4,5,6,7-四氢吡唑并[1,5-a]哌嗪-3-甲酸乙酯的合成  

Synthesis of 4,5,6,7-Tetrahydro-pyrazolo[1,5-a]piperazine-3-carboxylic Acid Ethyl Ester

作　　者：陈寿林[1] 滕大为[1] CHEN Shou-lin TENG Da- wei(College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, Chin)

机构地区：[1]青岛科技大学化工学院,山东青岛266042

出　　处：《化学试剂》2017年第2期207-210,217,共5页Chemical Reagents

摘　　要：以4-氯-3-氧代丁酸乙酯为原料,经与叔丁醇钾醚化、DMF-DMA缩合、水合肼环合、脱叔丁基、羟基氧化、还原氨化、分子内环合以及氢化脱苄等反应合成了标题化合物。并对其中关键的羟基氧化反应和分子内环化反应的工艺条件进行了优化,获得了较优的工艺条件:在羟基氧化反应中以二氧化锰为氧化剂、氯仿为溶剂;在分子内环化反应中以甲基磺酰氧基(OMs)为离去基团。目标化合物的总收率为39.5%,其结构经~1HNMR、^(13)CNMR、MS和元素分析进行了确定。The title compound was synthesized from 4-chloro-3-oxo-butyric acid ethyl ester by the reactions of etherification with tBu OK,condensation with DMF-DMA,cyclization with N_2H_4·H_2O,removal of t-butyl group,oxidation of hydroxyl group,reductive amination with N-benzyl ethanolamine,intramolecular cyclization and hydrogenation debenzylation. The optimum conditions of oxidation of hydroxyl group and intramolecular cyclization were obtained. For oxidation of hydroxyl group： MnO_2 as oxidizing agent,chloroform as solvent. For intramolecular cyclization： methylsulfonyloxy group（OMs） as leaving group. The overall yield is39. 5%. The aimed compound was confirmed by-1HNMR,-（13）CNMR,MS and elemental analysis.

关 键 词：4 5 6 7-四氢吡唑并[1 5-a]哌嗪 4-氯-3-氧代丁酸乙酯 环合反应 

分 类 号：O626.1[理学—有机化学]