Reactions of acetylene ketones in superacids

Article abstract of DOI:10.1134/S1070428007050107

Vinyl type cations ArC⁺=CHCOR generated from acetylene ketones ArC⁺ = CCOR in superacids HSO₃F and CF₃SO ₃H react with diverse benzene derivatives to form alkenylation products, E-/Z-isomers of diaryl

Full text of DOI:10.1134/S1070428007050107

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 5, pp. 691−705. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © S.A. Aristov, A.V. Vasil’ev, G.K. Fukin, A.P. Rudenko, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 5,
pp. 696−710.
Dedicated to Professor V.A.Ostrovskii on occasion of his sixtieth birthday
Reactions of Acetylene Ketones in Superacids
S. A. Aristova, A. V. Vasil’eva, 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, Nizhnii Novgorod, Russia
Received December 6, 2006
Abstract—Vinyl type cationsArC+=CHCOR generated from acetylene ketonesArC≡CCOR in superacids HSO3F
and CF3SO3H react with diverse benzene derivatives to form alkenylation products, E-/Z-isomers of
diarylpropenone structures Ar(Ar')C=CHCOR. The alkenylation of aromatic compounds with acetylene ketones
in superacids occurs with the primary syn-addition of a hydrogen and an aryl residue to the acetylene bond
followed by transformation of the product into anti-isomer under the conditions of the reaction.
DOI: 10.1134/S1070428007050107
derivatives: 4-arylbut-3-yn-2-ones Ia–Ig, 1,3-diaryl-
propynones IIa and IIb, 4-(4-methylphenyl)-1,1,1-tri-
fluorobut-3-yn-2-one (IIIa), and also of ethyl 4-aryl-2-
oxobut-3-ynoates IVa–IVc and diethyl (arylethynyl)-
phosphonates Va and Vb.
A special attention paid in the organic chemistry to
acetylene ketones is caused by the multitude of their
chemical characteristics and transformations [1], and also
by their biological action [2]. New opportunities were
opened in the chemistry of acetylene derivatives by the
application of superacid media (HSO3F, CF3SO3H, HF/
SbF5) where the protonation of a triple carbon-carbon
bond led to the formation of highly reactive vinyl type
carbocations [3–9].
O
O
C C C
C C C
Me
Ph
R
R
Iа_Ig
IIа, IIb
This report concerns the generation in superacids
HSO3F and CF3SO3H of vinyl type cations A from
acetylene ketones I (Scheme 1) and the study of ions A
reaction with benzene derivatives proceeding by the
electrophilic substitution mechanism and providing
products of aromatic ring alkenylation E-/Z-B.
O
O
C C C
Me
C C C
CO2Et
CF3
R
IIIа
IVа_IVc
O
In this study the protonation and reactions in super-
acids were investigated of the following acetylene
C C PH(OEt)2
R
Vа, Vb
Scheme 1.
I, R = H (a), 4-Me (b), 2,4-Me2 (c), 2,4,6-Me3 (d),
2,3,5,6-Me4 (e), Me5 (f), 4-MeO (g); II, R = 2,4-Me2 (a),
2,4,6-Me3 (b); IV, R = 4-Me (a), 2,4,6-Me3 (b), 4-MeO
(c); V, R = 2,4,6-Me3 (a), 4-MeO (b).
O
O
H+ (superacid)
C
C C C
C C
H
I
The protonation of 4-phenylbut-3-yn-2-one (Ia)
1
studied by H and 13C NMR spectroscopy showed that
А
O
this acetylene ketone in HSO3F both at –80 and 0°C exist-
ed as a stable ion PhC≡C–C(OH)+Me C O-protonated at
the carbonyl group (see EXPERIMENTAL). In HSO3F
even at 0°C cation C did not react with benzene, 1-methoxy-
4-fluorobenzene, and 1-acetyl-2,3,5,6-tetramethylbenz-
C
ArH
_H+
C C
Ar
H
E-/Z-B
691

ARISTOV et al.
692
С37
С33
protonation compared to compound Ia. In HSO3F at
–30°C ketone Ib was protonated at the acetylene atom
C3 and quickly transformed into fluorosulfonate
(4-MeC6H4)(FO2SO)C=CHCOMe Z-(VI) (see EXPERI-
MENTAL), a product of anti-addition of the fluoro-
sulfonic acid to the triple carbon-carbon bond. A similar
formation of anti-adducts resulting from the isomeriza-
tion of the primarily arising syn-products of fluoro-
sulfonic and trifluoromethanesulfonic acids addition to
the acetylene bond of 3-arylpropynic acids derivatives
we observed before [9].
С32
С31
С36
С34
С35
С18
С38
С30
С21
С22
С14
С13
С15
С16
С19
O2
С23
С24
С12
С20
С11
С10
С25
С26
H22
С29
С9
С2
The introduction of two or more methyl groups into
the aromatic ring of acetylene compounds I–V sig-
nificantly increases the nucleophilicity of the aromatic
π-system.As a result vinyl type cations A1–3 (Scheme 2)
generated in HSO3F from trimethyl derivatives Id, IIb,
and Va despite the sterical hindrances attacked the
aromatic rings of the initial substrates forming dimers
Ε-(VIIa–VIIc), products of syn-addition of hydrogen and
aryl moiety to the acetylene bond; in this case fluoro-
sulfonates were not obtained.
С8
O1
С28
С3
С27
С4
С7
С6
С5
Fig. 1. Molecular structure of (E)-3-(2,4,6-trimethylphenyl)-
3-[2,4,6-trimethyl-3-(phenylcarbonylethynyl)phenyl]-1-
phenylpropenone E-(VIIb).
ene. In superacids the reactivity is demonstrated by the
C-protonated forms of the acetylene carbonyl com-
pounds, vinyl type cations A (Scheme 1) [3–5, 9].
X-Ray diffraction analysis demonstrated that com-
pound Ε-VIIb possessed a double C=C bond of Ε-con-
figuration. An interesting feature of the Ε-VIIb dimer
structure is no distortion in its geometric parameters near
the sterically overloaded C21 atom (Fig. 1). This atom
has a traditional planar trigonal surrounding character-
The presence in the aromatic ring of acetylene ketone
Ib of an electron-donor methyl group increased the
basicity of the triple bond C≡C and facilitates its
Scheme 2.
Me
Me
X
+
HSO3F
_75... _50oC, 0.3_1 h
C C X
Me
C C
Me
H
Me
Me
_
Id, IIb, Vа
А1 3
Me
Me
Me
X
H C C
Me
Id, IIb, Vа
Me
Me
X
H
Me
Me
C C
H
Me
_H+
+
Me
Me
C
Me
C
C
C
X
X
_
D1 3
syn-E-VIIа (53%), b (60%), c (10%)
X = COMe (A1, D1, Ε-VIIa), COPh (A2, D2, Ε-VIIb), PO(OEt)2 (A3, D3, Ε-VIIc).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

REACTIONS OF ACETYLENE KETONES IN SUPERACIDS
693
Scheme 3.
Me
Me
O
C Ph
H
Me
Me
Me
Me
C C
C C
+
Me
O
HSO3F
_20oC, 0.5 h
H
C Ph
C C C
Me
O
Ph
IIа
Me
C
C
Me
C
C
C Ph
C Ph
O
O
syn-E-VIId, 14%
anti-Z-VIId, 14%
istic of sp2-hybridized carbon atoms. The distances
at relatively high temperature (–20°C) evidently due to
the presence in the structure of these compounds of
electron-withdrawing groups –(Ar)C=CHX [X = COMe,
COPh, PO(OEt)2] reducing the basicity of the acetylene
bond.
C21–C15, C21–C30, and C21–C22 are 1.509(2), 1.503(2),
°
and 1.350(2) A respectively and are characteristic of
ordinary C–C and double C=C bonds [10]. Aromatic
rings at C21 atom are virtually perpendicular to each other
(92.6 deg), and this position considerably reduces their
mutual nonvalence interactions. The molecules of
compound Ε-VIIb in the crystal form centrosymmetrical
dimers owing to the interaction O1...H22 of the neighbor
molecules (Fig. 2). The O1...H22 distances amount to
2.31(3) A that is somewhat less than van der Waals
contacts O...H [11].
In the presence of alien π-nucleophiles (substituted
benzene molecules) ion A4 obtained from ketone Ib in
HSO3F and CF3SO3H at –30°C did not form fluoro-
sulfonate Z-VI (see above), but reacted with aromatic
compounds leading to the formation of alkenylation
Scheme 4.
O
On keeping a solution of dimethyl-substituted ketone
IIa in HSO3F at –20°C for 0.5 h a mixture was obtained
of isomeric dimers E-/Z-VIId in 1:1 ratio (Scheme 3).
Me
C C C
Me
Ib
O
It should be noted that the triple bond C≡C in dimers
Ε-/Z-VIIa–VIId is inert to protonation by HSO3F even
C Me
HSO3F or CF3SO3H
_30oC
Me
C C
H
A4
Me
Me
O1A
R
O
22B
H
C Me
A
O2
+
C C
C C
O2B
A
H22
_H+
C Me
H
1
B
O
O
R
R
anti-E-VIIIа (42%),
Z-VIIIb (24%),
c (47%), d (30%)
syn-Z-VIIIа (42%),
E-VIIIb (24%), d (30%)
Fig. 2. A fragment of crystal lattice of (E)-3-(2,4,6-trimethyl-
phenyl)-3-[2,4,6-trimethyl-3-(phenylcarbonylethynyl)-
phenyl]-1-phenylpropenone E-(VIIb).
R = H (a), 4-MeO (b), 4-MeCO-2,3,5,6-Me4 (c),
3,4-Cl2 (d).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

ARISTOV et al.
694
O1
Scheme 5.
Me
C7
C2
C4
R
C1
O
C3
C6
Me
+
C C C
Me
H9
C9
C5
C18
C13
Ic
Me
Me
Me
C8
O2
C12
C10
O
C22
C14
C15
C20
C Me
H
C19
HSO3F
_75oC, 1_2 h
C17
C16
C21
C11
+
C C
Me
C C
H
C Me
O
R
R
Fig. 3. Molecular structure of (Z)-4-(4-methoxyphenyl)-4-
(pentamethylphenyl)but-3-en-2-one Z-(XIVb).
syn-Z-IXа (51%),
E-IXb (17%)
anti-E-IXа (25%),
Z-IXb (34%)
R = 3,4-MeO2 (a), 2-MeO-5-F (b).
products E-/Z-VIIIa–VIIId (Scheme 4). We did not
enumerate the initial substituted benzenes presented in
Schemes 4–14 since their structure was unambiguously
determined by the substituents in the aryl fragments of
the final alkenylation products Ar(Ar')C=CHCOR.
of ketone Id with methoxybenzene in HSO3F at –50°C
(Scheme 6). The attempt to carry out isomerization of
the isolated individual substance Z-X in HSO3F at
a higher temperature (–30°C) resulted in sulfofluorinated
product Z-XI. A partial isomerization into the E-form of
compound X (see EXPERIMENTAL) succeeded at the
use of CF3SO3H acid devoid of sulfonation properties
(Scheme 6).
The precise E-/Z-configuration of 4,4-diarylbutenones
Ar(Ar')C=CHCOMe E-/Z-VIIIa–VIIId–XVa–XVd
presented in Schemes 4–10 was established by X-ray dif-
fraction analysis (for compound Z-XIVb, Fig. 3) and
1H NMR spectroscopy. The reference signal used for
stereochemical estimation of E-/Z-configuration was the
resonance of the vinyl proton at the double bond =C=CH–.
The signal of the vinyl protons of E-isomers is observed
mostly upfield, at δ 6.00–6.53 ppm, and that of Z-isomers
downfield, in the region δ 6.46–6.90 ppm (see a similar
dependence for related structure in [5, 12, 13]).
We failed to obtain alkenylation product of 1-acetyl-
2,3,5,6-tetramethylbenzene with ketone Id for the
intermediately formed vinyl type cation A1 attacked the
aromatic ring of initial compound Id giving dimer
E-VIIa (Scheme 2) and did not react with the π-system
of the above benzene derivative whose nucleophilicity
is reduced by the presence in the structure of the acetyl
group.
The greater number of alkyl substituents and the
presence of a strong electron-donor methoxy group at
the aromatic ring of arylacetylene ketonesArC≡CCOMe
facilitated the protonation of the triple bond C≡C.
Dimethyl-substituted ketones and those with more methyl
substituents Ic–If and also methoxy derivative Ig are
protonated in HSO3F and react with aromatic compounds
at lower temperature (–75...–50°C) than monomethyl-
substituted ketone Ib (–30°C, Scheme 4).
The π-system of a benzene molecule possesses higher
π-nucleophilicity than the tetra-substituted aromatic ring
of compound IIb, and the reaction of benzene with cation
A2 gives rise to alkenylation product Z-XII (Scheme 7)
and not the corresponding dimer E-VIIb (cf. with
Scheme 2).
Acetylene ketones Ie and If, tetra- and pentamethyl-
substituted in the aromatic ring, in HSO3F (–75°C) and
CF3SO3H (20°C) in reaction with methoxybenzene and
benzene gave stereoselectively only the products of syn-
addition Z-XIII, Z-XIVa, and Z-XIVb (Schemes 8 and
9). The structure of compound Z-XIVb was established
by X-ray diffraction analysis (Fig. 3).
Ketone Ic in HSO3F reacted with methoxy-substituted
benzenes (Scheme 5) giving mixtures of E-/Z-isomers
of compounds IXa and IXb as products of syn- and anti-
addition to the triple bond C≡C.
A stereochemically pure product of syn-addition to
the acetylene bond, adduct Z-X, was obtained by reaction
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

REACTIONS OF ACETYLENE KETONES IN SUPERACIDS
695
Scheme 6.
Me
Me
SO2F
Me
O
C Me
C C
Me
H
OMe
Me
O
Me
Me
MeO
Me
O
HSO3F
_50oC, 20 min
C Me
Me
Z-XI, 96%
+
Me
C C C
Me
C C
H
Me
Id
MeO
H
Me
syn-Z-X, 53%
C C
C Me
O
MeO
anti-E-X
Scheme 7.
Me
Me
Me
O
Me
O
Me
Me
C Ph
O
CF3SO3H
+
C Ph
Me
C C
Me
C C C
_H+
10oC
C C
Ph
H
H
Me
IIb
A2
Scheme 8.
syn-Z-XII, 62%
Me
OMe
Me
Me
O
Me
Me
O
HSO3F
_75oC, 0.5 h
C Me
Me
+
C C C
Me
C C
H
Me
Me
Ie
MeO
syn-Z-XIII, 9%
Similar to the structure of Ε-VIIb (Fig. 1) the
corresponding olefin atom C8 in compound Z-XIVb
possesses planar trigonal surrounding typical of sp2-
hybridized carbon. The pentamethylphenyl ring is located
nearly normal (92.3 deg) to the plane of the fragment
C1-11–O1,2 (Fig. 3). Besides in the structure of Z-XIVb
the dihedral angle between the planes of the fragments
C8–C9–H9 and C8–C4–C3 is 174.9 deg. Therefore the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

ARISTOV et al.
696
vinyl atom H9 is located “at the side” of the methoxy-
phenyl ring in the region of proton deshielding. This
proton in the 1H NMR spectrum gives rise to a downfield
signal at δ 6.77 ppm (see EXPERIMENTAL) character-
istic of Z-isomers of 4,4-diarylbutenones E-/Z-VIIIa–
VIIId–XVa–XVd (see above).
Acetylene derivatives IVa–IVc containing both keto
and ester groups reacted with methoxybenzene in
superacids to give alkenylation products E-/Z-XVIa–
XVc (Scheme 11).
On keeping solutions of acetylene compounds IVa
and IVc in HSO3F in the absence of “alien” aromatic
substrates in the reaction mixture followed by treating
with hydrochloric acid cooled to –70°C we obtained enol
forms XIXa and XIXc of the corresponding oxoacids
XVIIIa and XVIIIc arising through hydrolysis of
the intermediate fluorosulfonates XVIIa and XVIIc
(Scheme 12). The stable existence of these enol forms is
characteristic of various aromatic ketoacids [15].
Methoxy-substituted ketone Ig reacted with benzene
in a system CF3SO3H–CH2Cl2 (–30°C) providing
a mixture of isomers Z-XVa and E-XVb in a ratio 2:1 in
overall yield 98% (Scheme 10). In HSO3F at –75°C in
reaction with sterically hindered substrates compound
Ig led to the formation of anti-addition adducts Z-XVc
and Z-XVd (Scheme 10).
On the other hand the vinyl type cation generated in
HSO3F at –75°C from acetylene ketone Ig did not react
with the pentamethylbenzene that existed in HSO3F
in a form of arenonium ion [14].
Similar to acetylene carbonyl derivatives Ib–Ig, IIa
and IIb, IVa–IVc (see also [5]) acetylene phosphonates
Va and Vb reacted with aromatic compounds in
Scheme 9.
Me
Me
Me
Me
Me
O
Me
Me
Me
Me
R
O
HSO3F or CF3SO3H
C Me
Me
+
C C C
C C
Me
H
Iе
R
syn-Z-XIVа (68%),
b (40%)
R = H (a), 4-MeO (b).
Scheme 10.
MeO
MeO
O
R
H
O
C Me
HSO3F or CF3SO3H
C C
+
MeO
+
C C C
C C
C Me
Me
H
O
Ig
R
R
syn-Z-XVа (65%),
b (70%)
anti-E-XVа (33%),
Z-XVc (10%), d (45%)
R = H (a), 4-MeO (b), 4-MeCO-2,3,5,6-Me4 (c), 4-SO2F-2,3,5,6-Me4 (d).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

REACTIONS OF ACETYLENE KETONES IN SUPERACIDS
697
carbonyl group activated by protonation in HSO3F [16–
18] on the aromatic ring of the 1,4-dimethylbenzene.
superacids via formation of vinyl type cations A5,6
(Scheme 13).
The characteristic feature of the addition to acetylene
bond in superacids at low temperature is the primary
formation of adducts originating from the syn-addition
that under the reaction conditions can isomerize into the
Trifluoromethylketone IIIa in reaction with 1,4-di-
methylbenzene in HSO3F gave rise to indenol XXI
(Scheme 14). In this event an additional electrophilic
attack occurred of C2 atom from the trifluoromethyl-
Scheme 11.
R
R
OMe
O
H
O
HSO3F or CF3SO3H
C CO2Et
C C
+
+
C C C
C C
R
C CO2Et
CO2Et
H
O
IVа_IVc
MeO
MeO
anti-Z-XVIа, 18%
syn-E-XVIа (18%),
Z-XVIb (19%), XVIbc
(27%)
R = 4-Me (a), 2,4,6-Me3 (b), 4-MeO (c).
Scheme 12.
R
O
O
HSO3F
R
C C C
C CO2Et
H
CO2Et
C C
FO2SO
IVа, IVc
XVIIа, XVIIc
OH
O
C
O
O
C
H2O, HCl
C
C
H
C
CO2H
C
CO2H
H2
R
R
XVIIIа, XVIIIc
XIXа (85%), XIXc (20%)
R = Me (a), MeO (c).
Scheme 13.
R
OMe
O
P(OEt)2
C C
H
O
O
P(OEt)2
H
HSO3F
_75oC
R
C C
C C P(OEt)2
_H+
R
Vа, Vb
A5,6
MeO
syn-Z-XXа (28%), syn-Z-XXb
(20%)
R = 2,4,6-Me3 (A5, XXa), 4-MeO (A6, XXb).
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ARISTOV et al.
698
In X-ray experiments the sets of reflections intensities
were measured on an automatic diffractometer Smart
Apex (graphite monochromator, MoKα radiation, ω-θ
scanning). The structures were solved by the direct
products of anti-type [5, 9]. In alkenylation of benzene
derivatives in superacids the acetylene ketones first also
provide products of syn-addition to the triple C≡C bond
that convert into anti-isomers in superacids at higher
temperature as has been demonstrated by an example of
isomerization of compound Z-X into E-X in CF3SO3H
at 20°C (Scheme 6). The alkenylation at higher tempera-
ture in HSO3F (–30...–20°C) (Scheme 3; E-/Z-VIIIb and
E-/Z-VIIId in Scheme 4) or in CF3SO3H (–30°C) (E-/Z-
XVa in Scheme 10; E-/Z-VIIIa in Scheme 4; E-/Z-XVIa
in Scheme 11) commonly resulted in the formation of a
mixture of E-/Z-isomers. The presence of three and more
methyl groups (with two of them located in the ortho-
position) in one of the aromatic rings of the final
alkenylation products prevented the isomerization of the
primarily formed syn-adducts into the anti-forms
(Schemes 1, 6–9) even at relatively high temperature,
10–20°C (compounds Z-XII and Z-XIVa). On the other
hand, the presence in the composition of the final
products of methoxy-substituted benzene rings facilitated
the isomerization (Schemes 5 and 10).
method and refined by least-squares procedure for F2
hkl
in aniso-tropic approximation for all nonhydrogen atoms.
The hydrogen atoms were found from the difference
Fourier synthesis and were refined isotropically. All
calculations were performed applying software package
SHELXTL v. 6.10 [19].
A single crystal of compound E-VIIb of the size
0.28×0.28×0.25 mm for X-ray diffraction study was
grown by slow evaporation of the methanol solution of
the compound at room temperature within several days.
Crystals of C36H32O2 at 100 K triclinic, a 8.5188(7),
°
b 12.3964(10), c 12.6157(10) A, α 89.481(2), β
°
80.585(2), γ 85.958(2)°, V 1311.03(18) A3, Z 2, space
group P-1, dcalc 1.258 g/cm3, μ 0.076 mm–1, 1.64 ≤ θ ≤
29.19°, 9789 reflections were measured, 6833 among
them independent (Rint 0.0184), R1 0.0597 [I > 2σ(I)],
wR2 0.1563 (for all reflections).
A single crystal of compound Z-XIVb of the size
0.32×0.13×0.12 mm for X-ray diffraction study was
grown by slow evaporation of the compound solution in
a mixture hexane–ethyl acetate at room temperature
within several days. Crystals of C22H26O2 at 100 K mono-
The findings presented in this study show that vinyl
type cations ArC+=CHCOR generated in superacids
HSO3F and CF3SO3H from arylacetylene ketones
ArC≡CCOR (R = Ar, Me, CO2Et) react efficiently
(reaction time 15–120 min, yields up to 98%), regio-
selectively and often stereoselectively with benzene
derivatives forming diarylpropenone structures
Ar(Ar')C=CHCOR.
°
clinic, a 8.8758(6), b 14.5332(9), c 14.1883(9) A,
°
β 101.864(1)°, V 1791.1(2)
A
3, Z 4, space group P2(1)/C,
dcalc 1.196 g/cm3, μ 0.075 mm–1, 2.03 ≤ θ ≤ 26.00°, 10608
reflections were measured, 3511 among them independ-
ent (Rint 0.0213), R1 0.0422 [I > 2σ(I)], wR2 0.1119 (for
all reflections).
EXPERIMENTAL
4-Arylbut-3-yn-2-ones Ia–Ig were synthesized by
procedure [20]. Preparation and characteristics of
4-phenylbut-3-yn-2-one (Ia), 4-(4-methylphenyl)but-3-
yn-2-one (Ib), 4-(2,4-dimethylphenyl)but-3-yn-2-one
(Ic), and 4-(4-methoxyphenyl)but-3-yn-2-one (Ig) we
published before [21].
1H and 13C NMR spectra were registered on a
spectrometer Bruker AM-500 at operating frequencies
500 and 125.76 MHz respectively from solutions in
CDCl3 and (CD3)2SO. As internal references served the
residual signals of CHCl3 (δ 7.25 ppm) and
(CD3)(CD2H)SO (δ 2.50 ppm) in the 1H NMR spectra,
and the signals of solvents CDCl3 (δ 77.0 ppm) and
(CD3)2SO (δ 39.52 ppm) in the 13C NMR spectra. IR
spectra of compounds solutions in CHCl3 were recorded
on a spectrophotometer Specord 75IR. Mass spectra were
taken on MKh-1321 device, ionizing electrons energy
70 eV, direct sample admission into the ion source at
4-(2,4,6-Trimethylphenyl)but-3-yn-2-one (Id).
1
Yield 60%, mp 35–37°C. H NMR spectrum (CDCl3),
δ, ppm: 2.29 s (3H, CH3CO), 2.43 s (6H, 2CH3), 2.46 s
(3H, CH3), 6.89 s (2Harom). Found, %: C 83.75; H 7.43.
C13H14O. Calculated, %: C 83.83; H 7.58.
4-(2,3,5,6-Tetramethylphenyl)but-3-yn-2-one (Ie).
1
Yield 25%, mp 93–94°C. H NMR spectrum (CDCl3),
δ, ppm: 2.22 s (6H, 2CH3), 2.38 s (6H, 2CH3), 2.48 s
(3H, CH3CO), 7.01 s (1H, Harom). Found, %: C 84.06;
H 8.20. C14H16O. Calculated, %: C 83.96; H 8.05.
100–120°C. H and 13C NMR spectra in HSO3F were
1
measured on a spectrometer Bruker Avance 400 at
operating frequencies 400 and 100 MHz respectively,
internal reference CH2Cl2, δH 5.32, δC 53.84 ppm.
4-(2,3,4,5,6-Pentamethylphenyl)but-3-yn-2-one
1
(If). Yield 20%, mp 78–80°C. H NMR spectrum
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REACTIONS OF ACETYLENE KETONES IN SUPERACIDS
699
(CDCl3), δ, ppm: 2.18 s (3H, CH3), 2.20 s (6H, 2CH3),
2.45 s (3H, CH3), 2.47 s (6H, 2CH3). Found, %: C 84.15;
H 8.61. C15H18O. Calculated, %: C 84.07; H 8.47.
87.76 C, 99.71 t (J 5 Hz), 110.70 t (J 8 Hz), 111.58 d.d
(J 161, 4 Hz), 136.06 d.d (J 163, 7 Hz), 159.44 t
(J 2.2 Hz), 162.65 m, 169.25 C. Found, %: C 67.30;
H 5.36. C13H12O4. Calculated, %: C 67.23; H 5.21.
1,3-Diarylpropynones IIa and IIb were synthesized
by procedure [22]. Preparation and characteristics of
3-(2,4,6-trimethylphenyl)-1-phenylpropynone (IIb) we
published before [4].
The preparation and characteristics of diethyl (2,4,6-
trimethylphenylethynyl)phosphonate (Va) and diethyl
(4-methoxyphenylethynyl) phosphonate (Vb) we report-
ed before [25].
3-(2,4-Dimethylphenyl)-1-phenylpropynone (IIa).
1
Yield 56%, mp 57–59°C. H NMR spectrum (CDCl3),
Generation of 2-hydroxy-4-phenylbut-3-yn-2-
ylium C in HSO3F. To 0.8 ml of HSO3F (mp –89°C)
frozen in an NMR tube at –110°C (ethanol–liquid nitro-
gen) was added 30 mg of compound Ia. The temperature
was raised to –78°C, into the ampule was inserted to the
bottom a Teflon capillary of 1 mm internal diameter, and
a weak flow of argon was passed through the capillary
for 10 min till the formation of a homogeneous solution
of ion C. The capillary was removed, and 3 mg of CH2Cl2
was added. 1H NMR spectrum (HSO3F, –80°C), δ, ppm:
3.12 s (3H, Me), 7.68 t (2Hm, J 8.0 Hz), 7.92 t (1Hï ,
δ, ppm: 2.36 s (3H, CH3), 2.55 s (3H, CH3), 7.04 d
(1Harom, J 7.8 Hz), 7.10 s (1Harom), 7.51 t 2Harom, J 7.6
Hz), 7.54 d (1Harom, J 7.8 Hz), 7.61 t (1Harom, J 7.6 Hz),
8.22 d (2Harom, J 7.6 Hz). Found, %: C 87.18; H 5.90.
C17H14O. Calculated, %: C 87.15; H 6.02.
4-(4-Methylphenyl)-1,1,1-trifluorobut-3-yn-2-one
(IIIa) was obtained as in [23]. Yield 40%, oily substance.
1H NMR spectrum (CDCl3), δ, ppm: 2.42 s (3H, Me),
7.25 d (2Harom, J 7.9 Hz), 7.56 d (2Harom, J 7.9 Hz). Found,
%: C 62.25; H 3.30. C11H7F3O. Calculated, %: C 62.27;
H 3.33. Ethyl 4-aryl-2-oxobut-3-ynoates IVa–IVc were
prepared by procedure [24].
1
J 8.0 Hz), 8.01 d (2Ho, J 8.0 Hz). H NMR spectrum
(HSO3F, 0°C), δ, ppm: 3.15 s (3H, Me), 7.71 t (2Hm,
J 8.0 Hz), 7.95 t (1Hï , J 8.0 Hz), 8.03 d (2Ho, J 8.0 Hz).
13C NMR spectrum (HSO3F, –80°C), δ, ppm: 29.93 (C1),
92.40 (C2), 116.13 (C3), 130.47 (Co), 136.75 (Ci),
138.35(Cm), 139.13 (Cï ), 202.82 (C2=OH+).
Ethyl 4-(4-methylphenyl)-2-oxobut-3-ynoate (IVa).
Yield 37%, mp 38–40°C. IR spectrum, ν, cm–1: 1680
1
(C=O), 1725 (C=O), 2190 (C≡C). H NMR spectrum
(CDCl3), δ, ppm: 1.41 t (3H, CH3, J 6.9 Hz), 2.40 s (3H,
Alkenylation of aromatic compounds with
arylacetylene derivatives Ia–Ig–Va, and Vb in
superacids HSO3F and CF3SO3H. To a solution of
0.13–1.00 mmol of aromatic compound in 0.5–2.0 ml of
HSO3F or CF3SO3H at –75–20OC while vigorous stirring
was gradually added within 10–30 min 0.09–0.47 mmol
of arylacetylene derivative Ia–Ig–Va, and Vb. The
reaction mixture was stirred for more 5–90 min and then
poured into 15–30 ml of concn. HCl cooled to –70°C.
The mixture obtained was warmed to room temperature
and extracted with chloroform (3×30 ml). The combined
extracts were washed with water, with saturated water
solution of NaHCO3, again with water, dried with
Na2SO4, the solvent was distilled off in a vacuum of
a water-jet pump, and the residue was subjected to
column chromatography on silica gel (eluent petroleum
ether–ethyl acetate). Yield of the final products E-/Z-
VIIa–VIId–XXI was estimated from the weight of the
fractions obtained by chromatography.
CH3), 4.39 q (2H, OCH2, J 6.9 Hz), 7.21 d (2Harom
,
J 7.7 Hz), 7.55 d (2Harom, J 7.7 Hz). 13C NMR spectrum
(CDCl3), δ, ppm: 13.92, 21.80, 63.17, 87.26, 98.87,
115.90, 129.60, 133.84, 142.91, 159.31, 169.50. Found,
%: C 72.27; H 5.63. C13H12O3. Calculated, %: C 72.21;
H 5.59.
Ethyl 4-(2,4,6-trimethylphenyl)-2-oxobut-3-ynoate
(IVb). Yield 18%, mp 62–64°C. IR spectrum, ν, cm–1:
1
1680 (C=O), 1730 (C=O), 2180 (C≡C). H NMR
spectrum (CDCl3), δ, ppm: 1.41 t (3H, CH3, J 7.3 Hz),
2.31 s (3H, CH3), 2.49 s (6H, 2CH3), 4.40 q (2H, OCH3,
J 7.3 Hz), 6.92 s (2Harom). -13C NMR spectrum (CDCl3),
δ, ppm: 13.96, 20.73, 21.64, 63.07, 95.33, 97.28, 115.97,
128.21, 142.50, 144.10, 159.32, 169.17. Found, %: C
73.80; H 6.63. C15H16O3. Calculated, %: C 73.75; H 6.60.
Ethyl 4-(4-methoxyphenyl)-2-oxobut-3-ynoate
(IVc). Yield 30%, mp 53–55°C. IR spectrum, ν, cm–1:
1
1680 (C=O), 1730 (C=O), 2180 (C≡C). H NMR
spectrum (CDCl3), δ, ppm: 1.37 t (3H, CH3, J 7.1 Hz),
3.81 s (3H, OCH3), 4.35 q (2H, OCH2, J 7.1 Hz), 6.88 d
(2Harom, J 8.8 Hz), 7.57 d (2Harom, J 8.8 Hz). -13C NMR
spectrum (CDCl3), δ, ppm: 13.94 q (CH3, J 127 Hz),
55.47 q (OCH3, J 144 Hz), 63.09 t.q (CH2, J 148, 5 Hz),
(Z)-4-(4-Methylphenyl)-4-(fluorosulfonyloxy)but-
3-en-2-one Z-(VI) was obtained by keeping a solution
of 50 mg (0.31 mmol) of compound Ib in 1 ml of HSO3F
at –30°C for 1 h. Yield 65 mg (80%). Oily substance.
1H NMR spectrum (CDCl3), δ, ppm: 2.40 s (6H, 2CH3),
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ARISTOV et al.
700
6.47 s (1H, HC=), 7.27 d (2Harom, J 7.8 Hz), 7.52 d
(1Harom, J 7.8 Hz). Mass spectrum: m/z 258 [M]+. Found,
%: C 67.30; H 5.36. C11H11FO4S. Calculated, %: C 51.16;
H 4.29. M 258.26.
2Me), 3.70–3.78 m (2H, CH2), 3.86–3.94 m (2H, CH2),
4.21 quintet (4H, 2CH2, J 7.1 Hz), 5.83 d (1H, HC=,
J 15.2 Hz), 6.79 s (2Harom), 6.89 br.s (1Harom). Mass
spectrum, m/z (Irel , %): 562 [M + 2]+ (3), 561 [M + 1]+
(14), 560 [M]+ (38), 545 (10), 423 (100), 422 (91), 407
(23), 224 (15), 183 (17). Found, %: C 64.30; H 7.59.
C30H42O6P2. Calculated, %: C 64.27; H 7.55. M 560.25.
(E)-4-[2,4,6-Trimethyl-3-(methylcarbonyl-
ethynyl)phenyl]-4-(2,4,6-trimethylphenyl)but-3-en-2-
one E-(VIIa) was obtained by keeping a solution of 30
mg (0.16 mmol) of compound Id in 0.5 ml of HSO3F at
–50°C for 20 min. Yield 32 mg (53%). Oily substance.
IR spectrum, ν, cm–1: 1620 (C=O), 1685 (C=O), 2200
(C≡C). 1H NMR spectrum (CDCl3), δ, ppm: 1.89 s (3H,
Me), 2.07 s (6H, 2Me), 2.42 s (3H, Me), 2.44 s (3H,
Me), 6.19 s (1H, HC=), 6.83 s (2Harom), 6.91 br.s (1Harom).
Mass spectrum, m/z (Irel , %): 372 [M]+ (3), 357 (100),
171 (7), 43 (30). Found, %: C 83.89; H 7.63. C26H28O2.
Calculated, %: C 83.83; H 7.58. M 372.51.
(E)-3-(2,4-Dimethylphenyl)-3-[2,4-dimethyl-5-
(phenylcarbonylethynyl)phenyl]-1-phenylpropenone
E-(VIId) and (Z)-3-(2,4-dimethylphenyl)-3-[2,4-
dimethyl-5-(phenylcarbonylethynyl)phenyl]-1-
phenylpropenone Z-(VIId) were obtained by keeping
a solution of 110 mg (0.47 mmol) of compound IIa in 1
ml of HSO3F at –20°C for 0.5 h. Oily mixture of isomers
E-VIId [31 mg (14%)] and Z-VIId [31 mg (14%)].
1
Compound E-VIId. H NMR spectrum (CDCl3), δ,
(E)-3-(2,4,6-Trimethylphenyl)-3-[2,4,6-trimethyl-
3-(phenylcarbonylethynyl)phenyl]-1-phenylprope-
none E-(VIIb) was obtained by keeping a solution of
74 mg (0.3 mmol) of compound IIb in 1.5 ml of HSO3F
at –50°C for 0.5 h. Yield 89 mg (60%), mp 182–184°C.
IR spectrum, ν, cm–1: 1620 (C=O), 1650 (C=O), 2180
(C≡C). 1H NMR spectrum (CDCl3), δ, ppm: 2.08 s (6H,
2CH3), 2.21 s (6H, 2CH3), 2.56 s (6H, 2CH3), 6.75 s
(1H, HC=), 6.98 s (1Harom), 7.40 t (2Harom, J 7.7 Hz),
7.50 t (3Harom, J 7.7 Hz), 7.61 t (1Harom, J 7.2 Hz), 7.91 d
(2Harom, J 7.7 Hz), 8.22 d (2Harom, J 7.2 Hz). 13C NMR
spectrum (CDCl3), δ, ppm: 20.88 q.t (J 126.0, 4.6 Hz),
21.10 q.m (J 127.0, 4.6 Hz), 21.16 q.m (J 125.0, 3.8 Hz),
91.50 s, 95.62 s, 119.36 m , 128.36 d.d (J 161.0, 6.7 Hz),
128.59 d.d (J 161.0, 7.2 Hz), 129.32 d.m (J 155.0,
5.5 Hz), 129.43 d.m (J 161.0, 7.2 Hz), 130.63 d.m
(J 151.0, 5.1 Hz), 132.63 d.m (J 152.0, 7.6 Hz),
133.89 d.t (J 158.0, 7.2 Hz), 135.09 m, 136.21 d
(J 4.2 Hz), 137.14 t (J 7.2 Hz), 137.37 q (J 5.9 Hz),
137.83 t (J 7.0 Hz), 138.90 s, 140.37 s, 141.69 d
(J 4.2 Hz), 142.16 d (J 5.0 Hz), 150.69 s, 177.93 s,
191.12 s. Mass spectrum, m/z (Irel , %): 496 [M]+ (8),
481 (100), 391 (15), 248 [M]++ (6), 105 (40), 77 (29). Found,
%: C 87.10; H 6.51. C36H32O2. Calculated, %: C 87.06;
H 6.49. M 496.24.
ppm (extricated from the spectrum of isomers mixture):
2.05 s (3H, CH3), 2.25 s (3H, CH3), 2.33 s (3H, CH3),
2.56 s (3H, CH3), 7.15 s (1H, HC=), 6.87–7.07 m (Harom),
7.47–7.53 m (Harom), 7.88–7.91 m (Harom).
1
Compound Z-VIId. H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
2.14 s (3H, CH3), 2.30 s (3H, CH3), 2.32 s (3H, CH3),
2.52 s (3H, CH3), 7.32 s (Harom), 7.37–7.43 m (Harom),
7.58– 7.63 m (Harom), 8.17–8.21 m (Harom). Mass spec-
trum (isomers mixture), m/z (Irel, %): 468 [M]+ (16), 453
(82), 363 (10), 135 (9), 105 (100), 77 (65). Found, %:
C 87.21; H 6.05. C34H28O2. Calculated, %: C 87.15;
H 6.02. M 468.21.
(E)-(4-Methylphenyl)-4-phenylbut-3-en-2-one E-
(VIIIa) and (Z)-(4-methylphenyl)-4-phenylbut-3-en-
2-one Z-(VIIIa) were obtained from 30 mg (0.19 mmol)
of compound Ib and 44 mg (0.57 mmol) of benzene in
a mixture of 1 ml of CF3SO3H and 0.8 ml of CH2Cl2 at
–30°C in 0.5 h. Oily mixture of isomers E-VIIIa [19 mg
(42%)] and Z-VIIIa [19 mg (42%)].
Compound E-VIIIa. 1H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.89 s (3H, Me), 2.40 s (3H, Me), 6.53 s (1H, HC=),
7.09–7.41 m (9Harom).
Compound Z-VIIIa. 1H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.85 s (3H, Me), 2.35 s (3H, Me), 6.57 s (1H, HC=),
7.09–7.41 m (9Harom). Mass spectrum (isomers mixture),
m/z (Irel, %): 237 [M + 1]+ (12), 236 [M]+ (65), 235 (62),
221 (100), 193 (13), 178 (33), 119 (15), 115 (20), 43
(12). Found, %: C 86.45; H 6.85. C17H16O. Calculated,
%: C 86.40; H 6.82. M 236.12.
(E)-2-(2,4,6-Trimethylphenyl)-2-(2,4,6-trimethyl-
3-phosphonylethynylphenyl)ethenylphosphonate
E-(VIIc) was obtained by keeping a solution of 28 mg
(0.11 mmol) of compound Va in 0.5 ml HSO3F at –75°C
for 1 h. Yield 6 mg (10%). Oily substance. IR spectrum,
1
ν, cm–1: 2170 (C≡C). H NMR spectrum (CDCl3), δ,
ppm: 1.12 t (6H, 2CH3, J 7.1 Hz), 1.39 t (6H, 2CH3,
J 7.1 Hz), 2.18 s (3H, Me), 2.23 s (3H, Me), 2.40 s (6H,
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701
(E)-4-(4-Methylphenyl)-4-(4-methoxyphenyl)but-
3-en-2-one E-(VIIIb) and (Z)-4-(4-methylphenyl)-4-
(4-methoxyphenyl)but-3-en-2-one Z-(VIIIb) were
obtained from 51 mg (0.32 mmol) of compound Ib and
68 mg (0.63 mmol) of methoxybenzene in 1 ml of HSO3F
at –30°C in 0.5h. Oily mixture of isomers E-VIIIb [20
mg (24%)] and Z-VIIIb [20 mg (24%)].
Compound E-VIIIb. 1H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.88 s (3H, Me), 2.35 s (3H, Me), 3.85 s (3H, OMe),
6.48 s (1H, HC=.), 6.92 d (2Harom, J 8.6 Hz), 7.13 d
(2Harom, J 8.3 Hz), 7.14 d (2Harom, J 8.6 Hz), 7.18 d
(2Harom, J 8.3 Hz).
Compound Z-VIIIb. 1H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.85 s (3H, Me), 2.40 s (3H, Me), 3.80 s (3H, OMe),
6.50 s (1H, HC=), 6.83 d (2Harom, J 8.8 Hz), 7.09 d
(2Harom, J 8.0 Hz), 7.21 d (2Harom, J 8.0 Hz), 7.23 d
(2Harom, J 8.8 Hz). Mass spectrum (isomers mixture), m/
z (Irel , %): 266 [M]+ (68), 265 (43), 251 (100), 165 (34),
135 (43), 119 (28), 43 (37). Found, %: C 81.09; H 6.76.
C18H18O2. Calculated, %: C 81.17; H 6.81. M 266.13.
(70 eV, isomers mixture), m/z (Irel, %): 308 [M + 4]+ (3),
306 [M + 2]+ (17), 304 [M]+ (24), 291 (61), 289 (100),
226 (20), 191 (18), 189 (21), 119 (25), 115 (14), 91 (12).
Mass spectrum (18 eV, isomers mixture), m/z (Irel, %):
308 [M + 4]+ (11), 306 [M + 2]+ (62), 304 [M]+ (100),
303 (16), 291 (16), 289 (86), 269 (14), 271 (3). Found,
%: C 66.96; H 4.65. C17H14Cl2O. Calculated, %: C 66.90;
H 4.62. M 304.04.
(E)-4-(2,4-Dimethylphenyl)-4-(3,4-dimethoxy-
phenyl)but-3-en-2-one E-(IXa) and (Z)-4-(2,4-
dimethylphenyl)-4-(3,4-dimethoxyphenyl)but-3-en-2-
one Z-(IXa) were obtained from 50 mg (0.29 mmol) of
compound Ic and 59 mg (0.43 mmol) of 1,2-dimethoxy-
benzene in 0.6 ml of HSO3F at –75°C in 1 h. Oily mixture
of isomers E-IXa [22 mg (25%)] and Z-IXa [45 mg
(51%)].
1
Compound E-IXa. H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
2.01 s (3H, Me), 2.03 s (3H, Me), 2.32 s (3H, Me),
3.78 s (3H, OMe), 3.88 s (3H, OMe), 6.10 s (1H, HC=),
6.73–7.20 m (6Harom).
1
Compound Z-IXa. H NMR spectrum (CDCl3), δ,
(Z)-4-(4-Acetyl-2,3,5,6-tetramethylphenyl)-4-(4-
methylphenyl)but-3-en-2-one Z-(VIIIc) was obtained
from 51 mg (0.32 mmol) of compound Ib and 85 mg
(0.48 mmol) of 1-acetyl-2,3,5,6-tetramethylbenzene in
1 ml of HSO3F at –30°C in 1 h. Yield 50 mg (47%). Oily
ppm (extricated from the spectrum of isomers mixture):
1.74 s (3H, Me), 2.03 s (3H, Me), 2.36 s (3H, Me),
3.82 s (3H, OMe), 3.86 s (3H, OMe), 6.65 s (1H, HC=),
6.73–7.20 m (6Harom). Mass spectrum (isomers mixture),
m/z (Irel, %): 311 [M + 1]+ (10), 310 [M]+ (54), 295 (100),
165 (41). Found, %: C 77.45; H 7.22. C20H22O3.
Calculated, %: C 77.39; H 7.14. M 310.16.
1
substance. H NMR spectrum (CDCl3), δ, ppm: 1.78 s
(3H, Me), 1.98 s (6H, 2Me), 2.13 s (6H, 2Me), 2.34 s
(3H, Me), 2.51 s (3H, Me), 6.86 s (1H, HC=), 7.12 d
(2Harom, J 7.7 Hz), 7.20 d (2Harom, J 7.7 Hz). Mass
spectrum, m/z (Irel, %): 334 [M]+ (10), 319 (35), 290 (10),
275 (15), 247 (25), 43 (100). Found, %: C 82.54; H 7.80.
C23H26O2. Calculated, %: C 82.60; H 7.84. M 334.19.
(E)-4-(2,4-Dimethylphenyl)-4-(2-methoxy-5-
fluorophenyl)but-3-en-2-one E-(IXb) and (Z)-4-(2,4-
dimethylphenyl)-4-(2-methoxy-5-fluorophenyl)but-3-
en-2-one Z-(IXb) were obtained from 50 mg (0.29 mmol)
of compound Ic and 55 mg (0.44 mmol) of 1-methoxy-
4-fluorobenzene in 0.6 ml of HSO3F at –75°C in 2 h.
Oily mixture of isomers E-IXb [15 mg (17%)] and
Z-IXb [30 mg (34%)].
(E)-4-(3,4-Dichlorophenyl)-4-(4-methylphenyl)-
but-3-en-2-one E-(VIIId) and (Z)-4-(3,4-dichloro-
phenyl)-4-(4-methylphenyl)but-3-en-2-one Z-(VIIId)
were obtained from 51 mg (0.32 mmol) of compound Ib
and 94 mg (0.64 mmol) of 1,2-dichlorobenzene in 1 ml
of HSO3F at –30°C in 1.3 h. Oily mixture of isomers
E-VIIId [29 mg (30%)] and Z-VIIId [29 mg (30%)].
1H NMR spectrum (CDCl3), δ, ppm (isomers mixture):
1.89 s (3H, Me), 2.06 s (3H, Me), 2.36 s (3H, Me),
2.41 s (3H, Me), 6.48 s (1H, HC=, E-VIIId), 6.61 s (1H,
HC=, Z-VIIId), 7.05 d.d (1Harom, J 8.2, 1.8 Hz), 7.07 d
(2Harom, J 7.7 Hz), 7.11 d.d (1Harom, J 8.4, 2.1 Hz), 7.15 s
1
Compound E-IXb. H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.79 s (3H, Me), 2.06 s (3H, Me), 2.34 s (3H, Me),
3.77 s (3H, OMe), 6.74 s (1H, HC=), 6.64–7.05 m
(6Harom).
1
Compound Z-IXb. H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
2.07 s (3H, Me), 2.10 s (3H, Me), 2.30 s (3H, Me),
3.72 s (3H, OMe), 6.26 s (1H, HC=), 6.64–7.05 m
(6Harom). Mass spectrum (isomers mixture), m/z (Irel, %):
298 [M]+ (11), 283 (68), 267 (100), 43 (33). Found, %:
(4Harom), 7.22 d (1Harom, J 7.7 Hz), 7.28 d (1Harom
J 1.8 Hz), 7.34 d (1Harom, J 2.1 Hz), 7.38 d (1Harom
,
,
J 8.4 Hz), 7.46 d (1Harom, J 8.2 Hz). Mass spectrum
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ARISTOV et al.
702
C 76.56; H 6.45. C19H19FO2. Calculated, %: C 76.49;
H 6.42. M 298.14.
311 (89), 249 (10), 235 (14), 221 (40), 220 (100), 206
(29), 115 (31), 105 (87), 91 (24), 77 (71). Found, %:
C 88.40; H 6.70. C24H22O. Calculated, %: C 88.31;
H 6.79. M 326.17.
(Z)-4-(4-Methoxyphenyl)-4-(2,4,6-trimethyl-
phenyl)but-3-en-2-one Z-(X) was obtained from 30 mg
(0.16 mmol) of compound Id and 21 mg (0.19 mmol) of
methoxybenzene in 0.5 ml HSO3F at –50°C in 20 min.
Yield 25 mg (53%). Oily substance. 1H NMR spectrum
(CDCl3), δ, ppm: 1.73 s (3H, Me), 2.03 s (6H, 2Me),
2.33 s (3H, Me), 3.80 s (3H, OMe), 6.76 s (1H, HC=),
(Z)-4-(4-Methoxyphenyl)-4-(2,3,5,6-tetramethyl-
phenyl)but-3-en-2-one Z-(XIII) was obtained from
60 mg (0.3 mmol) of compound Ie and 38 mg
(0.36 mmol) of methoxybenzene in 1 ml of HSO3F at
–75°C in 0.5 h. Yield 10 mg (9%). Oily substance.
1H NMR spectrum (CDCl3), δ, ppm: 1.65 s (3H, Me),
1.97 s (6H, 2Me), 2.24 s (6H, 2Me), 3.80 s (3H, OMe),
6.78 s (1H, HC=), 6.82 d (2Harom, J 8.9 Hz), 7.00 s
(1Harom), 7.27 d (2Harom, J 8.9 Hz). Mass spectrum, m/z
(Irel, %): 308 [M]+ (56), 293 (100), 264 (95), 246 (27),
187 (27), 157 (22), 43 (62). Found, %: C 81.85; H 7.90.
C21H24O2. Calculated, %: C 81.78; H 7.84. M 308.18.
6.82 d (2Harom, J 8.9 Hz), 6.93 s (2Harom), 7.27 d (2Harom
,
J 8.9 Hz). Mass spectrum, m/z (Irel, %): 294 [M]+ (57),
279 (100), 250 (66), 173 (29), 147 (29), 135 (23), 43
(57). Found, %: C 81.52; H 7.48. C20H22O2. Calculated,
%: C 81.60; H 7.53. M 294.16.
(E)-4-(4-Methoxyphenyl)-4-(2,4,6-trimethyl-
phenyl)but-3-en-2-one E-(X) was obtained by keeping
a solution of 20 mg (0.07 mmol) of compound Z-X in
CF3SO3H at 20OC for 20 h. Yield 10 mg (50%). Oily mix-
ture with initial compound Z-X in a ratio 1:1. 1H NMR
spectrum (CDCl3), δ, ppm (extricated from the spectrum
of isomers mixture): 2.11 s (3H, Me), 2.14 s (6H, 2Me),
2.28 s (3H, Me), 3.80 s (3H, OMe), 6.00 s (1H, HC=),
(Z)-4-(Pentamethylphenyl)-4-phenylbut-3-en-2-
one Z-(XIVa) was obtained from 26 mg (0.12 mmol) of
compound If and 38 mg (0.36 mmol) of benzene in
1.5 ml of CF3SO3H at 20°C in 0.75 h. Yield 24 mg (68%),
1
mp 84–85°C (49.2–50.5°C [11]). H NMR spectrum
(CDCl3), δ, ppm: 1.68 s (3H, Me), 2.03 s (6H, 2Me),
2.22 s (6H, 2Me), 2.28 s (3H, Me), 6.82 s (1H, HC=),
7.30–7.35 m (5H, Harom).
6.81 d (2Harom, J 8.6 Hz), 6.87 s (2Harom), 7.15 d (2Harom
,
J 8.6 Hz). Mass spectrum, m/z (Irel , %): 294 [M]+ (57),
279 (100), 250 (66), 173 (29), 147 (29), 135 (23), 43
(57). Found, %: C 81.62; H 7.55. C20H22O2. Calculated,
%: C 81.60; H 7.53. M 294.16.
(Z)-4-(4-Methoxyphenyl)-4-(pentamethylphenyl)-
but-3-en-2-one Z-(XIVb) was obtained from 30 mg
(0.14 mmol) of compound If and 18 mg (0.17 mmol) of
methoxybenzene in 1 ml of HSO3F at –75°C in 1.5 h.
Yield 18 mg (40%), mp 129–131°C. 1H NMR spectrum
(CDCl3), δ, ppm: 1.64 s (3H, Me), 2.01 s (6H, 2Me),
2.23 s (6H, 2Me), 2.28 s (3H, Me), 3.79 s (3H, OMe),
6.77 s (1H, HC=), 6.82 d (2Harom, J 8.9 Hz), 7.29 d
(2Harom, J 8.9 Hz). Mass spectrum, m/z (Irel, %): 322 [M]+
(55), 307 (100), 278 (90), 264 (31), 263 (31), 249 (24),
201 (26), 43 (60). Found, %: C 82.03; H 8.17. C22H26O2.
Calculated, %: C 81.95; H 8.13. M 322.19.
(Z)-4-(4-Methoxyphenyl)-4-(2,4,6-trimethyl-3-
fluorosulfonylphenyl)but-3-en-2-one Z-(XI) was
obtained by keeping a solution of 10 mg (0.03 mmol) of
compound Z-X in 0.5 ml HSO3F at –30°C for 1.5 h. Yield
12 mg (96%). Oily substance. 1H NMR spectrum (CDCl3),
δ, ppm: 2.05 s (3H, Me), 2.07 s (6H, 2Me), 2.40 s (3H,
Me), 2.70 s (3H, Me), 3.81 s (3H, OMe), 6.85 d
(2Harom, J 9.0 Hz), 6.92 s (1H, HC=), 7.14 s (1Harom),
7.24 d (2Harom, J 9.0 Hz). Mass spectrum, m/z (Irel, %):
376 [M]+ (61), 361 (100), 332 (60), 135 (60), 131 (32),
108 (30). Found, %: C 63.80; H 5.37. C20H21FO4S.
Calculated, %: C 63.81; H 5.62. M 376.11.
(E)-4-(4-Methoxyphenyl)-4-phenylbut-3-en-2-one
E-(XVa) and (Z)-4-(4-methoxyphenyl)-4-phenyl-
but-3-en-2-one Z-(XVa) were obtained from 30 mg
(0.17 mmol) of compound Ig and 27 mg (0.34 mmol) of
benzene in a mixture of 1 ml of CF3SO3H and 0.5 ml of
CH2Cl2 at –30°C in 20 min. Oily mixture of isomers
E-(XVa) [28 mg (65%)] and Z-(XVa) [14 mg (33%)].
(Z)-3-(2,4,6-Trimethylphenyl)-1,3-diphenyl-
propenone Z-(XII) was obtained from 50 mg (0.2 mmol)
of compound IIb and 78 mg (1 mmol) of benzene in
2 ml of CF3SO3H at 10°C in 20 min. Yield 40 mg (62%).
Oily substance. IR spectrum, ν, cm–1: 1640 (C=O), 1660
(C=O), 1700 (C≡C). 1H NMR spectrum (CDCl3), δ, ppm:
2.04 s (6H, 2CH3), 2.30 s (3H, CH3), 6.88 s (2Harom),
7.34–7.37 m (3Harom), 7.41–7.45 m (4Harom), 7.52 t
1
Compound E-XVa. H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.83 s (3H, CH3), 3.81 s (3H, OCH3), 6.54 s (1H, HC=),
6.80–7.22 m (9Harom).
1
Compound Z-XVa. H NMR spectrum (CDCl3), δ,
(1Harom, J 7.4 Hz), 7.63 s (1H, HC=), 7.95 d (2Harom
,
J 7.4 Hz). Mass spectrum, m/z (Irel, %): 326 [M]+ (67),
ppm (extricated from the spectrum of isomers mixture):
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

REACTIONS OF ACETYLENE KETONES IN SUPERACIDS
703
1.91 s (3H, CH3), 3.85 s (3H, OCH3), 6.49 s (1H, HC=),
6.80–7.22 m (9Harom). Mass spectrum (isomers mixture),
m/z (Irel, %): 252 [M]+ (100), 237 (84), 213 (12),
165 (22), 135 (30), 105 (18), 43 (16). Found, %: C 80.90;
H 6.32. C17H16O2. Calculated, %: C 80.93; H 6.39.
M 252.12.
C 64.65; H 5.96. C21H23FO4S. Calculated, %: C 64.60;
H 5.94. M 390.13.
(E)-Ethyl 4-(4-methylphenyl)-4-(4-methoxy-
phenyl)-2-oxobut-3-enoate E-(XVIa) and (Z)-ethyl 4-
(4-methylphenyl)-4-(4-methoxyphenyl)-2-oxobut-3-
enoate Z-(XVIa) were obtained from 22 mg (0.1 mmol)
of compound IVa and 13 mg (0.12 mmol) of methoxy-
benzene in 1.5 ml of CF3SO3H at –30°C in 15 min. Oily
mixture of isomers E-XVIa [6 mg (18%)] and Z-XVIa
[6 mg (18%)].
Compound E-XVIa. 1H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.18 t (3H, Me, J 7.2 Hz), 2.38 s (3H, Me), 3.83 s (3H,
OMe), 3.90 q (2H, CH2, J 7.2 Hz), 6.78 s (1H, HC=),
6.89 d (2Harom, J 9.0 Hz), 7.17 d (2Harom, J 8.3 Hz), 7.18 d
(2Harom, J 9.0 Hz), 7.24 d (2Harom, J 8.3 Hz).
Compound Z-XVIa. 1H NMR spectrum (CDCl3), δ,
ppm (extricated from the spectrum of isomers mixture):
1.17 t (3H, Me, J 7.2 Hz), 2.39 s (3H, Me), 3.83 s (3H,
OMe), 3.86 q (2H, CH2, J 7.2 Hz), 6.82 s (1H, HC=.),
6.86 d (2Harom, J 8.9 Hz), 7.11 d (2Harom, J 8.4 Hz), 7.17 d
(2Harom, J 8.4 Hz), 7.31 d (2Harom, J 8.9 Hz). Mass
spectrum (isomers mixture), m/z (Irel, %): 324 [M]+ (4),
251 (100), 135 (15), 119 (11). Found, %: C 74.10; H 6.26.
C20H20O4. Calculated, %: C 74.06; H 6.21. M 324.14.
4,4-Bis(4-methoxyphenyl)but-3-en-2-one (XVb)
was obtained from 50 mg (0.29 mmol) of compound Ig
and 48 mg (0.44 mmol) of methoxybenzene in 1 ml of
HSO3F at –75°C in 1 h. Yield 57 mg (70%), mp 85–
1
86°C. IR spectrum, ν, cm–1: 1650 (C=O). H NMR
spectrum (CDCl3), δ, ppm: 1.86 s (3H, Me), 3.80 s (3H,
OMe), 3.84 s (3H, OMe), 6.46 s (1H, HC=.), 6.83 d
(2Harom, J 8.7 Hz), 6.92 d (2Harom, J 8.6 Hz), 7.12 d
(2Harom, J 8.6 Hz), 7.22 d (2Harom, J 8.7 Hz). 13C NMR
spectrum (CDCl3), δ, ppm: 30.13 q (J 127.2 Hz), 55.22 q
(J 144.1 Hz), 55.27 q (J 144.1 Hz), 113.71 d.d (J 159.4,
3.8 Hz), 113.71 d.d (J 159.4, 3.8 Hz), 125.73 d
(J 155.6 Hz), 130.05 d.d (J 150.1, 7.2 Hz), 131.23 d.d
(J 150.5, 7.2 Hz), 131.27 quintet (J 8.2 Hz), 133.54
quintet (J 6.9 Hz), 153.91 s, 160.19 m, 160.79 m, 200.19 q
(J 5.1 Hz). Mass spectrum, m/z (Irel, %): 282 [M]+ (83),
281 (48), 267 (98), 135 (100), 135 (30), 43 (36). Found,
%: C 76.62; H 6.45. C18H18O3. Calculated, %: C 76.57;
H 6.43. M 282.13.
(Z)-4-(4-Acetyl-2,3,5,6-tetramethylphenyl)-4-(4-
methoxyphenyl)but-3-en-2-one Z-(XVc) was obtained
from 50 mg (0.29 mmol) of compound Ig and 51 mg
(0.29 mmol) of 1-acetyl-2,3,5,6-tetramethylbenzene in
1 ml of HSO3F at –75°C in 20 min. Yield 10 mg (10%).
Oily substance. IR spectrum, ν, cm–1: 1620 (C=O), 1690
(C=O). 1H NMR spectrum (CDCl3), δ, ppm: 1.77 s (3H,
Me), 1.98 s (6H, 2Me), 2.14 s (6H, 2Me), 2.51 s (3H,
(Z)-Ethyl 4-(4-methoxyphenyl)-2-oxobut-4-(2,4,6-
trimethylphenyl)-3-enoate Z-(XVIb) was obtained
from 29 mg (0.12 mmol) of compound IVb and 16 mg
(0.15 mmol) of methoxybenzene in 1 ml of HSO3F at
–75°C in 1.5 h.Yield 8 mg (19%). Oily substance. 1H NMR
spectrum (CDCl3), δ, ppm: 1.19 t (3H, Me, J 7.2 Hz),
2.00 s (6H, 2Me), 2.30 s (3H, Me), 3.81 s (3H, OMe),
3.83 q (2H, CH2, J 7.2 Hz), 6.85 d (2Harom, J 8.9 Hz),
Me), 3.80 s (3H, OMe), 6.82 s (1H, HC=), 6.83 d (2Harom
,
6.88 s (2Harom), 7.15 s (1H, HC=), 7.34 d (2Harom
,
J 8.9 Hz), 7.25 d (2Harom, J 8.9 Hz). Mass spectrum,
m/z (Irel, %): 351 [M + 1]+ (12), 350 [M]+ (48), 335 (70),
306 (34), 263 (34), 229 (17), 175 (10), 160 (10), 135
(11), 43 (100). Found, %: C 78.85; H 7.56. C23H26O3.
Calculated, %: C 78.83; H 7.48. M 350.19.
J 8.6 Hz). Mass spectrum, m/z (Irel, %): 352 [M]+ (6),
279 (100), 147 (30), 135 (25), 119 (6), 43 (2). Found, %:
C 74.93; H 6.81. C22H24O4. Calculated, %: C 74.98;
H 6.86. M 352.17.
Ethyl 4,4-bis(4-methoxyphenyl)-2-oxobut-3-
enoate (XVIc) was obtained from 51 mg (0.22 mmol)
of compound IVc and 24 mg (0.22 mmol) of methoxy-
benzene in 1 ml HSO3F at –75°C in 1 h. Yield 20 mg
(27%). Oily substance. IR spectrum, ν, cm–1: 1620 (C=O),
1715 (C=O). 1H NMR spectrum (CDCl3), δ, ppm: 1.18 t
(3H, Me, J 7.2 Hz), 3.83 s (3H, OMe), 3.84 s (3H, OMe),
3.90 q (2H, CH2, J 7.2 Hz), 6.77 s (1H, HC=), 6.87 d
(2Harom, J 8.8 Hz), 6.89 d (2Harom, J 8.6 Hz), 7.17 d
(2Harom, J 8.6 Hz), 7.31 d (2Harom, J 8.8 Hz). Mass
spectrum, m/z (Irel, %): 340 [M]+ (6), 267 (100), 248 (6),
(Z)-4-(4-Methoxyphenyl)-4-(2,3,5,6-tetramethyl-4-
fluorosulfonylphenyl)but-3-en-2-one Z-(XVd) was
obtained from 50 mg (0.29 mmol) of compound Ig and
95 mg (0.44 mmol) of 1,2,4,5-tetramethyl-3-fluoro-
sulfonylbenzene in 2 ml of HSO3F at –75°C in 1.5 h.
Yield 51 mg (45%). Oily substance. 1H NMR spectrum
(CDCl3), δ, ppm: 2.03 s (3H, Me), 2.06 s (6H, 2Me),
2.58 s (6H, 2Me), 3.80 s (3H, OMe), 6.86 d (2Harom
,
J 8.9 Hz), 6.90 s (1H, HC=.), 7.22 d (2Harom, J 8.9 Hz).
Mass spectrum, m/z (Irel, %): 390 [M]+. Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

ARISTOV et al.
704
135 (45). Found, %: C 70.65; H 6.05. C20H20O5.
Calculated, %: C 70.57; H 5.92. M 340.13.
(CDCl3), δ, ppm: 1.14 t (6H, 2CH3, J 7.1 Hz), 3.80 s
(3H, OMe), 3.83 s (3H, OMe), 3.85–3.94 m (4H, 2CH2),
5.99 d (1H, HC=, J 15.6 Hz), 6.82 d (2Harom, J 8.7 Hz),
6.89 d (2Harom, J 8.6 Hz), 7.22 d (2Harom, J 8.7 Hz),
7.32 d (2Harom, J 8.6 Hz). Mass spectrum, m/z (Irel, %):
377 [M + 1]+ (12), 376 [M]+ (44), 319 (10), 266 (13),
240 (100), 225 (94), 160 (15), 135 (19). Found, %:
C 63.90; H 6.71. C20H25O5P. Calculated, %: C 63.82;
H 6.69. M 376.14.
4-Hydroxy-4-(4-methylphenyl)-2-oxobut-3-enoic
acid (XIXa) was obtained by keeping a solution of
50 mg (0.23 mmol) of compound (IVa) in 1 ml HSO3F
at –50°C for 15 min. Yield 40 mg (85%), mp 135–137°C
(decomp.). 1H NMR spectrum [(CD3)2SO], δ, ppm: 2.40
C (3H, Me), 7.08 C (1H, HC=), 7.39 d (2Harom, J 8.4 Hz),
7.98 d (2Harom, J 8.4 Hz). 13C [(CD3)2SO], δ, ppm:
21.3 q.t (J 127.0, 4.3 Hz), 97.7 d (J 169.4 Hz), 128.0 d.d
(J 161.4, 6.1 Hz), 129.7 d of quintets (J 160.9, 5.2 Hz),
132.0 t (J 7.1 Hz), 144.9 m, 163.2 d (J 2.2 Hz), 169.7 C,
190.5 m. Mass spectrum, m/z (Irel, %): 206 [M]+ (27),
161 (100), 119 (22), 115 (5), 69 (84). Found, %: C 63.89;
H 4.91. C11H10O4. Calculated, %: C 64.07; H 4.89.
M 206.06.
4,7-Dimethyl-3-(4-methylphenyl)-1-trifluoro-
methylinden-1-ol (XXI) was obtained from 51 mg
(0.24 mmol) of compound IIIa and 51 mg (0.48 mmol)
of 1,4-dimethylbenzene in 1 ml of HSO3F at –50°C in
1 h. Yield 8 mg (10%). Oily substance. 1H NMR spectrum
(CDCl3), δ, ppm: 2.06 s (3H, Me), 2.33 s (3H, Me),
2.33 s (1H, OH), 6.74 s (1H, HC=), 6.94 d (1Harom
J 7.7 Hz), 7.06 d (1Harom, J 7.7 Hz), 7.11 d (2Harom
,
,
4-Hydroxy-4-(4-methoxyphenyl)-2-oxobut-3-enoic
acid (XIXc) was obtained by keeping a solution of
51 mg (0.22 mmol) of compound IVc in 2 ml of CF3SO3H
at –30°C for 0.5 h followed by the treatment and workup
of the reaction mixture analogously to common
procedures after alkenylation. Yield 10 mg (20%), mp
180°C (decomp.). IR spectrum, ν, cm–1: 1680 (C=O),
J 7.9 Hz), 7.22 d (2Harom, J 7.9 Hz). Mass spectrum,
m/z (Irel, %): 318 [M]+ (100), 303 (15), 249 (59),
226 (34), 221 (6), 206 (13), 129 (13), 92 (32). Found, %:
C 71.73; H 5.41. C19H17F3O. Calculated, %: C 71.69;
H 5.38. M 318.12.
The study was carried out under a financial support
of the Committee on Science and Higher Education of
the Saint-Petersburg Government (grants PD 05-1.3-81
for young Candidates of Sciences and M06-2.5Q-208
for students and post-graduates) and of the Russian
Foundation for Basic Research (grant 06-03-32728-a).
1
3300 (O–H). H NMR spectrum [(CD3)2SO], δ, ppm:
3.87 s (3H, OMe), 7.06 s (1H, HC=.), 7.10 d (2Harom
,
J 8.9 Hz), 8.07 d (2Harom, J 8.9 Hz). 1H NMR spectrum
(CDCl3), δ, ppm: 3.90 s (3H, OMe), 7.99 d (2Harom
,
J 8.9 Hz), 8.09 s (1H, HC=), 8.99 d (2Harom, J 8.9 Hz),
15.40 br.s (2H, OH, COOH). Found, %: C 59.60; H 4.59.
C11H10O5. Calculated, %: C 59.46; H 4.54.
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at –75°C in 15 min. Yield 11 mg (28%). Oily substance.
1H NMR spectrum (CDCl3), δ, ppm: 1.15 t (6H, 2CH3,
J 7.0 Hz), 2.10 s (6H, 2Me), 2.29 s (3H, Me), 3.78 s (3H,
OMe), 3.85 s (4H, 2CH2, J 7.0 Hz), 6.36 d (1H, HC=,
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C 68.03; H 7.53. M 388.18.
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