isopropyl decachlorobenzilate | 112312-91-1

• 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: isopropyl decachlorobenzilate
• 英文别名: isopropyl decachlorobenzylate；Propan-2-yl 2-hydroxy-2,2-bis(2,3,4,5,6-pentachlorophenyl)acetate
• CAS: 112312-91-1
• 化学式: C₁₇H₈Cl₁₀O₃
• 分子量: 614.779
• InChiKey: UGQBXRBAVFNJBK-UHFFFAOYSA-N

物化性质

• 沸点：
  620.5±50.0 °C(Predicted)
• 密度：
  1.724±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  isopropyl decachlorobenzilate 在 三溴化磷 、 sodium hydride 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 2.0h， 生成 bis(pentachlorophenyl)ketene methyl isopropyl acetal
  参考文献：
  名称：

  Synthesis of the sterically hindered bis(pentachlorophenyl)acetic acid and derived stable free radicals

  摘要：

  Bis(pentachlorophenyl)acetic acid esters were synthesized from the alpha-hydroxydiaryl acetate esters 13 via the free radicals 15 formed on homolytic cleavage of the alpha-chloro compounds 14. The acid 8 underwent rapid decarboxylation in basic solution (e.g., Et3N in THF) but could be dehydrated to the corresponding ketene 17. Nucleophilic addition to the ketene provided a route to the corresponding amides (21 and 19) and nitrile 20, the enolates of which underwent ready oxidation to the corresponding stable free radicals 15, 22, and 23. Evidence for the structure and unusual stability of these free radicals is presented. Attempts to observe enols of acids or esters on the addition of water or alcohols to the sterically hindered ketene 17 were unsuccessful.

  DOI：

  10.1021/jo00042a021
• 作为产物：
  描述：

  六氯苯 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 生成 isopropyl decachlorobenzilate
  参考文献：
  名称：

  立体稳定的α-酰基自由基：α-异丙氧基羰基，N-吗啉代羰基和氰基双（五氯苯基）甲基。

  摘要：

  这三个标题的基团，，和已用碘相应碳负离子的氧化来合成。自由基是红色至紫色的空气稳定固体，其ir和esr光谱显示未成对电子与羰基或氰基之间存在相当大的相互作用。

  DOI：

  10.1016/s0040-4039(01)81019-4

文献信息

• Synthesis of Sterically Congested Acetic Acid Derivatives: The Reaction of Hindered α-Oxo Esters with Pentasubstituted Aryl Grignard Reagents
  作者：A. F. Hegarty、P. O'Neill

  DOI：10.1055/s-1993-25911

  日期：——

  The reactions of pentamethylphenylmagnesium bromide and pentachlorophenylmagnesium chloride with tert-butyl 2-oxo-3,3-dimethylbutanoate to give the 2-aryl-2-hydroxy-3, 3-dimethylbutanoate esters were investigated. Attempted acid catalysed dealkylation of the tert-butyl 2-hydroxy-3,3-dimethyl-2-(pentamethylphenyl) butanoate to the corresponding acid was accompanied by skeletal rearrangement, while the corresponding pentachlorophenyl ester reacted normally. The corresponding α- pentachlorophenyl α-α-tert-butyl acetic acid 15 was synthesised without rearrangement. The reaction of pentachlorophenylmagnesium chloride with diisopropyl oxalate gave the α-oxo ester 18, which reacted with pentamethylphenylmagnesium bromide to afford the unsymmetrical diarylacetate ester 22. The corresponding acid chloride 25 could not be converted to the interesting unsymmetrical diarylketene 26.

  研究了五甲基苯基溴化镁和五氯苯基氯化镁与2-氧代-3,3-二甲基丁酸叔丁酯的反应生成2-芳基-2-羟基-3,3-二甲基丁酸酯。尝试将2-羟基-3,3-二甲基-2-(五甲基苯基)丁酸叔丁酯酸催化脱烷基化为相应的酸，同时伴随骨架重排，而相应的五氯苯酯反应正常。无需重排即可合成相应的α-五氯苯基α-α-叔丁基乙酸15。五氯苯基氯化镁与草酸二异丙酯反应得到α-氧代酯18，其与五甲基苯基溴化镁反应得到不对称二芳基乙酸酯22。相应的酰氯25不能转化为有趣的不对称二芳基乙烯酮26。
• HEGARTY A. F.; ONEILL P., TETRAHEDRON LETT., 28,(1987) N 8, 901-904
  作者：HEGARTY A. F.、 ONEILL P.

  DOI：——

  日期：——
• Synthesis of the sterically hindered bis(pentachlorophenyl)acetic acid and derived stable free radicals
  作者：Pat O'Neill、Anthony F. Hegarty

  DOI：10.1021/jo00042a021

  日期：1992.7

  Bis(pentachlorophenyl)acetic acid esters were synthesized from the alpha-hydroxydiaryl acetate esters 13 via the free radicals 15 formed on homolytic cleavage of the alpha-chloro compounds 14. The acid 8 underwent rapid decarboxylation in basic solution (e.g., Et3N in THF) but could be dehydrated to the corresponding ketene 17. Nucleophilic addition to the ketene provided a route to the corresponding amides (21 and 19) and nitrile 20, the enolates of which underwent ready oxidation to the corresponding stable free radicals 15, 22, and 23. Evidence for the structure and unusual stability of these free radicals is presented. Attempts to observe enols of acids or esters on the addition of water or alcohols to the sterically hindered ketene 17 were unsuccessful.
• Sterically stabilized α-acyl free radicals: α-isoproproxycarbonyl, N-morpholinocarbonyl and cyano bis(pentachlorophenyl)methyl radicals.
  作者：A.F. Hegarty、P O'Neill

  DOI：10.1016/s0040-4039(01)81019-4

  日期：1987.1

  The three title radicals, , and have been synthesised by oxidation of the corresponding carbanions with iodine. The radicals are red to purple air stable solids and their ir and esr spectra show considerable interaction between the unpaired electron and the carbonyl or cyano group.

  这三个标题的基团，，和已用碘相应碳负离子的氧化来合成。自由基是红色至紫色的空气稳定固体，其ir和esr光谱显示未成对电子与羰基或氰基之间存在相当大的相互作用。