2-Prop-2-enyl-1,3-dioxane | 854840-27-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 2-Prop-2-enyl-1,3-dioxane
• CAS: 854840-27-0
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: IUUWFQTVAKZVKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,3-bis-vinyloxy-propane 在 2,6-二叔丁基吡啶 、 2C₃₂H₁₂BF₂₄^(1-)*C₇₂H₈₀Cl₂N₄Pd₂⁽⁴⁺⁾ 作用下， 以 二氯甲烷-D2 为溶剂， 反应 24.0h， 以60%的产率得到2-Prop-2-enyl-1,3-dioxane
  参考文献：
  名称：

  钯催化乙烯醚二聚化为乙缩醛

  摘要：

  (α-二亚胺)PdCl(+) 物质将烷基和甲硅烷基乙烯基醚催化二聚化为 β,γ-不饱和 CH(2)=CHCH(2)CH(OR)(2) 缩醛，并将二乙烯基醚环化为类似的环状缩醛. 一种可能的机制包括原位生成活性 PdOR 醇盐物质，双乙烯基醚插入生成 Pd{CH(2)CH(OR)CH(2)CH(OR)(2)} 物质，以及β-OR 消除以生成 Pd{CH(2)CH(OR)CH(2)CH(OR)(2)} 物质生成缩醛产物。在乙烯基醚的存在下，(α-二亚胺)PdCl(+) 物质可用于引发乙烯聚合。

  DOI：

  10.1021/ja104523y

文献信息

• [EN] MACROCYCLIZATION REACTIONS AND INTERMEDIATES USEFUL IN THE SYNTHESIS OF ANALOGS OF HALICHONDRIN B<br/>[FR] RÉACTIONS DE MACROCYCLISATION ET INTERMÉDIAIRES UTILES DANS LA SYNTHÈSE D'ANALOGUES DE L'HALICHONDRINE B
  申请人：EISAI R&D MAN CO LTD

  公开号：WO2015066729A1

  公开（公告）日：2015-05-07

  The invention provides methods for the synthesis of eribulin or a pharmaceutically acceptable salt thereof (e.g., eribulin mesylate) through a macrocyclization strategy. The macrocyclization strategy of the present invention involves subjecting a non-macrocyclic intermediate to a carbon-carbon bond-forming reaction (e.g., an olefination reaction (e.g., Horner-Wadsworth-Emmons olefination), Dieckmann reaction, catalytic Ring-Closing Olefin Metathesis, or Nozaki-Hiyama-Kishi reaction) to afford a macrocyclic intermediate. The invention also provides compounds useful as intermediates in the synthesis of eribulin or a pharmaceutically acceptable salt thereof and methods for preparing the same.

  该发明提供了一种通过大环化策略合成厄立宾或其药用可接受盐（例如，厄立宾甲磺酸盐）的方法。本发明的大环化策略涉及将非大环中间体经过碳-碳键形成反应（例如，烯化反应（例如，Horner-Wadsworth-Emmons烯化反应）、迪克曼反应、催化环闭合烯烃交换反应，或Nozaki-Hiyama-Kishi反应）以获得大环中间体。该发明还提供了在合成厄立宾或其药用可接受盐时作为中间体有用的化合物以及制备这些化合物的方法。
• [EN] PRINS REACTION AND COMPOUNDS USEFUL IN THE SYNTHESIS OF HALICHONDRIN MACROLIDES AND ANALOGS THEREOF<br/>[FR] RÉACTION DE PRINS ET DE COMPOSÉS UTILES DANS LA SYNTHÈSE DE MACROLIDES D'HALICHONDRINE ET DE SES ANALOGUES
  申请人：EISAI R&D MAN CO LTD

  公开号：WO2019136145A1

  公开（公告）日：2019-07-11

  The invention provides methods utilizing Prins reaction in the preparation of compounds that may be useful as intermediates in the synthesis of halichondrin macrolides and analogs thereof. The invention also provides compounds that may be useful as intermediates in the synthesis of a halichondrin macrolides and methods for preparing the same.

  该发明提供了利用普林斯反应在合成半人马毒素大环内酯及其类似物中可能用作中间体的化合物的方法。该发明还提供了可能用作半人马毒素大环内酯合成中间体的化合物以及其制备方法。
• METHOD FOR PRODUCING CONJUGATED DIENE
  申请人：KURARAY CO., LTD.

  公开号：US20180290947A1

  公开（公告）日：2018-10-11

  A method for producing a conjugated diene, including a step A of allowing an α-olefin and formaldehyde to react with each other to produce a γ,δ-unsaturated alcohol in the presence of an alcohol; and a step B of subjecting the γ,δ-unsaturated alcohol to a dehydration reaction at 135 to 210° C. in the presence of an aqueous solution of an acidic catalyst.

  一种生产共轭二烯的方法，包括步骤A：在醇的存在下，使α-烯烃和甲醛发生反应，生成γ,δ-不饱和醇；以及步骤B：在含有酸性催化剂的水溶液存在下，将γ,δ-不饱和醇进行脱水反应，反应温度为135到210摄氏度。
• METHOD FOR PRODUCING GAMMA, DELTA-UNSATURATED ALCOHOL
  申请人：KURARAY CO., LTD

  公开号：US20200062680A1

  公开（公告）日：2020-02-27

  A method for producing a γ,δ-unsaturated alcohol of formula (2): wherein R 1 to R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally substituted with a hydroxy group, an alkenyl group having 2 to 10 carbon atoms and optionally substituted with a hydroxy group, or an aryl group having 6 to 12 carbon atoms and optionally substituted with a hydroxy group, provided that R 1 and R 3 may bond to each other to form a ring, through a reaction of an α-olefin of formula (1) and formaldehyde under a heating condition: the method including a step of bringing the α-olefin into contact with an aqueous formaldehyde solution in the presence of an alcohol having 3 to 10 carbon atoms, with the aqueous formaldehyde solution being subjected to preheating at 30 to 220° C. before the step.

  一种用于制备式(2)的γ,δ-不饱和醇的方法：其中R1至R3分别独立表示氢原子、具有1至10个碳原子并且可选择地取代为羟基的烷基基团、具有2至10个碳原子并且可选择地取代为羟基的烯基基团，或者具有6至12个碳原子并且可选择地取代为羟基的芳基基团，前提是R1和R3可以结合在一起形成环，通过式(1)的α-烯烃和甲醛在加热条件下反应：该方法包括将α-烯烃与具有3至10个碳原子的醇存在下的水甲醛溶液接触的步骤，其中该水甲醛溶液在该步骤之前经过30至220°C的预热。
• PRODUCTION METHOD FOR GAMMA, DELTA-UNSATURATED ALCOHOLS
  申请人：KURARAY CO., LTD.

  公开号：US20170197895A1

  公开（公告）日：2017-07-13

  Provided is a method from which a γ,δ-unsaturated alcohol having a much more smaller amount of inclusion of formic acid and a formic acid ester and having a high purity can be obtained in a high yield. Specifically, provided is a method for producing a γ,δ-unsaturated alcohol by causing a reaction between an α-olefin and formaldehyde, the method including a step of bringing a reaction liquid obtained through the reaction into contact with an alkaline aqueous solution so as to provide an aqueous solution having pH of 9 to 13.

  提供了一种方法，可以在高产率下获得含有较少甲酸和甲酸酯的γ,δ-不饱和醇，并具有高纯度。具体来说，提供了一种通过使α-烯烃和甲醛发生反应来生产γ,δ-不饱和醇的方法，该方法包括将通过反应得到的反应液与碱性水溶液接触的步骤，以提供pH为9至13的水溶液。