(4Z)-7,8-diethyl-2,3-dimethyl-(9H)-dipyrrin-1-one | 270928-62-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (4Z)-7,8-diethyl-2,3-dimethyl-(9H)-dipyrrin-1-one
• 英文别名: 2,3-dimethyl-7,8-diethyl-(10H)-dipyrrin-1-one；2,3-dimethyl-7,8-diethyl-10H-dipyrrin-1-one；3,4-dimethyl-7,8-diethyl-9H-dipyrrinone；(5Z)-5-[(3,4-diethyl-1H-pyrrol-2-yl)methylidene]-3,4-dimethylpyrrol-2-one
• CAS: 270928-62-6
• 化学式: C₁₅H₂₀N₂O
• 分子量: 244.337
• InChiKey: FXICBYZYDOYKFB-QPEQYQDCSA-N

物化性质

• 沸点：
  452.2±45.0 °C(Predicted)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  44.9
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (4Z)-7,8-diethyl-2,3-dimethyl-(9H)-dipyrrin-1-one 在 sodium hydroxide 、 sodium tetrahydroborate 、 三氯化铝 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 异丙醇 为溶剂， 反应 22.67h， 生成 (4Z)-9-(5-carboxypentyl)-2,3-dimethyl-7,8-diethyl-(10H)-dipyrrin-1-one
  参考文献：
  名称：

  Amide–Amide Hydrogen Bonding. Semirubin Amides

  摘要：

  Semirubins are analogs for one-half of the bilirubin structure and capable of intramolecular hydrogen bonding. Semirubin amides of ammonia and primary amines are also capable of intramolecular hydrogen bonding. From a combination of spectroscopic methods (H-1 NMR, NOE, and VPO), the primary amide is found to engage very effectively in intramolecular hydrogen bonding. The secondary and tertiary amides engage in both intramolecular (i) and intermolecular (ii) hydrogen bonding: N-methyl (i, monomer + ii, dimer), N-tert-butyl (ii, dimer), N,N-diethyl (i, monomer + ii, dimer). With an oxo-group at C(10), all of the amides are monomeric and most engage in intramolecular hydrogen bonding.

  DOI：

  10.1007/s00706-005-0433-5
• 作为产物：
  描述：

  3,4-二乙基-5-甲基-2-吡咯羧酸乙酯 在 氢氧化钾 、 ammonium cerium(IV) nitrate 、 potassium acetate 、 sodium acetate 作用下， 以 甲醇 为溶剂， 反应 11.5h， 生成 (4Z)-7,8-diethyl-2,3-dimethyl-(9H)-dipyrrin-1-one
  参考文献：
  名称：

  Synthesis and Metabolism of the First Thia-Bilirubin

  摘要：

  A symmetrical C(10)-thiabilirubin analogue, 8,12-bis(2-carboxyethyl)-2,3,17,18-tetraethyl-7,13-dimethyl-10-thia-(21H,23H,24H)-bilin-1,19-dione (1), was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-10H-dipyrrin-1-one in one step by reaction with sulfur dichloride. The thia-rubin exhibited the expected IR, W-vis, and NMR spectroscopic properties, which are rather similar to those of mesobilirubin-XIII alpha. Like bilirubin and mesobilirubin, 1 adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C-S bond lengths and smaller bond angles at C-S-C, as compared to C-CH2-C, lead to an interplanar angle between the two dipyrrinones of only 74 degrees -or considerably less than that of bilirubin (similar to 100 degrees). On normal- and reversed-phase chromatography, 1 is substantially less polar than bilirubin. Despite this conformational distortion, 1 is metabolized in normal rats to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase, 1 (like bilirubin) was not excreted in bile.

  DOI：

  10.1021/jo001598w

文献信息

• Amide to carboxylic acid hydrogen bonding. The dipyrrinone receptor
  作者：Michael T. Huggins、Nicholas T. Salzameda、David A. Lightner

  DOI：10.1080/10610278.2010.521836

  日期：2011.3.1

  Hydrogen bonding between carboxylic acid and amide groups was demonstrated for a series of amides called [n]-semirubins consisting of a dipyrrinone attached to the end of an n-carbon alkanoic acid. Such hydrogen bonding is more effective than the alternative amide to amide or acid to acid types for all of the semirubins studied: n = 1, 3–7, 10 and 20. As determined by 1H NMR and vapour pressure osmometry

  羧酸和酰胺基团之间的氢键已被一系列称为 [n]-半红素的酰胺证明，该酰胺由连接到 n-碳链烷酸末端的双吡喃酮组成。对于所有研究的半红宝石，这种氢键比替代酰胺到酰胺或酸到酸类型更有效：n = 1、3-7、10 和 20。根据 1H NMR 和蒸气压渗透法测定，[n]-半红素，其中 n = 5–20，在 CHCl3 或 CDCl3 中以分子内氢键键合；[4]-半红素是分子间氢键的二聚体；[3]-半红素是四聚体；和 [1]-半红素是一种二聚体——所有的都与羧酸和酰胺形成氢键。双吡喃酮酰胺和相邻的吡咯构成了羧酸基团的有效受体。
• Carboxylic acid to amide hydrogen bonding. 10-Oxo-semirubins
  作者：Nicholas T. Salzameda、Michael T. Huggins、David A. Lightner

  DOI：10.1016/j.tet.2006.06.034

  日期：2006.9

  as hydrogen bonding receptors for carboxylic acids, as found in a large number of 10-oxo-semirubins (1–6). The latter can be synthesized readily by Friedel–Crafts coupling of 9-H dipyrrinones with half-ester acid chlorides or diacid dichlorides of α,ω-dicarboxylic acids, ranging from C2 to C10. With ω-oxo-alkanoic acid chains of C5 or ≥C5, intramolecular hydrogen bonding is observed. With acid chains

  使用它们的酰胺（和吡咯）基团，dipyrrinones充当氢键受体的羧酸，如在大量的10-氧代- semirubins（发现1 - 6）。后者可以很容易地通过9- H二氢吡啶酮与α，ω-二羧酸的半酯酰氯或二酸二氯化物（范围为C 2至C 10）的Friedel-Crafts偶联来合成。用C的ω氧代链烷酸链5或≥C 5，分子内氢键是观察。酸链＜C 5时，未观察到氢键。具有特征性的（对于二吡啶酮），10-氧代-二吡啶酮酸（1 – 6）及其相应的酯（1e - 6e）在促进氢键的溶剂中仍为单体。
• Hydrogen-Bonded Dimers in Dipyrrinones and Acyldipyrrinones
  作者：Michael T. Huggins、David A. Lightner

  DOI：10.1007/s007060170131

  日期：2001.2.15

  as determined by analysis of variable temperature 1H NMR data. In contrast, when the 9-acyl group is replaced by formyl or when the acyl group is fixed in a syn orientation to the pyrrole NH, the dipyrrinone is strongly prone to dimerization in CHCl3.

   9-酰基-二吡咯烷酮9-丁酰基-2,3,7,8-四甲基-（10 H ）-二吡喃-1-酮的晶体结构测定 表明存在分子间氢键合的二聚体。然而，在CHCl 3溶液中，颜料是单体的，如通过蒸气压渗透压测量法测定的。在C（8），9酰基dipyrrinone仅表现出弱的倾向，在CHCl形成二聚体缺少的烷基3（ ķ 甲 〜60  中号 -1如通过可变温度的分析测定）1 H NMR数据。相反，当9-酰基被甲酰基取代时或当酰基固定在 合成物中时 在吡咯NH的方向上，二吡啶酮在CHCl 3中强烈倾向于二聚。
• Stereochemistry and Conformational Analysis of Hemirubin
  作者：Michael T. Huggins、David A. Lightner

  DOI：10.1016/s0040-4020(00)00087-9

  日期：2000.3

  Intramolecularly hydrogen-bonded analogs of the natural bile pigment, bilirubin, are very scarce. Nuclear Overhauser effect NMR studies of the newest analog, a hemirubin (1), confirms intramolecular hydrogen bonding and a ridge-tile-shaped conformation. H-1 NMR studies of 1 at sufficiently low temperatures detect conformational enantiomerization, for which an activation barrier of Delta G(double dagger)similar to 16 kcal/mol at 25 degrees C in CDCl3 has been estimated. Evidence for the presence of dimeric association at low temperatures or high concentrations of 1 is found by the appearance of new sets of resonances, data from which may be used to calculate: Delta G degrees(298) (K) + 3.4 kca/mol, Delta H degrees - 5.6 kcal/mol and Delta S degrees -30.3 cal/deg/mol. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Amide–Amide Hydrogen Bonding. Semirubin Amides
  作者：Nicholas T. Salzameda、David A. Lightner

  DOI：10.1007/s00706-005-0433-5

  日期：2006.3

  Semirubins are analogs for one-half of the bilirubin structure and capable of intramolecular hydrogen bonding. Semirubin amides of ammonia and primary amines are also capable of intramolecular hydrogen bonding. From a combination of spectroscopic methods (H-1 NMR, NOE, and VPO), the primary amide is found to engage very effectively in intramolecular hydrogen bonding. The secondary and tertiary amides engage in both intramolecular (i) and intermolecular (ii) hydrogen bonding: N-methyl (i, monomer + ii, dimer), N-tert-butyl (ii, dimer), N,N-diethyl (i, monomer + ii, dimer). With an oxo-group at C(10), all of the amides are monomeric and most engage in intramolecular hydrogen bonding.