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1、天津大學博士學位論文吲哚類化合物的合成及其相關問題研究姓名：郭翔海申請學位級別：博士專業(yè)：應用化學指導教師：沈家祥;陳立功20060101天津大學博士學位論文中文摘要到RaneyNi-Rh體系時，效果最佳。5、發(fā)現(xiàn)在環(huán)化反應中，高溫、有氧存在、RaneyNi催化下，吲哚(可能與鄰氨基苯乙醇也有關)能夠發(fā)生二聚反應生成不對稱的2，3’-二吲哚。此外，本文利用鄰硝基乙苯，平行地運用羥甲基化、氫化還原和閉環(huán)反應，順利地合成了3．甲基吲哚，總收率也達到約70％。本文設計了兩條5．甲氧基吲哚的合成路線。路線一是從鄰硝
2、基乙苯出發(fā)、探索Bamberger反應的模型實驗。路線二從鄰硝基甲苯出發(fā)，在羥甲基化為鄰硝基苯乙醇之后采用鋅粉還原成相應的羥胺，在甲醇中進行擴展Bamberger反應得到2．浯羥基乙基)-4-甲氧基苯胺。通過RuCl2(PPh3)3催化閉環(huán)，經(jīng)提取分離得到5．甲氧基吲哚。對于鄰硝基苯乙醇起，還原、轉位、閉環(huán)三步收率分別為62％、27．6％和89．9％，總約15％。關鍵詞：吲哚，3-甲基吲哚，5-甲氧基吲哚，RaneyNi，Bamberger反應天津大學博士學位論文AbsWactABSTRACTtndolei
3、sanimportantfinechemicalwidelyusedforthesynthesesofpharmaceuticals,agriculturalchemicals，perfumes，dyes，andadditivestofoodsandfeedstocks．3-Methylindoleand5一methoxyindolea∞importantintermediatestoanumberofusefulindolederivatives．Therefore，facileandeconomical
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
