Synthesis of substituted indenes from 3-phenyl-2-propyn-1-ol derivatives

Full text of DOI:10.1134/S1070428007050284

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 5, pp. 784−786. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.O. Shchukin, A.V. Vasil'ev, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 5, pp. 785−787.
SHORT
COMMUNICATIONS
Synthesis of Substituted Indenes from 3-Phenyl-2-propyn-1-ol
Derivatives
A. O. Shchukin andA. V. Vasil’ev
St. Petersburg State Academy of Forestry Engineering, St. Petersburg, 194021 Russia
e-mail: aleksvasil@mail.ru
Received November 15, 2006
DOI: 10.1134/S1070428007050284
A similar reaction of 2-methyl-4-(4-methylphenyl)-3-
butyn-2-ol (Id) provided a mixture of products IId and
IIe in a ratio 3:1 with an overall yield 30%. Therewith
after the addition of the benzene molecule to acetylene
alcohol Id the indene system of compounds IId and IIe
was formed by the cyclization at the tolyl and the phenyl
rings respectively.
Indene series compounds attract deep interest due to
the opportunities of their practical application [1].
Nowadays indenes preparation procedures are exten-
sively developed with the use of expensive catalysts
based on transition metals; palladium, platinum, ruthenium,
and niobium [2]. We recently reported on a method of
substituted indenes synthesis by reaction of acetylene
carbonyl compounds with benzene in the presence of
aluminum bromide [3].
OH
+
Me
Me
We present here a new preparation method for indene
compounds from 3-phenyl-2-propyn-1-ol derivatives Ia–
Id. Stirring for 15 min at room temperature benzene
solutions of compounds Ia–Id in the presence of alumi-
num bromide (at a molar ratio substrate I : AlBr3 : benz-
ene = 1:5:50) followed with the treatment of the reaction
mixture with water, the extraction of the reaction products
into chloroform, and their isolation by column
chromatography on silica gel (eluent hexane–ethyl
acetate) led to the formation of substituted indenes IIa–
IIc in 9–53% yield.
Me
Id
Me
Me
Me
Me
1
7
2
AlBr3
20oC, 5 min
Me
6
5
3
+
4
IId
IIe
Me
OH
+
R
The structure of compounds IId and IIe in the mixture
R'
inseparable by the common column chromatography on
silica gel was established by H NMR and GC-MS
1
_
Iа Ic
spectroscopy. According to the GC-MS analysis both
compounds have identical molecular ions [M]+ 234 and
similar mass spectra of fragment ions. Acareful analysis
of 1H NMR spectrum of the mixture of compounds IId
and IIe revealed that the spectrum of the principal
component of the mixture contained proton signals
characteristic of 1,2,4-trisubstituted benzene ring. This
group of signals consisted of two doublets at δ 7.08 and
R
R'
AlBr3
20oC, 15 min
_
IIа IIc
R = R' = Me (a), R = Ph, R' = Me (b), R = R' = Ph (c).
784

SYNTHESIS OF SUBSTITUTED INDENES FROM 3-PHENYL-2-PROPYN-1-OL DERIVATIVES
785
7.38 ppm with coupling constants J 7.8 Hz and a singlet
at δ 7.20 ppm. This combination of signals corresponds
to the indene system of compound IId. The mentioned
doublets belong to protons H4 and H5, and the singlet, to
proton H7 of the indene ring. In the 1H NMR spectrum
of isomer IId appeared also multiplets characteristic of
the phenyl ring attached to the position 3 of the indene
structure: a doublet at δ 7.59 ppm (ortho-protons), a triplet
at 7.42 ppm (meta-protons), and a triplet at δ 7.34 ppm
(para-proton), J 7.5 Hz. Similar chemical shifts of these
protons were observed in the spectra of other 3-phenyl-
substituted indenes (see 1H NMR spectra in [3]).
J 7.3, 1.3 Hz), 7.37–7.40 m (1Harom), 7.43 t.t (2Harom
J 7.3, 1.3 Hz), 7.48–7.51 m (1Harom), 7.59 d.t (2Harom
J 7.3, 1.3 Hz). Mass spectrum, m/z (Irel, %): 220 (87)
[M]+, 205 (100), 189 (12), 178 (10), 101 (14). Found, %:
C 93.11; H 7.04. C17H16. Calculated, %: C 92.68; H 7.32.
,
,
1-Methyl-1,3-diphenylindene (IIb). Yield 53%.
1,1,3-Triphenylindene (IIc). Yield 50%. The
characteristics of compounds IIb and IIc we already
published in [3].
1,1,6-Trimethyl-3-phenylindene (IId) and 1,1-
dimethyl-3-(4-methylphenyl)indene (IIe) were
obtained in a form of an oily mixture in an overall yield
30% and in a ratio 3:1. 1H NMR spectrum of compound
IId (extricated from the spectrum of the mixture), δ, ppm:
1.38 c (6H, 2Me), 2.42 c (3H, Me), 6.34 c (1H, =CH–),
2-Methyl-4-phenyl-3-butyn-2-ol (Ia) and 2-methyl-4-
(4-methylphenyl)-3-butyn-2-ol (Id) were prepared by
procedure [4] reacting in diethylamine 2-methyl-3-butyn-
2-ol with iodobenzene and 4-iodotoluene respectively.
2,4-Diphenyl-3-butyn-2-ol (Ib) and 1,1,3-triphenyl-2-
propyn-1-ol (Ic) were obtained by method [5] by a reac-
tion of phenylacetylene lithium derivative with
acetophenone and benzophenone respectively.
7.08 d (1Harom, J 7.8 Hz), 7.20 c (1Harom), 7.34 t (1Harom
J 7.5 Hz), 7.38 d (1Harom, J 7.8 Hz), 7.42 t (2Harom
,
,
J 7.5 Hz), 7.59 d (2Harom, J 7.5 Hz). Mass spectrum,
m/z (Irel, %): 234 (100) [M]+, 219 (91), 204 (38), 189 (9),
101 (13). 1H NMR spectrum of compound IIe (extricated
from the spectrum of the mixture), δ, ppm: 1.38 s (6H,
2Me), 2.40 s (3H, Me), 6.37 s (1H, =CH–), 7.22–7.26 m
2-Methyl-4-phenyl-3-butyn-2-ol (Ia). Yield 70%,
mp 56–57°C (oily substance [6]). IR spectrum, ν, cm–1:
3600 (OHfree), 3500–3200 (OHbound), 2220 (C≡C).
1H NMR spectrum, δ, ppm: 1.61 s (6H, 2Me), 2.19 br.s
(1H, OH), 7.27–7.30 m (3Harom), 7.39–7.42 m (2Harom).
(5Harom), 7.49 d (2Harom, J 7.8 Hz), 7.51 d (1Harom
,
J 7.5 Hz). Mass spectrum, m/z (Irel, %): 234 (90) [M]+,
219 (100), 204 (31), 189 (9), 101 (14). Found for the
mixture of compounds IId and IIe, %: C 91.98; H 7.48.
C18H18. Calculated, %: C 92.26; H 7.74.
2,4-Diphenyl-3-butyn-2-ol (Ib). Yield 32%, mp 72–
73°C {bp 130–131°C (5×10–2 mm Hg) [5]}. IR spectrum,
ν, cm–1: 3600 (OHfree), 3500–3200 (OHbound), 2250
IR spectra of compounds dissolved in chloroform were
recorded on a spectrophotometer Specord 75 IR. 1H and
13C NMR spectra were registered on a spectrometer
BrukerAM-500 at operating frequencies 500 and 125.76
MHz respectively from solutions in CDCl3. As internal
references served the residual signals of CHCl3
(δ 7.25 ppm) in the 1H NMR spectra, and the signals of
CDCl3 (δ 77.0 ppm) in the 13C NMR spectra. GC-MS
analysis was carried out on G 2570A GC/MSD system
ofAgilent Technologies equipped with a flame-ionization
detector, ionizing electrons energy 70 eV, separator
temperature 250°C, ion source temperature 280°C,
capillary quartz column 30000 × 0.25 mm, stationary phase
Ultra-2 (95% of methylsilicone, 5% of phenylmethy-
lsilicone) 0.25 μm thick, oven temperature ramp from
100°C to 270°C, heating rate 5 deg/min, carrier gas helium,
flow rate 1 ml/min, sample volume 1 μl of 3–5% solvent.
1
(C≡C). H NMR spectrum, δ, ppm: 1.87 s (3H, Me),
2.44 br.s (1H, OH), 7.30–7.33 m (4Harom), 7.39 t (2Harom
J 7.7 Hz), 7.46–7.49 m (2Harom), 7.73 d (2Harom
J 7.7 Hz).
,
,
1,1,3-Triphenyl-2-propyn-1-ol (Ic). Yield 20%, mp
79–81°C (mp 81–82°C [7], oily substance [8]). IR
spectrum, ν, cm–1: 3600 (OHfree), 3500–3200 (OHbound),
2320 (C≡C). 1H NMR spectrum, δ, ppm: 2.96 br.s (1H,
OH), 7.28 t.t (2Harom, J 7.3, 1.3 Hz), 7.32–7.37 m (7Harom),
7.51–7.53 m (2Harom), 7.69 d.t (4Harom, J 8.4, 1.2 Hz).
2-Methyl-4-(4-methylphenyl)-3-butyn-2-ol (Id).
Yield 50%, mp 50–52°C. IR spectrum, ν, cm–1: 3600
1
(OHfree), 3500–3150 (OHbound), 2220 (C≡C). H NMR
spectrum, δ, ppm: 1.60 s (6H, 2Me), 1.99 br.s (1H, OH),
2.33 s (3H, Me), 7.09 d (2Harom, J 8.1 Hz), 7.30 d (2Harom
,
J 8.1 Hz). Found, %: C 82.47; H 8.01. C12H14O.
Calculated, %: C 82.72; H 8.10.
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,
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