Reactions of vinyl type carbocations generated in fluorosulfonic acid with benzene derivatives. New synthesis of alkyl 3,3-diarylpropenoates

Article abstract of DOI:10.1007/s11178-005-0340-6

Vinyl type carbocations ArC⁺=CHX [X = CO₂H, CO ₂Alk, C≡N, P(O)(OAlk)₂] generated from alkyl 3-arylpropynoates and related compounds in fluorosulfonic acid at -75 to -20°C react with various benzene derivatives,

Full text of DOI:10.1007/s11178-005-0340-6

Russian Journal of Organic Chemistry, Vol. 41, No. 9, 2005, pp. 1316–1328. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 9, 2005,
pp. 1341–1353.
Original Russian Text Copyright © 2005 by Savechenkov, Rudenko, Vasil’ev, Fukin.
Dedicated to Full Member of the Russian Academy of Sciences
N.S. Zefirov on His 70th Anniversary
Reactions of Vinyl Type Carbocations Generated
in Fluorosulfonic Acid with Benzene Derivatives. New Synthesis
of Alkyl 3,3-Diarylpropenoates
1
1
1
2
P. Yu. Savechenkov , A. P. Rudenko , A. V. Vasil’ev , and G. K. Fukin
1
St. Petersburg Academy of Forestry Engineering, Institutskii per. 5, St. Petersburg, 194021 Russia
e-mail: aleksvasil@notmail.com
2
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhnii Novgorod, Russia
Received February 22, 2005
+
Abstract—Vinyl type carbocations ArC =CHX [X = CO
2
H, CO
2
Alk, C≡N, P(O)(OAlk)
2
] generated from
alkyl 3-arylpropynoates and related compounds in fluorosulfonic acid at –75 to –20°C react with various
benzene derivatives, following the mechanism of electrophilic substitution of hydrogen. A new procedure for
the synthesis of alkyl 3,3-diarylpropenoates having various substituents in the aryl fragments has been
developed on the basis of protonation of the triple bond in alkyl 3-arylpropynoates.
Acetylenic compounds and products of their
various transformations are widely used in the prepara-
tion of practically important substances, materials, and
compositions; therefore, theoretical, synthetic, and ap-
plied aspects of the reactivity of these compounds are
continuously and extensively studied [1]. A new line in
the chemistry of alkynes is alkenylation of arenes with
acetylene derivatives in the presence of Lewis acids,
such as Sc(OTf) and Hf(OTf) [2], or catalysts based
While studying transformations of acetylenic com-
pounds in superacids [4–10] we have revealed a key
reaction based on protonation of the triple bond in
acetylene derivative to give vinyl type carbocation
which then reacts with appropriate aromatic substrate
[6–8]. It seems to be reasonable to estimate the syn-
thetic potential of this new reaction and its scope upon
variation of donor–acceptor properties of substituents
in the acetylenic and aromatic components. Scheme 1
illustrates the reaction mechanism which involves
3
4
on palladium(II) complexes [3].
Scheme 1.
OH
H+
H+
Ar
Ar
–
OMe
O
A
Ar
H
Ar
OMe
H+
H
RC H
6 5
C
C
COOMe
COOMe
H
R
B
C
Ar
Ar
COOMe
H
+
–
H+
H
COOMe
Z Isomer
R
R
E Isomer
1
070-4280/05/4109-1316 © 2005 Pleiades Publishing, Inc.

REACTIONS OF VINYL TYPE CARBOCATIONS
1317
Scheme 2.
H
Y
Y
H
HSO F, –75 to –20°C
3
X
Y
+
+
R
X
X
R
R
E Isomers
Z Isomers
I–VIII
IX, Xa–Xl, XIa–XIh, XIIa–XIIc, XIIIa, XIIIb, XIVa, XIVb
XVa–XVc, XVIa, XVIb
I, IX, X = MeO, Y = CO
2
Me, R = 4-MeO (a); II, X, X = Me, Y = CO
), 2-Me-5-MeOCOC≡C (b ), 2-MeOCOC≡C-5-Me (b ), 2,3,5,6-Me
e), 2,3,5,6-Me -4-FSO (f), 2,4,6-Me -3-O N (g), 3-F-4-MeO (h), 2-EtO-5-Br (i), 3,4-(MeO)
Me, R = H (a), 4-t-Bu (b), 2,4-Me (c), 2,3-Me (d ), 3,4-Me (d ), 2,5-Me (e), 2,4,5-Me
-MeO-5-F (h); IV, XII, X = F, Y = CO Me, R = 2,3,5,6-Me -4-FSO (a), 3,4-Cl (b), 2,5-(MeO) (c); V, XIII, X = I, Y = CO
R = 2,3,5,6-Me -4-MeCO (a); X = 3-O N-4-MeO, Y = CO Et, R = 2,3,5,6-Me -4-MeCO (b); VI, XIV, X = H, Y = CO H, R =
(a), 2,3,5,6-Me -4-MeCO (b); VII, XV, X = H, Y = CN, R = 2,3,5,6-Me -4-FSO (a), X = 4-Cl, Y = 4-NCC , R =
-4-MeCO (b); X = H, Y = 4-MeOCOC , R = 2,3,5,6-Me -4-MeCO (c); VIII, XVI, X = H, Y = P(O)(OEt) , R =
,3,5,6-Me -4-FSO (a), 3,4-(MeO)
2
Me, R = 2,3,5,6-Me
-4-NC CH (c), 2,3,5,6-Me
(j), 2-MeO-5-F (k
(f), 2,3,5,6-Me
4
(a
1
), 2,3,5,6-Me
-4-NC (d), 2,3,5,6-Me
); III, XI, X = H,
-4-H N (g),
Et,
4
(MeOCOCH=CTol-4)
(
(
a
2
1
2
4
2
4
4
-4-MeCO
4
2
3
2
2
1
Y = CO
2
2
2
1
2
2
2
3
4
2
2
2
4
2
2
2
2
4
2
2
4
2
2
2
,3,5,6-Me
,3,5,6-Me
4
4
4
2
6 4
H
4
6
H
4
4
2
2
4
2
2
(b).
F
H
F
COOMe
Me
O
Me
O
O
E-Xk2
Xl1
equilibrium protonation of methyl 3-arylpropynoate at
the carbonyl oxygen atom with formation of a fairly
stable cation A (O-protonation) [9]. Slow protonation
of carbon atom at the triple bond leads to reactive ion
B (C-protonation) which reacts with appropriate aro-
matic substrate to afford arenium ion C. Deprotonation
of the latter yields methyl (E)- or/and (Z)-3,3-diaryl-
propenoates.
keeping with published data [3]. The maximal differ-
ence in the chemical shifts of that proton between the Z
and E isomers, ∆δ = δ – δ = 0.78–0.89 ppm, was
Z
E
observed for compounds Xa , Xf, XIVa, and XVIa
1
with sterically loaded aromatic fragments due to mag-
netically anisotropic properties of the latter. According
to the X-ray diffraction data for compound E-Xc, the
1
1
12 13
3
2
2
dihedral angle between the C C C and C C H
planes is 97.6°, so that the vinyl proton appears above
the plane of the tetramethyl-substituted benzene ring.
The set of the examined acetylenic (compounds I–
VIII) and aromatic substrates is shown in Scheme 2;
no special numbering was used for aromatic substrates,
for their structure unambiguously follows from the
structure of the corresponding alkenylation products.
The experimental conditions were selected with
account taken of the reactivity of type B carbocations
and arene nucleophilicity. The configuration (E or Z)
of products IX–XVI was determined on the basis of
1
2
In the H NMR spectrum of E-Xc, the H signal is
located at δ 5.79 ppm. For comparison, the correspond-
ing proton in structure Z-XVIa (see figure) resides at
the side of the phenyl ring (in the deshielded region),
and it resonates in a weaker field (δ 6.53 ppm; cf.
δ 5.66 ppm for E-XVIa).
By analogy with the previously described addition
of superacids (HSO F and CF SO H) to 3-arylpropyn-
1
the H NMR data (see Experimental) and the X-ray
3
3
3
diffraction data for compounds E-Xb , E-Xc, E-XIi,
oic acid derivatives [9], the reactions of acetylenic
compounds examined in the present work (Scheme 2)
occur as syn addition of proton and aryl residue at the
triple bond, yielding at –75°C mainly E isomers of IX–
XVI. Above –50°C, the E isomers are converted into
the corresponding Z isomers (anti-addition products).
1
and Z-XVIa (see figure). The E isomers of IX–XVI
1
characteristically showed in the H NMR spectra
a signal at δ δ 5.32–6.30 ppm from the vinyl =CH–
proton, while the corresponding signal of the Z isomers
was located in a weaker field (δ 6.28–6.66 ppm), in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

1
318
SAVECHENKOV et al.
2
1
1
(
a)
19
H
O
(b)
N
20
11
C
C
2
C
1
5
16
2
2
1
C
C
2
C
C
11
O
1
7
2
C
C
21
H
1
8
C
C
1
1
6
3
C
1
3
C
2
O
21
C
C
C
13
1
5
19
C
C
3
1
C
14
C
C
3
C
4
O
C
1
2
2
0
9
C
9
1
2
C
2
11
17
14
C
O
C
C
4
C
C
C
C
18
5
C
8
C
C
C
8
5
C
4
C
O
7
C
6
2
2
C
C
7
6
10
C
C
C
1
0
C
6
(c)
C
(d)
7
7
C
C
8
5
C
C
1
F
6
C
8
C
9
C
4
C
5
1
4
2A
15
C
O
C
3
C
4
C
1
3A
C
1
4A
C
C
10A
C
1
1A
C
1
2
2
'
S
C
O
1
0
1
3
C
3
1
9
1
C
C
1
H
O
12
C
C
C
1
2
F
11
10
13
1
2
C
C
C
C
C
1
1
1
C
1
4
C
C
1
P
3A'
2
2
O
3
H
O
1
7
1
O
16A
C
O
C
3
'
O
15A
C
C
1
6
15
C
1
6
C
Structure of molecules (a) E-Xb
1
, (b) E-Xc, (c) E-XIi, and (d) Z-XVIa according to the X-ray diffraction data (hydrogen atoms,
except for vinylic, are not shown).
For example, compound Z-Xf was obtained by keeping
a solution of its isomer E-Xf in fluorosulfonic acid
for 1 h at –30°C.
Various aromatic compounds are capable of react-
ing with carbocations B (Schemes 1, 2): unsubstituted
benzene, alkylbenzenes, and methoxybenzenes. Ions B
also effectively react with deactivated compounds
tion of ester I in HSO F in the presence of anisole gave
3,3-diarylpropenoate IXa in a good yield. Compound
3
IXa is the product of regioselective attack of cation B
at the para position with respect to the methoxy group
Scheme 3). The reaction with 1,2,4,5-tetramethyl-
1
(
benzene (durene) gives a mixture of mono- and bis-
alkylation products. This aromatic substrate in HSO3F
exists mainly as arenium ion [10]; however, just
neutral 1,2,4,5-tetramethylbenzene species (which are
(
with reduced π-nucleophilicity), e.g., 1,2-dichloroben-
zene, and 2,4,6-trimethylnitrobenzoene, as well as
with sterically hindered aromatic substrates, such as
present in a small concentration) react with cation B2
generated from methyl 3-(4-methylphenyl)propynoate
1
-acetyl-2,3,5,6-tetramethylbenzene, 2,3,5,6-tetra-
(
II). Monoadduct E-Xa reacts with B to give
methylbenzonitrile, etc. (see Experimental). Less nu-
cleophilic systems like methyl 4-methoxybenzoate and
1 2
E,E-Xa (Scheme 4). The two steps in the synthesis of
2
bis-adduct E,E-Xa are stereoselective, but the mono-
4
-methylnitrobenzene failed to produce alkenylation
2
adduct undergoes partial isomerization.
products in reactions with compounds II and IV.
Let us consider particular reactions of vinyl type
cations B with various benzene derivatives. Dissolu-
When a solution of acetylenic compound II in
HSO F was kept at –75°C in the absence of aromatic
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

REACTIONS OF VINYL TYPE CARBOCATIONS
1319
Scheme 3.
COOMe
H
HSO F, –75°C
3
MeO
COOMe
MeO
C
H
C
I
B1
H
COOMe
COOMe
PhOMe
PhOMe
MeO
H
OMe
MeO
OMe
C1
IXa
Scheme 4.
COOMe
H
HSO F, –75°C
3
Me
COOMe
H
Me
C
C
II
B2
Me
Me
Me
COOMe
H
COOMe
Me
Me
Me
Me
Me
Me
Me
+
Me
Me
Me
Me
Me
MeOCO
H
E/Z-Xa (E:Z = 3:1)
E,E-Xa2
1
substrate, cation B stereoselectively attacked the tolyl
X-ray analysis (see figure). The relative inertness of
2
fragment in initial compound II to produce arenium
ions C and C . After deprotonation, final regio-
the triple bond in compounds E-Xb and E-Xb to
1
2
HSO F may be rationalized in terms of reduced
2
3
3
isomeric products E-Xb and E-Xb were isolated
basicity of the acetylenic carbon atoms due to electron-
1
2
(
Scheme 5). The structure of E-Xb was proved by
withdrawing effect of the C(Ar)=CHCO Me group.
1
2
Scheme 5.
Me
Me
Me
H
HSO F, –75°C
II
3
COOMe
H
II
B2
+
COOMe
H
H
Me
COOMe
COOMe
C2
C3
Me
MeOCO
Me
H
Me
COOMe
+
–
H+
COOMe
H
Me
COOMe
E-Xb1
E-Xb2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

1
320
SAVECHENKOV et al.
Scheme 6.
H
OMe
COOMe
H
COOMe
F
HSO F, –75°C
3
II
+
F
OMe
H
+
Me
MeO
H
Me
F
C4
C5
H
COOMe
MeOCO
OMe
OMe
C4
+
–
H+
Me
H
Me
F
F
E-Xk1
Z-Xk1
COOMe
F
C5
–
H+
O
Me
E-Xk2
Scheme 7.
C H Me-4
6
4
F
HSO F, –75°C
3
II
+
F
OH
+
E-Xk2
O
O
Xl1
Scheme 6 shows the transformations of ester II in
Apart from 3-arylpropynoic acids and their esters
I–VI, other structurally related compounds were
brought into reactions with aromatic substrates in
reaction with p-fluoroanisole. Here, different nucleo-
philic centers in p-fluoroanisole are involved in forma-
tion of new covalent bond. Apart from conventional
electrophilic substitution of hydrogen, ipso attack on
the carbon atom attached to fluorine leads to inter-
HSO F. Nitrile VIIa and phosphonate VIII reacted,
3
respectively, with 2,3,5,6-tetramethylbenzenesulfonyl
fluoride and 1,2-dimethoxybenzene to afford the corre-
sponding alkenylation products E-XVa and E/Z-XVIb
(Scheme 9). Likewise, triarylethenes Z-XVb and
Z-XVc were obtained by reaction of diarylacetylenes
VIIb and VIIc with 2,3,5,6-tetramethylacetophenone
(Scheme 10).
mediate arenium ion C which undergoes demethyla-
5
tion to give E-Xk . Under analogous conditions, the
2
reaction of methyl 3-(4-methylphenyl)propynoate (II)
with p-fluorophenol resulted in formation of com-
pound E-Xk and intramolecular cyclization product,
2
substituted coumarin Xl (Scheme 7).
1
To conclude, we have developed a new procedure
for the synthesis of alkyl 3,3-diarylpropenoates and
related compounds having various substituents in the
aryl fragments. Systematic study of reactions of vinyl
2
,3,5,6-Tetramethylaniline in fluorosulfonic acid is
completely protonated at the nitrogen atom, and it ex-
ists exclusively as arylammonium ion [11] (Scheme 8).
Therefore, further transformations of ester III involve
type cations generated in HSO F with various benzene
3
ion B and 2,3,5,6-tetramethylphenylammonium ion,
derivatives has been performed for the first time.
A multistep mechanism has been proposed for these
reactions. It implies protonation of the triple bond in
acetylenic compound to give vinyl type carbocation,
followed by addition of aromatic substrate and depro-
tonation of the arenium ion thus formed.
3
giving rise to “exotic” doubly charged arenium ion C6
whose deprotonation yields arylammonium ion D. The
final product (compound E-XIh) was isolated from
the reaction mixture by treatment with a solution of
sodium carbonate.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

REACTIONS OF VINYL TYPE CARBOCATIONS
1321
Scheme 8.
NH2
NH3
Me
Me
Me
Me
COOMe
H
Me
Me
Me
Me
HSO F, –30°C
3
Ph
COOMe
Ph
+
Ph
C
C
+
III
B3
Ph
COOMe
Ph
COOMe
COOMe
H
Me
Me
Me
H
Na CO3
H
2
H
Me
Me
H+
Me
Me
–H+
Me
Me
–
H N
Me
H N
Me
H N
Me
E-XIg
3
3
2
C6
D
Scheme 9.
Ph
CN
H
SO2F
Me
Me
Me
Me
HSO F, –30°C
3
Ph
CN
+
Me
Me
Me
FSO2
Me
VIIa
E-XVa
Ph
P(O)(OEt)2
H
Ph
H
MeO
MeO
P(O)(OEt)2
HSO F, –75°C
3
Ph
P(O)(OEt)2
+
MeO
+
MeO
MeO
MeO
VIII
E-XVIb
Z-XVIb
Scheme 10.
Ar
H
Ac
Me
Me
Me
Me
Me
Me
HSO F, –75°C
3
Ar
R
+
Me
Ac
R
Me
VIIb, VIIc
Z-XVb, Z-XVc
6 4
Ar = 4-ClC H , R = CN (b); Ar = Ph, R = MeOCO (c).
EXPERIMENTAL
an MKh-1321 instrument. The molecular weights were
determined from the high-resolution mass spectra
recorded on a Finnigan MAT 8200 spectrometer.
1
13
19
The H, C, and F NMR spectra were recorded
on a Bruker AM-500 spectrometer at 500, 125.76, and
70.7 MHz, respectively, using CDCl as solvent.
X-Ray analysis of single crystals of compounds
4
E-Xb , E-Xc, E-XIi, and Z-XVIa was performed on
3
1
The chemical shifts were measured relative to the
a Smart APEX automatic diffractometer (MoK irra-
α
1
13
solvent signals ( H: CHCl , δ 7.25 ppm; C: CDCl3,
diation, graphite monochromator, ω–θ scanning). The
3
1
9
δ 77.0 ppm) or CFCl ( F: δ 0.0 ppm). The IR
structures were solved by the direct method and were
C
3
F
2
hkl
spectra were obtained on a Specord 75IR spectrometer
refined with respect to F by the least-squares proce-
from solutions in CHCl . The mass spectra were run on
dure in anisotropic approximation for all non-hydrogen
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

1
322
SAVECHENKOV et al.
atoms. Hydrogen atoms were localized by the Fourier
difference synthesis, and their positions were refined
in isotropic approximation. All calculations were
performed with the use of SHELXTL 6.10 software
package [12].
compounds Z-Xa and E,E-Xa ) from 96 mg
1 2
(0.50 mmol) of compound II and 70 mg (0.50 mmol)
of 1,2,4,5-tetramethylbenzene in 1.5 ml of HSO F at
3
–75°C (reaction time 40 min). Chromatographic sepa-
ration gave 15 mg (10%) of an oily product (a mixture
1
with II and Z-Xa ). H NMR spectrum (from the spec-
1
The synthesis and properties of acetylene deriva-
tives, methyl 3-(4-methoxyphenyl)propynoate (I),
methyl 3-(4-methylphenyl)propynoate (II), methyl
trum of the mixture), δ, ppm: 2.09 s (6H, Me), 2.21 s
(
(
6H, Me), 2.31 s (3H, Me), 3.69 s (3H, OMe), 5.82 s
1H, HC=), 6.93 s (1H, Harom), 7.06 d (2H, Harom, J =
3
-phenylpropynoate (III), methyl 3-(4-fluorophenyl)-
8.1 Hz), 7.16 d (2H, Harom, J = 8.0 Hz).
propynoate (IV), ethyl 3-(4-iodophenyl)propynoate
(
(
Va), ethyl 3-(4-methoxy-3-nitrophenyl)propynoate
Vb), 3-phenylpropynoic acid (VI), and 3-phenylprop-
Methyl (Z)-3-(2,3,5,6-tetramethylphenyl)-3-(4-
tolyl)propenoate (Z-Xa ) was obtained (together with
1
ynenitrile (VIIa), were reported in [8, 9]. 4-(4-Chloro-
phenylethynyl)benzonitrile (VIIb) and methyl
E-Xa and E,E-Xa ) from 96 mg (0.50 mmol) of com-
pound II and 70 mg (0.50 mmol) of 1,2,4,5-tetra-
1
2
4
-phenylethynylbenzoate (VIIc) were described in
methylbenzene in 1.5 ml of HSO F at –75°C (reaction
3
[
13]; and diethyl phenylethynylphosphonate (VIII)
time 40 min). Chromatographic separation gave 5 mg
was synthesized according to [14].
(3%) of an oily product (a mixture with II and E-Xa ).
1
1
H NMR spectrum (from the spectrum of the mixture),
δ, ppm: 2.23 s (6H, Me), 2.31 s (6H, Me), 2.33 s (3H,
Me), 3.57 s (3H, OMe), 6.61 s (1H, HC=), 6.96 s (1H,
Harom), 7.11 d (2H, Harom, J = 8.2 Hz), 7.22 d (2H,
Harom, J = 8.2 Hz).
General procedure for reactions of acetylene
derivatives I–VIII with aromatic compounds in
fluorosulfonic acid. A solution of 0.15–1.12 mmol of
aromatic compound in 0.5–1.5 ml of fluorosulfonic
acid was cooled to –75 to –20°C, and 0.1–0.5 mmol of
acetylene derivative I–VIII was slowly added (over
a period of 10–30 min) under vigorous stirring. The
mixture was stirred for 5–60 min, poured into 15–
(E,E)-1,4-Bis[2-methoxycarbonyl-1-(4-tolyl)-
ethenyl]-2,3,5,6-tetramethylbenzene (E,E-Xa ) was
2
obtained (together with compounds E-Xa and Z-Xa )
1
1
3
–
0 ml of concentrated hydrochloric acid cooled to
60°C, and treated with chloroform (3×30 ml). The
from 96 mg (0.50 mmol) of compound II and 70 mg
(0.50 mmol) of 1,2,4,5-tetramethylbenzene in 1.5 ml of
combined extracts were washed in succession with
HSO F at –75°C (reaction time 40 min). Yield 55 mg
3
1
water, a saturated aqueous solution of NaHCO , and
(22%), mp 218–220°C. H NMR spectrum (CDCl ,
3
3
water again, dried over Na SO , and evaporated under
a mixture of two atropoisomers, syn:anti = 1:1), δ,
ppm: 2.11 s (12H, Me), 2.13 s (12H, Me), 2.32 s (6H,
Me), 2.33 s (6H, Me), 3.69 s (6H, OMe), 3.69 s (6H,
OMe), 5.82 s (2H, HC=), 5.85 s (2H, HC=), 7.09 d
(4H, Harom, J = 8.2 Hz), 7.10 d (4H, Harom, J = 8.2 Hz),
2
4
reduced pressure (water-jet pump). The residue was
subjected to chromatographic separation on silica gel
using petroleum ether–ethyl acetate as eluent. The
yields of compounds E/Z-IX–XVI are given for the
products isolated by chromatography.
7.16 d (4H, Harom, J = 8.2 Hz), 7.18 d (4H, Harom, J =
+
8
4
.2 Hz). Mass spectrum, m/z (I , %): 482 (100) [M] ,
rel
Methyl 3,3-bis(4-methoxyphenyl)propenoate
+
67 (18) [M – Me] , 450 (42), 435 (36), 408 (24), 391
(
IX) was obtained from 32 mg (0.17 mmol) of com-
(
2
15), 377 (15), 375 (12), 363 (14), 335 (11), 319 (12),
75 (11), 247 (12), 241 (12), 175 (12), 119 (18), 105
pound I and 80 mg (0.74 mol) of anisole in 1 ml of
HSO F at –75°C (reaction time 30 min). Yield 27 mg
3
1
(11), 91 (11), 59 (14). Found, %: C 79.36; H 7.00.
(
54%), oily substance. H NMR spectrum, δ, ppm:
C H O . Calculated, %: C 79.64; H 7.10. M 482.61.
3
2
34
4
3
.62 s (3H, OMe), 3.81 s (3H, OMe), 3.84 s (3H,
OMe), 6.22 s (1H, HC=), 6.83 d (2H, Harom, J =
.8 Hz), 6.90 d (2H, Harom, J = 8.6 Hz), 7.14 d (2H,
Methyl (E)-3-(5-methoxycarbonylethynyl-2-
8
methylphenyl)-3-(4-tolyl)propenoate (E-Xb ) was
1
Harom, J = 8.6 Hz), 7.23 d (2H, Harom, J = 8.8 Hz). Mass
obtained (together with E-Xb ) by keeping a solution
of 50 mg (0.29 mmol) of compound II in 1 ml of
2
+
spectrum, m/z (I , %): 298 (100) [M] , 267 (47) [M –
rel
+
OMe] , 240 (13), 239 (10), 225 (17), 153 (11), 152
HSO F for 45 min at –75°C. Yield 64 mg (64%).
3
(
11), 135 (53). Found, %: C 72.31; H 6.19. C H O .
Compound E-Xb was described previously [6].
1
8
18
4
1
Calculated, %: C 72.47; H 6.08. M 298.33.
Methyl (E)-3-(2-methoxycarbonylethynyl-5-
Methyl (E)-3-(2,3,5,6-tetramethylphenyl)-3-(4-
methylphenyl)-3-(4-tolyl)propenoate (E-Xb
2
) was
tolyl)propenoate (E-Xa ) was obtained (together with
obtained (together with E-Xb ) by keeping a solution
1
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

REACTIONS OF VINYL TYPE CARBOCATIONS
1323
of 50 mg (0.29 mmol) of compound II in 1 ml of
fonyl fluoride in 1.0 ml of HSO F at –50°C (reaction
3
HSO F for 45 min at –75°C. Yield 11 mg (11%).
time 15 min). Compound Z-Xf was also formed in
3
Compound E-Xb was described previously [6].
quantitative yield by keeping a solution of 30 mg
2
(
6
0.08 mmol) of isomer E-Xf in 0.5 ml of HSO F for
0 min at –30°C. Oily substance. H NMR spectrum,
3
Methyl (E)-3-(4-cyanomethyl-2,3,5,6-tetra-
methylphenyl)-3-(4-tolyl)propenoate (E-Xc) was
obtained from 30 mg (0.17 mmol) of compound II and
1
δ, ppm: 2.06 s (6H, Me), 2.35 s (3H, Me), 2.59 d (6H,
Me, JHF = 2.0 Hz), 3.60 s (3H, OMe), 6.66 s (1H,
HC=), 7.15 s (1H, Harom). Found, %: C 64.97; H 6.12.
3
3 mg (0.19 mmol) of 2-(2,3,5,6-tetramethylphenyl)-
acetonitrile in 0.6 ml of HSO F at –75°C (reaction
3
C H FO S. Calculated, %: C 64.60; H 5.94. M 390.47.
time 45 min). Yield 44 mg (75%). Compound E-Xc
21 23
4
was described previously [6].
Methyl (E)-3-(4-tolyl)-3-(2,4,6-trimethyl-3-nitro-
phenyl)propenoate (E-Xg) was obtained from 60 mg
Methyl (E)-3-(4-cyano-2,3,5,6-tetramethyl-
phenyl)-3-(4-tolyl)propenoate (E-Xd) was obtained
from 30 mg (0.17 mmol) of compound II and 32 mg
(
0.34 mmol) of compound II and 62 mg (0.39 mmol)
of 1,3,5-tetramethyl-2-nitrobenzene in 1.2 ml of
HSO F at –75°C (reaction time 45 min). Yield 18 mg
(
0
0.20 mmol) of 2,3,5,6-tetramethylbenzonitrile in
.6 ml of HSO F at –75°C (reaction time 45 min).
3
1
(9%), mp 83–85°C. H NMR spectrum, δ, ppm: 2.13 s
3
Yield 15 mg (26%), mp 115–118°C. IR spectrum, ν,
cm : 1610 (C=C), 1720 (C=O), 2220 (C≡N). H NMR
spectrum, δ, ppm: 2.14 (6H, Me), 2.32 s (3H, Me),
(3H, Me), 2.19 s (3H, Me), 2.27 s (3H, Me), 2.33 s
(3H, Me), 3.70 s (3H, OMe), 5.83 s (1H, HC=), 6.99 s
(1H, Harom), 7.09 d (2H, Harom, J = 7.9 Hz), 7.12 d (2H,
–1
1
2
7
8
3
2
.46 s (6H, Me), 3.70 s (3H, OMe), 5.76 s (1H, HC=),
Harom, J = 7.9 Hz). Mass spectrum, m/z (Irel, %): 339
+
+
+
.09 d (2H, Harom, J = 8.3 Hz), 7.12 d (2H, Harom, J =
(43) [M] , 332 (71) [M – OH] , 308 [M – OMe] , 290
(100), 262 (18), 248 (14), 233 (22), 219 (22), 202 (28),
174 (15), 119 (25), 91 (14). Found, %: C 70.54;
+
.3 Hz). Mass spectrum, m/z (I , %): 333 (69) [M] ,
rel
+
+
18 (23) [M – Me] , 302 (23) [M – OMe] , 286 (35),
73 (100), 259 (78), 245 (27), 244 (24), 228 (17), 182
H 6.20. C20H21NO . Calculated, %: C 70.78; H 6.24.
4
(
12), 119 (13), 115 (17), 105 (12), 91 (14), 59 (12).
M 339.39.
Found, %: C 79.51; H 6.87. C H NO . Calculated,
2
2
23
2
Methyl (E)-3-(3-fluoro-4-methoxyphenyl)-3-(4-
tolyl)propenoate (E-Xh) and methyl (Z)-3-(3-fluoro-
4-methoxyphenyl)-3-(4-tolyl)propenoate (Z-Xh)
were obtained as an oily mixture of E and Z isomers
at a ratio of 2:1 [E-Xh, 18 mg (35%); Z-Xh, 9 mg
(17%)] from 30 mg (0.17 mmol) of compound II and
101 mg (0.80 mmol) of 1-fluoro-2-methoxybenzene in
%: C 79.25; H 6.95. M 333.42.
Methyl (E)-3-(4-acetyl-2,3,5,6-tetramethyl-
phenyl)-3-(4-tolyl)propenoate (E-Xe) was obtained
from 30 mg (0.17 mmol) of compound II and 33 mg
(
0.19 mmol) of 2,3,5,6-tetramethylacetophenone in
0
2
.6 ml HSO F at –75°C (reaction time 50 min). Yield
0 mg (33%), mp 116–118°C. IR spectrum, ν, cm :
3
–
1
0.6 ml of HSO F at –75°C (reaction time 45 min).
3
1
1
350, 1435, 1515, 1620, 1695 (C=O), 1725 (C=O).
H NMR spectrum (recorded for isomer mixture), δ,
1
H NMR spectrum, δ, ppm: 2.10 s (12H, Me), 2.32 s
3H), 2.48 s (3H, Me), 3.69 s (3H, OMe), 5.79 s
1H, HC=), 7.08 d (2H, Harom, J = 8.0 Hz), 7.14 d
2H, Harom, J = 8.0 Hz). Found, %: C 78.62; H 7.57.
ppm: E-Xh: 2.39 s (3H, Me), 3.61 s (3H, OMe), 3.89 s
(
(
(
(
3H, OMe), 6.26 s (1H, HC=), 6.72–7.23 m (7H,
Harom); Z-Xh: 2.36 s (3H, Me), 3.63 s (3H, OMe), 3.92 s
(3H, OMe), 6.28 s (1H, HC=), 6.72–7.23 m (7H,
C H O . Calculated, %: C 78.83; H 7.48. M 350.45.
23
26
3
H
). Mass spectrum (E/Z), m/z (I , %): 300 (100)
arom rel
+
+
Methyl (E)-3-(4-fluorosulfonyl-2,3,5,6-tetra-
[M] , 269 (71) [M – OMe] , 242 (14), 241 (16), 226
methylphenyl)-3-(4-tolyl)propenoate (E-Xf) was
obtained from 30 mg (0.17 mmol) of compound II
and 41 mg (0.19 mmol) 2,3,5,6-tetramethylbenzenesul-
(10), 183 (16), 153 (23), 119 (22). Found, %: C 72.30;
H 5.50. C18H17FO . Calculated, %: C 71.99; H 5.71.
3
M 300.32.
fonyl fluoride in 1.5 ml of HSO F at –75°C (reaction
time 45 min). Yield 25 mg (38%). Compound E-Xf
was described previously in [6].
3
Methyl (E)-3-(5-bromo-2-ethoxyphenyl)-3-(4-
tolyl)propenoate (E-Xi) was obtained from 30 mg
(
0.17 mmol) of compound II and 140 mg (0.70 mmol)
Methyl (Z)-3-(4-fluorosulfonyl-2,3,5,6-tetra-
methylphenyl)-3-(4-tolyl)propenoate (Z-Xf), 7 mg
of 1-bromo-4-ethoxybenzene in 0.6 ml HSO F at
3
–75°C (reaction time 40 min). Yield 29 mg (45%),
1
(
(
10%), was obtained together with isomer E-Xf, 33 mg
50%), from 30 mg (0.17 mmol) of compound II and
mp 99–100°C. H NMR spectrum, δ, ppm: 1.06 t (3H,
J = 7.0 Hz), 2.34 s (3H, Me), 3.63 s (3H, OMe), 3.79 q
4
1 mg (0.19 mmol) of 2,3,5,6-tetramethylbenzenesul-
(2H, CH , J = 7.0 Hz), 6.15 s (1H, HC=), 6.70 d (1H,
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

1
324
SAVECHENKOV et al.
1
9
Harom, J = 8.7 Hz), 7.10 s (4H, Harom), 7.30 d (1H,
Harom, J = 2.4 Hz), 7.36 d (1H, Harom, J = 2.3 Hz),
Harom, J = 8.2 Hz). F NMR spectrum: δ –120.83 ppm,
F
+
m. Mass spectrum, m/z (I , %): 300 (41) [M] , 269
rel
+
7
.36 d.d (1H, Harom, J = 8.7, 2.3 Hz). Mass spectrum,
(100) [M – OMe] , 227 (28), 199 (15), 183 (11), 105
+
+
m/z (I , %): 376 (35) [M + 2] , 374 (34) [M] , 331
(10). Found, %: C 71.69; H 5.82. C H FO . Calculat-
ed, %: C 71.99; H 5.71. M 300.32.
rel
18 17
3
+
(
(
21), 329 (21) [M – OEt] , 317 (11), 315 (14), 303
45), 301 (47), 300 (27), 288 (27), 286 (27), 222 (100),
Methyl (E)-3-(1-fluoro-4-oxo-2,5-cyclohexadi-
enyl)-3-(4-tolyl)propenoate (E-Xk ), 20 mg (21%),
was obtained together with E-Xk and Z-Xk from
0 mg (0.34 mmol) of compound II and 222 mg
2
(
08 (15), 207 (18), 179 (30), 178 (36), 165 (18), 152
15), 89 (11), 59 (18). Found, %: C 60.63; H 5.06.
C H BrO . Calculated, %: C 60.81; H 5.10. M 375.26.
2
1
1
19
19
3
6
Methyl (E)-3-(3,4-dimethoxyphenyl)-3-(4-tolyl)-
propenoate (E-Xj) was obtained from 30 mg
0.17 mmol) of compound II and 100 mg (0.72 mmol)
of 1,2-dimethoxybenzene in 0.6 ml of HSO F at –75°C
(1.76 mmol) of 1-fluoro-4-methoxybenzene in 1.2 ml
of HSO F at –75°C (reaction time 40 min). It was also
3
(
isolated in an amount of 56 mg (68%) (together with
3
E-Xl ) in the reaction of 50 mg (0.29 mmol) of com-
1
(
1
reaction time 45 min). Yield 9 mg (17%), mp 98–
01°C. H NMR spectrum, δ, ppm: 2.39 s (3H, Me),
pound II and 36 mg (0.32 mmol) of 4-fluorophenol in
1
1.0 ml of HSO F at –75°C (reaction time 60 min). Oily
3
–
1
3
.61 s (3H, OMe), 3.88 s (3H, OMe), 6.27 s (1H,
substance. IR spectrum, ν, cm : 1065, 1165, 1610,
1625, 1675, 1690, 1725 (C=O). H NMR spectrum, δ,
1
HC=), 6.77 d (1H, Harom, J = 8.4 Hz), 6.80 d.d (1H,
Harom, J = 8.4, 2.0 Hz), 6.88 d (1H, Harom, J = 2.0 Hz),
ppm: 2.31 s (3H, Me), 3.55 (3H, OMe), 6.19 d (2H,
7
7
2
.10 d (2H, Harom, J = 7.9 Hz), 7.18 d (2H, Harom, J =
HC=, J = 10.0 Hz), 6.48 s (1H, HC=), 6.80 d.d (2H,
+
.9 Hz). Mass spectrum, m/z (I , %): 312 (100) [M] ,
HC=, J = 10.0, 7.0 Hz), 6.89 d (2H, Harom, J = 8.1 Hz),
rel
+
13
81 (28) [M – OMe] , 265 (5), 254 (7), 165 (22), 119
7.08 d (2H, Harom, J = 8.1 Hz). C NMR spectrum, δ ,
C
(
14). Found, %: C 72.90; H 6.40. C H O . Calcu-
ppm: 21.24 q (J = 126.8 Hz), 51.54 q (J = 147.1 Hz),
1
9
20
4
1
lated, %: C 73.06; H 6.45. M 312.36.
89.16 d ( J = 176.3 Hz), 120.05 d.d (J = 164.0,
CF
3
JCF = 11.0 Hz), 128.02 d.d (J = 158.6, 6.5 Hz),
Methyl (E)-3-(5-fluoro-2-methoxyphenyl)-3-(4-
1
1
28.53 d.q (J = 158.6, 5.0 Hz), 130.48 d.d.d (J =
tolyl)propenoate (E-Xk ) was obtained (together
with compounds Z-Xk and E-Xk ) from 60 mg
(
of 1-fluoro-4-methoxybenzene in 1.2 ml of HSO F at
–
mp 79–82°C. H NMR spectrum, δ, ppm: 2.35 s (3H,
Me), 3.62 s (3H, OMe), 3.64 s (3H, OMe), 6.25 s (1H,
HC=), 6.79–6.84 m (2H, Harom), 6.97 t.d (1H, Harom, J =
1
3
3
68.3, 3.4, J = 8.2 Hz), 130.52 d ( J = 2.7 Hz),
CF
CF
1
2
1
38.42 s (J = 6.5 Hz), 142.72 d.d.d (J = 167.8, 5.1,
0.34 mmol) of compound II and 222 mg (1.76 mmol)
2
2
JCF = 22.4 Hz), 153.05 d.q [J = 4.0, J = 20.8 Hz),
CF
3
4
1
65.21 m (J = 3 Hz), 184.01 d ( J = 5.5 Hz).
75°C (reaction time 40 min). Yield 18 mg (18%),
CF
1
9
1
F NMR spectrum: δ –145.73 ppm. Mass spectrum,
F
+
+
m/z (I , %): 286 (6) [M] , 268 (3) [M – H O] , 227
rel
2
(
1
10), 207 (10), 199 (12), 183 (15), 176 (15), 175 (100),
19 (23), 116 (31), 115 (45), 91 (29), 59 (22), 53 (10).
8
.4, 3.0 Hz), 7.09 d (2H, Harom, J = 8.2 Hz), 7.12 d (2H,
+
1
9
Found: m/z 286.1041 [M] . C H FO . Calculated:
Harom, J = 8.2 Hz). F NMR spectrum: δ –120.45 ppm,
m. Mass spectrum, m/z (I , %): 300 (49) [M] , 269
[
17 15
3
F
+
M 286.1005.
rel
+
M – OMe] , 227 (34), 226 (30), 199 (21), 196 (13),
6-Fluoro-4-(4-tolyl)-2H-chromen-2-one (Xl ) was
1
1
83 (16), 119 (10), 105 (16). Found, %: C 71.88;
obtained (together with compound E-Xk ) from 50 mg
2
N 5.60. C H FO . Calculated, %: C 71.99; H 5.71.
(0.29 mmol) of compound II and 36 mg (0.32 mmol)
18
17
3
M 300.32.
of 4-fluorophenol in 1.0 ml of HSO F at –75°C (reac-
3
tion time 60 min). Yield 7 mg (9%), mp 181–183°C.
Methyl (Z)-3-(5-fluoro-2-methoxyphenyl)-3-(4-
–
1
IR spectrum, ν, cm : 700, 740, 1065, 1120, 1440,
tolyl)propenoate (Z-Xk ) was obtained (together with
1
1
1
680, 1695, 1730. H NMR spectrum, δ, ppm: 2.45 s
E-Xk and E-Xk ) from 60 mg (0.34 mmol) of com-
1
2
(
3H, Me), 6.40 s (1H, HC=), 7.21 d.d (1H, Harom, J =
pound II and 222 mg (1.76 mmol) of 1-fluoro-4-meth-
9
7
.0, 2.9 Hz), 7.25 t.d (1H, Harom, J = 8.3, 2.9 Hz),
oxybenzene in 1.2 ml of HSO F at –75°C (reaction
3
1
9
.37 d.d (1H, Harom, J = 9.0, 5.6 Hz). F NMR
time 40 min). Yield 10 mg (10%), mp 86–89°C.
H NMR spectrum, δ, ppm: 2.34 s (3H, Me), 3.60 s
3H, OMe), 3.66 s (3H, OMe), 6.45 s (1H, HC=),
.77 d.d (1H, Harom, J = 8.5, 3.2 Hz), 6.87 d.d (1H,
Harom, J = 9.1, 4.3 Hz), 7.03 t.d (1H, Harom, J = 8.4,
.2 Hz), 7.11 d (2H, Harom, J = 8.2 Hz), 7.20 d (2H,
+
1
spectrum: δ –113.80 ppm. Found: m/z 254.0751 [M] .
F
C H FO . Calculated: M 254.0743.
(
6
16 11
2
Methyl 3,3-diphenylpropenoate (XIa) was obtain-
ed from 50 mg (0.31 mmol) of compound III and
3
87 mg (1.12 mmol) of benzene in 1.0 ml of HSO F at
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

REACTIONS OF VINYL TYPE CARBOCATIONS
1325
–
30°C (reaction time 30 min). Yield 60 mg (82%), oily
(2,4,5-trimethylphenyl)propenoate (Z-XIf ) were
obtained from 50 mg (0.31 mmol) of compound III
2
1
substance. H NMR spectrum, δ, ppm: 3.62 s (3H,
OMe), 6.39 s (1H, HC=), 7.20–7.45 m (10H, Harom).
and 61 mg (0.51 mmol) of 1,2,4-trimethylbenzene in
+
Found: m/z 238.1007 [M] . C H O . Calculated:
1.0 ml of HSO F at –30°C (reaction time 30 min). Oily
1
6
14
2
3
M 238.0994.
isomer mixture: Z-XIf
1
, 19 mg (22%); Z-XIf
2
, 19 mg
1
(
22%). H NMR spectrum (isomer mixture), δ, ppm:
Methyl (Z)-3-(4-tert-butylphenyl)-3-phenylprop-
enoate (Z-XIb) was obtained from 50 mg (0.31 mmol)
of compound III and 87 mg (0.65 mmol) of tert-butyl-
1
2
3
.96 s (3H, Me), 2.02 s (3H, Me), 2.22 s (3H, Me),
.26 s (3H, Me), 2.27 s (3H, Me), 2.28 s (3H, Me),
.60 s (3H, OMe), 3.61 s (3H, OMe), 6.49 s (1H,
benzene in 1.0 ml of HSO F at –30°C (reaction time
3
1
HC=), 6.51 s (1H, HC=), 6.71 s (1H, Harom), 6.80 s
1H, Harom), 6.98 s (1H, Harom), 7.01 s (1H, Harom),
.28–7.36 m (10H, Harom). Found (isomer mixture):
3
0 min). Yield 73 mg (80%), oily substance. H NMR
(
spectrum, δ, ppm: 1.36 s (9H, t-Bu), 3.63 s (3H, OMe),
.39 s (1H, HC=), 7.12–7.45 m (9H, Harom). Found:
7
6
+
+
m/z 280.1471 [M] . C H O . Calculated: M 280.1463.
1
9
20
2
m/z 294.1632 [M] . C H O . Calculated: M 294.1620.
2
0
22
2
Methyl (E)-3-(4-amino-2,3,5,6-tetramethylphen-
yl)-3-phenylpropenoate (E-XIg) was obtained from
Methyl (Z)-3-(2,4-dimethylphenyl)-3-phenyl-
propenoate (Z-XIc) was obtained from 50 mg
5
(
0 mg (0.31 mmol) of compound III and 46 mg
0.31 mmol) of 2,3,5,6-tetramethylaniline in 1.0 ml of
HSO F at –30°C (reaction time 30 min). Yield 14 mg
(
0.31 mmol) of compound III and 87 mg (0.82 mmol)
of 1,3-dimethylbenzene in 1.0 ml of HSO F at –30°C
3
(
reaction time 30 min). Yield 63 mg (76%), oily sub-
3
1
1
(
15%), mp 187–189°C. H NMR spectrum, δ, ppm:
stance. H NMR spectrum, δ, ppm: 2.03 s (3H, Me),
2
5
.09 s (6H, Me), 2.14 s (6H, Me), 3.66 s (3H, OMe),
2
6
.36 s (3H, Me), 3.61 s (3H, OMe), 6.51 s (1H, HC=),
.90–7.40 m (8H, Harom). Found: m/z 266.1281 [M] .
+
.87 s (1H, HC=), 7.24–7.28 m (5H, Harom). Found:
+
m/z 309.1805 [M] . C H NO . Calculated: M 309.1729.
C H O . Calculated: M 266.1307.
20 23
2
18
18
2
Methyl (Z)-3-(2,3-dimethylphenyl)-3-phenyl-
Methyl (E)-3-(5-fluoro-2-methoxyphenyl)-3-
phenylpropenoate (E-XIh) was obtained (together
with Z-XIh) from 50 mg (0.31 mmol) of compound III
and 111 mg (0.88 mmol) of 1-fluoro-4-methoxy-
propenoate (Z-XId ) and methyl (E,Z)-3-(3,4-di-
1
methylphenyl)-3-phenylpropenoate (E,Z-XId ) were
2
obtained from 50 mg (0.31 mmol) of compound III
and 87 mg (0.82 mmol) of 1,2-dimethylbenzene in
benzene in 1.0 ml of HSO F at –50°C (reaction time
3
1
1
.0 ml of HSO F at –30°C (reaction time 30 min). Oily
60 min). Yield 12 mg (13%), mp 79–82°C. H NMR
spectrum, δ, ppm: 3.61 s (3H, OMe), 3.62 s (3H,
OMe), 6.30 s (1H, HC=), 6.79–6.84 m (2H, Harom),
6.98 t.d (1H, Harom, J = 8.4, 3.1 Hz), 7.19–7.22 m (2H,
3
isomer mixture: Z-XId , 34 mg (41%); E-XId , 14 mg
1
2
1
(
(
17%); Z-XId , 14 mg (17%). H NMR spectrum
2
isomer mixture), δ, ppm: 2.01 s (3H, Me), 2.24 s (3H,
Me), 2.26 s (3H, Me), 2.27 (3H, Me), 2.31 s (3H, Me),
Harom), 7.29–7.33 m (3H, H ). Mass spectrum, m/z
arom
+
+
2
3
.32 s (3H, Me), 3.60 s (3H, OMe), 3.60 s (3H, OMe),
.64 s (3H, OMe), 6.32 s (1H, HC=), 6.36 s (1H,
(I , %): 286 (30) [M] , 255 (100) [M – OMe] , 239
rel
(10), 212 (48), 196 (13), 183 (87), 165 (18), 157 (17),
149 (13), 133 (10), 115 (10), 107 (20), 105 (13), 91
(43), 77 (28), 63 (23), 59 (27), 51 (33). Found, %:
C 71.50; H 5.37. C H FO . Calculated, %: C 71.32;
HC=), 6.54 s (1H, HC=), 6.75–7.40 m (24H, Harom).
+
Found (isomer mixture): m/z 266.1281 [M] . C H O .
1
8
18
2
Calculated: M 266.1307.
1
7
15
3
H 5.28. M 286.30.
Methyl (Z)-3-(2,5-dimethylphenyl)-3-phenyl-
propenoate (Z-XIe) was obtained from 50 mg
Methyl (Z)-3-(5-fluoro-2-methoxyphenyl)-3-
phenylpropenoate (Z-XIh) was obtained (together
with E-XIh) from 50 mg (0.31 mmol) of compound
III and 111 mg (0.88 mmol) of 1-fluoro-4-methoxy-
(
0.31 mmol) of compound III and 87 mg (0.82 mmol)
of 1,4-dimethylbenzene in 1.0 ml of HSO F at –30°C
3
(
reaction time 30 min). Yield 78 mg (95%), oily sub-
1
stance. H NMR spectrum, δ, ppm: 2.06 s (3H, Me),
benzene in 1.0 ml of HSO F at –50°C (reaction time
3
1
2
6
.33 s (3H, Me), 3.61 s (3H, OMe), 6.53 s (1H, HC=),
6
0 min). Yield 13 mg (15%), mp 86–89°C. H NMR
.87 d (1H, Harom, J = 1.5 Hz), 7.10 d.d (1H, Harom
,
spectrum, δ, ppm: 3.61 s (3H, OMe), 3.66 s (3H,
OMe), 6.46 s (1H, HC=), 6.79 d.d (1H, Harom, J = 8.4,
3.1 Hz), 6.88 d.d (1H, Harom
J = 7.7, 1.5 Hz), 7.14 d (1H, Harom, J = 7.7 Hz), 7.30–
+
7
.38 m (5H, Harom). Found: m/z 266.1336 [M] .
, J = 9.0, 4.4 Hz), 7.04 t.d
C H O . Calculated: M 266.1307.
18
18
2
(1H, Harom, J = 8.5, 3.1 Hz), 7.29–7.35 m (5H, Harom).
+
Methyl (Z)-3-phenyl-3-(2,3,5-trimethylphenyl)-
propenoate (Z-XIf ) and methyl (Z)-3-phenyl-3-
Mass spectrum, m/z (Irel, %): 286 (13) [M] , 255 (63)
+
[M – OMe] , 231 (10), 212 (45), 199 (13), 196 (14),
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

1
1
326
SAVECHENKOV et al.
83 (100), 170 (16), 165 (22), 157 (22), 153 (34), 107
Ethyl (E)-3-(4-acetyl-2,3,5,6-tetramethylphenyl)-
3-(4-iodophenyl)propenoate (E-XIIIa) was obtained
from 60 mg (0.20 mmol) of compound Va and 52 mg
(0.30 mmol) of 2,3,5,6-tetramethylacetophenone in
(
20), 105 (23), 91 (28), 77 (40), 63 (20), 59 (22).
Found, %: C 71.45; H 5.41. C H FO . Calculated, %:
C 71.32l; H 5.28. M 286.30.
1
7
15
3
1
.2 ml of HSO F at –50°C (reaction time 60 min).
Methyl (E)-3-(4-fluorophenyl)-3-(4-fluorosulfon-
yl-2,3,5,6-tetramethylphenyl)propenoate (E-XIIa)
was obtained from 30 mg (0.17 mmol) of compound
IV and 56 mg (0.26 mmol) of 2,3,5,6-tetramethylben-
3
1
Yield 12 mg (12%), oily substance. H NMR spec-
trum, δ, ppm: 1.24 t (3H, Me, J = 7.1 Hz), 2.10 s (12H,
Me), 2.47 s (3H, Me), 4.16 q (2H, OCH , J = 7.1 Hz),
5
2
.84 s (1H, HC=) 6.99 d (2H, Harom, J = 8.3 Hz), 7.60 d
zenesulfonyl fluoride in 0.5 ml of HSO F at –30°C
3
(
2H, Harom, J = 8.3 Hz). Mass spectrum, m/z (I , %):
(
reaction time 60 min). Yield 46 mg (68%), mp 101–
rel
+
+
1
4
76 (67) [M] , 461 (97) [M – Me] , 431 (11) [M –
1
2
5
7
03°C. H NMR spectrum, δ, ppm: 2.21 s (6H, Me),
.58 d (6H, Me, JHF = 2.2 Hz), 3.72 s (3H, OMe),
.81 s (1H, HC=), 7.00 t (2H, Harom1, J = 8.7 Hz),
+
OEt] , 429 (14), 414 (14), 402 (17), 359 (12), 233 (10),
17 (19), 203 (22), 202 (22), 175 (15.5), 43 (100).
Found, %: C 57.70; H 5.30. C H IO . Calculated, %:
2
9
.24 d.d (2H, Harom, J = 8.4, 5.4 Hz). F NMR spec-
23 25
3
C 57.99; H 5.29. M 476.35.
trum: δ 72.89 ppm, m (1F, FO S, J = 2.5 Hz). Mass
F
2
+
spectrum, m/z (I , %): 394 (59) [M] , 379 (22) [M –
Ethyl (E)-3-(4-acetyl-2,3,5,6-tetramethylphenyl)-
3-(4-methoxy-3-nitrophenyl)propenoate (E-XIIIb)
and ethyl (Z)-3-(4-acetyl-2,3,5,6-tetramethyl-
phenyl)-3-(4-methoxy-3-nitrophenyl)propenoate
Z-(XIIIb) were obtained from 30 mg (0.12 mmol) of
compound Vb and 50 mg (0.28 mmol) of 2,3,5,6-
rel
+
+
Me] , 363 (22) [M – OMe] , 334 (100), 320 (33), 310
24), 252 (37), 251 (63), 237 (35), 221 (22), 119 (17),
15 (15), 59 (30). Found, %: C 60.68; H 5.13.
C H F O S. Calculated, %: C 60.90; H 5.11. M 394.43.
(
1
20
20
2
4
Methyl (E)-3-(3,4-dichlorophenyl)-3-(4-fluoro-
phenyl)propenoate (E-XIIb) and methyl (Z)-3-(3,4-
dichlorophenyl)-3-(4-fluorophenyl)propenoate
tetramethylacetophenone in 0.6 ml of HSO F at –20°C
3
(
reaction time 60 min). Oily isomer mixture: E-XIIIb,
(
Z-XIIb) were obtained from 30 mg (0.17 mmol) of
15 mg (29%); Z-XIIIb, 8 mg (15%). IR spectrum, ν,
cm : 1015, 1180, 1280, 1350, 1525, 1615, 1690
(C=O), 1715 (C=O). H NMR spectrum, δ, ppm:
E-XIIIb: 1.24 t (3H, Me, J = 7.1 Hz), 2.09 s (6H, Me),
–
1
compound IV and 50 mg (0.34 mmol) of 1,2-dichloro-
1
benzene in 0.5 ml of HSO F at –30°C (reaction time
3
6
0 min). Oily isomer mixture: E-XIIb, 10 mg (19%);
1
Z-XIIb, 9 mg (17%). H NMR spectrum (isomer mix-
ture), δ, ppm: 3.63 s (3H, OMe), 3.64 s (3H, OMe),
2.10 s (6H, Me), 2.48 s (3H, Me), 4.18 q (2H, OCH ,
2
J = 7.1 Hz), 5.85 s (1H, HC=) 6.98 d (1H, Harom, J =
8.8 Hz), 7.48 d.d (1H, Harom, J = 8.6, 2.0 Hz), 7.79 d
(1H, Harom, J = 2.0 Hz); Z-XIIIb: 1.07 t (3H, J =
7.1 Hz), 1.95 s (6H, Me), 2.12 s (6H, Me), 2.50 s (3H,
Me), 3.95 s (3H, OMe), 4.01 q (2H, CH
6.61 s (1H, HC=), 6.98 d (1H, Harom, J = 8.9 Hz),
7.31 d.d (1H, Harom, J = 8.5, 2.0 Hz), 7.91 d (1H, Harom
J = 2.0 Hz). Found, %: C 67.50; H 6.35. C H NO .
6.32 s (1H, HC=), 6.33 s (1H, HC=), 7.01–7.54 m
(
(
[
(
14H, Harom). Mass spectrum (isomer mixture), m/z
+
+
I , %): 328 (5) [M + 4] , 326 (32) [M + 2] , 324 (48)
rel
+
+
M] , 297 (7), 295 (45), 293 (67) [M – OMe] , 230
2
, J = 7.1 Hz),
57), 194 (50), 167 (35), 149 (100), 123 (38). Found,
%
: C 58.67; H 3.26. C H Cl FO . Calculated, %:
,
1
6
11
2
2
C 59.10; H 3.41. M 325.16.
Methyl (Z)-3-(2,5-dimethoxyphenyl)-3-(4-fluoro-
phenyl)propenoate (Z-XIIc) was obtained from
24 27
6
Calculated, %: C 67.75; H 6.40. M 425.47.
(E)-3-Phenyl-3-(2,3,5,6-tetramethylphenyl)-
propenoic acid (E-XIVa) and (Z)-3-phenyl-3-
(2,3,5,6-tetramethylphenyl)propenoic acid (Z-XIVa)
were obtained from 30 mg (0.21 mmol) of compound
VI and 110 mg (0.82 mmol) of 1,2,4,5-tetramethylben-
3
0 mg (0.17 mmol) of compound IV and 36 mg
0.26 mmol) of 1,4-dimethoxybenzene in 0.6 ml of
HSO F at –30°C (reaction time 30 min). Yield 25 mg
(
3
1
(
47%), oily substance. H NMR spectrum, δ, ppm:
.60 s (3H, OMe), 3.63 s (3H, OMe), 3.74 s (3H,
OMe), 6.39 s (1H, HC=), 6.60 d (1H, Harom, J =
3
zene in 0.5 ml of HSO F at –30°C (reaction time
30 min). E/Z Ratio 1:1. Yield of E-XIVa 11 mg
3
1
.5 Hz), 6.86–6.90 m (2H, Harom), 6.98 t (2H, Harom, J =
(19%), mp 210–212°C (isomer mixture). Yield of
Z-XIVa 29 mg (49%), mp 205–208°C. H NMR spec-
1
8.6 Hz), 7.30 d.d (2H, Harom, J = 8.7, 5.4 Hz). Mass
+
spectrum, m/z (I , %): 316 (75) [M] , 285 (100) [M –
OMe] , 270 (10), 242 (15), 171 (10), 170 (10), 149
trum, δ, ppm: E-XIVa: 2.09 s (6H, Me), 2.21 s (6H,
Me), 5.86 s (1H, HC=), 6.95 s (1H, Harom), 7.26–
7.36 m (5H, Harom), 10.0 br.s (1H, COOH); Z-XIVa:
1.95 s (6H, Me), 2.23 s (6H, Me), 6.64 s (1H, HC=),
6.99 s (1H, Harom), 7.26–7.36 m (5H, Harom), 9.0 br.s
rel
+
(
10), 124 (27), 123 (16), 109 (32), 81 (11). Found, %:
C 68.26; H 5.51. C H FO . Calculated, %: C 68.35;
H 5.42. M 316.32.
1
8
17
4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

REACTIONS OF VINYL TYPE CARBOCATIONS
1327
(
(
1H, COOH). Mass spectrum (isomer mixture), m/z
I , %): 280 (100) [M] , 265 (47) [M – Me] , 247 (10),
rel
(48). Found, %: C 78.27; H 5.87. C H ClNO. Cal-
culated, %: C 78.34; H 5.84. M 413.94.
27
24
+
+
2
(
7
34 (27), 220 (44), 219 (51), 206 (46), 189 (12), 143
10), 133 (15), 115 (20), 96 (14), 95 (14), 91 (17),
7 (12), 44 (15). Found, %: isomer mixture: C 81.35;
H 7.23; Z-XIVa: C 81.31; H 7.26. C H O . Calculat-
Methyl (Z)-4-[2-(4-Acetyl-2,3,5,6-tetramethyl-
phenyl)-2-phenylethenyl]benzoate (Z-XVc) was
obtained from 50 mg (0.21 mmol) of compound VIIc
and 74 mg (0.42 mmol) of 2,3,5,6-tetramethylaceto-
1
9
20
2
ed, %: C 81.40; H 7.19. M 280.36.
E)-3-(4-Acetyl-2,3,5,6-tetramethylphenyl)-3-
phenylpropenoic acid (E-XIVb) was obtained from
0 mg (0.21 mmol) of compound VI and 50 mg
0.28 mmol) of 2,3,5,6-tetramethylacetophenone in
.6 ml of HSO F at –30°C (reaction time 30 min).
phenone in 1.0 ml of HSO F at –75°C (reaction time
3
1
(
15 min). Yield 10 mg (12%), mp 170–172°C. H NMR
spectrum, δ, ppm: 2.13 s (6H, Me), 2.19 s (6H, Me),
2.49 s (3H, Me), 3.90 s (3H, MeO), 6.47 s (1H, HC=),
7.07–7.34 m (7H, Harom), 7.88 d (2H, Harom, J =
8.2 Hz). Found, %: C 81.39; H 6.80. C H O . Cal-
3
(
0
3
28 28
3
1
Yield 18 mg (27%), mp 240–243°C. H NMR spec-
culated, %: C 81.52; H 6.84. M 412.20.
trum, δ, ppm: 2.10 s (6H, Me), 2.11 s (6H, Me), 5.86 s
Diethyl (E)-[2-(4-fluorosulfonyl-2,3,5,6-tetra-
methylphenyl)-2-phenylethenyl]phosphonate
E-XVIa) and diethyl (Z)-[2-(4-fluorosulfonyl-
,3,5,6-tetramethylphenyl)-2-phenylethenyl]phos-
phonate (Z-XVIa) were obtained from 50 mg
(
1H, HC=), 6.99 s (1H, Harom), 7.27–7.32 m (5H,
Harom), 10.2 br.s (1H, COOH). Mass spectrum, m/z
(
2
+
+
(
I , %): 322 (38) [M] , 307 (100) [M – Me] , 261 (5),
rel
2
34 (6), 233 (6), 220 (9), 219 (10), 203 (9), 115 (6), 43
(
19). Found, %: C 78.10; H 7.00. C H O . Calculat-
2
1
22
3
(
(
0.21 mmol) of compound VIII and 50 mg
0.23 mmol) of 2,3,5,6-tetramethylbenzenesulfonyl
ed, %: C 78.23; H 6.88. M 322.40.
(
E)-3-(4-Fluorosulfonyl-2,3,5,6-tetramethylphen-
fluoride in 1.0 ml of HSO F at –30°C (reaction time
60 min). Yield of E-XVIa 6 mg (6%). H NMR spec-
trum (from the spectrum of isomer mixture), δ, ppm:
1.14 t (6H, Me, J = 7.0 Hz), 2.22 s (6H, Me), 2.57 d
3
1
yl)-3-phenylpropenonitrile (E-XVa) was obtained
from 20 mg (0.16 mmol) of compound VIIa and
2 mg (0.24 mmol) of 2,3,5,6-tetramethylbenzenesul-
fonyl fluoride in 0.5 ml of HSO F at –30°C (reaction
time 90 min). Yield 12 mg (22%), mp 180–183°C.
IR spectrum, ν, cm : 1060, 1380, 1410, 2220 (C≡N).
H NMR spectrum, δ, ppm: 2.15 s (6H, Me), 2.58 d
6H, Me, J = 2.2 Hz), 5.32 s (1H, HC=), 7.40–
.48 m (3H, Harom), 7.56 d (2H, Harom, J = 8.0 Hz).
Mass spectrum, m/z (I , %): 343 (75) [M] , 328 (44)
M – Me] , 259 (100), 244 (58), 233 (19), 230 (14),
20 (14), 217 (19), 203 (19), 202 (22), 115 (17), 108
14), 101 (18), 91 (15), 77 (17), 51 (11), 39 (14).
Found, %: C 66.41; H 5.26. C H FNO S. Calculated,
5
3
(6H, Me, JHF = 1.9 Hz), 4.18–4.25 m (4H, OCH ),
2
2
5.66 d (1H, HC=, J = 14.7 Hz), 7.23–7.40 m
HP
–
1
(5H, Harom). Found (for isomer mixture), %: C 58.76;
H 6.53. C H FO PS. Calculated, %: C 58.14; H 6.21.
1
22
28
5
5
(
7
HF
M 454.49. Yield of Z-XVIa 50 mg (52%), mp 150–
1
157°C. H NMR spectrum, δ, ppm: 1.14 t (6H, Me,
+
rel
J = 7.0 Hz), 2.14 s (6H, Me), 2.60 d (6H, Me, JHF =
+
[
2
(
1.9 Hz), 3.73–3.91 m (4H, OCH ), 6.53 d (1H, HC=,
2
2
JHP = 15.3 Hz), 7.23–7.27 m (2H, Harom), 7.31–7.40 m
(3H, Harom). Mass spectrum (isomer mixture), m/z
+
1
9
18
2
(I , %): 454 (23) [M] , 370 (10), 316 (100) [M –
rel
+
%
: C 66.45; H 5.28. M 343.42.
Z)-4-[2-(4-Acetyl-2,3,5,6-tetramethylphenyl)-2-
4-chlorophenyl)ethenyl]benzonitrile (Z-XVb) was
P(O)(OEt) ] , 301 (10), 233 (47), 217 (18), 203 (16),
2
1
39 (33), 138 (67), 111 (49), 81 (18). Found, %:
(
C 57.84; H 6.13. C H FO PS. Calculated, %: C 58.14;
(
22 28
5
H 6.21. M 454.49.
obtained from 30 mg (0.13 mmol) of compound VIIb
and 44 mg (0.25 mmol) of 2,3,5,6-tetramethylaceto-
Diethyl (E)-[2-(3,4-dimethoxyphenyl)-2-phenyl-
ethenyl]phosphonate (E-XVIb) and diethyl (Z)-[2-
(3,4-dimethoxyphenyl)-2-phenylethenyl]phos-
phonate (Z-XVIb) were obtained from 50 mg
(0.21 mmol) of compound VIII and 58 mg
(0.42 mmol) of 1,2-dimethoxybenzene in 1.0 ml of
phenone in 1.0 ml of HSO F at –75°C (reaction time
3
1
5 min). Yield 22 mg (40%), mp 201–205°C. IR spec-
–1
trum, ν, cm : 1350, 1415, 1485, 1600, 1690 (C=O),
2
1
235 (C≡N). H NMR spectrum, δ, ppm: 2.12 s (6H,
Me), 2.15 s (6H, Me), 2.49 s (3H, Me), 6.46 s (1H,
HC=), 6.99 d (2H, Harom, J = 8.4 Hz), 7.15 d (2H,
Harom, J = 8.4 Hz), 7.27 d (2H, Harom, J = 8.1 Hz), 7.52 d
HSO F at –30°C (reaction time 30 min). Yield of
3
1
E-XVIb 22 mg (28%). H NMR spectrum (from the
(
4
3
2H, Harom, J = 8.1 Hz). Mass spectrum, m/z (I , %):
spectrum of isomer mixture), δ, ppm: 1.11 t (6H, Me,
J = 7.1 Hz), 3.80 s (6H, OMe), 3.83–3.94 m (4H,
rel
+
15 (23) [M + 2], 413 (60) [M] , 400 (38), 399 (38),
+
2
98 (100) [M – Me] , 355 (10), 297 (10), 153 (10), 43
OCH ), 6.11 d (1H, HC=, J = 15.3 Hz), 6.75–
2
HP
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

1
328
SAVECHENKOV et al.
6
.77 m (2H, Harom), 6.84 s (1H, Harom), 7.33–7.38 m
4. Vasilyev, A.V., Walspurger, S., Pale, P., and Som-
mer, J., Tetrahedron Lett., 2004, vol. 45, p. 3379.
(
5H, Harom). Found (mixture of isomers), %: C 63.41;
H 6.50. C H O P. Calculated, %: C 63.82; H 6.69.
M 376.38. Yield of Z-XVIb 22 mg (28%). H NMR
spectrum (from the spectrum of isomer mixture), δ,
5. Vasilyev, A.V., Walspurger, S., Haouas, M., Som-
mer, J., Pale, P., and Rudenko, A.P., Org. Biomol.
Chem., 2004, vol. 2, p. 3483; Vasil’ev, A.V., Wals-
purger, S., Pale, P., Sommer, J., Haouas, M., and
Rudenko, A.P., Russ. J. Org. Chem., 2004, vol. 40,
p. 1769.
20
25
5
1
ppm: 1.14 t (6H, Me, J = 7.1 Hz), 3.80 s (6H, OMe),
2
3
.83–3.94 m (4H, OCH ), 6.04 d (1H, HC=, J
=
2
HP
15.5 Hz), 6.85 d (1H, Harom, J = 8.3 Hz), 6.91 d.d (1H,
6
7
8
. Savechenkov, P.Yu., Rudenko, A.P., and Vasil’-
ev, A.V., Russ. J. Org. Chem., 2004, vol. 40, p. 1065.
Harom, J = 8.3, 2.0 Hz), 7.03 d (1H, Harom, J = 2.0 Hz),
.27–7.32 m (5H, Harom).
7
. Rudenko, A.P., Savechenkov, P.Yu., and Vasil’-
ev, A.V., Russ. J. Org. Chem., 2004, vol. 40, p. 1377.
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