Oxygen replacement by fluorine in carbonyl derivatives of perfluoroaromatic compounds and isomerization of perfluoroindan-1,3-dione to perfluoro-3-methylenephthalide under the action of HF/SbF5

Article abstract of DOI:10.1016/j.jfluchem.2006.08.006

When acted upon by HF/SbF₅ at 95 °C, carbonyl groups of perfluorinated acetophenone (10), 3,4-dihydronaphthalen-1(2H)-one (8), 2,3-dihydronaphthalene-1,4-dione (9), benzocyclobutenone (6), benzocyclobutenedione (7) and indan-1-one (1) are converted into difluoromethylene groups to give the corresponding perfluoroaromatic products. Perfluoroindan-2-one (5), under the same conditions, is transformed to bis(perfluoroindan-2-yl) ether (21). On heating with HF/SbF₅, perfluoroindan-1,3-dione (2) isomerizes into perfluoro-3-methylenephthalide (4) at 95 °C, and gives 4,5,6,7-tetrafluoro-3-trifluoromethyl-phthalide (14) at 130 °C. Compound 4 in the absence of a solvent dimerizes giving perfluorodispiro[phthalide-3,1′-cyclobutane-2′,3″-phthalide] (18), and when heated with SbF₅ at 130 °C, it is converted into perfluoro-3-methylphthalide (3). When acted upon by HF/SbF₅ at 95 °C, perfluorinated benzoic acid (12) and phthalic anhydride (13) give the corresponding products with trifluoromethyl groups.

Full text of DOI:10.1016/j.jfluchem.2006.08.006

Journal of Fluorine Chemistry 127 (2006) 1574–1583
www.elsevier.com/locate/fluor
Oxygen replacement by fluorine in carbonyl derivatives of
perfluoroaromatic compounds and isomerization of perfluoroindan-1,
3-dione to perfluoro-3-methylenephthalide under the action of HF/SbF5
§
*
Yaroslav V. Zonov, Victor M. Karpov , Vyacheslav E. Platonov,
Tatjana V. Rybalova, Yuri V. Gatilov
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Novosibirsk 630090, Russia
Received 28 June 2006; received in revised form 22 August 2006; accepted 25 August 2006
Available online 3 September 2006
Dedicated to the Centenary of Academician, Professor I.L. Knunyants.
Abstract
When acted upon by HF/SbF5 at 95 8C, carbonyl groups of perfluorinated acetophenone (10), 3,4-dihydronaphthalen-1(2H)-one (8), 2,3-
dihydronaphthalene-1,4-dione (9), benzocyclobutenone (6), benzocyclobutenedione (7) and indan-1-one (1) are converted into difluoromethylene
groups to give the corresponding perfluoroaromatic products. Perfluoroindan-2-one (5), under the same conditions, is transformed to bis(per-
fluoroindan-2-yl) ether (21). On heating with HF/SbF5, perfluoroindan-1,3-dione (2) isomerizes into perfluoro-3-methylenephthalide (4) at 95 8C,
and gives 4,5,6,7-tetrafluoro-3-trifluoromethyl-phthalide (14) at 130 8C. Compound 4 in the absence of a solvent dimerizes giving perfluor-
odispiro[phthalide-3,10-cyclobutane-20,300-phthalide] (18), and when heated with SbF5 at 130 8C, it is converted into perfluoro-3-methylphthalide
(3). When acted upon by HF/SbF5 at 95 8C, perfluorinated benzoic acid (12) and phthalic anhydride (13) give the corresponding products with
trifluoromethyl groups.
# 2006 Elsevier B.V. All rights reserved.
Keywords: Perfluorinated; Acetophenone; Benzoic acid; Phthalic anhydride; Indan-1-one; Indan-2-one; Indan-1,3-dione; 3,4-Dihydronaphthalen-1(2H)-one; 2,3-
Dihydronaphthalene-1,4-dione; Benzocyclobutenone; Benzocyclobutenedione; Antimony pentafluoride; Replacement of carbonyl oxygen by fluorine
1. Introduction
transformed to perfluoro-3-methylphthalide (3), for example,
via the intermediate complex 2a and perfluoro-3-methyle-
nephthalide (4) according to Scheme 1 [6].
Previously, cationoid skeletal transformations of perfluori-
nated benzocyclobutene, indan, tetralin and their perfluoroalkyl
and perfluoroaryl derivatives under the action of antimony
pentafluoride have been found and investigated, see for
example articles [2–5] and references [1–7] cited in article
[3]. Recently, we have found that carbon framework of
perfluoroketones can also change under the action of SbF5 [6].
Thus, perfluoroindan-1-one (1) heated with SbF5 and then
treated with water, gives perfluoro-2-ethylbenzoic acid together
with the products of ketone 1 disproportionation–perfluor-
oindan and perfluoroindan-1,3-dione (2). The latter is
We have now investigated the behaviour of the protonated
diketone2,whichisacationicanalogofcomplex2a,ketone1and
other perfluoroaromatic carbonyl derivatives in superacid
medium with the aim of studying the possibility of their
cationoid skeletal transformations. This work describes the
behaviour of compounds 1, 2, perfluorinated indan-2-one (5),
benzocyclobutenone (6), benzocyclobutenedione (7), 3,4-dihy-
dronaphthalen-1(2H)-one (8), 2,3-dihydronaphthalene-1,4-
dione (9), acetophenone (10), benzaldehyde (11), benzoic acid
(12) and phthalic anhydride (13), in the system of HF/SbF5.
2. Results and discussion
§
Preliminary communication see [1].
When heated with HF/SbF5 at 95 8C for 3 h, indandione 2
isomerizes to phthalide 4. The reaction mixture also contains
* Corresponding author. Fax: +7 3833 30 9752.
E-mail address: karpov@nioch.nsc.ru (V.M. Karpov).
0022-1139/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2006.08.006

Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
1575
The 19F NMR spectrum exhibits signals of two pseudo-AB-
systems at ꢁ116.3 (2F, ddm, J = 224, 19 Hz) and ꢁ120.4 (2F,
ddm, J = 224, 31 Hz); ꢁ117.2 (2F, dtm, J = 224, 34 Hz) and
ꢁ122.7 (2F, dm, J = 224 Hz) ppm assigned to the CF2 groups of
E-18 and Z-18, respectively. The fine structures of the pseudo-
AB-system signals indicate that each fluorine atom of the CF2
groups of E-18 has spatial proximity to one benzene fluorine
atom. For Z-18, one fluorine atom of every CF2 groups has two
closely located benzene fluorine atoms and the other fluorine
atom of the CF2 groups has no closely located benzene fluorine
atoms.
According to a single crystal X-ray structure determination
for E-18, distances (F-4)-(F-A), (F0-4)-(F-B0) are equal to
00
00
˚
2.894(3), 2.786(3) A, and (F-4 )-(F-A ), (F-4 )-(F-B) are equal
˚
to 2.936(3), 2.755(3) A, respectively (Scheme 2, Fig. 1).
Scheme 1.
On heating at 180 8C Z-18 isomer is transformed into isomer
E-18 apparently through the intermediate diradical 18a. Gas
phase DFT (PBE/TZ2P, PRIRODA program [9]) calculations
show that isomer E-18 is more stable by 6.1 kcal molꢁ1 than Z-
18. Attempts to trap diradical 18a with bromine were
unsuccessful. Thus, when heated with dibromine at 180 8C
the mixture of E-18 and Z-18 isomers was transformed into
isomer E-18, which contained small amounts of phthalide 17.
When the temperature was raised to 260 8C, dimer 18 was
divided into parts to give phthalide 17 (Scheme 2).
Indanone 1 obtained in the reaction of diketone 2 with HF/
SbF5, apparently, is a product of oxygen replacement by
fluorine in indandione 2 under the reaction conditions (Scheme
2). It has been found that when acted upon by HF/SbF5 at 95 8C,
the carbonyl group of indanone 1 is also converted into
difluoromethylene group to give perfluoroindan (15). The
reaction mixture also contains unchanged ketone 1 (Scheme 3).
As far as we are aware, there are no previous reports of HF/SbF5
being used as a fluorinating agent for replacement of carbonyl
oxygen by fluorine [10,11].
small amounts of 4,5,6,7-tetrafluoro-3-trifluoromethylphtha-
lide (14), indanone 1 and unchanged compound 2 (Scheme 2).
Increase in the reaction time (43 h) leads to the formation of a
mixture contained phthalides 3, 4, 14 and small amounts of
perfluoroindan (15). Phthalide 14 is the main product of the
reaction of indandione 2 with HF/SbF5 at 130 8C. As far as we
know, transformation of indandione 2 to phthalide 4 is the first
example of isomerization of fluorinated indandiones into 3-
methylenephthalides. However, earlier it was reported that
2,2-diphenylindan-1,3-dione under the action of trifluoro-
methanesulfonic acid isomerizes to 3-(diphenylmethyle-
ne)phthalide [7].
The probable mechanism for the isomerization of indan-
dione 2 to phthalide 4 can be formulated as shown in Scheme 2.
Initially, protonation of compound 2 gives 1-hydroxy-perfluor-
oindan-3-one-1-yl cation (2c). Opening of the five-membered
ring in ion 2c leads to cation 16. Intramolecular cyclization of
the latter and subsequent deprotonation gives phthalide 4.
Compound 4 adds HF to form phthalide 14, apparently, with
intermediate generation of 1-hydroxy-perfluoro-3-methylene-
phthalan-1-yl cation (4c) (its formation will be discussed
below) according to Scheme 2.
One possible route for the transformation of ketone 1 to
indan 15 is presented in Scheme 3. Compound 1 is protonated
to give the 1-hydroxy-perfluoroindan-1-yl cation (1c) (its
formation will be discussed below), which adds fluoride anion
to form perfluoroindan-1-ol (19). The protonation of the latter
with subsequent elimination of water leads to the perfluor-
oindan-1-yl cation (15c), which adds fluoride anion to produce
compound 15.
Another possible route for the transformation of ketone 1 to
indan 15 is presented in Scheme 4. The initially generated
cation 1c reacts with indanone 1 to give compound 20 after
fluoride anion addition. The protonation of compound 20 with
subsequent elimination of water leads to the perfluoro-1-
(indan-1-yloxy)indan-1-yl cation (20c), which is split into
indanone 1 and cation 15c. The latter adds fluoride anion to
form indan 15.
When heated with SbF5 at 125 8C, compound 4 is fluorinated
to give phthalide 3. Compound 4, treated with dibromine, forms
3-bromo-3-(bromodifluoromethyl)-4,5,6,7-tetrafluorophtha-
lide (17) (Scheme 2). In the absence of a solvent, compound 4
cyclodimerizes to give perfluorodispiro[phthalide-3,10-cyclo-
butane-20,300-phthalide] (18) rather than its isomer with a 1,3-
disubstituted cyclobutane fragment. The formation of dimer 18
could be explained by the higher stability of the intermediate
benzyl–benzyl diradical 18a rather than 18b, cf. [8].
Based on NMR data, dimer 18 is formed as a mixture of two
isomers with the ratio of E:Z ꢀ 50:50. The 13C NMR spectrum
1
exhibits two signals at 116.9 (ddt, JCF = 302, 297,
When heated with HF/SbF5 at 95 8C, perfluoroindan-2-one
(5) gives bis(perfluoroindan-2-yl) ether (21) and perfluoro-2-
(indan-2-yloxy)indan-1-one (22) (Scheme 5). One can assume
that ether 21 reacts with oxides, formed under the reaction
conditions, to give product 22. The reaction mixture does not
contain compounds 5 and 15. When the temperature is raised to
1
2
2JCF = 27 Hz) and 116.8 (tt, JCF = 301, JCF = 27 Hz) ppm,
assigned to the CF2 groups of 1,2-disubstituted cyclobutane
fragment. At the same time these data exclude the structures
with a 1,3-disubstituted cyclobutane fragment, for which
2
signals of CF2 groups should not have JCF.

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Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
Scheme 2.
130 8C, a more complex mixture is obtained that contains
products 14, 15, 21 and 22 together with unidentified
impurities. It has been shown in a separate experiment that
in an HF/SbF5 solution at room temperature compound 5 exists
as perfluoroindan-2-ol (23).
Formation of ether 21 may be represented by Scheme 5. The
lower relative stability of cation 24c than that of cation 15c
should hinder the cleavage of cation 21c to indanone 5 and
cation 24c as compared with transformation of cation 20c to
indanone 1 and cation 15c. As a result, cation 21c adds fluoride
anion to give ether 21. On heating at 130 8C, compound 21
apparently undergoes acidic cleavage to form indan 15.
The reaction of perfluorobenzocyclobutenone (6) with HF/
SbF5 at 95 8C leads to the formation of perfluorobenzocyclo-
butene (25) together with o-H-perfluoroethylbenzene (26). The
reaction mixture also contains unchanged compound 6 (Scheme
6). Fluorobenzene 26, apparently, is a product of opening of the
four-membered ring of compound 25 with HF under the reaction
conditions [12]. Perfluorobenzocyclobutenedione (7) also reacts
with HF/SbF5 at 95 8C to give ketone 6 together with product 25
and unchanged compound 7 (Scheme 6).
When 3,4-dihydronaphthalen-1(2H)-one (8) is heated with
HF/SbF5 at 95 8C, the carbonyl group is converted into
difluoromethylene to form perfluorotetralin (27). The reaction
mixture also contains small amounts of unchanged ketone 8
(Scheme 7). Under the same conditions 2,3-dihydronaphtha-
lene-1,4-dione (9) gives compounds 8 and 27 together with
starting diketone 9.

Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
1577
Scheme 3.
resulting mixture was heated at 95 8C, fluorotoluene 29 was
transformed mainly into aldehyde 11 (Scheme 9).
It was mentioned above that compound 5 in an HF/SbF5
solution adds HF to form hydroxyindan 23 (Scheme 5). When
dissolved in an HF/SbF5 system, compound 1 is protonated to
give equilibrium of indanone 1 and cation 1c, shifted towards
cation 1c. Analogously to that, cation 4c, 1-hydroxy-
perfluorobenzocyclobuten-1-yl (6c) and 1-hydroxy-perfluoro-
tetralin-1-yl (8c) cations were generated from compounds 4, 6
and 8, respectively (Schemes 2 and 10).
Fig. 1. Molecular structure of perfluorodispiro[phthalide-3,10-cyclobutane-
20,300-phthalide] (E-18) in crystal. Thermal ellipsoids are drawn at the 25%
00
˚
probability level. Selected bond lengths (A) and torsion angle (8): C3–C3
1.581(3), C3–C10 1.569(3), C300–C11 1.567(3), C10–C11 1.555(3), C10–C3–
C300–C11 8.4(2).
The reaction of perfluoroacetophenone (10) with HF/SbF5 at
95 8C leads to the formation of perfluoroethylbenzene (28) in
good yield. In contrast, perfluorobenzaldehyde (11) under the
reaction conditions gives difluoromethylpentafluorobenzene
(29) in very low yield (Scheme 8).
Perfluorobenzoic acid (12) also reacts with HF/SbF5. Thus,
prolonged heating of acid 12 with HF/SbF5 at 95 8C with
further treatment of the reaction mixture with water gives
perfluorotoluene (30) together with perfluorobenzoyl fluoride
(31). The mixture also contains acid 12 (Scheme 8). The
interaction of tetrafluorophthalic anhydride (13) with HF/SbF5
leads to the formation of perfluoro-2-methylbenzoic acid (32),
perfluoro-o-xylene (33) and perfluorophthalide (34) together
with tetrafluorophthalic acid (Scheme 8).
Assignment of signals in the 19F NMR spectra of cations 1c,
4c, 6c and 8c was made by analogy with that for
perfluorobenzocyclobuten-1-yl [13], 1-chlorooctafluoroindan-
1-yl [14], perfluoro-3-methyleneindan-1-yl [15], perfluoro-1-
phenylbenzocycloalken-1-yl [16], polyfluorinated benzyl [17]
and diphenylmethyl cations [18], for which changes in
chemical shift in going from precursor to ion (DdF) are
attributed to direct participation of fluorine atoms in charge
distribution and in an conjugation. It should be noted that for
the benzene moiety of cations 1c, 6c and 8c down-field DdF
resemble those of perfluoro-1-phenylbenzocycloalken-1-yl
cations [16], a smaller scale of DdF can be due to a less
positive charge transfer onto ring.
The reactions of polyfluorinated carbonyl derivatives with
HF/SbF5 seem to be reversible. For example, in the case of
compounds 11 and 29 equilibrium apparently is shifted towards
aldehyde 11 (Scheme 8). Indeed, when fluorotoluene 29 was
added to a mixture of compound 28 and inorganic oxides [O<]
formed in the reaction of ketone 10 with HF/SbF5 and the
The 19F NMR spectrum of indandione 2 solution in an HF/
SbF5 medium exhibits three unresolved signals with equal
intensities and dF ꢁ107.1, ꢁ110.8 and ꢁ112.5 ppm. This
testifies that for cation 2c there is an exchange of H+ between
two oxygen atoms of ion 2c or/and there is the fast equilibrium
between cation 2c and dication 2dc (Scheme 11).
Scheme 4.

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Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
Scheme 5.
Scheme 6.
Using DdF values of cation 1c as increments, calculation of
recorded on a Bruker WP-200 SY instrument (188.3 and
200 MHz, respectively) whereas 13C NMR spectra of
compounds 14 and 18 were recorded on a Bruker AV 300
(75.5 MHz) and Bruker AM 400 (100.6 MHz) instruments,
respectively. Chemical shifts are given in d ppm from CCl3F
(19F) and TMS (1H and 13C); C6F6 (ꢁ162.9 ppm from CCl3F),
(Me3Si)2O, CHCl3 (0.04 and 7.24 ppm from TMS) and
(CD3)2CO (29.8 ppm from TMS) were used as internal
standards. GC–MS: Hewlett Packard G1081A, combined with
Hewlett Packard 5890 with mass selective detector HP 5971 (EI
70 eV). The molecular masses of the compounds were
determined by high-resolution mass spectrometry on a
Finnigan Mat 8200 instrument (EI 70 eV). Contents (yields)
of products in the reaction mixtures were established by GC–
MS method and 19F NMR spectroscopic data.
DdF for cation 2c gives dF ꢁ98.0(F-5), ꢁ102.4 (F-7), ꢁ123.3
(F-4), ꢁ128.1 (F-6), ꢁ113.4 (F-2) ppm. In the case of exchange
of H+ between the carbonyl groups of cation 2c the signals
should be situated at ꢁ113.0 (F-5, F-6), ꢁ112.8 (F-4, F-7),
ꢁ113.4 (F-2) ppm. The spectrum of dication 2dc should have
signals, which are significantly shifted downfield from
ꢁ113 ppm. These calculated and experimental data apparently
testify that in an HF/SbF5 solution there is the equilibrium
between cation 2c and dication 2dc, shifted towards the former.
Behaviour of diketones 7 and 9 in an HF/SbF5 solution is
similar to that of compound 2 under the same conditions.
3. Experimental
The X-ray diffraction experiment was carried out on a
Bruker P4 diffractometer (graphite-monochromated Mo Ka
radiation) at room temperature. Intensity data were collected
using u/2u-scan, 2u < 608. Reflection intensities were corrected
for absorption by integration method. The structure was solved
by direct methods, using SHELXS-97 program and refined by
anisotropic full-matrix least-squares against F2 of all reflec-
tions using SHELXL-97 program. Crystallographic data for the
structure of E-18 in this paper have been deposited at the
Cambridge Crystallographic Data Centre as supplementary
IR spectra were taken on a Bruker Vector 22 IR spectro-
photometer. UV spectra were measured on a Hewlett Packard
1
8453 UV spectrophotometer. 19F and H NMR spectra were
Scheme 7.

Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
1579
Scheme 8.
Scheme 9.
publication no. CCDC 611160. Copy of the data can be
obtained, free of charge, on application to CCDC, 12 Union
Road, Cambridge CB21EZ, UK (fax: +44 122 3336033 or e-
mail: deposit@ccdc.cam.ac.uk).
contained compounds 1, 2, 4 and 14 in the ratio 2:5:92:1 (19F
NMR). The solution was washed with 5% hydrochloric acid
(removal of 2) and dried over MgSO4. The solvent was
distilled off to give 0.58 g of mixture, which contained
compounds 1, 4, 14 and 18 (<5%). The mixture in a sealed
ampoule was heated at 130 8C for 7 h to give 0.56 g (yield
70%) of compound 18 (E:Z ꢀ 50:50). Analytical sample of
compound 18 (E:Z ꢀ 40:60) was prepared by crystallization
(CH2Cl2-hexane) and then sublimation (170 8C, 2 Torr).
Perfluorodispiro[phthalide-3,10-cyclobutane-20,300-phtha-
lide] (18), mixture of two isomers, ratio E:Z ꢀ 40:60: mp
153–197 8C. UV (C2H5OH) lmax, nm (lg e): 202 (4.56), 262
(3.84), 272 (3.86), 311 (3.53). IR (KBr) n, cmꢁ1: 1821
(C O); 1523, 1507 [fluorinated aromatic ring (FAR)].
The structures of the compounds were established by
elemental analysis, HRMS and spectral characteristics. The
structure of compound E-18 was confirmed by single crystal X-
ray diffraction as well. Assignment of signals in the 19F NMR
spectra was made on the basis of chemical shifts of the signals,
their fine structure and integral intensities. Compounds 1–3, 6–
13, 15, 25–31, 33 were identified by comparison of the 19F
NMR data with those for authentic samples.
Mixture of HF/SbF5 (molar ratio HF:SbF5 = 1.8-2.15: 1)
was used in all experiments.
13
E-isomer: NMR C ((CD3)2CO): d 160.8 (C-1, C-100),
3.1. Reaction of perfluoroindan-1,3-dione (2) with HF/
SbF5
147-144 (C-4, C-400, C-5, C-500, C-6, C-600, C-7, C-700), 120.7
and 112.8 (C-3a, C-3a00 and C-7a, C-7a00), 116.9 (C-30, C-
40(CF2)), 89.7–89.5 (C-3, C-300). NMR 19F ((CH3)2CO): d
ꢁ116.3 (2F, F-A, F-A0), ꢁ120.4 (2F, F-B, F-B0), ꢁ132.0 (2F,
F-4, F-400), ꢁ139.6 (2F, F-7, F-700), ꢁ142.3 (2F, F-5, F-500),
1. A mixture of 0.8 g of compound 2, 1.2 g of HF/SbF5 (molar
ratio of 2:HF:SbF5 = 1:2.7:1.5) was heated in a TeflonTM
closed container (20 ml) at 95 8C for 3 h. The mixture was
poured into 5% hydrochloric acid and extracted with
CH2Cl2. The extract was dried over MgSO4. The solution
ꢁ147.5 (2F, F-6, F-600); JA,B = 224 Hz, J4,A = 19 Hz, J4;B
0 ¼
31 Hz J4,5 = 20 Hz, J4,6 = 7 Hz, J4,7 = 17 Hz, J5,6 = 18 Hz,
J
5,7 = 9 Hz, J6,7 = 20 Hz.
13
Z-isomer: NMR C ((CD3)2CO): d 161.4 (C-1, C-100),
147-144 (C-4, C-400, C-5, C-500, C-6, C-600, C-7, C-700), 121.4
and 112.2 (C-3a, C-3a00, and C-7a, C-7a00), 116.8 (C-30, C-40
(CF2)), 89.7–89.5 (C-3, C-300). NMR 19F ((CH3)2CO): d
ꢁ117.2 (2F, F-A, F-A0), ꢁ122.7 (2F, F-B, F-B0), –130.2 (2F,
F-4, F-400), ꢁ138.8 (2F, F-7, F-700), ꢁ141.9 (2F, F-5, F-500),
ꢁ147.3 (2F, F-6, F-600); JA,B = 224 Hz, J4;A ¼ J4;A0 ¼ 34 Hz,
J4,5 ꢀ 20 Hz, J4,6 ꢀ 5 Hz, J4,7 ꢀ 17 Hz, J5,6 ꢀ 18 Hz,
J5,7 ꢀ 10 Hz, J6,7 ꢀ 21 Hz (spectrum is not of the first
order). Anal. Calcd for C18F12O4: M 508; C, 42.5%; Found
(mixture of E and Z-isomers): M 506 (acetone); C, 42.8%.
Scheme 10.

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Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
Scheme 11.
Perfluoro-3-methylenephthalide (4): IR (CCl4) n, cmꢁ1
:
with CH2Cl2. The extract was dried over MgSO4. The
1823, 1809 (C O); 1734 (C CF2); 1526, 1497 (FAR). 19F
NMR (CH2Cl2): d ꢁ84.8 (1F, F-3t), ꢁ99.1 (1F, F-3c),
ꢁ137.3 (1F, F-4), ꢁ138.1 (1F, F-7), ꢁ141.8 (1F, F-5),
ꢁ150.2 (1F, F-6); J3c,3t = 33 Hz, J3c,4 = 54 Hz, J3c,5 = 2 Hz,
solvent was distilled off to give 0.71 g of mixture, which
contained (19F NMR) 30% (yield 22%) of 3-hydroxy-
perfluoro-3-methylphthalide [6], 64% (47%) of 3, 3% (2%)
of 14, 4% (2%) of perfluoro-2-ethylbenzoic acid [6].
2. A mixture of 1.44 g of compound 2, 2.17 g of HF/SbF5
(molar ratio of 2:HF:SbF5 = 1:2.7:1.5) was heated in a nickel
bomb (10 ml) at 95 8C for 3 h. The mixture was poured into
5% hydrochloric acid and extracted with CCl4. The extract
was dried over MgSO4. Dibromine (1.5 g) was added into the
extract at room temperature and the mixture was kept at this
temperature for 20 h. The mixture was washed with aqueous
solutions of Na2SO3, then with NaHCO3 and dried over
MgSO4. The solvent was distilled off to give 1.96 g (yield
83%) of compound 17, which was additionally purified by
short-path distillation (90 8C, 3–4 Torr).
J
J
J
3c,6 = 6 Hz,
J3c,7 = 2 Hz,
J3t,4 = 7 Hz,
J3t,5 = 3 Hz,
3t,6 = 8 Hz, J4,5 = 19 Hz, J4,6 = 4 Hz, J4,7 = 19 Hz,
5,6 = 18 Hz, J5,7 = 10 Hz, J6,7 = 20 Hz.
2. In a nickel bomb (10 ml) analogously to the previous
procedure, the reaction of indandione 2 (0.58 g), 1.46 g of
HF/SbF5 (molar ratio, 1:4.9:2.5) gave (95 8C, 43 h) a
solution (CHCl3), contained compounds 3, 4, 14 and 15 in
the ratio 12:35:50:3 (19F NMR). The solvent was removed in
vacuo at 20 8C to give 0.53 g of mixture of compounds 3, 4,
14 and 15 (yield 10, 30, 43, 3%, respectively).
3. Analogously to procedure (1), the reaction of indandione 2
(0.77 g), 1.93 g of HF/SbF5 (molar ratio, 1:4.9:2.5) gave
(130 8C, 11 h) a solution (CHCl3), contained compounds 3,
14 and 15 in the ratio 2:97:1 (19F NMR). The mixture was
spontaneously evaporated in the air to dryness to give 0.72 g
(yield 87%) of compound 14.
3-Bromo-3-(bromodifluoromethyl)-4,5,6,7-tetrafluorophtha-
lide (17): liquid. IR (CCl4) n, cmꢁ1: 1836 (C O); 1522, 1505
(FAR). 19F NMR (CH2Cl2): d ꢁ55.1 (1FA) and ꢁ56.2 (1FB,
CF2Br), ꢁ133.0 (1F, F-4), ꢁ135.4 (1F, F-7), ꢁ138.6 (1F, F-5),
ꢁ145.1 (1F, F-6); JA,B = 170 Hz, JA,4 = 32 Hz, JB,4 = 13 Hz,
4,5,6,7-Tetrafluoro-3-trifluoromethyl-phthalide (14): mp
93.5–94.5 8C (hexane). UV (hexane) lmax, nm (lg e): 225
(3.90), 231 (3.88), 277 (3.22). IR (CCl4) n, cmꢁ1: 2965 (CH);
1823, 1796 (C O); 1520, 1504 (FAR). 1H NMR (CCl4): d 5.77
J
J
4,5 = 20 Hz,
J4,6 = 8 Hz,
J4,7 = 19 Hz,
J5,6 = 18 Hz,
5,7 = 11 Hz, J6,7 = 20 Hz. HRMS m/z, 332.8945 (M+-Br).
Calcd for C9BrF6O2 = 332.8986. Anal. Calcd for C9Br2F6O2:
Br, 38.6; F, 27.5%. Found: Br; 38.8; F, 27.8%.
(q, JHꢁCF ¼ 5 Hz, H-3). 13C NMR (CDCl3): d 161.6 (s, C-1),
3
1
145.7 (ddd, JCF = 266 Hz, JCF = 16, 13 Hz) and 142.7 (dt,
2
3.3. Heating of dimer18 with Br2 and in its absence
1JCF = 262 Hz, JCF = 14 Hz, C-5 and C-6), 144.9 (dd,
2
1JCF = 268 Hz, JCF = 12 Hz) and 142.5 (dd, JCF = 260 Hz,
1. 0.16 g of dimer 18 (E:Z ꢀ 50:50) in ampoule, sealed under
argon, was heated at 180 8C for 21 h to give 0.16 g of
compound E-18 without Z-18 (19F NMR).E-Perfluorodispir-
o[phthalide-3,10-cyclobutane-20,300-phthalide] (E-18): mp
172–173 8C (CH2Cl2 – hexane). UV (C2H5OH) lmax, nm
(lg e): 205 (4.54), 274 (3.73), 282 (3.71), 313 (3.27), 321
(3.27). IR (KBr) n, cmꢁ1: 1820 (C O); 1522, 1507
[fluorinated aromatic ring (FAR)]. Single crystals of
compound E-18 were grown by slow evaporation of a
solvent from CH2Cl2 – hexane solution.
2
1
2JCF = 13 Hz, C-4 and C-7), 122.2 (d, 2JCF = 15 Hz) and 110.2
2
(d JCF = 13 Hz, C-3a and C-7a), 121.3 (q, JCF = 281 Hz,
1
CF3), 74.0 (dq, JCH = 162 Hz, JCF = 38 Hz, C-3). 19F NMR
1
2
(CCl4): d ꢁ77.7 (3F, CF3), ꢁ136.7 (1F, F-7), ꢁ138.9 (1F, F-4),
ꢁ142.0 (1F, F-5), ꢁ148.0 (1F, F-6); JHꢁCF ¼ 5 Hz,
3
JCF Fð4Þ ¼ 14 Hz, J4,5 = 20 Hz, J4,6 = 6 Hz, J4,7 = 19 Hz,
3
J
5,6 = 18 Hz, J5,7 = 10 Hz, J6,7 = 20 Hz. HRMS m/z,
273.9855 (M+). Calcd for C9HF7O2 = 273.9865.
3.2. Reactions of perfluoro-3-methylenephthalide (4) with
SbF5 and Br2
Crystallographic data and refinement parameters:
Formula C18F12O4, M = 508.18, monoclinic, space group
˚
Cc, a = 11.5028(10), b = 19.2746(11), c = 7.8848(5) A,
3
˚
1. In a nickel bomb (10 ml) analogously to procedure (1) of the
previous experiment, the reaction of indandione 2 (0.84 g),
1.3 g of HF/SbF5 (molar ratio, 1:3.2:1.5) gave (95 8C, 3 h)
0.74 g of mixture of compounds 1, 2, 4 and 14 in the ratio
11:8:79:2 (19F NMR). The mixture was heated at 125 8C for
3 h with 2.71 g of SbF5 (molar ratio, 4:SbF5 = 1:3.8). The
mixture was poured into 5% hydrochloric acid and extracted
b = 94.855(6)8, V = 1741.9(2) A , Z = 4, Dcalc = 1.938 g/
cm3, m = 0.219 mmꢁ1, 2842 total reflexions, 2655 unique
reflexions (Rint = 0.0474), R = 0.0300 for 2478 I > 2s(I),
308 parameters, wR2 ¼ 0:0868 and GOF = 1.049 for all data,
max/min Dr 0.217/ꢁ0.153.
2. A mixture of 0.17 g of dimer 18 (E:Z ꢀ 50:50) with 0.6 g of
Br2 (molar ratio, 1:11) in a sealed ampoule was heated at

Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
1581
180 8C for 19 h. A mixture was dissolved in CH2Cl2, washed
with aqueous solution of Na2SO3 and dried over MgSO4. The
solvent was distilled off to give 0.16 g of a mixture of
compounds E-18 and 17 in the molar ratio 95:5 (19F NMR),
yield 90 and 2%, respectively.
Perfluoro-2-(indan-2-yloxy)indan-1-one (22): mp 148.5–
150 8C. UV (hexane) lmax, nm (lg e): 215 (4.11), 243 (4.03),
251 (4.08), 269 (3.22), 293 (3.26). IR (KBr) n, cmꢁ1: 1775
(C O); 1519 (FAR). 19F NMR (ether): d ꢁ95.5 and ꢁ96.5
(A-components of two AB-systems), ꢁ111.4 and ꢁ111.8
(B-components of two AB-systems, 2CF2, JA,B = 263 Hz),
ꢁ99.8 (1FA) and ꢁ110.8 (1FB, JA,B = 267 Hz, CF2), ꢁ127.6
(1F, F-2), ꢁ132.9 (1F, F-7), ꢁ134.3 (1F, F-20), ꢁ136.3 (1F,
F-5), ꢁ137.7 (1F, F-4), ꢁ138.6 (2F, F-40, F-70), ꢁ142.9 (2F,
F-50, F-60), ꢁ143.7 (1F, F-6); J4,3A and J4,3B = 6 and 8 Hz,
3. Analogously to the previous procedure, the reaction of dimer
18 (0.06 g) with Br2 (0.32 g) (molar ratio, 1:17) gave
(260 8C, 9 h) 0.09 g of a mixture contained ꢀ95% (yield
87%) of compound 17 (NMR 19F).
3.4. Reaction of perfluoroindan-1-one (1) with HF/ SbF5
J
J
4,5 = 20 Hz, J4,6 = 8 Hz, J4,7 = 18 Hz, J5,6 = 18 Hz,
5,7 = 13 Hz, J6,7 = 20 Hz. HRMS m/z, 551.9641 (M+).
1. A mixture of 0.61 g of compound 1, 1.4 g of HF/SbF5 (molar
ratio of 1:HF:SbF5 = 1:4.9:2.5) was heated in a nickel bomb
(10 ml) at 95 8C for 15.5 h. The mixture was poured into 5%
hydrochloric acid and extracted with CH2Cl2. The extract
was dried over MgSO4. The solvent was distilled off to give
0.52 g of mixture, which contained compounds 1 and 15 in
the ratio 48:52 (yield 38 and 42%).
Calcd for C18F16O2 = 551.9643.
3. Analogously to the previous procedure, the reaction of
indanone 5 (0.56 g) and HF/SbF5 (1.29 g) (molar ratio,
1:4.9:2.5) gave (130 8C, 11 h) 0.42 g of mixture, which
contained 15% of 14, 11% of 15, 17% of 21, 21% of 22
together with unidentified impurities (19F NMR, GC–MS).
2. Analogously to the previous procedure, the reaction of
indanone 1 (0.6 g) and HF/SbF5 (1.39 g) (molar ratio,
1:4.9:2.5) gave (95 8C, 43 h) 0.54 g of mixture, which
contained compounds 1 and 15 in the ratio 14:86 (yield 12
and 72%).
3.6. Reaction of perfluorinated benzocyclobutenone (6),
benzocyclobutenedione (7), 3,4-dihydronaphthalen-1(2H)-
one (8) and 2,3-dihydronaphthalene-1,4-dione (9) with HF/
SbF5
1. A mixture of 0.5 g of compound 6, 1.41 g of HF/SbF5 (molar
ratio of 6:HF:SbF5 = 1:4.9:2.5) was heated in a nickel bomb
(10 ml) at 95 8C for 15.5 h. The mixture was poured into 5%
hydrochloric acid and extracted with CH2Cl2. The extract
was dried over MgSO4. The solvent was distilled off to give
0.47 g of mixture, which contained (19F NMR) compounds
6, 25 and 26 in the ratio 50:39:11 (yield 44, 34 and 10%,
respectively).
3.5. Reaction of perfluoroindan-2-one (5) with HF/SbF5
1. To 0.89 g of HF/SbF5 placed in an ampoule with Teflon
FEP inliner for recording of NMR spectra 0.38 g of ketone
5 (molar ratio, 5:HF:SbF5 = 1:5.4:2.5) was added. The
mixture was stirred and 19F NMR spectrum of the solution
was recorded. The spectrum contained ill-resolved signals
of compound 23. 19F NMR (188.3 MHz, C6F6 was used as
external standard): d ꢁ113.4 (2FA) and ꢁ124.8 (2FB,
2. Analogously to the previous procedure, the reaction of
compound 7 (0.37 g) and HF/SbF5 (1.14 g) (molar ratio,
1:4.9:2.5) gave (95 8C, 15.5 h) 0.35 g of mixture, which
contained compounds 6, 7 and 25 in the ratio 43:41:16 (yield
38, 36 and 14%, respectively).
J
A,B = 250 Hz, CF2-1,3); ꢁ132.9 (1F, F-2); ꢁ134.5 (2F, F-
4, F-7); ꢁ143.9 (2F, F-5, F-6) ppm. The solution was
poured into 5% hydrochloric acid and extracted with ether.
The extract was dried over MgSO4. The solvent was
distilled off to give 0.33 g (yield 93%) of 2,2-dihydrox-
yperfluoroindan (19F NMR), which is hydrate form of
ketone 5 [19].
3. Analogously to procedure (1), the reaction of compound 8
(0.59 g) and HF/SbF5 (1.15 g) (molar ratio, 1:4.9:2.5) gave
(95 8C, 15.5 h) 0.53 g of mixture, which contained
compounds 8, and 27 in the ratio 10:90 (yield 8 and 76%,
respectively).
2. A mixture of 0.6 g of compound 5, 1.39 g of HF/SbF5 (molar
ratio of 5:HF:SbF5 = 1:4.9:2.5) was heated in a nickel bomb
(10 ml) at 95 8C for 16 h. The mixture was poured into 5%
hydrochloric acid and extracted with CH2Cl2. The extract
was dried over MgSO4. The solvent was distilled off to give
0.52 g of mixture, which contained compounds 21 and 22 in
the ratio 79:21 (yield 66 and 18%). The individual
compounds 21 (0.34 g) and 22 (0.09 g) were isolated by
silica gel column chromatography (CCl4 as eluent) and then
purified by sublimation (130 8C, 2 Torr).
4. A mixture of 0.59 g of compound 9, 1.21 g of HF/SbF5
(molar ratio of 9:HF:SbF5 = 1:4.9:2.5) was heated in a nickel
bomb (10 ml) at 95 8C for 15.5 h. The mixture was poured
into 5% hydrochloric acid and extracted with ether. The
extract was dried over MgSO4. The solvent was distilled off,
the mixture obtained was dissolved in CH2Cl2 and dried over
MgSO4. The solvent was distilled off to give 0.51 g of
mixture, which contained (19F NMR) compounds 8, 9 and 27
in the ratio 41:44:15 (yield 35, 36 and 12%, respectively).
Bis( perfluoroindan-2-yl) ether (21): mp 152–152.5 8C.
UV (C2H5OH) lmax, nm (lg e): 267 (3.32). IR (KBr) n, cmꢁ1
:
3.7. Reaction of perfluorinated acetophenone (10) and
benzaldehyde (11) with HF/SbF5
1522 (FAR). 19F NMR (376.4 MHz, ether): d ꢁ95.1 (4FA)
and ꢁ112.7 (4FB, JA,B = 264 Hz, CF2-1, CF2-3), ꢁ133.8 (2F,
F-2), ꢁ138.5 (4F, F-4, F-7), ꢁ142.7 (4F, F-5, F-6). HRMS m/
z, 573.9662 (M+). Calcd for C18F18O = 573.9662.
1. In a nickel bomb (10 ml) analogously to procedure (1) of the
previous experiment, the reaction of compound 10 (0.62 g)

1582
Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
and HF/SbF5 (1.5 g) (molar ratio, 1:4.9:2.5) gave (95 8C,
15.5 h) 0.54 g (yield 80%) of compound 28.
J4,5 = 20 Hz,
J4,6 = 8 Hz,
J4,7 = 19 Hz,
J5,6 = 17 Hz,
J5,7 = 12 Hz, J6,7 = 20 Hz. HRMS m/z, 241.9813 (M+). Calcd
for C9F8O2 = 241.9802. Tetrafluorophthaloyl difluoride as
acyclic isomer of compound 34 was characterized in Ref. [20].
Perfluoro-2-methylbenzoic acid (32): mp 90.5–92 8C. UV
(hexane) lmax, nm (lg e): 212 (3.73), 268 (3.14). IR (CCl4) n,
cmꢁ1: 3504, 3038 (OH); 1773, 1733 (C O); 1530, 1487 (FAR).
1H NMR (CCl4): d 11.19 (s, OH). 19F NMR (CCl4): d ꢁ58.4
(3F, CF3), ꢁ136.7 (1F, F-3), ꢁ139.3 (1F, F-6), ꢁ147.2 (1F, F-
2. Analogously to the previous procedure, the reaction of
compound 11 (0.45 g) and HF/SbF5 (1.45 g) (molar ratio,
1:4.9:2.5) gave (95 8C, 18 h) 0.35 g of mixture, which
contained (19F NMR) compound 11 and small amount
(<3%) of compound 29.
3. A mixture of 0.74 g of compound 10, 1.84 g of HF/SbF5
(molar ratio of 10:HF:SbF5 = 1:5.4:2.5) was heated in a
nickel bomb (10 ml) at 95 8C for 15.5 h. Then compound 29
(0.61 g, molar ratio of 10:29 = 1:1) was added to the reaction
mixture. The resulting mixture was heated at 95 8C for 22 h
and treated analogously to procedure (1). It was obtained
1.24 g of mixture, which contained (19F NMR) compounds
11, 28 and 29 in the ratio 47:48:5 (yield 87, 88 and 10%,
respectively).
5), ꢁ150.1 (1F, F-4); JCF ꢁFð3Þ ¼ 19 Hz, J3,4 = 20 Hz,
3
J
J
3,5 = 9 Hz,
J3,6 = 12 Hz,
J4,5 = 20 Hz,
J4,6 = 6 Hz,
5,6 = 21 Hz. HRMS m/z, 261.9879 (M+). Calcd for
C8HF7O2 = 261.9865.
3.9. Protonation of perfluorinated indan-1-one (1),
benzocyclobutenone (6) and 3,4-dihydronaphthalen-1(2H)-
one (8) with HF/SbF5
4. A mixture of 0.38 g of compound 29, 1.14 g of HF/SbF5
(molar ratio of 29:HF:SbF5 = 1:5.4:2.5) was kept in a Teflon
container at room temperature for 24 h. The mixture was
poured into 5% hydrochloric acid and extracted with
CH2Cl2. The extract was dried over MgSO4. The solution
contained compounds 11 and 29 in the ratio 33:67 (19F
NMR).
1. To 0.6 g of HF/SbF5 placed in an ampoule with Teflon FEP
inliner for recording of NMR spectra 0.26 g of ketone 1
(molar ratio, 1:HF:SbF5 = 1:4.9:2.5) was added. The mixture
was stirred and 19F NMR spectrum of the solution was
recorded (Table 1), perfluoroindan (the most upfield signal
19.5 ppm from C6F6) was used as internal standard. The
solution was poured into 5% hydrochloric acid and extracted
with CH2Cl2. The extract was dried over MgSO4. The
solvent was distilled off to give 0.23 g (yield 88%) of ketone
1 (19F NMR).
3.8. Reaction of perfluorinated benzoic acid (12) and
phthalic anhydride (13) with HF/SbF5
1. A mixture of 0.56 g of acid 12, 1.73 g of HF/SbF5 (molar
ratio of 12:HF:SbF5 = 1:5.4:2.5) was heated in a nickel bomb
(10 ml) at 95 8C for 15 h. The mixture was poured into 5%
hydrochloric acid and extracted with CH2Cl2. The extract
was dried over MgSO4. The solvent was distilled off to give
0.43 g of mixture, which contained (19F NMR) compounds
12, 30 and 31 in the ratio 31:57:12 (yield 22, 41 and 9%,
respectively).
2. Analogously to the previous procedure, solution of
compound 6 (0.26 g) in HF/SbF5 was prepared and 19F
NMR spectrum was measured, then compound 6 (0.22 g,
yield 85%) was recovered.
Table 1
19F NMR spectra of ketones 1, 6, 8 (CH2Cl2) and cations 1c, 6c, 8c (HF/SbF5)
2. A mixture of 0.5 g of anhydride 13, 2.91 g of HF/SbF5
(molar ratio of 13:HF:SbF5 = 1:9.8:5) was heated in a nickel
bomb (10 ml) at 95 8C for 62 h. The mixture was poured into
5% hydrochloric acid and extracted with CH2Cl2 and then
with ether. The extracts were dried over MgSO4. The solvent
from ether extract was distilled off to give 0.1 g of
tetrafluorophthalic acid. The CH2Cl2 extract contained
compounds 13, 32, 33 and 34 in the ratio 20:17:4:59 (19F
NMR). This extract was washed with aqueous solution of
NaHCO3 and dried over MgSO4. The solvent was distilled
off to give 0.26 g of product containing compounds 13, 33
and 34 in the ratio 5:3:92 (19F NMR). Phthalide 34 was
additionally purified by short-path distillation (110 8C,
40 Torr). The aqueous solution was acidified with HCl,
extracted with CH2Cl2 and dried over MgSO4. The solvent
was distilled off to give 0.08 g (yield 13%) of acid 32, which
was purified by sublimation (100 8C, 2 Torr).
1
1c
6
6c
8
8c
d (ppm)
F-2
ꢁ132.4
ꢁ142.6
ꢁ134.7
ꢁ136.5
ꢁ109.0
ꢁ125.2
–
ꢁ103.5
ꢁ135.4
ꢁ97.4
ꢁ128.5
ꢁ105.1
ꢁ115.0
–
ꢁ125.9
ꢁ140.8
ꢁ133.9
ꢁ133.4
ꢁ96.8
–
ꢁ106.9
ꢁ129.4
ꢁ98.8
ꢁ126.6
ꢁ84.4
–
ꢁ132.7
ꢁ144.0
ꢁ137.7
ꢁ134.0
ꢁ106.8
ꢁ133.7
ꢁ127.6
ꢁ94.4
F-3
ꢁ138.0
ꢁ100.2
ꢁ122.9
ꢁ105.6
ꢁ131.8
ꢁ117.8
F-4
F-5
F-6
F-7
F-8
–
–
JF,F (Hz)
J2,3
20
13
18
–
18
36
13
–
20
12
25
2
16
30
22
–
20
15
13
2
19
41
6
J2,4
J2,5
J2,6
J3,4
18
9
17
12
–
17
8
17
13
–
20
9
19
13
–
Perfluorophthalide (34): liquid. IR (CCl4) n, cmꢁ1: 1861,
1841 (C O); 1523, 1508 (FAR). 19F NMR (CH2Cl2): d ꢁ76.7
(2F, F-3), ꢁ133.6 (1F, F-7), ꢁ137.5 (1F, F-4), ꢁ138.2 (1F, F-5),
J3,5
J3,6
2
–
2
J4,5
20
7
19
6
20
3
18
–
20
22
19
25
J5,6
ꢁ143.3 (1F, F-6);
J3,4 = 4 Hz, J3,6 = 2 Hz, J3,7 = 2 Hz,

Y.V. Zonov et al. / Journal of Fluorine Chemistry 127 (2006) 1574–1583
1583
[2] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, G.G. Yakobson, Bull. Soc.
Chim. Fr. (1986) 980–985.
3. Analogously to procedure (1), solution of ketone 8 (0.34 g)
in HF/SbF5 was prepared and 19F NMR spectrum was
measured, then ketone 8 (0.3 g, yield 88%) was recovered.
[3] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, V.R. Sinyakov, J. Fluorine
Chem. 107 (2001) 53–57.
[4] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, V.R. Sinyakov, J. Fluorine
Chem. 117 (2002) 73–81.
3.10. Protonation of perfluorinated indan-1,3-dione (2), 3-
methylenephthalide (4), benzocyclobutenedione (7) and
2,3-dihydronaphthalene-1,4-dione (9) in HF/SbF5
[5] V.R. Sinyakov, T.V. Mezhenkova, V.M. Karpov, V.E. Platonov, J. Fluorine
Chem. 125 (2004) 49–53.
[6] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, J. Fluorine Chem. 126 (2005)
437–443.
1. Analogously to the previous experiments, solution of
compound
[7] D.A. Klumpp, S. Fredrick, S. Lau, K.K. Jin, R. Bau, G.K.S. Prakash, G.A.
Olah, J. Org. Chem. 64 (1999) 5152–5155.
2 (0.29 g) in an HF/SbF5 (molar ratio,
2:HF:SbF5 = 1:4.9:2.5) was prepared and 19F NMR spectrum
was recorded (spectrum of 2c is given in Section 2 of the
[8] R.D. Chambers, Fluorine in Organic Chemistry, Wiley, New York, 1973,
pp. 179–186.
[9] D.N. Laikov, Chem. Phys. Lett. 281 (1997) 151–156.
[10] L.M. Yagupolskii, in: B. Baasner, H. Hageman, J.C. Tatlow (Eds.),
Methods of Organic Chemistry (Houben-Weyl). Organo-Fluorine Com-
pounds, vol. E10a, Thieme, Stuttgart, 2000, pp. 509–534.
[11] R.D. Chambers, Fluorine in Organic Chemistry, Blackwell Publishing,
Oxford, 2004, 406 pp..
paper). Then the solution was heated at 95 8C for 3 h and 19
F
NMR spectrum of solution of compound 4 in HF/SbF5 was
measured at r.t. The solution was poured into 5% hydrochloric
acid and extracted with CHCl3. The extract was dried over
MgSO4. Thesolventwasdistilledofftogive 0.19 gofmixture,
which contained (19F NMR) compounds 1, 4, 14 and 15 in the
ratio6:73:19:2(yield4,46,12and1%,respectively).19FNMR
of 4c (HF/SbF5): d –63.3 (1F, F-3t), ꢁ75.1 (1F, F-3c), ꢁ124.4
(1F, F-7), ꢁ125.2 (1F, F-5), ꢁ132.5 (1F, F-4), ꢁ144.4 (1F, F-
6); J3c,3t = 24 Hz, J3c,4 = 41 Hz, J3c,6 = 4 Hz, J3t,4 = 7 Hz,
[12] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, L.N. Shchegoleva, Izv.
Akad. Nauk SSSR Ser. Khim. (1991) 2618–2623;
V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, L.N. Shchegoleva, Bull.
Acad. Sci. USSR Div. Chem. Sci. 40 (1991) 2292–2296, English
translation.
[13] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, G.G. Yakobson, J. Fluor-
ine Chem. 28 (1985) 121–137.
J
J
3t,5 = 4 Hz,
J3t,6 = 7 Hz,
4,7 = 17 Hz, J5,6 = 17 Hz, J5,7 = 19 Hz, J6,7 = 18 Hz.
J4,5 = 17 Hz,
J4,6 = 8 Hz,
[14] V.M. Karpov, V.E. Platonov, Zh. Org. Khim. 30 (1994) 789;
V.M. Karpov, V.E. Platonov, Russ. J. Org. Chem. 30 (1994) 841–842,
English translation.
2. Analogously to procedure (1) of the previous experiment,
solution of compound 7 (0.26 g) in HF/SbF5 was prepared
and 19F NMR spectrum was measured, then compound 7
(0.19 g, yield 73%) was recovered. 19F NMR of 7c (HF/
SbF5): d ꢁ109.3 (2F) and ꢁ111.8 (2F) (F-3, F-4, F-5, F-6).
3. Analogously to the previous experiments, solution of
compound 9 (0.31 g) in HF/SbF5 was prepared and 19F
NMR spectrum was recorded, then compound 9 (0.2 g, yield
65%)wasrecovered.19FNMRof9c(HF/SbF5):dꢁ103.4(2F)
and ꢁ115.6 (2F) (F-5, F-6, F-7, F-8), ꢁ119.9 (4F, 2F-2, 2F-3).
[15] V.M. Karpov, V.E. Platonov, I.P. Chuikov, L.N. Shchegoleva, Zh. Org.
Khim. 35 (1999) 87–91;
V.M. Karpov, V.E. Platonov, I.P. Chuikov, L.N. Shchegoleva, Russ. J. Org.
Chem. 35 (1999) 80–84, English translation.
[16] V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, V.R. Sinyakov, L.N.
Shchegoleva, Zh. Org. Khim. 38 (2002) 1210–1217;
V.M. Karpov, T.V. Mezhenkova, V.E. Platonov, V.R. Sinyakov, L.N.
Shchegoleva, Russ. J. Org. Chem. 38 (2002) 1158–1165, English
translation.
[17] Yu.V. Pozdnyakovich, V.D. Shteingarts, J. Fluorine Chem. 4 (1974) 283–
296.
[18] Yu.V. Pozdnyakovich, V.D. Shteingarts, J. Fluorine Chem. 4 (1974) 297–
316.
Acknowledgement
[19] I.P. Chuikov, V.M. Karpov, V.E. Platonov, Izv. Akad. Nauk Ser. Khim.
(1992) 1412–1419;
We gratefully acknowledge the Russian Foundation for Basic
Researches (project no. 06-03-32170) for financial support.
I.P. Chuikov, V.M. Karpov, V.E. Platonov, Bull. Russ. Acad. Sci. Div.
Chem. Sci. 41 (1992) 1104–1110, English translation.
[20] G.G. Yakobson, V.N. Odinokov, N.N. Vorozhtsov Jr., Zh. Obshch. Khim.
36 (1966) 139–142 (J. Gen. Chem. USSR, Russ.);
G.G. Yakobson, V.N. Odinokov, N.N. Vorozhtsov Jr., Chem. Abstr. 64
(1966) 14124h.
References
[1] Ya.V. Zonov, V.M. Karpov, V.E. Platonov, Mendeleev Commun. (2006)
167–168.