diethyl 2-(pyridin-4-ylmethylene)malonate | 52601-17-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2-(pyridin-4-ylmethylene)malonate
• 英文别名: Diethyl-(4-pyridylmethylen)-malonat；4-(ββ-Dicarbethoxyvinyl)pyridin；4-(ββ-Bisethoxycarbonylvinyl)pyridin；4-Pyridylmethylenmalonsaeure-diethylester；pyridin-4-ylmethylene-malonic acid diethyl ester；[4]pyridylmethylene-malonic acid diethyl ester；[4]Pyridylmethylen-malonsaeure-diaethylester；Diethyl (4-pyridylmethylene)malonate；diethyl 2-(pyridin-4-ylmethylidene)propanedioate
• CAS: 52601-17-9
• 化学式: C₁₃H₁₅NO₄
• mdl: MFCD07800526
• 分子量: 249.266
• InChiKey: CMRLNKVVIHIYMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  65.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 2-(pyridin-4-ylmethylene)malonate 生成 2-(pyridin-4-ylmethyl)malonic acid
  参考文献：
  名称：

  MIMURA, TEHTSUTARO;NAKAMURA, YASUXISA;NISINO, DZYUNKO;SAVAYAMA, TADAXIRO;+

  摘要：

  DOI：
• 作为产物：
  描述：

  hydroxy-[4]pyridylmethyl-malonic acid diethyl ester 在 乙酸酐 作用下， 生成 diethyl 2-(pyridin-4-ylmethylene)malonate
  参考文献：
  名称：

  Rubzow; Dorochowa, Zhurnal Obshchei Khimii, 1959, vol. 23, p. 706,708; engl. Ausg. S. 733, 734

  摘要：

  DOI：

文献信息

• N-Heterocyclic Carbene–Cu-Catalyzed Enantioselective Allenyl Conjugate Addition
  作者：Qinglei Chong、Shuoqing Zhang、Fengchang Cheng、Jiping Wang、Xin Hong、Fanke Meng

  DOI：10.1021/acs.orglett.8b03029

  日期：2018.11.2

  A catalytic enantioselective conjugate addition with commercially available allenylboronic acid pinacol ester as nucleophile promoted by a chiral copper complex of N-heterocyclic carbene (NHC) is disclosed. This process constitutes an unprecedented instance of the conjugate addition that introduces an allenyl group into α,β-unsaturated carbonyl compounds, affording products that are otherwise difficult

  公开了由N-杂环卡宾（NHC）的手性铜配合物促进的与作为亲核体的市售的烯丙基硼酸频哪醇酯的催化对映选择性共轭加成。此过程构成了共轭加成的空前实例，该共轭加成将一个烯基引入到α，β-不饱和羰基化合物中，从而提供了难以获得的产物，收率高达92％，烯丙基加成选择性> 98％和对映体96：4比率。进行DFT计算以阐明对映选择性的起源。
• Enantioselective Conjugate Addition of Nitroalkanes to Alkylidenemalonates Promoted by Thiourea-Based Bifunctional Organocatalysts
  作者：Michel Chiarucci、Marco Lombardo、Claudio Trombini、Arianna Quintavalla

  DOI：10.1002/adsc.201100732

  日期：2012.2

  Cinchona alkaloids-derived bifunctional thioureas efficiently catalyse the enantioselective conjugate addition of nitroalkanes to alkylidenemalonates with syn-diastereopreference, opening a route to the synthesis of optically active γ-amino acid derivatives.

  金鸡纳生物碱衍生的双官能硫脲可有效催化硝基苯丙氨酸与顺式-非对映体优先的对映选择性共轭加成反应，为合成旋光性γ-氨基酸衍生物开辟了道路。
• Blaise reaction: synthesis, skeletal diversification of C(4) substituted 5-ylidenepyrrol-(5<i>H</i>)-ones and the role of the strategically located ester on the reactivity of the nitriles
  作者：H. Surya Prakash Rao、Ashiq Hussain Padder

  DOI：10.1039/d0nj00231c

  日期：——

  classical Blaise reaction. The products were further transformed to useful small organic molecules (SOMs). Studies on the reactivity of nitriles via intra and inter-molecular competition experiments showed that anchimeric assistance from the neighbouring and strategically located ester is crucial for higher reactivity of the nitrile in the 3-cyanopropionates towards the Blaise reaction.

  通过经典的布莱斯反应的有用变化，我们已经从3-芳基/杂芳基/烷基3-氰基丙酸酯和乙基/甲基溴乙酸酯中轻松合成了几个C（4）取代的5-亚吡咯烷基- （5 H）- 。将产物进一步转化为有用的有机小分子（SOM）。通过分子内和分子间竞争实验对腈的反应性进行的研究表明，邻位和关键位置的酯的邻氨基苯甲酸辅助对于3-氰基丙酸酯中腈对Blaise反应的更高反应性至关重要。
• Process and intermediates for production of donepezil and related compounds
  申请人：Finetech Laboratories Ltd.

  公开号：US06492522B1

  公开（公告）日：2002-12-10

  The present invention relates to a new process for the preparation of acetylcholinesterase inhibitors of formula (I) or a salt thereof, wherein: R1 is N-acyl-4-piperidyl; N-alkoxycarbonyl-4-piperidyl; N-alkyl-4-piperidyl; N-benzyl-4-piperidyl; N-(&ohgr;-aralkyl)-4-piperidyl; 4-pyridyl; R4, R5, R6, and R7 are identical or different and each represents hydrogen, straight-chain or branched alkyl, aryl, hydroxy, alkoxy, aryloxy, benzyloxy, acyloxy, alkylthio, arylthio, benzylthio, acylamino, phthalimido or halogen; n is 1, 2 or 3; m is 1, 2, 3, 4, or 5. This process comprises cyclisation of a compound of formula (II) or salts thereof, wherein R1, R4, R5, R6 and R7, m and n are as defined above; R2 is selected from a derivatised or non-derivatised carboxyl, cyano, N-substituted aminocarbonyl groups or hydrogen; R3 is selected from a derivatised or non-derivatised carboxyl, cyano or N-substituted aminocarbonyl groups, optionally in the presence of acids and/or solvents. One of the most potent acetylcholinesterase inhibitors of the class of compounds prepared according to the present invention is donepezil.

  本发明涉及一种制备式（I）或其盐的乙酰胆碱酯酶抑制剂的新工艺，其中：R1为N-酰基-4-哌啶基；N-烷氧羰基-4-哌啶基；N-烷基-4-哌啶基；N-苄基-4-哌啶基；N-(&ohgr;-芳基烷基)-4-哌啶基；4-吡啶基；R4、R5、R6和R7相同或不同，每个代表氢、直链或支链烷基、芳基、羟基、烷氧基、芳氧基、苄氧基、酰氧基、烷硫基、芳硫基、苄硫基、酰基氨基、邻苯二甲酰亚氨基或卤素；n为1、2或3；m为1、2、3、4或5。该工艺包括将式（II）化合物或其盐环化，其中R1、R4、R5、R6和R7、m和n如上定义；R2选择自衍生或非衍生羧基、氰基、N-取代氨基羰基基团或氢；R3选择自衍生或非衍生羧基、氰基或N-取代氨基羰基基团，可选地在酸和/或溶剂的存在下。根据本发明制备的化合物类中最有效的乙酰胆碱酯酶抑制剂之一是多奈哌齐。
• Diboron(4)‐Catalyzed Remote [3+2] Cycloaddition of Cyclopropanes via Dearomative/Rearomative Radical Transmission through Pyridine
  作者：Ming Xu、Zhijun Wang、Zhaohui Sun、Yizhao Ouyang、Zhengwei Ding、Tao Yu、Liang Xu、Pengfei Li

  DOI：10.1002/anie.202214507

  日期：2022.12.23

  Previously challenging pyridinyl cyclopentanes, cyclopentenes and bicyclo[2.1.1]hexanes with multiple substituents now can be efficiently prepared via a remote [3+2] cycloaddition reaction. The reaction features a simple diboron(4) catalyst, modular disconnection mode, broad scope, high atom economy and a unique dearomative/rearomative mechanistic process.

  以前具有挑战性的具有多个取代基的吡啶基环戊烷、环戊烯和双环 [2.1.1] 己烷现在可以通过远程 [3+2] 环加成反应有效地制备。该反应具有简单的二硼 (4) 催化剂、模块化断开模式、广泛的范围、高原子经济性和独特的脱芳烃/重芳烃机理过程。