3,4-diisopropyl-hexane-2,5-dione | 100250-29-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-diisopropyl-hexane-2,5-dione
• 英文别名: 3,4-Diisopropyl-2,5-hexanedione；3,4-di(propan-2-yl)hexane-2,5-dione
• CAS: 100250-29-1
• 化学式: C₁₂H₂₂O₂
• 分子量: 198.305
• InChiKey: YNJBURGZLQLQNE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,4-diisopropyl-hexane-2,5-dione 在 palladium dihydroxide N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 过氧化氢苯甲酰 、 氢气 、 对甲苯磺酸 作用下， 以 甲醇 、 四氯化碳 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 21.0h， 生成
  参考文献：
  名称：

  Molecular self-assembly through hydrogen bonding: aggregation of five molecules to form a discrete supramolecular structure

  摘要：

  This article describes reactions of the trivalent melamine derivatives C6H3-1,3,5-[CONHC6H4-3-N(CH2C6H4-4-C(CH3)3) COC6H3-2-(NHC3N3(NH2)(NHCH2CH2C(CH3)3))-5-Br]3 (hubM3) and (CH3)3COC(O)NHC[CH2O(CH2) 3-SCH2C(O)NHC6H4-2-NHC3N3(NH2)(NH(CH2)2C(CH3)3)]3 (trisM3) with the bivalent isocyanurate derivatives C6H2-1,5-[CH(CH3)2]2-2,4-[CH2NC(O)NHC(O)NHC(O)]2 (benzCA2) and C4O-2,5-[CH(CH3)2]2-3,4-[CH2NC(O)NHC(O)-NHC(O)]2 (furanCA2) in CHCl3 to afford a series of supramolecular aggregates containing 2 equiv of the tris melamine and 3 equiv of the bis cyanurate (2 + 3 complexes). These complexes consist of two parallel hydrogen-bonded lattices that incorporate 36 hydrogen bonds. The structures have been characterized by H-1 NMR, C-13 NMR, and UV spectroscopies, gel permeation chromatography, and vapor pressure osmometry. These techniques demonstrate that the 2 + 3 aggregates in CHCl3 solution are stable and structurally well-defined. hubM3 is more rigid than trisM3. This difference in rigidity is used to probe the relationship between the molecular structure of the trivalent melamine derivative and the geometry and stability of the resulting aggregate. (hubM3)2(benzCA2)3 and (hubM3)2(furanCA2)3 each seem to exist in one isomeric form; (trisM3)2(benzCA2)3 and (trisM3)2(furanCA2)3 are both mixtures of isomers (due, probably, to the relative flexibility of the arms of trisM3).

  DOI：

  10.1021/ja00057a015

文献信息

• Stereoisomer effects on the Paal-Knorr synthesis of pyrroles
  作者：Gyongyi Szakal-Quin、Doyle G. Graham、David S. Millington、David A. Maltby、Andrew T. McPhail

  DOI：10.1021/jo00355a010

  日期：1986.3
• Intermediates in the Paal-Knorr Synthesis of Furans
  作者：Venkataraman Amarnath、Kalyani Amarnath

  DOI：10.1021/jo00107a006

  日期：1995.1

  New experimental evidence for the mechanism of the Paal-Knorr reaction involving the acid-catalyzed cyclization of a 1,4-diketone to form a furan is reported. In aqueous or alcoholic solutions containing hydrochloric acid and in chloroform containing boron trifluoride-etherate d,l- and meso-3,4-diethyl-2,5-hexanediones (2r and 2m) cyclize at unequal rates; the stereochemical configuration of the unchanged done is preserved during the reaction. This disagrees with the commonly accepted mechanism involving the ring closure of the rapidly formed monoenol (11b) followed by loss of water. A pathway involving the rapid protonation of one of the carbonyls followed by the electrophilic attack on the protonated carbonyl by the enol being formed at the other carbonyl group (10c) is proposed to account for the difference in reaction rates between the diastereomers of 3,4-disubstituted 2,5-hexanediones (1-3). The following results also seem to support the intermediacy of 10c. The presence of two isopropyl groups in 3,4-diisopropyl-2,5-hexanedione (3) considerably reduces the rate of cyclization, The catalytic constants k(H)(+) for the cyclization of 2r and 2m are larger than the constants for enolization of methyl ketones. The diastereomers of 2,3-dimethyl-and 2,3-diethyl-1,4-diphenyl-1,4-butanediones (4 and 5), which could enolize only toward the center of the molecule, also react at different rates. The d,l and meso dideuterio analogs (d(2)-4r and d(2)-4m) exhibit a primary isotope effect during cyclization. The order of cyclization of 1,4-diphenyl-1,4-butanedione (6) and its analogs (7-9) reveals that the presence of electron-donating groups facilitate the reaction.
• Molecular self-assembly through hydrogen bonding: aggregation of five molecules to form a discrete supramolecular structure
  作者：Christopher T. Seto、John P. Mathias、George M. Whitesides

  DOI：10.1021/ja00057a015

  日期：1993.2

  This article describes reactions of the trivalent melamine derivatives C6H3-1,3,5-[CONHC6H4-3-N(CH2C6H4-4-C(CH3)3) COC6H3-2-(NHC3N3(NH2)(NHCH2CH2C(CH3)3))-5-Br]3 (hubM3) and (CH3)3COC(O)NHC[CH2O(CH2) 3-SCH2C(O)NHC6H4-2-NHC3N3(NH2)(NH(CH2)2C(CH3)3)]3 (trisM3) with the bivalent isocyanurate derivatives C6H2-1,5-[CH(CH3)2]2-2,4-[CH2NC(O)NHC(O)NHC(O)]2 (benzCA2) and C4O-2,5-[CH(CH3)2]2-3,4-[CH2NC(O)NHC(O)-NHC(O)]2 (furanCA2) in CHCl3 to afford a series of supramolecular aggregates containing 2 equiv of the tris melamine and 3 equiv of the bis cyanurate (2 + 3 complexes). These complexes consist of two parallel hydrogen-bonded lattices that incorporate 36 hydrogen bonds. The structures have been characterized by H-1 NMR, C-13 NMR, and UV spectroscopies, gel permeation chromatography, and vapor pressure osmometry. These techniques demonstrate that the 2 + 3 aggregates in CHCl3 solution are stable and structurally well-defined. hubM3 is more rigid than trisM3. This difference in rigidity is used to probe the relationship between the molecular structure of the trivalent melamine derivative and the geometry and stability of the resulting aggregate. (hubM3)2(benzCA2)3 and (hubM3)2(furanCA2)3 each seem to exist in one isomeric form; (trisM3)2(benzCA2)3 and (trisM3)2(furanCA2)3 are both mixtures of isomers (due, probably, to the relative flexibility of the arms of trisM3).