Reactions of trifluoromethyl-substituted arylacetylenes with arenes in superacids

Article abstract of DOI:10.1134/S1070428013030032

Protonation of the C≡C bond in trifluoromethyl-substituted arylacetylenes ArC≡CCF₃ by the action of superacids (CF ₃SO₃H or HSO₃F) generates vinyl cations ArC⁺=CHCF₃ which react with arenes Ar′H to give alkenes Ar(Ar′)C=CHCF₃. Protonation of the latter at the C=C bond in the reaction medium yields stable cations Ar(Ar′)C ⁺-CH₂CF₃ which are converted into E/Z-isomeric alkenes Ar(Ar′)C=CHCF₃ and/or alcohols Ar(Ar′)C(OH) CH₂CF₃ as a result of quenching of superacid reaction solution.

Full text of DOI:10.1134/S1070428013030032

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 3, pp. 327–341. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © H.M.H. Alkhafaji, D.S. Ryabukhin, V.M. Muzalevskiy, L.V. Osetrova, A.V. Vasilyev, V.G. Nenajdenko, 2013, published in Zhurnal
Organicheskoi Khimii, 2013, Vol. 49, No. 3, pp. 341–354.
Dedicated to Full Member of the Russian Academy of Sciences
I.P. Beletskaya on her jubilee
Reactions of Trifluoromethyl-Substituted Arylacetylenes
with Arenes in Superacids
H. M. H. Alkhafajia, D. S. Ryabukhina, V. M. Muzalevskiyb, L. V. Osetrovac,
A. V. Vasilyeva, d, and V. G. Nenajdenkob
a St. Petersburg State Forest Technical University, Institutskii per. 5, St. Petersburg, 194021 Russia
e-mail: aleksvasil@mail.ru
b Moscow State University, Vorob’evy gory 3, Moscow, 119899 Russia
e-mail: nen@acylium.chem.msu.ru
c Research Institute for Synthetic Rubber, Gapsal’skaya ul. 1, St. Petersburg, 198035 Russia
d St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received December 21, 2012
Abstract—Protonation of the C≡C bond in trifluoromethyl-substituted arylacetylenes ArC≡CCF3 by the action
of superacids (CF3SO3H or HSO3F) generates vinyl cations ArC+=CHCF3 which react with arenes Ar′H to give
alkenes Ar(Ar′)C=CHCF3. Protonation of the latter at the C=C bond in the reaction medium yields stable
cations Ar(Ar′)C+–CH2CF3 which are converted into E/Z-isomeric alkenes Ar(Ar′)C=CHCF3 and/or alcohols
Ar(Ar′)C(OH)CH2CF3 as a result of quenching of superacid reaction solution.
DOI: 10.1134/S1070428013030032
Fluorine-containing organic compounds are very
important for both theoretical and applied chemistry,
physics, biology, medicine, and other fields of science
and technology [1]. Development of new selective
methods for the synthesis and modification of
fluorinated compounds is a topical problem of organic
chemistry.
reactions of cations A with arenes, which afford their
alkenylation products II (Scheme 1). Alkenes II in turn
can also be protonated at the double bond with
CF3SO3H or HSO3F to form stable carbocations B
which were characterized by NMR spectroscopy. De-
pending on the conditions for quenching of superacid
solution, cations B may undergo deprotonation to give
back alkenes E/Z-II or may take up water molecule
with formation of alcohols III (Scheme 1).
The present study was aimed at generating vinyl
cations A by regioselective protonation of the triple
C≡C bond in trifluoromethyl-substituted acetylenes I
in superacids (CF3SO3H and HSO3F) and studying
The results of reactions of alkynes Ia–Ie with
various substituted benzenes, leading to the formation
Scheme 1.
Ar'
CF3
H
–H+
Ar
CF3
H
Ar'
CF3
Ar'
CF3
H+
H+
Ar'H
II
Ar
CF3
Ar
OH
Ar
H
Ar
CF3
H2O
–H+
Ar'
Ar
Ia–Ie
A
II
B
III
Ar = C6H4R; R = H (a), 4-Me (b), 4-MeO (c), 4-Cl (d), 2-O2N (e).
327

ALKHAFAJI et al.
328
δ 7.22 ppm
d, 2H
NOE
H
MeO
CF3
H δ 6.16 ppm
CF3
δ 6.11 ppm
δ 5.25 ppm
H
CF3
H
NOE
NOE
H
O2N
H
δ 7.07 ppm
δ 7.36 ppm
d.d, 1H
d, 1H
Cl
Cl
Cl
Cl
E-IIc
Z-IIc
E-IIx
Correlations between protons in the NOESY spectra (CDCl3, 20°C) of alkenes E-IIc, Z-IIc, and E-IIx.
of E/Z-alkenes IIa–IIx and alcohols IIIa–IIIu are
summarized in Tables 1 and 2 and Schemes 2–8.
reaction mixture under different conditions (Table 1).
Cation B1 generated from Ia in CF3SO3H is converted
via hydrolysis with water into approximately equal
amounts of alkene IIa and alcohol IIIa. The yield of
alcohol IIIa decreased when the superacid reaction
solution was treated with concentrated aqueous acids,
aqueous alkalies (Table 1, run nos. 5, 6), or aqueous
methanol, but only quenching with anhydrous systems
like MeOH–MeONa or MeCN completely suppressed
the formation of IIIa so that alkene IIa was obtained
as the only product.
Like 1,1-diarylpropene derivatives studied previ-
ously [2–5], alkenes IIa–IIx were assigned the E or Z
isomer structure on the basis of specific position of the
1
vinylic proton signal in their H NMR spectra. The
signal of the vinylic proton in the E isomers of IIa–IIx
is observed at δ 5.19–6.17 ppm, whereas the corre-
sponding proton of the Z isomers resonates in a weaker
field, δ 6.01–6.26 ppm (see Experimental).
Additional proofs for the steric structure of E/Z-IIc
and E-IIx were obtained by NOESY experiments (see
figure). The NOESY spectrum of pure compound IIx
displayed coupling between the vinylic proton (q,
δ 5.25 ppm) and ortho-protons in the unsubstituted
phenyl ring (d.d, δ 7.36 ppm). This coupling is
possible only for the E-isomer in which the above
protons appear spatially close to each other. Likewise,
NOESY experiment for a mixture of the E and Z
isomers of IIc revealed a strong correlation between
the vinylic proton (q, δ 6.11 ppm) and ortho-proton in
the 3,4-dichlorophenyl ring (d.d, δ 7.07 ppm), which is
typical of the E isomer. The vinylic proton in Z-IIc (q,
δ 6.16 ppm) is coupled with ortho-protons in the un-
substituted phenyl ring (d, δ 7.22 ppm).
The conversion of alkyne Ia in trifluoroacetic acid,
which is considerably weaker than CF3SO3H, was very
low (~5%), and we succeeded in detecting only traces
of products IIa and IIIa. In the reaction of Ia with
benzene in H2SO4 alkene IIa was formed in a poor
yield, and the major product was ketone IVa (72%).
Analogous products were obtained from alkyne Ic
(Scheme 3, Table 2). As in the previous case, quench-
ing of the reaction mixture with aqueous systems pro-
moted partial transformation of cation B2 into alcohol
IIIb, while anhydrous systems gave rise to isomeric
alkenes E/Z-IIb. In the reactions with H2SO4 and
CF3CO2H ketone IVb was also formed. In all cases,
the ratio of the E and Z isomers of IIb was ~1:3.
Scheme 2 illustrates the reaction of 3,3,3-trifluoro-
1-phenylprop-1-yne (Ia) with benzene in CF3SO3H,
CF3CO2H, or H2SO4, followed by quenching of the
The presence of an electron-donor methoxy group
in arylacetylene Ic facilitates protonation of the triple
C≡C bond in comparison with alkyne Ia. Even in such
Scheme 2.
Ph
Ph
CF3
H
–H+
CF3SO3H
C6H6
O
Ph
Ph
CF3
H2SO4
IIa
IIa
+
Ph
CF3
OH
Ph
CF3
CF3
H2O
–H+
Ph
Ph
IVa
Ia
B1
IIIa
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
329
Table 1. Reaction of 3,3,3-trifluoro-1-phenylpropyne (Ia) with benzene in superacids at 20°C (Scheme 2)
Reaction conditions
Yield, %
Run no.
Quenching system
acid
time, h
IIa
IIIa
01
02
03
04
05
06
07
08
09
10
11
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
CF3CO2Ha
H2SO4
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
3.0
1.0
H2O
36
91
34
08
19
17
10
27
12
–
Concd. aq. HCl
Concd. aq. HBr
Concd. H2SO4
NaHCO3–H2O
NaOH–H2O
MeOH–H2O
MeOH–MeONa
MeCN
68
72
73
61
81
96
98
–
H2O
Traces
b14b
Traces
–
H2O
a
Conversion of Ia <5%.
Ketone IVa was formed as the major product (yield 72%).
b
Table 2. Reaction of 3,3,3-trifluoro-1-(4-methoxyphenyl)propyne (Ic) with benzene in superacids at 20°C (Scheme 3)
Reaction conditions
Yield, %
Run no.
Quenching system
acid
time, h
E-IIb
Z-IIb
IIIb
IVb
overall
1
CF3SO3H
CF3SO3H
CF3SO3H
CF3SO3H
H2SO4
0.5
0.5
0.5
0.5
1.0
1.0
1.0
H2O
13
15
21
16
10
09
–
35
42
65
63
29
30
–
16
20
–
–
–
64
77
86
79
58
56
96
2
Concd. aq. HCl
MeOH–MeONa
MeCN
3
–
4
–
–
5
H2O
–
19
17
96
6
CF3CO2H
CF3CO2Ha
H2O
–
7
H2O
–
a
No benzene.
Scheme 3.
MeO
MeO
CF3
H
–H+
MeO
CF3
CF3SO3H
C6H6
Ph
E/Z-IIb
CF3
OH
Ph
B2
H2O
–H+
MeO
CF3
Ph
IIIb
MeO
Ic
CF3
H2SO4
or CF3COOH
E/Z-IIb
+
O
IVb
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

ALKHAFAJI et al.
330
Scheme 4.
CF3
H
CF3SO3H, 20°C, 0.5–1 h
or HSO3F, –75°C, 2 h
HO
Ph
Ph
Ph
H
CF3
+
CF3
+
CF3
ArH
+
Ph
Ar
E-IIb–E-IIh
Ar
Z-IIb–Z-IIh
Ar
IIIb, IIIc
Ia
Ar = C6HnR; R = 4-MeO (b), 3,4-Cl2 (c), 2,4-Me2 (d), 2,5-Me2 (e), 2,4,6-Me3 (f), 4-t-Bu (g), 3,4-(MeO)2 (h).
Scheme 5.
Me
Me
H
CF3
CF3SO3H, 20°C, 0.5–1 h
or HSO3F, –75°C, 2 h
CF3
+
H
+
CF3
ArH
Me
Ar
Ar
Z-IIi–Z-IIn
Ib
E-IIi–E-IIn
Me
+
CF3
Ar OH
IIIi, IIIk, IIIn
Ar = C6HnR; R = H (i), 2,4-Me2 (j), 3,4-Cl2 (k), 4-MeO (l), 3,4-(MeO)2 (m), 4-t-Bu (n).
Scheme 6.
MeO
MeO
H
CF3
CF3SO3H, 20°C, 0.5 h
CF3
H
+
CF3
ArH
+
MeO
Ar
Ar
Z-IIp–Z-IIr
Ic
IIo, E-IIp, E-IIr
MeO
+
CF3
Ar OH
IIIo
Ar = C6HnR; R = 4-MeO (o), 2,5-Me2 (p), 2,4-Me2 (q), 4-t-Bu (r).
a weak acid as CF3CO2H, compound Ic was converted
into alkenes E/Z-IIb and/or ketone IVb (cf. run nos. 6
and 7 in Table 2 and run no. 10 in Table 1).
derivatives (Schemes 5, 6) to produce alkenes E/Z-IIi–
E/Z-IIr in up to 94% yield, the E/Z ratio ranging from
~1:1 to 1:11 (see Experimental). Acetylenic substrates
Id and Ie with electron-withdrawing substituents
(Cl, NO2) in the aromatic ring are also capable of
reacting with arenes in superacids. The corresponding
vinyl cations A efficiently reacted with benzene,
anisole, 1,2-dimethoxybenzene, and 1,2-dichloroben-
zene (Schemes 7, 8). Quenching of the superacid solu-
tions with water gave 18–40% of alcohols IIIs–IIIu.
Acetylenic compounds Ia–Ie reacted with various
alkyl-, halogen-, and methoxy-substituted benzenes in
CF3SO3H or HSO3F (Schemes 4–8). The major prod-
ucts of the reactions of Ia with arenes in superacids
were isomeric alkenes E/Z-IIb–E/Z-IIh (overall yield
23–85%, E/Z ratio ~1:(1.2–4) (Scheme 4, see Experi-
mental). When the reaction mixtures were treated with
water, alcohols IIIb and IIIc were additionally formed
in 23 and 18% yield, respectively.
In most cases, the Z isomer predominated in mix-
tures of isomeric alkenes II. The isomer ratio is deter-
mined by different energies of intermediates and steric
requirements in alternative pathways of deprotonation
of cations B, leading to E or Z isomer (Scheme 1).
Vinyl cations A (Scheme 1) generated from com-
pounds Ib and Ic having electron-donor groups (Me,
MeO) in the aromatic ring reacted with benzene and its
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
331
Scheme 7.
Cl
Cl
Cl
H
CF3
CF3
CF3SO3H
20°C, 0.5 h
CF3
H
+
+
CF3
ArH
+
Cl
Ar OH
IIIs–IIIu
Ar
Ar
Id
E-IIs–E-IIv
Z-IIs–Z-IIv
Ar = C6HnR; R = H (s), 4-MeO (t), 3,4-Cl2 (u), 3,4-(MeO)2 (v).
Scheme 8.
NO2
H
CF3
CF3SO3H
20°C, 0.5 h
CF3
+
H
+
ArH
CF3
NO2 Ar
NO2 Ar
Ie
E-IIw, E-IIx
Z-IIw
Ar = C6H4R, R = H (w), 4-MeO (x).
One more specific feature of the reaction under
study may be noted. Cations B having several electron-
donor methyl or methoxy groups in the aromatic ring
were not converted into alcohols III even after hydro-
lytic decomposition of the reaction solutions. Alkenes
IId–IIf, IIj, IIm, and IIv were the only products
obtained from the corresponding dimethyl-, trimethyl-,
and dimethoxyphenylacetylenes (Schemes 4, 5, 7) as
a result of treatment of the reaction mixtures with
water, whereas alcohols III were not isolated (see
Experimental). This may be due to considerable delo-
calization of the positive charge over electron-donor
aryl fragment in cation B, which reduces the charge
and hence electrophilicity of the carbocationic center
thus hampering nucleophilic attack by water molecule.
reaction of Ia with benzene, from alkene IIa, and from
alcohol IIIa (Scheme 9). Cations B2 and B3 were
produced in similar ways (Schemes 10, 11).
1
In the H NMR spectra of B1–B3 we observed
a quartet signal at 4.48–4.90 ppm from the CH2
protons coupled with fluorine nuclei in the neighboring
CF3 group, and the latter gave a triplet at δF –58.56 to
–60.02 ppm in the 19F NMR spectrum. The cationic
carbon atom resonated in the 13C NMR spectra at
δC ~182–207 ppm. The upfield shift of the C+ signal in
going from B1 to B2 and then to B3 reflects the effect
of the electron-donor p-methoxyphenyl group on charge
delocalization (Table 3).
In addition, we examined transformations of
chloro- and bromodifluoromethyl-substituted aryl-
acetylenes Va and Vb. The reactions of Va and Vb
with benzene in CF3SO3H at 0 or 20°C resulted in the
formation of complex mixtures of oligomeric products.
Obviously, solvolysis of the CF2X group in superacid
Intermediate cations B1–B3 are stable in CF3SO3H
at 20°C, and they may be characterized by NMR
spectroscopy (Table 3). These cations can be generated
in CF3SO3H solution in several ways. Cation B1 was
generated in CF3SO3H directly in an NMR ampule by
+
generates reactive cationic species CF2 which are in-
volved in alternative reaction pathways. We succeeded
in retaining the CF2X fragment intact by carrying out
the reaction in HSO3F at low temperature (–75°C;
Scheme 12). Under these conditions, from chloro-
difluoro derivative Va we obtained E/Z-alkenes VIa
and alcohol VII, and bromodifluoro derivative afford-
ed only alkenes E/Z-VIb (see Experimental).
Scheme 9.
CF3SO3H
C6H6
Ph
Ph
CF3
CF3SO3H
Ia
IIa or IIIa
B1
Scheme 10.
To conclude, the reaction of trifluoromethyl-sub-
stituted arylacetylenes with arenes in Brønsted super-
acids (CF3SO3H or HSO3F) may be regarded as a new
method for the synthesis of 1,1-diaryl-3,3,3-trifluoro-
propenes and 1,1-diaryl-3,3,3-trifluoropropan-1-ols.
This approach is advantageous due to its high effi-
ciency, selectivity, and generally high yields.
MeO
CF3SO3H
CF3SO3H
E/Z-IIb
IIIb
CF3
Ph
B2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

ALKHAFAJI et al.
332
Scheme 11.
F3C
H
F3C
CF3SO3H
MeO
OMe
MeO
OMe
IIo
B3
Scheme 12.
Cl
Cl
Cl
H
CF2X
CF2Cl
HSO3F, –75°C, 1 h
C6H6
CF2X
H
+
+
Cl
CF2X
Ph OH
VII
Ph
Ph
Z-VIa, Z-VIb
Va, Vb
E-VIa, E-VIb
X = Cl (a), Br (b).
EXPERIMENTAL
checked by TLC on Silufol UV-254 plates. The prod-
uct mixtures were separated by column chromatog-
raphy on silica gel (40–100 μm, Chemapol) using pe-
troleum ether–ethyl acetate as eluent. The synthesis
and properties of trifluoromethyl-substituted arylace-
tylenes Ia–Ie were given in [6].
The 1H, 19F, and 13C NMR spectra were recorded at
20°C on a Bruker AM-500 spectrometer at 500, 470,
and 125.76 MHz, respectively, using CDCl3 as solvent
1
and reference (for H and 13C; CHCl3, δ 7.26 ppm;
CDCl3, δC 77.0 ppm); the 19F chemical shifts were
Alkenylation of aromatic compounds with tri-
fluoromethyl- and halodifluoromethyl-substituted
arylacetylenes Ia–Ie, Va, and Vb in superacids
CF3SO3H and HSO3F (general procedure). Arylace-
tylene Ia–Ie, 0.3 mmol, was gradually added under
vigorous stirring over a period of 1–2 min to a solution
of 0.45 mmol of the corresponding aromatic compound
in 1 ml of CF3SO3H at 20°C or HSO3F at –75°C. The
mixture was stirred for 0.5–3 h and treated with H2O,
concentrated aqueous HCl, concentrated aqueous HBr,
H2SO4, NaHCO3–H2O, NaOH–H2O, MeOH–H2O,
MeOH–MeONa, or MeCN (CF3SO3H) or with frozen
concentrated aqueous HCl at –75°C (HSO3F). The
measured relative to CFCl3 (δF 0.0 ppm). The H, 13C,
1
and 19F NMR spectra of solutions in CF3SO3H were
recorded at 20°C on the same instrument using CH2Cl2
(δ 5.32, δC 53.84 ppm) and CFCl3 (δF 0.0 ppm) as
internal references. The IR spectra were obtained from
solutions in CHCl3 on an FSM-1201 spectrometer. The
elemental compositions were determined on a Euro-
Vector EA-300 analyzer. GC–MS analysis was per-
formed on an Agilent Technologies G2570A GC/MSD
6850s instrument (electron impact, 70 eV; HP-5MS
capillary column, 3 m × 0.25 mm, film thickness
0.25 μm). The purity of the isolated compounds was
Table 3. 1H, 13C, and 19F NMR spectra (δ, ppm) of cations B1–B3 (CF3SO3H, 20°C)
Cation
1H
13C
19F (CF3)
–58.56 t
B1
4.90 q (2H, CH2, J = 8.5 Hz), 8.07 t (4H, Harom, J = 39.75 q (CH2, J = 32 Hz), 119.05 q (CF3, J =
7.5 Hz), 8.20 d (4H, Harom, J = 7.5 Hz), 8.54 t
(2H, Harom, J = 7.5 Hz)
278 Hz), 127.97 (Cm), 137.88 (Ci), 137.76 (J = 8.5 Hz)
(Co), 145.25 (Cp), 206.97 (C+)
B2
B3
4.46 s (3H, MeO), 4.53 q (2H, CH2, J = 8.5 Hz), 37.91 q (CH2, J = 31 Hz), 55.60 (MeO),
–59.64 t
7.53 d (2H, Harom, J = 8.0 Hz), 7.76 d (2H,
Harom, J = 7.0 Hz), 7.83 t (2H, Harom, J = 7.0 Hz),
119.67 q (CF3, J = 277 Hz), 126.10, (J = 8.5 Hz)
126.61, 131.76, 131.90, 134.53, 134.70,
135.05, 178.80, 185.42 (C+)
8.04 d (2H, Harom, J = 8.0 Hz), 8.67 t (1H, Harom
,
J = 7.0 Hz)
4.28 s (6H, MeO), 4.48 q (2H, CH2, J = 8.5 Hz), 37.05 q (CH2, J = 31 Hz), 53.77 (MeO),
–60.02 t
7.46 d (4H, Harom, J = 8.0 Hz), 8.06 d (4H,
Harom, J = 8.0 Hz)
119.82 q (CF3, J = 276 Hz), 114.22, (J = 8.5 Hz)
130.09, 139.74, 170.95, 181.98 (C+)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
333
products were extracted into chloroform (3×30 ml),
the combined extracts were washed in succession with
water (2 ×20 ml), a saturated aqueous solution of
NaHCO3 (2×20 ml), and water again (2×20 ml), dried
over Na2SO4, and evaporated under reduced pressure,
and the residue was separated by column chromatog-
raphy on silica gel using petroleum ether–ethyl acetate
as eluent. The yields of isomeric alkenes E/Z-II and III
were determined by weighing the fractions isolated by
chromatography.
c. From 50 mg (0.29 mmol) of Ia and 41 mg
(0.38 mmol) of anisole in 1 ml of HSO3F (–75°C, 2 h);
quenching with concentrated aqueous HCl cooled to
–75°C. Yield 5 mg (7%, E), 14 mg (18%, Z), E/Z ~1:3.
Isomer mixture. IR spectrum, ν, cm–1: 2958, 1639,
1606, 1511, 1271, 1128. 13C NMR spectrum, δC, ppm:
55.3, 55.6, 113.5 q (J = 32.3 Hz), 114.9 q (J =
32.3 Hz), 123.2 q (J = 281.9 Hz), 127.9, 128.1, 128.2,
128.3, 128.4, 129.0, 129.1, 129.3, 130.6, 130.8, 132.4,
151.8 q (J = 5.4 Hz), 160.5, 160.6. Mass spectrum, m/z
(Irel, %): 278 (90) [M]+, 263 (25), 195 (80), 167 (100).
Cation B1. a. Arylacetylene Ia, 20 mg, was added at
20°C to a mixture of 0.05 ml of benzene and 0.5 ml
The spectra of particular isomers of IIb–IIn, IIp,
and IIr–IIw were derived from the spectra of the
corresponding isomer mixtures.
1
of CF3SO3H in an NMR ampule, and H, 13C, and
19F NMR spectra were recorded.
E-IIb. 1H NMR spectrum, δ, ppm: 3.85 s (3H,
OMe), 6.04 q (1H, =CH, J = 8.3 Hz), 6.84–7.39 m
(9H, Harom). 19F NMR spectrum: δF –55.44 ppm, d
(CF3, J = 8.3 Hz).
Z-IIb. 1H NMR spectrum, δ, ppm: 3.81 s (3H,
OMe), 6.05 q (1H, =CH, J = 8.5 Hz), 6.84–7.39 m
(9H, Harom). 19F NMR spectrum: δF –55.11 ppm, d
(CF3, J = 8.5 Hz).
b. Alkene IIa, 20 mg, was added at 20°C to 0.5 ml
1
of CF3SO3H in an NMR ampule, and H, 13C, and
19F NMR spectra were recorded.
c. Alcohol IIIa, 20 mg, was added at 20°C to 0.5 ml
1
of CF3SO3H in an NMR ampule, and H, 13C, and
19F NMR spectra were recorded.
Cation B2. a. Alkene E/Z-IIb, 20 mg, was added at
20°C to 0.5 ml of CF3SO3H in an NMR ampule, and
1H, 13C, and 19F NMR spectra were recorded.
(E)- and (Z)-1-(3,4-Dichlorophenyl)-3,3,3-tri-
fluoro-1-phenylpropenes (IIc). Yellow oily substance
(isomer mixture). a. From 100 mg (0.59 mmol) of Ia
and 112 mg (0.76 mmol) of o-dichlorobenzene in 1 ml
of CF3SO3H (20°C, 1 h); quenching with H2O. Yield
17 mg (9%, E), 26 mg (14%, Z), E/Z ratio ~1:1.7.
b. Alcohol IIIb, 20 mg, was added at 20°C to
1
0.5 ml of CF3SO3H in an NMR ampule, and H, 13C,
and 19F NMR spectra were recorded.
Cation B3. Alkene IIo, 20 mg, was added at 20°C to
1
0.5 ml of CF3SO3H in an NMR ampule, and H, 13C,
and 19F NMR spectra were recorded.
b. From 50 mg (0.29 mmol) of Ia and 56 mg
(0.38 mmol) of o-dichlorobenzene in 1 ml of CF3SO3H
(20°C, 1 h); quenching with MeCN. Yield 32 mg
(34%, E), 38 mg (41%, Z), E/Z ratio ~1:1.2.
Isomer mixture. IR spectrum, ν, cm–1: 2952, 1644,
1471, 1274, 1127. Mass spectrum, m/z (Irel, %): 316
(100) [M]+, 281 (50), 261 (40), 246 (45), 212 (70).
Found, %: C 56.87; H 2.79. C15H9Cl2F3. Calculated,
%: C 56.81; H 2.86. M 316.00.
E-IIc. 1H NMR spectrum, δ, ppm: 6.11 q (1H,
=CH, J = 8.2 Hz), 7.07 d.d (1H, Harom, J = 8.3 Hz,
1.9 Hz), 7.26 d (2H, Harom, J = 8.2 Hz), 7.36–7.42 m
(3H, Harom), 7.47 d (2H, Harom, J = 8.2 Hz). 19F NMR
spectrum: δF –55.92 ppm, d (CF3, J = 8.2 Hz).
Z-IIc. 1H NMR spectrum, δ, ppm: 6.16 q (1H,
=CH, J = 7.8 Hz), 7.10 d.d (1H, Harom, J = 8.3 Hz),
7.22 d (2H, Harom, J = 8.0 Hz), 7.34 d (2H, Harom, J =
8.0 Hz), 7.36–7.42 m (3H, Harom). 19F NMR spectrum:
δF –55.64 ppm, d (CF3, J = 7.8 Hz).
3,3,3-Trifluoro-1,1-diphenylpropene (IIa). Yellow
oily substance [7]. IR spectrum, ν, cm–1: 2930, 1700,
1
1638, 1601, 1271, 1129. H NMR spectrum, δ, ppm:
6.14 q (1H, =CH, J = 8.6 Hz), 7.25–7.26 m (4H,
H
H
arom), 7.32–7.36 m (3H, Harom), 7.39–7.40 m (3H,
arom). 13C NMR spectrum, δC, ppm: 115.47 s (J =
33.9 Hz), 123.1 s (J = 269 Hz), 127.95, 128.03, 128.47,
129.11, 129.38. 19F NMR spectrum: δF –55.57 ppm, d
(CF3, J = 8.6 Hz). Mass spectrum, m/z (Irel, %): 248
(100) [M]+, 227 (20), 179 (70), 165 (65).
(E)- and (Z)-3,3,3-Trifluoro-1-(4-methoxyphe-
nyl)-1-phenylpropenes (IIb). Yellow oily substance
(isomer mixture) [8]. a. From 100 mg (0.59 mmol) of
Ia and 82 mg (0.76 mmol) of anisole in 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with H2O. Yield
18 mg (11%, E), 54 mg (34%, Z), E/Z ratio ~1:3.
b. From 50 mg (0.29 mmol) of Ia and 41 mg
(0.38 mmol) of anisole in 1 ml of CF3SO3H (20°C,
1 h); quenching with MeCN. Yield 21 mg (28%, E),
44 mg (57%, Z), E/Z ratio ~1:2.
(E)- and (Z)-1-(2,4-Dimethylphenyl)-3,3,3-tri-
fluoro-1-phenylpropenes (IId). Yellow oily substance
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

ALKHAFAJI et al.
334
1
(isomer mixture). From 50 mg (0.29 mmol) of Ia and
40 mg (0.38 mmol) of m-xylene in 1 ml of CF3SO3H
(20°C, 0.5 h); quenching with water. Yield 18 mg
(22%, E), 37 mg (46%, Z), E/Z ratio ~1:2.3.
Z-IIf. H NMR spectrum, δ, ppm: 2.07 s (6H, Me),
2.31 s (3H, Me), 6.37 q (1H, =CH, J = 8.1 Hz),
7.17–7.38 m (7H, Harom). 19F NMR spectrum:
δF –56.11 ppm, d (CF3, J = 8.1 Hz).
E-IId. 1H NMR spectrum, δ, ppm: 2.04 s (3H, Me),
2.33 s (3H, Me), 5.78 q (1H, =CH, J = 8.3 Hz),
6.82–7.33 m (8H, Harom). 19F NMR spectrum:
δF –56.34 ppm, d (CF3, J = 8.3 Hz).
Z-IId. 1H NMR spectrum, δ, ppm: 2.00 s (3H, Me),
2.36 s (3H, Me), 6.25 q (1H, =CH, J = 7.8 Hz),
6.82–7.33 m (8H, Harom). 19F NMR spectrum:
δF –56.78 ppm, d (CF3, J = 7.8 Hz).
Isomer mixture. Mass spectrum, m/z (Irel, %): 290
(30) [M]+, 275 (15), 207 (100), 192 (98), 183 (15).
Found, %: C 74.52; H 5.93. C18H17F3. Calculated, %:
C 74.47; H 5.90. M 290.13.
(E)- and (Z)-1-(4-tert-Butylphenyl)-3,3,3-tri-
fluoro-1-phenylpropenes (IIg). Yellow oily substance
(isomer mixture). From 50 mg (0.29 mmol) of Ia and
47 mg (0.38 mmol) of tert-butylbenzene. a. In 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with water. Yield
5 mg (6%, E), 36 mg (40%, Z), E/Z ratio ~1:6.
Isomer mixture. Mass spectrum, m/z (Irel, %): 276
(20) [M]+, 193 (100), 178 (60). Found, %: C 73.84;
H 5.43. C17H15F3. Calculated, %: C 73.90; H 5.47.
M 276.11.
b. In 1 ml of HSO3F (–75°C, 0.5 h); quenching with
concentrated aqueous HCl cooled to –75°C. Yield
11 mg (12%, E), 46 mg (52%, Z), E/Z ratio ~1:4.
E-IIg. 1H NMR spectrum, δ, ppm: 1.31 s (9H,
t-Bu), 6.08 q (1H, =CH, J = 8.6 Hz), 7.16–7.39 m (9H,
Harom). 19F NMR spectrum: δF –56.85 ppm, d (CF3, J =
8.6 Hz).
Z-IIg. 1H NMR spectrum, δ, ppm: 1.34 s (9H,
t-Bu), 6.13 q (1H, =CH, J = 8.6 Hz), 7.16–7.39 m
(9H, Harom). 19F NMR spectrum: δF –56.54 ppm, d
(CF3, J = 8.6 Hz).
(E)- and (Z)-1-(2,5-Dimethylphenyl)-3,3,3-tri-
fluoro-1-phenylpropenes (IIe). Yellow oily substance
(isomer mixture). From 50 mg (0.29 mmol) of Ia and
40 mg (0.38 mmol) of p-xylene in 1 ml of CF3SO3H
(20°C, 0.5 h); quenching with water. Yield 9 mg (11%,
E), 35 mg (43%, Z), E/Z ratio ~1:4.
Isomer mixture. IR spectrum, ν, cm-1: 2953, 1643,
1496, 1272, 1131. 13C NMR spectrum, δC, ppm: 19.0,
20.9, 115.4 q (J = 32.3 Hz), 117.7 q (J = 34.1 Hz),
123.1 q (J = 269.3 Hz), 127.0, 127.9, 128.6, 128.8,
129.0, 129.2, 129.3, 129.6, 129.9, 130.0, 130.6, 132.5,
134.7, 136.1, 138.5, 151.8 q (J = 5.4 Hz). Mass spec-
trum, m/z (Irel, %): 276 (30) [M]+, 193 (100), 178 (80).
Found, %: C 73.94; H 5.46. C17H15F3. Calculated, %:
C 73.90; H 5.47. M 276.11.
E-IIe. 1H NMR spectrum, δ, ppm: 2.04 s (3H, Me),
2.33 s (3H, Me), 5.79 q (1H, =CH, J = 8.6 Hz),
6.99–7.34 m (8H, Harom). 19F NMR spectrum:
δF –56.37 ppm, d (CF3, J = 8.6 Hz).
Z-IIe. 1H NMR spectrum, δ, ppm: 2.04 s (3H, Me),
2.33 s (3H, Me), 6.26 q (1H, =CH, J = 8.1 Hz),
6.99–7.34 m (8H, Harom). 19F NMR spectrum:
δF –57.89 ppm, d (CF3, J = 8.1 Hz).
Isomer mixture. Mass spectrum, m/z (Irel, %): 304
(30) [M]+, 289 (100), 261 (10), 171 (12), 151 (23).
Found, %: C 74.98; H 6.29. C19H19F3. Calculated, %:
C 74.94; H 6.25. M 304.14.
(E)- and (Z)-1-(3,4-Dimethoxyphenyl)-3,3,3-tri-
fluoro-1-phenylpropenes (IIh). Yellow oily substance
(isomer mixture). From 50 mg (0.29 mmol) of Ia and
52 mg (0.38 mmol) of o-dimethoxybenzene in 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with MeCN. Yield
28 mg (31%, E), 46 mg (50%, Z), E/Z ratio ~1:1.6.
E-IIh. 1H NMR spectrum, δ, ppm: 3.82 s (3H,
OMe), 3.90 s (3H, OMe), 6.05 q (1H, =CH, J =
8.4 Hz), 6.77–7.38 m (8H, Harom). 19F NMR spectrum:
δF –56.06 ppm, d (CF3, J = 8.4 Hz).
Z-IIh. 1H NMR spectrum, δ, ppm: 3.80 s (3H,
OMe), 3.86 s (3H, OMe), 6.07 q (1H, =CH, J =
8.4 Hz), 6.77–7.38 m (8H, Harom). 19F NMR spectrum:
δF –55.75 ppm, d (CF3, J = 8.4 Hz).
(E)- and (Z)- 3,3,3-Trifluoro-1-phenyl-1-(2,4,6-
trimethylphenyl)propenes (IIf). Yellow oily sub-
stance (isomer mixture). From 50 mg (0.29 mmol) of
Ia and 45 mg (0.38 mmol) of mesitylene in 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with water. Yield
4 mg (5%, E), 16 mg (18%, Z), E/Z ratio ~1:4.
1
Isomer mixture. Mass spectrum, m/z (Irel, %): 308
(100) [M]+, 261 (10), 233 (15), 152 (20). Found, %:
C 66.28; H 4.86. C17H15F3O2. Calculated, %: C 66.23;
H 4.90. M 308.10.
E-IIf. H NMR spectrum, δ, ppm: 2.17 s (6H, Me),
2.28 s (3H, Me), 5.67 q (1H, =CH, J = 8.6 Hz),
7.17–7.38 m (7H, Harom). 19F NMR spectrum:
δF –56.11 ppm, d (CF3, J = 8.6 Hz).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
335
(E)- and (Z)-3,3,3-Trifluoro-1-(4-methylphenyl)-
1-phenylpropenes (IIi). Yellow oily substance (isomer
mixture). a. From 100 mg (0.54 mmol) of Ib and
56 mg (0.70 mmol) of benzene in 1 ml of CF3SO3H
(20°C, 0.5 h); quenching with H2O. Yield 18 mg
(13%, E), 27 mg (19%, Z), E/Z ratio ~1:1.5.
J = 8.2 Hz), 6.82–7.16 m (7H, Harom). 19F NMR spec-
trum: δF –56.27 ppm, d (CF3, J = 8.2 Hz).
1
Z-IIj. H NMR spectrum, δ, ppm: 2.01 s (3H, Me),
2.28 s (3H, Me), 2.36 s (3H, Me), 6.23 q (1H, =CH,
J = 8.0 Hz), 6.82–7.16 m (7H, Harom). 19F NMR spec-
trum: δF –57.57 ppm, d (CF3, J = 8.2 Hz).
b. From 50 mg (0.27 mmol) of Ib and 28 mg
(0.35 mmol) of benzene in 1 ml of CF3SO3H (20°C,
0.5 h); quenching with NaOH–H2O. Yield 13 mg
(18%, E), 19 mg (27%, Z), E/Z ratio ~1:1.5.
(E)- and (Z)-1-(3,4-Dichlorophenyl)-3,3,3-tri-
fluoro-1-(4-methylphenyl)propenes (IIk). Yellow
oily substance (isomer mixture). From 100 mg
(0.54 mmol) of Ib and 96 mg (0.65 mmol) of o-di-
chlorobenzene in 1 ml of CF3SO3H (20°C, 0.5 h);
quenching with water. Yield 13 mg (7%, E), 27 mg
(15%, Z), E/Z ratio ~1:2.
c. From 50 mg (0.27 mmol) of Ib and 28 mg
(0.35 mmol) of benzene in 1 ml of CF3SO3H (20°C,
0.5 h); quenching with MeONa–MeOH. Yield 26 mg
(37%, E), 39 mg (55%, Z), E/Z ratio ~1:1.5.
E-IIk. 1H NMR spectrum, δ, ppm: 2.35 s (3H, Me),
6.05 q (1H, =CH, J = 8.1 Hz), 7.09–7.47 m (7H,
d. From 50 mg (0.27 mmol) of Ib and 28 mg
(0.35 mmol) of benzene in 1 ml of CF3SO3H (20°C,
0.5 h); quenching with MeCN. Yield 19 mg (27%, E),
41 mg (58%, Z), E/Z ~1:2.2.
H
arom). 19F NMR spectrum: δF –56.57 ppm, d (CF3,
J = 8.1 Hz).
Z-IIk. 1H NMR spectrum, δ, ppm: 2.37 s (3H, Me),
6.13 q (1H, =CH, J = 8.2 Hz), 7.09–7.47 m (7H,
arom). 19F NMR spectrum: δF –56.16 ppm, d (CF3,
J = 8.2 Hz).
Isomer mixture. IR spectrum, ν, cm–1: 2925, 1642,
1610, 1511, 1270, 1127. 13C NMR spectrum, δC, ppm:
21.2, 21.3, 114.5 q (J = 34.1 Hz), 115.1 q (J =
33.2 Hz), 123.2 q (J = 271.1 Hz), 123.3 q (J =
270.2 Hz), 127.9, 128.0, 128.1, 128.3, 128.4, 128.7,
129.1, 129.2, 129.3, 134.3, 137.2, 137.4, 138.4, 139.6,
140.4, 152.3 q (J = 5.4 Hz), 152.6 q (J = 5.4 Hz). Mass
spectrum, m/z (Irel, %): 262 (100) [M]+, 247 (15), 193
(20), 179 (55). Found, %: C 73.32; H 5.06. C16H13F3.
Calculated, %: C 73.27; H 5.00. M 262.10.
H
Isomer mixture. Mass spectrum, m/z (Irel, %): 330
(70) [M]+, 295 (100), 275 (50), 260 (70), 238 (8).
Found, %: C 57.98; H 3.30. C16H11Cl2F3. Calculated,
%: C 58.03; H 3.35. M 330.02.
(E)- and (Z)-3,3,3-Trifluoro-1-(4-methoxyphe-
nyl)-1-(4-methylphenyl)propenes (IIl). Yellow oily
substance (isomer mixture). From 100 mg (0.54 mmol)
of Ib and 76 mg (0.7 mmol) of anisole in 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with water. Yield
58 mg (38%, E), 48 mg (31%, Z), E/Z ratio ~1.2:1.
1
E-IIi. H NMR spectrum, δ, ppm: 2.41 s (3H, Me),
6.13 q (1H, =CH, J = 8.4 Hz), 7.15–7.40 m (9H,
H
arom). 19F NMR spectrum: δF –57.48 ppm, d (CF3,
J = 8.4 Hz).
1
1
E-IIl. H NMR spectrum, δ, ppm: 2.40 s (3H, Me),
Z-IIi. H NMR spectrum, δ, ppm: 2.37 s (3H, Me),
3.80 s (3H, OMe), 6.00 q (1H, =CH, J = 8.6 Hz), 6.83–
7.20 m (8H, Harom). 19F NMR spectrum: δF –55.77 ppm,
d (CF3, J = 8.6 Hz).
6.10 q (1H, =CH, J = 8.5 Hz), 7.15–7.40 m (9H,
arom). 19F NMR spectrum: δF –57.35 ppm, d (CF3,
J = 8.5 Hz).
(E)- and (Z)-1-(2,4-Dimethylphenyl)-3,3,3-tri-
H
1
Z-IIl. H NMR spectrum, δ, ppm: 2.36 s (3H, Me),
3.84 s (3H, OMe), 6.05 q (1H, =CH, J = 8.1 Hz), 6.83–
7.20 m (8H, Harom). 19F NMR spectrum: δF –56.23 ppm,
d (CF3, J = 8.1 Hz).
fluoro-1-(4-methylphenyl)propenes (IIj). Yellow oily
substance (isomer mixture). From 50 mg (0.27 mmol)
of Ib and 28 mg (0.35 mmol) of m-xylene in 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with H2O. Yield
11 mg (11%, E), 27 mg (35%, Z), E/Z ratio ~1:3.
Isomer mixture. Mass spectrum, m/z (Irel, %): 292
(85) [M]+, 277 (30), 209 (100), 181 (90), 165 (50).
Found, %: C 69.91; H 5.20. C17H15F3O. Calculated, %:
C 69.85; H 5.17. M 292.11.
Isomer mixture. IR spectrum, ν, cm–1: 2924, 1641,
1610, 1271, 1130. Mass spectrum, m/z (Irel, %): 290
(30) [M]+, 275 (25), 207 (80), 192 (100), 178 (8).
Found, %: C 74.42; H 5.86. C18H17F3. Calculated, %:
C 74.47; H 5.90. M 290.13.
(E)- and (Z)-1-(3,4-Dimethoxyphenyl)-3,3,3-tri-
fluoro-1-(4-methylphenyl)propenes (IIm). Yellow
oily substance (isomer mixture). From 50 mg
(0.27 mmol) of Ib and 48 mg (0.35 mmol) of o-di-
methoxybenzene in 1 ml of CF3SO3H (20°C, 0.5 h);
1
E-IIj. H NMR spectrum, δ, ppm: 2.12 s (3H, Me),
2.22 s (3H, Me), 2.32 s (3H, Me), 5.73 q (1H, =CH,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

ALKHAFAJI et al.
336
quenching with water. Yield 40 mg (46%, E), 40 mg
(46%, Z), E/Z ratio ~1:1.
E-IIm. 1H NMR spectrum, δ, ppm: 2.36 s (3H,
Me), 3.81 s (3H, OMe), 3.86 s (3H, OMe), 6.03 q (1H,
=CH, J = 8.4 Hz), 6.75–7.19 m (7H, Harom). 19F NMR
spectrum: δF –55.73 ppm, d (CF3, J = 8.4 Hz).
Z-IIm. 1H NMR spectrum, δ, ppm: 2.39 s (3H,
Me), 3.82 s (3H, OMe), 3.91 s (3H, OMe), 6.02 q (1H,
=CH, J = 8.2 Hz), 6.75–7.19 m (7H, Harom). 19F NMR
spectrum: δF –55.90 ppm, d (CF3, J = 8.4 Hz).
quenching with concentrated aqueous HCl cooled to
–75°C. Yield 63 mg (82%).
Yellow oily substance. IR spectrum, ν, cm–1: 2959,
1
1714, 1642, 1605, 1513, 1270, 1128. H NMR spec-
trum, δ, ppm: 3.81 s (3H, OMe), 3.84 s (3H, OMe),
5.97 q (1H, =CH, J = 8.5 Hz), 6.83 d (2H, Harom, J =
8.8 Hz), 6.90 d (2H, Harom, J = 8.8 Hz), 7.16 d (2H,
H
arom, J = 8.8 Hz), 7.17 d (2H, Harom, J = 8.8 Hz).
13C NMR spectrum, δC, ppm: 55.2, 55.3, 112.8 q (J =
33.5 Hz), 113.3, 113.7, 123.3 q (J = 270 Hz), 128.2,
129.5, 129.7, 130.6, 132.9, 159.7, 160.6. 19F NMR
spectrum: δF –55.74 ppm, d (CF3, J = 8.5 Hz). Mass
spectrum, m/z (Irel, %): 308 (100) [M]+, 277 (24), 225
(90), 210 (28), 195 (7), 181 (8), 165 (10). Found, %:
C 66.28; H 4.94. C17H15F3O2. Calculated, %: C 66.23;
H 4.90. M 308.10.
Isomer mixture. Mass spectrum, m/z (Irel, %): 322
(100) [M]+, 307 (10), 291 (11), 275 (15), 247 (15).
Found, %: C 67.13; H 5.36. C18H17F3O2. Calculated,
%: C 67.07; H 5.32. M 322.12.
(E)- and (Z)-1-(4-tert-Butylphenyl)-3,3,3-tri-
fluoro-1-(4-methylphenyl)propenes (IIn). Yellow
oily substance (isomer mixture). From 50 mg
(0.27 mmol) of Ib and 47 mg (0.35 mmol) of tert-
butylbenzene in 1 ml of CF3SO3H (20°C, 0.5 h);
quenching with water. Yield 19 mg (22%, E), 25 mg
(29%, Z), E/Z ratio ~1:1.3.
E-IIn. 1H NMR spectrum, δ, ppm: 1.32 s (9H,
t-Bu), 2.39 s (3H, Me), 6.06 q (1H, =CH, J = 8.4 Hz),
6.98–7.41 m (8H, Harom). 19F NMR spectrum:
δF –56.09 ppm, d (CF3, J = 8.4 Hz).
(E)- and (Z)-1-(2,5-Dimethylphenyl)-3,3,3-tri-
fluoro-1-(4-methoxyphenyl)propenes (IIp). Yellow
oily substance (isomer mixture). From 50 mg
(0.25 mmol) of Ic and 34 mg (0.325 mmol) of
p-xylene in 1 ml of CF3SO3H (20°C, 0.5 h); quenching
with MeCN. Yield 5 mg (6%, E), 51 mg (67%, Z),
E/Z ratio ~1:11.
E-IIp. 1H NMR spectrum, δ, ppm: 2.00 s (3H, Me),
2.32 s (3H, Me), 3.86 s (3H, OMe), 6.16 q (1H, =CH,
J = 9.1 Hz), 6.83–7.20 m (7H, Harom). 13C NMR spec-
trum (most characteristic signals), δC, ppm: 21.3,
114.9, 127.6, 129.0, 131.0. 19F NMR spectrum:
δF –57.46 ppm, d (CF3, J = 9.1 Hz). Mass spectrum:
m/z 306 [M]+.
Z-IIp. 1H NMR spectrum, δ, ppm: 2.02 s (3H, Me),
2.34 s (3H, Me), 3.80 s (3H, OMe), 6.18 q (1H, =CH,
J = 8.4 Hz), 6.83–7.20 m (7H, Harom). 13C NMR spec-
trum, δC, ppm: 21.2, 21.2, 55.3, 113.5 q (J = 32.3 Hz),
113.9, 123.4 q (J = 269.3 Hz), 126.0, 126.7, 128.4,
130.8, 133.5, 137.8, 137.9, 151.2 (J = 5.4 Hz), 160.6.
19F NMR spectrum: δF –56.31 ppm, d (CF3, J =
8.4 Hz). Mass spectrum: m/z 306 [M]+. Found, %:
C 70.62; H 5.64. C18H17F3O. Calculated, %: C 70.58;
H 5.59. M 306.12.
Z-IIn. 1H NMR spectrum, δ, ppm: 1.34 s (9H,
t-Bu), 2.35 s (3H, Me), 6.08 q (1H, =CH, J = 8.4 Hz),
6.98–7.41 m (8H, Harom). 19F NMR spectrum:
δF –56.01 ppm, d (CF3, J = 8.4 Hz).
Isomer mixture. Mass spectrum, m/z (Irel, %): 318
(25) [M]+, 303 (100), 275 (10), 261 (4). Found, %:
C 75.41; H 6.59. C20H21F3. Calculated, %: C 75.45;
H 6.65. M 318.16.
3,3,3-Trifluoro-1,1-bis(4-methoxyphenyl)pro-
pene (IIo). a. From 50 mg (0.25 mmol) of Ic and
35 mg (0.33 mmol) of anisole in 1 ml of CF3SO3H
(20°C, 0.25 h); quenching with water. Yield
10 mg (13%).
(Z)-1-(2,4-Dimethylphenyl)-3,3,3-trifluoro-
1-(4-methoxyphenyl)propene (IIq) was obtained
from 50 mg (0. 25 mmol) of Ic and 34 mg
(0.325 mmol) of o-xylene in 1 ml of CF3SO3H. Yellow
oily substance. Yield 32 mg (42%). 1H NMR spectrum,
δ, ppm: 2.27 s (3H, Me), 2.36 s (3H, Me), 3.79 s (3H,
OMe), 6.17 q (1H, =CH, J = 7.6 Hz), 6.81–6.83 m
(4H, Harom), 7.03 s (1H, Harom), 7.18 d (2H, Harom, J =
8.6 Hz). 19F NMR spectrum: δF –57.35 ppm, t (CF3,
J = 7.6 Hz). Mass spectrum, m/z (Irel, %): 306 (20)
b. From 50 mg (0.25 mmol) of Ic and 35 mg
(0.33 mmol) of anisole in 1 ml of CF3SO3H (20°C,
0.25 h); quenching with MeCN. Yield 72 mg (94%).
c. From 100 mg (0.5 mmol) of Ic and 70 mg
(0.65 mmol) of anisole in 1 ml of HSO3F (–75°C,
0.25 h); quenching with concentrated aqueous HCl
cooled to –75°C. Yield 60 mg (39%).
d. From 50 mg (0.25 mmol) of Ic and 35 mg
(0.33 mmol) of anisole in 1 ml of HSO3F (–75°C, 1 h);
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
337
[M]+, 275 (10), 223 (100), 208 (35), 192 (28), 179
(10). Found, %: C 70.53; H 5.62. C18H17F3O. Cal-
culated, %: C 70.58; H 5.59. M 306.12.
(E)- and (Z)-1-(4-Chlorophenyl)-3,3,3-trifluoro-
1-(4-methoxyphenyl)propenes (IIt). Yellow oily sub-
stance (isomer mixture) [9]. From 50 mg (0.24 mmol)
of Id and 35 mg (0.32 mmol) of anisole in 1 ml of
CF3SO3H (20°C, 1 h); quenching with water. Yield
13 mg (18%, E), 16 mg (21%, Z), E/Z ratio ~1:1.
(E)- and (Z)-1-(4-tert-Butylphenyl)-3,3,3-tri-
fluoro-1-(4-methoxyphenyl)propenes (IIr). Yellow
oily substance (isomer mixture). From 50 mg
(0.25 mmol) of Ic and 44 mg (0.325 mmol) tert-butyl-
benzene in 1 ml of HSO3F (–75°C, 1 h); quenching
with concentrated aqueous HCl cooled to –75°C. Yield
14 mg (16%, E), 14 mg (17%, Z), E/Z ratio ~1:1.
E-IIr. 1H NMR spectrum, δ, ppm: 1.31 s (9H,
t-Bu), 3.80 s (3H, Me), 6.00 q (1H, =CH, J = 8.4 Hz),
6.83–7.50 m (8H, Harom). 19F NMR spectrum:
δF –56.27 ppm, d (CF3, J = 8.4 Hz).
Isomer mixture. IR spectrum, ν, cm–1: 2960, 1726,
1639, 1605, 1513, 1273, 1130.
E-IIt. 1H NMR spectrum, δ, ppm: 3.65 s (3H,
OMe), 6.17 q (1H, =CH, J = 8.3 Hz), 6.84–7.38 m
(8H, Harom). 19F NMR spectrum: δF –56.33 ppm, d
(CF3, J = 8.3 Hz). Mass spectrum, m/z (Irel, %):
312 (100) [M]+, 277 (50), 229 (45), 201 (10), 178 (8),
165 (70).
Z-IIt. 1H NMR spectrum, δ, ppm: 3.68 s (3H,
OMe), 6.05 q (1H, =CH, J = 8.3 Hz), 6.84–7.38 (8H,
Z-IIr. 1H NMR spectrum, δ, ppm: 1.34 s (9H,
t-Bu), 3.83 s (3H, OMe), 6.03 q (1H, =CH, J =
8.1 Hz), 6.83–7.50 m (8H, Harom). 19F NMR spectrum:
δF –56.07 ppm, d (CF3, J = 8.1 Hz).
H
arom). 19F NMR spectrum: δF –55.85 ppm, d (CF3, J =
8.3 Hz). Mass spectrum, m/z (Irel, %): 312 (60) [M]+,
277 (10), 229 (100), 201 (80), 178 (20), 165 (90).
Isomer mixture. Mass spectrum, m/z (Irel, %): 334
(65) [M]+, 319 (100), 291 (10), 277 (10). Found, %:
C 71.87; H 6.37. C20H21F3O. Calculated, %: C 71.84;
H 6.33. M 334.15.
(E)- and (Z)-1-(4-Chlorophenyl)-1-(3,4-dichloro-
phenyl)-3,3,3-trifluoropropenes (IIu). Yellow oily
substance (isomer mixture). From 50 mg (0.24 mmol)
of Id and 47 mg (0.32 mmol) of o-dichlorobenzene
in 1 ml of CF3SO3H (20°C, 1 h); quenching with
water. Yield 10 mg (12%, E), 12 mg (14%, Z),
E/Z ratio ~1:1.
E-IIu. 1H NMR spectrum, δ, ppm: 6.10 q (1H,
=CH, J = 7.6 Hz), 7.04–7.54 m (7H, Harom). 19F NMR
spectrum: δF –56.63 ppm, d (CF3, J = 7.6 Hz).
(E)- and (Z)-1-(4-Chlorophenyl)-3,3,3-trifluoro-
1-phenylpropenes (IIs). Yellow oily substance
(isomer mixture) [9]. From 50 mg (0.24 mmol) of Id
and 25 mg (0.32 mmol) of benzene in 1 ml of
CF3SO3H (20°C, 1 h). a. Quenching with water. Yield
10 mg (15%, E), 10 mg (15%, Z), E/Z ratio ~1:1.
b. Quenching with NaOH–H2O. Yield 22 mg
(32%, E), 22 mg (32%, Z), E/Z ratio ~1:1.
Z-IIu. 1H NMR spectrum, δ, ppm: 6.14 q (1H,
=CH, J = 7.6 Hz), 7.04–7.54 m (7H, Harom). 19F NMR
spectrum: δF –56.47 ppm, d (CF3, J = 7.6 Hz).
c. Quenching with MeCN. Yield 26 mg (39%, E),
26 mg (39%, Z), E/Z ratio ~1:1.
Isomer mixture. Mass spectrum, m/z (Irel, %): 350
(100) [M]+, 331 (10), 315 (65), 295 (25), 280 (80), 246
(83), 225 (30), 210 (15). Found, %: C 51.29; H 2.33.
C15H8Cl3F3. Calculated, %: C 51.24; H 2.29. M 349.96.
Isomer mixture. IR spectrum, ν, cm–1: 2924, 1642,
13
1593, 1490, 1272, 1130. C NMR spectrum, δC, ppm:
115.7 q (J = 34.1 Hz), 115.9 q (J = 34.1 Hz), 122.8 q
(J = 271.1 Hz), 122.9 q (J = 271.1 Hz), 127.9, 128.1,
128.4, 128.6, 128.7, 129.0, 129.2, 129.6, 130.5, 134.7,
135.5, 135.6, 136.8, 138.5, 139.6, 151.3 (J = 5.4 Hz).
E-IIs. 1H NMR spectrum, δ, ppm: 6.10 q (1H,
=CH, J = 8.5 Hz), 7.16–7.40 m (9H, Harom). 19F NMR
spectrum: δF –56.37 ppm, d (CF3, J = 8.5 Hz). Mass
spectrum, m/z (Irel, %): 282 (100) [M]+, 247 (75), 227
(44), 199 (32), 178 (90).
Z-IIs. 1H NMR spectrum, δ, ppm: 6.13 q (1H, =CH,
J = 8.5 Hz), 7.16–7.40 m (9H, Harom). 19F NMR spec-
trum: δF –56.24 ppm, d (CF3, J = 8.5 Hz). Mass spec-
trum, m/z (Irel, %): 282 (100) [M]+, 247 (70), 227 (42),
199 (33), 178 (92).
(E)- and (Z)-1-(4-Chlorophenyl)-1-(3,4-dime-
thoxyphenyl)-3,3,3-trifluoropropenes (IIv). Yellow
oily substance (isomer mixture). From 50 mg
(0.24 mmol) of Id and 44 mg (0.32 mmol) of o-di-
methoxybenzene in 1 ml of CF3SO3H (20°C, 1 h);
quenching with water. Yield 44 mg (54%, E), 14 mg
(17%, Z), E/Z ratio ~3.2:1.
E-IIv. 1H NMR spectrum, δ, ppm: 3.82 s (3H,
OMe), 3.87 s (3H, OMe), 6.06 q (1H, =CH, J =
8.4 Hz), 6.62–7.37 m (7H, Harom). 19F NMR spectrum:
δF –55.81 ppm, d (CF3, J = 8.4 Hz). Mass spectrum,
m/z (Irel, %): 342 (100) [M]+, 327 (5), 295 (8), 277 (4),
264 (8), 249 (15).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

ALKHAFAJI et al.
Z-IIv. 1H NMR spectrum, δ, ppm: 3.82 s (3H,
338
130.6, 130.8, 130.9, 157.3, 160.2. 19F NMR spectrum:
δF –70.50 ppm, d (CF3, J = 9.1 Hz). Mass spectrum,
m/z (Irel, %): 323 (1) [M]+, 307 (70), 292 (5), 278 (8),
264 (7), 248 (4), 238 (100), 210 (20), 189 (35). Found,
%: C 59.39; H 3.69. C16H12F3NO2. Calculated, %:
C 59.45; H 3.74. M 323.08.
OMe), 3.87 s (3H, OMe), 6.01 q (1H, =CH, J =
8.4 Hz), 6.62–7.37 m (7H, Harom). 19F NMR spectrum:
δF –56.24 ppm, d (CF3, J = 8.4 Hz). Mass spectrum,
m/z (Irel, %): 342 (100) [M]+, 327 (5), 295 (8), 277 (4),
264 (8), 249 (15).
Isomer mixture. 13C NMR spectrum, δC, ppm: 55.8,
55.9, 110.5, 110.7, 110.9, 111.3, 114.2 q (J = 34.1 Hz),
115.2 q (J = 34.1 Hz), 121.5, 123.1 q (J = 269.3 Hz),
128.3, 128.6, 128.7, 128.8, 129.1, 129.4, 129.8, 130.5,
132.2, 134.5, 135.7, 148.9, 150.4, 150.9 q (J = 5.4 Hz).
Found, %: C 59.62; H 4.16. C17H14ClF3O2. Calculated,
%: C 59.57; H 4.12. M 342.06.
3,3,3-Trifluoro-1,1-diphenylpropan-1-ol (IIIa).
Yellow oily substance. IR spectrum, ν, cm–1: 3472,
1
3030, 1449, 1262, 1124. H NMR spectrum, δ, ppm:
2.65 s (1H, OH), 3.21 q (2H, CH2, J = 10 Hz), 7.26 t
(2H, Harom, J = 7.6 Hz), 7.34 t (4H, Harom, J = 7.6 Hz),
7.42 d (4H, Harom, J = 7.6 Hz). 13C NMR spectrum, δC,
ppm: 45.0 q (J = 25.4 Hz), 76.2 q (J = 99.5 Hz),
125.7 q (J = 277 Hz), 125.6, 127.5, 128.4, 145.2.
19F NMR spectrum: δF –62.14 ppm, t (CF3, J = 10 Hz).
Mass spectrum, m/z (Irel, %): 266 (10) [M]+, 248 (5),
183 (100), 105 (80), 77 (30). Found, %: C 67.61;
H 4.86. C15H13F3O. Calculated, %: C 67.66; H 4.92.
M 266.09.
(E)- and (Z)-3,3,3-Trifluoro-1-(2-nitrophenyl)-1-
phenylpropenes (IIw). Yellow oily substance (isomer
mixture). a. From 100 mg (0.46 mmol) of Ie and
46 mg (0.6 mmol) of benzene in 1 ml of CF3SO3H
(20°C, 1 h); quenching with water. Yield 36 mg
(27%, E), 36 mg (27%, Z), E/Z ratio ~1:1.
3,3,3-Trifluoro-1-(4-methoxyphenyl)propan-1-ol
(IIIb). a. From 100 mg (0.59 mmol) of Ia and 82 mg
(0.76 mmol) of anisole in 1 ml of CF3SO3H (20°C,
0.5 h); quenching with water. Yield 40 mg (23%).
b. From 50 mg (0.23 mmol) of Ie and 23 mg
(0.3 mmol) of benzene in 1 ml of CF3SO3H (20°C,
1 h); quenching with MeCN. Yield 40 mg (59%, E),
23 mg (35%, Z), E/Z ratio ~1.7:1.
E-IIw. 1H NMR spectrum, δ, ppm: 5.19 q (1H,
=CH, J = 9.5 Hz), 6.95–7.45 m (9H, Harom). 19F NMR
spectrum: δF –66.70 ppm, d (CF3, J = 9.5 Hz). Mass
spectrum, m/z (Irel, %): 292 (45) [M]+, 276 (70), 224
(100), 207 (40), 195 (70), 178 (50), 167 (90).
Z-IIw. 1H NMR spectrum, δ, ppm: 6.10 q (1H,
=CH, J = 7.6 Hz), 6.95–7.45 m (9H, Harom). 19F NMR
spectrum: δF –57.77 ppm, d (CF3, J = 7.6 Hz). Mass
spectrum, m/z (Irel, %): 292 (45) [M]+, 276 (70), 224
(100), 207 (40), 195 (70), 178 (50), 167 (90).
Isomer mixture. IR spectrum, ν, cm–1: 2955, 1716,
1625, 1530, 1267, 1132. Found, %: C 61.39; H 3.37.
C15H10F3NO2. Calculated, %: C 61.44; H 3.44.
M 292.07.
b. From 50 mg (0.29 mmol) of Ia and 41 mg
(0.38 mmol) of anisole in 1 ml of HSO3F (–75°C, 2 h);
quenching with concentrated aqueous HCl cooled to
–75°C. Yield 5 mg (3%). Yellow oily substance. IR
spectrum, ν, cm-1: 3438, 2960, 1463, 1273, 1124.
1H NMR spectrum, δ, ppm: 2.57 s (1H, OH), 3.17 q
(2H, CH2, J = 10.2 Hz), 3.78 s (3H, OMe), 6.85 d (2H,
Harom, J = 8.8 Hz), 7.26 t (1H, Harom, J = 7.7 Hz), 7.30–
7.34 m (4H, Harom), 7.40 d (2H, Harom, J = 7.7 Hz).
19F NMR spectrum: δF –62.44 ppm, t (CF3, J =
10.4 Hz). Mass spectrum, m/z (Irel, %): 296 (20) [M]+,
213 (100), 135 (90), 105 (30). Found, %: C 64.81;
H 5.04. C16H15F3O2. Calculated, %: C 64.86; H 5.10.
M 296.10.
1-(3,4-Dichlorophenyl)-3,3,3-trifluoro-1-phenyl-
propan-1-ol (IIIc) was obtained from 100 mg
(0.59 mmol) of Ia and 112 mg (0.76 mmol) of o-di-
chlorobenzene in 1 ml of CF3SO3H (20°C, 1 h);
quenching with water. Yield 36 mg (18%). Yellow oily
substance. IR spectrum, ν, cm–1: 3472, 3063, 1715,
(E)-3,3,3-Trifluoro-1-(4-methoxyphenyl)-1-(2-ni-
trophenyl)propene (IIx) was obtained from 50 mg
(0.23 mmol) of Ie and 32 mg (0.3 mmol) of anisole in
1 ml of CF3SO3H (20°C, 0.5 h); quenching with water.
1
Yellow oily substance. H NMR spectrum, δ, ppm:
1
3.79 s (3H, OMe), 5.25 q (1H, =CH, J = 9.1 Hz),
6.91 d (2H, Harom, J = 8.6 Hz), 6.99 t (1H, Harom, J =
8.6 Hz), 7.28 t (1H, Harom, J = 9.1 Hz), 7.36 d (1H,
1470, 1380, 1271, 1127. H NMR spectrum, δ, ppm:
2.71 s (1H, OH), 3.17 q (2H, Harom, J = 10.2 Hz), 7.21–
7.57 m (8H, Harom). 13C NMR spectrum, δC, ppm: 29.7,
44.7 q (J = 25.4 Hz), 75.0 q (J = 99.5 Hz), 125.4 q
(J = 277 Hz), 125.2, 125.3, 127.8, 128.1 128.3, 128.7,
129.0, 130.2, 144.3, 145.2, 167.8. 19F NMR spectrum:
δF –62.18 ppm, t (CF3, J = 10.2 Hz). Mass spectrum,
H
arom, J = 9.1 Hz), 7.41 d (2H, Harom, J = 8.6 Hz),
7.57 d (1H, Harom, J = 9.1 Hz). 13C NMR spectrum, δC,
ppm: 55.3, 114.5 q (J = 33.2 Hz), 115.4, 119.2, 122.7,
124.5 q (CF3, J = 279.28 Hz), 124.9, 126.4, 128.4,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
339
m/z (Irel, %): 334 (10) [M]+, 251 (100), 173 (55), 145
(45). Found, %: C 53.72; H 3.35. C15H11F3O. Calculat-
ed, %: C 53.76; H 3.31. M 334.01.
spectrum, m/z (Irel, %): 336 (10) [M]+, 318 (30), 303
(100), 275 (12), 253 (70), 237 (8). Found, %: C 71.46;
H 6.95. C20H23F3O. Calculated, %: C 71.41; H 6.89.
M 336.17.
3,3,3-Trifluoro-1-(4-methylphenyl)-1-phenyl-
propan-1-ol (IIIi). a. From 100 mg (0.54 mmol) of Ib
and 56 mg (0.70 mmol) of benzene in 1 ml of
CF3SO3H (20°C, 0.5 h); quenching with water. Yield
45 mg (30%).
3,3,3-Trifluoro-1,1-bis(4-methoxyphenyl)propan-
1-ol (IIIo) was obtained from 50 mg (0.25 mmol) of Ic
and 35 mg (0.33 mmol) of anisole in 1 ml of CF3SO3H
(20°C, 0.25 h); quenching with water. Yield 41 mg
(50%). Yellow oily substance. IR spectrum, ν, cm–1:
b. From 50 mg (0.27 mmol) of Ib and 28 mg
(0.35 mmol) of benzene in 1 ml of CF3SO3H (20°C,
0.5 h); quenching with NaOH–H2O. Yield 19 mg
(25%). Oily substance. IR spectrum, ν, cm–1: 3491,
1
3486, 2956, 1607, 1511, 1250, 1126. H NMR spec-
trum, δ, ppm: 2.52 s (1H, OH), 3.12 q (2H, CH2, J =
10.4 Hz), 3.78 s (6H, MeO), 6.84 d (4H, Harom, J =
8.8 Hz), 7.29 d (4H, Harom, J = 8.8 Hz). 13C NMR spec-
trum, δC, ppm: 45.2 t.q (CH2, J = 129.37, 25.4 Hz),
55.2 q (OCH3, J = 142.90 Hz), 75.2 t (COH, J =
4.46 Hz), 113.7 d.d (Carom, J = 158.81, 4.9 Hz), 125.8 q
(CF3, J = 281.3 Hz), 130.0 d.d (Carom, J = 156.59,
7.1 Hz), 137.6 (Carom, J = 6.2 Hz), 158.9 (Carom, J =
5.8 Hz). 19F NMR spectrum: δF –63.00 ppm, t (CF3,
J = 10.4 Hz). Mass spectrum, m/z (Irel, %): 326 (20)
[M]+, 308 (35), 243 (90), 225 (32), 135 (100). Found,
%: C 62.52; H 5.20. C17H17F3O3. Calculated, %:
C 62.57; H 5.25. M 326.11.
1
3060, 1723, 1461, 1370, 1264, 1120. H NMR spec-
trum, δ, ppm: 2.32 s (3H, CH3), 2.64 s (1H, OH),
3.18 q (2H, CH2, J = 10.3 Hz), 7.14 d (2H, Harom, J =
7.6 Hz), 7.25 d (1H, Harom, J = 7.6 Hz), 7.29–7.34 m
(4H, Harom), 7.41 d (2H, Harom, J = 7.6 Hz). 13C NMR
spectrum, δC, ppm: 29.7, 44.9 q (J = 25.4 Hz), 75.5 q
(J = 99.5 Hz), 125.4, 125.5, 125.7 q (J = 277 Hz),
127.4, 128.3, 129.1, 132.5, 137.2, 142.3, 145.3.
19F NMR spectrum: δF –62.15 ppm, t (CF3, J =
10.3 Hz). Mass spectrum, m/z (Irel, %): 280 (10) [M]+,
262 (8), 197 (100), 189 (5). Found, %: C 67.98;
H 5.36. C16H15F3O. Calculated, %: C 68.56; H 5.39.
M 280.11.
1-(4-Chlorophenyl)-3,3,3-trifluoro-1-phenylpro-
pan-1-ol (IIIs) was obtained from 50 mg (0.24 mmol)
of Id and 25 mg (0.32 mmol) of benzene in 1 ml of
CF3SO3H (20°C, 1 h). a. Quenching with water. Yield
22 mg (30%).
1-(3,4-Dichlorophenyl)-3,3,3-trifluoro-1-(4-meth-
ylphenyl)propan-1-ol (IIIk) was obtained from
100 mg of (0.54 mmol) of Ib and 96 mg (0.65 mmol)
of o-dichlorobenzene in 1 ml of CF3SO3H (20°C,
0.5 h); quenching with water. Yield 55 mg (29%).
b. Quenching with NaOH–H2O, yield 13 mg (18%).
Yellow oily substance. IR spectrum, ν, cm–1: 3488,
1
1
Yellow oily substance. H NMR spectrum, δ, ppm:
2954, 1510, 1248, 1122. H NMR spectrum, δ, ppm:
2.32 s (3H, Me), 2.64 s (1H, OH), 3.14 q (2H, CH2, J =
10.2 Hz), 7.15 d (2H, Harom, J = 8.2 Hz), 7.21 d.d (1H,
2.62 s (1H, OH), 3.17 q (2H, CH2, J = 10.0 Hz), 7.27–
7.39 m (9H, Harom). 13C NMR spectrum, δC, ppm: 29.7,
44.9 q (J = 25.4 Hz), 75.3 q (J = 99.5 Hz), 125.4,
125.6 q (J = 277 Hz), 127.1, 127.8, 128.5, 128.6,
133.4, 143.5, 144.9. 19F NMR spectrum: δF –62.88 ppm,
t (CF3, J = 10.0 Hz). Mass spectrum, m/z (Irel, %): 300
(10) [M]+, 282 (9), 247 (8), 217 (100), 139 (65), 105
(34), 77(26). Found, %: C 59.86; H 4.06. C15H12ClF3O.
Calculated, %: C 59.91; H 4.02. M 300.05.
H
arom, J = 8.4, 2.1 Hz), 7.25 d (2H, Harom, J = 8.2 Hz),
7.37 d (1H, Harom, J = 8.4 Hz), 7.51–7.53 m (1H,
arom), 7.69–7.71 m (1H, Harom). 19F NMR spectrum:
H
δF –62.93 ppm, t (CF3, J = 10.2 Hz). Mass spectrum,
m/z (Irel, %): 348 (20) [M]+, 330 (10), 265 (100),
203 (10), 173 (70). Found, %: C 55.01; H 3.70.
C16H13Cl2F3O. Calculated, %: C 55.04; H 3.75.
M 348.03.
1-(4-Chlorophenyl)-3,3,3-trifluoro-1-(4-methoxy-
phenyl)propan-1-ol (IIIt) was obtained from 50 mg
(0.24 mmol) of Id and 35 mg (0.32 mmol) of anisole
in 1 ml of CF3SO3H (20°C, 1 h); quenching with water.
Yield 22 mg (28%). Yellow oily substance. IR spec-
trum, ν, cm–1: 3484, 2954, 1512, 1254, 1118. 1H NMR
spectrum, δ, ppm: 2.60 s (1H, OH), 3.14 q (2H, CH2,
J = 10.4 Hz), 6.84–7.26 m (8H, Harom). 13C NMR spec-
trum, δC, ppm: 29.7, 45.0 q (J = 25.4 Hz), 55.3, 75.1 q
(J = 99.5 Hz), 113.8, 125.6 q (J = 277 Hz), 126.8,
1-(4-tert-Butylphenyl)-3,3,3-trifluoro-1-(4-meth-
ylphenyl)propan-1-ol (IIIn) was obtained from 50 mg
(0.27 mmol) of Ib and 47 mg (0.35 mmol) of tert-
butylbenzene in 1 ml of CF3SO3H (20°C, 0.5 h);
quenching with water. Yield 21 mg (23%). Yellow oily
1
substance. H NMR spectrum, δ, ppm: 1.30 s (9H,
t-Bu), 2.32 s (3H, Me), 2.58 s (1H, OH), 3.18 q (2H,
19
CH2, J = 10.2 Hz), 7.15–7.42 m (8H, Harom). F NMR
spectrum: δF –62.88 ppm, t (CF3, J = 10.2 Hz). Mass
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

ALKHAFAJI et al.
340
127.1, 128.4, 133.3, 137.1, 143.7, 159.0. 19F NMR
spectrum: δF –62.97 ppm, t (CF3, J = 10.4 Hz). Mass
spectrum, m/z (Irel, %): 330 (12) [M]+, 312 (10), 277
(100), 139 (85), 111 (34), 77 (18). Found, %: C 58.16;
H 4.32. C16H14ClF3O2. Calculated, %: C 58.11; H 4.27.
M 330.06.
E-VIa. 1H NMR spectrum, δ, ppm: 6.33 t (1H,
=CH, J = 11.7 Hz), 7.16–7.40 m (9H, Harom). 19F NMR
spectrum: δF –41.13 ppm, d (CF3, J = 11.7 Hz).
Z-VIa. 1H NMR spectrum, δ, ppm: 6.30 t (1H,
=CH, J = 11.7 Hz), 7.16–7.40 m (9H, Harom). 19F NMR
spectrum: δF –41.24 ppm, d (CF3, J = 11.7 Hz).
1-(4-Chlorophenyl)-1-(3,4-dichlorophenyl)-3,3,3-
trifluoropropan-1-ol (IIIu) was obtained from 50 mg
(0.24 mmol) of Id and 47 mg (0.32 mmol) of o-di-
chlorobenzene in 1 ml of CF3SO3H (20°C, 1 h);
quenching with water. Yield 35 mg (40%). Yellow oily
Isomer mixture. Mass spectrum, m/z (Irel, %): 298
(10) [M]+, 263 (100), 243 (12), 227 (9), 207 (11), 161
(31). Found, %: C 60.18; H 3.32. C15H10Cl2F2. Cal-
culated, %: C 60.23; H 3.37. M 298.01.
1
substance. H NMR spectrum, δ, ppm: 2.76 s (1H,
(E)- and (Z)-3-Bromo-1-(4-chlorophenyl)-3,3-di-
fluoro-1-phenylpropenes (VIb). Yellow oily sub-
stance (isomer mixture). From 100 mg (0.38 mmol) of
Vb and 59 mg (0.76 mmol) of benzene in 1 ml of
HSO3F (–75°C, 1 h); quenching with concentrated
aqueous HCl cooled to –75°C. Yield 13 mg (10%, E),
16 mg (12%, Z), E/Z ratio ~1:1.2.
OH), 3.13 q (2H, CH2, J = 10.0 Hz), 7.19–7.53 m (7H,
H
arom). 19F NMR spectrum: δF –62.90 ppm, t (CF3, J =
10.4 Hz). Mass spectrum, m/z (Irel, %): 368 (12) [M]+,
285 (100), 173 (75), 139 (95), 111 (78). Found, %:
C 48.67; H 2.68. C15H10Cl3F3O. Calculated, %:
C 48.75; H 2.73. M 367.97.
E-VIb. 1H NMR spectrum, δ, ppm: 6.37 t (1H,
=CH, J = 12.8 Hz), 7.14–7.40 m (9H, Harom). 19F NMR
spectrum: δF –34.28 ppm, d (CF3, J = 12.8 Hz).
Z-VIb. 1H NMR spectrum, δ, ppm: 6.40 t (1H,
=CH, J = 12.8 Hz), 7.14–7.40 m (9H, Harom). 19F NMR
spectrum: δF –34.20 ppm, d (CF3, J = 12.8 Hz).
3,3,3-Trifluoro-1-phenylpropan-1-one (IVa). Yel-
low oily substance [10, 11]. IR spectrum: ν 1690 cm–1
1
(C=O). H NMR spectrum, δ, ppm: 3.79 q (2H, CH2,
J = 9.8 Hz), 7.50 t (2H, Harom, J = 7.6 Hz), 7.63 t (1H,
H
arom, J = 7.6 Hz), 7.92 d (1H, Harom, J = 7.6 Hz).
13C NMR spectrum, δC, ppm: 42.0 q (CH2, J =
28.1 Hz), 124.0 q (CF3, J = 275.2 Hz), 128.3, 128.9,
134.1, 135.8, 189.7 q (C=O, J = 1.8 Hz). 19F NMR
spectrum: δF –65.64 ppm, t (CF3, J = 9.8 Hz). Mass
spectrum, m/z (Irel, %): 188 (20) [M]+, 105 (100), 77
(70), 51 (20).
Isomer mixture. Mass spectrum, m/z (Irel, %): 342
(10) [M]+, 263 (100), 243 (10), 227 (10), 207 (12),
161 (25), 127 (47). Found, %: C 52.38; H 2.88.
C15H10BrClF2. Calculated, %: C 52.43; H 2.93.
M 341.96.
3,3,3-Trifluoro-1-(4-methoxyphenyl)propan-
1-one (IVb). mp 44–46°C [10, 11]. IR spectrum:
ν 1686 cm–1 (C=O). 1H NMR spectrum, δ, ppm: 3.74 q
(2H, CH2, J = 10.0 Hz), 3.88 s (3H, OMe), 6.96 d (2H,
3-Chloro-1-(4-chlorophenyl)-3,3-difluoro-1-phe-
nylpropan-1-ol (VII) was obtained from 100 mg
(0.45 mmol) of Va and 70 mg (0.9 mmol) of benzene
in 1 ml of HSO3F (–75°C, 1 h); quenching with con-
centrated aqueous HCl cooled to –75°C. Yield 22 mg
H
arom, J = 8.3 Hz), 7.91 d (2H, Harom, J = 8.3 Hz).
13C NMR spectrum, δC, ppm: 41.8 q.t (CH2, J = 128.5,
28.1 Hz), 55.5 q (OMe, J = 143.9 Hz), 114.1 d.d (J =
161.0, 4.4 Hz), 124.1 q.t (CF3, J = 275.3, 8.0 Hz),
129.0 t (J = 7.1 Hz), 130.8 d.d (J = 159.7, 6.9 Hz),
164.4 d (J = 8.0 Hz), 188.1 q (C=O, J = 2.2 Hz).
19F NMR spectrum: δF –62.62 ppm, t (CF3, J =
9.8 Hz). Mass spectrum, m/z (Irel, %): 218 (36) [M]+,
135 (100), 107 (11), 92 (14), 77 (19). M 218.06.
1
(15%). Yellow oily substance. H NMR spectrum, δ,
ppm: 1.26 s (1H, OH), 3.45 t (2H, CH2, J = 13.6 Hz),
7.16–7.40 m (9H, Harom). 19F NMR spectrum:
δF –41.89 ppm, t (CF3, J = 13.6 Hz). Mass spectrum,
m/z (Irel, %): 316 (8) [M]+, 263 (10), 217 (100), 139
(50), 105 (36), 77 (21). Found, %: C 56.85; H 3.86.
C15H12Cl2F2O. Calculated, %: C 56.80; H 3.81.
M 316.02.
(E)- and (Z)-3-Chloro-1-(4-chlorophenyl)-3,3-di-
fluoro-1-phenylpropenes (VIa). Yellow oily sub-
stance (isomer mixture). From 100 mg (0.45 mmol) of
Va and 70 mg (0.9 mmol) of benzene in 1 ml of
HSO3F (–75°C, 1 h); quenching with concentrated
aqueous HCl cooled to –75°C. Yield 36 mg (27%, E),
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 12-03-00311-a) and by the Ministry of Education
of the Russian Federation (Federal special-purpose
program “Scientific and Scientific–Pedagogical Staff
of Innovation Russia 2009–2013,” contract
no. 14.B37.21.0794, Sept 03, 2012).
1
30 mg (22%, Z), E/Z ratio ~1.2:1. The H NMR spec-
tra of particular isomers of VIa and VIb were derived
from the spectra of their mixtures.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

REACTIONS OF TRIFLUOROMETHYL-SUBSTITUTED ARYLACETYLENES
341
5. Aristov, S.A., Vasil’ev, A.V., Fukin, G.K., and Ruden-
REFERENCES
ko, A.P., Russ. J. Org. Chem., 2007, vol. 43, p. 691.
1. Furin, G.G. and Fainzil’berg, A.A., Sovremennye metody
ftorirovaniya organicheskikh soedinenii (Modern
Methods for Fluorination of Organic Compounds),
Moscow: Nauka, 2000; Hiyama, T., Organofluorine
Compounds. Chemistry and Applications, Berlin:
Springer, 2000; Chambers, R.D., Fluorine in Organic
Chemistry, Oxford: Blackwell, 2004; Kirsch, P., Modern
Fluoroorganic Chemistry: Synthesis, Reactivity, Applica-
tions, Weinheim: Wiley-VCH, 2004; Uneyama, K.,
Organofluorine Chemistry, Oxford: Blackwell, 2006;
Theodoridis, G., Advances in Fluorine Science, Tres-
saud, A., Ed., Amsterdam: Elsevier, 2006, vol. 2, p. 121;
Bégué, J.P. and Bonnet-Delpon, D., Bioorganic and
Medicinal Chemistry of Fluorine, Hoboken: Wiley, 2008;
Fluorine and Health. Molecular Imaging, Biomedical
Materials and Pharmaceuticals, Tressaud, A. and
Haufe, G., Amsterdam: Elsevier, 2008, p. 553;
Fluorinated Heterocycles, Gakh, A. and Kirk, K.L., Eds.,
Oxford: Oxford Univ., 2008; Fainzil’berg, A.A. and
Furin, G.G., Ftoristyi vodorod kak reagent i sreda v
khimicheskikh reaktsiyakh (Hydrogen Fluoride as
Reagent and Medium in Chemical Reactions), Moscow:
Nauka, 2008; Fluorinated Heterocyclic Compounds:
Synthesis, Chemistry and Applications, Petrov, V.A., Ed.,
Hoboken: Wiley, 2009.
6. Rulev, A.Yu., Ushakov, I.A., Kondrashov, E.V., Muza-
levskiy, V.M., Nenajdenko, V.G., and Shastin, A.V.,
J. Fluorine Chem., 2011, vol. 132, p. 945; Nenajden-
ko, V.G., Muzalevskiy, V.M., Balenkova, E.S., Shas-
tin, A.V., Kondrashov, E.V., Ushakov, I.A., and
Rulev, A.Yu., J. Org. Chem., 2010, vol. 75, p. 5679;
Muzalevskiy, V.M., Nenajdenko, V.G., Balenkova, E.S.,
Shastin, A.V., and Haufe, G., Synthesis, 2009, no. 13,
p. 2249; Rulev, A.Yu., Muzalevskiy, V.M., Kondra-
shov, E.V., Ushakov, I.A., Shastin, A.V., Balenko-
va, E.S., Haufe, G., and Nenajdenko, V.G., Eur. J. Org.
Chem., 2010, p. 300; Goldberg, A.A., Muzalev-
skiy, V.M., Shastin, A.V., Balenkova, E.S., and Nenaj-
denko, V.G., J. Fluorine Chem., 2010, vol. 131, p. 384;
Nenajdenko, V.G., Muzalevskiy, V.M., Shastin, A.V.,
Balenkova, E.S., and Haufe, G., J. Fluorine Chem.,
2007, vol. 128, p. 818; Nenajdenko, V.G., Varseev, G.N.,
Korotchenko, V.N., Shastin, A.V., and Balenkova, E.S.,
J. Fluorine Chem., 2004, vol. 125, p. 1339; Korotchen-
ko, V.N., Shastin, A.V., Nenajdenko, V.G., and Balenko-
va, E.S., Tetrahedron, 2001, vol. 57, p. 7519.
7. Cho, E.J. and Buchwald, S.L., Org. Lett., 2011, vol. 13,
p. 6552.
8. Konno, T., Chae, J., Tanaka, T., Ishihara, T., and
Yamanaka, H., J. Fluorine Chem., 2006, vol. 127, p. 36.
2. Savechenkov, P.Yu., Rudenko, A.P., Vasil’ev, A.V., and
9. Konno, T., Daitoh, T., Noiri, A., Chae, J., Ishihara, T.,
Fukin, G.K., Russ. J. Org. Chem., 2005, vol. 41, p. 1316.
and Yamanaka, H., Org. Lett., 2004, vol. 6, p. 933.
3. Shchukin, A.O., Vasil’ev, A.V., Aristov, S.A., Fukin, G.K.,
and Rudenko, A.P., Russ. J. Org. Chem., 2008, vol. 44,
p. 965.
10. Pham, P.V., Nagib, D.A., and MacMillan, D.W.C.,
Angew. Chem., Int. Ed., 2011, vol. 50, p. 6119.
11. Zhang, Ch.-P., Wang, Z.-L., Chen, Q.-Y., Xiao, J.-C.,
Zhang, C.-T., and Gu, Y.-C., Chem. Commun., 2011,
vol. 47, p. 6632.
4. Shchukin, A.O., Vasilyev, A.V., and Rudenko, A.P.,
Tetrahedron, 2008, vol. 64, p. 6334.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013