ethyl 4-bromobut-2-ynoate | 39595-70-5

• 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: ethyl 4-bromobut-2-ynoate
• CAS: 39595-70-5
• 化学式: C₆H₇BrO₂
• 分子量: 191.024
• InChiKey: XTUNBSQHSNLFLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 4-bromobut-2-ynoate 在 羟胺 、 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 0.25h， 以98 mg的产率得到5-(溴甲基)异噁唑-3(2H)-酮
  参考文献：
  名称：

  Substituted pyrazolones require N2 hydrogen bond donating ability to protect against cytotoxicity from protein aggregation of mutant superoxide dismutase 1

  摘要：

  Amyotrophic lateral sclerosis (ALS) is a debilitating and fatal neurodegenerative disease. Although the cause remains unknown, misfolded protein aggregates are seen in neurons of sporadic ALS patients, and familial ALS mutations, including mutations in superoxide dismutase 1 (SOD1), produce proteins with an increased propensity to misfold and aggregate. A structure activity relationship of a lead scaffold exhibiting neuroprotective activity in a G93A-SOD1 mouse model for ALS has been further investigated in a model PC12 cellular assay. Synthesis of biotinylated probes at the N-1 nitrogen of the pyrazolone ring gave compounds (5d-e) that retained activity within 10-fold of the proton-bearing lead compound (5a) and were equipotent with a sterically less cumbersome N-1-methyl substituted analogue (5b). However, when methyl substitution was introduced at N-1 and N-2 of the pyrazolone ring, the compound was inactive (5c). These data led us to investigate further the pharmacophoric nature of the pyrazolone unit. A range of N-1 substitutions were tolerated, leading to the identification of an N-1-benzyl substituted pyrazolone (5m), equipotent with 5a. Substitution at N-2 or excision of N-2, however, removed all activity. Therefore, the hydrogen bond donating ability of the N-2-H of the pyrazolone ring appears to be a critical part of the structure, which will influence further analogue synthesis. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2012.08.114
• 作为产物：
  描述：

  ethyl 4-((tetrahydro-2H-pyran-2-yl)oxy)but-2-ynoate 在 4-甲基苯磺酸吡啶 、 三乙胺 、 lithium bromide 作用下， 以 乙醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 6.25h， 生成 ethyl 4-bromobut-2-ynoate
  参考文献：
  名称：

  MacInnes, Iain; Walton, John C., Journal of the Chemical Society. Perkin transactions II, 1987, p. 1077 - 1082

  摘要：

  DOI：

文献信息

• Copper(I)‐catalyzed Cyclization Reactions of Ethyl ( <i>E</i> )‐α‐Ethynyl‐β‐Aryl‐α,β‐Unsaturated Esters with <i>N</i> ‐Sulfonyl Azides: Synthesis of 1‐Aminonaphthalene, 3‐Aminobenzofuran, and 3‐Aminothiobenzofuran Derivatives
  作者：Jeong‐Yu Son、Gi Uk Han、Gi Hoon Ko、Chanyoung Maeng、Seohyun Shin、Phil Ho Lee

  DOI：10.1002/bkcs.11755

  日期：2019.7

  4‐(alkyl or arylsulfonamido)‐2‐naphthoates from ethyl (E)‐α‐ethynyl‐β‐aryl‐α,β‐unsaturated esters (1) and N‐sulfonyl azides (2) in the presence of 2,6‐lutidine in THF at 60 °C for 3 h was developed in one step, in which a copper(I)‐catalyzed 1,3‐dipolar cycloaddition, ketenimine formation, and 6π‐electrocyclization followed by [1,3]‐H shift tandem reaction took place. This method enabled efficient synthesis

  在存在条件下由乙基（E）-α-乙炔基-β-芳基-α，β-不饱和酯（1）和N-磺酰基叠氮化物（2）合成4-（烷基或芳基磺酰胺基）-2-萘甲酸乙酯的合成方法一步制得了60℃下3,6,6-二甲基吡啶在THF中3小时，其中铜（I）催化1,3-偶极环加成，烯酮亚胺形成和6π-电环化，然后进行[1,3 ] -H移位串联反应发生。这种方法可以在释放分子氮的情况下有效合成各种1-氨基萘和3-氨基苯并呋喃以及3-氨基苯并噻吩衍生物。
• Phosphine‐Catalyzed (4+1) Annulation: Rearrangement of Allenylic Carbamates to 3‐Pyrrolines through Phosphonium Diene Intermediates
  作者：Brian R. Blank、Ian P. Andrews、Ohyun Kwon

  DOI：10.1002/cctc.202000626

  日期：2020.9.4

  and mononucleophiles unexpectedly unveiled that a phosphine‐catalyzed (4+1) reaction for the construction of cyclopentene products, previously reported by Tong, might not occur through a phosphonium diene, as had been proposed, but rather through multiple mechanisms working in concert. Consequently, our phosphine‐catalyzed rearrangement is most likely the first transformation to involve the unequivocal

  我们开发了一种膦催化的 (4+1) 环状重排，用于通过鏻二烯中间体从烯基氨基甲酸酯制备 3-吡咯啉。我们采用这种方法合成了一系列 1,3-二取代和 1,2,3-三取代-3-吡咯啉，包括通常难以制备的 2-烷基变体。使用乙酸丙二烯酯和单亲核试剂的机械研究出人意料地发现，Tong 先前报道的用于构建环戊烯产品的膦催化 (4+1) 反应可能不会通过鏻二烯发生，如已提出的那样，而是通过多个机制协同工作。最后，我们的膦催化重排很可能是第一个涉及沿反应途径明确形成鏻二烯中间体的转化。为了证明这种新开发反应的合成效用，我们完成了吡咯里西啶生物碱 (±)-trachelanthamidine 和 (±)-supinidine 的简明正式合成。
• Gold(I)-Catalyzed Cycloisomerization of <i>ortho</i> -(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings
  作者：Wei Fang、Yin Wei、Xiang-Ying Tang、Min Shi

  DOI：10.1002/chem.201700600

  日期：2017.5.17

  Gold(I)‐catalyzed cycloisomerization of ortho‐(propargyloxy)arenemethylenecyclopropanes afforded two different types of products, that is, products of methylenecyclopropane migration and cycloisomerization products of the methylenecyclopropane moiety, controlled jointly by electronic and steric effects of the adjacent substituents. Furthermore, the corresponding cycloisomerization products could be

  金（I）催化的邻-（炔丙基氧基）亚芳基亚甲基环丙烷的环异构化提供了两种不同类型的产物，即亚甲基环丙烷迁移的产物和亚甲基环丙烷部分的环异构化产物，受相邻取代基的电子和空间效应共同控制。此外，相应的环异构化产物也可以以对映异构体富集的方式产生。
• Synthesis of (E)-α-Ethynyl-α,β-unsaturated Esters from Allenyl Acetates Catalyzed by DABCO and Their Application to Sonogashira Cross-Coupling Reactions
  作者：Hyun-Seok Kim、Doo-Sup Shin、Kwang-Moo Lee、Sang-Kyu Lee、Sang-Hyuk Kim、Phil-Ho Lee

  DOI：10.5012/bkcs.2010.31.03.742

  日期：2010.3.20

  esters from another precursor without the use of (Z)-α-halo-α,β-unsaturated esters. As part of our continuing studies into the utility of allene groups, we report herein the preparation of the selective synthesis of (E)-α-ethynyl-α,β-unsaturated esters from allenyl acetates catalyzed by DABCO and their application to Sonogashira cross-coupling reaction (Scheme 1). First, various allenyl acetates were

  1 PPTS (0.2) CH2Cl2 6 0 2 AcOH (0.2) DMF 12 0 3 吡啶 (0.2) DMF 0.67 75 4 PPh3 (0.2) DMF 0.5 69 5 DABCO (0.2) DMF 0.5 75 6 DABCO (0.2) THF 4.5 50 7 DABCO (0.2) CH3CN 4.5 70 8 DABCO (0.1) DMF 2.5 81 由于 α-乙炔基-α,β-不饱和酯的合成是有机合成化学中具有挑战性的问题之一，许多有效的合成方法已被用于制备这些化合物。报道。然而，仍然需要一种高选择性的 (E)-α-乙炔基-α,β-不饱和酯合成方法。通常，这些化合物的选择性合成是通过过渡金属催化的(Z)-α-卤代-α,β-不饱和酯与末端炔烃的交叉偶联反应通过Sonogashira交叉偶联反应完成的。然而，该方法受到限制，因为 (Z)-α-halo-α 的
• Stereoselective DABCO-Catalyzed Synthesis of (<i>E</i>)-α-Ethynyl-α,β-Unsaturated Esters from Allenyl Acetates
  作者：Yongsik Choe、Phil Ho Lee

  DOI：10.1021/ol9001703

  日期：2009.3.19

  (E)-alpha-Ethynyl-alpha,beta-unsaturated esters were exclusively prepared in good to excellent yields from treatment of allenyl acetates with 10 mol % DABCO in DMF at room temperature.

  (E)-α-炔基-α,β-不饱和酯从艾林基甲酯用10摩尔% DABCO在DMF常温下处理可得到优良收率。