Formation and skeletal transformations of perfluoroindan-1-one and perfluoroindan-1,3-dione in the reaction of perfluoroindan with SiO 2/SbF5

Article abstract of DOI:10.1016/j.jfluchem.2004.09.035

Perfluoroindan-1-one (2) is obtained in the reaction of perfluoroindan (1) with SiO₂/SbF₅ at 70°C. Compound 1 heated with SiO₂/SbF₅ at 130°C and then treated with water, gives 3-hydroxy-perfluoro-3-methylphthalide (4). Ketone 2 is converted, under the action of SbF₅ at 130°C, to perfluoro-2-ethylbenzoic acid (9) and disproportionates to compound 1 and perfluoroindan-1,3-dione (3); the latter is transformed to phthalide 4 under the reaction conditions.

Full text of DOI:10.1016/j.jfluchem.2004.09.035

Journal of Fluorine Chemistry 126 (2005) 437–443
www.elsevier.com/locate/fluor
Formation and skeletal transformations of
perfluoroindan-1-one and perfluoroindan-1,3-dione in
the reaction of perfluoroindan with SiO2/SbF5
*
Yaroslav V. Zonov, Victor M. Karpov , Vyacheslav E. Platonov
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Novosibirsk 630090, Russia
Received 8 July 2004; received in revised form 28 September 2004; accepted 28 September 2004
Available online 15 December 2004
Dedicated to Professor Richard D. Chambers, on the occasion of 70th birthday
Abstract
Perfluoroindan-1-one (2) is obtained in the reaction of perfluoroindan (1) with SiO2/SbF5 at 70 8C. Compound 1 heated with SiO2/SbF5 at
130 8C and then treated with water, gives 3-hydroxy-perfluoro-3-methylphthalide (4). Ketone 2 is converted, under the action of SbF5 at
130 8C, to perfluoro-2-ethylbenzoic acid (9) and disproportionates to compound 1 and perfluoroindan-1,3-dione (3); the latter is transformed
to phthalide 4 under the reaction conditions.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Skeletal transformations; Perfluoroindan; Perfluoroindan-1-one; Perfluoroindan-1,3-dione; Silicon dioxide; Antimony pentafluoride; NMR
spectroscopy
1. Introduction
proceeds under the action of SiO2/SbF5 to give the
corresponding acids in a good yield [6].
Perfluorinated benzocycloalkenes (benzocyclobutene,
indan, tetralin) and their perfluoroalkyl and perfluoroaryl
derivatives, when heated with antimony pentafluoride,
undergo skeletal transformations leading to cleavage,
expansion or contraction of the alicyclic ring of benzocy-
cloalkenes [1–4] (see also [1–7] in Ref. [2]). For example,
when heated with SbF5 in a nickel bomb, perfluoro-1-
methylindan is transformed to perfluoro-2-isopropyltoluene
[1], and when heated with SbF5 in a glass ampoule, it reacts
with glass as a source of inorganic oxides to give perfluoro-
4-methyl-1H-isochromene [5] (Scheme 1).
In this connection it seemed reasonable to study the
reaction of perfluorobenzocycloalkenes with silica in the
presence of SbF5 and transformations of the carbonyl
derivatives of perfluorobenzocycloalkenes under the action
of antimony pentafluoride. This work describes the reactions
of perfluoroindan (1) with SiO2 and with a glass in an
SbF5 medium and transformations of perfluoroindan-1-one
(2) and perfluoroindan-1,3-dione (3) under the action of
antimony pentafluoride.
It should be noted that the carbonyl group of
perfluorinated 3-methylindenone, 1-methylindan-2-one,
indan-2-one [7] and indanone 2 [8] is involved in the
reactions with H2O2 in the HF–SbF5 system to form six-
membered oxygen containing heterocyclic compounds.
When heated with antimony pentafluoride, perfluorinated
ketones [9] and vinylketones [10] having a CF3 group in the
position b to the carbonyl group undergo intramolecular
cyclization to give derivatives of oxolane and 2,5-
dihydrofuran, respectively.
Apparently, the reaction with glass proceeds via
intermediate formation of perfluoro-3-methylindan-1-one.
On the other hand, selective ‘‘hydrolysis’’ of CF3 groups in
perfluorinated methyl- and propenyl-benzene derivatives
* Corresponding author. Fax: +7 383 234 4752.
E-mail address: karpov@nioch.nsc.ru (V.M. Karpov).
0022-1139/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.09.035

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Y.V. Zonov et al. / Journal of Fluorine Chemistry 126 (2005) 437–443
Scheme 3.
pound 4 with perfluoro-3-methylphthalide (5) and a small
amount of tetrafluorophthalic acid (6). The latter is the main
product of the reaction at 180 8C. Phthalides 4, 5 are,
probably, formed via intermediate diketone 3. Indeed, a
separate experiment has shown that the reaction of diketone
3 with antimony pentafluoride gives phthalides 4 and 5 with
small amounts of acid 6 (Scheme 4).
Scheme 1.
2. Results and discussion
Transformation of diketone 3 to products 4, 5 in the
presence of antimony pentafluoride, possibly, proceeds in
the following way (Scheme 5). At first complex 3c is
formed from diketone 3 and SbF5. The five-membered
cycle of the complex 3c may undergo ring opening to give
the intermediate 7. The latter is further fluorinated yielding
perfluoro-2-acetylbenzoyl fluoride (5a) and then product
5, or/and intermediate 7 is transformed into perfluoro-3-
methylenephthalide (8) which is fluorinated to product 5.
Hydrolysis of compounds 5 and 5a leads to phthalide 4.
It has been shown that indanone 2 also undergoes skeletal
transformations under the action of SbF5 at high tempera-
ture. Thus, indanone 2, heated with antimony pentafluoride
at 130 8C (2 h) and then treated with water, gives a mixture
of perfluoro-2-ethylbenzoic acid (9), phthalides 4, 5 and
indan 1. The reaction mixture also contains unchanged
ketone 2 (Scheme 6).
Transformation of indanone 2 in the presence of SbF5 to
the acid 9 may be represented by Scheme 6. At first
compound 2 with SbF5 seems to generate the cation 10. The
five-membered cycle of the latter may undergo ring opening
analogous to that in perfluoro-1-methylindan (Scheme 1)
and indan 1 under the action of SbF5 [1]. This yields the
benzoyl type ion 11, which adds fluoride anion and then
undergoes fluorination to form product 12. Hydrolysis of the
latter gives the acid 9.
We have found that reaction of indan 1 with SiO2 (SiO2
was prepared by heating of silica gel at 400–450 8C) in the
presence of 1.5 mol of SbF5 per 1 mol of compound 1 at
70 8C (5 h) gives indanone 2 and small amount of
indandione 3. Increase in the reaction time (13 h) leads to
a small increase of diketone 3 yield. Decrease of SbF5 from
1.5 to 0.5 mol per 1 mol of indan 1 lowers the conversion of
the latter (Scheme 2).
The formation of indanone 2 and diketone 3 can be
rationalized by a mechanism involving the interaction of the
perfluoroindan-1-yl cation initially generated [11] and
perfluoroindan-3-one-1-yl cation with SiO2 according to
the Scheme 2.
Formation of indanone 2 as the dominant component in
comparison with diketone 3 from indan 1 could be explained
by the fact that indanone 2 gives complex 2c (its formation
will be discussed below) with antimony pentafluoride
(Scheme 3). As a result, the reaction of indanone 2 with
SiO2/SbF5 should be difficult as compared with indan 1. On
the other hand, the complexing decreases the amounts of
‘‘free’’ SbF5, and the reaction of indan 1 with SiO2 is
impeded.
The reaction of indan 1 with SiO2 (70–75 8C) in the
presence of 3 mol of SbF5 per 1 mol of compound 1 gives,
after treatment reaction mixture with water, indanone 2,
Fluorination of indanone 2 to product 12 under the action
of antimony pentafluoride with cleavage of the bond C(O)–
CF2 in indanone 2 (not in the cation 10) seems unlikely,
indandione
3
together with 3-hydroxy-perfluoro-3-
methylphthalide (4). The reaction at 130 8C forms com-
Scheme 2.

Y.V. Zonov et al. / Journal of Fluorine Chemistry 126 (2005) 437–443
439
Scheme 4.
because perfluoro-3,3-diethylindan-1-one (13) is the only
product of the reaction of perfluoro-1,1-diethylindan (14)
with SiO2/SbF5 at 130 8C (Scheme 6).
Formation of the products 1, 4, 5 in the reaction of
indanone 2 with antimony pentafluoride could be explained
by disproportionation of ketone 2 to indan 1 and indandione
3 (Scheme 7), which gives products 4 and 5 under the
reaction conditions, that was shown above.
Packard 8453 UV spectrophotometer. 19F NMR and 1H
spectra were recorded on a Bruker WP-200 SY instrument
(188.3 and 200 MHz, respectively) whereas 13C NMR
spectrum of the compound 4 was recorded on a Bruker AM
400 instrument (100.6 MHz). Chemical shifts are given in d
ppm downfield from C6F6 (19F) and TMS (1H and 13C); C6F6
(ꢀ162.9 ppm from CCl3F), (Me3Si)2O, CHCl3 (0.04 and
7.24 ppm from TMS) and CDCl3 (76.9 from TMS) were
used as internal standards. The molecular masses of the
compounds were determined by high-resolution spectro-
metry on a Finnigan Mat 8200 instrument (EI 70 eV).
Contents (yields) of products in the reaction mixtures were
established by GLC and 19F NMR spectroscopic data.
The structures of the compounds were established by
elemental analysis, HRMS and spectral characteristics.
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 2, 3, 6 were identified
by comparison of the 19F NMR data with data for authentic
samples [12,13].
When a solution of ketone 2 in indan 1 was heated with
SbF5, ketone 2 disproportionated to a lesser extent as
compared with ketone 2 in the absence of indan 1. As a
result, the acid 9 is formed in higher yield. When heated
with antimony pentafluoride at 130 8C in a glass ampoule
during a lengthy period of time (35 h), indan 1 reacts with
glass to give, after hydrolysis, acid 9 and, unexpectedly,
perfluoro-2-ethylbenzoic anhydride 9a only with a small
admixture of compounds 4 and 5 (Scheme 6). This may be
explained by the smaller relative rate of the reaction of
indan 1 with glass as compared with SiO2 and, as a
consequence, formation of ketone 2 in small concentration
can occur. As a result, ketone 2 is transformed rather to
acid 9 (first reaction order for 2, Scheme 6), than
disproportionating to indan 1 and diketone 3 (second
reaction order for 2, Scheme 7).
Formally, compounds 4 and 5 could exist as phthalides 4,
5 and/or their open-chain forms 4a and 5a, respectively
(Scheme 5). According to the 19F NMR spectrum,
compound 5 exists in the phthalide form. Signals at
4.71 ppm (OH, 1H NMR) and at 99.3 ppm (C-3, 13C
NMR) testify to phthalide form of compound 4. This is in
accord with the fact that in a solution and in the solid state 2-
acetylbenzoic acid exists in the phthalide form [14,15].
Assignment of signals in the 19F NMR spectrum of
complex 2c (signals were not well resolved) was made by
3. Experimental
IR spectra were taken on a Bruker Vector 22 IR
spectrophotometer. UV spectra were measured on a Hewlett
Scheme 5.

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Y.V. Zonov et al. / Journal of Fluorine Chemistry 126 (2005) 437–443
Scheme 6.
organic and inorganic products (from ether extract). By
sublimation of the latter at 70–75 8C (15 Torr, then
2 Torr) a mixture (0.2 g), containing 73% of indanone 2
and 27% of indandione 3 (GLC), was isolated.
2. Analogously to the previous procedure, the reaction of
indan 1 (3.64 g), SiO2 (0.64 g) and SbF5 (3.97 g) (molar
ratio, 1:0.88:1.5) gave (70 8C, 13 h) 2.64 g (yield 78%) of
indanone 2 (from CH2Cl2 extract) and 0.32 g of
indandione 3 (from ether extract).
analogy with that for 1-chlorooctafluoroindan-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 complex 2c
down-field DdF resemble those of 1-chlorooctafluoroindan-
1-yl cation [16], a smaller scale of DdF can be due to a less
positive charge transfer onto ring.
3. Analogously to procedure (1), the reaction of indan 1
(3.58 g), SiO2 (0.63 g) and SbF5 (1.2 g) (molar ratio,
1:0.88:0.5) gave (70 8C, 4 h) 2.8 g of a mixture
containing 39% (yield 33%) of 2 and 59% (46%) of
indan 1.
4. Analogously to procedure (1), the reaction of indan 1
(16.62 g), SiO2 (1.17 g) and SbF5 (24.18 g) (molar ratio,
1:0.51:2) gave (70 8C, 9 h) 13.12 g (yield 85%) of
indanone 2.
3.1. Reaction of perfluoroindan (1) with SiO2/SbF5
at 70 8C
1. A mixture of 3.37 g of compound 1, 0.6 g of SiO2 and
3.68 g of SbF5 (molar ratio, 1:0.88:1.5) was stirred at
70 8C for 5 h. The mixture was poured into 5%
hydrochloric acid (0–5 8C) and extracted with CH2Cl2
and then with ether. The extracts were dried over MgSO4.
The solvents were distilled off to give 2.51 g (yield 80%)
of indanone 2 (from CH2Cl2 extract) and 0.41 g of
5. A mixture of compound 1 (1.42 g), SiO2 (0.46 g) and
SbF5 (3.25 g) (molar ratio, 1:1.54:3) was stirred at
Scheme 7.

Y.V. Zonov et al. / Journal of Fluorine Chemistry 126 (2005) 437–443
441
70–75 8C for 4.5 h. The mixture was poured into 5%
hydrochloric acid (0–5 8C) and extracted with ether. The
solvent was distilled off to give 1.08 g of product,
containing compounds 2, 3 and 4 in the ratio 38:43:19
(19F NMR), yield 31, 34 and 15%, respectively.
2. Analogously to the previous procedure, a mixture of
indan 1 (1.46 g), SiO2 (0.33 g) and SbF5 (3.19 g) (molar
ratio, 1:1.1:3) was heated at 85 8C (2 h) and then at
130 8C (3 h). The mixture was treated with 5%
hydrochloric acid (0–5 8C), extracted with ether and
dried over MgSO4. The ether solution contained
compounds 4, 5 and 6 in the ratio 42:52:6 (19F NMR).
An amount of 5 ml of 5% hydrochloric acid was added
into the solution and the mixture was stirred at room
temperature for 10 h. The ether solution was dried over
MgSO4. The solvent was distilled off to give 1.3 g of
product containing compounds 4 and 6 in the ratio 94:6
(19F NMR).
3.2. Reaction of perfluoroindan (1) with
SiO2/SbF5 at 130 and 180 8C
1. A mixture of compound 1 (2.48 g), SiO2 (0.55 g) and
SbF5 (5.42 g) (molar ratio, 1:1.1:3) was stirred at 90 8C
for 0.5 h. Then for 0.5 h the temperature of the bath was
raised to 130 8C, and the mixture was kept at this
temperature for 2 h. The mixture was poured into 5%
hydrochloric acid (0–5 8C) and extracted with CH2Cl2
and then with ether. The extracts were dried over
MgSO4. The ether was distilled off and the residue was
sublimed to give 0.11 g of a mixture of compounds 3, 4
and 6 in the ratio 9:24:67 (19F NMR). The CH2Cl2
extract, contained phthalides 4 and 5 in the ratio 27:73
(19F NMR), was washed with aqueous solution of
NaHCO3 and dried over MgSO4. The solvent was
distilled off to give 1.39 g (yield 57%) of compound 5,
which was additionally purified by short-path distilla-
tion (80 8C, 40 Torr). The aqueous solution was
acidified with HCl, extracted with CH2Cl2 and dried
over MgSO4. The solvent was distilled off to give 0.48 g
(yield 20%) of compound 4, which was sublimed
(130 8C, 20 Torr).
3. A mixture of indan 1 (1.19 g), SiO2 (0.53 g) and SbF5
(2.6 g) (molar ratio, 1:2.2:3) was heated at 85 8C (2 h).
Then for 4 h a temperature was raised to 180 8C, and the
mixture was kept at this temperature for 3 h. The mixture
was treated with 5% hydrochloric acid (0–5 8C),
extracted with ether and dried over MgSO4. The solvent
was distilled off to give after sublimation (130 8C, 1 Torr)
0.8 g of product containing compounds 4 and 6 in the
ratio 8:92 (19F NMR).
3.3. Reaction of perfluoroindan (1) with glass in
the presence of SbF5 at 130 8C
A mixture of compound 1 (1.03 g) and SbF5 (3.0 g)
(molar ratio, 1:4) in a sealed ampoule was heated at 130–
135 8C for 35 h. The mixture was treated with 5%
hydrochloric acid (0–5 8C), stirred at 30 8C for 3 h and
extracted with CH2Cl2. The extract was washed with
aqueous solution of NaHCO3 and dried over MgSO4. The
solvent was distilled off to give 0.36 g of a mixture of
compounds 1, 5 and 9a in the molar ratio 34:34:32 (19F
NMR). The mixture was spontaneously evaporated in the air
to dryness to give 0.18 g (yield 17%) of compound 9a. The
aqueous solution was acidified with HCl, extracted with
CH2Cl2 and dried over MgSO4. The solvent was distilled off
to give 0.48 g of a mixture of compounds 4 and 9 in the ratio
10:90 (19F NMR). The yield of acid 9 is 41%. Analytical
samples of compounds 9 and 9a were prepared by
sublimation (80 8C, 1 Torr) and (110 8C, 3 Torr), respec-
tively, and then crystallization.
3-Hydroxy-perfluoro-3-methylphthalide (4): mp 99–
100 8C (benzene–hexane). UV (C2H5OH) lmax, nm (lg
e): 228 (3.91), 278 (3.30). IR (CCl4) n, cmꢀ1: 3549, 3382
(OH); 1826, 1796 (C=O); 1521, 1506 [fluorinated
1
aromatic ring (FAR)]. H NMR (200 MHz, CDCl3): d
4.71 (s, OH). 13C NMR (100.6 MHz, CDCl3): d 160.8 (s,
1
C-1), 146.1 (dt, JCF = 267 Hz, JCF = 14 Hz) and 143.5
2
1
(dt, JCF = 263 Hz, JCF = 14 Hz, C-5 and C-6), 144.5
2
1
(dd, JCF = 267 Hz, JCF = 13 Hz) and 142.9 (dd,
2
2
1JCF = 264 Hz, JCF = 13 Hz, C-4 and C-7), 123.4 (d,
2
2JCF = 14 Hz) and 110.8 (d JCF = 12 Hz, C-3a and
1
C-7a), 120.6 (q, JCF = 286 Hz, CF3), 99.3 (q,
2JCF = 37 Hz, C-3). 19F NMR (188.3 MHz, CDCl3): d
79.7 (3F, CF3), 26.8 (1F, F-7), 26.3 (1F, F-4), 23.1 (1F,
F-5), 17.0 (1F, F-6); JCF -Fð4Þ = 13 Hz, J4,5 = 20 Hz,
Perfluoro-2-ethylbenzoic acid (9): mp 83.5–84.5 8C
(hexane). UV (C2H5OH) lmax, nm (lg e): 271 (3.34). IR
(CCl4) n, cmꢀ1: 3502, 3080 (OH); 1774, 1733 (C=O); 1528,
F
NMR (188.3 MHz, CCl4): d 77.6 (3F, CF3), 53.0 (2F, CF2),
3
J
J
4,6 = 7 Hz, J4,7 = 20 Hz, J5,6 = 18 Hz, J5,7 = 11 Hz,
6,7 = 20 Hz. Anal. Calcd. for C9HF7O3: C, 37.3; H,
1482 (FAR). 1H NMR (200 MHz, CCl4): d 11.14 (s, OH). 19
0.3; F, 45.8%. Found: C, 37.3; H, 0.3; F, 45.9%.
Perfluoro-3-methylphthalide (5): liquid. UV (hexane)
l
max, nm (lg e): 230 (3.96), 282 (3.45). IR (CCl4) n,
29.3 (1F, F-3), 23.8 (1F, F-6), 16.8 (1F, F-5), 12.9 (1F, F-4);
J
cmꢀ1: 1844 (C=O); 1522, 1508 (FAR). 19F NMR
(188.3 MHz, CCl4): d 79.7 (3F, CF3), 36.6 (1F, F-3),
28.9 (1F, F-7), 28.3 (1F, F-4), 23.7 (1F, F-5), 19.3 (1F, F-
JCF ꢀCF = 2 Hz,
J
CF ꢀFð3Þ = 15 Hz,
CF -Fð3Þ = 22 Hz,
3
2
3
2
J3,4 = 21 Hz, J3,5 = 10 Hz, J3,6 = 11 Hz, J4,5 = 20 Hz,
4,6 = 6 Hz, J5,6 = 22 Hz. HRMS m/z, 311.9833 (M+). Calcd.
for C9HF9O2 = 311.9829.
J
6);
J
CF ꢀFð3Þ = 5 Hz, JCF -Fð4Þ = 15 Hz, J3,4 = 3 Hz,
3
3
J
J
3,6 = 3 Hz, J4,5 = 20 Hz, J4,6 = 8 Hz, J4,7 = 19 Hz,
5,6 = 17 Hz, J5,7 = 11 Hz, J6,7 = 20 Hz. HRMS m/z,
Perfluoro-2-ethylbenzoic anhydride (9a): mp 86.5–
87.5 8C (hexane). UV (hexane) lmax, nm (lg e): 271
(3.40). IR (CCl4) n, cmꢀ1: 1845, 1796 (C=O); 1528, 1481
291.9771 (M+). Calcd. for C9F8O2 = 291.9771.

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Y.V. Zonov et al. / Journal of Fluorine Chemistry 126 (2005) 437–443
(FAR). 19F NMR (188.3 MHz, CCl4): d 77.5 (3F, CF3), 53.2
(2F, CF2), 30.1 (1F, F-3), 24.3 (1F, F-6), 17.5 (1F, F-5), 14.7
The solvent was distilled off to give 0.13 g (yield 72%) of
indanone 2.
(1F, F-4); JCF ꢀCF = 2 Hz, JCF -Fð3Þ = 15 Hz, JCF -Fð3Þ
=
3
2
3
2
3.7. Reaction of perfluoro-1,1-diethylindan (14) with
SiO2/SbF5
21 Hz, J3,4 = 21 Hz, J3,5 = 10 Hz, J3,6 = 11 Hz, J4,5 = 20 Hz,
4,6 = 6 Hz, J5,6 = 21 Hz. HRMS m/z, 605.9560 (M+). Calcd.
for C18F18O3 = 605.9564.
J
A mixture of 2.73 g of compound 14, 0.2 g of SiO2 and
3.56 g of SbF5 (molar ratio, 1:0.61:3) was stirred at 130–
135 8C for 3 h. The mixture was poured into 5%
hydrochloric acid (0–5 8C) and extracted with CH2Cl2.
The extract was dried over MgSO4. The solvent was distilled
off to give 2.54 g (yield 97%) of ketone 13.
Perfluoro-3,3-diethylindan-1-one (13): bp 58 8C (3 torr).
UV (hexane) lmax, nm (lg e): 253 (4.10), 289 (3.46), 294
(3.46). IR (CCl4) n, cmꢀ1: 1781 (C=O); 1513 (FAR). 19F
NMR (188.3 MHz, CH2Cl2): d 85.7 (6F, m, 2CF3), 58.3 (4F,
m, 2CF2), 50.7 (2F, m, F-2), 35.8 (1F, m, F-4), 30.2 (1F, F-7),
27.6 (1F, F-5); 19.0 (1F, F-6); J4,5 = 19 Hz, J4,6 = 10 Hz,
3.4. Reaction of perfluoroindan-1,3-dione (3) with SbF5
A mixture of compound 3 (0.6 g) and SbF5 (1.53 g)
(molar ratio, 1:3) in a sealed ampoule was heated at 130 8C
for 2 h. The mixture was treated with 5% hydrochloric acid
(0–5 8C), extracted with CH2Cl2 and then with ether. The
extracts were dried over MgSO4. The solvents were distilled
off to give 0.62 g (yield 90%) of a mixture of phthalides 4
and 5 in the ratio 20:80 (19F NMR) from CH2Cl2 extract, and
0.02 g of the acid 6 from ether extract.
J
4,7 = 16 Hz, J5,6 = 19 Hz, J5,7 = 13 Hz, J6,7 = 21 Hz.
3.5. Reaction of perfluoroindan-1-one (2) with SbF5
HRMS m/z, 475.9742 (M+). Calcd. for C13F16O = 475.9694.
1. A mixture of compound 2 (0.94 g) and SbF5 (2.22 g)
(molar ratio, 1:3) in a sealed ampoule was heated at
130 8C for 3 h. The mixture was poured into 5%
hydrochloric acid (0–5 8C), extracted with CH2Cl2.
The extract was dried over MgSO4. The solvent was
distilled off to give 0.88 g of a mixture, containing (19F
NMR) 31% (yield 27%) of 1, 19% (17%) of 2, 12%
(10%) of 4, 19% (17%) of 5, 19% (16%) of 9.
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2. To a mixture of indan 1 (1.22 g, 4.09 mmol) and SbF5
(2.12 g, 9.78 mmol) stirred at 130 8C, ketone 2 (0.67 g,
2.44 mmol) was added for 1 h. Then indan 1 (0.3 g,
1.01 mmol) was added to the mixture and the latter was
stirred at 130 8C for 2.5 h. The mixture was poured into
5% hydrochloric acid (0–5 8C) and extracted with
CH2Cl2. The extract was dried over MgSO4. The solvent
was distilled off to give 2.13 g of a mixture, containing
(19F NMR) 66% of 1, 1% of 2, 3% (yield 10%) of 4, 4%
(11%) of 5, 26% (74%) of 9.
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