New approach to the synthesis of trifluoromethylvinyl sulfides

Article abstract of DOI:10.1007/s11172-007-0236-4

Nucleophilic substitution reaction of halogen atom in β-chloro-and β-bromo-β-trifluoromethylstyrenes by thiolates was studied. Stereo-and regioselectivity of the reaction with respect to the electronic and sterical properties of substituents in the aromat

Full text of DOI:10.1007/s11172-007-0236-4

Russian Chemical Bulletin, International Edition, Vol. 56, No. 8, pp. 1526—1533, August, 2007
1526
New approach to the synthesis of trifluoromethylvinyl sulfides*
V. M. Muzalevskiy,a A. V. Shastin,b E. S. Balenkova,a and V. G. Nenajdenkoa
ꢀ
аDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: nen@acylium.chem.msu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
Chernogolovka, 142432 Moskovskaya obl., Russian Federation.
Eꢀmail: shastin@icp.ac.ru
Nucleophilic substitution reaction of halogen atom in βꢀchloroꢀ and βꢀbromoꢀβꢀ
trifluoromethylstyrenes by thiolates was studied. Stereoꢀ and regioselectivity of the reaction
with respect to the electronic and sterical properties of substituents in the aromatic ring of
starting styrenes was investigated. Regioisomer with geminal trifluoromethyl and alkylꢀ or
arylthio groups was found to be formed predominantly or exclusively. The reaction proceeds
stereoselectively in nearly quantitative yields. On this basis, a new convenient stereoselective
method for the synthesis of trifluoromethylvinyl sulfides was elaborated.
Key words: catalytic olefination reaction, βꢀhaloꢀβꢀtrifluoromethylstyrenes, nucleophilic
substitution, regioselectivity, trifluoromethylvinyl sulfides.
Fluoroꢀcontaining organic compounds are under the
styrenes, which are used for the synthesis of βꢀalkylꢀ and
βꢀarylꢀβꢀtrifluoromethylstyrenes,6 potential antiꢀcancer
drugs.7 By oxidation, sulfides can be easily converted to
sulfones ArC(H)=C(SO2R)CF3 (see Refs 8 and 9), which
are of interest as prospective "building blocks" for the
synthesis of fluoroꢀcontaining compounds and which have
been already used in the synthesis of 3ꢀarylꢀ4ꢀtrifluoroꢀ
methylpyrroles.9 There are two approaches to the syntheꢀ
sis of such sulfides known from the literature. The first
one is based on the Wittig reaction with thioesters of
perfluorocarboxylic acids,10 the second one includes the
substitution of halogen atom in βꢀchloroꢀβꢀtrifluoroꢀ
methylꢀαꢀformylstyrenes by alkylthio or arylthio group
with subsequent decarbonylation under base treatment.11
However, both methods have disadvantages. In the first
method, the use of expensive starting perfluorothioacetates
is required, while the second is a multiꢀstep one.
intensive investigation due to their high physiological acꢀ
tivity.1 A large number of works deals with the elaboration
of new methods for their synthesis.2 Earlier, a new reacꢀ
tion of catalytic olefination of aldehydes and ketones was
discovered by our research group.3 It was found that
Nꢀunsubstituted hydrazones of carbonyl compounds upon
treatment with polyhaloalkanes in the presence of a base
and catalytic amounts of copper salts are transformed to
various substituted alkenes. Inexpensive starting comꢀ
pounds and simplicity of carrying out the experiment and
products isolation are the advantages of this method. Thus,
this reaction does not require an inert atmosphere and an
excess of organometallic or organophosphorus compounds
as, for example, in the Wittig reaction.
On the basis of catalytic olefination reaction, we elaboꢀ
rated new methods for the synthesis of various fluoroꢀ
containing alkenes.4 Obtained by these methods βꢀchloroꢀ
βꢀtrifluoromethylstyrenes4а and βꢀbromoꢀβꢀtrifluoroꢀ
methylstyrenes4d are of particular interest, since the presꢀ
ence of halogen atom gives the opportunity for their furꢀ
ther functionalization. Thus, recently we successfully perꢀ
formed a substitution of bromine atom by a nitrile group
in β,βꢀbromofluorostyrenes and βꢀbromoꢀβꢀtrifluoroꢀ
methylstyrenes.5
Results and Discussion
It was found that both βꢀchloroꢀβꢀtrifluoromethylꢀ
styrenes 1 and βꢀbromoꢀβꢀtrifluoromethylstyrenes 2 easily
react with ethanethiol in ethanol in the presence of
1.2 equiv. of KOH to form vinyl sulfides 3 and 4 (Scheme 1
and Table 1). In case of electronꢀwithdrawing substituꢀ
ents in aromatic ring, such as nitro or carboxymethyl
groups, the reaction is fast and exothermic at room temꢀ
perature. In all the other cases, a reflux of the reaction
mixture for 5—10 min is required for the reaction to come
to a full completion. A general nature of the reaction
We assumed that in case of thiols the substitution would
lead to βꢀalkylthioꢀ and βꢀarylthioꢀβꢀtrifluoromethylꢀ
* Dedicated to Academician V. A. Tartakovsky in honor of his
75th anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1469—1475, August, 2007.
1066ꢀ5285/07/5608ꢀ1526 © 2007 Springer Science+Business Media, Inc.

Synthesis of trifluoromethyl(vinylsulfides)
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
1527
Scheme 1
with the only difference that, in addition to the electronic
factors (–Iꢀeffect of bromine atom), steric hindrance,
caused by substituent in orthoꢀposition, also interfere with
the direction of nucleophilic attack. The content of
regioisomer 4 increases with the decrease of electronꢀ
withdrawing properties of the aromatic substituent, and
for donating substrates 2i and 2l with paraꢀmethoxy group,
regioisomer 4 becomes predominant. Similarly to the case
of styrenes with electronꢀwithdrawing substituents, the
steric factors strongly affect the direction of nucleophilic
attack in styrenes with electronꢀdonating substituents. For
example, for styrene 2k with orthoꢀmethoxy group, the
content of regioisomer 4 is 14 times as less as for styꢀ
rene 2i. Thus, regioselectivity of the reaction is defined by
the electronic and steric properties of aryl (heteroaryl)
substituent. In case of electronꢀwithdrawing and steriꢀ
cally hindered substituents, the reaction proceeds with
the formation of a single regioisomer 3.
Despite the fact that the starting substrates 1 and 2 are
mixtures of Zꢀ and Eꢀisomers (with Zꢀisomer being preꢀ
dominant, see Experimental), the formed from them comꢀ
pounds 3 and 4 have Zꢀconfiguration, and only for styꢀ
renes 1c, 1d, and 2d with electronꢀwithdrawing substituꢀ
ents in orthoꢀposition to the double bond, formation of
admixtures of Eꢀisomers are observed. The ratio of
Z/Eꢀisomers in products 3c and 3d was 7/1 and 20/1,
respectively. Thus, formation of the sulfides proceeds
stereoselectively. To assign a configuration of the double
bond in sulfides 3, the spinꢀspin coupling constant values
3JH,C of carbon atom in trifluoromethyl group and vinylic
proton were determined. It was found that they are within
the interval 5.9—6.6 Hz, which corresponds to Zꢀisoꢀ
mers.12 A configuration of regioisomer 4 was determined
from the NOE experiment for sulfide 4i.
X = Cl (1), Br (2)
Table 1. Reaction of βꢀchloroꢀ and βꢀbromoꢀβꢀtrifluoromethylꢀ
styrenes with ethanethiol
Comꢀ
pound
1—4
R
Yield of 3 + 4 (%)
3 : 4
X=Cl
X=Br
a
a
b
c
d
e
f
4ꢀNO2C6H4
3ꢀNO2C6H4
2ꢀNO2C6H4
2ꢀBrC6H4
96
95
76
89
—
—
—
1 : 0
12 : 1
1 : 0
1 : 0
1 : 0
1 : 0
1 : 0
5 : 1
0.5 : 1
3 : 1
7 : 1
1 : 1
2 : 1
1 : 1
a
a
85
a
2ꢀBrꢀ5ꢀMeOC6H3
4ꢀMeCO2C6H4
2ꢀPy
—
94
81b
92
89b
a
g
h
i
—
4ꢀClC6H4
90
93
93
95
85
89
96
76
a
4ꢀMeOC6H4
3ꢀMeOC6H4
2ꢀMeOC6H4
3,4ꢀ(MeO)2C6H3
Ph
—
—
—
—
a
j
k
l
a
a
a
m
n
—
4ꢀMeC6H4
64
According to the NOE data for compound 4i, the irraꢀ
diation of vinylic proton showed the nuclear Overhauser
effect with orthoꢀprotons of phenyl ring, at the same time,
interaction with CH2 protons of the thioalkyl group was
not observed, which points out to the sameꢀside position
of the vinylic proton and phenyl ring with respect to the
double bond. Thus, the configuration of compound 4i
and, most likely, the other sulfides 4 corresponds to
Zꢀisomer.
In order to investigate the synthetic potential of the
method, we carried out a series of reactions of styrene 1a,
taken as a mixture of isomers, with a number of thiols. It
was found that for all the thiols under consideration, simiꢀ
larly to ethanethiol, the substitution reaction of chlorine
atom proceeds regioꢀ and stereoselectively with high yields
of the target vinyl sulfides, both with alkyl (5b, 5d) and
aryl (5c, 5e, 5f) substituents (Scheme 2 and Table 2).
In conclusion, a nucleophilic substitution reaction of
halogen atom in βꢀchloroꢀ and βꢀbromoꢀβꢀtrifluoroꢀ
methylstyrenes by thiols was investigated. Regioꢀ and
stereoselectivity of the reaction was studied. A new conꢀ
a Reaction was not conducted.
b Transesterification to ethyl ester took place.
allows one to obtain trifluoromethylvinyl sulfides, conꢀ
taining both electronꢀwithdrawing and electronꢀdonating
substituents. The total yield of vinyl sulfides 3 and 4 was
high and in a number of cases was nearly quantitative.
The ratios of regioisomers 3 and 4 were determined by
the comparison of the integral intensities for the vinyl
1
protons in Н NMR spectra. It should be noted that the
nature of halogen atom in the starting styrenes does not
influence the ratio and total yield of sulfides 3 and 4.
Regioselectivity of the reaction is affected by the nature of
substituents in the aromatic ring. The presence of the
strong –М electronꢀwithdrawing groups in the aromatic
ring in orthoꢀ and paraꢀpositions to the double bond leads
to a shift of electron density toward the aromatic ring. In
this case, a nucleophile exclusively attacks carbon, bearꢀ
ing a halogen atom, to form a single regioisomer 3. Simiꢀ
lar results are also observed for orthoꢀbromo derivatives

1528
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
Muzalevskiy et al.
Scheme 2
this was extracted with dichloromethane (3×100 mL). The comꢀ
bined extract was washed with water (100 mL) and brine
(100 mL) and dried with Na2SO4. Dichloromethane was reꢀ
moved in vacuo, the residue was dissolved in hexane or in the
appropriate hexaneꢀdichloromethane mixture and run through
a short layer of silica gel. Attempted chromatographic separaꢀ
tion of Zꢀ and Eꢀisomers of alkenes failed.
The spectral data for compounds 1a,b,h,i,m,n agree with
those described in the literature.4a
1ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀnitrobenzene (1a)
was obtained from 4ꢀnitrobenzaldehyde. A mixture of Z/Eꢀisoꢀ
mers (7/1 after purification), the yield was 60%, yellow crystals,
m.p. 63—64 °C (Ref. 4a data: m.p. 64—65 °C).
1ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ3ꢀnitrobenzene (1b)
was obtained from 3ꢀnitrobenzaldehyde. A mixture of Z/Eꢀisoꢀ
mers (3/1 after purification), the yield was 74%, yellow oil.
1ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ2ꢀnitrobenzene (1c)
was obtained from 2ꢀnitrobenzaldehyde. A mixture of Z/Eꢀisoꢀ
mers (5/1 after purification), the yield was 68%, colorless oil.
Found (%): C, 42.87; H, 2.05. C9H5ClF3NO2. Calculated (%):
C, 42.97; H, 2.00. IR, ν/cm–1: 1330, 1560 (NO2), 1615 (C=C).
1H NMR (CDСl3, δ) of Zꢀisomer: 7.60—7.70 (m, 3 Н, Ar); 7.78
(s, 1 Н, СH=CCF3); 8.23 (dd, 1 Н, Ar, J = 8.1 Hz, J = 1.0 Hz);
Eꢀisomer: 7.40 (d, 1 Н, Ar, J = 7.8 Hz); 7.57 (s, 1 Н, СH=CCF3);
7.58—7.80 (m, 3 Н, Ar). 13C NMR (CDСl3, δ) of Zꢀisomer:
120.4 (q, CF3, J = 272.3 Hz); 122.6 (q, C—CF3, J = 38.1 Hz);
129.5 (q, CH=CCF3, J = 4.4 Hz); 125.1, 127.5, 130.4, 131.3,
133.9, 147.2 (Ar); Eꢀisomer: 120.1 (q, CF3, J = 273.7 Hz); 122.3
(q, C—CF3, J = 37.3 Hz); 133.7 (q, CH=CCF3, J = 2.9 Hz);
124.9, 128.5, 130.1, 131.0, 133.8, 146.3 (Ar).
Table 2. Reaction of styrene 1а with thiols
Compounds
R
Yield of 5 (%)
Ratio Z/E
a
b
c
d
e
f
Et
PhCH2
2ꢀNH2C6H4
EtCO2CH2
4ꢀClC6H4
4ꢀMeC6H4
96
91
81
72
85
88
1/0
1/0
1/0
12/1
7/1
7/1
venient stereoselective method for the synthesis of triꢀ
fluoromethylvinyl sulfides was elaborated.
1ꢀBromoꢀ2ꢀ[2ꢀchloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzene
(1d) was obtained from 2ꢀbromobenzaldehyde. A mixture of
Z/Eꢀisomers (3/1 after purification), the yield was 41%, colorꢀ
less oil. Found (%): C, 38.08; H, 2.01. C9H5BrClF3. Calculated
(%): C, 37.86; H, 1.77. IR, ν/cm–1: 1620 (C=C). 1H NMR
(CDСl3, δ) of Zꢀisomer: 7.30, 7.43 (both dt, 1 Н each, Ar, J =
7.8 Hz, J = 1.1 Hz); 7.58 (s, 1 Н, СH=CCF3); 7.69, 7.83
(both dd, 1 Н each, Ar, J = 7.8 Hz, J = 1.1 Hz); Eꢀisomer:
7.26—7.39 (m, 4 Н, Ar and СH=CCF3); 7.83 (dd, 1 Н, Ar, J =
8.1 Hz, J = 0.8 Hz). 13C NMR (CDСl3, δ) of Zꢀisomer: 120.7
(q, CF3, J = 272.3 Hz); 122.2 (q, C—CF3, J = 36.6 Hz); 130.6
(q, CH=CCF3, J = 4.4 Hz); 124.6, 127.3, 130.5, 131.0, 131.9,
133.0 (Ar); Eꢀisomer: 120.3 (q, CF3, J = 274.4 Hz); 122.6 (q,
C—CF3, J = 36.6 Hz); 136.1 (q, CH=CCF3, J = 2.9 Hz); 124.8,
127.2, 130.3, 130.4, 132.4, 133.5 (Ar).
Experimental
1
Н and 13С NMR spectra were recorded on a Bruker
AMX 400 spectrometer (400 and 100 МHz, respectively) in
CDCl3; Me4Si was used as the internal standard. IR spectra
were recorded on a URꢀ20 spectrophotometer for neat samples.
TLC analysis was carried out on Silufol UVꢀ254 plates with
visualization in acidified KMnO4 solution, in a chamber with
iodine vapors, or under the UVꢀlight. Column chromatography
was performed on Merck silica gel (63—200 mesh). Starting
styrenes 1 and 2 were obtained according to the literature
procedures.4a,d
Synthesis of βꢀchloroꢀβꢀtrifluoromethylstyrenes (general proꢀ
cedure). Ethanol (50 mL) and 100% hydrazine hydrate (5 mL,
0.1 mol) were placed in a 500ꢀmL roundꢀbottom flask, and a
solution of the corresponding aldehydes (0.1 mol) in ethanol
(150 mL) was slowly added to this with vigorous stirring. The
reaction mixture was stirred until entire disappearance of the
carbonyl compounds (TLC monitoring), 1,2ꢀethylenediamine
(10 mL, 0.15 mol) and CuCl (1 g, 0.01 mol) were added, and
this was cooled to 5—10 °С in an ice bath. After this, a solution
of CCl3CF3 (28 g, 0.15 mol) in ethanol (50 mL) was poured in
with caution (vigorous gas emission and foaming!). After the
exothermic reaction was over (~0.5—1 h), the ice bath was
removed, and this reaction mixture was stirred at room temperaꢀ
ture for 16 h. Then the reaction mixture was concentrated to
50—60 mL, the formed precipitate was filtered off, the filtrate
was quenched with 0.1 М aq. hydrochloric acid (1 L) (in case of
2ꢀpyridinecarbaldehyde, water was used for the quenching), and
Methyl 4ꢀ[2ꢀchloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzoate (1f)
was obtained from methyl 4ꢀformylbenzoate. A mixture of
Z/Eꢀisomers (4/1 after purification), the yield was 55%, colorꢀ
less crystals, m.p. 51—54 °C. Found (%): C, 49.71; H, 3.05.
C
11H8ClF3O2. Calculated (%): C, 49.93; H, 3.05. IR, ν/cm–1
:
1610 (C=C), 1720 (C=O, CO2Et). 1H NMR (CDСl3, δ)
of Zꢀisomer: 3.88 (s, 3 Н, CO2СН3); 7.27 (s, 1 Н, СH=CCF3),
7.69, 8.02 (both d, 2 Н each, Ar, J = 8.5 Hz); Eꢀisomer: 3.87 (s,
3 Н, CO2СН3); 7.23 (s, 1 Н, СH=CCF3); 7.26, 7.97 (both d,
2 Н each, Ar, J = 8.3 Hz). 13C NMR (CDСl3, δ) of Zꢀisomer:
52.1 (CO2СН3); 120.6 (q, CF3, J = 272.3 Hz); 121.3 (q, C—CF3,
J = 37.3 Hz); 129.8 (q, CH=CCF3, J = 5.2 Hz); 129.6, 129.7,
131.2, 135.6 (Ar); 166.1 (CO2СН3); Eꢀisomer: 52.0 (CO2СН3);
120.3 (q, CF3, J = 274.5 Hz); 122.6 (q, C—CF3, J = 38.1 Hz);
136.0 (q, CH=CCF3, J = 2.9 Hz); 128.3, 129.4, 130.5, 136.8
(Ar); 166.2 (CO2СН3).

Synthesis of trifluoromethyl(vinylsulfides)
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
1529
2ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]pyridine (1g) was obꢀ
tained from 2ꢀpyridinecarbaldehyde. A mixture of Z/Eꢀisomers
(5/1 after purification), the yield was 62%, colorless oil.
Found (%): C, 46.35; H, 2.47. C8H5ClF3N. Calculated (%):
C, 46.29; H, 2.43. IR, ν/cm–1: 1610 (C=C). 1H NMR (CDСl3, δ)
of Zꢀisomer: 7.07—7.27 (m, 1 Н, Py); 7.35 (s, 1 Н, СH=CCF3);
7.58—7.66 (m, 1 Н, Py); 7.81 (d, 1 Н, Py, J = 7.8 Hz); 8.53—8.58
(m, 1 Н, Py); Eꢀisomer: 7.07—7.27 (m, 3 Н, Py and СH=CCF3);
7.51—7.58, 8.47—8.51 (both m, 1 Н each, Py). 13C NMR
(CDСl3, δ) of Zꢀisomer: 120.6 (q, CF3, J = 272.3 Hz); 120.8 (q,
C—CF3, J = 33.7 Hz); 131.3 (q, CH=CCF3, J = 4.4 Hz); 123.9,
124.6, 136.2, 149.8, 150.8 (Py); Eꢀisomer: 120.0 (q, CF3, J =
274.5 Hz); 120.4 (q, C—CF3, J = 37.3 Hz); 136.3 (q, CH=CCF3,
J = 2.2 Hz); 123.2, 123.8, 136.1, 149.4, 151.3 (Py).
1ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀchlorobenzene
(1h) was obtained from 4ꢀchlorobenzaldehyde. A mixture of
Z/Eꢀisomers (3/1 after purification), the yield was 76%, colorꢀ
less oil.
1ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethoxybenzene
(1i) was obtained from 4ꢀmethoxybenzaldehyde. A mixture of
Z/Eꢀisomers (10/1 after purification), the yield was 55%, colorꢀ
less oil.
7.57—7.62 (m, 1 Н, Ar). 13C NMR (CDСl3, δ) of Zꢀisomer:
113.0 (q, C—CF3, J = 36.6 Hz); 120.8 (q, CF3, J = 272.3 Hz);
134.6 (q, CH=CCF3, J = 5.1 Hz); 124.0, 127.2, 131.0, 132.1,
132.9, 133.3 (Ar); Eꢀisomer: 113.4 (q, C—CF3, J = 38.8 Hz);
120.4 (q, CF3, J = 274.4 Hz); 140.4 (q, CH=CCF3, J = 2.9 Hz);
126.1, 127.3, 130.3, 130.5, 132.4. The rest of the signals of
Eꢀisomer are overlapped with those of Zꢀisomer.
1ꢀBromoꢀ2ꢀ[2ꢀbromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethꢀ
oxybenzene (2e) was obtained from 2ꢀbromoꢀ5ꢀmethoxybenzꢀ
aldehyde. A mixture of Z/Eꢀisomers (4/1 after purification), the
yield was 33%, colorless oil. Found (%): C, 33.19; H, 2.02.
C10H7Br2F3O. Calculated (%): C, 33.37; H, 1.96. IR, ν/cm–1
:
1620 (C=C). 1H NMR (CDСl3, δ) of Zꢀisomer: 3.85 (s, 3 H,
OCH3); 6.85 (dd, 1 Н, Ar, J = 8.8 Hz, J = 3.0 Hz); 7.31 (d, 1 Н,
Ar, J = 3.0 Hz); 7.52 (d, 1 Н, Ar, J = 8.8 Hz); 7.74 (s, 1 Н,
СH=CCF3); Eꢀisomer: 3.81 (s, 3 H, OCH3), 6.81 (dd, 1 Н, Ar,
J = 8.6 Hz, J = 2.8 Hz); 7.05 (d, 1 Н, Ar, J = 2.8 Hz); 7.43 (s,
1 Н, СH=CCF3); 7.47 (d, 1 Н, Ar, J = 8.6 Hz). 13C NMR
(CDСl3, δ) of Zꢀisomer: 55.6 (OCH3); 112.9 (q, C—CF3, J =
36.6 Hz); 120.8 (q, CF3, J = 272.2 Hz); 134.5 (q, CH=CCF3,
J = 5.1 Hz); 114.4, 115.7, 117.1, 133.5, 133.8, 158.6 (Ar);
Eꢀisomer: 55.8 (OCH3); 120.3 (q, CF3, J = 273.7 Hz); 140.4 (q,
CH=CCF3, J = 2.9 Hz); 114.0, 116.4, 117.2, 133.0, 134.2,
159.2 (Ar).
[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzene (1m) was obꢀ
tained from benzaldehyde. A mixture of Z/Eꢀisomers (6/1 after
purification), the yield was 50%, colorless oil.
1ꢀ[2ꢀChloroꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethylbenzene
(1n) was obtained from 4ꢀmethylbenzaldehyde. A mixture of
Z/Eꢀisomers (6/1 after purification), the yield was 59%, colorꢀ
less oil.
Methyl 4ꢀ[2ꢀbromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzoate (2f)
was obtained from methyl 4ꢀformylbenzoate. A mixture of
Z/Eꢀisomers (5/1 after purification), the yield was 63%, colorꢀ
less oil.
1ꢀ[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀchlorobenzene
(2h) was obtained from 4ꢀchlorobenzaldehyde. A mixture of
Z/Eꢀisomers (8/1 after purification), the yield was 56%, colorꢀ
less oil.
1ꢀ[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethoxybenzene
(2i) was obtained from 4ꢀmethoxybenzaldehyde. A mixture of
Z/Eꢀisomers (8/1 after purification), the yield was 73%, colorꢀ
less oil.
1ꢀ[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ3ꢀmethoxybenzene
(2j) was obtained from 3ꢀmethoxybenzaldehyde. A mixture of
Z/Eꢀisomers (6/1 after purification), the yield was 68%, colorꢀ
less oil. Found (%): C, 42.68; H, 2.85. C10H8BrF3O. Calcuꢀ
lated (%): C, 42.73; H, 2.87. IR, ν/cm–1: 1620 (C=C). 1H NMR
(CDСl3, δ) of Zꢀisomer: 3.88 (s, 3 Н, OCH3); 7.03 (dd, 1 Н, Ar,
J = 7.9 Hz, J = 1.8 Hz); 7.31 (d, 1 Н, Ar, J = 7.9 Hz); 7.63 (s,
1 Н, СH=CCF3); 7.36 (s, 1 Н, Ar); 7.31 (t, 1 Н, Ar, J = 7.9 Hz);
Eꢀisomer: 3.85 (s, 3 Н, OCH3); 6.86 (s, 1 Н, СH=CCF3); 6.91
(d, 1 Н, Ar, J = 8.0 Hz); 6.95 (dd, 1 Н, Ar, J = 8.0 Hz, J =
2.2 Hz). 13C NMR (CDСl3, δ) of Zꢀisomer: 55.2 (OCH3); 109.6
(q, C—CF3, J = 36.6 Hz); 121.1 (q, CF3, J = 271.5 Hz); 134.4
(q, CH=CCF3, J = 5.1 Hz); 114.7, 115.9, 122.3, 129.6, 133.6,
159.6 (Ar); Eꢀisomer: 55.2 (OCH3); 141.5 (q, С=CНCF3, J =
2.2 Hz); 117.1, 117.6, 120.7, 129.8, 135.0, 159.4 (Ar). The rest
of the signals of Eꢀisomer are overlapped with those of Zꢀisomer.
1ꢀ[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ2ꢀmethoxybenzene
(2k) was obtained from 2ꢀmethoxybenzaldehyde. A mixture of
Z/Eꢀisomers (7/1 after purification), the yield was 43%, colorꢀ
less oil. Found (%): C, 42.85; H, 2.96. C10H8BrF3O. Calcuꢀ
lated (%): C, 42.73; H, 2.87. IR, ν/cm–1: 1620 (C=C). 1H NMR
(CDСl3, δ) of Zꢀisomer: 3.91 (s, 3 Н, OCH3); 6.97 (d, 1 Н, Ar,
J = 7.9 Hz); 7.08 (t, 1 Н, Ar, J = 7.9 Hz); 7.40 (td, 1 Н, Ar, J =
7.9 Hz, J = 1.3 Hz); 7.95 (s, 1 Н, СH=CCF3); 7.98 (dd, 1 Н, Ar,
J = 7.9 Hz, J = 1.3 Hz); Eꢀisomer: 3.89 (s, 3 Н, OCH3); 6.94
Synthesis of βꢀbromoꢀβꢀtrifluoromethylstyrenes (general proꢀ
cedure). DMSO (50 mL) and 100% hydrazine hydrate (5 mL,
0.1 mol) were placed in a 500ꢀmL roundꢀbottom flask, and a
solution of the corresponding aldehydes (0.1 mol) in DMSO
(150 mL) was slowly added to this with vigorous stirring. The
reaction mixture was stirred until entire disappearance of the
carbonyl compounds (TLC monitoring), 25% aq. ammonia
(8 mL) and CuCl (1 g, 0.01 mol) were added, and this was
cooled to 5—10 °С in an ice bath. After this, a solution of
CF3CBr3 (32 g, 0.1 mol) in DMSO (50 mL) was poured in with
caution (vigorous gas emission and foaming!). After the exotherꢀ
mic reaction was over (~0.5 h), the ice bath was removed, and
this reaction mixture was stirred at room temperature for 16 h.
Then the reaction mixture was quenched with 0.1 М aq. hydroꢀ
chloric acid (1.5 L) and extracted with dichloromethane
(3×100 mL). The combined extract was washed with water
(100 mL) and brine (100 mL) and dried with Na2SO4. Diꢀ
chloromethane was removed in vacuo, the residue was dissolved
in hexane or in the appropriate hexaneꢀdichloromethane mixꢀ
ture and run through a short layer of silica gel. Attempted chroꢀ
matographic separation of Zꢀ and Eꢀisomers of alkenes failed.
The spectral data for compounds 2f,h,i,n agree with those
described in the literature4d
.
1ꢀBromoꢀ2ꢀ[2ꢀbromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzene
(2d) was obtained from 2ꢀbromobenzaldehyde. A mixture of
Z/Eꢀisomers (2/1 after purification), the yield was 46%, colorꢀ
less oil. Found (%): C, 32.50; H, 1.58. C9H5Br2F3. Calcuꢀ
lated (%): C, 32.76; H, 1.53. IR, ν/cm–1: 1620 (C=C). 1H NMR
(CDСl3, δ) of Zꢀisomer: 7.34—7.38 (m, 1 Н, Ar); 7.43 (td, 1 Н,
Ar, J = 7.7 Hz, J = 1.0 Hz); 7.65—7.69 (m, 1 Н, Ar); 7.75 (dd,
1 Н, Ar, J = 7.7 Hz, J = 1.0 Hz); 7.78 (s, 1 Н, СH=CCF3);
Eꢀisomer: 7.24—7.35 (m, 3 Н, Ar), 7.49 (s, 1 Н, СH=CCF3),

1530
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
Muzalevskiy et al.
(d, 1 Н, Ar, J = 7.8 Hz); 7.00 (t, 1 Н, Ar, J = 7.8 Hz); 7.31 (d,
1 Н, Ar, J = 7.8 Hz); 7.41 (td, 1 Н, Ar, J = 7.8 Hz, J = 1.3 Hz);
7.60 (s, 1 Н, СH=CCF3). 13C NMR (CDСl3, δ) of Zꢀisomer:
55.5 (OCH3); 109.7 (q, C—CF3, J = 36.6 Hz); 121.2 (q, CF3,
J = 270.8 Hz); 110.6, 120.1, 121.5, 129.4, 131.5, 157.7 (Ar);
Eꢀisomer: 55.5 (OCH3); 120.7 (q, CF3, J = 273.0 Hz); 138.0 (q,
С=CНCF3, J = 2.9 Hz); 110.4, 120.3, 122.6, 129.8, 130.9,
156.7 (Ar). The rest of the signals of Eꢀisomer are overlapped
with those of Zꢀisomer.
lated (%): C, 47.65; H, 3.64. IR, ν/cm–1: 1340, 1520 (NO2),
1620 (C=C). 1H NMR (CDСl3), δ: 1.21 (t, 3 Н, SCH2СН3, J =
7.4 Hz); 2.80 (q, 2 Н, SCH2СН3, J = 7.4 Hz); 7.49 (s, 1 Н,
СH=CCF3); 7.92, 8.24 (both d, 2 Н each, Ar, J = 7.4 Hz).
13C NMR (CDСl3), δ: 14.4 (SCH2СН3); 28.5 (SCH2СН3); 123.0
(q, CF3, J = 275.2 Hz); 128.5 (q, C—CF3, J = 32.2 Hz); 136.0
(q, CH=CCF3, J = 5.1 Hz); 123.5, 130.9, 140.0, 147.7 (Ar).
1ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ3ꢀ
nitrobenzene (3b) was obtained as a 12/1 mixture with
1ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ3ꢀnitrobenꢀ
zene (4b) from 1b. The yield was (3 + 4) 95%, yellow oil.
Found (%): C, 47.60; H, 3.51. C11H10F3NO2S. Calculated (%):
C, 47.65; H, 3.64. IR, ν/cm–1: 1340, 1530 (NO2), 1620 (C=C).
1H NMR (CDСl3, δ) of regioisomer 3b: 1.24 (t, 3 Н, SCH2СН3,
J = 7.4 Hz); 2.82 (q, 2 Н, SCH2СН3, J = 7.4 Hz); 7.51 (s, 1 Н,
СH=CCF3); 7.62 (t, 1 Н, Ar, J = 8.0 Hz); 8.07 (d, 1 Н, Ar, J =
8.0 Hz); 8.22 (dd, 1 Н, Ar, J = 8.0 Hz, J = 1.4 Hz); 8.70 (s, 1 Н,
Ar); regioisomer 4b: 1.11 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.44
(q, 2 Н, SCH2СН3, J = 7.4 Hz); 6.00 (q, 1 Н, CHCF3, J =
7.8 Hz); 7.87 (d, 1 Н, Ar, J = 8.1 Hz); 8.28 (dd, 1 Н, Ar, J =
8.1 Hz, J = 1.3 Hz); 8.63 (s, 1Н, Ar). 13C NMR (CDСl3, δ)
of regioisomer 3b: 14.4 (SCH2СН3); 28.7 (SCH2СН3); 123.1 (q,
CF3, J = 275.2 Hz); 123.2 (q, C—CF3, J = 32.2 Hz); 136.4 (q,
CH=CCF3, J = 5.9 Hz); 123.9, 124.8, 129.4, 135.2, 136.0, 148.2
(Ar); regioisomer 4b: 14.8 (SCH2СН3); 26.8 (SCH2СН3); 120.8
(q, С=CНCF3, J = 34.4 Hz); 121.5 (q, CF3, J = 270.8 Hz);
123.2, 124.4, 129.5, 137.9, 139.3, 148.1 (Ar). The rest of the
signals of 4b are overlapped with those of regioisomer 3b.
1ꢀ[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ1,2ꢀdimethoxyꢀ
benzene (2l) was obtained from 1,2ꢀdimethoxybenzaldehyde.
A mixture of Z/Eꢀisomers (8/1 after purification), the yield
was 54%, colorless oil. Found (%): C, 42.38; H, 3.20.
C11H10BrF3O2. Calculated (%): C, 42.47; H, 3.24. IR, ν/cm–1
:
1610 (C=C). 1H NMR (CDСl3, δ) of Zꢀisomer: 3.89 (s, 6 Н,
2 OCH3); 6.88 (d, 1 Н, Ar, J = 8.5 Hz); 7.29 (dd, 1 Н, Ar, J =
8.5 Hz, J = 1.8 Hz); 7.41 (d, 1 Н, Ar, J = 1.8 Hz); 7.49 (s, 1 Н,
СH=CCF3); Eꢀisomer: 3.86 (s, 6 Н, OCH3); 7.15 (dd, 1 Н, Ar,
J = 8.6 Hz, J = 1.5 Hz). 13C NMR (CDСl3, δ) of Zꢀisomer: 55.9
(2 OCH3); 106.5 (q, C—CF3, J = 36.6 Hz); 121.2 (q, CF3, J =
270.8 Hz); 133.8 (q, CH=CCF3, J = 5.9 Hz); 110.8, 112.1,
124.1, 124.9, 148.7, 150.7 (Ar); Eꢀisomer: 55.9 (OCH3); 141.5
(q, С=CНCF3, J = 2.9 Hz); 111.0, 111.5, 122.1, 125.3, 148.6,
150.0 (Ar). The rest of the signals of Eꢀisomer are overlapped
with those of Zꢀisomer.
[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzene (2m) was obꢀ
tained from benzaldehyde. A mixture of Z/Eꢀisomers (6/1 after
purification), the yield was 73%, colorless oil. Found (%):
C, 43.27; H, 2.38. C9H6BrF3. Calculated (%): C, 43.06; H, 2.41.
IR, ν/cm–1: 1610 (C=C). 1H NMR (CDСl3, δ) of Zꢀisomer:
7.49—7.54 (m, 3 Н, Ar); 7.69 (s, 1 Н, СH=CCF3); 7.77—7.83
(m, 2 Н, Ar); Eꢀisomer: 7.34—7.83 (m, 2 Н, Ar); 7.42—7.47 (m,
3 Н, Ar); 7.60 (s, 1 Н, СH=CCF3). 13C NMR (CDСl3, δ)
of Zꢀisomer: 109.6 (q, C—CF3, J = 36.6 Hz); 121.1 (q, CF3, J =
271.5 Hz); 134.5 (q, CH=CCF3, J = 5.1 Hz); 128.6, 129.7,
130.2, 132.5 (Ar); Eꢀisomer: 128.4, 129.1, 128.3, 133.9 (Ar);
141.7 (q, CH=CCF3, J = 2.9 Hz). The rest of the signals of
Eꢀisomer are overlapped with those of Zꢀisomer.
1ꢀ[2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ2ꢀnitrobenzene
(3c) was obtained from 1c. A mixture of Z/Eꢀisomers (7/1 after
purification), the yield was 76%, yellow oil. Found (%): C, 46.86;
H, 3.08. C11H10F3NO2S. Calculated (%): C, 47.65; H, 3.64. IR,
1
ν/cm–1: 1330, 1560 (NO2); 1615 (C=C). H NMR (CDСl3, δ)
of Zꢀisomer: 1.11 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.61 (q, 2 Н,
SCH2СН3, J = 7.4 Hz); 7.56—7.79 (m, 3 Н, Ar); 7.85 (s, 1 Н,
СH=CCF3); 8.20 (d, 1 Н, Ar, J = 8.3 Hz); Eꢀisomer: 1.32 (t,
3 Н, SCH2СН3, J = 7.3 Hz); 2.71 (q, 2 Н, SCH2СН3, J =
7.3 Hz); 8.24 (d, 1 Н, Ar, J = 8.3 Hz). 13C NMR (CDСl3, δ)
of Zꢀisomer: 14.3 (SCH2СН3); 28.4 (SCH2СН3); 123.1 (q, CF3,
J = 273.7 Hz); 126.7 (q, C—CF3, J = 32.2 Hz); 137.8 (q,
CH=CCF3, J = 5.9 Hz); 124.7, 129.8, 130.1, 131.8, 133.5,
147.3 (Ar); Eꢀisomer: 14.4 (SCH2СН3); 32.9 (SCH2СН3); 126.7
(q, C—CF3, J = 38.1 Hz); 129.5 (q, CH=CCF3, J = 4.4 Hz);
125.1, 127.5, 130.4, 131.3, 133.8, 147.2 (Ar). The rest of the
signals of Eꢀisomer are overlapped with those of Zꢀisomer.
1ꢀBromoꢀ2ꢀ[2ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benꢀ
zene (3d) was obtained from 1d and 2d. A mixture of Z/Eꢀisoꢀ
mers (20/1 after purification), the yield was 89% (from 1d),
85% (from 2d), colorless oil. Found (%): C, 42.47; H, 3.14.
1ꢀ[2ꢀBromoꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethylbenzene
(2n) was obtained from 4ꢀmethylbenzaldehyde. A mixture of
Z/Eꢀisomers (9/1 after purification), the yield was 72%, colorꢀ
less oil.
The synthesis of trifluoromethylvinyl sulfides (general proceꢀ
dure). Ethanol (5 mL), KOH (0.34 g, 5.5 mmol), and thiol
(6 mmol) were placed in a 25ꢀmL roundꢀbottom flask, and this
was stirred for 5 min until complete dissolution of KOH. Then,
a solution of the corresponding styrenes 1 or 2 (5 mmol) in
ethanol (5 mL) was added with vigorous stirring, and the reacꢀ
tion mixture was refluxed for 5—10 min (TLC monitoring). The
reaction mixture was poured in water (100 mL), extracted with
dichloromethane (3×100 mL). The combined extract was washed
with brine and dried with Na2SO4. Dichloromethane was reꢀ
moved in vacuo, the residue was dissolved in hexane or in the
appropriate hexaneꢀdichloromethane mixture and run through
a short layer of silica gel. Attempted chromatographic separaꢀ
tion of isomeric of alkenes failed.
C11H10BrF3S. Calculated (%): C, 42.46; H, 3.24. IR, ν/cm–1
:
1625 (C=C). 1H NMR (CDСl3, δ) of Zꢀisomer: 1.18 (t, 3 Н,
SCH2СН3, J = 7.4 Hz); 2.68 (q, 2 Н, SCH2СН3, J = 7.4 Hz);
7.26 (td, 1 Н, Ar, J = 7.6 Hz, J = 1.2 Hz); 7.39 (td, 1 Н, Ar, J =
7.6 Hz, J = 0.9 Hz); 7.63 (s, 1 Н, СH=CCF3); 7.65 (dd, 1 Н, Ar,
J = 7.6 Hz, J = 1.2 Hz); 7.77 (dd, 1 Н, Ar, J = 7.6 Hz, J =
0.9 Hz); Eꢀisomer: 1.45 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.95 (q,
2 Н, SCH2СН3, J = 7.4 Hz). 13C NMR (CDСl3, δ) of Zꢀisoꢀ
mer: 14.3 (SCH2СН3); 28.2 (SCH2СН3); 123.3 (q, CF3, J =
274.5 Hz); 126.7 (q, C—CF3, J = 31.5 Hz); 138.7 (q, CH=CCF3,
J = 5.9 Hz); 124.2, 127.1, 130.4, 131.1, 132.6, 134.3 (Ar);
Eꢀisomer: 15.3 (SCH2СН3); 29.8 (SCH2СН3); 129.8 (q,
Regioisomers 3, 4 and Eꢀ, Zꢀstereoisomers failed to be isoꢀ
lated by chromatography.
1ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀnitroꢀ
benzene (3a) was obtained from 1a. The yield was 96%, yellow
oil. Found (%): C, 47.94; H, 3.69. C11H10F3NO2S. Calcuꢀ

Synthesis of trifluoromethyl(vinylsulfides)
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
1531
CH=CCF3, J = 5.1 Hz). The rest of the signals of Eꢀisomer are
overlapped with those of Zꢀisomer.
Found (%): C, 54.88; H, 4.93. C12H13F3OS. Calculated (%):
C, 54.95; H, 5.00. IR, ν/cm–1: 1620 (C=C). 1H NMR (CDСl3, δ)
of regioisomer 3i: 1.26 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.80 (q,
2 Н, SCH2СН3, J = 7.4 Hz); 3.87 (s, 3 Н, OCH3); 6.97 (d, 2 Н,
Ar, J = 8.7 Hz); 7.46 (s, 1 Н, СH=CCF3); 7.92 (d, 2 Н, Ar, J =
8.7 Hz); regioisomer 4i: 1.11 (t, 3 Н, SCH2СН3, J = 7.3 Hz);
2.48 (q, 2 Н, SCH2СН3, J = 7.3 Hz); 3.87 (s, 3 Н, OCH3); 5.88
(q, 1 Н, CHCF3, J = 8.6 Hz); 6.97, 7.47 (both d, 2 Н each, Ar,
J = 8.9 Hz). 13C NMR (CDСl3, δ) of regioisomer 3i: 14.4
(SCH2СН3); 28.7 (SCH2СН3); 55.3 (OCH3); 120.5 (q, C—CF3,
J = 31.5 Hz); 124.0 (q, CF3, J = 274.5 Hz); 139.3 (q, CH=CCF3,
J = 5.1 Hz); 113.8, 126.2, 132.4, 160.8 (Ar); regioisomer 4i:
14.9 (SCH2СН3); 26.8 (SCH2СН3); 55.3 (OCH3); 117.5
(q, С=CНCF3, J = 34.4 Hz); 123.0 (q, CF3, J = 270.8 Hz);
151.0 (q, С=CНCF3, J = 5.1 Hz); 114.1, 126.2, 129.5,
160.8 (Ar).W
1ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ3ꢀ
methoxybenzene (3j) was obtained as a 3/1 mixture with
1ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ3ꢀmethoxyꢀ
benzene (4j) from 2j. The yield was (3 + 4) 95%, colorless oil.
Found (%): C, 54.48; H, 4.85. C12H13F3OS. Calculated (%):
C, 54.95; H, 5.00. IR, ν/cm–1: 1610 (C=C). 1H NMR (CDСl3, δ)
of regioisomer 3j: 1.26 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.81 (q,
2 Н, SCH2СН3, J = 7.4 Hz); 3.87 (s, 3 Н, OCH3); 6.95—7.02
(m, 1 Н, Ar); 7.34—7.39 (m, 2 Н, Ar); 7.49 (s, 1 Н, СH=CCF3);
7.64 (s, 1 Н, Ar); regioisomer 4j: 1.14 (t, 3 Н, SCH2СН3, J =
7.3 Hz); 2.49 (q, 2 Н, SCH2СН3, J = 7.3 Hz); 3.87 (s, 3 Н,
OCH3); 5.94 (q, 1 Н, CHCF3, J = 8.1 Hz); 7.05—7.12 (m, 2 Н,
Ar); 7.28—7.34, 7.35—7.39 (both m, 1 Н each, Ar). 13C NMR
(CDСl3, δ) of regioisomer 3j: 14.4 (SCH2СН3); 28.6
(SCH2СН3); 55.2 (OCH3); 123.7 (q, CF3, J = 273.7 Hz); 124.0
(q, C—CF3, J = 31.5 Hz); 139.1 (q, CH=CCF3, J = 5.1 Hz);
115.2, 115.6, 123.1, 129.4, 134.9, 159.5 (Ar); regioisomer 4j:
15.0 (SCH2СН3); 26.8 (SCH2СН3); 55.3 (OCH3); 118.4 (q,
С=CНCF3, J = 34.4 Hz); 122.9 (q, CF3, J = 270.8 Hz); 151.4
(q, С=CНCF3, J = 5.1 Hz); 113.6, 120.5, 129.7, 138.9,
159.9 (Ar). The rest of the signals are overlapped with those of
regioisomer 3j.
1ꢀBromoꢀ2ꢀ[(1Z )ꢀ2ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ
4ꢀmethoxybenzene (3e) was obtained from 2e. The yield was 94%,
colorless oil. Found (%): C, 42.33; H, 3.42. C12H12BrF3OS.
Calculated (%): C, 42.24; H, 3.55. IR, ν/cm–1: 1620 (C=C).
1H NMR (CDСl3), δ: 1.19 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.69
(q, 2 Н, SCH2СН3, J = 7.4 Hz); 3.84 (s, 3 H, OCH3), 6.82 (dd,
1 Н, Ar, J = 8.8 Hz, J = 2.9 Hz); 7.38 (d, 1 Н, Ar, J = 2.9 Hz);
7.50 (d, 1 Н, Ar, J = 8.8 Hz); 7.58 (s, 1Н, СH=CCF3). 13C NMR
(CDСl3), δ: 14.4 (SCH2СН3); 28.3 (SCH2СН3); 55.6 (OCH3);
123.3 (q, CF3, J = 273.7 Hz); 126.7 (q, C—CF3, J = 31.5 Hz);
138.5 (q, CH=CCF3, J = 5.6 Hz); 114.7, 116.2, 116.8, 133.2,
134.7, 158.5 (Ar).
Ethyl 4ꢀ[(1Z )ꢀ2ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benꢀ
zoate (3f) was obtained from 1f and 2f. The yield was 81%
(from 1f), 89% (from 2f), colorless oil. Found (%): C, 53.85;
H, 4.47. C14H15F3O2S. Calculated (%): C, 55.25; H, 4.97. IR,
ν/cm–1: 1610 (C=C), 1720 (C=O, CO2Et). 1H NMR (CDСl3),
δ: 1.16 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 1.39 (t, 3 Н,
CO2CH2СН3, J = 7.1 Hz); 2.73 (q, 2 Н, SCH2СН3, J = 7.4 Hz);
4.38 (q, 2 Н, CO2CH2СН3, J = 7.1 Hz); 7.46 (s, 1 Н,
СH=CCF3); 7.81, 8.06 (both d, 2 Н each, Ar, J = 8.5 Hz).
13C NMR (CDСl3), δ: 14.2, 14.3 (both СН3); 28.5 (SCH2СН3);
61.1 (CO2CH2СН3); 123.3 (q, CF3, J = 275.2 Hz); 126.3 (q,
C—CF3, J = 30.7 Hz); 137.3 (q, CH=CCF3, J = 5.9 Hz); 129.5,
130.0, 131.0, 137.9 (Ar); 165.9 (CO2CH2СН3).
2ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]pyridine
(3g) was obtained from 1g. The yield was 92%, colorless oil.
Found (%): C 51.29; H 4.33. C10H10F3NS. Calculated (%):
C, 51.49; H 4.32. IR, ν/cm–1: 1610 (C=C). 1H NMR (CDСl3),
δ: 1.19 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.81 (q, 2 Н, SCH2СН3,
J = 7.4 Hz); 7.21—7.24 (m, 1 Н, Py); 7.47 (s, 1 Н, СH=CCF3);
7.70 (td, 1 Н, Py, J = 7.7 Hz, J = 1.7 Hz); 7.95 (d, 1 Н, Py, J =
7.7 Hz); 8.64—8.67 (m, 1 Н, Py). 13C NMR (CDСl3), δ: 14.2
(SCH2СН3); 28.2 (SCH2СН3); 123.2 (q, CF3, J = 274.4 Hz);
127.9 (q, C—CF3, J = 31.5 Hz); 136.7 (q, CH=CCF3, J =
5.9 Hz); 123.3, 125.3, 136.1, 149.5, 152.9 (Py).
1ꢀChloroꢀ4ꢀ[(1Z )ꢀ2ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropꢀ
enyl]benzene (3h) was obtained as a 5/1 mixture with 1ꢀchloroꢀ
4ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzene (4h)
from 1h and 2h. The yield was (3 + 4) 90% (from 1h), 93%
(from 2h), colorless oil. Found (%): C, 49.62; H, 3.73.
1ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ2ꢀ
methoxybenzene (3k) was obtained as a 7/1 mixture with
1ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ2ꢀmethoxyꢀ
benzene (4k) from 2k. The yield was (3 + 4) 85%, colorless oil.
Found (%): C, 55.37; H, 5.03. C12H13F3OS. Calculated (%):
C, 54.95; H, 5.00. IR, ν/cm–1: 1620 (C=C). 1H NMR (CDСl3,
δ) of regioisomer 3k: 1.21 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.75
(q, 2 Н, SCH2СН3, J = 7.4 Hz); 3.89 (s, 3 Н, OCH3); 6.95 (d,
1 Н, Ar, J = 8.0 Hz); 7.04 (t, 1 Н, Ar, J = 7.6 Hz); 7.40 (td, 1 Н,
Ar, J = 8.0 Hz, J = 1.1 Hz); 7.81 (s, 1 Н, СH=CCF3); 8.05 (dd,
1 Н, Ar, J = 7.6 Hz, J = 1.1 Hz); regioisomer 4k: 1.11 (t, 3 Н,
SCH2СН3, J = 7.3 Hz); 2.37 (q, 2 Н, SCH2СН3, J = 7.3 Hz);
3.88 (s, 3 Н, OCH3); 5.71 (q, 1 Н, CHCF3, J = 8.5 Hz); 6.98 (d,
1 Н, Ar, J = 8.8 Hz); 7.26 (dd, 1 Н, Ar, J = 7.6 Hz, J = 1.5 Hz).
13C NMR (CDСl3, δ) of regioisomer 3k: 14.2 (SCH2СН3); 28.3
(SCH2СН3); 55.5 (OCH3); 123.4 (q, C—CF3, J = 30.7 Hz);
123.8 (q, CF3, J = 273.7 Hz); 134.9 (q, CH=CCF3, J = 5.9 Hz);
110.5, 120.1, 122.5, 130.3, 131.0, 157.8 (Ar); regioisomer 4k:
14.5 (SCH2СН3); 26.1 (SCH2СН3); 55.6 (OCH3); 116.0 (q,
С=CНCF3, J = 34.4 Hz); 123.2 (q, CF3, J = 270.8 Hz); 148.7
(q, С=CНCF3, J = 5.9 Hz); 111.1, 120.6, 126.2, 130.2, 130.4,
156.3 (Ar). The rest of the signals of 4k are overlapped with
those of regioisomer 3k.
C11H10ClF3S. Calculated (%): C, 49.54; H, 3.78. IR, ν/cm–1
:
1620 (C=C). 1H NMR (CDСl3, δ) of regioisomer 3h: 1.23 (t,
3 Н, SCH2СН3, J = 7.4 Hz); 2.79 (q, 2 Н, SCH2СН3, J =
7.4 Hz); 7.41 (d, 2 Н, Ar, J = 8.6 Hz); 7.45 (s, 1 Н, СH=CCF3);
7.79 (d, 2 Н, Ar, J = 8.6 Hz); regioisomer 4h: 1.11 (t, 3 Н,
SCH2СН3, J = 7.3 Hz); 2.44 (q, 2 Н, SCH2СН3, J = 7.3 Hz);
5.91 (q, 1 Н, CHCF3, J = 7.9 Hz). 13C NMR (CDСl3, δ) of
regioisomer 3h: 14.4 (SCH2СН3); 28.6 (SCH2СН3); 123.5 (q,
CF3, J = 274.4 Hz); 124.5 (q, C—CF3, J = 31.5 Hz); 137.9 (q,
CH=CCF3, J = 5.1 Hz); 128.7, 131.6, 132.1, 135.5 (Ar);
regioisomer 4h: 14.9 (SCH2СН3); 26.7 (SCH2СН3); 119.2 (q,
С=CНCF3, J = 34.4 Hz); 129.0, 129.4, 135.7, 136.0 (Ar). The
rest of the signals of 4h are overlapped with those of regioꢀ
isomer 3h.
1ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀ
methoxybenzene (3i) was obtained as a 0.5/1 mixture with
1ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethoxyꢀ
benzene (4i) from 2i. The yield was (3 + 4) 93%, colorless oil.

1532
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
Muzalevskiy et al.
4ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ1,2ꢀ
dimethoxybenzene (3l) was obtained as a 1/1 mixture with
4ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ1,2ꢀdimethꢀ
oxybenzene (4l) from 2l. The yield was (3 + 4) 89%, colorless oil.
Found (%): C, 53.37; H, 5.28. C13H15F3O2S. Calculated (%):
C, 53.41; H, 5.17. IR, ν/cm–1: 1610 (C=C). 1H NMR (CDСl3, δ)
of regioisomer 3l: 1.21 (t, 3 Н, SCH2СН3, J = 7.4 Hz); 2.76 (q,
2 Н, SCH2СН3, J = 7.4 Hz); 3.89 (s, 6 Н, OCH3); 6.87 (d, 1 Н,
Ar, J = 8.3 Hz); 7.31 (dd, 1 Н, Ar, J = 8.3 Hz, J = 1.8 Hz); 7.38
(s, 1 Н, СH=CCF3); 7.80 (d, 1 Н, Ar, J = 1.8 Hz); regioisomer 4l:
1.07 (t, 3 Н, SCH2СН3, J = 7.3 Hz); 2.44 (q, 2 Н, SCH2СН3,
J = 7.3 Hz); 3.89 (s, 6 Н, OCH3); 5.86 (q, 1 Н, CHCF3, J =
8.1 Hz); 6.87 (d, 1 Н, Ar, J = 8.3 Hz); 7.01 (d, 1 Н, Ar, J =
2.0 Hz); 7.04 (dd, 1 Н, Ar, J = 8.3 Hz, J = 2.0 Hz). 13C NMR
(CDСl3, δ) of regioisomer 3l: 14.5 (SCH2СН3); 28.8
(SCH2СН3); 55.8, 56.0 (both OCH3); 120.4 (q, C—CF3, J =
30.7 Hz); 123.9 (q, CF3, J = 273.7 Hz); 139.4 (q, CH=CCF3,
J = 5.1 Hz); 111.0, 112.6, 125.2, 130.0, 150.3, 150.4 (Ar);
regioisomer 4l: 15.0 (SCH2СН3); 26.8 (SCH2СН3); 55.8, 55.9
(both OCH3); 117.7 (q, С=CНCF3, J = 34.4 Hz); 122.9 (q,
CF3, J = 270.8 Hz); 150.0 (q, С=CНCF3, J = 5.9 Hz); 110.6,
111.0, 120.9, 126.3, 148.6, 149.0 (Ar).
[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]benzene (3m)
was obtained as a 2/1 mixture with [(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀ
trifluoroꢀ1ꢀpropenyl]benzene (4m) from 2m. The yield was (3 + 4)
96%, colorless oil. Found (%): C, 56.69; H, 4.81. C11H11F3S.
Calculated (%): C, 56.88; H, 4.77. IR, ν/cm–1: 1610 (C=C).
1H NMR (CDСl3, δ) of regioisomer 3m: 1.29 (t, 3 Н, SCH2СН3,
J = 7.4 Hz); 2.84 (q, 2 Н, SCH2СН3, J = 7.4 Hz); 7.43—7.52
(m, 3 Н, Ar); 7.58 (s, 1 Н, СH=CCF3); 7.91 (d, 2 Н, Ar, J =
6.8 Hz); regioisomer 4m: 1.16 (t, 3 Н, SCH2СН3, J = 7.3 Hz);
2.51 (q, 2 Н, SCH2СН3, J = 7.3 Hz); 5.96 (q, 1 Н, CHCF3, J =
8.1 Hz); 7.54—7.59 (m, 2 Н, Ar). 13C NMR (CDСl3, δ) of
regioisomer 3m: 14.4 (SCH2СН3); 28.6 (SCH2СН3); 123.8 (q,
CF3, J = 273.7 Hz); 123.9 (q, C—CF3, J = 31.5 Hz); 139.3 (q,
CH=CCF3, J = 5.1 Hz); 128.4, 129.7, 130.4, 133.7 (Ar);
regioisomer 4m: 14.9 (SCH2СН3); 26.7 (SCH2СН3); 118.5 (q,
С=CНCF3, J = 34.4 Hz); 123.0 (q, CF3, J = 270.8 Hz); 151.6
(q, С=CНCF3, J = 5.1 Hz); 128.2, 128.8, 129.7, 137.6 (Ar). The
rest of the signals of 4m are overlapped with those of regioꢀ
isomer 3m.
1ꢀ[(1Z )ꢀ2ꢀ(Benzylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀnitroꢀ
benzene (5b) was obtained from 1а. The yield was 91%, yellow
oil. Found (%): C, 54.89; H, 3.50. C16H12F3NO2S. Calcuꢀ
lated (%): C, 56.63; H, 3.56. IR, ν/cm–1: 1350, 1530 (NO2),
1620 (C=C). 1H NMR (CDСl3), δ: 3.97 (s, 2 Н, CH2);
7.11—7.17 (m, 2 Н, Ph); 7.19—7.24 (m, 3 Н, Ph); 7.54 (s, 1 Н,
СH=CCF3); 7.59, 8.20 (both d, 2 Н each, 4ꢀNO2C6H4, J =
8.8 Hz). 13C NMR (CDСl3), δ: 39.1 (CH2); 123.4 (q, CF3, J =
275.2 Hz); 127.1 (q, C—CF3, J = 31.5 Hz); 139.1 (q, CH=CCF3,
J = 5.1 Hz); 123.2, 127.7, 128.6, 129.2, 130.8, 136.0, 139.6,
147.7 (Ar).
2ꢀ{(Z)ꢀ[2ꢀ(4ꢀNitrophenyl)ꢀ1ꢀ(trifluoromethyl)vinyl]thio}pheꢀ
nylamine (5с) was obtained from 1а. The yield was 81%, orange
crystals, m.p. 81—82 °С. Found (%): C, 52.97; H, 3.48.
C15H11F3N2O2S. Calculated (%): C, 52.94; H, 3.26. IR,
ν/cm–1: 1350, 1510 (NO2), 1620 (C=C), 2950 br. (NH).
1H NMR (CDСl3), δ: 4.07 (s, 2 Н, NH2); 6.60—6.67 (m,
2 Н, 2ꢀNH2C6H4); 7.11 (td, 1 Н, 2ꢀNH2C6H4, J = 7.7 Hz,
J = 1.5 Hz); 7.23 (dd, 1 Н, 2ꢀNH2C6H4, J = 7.7 Hz, J =
1.2 Hz); 7.55 (s, 1 Н, СH=CCF3); 7.80 (d, 2 Н, 4ꢀNO2C6H4,
J = 8.8 Hz); 8.25 (d, 2 Н, 4ꢀNO2C6H4, J = 8.8 Hz).
13C NMR (CDСl3), δ: 122.5 (q, CF3, J = 275.2 Hz); 128.7
(q, C—CF3, J = 31.5 Hz); 135.3 (q, CH=CCF3, J = 5.1 Hz);
112.4, 115.5, 118.8, 123.5, 130.7, 131.0, 135.6, 139.6, 147.8,
148.1 (Ar).
Ethyl [(2ꢀ(4ꢀnitrophenyl)ꢀ1ꢀ(trifluoromethyl)vinyl)thio]aceꢀ
tate (5d) was obtained from 1a. A mixture of Z/Eꢀisomers
(12/1 after purification), the yield was 72%, yellow oil.
Found (%): C, 46.48; H, 3.75. C13H12F3NO4S. Calculated (%):
C, 46.57; H, 3.61. IR, ν/cm–1: 1360, 1530 (NO2), 1620 (C=C),
1740 (C=O, CO2Et). 1H NMR (CDСl3, δ) of Zꢀisomer: 1.19
(t, 3 Н, OCH2СН3, J = 7.1 Hz); 3.52 (s, 2 Н, SСH2); 4.07 (q,
2 Н, OCH2СН3, J = 7.1 Hz); 7.55 (s, 1 Н, СH=CCF3);
7.97, 8.26 (both d, 2 Н each, Ar, J = 8.9 Hz); Eꢀisomer: 1.30
(t, 3 Н, OCH2СН3, J = 7.2 Hz); 3.63 (s, 2 Н, SСH2); 4.24
(q, 2 Н, OCH2СН3, J = 7.2 Hz); 7.45 (s, 1 Н, СH=CCF3);
7.45, 8.21 (both d, 2 Н each, Ar, J = 8.7 Hz). 13C NMR
(CDСl3, δ) of Zꢀisomer: 14.0 (OCH2СН3); 35.3 (SCH2); 61.9
(OCH2СН3); 122.9 (q, CF3, J = 275.2 Hz); 126.5 (q, C—CF3,
J = 32.2 Hz); 138.3 (q, CH=CCF3, J = 5.1 Hz); 123.6,
131.1, 139.4, 148.0, (Ar); 168.1 (CO2C2H5); Eꢀisomer: 14.2
(OCH2СН3); 35.3 (SCH2); 61.9 (OCH2СН3); 123.5 (Ar); 129.3
(q, CH=CCF3, J = 2.2 Hz). The rest of the signals of Eꢀisomer
are overlapped with those of Zꢀisomer.
1ꢀChloroꢀ4ꢀ[(2ꢀ(4ꢀnitrophenyl)ꢀ1ꢀ(trifluoromethyl)viꢀ
nyl)thio]benzene (5e) was obtained from 1a. A mixture of
Z/Eꢀisomers (7/1 after purification), the yield was 85%, yellow
oil. Found (%): C, 50.04; H, 2.33. C15H9ClF3NO2S. Calcuꢀ
lated (%): C, 50.08; H, 2.52. IR, ν/cm–1: 1350, 1530 (NO2),
1620 (C=C). 1H NMR (CDСl3, δ) of Zꢀisomer: 7.19—7.26 (m,
4 Н, 4ꢀClC6H4); 7.73 (s, 1 Н, СH=CCF3); 7.88, 8.24 (both d,
2 Н each, 4ꢀNO2C6H4, J = 8.7 Hz); Eꢀisomer: 7.01 (s, 1 Н,
СH=CCF3); 7.41 (d, 2 Н, 4ꢀClC6H4, J = 8.6 Hz); 7.45 (d, 2 Н,
4ꢀNO2C6H4, J = 8.7 Hz); 7.49 (d, 2 Н, 4ꢀClC6H4, J = 8.6 Hz);
8.21 (d, 2 Н, 4ꢀNO2C6H4, J = 8.7 Hz). 13C NMR (CDСl3, δ) of
Zꢀisomer: 122.7 (q, CF3, J = 275.2 Hz); 127.1 (q, C—CF3, J =
32.2 Hz); 139.6 (q, CH=CCF3, J = 5.1 Hz); 123.6, 129.5, 130.7,
130.9, 131.0, 134.0, 139.0, 148.2 (Ar); Eꢀisomer: 129.3 (q,
CH=CCF3, J = 2.2 Hz); 123.5, 130.1, 134.0, 137.7 (Ar). The
rest of the signals of Eꢀisomer are overlapped with those of
Zꢀisomer.
1ꢀ[(1Z )ꢀ2ꢀ(Ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀ
methylbenzene (3n) was obtained as a 1/1 mixture with
1ꢀ[(1Z )ꢀ1ꢀ(ethylthio)ꢀ3,3,3ꢀtrifluoroꢀ1ꢀpropenyl]ꢀ4ꢀmethylꢀ
benzene (4n) from 1n and 2n. The yield was (3 + 4) 64% (from
1n), 76% (from 2n), colorless oil. Found (%): C, 58.33; H, 4.99.
C12H13F3S. Calculated (%): C, 58.52; H, 5.32. IR, ν/cm–1
:
1610 (C=C). 1H NMR (CDСl3, δ) of regioisomer 3n: 1.27 (t,
3 Н, SCH2СН3, J = 7.4 Hz); 2.45 (s, 3 Н, CH3); 2.82 (q, 2 Н,
SCH2СН3, J = 7.4 Hz); 7.28 (d, 2 Н, Ar, J = 7.7 Hz); 7.51 (s,
1 Н, СH=CCF3); 7.81 (d, 2 Н, Ar, J = 7.7 Hz); regioisomer 4n:
1.13 (t, 3 Н, SCH2СН3, J = 7.3 Hz); 2.46 (s, 3 Н, CH3); 2.49 (q,
2 Н, SCH2СН3, J = 7.3 Hz); 5.92 (q, 1 Н, CHCF3, J = 8.1 Hz);
7.28, 7.43 (both d, 2 Н each, Ar, J = 7.5 Hz). 13C NMR
(CDСl3, δ) of regioisomer 3n: 14.2 (SCH2СН3); 21.4 (СН3);
28.6 (SCH2СН3); 122.1 (q, C—CF3, J = 30.7 Hz); 123.8 (q,
CF3, J = 273.0 Hz); 139.4 (q, CH=CCF3, J = 5.1 Hz); 129.2,
130.5, 130.9, 140.1 (Ar); regioisomer 4n: 14.9 (SCH2СН3); 21.2
(CH3); 26.7 (SCH2СН3); 118.0 (q, С=CНCF3, J = 34.4 Hz);
123.0 (q, CF3, J = 270.8 Hz); 151.4 (q, С=CНCF3, J = 5.1 Hz);
128.0, 129.4, 134.6, 139.8 (Ar).

Synthesis of trifluoromethyl(vinylsulfides)
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 8, August, 2007
1533
1ꢀMethylꢀ4ꢀ[(2ꢀ(4ꢀnitrophenyl)ꢀ1ꢀ(trifluoromethyl)viꢀ
nyl)thio]benzene (5f) was obtained from 1a. A mixture of
Z/Eꢀisomers (7/1 after purification), the yield was 88%, yellow
oil. Found (%): C, 56.71; H, 3.63. C16H12F3NO2S. Calcuꢀ
lated (%): С, 56.63, H, 3.56. IR, ν/cm–1: 1350, 1530 (NO2),
1620 (C=C). 1H NMR (CDСl3, δ) of Zꢀisomer: 2.31 (s, 3 Н,
СH3); 7.08, 7.20 (both d, 2 Н each, 4ꢀCH3C6H4, J = 8.1 Hz);
7.67 (s, 1 Н, СH=CCF3); 7.89, 8.22 (both d, 2 Н each,
4ꢀNO2C6H4, J = 8.7 Hz); Eꢀisomer: 2.41 (s, 3 Н, СH3); 6.72 (s,
1 Н, СH=CCF3); 7.27 (d, 2 Н, 4ꢀCH3C6H4, J = 8.0 Hz); 7.41
(d, 2 Н, 4ꢀNO2C6H4, J = 8.7 Hz); 7.49 (d, 2 Н, 4ꢀCH3C6H4,
J = 8.0 Hz); 8.18 (d, 2 Н, 4ꢀNO2C6H4, J = 8.7 Hz). 13C NMR
(CDСl3, δ) of Zꢀisomer: 21.0 (СН3); 122.8 (q, CF3, J =
275.2 Hz); 128.2 (q, C—CF3, J = 32.2 Hz); 138.2 (q, CH=CCF3,
J = 5.1 Hz); 123.5, 128.4, 130.1, 130.2, 130.9, 138.1, 139.4,
148.0 (Ar); Eꢀisomer: 21.3 (СН3); 129.3 (q, CH=CCF3, J =
1.5 Hz); 123.4, 130.8, 134.0, 140.0, 141.1, 147.4 (Ar). The rest
of the signals of Eꢀisomer are overlapped with those of Zꢀisomer.
Nenajdenko, A. V. Shastin, V. N. Korotchenko, G. N.
Varseev, and E. S. Balenkova, Eur. J. Org. Chem., 2003, 302;
(c) V. G. Nenajdenko, G. N. Varseev, V. N. Korotchenko,
A. V. Shastin, and E. S. Balenkova, J. Fluorine Chem., 2003,
124, 115; (d) V. G. Nenajdenko, G. N. Varseev, V. N.
Korotchenko, A. V. Shastin, and E. S. Balenkova, J. Fluoꢀ
rine Chem., 2004, 125, 1339; (e) V. G. Nenajdenko, G. N.
Varseev, A. V. Shastin, and E. S. Balenkova, J. Fluorine
Chem., 2005, 126, 907; (f) A. V. Shastin, V. M. Muzalevsky,
E. S. Balenkova, and V. G. Nenajdenko, Mendeleev Commuꢀ
nications, 2006, 16, 179.
5. V. G. Nenajdenko, V. M. Muzalevskiy, A. V. Shastin, E. S.
Balenkova, and G. Haufe, J. Fluorine Chem., 2007, 128, 818.
6. J.ꢀP. Begue, D. BonnetꢀDelpon, and M. Rock, Tetrahedron
Lett., 1996, 37, 171.
7. I. H. Jeong, Y. S. Park, M. S. Kim, and Y. S. Song, J. Fluorine
Chem., 2003, 120, 195.
8. J.ꢀP. Begue, A. M'Bida, D. BonnetꢀDelpon, B. Novo, and
G. Resnati, Synthesis, 1996, 399.
9. H. Uno, M. Tanaka, T. Inoue, and N. Ono, Synthesis,
1999, 471.
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Received June 26, 2007;
in revised form August 2, 2007