2-ethoxy-6-methyl-3,4-dihydro-2H-pyran | 52438-71-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-ethoxy-6-methyl-3,4-dihydro-2H-pyran
• 英文别名: 2H-Pyran, 2-ethoxy-3,4-dihydro-6-methyl-
• CAS: 52438-71-8
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: ZEXJBQAOQUBOAP-UHFFFAOYSA-N

物化性质

• 沸点：
  189.3±39.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-ethoxy-6-methyl-3,4-dihydro-2H-pyran 在 硫酸 作用下， 反应 1.0h， 以74%的产率得到2-环己烯-1-酮
  参考文献：
  名称：

  Thuy, Vu Moc; Maitte, Pierre, Journal of Heterocyclic Chemistry, 1987, vol. 24, p. 497 - 499

  摘要：

  DOI：
• 作为产物：
  描述：

  丁烯酮 、 乙烯基乙醚 在 florisil 作用下， 反应 15.0h， 以50%的产率得到2-ethoxy-6-methyl-3,4-dihydro-2H-pyran
  参考文献：
  名称：

  通过色谱吸附剂的吸附极大地加速了Diels-Alder反应

  摘要：

  描述了在不存在溶剂的情况下在色谱吸附剂表面进行[4 + 2]环加成反应的新方法的开发，该方法导致反应条件的缓和和选择性的提高。

  DOI：

  10.1016/s0040-4039(00)80045-3

文献信息

• Kinetic effects in water and ethylene glycol. Application to high pressure organic synthesis
  作者：Ge´rard Jenner、Ridha Ben Salem

  DOI：10.1039/b000241k

  日期：——

  The kinetic effect of various Diels–Alder and Michael reactions is studied in water and ethylene glycol vs. organic solvents. The rate enhancement is considerable in water, much less in ethylene glycol. It is proposed that strong solvophobic interactions operate in water whereas the kinetic results in glycol are best explained by hydrogen bonding and polarity effects. From a synthetic point of view, use of the properties of water (hydrophobic interactions) or ethylene glycol (ionogenic medium) associated with the kinetic effect of high pressure may constitute an interesting multiactivation method to increase chemical reactivity. Examples of triactivation (high pressure catalytic Diels–Alder reactions in ethylene glycol) are given.

  在水和乙二醇与有机溶vents中，研究了各种Diels-Alder和Michael反应的动力学效应。水中的速率提升非常显著，而在乙二醇中则大为减少。提出在水中的强烈疏溶剂相互作用，而乙二醇中的动力学结果最好用氢键和极性效应来解释。从合成的角度来看，利用水的性质（疏水相互作用）或乙二醇（离子化介质）与高压动力学效应相结合，可能构成一种有趣的多重激活方法，以提高化学反应性。给出了三重激活的例子（高压催化Diels-Alder反应在乙二醇中）。
• A Novel Method of Crossed-Aldol Condensation: Alkylation of Trimethylsilyl Enol Ethers by Alkyl 1-Chloro-2-arylthioalkyl Ethers
  作者：M. A. Ibragimov、M. I. Lazareva、W. A. Smit

  DOI：10.1055/s-1985-31370

  日期：——

  Trimethylsilyl enol ethers 5, derived from aldehydes or ketones, react with alkyl 1-chloro-2-arylthioalkyl ethers 3 (β-arylthio-α-chloroethers, prepared in situ from vinyl ethers 1 and arenesulfenyl chlorides 2) to give the 2-alkoxy-3-arylthioalkyl ketone derivatives 6 in the presence of a Lewis acid.

  从醛或酮衍生的三甲硅基烯醇醚5与烷基1-氯-2-芳硫基烷基醚3（β-芳硫基-α-氯代醚，由乙烯基醚1和芳磺酰氯2原位制备）在路易斯酸存在下反应，生成2-烷氧基-3-芳硫基烷基酮衍生物6。
• Oxidative rearrangement of 2-alkoxy-3,4-dihydro-2H-pyrans: stereocontrolled synthesis of 4,5-cis-disubstituted tetrahydrofuranones including whisky and cognac lactones and crobarbatic acid
  作者：Alan Armstrong、Cassim Ashraff、Hunsuk Chung、Lorraine Murtagh

  DOI：10.1016/j.tet.2009.04.013

  日期：2009.6

  Oxidation of 2-alkoxy-3,4-dihydro-2H-pyrans 3 with dimethyldioxirane or MTO/urea–H2O2 followed by Jones oxidation leads to rearrangement and stereocontrolled formation of 4,5-cis-disubstituted tetrahydrofuranones. The method is applied to the synthesis of the whisky lactone 9, cognac lactone 10 and crobarbatic acid 17.

  用二甲基二环氧乙烷或MTO /脲-H 2 O 2氧化2-烷氧基-3,4-二氢-2 H-吡喃3，然后进行琼斯氧化，导致4,5-顺式-二取代的四氢呋喃酮的重排和立体形成。该方法适用于威士忌内酯9，白兰地内酯10和巴巴果酸17的合成。
• Characterization of Aroma-Active Compounds in Italian Tomatoes with Emphasis on New Odorants
  作者：Johanna Kreissl、Peter Schieberle

  DOI：10.1021/acs.jafc.7b01108

  日期：2017.6.28

  5-dimethyl-3(2H)-furanone. Of the further odorants, 13 compounds have previously not been reported as tomato odorants. Although most of these showed lower FD-factors, in particular, the coconut/dill-like smelling wine lactone ((3S,3aS,7aR)-3a,4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2(3H)-one) appeared with a quite high FD factor. In addition, a fruity, almond-like odorant (6) with an FD factor of 1024 was

  通过溶剂萃取和随后的SAFE蒸馏，从意大利葡萄番茄中制得香气馏出物，产生强烈的总体香气。gc /嗅觉测定法和香气提取物稀释分析的应用揭示了44种气味活性化合物，其中42种可以被识别。对绿色，草绿色（Z）-3-己烯醛，金属味反式-4,5-环氧-（E）-2-癸烯，马铃薯样3-（甲硫基）确立了最高的气味活性值2048丙醛和焦糖状的4-羟基-2,5-二甲基-3（2 H）-呋喃酮。在其他增香剂中，以前没有13种化合物被报道为番茄增香剂。尽管其中大多数显示出较低的FD因子，尤其是椰子/莳萝味的葡萄酒内酯（（3S，3a S，7a R）-3a，4,5,7a-四氢-3,6-二甲基苯并呋喃-2（3 H）-one）的FD系数很高。此外，还检测到FD系数为1024的果味杏仁状增香剂（6）。通过应用高分辨率质谱法和极性考虑因素，提出了甲基-2-乙氧基四氢吡喃异构体的结构用于6。合成了五个可能的异构体中的四个，即3-
• Reductive cleavage of 2-alkoxy- and 2-aryloxy-tetrahydropyrans with LiAlH₄–AlCl₃
  作者：U. E. Diner、R. K. Brown

  DOI：10.1139/v67-416

  日期：1967.11.1

  A series of 2-alkoxy- and 2-aryloxy-tetrahydropyrans has been hydrogenolyzed in ether by LiAlH₄–AlCl₃. As the alkyl group attached to the exo oxygen atom is changed from primary to tertiary, the proportion of ring cleavage to side-chain cleavage increases. Only side-chain cleavage occurs with the 2-aryloxytetrahydropyrans. The results are explained in terms of the polar properties of the alkyl or aryl group attached to the ring oxygen or the side-chain oxygen. Any control by steric factors is considered to be submerged by the polar effects, but does have a clearly apparent directive effect when the polar factors are equal for the two routes of cleavage. The results of the hydrogenolysis of 6-substituted 2-alkoxytetrahydropyrans could be explained on the same basis.The configurations of the cis and trans isomers of the disubstituted tetrahydropyrans were determined by nuclear magnetic resonance spectroscopy. Their conformational preference is discussed.

  一系列2-烷氧基和2-芳氧基四氢吡喃在乙醚中通过LiAlH₄-AlCl₃进行氢解反应。当连接到外部氧原子的烷基团从一次碳变为三次碳时，环裂解与侧链裂解的比例增加。对于2-芳氧基四氢吡喃，只发生侧链裂解。结果可以通过连接到环氧原子或侧链氧原子的烷基或芳基团的极性性质来解释。虽然立体因素的控制被认为被极性效应所掩盖，但当两种裂解途径的极性因素相等时，立体因素确实具有明显的指导作用。对于6-取代的2-烷氧基四氢吡喃的氢解结果也可以用相同的基础来解释。二取代四氢吡喃的顺式和反式异构体的构型是通过核磁共振波谱确定的。它们的构象偏好被讨论。