent with the
spectra of the reaction mixtures obtained after
interaction of azides A-3 and A-5 with a tri-o-
tolylphosphine.
Scheme 6.
XeF2
F
F
110oC
P
It is known that triarylphosphines are compounds
fairly resistant to oxidation [3], and their oxidative
fluorination with fluoroazides has not yet been studied.
We decided to implement such a fluorination with the
azides A-3 and A-5 using several arylphosphines as
example (Scheme 6) and found that the oxidation of
triphenyl- and tri-o-tolylphosphines occurs only when
heating the reaction mixture in a steel autoclave at
100°C for 6 h. Upon completion of the reaction in 31Р
NMR spectra of the reaction mixtures, as expected, a
signal of difluoro (triphenyl)phosphorane or difluoro
(tri-o-tolyl)phosphorane was observed. However,
along with the signals of difluorophosphoranes, there
were signals belonging to triphenylphosphine oxide,
or, respectively, tri-o-tolylphosphine oxide, which are
probably formed by the reaction with the glassware
surface of phosphoranes very prone to hydrolysis. The
ratio of organophosphorus products in the reaction
R'
+ NC
R3P + N3CF2R'
R3P
O +
R3P
XIII
CH3
XII
,
,
;
R =
O
O
.
R' =
N
N
F
F
As shown earlier [4], α,α-difluoroazides interact
with the compounds of the elements of groups V and
VI by the scheme, similar to Scheme 1, resulting in the
formation of high valent fluorides of these elements.
Table 1. The ratio of organophosphorus products of trialkyl-
Table 2. The ratio of organophosphorus products of tri-
phosphites fluorination (%)
amidophosphite fluorination (%)
Azide Тreaction, оС
VIII
IX
X
XI
Azide
R
Тreaction, оС
II
III IV
V
VI VII
25
110
25
100
–
–
8
–
27
–
–
65
–
А-3
CH3
C2H5
CH3
C2H5
25
80
25
25
80
–
–
9
–
19
–
35
29
19
–
37
–
А-3
100
100
–
–
А-4
А-5
60 11
25
–
–
–
11
17
–
25
46
–
17
–
28
37
–
–
А-5
110
25
32
–
14
–
54
–
100
А-6
–
21
67 12
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INTERACTION OF α,α-DIFLUOROAZIDES
1649
Table 3. The ratio of organophosphorus products of triaryl-
phosphines fluorination (%)
To confirm this, we carried out the reaction of azides
A-3 and A-5 with triphenylantimony (Scheme 7). The
reaction was performed in a Teflon tube, placed in a
steel autoclave, for 6 hours at 100°C. After completion
of the reaction a signal of (Рh)3SbF2 was observed in
19F NMR spectra.
Azide
R
XII
XIII
phenyl
о-tolyl
phenyl
о-tolyl
82
73
52
55
18
27
48
45
А-3
А-5
Scheme 7.
F
F
110oC
Ph3Sb + N3CF2R
+ RCN
Ph3Sb
heated at 50°C with 7.6 g (0.118 mol) of sodium azide
in 100 ml of DMSO for 24 h. The reaction mixture was
poured into water, the products were extracted with
ethyl acetate. The solvent was evaporated, and the
residue distilled in a vacuum, bp 73°C (0.1 mm Hg),
Thus, we have shown that the new α,α-difluoro-
azides A-3–A-6, as well as already studied azides A-
1and A-2, are good oxidative fluorinating agents. They
easily react with trialkylphosphites and hexa-
ethyltriamidophosphite. Oxidative fluorination of
triarylphosphines and (Рh)3Sb by the azides A-3 and
A-5 requires harsher conditions.
1
yield 19.2 g (90%). Н NMR spectrum (DMSO-d6):
1.56 m (4Н, 2СН2), 1.72 m (4Н, 2СН2), 3.51 t (2Н,
СН2), 3.59 t (2Н, СН2). 19F NMR spectrum (DMSO-
d6): 1.90 (s, CF2). 13С NMR (DMSO-d6): 25.40, 25.85,
1
26.86, 28.80, 47.40, 47.70, 115.50 t (СF2, JCF = 268
Hz), 157.90 t (СО, 2JCF =32 Hz).
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker DPX-
400(400 MHz) spectrometer. 13С, 19F, and 31Р NMR
spectra were recorded on a Bruker CXP-200 instru-
ment at operating frequencies 53 MHz (13С), 188 MHz
(19F), and 81 MHz(31Р). Chemical shifts are given in
parts per million. Azides A-1 [1] and A-2 [5] were
synthesized according to the procedures described in
the literature. Solvents used in the current work were
purified and dried by standard methods.
N-Cyclohexyl-azidodifluoroacetamide (A-4). 23 g
(0.090 mol) of 2-bromo-N-cyclohexyl-2,2-difluoro-
acetamide was heated at 50°C with 7.0 g (0.108 mol)
of sodium azide in 100 ml of DMSO for 24 h. The
reaction mixture was poured into water, the products
were extracted with ethyl acetate. Removal of the
solvent gave pure product. Yield 17.6 g (90%), mp 52–
1
53°C. Н NMR spectrum (CDCl3): 1.24 m (3Н), 1.38
m (2Н), 1.65 m (1Н), 1.75 m (2Н), 1.98 m (2Н), 3.79
19
m (1Н, СНNH), 6.18 (s, 1Н, NH). F NMR spectrum
1-[Bromo(difluoro)acetyl]azepane. 25 g (0.123 mol)
of ethyl bromodifluoroacetate and 18.3 g (0.185 mol)
of azepane in 50 ml of tetrahydrofuran was stirred at
room temperature for 3 h. The reaction mixture was
evaporated and the residue was distilled in a vacuum,
(CDCl3): 6.0 (s, CF2).
1-(3-Azido-2,2,3,3-tetrafluoropropanoyl)azepane
(A-5). A solution of 5 g (0.025 mol) of methyl 3-azido-
2,2,3,3-tetrafluoropropanoate and 2.6 g ( 0.026 mol) of
azepane in 10 ml of methylene chloride was stirred for
3 h at room temperature, after which the reaction
mixture was evaporated, and the residue was distilled
in a vacuum, bp 105°C (0.1 mm Hg), yield 4.7 g
1
bp 90°C (0.1 mm Hg), yield 25.2 g (80%). Н NMR
spectrum (DMSO-d6): 1.58 m (4Н, 2СН2), 1.69 m (2Н,
СН2), 1.79 m (2Н, СН2), 3.51 t (2Н, СН2), 3.63 t (2Н,
СН2).
1
(70%). Н NMR spectrum (DMSO-d6): 1.51 m (4Н,
N-Cyclohexyl-bromodifluoroacetamide. 25
g
2СН2), 1.72 m (4Н, 2СН2), 3.51 m (2Н, СН2), 3.61 m
(0.123 mol) of ethyl bromodifluoroacetate and 18.3 g
(0.185 mol) of cyclohexylamine in 50 ml of tetrahyd-
rofuran was stirred at room temperature for 3 h. The
reaction mixture was evaporated, the residue was dis-
tilled in a vacuum, bp 78°C (0.1 mm Hg), yield 23.6 g
(2Н, СН2). 19F NMR spectrum (DMSO-d6): –34.5 t
3
3
(2F, CF2, JFF = 9 Hz), –12.6 t (2F, CF2, JFF = 9 Hz).
13С NMR spectrum (DMSO-d6): 25.34, 25.74, 26.80,
1
28.82, 47.07, 47.65, 109.69 t.t (СF2, JСF = 272 Hz,
2JСF = 35 Hz), 115.2 t.t (СF2, JCF = 272 Hz, JCF = 35
1
2
1
(75%). Н NMR spectrum (DMSO-d6): 1.34 m (5Н),
Hz), 157.4 t (СО, 2JCF = 26 Hz).
1.73 m (3Н), 2.0 m (2Н), 3.80 m (1Н, СНNH), 6.07 (s,
1Н, NH).
3-Azido-N-cyclohexyl-2,2,3,3-tetrafluoropropan-
amide (A-6). A solution of 5 g (0.025 mol) of methyl
3-azido-2,2,3,3-tetrafluoropropanoate in 10 ml of
[Azido(difluoro)acetyl]azepane (A-3). 25
g
(0.098 mol) of 2-[bromo(difluoro)acetyl]azepane was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1650
LERMONTOV et al.
methylene chloride was cooled to −10°C and slowly
added to a solution of 2.6 g (0.026 mol) of cyclo-
hexylamine in 3 ml of methylene chloride at such a
rate that the temperature of the reaction mixture did
not exceed −5°C. After the addition of the amine the
reaction mixture was stirred at 0°C for further 2 h, then
evaporated and distilled in a vacuum, bp 85°C (0.1 mm
trum, δР, ppm: 34.0; [(С2Н5О)2РОF] [10]. 31Р NMR:
+
–9.2 d (1JP–F = 963 Hz); Р(ОС2Н5)4 РF6– [8] 31Р NMR
spectrum: –5 s, –147 hep (1JP–F = 700 Hz).
A-5: In the of 31Р NMR spectrum (CDCl3) of the
reaction mixture the following signals were observed:
+
35.0 [(С2Н5О)2Р(О)С2Н5], 0,2 [Р(ОС2Н5)4 ], –7.5 d
(JP–F = 972 Hz) [(С2Н5О)2РОF], –140.3 hep (JP–F
=
1
Hg), yield 4.0 g (60%). Н NMR spectrum (СDCl3):
711 Hz) (РF6–).
1.22 m (3Н), 1.38 m (2Н, СН2), 1.64 m (1Н), 1.75 m
(2Н, СН2), 1.95 m (2Н, СН2), 3.83 m (1Н, СНNH),
When the reaction was performed at room
temperature for 3 h, in 31Р NMR spectrum (CDCl3) of
19
6.16 (s, 1Н, NH). F NMR spectrum (CDCl3): –43.75
3
3
the reaction mixture the following signals were
t (2F, CF2, JFF = 9 Hz), –12.74 t (2F, CF2, JFF = 9
4
observed, δР, ppm: 1.2 t.t (3JP–F = 16,4 Hz, JP–F
=
Hz).
4.6 Hz) [(С2Н5О)3Р=N–CF2R], 0,2 [Р(ОС2Н5)4+], –73.6
Interaction of azides A-3 and A-5 with tri-
methylphosphite. A solution of 20% molar excess of
an azide in benzene was slowly added dropwise to a
solution of 1 mmol of trimethylphosphite in benzene
under nitrogen atmosphere so that the temperature of
the reaction mixture did not exceed 25°C. The reaction
mixture was stirred for further 3 h at room temperature
and evaporated.
t (JP–F = 723 Hz) [(С2Н5О)3РF2], –140.3 hep (JP–F
=
711 Hz) (РF6–). [(С2Н5О)3РF2] [11]. 31Р NMR spec-
trum: –74.78 t (JP–F = 722 Hz).
Interaction of azides A-3–A-6 with hexaethyltri-
amidophosphite. A solution of 20% molar excess of
an azide in toluene was added to a solution of 1 mmol
of hexaethyltriamidophosphite in toluene under
nitrogen atmosphere. After stirring the reaction
mixture for 5 hours at room temperature, a sample was
taken for 31Р NMR spectrum, and the mixture was
boiled for further 3 h, after which 31Р NMR spectrum
was taken again.
(СН3О)3Р+ A-3: Upon completion of the reaction
in the 31Р NMR spectrum (CDCl3) of the reaction
mixture the following signals were observed: δР
34.3 ppm [СН3РО(ОСН3)2], 3.5 [СН3О)3РО], 0
[Р(ОСН3)4+], –71.0 t (JP–F = 721 Hz) [(СН3О)3РF2],
–
А-3: Troom: 42.7 ppm {[(С2Н5)2N]3Р=N–N=N–
CF2R}. t = 110°C, δ, ppm: –2.3 d (JP–F = 955 Hz)
{[(С2Н5)2N]2РОF}, –13.9 t (JP–F = 951 Hz) {[(С2Н5)2N]·
РОF2}, –58.8 t (JP–F = 697 Hz) {[(С2Н5)2N]3· РF2} [12].
–143.3 septet (JP–F = 711 Hz) (РF6 ). СН3РО(ОСН3)2
32.2 [6] 31Р NMR spectrum: 32.2; (СН3О)3РО [7] 31Р
NMR spectrum: 1.0; Р(ОСН3)4+РF6– [8] 31Р NMR: 0 s,
–147.0 septet (1JP–F = 700 Hz); (СН3О)3РF2 [9]. 31Р
NMR spectrum: –70.0 t (1JP–F = 706 Hz).
A-4: Troom: 42.3 ppm {[(С2Н5)2N]3Р=N–N=N–
(СН3О)3Р + A-5: Upon completion of the reaction
CF2R} [1].
in the 31Р NMR spectrum (CDCl3) of the reaction
А-5: Troom: 42.8 ppm {[(С2Н5)2N]3Р=N–N=N–
CF2R}. t = 110оС, δ, ppm:–2.3 d (JP–F = 955 Hz)
{(С2Н5)2N]2РОF}, –13.9 t (JP–F = 951 Hz) {[(С2Н5)2N]·
РОF2}, –58.8 t (JP–F = 697 Hz) {[(С2Н5)2N]3РF2}.
mixture the following signals were found: δР 34.3 ppm
4
[СН3РО(ОСН3)2], 5.8 t.t (3JP–F = 14,5 Hz, JP–F
=
5.5 Hz) [(СН3О)3Р=N–CF2R], 3.5 [(СН3О)3РО], 0.0
[Р(ОСН3)4+], –71.0 t (1JP–F = 721 Hz) [(СН3О)3РF2],
–143.3 hep (JP–F = 711 Hz) (РF6–).
А-6: Troom: 42.7 ppm {[(С2Н5)2N]3Р=N–N=N–CF2R}.
In the case of azides A-4 and A-6 containing NH-
fragment in their structure, 31Р NMR spectrum of the
reaction mixture after heat treatment along with the
signals of pentavalent phosphorus of the compounds
X–XII contained a number of signals of by-products.
Interaction of azides A-3 and A-5 with
triethylphosphite. A solution of 20% molar excess of
an azide in benzene was added to a solution of 1 mmol
of triethylphosphite in benzene under nitrogen
atmosphere. The reaction mixture was boiled for 3 h,
cooled, and evaporated.
A-3: In the 31Р NMR spectrum (CDCl3) of the
reaction mixture the following signals were observed:
35.0 [(С2Н5О)2Р(О)С2Н5], 0.2 [Р(ОС2Н5)4+], –7.5 d
Interaction of azides A-3 and A-5 with tri-
phenylphosphine. A steel autoclave was loaded with a
solution of 1 mmol of triphenylphosphine and a 20%
molar excess of an azide in 5 ml of methylene
chloride. Autoclave was kept at 100°C for 6 h, cooled,
and the reaction mixture was evaporated.
(JP–F = 972 Hz) [(С2Н5О)2РОF], –140.3 hep (JP–F
=
711 Hz) (РF6–). (С2Н5О)2Р(О)С2Н5 [5]. 31Р NMR spec-
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INTERACTION OF α,α-DIFLUOROAZIDES
1651
А-3: 31Р NMR spectrum, δ, ppm: 35.5 [(Рh)3Р=О),
–53.5 t (JP–F = 655 Hz) [(Рh)3PF2]. Lit. (Рh)3PF2 [13],
–54.3 t (JP–F = 664 Hz).
А-5: 31Р NMR spectrum, δ, ppm: 35.5 [(Рh)3Р=О],
–53.5 t (JP–F = 655 Hz) [(Рh)3PF2].
–153.2 s (CFCl3). In both reactions the yield of
difluoride was 95%.
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In both cases, no signal corresponding to the
starting phosphine were observed in 31Р NMR spectra
of the reaction mixture.
Interaction of azides A-3 and A-5 with tri-o-
tolylphosphine. The reactions were performed similar
to the reaction with triphenylphosphine.
А-3: 31Р NMR spectrum, δ, ppm: 41.5 [(о-Тоl)3Р=О],
–33.5 t (JP–F = 687 Hz) [(о-Тоl)3PF2].
А-5: 31Р NMR spectrum, δ, ppm: 41.5 [(о-Тоl)3Р=О],
–33.5 t (JP–F = 687 Hz) [(о-Тоl)3PF2]. In both cases, no
signal corresponding to the starting phosphine were
observed in 31Р NMR spectra of the reaction mixture.
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Р(o-Tol)3 + XeF2: To a solution of 0.304 g
(1 mmol) of tri-o-tolylphosphine in toluene 0.169 g
(1 mmol) of xenon difluoride was added in small
portions under nitrogen atmosphere. The reaction
mixture was stirred for 1 h at room temperature. 31Р
8. Kolditz, L., Lehmann, K., Wieker, W., and Grim-
mer, A.-R., Z. Anorg. Allg. Chem., 1968, vol. 360,
nos. 5–6, p. 259.
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NMR spectrum: 41.5 [(о-Тоl)3Р=О], –33.5 t (JP–F
687 Hz) [(о-Тоl)3PF2].
=
10. Sheluchenko, V.V., Landau, M.A., Dubov, S.S.,
Neimysheva, А.А., and Knunyants, I.L., Dokl. Akad.
Nauk SSSR, 1967, vol. 177, no. 2, p. 376.
Interaction of azides A-3 and A-5 with
triphenylantimony. A steel autoclave containing a
Teflon tube loaded with a solution of 1 mmol of SbPh3
and 20% molar excess of an azide in 5 ml of benzene
was kept at 100°C for 6 h. Upon cooling a measured
amount of 1-fluoro-4-metoxybenzene was added as
internal standard to determine the yield of (Рh)3SbF2
11. Mahmood, T. and Shreeve, J.M., Inorg. Chem., 1985,
vol. 24, no. 9, p. 1395.
12. Jeanneaux, F. and Riess, J.G., Nouv. J. Chem., 1979,
vol. 3, p. 263; Lermontov, S.A., Popov, A.V., Sukho-
zhenko, I.I., Zavel’skii, VO., and Matrynov, I.V., Izv.
Akad. Nauk SSSR, Ser. Khim., 1990, no. 3, p. 682.
13. Ramirez, F., Gulati, A.S., and Smith, C.P., J. Am. Chem.
Soc., 1967, vol. 89, no. 24, p. 6283.
19
and the whole was evaporated. In F NMR spectra of
14. Ruppert, I. and Bastian, V., Angew. Chem., Int. Ed.
Engl., 1978, vol. 17, no. 3, p. 214.
the reaction mixture a signal of (Рh)3SbF2 was
observed. 19F NMR spectrum: –74.0 s. Lit. [14] δF
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