118-12-7Relevant articles and documents
A NEW METHOD OF SYNTHESIS OF CONJUGATED SYSTEMS WITH TRIS(FLUOROMETHINE) CHAIN
Pazenok, S. V.,Kovtyukh, I. P.,Yagupolskii, L. M.
, p. 4595 - 4598 (1991)
The interaction of compounds having the active methylene group with perflouroallyliodide leads to the formation of conjugated systems with the tris(fluoromethine) chain.
Synthesis of spiropyran with methacrylate at the benzopyran moiety and control of the water repellency and cell adhesion of its polymer film
Ajiro, Hiroharu,Ando, Tsuyoshi,Murase, Nobuo
, p. 1489 - 1495 (2020)
Stimuli-responsive materials have been actively researched over the past few decades. Among such materials, spiropyran is one of the most attractive compounds because the structure and polarity of the material are dramatically changed after photo irradiation, unlike other materials. In this work, we designed and synthesized a spiropyran derivative (SpMA) with a methacryloyl group on the nitrobenzene ring of a spiropyran skeleton. The UV spectra of the newly synthesized SpMA showed the photo-isomerization of spiropyran. The maximum absorption wavelength (λmax) of SpMA was 616 nm in n-hexane, a nonpolar solvent, although λmax of SpMA was 532 nm in methanol, a polar protic solvent, which resulted in an 84 nm blue-shift. SpMA was successfully polymerized by ruthenium (Ru)-catalyzed living radical polymerization. Poly(SpMA) (PSpMA) was then spin-coated on a PET substrate in order to control the surface properties of water repellency and cell adhesion. The water repellency was decreased approximately 10° under UV irradiation, because of the polarity change of PSpMA caused by photo-isomerization from the spiropyran (SP) type to the merocyanine (MC) type. In addition, NIH3T3 cells were spread only on 6% of the surface of the PSpMA thin film after UV irradiation compared with no UV irradiation. The polarity change of PSpMA by photo-isomerization is also believed to be the reason for this behavior. As a result, we successfully synthesized a photo-controllable cell culture scaffold.
Crystal and solution structures of photochromic spirobenzothiopyran. First full characterization of the meta-stable colored species
Hirano, Masafumi,Osakada, Kohtaro,Nohira, Hiroyuki,Miyashita, Akira
, p. 533 - 540 (2002)
Full elucidation for stable, colorless, and meta-stable colored structures of a new spirobenzothiopyran has been achieved both in the solid state and in a solution. 1′,3′,3′-Trimethyl-6-nitrospiro[(2H)-1-benzothiopyran-2, 2′-indoline] with an ester group as a substituent at the 8-position of 1-sp shows photochromism. The blue-green colored species resulted from UV irradiation (365 nm) in one minute and spontaneously bleaches within one minute in acetone and methanol at 27 °C. UV exposure (365 nm) of 1-sp in methanol for 3 h at room temperature results in the growth of deep blue needlelike single crystals of the open form of spirobenzothiopyran, photomerocyanine 1-pmc, whose structures in the solid state and in solution were obtained unambiguously. The X-ray structural analysis of 1-pmc revealed the molecular structure of the zwitterionic photomerocyanine with s-trans,s-trans conformation. 1-pmc is soluble to polar solvents and thermally returns to 1-sp. In the DMSO solution, 1-pmc is found to return slowly to 1-sp (1-pmc gave only 18% of 1-sp for 30 min at 22 °C). The detailed NMR studies in DMSO-d6 including COSY and NOE techniques as well as isotope labeling of the compound showed the structure with s-trans,s-cis conformation in a solution.
Interaction studies between photochromic spiropyrans and transition metal cations: The curious case of copper
Natali, Manuel,Giordani, Silvia
, p. 1162 - 1171 (2012)
A series of four spiropyrans bearing different substituents on the indolic nitrogen were synthesized and their capability of binding mono and bivalent transition metal cations in solution was assessed via UV-visible absorption spectroscopy. All the compounds responded selectively to the presence of Cu(ii) ions producing intense absorption bands in the visible region of their spectra. Bidimensional 1H-NMR and MALDI-TOF MS spectroscopies revealed the formation of SP dimers mediated by Cu(ii). This is the first example of cross-coupling mediated by copper(ii) in mild conditions causing the symmetric dimerization of spiropyran dyes. The Royal Society of Chemistry 2012.
Structures of Lithium Salts of 2,3,3-Trimethylindolenine and Its 5-Methoxy Derivative in Solution and the Solid State
Jackman, L. M.,Scarmoutzos, L. M.,Smith, B. D.,Williard, Paul G.
, p. 6058 - 6063 (1988)
An X-ray crystal structure of lithium 2,3,3-trimethylindolenide etherate shows it to be a disolvated dimer having a η3-azaallyl-type structure.The structures of the salt in several solvents have been established by studies of 13C chemical shifts, 6Li, 15N spin-spin splitting, 7Li quadrupole splitting constants, and apparent degrees of aggregation determined by vapor pressure barometry.It is the η3-azaallyl dimer disolvate in diethyl ether, a tetrasolvated dimer in dioxolane, a mixture of monomer splitting constants of 230, 156, 180 - 190 (0.27 - 0.75 M), and 217 kHz, respectively.In diethyl ether with 4 equiv of hexamethylphosphoric triamide, the salt is a mixture of monomeric and triple ion species.Lithium 5-methoxy-2,3,3-trimethylindolenide forms similar species except that, in tetrahydrofuran, the tendency for dimer formation is enhanced, which leads to a higher proportion of C- to N-methylation in its reaction with methyl chloride in that solvent.
Unusual thermo(photo)chromic properties of some mononitro- and dinitro- substituted 3′-alkyl indolospirobenzopyrans This paper is dedicated to the memory of Dr Thomas G. Nevell.
Abdullah, Ayse,Nevell, Thomas G.,Sammes, Peter G.,Roxburgh, Craig J.
, p. 57 - 72 (2015)
Isomeric equilbria of dinitro-substituted indolospirobenzopyrans, possessing 3′-gem-methyl- or 3′-cyclohexyl-substitutents, have been investigated using 1H NMR spectroscopy at six temperatures, ranging from 298 K to 410 K; isomerisation processes in a methanolic solution have been monitored by spectrophotometry. For the mononitro-substituted compounds, equilibrium favoured the colourless spirocyclic isomers. Reversion of the coloured merocyanine isomers, generated by UV irradiation, followed first-order kinetics. For the dinitro-substituted compounds the coloured merocyanine isomers predominated. Following decolourisation by visible light photoirradiation, reversion towards the merocyanine structures were particularly slow, absorbances unusually increasing sigmoidally. UV. spectral observations for the gem-methyl- 1 and 3′-cyclohexyl-substituted systems 2 are qualitatively consistent with the simultaneous involvement of two relatively slow rate determining steps, possessing slowly forming and long-lived intermediates - postulated to be the oxygen protonated pyran-ring of the spirocyclic structure and TCC merocyanine isomer, the latter undergoing relatively slow isomerisation about the central β-alkenic bond to the TTC isomer.
NOVEL SQUARYLIUM COMPOUNDS, AND COMPOSITIONS COMPRISING SAME
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Paragraph 0107; 0113-0115, (2021/04/29)
The present disclosure is disclosed herein. The present invention relates to a novel squarylium compound and a near infrared absorbing resin composition containing the squarylium compound.
Method for preparing indoline
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Paragraph 0016; 0018; 0019; 0021; 0024, (2021/01/12)
The invention relates to a method for preparing indoline. The metho is characterized by comprising the following steps of: a, performing condensation and cyclization on phenylhydrazine hydrochloride or substituted phenylhydrazine hydrochloride and a methyl ketone compound in a solvent under a non-catalytic condition to generate C2-methylindole or a derivative thereof, and conducting cooling, salting-out, suction filtration and desolventizing successively; b, subjecting the condensation ring-closing product C2-methylindole or the derivative thereof to reacting with chloromethane under the conditions of pressurization, solvent presence and catalysis to generate corresponding quaternary ammonium salt or quaternary ammonium salt containing substituent groups; and c, dissolving the salt generated in the step b in water, then carrying out alkaline hydrolysis in a solvent and alkali liquor, and successively performing layering, desolvation and distillation to obtain a product, namely 1,3,3-trimethyl-2-methyleneindoline or a derivative thereof. The whole technological process is simple, the amount of three wastes is small, the cost is low, the yield is high, and the method is a green technology suitable for industrial amplification and outstanding in economic benefit.
Methylation synthesis method of N-heterocyclic compound
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Paragraph 0013, (2021/02/06)
The invention relates to a methylation synthesis method of an N-heterocyclic compound, which is characterized by comprising the following steps of a, methylation reaction: sequentially adding an N-heterocyclic compound and dimethyl carbonate into a reaction kettle, carrying out gas replacement, heating, keeping the temperature and pressure, and reacting, wherein the reaction temperature is 80-250DEG C, and the pressure is 0.3-8.0 MPa, and b, rectification: after the reaction is completed, reducing the pressure, carrying out reduced pressure rectification on the reaction mother liquor to obtain a methylation product, and recovering dimethyl carbonate and byproduct methanol. The dimethyl carbonate reagent is used for synthesizing the N-methylation product under the pressurization condition,and compared with methyl iodide and dimethyl sulfate, dimethyl carbonate is low in toxicity and more environmentally friendly; the reaction conversion rate is high, the operation is simple, and the reaction cost is low. Meanwhile, the methylation reaction selectivity is extremely good, and the method is suitable for high-selectivity synthesis of series products such as 1-methyl-1H-indole, 1, 3, 3-trimethyl-2-methylene indoline and the like.
Novel Spiropyran Based Composition and Application Thereof as Security Tag
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Paragraph 0061; 0063, (2018/06/30)
The present invention discloses the spiropyran compound of formula (I), process for preparation thereof and a composition comprising spiropyran compound of formula (I) on a support, wherein said support selected from polymers such as Poly (ethylene oxide), Polydimethylsiloxane (PDMS), Ethylene propylene diene monomer (EPDM).
