吲哚类化合物的合成及其相关问题研究

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1、天津大学博士学位论文吲哚类化合物的合成及其相关问题研究姓名：郭翔海申请学位级别：博士专业：应用化学指导教师：沈家祥;陈立功20060101天津大学博士学位论文中文摘要到RaneyNi-Rh体系时，效果最佳。5、发现在环化反应中，高温、有氧存在、RaneyNi催化下，吲哚(可能与邻氨基苯乙醇也有关)能够发生二聚反应生成不对称的2，3’-二吲哚。此外，本文利用邻硝基乙苯，平行地运用羟甲基化、氢化还原和闭环反应，顺利地合成了3．甲基吲哚，总收率也达到约70％。本文设计了两条5．甲氧基吲哚的合成路线。路线一是从邻硝

2、基乙苯出发、探索Bamberger反应的模型实验。路线二从邻硝基甲苯出发，在羟甲基化为邻硝基苯乙醇之后采用锌粉还原成相应的羟胺，在甲醇中进行扩展Bamberger反应得到2．浯羟基乙基)-4-甲氧基苯胺。通过RuCl2(PPh3)3催化闭环，经提取分离得到5．甲氧基吲哚。对于邻硝基苯乙醇起，还原、转位、闭环三步收率分别为62％、27．6％和89．9％，总约15％。关键词：吲哚，3-甲基吲哚，5-甲氧基吲哚，RaneyNi，Bamberger反应天津大学博士学位论文AbsWactABSTRACTtndolei

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4、synthesesofthesearticlesa∞intensivelypursuedbyresearchworkersinthefield．Duringinitiationofthisresearch,thefirstthingcfllnetoourmindwiltstotakeadvantageofthesuperfluoussupplyofo-nitroethylbenzeneasstartingmaterialwhichwasabyproductfTomproductionofchMramphen

5、icolbyauniqueprocessdevelopedyearsagoinChina．Therewasapresumptioninourmind越thetimethatfimctionalizationoftheethylsideohalnonbenzeneringmighthelptomoderatetheindoleproducingtemperature，andconsequentlyincreasetheselectivityofthereaction．Thenuponthisassumptio

6、n,weformulatedschumeltouppmachthesolution．Schemelwastostartfromo-nitroethylbenzeue．Conventionalsequenceofoxidationandreductionwasexpectedtogivehighyieldof2-(1-hydroxyethyl)一anilinewhichwastobesubmittedtoindolesynthesis．However,experimentalresultsfromeverys

7、tepfailedooi"expectationandthelaststeptoindolegaveonlyalowyieldof18．8％．ThisforcedllstogiveupfLLrtherdevelopmentworkonthisscheme．Scheme2tookreferencesfromthepublishedworkofWatanabeandthatofRyuichi．Usingo-nitrotolueneasstm血gmaterial，hydroxymethylationwithfor

8、maldehydeunderalkalineconditionsgaveo-nitrophenylethan01．InthisstudywechosetodevelopaRaneyNicatalystusedbothforreductionofthenitrogroupaswellasfortheindoleproductioninthelaststep．Thefinalresultforthethreecons