Synthesis and skeletal rearrangements of perfluorinated 4-alkyl- and 4-phenyl-tetralin-1-ones under the action of antimony pentafluoride

Article abstract of DOI:10.1016/j.jfluchem.2011.10.006

Heating of perfluorinated 1-methyl- and 1-ethyltetralins with SiO ₂ in an SbF₅ medium at 100 °C results in perfluoro-4-alkyltetralin-1-ones formation. Perfluoro-4-methyltetralin-1-one, under the action of SbF₅ at 180 °C with subsequent treatment of the reaction mixture with water, is converted to perfluoro-3,3-dimethylindan-1- one and perfluoro-3,4-dimethylisochromen-1-one. Perfluoro-4-ethyltetralin-1-one, under similar conditions, forms perfluoro-3-ethyl-3-methylindan-1-one, perfluoro-4-ethyl-3-methylisochromen-1-one and perfluoro-2-methyltetralin. Reaction of perfluorotetralin-1-one with pentafluorobenzene in the presence of SbF₅ at 50-55 °C leads to the formation of perfluoro-4- phenyltetralin-1-one, which under the action of SbF₅ at 75 °C isomerizes into perfluoro-3-methyl-3-phenylindan-1-one. Heating of the latter with SbF₅ at 75-95 °C gives, after treatment of the reaction mixture with water, perfluoro-2-(2-methylphenyl)-3-phenylpropenoic acid and perfluoro-4-methyl-3-phenylisochromen-1-one.

Full text of DOI:10.1016/j.jfluchem.2011.10.006

Journal of Fluorine Chemistry 135 (2012) 159–166
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis and skeletal rearrangements of perfluorinated 4-alkyl- and
4-phenyl-tetralin-1-ones under the action of antimony pentafluoride
*
Yaroslav V. Zonov, Victor M. Karpov , Vyacheslav E. Platonov
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Novosibirsk 630090, Russia
A R T I C L E I N F O
A B S T R A C T
Article history:
Heating of perfluorinated 1-methyl- and 1-ethyltetralins with SiO2 in an SbF5 medium at 100 8C results in
perfluoro-4-alkyltetralin-1-ones formation. Perfluoro-4-methyltetralin-1-one, under the action of SbF5
at 180 8C with subsequent treatment of the reaction mixture with water, is converted to perfluoro-3,3-
dimethylindan-1-one and perfluoro-3,4-dimethylisochromen-1-one. Perfluoro-4-ethyltetralin-1-one,
under similar conditions, forms perfluoro-3-ethyl-3-methylindan-1-one, perfluoro-4-ethyl-3-methyli-
sochromen-1-one and perfluoro-2-methyltetralin. Reaction of perfluorotetralin-1-one with pentafluor-
obenzene in the presence of SbF5 at 50–55 8C leads to the formation of perfluoro-4-phenyltetralin-1-one,
which under the action of SbF5 at 75 8C isomerizes into perfluoro-3-methyl-3-phenylindan-1-one.
Heating of the latter with SbF5 at 75–95 8C gives, after treatment of the reaction mixture with water,
perfluoro-2-(2-methylphenyl)-3-phenylpropenoic acid and perfluoro-4-methyl-3-phenylisochromen-1-
one.
Received 28 June 2011
Received in revised form 16 September 2011
Accepted 8 October 2011
Available online 12 October 2011
Keywords:
Perfluorinated
Tetralinones
Indanones
Isochromenones
Skeletal transformations
Antimony pentafluoride
ß 2011 Elsevier B.V. All rights reserved.
1. Introduction
by an alkyl group makes impossible the disproportionation of the
initial ketone. Skeletal transformations of substituted polyfluor-
Previously, skeletal transformations of carbonyl derivatives of
perfluorinated benzocyclobutene, indan, tetralin and a number of
theirperfluoroalkylderivativesundertheactionofSbF5 orSiO2–SbF5
have been found [1–7]. Carbocationic skeletal rearrangements of
polyfluorinated ketones had not been known before. In this
connection investigation of skeletal transformations of polyfluor-
obenzocycloalkenones is important to fundamental organic chem-
istry and can be useful for expansion of the range of available
reactions of polyfluorinated compounds which find broad applica-
tion in various fields, especially in materials science [8,9].
otetralones have not been investigated before. In this connection
this work describes synthesis and behaviour of perfluorinated 4-
methyl- (2), 4-ethyl- (3) and 4-phenyl-tetralin-1-one (4) in the
presence of SbF5 with the view of studying the possibility of their
cationic skeletal transformations and influence of a substituent in
the aliphatic ring on the reaction route.
2. Results and discussion
2.1. Skeletal rearrangements of tetralones 2–4 under the action of
In our previous studies it was found that skeletal transforma-
tions of perfluorobenzocycloalken-1-ones under the action of SbF5
occur along with disproportionation to benzocycloalkenes and
benzocycloalkenediones, which also undergo skeletal transforma-
tions under these reaction conditions [3]. As a result, the reactions
proceed unselectively. Thus, the reaction of perfluorotetralin-1-
one (1) with SbF5 gives a mixture of perfluorinated tetralin,
benzocondensed five- and six-membered oxygen-containing
heterocyclic compounds and alkylbenzoic acids (Scheme 1).
Rearrangements of perfluorinated alkyl substituted benzocy-
clobutenones [4,7] and indanones [5,6] proceed more selectively
because the replacement of the fluorine atom in benzylic position
SbF5
We have found that perfluoro-4-alkyltetralin-1-ones undergo
skeletal transformations under the action of SbF5 at high
temperature. Thus, heating of methyltetralone 2 with antimony
pentafluoride at 180 8C with further treatment of the reaction
mixture with water leads to the formation of perfluoro-3,3-
dimethylindan-1-one (5) and perfluoro-3,4-dimethylisochromen-
1-one (6) as major products (Scheme 2).
The formation of similar products is also observed in the
reaction of ethyltetralone 3 with SbF5 at 180 8C, but in this case the
reaction mixture contains perfluoro-3-ethyl-3-methylindan-1-one
(7) and perfluoro-4-ethyl-3-methylisochromen-1-one (8) together
with significant amount of perfluoro-2-metyltetralin (9) (Scheme
2). The latter product has a modified carbon framework containing
one carbon atom less than the parent ketone 3. The reaction
* Corresponding author. Fax: +7 3832 34 4752.
E-mail address: karpov@nioch.nsc.ru (V.M. Karpov).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.10.006

160
Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
O
SbF5, t > 120oC
F
F
F
(CF2)n
F
F
F
F
(CF2)n
(CF2)n
+
n = 0 , 1 , 2.
O
O
F
X C2F5
X
1) SbF5,
CF3
AlkF
CF3
+
180oC
2) H2O
O
+
F
F
F
F
F
+
+
F
F
O
O
COOH
O
1
O
O
O
X = F, OH; AlkF = CF3, CF2CF3, CF2CF2CF3, CF(CF3)2.
Scheme 1.
CF3
CF3
F
F3C CF3
1) SbF5, 180oC, 9 h
2) H2O
CF3
+
F
F
F
F
O
2
O
5
6
O
O
content: 22%
72%
C2F5
C2F5
F
C2F5
CF3
F3C C2F5
F3C C2F5
CF3
+
C CFCF3
1) SbF5
2) H2O
+
F
F
+
F
F
+
F
F
F
F
F
O
COOH
O
7
8
10
9
14%
10%
3
O
O
11
-
5%
180oC, 11 h
34%
7%
34%
4%
3%
-
130oC, 15.5 h
Scheme 2.
mixture also contains small amounts of perfluoro-1-ethyl-1-
methylindan (10). Interaction of ethyltetralone 3 with SbF5 at
130 8C leads to the formation of a mixture of compounds 7–9
together with perfluoro-2-(pent-2-en-3-yl)benzoic acid (11) and a
large amount (74%) of unchanged ketone 3.
The dialkylindanones 5 and 7 formed in the reaction of
tetralones 2 and 3 with antimony pentafluoride are products of
a six-membered aliphatic ring contraction. Scheme 3 illustrates
this transformation using tetralone 3 as an example. Apparently,
ketone 3 under the action of SbF5 generates the benzyl type cation
12, which undergoes isomerization into cation 13 by migration of
an alkyl moiety. Subsequent addition of fluoride anion gives the
dialkylindanone 7. This scheme is analogous to that for the six-
membered aliphatic ring contraction in the reaction of perfluori-
nated 5-ethyl- and 5,8-diethyl-tetralins under the action of
antimony pentafluoride [10].
Cleavage of the six-membered aliphatic ring is another route of
transformation of tetralones 2 and 3 under the action of SbF5. This
route leads to the formation of isochromenone 6 from tetralone 2
and products 8, 11 from tetralone 3. The latter transformation can
be rationalized by Scheme 4. Initially, ketone 3 under the action of
SbF5 seems to generate cation 14. The alicyclic six-membered ring
of the latter may undergo ring opening to yield the benzoyl type
ion 15. Fluoride anion addition to cation 15 and isomerization of
the double bond inside the chain form the acyl fluoride 16. This
scheme is analogous to that for the six-membered ring opening of
perfluorinated tetralin-1-one (1) and tetralin-1,4-dione under the
action of antimony pentafluoride [3]. Compound 16 under the
action of antimony pentafluoride generates the allyl type cation 17.
Intramolecular attack of the positively charged carbon atom of the
allylic system of cation 17 at the fluorocarbonyl oxygen atom and
subsequent isomerization of the double bond into the endocyclic
position gives the isochromenyl cation 18. The formation of
perfluoroalkylisochromenyl cations in the reaction of 2-alkenyl-
benzoyl fluorides with SbF5 was observed earlier [3,4]. Hydrolysis
of a salt of cation 18 and acyl fluoride 16 gives compounds 8 and 11,
respectively (Scheme 4). Transformation of tetralone
2 to
isochromenone 6 proceeds in a similar way.
The mechanism of methyltetralin 9 formation in the reaction of
tetralone 3 with antimony pentafluoride is unclear. However, it
may be conjectured that the route of this transformation includes a
series of cationic rearrangements and decarbonylation [11] of an
intermediate acyl fluoride.
Phenyltetralone 4 also undergoes ring contraction under the
action of SbF5. Thus, heating of a solution of phenyltetralone 4 in an
SbF5 medium at 75 8C with further treatment of the reaction
mixture with water leads to the formation of perfluoro-3-methyl-
3-phenylindan-1-one (19). The reaction mixture also contains
+
C2F5
F
C2F5
F2C C2F5
F3C C2F5
F
+
-
-
-F
F
F
F
F
F
F
F
O
O
3
12
13
7
O
O
Scheme 3.

Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
161
C2F5
C2F5
F
C2F5
C CFCF3
CF3
F
F
F
O
O
COOH
11
3
8
O
-
-F
H2O
H2O
C2F5
CF2CF3
CFCF3
CFCF3
+
C2F5
C2F5
F
CF3
+
F
-
CFCF3
CF
CF2
F
F
F
F
F
F
+
O
+
F
-
-F
C O
F
C O
F
C O
18
O
14
15
16
17
Scheme 4.
perfluoro-2-(2-methylphenyl)-3-phenylpropenoic acid (20) and
small amounts of perfluoro-4-methyl-3-phenylisochromen-1-one
(21) (Scheme 5). The reaction of phenyltetralone 4 with SbF5 in the
presence of HF (1.5 equiv.) gives indanone 19 without producing
compounds 20 and 21.
Milder conditions of ring contraction reaction of tetralone 4 as
compared with the corresponding reactions of tetralones 2 and 3
can be attributed to a higher concentration of reacting perfluoro-4-
oxo-1-phenyltetralin-1-yl cation (22) as compared to the corre-
sponding perfluoro-4-oxo-1-alkyltetralin-1-yl cations (for the
mechanism of ring contraction, see Scheme 3). Indeed, according
to 19F NMR data phenyltetralone 4 dissolved in SbF5 is transformed
to a salt of cation 22, whereas the tetralones 2 and 3 give
complexes 2c and 3c in which antimony pentafluoride is attached
to the oxygen atom of the carbonyl group (Scheme 5). Therefore,
perfluoro-4-oxo-1-alkyltetralin-1-yl cations are not formed in
sufficient concentration for 19F NMR detection.
Compounds 20 and 21 formed in the reaction of phenylte-
tralone 4 with SbF5 at 75 8C are products of further transformations
of indanone 19 under the reaction conditions. Thus, heating of
indanone 19 with antimony pentafluoride at 75 8C gives a mixture
of compounds 20 and 21 in similar ratio. Increasing of the reaction
temperature to 95 8C leads to the formation of compound 21 as the
major product (Scheme 6). It should be noted that, in contrast to
indanone 19, participation of indanones 5 and 7 in the formation of
products 6, 8, 9, 11 seems unlikely, since it has been shown in a
separate experiment that compounds 5 and 7 practically do not
change under the reaction conditions of tetralones 2, 3 with SbF5.
Formation of compounds 20 and 21 in the reaction of indanone
19 with SbF5 apparently proceeds in the following way (Scheme 6).
At first, compound 19 with SbF5 seems to generate cation 23. Then
the pentaflurophenyl group migration to the cationic center leads
to the formation of cation 24. The five-membered ring of the latter
may undergo ring opening to yield the benzoyl type ion 25, which
isomerizes into the allyl type cation 26. Another way to ion 26 is
pentaflurophenyl group migration in cation 27 with subsequent
ring opening and addition-elimination of a fluoride ion. An
intramolecular attack of one or another positively charged carbon
atom of the allyl system of cation 26 at the fluorocarbonyl oxygen
atom can give cation 28 or cation 29. Isomerization of cation 28
into cation 30 followed by ring opening and addition-elimination
of a fluoride ion results in the formation of the acyl type cation 31.
Its hydrolysis gives acid 20. Isomerization of the double bond of
cation 29 into the endocyclic position forms cation 32. Its
hydrolysis gives compound 21.
As already mentioned, the reaction of phenyltetralone 4 with
SbF5 in the presence of HF gives the indanone 19 without
compounds 20 and 21. Taking into account the proposed reaction
routes this effect of HF can be explained by suppression of
generation of unstable cations 23 and/or 27, which are supposed to
be the intermediates in products 20 and 21 formation (Scheme 6).
However, generation of the more stable cation 22 in a concentra-
tion sufficient for the reaction in this medium is still possible
(Scheme 5).
2.2. Synthesis of tetralones 2–4
The required alkyltetralones 2 and 3 were synthesized in high
yield by the reaction of tetralins 33 and 34 with SiO2 in the
presence of SbF5 (Scheme 7). This method has been used earlier for
SbF5-HF
75oC
COOH
C CFC6F5
CF3
C6F5
C6F5
F3C C6F5
+
C6F5
SbF5
20oC
1) SbF5
75oC, 43 h
2) H2O
+
+
F
F
F
F
F
F
F
F
O
CF3
O
21
20
4
22
19
O
O
O
content: 71%
26%
3%
R
F
R
F
SbF5
20oC
F
F
_
+
O
O SbF5
2c
3c
2
R=CF3
R=C2F5
3
Scheme 5.

162
Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
COOH
C CFC6F5
CF3
F3C C6F5
F
C6F5
1) SbF5
2) H2O
+
F
F
F
O
CF3
20
O
21
5%
75%
19
O
75oC, 29 h content: 24%
95oC, 33 h
-
8%
-
-F
-F
H2O
+
CF2
CF3
CF2C6F5
+
F
F2C C6F5
F3C C6F5
C6F5
F
-
C6F5
+
_
F
+
F
F
F
F
F
F
F
O
O
+
F
+
F
O
O
O
23
29
27
32
-
+
+
_
F
CF2
+
CF3
CF2
CF3
-
C6F5
+
CFC6F5
+
_
CFC6F5
O
CFC6F5
F
F
F
F
F
+
F
C O
F
C
C O
F
O
24
26
25
26
+
CFC6F5
COF
CFC6F5
CFC6F5
CO
F
F
F
-
-
+
_
+
_
H2O
CFC6F5
CF3
+
F
F
20
F
F
F
F
+
O
O
+
F
CF2
F
F
31
30
28
Scheme 6.
the synthesis of mono- and di-carbonyl derivatives of perfluor-
obenzocycloalkenes [3].
isomerization of the double bond to an endocyclic position. As a
result perfluoro-4-methyl-1,2-dihydronaphthalene (37) was
formed. Chlorination of double bond in compound 37 with PCl5
at 235 8C and subsequent heating of the product obtained with CsF
at 270 8C gave methyltetralin 33 together with perfluoro-5-
methyltetralin (38).
It should be noted that 19F NMR data for compounds named in
article [12] as ‘‘perfluorinated 1- and 2-methyltetralins’’ correspond
with the structures of perfluorinated 5- and 6-methyltetralins,
Methyltetralin 33 was obtained by the following method
(Scheme 7). Initially 2,2,3,3,4,4,5,6,7,8-decafluoro-1-methyltetra-
lin-1-ol (35) was prepared by reaction of tetralone 1 with CH3Li.
Treatment of compound 35 with SOCl2 at 75 8C and subsequent
chlorination with PCl5 at 240 8C gave 1-(dichloromethylene)-
2,2,3,3,4,4,5,6,7,8-decafluorotetralin (36). Heating of the latter
with CsF at 260 8C led to chlorine replacement by fluorine with
R
R
F
SiO2-SbF5
100oC
F
F
F
O
33
2, yield 96%
3, 96%
R=CF3
R=C2F5 34
O
CCl2
F
CH3
HO
1) CH3Li, 5oC
2) H2O
1) SOCl2, 75oC
2) PCl5, 240oC
F
F
F
F
F
36
77%
1
35
yield 49%
CsF, 260oC
CF3
CF3
CF3
1) PCl5, 235oC
2) CsF, 270oC
+
:
F
F
F
F
F
F
38
33
50
37
94%
50
Scheme 7.

Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
163
C6F5
F3C C6F5
F
1) C6F5H ,SbF5, 50-55oC
+
F
F
F
F
F
2) HF
3) H2O
O
O
O
1
4
19
:
76
24
mixture yield 30%
Scheme 8.
containing CF3 group in the aromatic ring, and disagree with the 19
F
of HF in the reaction media allow to prevent indanone 19
NMR spectra of 1- and 2-methyltetralins 33 and 9 obtained in this
work.
rearrangements.
Perfluoro-1-phenyltetralin does not react with SiO2 in the
presence of SbF5 at 70 8C, therefore phenyltetralone 4 was
synthesized by reaction of tetralone 1 with pentafluorobenzene
in the presence of SbF5 at 50–55 8C with further treatment of the
reaction mixture with anhydrous HF and then with water (Scheme
8). The reaction proceeds more slowly as compared with the
corresponding reaction of perfluorotetralin [13], the reaction
4. Experimental
IR spectra were taken on a Bruker Vector 22 IR spectrophotom-
eter. 19F and 1H NMR spectra were recorded on a Bruker AV 300
instrument (282.4 MHz and 300 MHz, respectively). Chemical
shifts are given in
d
ppm from CCl3F (19F) and TMS (1H), J values in
Hz; C6F6 and SO2ClF (À162.9 and 99.9 ppm from CCl3F) and CHCl3
(7.24 ppm from TMS) were used as internal standards. The
molecular masses of the compounds were determined by high-
resolution spectrometry on a Thermo Electron Corporation DFS
instrument (EI 70 eV). Contents of products in the reaction
mixtures were established by 19F NMR spectroscopic data.
New compounds 2, 3, 7, 19–21 and 35–37 were isolated and
characterized in the individual state; compound 4 – in the mixture
with isomer 19. Isomeric compounds 9 and 10, 33 and 38 were
isolated and characterized in their mixtures.
Antimony pentafluoride was distilled at atmospheric pressure
(bp 142–143 8C); SiO2 was prepared by heating of silica gel at 400–
450 8C; ketone 1 and compound 34 were synthesized according to
Refs. [14,15], respectively. The reactions were carried out in
glassware or in a nickel bomb (V = 10 ml).
mixture after 50 h contains phenyltetralone
4 along with
considerable amount of unchanged ketone 1. Despite the low
reaction temperature the reaction mixture also contains small
amounts of indanone 19.
2.3. 19F NMR characterization
The structures of the compounds were established by HRMS
and spectral characteristics. Assignment of signals in the 19F NMR
spectra of compounds was made on the basis of chemical shifts of
the signals, their fine structure and integral intensities. Patterns
observed in the spectra of indanones 7, 19 are in agreement with
those for compound 5 [14] and perfluoroindan-1-one [2], in the
spectra of tetralones 2, 3, 4 – with those for tetralone 1 [3], in the
spectrum of methyltetralin 33 – with those for ethyltetralin 34
[15], in the spectrum of compound 21
– with those for
4.1. Reaction of perfluoro-4-methyltetralin-1-one (2) with SbF5
dimethylisochromenone 6 [5]. Compound 20 is formed as a
mixture of E- and Z-isomers. Their configuration was not assigned
because resolution of signals in the 19F NMR spectrum was
insufficient for fine structure analysis. Compounds 5 [14], 6 [5], 8,
11 [4] were identified by comparison of the 19F NMR data with data
for authentic samples. Assignment of signals in the 19F NMR
spectrum of cation 22 was made by analogy with that for
perfluoro-1-phenyltetralin-1-yl cation [13]. Assignment of signals
in the 19F NMR spectra of complexes 2c and 3c was made by
analogy with that for complex of tetralone 1 with SbF5 [3] and
perfluoro-1-hydroxytetralin-1-yl cation [2].
A solution of compound 2 (0.97 g) in SbF5 (5.96 g) (molar ratio,
1:11) was prepared and 19F NMR spectrum of the solution was
recorded at 20 8C. The spectrum contained signals of complex 2c.
Then the solution was heated at 180 8C for 9 h in the nickel bomb.
The mixture was treated with 5% hydrochloric acid and extracted
with CH2Cl2. The extract was washed with aqueous solution of
NaHCO3 and dried over MgSO4. The solvent was distilled off to give
0.65 g of a mixture containing (GC–MS) 22% of 5, 56% of 6 and 6% of
perfluoro-4-fluorocarbonyl-3-methylisochromen-1-one [5] to-
gether with unidentified impurities.
3. Conclusion
4.1.1. Complex (2c)
19F NMR (SbF5):
d
À72.6 (3F, CF3), À100.3 (1F, F-8), À104.5 (1F,
Novel perfluoro-4-R-tetralin-1-ones (R = CF3 (2), C2F5 (3), C6F5
(4)) were synthesized. The behaviour of tetralones 2–4 under the
action of SbF5 was investigated. As a result new carbocationic
skeletal rearrangements were found. These compounds undergo
six-membered aliphatic ring contraction to give the corresponding
perfluoro-3-R-3-methylindan-1-ones 5, 7 and 19. In the case of
alkyltetralones 2 and 3 ring contraction occurs along with ring
cleavage leading finally to the formation of isochromenones 6 and
8; in the reaction of ethyltetralone 3 is also formed considerable
amount of 2-methyltetralin. The pentafluorophenyl group in
tetralone 4 facilitates the process of ring contraction in comparison
with the perfluoroalkyl groups. The indanone 19 formed in the
reaction of tetralone 4 with SbF5 undergoes skeletal rearrange-
ments under the reaction conditions to give diarylpropenoic acid
20 and isochromenone 21, whereas the formation of indanones 5
and 7 is not accompanied by further transformations. The presence
F-6), À110.5 (1FA) and À121.4 (1FB, JA,B = 324, CF2-2), À115.6 (1FA)
and À132.2 (1FB, JA,B = 278, CF2-3), À121.4 (1F, F-5), À138.2 (1F, F-
7), À183.2 (1F, F-4).
4.2. Reaction of perfluoro-4-ethyltetralin-1-one (3) with SbF5
1. A solution of compound 3 (1.03 g) in SbF5 (6.29 g) (molar ratio,
1:12) was prepared and 19F NMR spectrum of the solution was
recorded at 20 8C. The spectrum contained signals of complex 3c.
Then the solution was heated at 130 8C for 15.5 h in the nickel
bomb. The mixture was treated with 5% hydrochloric acid and
extracted with CH2Cl2. The extract was dried over MgSO4. The
solvent was distilled off to give 0.96 g of a mixture of compounds
3, 7, 8, 9 and 11 (E:Z ꢀ 15:85) in the ratio 74:7:4:10:5.
2. A mixture of compound 3 (1.12 g) and SbF5 (6.80 g) (molar ratio,
1:12) was heated at 180 8C for 3 h in a nickel bomb. The mixture

164
Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
was treated with 5% hydrochloric acid and extracted with
washed with aqueous solution of NaHCO3 and dried over MgSO4.
The solvent was distilled off to give 0.13 g of a mixture, which
contained compounds 19 and 21 in the ratio 96:4. An analytical
sample of indanone 19 was prepared by crystallization. The
aqueous solution of NaHCO3 was acidified with HCl, extracted with
CH2Cl2 and dried over MgSO4. The solvent was distilled off and the
residue was sublimed (150 8C, 3 Torr) to give 0.04 g of acid 20
(mixture of isomers in the ratio 80:20).
CH2Cl2. The extract was washed with aqueous solution of
NaHCO3 and dried over MgSO4. The solvent was distilled off to
give 0.85 g of a mixture containing ꢀ90% compounds 7, 8, 9 and
10 in the ratio 40:32:27:1. The solvent was distilled off and the
residue was dissolved in 5 ml of diethyl ether. To this solution
10 ml of water and 1 g of NaHCO3 were added. The mixture was
stirred at room temperature for 5 days, and then organic layer
was separated and dried over MgSO4. The solvent was distilled
off to give 0.47 g of a mixture of compounds 7, 9 and 10 in the
ratio 60:39:1.
3. Analogously to the previous experiment, the reaction of
compound 3 (0.85 g) and SbF5 (5.43 g) (molar ratio, 1:12.5)
gave (180 8C, 11 h) 0.64 g of a mixture containing ꢀ85% of
compounds 7, 8, 9 and 10 in the ratio 40:40:16:4 and
subsequent hydrolysis gave 0.33 g of a mixture of compounds
7, 9 and 10 in the ratio 68:26:6. Column chromatography
(hexane as eluent) of mixture (1.30 g) with the same composi-
tion (obtained in several analogous experiments) gave 0.39 g of
individual compound 7 and 0.25 g of a mixture containing
compounds 9 and 10 in the ratio 80:20. Column chromatogra-
phy of this mixture gave a fraction (0.02 g) containing (GC–MS)
7% of tetralin 9 and 86% of indan 10, and a fraction (0.06 g)
containing (GC–MS) 84% of tetralin 9 and 12% of indan 10.
4.3.1. Perfluoro-4-oxo-1-phenyltetralin-1-yl cation (22)
19F NMR (SbF5–SO2ClF):
(1F, F-para), À110.2 (4F, F-ortho, EF2-2), À112.7 (1F, F-5), À122.3
(2F, EF2-3), À130.0 (1F, F-7), À148.4 (2F, F-meta).
d
À77.1 (1F, F-6), À88.8 (1F, F-8), À96.2
4.3.2. Perfluoro-3-methyl-3-phenylindan-1-one (19)
mp 73.5–74 8C (hexane). IR (CCl4)
1504 (FAR). 19F NMR [CO(CD3)2]:
n
, cmÀ1: 1772 (C55O); 1531,
À61.3 (3F, CF3), À104.7 (1FA)
d
and À113.9 (1FB, JA,B = 283, CF2), À132.1 (2F, F-ortho), À133.5 (1F,
F-7), À135.2 (1F, F-4), À135.9 (1F, F-5), À147.2 (1F, F-6), À148.7
(1F, F-para), À159.8 (2F, F-meta); JCF3–F(2A) = 2.5, JCF3–F(2B) = 25.5,
JCF3–F(ortho) = 26.5, JCF3–F(4) = 19.5, Jortho,para = 6,
Jortho,2A = 16.5,
Jortho,2B = 2.5,
Jortho,4 = 2, Jmeta,para = 21, J4,5 = 19.5, J4,6 = 7.5,
J4,7 = 15.5, J5,6 = 18.5, J5,7 = 13, J6,7 = 20.5. HRMS m/z, 473.9721
(M+). Calcd. for C16F14O = 473.9720.
4.2.1. Complex (3c)
4.3.3. Perfluoro-2-(2-methylphenyl)-3-phenylpropenoic acid (20)
Mixture of two isomers, ratio 20a:20b = 80:20; mp 132–143 8C
19F NMR (SbF5):
d
À78.5 (3F, CF3), À109.9 (1FA) and À120.1
(1FB, JA,B = 328, CF2-2), À100.6 (1F, F-8), À104.7 (1F, F-6), À112.2
(1FA) and À130.0 (1FB, JA,B = 274, CF2-3), À113.7 (1FA) and À115.0
(1FB, JA,B = 302, CF2CF3), À121.5 (1F, F-5), À138.1 (1F, F-7), À185.2
(1F, F-4).
(hexane). IR (CCl4)
n
, cmÀ1: ꢀ3000 b (OH); 1754, 1719, 1670, 1647
(O55C–C55C); 1511, 1485 (FAR). 1H NMR (CDCl3):
d 9.10 (bs, OH).
2
β
3
5
β
β
COOH
6
α
4
β
C
CF3
F
5
α
4.2.2. Perfluoro-3-ethyl-3-methylindan-1-one (7)
Liquid. IR (CCl4)
aromatic ring (FAR)]. 19F NMR (CDCl3):
(3F, CF2CF3), À108.4 (1FA) and À110.2 (1FB, JA,B = 297, CF2CF3),
À114.9 (1FA) and À118.8 (1FB, JA,B = 284, CF2-2), À130.5 (1F, F-4),
À132.8 (1F, F-7), À136.6 (1F, F-5), À144.7 (1F, F-6); J4,5 = 19.5,
J4,6 = 9, J4,7 = 16.5, J5,6 = 19, J5,7 = 13, J6,7 = 21. HRMS m/z, 425.9710
(M+). Calcd. for C12F14O = 425.9725.
n
, cmÀ1: 1784 (C55O); 1515, 1507 [fluorinated
F
6
β
4
α
d
À63.7 (3F, CF3-3), À78.9
CF3
3α
Isomer 20a: 19F NMR (CDCl3):
À135.5 (1F, F-6 ), À137.5 (1F, F-3
), À148.3 (1F, F-5
d
À57.6 (3F, CF3), À65.7 (1F, F-3),
, F-6 ),
a
b
b
a
), À137.9 (2F, F-2
b
b
À147.9 (1F, F-4
a
), À150.9 (1F, F-4
a
), À161.2
(2F, F-3
b
,
F-5
); JCF3–F(3 ) = 22, J3,6 = 4, J3,4 = 4, J3
= 21,
,4
a
a
a
b
a
J3
J2
= 8, J3
= J6
= 10.5, J4
= 20.5, J4
= 5.5, J5 = 22.5,
,6
a a
,5
,6
a
,5
a
,6
a
b
a
b
a
a
a
a
4.2.3. Perfluoro-2-methyltetralin (9)
= 4, J3
= J5 = 21.
,4
b b
,4
,4
,4
b
b
b
b
Liquid. 19F NMR (hexane):
d
À70.6 (3F, CF3), À95.9 (1FA) and
Isomer 20b: À57.6 (3F, CF3), À69.0 (1F, F-3), À135.4 (1F, F-6
a),
b),
b).
À102.1 (1FB, JA,B = 305, CF2-1), À96.6 (1FA) and À116.9 (1FB,
JA,B = 293, CF2-4), À119.5 (1FA) and À136.7 (1FB, JA,B = 286, CF2-3),
À135.0 (1F) and À135.6 (1F, F-5, F-8), À145.1 (2F, F-6, F-7), À185.7
(1F, F-2). HRMS m/z, 397.9770 (M+). Calcd. for C11F14 = 397.9776.
À136.2 (1F, F-3
a
), À136.8 (2F, F-2
b
, F-6
b
), À146.0 (1F, F-4
, F-5
À147.4 (1F, F-5
a
), À149.6 (1F, F-4
a
), À159.3 (2F, F-3
b
HRMS (mixture of two isomers) m/z, 471.9768 (M+). Calcd. for
C16H1F13O2 = 471.9764.
4.2.4. Perfluoro-1-ethyl-1-methylindan (10)
4.4. Reaction of perfluoro-4-phenyltetralin-1-one (4) with SbF5 in the
presence of HF
Liquid. 19F NMR (hexane):
d
À63.5 (3F, CF3-1), À78.1 (3F,
CF2CF3), À104.0 (1FA) and À107.4 (1FB, JA,B = 260, CF2-3), À106.4
(1FA) and À107.7 (1FB, JA,B = 298, CF2CF3), À115.6 (2F, CF2-2),
À129.8 (1F, F-7), À138.7 (1F, F-4), À143.7 (1F, F-6), À145.2 (1F, F-
5); J4,5 = 20.5, J4,6 = 8, J4,7 = 16, J5,6 = 18.5, J5,7 = 9.5, J6,7 = 19. HRMS
m/z, 447.9739 (M+). Calcd. for C12F16 = 447.9744.
A
mixture of SbF5, HF and perfluoro-1-phenylindan was
prepared by the reaction of C6F5H (0.11 g, 0.65 mmol) with
perfluoroindan (0.19 g, 0.64 mmol) in SbF5 (1.11 g, 5.10 mmol)
[13]. Then the mixture of isomers 4:19 = 76:24 (0.20 g, 0.43 mmol)
was added. The resulting solution was heated at 75 8C for 48 h,
treated with 5% hydrochloric acid, extracted with CH2Cl2 and dried
over MgSO4. The solvent was distilled off to give 0.44 g of a
mixture, which contained compound 19, perfluoro-1-phenylindan
and perfluoro-1-phenylindan-1-ol in the ratio 40:15:45.
4.3. Reaction of perfluoro-4-phenyltetralin-1-one (4) with SbF5
To a mixture of isomers 4 and 19 (0.19 g) in the ratio 76:24 and
SbF5 (1.19 g) (molar ratio (4 + 19):SbF5 = 1:13.5) SO2ClF (0.14 g)
was added at 0 8C and 19F NMR spectrum of the solution was
measured at 20 8C. The spectrum contained signals of cation 22 and
indanone 19 in the ratio 75:25. The solution was heated at 75 8C for
43 h and then poured into 5% hydrochloric acid and extracted with
CH2Cl2. The extract was dried over MgSO4. The solution contained
compounds 19, 20 and 21 in the ratio 71:26:3. The extract was
4.5. Reaction of perfluoro-3-methyl-3-phenylindan-1-one (19) with
SbF5
1. A mixture of compound 19 (0.20 g) and SbF5 (1.27 g) (molar
ratio, 1:13.8) was heated at 75 8C for 29 h. The mixture was

Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
165
treated with 5% hydrochloric acid and extracted with CH2Cl2.
The solution contained compounds 19, 20 and 21 in the ratio
71:24:5. The extract was washed with aqueous solution of
NaHCO3 and dried over MgSO4. The solvent was distilled off to
give 0.15 g of mixture containing compounds 19 and 21 in the
ratio 93:7. The aqueous solution of NaHCO3 was acidified with
HCl, extracted with CH2Cl2 and dried over MgSO4. The solvent
was distilled off and the residue was sublimed (140 8C, 3 Torr) to
give 0.04 g of acid 20 (mixture of isomers in the ratio 80:20).
2. Analogously to the previous experiment, the reaction of
compound 19 (0.11 g) and SbF5 (1.17 g) (molar ratio, 1:23)
gave (75 8C, 12 h, then 95 8C 33 h) an extract containing
compounds 19, 20 and 21 in the ratio 17:8:75. The extract
was washed with aqueous solution of NaHCO3 and dried over
MgSO4. The solvent was distilled off to give 0.09 g of a mixture
containing compounds 19 and 21 in the ratio 19:81. Crystalli-
zation from hexane gave 0.042 g of compound 21.
J6,8 = 8.5, J7,8 = 21. HRMS m/z, 391.9211 (M+). Calcd. for
11Cl2F10 = 391.9212. Anal. Calcd. for C11Cl2F10 C, 33.6; Cl,
18.0%. Found: C, 33.5; Cl, 18.0%.
C
:
3. A mixture of compound 36 (3.17 g) and CsF (6.7 g) (molar ratio,
1:5.5) was heated at 250–260 8C (6 h) in a sealed ampoule, then
volatile products were separated by distillation. Resulting
mixture, which contained compounds 36 and 37 in the ratio
12:88, was heated with CsF (3.48 g) at 250–260 8C (10 h) again.
Distillation gave 2.74 g (yield 94%) of product 37.
4.6.3. Perfluoro-4-methyl-1,2-dihydronaphthalene (37)
Liquid. 19F NMR (CDCl3):
d
À60.5 (3F, CF3), À113.3 (1F, F-3),
À122.2 (2F, CF2-1), À130.3 (1F, F-5), À132.0 (2F, CF2-2), À136.2
(1F, F-8), À146.1 (1F, F-6), À148.6 (1F, F-7); J1,3 = 2, J1,6 = 2.5,
J1,8 = 36, J2,3 = 16, J2,4 = 2, J3,4 = 29.5, J3,5 = 5.5, J3,6 = 1.5, J3,7 = 6,
J3,8 = 2, J4,5 = 35.5, J5,6 = 20, J5,7 = 8, J5,8 = 11, J6,7 = 19.5, J6,8 = 9.5,
J7,8 = 21. HRMS m/z, 359.9804 (M+). Calcd. for C11F12 = 359.9803.
4.5.1. Perfluoro-4-methyl-3-phenylisochromen-1-one (21)
4. A mixture of compound 37 (2.61 g) and PCl5 (3.15 g) (molar ratio,
1:2) was heated at 225–235 8C (6 h) in a sealed ampoule. Reaction
mixture was treated with water, extracted with CH2Cl2 and dried
over MgSO4. The solvent was distilled off and the residue was
heated with CsF (5.41 g) at 250–260 8C (9 h) and then at 260–
270 8C (8.5 h) in a sealed ampoule. Distillation of reaction mixture
gave 2.71 g (yield 94%) of tetralins 33 and 38 in the ratio 50:50.
Mp 137.5–138.5 8C (hexane). IR (CCl4)
1512, 1483 (FAR). 19F NMR (CDCl3):
n
, cmÀ1: 1790 (C55O);
À58.6 (3F, CF3), À130.8 (1F,
d
F-8), À132.2 (1F, F-5), À139.7 (2F, F-ortho), À140.3 (1F, F-6),
À148.1 (1F, F-para), À148.9 (1F, F-7), À160.5 (2F, F-meta); JCF3–
F(5) = 46, JCF3–F(ortho) = 2, Jortho,para = 4, Jmeta,para = 21, J5,6 = 19,
J5,7 = 6.5, J5,8 = 13, J6,7 = 20.5, J6,8 = 12, J7,8 = 20.5. HRMS m/z,
451.9700 (M+). Calcd. for C16F12O2 = 451.9701.
4.6.4. Perfluoro-1-methyltetralin (33) and perfluoro-5-methyltetralin
(38)
4.6. Synthesis of perfluoro-4-methyltetralin-1-one (2)
1. To a stirred solution of tetralone 1 (7.69 g) in 20 ml of dry diethyl
ether 46 ml of ether solution of CH3Li (molar ratio, 1:1) was
slowly added at 5 8C under argon atmosphere. The mixture was
treated with 60 ml 5% hydrochloric acid. Organic layer was
separated and the ether was distilled off the residue was
dissolved in CH2Cl2 and dried over MgSO4. Solution contained
compounds 1 and 35 in the ratio 23:77. Vacuum distillation gave
5.32 g of the product (bp 60–66 8C, 3 Torr) containing com-
pounds 1 and 35 in the ratio 5:95. Individual compound 35
(3.92 g, yield 49%) was obtained by crystallization from hexane.
Mixture of two isomers, ratio 33:38 = 50:50; liquid. Compound
33:19FNMR(CDCl3):
d
À72.6(3F,CF3),À100.1(1FA)andÀ107.6(1FB,
JA,B = 292, CF2-4), À123.6 (1FA) and À133.5 (1FB, JA,B = 281, CF2-2 or
CF2-3), À130.6 (1FA) and À136.5 (1FB, JA,B = 286, CF2-2 or CF2-3),
À131.5 (1F, F-8), À134.3 (1F, F-5), À143.9 (1F, F-7), À144.4 (1F, F-6),
À177.6 (1F, F-1); JCF3–F(1) = 8.5, JCF3–F(8) = 26.5, J1,8 = 32.5, J4A,5 = 21,
J4B,5 = 22, J5,6 = 21.5, J5,7 = 9.5, J5,8 = 11.5, J6,7 = 20.5, J6,8 = 10, J7,8 = 20.
Compound 38: 19F NMR (CDCl3):
d
À55.6 (3F, CF3), À103.3 (2F,
CF2-4), À105.5 (2F, CF2-1), À117.4 (1F, F-6), À123.0 (1F, F-8),
À135.5 (2F) and À136.1 (2F, CF2-2, CF2-3), À145.4 (1F, F-7);
J1,8 = 21, J4,5 = 24.5, J5,6 = 29.5, J6,7 = 20.5, J6,8 = 20.5, J7,8 = 20.5.
HRMS (mixture of 33 and 38) m/z, 397.9768 (M+). Calcd. for
4.6.1. 2,2,3,3,4,4,5,6,7,8-Decafluoro-1-methyltetralin-1-ol (35)
Mp 51–52 8C (hexane). IR (CCl4)
(FAR). 1H NMR (CDCl3): 2.87 (1H, OH), 1.86 (3H, CH3). 19F NMR
(CDCl3):
n
, cmÀ1: 3589 (OH); 1527, 1491
C
11F14 = 397.9771
d
d
À100.7 (1FA) and À111.9 (1FB, JA,B = 290, CF2-4), À128.5
5. A mixture of tetralins 33 and 38 (2.59 g), SiO2 (0.58 g) and SbF5
(5.36 g) (molar ratio, 0.5:0.5:1.5:4) was stirred at 75 8C (6.5 h)
and then at 100 8C (1 h). The mixture was treated with 5%
hydrochloric acid and extracted with CH2Cl2. The extract was
washed with aqueous solution of NaHCO3 and dried over
MgSO4. The extract was dried over MgSO4. The solvent was
distilled off to give 1.17 g (yield 96%) of ketone 2.
(1FA) and À135.4 (1FB, JA,B = 271, CF2-2 or CF2-3), À128.8 (1FA) and
À139.1 (1FB, JA,B = 273, CF2-2 or CF2-3), À136.3 (1F, F-8), À137.7
(1F, F-5), À146.7 (1F, F-7), À151.3 (1F, F-6); J4A,5 = 13, J4B,5 = 29,
J5,6 = 21, J5,7 = 8, J5,8 = 12, J6,7 = 20.5, J6,8 = 7, J7,8 = 20.5. HRMS m/z,
342.0065 (M+). Calcd. for C11H4F10O = 342.0097.
2. A mixture of compound 35 (3.82 g), SOCl2 (2.5 ml) (molar ratio,
1:3), CCl4 (2 ml) and DMF (3 drops) was heated at 75 8C (19 h).
The mixture was treated with water and extracted with CCl4.
The extract was dried over MgSO4. The solvent was distilled off
and the residue was heated with PCl5 (12.59 g) at 235–240 8C
(24 h) in a sealed ampoule. Reaction mixture was treated with
water, extracted with CH2Cl2 and dried over MgSO4. Vacuum
distillation gave 3.38 g (yield 77%) of compound 36.
4.6.5. Perfluoro-4-methyltetralin-1-one (2)
Mp 29–31 8C. IR (CCl4)
19F NMR (Et2O):
À73.9 (3F, CF3), À117.8 (1FA) and À127.2 (1FB,
n
, cmÀ1: 1738 (C55O); 1518, 1487 (FAR).
d
CF2-2), À118.6 (1FA) and À132.9 (1FB, CF2-3), À131.5 (1F, F-8),
À132.6 (1F, F-5), À137.6 (1F, F-6), À144.5 (1F, F-7), À185.3 (1F, F-
4); JCF3–F(2A) = 21, JCF3–F(3A) = 5, JCF3–F(3B) = 16, JCF3–F(4) = 10, JCF3–
F(5) = 16, J2A,2B = 303, J2A,3A = 3, J2A,3B = 12.5, J2B,3A = 13, J2B,3B = 10,
J2B,4 = 10, J3A,3B = 273, J3A,4 = 16, J3B,4 = 12.5, J4,5 = 49.5, J4,7 = 1.5,
J4,8 = 2, J5,6 = 20, J5,7 = 10, J5,8 = 12.5, J6,7 = 19.5, J6,8 = 15.5, J7,8 = 20.
HRMS m/z, 375.9753 (M+). Calcd. for C11F12O = 375.9752.
4.6.2. 1-(Dichloromethylene)-2,2,3,3,4,4,5,6,7,8-decafluorotetralin
(36)
Liquid, bp 68–69 8C (2 Torr). 19F NMR (CDCl3):
d
À106.2 (1FA)
and À111.8 (1FB, JA,B = 285, CF2-2 or CF2-4), À108.8 (1FA) and
À120.2 (1FB, JA,B = 260, CF2-2 or CF2-4), À126.4 (1F, F-8), À131.7
(1FA) and À134.6 (1FB, JA,B = 253, CF2-3), À137.7 (1F, F-5), À146.7
(1F, F-7), À148.9 (1F, F-6); J5,6 = 21, J5,7 = 8.5, J5,8 = 12, J6,7 = 20,
4.7. Synthesis of perfluoro-4-ethyltetralin-1-one (3)
A mixture of compound 34 (3.74 g), SiO2 (0.51 g) and SbF5
(5.44 g) (molar ratio, 1:1:3) was stirred at 70 8C (1.5 h) and then at

166
Y.V. Zonov et al. / Journal of Fluorine Chemistry 135 (2012) 159–166
100 8C (3 h). The mixture was treated with 5% hydrochloric acid
and extracted with CH2Cl2. The extract was dried over MgSO4. The
solvent was distilled off to give 3.40 g (yield 96%) of ketone 3.
Jortho,para = 5, Jmeta,para = 21, J4,5 = 8, J4,6 = 2, J4,7 = 6, J5,6 = 20.5, J5,7 = 8,
J5,8 = 12, J6,7 = 20, J6,8 = 13.5, J7,8 = 20. HRMS (mixture of 4 and 19)
m/z, 473.9718 (M+). Calcd. for C16F14O = 473.9720.
4.7.1. Perfluoro-4-ethyltetralin-1-one (3)
Acknowledgement
Liquid. IR (CCl4)
NMR (Et2O):
n
, cmÀ1: 1740 (C55O); 1517, 1489 (FAR). 19F
d
À79.4 (3F, CF3), À114.7 (1FA) and À131.0 (1FB,
We gratefully acknowledge the Russian Foundation for Basic
Researches (Project No. 10-03-00120) for financial support.
JA,B = 269, CF2-3), À115.8 (1FA) and À125.4 (1FB, JA,B = 305, CF2-2),
À116.2 (1FA) and À117.8 (1FB, JA,B = 300, CF2CF3), À131.8 (1F, F-8),
À132.8 (1F, F-5), À138.0 (1F, F-6), À144.3 (1F, F-7), À188.3 (1F, F-
4); J4,5 = 59, J4,8 = 2.5, J5,6 = 20, J5,7 = 10, J5,8 = 12.5, J6,7 = 20, J6,8 = 15,
J7,8 = 20. HRMS m/z, 425.9733 (M+). Calcd. for C12F14O = 425.9725.
References
[1] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, J. Fluorine Chem. 126 (2005) 437–443.
[2] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, T.V. Rybalova, Yu.V. Gatilov, J. Fluorine
Chem. 127 (2006) 1574–1583.
[3] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Yu.V. Gatilov, Zh. Org. Khim. 44 (2008)
212–226;
4.8. Synthesis of perfluoro-4-phenyltetralin-1-one (4)
Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Yu.V. Gatilov, Russ. J. Org. Chem. 44
(2008) 202–217.
A mixture of compound 1 (0.76 g), C6F5H (0.78 g) and SbF5
(4.01 g) (molar ratio, 1:2:8) was heated at 50–55 8C (50 h) in a
sealed ampoule. Reaction mixture was placed in a Teflon container,
dissolved in 10 ml of anhydrous HF, kept at room temperature for
2 h, poured to ice and extracted with CH2Cl2. The extract was dried
over MgSO4. Solution obtaining after incomplete solvent distilla-
tion contained compounds 1, 4, 19, C6F5H and C6F5C6F5 in the ratio
46:21:7:18:8. The mixture was spontaneously evaporated in the
air to dryness and the residue was sublimed (100 8C, 3 Torr) to give
0.33 g (yield 30%) of mixture containing tetralone 4 and indanone
19 in the ratio 76:24.
[4] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, J. Fluorine Chem. 129 (2008) 1206–1208.
[5] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, J. Fluorine Chem. 128 (2007) 1065–1073.
[6] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Zh. Org. Khim. 47 (2011) 217–222;
Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Russ. J. Org .Chem. 47 (2011) 207–213.
[7] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Zh. Org. Khim. 46 (2010) 1512–1520;
Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Russ. J. Org. Chem. 46 (2010) 1517–1526.
[8] P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications,
Wiley-VCH, Weinheim, 2004.
[9] R.E. Banks, B.E. Smart, J.C. Tatlow (Eds.), Organofluorine Chemistry: Principles and
Commercial Applications, Plenum, New York, 1994.
[10] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, Zh. Org. Khim. 33 (1997) 755–761;
V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, Russ. J. Org. Chem. 33 (1997)
694–699.
[11] C.G. Krespan, V.A. Petrov, Chem. Rev. 96 (1996) 3269–3301.
[12] F.J. Weigert, J. Fluorine Chem. 65 (1993) 67–71.
[13] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, V.R. Sinyakov, L.N. Shchegoleva, Zh.
Org. Khim. 38 (2002) 1210–1217;
4.8.1. Perfluoro-4-phenyltetralin-1-one (4)
Mixture of isomers 4 and 19 in the ratio 76:24. 19F NMR (CDCl3):
V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, V.R. Sinyakov, L.N. Shchegoleva,
Russ. J. Org. Chem. 38 (2002) 1158–1165.
[14] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, J. Fluorine Chem. 128 (2007) 1058–1064.
[15] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, G.G. Yakobson, J. Fluorine Chem. 28
(1985) 121–137.
d
À120.5 (1FA) and À131.5 (1FB, JA,B = 277, CF2-2 or CF2-3), À122.1
(1FA) and À134.3 (1FB, JA,B = 281, CF2-2 or CF2-3), À132.9 (1F, F-5),
À133.5 (1F, F-8), À137.5 (2F, F-ortho), À139.2 (1F, F-6), À146.0 (1F,
F-7), À148.3 (1F, F-para), À152.2 (1F, F-4), À160.1 (2F, F-meta);