Alkenylation of arylamines and N-arylacetamides with acetylene compounds in superacids

Article abstract of DOI:10.1134/S1070428008070063

Vinyl type cations generated in superacid HSO₃F by the protonation of the triple bond of acetylene compounds efficiently react with arylammonium ions and N-arylacetamides yielding alkenylation products of the aromatic rings in the given amino d

Full text of DOI:10.1134/S1070428008070063

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 965−979. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.O. Shchukin, A.V. Vasil’ev, S.A. Aristov, G.K. Fukin, A.P. Rudenko, 2008, published in Zhurnal Organicheskoi Khimii, 2008,
Vol. 44, No. 7, pp. 977−990.
Alkenylation of Arylamines and N-Arylacetamides
with Acetylene Compounds in Superacids
A. O. Shchukina, A. V. Vasil’eva, S. A. Aristova, G. K. Fukinb, and A. P. Rudenkoa
aSt. Petersburg State Academy of Forestry Engineering, St. Petersburg, 194021 Russia
e-mail: aleksvasil@mail.ru
bRazuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,Russia
Received December 7, 2007
Abstract—Vinyl type cations generated in superacid HSO3F by the protonation of the triple bond of acetylene
compounds efficiently react with arylammonium ions and N-arylacetamides yielding alkenylation products of the
aromatic rings in the given amino derivatives. The regio- and stereoselectivity of electrophilic aromatic substitution
was investigated involving vinyl type cations and arylammonium ions or N-arylacetamides in HSO3F.
DOI: 10.1134/S1070428008070063
Here we report on reactions of acetylene compounds
Ia–Id (Scheme 1) with arylamines and N-arylacetamides
in superacid HSO3F at low temperature –75...–30°C.
Problems are considered of regio- and stereoselectivity
of electrophilic aromatic substitution involving vinyl type
cations and arylammonium ions or N-arylacetamides.
Arylamines (aniline derivatives) are widely employed
in the synthesis of organic compounds [1], they are
practically important for production of dyes,
pharmaceuticals, and other valuable products [2]. The
development of procedures for aniline derivatives
preparation is an urgent target.
Aniline derivatives exist in superacids as arylam-
monium ions B [9] (Scheme 1). Reactions of cations A
formed of compounds I with ions B occur through
a unique for electrophilic aromatic substitution
In a series of studies [3–8] we demonstrated a new
method for aromatic compounds alkenylation with vinyl
type cations generated by the protonation of an acetylene
bond of alkynes in superacids.
Scheme 1.
NH2
Ar C C Y
I
R
H+ (super-
acid)
H+ (siper-
Ar
Ar
acid)
Ar
Y
H
NH3
C CHY
NH3
C CHY
NaHCO3 H2O
C C
H
_
+
Ar C CHY
R
R
R
R
NH3
NH2
E-, Z- (syn-, anti-) IIa_IId
B
A
C
O
Ar C C Y
= R
C C C
X = OMe, R = H (a), Me (b), MeO (c); X = R = Me (d).
X
Ia_Id
965

SHCHUKIN et al.
966
The precise E-/Z-configuration of alkenylation
products of arylamines and their derivatives E-/Z-(IIa–
IIz and IIIa–IIIm) presented on Schemes 2–14 was
established from the data of XRD analysis of Ε-IIIj
substance (see the figure) and 1H NMR spectra. Like in
[7, 8] the stereochemical reference for establishing the
E-/Z-configuration of compounds IIa–IIz and IIIa–IIIm
was the signal of the vinyl proton at the double bond
=C=CH–. This proton signal in the majority of E-isomers
is observed at δ 5.78–6.42 ppm, and in Z-isomers, in the
region δ 6.45–6.88 ppm.
Electron-acceptor group NH+3 deactivates the π-system
of the aromatic ring in ion B (Scheme 1) with respect to
electrophilic substitution. For instance, the protonated
forms of aniline and N,N-dimethylaniline in HSO3F at
–30°C do not react with vinyl type cations formed from
compounds Ia and Id and do not give products of II
structure.
The presence of one methyl group in the aromatic
ring of 2-methylaniline made it possible to involve the
corresponding arylammonium ion into the substitution
reaction with the vinyl cataion generated from compound
Ib (Scheme 2). As a result of a concerted orientation of
Structure of (E)—methyl 3-(3-acetylamino-6-tetr-butyl-2,4-
dimethylphenyl)-3-(4-methylphenyl)propenoate E-IIIj
according to XRD data.
intermediate formation of a double-charged arenonium
ion C. The deprotonation of ion C and the subsequent
workup of the reaction mixture (treating with concn.
HCl at –70°C, then neutralization with a saturated
aqueous NaHCO3 solution) resulted in the final products
II of alkenylation of the aromatic rings in the initial
arylamines (Scheme 1).
Scheme 2.
Me
(1) HSO3F (_75oC, 1 h)
NH3
_
Me
CO2Me
H
(2) NaHCO3 H2O
We formerly established [7, 8, 10, 11] that the proton
and the aryl moiety (or the superacid anion) added to the
triple bond of acetylene substrate in superacids at low
temperature (–75...–50°C) by a syn-type. At higher
temperature (–30...20°C) in the superacids the syn-
products transformed into anti-isomers.
Ib+
C C
H2N
Me
syn-E-IIa (17%)
Scheme 3.
R
O
H
NH3
Me
C OMe
(1) HSO3F (_30oC, 0.5_1 h)
(2) NaHCO3 H2O
Me
C C
+
Me
C C
_
C X
H
Ia, Id
+
O
NH2
anti-Z-IIb (2%), IIc
NH2
(10%)
syn-E-IIb (12%)
X = OMe, R = H (b); X = R = Me (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
967
electron-donor CH3 group and electron-acceptor NH3+
group the substitution occurred in the para-position to
the methyl group with the stereoselective formation of a
product of syn-addition Ε-IIa.
In reaction of acetylene derivatives Ia and Id with
4-methylphenylammonium ion in HSO3F at –30°C
formed a mixture of substances E-/Z-IIb or compound
Z-IIc respectively that were products of substitution in
the ortho-position to the methyl group of the initial
4-methylaniline (Scheme 3). A similar regioselectivity
(Schemes 2 and 3) was previously observed in reaction
of trifluoromethylation and bromination of 2- and
4-methylanilines in superacids [12, 13].
This character of spectra excluded the formation of
alternative substitution products in positions 3 or 6 of
the aromatic ring of the initial amine, for in this case the
aromatic protons would appear in the 1H NMR spectra
of the alkenylation product as doublets.
1
Similarly the analysis of H NMR spectra of the
individually isolated products E-(IIg and IIh) of alken-
ylation of 3,4-dimethylphenylammonium ion (Scheme 5)
unambiguously indicated the formation of two isomers
originating from the substitution at the positions 6 and 5
of the ring of arylammonium ion respectively. In the
spectrum of compound E-IIg two singlets are observed
at δ 6.43 and 6.83 ppm belonging to aromatic protons in
the positions 3 and 6 of the ring substituted with amino
group. In the spectrum of isomer E-IIh two characteristic
doublets appeared at δ 6.39 and 6.51 ppm with a coupling
constant of 2.3 Hz corresponding to two aromatic protons
in the meta-position to each other (see Experimental).
The alkenylation of 2,4-dimethylphenylammonium
ion with acetylene derivatives Ia, Ib, and Id occurred
regioselectively exclusively in the position 5 of the ring
of the arylammonium ion giving products of syn- and
1
anti-addition E-/Z-(IId–IIf) (Scheme 4). The H NMR
Vinyl type cations generated from acetylene substrates
Ia–Id in HSO3F at –75...–30°C are sufficiently reactive
for the electrophilic attack even on sterically hindered
arylammonium ions with methyl and bulky tert-butyl
spectra of compounds E-/Z-(IId–IIf) contain two narrow
singlets in the region δ 6.38–6.93 ppm corresponding to
aromatic protons in the positions 2 and 5 of the benzene
ring containing an amino group (see EXPERIMENTAL).
Scheme 4.
R
Me
Me
R
Me
Me
NH3
O
(1) HSO3F (_75. _30oC, 0.5_1 h)
..
...
(2) NaHCO3 H2O
C X
H
Me
_
C C
C C
+
Ia, Ib, Id
+
H
C X
O
Me
NH2
NH2
syn-E-IId (14%), IIe (24%) anti-Z-IIe (13%), IIf (56%)
X = OMe, R = H (d), Me (e); X = R = Me (f).
Scheme 5.
Me
Me
Me
NH3
Me
(1) HSO3F (_75oC, 0.75 h)
(2) NaHCO3 H2O
CO2Me
H
CO2Me
H
_
C C
C C
NH2
+
+
Ib
Me
Me
Me
Me
NH2
syn-E-IIg (34%)
syn-E-IIh (7%)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SHCHUKIN et al.
968
in HSO3F at –30°C for 1 h converted into anti-Z-isomer
IIv (Scheme 8).
substituents (Schemes 6–8). Therewith the preparative
yields of the alkenylation products E-/Z-(IIi–IIw) were
11–44% (see Experimental).
The electrophilic substitution involving 2-methoxy-
phenylammonium ion and vinyl cation generated from
acetylene ketone Id occurred at the position 5 of the ring
of arylammonium ion and yielded a mixture of com-
pounds E-/Z-IIy (Scheme 9). In a similar reaction with
acetylene ester Ib two compounds E-IIx and E-IIz were
obtained due to substitution of the positions 5 and 3 of
the aromatic ring of 2-methoxyphenylammonium ion
respectively (Scheme 9). The structure of compound E-
IIz was established from its 1H NMR spectrum contain-
ing a complex multiplet signal in the δ 6.64–6.71 ppm
characteristic of the spin system AΒC of three contiguous
aromatic protons in the ring with an amino group (see
EXPERIMENTAL).
Special attention required the formation of substances
E-(IIs and IIt) (Scheme 7) and E-(IIu and IIv), Z-IIw
(Scheme 8), products of substitution in ortho- and para-
+
position with respect to NH3 group despite its electron-
acceptor character. The chromatographic behavior of
compounds E-(IIs and IIt) also should be noted: Their
Rf values (TLC on silica gel) exceed the Rf value of the
initial 2,4,5-trimethylphenylamine. It is apparently due
to the spatial shielding of the ortho-amino group in
structures E-(IIs and IIt) and consequently to the
decrease in the sorption ability of compounds E-(IIs and
IIt).
The primary formation of products of syn-addition to
the acetylene bond of substrates Ia–Id was demonstrated
by an example of compound E-IIv that later after keeping
In contrast to phenylammonium ion (see above)
1-naphthylammonium ion easily undergoes alkenylation
Scheme 6.
R
Me
R’
O
NH3
R’
_
_
o
_
.
(1) HSO F ( 75... 30 C, 0.5 1.25 h)
.
3
H
C X
Me
Me
_
(2) NaHCO3 H2O
C C
C
C
R’
Ia, Ib, Id
Ia, Ib, Id +
+
+
Me
H
C
O
Me
Me
NH2
Me
NH2
Me
syn-E-IIi (20%), IIj (38%),
IIk (16%), IIl (34%),
IIm (2%)
anti-Z-IIk (44%), IIn (15%)
Scheme 7.
R
R
(1) HSO3F (_75..._30oC, 1_1.3 h)
O
NH3
CO2Me
C X
_
Me
(2) NaHCO3 H2O
_
Me
C C
Me
C C
Ia−Id +
Ia Id
+
+
H
NH2
H
Me
Me
Me
Me
NH2
Me
Me
syn-E-IIt (18%), IIu (19%)
syn-E-IIn (30%), o (11%), p (17%),
anti-Z-IIp (9%), IIs (16%)
X = OMe, R = H, R' = Me (i), t-Bu (l); X = OMe, R = Me, R' = Me (j), t-Bu (m); X = Me, R' = Me (k), t-Bu (n). X = OMe,
R = H (o), Me (p), MeO (q); X = R = Me (r); R = H (s), Me (t).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
969
Scheme 8.
R
Me
Me
(1) HSO3F (_75..._30oC,
O
NH3
0.5_1 h)
(1) HSO3F (_30oC, 1 h)
(2) NaHCO3 H2O
C X
H
Me
Me
Me
H
_
_
(2) NaHCO3 H2O
Me
C C
C C
Ia, Ib, Id
Ia, Ib, Id +
+
CO2Me
Me
Me
Me
Me
Me
H2N
H2N
Me
Me
syn-E-IIv (15%), w (25%),
anti-Z-IIx (31%)
anti-Z-IIw
X = OMe, R = H (u), Me (v); X = R = Me (w).
occurred predominantly at the carbonyl group oxygen.
Still the NHAc group behaves as ortho-, para-director
in the processes of electrophilic aromatic substitution
even in strong superacid systems like HF–SbF5, for
instance, in reactions of trifluoromethylation and
hydroxylation of N-arylacetamides [12, 16].
with acetylene ester Ia in HSO3F at –30°C within 1 h.
However this reaction possesses low regio- and stereo-
1
selectivity. In the H NMR spectrum of the mixture of
alkenylation products in the region characteristic of the
protons at the double bond =C=CH– at δ 6.17–6.76 ppm
8 singlets were registered corresponding to various regio
and stereo-(E-/Z-) isomeric products of the naphthalene
skeleton alkenylation.
N-Phenylacetamide unlike aniline proper (see above)
reacted with vinyl type cations generated from acetylene
derivatives Ia, Ib, and Id in HSO3F at –75...–30°C within
0.5–1 h giving substances E-/Z-(IIIa–IIIc), products of
substitution in the para-position of the phenyl ring of
the initial N-phenylacetamide (Scheme 10, see analogous
regioselectivity in [12]).
+
On the other hand the presence of two NH3 groups at
the benzene ring completely deactivated the π-system
for the electrophilic substitution. Thus the reaction of
1,3-diamine-2,4,6-trimethylbenzene with acetylene com-
pound Ib in HSO3F at –30°C in 0.5 h failed to provide
products of alkenylation of the corresponding aryl-
ammonium ion.
Mono- and dimethyl-substituted in the aromatic ring
N-arylacetamides gave rise to alkenylation products
E-/Z-(IIId–IIIf) in reactions with acetylene compounds
Ib and Id in HSO3F (Scheme 11). From N-4-methyl-
phenyl-acetamide formed the products of substitution in
the ortho-position to the methyl group E-IIId and Z-IIIe
N-Acetyl derivatives of arylamines (N-arylacet-
amides) readily enter into the alkenylation by acetylene
compounds in superacids. According to the published
data [14, 15] the protonation of amide group in superacids
Scheme 9.
Me
Me
Me
NH3
(1) HSO3F (_75..._30oC, 1 h)
(2) NaHCO3 H2O
O
OMe
H
_
C X
CO2Me
H
Ib, Id
+
C C
+
+
C C
C C
C Me
H
O
OMe
MeO
NH2
MeO
NH2
NH2
syn-E-IIz1 (17%)
syn-E-IIy (45%), IIz (4%) anti-Z-IIz (20%)
X = OMe (x), Me (y).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SHCHUKIN et al.
970
Z-(IIIh and IIIi) the signal from the proton attached to
the nitrogen in the NHAc group was not observed, in the
spectra of the other acetamides E-/Z-(IIIa–IIIm) the
signal of this proton appeared as a broadened singlet in
the region δ 6.6–7.6 ppm (see Experimental).
The reaction of N-2,4,5-trimethylphenylacetamide
with acetylene ester Ib in HSO3F at –75°C for 0.5 h
resulted in the formation of substitution products at each
(Scheme 11) as had been previously observed in the
trifluoromethylation of this amide in the system HF–SbF5
[12].
Analogously to arylammonium ions (Schemes 6–8)
the sterically hindered N-arylacetamide also reacts with
cations of vinyl type to give alkenylation products E-/Z-
(IIIg–IIIm) in 29–67% yield (see Experimental,
Schemes 12–14). In the 1H NMR spectra of compounds
Scheme 10.
Me
R
NHAc
O
H
C X
HSO3F
Ia, Ib, Id
Ia, Ib, Id +
C C
+
+
C C
_75..._30oC, 0.5_1 h
C Me
H
O
AcHN
AcHN
anti-Z-IIIc (3%)
syn-E-IIIa (4%), IIIb (18%), IIIc (3%)
X = OMe, R = H (a), Me (b); X = R = Me (c).
Scheme 11.
Me
Me
Me
R’
NHAc
R’
CO2Me
H
C C
C X
O
HSO3F
_75..._30oC, 0.5_1 h
Me
C C
Ib, Id +
Ib, Id
+
+
H
Me
R’
NHAc
NHAc
syn-E-IIId (29%), IIIf (13%) anti-Z-IIIe (17%), IIIf (13%)
R' = H (d); X = Me, R' = H (e); X = OMe, R' = Me (f).
Scheme 12.
Me
R
Me
Me
NHAc
H
CO2Me
Me
Me
HSO3F
_75..._30oC, 0.5_1.3 h
Ib_Id
Ib−Id +
R’
C C
C C
+
+
X
C
O
H
Me
R’
Me
Me
NHAc
NHAc
syn-E-IIIg (51%), IIIj (67%)
anti-Z-IIIh (52%), IIIi (29%)
R' = Me (g), t-Bu (j); X = R = OMe (h), Me (i).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
971
C2 atom of double bond did not occur (cf. with data in
[17]). O-Protonation in ion IV weakens the double bond
character of the fragment C2=C3 (resonance structure V
in Scheme 15) and facilitates the rotation around this
bond favoring the transformation of E-forms into their
Z-analogs at higher temperature (–30°C), as has been
shown by an example of isomerization of compounds E-
IIvtZ-IIv (Scheme 8).
position in the aromatic ring of the initial N-
arylacetamide, substances E-(IIIk and IIIl) (Scheme 13)
in a ratio ~1:1 in keeping with the ortho-, para-director
behavior of the NHAc group.
The study of protonation of compound E-IIp by 1H
NMR spectroscopy showed the formation of dication IV
in HSO3F at –80°C (Scheme 15). In the spectrum of ion
+
IV signals were observed from the NH3 group at δ 7.39
1
ppm [9] and of a proton which added to the carbonyl
oxygen (O-protonation) at δ 12.49 ppm [6, 11] (see
Experimental). In these conditions the protonation of the
In the same way according to H NMR spectrum
compound VI exists in HSO3F at –80°C as O-protonated
at the carbonyl group ion VII (see Experimental, Scheme
Scheme 13.
Me
Me
Me
NHAc
CO2Me
H
CO2Me
H
Me
HSO3F
_75oC, 0.5 h
C C
Me
C C
+
+
Ib
Me
Me
Me
Me
NHAc
Me
Me
-
æŁ
anti-E-IIIl (16%)
NHAc
syn-E-IIIk (20%)
Scheme 14.
Me
NHAc
Me
CO2Me
H
Me
Me
HSO3F
_75oC, 0.75 h
Me
C C
+
IbIb+
Me
Me
AcHN
Me
Me
syn-E-IIIm (32%)
Scheme 15.
Me
Me
Me
Me
HO
C OMe
C
H
Me
HO
O
1
C OMe
C OMe
HSO3F
_80oC
C C
C
Me
Me
3C C 2
Me
Me
H
Me
H
Me
Me
NH2
E-IIr
NH3
IV
NH3
V
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SHCHUKIN et al.
972
16). The protonation of the carbon atom of the double
bond the propenone fragment of molecule VI also was
not observed. The formation in HSO3F of O-proton-ated
form IV and VII underlies the E-/Z-isomerization in
superacids of 3,3-diarylpropenone structures E-/Z-(IIa–
IIz and IIIa–IIIm) considered in this study and the other
propenone systems [7, 8, 10, 11].
of a solution of the substance in methanol within several
days. Crystal of C25H31NO3 at 100 K orthorhombic
,
°
a 9.3382(8), b 14.1577(10), c 17.0069(10)
A, α = β = γ =
°
90°, V 2248.4(3) A3, Z 4, space group P-2, dcalc
1.162 g/cm3, μ 0.075 mm–1, 1.87 ≤ θ ≤ 29.37°, 23856
reflexions were measured, 6086 among them independent
(Rint 0.1193), R1 0.1247 [I > 2σ(I)], wR2 0.1098 (for all
reflexions).
As a result of this investigation a new method was
developed of regio- and stereoselective alkenylation of
arylamines (or N-arylacetamides) based on the reaction
of vinyl type cations with arylammonium ions (or N-aryl-
acetamides) in superacids.
The preparation and properties of methyl 3-phen-
ylpropionate (Ia), methyl 3-(4-methylphenyl)propionate
(Ib) are given in [19], methyl 3-(4-methoxyphenyl)-
propionate (Ic), in [20], 4-(4-methylphenyl)but-3-yn-2-
one (Id), in [21].
EXPERIMENTAL
Arylamines and N-arylacetamides were commercial
products. In alkenylation reactions arylamines proper
were used or their sulfates in an equivalent amount.
1H NMR spectra were registered on a spectrometer
Bruker AM-500 (operating frequency 500 MHz) from
solutions in CDCl3. The residual signal of CHCl3 (δH
7.25 ppm) was used as a reference. IR spectra were
recorded on a spectrophotometer Specord 75IR from
solutions in CHCl3. Mass spectra were taken on MKh-
1321 instrument, ionizing electrons energy 70 eV, direct
admission of the sample into the ion source at 100–
Alkenylation of arylamines and N-arylacetamides
with acetylene derivatives Ia–Id in HSO3F. General
procedure. To a solution of 0.1–0.8 mmol of arylamine
(or N-arylacetamide) in 0.7–1.0 ml of HSO3F at –75...
–30°C was added gradually in 10–20 min while vigorous
stirring 0.09–0.32 mmol of acetylene derivative Ia–Id.
The reaction mixture was stirred for 20–60 min more
and then it was poured into 15–20 ml of concn. HCl
cooled to –75°C. The mixture obtained after quenching
was diluted with water (30–50 ml), warmed to room
temperature, and extracted with chloroform (3×30 ml).
The combined extracts were washed with water, with
a saturated solution of NaHCO3, again with water, and
dried with Na2SO4, the solvent was distilled off in
a vacuum of a water-jet pump, the residue was subjected
to column chromatography on silica gel (eluent petroleum
ether–ethyl acetate). The yield of final products E-/Z-
(IIa–IIz) and E-/Z-(IIIa–IIIm) was evaluated by the
weight of fractions obtained by chromatography.
1
120°C. H NMR spectra in HSO3F at –80°C were
measured on a spectrometer Bruker Avance 400
(operating frequency 400 MHz) with respect to internal
reference CH2Cl2 (δH 5.32 ppm).
X-ray diffraction experiment was performed on an
automatic diffractometer Smart APEX (graphite
monochromator, MoKα radiation, ω-θ scanning). The
structure was solved by the direct method and refined
by the least-squares method by Fh2kl in an anisotropic
approximation for all nonhydrogen atoms. Hydrogen
atoms were found from the difference Fourier synthesis
and refined isotropically. All calculations were carried
out using software package SHELXTL v. 6.10 [18].
(E)-Methyl 3-(3-amino-4-methylphenyl)-3-(4-
methylphenyl)propenoate (IIa) was obtained from
30 mg (0.17 mmol) of compound Ib and 24 mg
(0.23 mmol) of 2-methylphenylamine in 1 ml of HSO3F
The single crystal of compound E-IIIj of the size
0.65×0.09×0.05 mm was obtained for XRD
measurements by slow evaporation at room temperature
Scheme 16.
Me
Me
Me
Me
Me
OH
O
Me
Me
C
Me
Me
C
HSO3F
_80oC
C
C
Me
Me
Me
C
C
Ph
Ph
VI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008
H
H
VII

ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
973
at –75°C in 1 h. Yield 8 mg (17%). Oily substance.
1H NMR spectrum, δ, ppm: 2.15 s (3H, Me), 2.38 s (3H,
Me), 3.59 br.s (2H, NH2), 3.60 s (3H, OMe), 6.28 s (1H,
spectrum, δ, ppm: 1.93 s (3H, Me), 2.14 s (3H, Me),
3.50 br.s (2H, NH2), 3.64 s (3H, OMe), 5.98 s (1H, =CH–
), 6.52 s (1Harom), 6.83 s (1Harom), 7.23–7.30 m (5Harom).
Mass spectrum, m/z (Irel, %): 281 (100) [M]+, 256 (30),
221 (30), 220 (20), 207 (40). Found, %: C 76.61; H 7.02;
N 4.95. C18H19NO2. Calculated, %: C 76.84; H 6.81;
N 4.98. M 281.14.
=CH–), 6.55 d (1Harom, J 1.7 Hz), 6.67 d.d (1Harom
J 7.8, 1.7 Hz), 6.99 d (1Harom, J 7.8 Hz), 7.09 d (2Harom
,
,
J 8 Hz), 7.17 d (2Harom, J 8 Hz). Mass spectrum, m/z
(Irel, %): 281 (100) [M]+, 266 (3), 250 (28). Found, %:
C 76.60; H 7.15; N 4.87. C18H19NO2. Calculated, %:
C 76.84; H 6.81; N 4.98. M 281.14.
(E)- and (Z)-Methyl 3-(5-amino-2,4-dimethyl-
phenyl)-3-(4-methylphenyl)propenoates (IIe) were
obtained from 30 mg (0.17 mmol) of compound Ib and
21 mg (0.17 mmol) of 2,4-dimethylphenylamine in 1 ml
of HSO3F at –75°C in 1 h as an oily isomers mixture.
(E)- and (Z)-Methyl 3-(5-amino-2-methylphenyl)-
3-phenylpropenoates (IIb) were obtained from 50 mg
(0.31 mmol) of compound Ia and 83 mg (0.775 mmol)
of 4-methylphenylamine in 1 ml HSO3F at –30°C in
30 min as an oily isomers mixture.
1
Compound E-IIe. Yield 13 mg (24%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.93 s (3H, Me), 2.14 s (3H, Me), 2.34 s (3H,
Me), 3.47 s (2H, NH2), 3.65 s (3H, OMe), 5.93 s (1H,
1
Compound E-IIb. Yield 11 mg (12%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.94 s (3H, Me), 3.64 s (3H, OMe), 3.58 br.s
(2H, NH2), 5.98 s (1H, =CH–), 6.54 d (1Harom, J 2.5 Hz),
=CH–), 6.51 s (1Harom), 6.82 s (1Harom), 7.09 d (2Harom
,
J 8 Hz), 7.14 d (2Harom, J 8 Hz).
6.59 d.d (1Harom, J 8.1, 2.5 Hz), 6.92 d (1Harom
J 8.1 Hz), 7.23–7.30 m (5Harom).
,
1
Compound Z-IIe. Yield 6 mg (13%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.94 s (3H, Me), 2.17 s(3H, Me), 2.34 s (3H,
Me), 3.60 s (3H, OMe), 3.69 s (2H, NH2), 6.38 s (1Harom),
1
Compound Z-IIb. Yield 1.5 mg (2%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.95 s (3H, Me), 3.60 s (3H, OMe), 3.58 br.s
(2H, NH2), 6.41 d (1Harom, J 2.5 Hz), 6.48 s (1H,
6.45 s (1H, =CH–), 6.92 s (1Harom), 7.10 d (2Harom
,
J 7.8 Hz), 7.23 d (2Harom, J 7.8 Hz). Mass spectrum
(isomers mixture), m/z (Irel, %): 295 (100) [M]+, 280 (9),
264 (26), 235 (22), 221 (38), 147.5 (5) [M]2+. Found, %:
C 77.41; H 7.05; N 4.73. C19H21NO2. Calculated, %:
C 77.26; H 7.17; N 4.74. M 295.16.
=CH–), 6.63 d.d (1Harom, J 8.1, 2.5 Hz), 7.02 d (1Harom
,
J 8.1 Hz), 7.23–7.30 m (5Harom). Mass spectrum (isomers
mixture), m/z (Irel, %): 267 (100) [M]+, 236 (33), 207
(56), 206 (47), 197 (47), 130 (33), 115 (28). Found, %:
C 76.47; H 6.30; N 5.43. C17H17NO2. Calculated, %:
C 76.38; H 6.41; N 5.24. M 267.13.
(Z)-4-(5-Amino-2,4-dimethylphenyl)-4-(4-
methylphenyl)but-3-en-2-one (IIf) was obtained from
50 mg (0.32 mmol) of compound Id and 77 mg
(0.64 mmol) of 2,4-dimethylphenylamine in 1 ml of
HSO3F at –30°C in 1 h. Yield 49 mg (56%). Oily
(Z)-4-(5-Amino-2-methylphenyl)-4-(4-methyl-
phenyl)but-3-en-2-one (IIc) was obtained from 50 mg
(0.32 mmol) of compound Id and 86 mg (0.8 mmol) of
4-methylphenylamine in 1 ml of HSO3F at –30°C in 1 h.
Yield 8 mg (10%). Oily substance. 1H NMR spectrum,
δ, ppm: 1.82 s (3H, Me), 1.95 s (3H, Me), 2.34 s (3H,
Me), 3.62 br.s (2H, NH2), 6.45 d (1Harom, J 2.4 Hz),
6.64 s (1H, =CH–), 6.66 d.d (1Harom, J 8.0, 2.4 Hz),
7.03 d (1Harom, J 8.0 Hz), 7.11 d (2Harom, J 8.1 Hz),
7.22 d (2Harom, J 8.1 Hz). Mass spectrum, m/z (Irel, %):
265 (70) [M]+, 250 (100), 222 (33), 207 (20), 130 (25),
43 (20). Found, %: C 81.64; H 7.36; N 5.20. C18H19NO.
Calculated, % : C 81.47; H 7.22; N 5.28. M 265.15.
1
substance. H NMR spectrum (CDCl3), δ, ppm: 1.80 s
(3H, Me), 1.93 s (3H, Me), 2.19 s (3H, Me), 2.33 s (3H,
Me), 3.55 br.s (2H, NH2), 6.43 s (1Harom), 6.63 s (1H,
=CH–), 6.93 s (1Harom), 7.10 d (2Harom, J 8.3 Hz), 7.22 d
(2Harom, J 8.3 Hz). Mass spectrum, m/z (Irel, %): 279 (53)
[M]+, 264 (100), 236 (30), 221 (20). Found, %: C 81.61;
H 8.02; N 4.93. C19H21NO. Calculated, %: C 81.68;
H 7.58; N 5.01. M 279.16.
(E)-Methyl 3-(2-amino-4,5-dimethylphenyl)-3-(4-
methylphenyl)propenoate (IIg) was obtained from
35 mg (0.2 mmol) of compound Ib and 49 mg (0.4 mmol)
of 3,4-dimethylphenylamine in 1 ml of HSO3F at –75°C
in 0.75 h. Yield 20 mg (34%), mp 200°C (decomp.).
1H NMR spectrum, δ, ppm: 2.13 s (3H, Me), 2.17 s (3H,
Me), 2.35 s (3H, Me), 3.42 br.s (2H, NH2), 3.64 s (3H,
(E)-Methyl 3-(5-amino-2,4-dimethylphenyl)-3-
phenylpropenoate (IId) was obtained from 50 mg
(0.31 mmol) of compound Ia and 94 mg (0.78 mmol) of
2,4-dimethylphenylamine in 1 ml of HSO3F at –30°C in
1
30 min. Yield 12 mg (14%). Oily substance. H NMR
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SHCHUKIN et al.
974
HSO3F at –30°C in 1.25 h. Yield 41 mg (44%). Oily
substance. IR spectrum, ν, Cm–1: 1590 (N–H), 1630
(C=O), 3300 (N–H), 3400 (N–H). 1H NMR spectrum, δ,
ppm: 1.72 s (3H, Me), 1.94 s (3H, Me), 1.95 s (3H, Me),
2.21 s (3H, Me), 2.33 s (3H, Me), 3.56 br.s (2H, NH2),
6.80 s (1H, =CH–), 6.86 s (1Harom), 7.10 d (2Harom, J 8.1
Hz), 7.24 d (2Harom, J 8.1 Hz). Mass spectrum, m/z (Irel,
%): 293 (100) [M]+, 278 (96), 263 (10), 234 (31), 220
(21). Found, %: C 81.90; H 7.68; N 4.71. C20H23NO.
Calculated, %: C 81.87; H 7.90; N 4.77. M 293.18.
OMe), 6.10 s (1H, =CH–), 6.43 s (1Harom), 6.83 s
(1Harom), 7.14 d (2Harom, J 8 Hz), 7.21 d (2Harom, J 8 Hz).
Mass spectrum, m/z (Irel, %): 295 (59) [M]+, 264 (70),
263 (88), 248 (26), 236 (100), 222 (23). Found, %:
C 77.21; H 7.17; N 4.82. C19H21NO2. Calculated, %:
C 77.26; H 7.17; N 4.74. M 295.16.
(E)-Methyl 3-(5-amino-2,3-dimethylphenyl)-3-(4-
methylphenyl)propenoate (IIh) was obtained from
35 mg (0.2 mmol) of compound Ib and 49 mg (0.4 mmol)
of 3,4-dimethylphenylamine in 1 ml of HSO3F at –75°C
1
(E)-Methyl 3-(3-amino-6-tert-butyl-2,4-dimethyl-
phenyl)-3-phenylpropenoate (IIl) was obtained from
29 mg (0.18 mmol) of compound Ia and 32 mg
(0.18 mmol) of 4-tert-butyl-2,6-dimethylphenylamine in
1 ml HSO3F at –30°C in 1.5 h. Yield 10 mg (16%). Oily
substance. 1H NMR spectrum, δ, ppm: 1.22 s (9H, CMe3),
2.01 s (3H, Me), 2.22 s (3H, Me), 3.62 br.s (2H, NH2),
3.72 s (3H, OMe), 5.91 s (1H, =CH–), 7.13 s (1Harom),
7.25 m (3Harom), 7.30 m (2Harom). Mass spectrum, m/z
(Irel, %): 337 (100) [M]+, 322 (87), 290 (21), 280 (7),
262 (43), 248 (47). Found, %: C 78.40; H 8.14; N 4.15.
C22H27NO2. Calculated, %: C 78.30; H 8.06; N 4.15.
M 337.2.
in 0.75 h. Yield 4 mg (7%). Oily substance. H NMR
spectrum, δ, ppm: 1.89 s (3H, Me), 2.15 s (3H, Me),
2.32 s (3H, Me), 3.65 s (5H, OMe, NH2), 5.91 s (1H,
=CH–), 6.39 d (1Harom, J 2.3 Hz), 6.51 d (1Harom, J 2.3
Hz), 7.09 d (2Harom, J 8 Hz), 7.14 d (2Harom, J 8 Hz).
Mass spectrum, m/z (Irel, %): 295 (100) [M]+, 280 (14),
264 (25), 236 (35), 221 (39). Found, %: C 77.08; H 7.45;
N 4.76. C19H21NO2. Calculated, %: C 77.26; H 7.17;
N 4.74. M 295.16.
(E)-Methyl 3-(3-amino-2,4,6-trimethylphenyl)-3-
phenylpropenoate (IIi) was obtained from 30 mg
(0.19 mmol) of compound Ia and 63 mg (0.47 mmol)
2,4,6-trimethylphenylamine in 1 ml of HSO3F at –30°C
in 0.5 h. Yield 11 mg (20%). Oily substance. IR spectrum,
ν, cm–1: 1620 (N–H), 1710 (C=O), 3300 (N–H), 3400
(E)-Methyl 3-(3-amino-6-tert-butyl-2,4-dimethyl-
phenyl)-3-(4-methylphenyl)propenoate (IIm) was
obtained from 22 mg (0.13 mmol) of compound Ib and
22 mg (0.13 mmol) of 4-tert-butyl-2,6-dimethyl-
phenylamine in 0.75 ml of HSO3F of –75°C in 1 h. Yield
15 mg (34%). Oily substance. 1H NMR spectrum, δ, ppm:
1.22 s (9H, CMe3), 2.00 s (3H, Me), 2.22 s (3H, Me),
2.31 s (3H, Me), 3.60 br.s (2H, NH2), 3.72 s (3H, OMe),
5.86 s (1H, =CH–), 7.05 d (2Harom, J 8.3 Hz), 7.13 s
(1Harom), 7.20 d (2Harom, J 8.3 Hz). Mass spectrum, m/z
(Irel, %): 351 (100) [M]+, 336 (83), 304 (17), 294 (14),
276 (34), 262 (43). Found, %: C 78.65; H 8.27; N 4.01.
C23H29NO2. Calculated, %: C 78.59; H 8.32; N 3.99.
M 351.22.
1
(N–H). H NMR spectrum, δ, ppm: 2.07 s (3H, Me),
2.08 s (3H, Me), 2.17 s (3H, Me), 3.50 br.s (2H, NH2),
3.67 s (3H, OMe), 5.87 s (1H, =CH–), 6.80 s (1Harom),
7.26 s (5Harom). Mass spectrum, m/z (Irel, %): 295 (100)
[M]+, 235 (21), 220 (43), 207 (15), 134 (21). Found, %:
C 77.23; H 7.01; N 4.65. C19H21NO2. Calculated, %:
C 77.26; H 7.17; N 4.74. M 295.16.
(E)-Methyl 3-(3-amino-2,4,6-trimethylphenyl)-3-
(4-methylphenyl)propenoate (IIj) was obtained from
15 mg (0.086 mmol) of compound Ib and 14 mg
(0.1 mmol) of 2,4,6-trimethylphenylamine in 0.7 ml of
HSO3F at –75°C in 1 h. Yield 10 mg (38%). Oily sub-
1
stance. H NMR spectrum, δ, ppm: 2.05 s (3H, Me),
(E)- and (Z)-4-(3-Amino-6-tert-butyl-2,4-
dimethylphenyl)-4-(4-methylphenyl)but-3-en-2-ones
(IIn) were obtained from 27 mg (0.17 mmol) of
compound Id and 30 mg (0.17 mmol) of 4-tert-butyl-
2,6-dimethylphenylamine in 1 ml of HSO3F at –30°C in
1 h as a crystalline isomers mixture of mp 148–151°C.
2.06 s (3H, Me), 2.16 s (3H, Me), 2.31 s (3H, Me),
3.51 br.s (2H, NH2), 3.68 s (3H, OMe), 5.82 s (1H,
=CH–), 6.79 s (1Harom), 7.06 d (2Harom, J 8.1 Hz), 7.15 d
(2Harom, J 8.1 Hz). Mass spectrum, m/z (Irel, %): 309 (100)
[M]+, 278 (7), 249 (13), 234 (25), 221 (14). Found, %:
C 77.48; H 7.47; N 4.53. C20H23NO2. Calculated, %:
C 77.64; H 7.49; N 4.53. M 295.16.
1
Compound E-IIn. Yield 1 mg (2%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.23 s (9H, CMe3), 1.99 s (3H, Me), 2.21 s
(3H, Me), 2.22 s (3H, Me), 2.32 s (3H, Me), 3.58 br.s
(2H, NH2), 6.05 s (1H, =CH–), 7.06 d (2Harom, J 8.2 Hz),
7.13 s (1Harom), 7.15 d (2Harom, J 8.2 Hz).
(Z)-4-(3-Amino-2,4,6-trimethylphenyl)-4-(4-
methylphenyl)but-3-en-2-one (IIk) was obtained from
50 mg (0.32 mmol) of compound Id and 106 mg
(0.79 mmol) of 2,4,6-trimethylphenylamine in 1 ml of
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ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
975
1
(Z)-Methyl 3-(3-amino-2,5,6-trimethylphenyl)-3-
(4-methoxyphenyl)propenoate (IIq) was obtained from
37 mg (0.19 mmol) of compound Ic and 34 mg
(0.25 mmol) of 2,4,5-trimethylphenylaminea in 1 ml of
HSO3F at –75°C in 1 h. Yield 5.5 mg (9%), mp 108–
Compound Z-IIn. Yield 8 mg (15%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.13 s (9H, CMe3), 1.73 s (3H, Me), 1.90 s
(3H, Me), 2.25 s (3H, Me), 2.33 s (3H, Me), 3.58 br.s
(2H, NH2), 6.88 s (1H, =CH–), 7.11 d (2Harom, J 8.2 Hz),
7.17 C (1Harom), 7.28 d (2Harom, J 8.2 Hz). Mass spectrum
(isomers mixture), m/z (Irel, %): 335 (5) [M]+, 320 (2),
278 (100). Found, %: C 82.45; H 8.73; N 4.20.
C23H29NO. Calculated, %: C 82.34; H 8.71; N 4.18.
M 335.22.
1
112°C. H NMR spectrum (CDCl3), δ, ppm: 1.85 s (3H,
Me), 1.86 s (3H, Me), 2.19 s (3H, Me), 3.48 br.s (2H,
NH2), 3.57 s (3H, OMe), 3.79 s (3H, OMe), 6.55 s (1H,
=CH–), 6.56 s (1Harom), 6.81 d (2Harom, J 8.9 Hz), 7.29 d
(2Harom, J 8.9 Hz). Mass spectrum, m/z (Irel, %): 325 (100)
[M]+, 250 (33), 237 (20), 134 (27). Found, %: C 73.86;
H 7.11; N 4.33. C20H23NO3. Calculated, %: C 73.82;
H 7.12; N 4.30. M 325.17.
(E)-Methyl 3-(3-amino-2,5,6-trimethylphenyl)-3-
phenylpropenoate (IIo) was obtained from 50 mg
(0.31 mmol) of compound Ia and 50 mg (0.37 mmol) of
2,4,5-trimethylphenylamine in 1 ml of HSO3F at –30°C
(Z)-4-(3-Amino-2,5,6-trimethylphenyl)-4-(4-
methylphenyl)but-3-en-2-one (IIr) was obtained from
42 mg (0.27 mmol) of compound Id and 47 mg
(0.35 mmol) of 2,4,5-trimethylphenylamine in 1 ml of
HSO3F at –30°C in 1.25 h. Yield 12.5 mg (16%). Oily
substance. 1H NMR spectrum, δ, ppm: 1.71 s (3H, Me),
1.89 s (3H, Me), 1.90 s (3H, Me), 2.20 s (3H, Me),
2.33 s (3H, Me), 3.52 br.s (2H, NH2), 6.60 s (1Harom),
6.80 s (1H, =CH–), 7.11 d (2Harom, J 7.9 Hz), 7.24 d
(2Harom, J 7.9 Hz). Mass spectrum, m/z (Irel, %): 293 (100)
[M]+, 278 (81), 258 (81), 234 (33). Found, %: C 81.80;
H 7.92; N 4.75. C20H23NO. Calculated, %: C 81.87; H 7.90;
N 4.77. M 293.18.
1
in 1 h. Yield 38 mg (30%), mp 126–128°C. H NMR
spectrum, δ, ppm: 2.02 s (3H, Me), 2.03 s (3H, Me),
2.17 s (3H, Me), 3.48 br.s (2H, NH2), 3.68 s (3H, OMe),
5.87 s (1H, =CH–), 6.53 s (1Harom), 7.27 m (5Harom).
Mass spectrum, m/z (Irel, %): 295 (100) [M]+, 264 (10),
248 (11), 236 (29), 220 (42), 134 (23). Found, %: C 77.35;
H 7.21; N 4.69. C19H21NO2. Calculated, %: C 77.26;
H 7.17; N 4.74. M 295.16.
(E)-Methyl 3-(3-amino-2,5,6-trimethylphenyl)-3-
(4-methylphenyl)propenoate (IIp) was obtained from
30 mg (0.17 mmol) of compound Ib and 29 mg
(0.22 mmol) of 2,4,5-trimethylphenylamine in 1 ml of
HSO3F at –75°C in 1 h. Yield 6 mg (11%), mp 116–
(E)-Methyl 3-(2-amino-3,5,6-trimethylphenyl)-3-
phenylpropenoate (IIs) was obtained from 50 mg
(0.31 mmol) of compound Ia and 50 mg (0.37 mmol) of
2,4,5-trimethylphenylamine in 1 ml of HSO3F at –30°C
1
118°C. H NMR spectrum, δ, ppm: 2.02 s (6H, 2Me),
2.17 s (3H, Me), 2.31 s (3H, Me), 3.50 br.s (2H, NH2),
3.68 s (3H, OMe), 5.82 s (1H, =CH–), 6.53 s (1Harom),
7.07 d (2Harom, J 8.2 Hz), 7.17 d (2Harom, J 8.2 Hz). Mass
spectrum, m/z (Irel, %): 309 (100) [M]+, 294 (8), 278 (10),
262 (11), 250 (21), 234 (36). Found, %: C 77.55; H 7.40;
N 4.56. C20H23NO2. Calculated, %: C 77.64; H 7.49;
N 4.53. M 309.17.
1
in 1 h. Yield 22 mg (18%), mp 98–100°C. H NMR
spectrum, δ, ppm: 2.04 s (3H, Me), 2.13 s (3H, Me),
2.15 s (3H, Me), 3.57 br.s (2H, NH2), 3.68 s (3H, OMe),
6.03 s (1H, =CH–), 6.86 s (1Harom), 7.29–7.30 m (3Harom),
7.35–7.37 m (2Harom). Mass spectrum, m/z (Irel, %): 295
(70) [M]+, 264 (29), 248 (8), 236 (100), 221 (29). Found,
%: C 77.30; H 7.28; N 4.74. C19H21NO2. Calculated, %:
C 77.26; H 7.17; N 4.74. M 295.16.
(E)-Methyl 3-(3-amino-2,5,6-trimethylphenyl)-3-
(4-methoxyphenyl)propenoate (IIq) was obtained
from 37 mg (0.19 mmol) of compound Ic and 34 mg
(0.25 mmol) of 2,4,5-trimethylphenylamine in 1 ml of
HSO3F at –75°C in 1 h. Yield 11 mg (17%). Oily
substance. 1H NMR spectrum, δ, ppm: 1.99 s (3H, Me),
2.00 s (3H, Me), 2.17 s (3H, Me), 3.48 br.s (2H, NH2),
3.69 s (3H, OMe), 3.78 s (3H, OMe), 5.78 s (1H,
=CH–), 6.53 s (1Harom), 6.79 d (2Harom, J 8.8 Hz), 7.24 d
(2Harom, J 8.8 Hz). Mass spectrum, m/z (Irel, %): 325 (100)
[M]+, 250 (34), 237 (22), 134 (28). Found, %: C 73.75;
H 7.15; N 4.36. C20H23NO3. Calculated, %: C 73.82;
H 7.12; N 4.30. M 325.17.
(E)-Methyl 3-(2-amino-3,5,6-trimethylphenyl)-3-
(4-methylphenyl)propenoate (IIt) was obtained from
30 mg (0.17 mmol) of compound Ib and 29 mg
(0.22 mmol) of 2,4,5-trimethylphenylamine in 1 ml of
HSO3F at –75°C in 1 h. Yield 10 mg (19%), mp 83–
1
84°C. H NMR spectrum, δ, ppm: 2.03 s (3H, Me),
2.11 s (3H, Me), 2.14 s (3H, Me), 2.32 s (3H, Me),
3.54 br.s (2H, NH2), 3.68 s (3H, OMe), 5.97 s (1H,
=CH–), 6.84 s (1Harom), 7.09 d (2Harom, J 8.3 Hz), 7.25 d
(2Harom, J 8.3 Hz). Mass spectrum, m/z (Irel, %): 309 (63)
[M]+, 293 (3), 278 (30), 262 (10), 250 (100), 234 (21).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SHCHUKIN et al.
976
J 8.2, 2 Hz), 6.78 d (1Harom, J 8.2 Hz), 7.11 d (2Harom
,
Found, %: C 77.61; H 7.38; N 4.55. C20H23NO2.
J 8.1 Hz), 7.20 d (2Harom, J 8.1 Hz). Mass spectrum,
m/z (Irel, %): 297 (100) [M]+, 282 (29), 266 (12), 222
(16), 194 (11). Found, %: C 72.70; H 6.41; N 4.65.
C18H19NO3. Calculated, %: C 72.71; H 6.44; N 4.71.
M 297.14.
Calculated, %: C 77.64; H 7.49; N 4.53. M 309.17.
(E)-Methyl 3-(4-amino-2,3,5,6-tetramethyl-
phenyl)-3-phenylpropenoate (IIu) was obtained and
characterized before [7].
(E)-Methyl 3-(4-amino-2,3,5,6-tetramethyl-
phenyl)-3-(4-methylphenyl)propenoate (IIv) was
obtained from 40 mg (0.23 mmol) of compound Ib and
41 mg (0.28 mmol) 2,3,5,6-tetramethylphenylamine in
1 ml of HSO3F at –75°C in 1 h. Yield 19 mg (25%), mp
(E)- and (Z)-4-(3-Amino-4-methoxyphenyl)-4-(4-
methylphenyl)but-3-en-2-ones (IIy) were obtained
from 30 mg (0.19 mmol) of compound Id and 30 mg
(0.25 mmol) of 2-methoxyphenylamine in 1 ml of HSO3F
at –30°C in 1 h as an oily isomers mixture.
1
197–199°C. H NMR spectrum, δ, ppm: 2.09 s (6H,
1
Compound E-IIy. Yield 2 mg (4%). H NMR
2Me), 2.13 s (6H, 2Me), 2.31 s (3H, Me), 3.62 br.s (2H,
NH2), 3.67 s (3H, OMe), 5.82 s (1H, =CH–), 7.06 d
(2Harom, J 7.5 Hz), 7.15 d (2Harom, J 7.5 Hz). Mass
spectrum, m/z (Irel, %): 323 (100) [M]+, 308 (24), 292
(12), 250 (47), 235 (52), 161.5 (10) [M]2+. Found, %:
C 78.01; H 7.70; N 4.35. C21H25NO2. Calculated, %:
C 77.98; H 7.79; N 4.33. M 323.19.
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.88 s (3H, Me), 2.35 s (3H, Me), 3.80 br.s
(2H, NH2), 3.89 s (3H, OMe), 6.42 s (1H, =CH–), 6.53 d
(1Harom, J 2 Hz), 6.59 d.d (1Harom, J 8.2, 2 Hz), 6.78 d
(1Harom, J 8.2 Hz), 7.11 d (2Harom, J 8.2 Hz), 7.20 d
(2Harom, J 8.2 Hz).
1
Compound Z-IIy. Yield 10.5 mg (20%). H NMR
(Z)-Methyl 3-(4-amino-2,3,5,6-tetramethyl-
phenyl)-3-(4-methylphenyl)propenoate (IIv) was
obtained by keeping a solution of 10 mg (0.03 mmol) of
compound E-IIv in 0.8 ml of HSO3F at –30°C for 1 h.
Yield 5 mg (50%). Oily substance. 1H NMR spectrum,
δ, ppm: 1.97 s (6H, 2Me), 2.10 s (6H, 2Me), 2.33 s (3H,
Me), 3.58 s (5H, OMe, NH2), 6.60 s (1H, =CH–), 7.09 d
(2Harom, J 8.3 Hz), 7.23 d (2Harom, J 8.3 Hz). Found, %:
C 77.88; H 7.85; N 4.38. C21H25NO2. Calculated, %:
C 77.98; H 7.79; N 4.33. M 323.19.
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.82 s (3H, Me), 2.40 s (3H, Me), 3.80 br.s
(2H, NH2), 3.85 s (3H, OMe), 6.47 s (1H, =CH–), 6.65
br.s (1Harom), 6.66 d.d (1Harom, J 8.2, 2.2 Hz), 6.70 d
(1Harom, J 8.2 Hz), 7.08 d (2Harom, J 7.9 Hz), 7.19 d
(2Harom, J 7.9 Hz). Mass spectrum (isomers mixture), m/
z (Irel, %): 281 (100) [M]+, 266 (69), 150 (38). Found,
%: C 76.89; H 6.71; N 5.03. C18H19NO2. Calculated, %:
C 76.84; H 6.81; N 4.98. M 281.14.
(E)-Methyl 3-(3-amino-2-methoxyphenyl)-3-(4-
methylphenyl)propenoate (IIz) was obtained from
28 mg (0.16 mmol) of compound Ib and 25 mg (0.20 mmol)
of 2-methoxyphenylamine on 1 ml of HSO3F at –75°C
in 1 h as an oily mixture with compound Z-IIx. Yield
8 mg (17%). 1H NMR spectrum, δ, ppm (extracted from
the spectrum of isomers mixture): 2.38 s (3H, Me),
3.59 s (3H, OMe), 3.76 br.s (2H, NH2), 3.85 s (3H,
OMe), 6.24 s (1H, =CH–), 6.64–6.71 m (3Harom), 7.08 d
(2Harom, J 7.9 Hz), 7.17 d (2Harom, J 7.9 Hz). Mass
spectrum, m/z (Irel, %): 297 (100) [M]+, 282 (29), 266
(12), 222 (16), 194 (11). Found, %: C 72.70; H 6.41;
N 4.65. C18H19NO3. Calculated, %: C 72.71; H 6.44;
N 4.71. M 297.14.
(Z)-4-(4-Amino-2,3,5,6-tetramethylphenyl)-4-(4-
methylphenyl)but-3-en-2-one (IIw) was obtained from
50 mg (0.32 mmol) of compound Id and 89 mg (0.60 mmol)
of 2,3,5,6-tetramethylphenylamine in 1 ml of HSO3F at
–30°C in 1 h. Yield 30 mg (31%). Oily substance. 1H NMR
spectrum, δ, ppm: 1.65 s (3H, Me), 2.00 s (6H, 2Me),
2.12 s (6H, 2Me), 2.33 s (3H, Me), 3.70 br.s (2H, NH2),
6.80 s (1H, =CH–), 7.10 d (2Harom, J 8.2 Hz), 7.24 d
(2Harom, J 8.2 Hz). Mass spectrum, m/z (Irel, %): 307 (100)
[M]+, 292 (98), 264 (33), 248 (27), 234 (22). Found, %:
C 82.28; H 8.21; N 4.48. C21H25NO. Calculated, %:
C 82.04; H 8.20; N 4.56. M 307.19.
(E)-Methyl 3-(3-amino-4-methoxyphenyl)-3-(4-
methylphenyl)propenoate (IIx) was obtained from
28 mg (0.16 mmol) of compound Ib and 25 mg (0.20 mmol)
2-methoxyphenylamine in 1 ml of HSO3F at –75°C in
(E)-Methyl 3-(4-acetylaminophenyl)-3-phenyl-
propenoate (IIIa) was obtained from 50 mg (0.31 mmol)
of compound Ia and 50 mg (0.37 mmol) of N-phenyl-
acetamide in 1 ml of HSO3F at –50°C in 1 h. Yield 4 mg
(4%). Oily substance. 1H NMR spectrum, δ, ppm: 2.15 s
(3H, Me), 3.63 s (3H, OMe), 6.31 s (1H, =CH–), 7.05–
1
1 h. Yield 21.5 mg (45%). Oily substance. H NMR
spectrum, δ, ppm: 2.34 s (3H, Me), 3.62 s (3H, OMe),
3.77 br.s (2H, NH2), 3.87 s (3H, OMe), 6.22 s (1H,
=CH–), 6.54 d (1Harom, J 2 Hz), 6.62 d.d (1Harom
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
977
7.55 m (10H, 9Harom, NH). Mass spectrum, m/z (Irel, %):
7.20 m (3Harom), 7.31 br.s (1H, NH), 7.56 d.d (1Harom
,
295 [M]+. Found, %: C 73.35; H 5.82; N 4.71. C18H17O3.
Calculated, %: C 73.20; H 5.80; N 4.74. M 295.12.
J 8.3, 2 Hz). Mass spectrum, m/z (Irel, %): 307 (37) [M]+,
292 (100), 264 (37), 250 (53), 222 (18), 130 (21), 43
(84). Found, %: C 78.38; H 6.80; N 4.56. C20H21NO2.
Calculated, %: C 78.15; H 6.89; N 4.56. M 307.16.
(E)-Methyl 3-(4-acetylaminophenyl)-3-(4-methyl-
phenyl)propenoate (IIIb) was obtained from 30 mg
(0.17 mmol) of compound Ib and 22 mg (0.16 mmol) of
N-phenylacetamide in 1 ml of HSO3F at –75°C in
(E)- and (Z)-Methyl 3-(5-acetylamino-2,4-di-
methylphenyl)-3-(4-methylphenyl)propenoates (IIIf)
were obtained from 30 mg (0.17 mmol) of compound Ib
and 27 mg (0.16 mmol) of N-2,4-dimethylphenyl-
acetamide in 1 ml of HSO3F at –75°C in 0.75 h as
a crystalline isomers mixture of mp 190–193°C. Yield
E-IIIf 7 mg (13%), Z-IIIf 7 mg (13%). 1H NMR spec-
trum, δ, ppm (isomers mixture): 1.96 s (3H, Me), 1.98 s
(3H, Me), 2.10 s (3H, Me), 2.14 s (3H, Me), 2.20 s (3H,
Me), 2.23 s (3H, Me), 2.32 s (6H, 2Me), 3.58 s (3H,
OMe), 3.63 s (3H, OMe), 5.95 s (1H, =CH–), 6.46 s (1H,
=CH–), 6.95 s (1Harom), 7.02 br.c (1H, NH), 7.04–
7.14 m (8H, 7Harom, NH), 7.22 d (2Harom, J 8.3 Hz),
7.39 s (1Harom), 7.46 s (1Harom). Mass spectrum, m/z (Irel,
%): 337 (73) [M]+, 322 (5), 305 (45), 277 (15), 263 (100),
248 (35), 221 (29), 220 (30), 43 (31). Found, %: C 74.85;
H 6.84; N 4.20. C21H23NO3. Calculated, %: C 74.75;
H 6.87; N 4.15. M 337.17.
1
0.75 h. Yield 9 mg (18%). Oily substance. H NMR
spectrum, δ, ppm: 2.15 s (3H, Me), 2.34 s (3H, Me),
3.61 s (3H, OMe), 6.30 s (1H, =CH–), 7.06–7.52 m (9H,
8Harom, NH). Mass spectrum, m/z (Irel, %): 309 (100)
[M]+, 278 (21), 267 (85), 254 (18), 236 (63), 209 (37).
Found, %: C 73.70; H 6.15; N 4.56. C19H19NO3.
Calculated, %: C 73.77; H 6.19; N 4.53. M 309.14.
(E)- and (Z)-N-{4-[1-(4-Methylphenyl)-3-oxobut-
1-enyl]phenyl}acetamides (IIIc) were obtained from
30 mg (0.19 mmol) of compound Id and 24 mg (0.18 mmol)
N-phenylacetamide in 1 ml of HSO3F at –30°C in 1 h as
an oily isomers mixture. Yield E-IIIc 2 mg (3%), Z-IIIc
2 mg (3%). 1H NMR spectrum, δ, ppm (isomers mixture):
1.86 s (3H, Me), 1.91 s (3H, Me), 2.17 s (3H, Me),
2.19 s (3H, Me), 2.35 s (3H, Me), 2.40 s (3H, Me),
6.50 s (1H, =CH–), 6.52 s (1H, =CH–), 7.05–7.30 m
(18H, 16Harom, 2NH). Mass spectrum (isomers mixture),
m/z (Irel, %): 293 (100) [M]+, 292 (56), 278 (100), 250
(25), 236 (63), 208 (21), 43 (91). Found, %: C 77.70;
H 6.52; N 4.68. C19H19NO2. Calculated, %: C 77.79;
H 6.53; N 4.77. M 293.14.
(E)-Methyl-3 (3-acetylamino-2,4,6-trimethyl-
phenyl)-3-(4-methylphenyl)propenoate (IIIg) was
obtained from 30 mg (0.17 mmol) of compound Ib and
33 mg (0.19 mmol) of N-2,4,6-trimethylphenylacetamide
in 1 ml of HSO3F at –75°C in 0.75 h. Yield 31 mg (51%).
(E)-Methyl 3-(5-acetylamino-2-methylphenyl)-3-
(4-methylphenyl)propenoate (IIId) was obtained from
30 mg (0.17 mmol) of compound Ib and 27 mg (0.18 mmol)
of N-4-methylphenylacetamide in 1 ml of HSO3F at
–75°C in 0.75 h. Yield 16 mg (29%). Oily substance.
1H NMR spectrum, δ, ppm: 1.98 s (3H, Me), 2.11 s (3H,
Me), 2.31 s (3H, Me), 3.65 s (3H, OMe), 5.93 s (1H,
1
Oily substance. H NMR spectrum, δ, ppm: 2.08 s (3H,
Me), 2.13 s (3H, Me), 2.16 s (3H, Me), 2.19 s (3H, Me),
2.30 s (3H, Me), 3.67 s (3H, OMe), 5.82 s (1H, =CH–),
6.80 br.s (1H, NH), 6.94 s (1H-arom), 7.05 d (2Harom
,
J 8.1 Hz), 7.13 d (2Harom, J 8.1 Hz). Mass spectrum,
m/z (Irel, %): 351 (100) [M]+, 336 (11), 319 (82), 309
(23), 304 (52), 291 (68), 277 (77). Found, %: C 75.28;
H 7.24; N 4.03. C22H25NO3. Calculated, %: C 75.19;
H 7.17; N 3.99. M 351.18.
=CH–), 7.05–7.11 m (6H, 5Harom, NH), 7.15 d (1Harom
,
J 2.1 Hz), 7.52 d.d (1Harom, J 8, 2.1 Hz). Mass spectrum,
m/z (Irel, %): 323 (100) [M]+, 308 (8), 291 (64), 263 (23),
249 (80), 234 (60), 221 (60), 207 (49), 43 (64). Found,
%: C 74.05; H 6.58; N 4.30. C20H21NO3. Calculated, %:
C 74.28; H 6.55; N 4.33. M 323.15.
(Z)-Methyl 3-(3-acetylamino-2,4,6-trimethyl-
phenyl)-3-(4-methoxyphenyl)propenoate (IIIh) was
obtained from 30 mg (0.16 mmol) of compound Ic and
36 mg (0.20 mmol) of N-2,4,6-trimethylphenylacetamide
in 1 ml of HSO3F at –75°C in 1 h. Yield 30 mg (52%),
N-{4-Methyl-3-[(Z)-1-(4-methylphenyl)-3-oxobut-1-
enyl]phenyl}acetamide (IIIe) was obtained from 37 mg
(0.23 mmol) of compound Id and 45 mg (0.30 mmol) of
N-4-methylphenylacetamide in 1 ml of HSO3F at –30°C
1
mp 185–187°C. H NMR spectrum (CDCl3), δ, ppm:
1.95 s (3H, Me), 1.98 s (3H, Me), 2.18 s (3H, Me),
2.24 s (3H, Me), 3.57 s (3H, OMe), 3.78 s (3H, OMe),
6.54 s (1H, =CH–), 6.82 d (2Harom, J 9 Hz), 6.82 s
(1Harom), 7.30 d (2Harom, J 9 Hz). Mass spectrum, m/z
(Irel, %): 367 [M]+ (96), 352 (18), 335 (100), 320 (54),
1
in 1 h. Yield 12 mg (17%), mp 168–170°C. H NMR
spectrum, δ, ppm: 1.85 s (3H, Me), 2.01 s (3H, Me),
2.12 s (3H, Me), 2.33 s (3H, Me), 6.70 s (1H, =CH–),
7.10 d (2Harom, J 7.9 Hz), 7.14 d (1Harom, J 2 Hz), 7.17–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

SHCHUKIN et al.
978
307 (61), 293 (78), 250 (57), 43 (83). Found, %: C 72.06;
H 6.86; N 3.92. C22H25NO4. Calculated, %: C 71.91;
H 6.86; N 3.81. M 367.18.
5.86 s (1H, =CH–), 6.56 br.s (1H, NH), 7.05–7.10 m
(3Harom), 7.13 d (2Harom, J 8.1 Hz). Mass spectrum
(isomers mixture), m/z (Irel, %): 351 (46) [M]+, 308 (100),
276 (36), 249 (48), 234 (24), 43 (20). Found, %: C 75.36;
H 7.23; N 3.95. C22H25NO3. Calculated, %: C 75.19;
H 7.17; N 3.99. M 351.18.
N-{2,4,6-Trimethyl-3-[(Z)-1-(4-methylphenyl)-3-
oxobut-1-enyl]phenyl}acetamide (IIIi) was obtained
from 32 mg (0.20 mmol) of compound Id and 47 mg
(0.26 mmol) of N-2,4,6-trimethylphenylacetamide in
1 ml of HSO3F at –30°C in 1.25 h. Yield 20 mg (29%).
Oily substance. 1H NMR spectrum, δ, ppm: 1.80 s (3H,
Me), 1.97 s (3H, Me), 2.01 s (3H, Me), 2.18 s (3H, Me),
2.25 s (3H, Me), 2.33 s (3H, Me), 6.82 s (1H, =CH–),
(E)-Methyl 3-(4-acetylamino-2,3,5,6-tetramethyl-
phenyl)-3-(4-methylphenyl)propenoate (IIIm) was
obtained from 30 mg (0.17 mmol) of compound Ib and
31 mg (0.16 mmol) of N-2,3,5,6-tetramethylphenyl-
acetamide in 1 ml of HSO3F at –75°C in 0.75 h. Yield
1
19 mg (32%), mp 180–185°C (decomp.). H NMR
6.87 s (1Harom), 7.10 d (2Harom, J 8.3 Hz), 7.23 d (2H-arom
,
J 8.3 Hz). Mass spectrum, m/z (Irel, %): 335 (40) [M]+,
320 (47), 317 (23), 292 (100), 278 (34), 250 (47), 234
(32), 135 (82). Found, %: C 78.56; H 7.54; N 4.10.
C22H25NO2. Calculated, %: C 78.77; H 7.51; N 4.18.
M 335.19.
spectrum, δ, ppm: 2.13 s (12H, 4Me), 2.23 s (3H, Me),
2.33 s (3H, Me), 3.68 s (3H, OMe), 5.81 s (1H, =CH–),
6.69 br.s (1H, NH), 7.07 d (2Harom, J 8 Hz), 7.16 d
(2Harom, J 8 Hz). Mass spectrum, m/z (Irel, %): 365 (100)
[M]+, 350 (34), 334 (13), 322 (30), 290 (21), 248 (25).
Found, %: C 75.58; H 7.60; N 3.79. C23H27NO3.
Calculated, %: C 75.59; H 7.45; N 3.83. M 365.20.
The generation and registering at –80°C of 1H NMR
spectra in HSO3F of ions IV and VII obtained from
compounds E-IIp and VI respectively was performed as
in [6]. The preparation and characteristics of (Z)-4-
(pentamethylphenyl)-4-phenylbut-3-en-2-one (VI) were
described before [8].
(E)-Methyl 3-(6-tert-butyl-3-acetylamino-2,4-
dimethylphenyl)-3-(4-methylphenyl)propenoate (IIIj)
was obtained from 25 mg (0.14 mmol) of compound Ib
and 29 mg (0.13 mmol) of N-4-tert.-butyl-2,6-dimethyl-
phenylacetamide in 1 ml of HSO3F at –75°C in 0.75 h.
1
Yield 35 mg (67%), mp 150°C (decomp.). H NMR
spectrum (CDCl3), δ, ppm: 1.24 s (9H, CMe3), 2.03 s
(3H, Me), 2.18 s (3H, Me), 2.25 s (3H, Me), 2.30 s (3H,
Me), 3.71 s (3H, OMe), 5.84 s (1H, =CH–), 6.74 br.s
3-(3-Ammonio-2,5,6-trimethylphenyl)-1-hydroxy-
3-(4-methylphenyl)-1-methoxyprop-2-en-1-ylium IV).
1H NMR spectrum (HSO3F), δ, ppm: 2.20 s (6H, 2Me),
2.38 s (3H, Me), 2.81 s (3H, Me), 4.41 s (3H, OMe),
(1H, NH), 7.04 d (2Harom, J 8.3 Hz), 7.17 d (2Harom
,
J 8.3 Hz), 7.28 s (1H-arom). Mass spectrum, m/z (Irel, %):
393 (25) [M]+, 336 (100), 333 (17), 304 (20), 219 (22),
43 (77). Found, %: C 76.47; H 7.90; N 3.56. C25H31NO3.
Calculated, %: C 76.30; H 7.94; N 3.56. M 393.23.
+
6.41 s (1H, =CH–), 7.34 s (1Harom), 7.39 s (3H, NH3 ),
7.62 s (1Harom), 7.69 s (1Harom), 8.22 s (1Harom), 8.30 s
(1Harom), 12.49 s (1H, C+–OH).
(E)-Methyl 3-(3-acetylamino-2,5,6-trimethyl-
phenyl)-3-(4-methylphenyl)propenoate (IIIk) and (E)-
methyl 3-(2-acetylamino-3,5,6-trimethylphenyl)-3-(4-
methylphenyl)propenoate (IIIl) were obtained from
30 mg (0.17 mmol) of compound Ib and 31 mg
(0.17 mmol) of N-2,4,5-trimethylphenylacetamide in
1 ml of HSO3F at –75°C in 0.75 h as a crystalline isomers
mixture of mp 148–152°C.
2-Hydroxy-4-pentamethylphenyl-4-phenylbut-3-
1
en-2-ylium (VII). H NMR spectrum (HSO3F), δ, ppm:
2.16 s (6H, 2Me), 2.49 s (6H, 2Me), 2.26 s (3H, Me),
3.32 s (3H, Me), 7.66 d (2HO, J 7 Hz), 7.72 t (2Hm,
J 7 Hz), 8.01 t (1Hï, J 7 Hz), 8.33 s (1H, =CH–).
REFERENCES
1
Compound E-IIIk. Yield 12 mg (20%). H NMR
1. Reutov, O.A., Kurts, A.L., and Butin, K.P.,
Organicheskaya khimiya (Organic Chemistry), Moscow:
Binom, 2004, vol. 3, p. 273; Joule, J.A. and Mius, K.,
Heterocyclic Chemistry, New York: Chapman & Hall,
1994. Gilchrist, T.L., Heterocyclic Chemistry, London:
Marshfield, Mass.: Pitman, 1985.
2. Reutov, O.A., Kurts, A.L., and Butin, K.P.,
Organicheskaya khimiya (Organic Chemistry), Moscow:
Binom, 2004, vol. 4, p. 554; Soldatenkov, A.T., Kolyadi-
na, N.M., and Shendrik, I.V., Osnovy organicheskoi khimii
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 2.13 s (3H, Me), 2.15 s (6H, 2Me), 2.24 s (3H,
Me), 2.32 s (3H, Me), 3.69 s (3H, OMe), 5.80 s (1H,
=CH-), 6.96 br.s (1H, NH), 7.04 s (1H-arom), 7.05–
7.10 m (2Harom), 7.13 d (2Harom, J 8.1 Hz).
1
Compound E-IIIl. Yield 10 mg (16%). H NMR
spectrum, δ, ppm (extracted from the spectrum of isomers
mixture): 1.94 s (3H, Me), 2.06 s (3H, Me), 2.09 s (3H,
Me), 2.23 s (3H, Me), 2.31 s (3H, Me), 3.67 s (3H, OMe),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

ALKENYLATION OF ARYLAMINES AND N-ARYLACETAMIDES
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ko, A.P., Zh. Org. Khim., 2007, vol. 43, p. 696.
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etaud, M.-P., New J. Chem., 1990, vol. 14, p. 283.
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19. Cavechenkov, P.Yu., Vasil’ev, A.V., and Rudenko, A.P.,
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Sommer, J., Eur. J. Org. Shem., 2007, p. 5740.
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