1,1-diethoxy-3,4-nonanedione | 208933-02-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-diethoxy-3,4-nonanedione
• 英文别名: 1,1-Diethoxynonane-3,4-dione
• CAS: 208933-02-2
• 化学式: C₁₃H₂₄O₄
• 分子量: 244.331
• InChiKey: ROZPKOGNAKVTJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-diethoxy-3,4-nonanedione 在 盐酸 、 sodium dihydrogenphosphate 作用下， 以 丙酮 、 乙腈 为溶剂， 反应 17.0h， 生成
  参考文献：
  名称：

  Independent Synthesis, Solution Behavior, and Studies on the Mechanism of Formation of a Primary Amine-Derived Fluorophore Representing Cross-linking of Proteins by (E)-4-Hydroxy-2-nonenal

  摘要：

  Lipid peroxidation in aging and degenerative disease results in the production of 4-hydroxy-2-alkenals that modify proteins and give rise to both protein cross-linking and fluorophore generation. Recent model studies demonstrated that the major ex/em 360/430 fluorophore formed from (E)-4-hydroxy-2-nonenal (HNE) or (E)-4-hydroxy-2-hexenal (HHE) and protein lysine-based amine is a 2-alkyl-2-hydroxy-1,2-dihydropyrrol-3-one iminium 1:2 cross-link (1), a structure that is further confirmed here using N-15-labeling, and which has pH stability characteristics the same as those of lipofuscin pigments isolated from human tissues. Fluorophore generation represents an overall four-electron oxidation, requires dioxygen, and is enhanced by the presence of Cu(II). The HNE-propylamine-derived fluorophore 1a was independently synthesized from either 3,4-dioxononanal (8) or (E)-4-oxo-2-nonenal (13), providing further evidence for its assigned structure and clues to how it forms from HNE. Mechanistic studies on HNE-derived fluorophore formation permit ruling out the initial reversible HNE-derived Schiff base Michael adduct (17) as an intermediate. In addition, the structurally related non-cross-link 2-pentyl-2-hydroxy-1,2-dihydropyrrol-3-one 9a that forms along with 1a from 8 does not form from HNE and does: not serve as a precursor to la in the HNE-amine reaction system. A mechanism involving two 2e oxidations following initial Schiff base formation is proposed that is consistent with intermediates independently accessed from 8 and 13.

  DOI：

  10.1021/jo982523j
• 作为产物：
  描述：

  1,1-diethoxy-3-nonyne 在 臭氧 、 二甲基硫 作用下， 以 氯仿 为溶剂， 反应 4.0h， 生成 1,1-diethoxy-3,4-nonanedione
  参考文献：
  名称：

  Independent Synthesis, Solution Behavior, and Studies on the Mechanism of Formation of a Primary Amine-Derived Fluorophore Representing Cross-linking of Proteins by (E)-4-Hydroxy-2-nonenal

  摘要：

  Lipid peroxidation in aging and degenerative disease results in the production of 4-hydroxy-2-alkenals that modify proteins and give rise to both protein cross-linking and fluorophore generation. Recent model studies demonstrated that the major ex/em 360/430 fluorophore formed from (E)-4-hydroxy-2-nonenal (HNE) or (E)-4-hydroxy-2-hexenal (HHE) and protein lysine-based amine is a 2-alkyl-2-hydroxy-1,2-dihydropyrrol-3-one iminium 1:2 cross-link (1), a structure that is further confirmed here using N-15-labeling, and which has pH stability characteristics the same as those of lipofuscin pigments isolated from human tissues. Fluorophore generation represents an overall four-electron oxidation, requires dioxygen, and is enhanced by the presence of Cu(II). The HNE-propylamine-derived fluorophore 1a was independently synthesized from either 3,4-dioxononanal (8) or (E)-4-oxo-2-nonenal (13), providing further evidence for its assigned structure and clues to how it forms from HNE. Mechanistic studies on HNE-derived fluorophore formation permit ruling out the initial reversible HNE-derived Schiff base Michael adduct (17) as an intermediate. In addition, the structurally related non-cross-link 2-pentyl-2-hydroxy-1,2-dihydropyrrol-3-one 9a that forms along with 1a from 8 does not form from HNE and does: not serve as a precursor to la in the HNE-amine reaction system. A mechanism involving two 2e oxidations following initial Schiff base formation is proposed that is consistent with intermediates independently accessed from 8 and 13.

  DOI：

  10.1021/jo982523j

文献信息

• Independent Synthesis, Solution Behavior, and Studies on the Mechanism of Formation of a Primary Amine-Derived Fluorophore Representing Cross-linking of Proteins by (<i>E</i>)-4-Hydroxy-2-nonenal
  作者：Guozhang Xu、Yahua Liu、Lawrence M. Sayre

  DOI：10.1021/jo982523j

  日期：1999.8.1

  Lipid peroxidation in aging and degenerative disease results in the production of 4-hydroxy-2-alkenals that modify proteins and give rise to both protein cross-linking and fluorophore generation. Recent model studies demonstrated that the major ex/em 360/430 fluorophore formed from (E)-4-hydroxy-2-nonenal (HNE) or (E)-4-hydroxy-2-hexenal (HHE) and protein lysine-based amine is a 2-alkyl-2-hydroxy-1,2-dihydropyrrol-3-one iminium 1:2 cross-link (1), a structure that is further confirmed here using N-15-labeling, and which has pH stability characteristics the same as those of lipofuscin pigments isolated from human tissues. Fluorophore generation represents an overall four-electron oxidation, requires dioxygen, and is enhanced by the presence of Cu(II). The HNE-propylamine-derived fluorophore 1a was independently synthesized from either 3,4-dioxononanal (8) or (E)-4-oxo-2-nonenal (13), providing further evidence for its assigned structure and clues to how it forms from HNE. Mechanistic studies on HNE-derived fluorophore formation permit ruling out the initial reversible HNE-derived Schiff base Michael adduct (17) as an intermediate. In addition, the structurally related non-cross-link 2-pentyl-2-hydroxy-1,2-dihydropyrrol-3-one 9a that forms along with 1a from 8 does not form from HNE and does: not serve as a precursor to la in the HNE-amine reaction system. A mechanism involving two 2e oxidations following initial Schiff base formation is proposed that is consistent with intermediates independently accessed from 8 and 13.