trans-3-ethyl-4-piperidineacetic acid ethyl ester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: trans-3-ethyl-4-piperidineacetic acid ethyl ester
• 英文别名: ethyl 2-[(3R,4R)-3-ethylpiperidin-4-yl]acetate
• 化学式: C₁₁H₂₁NO₂
• 分子量: 199.293
• InChiKey: ZMYQHFQMRLPPRB-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 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：

  trans-3-ethyl-4-piperidineacetic acid ethyl ester 在 盐酸 、 sodium hydroxide 、 sodium tetrahydroborate 、 N-氯代丁二酰亚胺 、 EDTA disodium salt 、 potassium tert-butylate 、 mercury(II) diacetate 、 二异丁基氢化铝 、 potassium carbonate 、 溶剂黄146 作用下， 以 甲醇 、 乙醚 、 乙醇 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 228.0h， 生成 萝巴新
  参考文献：
  名称：

  外消旋阿马里的全合成和19-外延-ajmalicine †

  摘要：

  外消旋。-阿马里新（31）和19-外延-ajmalicine（30）已经被会聚路径从预成型d合成，E形环部分25和27和色氨酰溴。还描述了在制备25和27中使用的反式-1-苯甲酰基-3-乙烯基-4-哌啶乙酸的两种合成（13）。

  DOI：

  10.1002/hlca.19810640544
• 作为产物：
  描述：

  trans-5-ethyl-2-oxo-4-piperidineacetic acid ethyl ester 在 sodium tetrahydroborate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 88.0h， 生成 trans-3-ethyl-4-piperidineacetic acid ethyl ester
  参考文献：
  名称：

  外消旋阿马里的全合成和19-外延-ajmalicine †

  摘要：

  外消旋。-阿马里新（31）和19-外延-ajmalicine（30）已经被会聚路径从预成型d合成，E形环部分25和27和色氨酰溴。还描述了在制备25和27中使用的反式-1-苯甲酰基-3-乙烯基-4-哌啶乙酸的两种合成（13）。

  DOI：

  10.1002/hlca.19810640544

文献信息

• Lactams. XXVI. Regioselectivity in the mercuric acetate-edetic acid oxidation of the ethyl 1-(2-aryl-2-hydroxyethyl)-3-ethyl-4-piperidineacetate system: Enhancement by a benzyloxy group in the aryl moiety and by the 3,4-cis configuration.
  作者：TOZO FUJII、MASASHI OHBA、MICHIKO TSUCHIDA、KIYOE SAITO、YUKO HIRANO、JUN SAKAGUCHI

  DOI：10.1248/cpb.34.496

  日期：——

  A quantitative analytical study to determine the isomer ratios of the 6-piperidones (type 7) and 2-piperidones (type 5) produced by the mercuric acetate-edetic acid (EDTA) oxidation of 1-(2-aryl-2-hydroxyethyl)-3-alkylpiperidines (±)-4c, d, f, h, 4e, g, i, j, and (±)-38 was carried out. It has been found that all the substrates with a benzyloxy group in the aryl moiety, regardless of its location, undergo oxidation at the 6-position preferentially as compared with the debenzyloxy derivatives such as (±)-4a, b. Comparison of the quantitative data from 4e and (±)-4f with those from (±)-4b indicated that the cis acetate chain at the 4-position increases the extent of the 6-oxidation, whereas a trans acetate chain at the same position has little effect. These two factors enhance the practical value of the "cincholoipon-incorporating method" for chiral syntheses of the 1-type Alangium alkaloids, in which the mercuric acetate-EDTA oxidation of 4e, g, i, j to the 6-piperidones (type 3)is one of the key synthetic operations.

  进行了一项定量分析研究，以确定由醋酸汞-乙二胺四乙酸（EDTA）氧化1-(2-芳基-2-羟基乙基)-3-烷基哌啶（±）-4c、d、f、h、4e、g、i、j和（±）-38生成的6-哌啶酮（类型7）和2-哌啶酮（类型5）的异构比。研究发现，所有具有苄氧基团的芳基底物，无论其位置如何，与去苄氧基衍生物（如±-4a、b）相比，更倾向于在6位发生氧化。将4e和（±）-4f的定量数据与（±）-4b的数据进行比较表明，4位的顺式乙酸链增加了6位氧化的程度，而同一位置的反式乙酸链则几乎没有影响。这两个因素增强了“金鸡纳碱引入法”在手性合成1类阿兰基麻黄碱中的实际应用价值，其中4e、g、i、j的醋酸汞-EDTA氧化生成6-哌啶酮（类型3）是关键的合成操作之一。
• A stereocontrolled synthesis of (.+-.)-emetine and (.+-.)-protoemetinol by intramolecular michael reaction.
  作者：YOSHIRO HIRAI、TAKASHI TERADA、ATSUSHI HAGIWARA、TAKAO YAMAZAKI

  DOI：10.1248/cpb.36.1343

  日期：——

  An intramolecular Michael reaction of 9 stereoselectively gave the tricyclic compound (10), which was converted to (±)-protoemetinol (2) and 13. Compound 13 is an important intermediate for the synthesis of (±)-emetine. A simpler preparation of 13 was also carried out by the intramolecular Michael reaction of 14, followed by reduction of the ketone moietv. Furthermore, the stereoselective formation of 26, which is an intermediate for the synthesis of (±)-emetine, was achieved by the floowing sequence of reactions : intramolecular Michael reaction, of the ketone moiety, and removal of the N-carbomethoxy group.

  9 的分子内迈克尔反应立体选择性地生成了三环化合物 (10)，然后转化为 (±)-protoemetinol (2) 和 13。化合物 13 是合成(±)-美丁的重要中间体。通过 14 的分子内迈克尔反应，然后还原酮莫埃特 v，也可以更简单地制备 13。此外，通过以下反应顺序：分子内迈克尔反应、酮基反应和去除 N-甲酰甲氧基反应，立体选择性地生成了 26，它是合成(±)-甜菜碱的中间体。
• Processes and intermediates for cis or trans 2- or
  申请人：Hoffmann-La Roche Inc.

  公开号：US03957800A1

  公开（公告）日：1976-05-18

  Cis or trans 2-(1-acyl-3-vinyl-4-piperidine)acetic acid esters and cis or trans 3-(1-acyl-3-vinyl-4-piperidine)propionic acid esters, antipodes and racemates thereof, are prepared, inter alia, from the corresponding cis or trans 2- or 3[1-acyl-3-(2-chloroethyl)-4-piperidine]acetic or propionic acid esters, respectively. The cis or trans 2- or 3-(1-acyl-3-vinyl-4-piperidine)acetic or propionic acid esters are useful as intermediates for the synthesis of quinine and quinidine and analogs and stereoisomers thereof.

  通过相应的顺式或反式2-或3-[1-酰基-3-(2-氯乙基)-4-哌啶]乙酸或丙酸酯，制备顺式或反式2-(1-酰基-3-乙烯基-4-哌啶)乙酸酯和顺式或反式3-(1-酰基-3-乙烯基-4-哌啶)丙酸酯，以及它们的对映体和消旋体。这些顺式或反式2-或3-(1-酰基-3-乙烯基-4-哌啶)乙酸酯或丙酸酯可用作奎宁、奎尼丁及其类似物和立体异构体的合成中间体。
• New N-(benzhydryloxyalkyl)-4-(carboxy/carbamoylmethyl) piperidine derivatives with antidepressant activity
  作者：Y El Ahmad、P Maillet、E Laurent、A Talab、JF Teste、MJ Cédat、PY Fiez-Vandal、R Dokhan、R Ollivier

  DOI：10.1016/s0223-5234(97)83972-4

  日期：1997.1

  Several benzhydryloxylalkylpiperidine derivatives were prepared with the aim of obtaining new antidepressant compounds. The influence of the length of the aliphatic chain and of aromatic and piperidine ring substitutions was studied. The pharmacological activity of compounds was investigated in vivo by means of a screening comprising four pharmacological tests: antagonism of reserpine and apomorphine hypothermia; increase of yohimbine induced mortality; and antagonism of immobility in tail suspension test. An in-depth pharmacological study was performed with the more active compounds and a binding study to serotonin (5-HT), norepinephrine (NE) and dopamine (DA) reuptake sites was performed for the preferred compounds. The most active compounds [+], [-]-cis-31, 32 and 46 exhibited an interesting psychopharmacological profile after intraperitoneal administration. This profile was confirmed by the oral route for 31 and 46. In vitro, these compounds showed a non-selective inhibition of DA, NE and 5-HT uptake.
• HIRAI, YOSHIRO;TERADA, TAKASHI;HAGIWARA, ATSUSHI;YAMAZAKI, TAKAO, CHEM. AND PHARM. BULL., 36,(1988) N 4, 1343-1350
  作者：HIRAI, YOSHIRO、TERADA, TAKASHI、HAGIWARA, ATSUSHI、YAMAZAKI, TAKAO

  DOI：——

  日期：——