ethyl 4-methyl-4-[N-(tert-butoxycarbonyl)aminooxy]-2-penteneoate | 211812-05-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 4-methyl-4-[N-(tert-butoxycarbonyl)aminooxy]-2-penteneoate
• 英文别名: ethyl (E)-4-methyl-4-[(2-methylpropan-2-yl)oxycarbonylamino]oxypent-2-enoate
• CAS: 211812-05-4
• 化学式: C₁₃H₂₃NO₅
• 分子量: 273.329
• InChiKey: NITXVIVLYJFWLJ-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  73.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 4-methyl-4-[N-(tert-butoxycarbonyl)aminooxy]-2-penteneoate 在 三甲基氯硅烷 、 potassium carbonate 、 nitrosonium tetrafluoroborate 、 三乙胺 、 sodium iodide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 Benzoic acid (3,3-dimethyl-oxiranyl)-ethoxycarbonyl-methyl ester
  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：

  N-Boc-2-氨基氧基-2-甲基丙酸乙酯 在 重铬酸吡啶 、 molecular sieve 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 30.0h， 生成 ethyl 4-methyl-4-[N-(tert-butoxycarbonyl)aminooxy]-2-penteneoate
  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.