Reactions of arylacetylenic compounds with arenes in the presence of aluminum halides

Article abstract of DOI:10.1134/S1070428010010082

Conjugated arylacetylenic ketones and aldehydes, propargyl-type alcohols, and arylacetylenes reacted with arenes in the presence of AlBr₃ or AlCl₃ as catalyst to give substituted indenes. 3-Arylpropynoic acids under analogous conditi

Full text of DOI:10.1134/S1070428010010082

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 1, pp. 82–97. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.O. Shchukin, A.V. Vasil’ev, E.V. Grinenko, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 1, pp. 81–97.
Reactions of Arylacetylenic Compounds with Arenes
in the Presence of Aluminum Halides
A. O. Shchukin, A. V. Vasil’ev, and E. V. Grinenko
St. Petersburg State Academy of Forestry Engineering, Institutskii per. 5, St. Petersburg, 194021 Russia
e.-mail: aleksvasil@mail.ru
Received April 8, 2009
Abstract—Conjugated arylacetylenic ketones and aldehydes, propargyl-type alcohols, and arylacetylenes
reacted with arenes in the presence of AlBr3 or AlCl3 as catalyst to give substituted indenes. 3-Arylpropynoic
acids under analogous conditions gave rise to 3,3-diarylindan-1-ones, while the corresponding methyl esters
were converted into methyl 3,3-diarylprop-2-enoates. The key intermediates in the transformations of
acetylenic ketones and aldehydes and propargyl-type alcohols into indene derivatives are resonance-stabilized
propargyl–allenyl cations –C≡C–C+ ↔ –C+=C=C which reacted with one of the resonance structures to give
isomeric indenes, depending on the substituent nature.
DOI: 10.1134/S1070428010010082
Since XIXth century various Lewis acids were
extensively used for the preparation of organic com-
pounds on both laboratory and industrial scales [1, 2].
Lewis acids are now used in organic synthesis as
reagents and catalysts in numerous processes involving
formation of carbon–carbon and carbon–heteroatom
bonds, oxidation, reduction, polymerization, etc.
[3–11]. Various Lewis acids have also found wide
application in the chemistry of alkynes [12]. However,
until recently the use of such common Lewis acids as
aluminum halides AlBr3 and AlCl3 for direct activation
of triple carbon–carbon bond was fairly limited and oc-
casional [13–15]. Effective participation of aluminum
halides in electrophilic activation of acetylenic com-
pounds was demonstrated by us only recently [16–18].
The goal of the present work was to study trans-
formations and reactivity of arylacetylenic compounds
in their reactions with arenes catalyzed by AlBr3 or
AlCl3. As substrates we used α,β-acetylenic carbonyl
compounds Ia–Ih, alcohols IIa–IIg, 3-arylpropynoic
acids IIIa–IIIc, methyl 3-arylpropynoates IVa and
IVb, and arylacetylenes Va–Vd.
Aluminum halides AlX3 are capable of coordinating
at two electron-donor centers in the –C3≡C2–C1=O
fragment of compounds I, at the carbonyl oxygen atom
and at the C3≡C2 bond (Scheme 1). As a result, three
types of cationic species may be formed. Cation VI is
formed via coordination at the carbonyl oxygen atom,
cation VIII involves coordination at both carbonyl
oxygen atom and triple carbon–carbon bond, and struc-
HO Me
HO Ph
O
OH
Me
Ph
Me
R
R
R
Ph
Me
R
Ia–Ih
IIa–IIe
IIf
IIg
O
O
R
R
CH
R
OH
OH
IIIa–IIIc
IVa, IVb
Va–Vd
I, R = R′ = H (a), R = Me, R′ = H (b), 4-Me (c), 2,4-Me2 (d), 2,4,6-Me3 (e), 4-MeO (f), 4-F (g); R = Ph, R′ = H (h); II, R = R′ =
H (a); R = H, R′ = Me (b); R = Me, R′ = H (c); R = F, R′ = H (d), Me (e); III, R = H (a), F (b), Me (c); IV, R = H (a), Me (b); V, R =
H (a), 2-F (b), 4-F (c), 4-Cl (d).
82

REACTIONS OF ARYLACETYLENIC COMPOUNDS WITH ARENES
83
Scheme 1.
O
AlnX3n
O
R
AlnX3n
3
2
1
3
2
1
Ar
Ar
Ar
Ar
Ar
R
VI
VII
δ–
3n
δ–
3n
AlnX
AlnX
O
R
O
R
AlnX3n
O
R
AlnX3n
AlnX3n
3
2
1
2
1
2
1
δ+
δ+
Ar
3
3
I
VIII
IX
δ–
3n
AlnX
O
R
2
1
δ+
3
X
X = Cl, Br.
ture X corresponds to coordination only at the triple
bond. Taking into account that the interaction between
AlX3 and carbonyl oxygen atom is much more ener-
getically favorable than coordination of AlX3 at the
acetylenic bond π-system [19, 20], the formation of
species X should be regarded as hardly probable. The
most probable is generation of intermediate cations VI
and VIII which can also be represented by canonical
structures VII and IX, respectively.
tions of acetylenic compounds Ia–Ih (see below).
These data indicate that initial addition of aromatic
compounds occurs at the C1 rather than C3 atom of
intermediate VI↔VII or VIII↔IX with formation of
structure XI (Scheme 2).
Acetylenic carbonyl compounds Ia–Ih and alcohols
IIa–IIg reacted with benzene and 1,2-dichlorobenzene
in the presence of AlBr3 or AlCl3 to give substituted
indenes XXa–XXq. Scheme 3 illustrates the most
probable paths of formation of final products XX in
the examined reactions. The structures of reactive in-
termediates XIIIa–XIIIm, XIVa–XIVm, XVa–XVn,
XVIa–XVIk, XVIn, XVIIa, XVIIb, XVIId–XVIIn,
XVIIIa–XVIIIk, XVIIIn, XIXa–XIXi, XIXk, and
XIXn and indenes XXa–XXq are shown in table; the
corresponding reaction paths (a and b; Scheme 3) are
also indicated.
Cationic species VI↔VII and VIII↔IX possess
two electrophilic centers, C1 and C3 (Scheme 1), which
can be involved in subsequent reactions with arenes
according to aromatic electrophilic substitution pat-
tern leading to structures XI and XII, respectively
(Scheme 2). However, 3,3-diarylprop-2-en-1-ones XII
did not react with aromatic compounds in the presence
of aluminum halides. For example, 1,3,3-triphenyl-
prop-2-en-1-one failed to react with benzene in the
presence of AlCl3 and HCl [21]. Moreover, in the
present work we also found that a ~1:1 mixture of
(E)- and (Z)-4-(4-methylphenyl)-4-phenylbut-3-en-2-
ones [22] remained unchanged after heating for 0.5 h
at 60°C in benzene in the presence of AlBr3 (according
to the general procedure for the reaction of acetylenic
compounds with arenes; see Experimental) and was
quantitatively recovered from the reaction mixture. No
structures like XII were detected in analogous reac-
The structure of indenes XXa–XXq, XXVa–XXVc,
and indanones XXIIa–XXIId (Schemes 4, 5, 8) was
determined by 1H, 13C, and 19F NMR spectroscopy and
mass spectrometry [16–18] with account taken of the
GC–MS data obtained by us previously [16]. The sub-
stitution pattern in the indene system and aromatic
fragments was established by detailed analysis of spin–
1
spin couplings in the H NMR spectra of XXa–XXq
and XXVa–XXVc (see Experimental and the data
reported in [16–18]).
Scheme 2.
H
AlnX3n
R
O
1
Ar
COR
H
Ar'H
3
2
VI
VII or VIII
IX
Ar
Ar'
Ar'
XI
XII
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SHCHUKIN et al.
84
Scheme 3.
Ar"
AlnX3n
–[AlnX3nOH]–
R
R
XI
II
–H+
R'
R
Ar"
Ar
Ar"
H+
3
2
1
(a) Ar"H
R
XX
Ar'
Ar
Ar
Ar
–H+
Ar'
Ar'
Ar'
R
XIII
XV
XVII
–H+
R"
Ar
R
Ar
R
Ar
R
H+
(b) Ar"H
3
2
1
XX'
Ar'
·
·
–H+
Ar
Ar'
Ar"
Ar'
Ar"
Ar'
R
XIV
XVI
XVIII
–H+
R'''
Ar"
Ar
R
XX"
Ar"
Ar'
XIX
With a view to elucidate the effect of electronic
properties of the Ar, Ar′, and R substituents on distri-
bution of the positive charge in structures XIII↔XIV
and direction (a or b; Scheme 3) of their further reac-
tions with arenes (π-nucleophiles), we examined trans-
formations of a series of arylacetylenic compounds Ia–
Ih and IIa–IIg (see table). In many cases, the structure
of indene XX formed as final product unambiguously
indicated the path of its formation. For example, com-
pound XXc can be formed only along path b through
intermediates XIVc, XVIc, and XVIIIc (see table,
run no. 3). Alternative path involving structures XIIIc
and XVc cannot lead to indene XXc. Likewise,
indenes XXe, XXf, XXh, and XXq are formed from
alkynes Ic, Id, IIc, and IIg according to path b (run
nos. 4–6, 14, 18), while compounds XXm–XXo origi-
nate from alkynes IIb and IIe following path a (run
nos. 12, 13, 16).
Propargyl-type alcohols II are synthetic equivalents
of species XI (Scheme 2). By the action of various
Lewis and Brønsted acids alcohols II give rise to
propynyl (alkynylcarbenium) cations XIII [23–27] that
may also be represented as allenyl cations XIV
(Scheme 3). Resonance-stabilized cationic interme-
diates XIII↔XIV are capable of reacting with arenes
along two pathways. The first of these involves attack
by the electrophilic C1 carbon atom in structure XIII
(path a), and the second implies addition at the C3
atom in structure XIV (path b). Path a gives alkyne
XV which is then protonated at the triple bond to
produce vinyl-type cation XVII, and intramolecular
cyclization of the latter finally yields indene structure
XX or XX′. Following alternative path b, cation XIV
is converted into allene XVI which is protonated at the
central carbon atom in the C=C=C allene triad [28] to
form resonance-stabilized allyl-type cations XVIII↔
XIX and finally indenes XX′ and XX″.
Comparison of the reactions of cations XIII↔XIV
with aromatic π-nucleophiles showed that electron-
donating substituents Ar, Ar′, and R (see table) capable
of essentially delocalizing positive charge (aromatic
systems), favor activation of the neighboring electro-
philic center, C1 in structure XIII or C3 in structure
XIV. Analogous conclusions were drawn previously
Intermediate formation of structures XV and XVI is
confirmed by the transformation of 1,1,3,3-tetraphen-
ylpropadiene (tetraphenylallene) into 1,1,3-triphenyl-
indene (XXl) in acid medium [29], as well as by the
synthesis of the latter from 1,3,3,3-tetraphenylprop-1-
yne (XXI) in a solution of AlBr3 in methylene chloride
(see Experimental). In addition, allyl-type alcohols in
H2SO4 or HSO3F give rise to substituted indenes XX
as a result of cyclization of cations XVIII↔XIX [30].
1
[24–26] on the basis of H and 13C NMR studies on
positive charge distribution in resonance stabilized
propargyl–allenyl cations. Other examples illustrating
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REACTIONS OF ARYLACETYLENIC COMPOUNDS WITH ARENES
91
and R in intermediates XIII ↔XIV. For example,
both cations XIIIa↔XIVa (run no. 1) contain phenyl
groups on C1 and C3; therefore, indene XXa can be
formed along paths a and b with approximately equal
probabilities. The same applies to indenes XXb and
XXk which may be formed through intermediate
cations XIIIb↔XIVb and XIIIi↔XIVi, respectively
(run nos. 2, 9, 11, 15), where substituents on the C1
and C3 atoms are characterized by comparable elec-
tron-donor properties.
dual reactivity of ions XIII↔XIV were reported in
[23, 27]. Some results of quantum-chemical calcula-
tions of charge and orbital parameters of resonance-
stabilized cations were reviewed in [23].
Although the observed empirical relation does not
allow us to estimate the contribution of hybridization
of the C1 (sp2) and C3 atoms (sp) to the overall electro-
philicity of these reaction centers in the series of
cations XIIIa↔XIV without special theoretical calcu-
lations, the above simple rule rationalizes formation of
many indene structures XXa–XXq. For instance, in-
dene XXq is formed from alcohol IIg according to
path b only (run no. 18) through allenyl structure
XIVm in which the electrophilic center is the C3 atom
conjugated with the p-tolyl group. Alternative path a
involves propargyl-type cation XIIIm in which the C1
atom bears two methyl groups that delocalize positive
charge less effectively.
In the final step of path b, only allylic cations
XVIII (Scheme 3, see table) undergo intramolecular
cyclization to indenes XX. The reactive electrophilic
center in XVIII is localized on the C1 atom bearing
less electron-donor substituents R and Ar′ than Ar′ and
Ar″ on C3 (cf. cations XVIIIa–XVIIIi, XVIIIk, and
XVIIIn with the corresponding structures XIXa–
XIXi, XIXk, and XIXn in table). This is consistent
with the previously reported data on the reactivity of
allyl-type cations (cyclization into substituted indenes
in acid medium through the most stable indanyl
cations) [30, 31].
The presence of a stronger electron-donating
2,4-dimethylphenyl substituent on the C3 atom in
XIIIf ↔XIVf (as compared to methyl and phenyl
groups on C1) determines formation of indene XXh
along path b through allenyl cation XIVf (run no. 6).
The formation of indene XXc (run no. 3) according to
path b suggests better stabilization of the cationic
center by phenyl group on C3 in allenyl cation XIVc as
compared to methyl and 3,4-dichlorophenyl substit-
uents on C1 in structure XIIIc. On the other hand, the
formation of indenes XXm and XXn exclusively along
path a (run nos. 12, 13) indicated that the reaction in-
volved propargyl-type cation XIIIk where the C1 atom
bears methyl and p-tolyl groups which better stabilize
positive charge than does phenyl substituent on C3.
We also observed aryl group exchange in the course
of formation of indene XXb from ketone Ic (run no. 4)
or alcohol IIb (run no. 12) in benzene (see Experimen-
tal). In both cases, the p-tolyl fragment was replaced
by phenyl group. Heating of a 1:1.4:4.6 mixture of
indenes XXb, XXd, and XXe (obtained from ketone
Ic; run no. 4) in excess benzene at 60°C over a period
of 1 h in the presence of 5 equiv of AlBr3 did not result
in increased fraction of substitution product XXb, and
the initial indene mixture was quantitatively recovered.
These findings could indicate aryl group exchange at
intermediate steps. Apart from aryl group exchange,
AlBr3 and AlCl3 promoted demethylation of the me-
thoxy group in the reaction leading to indene XXj.
In terms of the above approach we can predict
formation of indenes XX even when their structure
does not indicate unambiguously the path of their
formation (a or b; Scheme 3). Thus compound XXl
(run nos. 10, 17) is most likely to be formed according
to path a through propargyl-type cation XIIIj in which
the electrophilic C1 center is activated by the presence
of two phenyl groups, whereas only one phenyl group
is attached to C3. Likewise, it may be presumed that
indenes XXi and XXj are formed along path b (run
nos. 7, 8) since the corresponding allenyl cations XIVg
and XIVh are stabilized by strong electron-donating
2,4,6-trimethylphenyl and 4-methoxyphenyl substit-
uents, respectively, on C3.
The synthetic potential of the examined reactions is
limited to reactions of acetylenic compounds Ia–Ih
and IIa–IIg with benzene and 1,2-dichlorobenzene
(see table). The reactions with other arenes are not
selective, and they lead to complex mixture of prod-
ucts. Thus the reaction of acetylenic ketone Ib with
toluene according to the general procedure gave a mix-
ture of five isomeric indenes with different positions of
methyl groups in the indene system and aromatic rings
1
on C1 and C3 (according to the H NMR and GC–MS
data). Analogous reaction of ketone Ib with 1,2-di-
methylbenzene produced a mixture of more than
10 isomeric indenes (GC–MS data).
In some cases it is impossible to identify the path
leading to indenes XX, for it is difficult to estimate
electron-donor effects of similar substituents Ar, Ar′,
Indenes XXa–XXq were isolated in 12 (run no. 10)
to 94% yield (run no. 8). On the average, the yields of
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SHCHUKIN et al.
92
Scheme 4.
Ph
O
AlBr3, 60°C, 0.5–1 h
IIIa, IIIb
+ C6H6
R
XXIIa (30%), XXIIb (18%)
R = H (a), F (b).
Scheme 5.
O
Cl
R
AlBr3, 60°C, 0.5 h
IIIa, IIIc
+
Cl
Ar
Ar
XXIIc (5%), XXIId (6%)
Ar = 3,4-Cl2C6H3; R = H (c), Me (d).
XXa–XXq were 30–60% (see table). As a rule, alumi-
num bromide ensured higher yields than did AlCl3. For
example, the yields of indene XXj obtained in the
presence of AlCl3 and AlBr3 were 50 and 94%, respec-
tively (see Experimental and the data of [18]).
Unlike acetylenic ketones Ia–Ih and alcohols IIa–
IIg, 3-arylprop-2-ynoic acids IIIa and IIIb reacted
with benzene (Scheme 4) to give 3,3-diarylindan-1-
ones XXIIa and XXIIb, respectively. Analogous
ketones XXIIc and XXIId were obtained by reactions
of acids IIIa and IIIc, respectively, with 1,2-dichloro-
benzene (Scheme 5). In all cases, the yields were fairly
poor (5–30%).
the triple bond of compound IIIa involves the C3 atom
as electrophilic center activated by AlBr3 (structure
VIIIa). The subsequent intramolecular acylation
through intermediate XXIII yields final product
XXIIa. An alternative path involving initial acylation
of benzene with acid IIIa to give 1,3-diphenylprop-2-
yn-1-one (Ih) cannot be operative, for ketone Ih
should react with benzene under analogous conditions
with formation of indene XXl (run. no. 12) which was
not detected (Scheme 4; cf. [21]). Indanone XXIIa was
also formed from acid IIIa and benzene in trifluoro-
methanesulfonic acid [32].
Aluminum bromide does not activate the carbonyl
carbon atom (C1) in methyl 3-arylprop-2-ynoates IVa
and IVb, and the latter react with benzene to give the
corresponding alkenylation products XXIVa and
The most probable mechanism of formation of
indanones XXII is shown in Scheme 6 with acid IIIa
as an example. Addition of two benzene molecules at
Scheme 6.
AlnBr3n
OH
δ–
3n
AlnBr
O
O
AlnBr3n
AlBr3
–H+
2
1
2C6H6
δ+
Ph
IIIa
Ph
XXIIa
Ph
Ph
–H+ [AlBr3OH]–
3
OH
VIIIa
XXIII
Scheme 7.
Ph
O
Ph
O
AlBr3, 20–60°C, 0.5–0.75 h
OMe
IVa, IVb + C6H6
+
R
OMe
Me
XXIVa (18%), Z-XXIVb (25%)
R = H (a), Me (b).
E-XXIVb (20%)
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REACTIONS OF ARYLACETYLENIC COMPOUNDS WITH ARENES
93
XXIVb (Scheme 7), as in the reactions of esters IVa
and IVb in HSO3F [33]. Presumably, the positive
charge on C1 in intermediates VI↔VII or VIII↔IX
(R = OMe, Scheme 1) derived from IVa and IVb is
insufficient due to electron-donating effect of the me-
thoxy group.
on a Specord 75IR spectrophotometer. The mass spec-
tra (electron impact, 70 eV) were obtained on an MKh-
1321 instrument with direct sample admission into the
ion source; vaporizer temperature 100–120°C. Gas
chromatographic–mass spectrometric analysis was per-
formed on an Agilent Technologies G 2570A GC/MSD
instrument (electron impact, 70 eV; separator tempera-
ture 250°C, ion source temperature 280°C; Ultra-2
capillary column, 30000×0.25 mm, stationary phase
95% of methylsilicone–5% of phenylmethylsilicone,
film thickness 0.25 μm; oven temperature program-
ming from 100 to 270°C at a rate of 5 deg/min; carrier
gas helium, flow rate 1 ml/min; sample volume 1 μl,
3–5% solution).
Arylacetylenes Va–Vd reacted with benzene in the
presence of AlBr3 to afford indenes XXb and XXVa–
XXVc in 11–23% yield (Scheme 8), and the reaction
time was as short as 5 min at 20°C. It was found previ-
ously that indene XXb is formed in 17 and 43% yield
in the reaction of phenylacetylene (Va) with benzene
in the presence of H3PO4–BF3 [34] or CF3SO3H [35],
respectively. The authors [34, 35] postulated initial
formation of 1,1-diphenylethene whose subsequent
protonation yields 1,1-diphenylethan-1-yl cation
Ph2C+Me. Reaction of the latter with initial acetylene
Va, followed by intramoleclar cyclization of interme-
diate cationic species, leads to indene XXb as final
product. Presumably, analogous mechanism is typical
of reactions catalyzed by AlBr3 (Scheme 8).
3-Phenylprop-2-ynal (Ia), phenylethyne (Va),
2-fluorophenylethyne (Vb), 4-fluorophenylethyne
(Vc), 4-chlorophenylethyne (Vd), and 3-phenylpro-
pynoic acid (IIIa) were commercial products (from
Sigma–Aldrich). The syntheses and properties of the
other acetylenic substrates, 4-(4-methylphenyl)but-3-
yn-2-one (Ic), 4-phenylbut-3-yn-2-one (IIb), 4-(2,4-di-
methylphenyl)but-3-yn-2-one (Id), 4-(4-methoxyphen-
yl)but-3-yn-2-one (If) [40], 4-(2,4,6-trimethylphenyl)-
but-3-yn-2-one (Ie) [22]; 1,3-diphenylprop-2-yn-1-one
(Ih) [41]; 2,4-diphenylbut-3-yn-2-ol (IIa), 1,1,3-tri-
phenylprop-2-yn-1-ol (IIf), 2-methyl-4-(4-methyl-
phenyl)but-3-yn-2-ol (IIg) [17], 3-(4-fluorophenyl)-
propynoic acid (IIIb), 3-(4-methylphenyl)propynoic
acid (IIIc) [42], methyl 3-phenylpropynoate (IVa), and
methyl-3-(4-methylphenyl)propynoate (IVb) [43] were
reported previously.
Scheme 8.
Me
Ar
AlBr3, 20°C
5 min
Va–Vd
+ C6H6
Ar
XXb (23%), XXVa (11%)
XXVb (18%), XXVc (18%)
XXV, Ar = RC6H4; R = 2-F (a), 4-F (b), 4-Cl (c).
4-(4-Fluorophenyl)but-3-yn-2-one (Ig) was syn-
thesized by acylation of lithiated 4-fluorophenyl-
acetylene according to the procedure described in [44].
Thus the results of our study demonstrated the ef-
ficiency of aluminum halides, AlBr3 and AlCl3, in elec-
trophilic activation of various acetylenic compounds.
These reactions underlay simple preparative proce-
dures for the synthesis of indene derivatives that attract
interest as potential biologically active substances [36],
components of catalytic complexes for polymerization
of alkenes [37], and materials for other important
applications [38, 39].
1
Yield 20%, oily substance. H NMR spectrum
(acetone-d6), δ, ppm: 2.41 s (3H, Me), 7.27 t (2H,
Harom, J = 8.9 Hz), 7.71 d.d (2H, Harom, J = 8.9,
5.3 Hz). Found, %: C 74.09; H 4.40. C10H7FO. Calcu-
lated, %: C 74.07; H 4.35.
Acetylenic alcohols IIb–IIe were synthesized as
reported in [45] by reaction of the corresponding
lithiated arylacetylenes with substituted aceto-
phenones.
EXPERIMENTAL
2-(4-Methylphenyl)-4-phenylbut-3-yn-2-ol (IIb).
Yield 25%, oily substance [46]. IR spectrum, ν, cm–1:
3600 (OH), 3500–3200 (OHassoc), 2250 (C≡C).
1H NMR spectrum (CDCl3), δ, ppm: 1.87 s (3H, Me),
1
The H and 19F NMR spectra were recorded on
a Bruker AM-500 spectrometer at 500 and 470 MHz,
respectively. The chemical shifts were determined rela-
tive to the residual solvent signals (CHCl3, δ 7.25 ppm;
acetone-d5, δ 2.05 ppm) or CFCl3 (δF 0.0 ppm). The IR
spectra were measured from solutions in chloroform
2.37 s (3H, Me), 2.56 br.s (1H, OH), 7.20 d (2H, Harom
,
J = 8.1 Hz), 7.32–7.35 m (3H, Harom), 7.47–7.50 m
(2H, Harom), 7.63 d (2H, Harom, J = 8.1 Hz).
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SHCHUKIN et al.
94
4-(4-Methylphenyl)-2-phenylbut-3-yn-2-ol (IIc).
chromatography. The synthesis and properties of in-
denes XXa–XXf, XXi, XXk, XXl, XXn, XXo, and
XXq were reported in [16–18].
Yield 28%, oily substance. IR spectrum, ν, cm–1: 3580
1
(OH), 3500–3200 (OHassoc), 2230 (C≡C). H NMR
spectrum (CDCl3), δ, ppm: 1.86 s (3H, Me), 2.85 s
(3H, Me), 2.50 br.s (1H, OH), 7.13 d (2H, Harom, J =
1-Methyl-1,3-diphenylindene (XXb). a. The syn-
thesis of XXb from compounds Ib and IIa was
reported in [16, 17].
8.0 Hz), 7.29–7.44 m (5H, Harom), 7.73 d (2H, Harom
,
J = 8.0 Hz). Found, %: C 86.47; H 6.85. C17H16O. Cal-
culated, %: C 86.40; H 6.82.
b. Compound XXb was obtained from 61 mg
(0.6 mmol) of phenylacetylene (Va) in a solution of
0.8 g (3 mmol) of aluminum bromide in 2 ml
(22.4 mmol) of benzene at 20°C (reaction time 5 min).
Yield 39 mg (23%).
4-(4-Fluorophenyl)-2-phenylbut-3-yn-2-ol (IId).
1
Yield 20%, oily substance. H NMR spectrum
(CDCl3), δ, ppm: 1.86 s (3H, Me), 2.48 br.s (1H, OH),
7.01 t (2H, Harom, J = 8.8 Hz), 7.31 t.t (1H, Harom, J =
7.4, 1.5 Hz), 7.39 t (2H, Harom, J = 7.4 Hz), 7.45 d.d
(2H, Harom, J = 8.8, 5.4 Hz), 7.71 d.t (2H, Harom, J =
7.4, 1.5 Hz). Found, %: C 79.94; H 5.52. C16H13FO.
Calculated, %: C 79.98; H 5.45.
3-(2,4-Dimethylphenyl)-1-methyl-1-phenylin-
dene (XXg) and 1,4,6-trimethyl-1,3-diphenylindene
(XXh) were obtained as an oily isomer mixture from
31 mg (0.18 mmol) of compound Id in a solution of
0.29 g (1.1 mmol) of AlBr3 in 0.8 ml (9.1 mmol) of
benzene at 60°C (reaction time 0.5 h).
Compound XXg. Yield 5 mg (10%). 1H NMR spec-
trum (CDCl3), δ, ppm: 1.81 s (3H, Me), 2.27 s (3H,
Me), 2.38 s (3H, Me), 6.39 s (1H, 2-H), 7.07 br.d (1H,
4-(4-Fluorophenyl)-2-(4-methylphenyl)but-3-yn-
1
2-ol (IIe). Yield 23%, oily substance. H NMR spec-
trum (CDCl3), δ, ppm: 1.84 s (3H, Me), 2.36 s (3H,
Me), 2.42 br.s (1H, OH), 7.01 t (2H, Harom, J = 8.7 Hz),
7.19 d (2H, Harom, J = 8.2 Hz), 7.45 d.d (2H, Harom, J =
8.7, 5.4 Hz), 7.59 d (2H, Harom, J = 8.2 Hz). Found, %:
C 80.19; H 5.88. C17H15FO. Calculated, %: C 80.29;
H 5.95.
H
arom, J = 7 Hz), 7.13 br.s (1H, Harom), 7.15–7.42 m
(10H, Harom). Mass spectrum (GC–MS), m/z (Irel, %):
310 (100) [M]+, 295 (60), 279 (12), 265 (10), 203 (11),
202 (17).
1,3,3,3-Tetraphenylpropyne (XXI) was synthe-
sized according to the procedure reported in [47] from
phenylethynylmagnesium bromide and chloro(tri-
phenyl)methane. Yield 10%, mp 137–139°C; published
data [47]: mp 138–141°C. IR spectrum: ν 2300 cm–1,
1
Compound XXh. Yield 32 mg (57%). H NMR
spectrum (CDCl3), δ, ppm: 1.77 s (3H, Me), 1.98 s
(3H, Me), 2.28 s (3H, Me), 6.28 s (1H, 2-H), 6.80 s
(1H, Harom), 6.88 s (1H, Harom), 7.15–7.42 m (10H,
1
H
arom). Mass spectrum (GC–MS), m/z (Irel, %): 310
w (C≡C). H NMR spectrum (CDCl3): δ 7.24–
(100) [M]+, 295 (61), 279 (12), 265 (10), 203 (10), 202
(16). Found (for isomer mixture), %: C 92.96; H 7.21.
C24H22. Calculated, %: C 92.86; H 7.14. M 310.17.
7.51 ppm, m (20H, Harom).
Substituted indenes XXa–XXq, XXVa–XXVc,
indanones XXIIa–XXIId, and methyl 3,3-diaryl-
prop-2-enoates XXIVa and XXIVb (general proce-
dure). Acetylenic compound Ia–Ih, IIa–IIg, IIIa–IIIc,
IVa, IVb, or Va–Vd, 0.17–1.5 mmol, was added under
vigorous stirring to a solution of 0.85–7.5 mmol of
aluminum halide (AlBr3 or AlCl3) in 0.7–10 ml of
benzene or 1,2-dichlorobenzene, maintained at 20–
70°C. The mixture was stirred for 5–90 min, poured
into 30–50 ml of water, and extracted with chloroform
(3×30 ml). The extracts were combined, washed with
a saturated solution of sodium hydrogen carbonate and
water, and dried over sodium sulfate, the solvent was
distilled off under reduced pressure, and the residue
was subjected to chromatography on silica gel using
petroleum ether–ethyl acetate as eluent. The yields of
final products XXa–XXq, XXVa–XXVc, XXIIa–
XXIId, XXIVa, and XXIVb were determined by
weighing the corresponding fractions isolated by
4-(1-Methyl-1-phenylinden-3-yl)phenol (XXj).
a. The reaction of 50 mg (0.29 mmol) of compound If
with a solution of 0.38 g (1.45 mmol) of AlBr3 in 5 ml
(58 mmol) of benzene at 60°C (reaction time 0.5 h)
gave 80 mg (94%) of XXj.
b. Compound XXj was obtained from 30 mg
(0.17 mmol) of If in a solution of 0.37 g (2.55 mmol)
of AlCl3 in 1 ml (11.2 mmol) of benzene at 70°C (reac-
tion time 1 h). Yield 26 mg (50%), oily substance. IR
spectrum, ν, cm–1: 3600 (OH), 3500–3200 (OHassoc),
1
1605 (C=C). H NMR spectrum (CDCl3), δ, ppm:
1.79 s (3H, Me), 5.20 br.s (1H, OH), 6.51 s (1H, 2-H),
6.91 d (2H, Harom, J = 8.6 Hz), 7.17–7.33 m (8H,
H
arom), 7.53 d (3H, Harom, J = 8.6 Hz). Mass spectrum,
m/z (Irel, %): 298 (100) [M]+, 283 (73), 221 (10), 77
(8). Found, %: C 88.62; H 6.11. C22H18O. Calculated,
%: C 88.56; H 6.08. M 298.14.
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REACTIONS OF ARYLACETYLENIC COMPOUNDS WITH ARENES
95
1,1,3-Triphenylindene (XXl). a. The synthesis of
XXl from compounds Ih and IIf was reported in
[16, 17].
b. Compound XXl was obtained from 30 mg
(0.09 mmol) of 1,3,3,3-tetraphenylpropyne (XXI) in
a solution of 0.12 g (0.45 mmol) of AlBr3 in 4 ml of
methylene chloride at 20°C (reaction time 1 h),
following the general procedure for the synthesis of
substituted indenes. Yield 14 mg (47%).
3-(4-Fluorophenyl)-3-phenylindan-1-one
(XXIIb) was obtained from 100 mg (0.61 mmol) of
compound IIIb in a solution of 0.81 g (3 mmol) of
AlBr3 in 2 ml (22.5 mmol) of benzene at 60°C (reac-
tion time 0.5 h). Yield 33 mg (18%), mp 123–125°C.
1H NMR spectrum (CDCl3), δ, ppm: 3.49 s (2H, CH2),
7.17 d (3H, Harom, J = 7.7 Hz), 7.20–7.30 m (6H,
H
arom), 7.37 d (1H, Harom, J = 7.6 Hz), 7.42 t (1H, Harom
J = 7.6 Hz), 7.59 t (1H, Harom, J = 7.6 Hz), 7.81 d (1H,
arom, J = 7.6 Hz). 19F NMR spectrum (CDCl3):
,
H
1,5-Dimethyl-1,3-diphenylindene (XXm) was ob-
tained from 64 mg (0.27 mmol) of compound IIb in
a solution of 0.36 g (1.35 mmol) of AlBr3 in 1 ml
(11.2 mmol) of benzene at 60°C (reaction time 0.5 h).
The product was isolated as a mixture with compound
XXb [yield 26 mg (34%)].
δF –112.79 ppm, m. Mass spectrum, m/z (Irel, %): 302
(100) [M]+, 167 (32), 105 (94), 77 (90), 51 (35).
Found, %: C 83.35; H 5.04. C21H15FO. Calculated, %:
C 83.42; H 5.00. M 302.11.
3,3-Bis(3,4-dichlorophenyl)indan-1-one (XXIIc)
was obtained from 300 mg (2 mmol) of compound
IIIa in a solution of 2.7 g (10 mmol) of AlBr3 in 3 ml
(27 mmol) of 1,2-dichlorobenzene at 60°C (reaction
time 0.5 h). Yield 43 mg (5%), mp 128–130°C.
1H NMR spectrum (CDCl3), δ, ppm: 3.39 s (2H, CH2),
1
Compound XXm. Yield 17 mg (21%). H NMR
spectrum (CDCl3), δ, ppm: 1.79 s (3H, Me), 2.39 s
(3H, Me), 6.57 s (1H, 2-H), 7.04–7.40 m (9H, Harom),
7.44–7.48 m (2H, Harom), 7.62–7.65 m (2H, Harom).
Mass spectrum (GC–MS), m/z (Irel, %): 296 (100)
[M]+, 281 (73), 265 (20), 202 (15). Calculated:
M 296.16.
6.97 d.d (2H, Harom, J = 8.5, 2.0 Hz), 7.20 d (2H, Harom
J = 2.0 Hz), 7.31 d (1H, Harom, J = 7.6 Hz), 7.37 d (2H,
arom, J = 8.5 Hz), 7.49 t (1H, Harom, J = 7.6 Hz), 7.66 t
,
H
1-(3,4-Dichlorophenyl)-3-(4-fluorophenyl)-1,5-
dimethylindene (XXo) was obtained from 60 mg
(0.24 mmol) of compound IIe in a solution of 0.32 g
(1.2 mmol) of AlBr3 in 1 ml (9.6 mmol) of 1,2-di-
chlorobenzene at 70°C (reaction time 10 min). Yield
(1H, Harom, J = 7.6 Hz), 7.83 d (1H, Harom, J = 7.6 Hz).
Mass spectrum, m/z (Irel, %): 420 (48) [M]+, 385 (24),
361 (8), 322 (10), 275 (100), 212 (50), 176 (48), 143
(47), 125 (29). Found, %: C 59.82; H 2.67. C21H12Cl4O.
Calculated, %: C 59.75; H 2.87. M 419.96.
1
36 mg (40%), oily substance. H NMR spectrum
(CDCl3), δ, ppm: 1.74 s (3H, Me), 2.39 s (3H, Me),
6.43 s (1H, 2-H), 7.06 br.d (1H, Harom, J = 7.5 Hz),
3,3-Bis(3,4-dichlorophenyl)-6-methylindan-1-one
(XXIId) was obtained from 155 mg (0.97 mmol) of
compound IIIc in a solution of 1.29 g (4.84 mmol) of
AlBr3 in 2 ml (11 mmol) of 1,2-dichlorobenzene at
60°C (reaction time 0.5 h). Yield 25 mg (6%), oily
7.07 d.d (1H, Harom, J = 8.4, 2.2 Hz), 7.11 d (1H, Harom
J = 7.5 Hz), 7.15 t (2H, Harom, J = 8.8 Hz), 7.28 d (1H,
arom, J = 8.4 Hz), 7.29 br.s (1H, Harom), 7.37 d (1H,
,
H
1
Harom, J = 2.2 Hz), 7.57 d.d (2H, Harom, J = 8.8,
5.4 Hz). 19F NMR spectrum (CDCl3): δF –110.58 ppm,
m. Mass spectrum, m/z (Irel, %): 382 (100) [M]+, 367
(50), 297 (14), 237 (7), 220 (11), 147 (14). Found, %:
C 71.96; H 4.51. C23H17Cl2F. Calculated, %: C 72.07;
H 4.47. M 382.07.
substance. H NMR spectrum (CDCl3), δ, ppm: 2.43 s
(3H, Me), 3.36 s (2H, CH2), 6.97 d.d (2H, Harom, J =
8.5, 2.3 Hz), 7.19 d (1H, Harom, J = 8.0 Hz), 7.20 d
(2H, Harom, J = 2.3 Hz), 7.37 d (2H, Harom, J = 8.5 Hz),
7.47 d.d (1H, Harom, J = 8.0, 1.5 Hz), 7.61 br.s (1H,
H
arom). Mass spectrum, m/z (Irel, %): 434 (50) [M]+, 419
3,3-Diphenylindan-1-one (XXIIa) was obtained
from 188 mg (1.29 mmol) of compound IIIa in a solu-
tion of 1.72 g (6.44 mmol) of AlBr3 in 5 ml (56 mmol)
of benzene at 60°C (reaction time 1 h). Yield 108 mg
(30%), mp 127–128°C; published data [48]: mp 128–
(4), 399 (25), 289 (100), 226 (18), 189 (25). Found, %:
C 60.71; H 3.20. C22H14Cl4O. Calculated, %: C 60.58;
H 3.24. M 433.98.
Methyl 3,3-diphenylprop-2-enoate (XXIVa) was
obtained from 50 mg (0.31 mmol) of compound IVa in
a solution of 0.415 g (1.55 mmol) of AlBr3 in 1 ml
(11.2 mmol) of benzene at 60°C (reaction time 0.5 h).
Yield 14 mg (18%), oily substance; its properties were
reported in [33].
1
130°C. IR spectrum: ν 1700 cm–1 (C=O). H NMR
spectrum (CDCl3), δ, ppm: 3.48 s (2H, CH2), 7.15–
7.30 m (10H, Harom), 7.36 d (1H, Harom, J = 7.9 Hz),
7.42 t (1H, Harom, J = 7.4 Hz), 7.59 t (1H, Harom, J =
7.5 Hz), 7.79 d (1H, Harom, J = 7.7 Hz). Mass spectrum,
m/z (Irel, %): 284 (92) [M]+, 207 (95), 178 (94), 167
(32), 152 (28), 105 (100), 77 (90), 51 (45).
Methyl (E)-3-(4-methylphenyl)-3-phenylprop-2-
enoate (E-XXIVb) and methyl (Z)-3-(4-methylphen-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 1 2010

SHCHUKIN et al.
96
yl)-3-phenylprop-2-enoate (Z-XXIVb) (mixture of
isomers) were obtained from 47 mg (0.27 mmol) of
compound IVa in a solution of 0.36 g (1.35 mmol) of
AlBr3 in 0.8 ml (9.1 mmol) of benzene at 20°C (reac-
tion time 0.75 h). Oily substance. Yield 14 mg (20%)
(E isomer), 17 mg (25%) (Z isomer). H NMR spec-
trum (CDCl3), δ, ppm: E isomer: 2.40 s (3H, Me),
3.63 s (3H, OMe), 6.33 s (1H, 2-H), 7.10–7.40 m (9H,
(2.3 mmol) of AlBr3 in 1.4 ml (15.8 mmol) of benzene
at 20°C (reaction time 5 min). Yield 14 mg (18%), oily
substance. H NMR spectrum (CDCl3), δ, ppm: 1.77 s
(3H, Me), 6.51 s (1H, 2-H), 7.20 s (4H, Harom), 7.21–
7.24 m (2H, Harom), 7.28–7.32 m (1H, Harom), 7.42 d
(2H, Harom, J = 8.5 Hz), 7.48 d (1H, Harom, J = 7.6 Hz),
7.55 d (2H, Harom, J = 8.5 Hz). Mass spectrum, m/z (Irel,
%): 350 (100) [M]+, 335 (71), 315 (11), 299 (18), 265
(26), 202 (22), 131 (29). Found, %: C 75.10; H 4.67.
C22H16Cl2. Calculated, %: C 75.22; H 4.59. M 350.06.
1
1
Harom); Z isomer: 2.36 s (3H, Me), 3.60 s (3H, OMe),
6.36 s (1H, 2-H), 7.10–7.40 m (9H, Harom). Mass spec-
trum (isomer mixture), m/z (Irel, %): 252 (95) [M]+, 237
(5), 221 (100), 193 (33), 178 (52), 165 (18), 119 (23),
115 (34). Found (for isomer mixture), %: C 80.95;
H 6.43. C17H16O2. Calculated, %: C 80.93; H 6.39.
M 252.12.
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1
substance. H NMR spectrum (acetone-d6), δ, ppm:
1.78 s (3H, Me), 6.68 s (1H, 2-H), 7.02 t (2H, Harom
,
J = 8.9 Hz), 7.23–7.28 m (3H, Harom), 7.31–7.34 m
(2H, Harom), 7.38 d.d (2H, Harom, J = 8.9, 5.4 Hz),
7.53 d (1H, Harom, J = 7.5 Hz), 7.72 d.d (2H, Harom, J =
8.9, 5.4 Hz). 19F NMR spectrum (acetone-d6), δF, ppm:
–116.59 m (1F), –113.84 m (1F). Mass spectrum, m/z
(Irel, %): 318 (100) [M]+, 303 (82), 301 (17), 220 (11).
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C 83.00; H 5.07. M 318.12.
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