SYNTHESIS OF NEW PHOTOCHROMIC

CYCLOPENTENONE-FUSED NAPHTHO[1,2-b]PYRAN
OHO F F
H
O O O O
t-B O K
u
F O O O
H

F
O O
O

Céu M. Sousa, Luis M. Carvalho, Paulo J. Coelho

O F

P h
O O O

O 4 P h 3

%
7 6 3 %

Centro de Química, Univ. de Trás-os-Montes e Alto Douro, 5001-911 Vila Real, Portugal. pcoelho@utad.pt

INTRODUCTION SYNTHESIS

The continuous irradiation of naphtho[1,2-b]pyrans with UV light The reaction of naphthopyran-4-one 1 with the silyl enol ether 2 in the
produces two coloured photoisomers, named TC and TT, that in the absence presence of TiCl4 gave naphthopyran 3 with 75% yield. Basic hydrolysis of
of light return to the original colourless state. These compounds have met ester 3 gave the acid 4 that was subsequently converted to the respective
considerable success in the production of variable-transmission optical acyl chloride and cyclised under TiCl4 catalysis affording the
materials, namely photochromic plastic ophthalmic lenses, which darken in cyclopentenone-fused naphtho[1,2-b]pyran 5 with 48% yield.
the sunlight. Ph Ph
Ph Ph Ph Ph
Ph OSiMe3 O
Ph Ph O O
2
OCH3
O O Ph O Ph O NaOH
UV EtOH
TiCl4 , CH2Cl2 H3CO O
+ Ph
3
HO O
∆, vis 1 75% 76%
4

1) SOCl2
Closed Form 48 %
TC TT 2) TiCl4
Colourless Two coloured photoisomers
Ph Ph

O
Although exhibiting similar absorption spectra, these photoisomers show
very different thermal stabilities. While the TC isomer rapidly returns to the 5
uncoloured closed form, the TT isomer is thermally more stable and shows,
RESULTS O
2 3
normally, fading rates 10 -10 times slower. This isomer is thus responsible
for the persistence of a residual colour for several minutes/hours after the Continuous UV light irradiation (150 W ozone free Xe lamp) of a
-3
removal of the light source. This can be a serious limitation for organic uncoloured 10 M toluene solution of naphthopyran 5, at 20ºC, lead to the
ophthalmic lenses applications. development of a pale yellow colouration with a maximal absorption at 440
nm. When the UV irradiation was turned off, the absorbance decreased
1.4
Dark rapidely reaching the initial value in 1.5 min. The fading kinetic is mono-
1.2
exponential with a half-time life of 10 s which is consistent with the
1.0 formation of only one coloured photoisomer.
Although the photochromic behaviour of this compound was
Absorbance

0.8

0.6 reproducible, the maximum absorbance attained under UV continuous

0.4 irradiation decreased along with the increase of the number of

0.2 UV ligth colouration/decolouration cycles. This points to the degradation of the

compound under the experimental conditions.
0.0
0 20 40 60 80

Time (min)
0.006
OBJECTIVE
0.005
Dark

In order to prevent the formation of the long-lived TT-photoisomer we have

0.004
envisaged the preparation of some new naphthopyrans possessing an alkyl
Absorbance

bridge between the pyran double bond and the naphthalenic moiety. This 0.003

bridge can block the rotation that occurs after the pyran ring opening avoiding
0.002
the formation of the TT-isomer.

0.001
UV
Ph
Ph Ph
0.000
O O Ph
0 5 10 15 20 25
UV
Only one coloured Time (min)
photoisomer
∆, vis
Ph
Ph Ph
O O Ph
Acknowledgements: To FCT (Portugal's Foundation for Science and Technology) UV
for financial support through project PTDC/QUI/66012/2006.
∆
O O
5
Only one coloured photoisomer