Russian Chemical Bulletin, International Edition, Vol. 62, No. 2, pp. 435—437, February, 2013
435
Synthesis of (Е)ꢀ4ꢀphenylꢀ3ꢀbutenꢀ2ꢀone by the reaction of styrene
with acetic anhydride in the presence of zeolite catalysts*
A. M. Suleimanova,a N. G. Grigor´eva,a S. V. Bubennov,a A. F. Gizetdinova,b M. I. Tselyutina,b and B. I. Kutepova
aInstitute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 231 2750. Еꢀmail: nggꢀink@mail.ru
bOAO "Angarsk Plant of Catalysts and Organic Synthesis,"
665830 Angarsk, Irkutsk Region, Russian Federation
The high catalytic activity and selectivity of zeolites НBeta and НZSMꢀ12 were found in
the synthesis of (Е)ꢀ4ꢀphenylꢀ3ꢀbutenꢀ2ꢀone by the reaction of styrene with acetic anhydride.
Key words: styrene, acetic anhydride, 4ꢀphenylꢀ3ꢀbutenꢀ2ꢀone, zeolite catalysts.
formed into the H form using thermal treatment at 540 C for 4 h.
Prior to experiments the catalysts were heated in air for 4 h
at 540 C.
,ꢀUnsaturated aromatic ketones serve as the initial
substances for the synthesis of various organic compounds:
vitamins, drugs, and flavor and scented additives.1 One of
the most known ,ꢀunsaturated aromatic ketones is
4ꢀphenylꢀ3ꢀbutenꢀ2ꢀone (benzalacetone), which is synꢀ
thesized by the condensation of benzaldehyde with aceꢀ
tone in the presence of strong bases (Claisen—Schmidt
reaction).2,3 This method is complicated and multiꢀ
staged, uses large volumes of solutions of acids and bases,
and has a low yield of benzalacetone. Therefore, search for
new methods of synthesis of ,ꢀunsaturated aromatic
ketones, especially using heterogeneous catalysts, reꢀ
mains urgent.
In this work, we studied the catalytic properties of the
catalysts containing zeolites of various structures in the
reaction of styrene with acetic anhydride. The purpose of
the study is to develop a heterogeneous catalyst that can ve
applied in a simple method of synthesis of benzalacetone
used in diverse fields of application, including medicine.4—6
The reaction was carried out in a batch isothermal reactor at
80—130 C in the presence of 10—30 wt.% of the catalyst.
The conversion of styrene and composition of the reaction
products were determined by GLC and HPLC. Styrene dimers,
viz., (Е)ꢀ1,3ꢀdiphenylbutꢀ1ꢀene (2a), cisꢀ and transꢀ1ꢀmethylꢀ
3ꢀphenylindanes (2b,c), were identified using the beforehand
synthesized compounds.10 The molecular weight of the styrene
oligomers with the degree of oligomerization n = 28 was deterꢀ
mined by Rast´s method.11
NMR spectra were recorded on a Bruker AVANCEꢀ400
spectrometer with working frequencies of 400.13 (1Н) and
100.62 MHz (13С) in CDCl3. GLC analysis was carried out on
a Carlo Erba HRGS 5300 Mega Series chromatograph with
a flameꢀionization detector (capillary column 25 m, SEꢀ30 phase,
temperature programming from 50 to 280 C with a rising rate of
8 deg min–1, temperature of the detector 250 C, temperature of
the evaporator 300 C, helium as a carrier gas, 30 mL min–1).
HPLC analysis was carried out on an HPꢀ1090 chromatograph
with a refractometric detector and the polystyrene column Plgel
100Е using toluene as an eluent, the rate of toluene feed of
Experimental
0.8 mL min–1, and a ribbon velocity of 1.5 cm–1
.
Highꢀresolution mass spectra were obtained on a Trio 1000
instrument (Fisons) with the DBꢀ5 capillary column; temperaꢀ
ture programming from 50 to 320 C with a heating rate of
4 deg min–1; 70 eV.
Styrene (purity 99.9%, produced at the OAO "Salavatnefteꢀ
orgsintez") was preꢀdistilled. Acetic anhydride was used as reꢀ
ceived.
The following zeolites were used: НY4.9 and НY6.0 (the
lower index shows the molar ratio SiO2/Al2O3 (М)), НBeta
(М = 18), HZSMꢀ12 (М = 34). The starting zeolites NaY4.9 and
NaY6.0 were synthesized using earlier described procedures.7,8
Zeolite catalysts НY4.9 (degree of exchange of Nа+ ions by Н+
= 96%) and НY6.0 ( = 97%) were prepared by ion exchange in
a solution of NН4NО3 followed by calcination at 540 C. Zeoꢀ
lites Beta and ZSMꢀ12 synthesized in the NН4 form9 were transꢀ
(Е)ꢀ4ꢀPhenylbutꢀ3ꢀenꢀ2ꢀone (1). Styrene (0.6 mL, 0.005 mol)
was slowly added to a suspension of zeolite HBeta (0.21 g) and
acetic anhydride (1.9 mL, 0.02 mol). The mixture was stirred for
7 h at 130 C. After cooling, the catalyst was filtered off and the
mixture was distilled under reduced pressure. The yield was 82%;
b.p. 90 C (5 Torr), m.p. 42 C. Found (%): C, 82.46; H, 7.03.
1
С10H10O. Calculated (%): C, 82.15; H, 6.91. H NMR, : 2.33
(s, 3 H, Me); 6.69 (d, 1 H, =CH, J = 16.0 Hz); 7.32—7.53
(m, 6 H, =СН, Ar) (see Ref. 6). 13C NMR, : 27.47 (C(10));
126.09 (C(8)); 126.60—130.28 (Ar); 143.49 (C(7)); 198.29 (C(9)).
MS: m/z 146.
* Dedicated to the Academician of the Russian Academy of
Sciences S. M. Aldoshin on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0436—0438, February, 2013.
1066ꢀ5285/13/6202ꢀ0435 © 2013 Springer Science+Business Media, Inc.
Suleimanova
