3-hydroxymethyl-2-(1-propenyl)cyclohex-2-en-1-one | 620590-41-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-hydroxymethyl-2-(1-propenyl)cyclohex-2-en-1-one
• 英文别名: 3-(hydroxymethyl)-2-[(E)-prop-1-enyl]cyclohex-2-en-1-one
• CAS: 620590-41-2
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: BKYLSYMANOZWHL-DUXPYHPUSA-N

物化性质

• 沸点：
  323.8±21.0 °C(Predicted)
• 密度：
  1.133±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-hydroxymethyl-2-(1-propenyl)cyclohex-2-en-1-one 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 生成
  参考文献：
  名称：

  环氧喹诺尔A，B和C和环氧维醇A的全合成以及Diels-Alder反应中2 H-吡喃衍生物作为二烯组分的反应性

  摘要：

  描述了环氧喹啉A，B和C以及环氧双酚A（RKB-3564D）的全合成的两种形式的全部细节。在第一代合成中，HfCl 4介导的呋喃与科里的手性助剂的非对映选择性Diels-Alder反应已得到开发。在第二代合成中，开发了一种无色谱法制备碘代内酯的方法，该方法通过使用丙烯酰氯作为呋喃的Diels-Alder反应中的亲二烯体，并开发了由脂肪酶介导的环己烯醇衍生物的动力学拆分方法。第二代合成适合大规模制备。仿生级联反应涉及氧化，6π-电环化，然后Diels-Alder二聚化是环氧喹诺醇A，B和C的复杂七环结构形成的关键反应。 6π-电环化和正式的[4 + 4]环加成反应。2小时由氧化/6π-电环化生成的β-吡喃起良好的二烯作用，可与数个亲二烯体反应，一步生成多环化合物。氮杂五环化合物通过类似的级联反应合成，该级联反应由四个连续步骤组成：氧化，亚胺形成，6π-氮杂电子环化和Diels-Alder二聚化。

  DOI：

  10.1021/jo048425h
• 作为产物：
  描述：

  3-((phenylthio)methyl)-2-cyclohexenone 在 二(氰基苯)二氯化钯 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 manganese(IV) oxide 、 sodium tetrahydroborate 、 cerium(III) chloride 、 三苯胂 、 四丁基氟化铵 、 碘 、 三乙胺 、 间氯过氧苯甲酸 、 三氟乙酸酐 、 [双(三氟乙酰氧基)碘]苯 、 silver(l) oxide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 64.33h， 生成 3-hydroxymethyl-2-(1-propenyl)cyclohex-2-en-1-one
  参考文献：
  名称：

  Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

  摘要：

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.

  DOI：

  10.1021/jo0355303

文献信息

• Reaction modes of oxidative dimerization of epoxycyclohexenols
  作者：Mitsuru Shoji、Satoshi Kishida、Yusuke Kodera、Isamu Shiina、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1016/s0040-4039(03)01781-7

  日期：2003.9

  Of the 16 possible modes of the oxidation-6pi-electrocylization-Diels-Alder reaction cascade for an epoxyquinone, and eight for a 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one, only the endo-miti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero are respectively observed, while both the endo-anti(epoxide)-anti(Me)hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with epoxy-4-hydroxycyclohexenones owing to a hydrogen-bonding interaction. (C) 2003 Elsevier Ltd. All rights reserved.
• Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding
  作者：Mitsuru Shoji、Hiroki Imai、Isamu Shiina、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1021/jo0355303

  日期：2004.3.1

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.
• Total Synthesis of Epoxyquinols A, B, and C and Epoxytwinol A and the Reactivity of a 2<i>H</i>-Pyran Derivative as the Diene Component in the Diels−Alder Reaction
  作者：Mitsuru Shoji、Hiroki Imai、Makoto Mukaida、Ken Sakai、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1021/jo048425h

  日期：2005.1.1

  the total synthesis of epoxyquinols A, B, and C and epoxytwinol A (RKB-3564D) are described. In the first-generation synthesis, the HfCl4-mediated diastereoselective Diels−Alder reaction of furan with Corey's chiral auxiliary has been developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone, by using acryloyl chloride as the dienophile in the Diels−Alder reaction

  描述了环氧喹啉A，B和C以及环氧双酚A（RKB-3564D）的全合成的两种形式的全部细节。在第一代合成中，HfCl 4介导的呋喃与科里的手性助剂的非对映选择性Diels-Alder反应已得到开发。在第二代合成中，开发了一种无色谱法制备碘代内酯的方法，该方法通过使用丙烯酰氯作为呋喃的Diels-Alder反应中的亲二烯体，并开发了由脂肪酶介导的环己烯醇衍生物的动力学拆分方法。第二代合成适合大规模制备。仿生级联反应涉及氧化，6π-电环化，然后Diels-Alder二聚化是环氧喹诺醇A，B和C的复杂七环结构形成的关键反应。 6π-电环化和正式的[4 + 4]环加成反应。2小时由氧化/6π-电环化生成的β-吡喃起良好的二烯作用，可与数个亲二烯体反应，一步生成多环化合物。氮杂五环化合物通过类似的级联反应合成，该级联反应由四个连续步骤组成：氧化，亚胺形成，6π-氮杂电子环化和Diels-Alder二聚化。