4-(tetrahydropyran-2-yloxy)-but-2-ynal | 66725-78-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 4-(tetrahydropyran-2-yloxy)-but-2-ynal
• 英文别名: 2-Butynal, 4-[(tetrahydro-2H-pyran-2-yl)oxy]-；4-(oxan-2-yloxy)but-2-ynal
• CAS: 66725-78-8
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: QORMLGRJGANSMB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(tetrahydropyran-2-yloxy)-but-2-ynal 在 Lindlar's catalyst manganese(IV) oxide 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 35.5h， 生成 ethyl (4E)-2-diazo-3-oxo-6-(tetrahydro-pyran-2-yloxy)hex-4-enoate
  参考文献：
  名称：

  A new method for the synthesis of 2-cyclopenten-1-one-5-carboxylic ester derivatives via Rh2(OAc)4-mediated intramolecular C–H insertion reaction of 4Z-β-vinyl-α-diazo β-ketoesters

  摘要：

  2-Cyclopenten-1-one-5-carboxylic ester derivatives 14 are synthesized in a four- step-reaction sequence starting from alkynyl aldehydes 9 via 4Z-beta-vinyl-alpha-diazo beta-ketoesters intermediate 8. The synthetic method for 8 is described. When the delta substituent is an alkyl group, Rh(Il)-mediated decomposition of the diazo compounds 8 led to an intramolecular C-H insertion to afford 2-cyclopenten-1-one-5-carboxylic ester derivatives 14 in high yields. When the delta substituent is an aryl group, 2-hydroxynaphthoate 15 is obtained exclusively. In both cases, no Wolff rearrangement product was observed. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.05.106
• 作为产物：
  描述：

  4-(tetrahydro-pyran-2-yloxy)-but-2-yn-1-ol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到4-(tetrahydropyran-2-yloxy)-but-2-ynal
  参考文献：
  名称：

  Photoisomerization as a modulator of the DNA-cleaving efficiency of novel azo bispropargyl sulfones

  摘要：

  以偶氮苯为基础制备出了热稳定的 E 型双丙炔砜：用高压汞灯照射可将其转化为 Z 型异构体，后者具有更高的 DNA 切除效率。

  DOI：

  10.1039/b606653d

文献信息

• Synthesis of leukotriene B3 derivatives.
  作者：TOSHIO NAKAMURA、MITSUO NAMIKI、KEIICHI ONO

  DOI：10.1248/cpb.35.2635

  日期：——

  Four geometric isomers of a leukotriene B3 derivative (1b, 2b, 3b, 4b) and their nor derivatives (1a, 2a, 3a, 4a) were synthesized selectively from a common starting material by the same methodology using the Wittig-Horner reaction. All optical isomers of all-trans nor leukotriene B3 dimethylamide (1a), one of the eight compounds, were also synthesized.

  采用Wittig-Horner反应，通过相同的方法，从同一初始原料出发，选择性地合成了白三烯B3衍生物（1b、2b、3b、4b）及其去饱和衍生物（1a、2a、2a、2a）的四种几何异构体。同时，也合成了八种化合物之一的化合物（1a）的全反式去饱和白三烯B3二甲基酰胺的所有光学异构体。
• Highly efficient synthesis of α,β-acetylenic aldehydes from terminal alkynes using DMF as the formylating reagent
  作者：Michel Journet、Dongwei Cai、Lisa M. DiMichele、Robert D. Larsen

  DOI：10.1016/s0040-4039(98)01352-5

  日期：1998.9

  The formylation of lithium acetylides with DMF led to α,β-acetylenic aldehydes in excellent yields (>94%). A reverse quench into a phosphate buffer (10% aqueous KH2PO4,4 equiv) proved to be the key for this high-yielding reaction.

  乙炔锂与DMF的甲酰化反应可产生高产率（> 94％）的α，β-炔醛。反向骤冷到磷酸盐缓冲液（10％含水KH 2 PO 4证明，4当量），以对于此高产反应的关键。
• Synthesis of Pyrrolopyrazinones by Construction of the Pyrrole Ring onto an Intact Diketopiperazine
  作者：Susanna K. Maisto、Angela P. Leersnyder、Gwyneth L. Pudner、Jonathan R. Scheerer

  DOI：10.1021/acs.joc.0c01263

  日期：2020.7.17

  This study reveals an alternative sequence for the synthesis of compounds that contain the pyrrolodiketopiperazine structural motif. Starting with a diketopiperazine precursor, a mild aldol condensation precedes pyrrole annulation and bicyclic ring fusion. The derived intermediate aldol condensation products, which bear either a protected carbonyl or a functionalized alkyne, can be cyclized to the

  这项研究揭示了合成含有吡咯烷二酮哌嗪结构基序的化合物的替代序列。从二酮哌嗪前体开始，轻度的羟醛缩合先于吡咯环化和双环稠合。可以通过质子或金路易斯酸催化将衍生的带有保护的羰基或官能化的炔烃的中间醇醛缩合产物环化为吡咯烷二酮哌嗪。
• Highly efficient and mild synthesis of variously 5-substituted-4-carbaldehyde-1,2,3-triazole derivatives
  作者：Michel Journet、Dongwei Cai、Jason J Kowal、Robert D Larsen

  DOI：10.1016/s0040-4039(01)01923-2

  日期：2001.12

  Synthesis of variously 5-substituted-4-carbaldehyde-1,2,3-triazole derivatives 2 was accomplished by reacting sodium azide with α,β-acetylenic aldehydes 1 in DMSO at room temperature. Therefore, the reaction remains basic avoiding the generation of the hazardous explosive HN3, resulting in a safe process. This mild and general reaction was instantaneous and was essentially quantitative.

  通过使叠氮化钠与α，β-炔醛1在室温下于DMSO中反应，完成了各种5-取代的4-甲醛-1,2,3-三唑衍生物2的合成。因此，该反应仍然是基本的，避免了危险爆炸物HN 3的产生，从而确保了安全的过程。这种轻微和一般的反应是瞬时的，基本上是定量的。
• Selective oxidation of alcohol-<i>d</i>₁ to aldehyde-<i>d</i>₁ using MnO₂
  作者：Hironori Okamura、Yoko Yasuno、Atsushi Nakayama、Katsushi Kumadaki、Kohei Kitsuwa、Keita Ozawa、Yusaku Tamura、Yuki Yamamoto、Tetsuro Shinada

  DOI：10.1039/d1ra05405h

  日期：——

  The selective oxidation of alcohol-d1 to prepare aldehyde-d1 was newly developed by means of NaBD4 reduction/activated MnO2 oxidation. Various aldehyde-d1 derivatives including aromatic and unsaturated aldehyde-d1 can be prepared with a high deuterium incorporation ratio (up to 98% D). Halogens (chloride, bromide, and iodide), alkene, alkyne, ester, nitro, and cyano groups in the substrates are tolerated

  醇-d 1的选择性氧化制备醛-d 1是通过NaBD 4还原/活化的MnO 2氧化的新方法。各种醛-d 1衍生物，包括芳族和不饱和醛-d 1都可以以高氘掺入率（高达 98% D）制备。在温和条件下，底物中的卤素（氯化物、溴化物和碘化物）、烯烃、炔烃、酯、硝基和氰基是可耐受的。