300 W halogen–tungsten lamp with a sodium nitrite solution
filter.
Acknowledgements
This work was partly supported by a Grant-in-Aid for Scientific
Research (A) from the Ministry of Education, Science, Sports
and Culture of Japan (No. 06403023) and partly defrayed by
the Grant-in-Aid on Priority-Area-Research on ‘Photoreaction
Dynamics’ from the Ministry of Education, Science, Sports
and Culture of Japan (Nos. 06239246 and 07228246). This
work was partly sponsored by New Energy and Industrial
Technology Development Organization (NEDO)–Research
Institute of Innovative Technology for The Earth (RITE).
T. O. thanks the Japan Society for the Promotion of Science for
a Research Fellowship for Young Scientists. We thank Dr
Shinjiro Matsuoka for his helpful comments.
With regard to the photofixation in the system 18-crown-6–
KF, the following procedure, different from the above, was
undertaken: PPP was dispersed in a methanol solution contain-
ing potassium fluoride (80 µmol) and 18-crown-6 (80 µmol).
To the residual solid obtained after methanol was evaporated
from the dispersion solution a DMF solution (2 ml) containing
benzophenone (2.5 mM) and TEA (1 M) was added. The
resulting dispersion solution was supplied to the photoreaction
after being saturated with CO2. After photoreaction, the reac-
tion mixture was directly analyzed by HPLC as described
below.
Diphenylglycolic acid was identified as the major product
from the coincidence of the HPLC retention time and the
absorption spectrum recorded by the detector of the HPLC
instrument with those of the authentic sample purchased from
nacalai tesque. Analysis of diphenylglycolic acid and 1,1-
diphenylpropane-1,2-diol was carried out by HPLC using a
Wakosil-II column (4.6 × 150 mm) and a photo-diode array
detector (Hitachi Model L-3000) with a mixture of acetonitrile
and buffered aqueous solution (KH2PO4–NaOH; pH = 7) as
an eluent. 1,1-Diphenylpropane-1,2-diol was isolated by gel
permeation chromatography (GPC) with JAIGEL 2H and
JAIGEL 1H columns on a Nippon Bunseki Kogyo Model
LC-908 instrument using chloroform as an eluent and its
analytical data were compared with those of authentic (S)-(Ϫ)-
1,1-diphenylpropane-1,2-diol purchased from Aldrich. The
analytical data of the isolated compound are as follows:
δH(CDCl3) 1.12 (d, J 6.2, 3H), 1.85 (s, 1H), 2.98 (s, 1H), 4.83 (m,
J 6.2, 1H), 7.15–7.45 (m, 8H), 7.62 (d, 2H). The NMR spectrum
also contained other peaks due to remaining Et4NCl. GC–MS
(EI): m/z 183 [(M Ϫ CH3CHOH)ϩ, 43%], 105 (C6H5COϩ,
100%), 77 (C6H5ϩ, 85%). Benzophenone, benzhydrol and
benzopinacol were analyzed by HPLC using a Cosmosil-ODS
column (4.6 × 150 mm) and a UV detector (TOSOH Model
UV-8000) with a mixture of methanol and buffered aqueous
solution (KH2PO4–NaOH; pH = 7) as an eluent. Analysis of
formate (HCO2Ϫ) was performed by ion exchange chrom-
atography using a TSK gel SCX(Hϩ) column (7.8 × 300 mm) at
313 K and a UV detector (TOSOH Model UV-8011) with
aqueous phosphate solution (2 m) as an eluent.
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ϩ
23 TEA , Et3NHϩ or water contained in the system as moisture can
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Molecular orbital calculations
Semiempirical molecular orbital (MO) calculations were done
by MOPAC Ver. 6.1028–31 using the molecule modeling system
(Molgraph, Daikin Co.) installed in a workstation (COMTEC,
4DRPC). The geometries of the molecules were optimized
energetically using MNDO/PM3.
Paper 8/02043D
Received 13th March 1998
Accepted 18th June 1998
2004
J. Chem. Soc., Perkin Trans. 2, 1998