α-Hydroperoxyisobuttersaeure-tert-butylester | 35733-39-2

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氢过氧化物
• 英文名称: α-Hydroperoxyisobuttersaeure-tert-butylester
• 英文别名: Tert-butyl 2-hydroperoxy-2-methylpropanoate
• CAS: 35733-39-2
• 化学式: C₈H₁₆O₄
• 分子量: 176.213
• InChiKey: XSFXGMLNHGPEMJ-UHFFFAOYSA-N

物化性质

• 沸点：
  243.1±23.0 °C(Predicted)
• 密度：
  1.048±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-甲氧基丙烯 、 α-Hydroperoxyisobuttersaeure-tert-butylester 在 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以96%的产率得到Tert-butyl 2-(2-methoxypropan-2-ylperoxy)-2-methylpropanoate
  参考文献：
  名称：

  Preparation of Unsymmetrically Labeled Hydroperoxides. A Hydroxamate Ester−Nitrosation Approach

  摘要：

  Reaction of O-tertiary alkyl arylhydroxamate esters with nitrosyl chloride gives O-tertiary alkyl aryl peresters that can be hydrolyzed to the hydroperoxide. If the hydroxamate ester carbonyl oxygen or nitrosyl chloride is labeled with O-18, the label appears in the product hydroperoxide's terminal oxygen. This strategy, which derives from the pioneering work of Koenig, permits the preparation of a variety of(2-O-18) hydroperoxides, including tertiary alkyl and cumyl hydroperoxides. tert-Butyl alpha-hydroperoxyisobutyrate, 27, prepared in this way with an O-18 label in the terminal oxygen, serves as a useful precursor for the preparation of other unsymmetrically labeled peroxides and hydroperoxides. Hydroperoxide 27 is protected as a perketal with 2-methoxypropene, and a six-step sequence involving Dibal-H reduction, oxidation (PDC), and Wittig chemistry provides the allylic hydroperoxide 12 that is used in mechanistic studies. Hydroxamate esters that give peresters prone to undergo the Criegee rearrangement upon reaction with NOCl do not give useful yields of product hydroperoxides in the transformation and one hydroxamate ester 17 that reacts via an allylalkoxyl radical gives epoxides 20a and 20b as the major isolable products of reaction.

  DOI：

  10.1021/jo980654e
• 作为产物：
  描述：

  叔-丁基异丁酸酯 在 potassium tert-butylate 、 氧气 作用下， 以 乙二醇二甲醚 为溶剂， 生成 α-Hydroperoxyisobuttersaeure-tert-butylester
  参考文献：
  名称：

  碱性溶液中酮和酯的自氧化

  摘要：

  广泛研究了酮和酯在含有强碱的非质子溶剂（如醇盐）中的自氧化。注意其他弱酸性底物（例如腈，席夫碱和苯hydr）的自氧化。主要产物是α-氢过氧化物，当在低温下进行氧化时，可以高产率分离出α-氢过氧化物，从而防止其分解。

  DOI：

  10.1039/j29710002230

文献信息

• Kaloustian,J. et al., Bulletin de la Societe Chimique de France, 1971, p. 4411 - 4414
  作者：Kaloustian,J. et al.

  DOI：——

  日期：——
• US4579967A
  申请人：——

  公开号：US4579967A

  公开（公告）日：1986-04-01
• [EN] PREPARATION OF ALKYLTHIOPROPIONIC PENTAERYTHRITOL ESTERS<br/>[FR] PREPARATION D'ESTERS DE PENTAERYTHRITOL ALKYLTHIOPROPIONIQUE
  申请人：HAMPSHIRE CHEMICAL CORP.

  公开号：WO1997045482A1

  公开（公告）日：1997-12-04

  (EN) A process of the preparation of alkylthiopropionic pentaerythritol esters from pentaerythritol tetra-3-mercaptopropionate. In a first embodiment of the invention, pentaerythritol tetra-3-mercaptopropionate and an alpha-olefin are caused to react in the presence of a radical initiator. In a second embodiment of the invention, pentaerythritol tetra-3-mercaptopropionate and an alpha-olefin are caused to react photochemically.(FR) Procédé de préparation d'esters de pentaérythritol alkylthiopropionique à partir du tétra-3-mercaptopropionate de pentaérythritol. Selon un premier mode de réalisation, on fait réagir le tétra-3-mercaptopropionate de pentaérythritol et une alpha-oléfine en présence d'un initiateur radicalaire. Selon un second mode de réalisation, on fait réagir de manière photochimique le tétra-3-mercaptopropionate de pentaérythritol et une alpha-oléfine.
• Autoxidation of ketones and esters in basic solution
  作者：H. R. Gersmann、A. F. Bickel

  DOI：10.1039/j29710002230

  日期：——

  The autoxidation of ketones and esters in aprotic solvents containing strong bases such as alkoxides was investigated extensively. Attention was paid to the autoxidation of other weakly acidic substrates such as nitriles, Schiff bases, and phenylhydrazones. The primary products are the α-hydroperoxides, which can be isolated in high yields when the oxidation is carried out at low temperatures, thus

  广泛研究了酮和酯在含有强碱的非质子溶剂（如醇盐）中的自氧化。注意其他弱酸性底物（例如腈，席夫碱和苯hydr）的自氧化。主要产物是α-氢过氧化物，当在低温下进行氧化时，可以高产率分离出α-氢过氧化物，从而防止其分解。
• Preparation of Unsymmetrically Labeled Hydroperoxides. A Hydroxamate Ester−Nitrosation Approach
  作者：Ned. A. Porter、Sarah E. Caldwell、Jennifer R. Lowe

  DOI：10.1021/jo980654e

  日期：1998.8.1

  Reaction of O-tertiary alkyl arylhydroxamate esters with nitrosyl chloride gives O-tertiary alkyl aryl peresters that can be hydrolyzed to the hydroperoxide. If the hydroxamate ester carbonyl oxygen or nitrosyl chloride is labeled with O-18, the label appears in the product hydroperoxide's terminal oxygen. This strategy, which derives from the pioneering work of Koenig, permits the preparation of a variety of(2-O-18) hydroperoxides, including tertiary alkyl and cumyl hydroperoxides. tert-Butyl alpha-hydroperoxyisobutyrate, 27, prepared in this way with an O-18 label in the terminal oxygen, serves as a useful precursor for the preparation of other unsymmetrically labeled peroxides and hydroperoxides. Hydroperoxide 27 is protected as a perketal with 2-methoxypropene, and a six-step sequence involving Dibal-H reduction, oxidation (PDC), and Wittig chemistry provides the allylic hydroperoxide 12 that is used in mechanistic studies. Hydroxamate esters that give peresters prone to undergo the Criegee rearrangement upon reaction with NOCl do not give useful yields of product hydroperoxides in the transformation and one hydroxamate ester 17 that reacts via an allylalkoxyl radical gives epoxides 20a and 20b as the major isolable products of reaction.