- Synthesis of photochromic spirooxazines from 1-amino-2-naphthols
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A synthetic access to photochromic spirooxazines is developed through the condensation of methylene-substituted azaheterocycles on 1-amino-2- naphthols in presence of an oxidizing agent. Compared to usual preparation of this kind of compounds (via 1-nitroso-2-naphthols), yields are generally good and approaches to further spiroheterocyclic oxazines are possible.
- Lokshin, Vladimir,Samat, Andre,Guglielmetti, Robert
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- Light-induced change of the molecular charge in a spironaphthoxazine compound
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To evaluate the experimental conditions for the light-induced change of the molecular charge, the dependence of the photochromic reaction behaviour of the indolino spiro naphthoxazine compound 1,3,3-trimethyl-spiro[2H-indol 2,3'[3H]naphth[2,1-b]-[1,4]oxazine] on the pH value of the solution is investigated. In the absence of UV light an acid-base equilibrium between the spiro form and a protonated closed form is established. By irradiation under appropriate acidic conditions the spiro form can be transformed into an open cationic form through the merocyanine form. Between the two open forms an acid-base equilibrium is established. Except for the closed protonated form the structures are confirmed by mean of NMR. The kinetics of the thermal ring-closing reaction of both forms are investigated by flash photolysis. It is shown that the ring-closing reaction proceeds exclusively via the merocyanine form. The pK values determined for both equilibria give the pH range, in which the light-induced change of the molecular charge occurs.
- Rys,Weber,Wu
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- Photochromic Processes in Spiro(1,3,3-trimethylindolo-2,2'-naphth-1,4-oxazine) studied using Two-laser Two-colour Techniques
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The photochemistry of the photomerocyanine from the title compound shows dramatic differences between polar and non-polar media; in the latter it involves the intermediacy of a ground state species with a lifetime of ca. 4 μs which regenerates the merocyanine almost quantitatively.
- Bohne, C.,Fan, M. G.,Li, Z. J.,Lusztyk, J.,Scaiano, J. C.
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- Sub-picosecond transient absorption spectroscopy of substituted photochromic spironaphthoxazine compounds
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The photochromic reaction dynamics of spiroindolinenaphthoxazine and its 6′CN and 5′CHO substituted compounds is investigated in different solvents by femtosecond transient absorption spectroscopy. In addition to the formation of the merocyanine coloured form (ring-opened trans form, OF), another short-lived intermediate species is produced upon photoexcitation, which is not a precursor to the OF product but which is formed in parallel to it via a competing relaxation process. This species is ascribable to either a relaxed s-cis ring-opened isomer on the ground state potential energy surface or to a metastable minimum of the excited S1 state potential energy surface of the ring-closed form. The observed kinetics suggest that the production of OF (photocoloraton reaction) is controlled by the efficiency of the competing process rather than by an s-cis - trans isomerisation energy barrier.
- Buntinx, Guy,Poizat, Olivier,Foley, Sarah,Sliwa, Michel,Alo?se, Stéphane,Lokshin, Vladimir,Samat, André
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- Structures and photochromic properties of substituted spiroindolinonaphthoxazines
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Six indolinospironaphthoxazines were studied by X-ray diffraction analysis. It was demonstrated that the electronic nature of the substituents in the naphthoxazine and indoline fragments has no substantial effect on the Cspiro-O and Cspiro-N bond lengths. Photocolorability of the compounds under study depends only slightly on the above-mentioned bond lengths and correlates mainly with the energy of steric strain of the oxazine ring. The stability of the open forms of spiroindolinonaphthoxazines that formed upon photoirradiation is determined to a large extent by the electronic and steric nature of the substituents. The exception is the compound that contains the NO2 group in the indoline fragment. In the last-mentioned case, the cleavage of the ring occurs through a substantially different pathway.
- Aldoshin,Chuev,Filipenko,Utenyshev,Lokshin,Laregenie,Samat,Guglielmetti
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- The pH Control of the Decolouration Rate of Spironaphthoxazine Derivatives
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The thermal stablility of the coloured open form of 5-methoxy- (7) and 5'-piperidinomethyl-1,3,3-trimethylspiro(indoline-2,3'-naphthooxazine) (6) is strongly dependent on pH.
- Yamaguchi, Takeo,Tamaki, Takashi,Kawanishi, Yuji,Seki, Takahiro,Sakuragi, Masako
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Read Online
- A method for synthesizing spiroxime photochromic dyes using a microchannel reactor
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The present invention relates to a method of synthesizing a photochromic dye using a microchannel reactor. In the coupling ring process in the late stage of dye synthesis, after the temperature of the mobile phase system containing the reaction raw material is adjusted to the reaction temperature by the pre-reaction system, the above-mentioned mobile phase is pumped into the microchannel reactor by means of a constant current pump for mixed temperature control reaction, and a solution containing photochromic dye is obtained, and the photochromic dye is obtained by concentration, recrystallization, decolorization and drying. This method uses the high mixing and heat exchange efficiency of the microchannel to ensure the full mixing of the reactants and the accuracy of temperature control, the energy saving effect is good, the production cost is reduced, the purity of the product is high, the difficulty of subsequent processing is reduced, the mobile phase can be reused, and it is convenient for large-scale production, which has a broad application prospect.
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Paragraph 0032-0034
(2022/01/20)
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- Highly efficient green synthesis of the photochromic spironaphthoxazines using an eco-friendly choline hydroxide catalyst
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A greener route for the synthesis of the photochromic spironaphthoxazines employing a highly efficient, biodegradable and recyclable choline hydroxide catalyst in an aqueous medium has been described. This methodology offers diverse advantages such as mild reaction conditions, short reaction time (1 h), excellent yields (up to 91%), and operational simplicity that make it a useful and attractive option for the synthesis of the spironaphthoxazines. The choline hydroxide showed excellent catalytic performance until five recycles without significant loss of activity. The structures of synthesized spironaphthoxazines were deduced by their 1H NMR spectra and melting points.
- Vajekar, Shailesh N.,Shankarling, Ganapati S.
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supporting information
p. 338 - 347
(2019/12/03)
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- Spirooxazine photochromic compound
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The invention relates to a spirooxazine photochromic compound which has the following general formula (1), wherein R is selected from any one of the group consisting of H, NMe2, Cu (OH) 3, Me and oMe,R' is selected from any one selected from the group consisting of NMe2, CF3, H, NO2 and CN. The spirooxazine photochromic compound is prepared by reacting an indole iodide with a nitroso compound.
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Paragraph 0058; 0060; 0061; 0063
(2019/01/24)
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- Spiropyrans and spirooxazines and preparation method thereof
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The invention provides spiropyrans, naphthospiropyrans and spirooxazines. The invention also relates to a method for preparing the spiropyrans, the naphthospiropyrans and the spiroxazines by reactionof indole compounds, especially indole iodide, with alde
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Paragraph 0074; 0076; 0080; 0081; 0124; 0125
(2019/01/22)
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- Comparative Evaluation of Substituent Effect on the Photochromic Properties of Spiropyrans and Spirooxazines
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Spiropyrans and spirooxazines represent an important class of photochromic compounds with a wide variety of applications. In order to effectively utilize and design these photoswitches it is desirable to understand how the substituents affect photochromic properties, and how the different structural motifs compare under identical conditions. In this work a small library of photoswitches was synthesized in order to comparatively evaluate the effect of substituent modifications and structure on photochromism. The library was designed to modify positions that were believed to have the greatest effect on C-O bond lability and therefore the photochromic properties. Herein we report a comparative analysis of the UV and visible light responses of 30 spiropyrans, spiroindolinonaphthopyrans, and spirooxazines. The influence of gadolinium(III) binding was also investigated on the library of compounds to determine its effect on photoswitching. Both assays demonstrated different trends in substituent and structural requirements for optimal photochromism.
- Balmond, Edward I.,Tautges, Brandon K.,Faulkner, Andrea L.,Or, Victor W.,Hodur, Blanka M.,Shaw, Jared T.,Louie, Angelique Y.
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p. 8744 - 8758
(2016/10/14)
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- Phototriggered micromanufacturing using photoresponsive amorphous spirooxazine films
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In this study, a series of spirooxazine molecules possessing bulky substituents was synthesized. These molecules readily formed amorphous glasses and their glass transition temperatures increased with the bulkiness of substitution. Their amorphous thin films exhibited apparent photochromism due to the spirooxazine-merocyanine isomerism and high durability to UV light in a nitrogen atmosphere. When the amorphous spirooxazine films were irradiated with spatially patterned UV light, surface relief gratings were produced because of the lateral material transfer from the shaded areas to the irradiated areas around their glass transition temperatures. Surface relief structure growth rate has a good relationship with the amount of photogenerated merocyanine formed at the irradiated area. A mechanism based on the diffusion of the spiro form for surface relief formation in this system has been proposed.
- Ubukata, Takashi,Fujii, Shohei,Arimatsu, Kento,Yokoyama, Yasushi
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body text
p. 14410 - 14417
(2012/09/11)
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- Study of spectral and kinetic characteristics of products of photolysis of a trifunctional compound with light of different wavelengths
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Spectral and kinetic characteristics of intermediate products of photolysis of a novel phototrifunctional compound (PTC), whose molecule combines spironaphthoxazine, hydroxyazomethine, and azobenzene fragments, have been studied by microsecond flash photo
- Levin,Tatikolov,Zaichenko,Shienok,Kol'tsova,Mardaleishvili,Popov,Levchenkov,Berlin
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p. 259 - 265
(2012/11/13)
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- Synthesis and kinetics of photochemical reactions of novel bifunctional salicylideneiminospironaphthoxazines
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A series of novel photochemically bifunctional compounds was synthesized. Their molecules combine the photochromic spironaphthoxazine fragment with a salicylideneimine fragment containing various substituents. The latter can undergo intramolecular proton transfer in the electron-excited state. Photolysis products of three types, namely, open merocyanine forms having an enol or cis-keto form of the salicylideneimine moiety and a trans-keto form with the closed spiro fragment, were detected using pulse photolysis technique in toluene and methanol solutions. The spectral kinetic characteristics of the photoproducts were studied, and their quantum yields were measured. The effects of substituents in the salicylideneimine fragment and the solvent nature were discussed.
- Zaichenko,Levin,Mardaleishvili,Shienok,Kol'Tsova,Os'Kina,Tatikolov
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scheme or table
p. 2394 - 2401
(2010/02/16)
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- Direct nitration reactions of photochromic spirooxazines
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A direct nitration of photochromic spirooxazines was carried out by three different methods. The molecular structure of main products was determined by NMR 1H and 13C spectra. The nitration mechanisms were proposed. It was shown that only nitration by mixture of nitric and sulfuric acids gives photochromic compounds with nitrogroup in aryloxazine ring.
- Zaichenko,Shiyonok,Kol'tsova,Marevtsev
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p. 83/[383]-89/[389]
(2007/10/03)
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- One-pot synthesis of 6′-amino-substituted spirooxazines
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A one-pot synthesis of 6′-amino-substituted spiroindolinonaphth[2,1- b][1,4]oxazines is developed through the condensation of 2-methylene-1,3,3- trimethylindoline derivatives and 1-amino-2-naphthol in the presence of different secondary amines and oxidizing agents using methanol or toluene as the solvent. The main advantage of the method is its simplicity, and starting from readily accessible reagents, it allows the preparation of amino derivatives of spironaphthoxazine with good yields under mild reaction conditions. Georg Thieme Verlag Stuttgart.
- Koshkin,Lokshin,Samat,Gromov,Fedorova
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p. 1876 - 1880
(2007/10/03)
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- Microwave-Assisted Solvent-Free Synthesis of the Substituted Spiroindolinonaphth[2,1-b][1,4]oxazines
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The synthesis of the substituted spiroindolinonaphth[2,1-b][1,4]oxazines 3a-e is developed through the condensation of 2-methylene-1,3,3-trimethylindoline derivatives and 1-nitroso-2-naphthol under microwave irradiation. In the same conditions, in presence of morpholine the 6′-morpholinosubstituted compounds 4a, b, d, e are formed. The main advantages of the method are the short reaction time, solvent-free reaction condition, cleaner reaction products and the higher product yields in comparison with known methods of synthesis.
- Koshkin,Fedorova,Lokshin,Guglielmetti,Hamelin,Texier-Boullet,Gromov
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p. 315 - 322
(2007/10/03)
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- Effect of metal cations on the photochromic properties of spironaphthoxazines conjugated with aza-15(18)-crown-5(6) ethers
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Spironaphthoxazines conjugated with aza-15(18)-crown-5(6)-ether moieties at the 6′-position of the naphthalene fragment (crown-containing spironaphthoxazine, CSN) were synthesised and studied for the first time. The addition of Li+ and alkaline earth (Mg2+, Ca2+, Sr2+ and Ba2+) metal cations to CSN solutions results in a hypsochromic shift of the UV absorption band of the spiro form and a bathochromic shift of the absorption band of the merocyanine form in the visible region. In addition, the equilibrium shifts to the merocyanine form, and the lifetime of the photoinduced merocyanine form increases. Analysis of the spectral and kinetic data allows a complexation scheme to be proposed and the stability constants of the resulting complexes to be calculated. According to the results obtained, the complexation with Li+ and alkaline earth metal cations in acetonitrile initially involves the crown ether moiety; the participation of the merocyanine oxygen atom in the complexation process occurs at a high metal cation concentration. The UV-induced isomerisation of CSN into the merocyanine form causes a decrease of the cation binding ability.
- Fedorova, Olga A.,Strokach, Yuri P.,Gromov, Sergey P.,Koshkin, Alexander V.,Valova, Tatjana M.,Alfimov, Michael V.,Feofanov, Alexei V.,Alaverdian, Iouri S.,Lokshin, Vladimir A.,Samat, Andre,Guglielmetti, Robert,Girling, Reuben B.,Moore, John N.,Hester, Ronald E.
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p. 1137 - 1145
(2007/10/03)
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- Crown-containing spironaphthoxazines and spiropyrans. 2. Influence of metal cations on the photochromic properties of spironaphthoxazines linked with aza-15(18)-crown-5(6) ethers
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Spironaphthoxazines linked with aza-15(18)-crown-5(6) fragments were synthesized and studied for the first time. Addition of alkaline-earth cations to solutions of crown-containing spironaphthoxazines causes a hypsochromic shift of the absorption band of the spiro form and a bathochromic shift of the absorption band of the merocyanine form, shifts the equilibrium to the merocyanine form, and changes the lifetime of the photoexcited merocyanine form. The spectral and kinetic data were used to propose a mechanism of complexation and calculate the stability constants of the resulting complexes. The complexation involves the crown fragment and the merocyanine oxygen atom. The type of the complex is determined by the cation nature and size.
- Strokach,Fedorova,Gromov,Koshkin,Valova,Barachevsky,Alfimov,Lokshin,Samat,Guglielmetti
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- Oxidation of photochromic spirooxazines by coinage metal cations. Part I. Reaction with AgNO3: Formation and characterisation of silver particles
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Thermal oxidation of the zwitterionic form of two photochromic spirooxazines: 1,3-dihydro-1,3,3-trimethylspiro(2H-indole-2,3′-[3H]naphth[2,1-b]- [1,4]oxazine) (1) and 1,3-dihydro-1,3,3-trimethylspiro(2H-indole-2,3′-[3H]phenanthr[9,10-b]- [1,4]oxazine) (2) has been studied in the presence of silver ions in anaerobic conditions. The products of the reaction have been identified and a mechanism for their formation is proposed. In alcohols (MeOH, EtOH), the major degradation product is the indolinooxazole salt together with either methoxy- or ethoxy-substituted spirooxazines at the C2′ carbon atom of the C2′=N1′ bond. The four new spirooxazine derivatives display no photochromic properties although X-ray diffraction studies show that the bond lengths around the spiro carbon atom are similar to those observed for compounds revealing colouration. Photophysical properties of the indolinooxazole and of its hydroxylated derivative are also presented. High quantum yield and large Stokes shifts are observed. As a consequence of the reduction of silver ions to neutral atoms, silver colloids have been prepared after either thermal- or photo-oxidation of spirooxazine. They are stabilised by poly(N-vinylpyrrolidone). The formation and growth of silver colloids have been studied by electron microscopy, photon correlation spectroscopy and UV-vis absorption spectroscopy. The growth of silver particles of different sizes and morphologies is presented and the role of a photochromic electron donor on the growth process is discussed. The average particle sizes ranged from a few to approximately one hundred nanometers. The classical plasmon absorption band at 420 nm and a broad red-shifted peak at 790 nm due to the large non-spherical particles are thus observed. Both particle size and plasmon absorption are dependent upon UV irradiation. Size enlargement upon irradiation of silver colloids brings about colour changes from yellow through green to light blue.
- Uznanski,Amiens,Donnadieu,Coppel,Chaudret
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p. 1486 - 1494
(2007/10/03)
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- NMR studies of the structure of the photoinduced forms of photochromic spironaphthoxazines
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Irradiation at 355 nm with a pulsed laser of the colourless 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3′-[3H]-naphth[2,1-b][1,4] oxazine] results in formation of photomerocyanines (coloured forms of photochromic compounds); this and its chloro derivative were studied by NMR spectroscopy. This has allowed us to confirm the structure of the stereoisomers. The colourless and coloured forms exist in thermal equilibrium. Integration of certain photomerocyanine signals allowed us to calculate the thermal kinetics of bleaching k, the half-life τ and the activation enthalpy ΔH? at different low temperatures and from these temperature dependence studies of the thermal decay rate, the thermal energy barrier for the decay of the coloured metastable state to the colourless form was determined.
- Delbaere, Stephanie,Bochu, Christophe,Azaroual, Nathalie,Buntinx, Guy,Vermeersch, Gaston
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p. 1499 - 1501
(2007/10/03)
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- Coupling between Photochromism and Second-Harmonic Generation in Spiropyran- and Spirooxazine-Doped Polymer Films
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The photochemical ring opening of spiropyrans in polymethylmethacrylate (PMMA) host films in the presence of a high-voltage electric field (2-5 MV/cm) leads to a photo-orientation of photomerocyanines.Since photomerocyanines have rather high first-order hyperpolarizabilities, this photo-orientation leads to second-harmonic generation (SHG).The second-order susceptibility d33 of PMMA films doped with 6-nitro-1',3',3'-trimethylspiro (25percent w/w) has been measured at 10 pm/V.If a PMMA film doped with spiropyran and preoriented by corona poling at 90 deg C is irradiated in the UV, an SHG signal of photomerocyanine is also observed as a result of a memory effect of the orientation of spiropyran molecules.The photoswitching of this nonlinear optical property can be inverted by visible light irradiation.Only partially reversible switching is observed because of a gradual light-induced disorientation of photomerocyanine dipoles.Photochemical quantum yields of the spiropyranphotomerocyanine reaction have also been determined in PMMA for one system.Dipole moments and hyperpolarizabilities of closed and open forms have been calculated by semiempirical and finite field methods for an analogous system.
- Atassi, Yomen,Delaire, Jacques A.,Nakatani, Keitaro
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p. 16320 - 16326
(2007/10/02)
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- Photo reactive spiro-benzoxazine compounds
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A photo reactive material, such as a photochromic material, which has the following structure: STR1 where the variables, A, R, R', R", R*, R+, m, and n are defined in claim 1.
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- Sensibilisation du photochromisme de spirooxazines par transfert d'energie triplet-triplet
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The present publication describes sensitized photocoloration by triplet-triplet energy transfer of some photochromic spirooxazines.The dominant reaction leading to the colored dye product B in the direct photolysis of the spirooxazine (SPO) in toluene involves the singlet excited state but the results obtained in this work show that both triplet and singlet states are involved in the color-forming reaction.We employed sensitizers of decreasing triplet energy in an attempt to locate the triplet level in the SPO.From the triplet energies of the sensitizers of the SPO color formation it can be concluded that the energy of the spirooxazine triplet state is about 212 kJ.mol-1.The camphorquinone (CQ) sensitizes the formation of B.This compound is particularly suitable for investigation of sensitized photocoloration of spirooxazines since it absorbs in a region of the spectrum where SPO does not absorb (λmax = 471 nm).Then, it is possible to extend the photochromic properties of the SPO to the visible region (λ 500 nm) for industrial applications.The absorption spectra of the colored form were determined for the direct and sensitized photolysis in toluene solutions.
- Eloy, D.,Escaffre, P.,Gautron, R.,Jardon, P.
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p. 897 - 914
(2007/10/02)
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- SYNTHESE DE QUELQUES SPIRO ET SPIRO PHOTOCHROMIQUES. APPLICATION DE LA METHODOLOGIE DE LA RECHERCHE EXPERIMENTALE
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Some spiro I and spiro II substituted by different groups were synthesized in order to evaluate their photochromic properties and to optimize the preparation of spiroheterocyclic systems.In addition, some spiro III were also prepared as reference compounds.Their physical and spectroscopic characteristics (UV, 1H and 13C) were determined.A study using the experimental design methodology allowed to point out the most important factors for improving the reaction yields. KEYWORDS: Photochromism, spirooxazines, spiropyrans, synthesis, 1H NMR, experimental design methodology.
- Pottier, E.,Sergent, M.,Luu, R. Phan Tan,Guglielmetti, R.
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p. 719 - 740
(2007/10/02)
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- Photochromic lens
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A photochromic lens is composed of a lens member made of a lens resin; and a photochromic layer applied on at least one side of the lens member and formed of a resin of a three-dimensional network structure. The layer-forming resin contains a spirooxazine compound represented by the following general formula (I): STR1 wherein R1 means a hydrogen or halogen atom or a cyano, C1-6 alkyl or C1-6 alkoxy group, and R2 denotes a C1-6 alkyl group, --CH2)n COOH, --CH2)n CN, substituted arylalkyl group or --CH2)n COOR in which R is a C1-6 alkyl group and n stands for an integer of 1-4. The layer-forming resin may additionally contain a phenol resin and/or a phenolic compound. A hard coat layer may optionally be applied on the surface of the photochromic layer.
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- Photochromism of spiroindolinonaphthoxazine. I. Photophysical properties
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A solution of spiroindolinonaphthoxazine in a common organic solvent shows profound photochromic effect.The colorless form in ethanol displays three absorption bands (320, 235, 203 nm) in the ultraviolet region of the spectrum.The absorptionspectrum of the colored metastable form shows two prominent absorption peak at 612 and 578 nm.The triplet state energy level of the colorless form is estimated to be in the range from 2.4 * 104 to 2.1 * 104 cm-1 by the triplet-triplet energytransfer method.There exists a thermal equilibrium between the colorless and colored forms.From the measurement of absorbance of the colored form at different temperatures, the standard enthalpy of equilibrium is obtained (ΔH0 = 1500 cm-1).The thermal decay of the colored form to the colorless form depends strongly on temperature.The decay rate increases three times for every 10 deg C increase in temperature.From these temperature dependence studies of the thermal decay rate, the thermal energy barrier for the colored metastable state to decay to the colorless form is determined to be 6.9 x 103 cm-1.
- Chu, Nori Y. C.
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p. 300 - 305
(2007/10/02)
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