A novel approach to fluoro-containing alkenes

Article abstract of DOI:10.1016/S0040-4020(01)00701-3

A new and general one-pot transformation of aromatic aldehydes to fluorinated olefins containing -CH=C(Cl)CF₃ or -CH=C(F)CClF₂ moieties is described. Freons CCl₃CF₃ and CCl₂FCClF₂ were used as trifluoromethyl and difluoromethyl C₂-building blocks respectively. A proposed mechanism for the reaction is discussed.

Full text of DOI:10.1016/S0040-4020(01)00701-3

TETRAHEDRON
Pergamon
Tetrahedron 57 22001) 7519±7527
A novel approach to ¯uoro-containing alkenes
Vasily N. Korotchenko,a Alexey V. Shastin,b Valentine G. Nenajdenkoa,p
and Elisabeth S. Balenkovaa
aDepartment of Chemistry, Moscow State University, Leninskie Gory, Moscow 119899, Russia
bInstitute of Problems of Chemical Physics, Chernogolovka, Moscow region, 142432, Russia
Received 12 March 2001; revised 1 June 2001; accepted 28 June 2001
AbstractÐA new and general one-pot transformation of aromatic aldehydes to ¯uorinated ole®ns containing ±CHvC2Cl)CF3 or
±CHvC2F)CClF2 moieties is described. Freons CCl3CF3 and CCl2FCClF2 were used as tri¯uoromethyl and di¯uoromethyl C2-building
blocks respectively. A proposed mechanism for the reaction is discussed. q 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
coupling of freon-113a with aldehydes14 An organomercury
reagent also was suggested for the synthesis of such
alkenes.15
Fluorine-containing drugs and pesticides have achieved an
increasing interest in modern bioorganic chemistry due their
remarkable biological activity.1 Pharmaceutical and agri-
cultural chemicals that contain di- and tri¯uoromethyl
groups have been the subject of increased research activity
in recent years. Extensive studies have been made to
develop a cheaper and more ef®cient synthetic methodology
for the introduction of the tri¯uoromethyl and di¯uoro-
methyl group into various organic compounds. Usage of
new reagents and improved techniques for the selective
introduction of ¯uorine has become a major target in ¯uoro-
organic chemistry.
Recently we have elaborated a novel synthesis of 1,1-
dichlorostyrenes from benzaldehydes using a non-Wittig
approach. The method is based on a new catalytic redox
reaction between N-unsubstituted hydrazones and carbon
tetrachloride in the presence of copper2I) chloride and
aqueous ammonia, leading to the formation of the
carbon±carbon double bond.16,17 We also developed a
one-pot technique for the transformation of aldehydes into
the corresponding dichloroalkenes via hydrazones formed
in situ.18 The target dichlorostyrenes were obtained in high
yields.
Synthetic pyrethroids containing the CHvC2Cl)CF3 moiety
were found the highly important.2,3 Compounds containing
this group are also widely used as synthetic precursors of
tri¯uoromethylacetylenes in the synthesis of heterocycles
bearing tri¯uoromethyl group.4,5 1,1,1-Trihalo-2,2,2-tri-
¯uoroethanes are usually employed as a tri¯uoromethyl
C2-synthon for the preparation of such alkenes due to
their commercial availability. The classical route to
2-chloro-3,3,3-tri¯uoroprop-1-enylbenzenes is the reduc-
tive coupling of 1,1,1-trichloro-2,2,2-tri¯uoromethane
2freon-113a) or CHClBrCF3 2halothane)6 with aldehydes.
As a rule, literature approaches for the introduction of C-2
¯uorinated fragments are based on the use of either phos-
phorus chemistry 2Wittig approach)7 or organometallic
chemistry 2demands equivalent quantities of metal reduc-
tants)2,3,8±13 or on the combination of these two methods.
Alternative procedures include the electroreductive
We propose that founded reaction has general signi®cance
and may be used for the preparation of various types of
alkenes. An analogous approach can be applied to the syn-
thesis of 3-chloro-2,3,3-tri¯uoroprop-1-enylbenzenes 1 and
2-chloro-3,3,3-tri¯uoroprop-1-enylbenzenes 2 in the case of
chloro¯uorocarbons CFC-113 and CFC-113a 2Scheme 1).
Now we report the results of our investigations on the use of
CFC-113 and CFC-113a as di¯uoromethyl- and tri¯uoro-
methyl-containing C2-building blocks for the preparation
of ¯uorinated alkenes from aromatic aldehydes.
2. Results and discussion
2.1. Optimization of the reaction conditions
We started our investigation with the reaction between the
hydrazone of p-nitrobenzaldehyde and freon-113. This
hydrazone was chosen as a representative substrate due to
its stability. Previously we had found optimal conditions for
the reaction between CCl4 and hydrazones 2DMSO as
Keywords: catalysis; copper salts; ¯uoroalkenes; aromatic aldehydes;
freons.
Corresponding author. Tel.: 17-095-939-2276; fax: 17-095-932-8846;
e-mail: nen@acylium.chem.msu.ru
p
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020201)00701-3

7520
V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
copper salt, base and solvent molecules plays a signi®cant
role in the catalytic activity. A variety of bases such as
amines, diamines, aminoalcohols, aminoacids, pyridines,
potassium carbonate in some polar solvents: ethanol, aceto-
nitrile, DMSO, DMF were tested. In most cases no reaction
occurred and only traces of 1a were obtained. The maxi-
mum yield of 1a 239%) was obtained when the reaction was
carried out in ethanol using 1,2-ethylenediamine as base.
Previously we elaborated the one-pot technique for the
synthesis of dichlorostyrenes without isolation of hydra-
zones.18 It was found that yields of alkenes in general
were better than those in sequential two-stage procedures.
This approach was applied to the ¯uorinated alkene 1a and
the yield of 1a was increased up to 63% by the one-pot
technique.
Scheme 1. a: Cu2Cl2, CCl2F-CClF2 2CFC-113); b: Cu2Cl2, CCl3-CF3 2CFC-
113a).
solvent, CuCl 10 mol% as catalyst and aqueous ammonia as
base).17 However, using these conditions, only traces of the
desired ¯uorinated alkene 1a were obtained. In our opinion,
this difference can be explained by the lower oxidizing
ability of freon-113 in comparison with CCl4. We have
suggested that the main factors affecting the yield of the
target product are the nature of the solvent and base used.
We proposed that the formation of a complexes between the
Having found the optimal reaction conditions, we tried to
study the scope and limitations of the technique. A wide
range of aromatic aldehydes was converted to the corre-
Table 1. Synthesis of ¯uorinated alkenes
Ar
Yield 2%)
Z/E ratioa
Yield 2%)
Z/E ratiob
4-O2NC6H4, a
3-O2NC6H4, b
4-ClC6H4, c
3-ClC6H4, d
4-CH3OC6H4, e
4-BrC6H4, f
63
43
46
48
49
55
39
35
66
36
33
24
19
48
±
6/1
4/1
10/1
11/1
19/1
6/1
13/1
6/1
16/1
13/1
4/1
67
57
73
57
56
63
27
61
72
34
32
40
24
47
31
22
Trace
±
7/1
3/1
3/1
4/1
10/1
6/1
6/1
3/1
6/1
4/1
3/1
4/1
2/1d
10/0
10/0
6/1
±
C6H5, g
4-NCC6H4, h
4-CH3C6H4, i
4-FC6H4, j
2-FC6H4, k
2-ClC6H4, l
Terephthalaldehyde, m
1-Naphthyl, n
4-Me2NC6H4, o
2-CH3OC6H4, p
2-CF3C6H4
7/1
86/13/1c
10/0
±
±
±
±
±
±
±
2,6-Cl2C6H3
±
a
3
The structure of isomers was established by comparison of JH±F 2Jtrans<34 Hz.Jcis<20 Hz).
The structure of isomers was determined according by Fujita8±10 and Dmowski.19,20
Mixture of 2Z,Z), 2Z,E) and 2E,E) isomers.
b
c
d
Mixture of 2Z,Z) and 2Z,E) isomers.
Scheme 2. a: Cu2Cl2, CCl2F-CClF2 2CFC-113); b: Cu2Cl2, CCl3-CF3 2CFC-113a).
Table 2.
Aldehyde
Yield 2%)
Azine
Fluoroalkene 1
Total
Azine
Fluoroalkene 2
Total
4-O2NC6H4
4-CH3C6H4
4-Me2NC6H4
32
27
92
63
66
0
95
93
92
25
24
65
67
72
31
92
96
96

V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
7521
Scheme 3.
Scheme 4.
sponding 3-chloro-2,3,3-tri¯uoroprop-1-enylbenzenes
1
the sym-azine 2outside cycle).28 The step of copper20) oxi-
dation complete the outside catalytic cycle. These two
reactions 2and two cycles of copper transformation) are
competitive. Previously we studied the reaction of p-nitro-
phenyldiazomethane with CCl4 and observed the formation
of the corresponding alkene and sym-aldazine.17 Also we
showed that hydrazones dissolved in DMSO rapidly reacted
with an equimolar quantity of CuCl2 in the presence of
aqueous ammonia. The corresponding sym-azines were
isolated in nearly quantitative yield 2.94%).
and 2-chloro-3,3,3-tri¯uoroprop-1-enylbenzenes 2 bearing
various substituents in the aromatic ring. In most cases the
reaction proceeded smoothly to give the target products in
good yield 2Table 1).
2.2. Reaction mechanism
The synthesis of ¯uorinated alkenes 1 and 2 is accompanied
by slow nitrogen evolution and formation of sym-azines of
the aldehydes as by-products 2Scheme 2). The total yield of
dichlorostyrenes and azines is nearly quantitative 2Table 2).
According to Schemes 3 and 4 freons CCl3CF3 and
CCl2FCClF2 can also be converted to the corresponding
partially reduced freons CHCl2CF3 and CHClFCClF2,
formed as a result of two single electron transfer 2SET)
steps. Previously in the reaction of hydrazones with CCl4
we have detected chloroform as the result of similar reduc-
tion of CCl4 in the reaction media.17
Recently we have proposed a mechanism of similar reac-
tions of hydrazones with carbon tetrachloride. This mecha-
nism and the formation of some key intermediates have
been con®rmed experimentally.18 We believe that the reac-
tion with freons proceeds in a similar manner which can also
explain the formation of products obtained 2alkenes and
azines) from the corresponding hydrazones. The postulated
key intermediate of the reaction of hydrazones with poly-
halogenoalkanes is a copper±carbenoid complex I 2Scheme
3).21±27
We calculated the results of two consistent single electron
transfer on CCl3CF3 and CCl2FCClF2 and predicted the
formation of two possible isomeric radicals C2Cl2F3 2I and
II) and corresponding hydro¯uorocarbons CClHFCClF2 and
²
CCl2FCHF2 in the reaction with CFC-113 2Scheme 4).
Radical I is more stable than radical II 2DHformˆ5.6 kcal/
mol). The chromato-mass-spectra of the reaction mixture
con®rmed the formation of CClHFCClF2 and CCl2FCHF2
from CFC-113.29 These data supported the proposed
reaction mechanism.
The ®rst step of the catalytic cycle is the reaction of
copper2II) with hydrazone to give the corresponding
diazoalkane and two molecules of acid ®xed by the base.
The next step is the formation of a copper-carbene complex
I. The reaction is accompanied by the evolution of one
molecule of nitrogen. The complex I reacts with freon to
give the target ¯uorinated alkene and to regenerate the
catalyst 2inside cycle). Another type of carbenoid complex
I transformation is their reaction with diazoalkane to form
²
DFT technique 2TAINA program, D. N. Laikov, Moscow State
University), PBE 96 functional and the basis of triple-zeta quality.

7522
V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
in the reaction with CCl3CF3 abnormal products 10 are not
obtained.
The reaction is very sensitive to steric hindrance. We found
that the yields of alkenes 1 and 2 are generally lower in
the case of aldehydes bearing substituents in the ortho-
positions. Some ortho-substituted aldehydes do not give
the target alkenes in this reaction 2Table 1). Thus, alkene
2p was isolated in only 22% yield in the reaction with
CCl3CF3 however no product was obtained in the reaction
with CCl2FCClF2, probably because the CClF2 group is
more bulky than the CF3 moiety.
Scheme 5.
The reaction proceeds stereoselectively and the Z-isomers
are formed preferentially 2Table 1). We found that the Z/E
ratio depends on the electronic nature and position of sub-
stituents in the aromatic ring. The steric hindrance of the
polyhalogenoalkane also affects the stereoselectivity.
Generally, the reaction proceeds more stereoselectively in
the case of CCl2FCClF2 and for electron rich aldehydes.
These data supported the mechanism of reaction. The
copper atom in the proposed key intermediate of the
reaction 2the copper±carbenoid complex I) may also be
coordinated with the p-orbitals of the aromatic ring. In
the case of electron-donating substituents such interaction
is more effective and one side of the intermediate is less
accessible for the attack by freon. For example, in the case
of the reaction of 4-dimethylaminobenzaldehyde having a
strongly electron-donating substituent and 1-naphthyl-
carbaldehyde only the Z-alkenes were obtained. Possible
transition states are given on Scheme 6.
Scheme 6.
More detailed investigation of the reaction mixture by 19F
NMR and chromato-mass-spectrometry showed that in
the reaction with CCl2FCClF2 traces of the Z-isomer of
abnormal products 10 are also formed 2,2% by 19F NM R)
2Scheme 5). We assume that these compounds are formed as
a result of SET on radical II and subsequent loss of ¯uorid
ion, just as normal products 1 were formed as a result of
SET on radical I and subsequent loss of chlorid ion. The
ratio of 1 and 10 alkenes are corresponded the relative
stability of radicals I and II. In the case of reaction of
CCl2FCClF2 with 1-naphthylcarbaldehyde we observed
about 7% of the abnormal product 2by 19F NMR), whereas
1
The H and 19F chemical shifts and coupling constants for
Table 3. 1H, 19F chemical shifts, 1H±19F and 19F±19F coupling constants 2Hz) for 3-chloro-2,3,3-tri¯uoroprop-1-enylbenzenes
Aryl
1H Chemical shiftsa
H1 in Z H1 in E
19F Chemical shiftsb
Z Isomer of 1 E Isomer of 1
Coupling constantsb
Z Isomer of 1 E Isomer of 1
H±F2 F2±F3 H±F2 F2±F3
F2
F3
F2
F3
4-O2NC6H4
3-O2NC6H4
4-ClC6H4
3-ClC6H4
4-CH3OC6H4
4-BrC6H4
C6H5
6.42
6.68
2124.93
2126.18
2128.97
2127.47
2132.70
2128.33
2129.65
2124.95
2130.72
2130.90
2128.05
2129.32
2127.59f
2129.79
262.40
262.40
261.92
261.92
260.99
261.65
261.35
262.25
261.18
261.73
261.88
261.44
261.81f
261.12
2118.65
2119.43
2121.55
2122.82
2124.02
2121.00
2122.42
2118.84
2123.16
2122.32
2119.47
2120.53
2120.93g
±
258.62
258.67
258.52
258.35
258.12
258.24
257.98
258.54
258.02
258.41
259.55
258.30
258.38g
±
33.75
33.60
34.8
14.65
16.50
17.87
16.50
16.49
16.50
16.50
16.50
16.50
16.50
16.50
16.50
16.50f
16.50
19.37
19.20
20.85
20.08
21.62
20.32
21.06
19.83
21.06
20.57
19.82
19.33
20.57
±
14.65
13.75
13.75
13.80
13.75
13.75
13.75
13.75
13.75
13.75
13.75
13.75
13.75g
±
6.46
6.32
6.19
6.19
6.19
6.17
6.31
6.22
6.23
6.56
6.69
6.20f
6.99
6.73
6.64
6.52
6.54
6.48
6.50
6.60
6.56
6.55
6.52
6.55
6.52g
±
34.45
35.65
34.69
35.19
33.96
35.69
34.94
35.20
34.20
34.70
32.71
4-NCC6H4
4-CH3C6H4
4-FC6H4
c
d
2-FC6H4
2-ClC6H4
Terephthal aldehydee
1-Naphthyl
a
1H NMR 2376.29 MHz, CDCl3).
b
c
d
e
f
19F NMR 2376.29 MHz, CDCl3/CFCl3int).
Also were obtained signals of ¯uorine in ring with shift 2112.78 2Z) and 2115.04 2E).
Also were obtained signals of ¯uorine in ring with shift 2117.93 2Z) and 2119.47 2E).
Obtained as mixture of 2Z,Z), 2Z,E) and 2E,E) isomers 86/13/1 by 19F NMR spectra.
In 2Z,Z) isomer of 1m.
g
In 2Z,E) isomer of 1m.

V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
7523
Figure 1. Dependence of chemical shifts of F22) from Hammett constants.
Figure 2. Dependence of chemical shifts of F23) in Z-isomer of 1 from Hammett constants.
the ¯uoro-alkenes 1a±n are given in Table 3. The spectrum
of the four-spin system CHvCF2CClF2) comprising the
substituents on the ethylenic bond in 1 was interpreted as
AMX2. The identi®cation of the hydrogen atoms in the two
isomers was established on the basin of the values of their
coupling constants with the vinylic ¯uorine,30±32 thus the
3
trans relationship giving rise to the larger coupling JH±F
of approximately 34 Hz 2Fig. 3), while the cis coupling
3JH±F was approximately 20 Hz 2Fig. 4).
The chemical shifts of the vinylic and allylic ¯uorine and
coupling constants JH±F showed linear correlations with
3
Hammett substituent parameters for the para-substituents
when the s values were used 2Figs. 1±4). A less satisfactory
relationship was observed for E-isomers of alkenes 1 than
that for Z-isomers.
Figure 3. Coupling constants H±F2 in Z-isomer of 1.
Figure 4. Coupling constants H±F2 in E-isomer of 1.

7524
V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
3. Conclusion
NMR 2CDCl3) d 107.57, 120.01 2Jˆ288.4, 41.2 Hz),
123.73, 130.29 2Jˆ7.6, 3.1 Hz), 135.91, 147.68
2Jˆ3.1 Hz), 149.93 2Jˆ271.6, 32.1 Hz). MS 2EI, 70 eV);
m/z 2%): 251 263) [M1], 216 259) [M12Cl], 170 2100)
[M12Cl±NO2], 169 2100) [M12Cl±H±NO2].
A new general stereoselective synthesis of 3-chloro-2,3,3-
tri¯uoroprop-1-enylbenzenes and 2-chloro-3,3,3-tri¯uoro-
prop-1-enylbenzenes has been developed. The target
alkenes were prepared in good yield, from readily available
and inexpensive starting materials in a simple one-pot
procedure. The present approach proves to be a versatile
and advantageous alternative to classical routes to the
2-chloro-3,3,3-tri¯uoroprop-1-enylbenzenes.
4.2.2. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]-3-nitro-
benzene 1b. The title compound was obtained as a 4:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.25. IR 2Nujol) 2n, cm21
)
1710 2CvC), 1540 2NO2). C9H5ClF3NO2 2251.6): calcd C
42.97, H 2.00, found C 43.00, H 2.16. Major isomer 1b: 1H
NMR 2CDCl3) d 6.46 2d, Jˆ33.6 Hz, 1H), 7.63 2dd, Jˆ7.8,
7.8 Hz, 1H), 7.91 2d, Jˆ7.8 Hz, 1H), 8.22 2d, Jˆ7.8 Hz,
1H), 8.43 2s, 1H). 13C NMR 2CDCl3) d 107.53 2Jˆ7.6,
4.6 Hz), 120.2 2Jˆ285, 42 Hz), 124.04 2Jˆ2 Hz), 124.27
2Jˆ7.7 Hz), 129.93, 135.17 2Jˆ7.7 Hz), 135.48, 148.5,
149.85 2Jˆ262, 30 Hz).
4. Experimental
4.1. General
Melting points were determined in sealed capillaries and
are uncorrected. NMR spectra were recorded on a Varian
VXR-400 and Bruker AM400C spectrometers in CDCl 3 or
DMSO-d6 with TMS as an internal standard. The IR spectra
were obtained with UR-20 spectrometer. Column chroma-
tography was performed on silica gel 263±200 mesh,
Merck). Mass-spectra were recorded on a HP5890 mass
spectrometer with the 5989x-G detector.
4.2.3. 1-Chloro-4-[3-chloro-2,3,3-tri¯uoro-1-propenyl]-
benzene 1c. The title compound was obtained as a 10:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.55. IR 2Nujol) 2n, cm21
)
1710 2CvC). C9H5Cl2F3 2241.0): calcd C 44.85, H 2.09,
found C 44.84, H 2.21. Major isomer 1c: 1H NM R
2CDCl3) d 6.32 2d, Jˆ34.8 Hz, 1H), 7.23 2d, Jˆ8.7 Hz,
2H), 7.39 2d, Jˆ8.7 Hz, 2H). 13C NMR 2CDCl3) d 108.39
2Jˆ7.6, 3.7 Hz), 124.27 2Jˆ286.4, 41.3 Hz), 128.25
2Jˆ3.7 Hz), 129.12, 130.90 2Jˆ7.6 Hz), 135.49
2Jˆ3.7 Hz), 148.44 2Jˆ262, 30 Hz). MS 2EI, 70 eV); m/z
2%): 240 238) [M1], 205 2100) [M12Cl], 185 288)
[M12Cl±HF], 169 243) [M122Cl].
4.2. General procedure for 3-chloro-2,3,3-tri¯uoroprop-
1-enylbenzenes
A solution of aromatic aldehyde 210 mmol) in EtOH
250 mL) was added dropwise to a solution of 100%
N2H4´H2O 210 mmol, 0.49 mL) in EtOH 250 mL) and the
mixture was stirred until aldehyde disappeared 2TLC
monitoring). Then freshly puri®ed copper2I) chloride
21 mmol, 100 mg) and ethylenediamine 23.4 mL) were
added. After 10 min 1,1,2-trichloro-1,2,2-tri¯uoroethane
26 mL) was added dropwise at 208C. The reaction mixture
was stirred for 24 h, EtOH was evaporated in vacuo and
residue was quenched with hydrochloric acid 25%)
2300 mL) and extracted with CH2Cl2 23£50 mL). The
extracts were dried over sodium sulfate, dichloromethane
was evaporated in vacuo and the residue was puri®ed by
column chromatography 2hexane). E- and Z-isomeric
mixture of alkenes 1 and 2 could not be separated by column
chromatography.
4.2.4. 1-Chloro-3-[3-chloro-2,3,3-tri¯uoro-1-propenyl]-
benzene 1d. The title compound was obtained as a 11:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.50. IR 2Nujol) 2n, cm21
)
1700 2CvC). C9H5Cl2F3 2241.0): calcd C 44.85, H 2.09,
found C 44.84, H 2.56. Major isomer 1d: 1H NM R
2CDCl3) d 6.19 2d, Jˆ34.5 Hz, 1H), 7.22±7.26 2m, 2H),
7.33 2dt, Jˆ6.7, 1.7 Hz, 1H), 7.47 2s, 1H). 13C NM R
2CDCl3) d 108.30 2Jˆ7.6, 4.6 Hz), 120.42 2Jˆ288.4,
41.2 Hz), 127.78 2Jˆ6.1 Hz), 129.50, 129.57, 130.03,
131.45 2Jˆ 3.1 Hz), 134.84, 148.91 2Jˆ270.1, 32.0 Hz).
4.2.5. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]-4-methoxy
benzene 1e. The title compound was obtained as a 19:1
2-Chloro-3,3,3-tri¯uoroprop-1-enylbenzenes were similarly
prepared using 1,1,1-trichloro-2,2,2-tri¯uoroethane.
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.35. IR 2Nujol) 2n, cm21
)
1
All new compounds gave satisfactory 400 MHz H and
100 MHz 13C NMR and IR spectral data. 19F and selected
1H NMR data for minor isomers 1a±n are reported in Table
3. Most signals of the minor isomers of 1 and 2 usually
overlapped with the signals of major isomers. Physical
data for compounds 1a±n and 2a±p are as follows.
1700 2CvC). C10H8ClF3O 2236.6): calcd C 50.76, H 3.41,
found C 50.64, H 3.60. Major isomer 1e: 1H NMR 2CDCl3)
d 3.76 2s, 3H), 6.19 2d, Jˆ35.7 Hz, 1H), 6.84 2d, Jˆ8.7 Hz,
2H), 7.44 2d, Jˆ8.7 Hz, 2H). 13C NMR 2CDCl3) d 55.23,
109.18 2Jˆ7.6, 4.6 Hz), 114.28, 120.93 2Jˆ288.4, 41.2 Hz),
122.402Jˆ3.1 Hz), 131.332Jˆ7.6 Hz), 146.83 2Jˆ264.0,
32.0 Hz), 160.48 2Jˆ3.1 Hz). MS 2EI, 70 eV); m/z 2%):
236 235) [M1], 201 2100) [M12Cl], 181 254) [M12Cl±HF].
4.2.1. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]-4-nitro-
benzene 1a. The title compound was obtained as a 6:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
4.2.6. 1-Bromo-4-[3-chloro-2,3,3-tri¯uoro-1-propenyl]-
benzene 1f. The title compound was obtained as a 6:1
Colourless crystals, mp 36±378C. Rf 2Hexane) 0.20. IR
2Nujol) 2n, cm21) 1700 2CvC), 1530 2NO2). C9H5ClF3NO2
2251.6): calcd C 42.97, H 2.00, found C 43.24, H 2.04.
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.75. IR 2Nujol) 2n, cm21
1700 2CvC). C9H5BrClF3 2285.5): calcd C 37.86, H 1.77,
)
1
Major isomer 1a: H NMR 2CDCl3) d 6.42 2d, Jˆ33.8 Hz,
1H), 7.73 2d, Jˆ8.8 Hz, 2H), 8.26 2d, Jˆ8.8 Hz, 2H). 13C

V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
7525
found C 37.80, H 2.00. Major isomer 1f: 1H NMR 2CDCl3)
d 6.19 2d, Jˆ34.7 Hz, 1H), 7.32 2d, Jˆ8.7 Hz, 2H), 7.43 2d,
Jˆ8.7 Hz, 2H). 13C NMR 2CDCl3) d 108.48 2Jˆ7.6 Hz,
Jˆ3.1 Hz), 120.50 2Jˆ288.4, 41.2 Hz), 123.82 2Jˆ
4.6 Hz), 128.66 2Jˆ3.1 Hz), 131.08 2Jˆ7.6 Hz), 131.54,
148.51 2Jˆ268.6, 32.0 Hz). MS 2EI, 70 eV); m/z 2%): 286
229) [M1], 251 220) [M12Cl], 170 2100) [M12Cl±Br], 169
239) [M12Cl±H±Br].
2224.6): calcd C 48.13, H 2.24, found C 48.36, H 2.58.
Major isomer 1k: 1H NMR 2CDCl3) d 6.56 2d, Jˆ
35.2 Hz, 1H), 7.00±7.35 2m, 3H), 7.74 2dd, Jˆ7.9, 7.9 Hz,
1H). 13C NMR 2CDCl3) d 101.41 2Jˆ7.6, 4.6 Hz), 115.57
2Jˆ22.9 Hz), 120.62 2Jˆ288.4, 41.2 Hz), 124.50 2Jˆ
3.1 Hz), 130.32 2Jˆ13.7 Hz), 131.28 2Jˆ6.1, 3.1 Hz),
131.78 2Jˆ9.2 Hz), 149.23 2Jˆ267.0, 30.5 Hz), 160.39
2Jˆ253.3 Hz).
4.2.7. [3-Chloro-2,3,3-tri¯uoro-1-propenyl]benzene 1g.
The title compound was obtained as a 93:7 mixture of Z±
E isomers after puri®cation 2by 1H NMR). Colourless oil, bp
848C/18 torr. Rf 2Hexane) 0.85. IR 2Nujol) 2n, cm21) 1700
2CvC). C9H6ClF3 2206.6): calcd C 52.32, H 2.93, found C
4.2.12. 1-Chloro-2-[3-chloro-2,3,3-tri¯uoro-1-propenyl]-
benzene 1l. The title compound was obtained as a 7:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.60. IR 2Nujol) 2n, cm21
)
1700 2CvC). C9H5Cl2F3 2241.0): calcd C 44.85, H 2.09,
found C 44.37, H 2.33. Major isomer 1l: 1H NM R
2CDCl3) d 6.69 2d, Jˆ34.2 Hz, 1H), 7.15±7.19 2m, 2H),
7.28±7.33 2m, 1H), 7.61±7.70 2m, 1H). 13C NMR 2CDCl3)
d 105.50 2Jˆ3.1 Hz), 120.46 2Jˆ288.4, 41.2 Hz), 127.05,
129.80, 130.47, 130.67 2Jˆ10.7 Hz), 132.92, 134.18,
149.11 2Jˆ 270.1, 32.1 Hz).
1
52.33, H 2.98. Major isomer 1g: H NMR 2CDCl3) d 6.17
2d, Jˆ35.2 Hz, 1H), 7.21±7.25 2m, 3H), 7.40 2dd, Jˆ7.8,
1.8 Hz, 2H). 13C NMR 2CDCl3) d 109.53 2Jˆ7.6, 3.1 Hz),
120.75 2Jˆ288.4, 41.2 Hz), 128.86, 129.55 2Jˆ3.1 Hz),
129.76 2Jˆ7.6 Hz), 130.02 2Jˆ3.1 Hz), 148.17 2Jˆ267.0,
32.0 Hz).
4.2.8. 4-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]benzo-
nitrile 1h. The title compound was obtained as a 6:1
4.2.13. 1,4-Bis[3-chloro-2,3,3-tri¯uoro-1-propenyl]benzene
1m. The title compound was obtained as a 86/13/1 mixture
of 2Z,Z), 2Z,E) and 2E,E) isomers 2by 19F NMR spectra) after
puri®cation. Colourless crystals, mp 52±538C. Rf 2Hexane)
0.70. IR 2Nujol) 2n, cm21) 1700 2CvC). C12H6Cl2F6
2335.1): calcd C 43.01, H 1.80, found C 43.03, H 1.90.
Major isomer 1m: 1H NMR 2CDCl3) d 6.20 2d, Jˆ
34.7 Hz, 2H), 7.45 2s, 4H). 13C NMR 2CDCl3) d 108.74
2Jˆ7.6, 3.1 Hz), 120.61 2Jˆ288.4, 41.2 Hz), 130.11 2Jˆ
7.6 Hz), 130.95, 149.01 2Jˆ268.6, 32.0 Hz).
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.10. IR 2Nujol) 2n, cm21
)
2240 2CN), 17002CvC). C10H5ClF3N 2231.60): calcd C
51.86, H 2.18, found C 52.07, H 2.55. Major isomer 1h:
1H NMR 2CDCl3) d 6.31 2d, Jˆ34.0 Hz, 1H), 7.59 2d, Jˆ
8.9 Hz, 2H), 7.63 2d, Jˆ8.9 Hz, 2H). 13C NMR 2CDCl3) d
107.90 2Jˆ7.6, 4.6 Hz), 112.93 2Jˆ3.0 Hz), 120.07 2Jˆ
289.9, 41.2 Hz), 130.08 2Jˆ7.6 Hz), 132.03, 132.48,
134.152Jˆ4.6 Hz), 149.94 2Jˆ273.2, 32.1 Hz.
4.2.14. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]naphtha-
lene 1n. Colourless oil. Rf 2Hexane) 0.85. C13H8ClF3
4.2.9. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]-4-methyl-
benzene 1i. The title compound was obtained as a 16:1
1
2256.7): calcd C 60.84, H 3.14, found C 60.55, H 3.05. H
1
mixture of Z±E isomers after puri®cation 2by H NMR).
NMR 2CDCl3) d 6.99 2d, Jˆ32.7 Hz, 1H), 7.43±7.53 2m,
Colourless oil, bp 878C/15 torr. Rf 2Hexane) 0.85. IR
2Nujol) 2n, cm21) 1700 2CvC). C10H8ClF3 2220.6): calcd
C 54.44, H 3.65, found C 53.76, H 3.82. Major isomer 1i: 1H
NMR 2CDCl3) d 2.29 2s, 3H), 6.22 2d, Jˆ35.7 Hz, 1H), 7.12
2d, Jˆ8.1 Hz, 2H), 7.37 2d, Jˆ8.1 Hz, 2H). 13C NM R
2CDCl3) d 21.32, 109.46 2Jˆ7.6, 4.6 Hz), 120.82 2Jˆ
286.9, 41.2 Hz), 127.00 2Jˆ4.6 Hz), 129.57, 129.69 2Jˆ
7.6 Hz), 140.59, 148.33 2Jˆ265.6, 32.0 Hz).
3H), 7.73±7.89 2m, 4H). 13C NM R 2CDCl) d 106.38
3
2Jˆ4.6 Hz), 120.94 2Jˆ288.4, 41.2 Hz), 123.06, 125.19,
126.05, 126.78, 128.03 2Jˆ9.2 Hz), 128.77, 129.83,
131.18, 133.53, 148.93 2Jˆ265.5, 32.0 Hz). MS 2EI,
70 eV); m/z 2%): 256 280) [M1], 221 247) [M12Cl], 201
2100) [M12Cl±H±F], 171 291) [M12CClF2],152 217)
[M12F±CClF2].
4.2.15. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-4-nitro-
benzene 2a. The title compound was obtained as a 7:1
4.2.10. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]-4-¯uoro-
benzene 1j. The title compound was obtained as a 13:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Pale yellow crystals, mp 63±648C 2lit.4 64±658C). Rf 2Hex-
ane) 0.25. Major isomer 2a: H NMR 2CDCl3) d 7.32 2s,
1
Colourless oil, bp 878C/15 torr. Rf 2Hexane) 0.60. IR
2Nujol) 2n, cm21) 1700 2CvC), 1240 2Ar±F). C9H5ClF4
2224.6): calcd C 48.13, H 2.24, found C 48.29, H 2.54.
1H), 7.79 2d, Jˆ8.8 Hz, 2H), 8.23 2d, Jˆ8.8 Hz, 2H). Minor
isomer 2a: 1H NMR 2CDCl3) d 7.18 2s, 1H).
1
Major isomer 1j: H NMR 2CDCl3) d 6.23 2d, Jˆ34.9 Hz,
1H), 7.02 2dd, Jˆ8.7, 8.7 Hz, 2H), 7.48 2dd, Jˆ8.7, 5.3 Hz,
2H). 13C NMR 2CDCl3) d 108.46 2Jˆ7.6, 4.6 Hz), 116.02
2Jˆ22.9 Hz), 131.70 2Jˆ9.2, 7.6 Hz), 132.06 2Jˆ9.2 Hz),
120.65 2Jˆ288.4, 42.7 Hz), 147.91 2Jˆ267.0, 32.1 Hz),
162.68 2Jˆ250.3, 22.9 Hz).
4.2.16. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-3-nitro-
benzene 2b. The title compound was obtained as a 3:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Pale yellow oil. Rf 2Hexane) 0.30. IR 2Nujol) 2n, cm21
)
1620 2CvC), 1540 2NO2). C9H5ClF3NO2 2251.6): calcd C
42.97, H 2.00, found C 42.62, H 1.99. Major isomer 2b: 1H
NMR 2CDCl3) d 7.29 2s, 1H), 7.57 2d, Jˆ8.1 Hz, 1H), 7.92
2d, Jˆ8.1 Hz, 1H), 8.16 2dd, Jˆ8.1, 1.2 Hz, 1H), 8.48 2dd,
Jˆ1.2, 1.2 Hz, 1H). 13C NMR 2CDCl3) d 120.36 2Jˆ
271.6 Hz), 122.11 2Jˆ36.6 Hz), 124.17, 124.35, 128.52,
129.66, 132.89, 135.44, 148.08. Minor isomer 2b: 1H
4.2.11. 1-[3-Chloro-2,3,3-tri¯uoro-1-propenyl]-2-¯uoro-
benzene 1k. The title compound was obtained as a 4:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil, bp 878C/15 torr. Rf 2Hexane) 0.60. IR
2Nujol) 2n, cm21) 1700 2CvC), 1240 2Ar±F). C9H5ClF4

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V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
NMR 2CDCl3) d 7.22 2s, 1H), 7.49 2d, Jˆ7.5 Hz, 2H), 8.03
2br.s, 1H), 8.09±8.13 2m, 1H).
2CDCl3) d 113.09, 117.78, 120.17 2Jˆ271.6 Hz), 121.98
2Jˆ36.6 Hz), 128.93, 130.00, 131.92, 135.43. Minor isomer
1
2h: H NMR 2CDCl3) d 7.18 2s, 1H), 7.28 2d, Jˆ8.2 Hz,
4.2.17. 1-Chloro-4-[2-chloro-3,3,3-tri¯uoro-1-propenyl]-
benzene 2c. The title compound was obtained as a 4:1
2H), 7.55 2d, Jˆ8.2 Hz, 2H).
1
mixture of Z±E isomers after puri®cation 2by H NMR).
4.2.23. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-4-methyl-
benzene 2i. The title compound was obtained as a 6:1
mixture of Z±E isomers 6:1 after puri®cation 2by 1H
NMR). Colourless oil. Rf 2Hexane) 0.85. IR 2Nujol) 2n,
cm21) 1650 2CvC). C10H8ClF3 2220.6): calcd C 54.44, H
Colourless oil. Rf 2Hexane) 0.85. Major isomer 2c: 1H
NMR 2CDCl3) d 7.07 2s, 1H), 7.20 2d, Jˆ8.7 Hz, 2H),
7.48 2d, Jˆ8.7 Hz, 2H). Minor isomer 2c: 1H NM R
2CDCl3) d 7.03 2d, Jˆ8.4 Hz, 2H), 7.17 2d, Jˆ8.4 Hz, 2H).
1
3.65, found C 54.40, H 3.53. Major isomer 2i: H NM R
4.2.18. 1-Chloro-3-[2-chloro-3,3,3-tri¯uoro-1-propenyl]-
benzene 2d. The title compound was obtained as a 4:1
2CDCl3) d 2.25 2s, 3H), 7.08 2s, 1H), 7.10 2br.s, 2H), 7.49
2d, Jˆ8.2 Hz, 2H). 13C NMR 2CDCl3) d 21.21, 118.18 2Jˆ
36.6 Hz), 121.15 2Jˆ271.6 Hz), 129.03, 129.33, 130.03,
130.55 2Jˆ4.6 Hz), 140.60. Minor isomer 2i: 1H NM R
2CDCl3) d 2.22 2s, 3H), 7.07 2s, 1H).
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.85. IR 2Nujol) 2n, cm21
)
1660 2CvC). C9H5Cl2F3 2241.0): calcd C 44.85, H 2.09,
found C 44.73, H 2.08. Major isomer 2d: 1H NM R
2CDCl3) d 7.06 2s, 1H), 7.18±7.24 2m, 2H), 7.40 2d,
Jˆ7.2 Hz, 1H), 7.54 2s, 1H). 13C NMR 2CDCl3) d 120.83
2Jˆ36.6 Hz), 121.00 2Jˆ271.6 Hz), 127.99, 129.32
2Jˆ4.6 Hz), 128.30, 129.63, 129.78, 130.06, 134.67.
Minor isomer 2d: 1H NMR 2CDCl3) d 7.03 2s, 1H).
4.2.24. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-4-¯uoro-
benzene 2j. The title compound was obtained as a 4:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.75. IR 2Nujol) 2n, cm21
)
1660 2CvC), 1240 2Ar±F). C9H5ClF4 2224.6): calcd C
48.13, H 2.24, found C 48.14, H 2.65. Major isomer 2j:
1H NMR 2CDCl3) d 7.01 2dd, Jˆ8.8, 8.8 Hz, 2H), 7.15 2s,
1H), 7.62 2dd, Jˆ8.8, 5.5 Hz, 2H). 13C NMR 2CDCl3) d
115.80 2Jˆ21.4 Hz), 120.91 2Jˆ271.6 Hz), 127.74
2Jˆ3.1 Hz), 128.91 2Jˆ26.0 Hz), 129.46 2Jˆ4.6 Hz),
132.05 2Jˆ 7.6 Hz), 163.45 2Jˆ251.8 Hz). Minor isomer
4.2.19. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-4-methoxy-
benzene 2e. The title compound was obtained as a 10:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.40. IR 2Nujol) 2n, cm21
)
1610 2CvC). C10H8ClF3O 2236.6): calcd C 50.76, H 3.41,
found C 50.67, H 3.37. Major isomer 2e: 1H NMR 2CDCl3)
d 3.66 2s, 3H), 6.76 2d, Jˆ8.7 Hz, 2H), 7.04 2s, 1H), 7.52 2d,
Jˆ8.7 Hz, 2H). 13C NMR 2CDCl3) d 54.94, 113.94, 116.32
2Jˆ36.6 Hz), 121.26 2Jˆ271.6 Hz), 123.99, 130.04 2Jˆ
4.6 Hz), 131.80, 161.05. Minor isomer 2e: 1H NM R
2CDCl3) d 3.63 2s, 3H), 6.71 2d, Jˆ8.5 Hz, 2H), 7.00 2s,
1H), 7.07 2d, Jˆ8.5 Hz, 2H).
1
2j: H NMR 2CDCl3) d 6.95 2dd, Jˆ8.7, 8.7 Hz, 2H).
4.2.25. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-2-¯uoro-
benzene 2k. The title compound was obtained as a 3:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.75. IR 2Nujol) 2n, cm21
)
1660 2CvC), 1240 2Ar±F). C9H5ClF4 2224.6): calcd C
48.13, H 2.24, found C 48.37, H 2.42. Major isomer 2k:
1H NMR 2CDCl3) d 7.02 2dd, Jˆ9.7, 8.7 Hz, 1H), 7.11
2d, Jˆ7.4 Hz, 1H), 7.28±7.31 2m, 1H), 7.40 2s, 1H), 7.90
2ddd, Jˆ7.4, 7.4, 1.2 Hz, 1H). 13C NMR 2CDCl3) d
115.67 2Jˆ22.9 Hz), 119.51 2Jˆ45.8 Hz), 120.90 2Jˆ
271.6 Hz), 123.32, 124.07 2Jˆ3.1 Hz), 127.76 2Jˆ7.6 Hz),
129.71, 131.85 2Jˆ9.2 Hz), 160.68 2Jˆ251.8 Hz).
4.2.20. 1-Bromo-4-[2-chloro-3,3,3-tri¯uoro-1-propenyl]-
benzene 2f. The title compound was obtained as a 6:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.85. IR 2Nujol) 2n, cm21
)
1650 2CvC). C9H5BrClF3 2285.5): calcd C 37.86, H 1.77,
found C 37.53, H 1.84. Major isomer 2f: 1H NMR 2CDCl3)
d 7.09 2s, 1H), 7.41±7.44 2br.d, Jˆ1.8 Hz, 4H). 13C NM R
2CDCl3) d 120.01 2Jˆ36.6 Hz), 120.77 2Jˆ271.6 Hz),
124.44, 131.27, 131.51, 131.82, 135.75. Minor isomer 2f:
1H NMR 2CDCl3) d 6.98 2s, 1H), 7.03 2d, Jˆ8.4 Hz, 2H),
7.35 2d, Jˆ8.4 Hz, 2H).
1
Minor isomer 2k: H NMR 2CDCl3) d6.97 2dd, Jˆ8.7,
8.7 Hz, 1H.
4.2.26. 1-Chloro-2-[2-chloro-3,3,3-tri¯uoro-1-propenyl]-
benzene 2l. The title compound was obtained as a 4:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
4.2.21. [2-Chloro-3,3,3-tri¯uoro-1-propenyl]benzene 2g.
The title compound was obtained as a 6:1 mixture of Z±E
Colourless oil. Rf 2Hexane) 0.85. IR 2Nujol) 2n, cm21
)
1660 2CvC). C9H5Cl2F3 2241.0): calcd C 44.85, H 2.09,
found C 44.57, H 2.25. Major isomer 2l: 1H NM R
2CDCl3) d 7.21±7.24 2m, 2H), 7.33±7.36 2m, 1H), 7.47 2s,
1H), 7.72±7.74 2m, 1H). 13C NMR 2CDCl3) d 120.62 2Jˆ
271.6 Hz), 126.54, 126.64, 128.06 2Jˆ4.6 Hz), 129.71,
129.85 2Jˆ35.1 Hz), 130.25, 130.85, 134.08. Minor isomer
2l: 1H NMR 2CDCl3) d 7.13 2s, 1H).
1
isomers after puri®cation 2by H NMR). Colourless oil. Rf
1
2Hexane) 0.90. Major isomer 2g: H NMR 2CDCl3) d 7.18
2s, 1H), 7.28±7.33 2m, 3H), 7.58±7.62 2m, 2H). Minor
isomer 2g: 1H NMR 2CDCl3) d 7.11 2s).
4.2.22. 4-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]benzo-
nitrile 2h. The title compound was obtained as a 3:1
1
mixture of Z±E isomers after puri®cation 2by H NMR).
4.2.27. 1,4-Bis[2-chloro-3,3,3-tri¯uoro-1-propenyl]ben-
zene 2m. Colourless oil. Rf 2Hexane) 0.80. IR 2Nujol)
2n, cm21) 1650 2CvC). 1H NMR 2CDCl3) d 7.07 2d,
Jˆ1.0 Hz, 2H), 7.56 2s, 4H). 13C NMR 2CDCl3) d 120.92
2Jˆ36.6 Hz), 120.95 2Jˆ271.6 Hz), 129.69 2Jˆ4.6 Hz),
130.13, 133.18.
Colourless crystals, mp 69±708C. Rf 2Hexane) 0.15. IR
2Nujol) 2n, cm21) 2240 2CN), 1660 2CvC). C10H5ClF3N
2231.60): calcd C 51.86, H 2.18, found C 51.61, H 2.14.
1
Major isomer 2h: H NMR 2CDCl3) d 7.24 2s, 1H), 7.62
2d, Jˆ8.4 Hz, 2H), 7.72 2d, Jˆ8.4 Hz, 2H). 13C NM R

V. N. Korotchenko et al. / Tetrahedron 57 02001) 7519±7527
7527
5. Meazza, G.; Zanardi, G. J. Fluorine Chem. 1991, 55, 199±
206.
4.2.28. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]naphtha-
lene 2n. Colourless oil. Rf 2Hexane) 0.85. IR 2Nujol) 2n,
1
cm21) 1660 2CvC). H NMR 2CDCl3) d 6.94 2s, 1H),
6. Takagi, T.; Takeshi, A.; Isowaki, A.; Koyama, M.; Ando, A.;
Kumadaki, I. Chem. Pharm. Bull. 1995, 43, 1071±1075.
7. Li, X.; Fu, W.; Ma, S.; Jiang, X. Huaxue Xuebao 1989, 47,
360±366 Chem. Abstr., 1989, 111, 173568.
7.28±7.32 2m, 3H), 7.62±7.67 2m, 4H). 13C NMR 2CDCl3)
d 123.40, 124.96, 126.28, 126.86, 127.20, 128.75, 129.98.
MS 2EI, 70 eV); m/z 2%): 256 267) [M1], 221 2100)
[M12Cl], 201 282) [M12Cl±H±F], 152 264) [M12Cl±
CF3]. C13H8ClF3 2256.7): calcd C 60.84, H 3.14, found C
61.07, C 3.05.
8. Fujita, M.; Morita, T.; Hiyama, T. Tetrahedron Lett. 1986, 27,
2135±2138.
9. Fujita, M.; Hiyama, T. Bull. Chem. Soc. Jpn 1987, 60, 4377±
4384.
10. Fujita, M.; Hiyama, T.; Kondo, K. Tetrahedron Lett. 1986, 27,
2139±2142.
4.2.29. 4-[41Z)-2-Chloro-3,3,3-tri¯uoro-1-propenyl]-N,N-
dimethylaniline 2o. Colourless crystals, mp 74.5±758C. Rf
2Hexane) 0.30. IR 2Nujol) 2n, cm21) 1610 2CvC). 1H NM R
2CDCl3) d 2.89 2s, 6 H), 6.56 2d, Jˆ8.7 Hz, 2H), 7.02 2s,
1H), 7.56 2d, Jˆ8.7 Hz, 2H). 13C NMR 2CDCl3) d 39.80,
111.33, 113.17 2Jˆ36.6 Hz), 118.98, 121.59 2Jˆ271.6 Hz),
130.40 2Jˆ4.6 Hz), 131.77, 151.28. C11H11ClF3N 2249.7):
calcd C 52.92, H 4.44, found C 53.05, C 4.43.
11. Tanaka, H.; Yamashita, S.; Katayama, Y.; Torii, S. Chem.
Lett. 1986, 2043±2044.
12. Massardo, P.; Bettarin, F.; Piccardi, P.; Ramo, F. Eur. Pat.
Appl. EP 187,674. Chem. Abstr., 1986, 105, 172040.
13. Fujita, M.; Hiyama, T. Tetrahedron Lett. 1986, 27, 3655±
3658.
14. Shono, T.; Kise, N.; Oka, H. Tetrahedron Lett. 1991, 32,
6567±6570.
4.2.30. 1-[2-Chloro-3,3,3-tri¯uoro-1-propenyl]-2-methoxy-
benzene 2p. The title compound was obtained as a 6:1
15. Seyferth, D.; Mueller, D. C. J. Am. Chem. Soc. 1971, 93,
3714±3720.
1
mixture of Z±E isomers after puri®cation 2by H NMR).
Colourless oil. Rf 2Hexane) 0.40. IR 2Nujol) 2n, cm21
)
16. Shastin, A. V.; Korotchenko, V. N.; Nenajdenko, V. G.;
Balenkova, E. S. Russ. Chem. Bull. 1999, 48, 2184±2185.
17. Shastin, A. V.; Korotchenko, V. N.; Nenajdenko, V. G.;
Balenkova, E. S. Tetrahedron 2000, 56, 6557±6563.
18. Nenajdenko, V. G.; Shastin, A. V.; Korotchenko, V. N.;
Balenkova, E. S. Russ. Chem. Bull. 2001 2in press).
19. Dmowski, W. J. Fluorine Chem. 1985, 29, 273±286.
20. Dmowski, W. J. Fluorine Chem. 1985, 29, 287±296.
21. Juhl, K.; Hazell, R. G.; Jorgensen, K. A. J. Chem. Soc., Perkin
Trans. 1 1999, 16, 2293±2297.
1610 2CvC). C10H8ClF3O 2236.6): calcd C 50.76, H 3.41,
found C 50.40, H 3.19. Major isomer 2p: 1H NMR 2CDCl3)
d 3.68 2s, 3H), 6.75 2d, Jˆ8.4 Hz, 1H), 6.86 2dd, Jˆ7.7,
7.4 Hz, 1H), 7.23 2dd, Jˆ8.4, 7.4 Hz, 1H), 7.52 2s, 1H), 7.80
2d, Jˆ7.7 Hz, 1H). 13C NMR 2CDCl3) d 55.29, 110.52,
119.07 2Jˆ36.6 Hz), 120.20, 120.38, 121.15 2Jˆ
271.6 Hz), 126.05 2Jˆ4.6 Hz), 129.54, 131.44, 157.73.
1
Minor isomer 2p: H NMR 2CDCl3) d 3.66 2s, 3H), 7.14
2s, 1H).
22. Dakin, L. A.; Schaus, S. E.; Jacobsen, E. N.; Panek, J. S.
Tetrahedron Lett. 1998, 39, 8947±8950.
23. Gettwert, V.; Krebs, F.; Maas, G. Eur. J. Org. Chem. 1999, 5,
1213±1221.
Acknowledgements
24. Lee, C. K.; Chen, J. C. C.; Lee, K. M.; Liu, C. M.; Lin, I. J. B.
Chem. Mater. 1999, 11, 1237±1242.
Financial support from the Russian Foundation for Basic
Research 2Grants No. 00-03-32760 and 00-03-32763) is
gratefully acknowledged.
25. Aggarwal, V. K.; Abdel-Rahman, H.; Jones, R. V. H.; Lee,
H. Y.; Reid, B. D. J. Am. Chem. Soc. 1994, 116, 5973±5974.
26. Aggarwal, V. K.; Ford, J. G.; Jones, R. V. H.; Fieldhouse, R.
Tetrahedron: Asymmetry 1998, 9, 1801±1807.
27. Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem.
Rev. 2000, 100, 39±91.
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