OXIDATIVE CARBONYLATION OF AROMATIC HYDROCARBONS
1461
2,2 -diylpalladium VI. After the incertion of carbon
monoxide into one of Pd-C bonds compound II eli-
minates Pd(0) and converts to fluorenone I. Con-
sidering low total concentration of Pd compounds and
formation of compound I in considerable amounts
(about 30 calytic cycles) a possibility of formation of
compound V by the reaction of mononuclear com-
plexes ArPdO2CCF3 and Pd(O2CCF3) should be
excluded.
mp 225 227 C (compare [24]: mp 224 C). IR spect-
1
1
rum (KBr), , cm : 1682 (C=O), 1608 (C=Car). H
NMR spectrum [4:1 CDCl3-(CD3)2SO], , ppm: 8.3 d
(2H, J 8 Hz), 7.75 d (2H, J 8 Hz), 7.7 d (2H, J 7 Hz),
7.5 m (3H) (all sygnals from ArH).
The solid insoluble residue remained after the treat-
ing with aqueous sodium hydroxide was dried and
several times treated with hexane. After evaporation
of joined hexane extracts 0.196 g of fluorenone I, con-
taining less than 10% of Ph2 (according to GLC data)
was obtained. Fluorenone was purified by column
Note that formation of benzophenone (cont-
aminated with antraquinone) in the oxidative car-
bonylation of benzene in the presence of Pd(II) and chromatography on silica gel (elution with chloro-
Fe(III) chlorides take place only under extremely rigid
conditions (220 C and 11 MPa of CO [20]).
form) and crystallized from hexane. mp 82 84 C
(compare [24]: 84 C). IR spectrum (a film from chlo-
1
roform), , cm : 3604 (C HAr), 1712, 3396 (C=O),
1
1600 (C=CAr). H NMR spectrum, , ppm: 7.6 d (2H,
EXPERIMENTAL
J 7.5 Hz), 7.4 m (4H), 7.2 t (2H, J 6.8 Hz) (all signals
from ArH). 13C NMR spectrum, C, ppm: 193.8
(C=O), 144.3, 134.0 (quarternary CAr), 134.6, 128.9,
124.1, 120.2 (tertiary CAr).
IR spectra were recorded on a Bruker WP-200
1
spectrometer in the range 4000-400 cm-1. H and 13C
NMR spectra were obtained on a Bruker Spectrospin
DPX-300 in CDCl3 with iternal TMS at 20 C. Ana-
lysis of reaction mixtures and isomeric composition
of the target product was carried out by GLC accord-
ing to the published procedure [21], and also by TLC
(Silufol UV-254, elution with 9:1 chloroform-ethyl
acetate, development in UV light).
ACKNOWLEDGMENTS
This work was carried out with the financial
support of Russian Fundation for basic research (grant
no. 97-03-32847a).
Carbonylation at the pressures exceeding the atmo-
spheric one was carried out according to the procedure
described in [21]. Carbonylation at atmospheric
pressure was carried out in a glass thermostated re-
actor (at the temperature above 20 C) or in a round-
bottom flask. Stirring of reaction mixture was carried
out by means of a magnetic stirrer. Carbon monoxide
was injected in the reaction mixture from the gas
burette according to the consumption. Pd(II) [22] and
Rh(II) [23] acetates were synthesized according to the
published procedures. Biphenyl, MnO2, and Mn2O3
pure grade were used. Benzene, toluene, acetic acid,
acetic anhydride, and trifluoroacetic anhydride pure
grade were used after distillation. Trifluoroacetic acid
pure grade was distilled over sulfuric acid.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 9 2001