1-(3,4-二氢-2H-吡喃-6-基)乙酮 | 31518-15-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-(3,4-二氢-2H-吡喃-6-基)乙酮
• 英文名称: 2-acetyl-4,5-dihydropyran
• 英文别名: 3,4-dihydro-6-pivaloyl-2H-pyran；2-acetyl-5,6-dihydro-4H-pyran；1-(3,4-dihydro-2H-pyran-6-yl)ethanone；1-(5,6-dihydro-4H-pyran-2-yl)-ethanone
• CAS: 31518-15-7
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: AJPWDQUMQAHYFU-UHFFFAOYSA-N

物化性质

• 沸点：
  236.3±29.0 °C(Predicted)
• 密度：
  1.050±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(3,4-二氢-2H-吡喃-6-基)乙酮 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.5h， 生成 5-cyclohexyl-3,4,5,6-tetrahydro-2H-cyclopenta[b]pyran-7-one
  参考文献：
  名称：

  Polarizing the Nazarov Cyclization:  Efficient Catalysis under Mild Conditions

  摘要：

  Substituted divinyl ketones were studied in the Nazarov cyclization. alpha-Carbomethoxy divinyl ketones underwent efficient Nazarov cyclization with catalytic copper triflate (2 mol %) to give a single cyclopentenone regio- and stereoisomer. The efficiency of the cyclizations correlated with the ability of the substituents to favorably polarize the pi-system of the cationic intermediate.

  DOI：

  10.1021/ja037910b
• 作为产物：
  描述：

  (5-chloro-3,4-dihydro-2H-pyran-6-yl)methanol 生成 1-(3,4-二氢-2H-吡喃-6-基)乙酮
  参考文献：
  名称：

  LEBOUC A.; DELYUNAY J.; RIOBE O., SYNTHESIS, 1979, NO 8, 610-613

  摘要：

  DOI：

文献信息

• Iridium‐Catalyzed Direct CH Amidation with Weakly Coordinating Carbonyl Directing Groups under Mild Conditions
  作者：Jinwoo Kim、Sukbok Chang

  DOI：10.1002/anie.201310544

  日期：2014.2.17

  An iridium‐catalyzed direct CH amidation of weakly coordinating substrates, in particular of those bearing ester and ketone groups, under very mild conditions has been developed. The observed high reaction efficiency was achieved by the combined use of acetic acid and lithium carbonate as additives.

  已经开发了在非常温和的条件下弱配位的底物（特别是带有酯基和酮基的底物）的铱催化直接CH酰胺化反应。通过组合使用乙酸和碳酸锂作为添加剂，可以实现较高的反应效率。
• Cyclic vinyl ether carbanions—II
  作者：Robert K. Boeckman、Kenneth J. Bruza

  DOI：10.1016/s0040-4020(01)93274-0

  日期：——

  Conditions for metalation of a variety of cyclic vinyl ethers and reaction of the resulting carbanions with electrophiles are described. Effects of the vinyl ether structure on the relative rates of metalation are discussed. Applications of this methodology to the construction of various types of carbonyl compounds are presented.

  描述了各种环状乙烯基醚的金属化条件以及所得碳负离子与亲电子试剂的反应条件。讨论了乙烯基醚结构对相对金属化速率的影响。介绍了该方法在各种类型羰基化合物的构建中的应用。
• The use of diazophosphonates in the synthesis of cyclic ethers
  作者：Christopher J. Moody、Eric-Robert H.B. Sie、Janusz J. Kulagowski

  DOI：10.1016/s0040-4020(01)88479-9

  日期：1992.1

  described. The first involves the rhodium(II) catalysed O-H insertion of 2-propanol followed by Wadsworth-Emmons reaction to give the enol ethers 3, and deprotection and cyclisation to the cyclic enol ethers 5. The second route involves the preparation of aldehyde and ketone phosphonates 9, also by rhodium carbenoid O-H insertion reactions, followed by functional group interconversion. On treatment

  描述了两种基于重氮膦酸酯的环状醚的路线。首先涉及2-丙醇的铑（II）催化的OH插入，然后进行Wadsworth-Emmons反应以生成烯醇醚3，然后将其脱保护并环化成环状烯醇醚5。第二种途径涉及醛和酮膦酸酯9的制备，也通过铑类胡萝卜素OH插入反应，然后进行官能团互变而制备。在用氢化钠处理时，膦酸酯9经历分子内的Wadsworth-Emmons反应以给出环状醚13。
• Diastereoselective Synthesis of Five- and Seven-Membered Rings by [2+2+1], [3+2], [3+2+2], and [4+3] Carbocyclization Reactions of β-Substituted (Alkenyl)(methoxy)carbene Complexes with Methyl Ketone Lithium Enolates
  作者：José Barluenga、Jorge Alonso、Francisco J. Fañanás

  DOI：10.1002/chem.200500164

  日期：2005.8.19

  derived from a formal [2+2+1] carbocyclization reaction. However, the lithium enolates of acetone and tungsten complexes furnish formal [3+2+2] carbocyclization products. In the case of alkynyl methyl ketone lithium enolates, competitive formal [2+2+1] and [3+2] carbocyclization reactions occur and 1,3-cyclopentanediol and 3-cyclopentenol derivatives are formed. Conversely, alkenyl methyl ketone lithium enolates

  β-取代的烯基卡宾配合物与甲基酮烯醇锂反应，生成不同的碳环化产物，具体取决于烯醇锂的结构，卡宾配合物的金属以及反应介质。因此，芳基和烷基甲基酮烯醇锂与乙醚中的β-取代的烯基铬和钨卡宾络合物的反应提供了由正式的[2 + 2 + 1]碳环化反应衍生的1,3-环戊二醇衍生物。但是，丙酮和钨配合物的烯醇锂提供正式的[3 + 2 + 2]碳环化产物。在炔基甲基酮烯醇锂的情况下，发生竞争性形式的[2 + 2 + 1]和[3 + 2]碳环化反应，并形成1,3-环戊二醇和3-环戊烯醇衍生物。反过来，烯基甲基酮烯醇锂在相同反应条件下与烯基碳烯配合物反应，通过正式的[4 + 3]碳环化反应形成2-环庚烯酮衍生物。最后，当反应在配位介质存在下进行时，观察到的[3 + 2]碳环化模式与所使用的甲基酮烯醇锂的性质无关。
• Synthesis of Cp−Re Complexes via Olefinic C−H Activation and Successive Formation of Cyclopentadienes
  作者：Yoichiro Kuninobu、Yuta Nishina、Takashi Matsuki、Kazuhiko Takai

  DOI：10.1021/ja805921f

  日期：2008.10.29

  Treatment of an alpha,beta-unsaturated ketimine with an alpha,beta-unsaturated carbonyl compound in the presence of a rhenium complex, Re2(CO)10, gave a cyclopentadienyl-rhenium complex. This reaction proceeds via rhenium-catalyzed C-H bond activation of an olefinic C-H bond, insertion of an alpha,beta-unsaturated carbonyl compound into a Re-C bond of the alkenylrhenium intermediate, intramolecular

  在铼配合物 Re2(CO)10 存在下，用 α，β-不饱和羰基化合物处理 α，β-不饱和酮亚胺，得到环戊二烯基-铼配合物。该反应通过铼催化的 CH 键活化烯烃 CH 键、将 α,β-不饱和羰基化合物插入烯基铼中间体的 Re-C 键、分子内亲核环化、还原消除、消除苯胺以得到环戊二烯衍生物，然后由环戊二烯衍生物和铼络合物形成环戊二烯基-铼络合物。