3-(chloromethyl)-3-phenyl-1,2-dioxetane | 136749-73-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-(chloromethyl)-3-phenyl-1,2-dioxetane
• 英文别名: 3-(Chloromethyl)-3-phenyldioxetane
• CAS: 136749-73-0
• 化学式: C₉H₉ClO₂
• 分子量: 184.622
• InChiKey: IKHANRAIRKLWMQ-UHFFFAOYSA-N

物化性质

• 沸点：
  245.8±29.0 °C(Predicted)
• 密度：
  1.246±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  3-(chloromethyl)-3-phenyl-1,2-dioxetane 在 吗啉 作用下， 以 氘代氯仿 为溶剂， 反应 0.05h， 生成 alpha-氯乙酰苯 、 N-<(3-chloro-2-hydroxy-2-phenylpropyl)oxy>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
• 作为产物：
  描述：

  3-氯丙-1-烯-2-基苯 在 sodium hydroxide 、 1,3-二溴-5,5-二甲基海因 、 双氧水 作用下， 以 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 4.5h， 生成 3-(chloromethyl)-3-phenyl-1,2-dioxetane
  参考文献：
  名称：

  Adam, Waldemar; Heil, Markus, Chemische Berichte, 1992, vol. 125, # 1, p. 235 - 241

  摘要：

  DOI：

文献信息

• Reaction of 1,2-dioxetanes with heteroatom nucleophiles: adduct formation by nucleophilic attack at the peroxide bond
  作者：Waldemar Adam、Markus Heil

  DOI：10.1021/ja00040a017

  日期：1992.7

  The reactions of 3,3-disubstituted 1,2-dioxetanes 1 with numerous heteroatom nucleophiles, e.g., R 2 NH, R 3 N, RSH R 2 S, CN - , SCN - , Br - , Cl - , OH - , and O 2 .- , were investigated. Initial nucleophilic substitution at the sterically less hindered site of the dioxetane peroxide bond leads to addition, deoxygenation, and fragementation products. The observed S N 2 chemistry was substantiated

  3,3-二取代的 1,2-二氧杂环丁烷 1 与许多杂原子亲核试剂的反应，例如 R 2 NH、R 3 N、RSH R 2 S、CN - 、SCN - 、Br - 、Cl - 、OH - 和O 2 .- ，进行了调查。在二氧杂环丁烷过氧化物键的空间位阻较小的位点处的初始亲核取代导致加成、脱氧和断裂产物。观察到的 SN 2 化学反应得到二氧杂环丁烷 1c 的证实，因为溴离子被邻近的醇盐离子位点置换得到环氧化物产物
• Adam, Waldemar; Andler, Simone; Heil, Markus, Angewandte Chemie, 1991, vol. 103, # 10, p. 1395 - 1396
  作者：Adam, Waldemar、Andler, Simone、Heil, Markus

  DOI：——

  日期：——
• 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.
• Adam, Waldemar; Heil, Markus, Chemische Berichte, 1992, vol. 125, # 1, p. 235 - 241
  作者：Adam, Waldemar、Heil, Markus

  DOI：——

  日期：——