Synthesis and structure of indoline spiropyrans of the coumarin series

New indoline spiropyrans of the coumarin series were synthesized by the condensation of indoline and hydroxyformylcoumarin derivatives. Spiropyrans, viz., derivatives of 8-formyl-7-hydroxy-4-methylcoumarin and 5-formyl-6-hydroxy-4-methylcoumarin, under irradiation are transformed into open forms, which are recyclized in the dark. The compounds formed by the condensation of the indoline derivatives with 3-formyl-4-hydroxycoumarin have an open structure of the merocyanine dyes and are transformed into spiro forms neither in the dark nor under irradiation with the visible light. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2342–2349, October, 2005.     

Photochromism of indoline spiropyrans of the coumarin series in polymeric matrices

The photochromic properties and aggregation processes of merocyanine forms of indoline spiropyrans of the coumarin series in the block and film poly(methyl methacrylate) (PMMA) were studied and compared by spectral and kinetic methods. Photochromism of the synthesized compounds depends on their structure. The efficient formation of J-aggregates was observed for indoline spiropyrans of the coumarin series based on 8-formyl-7-hydroxy-4-methylcoumarin and 3-formyl-4-hydroxycoumarin. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 870–875, May, 2007.     

New indoline spiropyrans with highly stable merocyanine forms

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DFT modeling of indoline spiropyrans with a cationic substituent in the gas phase

Isomeric forms of indoline spiropyrans show unusual behavior compared with similar compounds, according to experimental data. DFT modeling for gas phase was made to consider the simplest case without environmental effects, which revealed the intramolecular reasons for occurrence of ring opening reaction depending on the particular structure of the compound. The questions of charge redistributions, the changes of geometry and chemical bonds in the structures are also discussed.     

Photochromic and thermochromic spiranes. 20.* Photochromic properties of solid-phase films of novel formyl-substituted spiropyrans of the indoline series

We have synthesized novel forrnyl-substituted spiropyrans of the indoline series. We have obtained solid phase amorphous films of the synthesized spiropyrans bv thermal vacuum deposition and established their capacity for photochrornic transformations. We have investigated the effect of the substituents on the spectral properties of the original and colored forms of the solid-phase spiropyran films. We have shown that the kinetic characteristics of the photochromic transformations of these compounds in solid-phase films depend considerably on the bulk of the substituents in the indoline and benzopyran moieties, and also their electron active properties in the latter. Along with reversible processes, in the solid-phase spiropyran films we have observed irreversible photoreactions leading to degradation of the photochromic system.Scientific-Research Institute of Physical and Organic Chemistry, Rostov State University, Rostov-na-Donu 344090. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 399–405, March, 1996. Original article submitted February 28, 1996.     

Photo-and thermochromic spiranes 31.* Structure and photochromic properties of functionalized benzoxazine spiropyrans

An X-ray diffraction study gave the structure of a 4-oxohydro-2H-1,3-benzoxazine spiropyran with molecular formula C₂₈H₂₅N₃O₇, in which the π-electron-withdrawing formyl group is replaced with a chelatophoric hydrazine fragment containing a methoxy group. The structural parameters of this spiropyran were determined and compared with the data for similar spiropyrans. The photochromic properties of this compound in acetonitrile were studied in the presence of zinc ions. Dedicated to Professor A. F. Prozharskii on the occasion of his 70th jubilee. * For Communication 30 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1699–1706, November, 2008.     

Photochromic and fluorescence properties of coumarin fulgimides

Four new fulgimides possessing a fluorescent coumarin unit were synthesized from the corresponding fulgides, and their photochromic as well as fluorescence properties were investigated. The open-ring forms of coumarin fulgimides were found to exhibit fluorescence in the visible region. Upon exposure to UV light, the fulgimides were transformed into the nonfluorescent closed-ring forms, which can be reverted to the initial fluorescent open-ring forms on exposure to visible light. The efficiency of quenching of fluorescence was as high as 95% at the photostationary state of UV irradiation.     

Preparation of N-methacryloxyethyl derivatives of spiropyrans of the indoline series

Reaction of 2,3,3-trimethylindolenine with ethylene iodohydrin gave 1-hydroxyethyl-2,3,3-trimethylindoleninium iodide, which gives 3a,4,4-trimethyloxazolidino[3,2-a]indoline on treatment with sodium carbonate solution. Condensation of the latter with 5-nitro- and 3-methoxy-5-nitrosalicylaldehydes gives, respectively, N-hydroxyethyl derivatives of 6-nitro- and 6-nitro-8-methoxyspiro(indoline-2,2-benzopyrans) (V, VI), while condensation with 3-nitrosalicylaldehyde gives 4,4-dimethyl-3a-(2-hydroxy-3-nitrostyryl)oxazolidino[3,2-a]indoline (VII). Acylation of nitrospiran V and oxazolidinoindoline VII with methacrylyl chloride in pyridine proceeds at the free hydroxyl groups, while a mixture of derivatives of 1-(-methacryloxyethyl)spiropyran and 3a-(2-methacryloxy-3-nitrostyryl)oxazolidinoindoline is formed under the same conditions from nitromethoxyspiropyran VI. Acylation of V in acetone in the presence of sodium bicarbonate gives 4,4-dimethyl-3a-(2-methacryloxy-5-nitrostyryl)oxazolindo-[3,2-a]indoline. The mechanism of the isomeric transformations of the various forms that contain spiropyran and oxazolidino-indoline rings was studied by means of electronic spectra. The photochromic properties of the spiropyrans were investigated.Communication VI from the series Photochromism of Organic Substances. See [1] for communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1362–1369, October, 1973.     

Photo- and thermochromic spiropyrans. 21. 8"-Formyl-3,6"-dimethyl-4-oxospiro(3,4-dihydro-2H-1,3-benzoxazine-2,2"-[2H ]chromene) possessing photochromic properties in the solid phase

Spiropyran of the chromene series, viz., 8"-formyl-3,6"-dimethyl-4-oxospiro(3,4-dihydro-2H-1,3-benzoxazine-2,2"-[2H]chromene), was synthesized. In the solid phase, this compound exhibits photochromic properties. These properties were examined and the crystal structure of the compound was established by X-ray diffraction analysis. The compound is a convenient starting reagent for the synthesis of new spiropyrans containing functional groups at position 8".     

Effects of coumarin substituents on the photophysical properties of newly synthesised phthalocyanine derivatives

In this study, synthesis of new ligands, 8-hydroxy-3-[p-(3′,4′-dicyanophenoxy)-phenyl]coumarin and 8-hexyloxy-3-[p-(3′,4′-dicyanophenoxy)-phenyl]coumarin, and their phthalocyanines, 2,9,16,23-tetrakis[8-hexyloxy-3-(4-oxyphenyl)coumarin]-metal-free and metallophthalocyanines {M[Pc(OBzCou)₄] (M = 2H, Zn(II), Co(II); Bz: benzene; Cou: coumarin)} were synthesised. The novel chromogenic compounds were characterised by elemental analysis: ¹H NMR, ¹³C NMR, MALDI-TOF, IR and UV–vis spectral data. The effect of coumarin substituents on the photophysical properties of metal-free (H₂Pc) and zinc phthalocyanines (ZnPc) derivatives has been examined. Spectrophotometric measurements revealed that coumarin-substituted ZnPc derivatives were in the unaggregated form, whereas those of H₂Pc species were in aggregated form. It means that substitution of coumarin derivative prevents the cluster formation in the presence of zinc ion in the centre of Pc.     

Photo- and ionochromic properties of new spirobenzochromene-pyranoquinoline

A compound of the new spirobipyran-quinoline series possesses weakly pronounced photochromic properties at room temperature. Its interaction with Co²⁺, Ni²⁺, Zn²⁺ and Cd²⁺ ions leads to intensely colored complexes absorbing in the λ> 600 nm region, which is important for the study of biological objects. Up to three merocyanine molecules are capable of binding one metal ion, which is not typical for the previously studied indoline analogs.     

Synthesis of some new fused coumarin derivatives

2-Hydrazino-4-hydroxy-5H- [1] -benzopyrano- [ 4,3-d ] -pyrim-idin-5-one (3) was prepared via condensation of 2 with hy-drazine hydrate. Treatment of 3 with methylene chloride, ethyl chloroformate, ethyl chloroacetate and benzaldehyde yielded the corresponding 2 - ( substituted ) hydrazino - 4 -hydro-xy-5H-[1]-benzopyrano-[4, 3-d]-pyrimidin-5-one (4, 5, 6, and 10), followed by cyclization of 4, 5 and 6 with dimethyl fonnamide and fused sodium acetate under reflux, while compound 10 was cyclized with bromine and sodium acetate in acetic acid. Compound 3 reacted with β-(toloyl) acrylic acid, ethyl α-cyano-p-methoxytinnamate, diethyl mal-onate and acetyl chloride affording the corresponding 2-(substituted) hydrazino-4-hydroxy-5H-[1]-benzopyrano-[4, 3-d]-pyrimidin-5-one (12, 13, 14, 15 and 16).     

荧光香豆素衍生物的合成及其光电性能研究

香豆素类衍生物是一类具有抗病毒等许多生理活性的化合物[1-3],其合成和性质的研究一直受到关注[4].     

Effect of Heat Treatment and Additives on the Photochromic and Mechanical Properties of Sol-Gel Derived Photochromic Coatings Containing Spirooxazine

The experimental results on the photochromic and mechanical properties of coatings containing 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3′-(3H)-naphth(2,1-b)(1,4) oxazine] (SO) derived from 3-glycidyl-oxypropyltrimethoxysilane (GPTMS), bisphenolA (BPA) and 1-methylimidazole (MI) by sol-gel processing are presented. It is shown that heat treatment temperature is a conflicting factor to the photochromic intensity (ΔA ₀), photostability and abrasion resistance of the photochromic coatings. With increasing densification temperature the matrix rigidity increases leading to a decrease of ΔA ₀ and at the same time an enhancement of both abrasion resistance and photostability, the optimum heat treatment temperature is 110°C under our experimental conditions. By the use of certain additives, e.g., fluorosilanes (FAS), not only ΔA ₀ but also the photostability and the abrasion resistance of the photochromic coatings have been further improved.     

香豆素酰胺类化合物的合成及光谱特性

用(取代)香豆素-3-甲酰氯(Ⅰa～Ⅰc)和取代2-氨基苯并噻唑(Ⅱa～Ⅱd)作用合成了12种新的目标化合物(Ⅲa～Ⅲl),用HRMS、IR、1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析。研究发现:在紫外光谱中,新化合物(Ⅲa～Ⅲl)和原料化合物(Ⅰa～Ⅰc)相比,因共轭链的增长而使其最大吸收波长(λmax)红移;12种化合物表现出比原料化合物(Ⅰa～Ⅰc)较强的荧光性能。     

Reversible photodimerization of coumarin derivatives dispersed in poly(vinyl acetate)

Four photoreactive coumarin derivatives were successfully synthesized from 7-hydroxy-coumarin and 7-hydroxy-4-methylcoumarin, i.e., 7-propionyloxy-4-methylcoumarin (M₁), 7-palmitoyloxy-4-methylcoumarin (M₂), 7-propionyloxycoumarin (M₃), and 7-palmitoy-loxycoumarin (M₄). Reversible photodimerization (350 or 300 nm) and photocleavage (254 nm) of these coumarin derivatives dispersed in poly(vinyl acetate) (PVAc) were investigated by tracing their UV absorbance variations at 310 nm. The M₂ and M₄ with long palmitoyl chain show much better photoreaction reversibility than M₁ and M₃ with short propionyl chain. Moreover, photodimerization rate (under 350 nm) of M₂ is greater than 200 times of that of M₁. This has been explained by the formation of suitable conformation for revers-ible photodimerization due to the hydrophobic interactions. Photodimerization of M₂ is ca. 3 times quicker than that of M₄, indicating 4-methyl substitution enhances pho-todimerization. The influence of photodimerization wavelength (350 and 300 nm) and photosensitizer (benzophenone) have also been investigated in detail. © 1995 John Wiley & Sons. Inc.