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托尼卟吩结构模型中D环结构单元的合成 被引量：1

Synthesis of the Ring-D Fragment of the Tolyporphin Model
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摘要 由乙酰乙酸乙酯(1)为原料经过肟化、还原缩合成环等反应首先合成knorr吡咯(4),然后再由knorr吡咯经氧化反应得到2,4-二乙氧羰基-3-甲基-5-甲酰基吡咯(5),5经皂化反应得到2-羧基-3-甲基-4-乙氧羰基-5-甲酰基吡咯(6),6再经溴化反应得到2-溴-3-甲基-4-乙氧羰基-5-甲酰基吡咯(7),最后,7通过皂化及脱羧得到托尼卟吩结构模型的重要中间体D环结构单元2-溴-3-甲基-5-甲酰基吡咯(Ⅴ)。合成产物的结构都通过1HNMR、IR和GC-MS或MS得到了表征。同时对第二步中氧化反应中的氧化剂以及第四步溴化反应中的溶剂进行了研究。结果表明,氧化反应中的最佳氧化剂为硝酸铈铵,产率达到91.5%,溴化反应中的最佳溶剂为甲醇,反应产率达到58%。 Knorr pyrrole （3, 5-dimethyl-2, 4-diethoxycarbonylpyrrole ） was prepared from ethyl acetoacetate by nitrosation and reductive condensation, and then oxidized to 2,4-diethoxycarbonyl-3-methyl-5-formylpyrrole, which was transformed to 2-carboxyl-3-methyl4-ethoxycarbonyl-5-formylpyrrole by saponification, and further bromination gave 2-brome-3-methyl4-ethoxycarbonyl-5-formylpyrrole.This compound, by saponification and decarboxylation, gave the target product 2-brome-3-methyl-5- formylpyrrole, the ring-D fragment of the tolyporphin model. Structures of all these compounds were characterized by ^1HNMR, IR and GC -MS or Mass. The optimum oxidant for the formylation reaction of Knorr pyrrolr was ceric ammonium nitrate（ yield 91.5.% ） and the optimum solvent for the bromination Knorr pyrrolr was ceric ammonium nitrate（ yield 91.5.% ） and the optimum solvent for the bromination reaction was methanol（yield 58% ）.
作者 蔡超君 胡炳成 吕春绪 刘登红
机构地区 南京理工大学化工学院
出处 《精细化工》 EI CAS CSCD 北大核心 2007年第3期299-303,共5页 Fine Chemicals
关键词 托尼卟吩结构模型 D环结构单元 2-溴-3-甲基-5-甲酰基吡咯 tolyporphin model the ring-D fragment 2-brom-3-methyl-5-formylpyrrole
分类号 O626.13 [理学—有机化学]
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参考文献15

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二级参考文献26

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共引文献7

同被引文献12

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  • 2蔡超君,胡炳成,吕春绪.2-乙氧羰基-3-溴-4-甲基-5-甲酰基-吡咯的合成[J].应用化学,2006,23(7):798-802. 被引量：7
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精细化工
2007年 第3期

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