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70 (1993) 157-161
157
Comparative photodegradation
study between spiro[indoline-oxazine]
and spiro[indoline-pyran]
derivatives in solution
G. Baillet,
Laboratok
(Received
de photochimie appIi@e,
1. Introduction
the degradation process was led mainly by photooxidation giving the salicylaldehyde derivatives and
oxindols compounds [9]. Recently, Yoshida et al.
[lo] have described H NMR and IR studies on
the resulting mixture of a photodegraded indolinospiropyran in the solid state and they also
came to the conclusion that an oxidation process
took place. Td date nothing has been published
concerning indolinospiro-oxazine
photoproduct
identification. So, it appeared interesting to compare the photoproducts obtained after irradiation
from the indolinospiropyran and indolinospirooxazine series in order to try to connect them
with mechanisms of degradation and to understand
the superior fatigue resistance of the Spiro-oxazine
series. In this work, the photochromic compounds
are degraded in toluene solution with the aim of
obtaining relatively easy information about the
photoproducts and later to investigate the fatigue
phenomenon in polymer matrix films.
2. Experimental details
2.1. Photodegradation experiments
1,3-dihydro-8-methoxy-6-nitro-1,3,3-trimethylspiro-[2H-indole-2,2-[3H]benzopyran](I),1,3-dihydro-1,3,3-trimethylspiro-[2H-indole-2,2-[3H]naphth[l,Zb]pyran](II),1,3-dihydm-1,3,3-trimethylspiro-[ZH-indole-2,3-[SH]naphth[2,lb][1,4]Q
158
II
111
compounds.
159
methylindoline
(Aldrich)
in methanol.
The
compound purified on silica (toluene/ethyl
acetate:
95/5) is a viscous plate yellow liquid: H NMR
(80 Ma)
in CDCk &.s(G(c~L~)~)
WH),
~3.15~-~3~
(s,3H) and &.7-7.2(n atom.) (OH);
JR
(gas
phase)
3069, 2977, 2939, 2896, 1741 (CO), 1612, 1486,
1376, 1340, 1242, 1123, 739 cm-; UVcmm
211,
252 nm; [M]+ = 175.
3,3-Dimethyloxindul
is a brown solid synthesized
by reaction of the phenylhydrazine
with isobutyric
acid and heat cyclization according to ref. 13: m.p.
145 C, H NMR
(80 MHz)
in CDCl,:
&3(G(cH3h (s,6H), &.o(~-~~ (s, 1H) and &.7-7.2(namm.j
(m,4H); IR (gas phase) 3477 (NH), 2981, 1764
(CO), 1474, 1146, 741 cm-; UVtCHJCNj 208, 248
nm; [M]* = 161.
160
and spim-amzincs
1586,1511,1377,1266,1234,1080,1~1,
800,743,
693,625cm-';WcmcNj 221,275,285,306,320
nm; [Ml+ = 169.
3.Results
.A
11m
&4
air0
lS,D
&a
1;s.
These results confirm Gautrons work concerning the photo-oxidation products of compound (I),
but very few high molecular weight products were
found.
In the same way, spiro[indolincFnaphthopyran] (II) leads mainly to oxindol type
derivatives and 2-hydroxy-1-naphthaldehyde
involving the chromenic part of the molecule. It is
interesting to note that 1,3,3-trimethyloxindol is
more abundant from this compound than from
the benzopyran derivative (I). A verification experiment by irradiating synthetic 1,3,34rimethyloxindol in toluene has shown that no 3,3-dimethyloxindol was formed. It is reasonable to consider
that 3,3-dimethyloxindol results from direct oxidation of the N-C& bond of the photochromic
compound itself.
Concerning the spironaphtho-oxazine (III) photoproducts involving the indoline part of the molecule are still oxidation derivatives like the oxindol
compounds and the dioxo derivative. The important
result with this series is that no direct oxidation
takes place on the right heterocyclic part of the
molecule. This part leads to the naphth[l,2dloxazole compound which could be considered
as a rearrangement product.
No l-nitroso-2-naphthol was detected with compound (III) whereas no naphthofuran was detected
with compound (II) as the corresponding heterocycle to the naphthoxazole.
This analytical study shows a difference in the
photo-oxidation processes between the spiro-oxazine and the spiropyran series: the introduction
of a nitrogen atom into the chromene heterocycle
seems to modify the ability of the photochromic
compound to oxidize. It seems clear that the diand trimethylated oxindols result from oxidation
of the Spiro carbon atom in the two series, whereas
the salicylaldehyde derivatives obtained with the
pyran series result from direct oxidation of the
carbon 4.
After the verification that oxidation processes
were responsible for photochromic compound degradation in the two series (no photolysis products
seem to be generated from these compounds in
the experimental conditions) it will be interesting
to study the mechanisms of these oxidation processes in order to assess the efficiency of antioxidizing agents and to improve their use.
161
Acknowledgments
We would like to thank C. Aubert for mass
spectrometry analyses and ESSILOR Int. for the
financial support of this work.
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