tert-Butyl-[(E)-4-(1-methoxy-1-methyl-ethylperoxy)-4-methyl-pent-2-enyloxy]-diphenyl-silane | 1026576-08-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-Butyl-[(E)-4-(1-methoxy-1-methyl-ethylperoxy)-4-methyl-pent-2-enyloxy]-diphenyl-silane
• 英文别名: tert-butyl-[(E)-4-(2-methoxypropan-2-ylperoxy)-4-methylpent-2-enoxy]-diphenylsilane
• CAS: 1026576-08-8
• 化学式: C₂₆H₃₈O₄Si
• 分子量: 442.671
• InChiKey: VLHFVMWAKCUQOD-HMMYKYKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.23
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-Butyl-[(E)-4-(1-methoxy-1-methyl-ethylperoxy)-4-methyl-pent-2-enyloxy]-diphenyl-silane 在 2,6-二叔丁基-4-甲基苯酚 、 溶剂黄146 作用下， 以 四氢呋喃 、 水 为溶剂， 以100%的产率得到(E)-5-(tert-Butyl-diphenyl-silanyloxy)-2-methyl-pent-3-en-2-yl-hydroperoxide
  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：

  (E)-4-(1-Methoxy-1-methyl-ethylperoxy)-4-methyl-pent-2-enoic acid ethyl ester 在 咪唑 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 tert-Butyl-[(E)-4-(1-methoxy-1-methyl-ethylperoxy)-4-methyl-pent-2-enyloxy]-diphenyl-silane
  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

文献信息

• 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.