3-溴丙酸乙酯 | 41658-03-1

• 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
• 中文名称: 3-溴丙酸乙酯
• 英文名称: ethyl 3-bromoprop-2-ynoate
• 英文别名: ethyl 3-bromopropiolate；ethyl bromopropiolate；ethyl 3-bromopropynoate；ethyl bromopropynoate
• CAS: 41658-03-1
• 化学式: C₅H₅BrO₂
• 分子量: 176.997
• InChiKey: DCZXXLMBYWALCP-UHFFFAOYSA-N

物化性质

• 熔点：
  21-22 °C
• 沸点：
  171.7±23.0 °C(Predicted)
• 密度：
  1.594±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2916190090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  3-溴丙酸乙酯 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 ethyl 3,4-dichloro-1,6-dicyano-2,5-dioxo-8-(4,5,6,7-tetrahydro-1H-indol-2-yl)bicyclo[4.2.0]octa-3,7-diene-7-carboxylate
  参考文献：
  名称：

  From 4,5,6,7-tetrahydroindole to functionalized furan-2-one–4,5,6,7-tetrahydroindole–cyclobutene sequence in two steps

  摘要：

  Ethyl 3-(4,5,6,7-tetrahydroindol-2-yl)propynoate, readily available from 4,5,6,7-tetrahydroindole and ethyl bromopropynoate, when treated with dichlorodicyanobenzoquinone (DDQ) in methanol affords furan-2-one-4,5,6,7-tetrahydroindole-cyclobutene sequence in a 52% yield. As kinetic and minor products, a furan-2-one isomer along with bicycloheptadienone have been either isolated or identified. The reaction has been shown to proceed via the isolable intermediate the [2+2]-cycloadduct of ethyl 3-(4,5,6,7-tetrahydroindo1-2-yl)propynoate with DDQ. Other alcohols react with the [2+2]-cycloadduct in a similar way. The effect of the alcohol structure on the products ratio has been analyzed. All the intermediates and products are formed as single diastereomer, thus indicating a concerted character of the rearrangement. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.018
• 作为产物：
  描述：

  丙炔酸乙酯 在 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 丙酮 为溶剂， 反应 8.0h， 以90%的产率得到3-溴丙酸乙酯
  参考文献：
  名称：

  通过[3,3]-σ重排合成苯并呋喃和苯并恶唑：O–NHAc作为多任务官能团

  摘要：

  杂环的合成在很大程度上取决于由X–Y（X，Y = C，O，N，S，I）键断裂引发的各种σ重排。然而，非常需要用于构建杂环文库的统一重排方法。通过对[3,3]-σ重排的计算分析的鼓励，我们现在可以通过使用包含sp杂化碳的化合物处理N-苯氧基乙酰胺（Ph-ONHAc）来快速合成氧杂杂环。该过程的普遍性可以通过天然产物（包括雌酮和批准的药物）的后期多元化来说明。实验和计算研究的组合表明，反应是通过类似Claisen的[3,3] -sigmatropic重排/环化过程进行的。

  DOI：

  10.1021/acs.oprd.9b00002

文献信息

• [EN] GLYCOLATE OXIDASE INHIBITORS FOR THE TREATMENT OF DISEASE<br/>[FR] INHIBITEURS DE GLYCOLATE OXYDASE POUR LE TRAITEMENT D'UNE MALADIE
  申请人：BIOMARIN PHARM INC

  公开号：WO2020257487A1

  公开（公告）日：2020-12-24

  Described herein are compounds, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or disorders associated with a defect in glyoxylate metabolism, for example a disease or disorder associated with the enzyme glycolate oxidase (GO) or alterations in oxalate metabolism. Such diseases or disorders include, for example, disorders of glyoxylate metabolism, including primary hyperoxaluria, that are associated with production of excessive amounts of oxalate.

  本文描述了化合物、制备这种化合物的方法、含有这种化合物的药物组合物和药物，以及使用这种化合物治疗或预防与甘氧酸代谢缺陷相关的疾病或紊乱的方法，例如与甘氧酸氧化酶（GO）或草酸代谢变化相关的疾病或紊乱。这些疾病或紊乱包括与产生过多草酸相关的甘氧酸代谢紊乱，例如原发性高草酸尿症。
• Bulky Trialkylsilyl Acetylenes in the Cadiot−Chodkiewicz Cross-Coupling Reaction
  作者：Joseph P. Marino、Hanh Nho Nguyen

  DOI：10.1021/jo025745x

  日期：2002.9.1

  tert-butyldimethylsilyl (TBS), and triisopropylsilyl (TIPS) acetylenes underwent the Cadiot-Chodkiewicz cross-coupling reaction with different bromoalkynes to form a variety of synthetically useful unsymmetrical diynes in good yields. The diyne alcohol 10 was transformed regio- and stereoselectively into enynes by hydrotelluration, carbometalation, and reduction reactions.

  庞大的三烷基甲硅烷基保护的炔烃，例如三乙基甲硅烷基（TES），叔丁基二甲基甲硅烷基（TBS）和三异丙基甲硅烷基（TIPS）乙炔，与不同的溴炔进行了Cadiot-Chodkiewicz交叉偶联反应，以良好的收率形成了各种合成有用的不对称二炔。二炔醇10通过加氢精制，碳金属化和还原反应被区域和立体选择性地转化为烯炔。
• Visible-Light-Induced Nickel-Catalyzed Cross-Coupling with Alkylzirconocenes from Unactivated Alkenes
  作者：Yadong Gao、Chao Yang、Songlin Bai、Xiaolei Liu、Qingcui Wu、Jing Wang、Chao Jiang、Xiangbing Qi

  DOI：10.1016/j.chempr.2019.12.010

  日期：2020.3

  Transition-metal-catalyzed cross-coupling reactions between naturally abundant sp3-hybridized carbon centers facilitate access to diverse molecules with complex three-dimensional structures. Organometallic compounds are among one of the most powerful reagents that are broadly used in carbon–carbon bond formations. Although sp2-hybridized organometallic compounds are widely employed in cross-couplings, sp3-hybridized

  自然丰富的sp 3-杂化碳中心之间的过渡金属催化交叉偶联反应有助于获得具有复杂三维结构的各种分子。有机金属化合物是最强大的试剂之一，广泛用于碳-碳键的形成。尽管sp 2-杂化的有机金属化合物广泛用于交叉偶联，但是sp 3-杂化的有机金属偶联剂的开发较少。在这里，我们报告可见光诱导的单个镍催化的C（sp 3）–C（sp 3），C（sp 3）–C（sp 2）和C（sp 3）–C（sp）使用烷基锆茂的交叉偶联反应，该反应很容易从末端或内部未活化的烯烃通过加氢锆和链步反应就地生成。该方法温和，适用于多种底物，包括伯，仲，叔烷基，芳基，烯基，炔基卤化物和各种烯烃。机理研究表明，镍催化的自由基交叉偶联是一种新颖的途径，代表了锆锆茂的首次可见光诱导的转变。
• Ruthenium-catalyzed [2+2] cycloadditions of bicyclic alkenes and ynamides
  作者：Karine Villeneuve、Nicole Riddell、William Tam

  DOI：10.1016/j.tet.2005.11.081

  日期：2006.4

  Ruthenium-catalyzed [2+2] cycloadditions between bicyclic alkenes and ynamides were investigated. The ynamide moiety was found to be compatible with the ruthenium-catalyzed cycloaddition conditions giving the corresponding cyclobutene cycloadducts in moderate to good yields (up to 97%). Diastereoselective cycloaddition utilizing chiral cyclic ynamides were also examined and a low to moderate level

  研究了钌催化的双环烯烃和乙酰胺之间的[2 + 2]环加成反应。发现该乙酰胺部分与钌催化的环加成条件相容，从而以中等至良好的产率（高达97％）给出了相应的环丁烯环加合物。还研究了利用手性环状炔酰胺的非对映选择性环加成反应，观察到低至中等水平的不对称诱导。
• <scp>TEMPO‐Regulated</scp>Regio‐ and Stereoselective<scp>Cross‐Dihalogenation</scp>with Dual Electrophilic X⁺Reagents
  作者：Yi Kong、Tongxiang Cao、Shifa Zhu

  DOI：10.1002/cjoc.202100472

  日期：2021.11

  method could enable wide applications in organic synthesis, which was exemplified by divergent synthesis of two pharmaceuticals. Detailed mechanistic investigations via radical clock reaction, pinacol ring expansion and Hammett experiments were conducted, which confirmed the intermediacy of halonium ion. In addition, a dynamic catalytic model based on the versatile catalytic role of TEMPO was proposed

  TEMPO 催化的交叉二卤化反应是通过氧化还原调节双亲电 X +试剂的复杂系统而建立的。形式上，ICl的，氯化溴，我2和Br 2产生在-原位，这使高区域选择性或立体选择性获得的iodochlorination，bromochlorination和均-二卤化产物无数与功能性的宽光谱。该方法条件温和，操作简单，可广泛应用于有机合成，例如两种药物的发散合成。通过详细的机械调查进行了自由基钟反应、频哪醇扩环和哈米特实验，证实了卤离子的中介作用。此外，提出了一种基于 TEMPO 多功能催化作用的动态催化模型来解释选择性结果。