Spirobenzopyran

Comprehensive and important reviews on photochromism of spiropyrans have been published by Bertelson1 and Guglielmetti2 In the present chapter, general synthetic methods and physical properties of spiropyrans with special reference to leuco dyes will be described. The chapter is divided into the spirobenzopyran, spironaphthooxazine, and spirothiopyran and related compounds. 

Experimental Preparation of 6-nitrospiropyran 2 (R = Bu). Triethyl-amine (2.65 g, 26 mmol) was added to a suspension of 2,3,3-trimethyl-7V-butylindolinium iodide (9.0 g, 26 mmol) and 5-nitro-salicylaldehyde (4.38 g, 26 mmol) in EtOH (100 ml) under stirring. The mixture was refluxed for 2 h, and filtered off. Recrystallization from hexane gave 6-nitrospiropyran 2 (R = Bu). Also, spiropyran 2 was isolated from the filtrate, which was evaporated under reduced pressure and then was chromatographed on silica gel with dichloromethane-methanol (60 1 v/v). Total yield of 2 (8.3 g) is 88%. 

Remarkable substituent effects on the absorption bands in the colored form are observed on substitution in positions 3, 6, and 8 of the spiroben-zopyran (Table 1). A nitro group at the 8-position yields a higher Xmax ( 40nm) compared with a nitro group at the 6-position due to interaction of phenolate anion and oxygen atom of the nitro group. In many cases, it 

The absorption bands for both quinoid and dipolar structures have been calculated by the PPP method.2,12 The calculations for a more simplified model of the colored form of some spirobenzopyrans using the normal parameters are shown in Table 2.12 In this case, the spiro carbon in the indoline moiety is ignored in the 7i-electron system, and the quinoid structure is assumed. 

PPP calculations reproduce the nitro substituent effect and heterocyclic effect on the /,max. For example, the bathochromic shift by substitution of a nitro group is calculated (ca.20nm). It is in good agreement with the experimental value determined (A,max = 598 nm) in toluene. PPP calculation exactly predicts the bathochromic shift by benzo-annelation of the indoline and benzopyran residues (Table 2). In the neutral quinoid form, the calculated charge densities for the ground and first excited states by PPP 

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Generally, measurement of absorption spectra of the colored form of spirobenzopyran is very difficult using normal spectrophotometry, as the colored form is thermally unstable. The absorption spectra of the colored form of 6,8-dinitro-BIPS 7, which is exceptionally stable in DMSO even at 23°C, are shown in Figure 1.4. Generally, it is possible to obtain a reasonable absorption spectrum of the colored form by the use of a rapid scanning spectrophotometer. 

Figurel.5. kmax of the colored form for spirobenzopyrans containing various heterocyclic systems in toluene.

NMR spectroscopy is a convenient method for structural study of the equilibrium between the colored and the colorless form of spirobenzopyran. In the H-NMR spectra, the chemical shifts of gem methyl groups in 3 -position, (V-methyl group,2,11 and methine protons in 3- and 4-position are important to distinguish between the colored and colorless forms. 

The quantum yields for photocoloration of spirobenzopyrans are collected in Ref. 1. Generally, the coloration quantum yields of spiroindolinobenzopyrans by UV irradiation (366 nm) at room temperature (15-25°C) are 0.1-0.7. Photobleaching quantum yields by visible light are very small (0.1) and less accurate, since both thermal and photobleaching occur simultaneously. 

Solid films of spiropyrans are important in optical data storage. Thin films of spirobenzopyran (1.0 (tm) have been prepared by vacuum deposition, and its reversible photochromism has been confirmed.39 The J-aggre-... 

The spiroindolinonaphthooxazine is generally very stable toward UV light, compared with spirobenzopyran. However, replacement of the indo-line ring with benzoxazine significantly reduced its photostability. 

Spiroindolinobenzothiopyrans can be prepared by condensation of Fischer s base with thiosalicylaldehyde derivatives 46 in ethanol, as shown in Scheme 22.71,89 93 Reaction of 1,2,3,3-tetramethylindolinium salt with carbamoylthiobenzaldehyde,92 which is an intermediate for preparation of thiosalicylaldehyde, also gives the spirobenzothiopyran in high yield via the corresponding indolinium salt, as shown in Scheme 22.94 Conversion of spirobenzopyrans to the corresponding spirobenzothiopyran by phosphorous pentasulfide in pyridine or xylene is possible, but the purification of the product is difficult. 

A class of crown spirobenzopyrans 10 exhibit thermally irreversible photochromism only in the presence of alkali-metal cations (Scheme 3). The favored complexation between 10 and lithium cation was thus revealed by the effect of lithium salt on the electronic absorption spectra of 10. Lithium complexation was also corroborated on the basis of FAB mass experiments. Before addition of Lil to 10, ion peaks for MH, [M + Na] and [M + K] were detected after the addition the signals decreased, while a peak for [M + Li]+ appeared (Figure 10) . 

SCHEME 3. Isomerization of spirobenzopyran 10 to colored merocyanine 10 M is induced by recognition of alkali metal cations as well as by UV irradiation ... 

As mentioned in sections 1.2.2.2 and 1.2.3.2, the photochromic reactions of spirobenzopyran and spironaphthoxazines show a marked solvent dependency and this is also the case with benzo and naphthopyrans. Consequently, spectral data collected from the literature is only comparable within any one study or where the same solvent has been used. This accounts for any discrepancies between one set of results and any other one listed in this and related sections of this chapter. The data normally quoted when discussing the properties of photochromic materials relate to the absorption maximum (2. ) of the coloured state, the change in optical density (absorbance) on exposure to the xenon light source (AOD) and the fade rate which is the time in seconds for the AOD to return to half of its equilibrium value. 

Salicylaldehyde is the starting material for the preparation (Scheme 12) of most spirobenzopyrans, which are important photochromic compounds. The reader interested in their synthesis and properties is referred to the recent excellent book by Bertelson.5... 

The chromene ring of spirobenzopyrans such as (168) and (169) is opened by treatment with mineral add and closed again by alkali — a reaction of potential importance in the thermochromic or photochromic application of such compounds (69T5995,74JOU1516). 

Light-driven (electron, cation) symport occurs when combining this system with the (nickel complex, macrocycle) process described above [6.62]. Photocontrol of ion extraction and transport has been realized with macrocyclic or acyclic ligands (containing, for instance, azo or spirobenzopyran groups) that undergo a reversible... 

The spiro carbon is a stereogenic center in spiropyrans, but because of the achiral structure of the open merocyanine form, the photochromic process will always lead to racemization unless additional chiral moieties are present. When a chiral substituent was introduced, remote from the spiro center, it was possible to isolate diastereo-isomers of the spiropyrans, but rapid epimerization at the spiro center occurred.1441 Diastereoselective switching was successful with 28, in which a stereogenic center was present close to the spiro carbon (Scheme 15).[45] Distinct changes in CD absorption at 250 nm were monitored upon irradiation with UV (250 nm) and with visible light (>530 nm) and a diastereomeric ratio of 1.6 1.0 was calculated for the closed form 28. Furthermore, a temperature-dependent CD effect was observed with this system it was attributed to an inversion of the diastereomeric composition at low temperatures. It might be possible to exploit such effects in dual-mode chiral response systems. A diastereoselective ring-closure was also recently observed in a photochromic N6-spirobenzopyran tricarbonyl chromium complex. 451 ... 

Figure 23.6 Chemical structure of spirobenzopyran in its protonated open-ring form (a) and its photoinduced closed-ring form (b).

More recently, Sugiura et al.11 developed a fully functional microvalve based on this photoresponsive behavior, which was composed of poly(/V-isopropylacrylamide) functionalized with the chromophore spirobenzopyran (pSPNIPAAm). The microvalve was fabricated in a polydimethylsiloxane (PDMS) microchannel by in situ photopolymerization. Blue light irradiation (18 to 30 s) to the gel induced photoisomerization of the spirobenzopyran chromophore which resulted in shrinkage due to dehydration of the gel, thus causing the microvalves to open, as seen in Figure 23.7. In this example, localized irradiation enabled independent control of three photoresponsive polymer gel microvalves, which had been fabricated on a single microchip. 

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