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J. Photochem. PhotobioL A: Chem.

70 (1993) 157-161

157

Comparative photodegradation
study between spiro[indoline-oxazine]
and spiro[indoline-pyran]
derivatives in solution
G. Baillet,
Laboratok
(Received

G. Giusti and R. Guglielmetti

de photochimie appIi@e,

CNRS UK4 1320, Fact&

de Luminy, 13288 Marseille Ct?dex 09 (France)

July 13, 1992; accepted September 17, 1992)

The photochromic compounds 1,3-dihydro-l,3,3-trimethylspiro[2H-indole-~3-[3H]naphth[2,l-b][1,4]oxazine], 1,3dihydro-1,3,3-trimethylspiro[2H-indole-2,2-[3H]naphth[l,2-b]p~an] and 1,3-dihydro-8-methoxy-6-nitro-1,3,3-t+


methylspiro[W-indole-2,2[3H]benzopyran] were degraded under UV light irradiation in toluene solution. The
resulting main photoproducts separated by gas chromatography and high performance liquid chromatography
were identified by different couplings with UV-visible diode array detection, mass spectromeq and Fourier
transform IR spectroscopy and were compared with synthetic standards. The different nature of the photoproducts
involving the chromene part of the molecules could suggest different mechanisms of degradation between the
spiropyran and Spiro-oxazine series and could explain the better fatigue resistance of the latter.

1. Introduction

Spiropyrans and Spiro-oxazines are thermally


reversible dyes under UV light irradiation which
exhibit photochromism in solution or as polymer
matrix films [l]. Recently, Spiro-oxazines have attracted considerable interest because of their good
fatigue resistance under a long period of irradiation
in comparison with spiropyran derivatives [2].
Quantitative
studies of the photostability of substituted spire-oxazines and mainly substituted spiropyrans have been carried out by flash photolysis
techniques in solution [3-8].
The literature concerning the qualitative degradation aspects of photochromic compounds in
terms of fragment identification is practically inconsistent. Indeed, it seems evident that photoproduct identification must be done in order to
propose mechanisms of degradation. This formal
approach could help to prevent fatigue resistance
by improving the synthesis strategies for obtaining
more stable photochromic compounds, This approach could be also fruitful in order to study the
role of different protective agents (i.e. hindered
amine light stabilizers, nickel complexes, UV
quenchers, etc.) which are known to maintain the
photochromism phenomenon. The major amount
of work involving photoproduct analysis has been
performed by R. Gautron on indolinospiropyrans
in solution, who had come to the conclusion that
lOlO-6030/93/$6.00

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

1993 - Elsevier Sequoia. All righta reserved

G. Baillet et al. / Photodegmdation of spimpyrans and spim-wines

158

II

Fig. 1. Structural formulae of the photochromic

111
compounds.

directly injected for gas chromatographic analysis


or, after evaporation under a stream of nitrogen,
is dissolved in acetonitrile for HPLC analysis.

Fig. 2. Gas chromatograpbic separation of photoproducts of (I),


(II) and (III). C&unn SE 54 25 mx0.32 mm, fijm 0.25 pm. T
injector 280 C (Ross) T detector 300 C (FID). pHe=O.9 bar.
80 C to 300 C at 5 C min-.

oxazine](III) (Fig. 1) were dissolved in anhydrous


toluene (SDS France) (C = lop3 M). The aerated
solutions were irradiated in a quartz flask with
magnetic stirring with a 500 W high-pressure mercury lamp I$BO Osram housed in a light box
(Arquantiel, Ile St Denis, France)_ The different
solutions containing the photochromic compounds
are analysed regularly by chromatography till the
complete bleaching of the solutions (I =2 hours,
II=2 days, III = 5 days). An aliquot of each is

2.2. Separation and identification ofphotoproducts


The current gas chromatographic system (GC)
consisted of a Varian Vista 6000 equipped with
a Ross injector and an FID detector. The column
was a Pierce 0.32 mmX 25 m capillary column
coated with a non-polar SE-54 phase (film 0.25
pm). The pressure of helium (carrier gas) was set
to 0.9 bar. The high performance liquid chromatograph consisted of a Beckman HPLC Gold
system coupled with a 168 diode array detector
to allow screening for peak purity and peak comparison. The separation system consisted of a C8
RX Zorbax reversed phase column (Rockland
technologies) 25 cmX4.6 mm with a gradient of
acetonitrile in water from 35% to 100% during
40 minutes set at 1 ml min- .
Mass spectra were obtained with an HP 5985
spectrometer under electronic impact mode (El)
(70 ev) and positive chemical ionisation mode
(CI+) with methane (150 ev).
IR spectra were obtained with a Nicolet 20 SXB
FTIR system coupled with a 60 m x 0.32 mm J&W
capillary column type DB-1 (film 0.25 pm) housed
in a Carlo Erba Vega 6000 gas chromatograph
equipped with an on-column injector. The different photoproducts separated by GC and HPLC
were identified initially by GC/MS and GC/FTIR.
Complete confirmation of the structures was carried out by comparing the mass spectra, IR spectra
and retention times with reference standards.
Screening with GC and HPLC allowed us to be
certain of detecting all compounds in the case of
non-volatile, thermolabile and non-responsive W
compounds.
2.3. Syntheses of reference compounds
The photochromic compounds (I) and (II) are
prepared according to the ref. 11, 12. The spironaphtho-oxazine (III) was supplied by Enichem
Synthesis (Milan, Italy). 5-Nitrovanillin and 2hydroxy-1-naphthaldehyde are commercially available (Aldrich). The 1,3,3-trimethyloxindol is prepared by ozonolysis of the 2-methylene-1,3,3-tri-

G. Baillet et aL I Phatodegradutionof spiqyrarw and +m-oxazines

159

Fig. 3. Mass spectra of photoproducts under electronic

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.

G. Baillet et al. i Photodegradation of spim~rans

160

and spim-amzincs

Napth[l,2-dloxazole, crystallized in cyclohexane,


is a white solid that consists of crystals formed in
plate-like configuration is obtained by the reaction
of 1-nitroso-Znaphthol with iodomethane in acetone according to ref. 14: m.p. 64 C, H NMR
(80 MHz) in CDCb: S~.T(~arom.)@-OH), &I(~~I~
GH)
(O-0,
57.9(H arom.) Cd, J=4IWH)
and SB.S(H
_,,)
(d, J=4Hz,lH);
IR (gas phase) 3070,1679,

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.

Fig. 4. GC/FT-IR spectrum of the 1,2,3,4-dihydro-2,3-dioxo4,4dimethylquinoline.

The chromatographic separations (GC/FID) of


the photoproducts for compounds (I), (II) and
(III) are shown in Fig. 2. The degradation process
leads mainly to oxidation products identified as
1,3,3-trimethyloxindol (I) and 3,3-dimethyloxindol
(3) for each of the three compounds. The chromene
part of compound (I) leads to 5-nitrovanillin
(3) and to the hydroxynaphthaldehyde
(4) for
compound (II). As to compound (III) it is interesting to notice the formation of the naphthoxazole
derivative (5;) as the fragment resulting from the
right heterocyclic part of the molecule. These
compounds have been identified formaIly by mass
spectrometry and by comparison with their synthetic references (Fig. 3). The structure of the
compound denoted by its raw formula C,,H,,NO,
(I;) on the chromatographic profiles has been
elucidated by quadripolar mass spectrometry,
IT-IR gas chromatography and by high resolution
mass spectrometry with a magnetic mass spectrometer (SCEA-CNRS-Vemaison,
France) after
concentrating collections of HPLC fractions (Fig.
4). The exact mass determined as being 189.16426
allows us to attribute reasonably the structure of
1,2,3,4-tetrahydro-2,3-dioxo-4,4-dimethylquinoline
to this compound, which would result from a ring
extension of the indoline cycle.
The kinetics of degradation for compounds (II)
and (III) measured by regular injection into the
chromatographic systems show that photoproduct
formation increases practically linearly as a function of time, indicating good stability of the photoproducts involved (Fig. 5).
4. Discussion

Fig. 5. Kinetics of photoproduct formation under UV light


irradiation for compounds (II) and (III): (I)- 1,3,3-trimethylox(4) = Z-hydroxy-l-naphthaldeindol, (2) = 3,3-dimethyloxindol,
(Q- 1,2,3,4-tetrahydro-2,3hyde,
(5) - naphth[l,2-dloxazole,
dioxo4,4-dimethylquinoline.

These results confirm Gautrons work concerning the photo-oxidation products of compound (I),
but very few high molecular weight products were

G. Baillet et al. I Photodegradation of spiropymns and spin-oxazkes

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

Do these processes take place via the reaction


of ambient oxygen with radical species that appear
during homolytic C-O bond dissociation under
light irradiation, or do they take place via photosensitized reactions (by the photoproducts themselves) involving 4 attack at the double bonds
of the merocyanine forms involving dioxetan as
intermediates? Further studies are in progress in
our laboratory, in order to explain the contribution
of each mechanism in the degradation processes.

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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