【作者】 胡卫林；

【导师】 蒋青；

【作者基本信息】 四川大学 ， 有机化学， 2003， 硕士

【摘要】 有机光致变色化合物在科学技术和日常生活中有着广泛的用途。其中，萘并吡喃是最有希望达到实用化的有机光致变色材料之一，由于这类化合物具有良好的光致变色性能，特别是较高的抗疲劳性和成色性，在有机光致变色镜片领域内有着重要的应用前景和商业价值。 萘并吡喃要真正的实用化，特别是在光学器件领域实际应用，其抗疲劳性和成色性还有待提高。本科研组在过去的研究工作中已获得兰色、紫红色的光致变色材料，为了获得中性色的变色镜片，必须有光致变红色的变色材料来进行调色。而光致变红色的有机光致变色化合物很难得到。有机光致变色化合物在紫外光或阳光的照射下，其开环式，只有吸收蓝光才能得到发射在红色的化合物，它的吸收波长应该是450nm左右。其开环体必须具有不太大的共轭度，共轭度增大，则会产生红移。从量子化学角度讲，在有共轭的情况下，电子云密度分布平均，且最大，才能得到吸收在蓝色。要得到这一类化合物，螺噁螓则较难，所以我们选择了萘并吡喃类化合物。萘并吡喃化合物具有较好的光响应性，较快的褪色速度及较好的光稳定性和抗疲劳性。为了得到消光系数大(即颜色深)，光致变红色的化合物，应考虑开环体的共轭度不是很大的萘并吡喃化合物，因此我们设计合成了以下化合物：3-(3-氯-苯并噻酚-2-基)-3-(4’-甲基苯基)-3H-萘并[2，1-b]吡喃、3-(3-氯-苯并噻酚-2-基)-3-苯基-3H-萘并[2，1-b]吡喃和3，3-二苯基-萘并[2，1-b]吡喃、3-苯基-3-(4’-甲基苯基)-3H-萘并[2，1-b]吡喃。经过对它们光致变色性能的测试，结果表明3-(3-氯-苯并噻酚-2-基)-3-(4’-甲基苯基)-3H-萘并[2，1-b]吡喃、3-(3-氯-苯并噻酚-2-基)-3-苯基-3H-萘并[2，1-b]吡喃均具有优良的光致变色和抗疲劳性能；发现在3位引入一个3-氯-苯并噻酚一Zee基以后，得到了一个光致变橘红色的光致变色化合物，其光致变色的各种性能均得到了明显的改善。 另外，我了「1之识寸6‘-氰基螺嗯嵘与6’一呱陡基螺唔嫉的合成方法进行了改进，首次采用微波快速合成光致变色的螺嗯嵘化合物，此法具有很强的适用性。更多还原

【Abstract】 Organic photochromic materials have attracted much interest for their extensive application prospects in both science and daily life. Among them, naphthopyran is one of the most promising candidates due to their outstanding properties such as high photocolourability and remarkable fatigue resistance. Despite of their many important applications, the more particularly advantageous known applications is ophthalmic lens for the purpose of screening light radiation as a function of its intensity.Although we have got fuchsia and blue spirooxazin photochromic materials, we still need red ones to obtain ophthalmic lens with neutral color, while this arose much difficulty, hi order to obtain red materials, we must design molecules with their open forms absorbing blue light with wavelength of ~ 450 nm under the sunlight or ultraviolet radiation. Thus, the open forms should have suitable conjugation length to avoid bathochromic shift. From the view of quantum chemistry, electron cloud density should be distributed symmetrically if the conjugate resists. As spirooxazins could not meet these requirements, herein, we choose naphthopyran derivatives, for their good optical response, fade speeds, intensity and anti-fatigue as well, as target molecules. However, their photocolourability and fatigue resistance must be improved for the practical application in ophthalmic lens field. For the purpose of getting red naphthopyran photochromic materials with good fatigue resistance as well as deep optical density, which should have large extinction coefficients withperfect conjugation degree, we designed and synthesized the following four compounds: 3,3-diphenyl-3H-naphtho[2,1-b]pyran, 3-(4’ -methylphenyl)-3-phenyl-3H-naphtho[[2,1-b]pyran,3-phenyl-3-(3-chloro-benzothiophen-2-yl)-3H-naphtho[2,1 -b]-pyran,3-(4’-methylphenyl)-3-(3’-chloro-benzothiophen-2’-yl)-3H-naphtho[2,1-b] -pyran. And their photochromic properties had been investigated, the results indicated that all of them have good photochromic and anti-fatigue properties. Especially that 3-(4’-methylphenyl)-3-(3’-chloro-benzothiophen-2’-yl)-3H-naphtho[2,1-b]pyran had particularly photochromic properties, such as high colourability (in their open form, in the visible region), and its open form exhibits jacinth color.Furthermore, we first adopted microwave technique to improve the synthesis of the spirooxazins compounds, and got two kinds of spirooxazins compounds with better yields.更多还原