Cyclization of phenyl 3-arylpropionates under the action of HSO 3F or AlBr3

Full text of DOI:10.1134/S1070428009080259

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 8, pp. 1252−1254. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © D.S. Ryabukhin, G.K. Fukin, A.V. Cherkasov, A.V. Vasil’eva, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 8, pp. 1260−1262.
SHORT
COMMUNICATIONS
Cyclization of Phenyl 3-Arylpropionates under the Action
of HSO3F or AlBr3
D. S. Ryabukhina, G. K. Fukinb, A. V. Cherkasovb, and A. V. Vasil’evaa
aSt. Petersburg State Academy of Forestry Engineering, St. Petersburg, 194021 Russia
e-mail: aleksvasil@mail.ru
bRazuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Russia
Received December 11, 2008
DOI: 10.1134/S1070428009080259
replacement of the para-tolyl group by a phenyl in the
structure of IIb under the action of AlBr3 in benzene
analogously to a similar exchange of aryl goups in indene
systems [5].
Superacids of Bro/ nsted type (HSO3F, CF3SO3H etc.)
and strong Lewis acids (SbF5, AlHlg3 etc.) are widely
used for superelectrophilic activation of organic com-
pounds in generation of reactive polycation intermediates
resulting from the protonation or coordination interaction
with basic (electron-donor) sites of the molecules of
organic substances [1]. These reactions underlie the
newly developed methods of synthesis of versatile
compounds [1], in particular, the synthesis of cyclic
structures of indan [2–7] and quinoline series [8–10]
from acetylene derivatives.
In the presence of AlBr3 compound Ib was brought
into an intermolecular reaction with benzene resulting in
indanone III. The most likely way of substance III
formation consists in the primary addition of two benzene
molecules to the acetylene bond of B species followed
by intramolecular acylation of the para-tolyl ring in the
structure C. Analogous mechanism operates in the
formation of 3,3-diphenylindanone from 3-phenylpropynic
acid and benzene in CF3SO3H [2].
We report here on the results of the study of phenyl
3-arylpropionates Ia and Ib transformation under the
action of HSO3F or AlBr3. The protonation in HSO3F or
the coordination with AlBr3 at the carbonyl oxygen and
acetylene bond of substrates Ia and Ib results in the
formation of cationic intermediates Aa, Ab or B respec-
tively reacting further along different paths (see the
scheme.
In HSO3F at –75°C in 0.5 h propionates Ia and Ib
were transformed into the products of intramolecular
cyclization, 4-arylcoumarines IIa and IIb, in 12 and 10%
yield respectively at a complete conversion of the initial
compounds.
The reaction of ester Ib in benzene for 1 h at 20°C
gave coumarines IIa and IIb and indanone III whose
structure was established by XRD analysis (see the
figure). In this case the overall yield of coumarines IIa
and IIb reached 38% and significantly exceeded the yield
of these compounds in HSO3F. 4-Phenylcoumarine (IIa)
formed under the reaction conditions as a result of the
Molecular atructure of 6-methyl-3,3-diphenylindan-1-one (III)
according to XRD data
1252

CYCLIZATION OF PHENYL 3-ARYLPROPIONATES
1253
Scheme.
R
O
H
O
O
R
R
HSO3F
_75oC, 0.5 h
OH+
_2H+
O
Iа, Ib
O
Aа, Ab
IIа (12%), IIb (10%)
AlnBr3n, C6H6
20оС, 1 h
δ−
O
AlnBr3n
δ+
δ−
Me
O
AlnBr3n
IIа (14%)
+ IIb (24%) +
Me
δ+
O
Ph
Ph
_AlnBr3n,
_PhOH
III (32%)
Ph
Ph
2 C6H6
δ−
AlnBr3n
δ+
B
O
PhO
Me
C
R = H (a), Me (b).
XRD study of compound III showed that C8 atom
possessed a tetrahedral coordination, the angle CC8C was
in the range 102.5(1)–114.4(2) deg. The distance C8–C
was 1.531(2)–1.556(2) , a characteristic value of the
ordinary C–C bond. The plane of the indan fragment
divided the C17C8C11 angle materially in halves. In the
(3H, Me), 7.20 t (4Harom, J 8.2 Hz), 7.27 t (1Harom
J 7.2 Hz), 7.41 t (2Harom, J 7.2 Hz), 7.51 d (2Harom
J 7.2 Hz). Found, %: C 81.36; H 5.14. C16H12O2.
,
,
Calculated, %: C 81.34; H 5.12.
4-Phenylcoumarine (IIa). To 2 ml of HSO3F cooled
to –75°C was added 200 mg (0.9 mmol) of propionate
Ia. The reaction mixture was stirred for 0.5 h at –75°C,
then it was poured into 30 ml of concn. HCl cooled to
–70°C. The mass obtained was diluted with water
(100 ml) and extracted with chloroform (3×50 ml). The
combined extracts were washed with water, with
saturated water solution of NaHCO3, again with water,
dried over Na2SO4, the solvent was distilled off in
a vacuum of a water-jet pump, the residue was subjected
to column chromatography on silica gel (eluent hexane–
ethyl acetate). Yield 24 mg (12%), mp 88–90°C (90–91
[14], 101–103°C [15]). IR spectrum, ν, cm–1: 1720
...
crystal of compound III intermolecular interactions O H
[2.41(2)–2.57(2) ] existed with the distance con-
siderably shorter that the sum of the van der Waals radii
of these atoms (2.7 [11]).
Phenyl 3-arylpropionates Ia and Ib were prepared
from phenol and 3-phenylpropynic and 3-(4-methyl-
phenyl)propynic acids respectively in CH2Cl2 in the
presence of dicyclohexylcarbodiimide and catalytic
quantities of pyridine [12].
Phenyl-3-phenylpropionate (Ia). Yield 35%, mp 38–
40°C (40°C [13]). IR spectrum, ν, cm–1: 2230 and 2210
(C≡C), 1720 (C=O). 1H NMR spectrum, δ, ppm: 7.19 d
1
(C=O). H NMR spectrum, δ, ppm: 6.38 s (1H, =CH–),
7.23 t (1Harom, J 7.6 Hz), 7.41 d (1Harom, J 8.2 Hz), 7.45–
7.56 m (7Harom). Mass spectrum, m/z (Irel, %): 222 (100)
[M]+, 221 (50), 124 (93), 165 (67), 149 (38), 94 (53).
(2Harom, J 7.6 Hz), 7.27 t (1Harom, J 7.6 Hz), 7.40 t (2Harom
J 7.4 Hz), 7.42 t (2Harom, J 7.6 Hz), 7.48 t (1Harom
J 7.4 Hz), 7.62 d (2Harom, J 7.4 Hz).
,
,
4-(4-Methylphenyl)coumarine (IIb) was similarly
obtained from 200 mg (0.8 mmol) of propionate Ib in
3 ml HSO3F at –75°C within 0.5 h. Yield 20 mg (10%),
Phenyl-3-(4-methylphenyl)propionate (Ib). Yield
52%, mp 82–84°C. IR spectrum, ν, cm–1: 2230 and 2210
(C≡C), 1720 (C=O). 1H NMR spectrum, δ, ppm: 2.40 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009

RYABUKHIN et al.
1254
CDCl3. The residual signal of CHCl3 (δ 7.25 ppm) served
as an internal reference. Mass spectra were measured
on an instrument MKh-1321 (70 eV). IR spectra were
recorded from solutions of compounds in CHCl3 on
a spectrophotometer FSM-1201. In performing XRD
analysis the experimental sets of intensities were
measured on an automatic diffractometer Smart APEX
mp 104–106°C (109–110 [15], 105–106°C [16]). IR
spectrum, ν, cm–1: 1720 (C=O). 1H NMR spectrum, δ,
ppm: 2.45 s (3H, Me), 6.36 s (1H, =CH–), 7.20 t (1Harom
,
J 8.0 Hz), 7.32–7.36 m (4Harom), 7.40 d (1Harom
,
J 8.0 Hz), 7.53 d (2Harom, J 9.0 Hz). Mass spectrum,
m/z (Irel, %): 236 (100) [M]+, 221 (53), 208 (93), 178
(24), 165 (27), 159 (26), 119 (20), 105 (17), 91 (14).
(graphite monochromator, MoKα radiation, ω-θ scanning).
Conversion of propionate Ib effected by AlBr3.
To a solution of 530 mg (2 mmol, 5 equiv) of AlBr3 in
4 ml of benzene at 20°C was added 87 mg (0.4 mmol) of
compound Ib. The reaction mixture was stirred for 1 h
at 20°C, then it was poured into 50 ml of water and
extracted with chloroform (3×50 ml). The combined
extracts were washed with water, with saturated water
solution of NaHCO3, again with water, dried over
Na2SO4, the solvent was distilled off in a vacuum, the
residue was subjected to column chromatography on silica
gel (eluent hexane–ethyl acetate). We obtained 12 mg
(14%) of compound IIa, 21 mg (24%) of compound IIb,
and also 36 mg (32%) of 6-methyl-3,3-diphenyl-indan-
1-one (III), mp 133–135°C. 1H NMR spectrum, δ, ppm:
2.42 s (3H, Me), 3.48 s (2H, CH2), 7.14–7.31 m (11Harom),
7.41 d (1Harom, J 7.9 Hz), 7.60 s (1Harom). Mass spectrum,
m/z (Irel, %): 298 (100) [M]+, 283 (41), 221 (55), 178
(24), 165 (27), 119 (12), 105 (15), 91 (10). Found, %:
C 88.60; H 6.04. C22H18O. Calculated, %: C 88.56; H 6.08.
M 298.14.
REFERENCES
1. Olah, G.A. and Klumpp, D.A., Superelectrophiles and
Their Chemistry, New York: Wiley, 2008, p. 351.
2. Rendy, R., Zhang, Y., McElrea, A., Gomez, A., and
Klumpp, D.A., J. Org. Shem., 2004, vol. 69, p. 2340.
3. Vasilyev, A.V., Walspurger, S., Haouas, M., Sommer, J.,
Pale, P., and Rudenko,A.P., Org. Biomol. Chem., vol. 2004,
p. 3483.
4. Vasil’ev, A.V., Walspurger, S., Pale, P., Sommer, J.,
Haouas, M., and Rudenko, A.P., Zh. Org. Khim., 2004,
vol. 40, p. 1819.
5. Vasil’ev, A.V. and Shchukin, A.O., Zh. Org. Khim., 2006,
vol. 42, p. 1256.
6. Shchukin, A.O. and Vasil’ev, A.V., Zh. Org. Khim., 2007,
vol. 43, p. 785.
7. Shchukin, A.O. and Vasilyev, A.V., Appl. Catal. A, 2008,
vol. 336, p. 140.
8. Koltunov, K.Yu., Walspurger, S., and Sommer, J., Chem.
Commun., 2004, p. 1754.
XRD of compound III. Crystals of the size 0.10 ×
0.08 × 0.05 mm C22H18O at 100(2) K monoclinic, a
10.1223(5), b 9.0874(5), c 17.8697(9) , α 90, b
104.238(1), γ 90 deg, V 1593.3(1) 3, Z 4, space group
P2(1)/n, dcalc 1.244 g/cm3, μ 0.074 mm–1, 3.06 ≤ θ ≤
27.00°, 10032 reflections measured, among them 3470
[Rint 0.0312] independent, R1 0.0474 [I > 2σ(I)], wR2
0.1217 (by all data). The structure was solved by the
direct method and refined by the least-squares method
on F2hkl in an anisotropis approximation for all nonhydrogen
atoms. The hydrogen atoms were revealed from the
difference Fourier sybthesis and isotropically refined.All
calculations were performed using software SHELXTL
v. 6.10 [17].
9. Koltunov, K.Yu., Walspurger, S., and Sommer, J., Eur. J.
Org. Shem., 2004, p. 4039.
10. Ryabukhin, D.S. and Vasil’ev,A.V., Zh. Org. Khim., 2008,
vol. 44, p. 1875.
11. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36, p. 3015.
12. Neises, B. and Steglich, W., Angew. Chem. Int. Ed., 1978,
vol. 17, p. 522.
13. Okajima, Y., Yakugaku Zasshi., 1960, vol. 80, p. 318; Chem.
Abstr., 1960, vol. 54, 18487h.
14. Koehl, W.J., J. Org. Chem., 1967, vol. 32, p. 614.
15. Yamamoto, Y. and Kirai, N., Org. Lett., 2008, vol. 10,
p. 5513.
16. Natarajan, M., Manimaran, T., and Ramakrishnan, V.T., Ind.
J. Chem. B., 1984, vol. 23, p. 529.
1H NMR spectra were registered on a spectrometer
Bruker AM-500 (operating frequency 500 MHz) in
17. Sheldrick, G.M., SHELXTL V. 6.10, Bruker, AXS, Inc.,
Madison, WI-53719, USA., 2000.
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