acetylperfluoroacetyl peroxide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: acetylperfluoroacetyl peroxide
• 英文别名: acetyltrifluoroacetyl peroxide；Acetyl 2,2,2-trifluoroethaneperoxoate
• 化学式: C₄H₃F₃O₄
• 分子量: 172.061
• InChiKey: FBYYUXKWLZLZTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  过氧乙酸 、 三氟乙酸酐 以 二氯甲烷 为溶剂， 以100%的产率得到acetylperfluoroacetyl peroxide
  参考文献：
  名称：

  Heterolytic decarboxylation involving acyltrifluoroacetyl peroxide intermediates

  摘要：

  Selective carboxylic acid decarboxylation was elaborated. Generation of acyltrifluoroacetyl peroxides from carboxylic peracids and trifluoroacetyl anhydride (Method A), as well as from trifluoroperacetic acid and acyltrifluoroacetyl anhydride (Method B), leads to simultaneous peroxide decomposition into the corresponding alkyltrifluoroacetates. DFT computations, as well as experimental data, support an acid-catalyzed heterolytic mechanism for acyltrifluoroacetyl peroxide decomposition. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)02151-2

文献信息

• Observation of a Stable Carbocation in a Consecutive Criegee Rearrangement with Trifluoroperacetic Acid
  作者：Pavel A. Krasutsky、Igor V. Kolomitsyn、Paul Kiprof、Robert M. Carlson、Andrey A. Fokin

  DOI：10.1021/jo991745u

  日期：2000.6.1

  Selective oxidative cleavage-cyclization of adamantane through the bridge carbon was developed in trifluoroperacetic acid (TFPAA). The methyl group in the bridge position was found to be the substituent that directs consecutive oxygen insertion into the cage structure during the course of a Criegee rearrangement. The formation of stable 5-methyl-4,6-dioxabishomoadamant-5-yl cation at -25 degrees C

  在三氟过氧乙酸（TFPAA）中开发了金刚烷通过桥碳的选择性氧化裂解环。发现在桥基位置的甲基是取代基，其在Criegee重排过程中指导连续的氧插入笼结构中。在-25℃下观察到稳定的5-甲基-4，6-二氧杂双恶金刚烷-5-基阳离子的形成。稳定的碳鎓离子形成可控制进一步转化的选择性。水解导致内立的3-endo-3-hydroxy-7-acetoxybicyclo [3.3。1]壬烷。获得其单晶X射线结构。温度升高会导致5-甲基-4，6-二氧杂双恶金刚烷5-基阳离子去质子化为内3-三氟乙酰氧基双环[3.3.1] non-6-ene，在三氟乙酸（TFAA）中经过TFPAA进一步环氧化和酸性环过环化。所描述的反应可用作合成双环[3.3.1]壬烷和氧杂金刚烷衍生物的简便方法。讨论了为每个转换提出的机制，以及从头开始的理论计算的相关草酸盐结构的应变能和稳定能。
• A Novel Catalytic Pathway for Perfluoroacyl Peroxide Synthesis
  作者：Pavel A. Krasutsky、Igor V. Kolomitsyn、Robert M. Carlson

  DOI：10.1021/ol016338v

  日期：2001.9.1

  [GRAPHICS]A new catalytic method for synthesis of bis(perfluoroacyl) peroxides (BPFAP) was elaborated by using hydrogen peroxide and perfluoroacyl anhydrides. The desired BPFAP were formed quantitatively in situ when perfluoroacyl anhydride was mixed with hydrogen peroxide (ratio greater than or equal to 2:1) in the presence of a catalytic amount of the carboxylate RfCOO- M+. The essentially irreversible character of this process was shown experimentally and supported on the basis of DFT calculations. The synthesis of new acetyltrifluoroacetyl peroxides is also described.