Reaction of acetylene carbonyl compounds with benzene in the presence of aluminum bromide: A new preparation method for substituted indenes

Full text of DOI:10.1134/S1070428006080252

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 8, pp. 1239-1241. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó A.V. Vasil’ev, A.O. Shchukin, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 8, pp. 1256-1258.
SHORT
COMMUNICATIONS
Reaction of Acetylene Carbonyl Compounds with Benzene
in the Presence of Aluminum Bromide: a New Preparation Method
for Substituted Indenes
A.V. Vasil’ev andA.O. Shchukin
St. Petersburg State Academy of Forestry Engineering, St. Petersburg, 194021 Russia
e-mail: aleksvasil@mail.ru
Received May 5, 2006
DOI: 10.1134/S1070428006080252
An opportunity was recently demonstrated for
generating from alkynes vinyl type cations using liquid
superacids HSO3F and CF3SO3H permitting the
investigation of reactions involving these cations [1–3].
The next step in development of this field is the study of
acetylene derivatives transformations in the presence of
Lewis acids and solid superacids. Lewis acids like
aluminum halides are widely employed in the organic
synthesis, in particular, for electrophilic activation of
substituted phenols and naphthols, heterocyclic
compounds, and enone structures in the reactions of
aromatic substitution and ionic hydrogenation [4].
2
ꢀ
0H
& & &
0H
,G
0H
3K
0H
3K
3K
ꢀ
ꢀꢁ,,E
$O%U
ꢀꢁ &ꢂꢃꢄꢃK
0H
,,,
0H
,,,E
The qualitative and quantitative composition of the
mixture of compounds IIIa, IIIb, and IIb inseparable
into components by the common column chromatography
on silica gel was established with the help of GC-MS
We found that that heating at 60°C for 1 h of acetylene
carbonyl compounds Ia–Ic in anhydrous benzene in the
presence of aluminum bromide at molar ratio substrate I
:AlBr3 : benzene equal to 1:5:80 followed by the quenching
of the reaction mixture with water, extraction of the
products into chloroform, and chromatographic isolation
on a column charged with silica gel (eluent hexane–
chloroform) led to the formation of substituted indenes
IIa–IIc in 12-38% yields.
1
procedure and H NMR spectroscopy. The GC-MS
analysis showed that two compounds in this mixture had
identical molecular ion peaks [M]+ 296 corresponding to
IIIa and IIIb isomers, but they were distinguished by
the fragment ions. The substance containing in its mass
spectrum ions of m/z 205 [M – 91]+ and 91 [MeC6H4]+
indicating the presence of a tolyl fragment possessed IIIb
structure. The other isomer with a molecular ion [M]+
296 lacking in its spectrum the characteristic ions of m/z
205 and 91 had IIIa structure. The third component of
the mixture with a molecular ion ([M]+ 282 according to
the GC-MS analysis was substituted indene IIb with the
1H NMR spectrum identical with that of an authentic
sample.
5
3K
2
$O%U
ꢀꢁ &ꢂꢃꢄꢃK
ꢀ
& & &
5
3K
B
B
, ꢁꢁꢁ,F
,, ꢁꢁꢁ,,F
R = H (a), Me (b), Ph (c).
Likewise acetylene ketone Id gave rise to a mixture
of three indene structures IIIa, IIIb, and IIb in an overall
yield 70%.
Isomers IIIa and IIIb originate from the indene system
formation by an intramolecular cyclization involving tolyl
1239

VASIL’EV, SHCHUKIN
1240
or phenyl ring respectively. Compound IIb formed either
as a demethylation product of compounds IIIa or IIIb in
the course of the reaction or as a result of aryl groups
exchange in the intermediate species on the route of
ketone Id conversion into the indene structures. The
formation of substituted indenes II and III involves the
condensation of two benzene molecules with the cation
intermediates generated from acetylene compounds I.
In these intermediates the carbonyl group carbon activated
by the Lewis acid and the vinyl cation center formed by
protonation of the triple carbon-carbon bond constitute
the electrophilic centers.
141.84 m, 142.04 m, 142.88 m, 143.49 d.d (J 166,
3.6 Hz), 154.35 m. Mass spectrum, m/z (Irel, %): 282
(100) [M]+, 268 (21), 267 (86), 265 (28), 252 (17), 203
(20), 191 (22), 165 (16), 131 (13), 126 (20), 77 (15).
1,1,3-Triphenylindene (IIc). Yield 12%, mp 136–
–1
138°C (publ.: mp 139–140°C [9]). IR spectrum, cm :
1
1600 (C=C). H NMR spectrum, d, ppm: 6.82 s (1H,
=CH–), 7.20–7.32 m (14Harom), 7.37 t (1Harom, J 6.8 Hz),
7.40 d (1Harom, J 7.6 Hz), 7.44 t (2Harom, J 7.5 Hz),
7.56 d (1Harom, J 7.5 Hz), 7.64 d (2Harom, J 8.0 Hz). Mass
spectrum, m/z (Irel, %): 344 (100) [M]+, 267 (32), 265
(27), 165 (6), 134 (5).
The detailed mechanism and the synthetic potential
of this new reaction for preparation of indene derivatives
[5, 6] require further special investigation.
1,6-Dimethyl-1,3-diphenylindene (IIIa) and 1-
methyl-3-(4-methylphenyl)-1-phenylindene (IIIb).
The compounds were obtained as an oily mixture with
compound IIb in an overall yield 70% with a ratio IIIa :
IIIb : IIb 4.3:1.3:1.0. 1H NMR spectrum of compound
IIIa (extracted from the spectrum of the mixture), d,
ppm: 1.80 s (3H, Me), 2.37 s (3H, Me), 6.53 s (1H, =CH–
), 7.09–7.66 m (13Harom). Mass spectrum, m/z (Irel, %):
296 (100) [M]+, 281 (74), 266 (12), 265 (21), 203 (24),
133 (12), 77 (8). 1H NMR spectrum of compound IIIb
(extracted from the spectrum of the mixture), d, ppm:
1.81 s (3H, Me), 2.43 s (3H, Me), 6.56 s (1H, =CH–),
7.09–7.66 m (13Harom). Mass spectrum, m/z (Irel, %): 296
(100) [M]+, 281 (90), 265 (26), 205 (15), 203 (28), 189
(12), 165 (10), 139 (11), 133 (22), 126 (14), 91 (8), 77 (9).
1H and 13C NMR spectra were registered on
a spectrometer Bruker AM-500 (operating frequencies
500 and 125.76 MHz respectively) in CDCl3.As internal
references served the residual signal of CHCl3
(dH 7.25 ppm) in the 1H NMR spectra and the signal of
CDCl3 solvent (dC 77.0 ppm) in the 13C NMR spectra.
IR spectra of compounds in chloroform solution were
recorded on a spectrophotometer Specord 75IR. Mass
spectra were taken on MKh-1321 instrument, ionizing
electrons energy 70eV, direct sample admission at the
ion source temperature 100–120°C. GC-MS analysis was
carried out on a Hewlett-Packard HP-5995 instrument
equipped with a flame-ionization detector, ionizing
electrons energy 70 eV, separator temperature 240°C,
that of ion source, 250°C, capillary quartz column
25000´0.32 mm, stationary phase Ultra-2 (95% of
methylsilicone, 5% of phenylmethylsilicone) 0.53 mm thick,
column temperature ramp from 100°C to 240°C at a rate
5–10 deg/min, carrier gas helium, flow rate 1 ml/min,
sample volume 2 ml of 3–5% solution.
3-Phenylpropynal (Ia) was a commercial product
purchased from Aldrich. The synthesis and character-
istics of initial compounds 4-phenylbut-3-yn-2-one (Ib),
1,3-diphenylpropynone (Ic), and 4-(4-methylphenyl)-
but-3-in-2-one (Id) were published previously [7].
1,3-Diphenylindene (IIa). Yield 18%, mp 67–68°C
–1
(publ.: mp 66–67°C [6]). IR spectrum, cm : 1600 (C=C).
1H NMR spectrum, d, ppm: 4.71 d (1H, J 2 Hz), 6.64 d
(1H, =CH–, J 2 Hz), 7.18 d (2Harom, J 7.5 Hz), 7.21 d
(1Harom, J 7.5 Hz), 7.23 d (1Harom, J 7.5 Hz), 7.26–
7.33 m (4Harom), 7.39 t (1Harom, J 7 Hz), 7.47 t (2Harom
J 7 Hz), 7.59 d (1Harom, J 7.5 Hz), 7.66 d (2Harom
,
,
J 7 Hz). 13C NMR spectrum, d, ppm: 55.38 d.m
(J 127.6 Hz), 120.56 d.d (J 159.4, 8.0 Hz), 124.31 d.d
(J 159.4, 8.0 Hz), 125.59 d.d (J 161.0, 7.4 Hz),
126.67 d.d (J 158.5, 7.2 Hz), 126.84 d.t (J 160.2,
7.4 Hz), 127.73 d.m, 127.81 d.m, 127.92 d.m, 128.60 d.d
(J 158.9, 7.6 Hz), 128.69 d.d (J 159.8, 8.0 Hz), 135.63 m,
136.29 d.d (J 169.1, 7.2 Hz), 139.52 q (J 8.5 Hz),
143.15 q (J 7.6 Hz), 144.61 m, 149.22 q (J 7.0 Hz). Mass
spectrum, m/z (Irel, %): 268 (100) [M]+, 267 (26),
265 (14), 262 (10), 191 (16), 189 (12), 165 (8), 126 (10).
1-Methyl-1,3-diphenylindene (IIb). Yield 38%,
mp 56–58°C (publ.: mp 59–59.5°C [8]). IR spectrum,
–1
1
cm : 1605 (C=C). H NMR spectrum, d, ppm: 1.82 s
(3H, Me), 6.60 s (1H, =CH–), 7.21–7.34 m (8Harom),
7.39 t (1Harom, J 7.2 Hz), 7.47 t (2Harom, J 7.2 Hz), 7.57 d
(1Harom, J 7.4 Hz), 7.66 d (2Harom, J 7.2 Hz). 13C NMR
spectrum, d, ppm: 22.98 q (J 122 Hz), 55.58 C,
120.90 d.d (J 158, 7.6 Hz), 123.20 d.d (J 157, 7.6 Hz),
125.85 d.d (J 159, 7.1 Hz), 126.17 d.t (J 156, 6.9 Hz),
126.46 d.t (J 159, 7.1 Hz), 126.62 d.d (J 158, 6.7 Hz),
127.69 d.q (J 160, 6.7 Hz), 127.73 m, 128.41 d.d (J 158,
7.1 Hz), 128.57 d.d (J 158, 7.6 Hz), 135.56 m (J 5.8 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

REACTION OFACETYLENE CARBONYL COMPOUNDS
1241
REFERENCES
Org. Khim., 1994, vol. 30, p. 90; Koltunov, K.Yu., Subboti-
na, E.N., and Repinskaya, I.B., Zh. Org. Khim., 1997, vol. 33,
p. 750; Koltunov, K.Yu., Repinskaya, I.B., and Borodkin, G.I.,
Zh. Org. Khim., 2001, vol. 37, p. 1610; Koltunov, K.Yu.,
Prakash, G.K.S., Rasul, G., and Olah, G.A., J. Org. Chem.,
2002, vol. 67, p. 4330; Koltunov, K.Yu., Prakash, G.K.S.,
Rasul, G., and Olah, G.A., J. Org. Chem., 2002, vol. 67,
p. 8943.
5. Ivchenko, N.B., Ivchenko, P.V., and Nifant’ev, I.E., Zh. Org.
Khim., 2000, vol. 36, p. 641.
6. Miller, W.G. and Pittman, C.U., J. Org. Chem., 1974, vol. 39,
p. 1955.
7. Vasil’ev, A.V., Rudenko, A.P., and Grinenko, E.V., Zh. Org.
Khim., 2000, vol. 36, p. 1193;Aristov, S.A., Vasil’ev,A.V., and
Rudenko,A.P., Zh. Org. Khim., 2006, vol. 42, p. 74.
8. Ryabov, V.D. and Korobkov, V.Yu., Zh. Org. Khim., 1980,
vol. 16, p. 377.
1. Vasilyev,A.V., Walspurger, S., Pale, P., and Sommer, J., Tetra-
hedron Lett., 2004, vol. 45, p. 3379; Vasilyev,A.V., Walspur-
ger, S., Haouas, M., Sommer, J., Pale, P., and Rudenko,A.P.,
Org. Biomol. Chem., 2004, p. 3483; Vasil’ev,A.V., Walspur-
ger, S., Pale, P., Sommer, J., Hao-uas, M., and Rudenko,A.P.,
Zh. Org. Khim., 2004, vol. 40, p. 1819; Walspurger, S., Vasily-
ev, A.V., Sommer, J., and Pale, P., Tetrahedron, 2005, vol. 61,
p. 3559.
2. Savechenkov, P.Yu., Rudenko, A.P., Vasil’ev, A. V., and Fu-
kin, G.K., Zh. Org. Khim., 2005, vol. 41, p. 1341.
3. Walspurger, S., Vasil’ev, A.V., Sommer, J., Pale, P.,
Savechenkov, P.Yu., and Rudenko,A.P., Zh. Org. Khim., 2005,
vol. 41, p. 1516.
4. Repinskaya, I.B., Barkhutova, D.D., Makarova, Z.S.,
Alekseeva, A.V., and Koptyug, V.A., Zh. Org. Khim., 1985,
vol. 21, p. 836; Koltunov, K.Yu. and Repinskaya, I.B., Zh.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006