芳环取代的俘精酸酐的合成及光致变色反应研究

本文报道四个芳环取代的俘精酸酐:2-亚异丙基-3-[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF1);2-亚异丁基-3-1[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF2);2-亚异丙基-3-[1-(α-萘基)-亚乙基]-丁二酸酐(NF1);2-亚异丙基-3-[1-(β-萘基)-亚乙基]-丁二酸酐(NF2)的合成及其光致变色性质.测定了它们在不同溶剂中光致变色前后的吸收光谱.利用纳秒级激光闪光光解技术研究了它们的光致变色过程,并讨论了其光致变色机理.结果表明,这类芳环取代的俘精酸酐的光致环合反应是经过激发单重态进行的快速过程.     

2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐的合成及其光致变色性能研究

在氢化钠和甲苯存在下, 1-苄基-3-甲基吲哚-2-甲醛与亚异丙基丁二酸二乙酯发生Stobbe缩合反应, 经过碱性水解和酸化得到二酸化合物, 接着在乙酰氯存在下脱水, 合成2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐. 研究了该俘精酸酐在不同溶剂中的光致变色性能.     

5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮的合成

报道俘精酸酐类化合物(E/Z)4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2,5-酮的拆分,及(E)和(Z)-5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮4(E)和4(Z)的合成,并对它们的光致变色特性进行了初步研究。     

5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮的合成

报道俘精酸酐类化合物(E/Z)4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2, 5-酮的拆分, 及(E)和(Z)-5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮 4(E)和4(Z)的合成, 并对它们的光致变色特性进行了初步研究。     

(口恶)唑环取代的俘精酸酐的合成及其光致变色性能的研究

合成了含噁唑环的俘精酸酐,4-（5-甲基-2-对甲氧苯基-4-乙酰基嘿唑）乙叉（异丙叉）丁二酸酐,研究了该化合物在不同溶剂中的光致变色性能,进行了光成色和光消色过程的动力学研究,并考察了溶剂极性对该化合物吸收光谱的影响。稳态动力学分析结果表明,该化合物呈色体的光消色反应遵循一级动力学规律,俘精酸酐本身的光反应比较复杂,不符合简单的动力学级数。     

基于5-氯-2-甲基噻吩的新型俘精酸酐的合成及其光致变色性能测定

针对杂环俘精酸酐良好的光致变色性能,以2-甲基噻吩和丁二酸二乙酯为原料,经过氯代、乙酰化、Stobbe缩合等反应合成了(E)-2-[1-(5-氯-2-甲基噻吩-3-基)乙亚基]-3-异丙亚基丁二酸酐,其结构经1H NMR,13C NMR,MS表征确认;初步考察了在不同的光照时间下目标产物的光致变色性能.     

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。     

吡咯取代的杂环俘精酸酐的合成及溶剂对其吸收光谱的影响

合成了五个新的3-乙酰基吡咯衍生物,以它们为原料,进一步合成了五个新的吡咯取代的俘精酸酐。研究了五个俘精酸酐化合物在不同溶剂中的光致变色性能,考察了溶剂极性对俘精酸酐及其光致变色反应产物(7,7a-二氢吲哚衍生物)吸收光谱的影响,结果表明,随溶剂极性的增加吸收光谱发生红移。对7,7a-二氢吲哚衍生物的影响远比对俘精酸酐本身的影响显著的多。     

吡咯取代的俘精酸酐及俘精酰亚胺的光致变色反应研究

对6个吡咯取代的俘精酸酐和1个俘精酰亚胺的光致变色行为进行了研究,发现取代基的不同对它们的光致变色过程有显著的影响.稳态动力学分析表明,呈色体(7,7a-二氢吲哚衍生物,II)的光消色反应遵循一级动力学反应规律.取代基对光消色反应的速率常数有一定的影响,对于呈色体(II)而言,2-3-位上有取代基的化合物,其光开环反应的速率常数明显大于2-或3-位无取代基的化合物.对于俘精酸酐的光反应而言,其反应比较复杂,不符合简单的动力学级数.在呈色体(II)的2-或3-位引入给电子基团可以使7,7a-二氢吲哚衍生物的吸收光谱发生红移,化合物II7的最大吸收波长在乙腈中可达720nm.溶剂极性的增大,可以使是色体的吸收光谱发生显著的红移,而对俘精酸酐本身的吸收光谱影响甚微.     

1,2-二甲基-3-吲哚甲叉(异丙叉)丁二酸酐(1)和1,2-二甲基-3-吲哚乙叉(异丙叉)丁二酸酐(2)的晶体结构

1.2-二甲基-3-吲哚甲叉(异丙叉)丁二酸酐(1)(C_(18)H_(17)NO_3)与1.2-二甲基-3-吲哚乙叉(异丙叉)丁二酸酐(2)(C_(19)H_(19)NO_3)同属于吲哚俘精酸类化合物,它们的分子结构非常类似,只是(1)中为吲哚甲叉,(2)中为吲哚乙叉.但它们的光色性却差别很大.化合物(1)无光致变色性,化合物(2)则表现为良好的光致变色性.其原因在于结构的不同。     

Structure and photochromic transformations of fulgides of the indole series

Previously undescribed fulgides of the indole series, viz., (1-methyl-3-indolylmethylene)- and (1-methyl-3-indolylethylidene) (isopropylidene)succinic anhydride, were synthesized. A Z conformation for (1-methyl-3-indolylmethylene) (isopropylidene)succinic anhydride and an E configuration for (1-methyl-3-indolylethylidene)-(isopropylidene) succinic anhydride were established by electronic and PMR spectroscopy and x-ray diffraction analysis. The photochromic properties of fulgides were observed and investigated. A scheme of photoinduced and thermal transformations of fulgides that includes a step involving Z E isomerization in the excited state is proposed. An additional photoisomer was recorded by pulse photolysis and fluorescence.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 33–41, January, 1990.     

Photochromism of fulgides and stereoelectronic factors: Synthesis of (E)-4(3)-adamantyhdene-(5)-dicyanomethylene-3(4)-[1-(2,5-dimethylfuryl)ethylidene]tetrahydrofuran-2-one 4 and 4a and (E)-4-adamantylidene-3-[2,6-dimethyl-3,5-bis(p-diethyl-aminostyryl)benzylidene]tetrahydrofuran-2,5-dione 10

In the search for fulgides with potential semiconductor laser compatibility, 4-adamantylidene-5-dicyanomemylene-3-[1-(2,5-dimethyl-3-furyl)ethylidene]tetrahydrofuran-2-one ( 4 ), along with its regioisomer 4a , have been synthesized from the corresponding fulgide 6 containing a succinic anhydride ring by reaction with malononitrile in the presence of diethylamine. Upon irradiation with a uv light at λ_max 350 run, a mixture of 4 and 4a revealed a considerably enhanced bathochromic shift to the visible region, λ_max 605 nm as compared with the starting fulgide 6 which, upon analogous uv irradiation, absorbed at λ_max 515 nm. In the search for semiconductor-laser-compatible fulgides with increased efficiency for the reverse bleaching reaction, another fulgide (E)–adamantylidene-3-[2,6-dimethyl-3,5-bis(p-diethylaminostyryl)-benzylidene]tetrahydrofuran-2,5-dione ( 10 ) was synthesized in seven steps starting from 2-bromo-m-xylene. However, 10 failed to undergo electrocyclic ring-closure upon irradiation with a uv light at λ_max 350 nm. The analogous fulgide 8 , which contains an isopropylidene functionality in place of the adamantyl group of 10 , was resynthesized for comparison, and showed two absorption maxima, one at 545 nm and the other at 620 nm. The missing physico-chemical data for 8 have also been provided.     

Structures and photochromic properties of fulgides based on naphtho[1,2-<Emphasis Type="Italic">b</Emphasis>]furan and benzo[<Emphasis Type="Italic">g</Emphasis>]indole

The novel heterocyclic fulgides, i.e. 3-isopropylidene-4-{1-[5-methoxy-1-(4-methoxy-phenyl)-2-methyl-1H-benzo[g]indol-3-yl]ethylidene}dihydrofuran-2,5-dione and 3-isopropylidene-4-[1-(1-benzyl-5-methoxy-2-methyl-1H-benzo[g]indol-3-yl)ethylidene]dihydrofuran-2,5-dione, were prepared and isolated as E-isomers. Photochromism, E-configuration, and high resistance to photocoloration—photobleaching of solutions of these fulgides as well as 3-isopropylidene-4-[1-(5-methoxy-2-methylnaphtho[1,2-b]furan-3-yl)ethylidene]dihydro-furan-2,5-dione and 3-isopropylidene-4-[1-(5-methoxy-2-methyl-1-phenyl-1H-benzo[g]indol-3-yl)ethylidene]dihydrofuran-2,5-dione synthesized previously were shown by X-ray diffraction analysis, ¹H NMR spectroscopy and electronic absorption spectroscopy. The novel fulgides show fluorescence and high thermal stability of photogenerated cyclic form. Repeated photo-coloration—photobleaching is accompanied by reversible photoinduced E—Z isomerization. Benzo[g]indolyl fulgides are characterized by the longer wavelength absorption of both original (E) and photoisomeric cyclic (C) forms as compared to naphthofuran fulgide.     

Synthesis and photochemical properties of the indoline series fulgides

Using the Stobbe condensation fulgides that undergo E, Z-isomerization on exposure to UV radiation are obtained from diethyl [2-(1,3,3-trimethyindoline-2-ilidene)ethylidene]succinate, and benzaldehyde and its derivatives; and from 1,2-dimethyl-3-formylindole and -formyl-1,3,3-trimethyl-2-methyleneindoline. The structure and photochemical changes of the fulgides were investigated by means of PMR.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 55–60, January, 1992.     

Nickel-catalyzed four-component connection of oraganoaluminium (organozinc), isoprene, aldehydes and amines: stereo- and regioselective synthesis of trisubstituted (E)-homoallylamines

Ni(acac)2 catalyzes the four-component connection reaction of trimethylaluminium (or diphenylzinc), isoprene, aromatic aldehydes and p-anisidine in this order and provides (E)-1-aryl-1-(p-methoxyphenyl)amino-3-methyl-3-hexenes (or (E)-1-aryl-1-(p-methoxyphenyl)amino-3-methyl-5-phenyl-3-pentenes) selectively in good yield.     

Studies on photochromic benzimidazol[1,2a]pyrrolidin-2-ones from the condensation of 2-methyl-3-benzothienylethylidene-(isopropylidene)succinic anhydride with 1,2-diaminobenzenes

Novel photochromic benzimidazol[1,2a]pyrrolidin-2-ones, which give thermally stable highly coloured photochromes, have been synthesised by condensation of 2-methyl-3-benzothienylethylidene(isopropylidene)succinic anhydride with 1,2-diaminobenzene and its 4,5-dimethyl and 4,5-dimethoxy derivatives. The photochromic properties are reported.     

Studies on Synthesis and Photochromism of a Novel Class of Fulgimide： （Z）-4-Oxazolylfulgimide

A novel class of fulgimide, (Z)-4-oxazolylfulgimide ((Z)-1-benzyl-4-isopropylidene-3-[1-(2-aryl-5-methyloxazolyl)ethylidene]tetrahydropyrrole-2,5-dione), was synthesized by the reaction of (Z)-4-oxazolyl fulgide (4-isopropylidene-3-[1-(2-aryl-5-methyloxazolyl) ethylidene]tetrahydrofuran-2,5-dione) with benzyl amine. Photochromic property of (Z)-4-oxazolylfulgimide was studied. Compared with (Z)-4-oxazolylfulgide, the absorption maximum of the colored form of (Z)-4-oxazolylfulgimide is bathochromic-shifted. Substituents on the aryl ring affect the absorption maximum of the open form and the colored form of (Z)-4-oxazolylfulgimide.     

Synthesis and applications of photochromic fulgides in optical information storages

A pyrryl substituted photocbromic fulgide, (1-p-methoxyphenyl-2-methyl-5-phenyl)-3-pyrryl-ethylidene (isopropylidene) succinic anhydride, was synthesized. Its chemical structure was identified by IR, 1H NMR MS and elemental analysis. The title compound was used to prepare the optical disks by the spin coating method and the vacuum evaporation method. The results of the static state examination show that the optical disks prepared with this kind of molecules possess excellent thermal stability and fatigue resistance, i.e. over 450 writing-erasing recycles, the relative contrast between writing state and erasing state remains at 40%.     

有机光功能材料分子设计研究: I. 俘精酸酐类光致变色材料量 子化学研究

用AM1对呋喃基取代的六种俘精酸酐类分子开环体、闭环体基态与激发态的结构进行了优化,所得俘精酸酐1的开环体基态平衡几何结构与已有的实验结果一致。计算结果能较好地解释俘精酸酐的热稳定性和光致变色性能,对取代基对俘精酸酐结构的影响取得了一些新的认识。根据俘精酸酐1开环体上各碳原子的净电荷密度,讨论了它的^1^3CNMR波谱。