methyl 3-(4-chlorophenyl)-2-methyl-3-oxopropanoate | 63490-31-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-(4-chlorophenyl)-2-methyl-3-oxopropanoate
• 英文别名: methyl 2-(4-chlorobenzoyl)-propionate；Methyl 2-methyl-3-(4-chlorophenyl)-3-keto-propanoate
• CAS: 63490-31-3
• 化学式: C₁₁H₁₁ClO₃
• 分子量: 226.66
• InChiKey: LXBFKTZDEGGTIF-UHFFFAOYSA-N

物化性质

• 沸点：
  307.5±17.0 °C(Predicted)
• 密度：
  1.216±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-(4-chlorophenyl)-2-methyl-3-oxopropanoate 在 吡啶 、 sodium acetate 、 苄基三甲基氢氧化铵 、 一水合肼 、 溶剂黄146 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 12.0h， 生成 methyl 3-(4-chlorophenyl)-1-[N-(4-chlorophenyl)carbamoyl]-4-methyl-2-pyrazoline-4-carboxylate
  参考文献：
  名称：

  Quantitative structure-activity relationships of insecticidal pyrazolines

  摘要：

  AbstractMethyl 3‐(4‐chlorophenyl)‐4‐methyl‐1‐[N‐(4‐substituted pheny1)carba‐moy1]‐2‐pyrazoline‐4‐carboxylates and related compounds were prepared. Their convulsant activity was determined as the minimum dose required to bring about the symptom within 1 h after injection against male adult American cockroaches, Periplaneta americana (L.). Insecticidal activity with metabolic inhibitors for oxidation and hydrolysis was measured 24 h after injection of the test compounds. Variations in each of the activities were analysed by using physicochemical substituent parameters and regression analysis. The findings indicated that the greater the hydrophobicity and the more the electron‐withdrawing property of the substituents, the higher were the activities. Variations in each of the two activities were parabolically related to the STERIMOL width parameter with an optimum value of about zero.

  DOI：

  10.1002/ps.2780420406
• 作为产物：
  描述：

  methyl 2-(4-chlorophenyl)carbonylprop-2-enoate 在 Rhodotorula glutinis CCT 2182 yeast 作用下， 以 乙醇 、 水 为溶剂， 反应 84.0h， 以21%的产率得到methyl 3-(4-chlorophenyl)-2-methyl-3-oxopropanoate
  参考文献：
  名称：

  Regio- and enantioselective bioreduction of methyleneketoesters using both polymeric resin and cellulose matrix

  摘要：

  Methyleneketoesters were prepared in >90% yield by performing an IBX oxidation of Morita-Baylis-Hillman adducts. A methodology was developed to achieve methyl 3-aryl-3-keto-2-methylenepropanoate reduction using a screening of yeast strains in three different reaction procedures to obtain products with both high yield and diastereoselectivity. The reactions conducted in water provided inferior yields (50%) for substrates 2b-c. Employing Amberlite (R) XAD7HP which was a substrate reservoir that also immediately extracted the products from the reaction medium after their formation, syn-4a-c and anti-4a-c were isolated in 60-70% yield, with high stereoselectivity (98-99% ee). The best results were obtained using substrates adsorbed on filter paper which provided products yields above 70%, a 99% ee and a diastereomoeric ratio (syn-4: anti-4) 9:1. Cellulose matrix has excellent potential to be successfully employed in general biocatalytic reactions. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2013.09.018

文献信息

• A General and Robust Method for the Preparation of (E)- and (Z)-Stereodefined Fully Substituted Enol Tosylates: Promising Cross-Coupling Partners
  作者：Hidefumi Nakatsuji、Yoo Tanabe、Yuichiro Ashida、Yuka Sato、Atsushi Honda

  DOI：10.1055/s-0035-1562482

  日期：——

  preparing (E)- and (Z)-stereodefined fully substituted enol tosylates is described. α-Substituted β-keto esters undergo (E)-selective enol tosylations using TsCl–Me2N(CH2)6NMe2 as the reagent (method A, 13 examples; 63–96%) and (Z)-selective enol tosylations using TsCl–TMEDA–LiCl as the reagent (method B, 13 examples; 62–99%). A plausible mechanism for the (E)- and (Z)-enol tosylation selectivity is proposed

  摘要 描述了一种制备（E）-和（Z）-立体定义的完全取代的烯醇甲苯磺酸盐的稳健方法。使用TsCl–Me 2 N（CH 2）6 NMe 2作为试剂，α取代的β-酮酯经历（E）选择性烯醇化（方法A，13例； 63–96％）和（Z）选择性烯醇使用TsCl–TMEDA–LiCl作为试剂进行甲苯磺酰化（方法B，13例； 62–99％）。提出了对于（E）-和（Z）-烯醇甲苯磺酰化选择性的合理机理。阿1 1 H NMR监测实验揭示的TsCl加上TMEDA形成的简单Ñ-磺酰胺基中间体。 描述了一种制备（E）-和（Z）-立体定义的完全取代的烯醇甲苯磺酸盐的稳健方法。使用TsCl–Me 2 N（CH 2）6 NMe 2作为试剂，α取代的β-酮酯经历（E）选择性烯醇化（方法A，13例； 63–96％）和（Z）选择性烯醇使用TsCl–TMEDA–LiCl作为试剂进行甲苯磺酰化（方法B，13例； 62–99％）。提
• Iron-catalysed 1,2-acyl migration of tertiary α-azido ketones and 2-azido-1,3-dicarbonyl compounds
  作者：Tonghao Yang、Yajun Lin、Chaoqun Yang、Wei Yu

  DOI：10.1039/c9gc02085c

  日期：——

  Iron-catalysed 1,2-acyl migration of tertiary α-azido ketones and 2-azido-1,3-dicarbonyl compounds provides a simple and atom-economical approach toward enamides and isoquinolones. This paper reports two catalyst systems for these transformations which employ iron(II) complexes [Fe(dpbz)]Br2 (dpbz = 1,2-bis(diphenylphosphino)benzene) and FeBr2/Et3N, respectively. [Fe(dpbz)]Br2 was found to be highly

  铁催化的α-叠氮基酮和2-叠氮基-1,3-二羰基化合物的1,2-酰基迁移为酰胺和异喹啉酮提供了一种简单且原子经济的方法。本文报道两种催化剂体系用于这些转化其采用铁（II）配合物的[Fe（dpbz）]溴2（dpbz = 1,2-双（二苯基膦基）苯）和FeBr 2 / ET 3 N，分别。发现[Fe（dpbz）] Br 2在将2-叠氮基-2,3-二氢-1 H-茚满-1-酮转化为异喹诺酮方面非常有效。另一方面，由于Et 3的有益作用，FeBr 2 / Et 3 N的试剂组合具有更宽的催化范围N.后一种催化剂体系可使2-叠氮基-2-甲基-1,3-二羰基化合物在温和条件下以良好的收率转化为相应的酰胺。
• N-aryl-3-aryl-4,5-dihydro-1H-pyrazole-1-carboxamides and methods of
  申请人：Rohm and Haas

  公开号：US04863947A1

  公开（公告）日：1989-09-05

  This invention relates to novel N-aryl-3-aryl-4,5-dihydro-1H-pyrazole-1-carboxamide compounds which are useful as pesticides, compositions containing those compounds, methods of controlling pests and processes for preparing these compounds.

  本发明涉及新颖的N-芳基-3-芳基-4,5-二氢-1H-吡唑-1-甲酰胺化合物，这些化合物作为农药具有实用性，包含这些化合物的组合物，控制害虫的方法以及制备这些化合物的工艺。
• Palladium Catalyzed Ring Expansion Reaction of Isoxazolones with Isocyanides: Synthesis of 1,3‐Oxazin‐6‐One Derivatives
  作者：Yi‐Ming Zhu、Wan Zhang、Hongkun Li、Xiao‐Ping Xu、Shun‐Jun Ji

  DOI：10.1002/adsc.202001200

  日期：2021.2.2

  A palladium catalyzed ring expansion reaction of isoxazolones with isocyanides was disclosed. In the reaction, a cascade process involving ring‐opening/cyclization was suggested. The reaction features high atomic economy due to no elimination of CO2 occurred. Moreover, products obtained demonstrate aggregation‐induced emission properties with relatively high solid‐state emission efficiencies.

  公开了异恶唑酮与异氰酸酯的钯催化的扩环反应。在反应中，提出了涉及开环/环化的级联过程。该反应由于没有消除CO 2而具有高原子经济性。此外，所获得的产品展示出具有较高固态发射效率的聚集诱发的发射特性。
• Sterically Hindered Chiral Ferrocenyl P,N,N-Ligands for Highly Diastereo-/Enantioselective Ir-Catalyzed Hydrogenation of α-Alkyl-β-ketoesters via Dynamic Kinetic Resolution
  作者：Chuan-Jin Hou、Xiang-Ping Hu

  DOI：10.1021/acs.orglett.6b02828

  日期：2016.11.4

  A new class of sterically hindered chiral ferrocenyl P,N,N-ligands have been prepared through a two-step transformation from (Sc,Rp)-PPFNH2, in which a new (R)-stereogenic center at the pyridinylmethyl position was generated in high diastereoselectivity. With these newly developed P,N,N-ligands, Ir-catalyzed asymmetric hydrogenation of various α-alkyl-substituted β-aryl-β-ketoesters via dynamic kinetic

  通过从（S c，R p）-PPFNH 2的两步转化制备了新型的空间位阻性手性二茂铁基二茂铁基P，N，N-配体，其中在吡啶基甲基位置上有一个新的（R）-立体异构中心产生的非对映异构体选择性高。借助这些新开发的P，N，N配体，首次在高非对映体和对映体选择性下，通过动态动力学拆分实现了Ir催化的各种α-烷基取代的β-芳基-β-酮酸酯的不对称氢化，导致了多种光学活性的反-β-羟基酯含量高达99％ee。研究表明，这些配体的吡啶基甲基位置上的额外立体中心对于实现这种氢化作用至关重要。