Synthesis and unexpected photochemical behaviour of biphotochromic systems involving spirooxazines and naphthopyrans linked by an ethylenic bridge

Article abstract of DOI:10.1016/S0040-4020(01)00693-7

Using the Wittig reaction, six new biphotochromic compounds have been prepared by the coupling of conveniently functionalised spiro[indoline-naphthoxazines] and naphthopyrans. Compared to molecules taken individually, unusual photochromic behaviour has been detected with compounds for which a double bond of Z-configuration links both entities by the 5 or 5′ positions of the naphthalenic parts. Indeed, in this case the thermally stable uncoloured and coloured forms (bistable system) can be photochemically converted acting as photochemical switches.

Full text of DOI:10.1016/S0040-4020(01)00693-7

TETRAHEDRON
Pergamon
Tetrahedron 57 72001) 7349±7359
Synthesis and unexpected photochemical behaviour of
biphotochromic systems involving spirooxazines and
naphthopyrans linked by an ethylenic bridge
p
Â
Â
Andre Samat, Vladimir Lokshin, Karine Chamontin, David Levi, Gerard Pepe
and Robert Guglielmetti
   Â
Faculte des Sciences de Luminy, Universite de la Mediterranee, UMR 6114 CNRS, Case 901, 163 Ave de Luminy,
13288 Marseille Cedex 9, France
Received 6April 2001; revised 3 July 2001; accepted 5 July 2001
AbstractÐUsing the Wittig reaction, six new biphotochromic compounds have been prepared by the coupling of conveniently function-
alised spiro[indoline±naphthoxazines] and naphthopyrans. Compared to molecules taken individually, unusual photochromic behaviour has
been detected with compounds for which a double bond of Z-con®guration links both entities by the 5 or 50 positions of the naphthalenic
parts. Indeed, in this case the thermally stable uncoloured and coloured forms 7bistable system) can be photochemically converted acting as
photochemical switches. q 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
With biphotochromic compounds linked by a non-conju-
gated chain 7A, Scheme 1), the main goals are to bring
structural modi®cations able to favour the auto-assembling
of the coloured photoinduced forms. On the other hand,
when the spacer hold complexing ability like polyethers,11
polyamides,4±6 or calix[4]arenes,16 the photomodulation of
the complexation, and the variation of the photochromic
properties by supramolecular effects are possible.
The light induced colour change of organic compounds, i.e.
photochromism, has been subjected to extensive investiga-
tion, due to a wide range of applications.1±3 Among the
different challenges in this ®eld, the design of molecules
in which two photochromic entities are covalently linked
is especially attractive. This kind of compounds, named
`biphotochromics' by H. DuÈrr,1 are a subject of interest
for a number of research teams, resulting in the increase
of publications and patents during the last few years.
Many families of organic photochromic compounds are
involved: spiropyrans,4±9 spirooxazines,10±13 dihydroindoli-
zines,13±16 Schiff bases,14 dihydroazulenes,17±18 diaryl-
naphthopyrans,12,19 dithienylethenes.18 The objectives of
these different studies are diverse and depend on the struc-
ture of the involved photochromic units but also on the kind
of linkage.
The objectives are different for annellated biphotochromics
7B, Scheme 1) including usually a shared aromatic
ring10,12,13 and for biphotochromic molecules for which
the spacer is a conjugated chain 7C).
Contrary to type A compounds, photochromic entities are
not independent here and their simultaneous photoexcitation
becomes problematic. Nevertheless, when this speci®city
occurs, unusual spectrokinetic properties of the coloured
Scheme 1.
Keywords: oxazines; chromenes; Wittig reactions; photochemistry.
Corresponding author. Tel.: 133-4-91-82-94-05; fax: 133-4-91-82-93-01; e-mail: samat@luminy.univ-mrs.fr
p
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020701)00693-7

7350
A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
species can be observed.13 On the other hand, providing that
a selective photoexcitation was possible, biphotochromics
of B and C types can be considered as multimode switching
systems.18
method to build the carbon±carbon double bond acting as
the linking arm between the two photochromic units. The
success of this aim was dependent on the possible function-
alisation of spiro[indoline±naphthoxazines] and naphtho-
pyrans, a work we developed in our laboratory for several
years20,25,26 and which has been extended in the present
paper.
In the frame of our studies related to photochromic spiro-
oxazines and diarylnaphthopyrans20±24 we have decided to
study biphotochromics including these two families of
compounds. Our work was especially devoted to type C
molecules 7Scheme 1) in which the spacer is an ethylenic
bond, the aim being to prepare and to make a preliminary
study of the photochromic behaviour of compounds 1±6.
Carboxaldehydes and phosphonium salts 7usual precursors
for the Wittig reaction) might be a priori easily prepared
from hydroxymethyl groups born by photochromic
molecules. In both series 7spirooxazines and naphthopyrans)
these derivatives can be obtained from two main starting
materials 7Scheme 3): 3-hydroxymethyl-2-naphthol 727
and 6-hydroxymethyl-2-naphthol 8; to our knowledge this
latest is not described in the literature, but can be afforded
by the reduction of 6-hydroxy-2-naphthaldehyde20. Then
the reaction of these naphthols 77 and 8) with 1,1-diphenyl-
propyn-1-ol28 leads to hydroxymethylated naphthopyrans 79
and 11), while their nitrosation, followed by a classical29
2. Results and discussion
2.1. Synthesis
To prepare biphotochromic compounds 1±6 7Scheme 2), we
have chosen the Wittig reaction as simple and ef®cient
Scheme 2.

A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
7351
Scheme 3. Reagents and conditions: 7a) 1,1-diphenylpropyn-1-ol, CH3CN, p-toluenesulphonic acid 7cat.), rt: 7b) NaNO2, H2SP4, Pyridine, 08C:
7c) 2-methylene-1,3,3-trimethylindoline 7Fischer base), EtOH or trichloroethylene, re¯ux: 7d) Br2/PPh3, CH2Cl2, rt: 7e) PCC, CH2Cl2, rt: 7f) PPh3, toluene,
re¯ux: 7g) SoCl2, Et2O, rt: 7h) Dess±Martin periodinane, CH2Cl2, rt.
condensation with the Fischer base, allow the preparation of
spirooxazines 713 and 14) bearing the same functional
groups on the 50 and 80 position, respectively.
solution of NaOH), in which the phosphonium salt acts as
phase transfer catalyst31 have been applied. In the case of the
preparation of compounds 1 and 4, two different combina-
tions for the starting materials have been used, both methods
giving comparable yield. Structure of compounds 1±6 has
These reactions and the transformations of hydroxymethyl-
ated intermediates into the expected precursors are
summarised on Scheme 3. Among the compounds included
in this scheme, the spirooxazine 13 has been already
mentioned in the literature30 but not fully characterised.
On the other hand, the synthesis of naphthopyrans 9, 16,
2420 and spirooxazine 2026 has been previously described
by our laboratory.
1
been established by H and 13C NMR spectroscopies, mass
spectrometry and elemental analysis. Molecular masses
con®rm without doubt the dimeric character of the
compounds.
1
Moreover, characteristic signals in H NMR spectra 7like
C7CH3)2:1.31±1.41 ppm, N±CH3: 2.65±2.75 ppm, H-100:
8.30±8.60 ppm for spirooxazine and H-2: 6.20±6.30 ppm
for naphthopyrans) allow to identify unambiguously the
nature of the involved photochromic units.
Oxazine and naphthopyran precursors 7aldehydes and phos-
phonium salts) have been used to perform Wittig reactions,
leading to biphotochromic compounds 1±6 with satisfying
yields 7Table 1). Biphasic conditions 7toluene/50% aqueous
As expected for Wittig reactions, mixtures of E and Z
Table 1. Preparation details of biphotochromics 1±6
Compound
Precusors
Isomer ratioa
Yield 7%) 7isolated isomer)
Phosphonium salt
Aldehyde
1
17
19
17
22
24
16
567 E)
52 7E)
75 7Z)
56 Z)
52 7Z)
6 0 7Z)
35
16
2
3
4
92/8 7Z/E)
93/7 7Z/E)
91/9 7Z/E)
20
16
7
22
1720
17
22
5
6
23
65/35
65/35 7Z/E)
24
55
a
Measured as the ratio of 1H NMR signals 7N±CH3) for the spirooxazine unit, H-2 for the naphthopyran one. NMR spectra were monitored using products
puri®ed by liquid chromatography but not recrystallised.

7352
A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
chromic unit, have been synthesised starting from the
phosphonium salt 25 7Scheme 4). As for 2, 3 and 4, these
compounds have been obtained as Z/E mixture with a highly
predominant isomer 795:5, 93:7, respectively, for 26 and
27), which was easily isolated.
In both cases the Z-con®guration of this isomer has been
1
con®rmed by H NMR 7coupling constant Jabˆ12.4 Hz).
Taking into account the structural similarity of biphoto-
chromes 2 and 3 with the model compounds 26, 27, one
can reasonably assume a Z-con®guration for the double
bond of the ®rst ones. Moreover, if prepared monocrystals
of 2 were not of suf®cient quality to obtain a complete
structure resolution by X-ray radiocrystallography, the Z
stereochemistry of the central double bond has been
con®rmed for this compound.
To facilitate the identi®cation of the stereochemistry of the
isolated isomer for compound 1, two model molecules 28
and 29 have been synthesised 7Scheme 4), the latest been
prepared from the phosphonium salt 17 and the 6-methoxy-
2-naphthaldehyde. In both cases a mixtures of isomers has
been obtained and a pure E-isomer has been isolated only
Figure 1. Balls and Sticks representation of the molecular structure of
compound 4.
isomers were obtained. The con®guration being certainly of
importance regarding the photochromic behaviour, the
major isomer has been isolated when possible 7Table 1).
Then compounds 1±4 were isolated as one pure isomer. In
contrast, compounds 5 and 6 were obtained as unseparable
mixtures.
1
with 29. The comparison of H NMR spectra of model
molecules and compound 1 allows to assign to this one
the E-con®guration. This conclusion takes into account
two main data: 7i) the NMR spectrum of 1 does not show
any signal between 6.70 and 7.20 ppm, while Ha and Hb
protons of Z-28 and Z-29 appear in this range; 7ii) signals of
H-6for compounds 1 and E-29 are shifted to low ®eld 77.94
and 7.95 ppm, respectively) compared to the shift of
the same proton for biphotochromics and models of
Z-con®guration in which the double bond is linked to the
5-position 72, 4, 26, Z-29).
In the case of the biphotochrome 4, the Z-con®guration of
the isolated isomer has been proved by H NMR spec-
1
trometry 76.75 and 6.92 ppm, respectively, for Ha and Hb,
Jabˆ12.4 Hz) and de®nitely con®rmed by X-ray crystallo-
graphy 7Fig. 1). Unfortunately this structural assignment is
not possible for the symmetrical compounds 2 7binaphtho-
pyran) and 3 7bispirooxazine) for which the coupling
between the Ha and Hb protons can not be observed under
the NMR-technique applied. Finally, to establish the exact
con®guration of the major isomer, two model molecules 26,
27 7to compare with 2 and 3, respectively) in which a
methoxy-substituted naphthalenic part mimics a photo-
Then the structural elucidation of the new compounds has
more especially shown that as well biphotochromics linked
from 5 and for 50 positions by a double bond 72±4) as their
model compounds 726 and 27) exhibited curiously a major
Z-con®guration.
Scheme 4.

A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
7353
upon UV excitation the opening of both photochromic
entities. The photochromic properties of 5 can be considered
as the superposition of the properties of the spirooxazine
and the chromene taken separately. Indeed, the coloured
form of 5 shows two absorption bands in the visible range
7447 and 612 nm) which can be attributed, respectively, to
chromenic and spirooxazinic moieties 7comparison with 30
and 31). The behaviour of 6 is very similar of the 5 one.
When the irradiation is stopped, each bond decreases
according to the thermal kinetic of each species. The
times for colouration 7reaching of the photostationary
state) and thermal fading in the case of 1, 5 and 6 are in
the range of few seconds, values which are generally
observed in these families of photochromes.32,33
Scheme 5.
2.2. Photochromic behaviour
The other three compounds 72±4) have shown very slow
colouration rates and thermal fading rates closed to zero.
In these conditions, the times of irradiation necessary to
reach a photostationary equilibrium are large 7several
dozen of minutes) and able to undergo degradation reac-
tions. It is the reason why the samples were irradiated during
four minutes only before monitoring the absorption
spectrum in the visible range.
When submitted to UV irradiation, spirooxazines and
diarylnaphthopyrans undergo generally a thermal reversible
colour change due to the C±O bond cleavage 7Scheme 5).3
The photochromic behaviour of biphotochromic compounds
1±6 and model compounds 26±28 has been evaluated under
continuous irradiation 7Xenon lamp) at room temperature
using toluene as solvent. Details of conditions is given in the
Section 3. Results are summarised in Table 2.
Compound 4 7in which the chromenic unit is linked to the 50
position of the spirooxazine unit) leads to the formation of
only one band near 590±600 nm. It seems that, in the
experimental conditions used, only the oxazinic ring is
opened, the naphthopyran acting simply as a conjugated
substituent 7comparison of 4 and 6 with the model
compound 27).
The characteristic parameters of unsubstituted 1,3,3-
trimethylspiro[indoline±naphthoxazine] 30 and 3,3-diphenyl-
naphthopyran 31 7Scheme 5) are given as references data.
Among the six new biphotochromic compounds 71±6) only
1, 5 and 6 show expected thermally reversible photochromic
properties which can be compared to those of 30 and 31.
Concerning binaphthopyrans 1 the comparison with the
photochromic parameters of the model compounds 26
shows unambiguously 7regarding especially the absorption
wavelength of coloured form) that only one pyran unit is
opened.
In the case of compound 2 in which two naphthopyrans are
linked via the 5-position an alone wide absorption band
7460±490 nm) is observed characteristic of the coloured
form of this family of compounds. But one cannot
precise if one or two pyran rings are opened, the molecule
being completely symmetrical. The bathochromic shift
7about 30 nm) observed, compared to the model
molecule 26, can be explained by the extension of
conjugated system.
On the other hand the biphotochromic system 5 associating
one spirooxazine unit and one chromene unit undergoes
Concerning the compounds 3, including two spirooxazine
units linked through the 50-position, the band corresponding
to the coloured form of the oxazine is effectively observed
7610 nm), but a second band of weaker intensity occurs also
at 447 nm 7Fig. 2). It should to be noted that this speci®c
behaviour is observed in a lesser extent in the case of the
model compound 27 which includes only one oxazine entity
7Fig. 2, shoulder at 465 nm). A possible explanation could
be related to the interaction between the two opened systems
as proposed during the study of the thermochromism of bis-
spiropyrans,34 but the actual origin of this band is dif®cult to
explain from the obtained spectroscopic results.
Table 2. Photochromic parameters obtained under continuous irradiation
7150 W Xenon lamp, 1024 M in toluene, 258C)
a
Compounds
l
max 7nm)
A1
kD 7s21
)
1
2
3
4460.560.04
490b
447
610
592
447
612
490
592
430±450
550b
484
592
432
0.40c
0.70c
1.20c
1.10c
0.20
0.10
0.08
0.18
0.50c
0.50c
0.28
0.04
0.1
ù0
ù0
4
5
ù0
0.05
0.15
0.12
0.18
ù0
6
26
27
28
30
31
As mentioned above, whole compounds 2±4 and model
compounds 26 and 27 lead under irradiation to thermally
stable coloured forms 7several days to several weeks in the
dark). To our knowledge, it is the ®rst time that bistable
systems are described in spirooxazine and chromene
series. Indeed, we have shown a possible photochemical
decolouration using visible light in the case of compound
3 7Fig. 3).
ù0
0.07
0.15
0.08
a
Only the kinetic of higher amplitude 7.80%) is given.
Wide band.
Compounds for which the photostationary state can not be reached. The
absorbency is measured after 4 min of irradiation.
b
c

7354
A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
Figure 2. UV±Visible spectra of uncoloured [7ab)] and coloured forms [7cd)] of compounds 3 and 27, respectively 7toluene, 1024 M, 208C).
Figure 3. Example of the photobleaching of the coloured form of 3 under UV±Visible irradiation. Spectra of compound 3 7toluene 1024 M, 208C), after 4 min
of UV irradiation by a Xenon lamp 7spectrum 7a)) followed by 10 min of visible irradiation 7light of a Xenon lamp ®ltered by a GG 400 ®lter) 7spectrum 7b)).
Scheme 6.
Regarding the thermal stability of photoinduced forms, the
behaviour of some of the new photochromic systems linked
by an ethylenic junction is unusual compared to molecules
taken individually. At this stage of our investigations we
cannot explain this phenomenon 7stabilisation due to the
extension of the p system, possible photochemical cis±
trans isomerisation of the central double bond). The fact
that stable systems involved two photochromic units linked
via the 5 or 50 positions by a double bond of Z-con®guration,
makes also possible the occurrence of electrocyclisation
reaction between the two aromatic systems as observed in
photochromic cis-stilbenes 7Scheme 6).35 In this case, these
new photochromics can act as photochemical multiswitches
systems. Further experiments, and especially a NMR study

A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
7355
under UV irradiation, in progress, could lighten these points
in a near future.
white solid, mp 867from heptane). 1H NMR 7CDCl3):
1.6671H, t, Jˆ5.8 Hz, OH); 4.8072H, d, Jˆ5.8 Hz, CH2);
6.2871H, d, Jˆ10.0 Hz, H-2); 7.10±7.2778H, m, H-1, H-5,
H-30, H-40); 7.35±7.4275H, m, H-6, H-20); 7.6571H, d,
Jˆ8.7 Hz, H-9); 7.6971H, s; H-7); 7.9671H, d, Jˆ8.7 Hz,
H-10). 13C NMR 7CDCl3): 65.37t); 83.77s); 115.27s);
119.37s); 120.07d); 120.17d); 123.07d); 127.87d); 128.57d);
129.17d); 129.37d); 130.07s); 130.17d); 130.27s) 130.87d);
133.07d); 144.87s); 152.37s). Anal. calcd for C26H20O2: C,
85.69; H, 5.53; found: C, 85.63; H, 5.56.
3. Experimental
3.1. Materials and methods
Solvents 7SDS Company, France) were used without further
puri®cation other than drying over molecular sieves. 1H and
13C NMR spectra were recorded on a Bruker BM 250
1
3.2.3. 6-Hydroxymethyl-1-nitroso-2-naphthol .12). At
08C, 3 ml of an aqueous sodium nitrite solution 720%)
was added slowly to a solution of naphthol 8 70.52 g,
3 mmol) in 5 ml of pyridine. Then, 10 ml of sulphuric
acid 730%) was added over a period of 30 min. After stirring
the mixture 1 h at 08, the precipitate was collected by ®ltra-
tion, washed repeatedly with water and dried to give 12 as
an orange powder which was used without further puri®ca-
spectrometer 7250 and 62.5 MHz, respectively, for H and
13C) using tetramethylsilane as internal standard. Chemical
shifts are given in ppm and coupling constants in Hz.
Melting points 78C),measured in capillary tubes on a
Buchi 510 apparatus, are uncorrected. Column chromato-
graphy was performed on silica gel Merck 60 770±
230 mesh). Elemental analysis was performed by the Micro-
analytical Center of the University of Aix-Marseille III. The
ion impact mass spectra were recorded on JEOL SX102
spectrometer. Photochromic measurements were performed
in toluene solutions of spectrometric grade 7Aldrich) at 208C
7to ^0.28). The analysis cell 7optical pathlength 10 mm)
was placed in a thermostated copper block inside the sample
chamber of a Beckman-DU-7500-diode-array spectro-
photometer. An Oriel 150 W high pressure Xe lamp was
used for irradiation. The identi®cation of previously
1
tion. Yield 0.55 g 790%), mp 139. H NMR 7Acetone-d6):
4.5171H, sl, OH); 4.7572H, s, CH2); 6.6071H, m, H-3);
7.5971H, d, Jˆ7.7 Hz, H-7); 7.6671H, s, H-5); 7.9871H, m,
H-4); 8.2271H, m, H-8); 14.2271H, sl, NOH).
3.3. General method for the synthesis of hydroxymethyl
substituted spirooxazines
1
reported compounds were made by H NMR and melting
points comparison with literature data.
A solution of 0.173 g 71 mmol) of 2-methylene-1,3,3-
trimethylindoline and 0.2 g 71.1 mmol) of corresponding
1-nitroso-2-naphthol 710 or 12) in 20 ml of trichloroethy-
lene 7ethanol for 10) was re¯uxed for 5 h. After removing of
the solvent under vacuum, compounds were puri®ed by
column chromatography on silica gel.
3.2. Starting materials
1,1-Diphenylpropyn-1-ol
7Interchim),
6-methoxy-2-
naphthaldehyde 7Avocado), 2-methylene-1,3,3-trimethyl-
indoline 7Aldrich) and Dess±Martin periodinane
7Lancaster) were commercially available. Compounds 7,27
9,20 10,36 16,20 20,26 24,20 25,37 were prepared according to
previously described methods.
3.3.1. 50-Hydroxymethyl-1,3,3-trimethylspiro[indoline-
2,30-[3H]naphth[2,1-b][1,4]oxazine] .13). 55%, yield,
eluent CH2Cl2. Crystallisation gave white cristals, mp 141
7from ethanol). 1H NMR 7CDCl3): 1.3573H, s, CH3);
1.3873H,s, CH3); 1.9171H, m, OH); 2.7273H, s, N±CH3);
3.2.1. 6-Hydroxymethyl-2-naphthol .8). A solution of
2.2 g 712.8 mmol) of 6-hydroxy-2-naphthaldehyde in
50 ml of dry THF was added slowly to a stirred suspension
of 0.5 g 713.1 mmol) of lithium aluminium hydride in 30 ml
of the same solvent at 08C 7argon atmosphere). After 2 h
stirring at ambient temperature, the mixture was carefully
acidi®ed with a solution 72N) of hydrochloric acid and
extracted several times with Et2O. The combined organic
extracts were washed with water, dried with MgSO4 and
evaporated. Crystallisation gave 1.8 g 781%) of white
solid, mp 169 7from ethanol) 1H NMR 7DMSO-d6):
4.5872H, d, Jˆ4.9 Hz, CH2); 5.2771H, t, Jˆ4.9 Hz, OH);
7.03±7.0872H, m, H-1, H-3); 7.3471H, dd, Jˆ8.4 and
1.4 Hz, H-7); 7.6271H, d, Jˆ8.4 Hz, H-4); 7.6671H, s,
H-5); 7.7171H, d, Jˆ8.4 Hz, H-8); 9.7371H, s, Ar±OH).
4.6271H, dd, Jˆ13.6and 7.0 Hz, H of CH ); 4.7371H, dd,
2
Jˆ13.6and 5.9 Hz, H of CH 2); 6.5571H, d, Jˆ7.6Hz, H-7);
6.8971H, ddd, Jˆ7.3, 7.3 and 0.8 Hz, H-5); 7.0871H, dd,
Jˆ7.3 and 0.8 Hz); 7.2171H, ddd, Jˆ7.6,7.6 and 1.2 Hz,
H-6); 7.4271H, ddd, Jˆ7.5, 7.5 and 1.1 Hz, H-80);
7.5771H, d, Jˆ7.5, 7.5 and 1.1 Hz, H-90); 7.7171H, s,
H-60); 7.7371H, d, Jˆ8.4 Hz, H-70); 7.7971H, s, H-20);
8.5471H, d, Jˆ8.4 Hz, H-100); 13C NMR 7CDCl3) 20.87q);
25.47q); 29.57q); 51.57s); 60.87t); 98.57s); 107.17d);
120.07d); 121.47d); 121.57d); 122.87d); 124.57d); 127.07d);
127.87d); 127.97d); 128.17d); 128.37s); 128.87s); 130.27s);
135.77s); 142.07s); 147.17s); 150.57d). Anal. calcd for
C23H22N2O2: C, 77.07; H, 6.19; N, 7.82; found: C, 77.11;
H, 6.15; N, 7.80.
3.3.2. 8-Hydroxymethyl-1,3,3-trimethylspiro[indoline-
2,30-[3H]naphth[2,1-b][1,4]oxazine] .14). 48% yield,
eluent pentane/ether 740:60). Crystallisation gave white
crystals, mp 178 7from ethanol). 1H NMR 7CDCl3):
1.3276H, s, CH3); 2.2871H, sl, OH); 2.7273H, s, N±CH3);
4.8072H, sl, CH2); 6.5571H, d, Jˆ7.6Hz, H-7); 6.8871H, dd,
Jˆ7.2 and 7.2 Hz, H-5); 6.9971H, d, Jˆ8.8 Hz, H-50);
7.0771H, d, Jˆ7.2 Hz, H-4); 7.2071H, ddd, Jˆ7.6, 7.6 and
1.1 Hz, H-6); 7.5471H, dd, Jˆ8.7 and 1.5 Hz, H-90);
3.2.2. 3,3-Diphenyl-8-hydroxymethyl-[3H]-naphtho[2,1-
b]pyran .11). A solution of 1.0 g 75.7 mmol) of 6-hydroxy-
methyl-2-naphthol 8, 1.2 g 75.7 mmol) of 1,1-diphenyl-2-
propyn-1-ol and a catalytic amount of p-toluensulfonic
acid, in 100 ml of CH3CN were stirred 12 h, at ambient
temperature. After evaporation of the solvent, the residue
was puri®ed by column chromatography, eluent pentane/
CH2Cl2 730:70). Crystallisation gave 1.53 g 775%) of

7356
A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
7.6071H, d, Jˆ8.8 Hz, H-60); 7.6771H, s, H-70); 7.7171H, s,
H-20); 8.5371H, d, Jˆ8.7 Hz, H-100). 13C NMR 7CDCl3):
21.07q); 25.77q); 29.97q); 52.17s); 65.67t); 98.87s);
107.47d); 117.37d); 120.17d); 121.77d); 122.27d); 123.27s);
125.87d); 126.87d); 128.37d); 129.47s); 130.47d); 130.57s);
136.17s); 137.07s); 144.57s); 147.87s); 151.37d). Anal. calcd
for C23H22N2O2: C, 77.07; H, 6.19; N, 7.82; found: C, 77.12;
H, 6.23; N, 7.72.
CH2); 6.2671H, d, Jˆ9.9 Hz, H-2); 7.18±7.3378H, m, H-1,
H-5, H-30, H-40); 7.46±7.4875H, m, H-6, H-2 0); 7.6071H, d,
Jˆ8.7 Hz, H-9); 7.6571H, s, H-7); 7.9271H, d, Jˆ8.7 Hz, H-
10). 13C NMR 7CDCl3): 46.57t); 82.67s); 114.07s); 118.87d);
119.37d); 122.17d); 126.97d); 127.07d); 127.57d); 127.97d);
128.07d); 128.27s); 128.97s); 129.57s); 129.87d); 132.57d);
144.67s); 151.07s). Anal. calcd for C26H19ClO: C, 81.56;
H, 5.00; found: C, 81.48; H, 4.94.
3.4. General method for the synthesis of bromomethyl
substituted photochromes
3.5. General method for the synthesis of phosphonium
salts
A solution of 1.06g 76.6mmol) of bromine in 50 ml of
anhydrous CH2Cl2 was added dropwise to a stirred solution
of 2.15 g 78.5 mmol) of Ph3P in 25 ml of the same solvent
7argon atmosphere, ambient temperature). After 1 h stirring
a resulting solution was added dropwise to a cooled 708)
solution of 5.5 mmol of hydroxymethyl substituted
compound 79 or 13) in 50 ml of anhydrous CH2Cl2. After
2 h of additional stirring at ambient temperature the solution
was washed with water, dried 7MgSO4) and evaporated. The
crude product was puri®ed by column chromatography on
silica gel.
A mixture of 3 mmol of halogenomethyl substituted
compound 715, 18 or 21) and 3 mmol of triphenylphosphine
was re¯uxed 12 h in 10 ml of anhydrous toluene 7o-xylene
for 18). After cooling, the precipitate was ®ltered off,
washed with cold toluene and dried.
3.5.1. .3,3-Diphenyl-[3H]naphtho[2,1-b]pyran-5-yl)methyl-
triphenylphosphonium bromide .17). 90% yield. White
1
solid, mp 257. H NMR 7CDCl3): 5.4172H, d, Jˆ14.1 Hz,
CH2); 6.1671H, d, Jˆ10.0 Hz, H-2); 7.03±7.75730H, m,
H-arom. and H-1); 7.8771H, d, Jˆ8.5 Hz, H-10).
3.4.1. 5-Bromomethyl-3,3-diphenyl-[3H]-naphtho[2,1-b]-
pyran .15). 68% yield, eluent CH2Cl2. White solid, mp
1267from heptane). 1H NMR 7CDCl3): 4.6572H, s, CH2);
6.1471H, d, Jˆ10.0 Hz, H-2); 7.17±7.2878H, m, H-1, H-8,
H-30, H-40); 7.36±7.4875H, m, H-9, H-20); 7.6271H, d,
Jˆ8.1 Hz, H-7); 7.6471H, s, H-6); 7.8871H, d, Jˆ8.4 Hz,
H-10). 13C NMR 7CDCl3): 28.67t); 83.17s); 114.37s);
119.57d); 121.27d); 124.07d); 126.47s); 127.07d); 127.17d);
127.57d); 127.67d); 128.57d); 128.67d); 128.77s); 130.07s);
130.67d); 144.67s); 148.27s). Anal. calcd for C26H19BrO: C,
85.69; H, 5.53; found: C, 85.59; H, 5.45.
3.5.2. .3,3-Diphenyl-[3H]naphtho[2,1-b]pyran-8-yl)methyl-
triphenylphosphonium chloride .19). 59% yield. White
1
solid, mp 253. H NMR 7CDCl3): 5.4472H, d, Jˆ14.3 Hz,
CH2); 6.2271H, d, Jˆ9.9 Hz, H-2); 7.05±7.68731H, m,
H-arom. and H-1).
3.5.3. .1,3,3-Trimethylspiro[indoline-2,30-[3H]naphtho-
[2,1-b][1,4]oxazine]-5-yl) methyltriphenylphosphonium
bromide .22). 92% yield. White solid, mp 238. H NMR
1
7CDCl3): 0.9573H, s, CH3); 1.2573H, s, CH3); 2.1273H, s,
N±CH3); 4.9571H, dd, Jˆ14.7 and 14.7 Hz, 1H of CH2);
5.6171H, dd, Jˆ14.7 and 14.7 Hz, 1H of CH2); 6.4971H,
d, Jˆ7.7 Hz, H-7); 7.0271H, dd, Jˆ7.1 and 7.1 Hz, H-5);
7.171H, d, Jˆ7.1 Hz, H-4); 7.31±7.76720H, m, H-arom. and
H-20); 7.9371H, d, Jˆ3.5 Hz, H-60); 8.4971H, d, Jˆ8.4 Hz,
H-100).
3.4.2. 50-Bromomethyl-1,3,3-trimethylspiro[indoline-2,30-
[3H]naphth[2,1-b][1,4]oxazine .21). 61% yield, eluent
CH2Cl2. White solid, mp 1567from heptane). 1H NMR
7CDCl3): 1.3473H, s, CH3); 1.3973H, s, CH3); 4.4471H, d,
Jˆ9.8 Hz, 1H of CH2); 4.5371H, d, Jˆ9.8 Hz, 1H of CH2);
6.5671H, d, Jˆ7.6Hz, H-7); 6.9071H, ddd, Jˆ7.3, 7.3 and
0.8 Hz, H-5); 7.1071H, dd, Jˆ7.3 and 0.8 Hz, H-4);
7.2171H, ddd, Jˆ7.6, 7.6 and 1.2 Hz, H-6); 7.4071H, dd,
Jˆ6.8 and 1.2 Hz, H-8); 7.5871H, dd, Jˆ6.8 and 1.2 Hz,
H-9); 7.7371H, d, Jˆ8.4 Hz, H-70); 7.7571H, s, H-60);
7.7971H, s, H-20); 8.5471H, d, Jˆ8.4 Hz, H-100). 13C
NMR 7CDCl3): 20.97q); 25.77q); 27.67t); 29.57q); 51.67s);
98.67s); 107.27d); 119.97d); 121.47d); 121.67d); 123.27s);
124.67d); 125.47s); 127.67d); 127.87d); 128.07d); 128.57s);
130.77d); 131.07s); 135.87s); 141.97s); 147.27s); 150.57d);
Anal. calcd for C23H21BrN2O: C, 65.57; H, 5.02; N, 6.65;
found: C, 65.52; H, 5.06; N, 6.61.
3.5.4. 80-Formyl-1,3,3-trimethylspiro[indoline-2,30-[3H]-
naphth[2,1-b][1,4]oxazine] .23). A solution of 0.36g
71 mmol) of spirooxazine 14 in 20 ml of dry CH2Cl2 was
added slowly to a solution of 0.42 g 71 mmol) of Dess±
Martin periodinane in 40 ml of the same solvent. After 1 h
stirring, 50 ml of ether was added and mixture ®ltered on
celite. After evaporation of the solvent, the residue was
puri®ed by column chromatography 7eluent CH2Cl2) to
give 0.21 g 759%) of yellow crystals. Mp 201 7from
1
heptane). H NMR 7CDCl3): 1.3573H, s, CH3); 1.3773H, s,
CH3); 2.7973H, s, N±CH3); 6.5971H, d, Jˆ7.7 Hz, H-7);
6.9171H, dd, Jˆ7.4 and 7.4 Hz, H-5); 7.08±7.1272H, m,
H-4 and H-50); 7.2171H, ddd, Jˆ7.2, 7.2 and 1.5 Hz,
H-6); 7.7971H, s, H-20); 7.8271H, d, Jˆ8.9 Hz, H-60);
8.0471H, dd, Jˆ8.7 and 1.5 Hz, H-90); 8.2471H, s, H-70);
8.6671H, d, Jˆ8.7 Hz, H-100); 10.1271H, s, CHO). 13C
NMR 7CDCl3): 20.97q); 25.77q); 29.87q); 52.37s); 99.47s);
107.57d); 118.47d); 120.37d); 121.77d); 122.97d); 123.47s);
124.67d); 128.37d); 128.57s); 132.17d); 132.97s); 134.37d);
134.47s); 135.87s); 147.17s); 147.67s); 151.87d); 192.27d).
Anal. calcd for C23H20N2O2: C, 77.51; H, 5.66; N, 7.86;
found: C, 77.65; H, 5.56; N, 7.64.
3.4.3. 8-Chloromethyl-3,3-diphenyl-[3H]naphtho[2,1-b]-
pyran .18). A solution of 0.42 g 73.5 mmol) of thionyl
chloride in 5 ml of anhydrous Et2O was added dropwise to
cooled 708) solution of 0.72 g 72 mmol) of compound 11 in
30 ml of anhydrous Et2O. After 2 h stirring at ambient
temperature the mixture was evaporated. The crude product
was puri®ed by column chromatography on silica gel, eluent
pentane/CH2Cl2 780:20) to give 0.38 g 750%) of white crys-
tals. Mp 127 7from heptane). 1H NMR 7CDCl3): 4.6772H, s,

A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
7357
3.6. General method for the synthesis of biphotochromic
compounds and models
126.97d); 127.57d); 127.67d); 128.17d); 128.27d); 128.47d);
128.57s); 128.67d); 128.97s); 129.27d); 129.37s); 129.77d);
130.37s); 136.07s); 142.57s); 144.87s); 144.97s); 147.77s);
148.97s); 151.07d). Anal. calcd for C49H38N2O2: C, 85.69;
H, 5.58; N, 4.08; found: C, 85.60; H, 5.59; N, 4.06. m/z 687
7MH1).
A 50% solution of NaOH 73 ml) was added to a stirred
solution of 1 mmol of phosphonium salt and 1 mmol of
aldehyde in 3 ml of CH2Cl2. After 2 h stirring 30 ml of
CH2Cl2 and 30 ml of water were added. The organic
phase was washed with water, dried 7MgSO4) and evapo-
rated. The crude product was puri®ed by column chromato-
graphy on silica gel.
Crystal data for 4 7C49H38N2O2) Mrˆ686.85, monoclinic,
Ê
aˆ10.94972), bˆ28.16576), cˆ11.76272) A, bˆ94.6972)8,
Ê 3
Vˆ3615712) A , space group P21/c, Zˆ4, Dcˆ1.261
Mg m23, F7000)ˆ1408, mˆ0.074 mm21, Tˆ293 K, uˆ0±
358, 0 , h , 11; 0 , k , 28; 212 , l , 12; re¯ections
collected 4934, independent re¯ections 4934 7full-matrix
least-squares on F2). Crystal being of poor quality hydrogen
atoms were not located. Atomic coordinates, thermal para-
meters and bond lengths and angles have been deposited at
the Cambridge Crystallographic Data Center.
3.6.1. 5-[2-.3,3-Diphenyl-[3H]naphtho[2,1-b]pyran-8-yl)-
ethenyl]-3,3-diphenyl-[3H]naphtho[2,1-b]pyran .1).
Eluent pentane/CH2Cl2 770:30). Pale yellow solid, mp 238
1
7from heptane). H 7CDCl3) NMR: 6.2771H, d, Jˆ9.9 Hz,
H-20); 6.2971H, d, Jˆ9.9 Hz, H-2); 7.18±7.78731H, m,
H-arom., Ha, Hb, H-1,H-10; 7.88±7.9572H, m, H-10 and
H-100); 7.9471H, s, H-6). Anal. calcd for C52H36O2: C,
90.15; H, 5.24; found: C, 90.07; H, 5.28. m/z 692 7M1).
3.6.5. 80-[2-.3,3-Diphenyl-[3H]naphtho[2,1-b]pyran-5-yl)-
ethenyl]-1,3,3-trimethylspiro [indoline-2,30-[3H]naphth-
[2,1-b][1,4]oxazine] .5). Eluent CH2Cl2. Yellow solid, mp
158 7from heptane). 1H NMR 7CDCl3): Major isomer:
1.3476H, s, CH3); 2.7573H, s, N±CH3); 6.2971H, d,
Jˆ9.9 Hz, H-2); 6.5571H, d, Jˆ7.6Hz, H-7a); 6.85±
7.95726H, m, H-arom., H-1, H-20, H-a, H-b); 8.5771H, d,
Jˆ8.8 Hz, H-100).
3.6.2. 1,2-Bis.3,3-diphenyl-[3H]naphtho[2,1-b]pyran-5-
yl)ethylene .2). Eluent pentane/ether 790:10). Yellow
solid, mp 228 7from heptane). H NMR 7CDCl3): 6.3072H,
1
d, Jˆ9.9 Hz, H-2); 7.00±7.34724H, m, H-arom., H-a and
H-1); 7.5578H, d, Jˆ7.2 Hz, H-20); 7.8672H, d, Jˆ8.5 Hz,
H-10). 13C NMR 7CDCl3): 82.77s); 114.77s); 120.37d);
121.17d); 123.57d); 126.47d); 126.87d); 126.97d); 127.07d);
127.67d); 128.37d); 128.87d); 128.97d); 129.27s); 129.77d);
145.07s); 149.27s). Anal. calcd for C52H36O2: C, 90.15; H,
5.24; found: C, 90.11; H, 5.19. m/z 692 7M1).
Minor isomer 1.3276H, s, CH3); 2.7173H, s, N±CH3);
6.3071H, d, Jˆ9.9 Hz, H-2); 6.5371H, d, Jˆ7.6Hz, H-7a);
6.85±7.95726H, m, H-arom., H-1, H-20, H-a, H-b); 8.2371H,
d, Jˆ8.8 Hz, H-100). Anal. calcd for C49H38N2O2: C, 85.69;
H, 5.58; N, 4.08; found: C, 85.58; H, 5.49; N, 4.05. m/z 687
7MH1).
3.6.3. 1,2-Bis.1,3,3-trimethylspiro[indoline-2,30-[3H]naphth-
[2,1-b][1,4]oxazin-50-yl)ethylene .3). Eluent pentane/
CH2Cl2 720:80). Grey solid, mp 249 7from heptane). H
1
3.6.6. 50-[2-.3,3-Diphenyl-[3H]naphtho[2,1-b]pyran-8-yl)-
ethenyl]-1,3,3-trimethylspiro [indoline-2,30-[3H]naphth-
[2,1-b][1,4]oxazine] .6). Eluent pentane/ether 795:5),
NMR 7CDCl3): 1.3176H, s, CH3); 1.3476H, s, CH3);
2.6673H, s, N±CH3); 2.6973H, s, N±CH3); 6.4972H, d,
Jˆ7.7 Hz, H-7); 6.5672H, s, H-a); 6.8572H, dd, Jˆ7.4 and
7.4 Hz, H-5); 7.0372H, d, Jˆ7.1 Hz, H-4); 7.1772H, dd,
1
white solid mp 230 7from heptane). H NMR 7CDCl3):
Major isomer 7Z): 1.3773H, s, CH3); 1.4173H, s, CH3);
2.7573H, s, N±CH3); 6.2571H, d, Jˆ9.5 Hz, H-2);
6.5271H, d, Jˆ12.6 Hz, H-a); 6.6271H, d, Jˆ7.5 Hz,
H-7a); 6.6571H, d, Jˆ12.6Hz, H-b); 6.97±7.85724H, m,
H-arom., H-20, H-1); 8.5071H, d, Jˆ8.3 Hz, H-100).
Jˆ7.6and 7.6Hz, H-6); 7.2372H, dd,
Jˆ8.1 and 8.1 Hz,
H-80); 7.3372H, d, Jˆ8.0 Hz, H-70); 7.4972H, dd, Jˆ7.1
and 7.1 Hz, H-90); 7.6272H, s, H-60); 7.7372H, s, H-20);
8.4872H, d, Jˆ8.3 Hz, H-100). 13C NMR 7CDCl3): 21.57q);
25.67q); 29.77q); 51.97s); 98.97s); 107.17d); 119.87d);
121.57d); 121.67d); 124.47d); 125.17d); 127.17d); 128.07d);
128.17d); 128.67s); 129.27d); 130.47s); 135.97s); 147.67s);
151.37d). Anal. calcd for C46H40N4O2: C, 81.15; H,
5.92; N, 8.23; found: C, 81.12; H, 5.91; N, 8.19. m/z 681
7MH1).
Minor isomer 7E) 1.3376H, s, CH3); 2.6673H, s, N±CH3);
6.2171H, d, Jˆ9.5 Hz, H-2); 6.4871H, d, Jˆ7.5 Hz, H-7a);
6.8871H, dd, Jˆ7.8 and 7.8 Hz, H-5a); 6.97±7.85724H, m,
H-arom., H-20, H-1); 8.5071H, d, Jˆ8.3 Hz, H-100). Anal.
calcd for C49H38N2O2: C, 85.69; H, 5.58; N, 4.08; found: C,
85.60; H, 5.59; N, 3.95. m/z 687 7MH1).
3.6.4. 50-[2-.3,3-Diphenyl-[3H]naphtho[2,1-b]pyran-5-yl)-
ethenyl]-1,3,3-trimethylspiro [indoline-2,30-[3H]naphth-
[2,1-b][1,4]oxazine] .4). Eluent pentane/ether 795:5).
3.6.7. 3,3-Diphenyl-5-[2-.3-methoxy-2-naphthyl)ethenyl]-
[3H]naphtho[2,1-b]pyran .26). Eluent CH2Cl2. Pale
yellow solid, mp 144 7from heptane). H NMR 7CDCl3):
1
White solid, mp 212 7from heptane). H NMR 7CDCl3):
1
1.3776H, s, CH3); 2.7173H, s, N±CH3); 6.2671H, d,
Jˆ9.8 Hz, H-2); 6.5671H, d, Jˆ7.7 Hz, H-7a); 6.7571H, d,
Jˆ12.4 Hz, H-a); 6.8971H, dd, Jˆ7.3 and 7.3 Hz, H-5a);
6.9271H, d, Jˆ12.4 Hz, H-b); 7.0971H, d, Jˆ7.3 Hz,
H-4a); 7.15±7.49720H, m, H-arom.); 7.7571H, s, H-20);
7.9171H, d, Jˆ8.4 Hz, H-10); 8.4871H, d, Jˆ8.4 Hz,
H-10); 8.4871H, d, Jˆ8.4 Hz, H-100). 13C NMR 7CDCl3);
21.37q); 25.57q); 29.67q); 51.97q); 82.77s); 98.97s); 107.17d);
114.97s); 119.87d); 120.17d); 121.27d); 121.37d); 121.67d);
123.07s); 123.77d); 124.17d); 124.97d); 125.37s); 126.57d);
3.8973H, s, OCH3); 6.3271H, d, Jˆ9.9 Hz, H-2); 6.9771H,
d, Jˆ12.3 Hz, H-a); 7.07±7.1574H, m, H-b, H-40, H-60 and
H-70); 7.20±7.37712H, m, H-arom., H-1); 7.4771H, s, H-10);
7.5574H, m, H-200); 7.6671H, d, Jˆ8.2 Hz, H-7); 7.8971H, d,
Jˆ8.5 Hz, H-10). 13C NMR 7CDCl3): 55.77q); 82.87s);
105.47d); 114.97s); 120.47d); 121.37d); 123.67d); 123.77d);
126.37d); 126.47d); 126.57d); 126.67d); 127.07d); 127.27d);
127.37s); 127.77d); 128.17d); 128.47d); 128.77s); 128.87d);
129.07s); 129.47d); 129.57d); 134.17s); 145.17s); 149.27s);

7358
A. Samat et al. / Tetrahedron 57 -2001) 7349±7359
4. Keum, S. R.; Lee, J. H.; Seok, M. K.; Yoon, C. M. Bull.
Korean Chem. Soc. 1994, 15, 275±277.
156.37s). Anal. calcd for C38H28O2: C, 88.34; H, 5.16;
found: C, 88.39; H, 5.13.
5. Keum, S. R.; Lee, J. H.; Seok, M. K. Dyes Pigments 1994, 25,
21±29.
3.6.8. 50-[2-.3-Methoxy-2-naphthyl)ethenyl]-1,3,3-trimethyl-
spiro[indoline-2,30-[3H]naphth[2,1-b][1,4]oxazine] .27).
Eluent CH2Cl2, White solid, mp 204 7from heptane). H
6. Keum, S. R.; Lim, S. S.; Min, B. H. Bull. Korean Chem. Soc.
1995, 16, 1007±1009.
1
NMR 7CDCl3): 1.3773H, s, CH3); 1.4073H, s, CH3);
2.7273H, s, N±CH3); 3.8573H, s, OCH3); 6.5571H, d,
Jˆ7.7 Hz, H-7a); 6.7171H, d, Jˆ12.4 Hz, H-a); 6.7971H,
d, Jˆ12.4 Hz, H-b); 6.8871H, dd, Jˆ7.4 and 7.4 Hz,
H-5a); 7.0871H, d, Jˆ7.4 Hz, H-4a); 7.1071H, s, H-4);
7.15±7.2473H, m, H-6, H-6a, H-7); 7.28±7.497m, 4H,
H-8, H-5, H-80, H-90); 7.5871H, s, H-1); 7.6171H, s, H-60);
7.6871H, d, Jˆ8.1 Hz, H-70); 7.7571H, s, H-20); 8.4771H, d,
Jˆ8.4 Hz, H-100). 13C NMR 7CDCl3):21.37q); 25.57q);
29.57q); 51.87s); 55.57q); 98.77s); 105.37d); 106.97d);
119.67d); 121.27d); 121.57d); 123.07s); 123.67d); 124.17d);
124.47d); 125.57s); 126.27d); 126.37d); 126.87d); 127.37d);
127.77d); 127.97d); 128.57s); 128.77d); 129.37d); 130.17s);
134.07s); 142.37s); 147.67s); 151.17d); 155.97s). Anal. calcd
for C35H30N2O2: C, 82.32; H, 5.92; N, 5.48; found: C, 82.28;
H, 6.02; N, 5.36.
7. Keum, S. R.; Choi, Y. K.; Kim, S. H.; Yoon, C. M. Dyes
Pigments 1999, 41, 41±47.
8. Young, J. C.; Rho, K. Y.; Kim, S. H.; Keum, S. R.; Yoon,
C. M. Dyes Pigments 2000, 44, 19±25.
9. Filley, J.; Ibrahim, M. A.; Nimlos, M. R.; Watt, A. S.; Blake,
D. M. J. Photochem. Photobiol. A: Chem. 1998, 117, 193±198.
10. Luchina, V. G.; Sychev, I. Yu.; Marevtsev, V. S.; Vlasenko,
T. Ya.; Khamchukov, Yu. D.; Cherkashin, M. I. Bull. Acad.
Sci. URSS 1993, 2152±2156.
11. Kang, T. J.; Chang, S. H.; Kim, D. J. Mol. Cryst. Liq. Crystal.
1996, 278, 181±188.
12. Melzig, M.; Zinner, H.; Optische Werke, G. Rodenstock Eur.
Patent 0 686 685 A2, 1995.
13. DuÈrr, H.; Ma, Y. Deutshe Offenlegungsschrift Patent 4444 244
09, 1994.
14. Holderbaum, M.; DuÈrr, H.; Hadjoudis, E. J. Photochem.
Photobiol. A: Chem. 1991, 58, 37±50.
3.6.9. 3,3-Diphenyl-8-[2-.3-methoxy-2-naphthyl)ethe-
nyl]-[3H]naphtho[2,1-b]pyran .28). Eluent pentane/ether
15. Bleisinger, H.; Scheidhauer, P.; DuÈrr, H.; Wintgens, V.; Valat,
P.; Kossanyi, J. J. Org. Chem. 1998, 63, 990±1000.
16. Weber, C.; DuÈrr, H.; Bonneau, R. Synthesis 1999, 1005±1012.
17. Gobbi, L.; Seiler, P.; Diederich, F. Angew. Chem. Int. Ed.
1999, 38, 674±677.
1
785:15). White solid, mp 208 7from heptane). H NMR
7CDCl3): Major isomer 7E): 3.9673H, s, OCH3); 6.2571H,
d, Jˆ9.9 Hz, H-2); 7.10±7.78722H, m, H-arom., H-a, H-b,
H-1); 7.8971H, d, Jˆ9.0 Hz, H-10); 8.0271H, s, H-7).
18. Mrozek, T.; Gorner, H.; Daub, J. Chem. Commun. 1999,
1487±1488.
Minor isomer 7Z) 3.8973H, s, OCH3); 6.1771H, d, Jˆ9.9 Hz,
H-2); 6.7972H, s, H-a and H-b); 7.10±7.78722H, m, H-
arom., H-1). Anal. calcd for C38H28O2: C, 88.34; H, 5.16;
found: C, 88.28; H, 5.10.
19. Knowles, D. B.; Van Gemert, B. PPG Industries US Patent
5,464,567, 1995.
20. Chamontin, K.; Lokshin, V.; Rossollin, V.; Samat, A.;
Guglielmetti, R. Tetrahedron 1999, 55, 5821±5830 and
references therein.
3.6.10. 3,3-Diphenyl-5-[2-.6-methoxy-2-naphthyl)ethe-
nyl]-[3H]naphtho[2,1-b]pyran .29). Eluent pentane/ether
790:10). Pale yellow solid, mp 139 7from heptane). 1H
NMR 7CDCl3) 7E-isomer): 3.9273H, s, OCH3); 6.3071H, d,
Jˆ9.9 Hz, H-2); 7.12±7.1572H, m, H-10 and H-30); 7.18±
7.85720H, m, H-arom., H-a, H-b,H-1); 7.9071H, d,
Jˆ8.5 Hz, H-10); 7.9571H, s, H-6). 13C NMR
7CDCl3):55.37q); 82.97s); 105.97d); 114.37s); 119.07d);
119.97d); 121.27d); 122.47d); 123.97d); 124.17d); 126.07d);
126.37d); 126.77d); 126.87d); 127.17s); 129.17s); 129.37s);
129.57d); 130.97d); 133.27s); 134.27s); 144.97s); 148.57s);
157.87s). Anal. calcd for C38H28O2: C, 88.34; H, 5.16;
found: C, 88.38; H, 5.21.
21. Aldoshin, S. M.; Chuev, I. I.; Filipenko, O. S.; Utenyshev,
A. N.; Lokshin, V.; Lareginie, P.; Samat, A.; Guglielmetti,
R. Russian Chem. Bull. 1998, 47, 1089±1097 and references
therein.
22. Pozzo, J. L.; Lokshin, V.; Samat, A.; Guglielmetti, R.; Dubest,
R.; Aubard, J. J. Photochem. Photobiol. A: Chem. 1998, 114,
185±191 and references therein.
23. Lokshin, V.; Samat, A.; Guglielmetti, R. Tetrahedron 1997,
53, 9669±9678 and references therein.
24. Pozzo, J. L.; Samat, A.; Guglielmetti, R.; Dubest, R.; Aubard,
J. Helv. Chim. Acta 1997, 80, 725±737 and references therein.
25. Lareginie, P.; Lokshin, V.; Samat, A.; Guglielmetti, R.;
Zaballos-Garcia, E. WO 96/04590, ESSILOR International,
1996.
26. Lokshin, V.; Chamontin, K.; Guglielmetti, R.; Samat, A. WO
97/05544, ESSILOR International, 1997.
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