3,3-bis(phenylmethyl)-1,2-dioxetane | 40814-69-5

• 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: 3,3-bis(phenylmethyl)-1,2-dioxetane
• 英文别名: 3,3-dibenzyl-1,2-dioxetane；3,3-dibenzyl-[1,2]dioxetane；1,1-Dibenzyl-1,2-dioxetan；3,3-Dibenzyl-1,2-dioxetan；3,3-Dibenzyldioxetane
• CAS: 40814-69-5
• 化学式: C₁₆H₁₆O₂
• 分子量: 240.302
• InChiKey: GKMWCNGSCFKERE-UHFFFAOYSA-N

物化性质

• 沸点：
  328.7±9.0 °C(Predicted)
• 密度：
  1.154±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  3,3-bis(phenylmethyl)-1,2-dioxetane 生成 二苄基甲酮
  参考文献：
  名称：

  Adam Waldemar, Andler Simone, J. Amer. Chem. Soc, 116 (1994) N 13, S 5674-5678

  摘要：

  DOI：
• 作为产物：
  描述：

  (2-苄基-2-丙烯-1-基)苯 在 18-冠醚-6 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 4.0h， 生成 3,3-bis(phenylmethyl)-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
• Evidence for a 1,4-dioxy diradical as an intermediate in the thermal decomposition of 3,3-dibenzyl-1,2-dioxetane
  作者：Waldemar Adam、Markus Heil

  DOI：10.1021/ja00049a009

  日期：1992.11

  The thermal decomposition of 3,3-dibenzyl-1,2-dioxetane (1) in CDCl 3 and CH 2 Cl 2 solutions afforded the expected decomposition product 1,3-diphenyl-2-propanone (2) and the novel rearrangement ketone 1-(benzyloxy)-3-phenyl-2-propanone (3) in ratios of (73±10):(27±10). A plausible mechanism for the formation of ketone 3 involves homolytic cleavage of the dioxetane peroxide bond with subsequent β cleavage

  3,3-二苄基-1,2-二氧杂环丁烷 (1) 在 CDCl 3 和 CH 2 Cl 2 溶液中的热分解得到预期的分解产物 1,3-二苯基-2-丙酮 (2) 和新的重排酮 1 -(苄氧基)-3-苯基-2-丙酮(3)，比例为(73±10):(27±10)。形成酮 3 的一种可能机制涉及二氧杂环丁烷过氧化物键的均裂断裂，随后 1,4-二氧基双自由基和所得自由基的笼内组合中苄基的 β 断裂
• .alpha.-Alkoxy ketones from the nucleophilic substitution on the peroxide bond of 3,3-disubstituted 1,2-dioxetanes by enamines
  作者：Waldemar Adam、Simone Andler、Markus Heil、Volkmar Voerckel

  DOI：10.1021/jo00035a025

  日期：1992.4

  The reaction of 1,2-dioxetanes with enamines as pi-nucleophiles was investigated. 3,3-Dibenzyl-1,2-dioxetane (1) was allowed to react with enamines 2a-c in methylene chloride to afford after hydrolysis the corresponding alpha-alkoxylated ketones 4a-c. Additionally, the reaction of the dimedone-derived enamine 3 with dioxetane 1 yielded the oxidized enamine adduct 4. Nucleophilic attack of the enamine beta-carbon (S(N)2 reactivity) on the sterically less hindered site of the dioxetane peroxide bond is proposed to constitute the initial step of the reaction.
• Thermolysis of 3,3-Bis(phenylmethyl)-1,2-dioxetane: Radical-Induced Formation of the Unusual Decomposition Product 3-Phenyl-1-(phenylmethoxy)-2-propanone
  作者：Waldemar Adam、Simone Andler

  DOI：10.1021/ja00092a019

  日期：1994.6

  The formation of the rearrangement ketone 3-phenyl-1-(phenylmethoxy)-2-propanone (3) in the thermolysis of 3,3-bis(phenylmethyl)-1,2-dioxetane (1) was rigorously probed for radical-induced chain decomposition. The latter mechanism appears to operate on the basis of the following experimental facts: (a) thermolysis of a mixture of the dioxetanes 1-h(4) and 1-d(4) afforded significant amounts of the crossover beta-keto ethers 3-h(2) and 3-d(2), (b) decomposition in toluene-d(8) in the presence of tert-butyl peroxalate (4) resulted in substantial incorporation of externally generated phenylmethyl-d(7) radicals in the form of the a-keto ether 3-d(7), and (c) in the presence of the triplet quenchers dibromomethane and 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH) the formation of the beta-keto ether 3 was suppressed. Clearly, in the thermolysis of dioxetane 1, free phenylmethyl radicals are generated through Norrish type I cleavage of triplet-excited 1,3-diphenyl-2-propanone (2). Attack on the dioxetane peroxide bond leads to the beta-keto ether 3 by beta cleavage of the resulting alkoxy radical with regeneration of the chain-carrying phenylmethyl radical.