Ethyl 4-(2-methylbut-3-yn-2-ylamino)benzoate | 171898-68-3

• 物质功能分类: 医药中间体 - 原料药中间体
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ethyl 4-(2-methylbut-3-yn-2-ylamino)benzoate
• CAS: 171898-68-3
• 化学式: C₁₄H₁₇NO₂
• 分子量: 231.294
• InChiKey: HYKLPSYOYMFJBF-UHFFFAOYSA-N

物化性质

• 沸点：
  357.7±27.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ethyl 4-(2-methylbut-3-yn-2-ylamino)benzoate 在 Lindlar's catalyst 喹啉 、 mercury(II) diacetate 、 氢气 、 对甲苯磺酸 作用下， 以 水 、 乙酸乙酯 、 丙酮 、 乙腈 为溶剂， 反应 16.34h， 生成 ethyl 2,2-dimethyl-3,4-dihydro-1H-quinoline-6-carboxylate
  参考文献：
  名称：

  摘要：

  Cyclization of the carbamate of 2-(dimethylallyl)aniline with phenylselanyl chloride (benzeneselenenyl chloride) gave a 1:1 mixture of a dihydroindole and a tetrahydroquinoline. With phenylselanyl bromide only the dihydroindole was obtained. Addition of methanol to the silica used in the procedure trapped the reaction at the non-cyclized stage forming a 3-methoxy-3-methyl-2-(phenylselanyl)butyl side chain. The sulfonamide of 2-(dimethylallyl)aniline only formed the dihydroindole with phenylselanyl chloride. The corresponding trifluoroacetamide derivative did not form any cyclized product under the same conditions. The dihydroindole could be converted into the corresponding alkene by oxidative removal of the phenylseleno group. 4-Ethoxycarbonyl-2-(3,3-dimethylallyl)aniline cyclized with mercuric nitrate to give, after a reductive workup, a 2,2-dimethyltetrahydroquinoline. The X-ray crystal structures of ethyl N-{2-[3-methoxy-3-methyl-2-(phenylselanyl)butyl] phenyl} carbamate and 2-[1-methyl-1-(phenylselanyl)ethyl]-1-[(4-methylphenyl)sulfonyl]indoline are reported.

  DOI：

  10.1071/ch99109
• 作为产物：
  描述：

  美雌醇 在 copper(l) iodide 盐酸 、 copper bronze 、 水 、 铜 、 三乙胺 、 calcium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 52.0h， 生成 Ethyl 4-(2-methylbut-3-yn-2-ylamino)benzoate
  参考文献：
  名称：

  Cooper; Lucas; Taylor, Synthesis, 2001, # 4, p. 621 - 625

  摘要：

  DOI：

文献信息

• The preparation and some chemistry of 2,2-dimethyl-1,2-dihydroquinolines
  作者：Natalie M. Williamson、A. David Ward

  DOI：10.1016/j.tet.2004.10.035

  日期：2005.1

  The cyclisation of N-(1,1-dimethylpropargyl) anilines, using cuprous chloride in refluxing toluene, yields 6-substituted-2,2-dimethyl-1,2-dihydroquinolines. The reactivity of the double bond in the heterocyclic ring of these products is exemplified by chlorination, to yield 6-substituted-3,4-cis-dichloro-2,2-dimethyl-1,2,3,4-tetrahydroquinolines which can be selectively dechlorinated to provide 6-

  在回流的甲苯中使用氯化亚铜使N-（1,1-二甲基炔丙基）苯胺环化，得到6-取代的2,2-二甲基-1,2-二氢喹啉。这些产物的杂环中双键的反应性例如通过氯化来产生6-取代的3,4-顺式-二氯-2，2-二甲基-1，2，3，4-四氢喹啉，其可以被选择性地脱氯以提供6-取代的3-氯-2，2-二甲基-1，2，3，4-四氢喹啉；环氧化产生环氧化物，其可以被氢解为相应的3-羟基产物，然后被氧化为3-酮衍生物；氧合反应得到4-羟基产物，从而得到4-酮衍生物。3,4-二氯产物的脱氯化氢提供了3-氯-1,2-二氢喹啉，可以将其水解为3-酮系统。氯化反应形成顺式3,4-二氯产物，以及部分水溶液中氯化N-乙酰基-2,2,6-三甲基-1,2-二氢喹啉，形成顺式氯醇。那N-乙酰基或N-三氟乙酰基基团参与加成过程。
• Purification Strategy for Direct Nucleophilic Procedures
  申请人：Cyr John

  公开号：US20110112293A1

  公开（公告）日：2011-05-12

  The present invention provides novel and advantageous processes for preparing and purifying chemical compounds such as pharmaceuticals. The processes comprise a nucleophilic substitution reaction with a moiety X wherein the leaving group L of a substrate S in the reaction is covalently attached to a purification moiety M. This concept offers a convenient and lime-saving way to purity the desired product S-X from non-reacted precursors S-L-M and by-products L-M.

  本发明提供了一种新颖和有利的制备和纯化化学化合物，如药物的方法。该方法包括使用一个官能团X进行亲核取代反应，其中反应底物S的离去基团L共价地连接到纯化官能团M上。这个概念提供了一种方便和节省时间的方法，以从未反应的前体S-L-M和副产物L-M中纯化所需的产品S-X。
• An improved synthesis of 2,2-disubstituted-1,2-dihydroquinolines and their conversion to 3-chloro-2,2-disubstituted-tetrahydroquinolines
  作者：Natalie M Williamson、Darren R March、A David Ward

  DOI：10.1016/0040-4039(95)01572-y

  日期：1995.10

  N-(1,1-disubstitutedpropargyl)anilines can be cyclised to 2,2-disubstituted-12-dihydroquinolines by refluxing them in toluene containing cuprous chloride. Electron donating groups in the para position of the ring enhance the reaction rare and electron withdrawing groups markedly decrease the rare. The derived N-acetyldihydroquinolines can be cis dichlorinated and selectively monodechlorinated at the benzylic position to produce 3-chlorotetrahydroquinolines.
• PURIFICATION STRATEGY FOR DIRECT NUCLEOPHILIC PROCEDURES
  申请人：Bayer Schering Pharma Aktiengesellschaft

  公开号：EP2276717A1

  公开（公告）日：2011-01-26
• [EN] PURIFICATION STRATEGY FOR DIRECT NUCLEOPHILIC PROCEDURES<br/>[FR] STRATÉGIE D'ÉPURATION POUR PROCESSUS NUCLÉOPHILIQUES DIRECTS
  申请人：BAYER SCHERING PHARMA AG

  公开号：WO2009127372A1

  公开（公告）日：2009-10-22

  The present invention provides novel and advantageous processes for preparing and purifying chemical compounds such as pharmaceuticals. The processes comprise a nucleophilic substitution reaction with a moiety X wherein the leaving group L of a substrate S in the reaction is covalently attached to a purification moiety M. This concept offers a convenient and time-saving way to purify the desired product S-X from non-reacted precursors S-L-M and by-products L-M.