N-<2-Hydroxy-2-(4-methoxyphenyl)propoxy>morpholine

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N-<2-Hydroxy-2-(4-methoxyphenyl)propoxy>morpholine
• 英文别名: 2-(4-Methoxyphenyl)-1-morpholin-4-yloxypropan-2-ol
• 化学式: C₁₄H₂₁NO₄
• 分子量: 267.325
• InChiKey: HQLFAUGCURLQMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  51.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3-甲基-3-(对甲氧基苯基)-1,2-二氧杂环丁烷 在 吗啉 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以60%的产率得到N-<2-Hydroxy-2-(4-methoxyphenyl)propoxy>morpholine
  参考文献：
  名称：

  The SN2 Reactivity of 3,3-Disubstituted 1,2-Dioxetanes with Morpholine

  摘要：

  The reaction of morpholine with the 3-aryl-3-methyldioxetanes 1a-c (Y = 4-OMe, H, 4-NO2), the 3-(methoxymethyl)-3-phenyldioxetane (1d), and the 3-(halomethyl) 3-phenyldioxetanes 1e,f (X = Cl, Br) was investigated to determine the S(N)2 reactivity of these dioxetanes and the product distribution of the hydroxylamine ether 2 adducts and the dioxetane fragmentation products 3. It was shown that the overall rectivity and the product distribution are strongly dependent on the substituents of the dioxetanes 1. Thus, the reactivity of the dioxetanes 1 toward morpholine was demonstrated to correlate with the electron-accepting propensity of the substituents in the 3-position, while the product distribution depends on the electronic features of the primary dipolar adduct, which results from nucleophilic attack at the dioxetane peroxide bond. Electron-donating substituents (Y = 4-OMe) favor proton transfer from the hydroxylammonium site to the alkoxide ion due to the enhanced basicity of the latter, and, therefore, the formation of the hydroxylamine ether 2 is promoted. Additionally, electron-accepting substituents (Y = NO2) facilitate the Grob fragmentation of the primary dipolar adduct to the dioxetane cleavage products 3. The unexpected formation of the hydroperoxide 4f in the reaction of the dioxetane If with morpholine was shown to result from acid-catalyzed ring opening of the dioxetane by morpholinium bromide and subsequent morpholine trapping of the resulting stabilized, bromine-bridged benzylic cation.

  DOI：

  10.1021/jo00114a044

文献信息

• The SN2 Reactivity of 3,3-Disubstituted 1,2-Dioxetanes with Morpholine
  作者：Waldemar Adam、Roland Stoessel、Alexander Treiber

  DOI：10.1021/jo00114a044

  日期：1995.5

  The reaction of morpholine with the 3-aryl-3-methyldioxetanes 1a-c (Y = 4-OMe, H, 4-NO2), the 3-(methoxymethyl)-3-phenyldioxetane (1d), and the 3-(halomethyl) 3-phenyldioxetanes 1e,f (X = Cl, Br) was investigated to determine the S(N)2 reactivity of these dioxetanes and the product distribution of the hydroxylamine ether 2 adducts and the dioxetane fragmentation products 3. It was shown that the overall rectivity and the product distribution are strongly dependent on the substituents of the dioxetanes 1. Thus, the reactivity of the dioxetanes 1 toward morpholine was demonstrated to correlate with the electron-accepting propensity of the substituents in the 3-position, while the product distribution depends on the electronic features of the primary dipolar adduct, which results from nucleophilic attack at the dioxetane peroxide bond. Electron-donating substituents (Y = 4-OMe) favor proton transfer from the hydroxylammonium site to the alkoxide ion due to the enhanced basicity of the latter, and, therefore, the formation of the hydroxylamine ether 2 is promoted. Additionally, electron-accepting substituents (Y = NO2) facilitate the Grob fragmentation of the primary dipolar adduct to the dioxetane cleavage products 3. The unexpected formation of the hydroperoxide 4f in the reaction of the dioxetane If with morpholine was shown to result from acid-catalyzed ring opening of the dioxetane by morpholinium bromide and subsequent morpholine trapping of the resulting stabilized, bromine-bridged benzylic cation.