1－苯基－3－甲基－4－（6－氢－4－氨基－5－硫杂－2，3－吡嗪）－吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过1－苯基－3－甲基－4－氯乙酰基－吡唑啉酮－5（PMCP）和氨基硫脲（ TSC）缩合，形成了一种含NNS六元杂环的光致变色化合物（PMCP－TSC）。利用元 素分析，MS，”1H NMR，IR和UV光谱进行了表征。通过紫外可见光谱对它的光致 变色性质进行了研究，测出了光致变色反应的动力学常数。并用X线单晶衍射仪测 定了PMCP－TSC变色后的晶体结构，该晶体属单斜晶系，具有P2_1/c空间群，a = 0.105 10(2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890 (10)°, V = 1.496 9(4) nm~3, Z - 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(- 1), F(000) = 672, R = 0.033 4, wR = 0.089 6。结构分析表明：其光致变色现 象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化。同时该化合物 经分子间氢键形成二聚体，又通过甲醇与本体分子之间的氢键使化合物形成具有三 维网络结构的超分子化合物。     

Synthesis,Structure and Photochromic Properties of 1-Phenyl-3-Methyl-4-(4-Bromobenzal)-Pyrazolone-5 Thiosemicarbazone

A new organic photochromic compound containing pyrazolone-ring, 1-phenyl-3-methyl-4-(4-bromobenzal)-pyrazolone-5 thiosemicarbazone (PM4BrBP-TSC), was synthesized and characterized by elemental analyses and single crystal X-ray diffraction. The X-ray determination indicated that PM4BrBP-TSC is of orthorhombic system, space group Pbca with cell dimensions of a = 12.184(2) Å, b = 18.121(3) Å, c = 18.554(4) Å, V = 4096.4(12) ų, Z = 8 and R = 0.0387. The photochromic properties and photocolored kinetics of PM4BrBP-TSC were studied by Time-dependent UV-Vis reflectance spectra and fluorescence spectra under 365 nm light irradiation. The crystal structure analysis showed that the photochromic properties were related to the photoisomerization from enol tautomer to keto one.     

A Theoretical Study on the Photochromic Mechanism of 1-Phenyl-3-methyl-4-（6-hydro-4-amino-5-sulfo-2,3-pyrazine）-pyrazole-5-one

The photochromic mechanism of 1-phenyl-3-methyl-4-（6-hydro-4-amino-5-sulfo-2,3- pyrazine）-pyrazole-5-one has been investigated using the density functional theory（DFT）. The solvent effect is simulated using the polarizable continuum model（PCM） of the self-consistent reaction field theory. According to the crystal structure of the title compound, an intramolecular proton transfer mechanism from enol to keto form was proposed to interpret its photochromism. Bader＇s atom-in-molecule（AIM） theory is used to investigate the nature of hydrogen bonds and ring structures. Time-dependent density functional theory（TDDFT） calculation results show that the photochromic process from enol to keto form is reasonable. The conformation and molecular orbital analysis of enol and keto forms explain why only intramolecular proton transfer is possible. The results from analyzing the energy and dipole moments of enol form, transition state and keto form in the gas phase and in different solvents have been used to assess the stability of the title compound.     

1,2-双[2-甲基-5-(3,4-二氟苯基)噻吩-3-基]全氟环戊烯的合成

在冰浴条件下, 2-甲基噻吩(1)与液溴反应生成3,5-二溴-2-甲基噻吩(2); 在－78 ℃条件下, 硼酸三丁酯加入2, 得到2-甲基-3-溴-5-硼酸基噻吩(3); 3,4-二氟溴苯与3反应得到2-甲基-3-溴-5-(3,4-二氟苯基)噻吩(4); 在－78 ℃下全氟环戊烯与4反应, 得到一种新的二芳基乙烯类光致变色化合物1,2-双[2-甲基-5-(3,4-二氟苯基)噻吩-3-基]全氟环戊烯(DT-1). 用IR, NMR, MS和元素分析确定了化合物DT-1的结构, 并对该化合物的光致变色特性进行了初步研究.     

Schiff base compounds derived from (R)-3-phenyl-2-phthalimidopropionic acid: photochromism, solvatochromism, and fluorescence

The photochromic behaviors of four Schiff bases derived from (R)-3-phenyl-2-phthalimidopropionic acid were studied to reveal the substituent effect on the photosensitivity. Upon ultraviolet light radiation, all of compounds 1–4 exhibit photochromic behavior in solution through intramolecular hydrogen atom transfer. In solid state, only compound 2 is photochromic, which may be due to the presence of meta-site methoxyl. In solution, the photochromic behavior of compound 3 is remarkable than the other compounds, which may be ascribed to the presence of para-site hydroxyl. Only compound 4 exhibits solvatochromism, which may be ascribed to the large dissociation tendency of the naphthol hydroxyl. The influences of acidity on the UV–Vis absorption spectra of the title compounds were also studied.     

Methacrylic Polymers Bearing in the Side-Chain an Optically Active Moiety Linked to the trans-4-Azobenzene Chromophore: Chiroptical Properties of Poly[(S)-(+)-N-methyl-(2-methacryloyloxypropanoyl)-4-aminoazobenzene]

The synthesis by radical homopolymerization of a novel optically active methacrylic polymer containing a side-chain chiral moiety linked to a photochromic chromophore has been carried out starting from the related monomer trans-(S)-(+)-N-methyl-(2-methacryloyloxypropanoyl)-4-aminoazobenzene. The chiroptical properties in solution of the polymer have been investigated by circular dichroism and compared with those of the corresponding low molecular weight model compound, trans-(S)-(+)-N-methyl-(2-pivaloyloxypropanoyl)-4-aminoazobenzene. The optical activity displayed by the polymer is discussed in terms of extent of chiral conformations assumed by the macromolecules as a consequence of dipole-dipole interactions between the azoaromatic chromophores.     

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".     

Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

IntroductionThe investigation of organic photochromic materials has increased considerably in recentyears because of their potential commercial application in several areas,such as high-densityoptical storage media,optical switching,etc.[1 ,2 ] .Though numerous organic photochromicmolecular systems or photoactive devices have been explored so far,those systems classifiedaccording to the photochromic structural units mainly belong to a small number of families:fulgides,spiropyrans and spiroxazi…     

2-(甲苯-4-磺酰胺基)-苯甲酸的晶体结构、光谱及热性质

报道了2-(甲苯-4-磺酰胺基)-苯甲酸(I)的元素分析和红外、核磁共振光谱性质并通过单晶X射线衍射确定了其晶体结构. 晶体属单斜晶系, 空间群为C2/c,晶胞参数为, a=2.7320(3) nm, b=0.85441(8) nm, c=1.17607(11) nm, α=90°, β=98.728(3)°, γ=90°, V=2.7135(5) nm3, Z=8. 晶体中分子单体通过N—H…O 和O—H…O氢键作用形成具有中心对称的二聚体, 且进一步通过两种不同的C—H…O 氢键和π…π作用形成超分子结构. 在不同的溶剂中, 化合物I的紫外吸收表现出明显的溶剂效应, 此外, 荧光光谱与DSC-TGA热重分析表明, 该化合物是一种耐热的荧光材料.     

Characterization of A New Organic Photochromic Compound

A new organic photochromic compound, 1-phenyl-3-methyl-4-(4-fluoro)-benzal-5-pyrazolone ethanyl-thiosemicarbazone (PM4FBP-ETSC) was found to undergo photochromic reactions in the solid state. Upon irradiation with 365nm light the white powder sample turned light yellow. The photochromic properties were characterized by the time-dependent UV-vis reflective spectra. The structure of PM4FBP-ETSC was determined by single crystal X-ray diffraction.     

Liquid crystalline properties and photochromism of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]-methoxy and -ethoxy anilines

New homologous series of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]-methoxy and -ethoxyanilines were synthesized. The phase transitions of these homologues were determined using differential scanning calorimetry and an polarizing microscopy: para-substituted homologues exhibit a nematic phase, while ortho-substituted members do show no mesomorphic phase. In addition, some members of these homologous series exhibit a photochromic property in the solid state.     

Synthesis and spectroscopic study on photochromism of a new thiosemicarbazone compound containing pyrazolone

A new photochromic compound 1,3-diphenyl-4-(4'-fluro)benzal-5-pyrazolone-4-ethyl thiosemicarbazone (DP4FBP-ETSC) was synthesized by direct condensation of 1,3-diphenyl-5-pyrazolone with N4-ethyl thiosemicarbazide. The product was characterized by elemental analysis, IR and 1H NMR spectra. The photochromic properties of the compound were studied using time-dependent fluorescence emission spectra, the UV-vis reflection spectra in the solid state and the UV-vis absorption spectroscopy in liquid. The reaction rate constant of compound was also analyzed. The results show that DP4FBP-ETSC can perform photochromism.     

Crystal structure and photochromism of 1-phenyl-3-methyl-4-benzyl-5-one-pyrazole S-methyl thiosemicarbazone

A new organic photochromic compound containing pyrazolone-ring photochromic functional unit: 1-phenyl-3-methyl-4-benzyl-5-one pyrazole S-methyl thiosemicarbazone (PMBP-smtsc) was synthesized. The photochromic properties and photochemical kinetics of PMBP-smtsc have been studied by UV reflectance spectra under irradiation of 365 nm light. The crystal structure analyses of photocolored product show the photochromism is due to the photoisomerization from enol form to keto form through an intermolecular proton transfer.     

Synthesis, crystal structure and characterization of photochromic 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene

A novel photochromic diarylethene, 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene (BEDTP), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its photochromic and fluorescent properties were also investigated. The results showed that this compound exhibited reversible photochromism, changing from colorless to magenta after irradiation with UV light both in solution and in the crystalline phase. In hexane solution, the open-ring isomer of BEDTP exhibited relatively strong fluorescence at 400 nm when excited at 282 nm. The fluorescence intensity decreased along with the photochromism upon irradiation with 254 nm light and its closed-ring isomer showed almost no fluorescence.     

1-(4-氯苯胺基)-4-(4-吡啶甲基)-2,3-二氮杂萘琥珀酸盐的合成与抑制肿瘤活性

研究了1-(4-氯苯胺基)-4-(4-吡啶甲基)-2,3-二氮杂萘琥珀酸盐的合成工艺,采用苯酞和吡啶甲醛为起始原料,经加成、重排、取代和成盐4步反应得到目标化合物。 中间体及目标化合物通过1H NMR、MS和HPLC进行了表征。 重结晶纯化后的目标化合物纯度为98.1%。 对荷瘤（人大肠癌HT 29细胞）裸鼠的抑癌活性测定表明,该化合物具有明显的抑制肿瘤生长作用。     

DFT study of the infrared and Raman spectra of photochromic Fulgide; 3-Dicyclopropylmethylene-4-E-[1-(2,5-dimethyl-3-furyl)ethylidene]-5-(4-nitrophenylcyanomethylenetetrahydrofuran-2-one

The present work reports a theoretical study of vibrational signatures of the photochromic molecular transformation between two photochromic heterocyclic isomers. Raman and infrared (IR) spectra of the E (ring-opened form) and C (ring-closed form) photoisomers of 3-Dicyclopropylmethylene-4-E-[1-(2,5-dimethyl-3-furyl)ethylidene]-5-(4-nitrophenylcyanomethylenetetrahydrofuran-2-one have been calculated in gas phase in the region of 3500–500 cm^?1 for both molecules in their ground state. Calculations of the structure parameters and frontier molecular orbitals were carried out using ab initio electronic structure theory at the Hartree-Fock, density functional theory, and Moller-Plesset perturbation theory levels, while calculations of the IR and Raman spectra were carried out using density functional theory with B3LYP functional and 6-31+g(d,p) basis set. After comparing the predicted spectra of both E-form and C-form, we were able to probe the changes that arise upon the ring-closure/ring-opening transformation. The computational results showed that the C-form is ≈?10.7 kcal/mol lower in energy than the E-form. In addition, two different derivatives were adopted for both E-form and C-form to demonstrate the effect of substituents on the stability of the photoisomers. The theoretical predictions agree well with the reported experimental data, accounting for the molecular structure transformation of the photochromic isomers.     

喹啉氧基并四苯二醌的合成和光致变色性质

喹啉氧基并四苯二醌的合成和光致变色性质;并四苯二醌; 喹啉; 光致变色; 光异构化     

Liquid crystalline properties and photochromism of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]-methoxy and -ethoxy anilines

New homologous series of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]-methoxy and -ethoxyanilines were synthesized. The phase transitions of these homologues were determined using differential scanning calorimetry and an polarizing microscopy: para-substituted homologues exhibit a nematic phase, while ortho-substituted members do show no mesomorphic phase. In addition, some members of these homologous series exhibit a photochromic property in the solid state.     

Synthesis of 4-hetaryl-5,6-(2,5-dimethyl-3-thienyl)-2-phenyl-4h-thiazines and investigation of their photochromism

The polar [4+2] cycloaddition reaction of 1,2-bis(2,5-dimethyl-3-thienyl)acetylene with thiobenzamide and certain aldehydes of the thiophene and furan series catalyzed by boron trifluoride etherate gives the corresponding 4-hetaryl-5,6-di(2,5-dimethyl-3-thienyl)-2-phenyl-4H-1,3-thiazines. The photochromic properties of the products have been studied.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 100–106, January, 2005.     

萘并萘醌酚醛树脂的合成和光致变色性质

通过6-氯-5,12-萘并萘醌(1)与酚醛树脂经亲棱取代,一步合成制备具有光致变色性的酚醛树脂(3)。在苯溶液中,光致变色聚合物(3)与光致变色化合物6-{4-[2-(4-羟基苯基)异丙基]苯氧基}-5,12-萘并萘醌(2)有相似的光致变色行为。但是,在聚合物(3)中,由于苯基处于聚合物骨架中不易迁移,使聚合物(3)的变色速度较化合物(2)明显减慢,化合物(2)的光异构化速度常数是聚合物(3)的3倍。同时发现溶剂对聚合物(3)的光诱导trans-ana异构化反应速度有明显影响,在氯仿中的反应速度常数约为在苯中的2倍。