3-tert-butoxycarbonyloxy-benzoic acid ethyl ester | 918402-86-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-tert-butoxycarbonyloxy-benzoic acid ethyl ester
• 英文别名: ethyl 3-((tert-butoxycarbonyl)oxy)benzoate；ethyl 3-(tert-butoxycarbonyloxy)benzoate；ethyl 3-tert-butoxycarbonyloxy-benzoate；ethyl 3-[(tert-butoxycarbonyl)oxy]benzoate；ethyl 3-[(2-methylpropan-2-yl)oxycarbonyloxy]benzoate
• CAS: 918402-86-5
• 化学式: C₁₄H₁₈O₅
• 分子量: 266.294
• InChiKey: GTJAYFZRMPMOCO-UHFFFAOYSA-N

物化性质

• 沸点：
  358.1±34.0 °C(Predicted)
• 密度：
  1.121±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-tert-butoxycarbonyloxy-benzoic acid ethyl ester 在 tetramethylpiperidyl MgCl LiCl 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以86%的产率得到3-tert-butoxycarbonyloxy-2-iodo-benzoic acid ethyl ester
  参考文献：
  名称：

  Highly Functionalized Benzene Syntheses by Directed Mono or Multiple Magnesiations with TMPMgCl·LiCl

  摘要：

  The direct magnesiation of highly functionalized aromatics bearing an ester, a nitrile, or a ketone can be readily performed by using an OBoc as a directing group and TMPMgCl-LiCl as a base. It allows, for example, the preparation of a meta-magnesiated benzophenone in > 95%. After quenching, highly functionalized and substituted benzenes are obtained.

  DOI：

  10.1021/ol0625536
• 作为产物：
  描述：

  二碳酸二叔丁酯 、 3-羟基苯甲酸乙酯 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到3-tert-butoxycarbonyloxy-benzoic acid ethyl ester
  参考文献：
  名称：

  Highly Functionalized Benzene Syntheses by Directed Mono or Multiple Magnesiations with TMPMgCl·LiCl

  摘要：

  The direct magnesiation of highly functionalized aromatics bearing an ester, a nitrile, or a ketone can be readily performed by using an OBoc as a directing group and TMPMgCl-LiCl as a base. It allows, for example, the preparation of a meta-magnesiated benzophenone in > 95%. After quenching, highly functionalized and substituted benzenes are obtained.

  DOI：

  10.1021/ol0625536

文献信息

• [EN] ORGANOZINC COMPLEXES AND PROCESSES FOR MAKING AND USING THE SAME<br/>[FR] COMPLEXES D'ORGANOZINC ET PROCÉDÉS POUR LEUR FABRICATION ET LEUR UTILISATION
  申请人：UNIV MUENCHEN L MAXIMILIANS

  公开号：WO2012085168A1

  公开（公告）日：2012-06-28

  Processes for making an organozinc reagents are disclosed comprising reacting (A) organomagnesium or organozinc complexes with (B) at least one coordination compound comprising one or more carboxylate groups and/or alcoholate groups and/or tertiary amine groups, optionally in combination with zinc ions and/or lithium ions and/or halide ions, wherein the halide ions are selected from chloride, bromide and iodide, the organozinc complex comprises an aryl group, a heteroaryl group or a benzyl group when the coordinating compound is a chelating polyamine, and the reaction is conducted in the presence of zinc complexed with at least one coordinating compound when reactant (A) comprises at least one organomagnesium complex. The resulting organozinc reagents may optionally be isolated from solvents to obtain a solid reagent. The reagents may be used for making organic compounds via Negishi cross-coupling reactions or via aldehyde and/or ketone oxidative addition reactions. The organozinc reagents are stable and, due to their high selectivity, permit maintenance of sensitive functional groups such as aldehydes during cross-coupling.

  公开了制备有机锌试剂的方法，包括将（A）有机镁或有机锌配合物与（B）至少一种含有一个或多个羧酸基团和/或醇基团和/或三级胺基团的配位化合物反应，可选地与锌离子和/或锂离子和/或卤离子结合，其中卤离子选自氯离子、溴离子和碘离子，当配位化合物为螯合多胺时，有机锌配合物包括芳基、杂环芳基或苄基，当反应物（A）包含至少一种有机镁配合物时，在存在至少一种配位化合物与锌络合物的情况下进行反应。所得的有机锌试剂可以选择性地从溶剂中分离出来以获得固体试剂。这些试剂可用于通过Negishi交叉偶联反应或通过醛和/或酮氧化加成反应制备有机化合物。有机锌试剂稳定，并且由于其高选择性，允许在交叉偶联过程中保持敏感的官能团，如醛基。
• Air-Stable Solid Aryl and Heteroaryl Organozinc Pivalates: Syntheses and Applications in Organic Synthesis
  作者：Sophia M. Manolikakes、Mario Ellwart、Christos I. Stathakis、Paul Knochel

  DOI：10.1002/chem.201403015

  日期：2014.9.15

  air‐stable, solid, polyfunctional aryl and heteroarylzinc pivalates were efficiently prepared by either magnesium insertion or Hal/Mg exchange followed by transmetalation with Zn(OPiv)2 (OPiv=pivalate). By reducing the amount of LiCl the air stability could be significantly enhanced compared with previously prepared reagents. An alternative route is directed magnesiation using TMPMgCl⋅LiCl (TMP=2,2,6,6‐

  通过插入镁或Hal / Mg交换，然后用Zn（OPiv）2（OPiv =新戊酸酯）进行金属转移，可以有效地制备各种空气稳定的固体多官能芳基和杂芳基锌新戊酸酯。与以前制备的试剂相比，通过减少LiCl的含量，可以显着提高空气稳定性。的替代路线是使用TMPMgCl涉及镁化⋅的LiCl（TMP = 2,2,6,6-四甲基），然后用锌（OPiv）转移金属化2，或者对于非常敏感的底物，直接浸锌通过使用TMPZnOPiv。这些锌试剂不仅对空气具有极好的稳定性，而且它们的C范围也很广。C键形成反应，例如烯丙基化和碳环化反应，以及醛的加成和1,4加成反应。可以通过使用过量的TMSC1来克服无所不在的新戊酸酯阴离子的副反应来进行酰化反应。
• Improved Air-Stable Solid Aromatic and Heterocyclic Zinc Reagents by Highly Selective Metalations for Negishi Cross-Couplings
  作者：Christos I. Stathakis、Sebastian Bernhardt、Valentin Quint、Paul Knochel

  DOI：10.1002/anie.201204526

  日期：2012.9.10

  Directed metalation using TMPMgCl⋅LiCl (TMP=2,2,6,6‐tetramethylpiperidide) and subsequent transmetalation with Zn(OPiv)2 leads to aryl and heteroaryl zinc pivalates. After solvent evaporation, easy‐to‐handle fine powders are obtained that retain most of their activity (>85 %) when exposed to air for 4 h. They smoothly undergo Negishi cross‐couplings, and technical‐grade solvents can be used without

  涉及金属化用TMPMgCl ⋅的LiCl（TMP = 2,2,6,6-四甲基）和用Zn（OPiv）随后转移金属化2所导致的芳基和杂芳基锌三甲基乙酸盐。溶剂蒸发后，将获得易于处理的细粉，当暴露于空气中4小时后，这些细粉可保留其大部分活性（> 85％）。它们可以平稳地进行Negishi交叉偶联，并且可以使用工业级溶剂而不会显着降低产量。
• ORGANOZINC COMPLEXES AND PROCESSES FOR MAKING AND USING THE SAME
  申请人：Knochel Paul

  公开号：US20140031545A1

  公开（公告）日：2014-01-30

  Processes for making an organozinc reagents are disclosed comprising reacting (A) organomagnesium or organozinc complexes with (B) at least one coordination compound comprising one or more carboxylate groups and/or alcoholate groups and/or tertiary amine groups, optionally in combination with zinc ions and/or lithium ions and/or halide ions, wherein the halide ions are selected from chloride, bromide and iodide, the organozinc complex comprises an aryl group, a heteroaryl group or a benzyl group when the coordinating compound is a chelating polyamine, and the reaction is conducted in the presence of zinc complexed with at least one coordinating compound when reactant (A) comprises at least one organomagnesium complex. The resulting organozinc reagents may optionally be isolated from solvents to obtain a solid reagent. The reagents may be used for making organic compounds via Negishi cross-coupling reactions or via aldehyde and/or ketone oxidative addition reactions. The organozinc reagents are stable and, due to their high selectivity, permit maintenance of sensitive functional groups such as aldehydes during cross-coupling.

  公开了制备有机锌试剂的工艺，包括将（A）有机镁或有机锌配合物与（B）至少一种配位化合物反应，该配位化合物包括一个或多个羧酸盐基和/或醇盐基和/或三级胺基，可选地与锌离子和/或锂离子和/或卤素离子组合，其中卤素离子选自氯离子、溴离子和碘离子，当配位化合物为螯合多胺时，有机锌配合物包括苯基、杂环基或苄基，并且当反应物（A）包括至少一个有机镁配合物时，在存在至少一种配位化合物的锌配合物的情况下进行反应。所得有机锌试剂可以选择从溶剂中分离出来以获得固体试剂。该试剂可用于通过Negishi交叉偶联反应或通过醛和/或酮氧化加成反应制备有机化合物。由于其高选择性，有机锌试剂稳定，并允许保持敏感的功能基团，如醛基在交叉偶联反应过程中。
• Organozinc complexes and processes for making and using the same
  申请人：Knochel Paul

  公开号：US09273070B2

  公开（公告）日：2016-03-01

  Processes for making an organozinc reagents are disclosed comprising reacting (A) organomagnesium or organozinc complexes with (B) at least one coordination compound comprising one or more carboxylate groups and/or alcoholate groups and/or tertiary amine groups, optionally in combination with zinc ions and/or lithium ions and/or halide ions, wherein the halide ions are selected from chloride, bromide and iodide, the organozinc complex comprises an aryl group, a heteroaryl group or a benzyl group when the coordinating compound is a chelating polyamine, and the reaction is conducted in the presence of zinc complexed with at least one coordinating compound when reactant (A) comprises at least one organomagnesium complex. The resulting organozinc reagents may optionally be isolated from solvents to obtain a solid reagent. The reagents may be used for making organic compounds via Negishi cross-coupling reactions or via aldehyde and/or ketone oxidative addition reactions. The organozinc reagents are stable and, due to their high selectivity, permit maintenance of sensitive functional groups such as aldehydes during cross-coupling.

  本发明揭示了制备有机锌试剂的方法，包括将（A）有机镁或有机锌配合物与（B）至少一种配位化合物反应，该配位化合物包括一个或多个羧酸基和/或醇基和/或三级胺基，可选择与锌离子和/或锂离子和/或卤化物离子组合使用，其中卤化物离子选自氯化物、溴化物和碘化物，当配位化合物为螯合多胺时，有机锌配合物包括芳基、杂环芳基或苄基，并且当反应物（A）包括至少一个有机镁配合物时，在有机锌试剂生成过程中存在至少一种与锌配位的配位化合物。所得到的有机锌试剂可以选择从溶剂中分离出来以获得固体试剂。这些试剂可以通过Negishi交叉偶联反应或通过醛和/或酮的氧化加成反应制备有机化合物。由于其高选择性，这些有机锌试剂是稳定的，并且允许在交叉偶联反应中维持敏感的功能基团，例如醛基。