8-des-ethylkryptopyrromethenone | 66585-50-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 8-des-ethylkryptopyrromethenone
• 英文别名: 5-(3,5-dimethyl-pyrrol-2-ylmethylene)-4-ethyl-3-methyl-1,5-dihydro-pyrrol-2-one；(5Z)-5-[(3,5-dimethyl-1H-pyrrol-2-yl)methylidene]-4-ethyl-3-methylpyrrol-2-one
• CAS: 66585-50-0
• 化学式: C₁₄H₁₈N₂O
• 分子量: 230.31
• InChiKey: GHKCBXUDTDLRRM-QPEQYQDCSA-N

物化性质

• 沸点：
  463.5±45.0 °C(predicted)
• 密度：
  1.113±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  8-des-ethylkryptopyrromethenone 在 sodium tetrahydroborate 、 三氯化铝 、 三氟化硼乙醚 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (Z,Z,Z)-1,19-Dioxo-2,7,8,12,13,18-hexamethyl-3,17-diethyl-1,19,22,24-tetrahydro-21H-bilin
  参考文献：
  名称：

  Efficient Routes to ω-Chloroalkyl Bilirubins and C12-N22 Bridged Biliverdins

  摘要：

  omega -Chloroalkyl biliverdins, prepared in three steps from 8-unsubstituted dipyrrinones in 70-80% overall yields, were reduced by sodium borohydride to provide the corresponding omega -chloroalkyl bilirubins in high yields. Upon treatment of the omega -chloroalkyl biliverdins with sodium hydroxide in ethanol, C12-N22 bridged biliverdins were obtained in high yields.

  DOI：

  10.1007/s007060170084
• 作为产物：
  描述：

  、 5,2'-bi<2-bromo-3,6-dimethylthieno<3,2-b>thiophene> 在 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 作用下， 以 乙醚 为溶剂， 反应 48.0h， 以2.3%的产率得到8-des-ethylkryptopyrromethenone
  参考文献：
  名称：

  3,6-二甲基噻吩并[3,2- b ]噻吩和3,6-二甲基硒代[3,2- b ]硒烯的二聚体，三聚体和四聚体的合成与表征

  摘要：

  最近已经容易获得3，6-二甲基噻吩并[3，2- b ]噻吩（1a）和3，6-二甲基硒代[3，2- b ]硒烯（1b）。从这些化合物开始，令人满意地合成了它们的二聚体，三聚体和四聚体，其中每个噻吩并噻吩单元和硒基硒烯单元均在其α位置连接，并通过UV / Vis光谱和CV氧化电势数据进行了表征。的二聚物的X射线单晶结构分析图1b显示，两名selenoloselenophene单位是与69.5大dibedral角°与扭转小号-顺式结构。

  DOI：

  10.1016/0040-4020(95)00854-3

文献信息

• Conformational analysis of symmetric bilirubin analogues with varying length alkanoic acids. Enantioselectivity by human serum albumin
  作者：Francesc R. Trull、Richard V. Person、David A. Lightner

  DOI：10.1039/a604897h

  日期：——

  Symmetric analogues of mesobilirubin-XIIIα, with propionic acid groups shortened to acetic and lengthened to undecanoic, exhibit induced circular dichroism (ICD) in pH 7.5 buffered aqueous [1–5% dimethyl sulfoxide (DMSO) co-solvent] solution in the presence of human serum albumin (HSA). The CD spectra exhibit bisignate Cotton effects with ωεmax434 = +87, ωεmax389 = -54 (acetic), ωεmax436 = +37, ωεmax388 = -42 (propionic), ωεmax420 = -15, ωεmax370 = +8 (butyric), [ωεmax433 = -97, ωεmax388 = +89 in 30% aqueous DMSO], ωεmax449 = +6, ωεmax397 = -46 (valeric), ωεmax440 = +57, ωεmax392 = -96 (caproic), ωεmax440 = +15, ωεmax393 = -21 (caprylic) and ωεmax448 = +18, ωεmax385 = -31 (undecanoic). These values result from chromophore conformation (i.e. exciton coupling) and enantioselectivity by the protein (i.e. preference for a given bilirubin enantiomer). The UV–VIS spectra of the acetic to butyric, caprylic and undecanoic complexes are similar in shape, with a shoulder in addition to the main band, and reminiscent of that of the bilirubin-IXα HSA complex, indicating an analogous, folded conformation for all. The spectra of the valeric and caproic complexes, in turn, are more symmetric and red-shifted, suggesting a more extended conformation. Experimental CD values in each of these two series have been interpreted in terms of the different enantioselectivity by the protein, with the right handed acetic and caproic enantiomers fitting best the protein binding site (ωωε ca. 150) and the protein showing a lower preference for the right handed propionic enantiomer (ωωε ca. 80) and even lower for the right handed valeric, caprylic and undecanoic enantiomer (ωωε ca. 50), but left handed butyric enantiomer (ωωε ca. 24).The differences observed in the UV–VIS spectra of each complexed (in aqueous buffer) vs. uncomplexed pigment (in MeOH), i.e. spectral shifts (7–11 nm for acetic to butyric and undecanoic, 12 nm for valeric and 16–18 nm for caproic and caprylic) and shape (reduction from two to one transition for valeric and caproic—but not for the rest) reflect the changes in pigment conformation induced by the protein. These changes are especially noticeable for the caproic and caprylic analogues.Taken collectively, the present results indicate that the length of the alkanoic acid chains at C8 and C12 is essential for determining not only the pigment conformation, but also the enantioselectivity by the protein (through specific pigment–protein interactions) and agree with previous suggestions that these interactions may involve (at least) one salt linkage and hydrogen bonding.The effect upon the ICD of each rubin-HSA complex of other parameters such as the percentage of DMSO used as carrier in the solution and the nature of the buffer has also been investigated. Surprisingly, an increase in the amount of DMSO from 3–30% results in dramatic changes in the observed CD of the butyric and (to a lesser extent) propionic, undecanoic complexes. These have been interpreted in terms of selective changes in the tertiary structure of the protein.

  对称的美索胆红素-XIIIα类似物，其丙酸基团缩短至醋酸或延长至十一酸，显示出在pH 7.5缓冲的水溶液中（含1-5%二甲基亚硫酰胺（DMSO）共溶剂）在存在人血清白蛋白（HSA）时的诱导圆二色性（ICD）。CD光谱显示出双标志的Cotton效应，具体为： ωÎεmax434 = +87，ωÎεmax389 = -54（醋酸），ωÎεmax436 = +37，ωÎεmax388 = -42（丙酸），ωÎεmax420 = -15，ωÎεmax370 = +8（丁酸），[ωÎεmax433 = -97，ωÎεmax388 = +89（30%水-混合DMSO）]，ωÎεmax449 = +6，ωÎεmax397 = -46（戊酸），ωÎεmax440 = +57，ωÎεmax392 = -96（癸酸），ωÎεmax440 = +15，ωÎεmax393 = -21（辛酸）以及ωÎεmax448 = +18，ωÎεmax385 = -31（十一酸）。这些值源于色素体构象（即激子耦合）和蛋白质的手性选择性（即对特定胆红素对映体的偏好）。醋酸到丁酸、辛酸和十一酸复合物的UV-VIS光谱形状相似，除了主带外还有一个肩带，类似于胆红素-IXα与HSA复合物的特征，表明所有复合物具有类似的折叠构象。而戊酸和癸酸复合物的光谱则更对称且红移，暗示出更扩展的构象。在这两系列中观察到的实验CD值被解释为蛋白质的不同手性选择性，其中右手的醋酸和癸酸对映体最适合蛋白质结合位点（ωωε约为150），而蛋白质对右手的丙酸对映体的偏好较低（ωωε约为80），对右手的戊酸、辛酸和十一酸对映体的偏好更低（ωωε约为50），但对左手的丁酸对映体的偏好则是最低的（ωωε约为24）。 在水缓冲液中复合（与未复合的色素在甲醇中比较）各复合物在UV-VIS光谱上观察到的差异， 即谱移（醋酸到丁酸和十一酸为7-11 nm，戊酸为12 nm，癸酸和辛酸为16-18 nm）和形状（戊酸和癸酸由两个跃迁减少为一个——而其他则没有）反映了蛋白质诱导的色素构象变化。这些变化在癸酸和辛酸的类似物中尤为明显。综合来看，本研究结果表明，C8和C12的烷基酸链长度对于确定色素构象以及蛋白质的手性选择性（通过特定的色素-蛋白质相互作用）至关重要，并且与先前的建议一致，即这些相互作用可能涉及至少一个盐桥和氢键。 还研究了诸如在溶液中作为载体使用的DMSO百分比和缓冲液性质等其他参数对每个红素-HSA复合物ICD的影响。令人惊讶的是，DMSO的含量从3%增加到30%时，观察到的丁酸和（在较小程度上）丙酸、十一酸复合物的CD发生了剧烈变化。这被解释为蛋白质三级结构的选择性变化。
• Synthesis and properties of a lipid bilirubin analog
  作者：Thomas Thyrann、David A. Lightner

  DOI：10.1016/0040-4020(95)00924-8

  日期：1996.1

  A new synthesis of dipyrrinone acids is described from the known dipyrrinone, 3-ethyl-2,7,9-trimethyl-(10H)-dipyrrin-1-one (11) with a free β-position. In six steps, 11 was converted to 5 with a C20 eicosanoic acid chain, and 5 was converted to a lipid analog (1) of bilirubin with eicosanoic acids replacing propionic at carbons C(8) and C(12). Unlike bilirubins with short acid chains, 1 behaves much

  由已知的二吡啶酮，具有游离β-位的3-乙基-2,7,9-三甲基-（10 H）-二吡喃-1-酮（11）描述了二吡啶酮酸的新合成。在六个步骤中，将11个碳20二十烷酸链转化为5，将5转化为胆红素的脂质类似物（1），其中二十碳酸取代了碳C（8）和C（12）上的丙酸。与具有短酸链的胆红素不同，1的行为与其二甲基酯（2）非常相似，并且可能采用螺旋形而不是特征性的岭-瓦构象。1与奎宁在CHCl 3中的圆二色性给出类似胆红素的双信号棉花效应：Δε438max⁡+ 18，Δε390max⁡−24 。
• Strongly fluorescent dipyrrinones-substituent effects
  作者：Stefan E. Boiadjiev、David A. Lightner

  DOI：10.1002/jhet.5570410631

  日期：2004.11

  Bright yellow N,N'-carbonyl-bridged dipyrrinones (substituted 3H,5H-dipyrrolo[1,2-c:2′,1′-f]pyrimidine-3,5-diones) were synthesized by reaction of the parent dipyrrinone with carbonyldiimidazole. Their solutions in organic solvents fluoresced strongly, with fluorescent quantum yields (ϕF)0.32-0.92.

  通过母体反应合成了亮黄色的N，N'-羰基桥联的二吡啶酮（取代的3 H，5 H -dipyrrolo [1,2- c：2'，1'- f ]嘧啶-3,5-二酮）。哌啶酮与羰基二咪唑。他们在有机溶剂中的溶液发出强烈的荧光，其荧光量子产率为（F）0.32-0.92。
• Synthesis and Spectroscopic Properties of a New Class of Strongly Fluorescent Dipyrrinones
  作者：Justin O. Brower、David A. Lightner

  DOI：10.1021/jo0110505

  日期：2002.4.1

  A new, highly fluorescent (Phi(F) > or = 0.8) chromophore has been synthesized in one step from dipyrrinones by reaction with N,N-carbonyldiimidazole to form the 3H,5H-dipyrrolo[1,2-c:2',1'-f]pyrimidine-3,5-dione nucleus.

  通过与N，N-羰基二咪唑反应形成3H，5H-dipyrrolo [1,2-c：2'，由二吡啶酮一步合成了一种新型的高荧光（Phi（F）>或= 0.8）发色团， 1'-f]嘧啶-3,5-二酮核。
• A linear dichroism study of pyrromethene-, pyrromethenone- and bilatriene-abc-derivatives
  作者：Heinz Falk、G�nther Vormayr、Leon Margulies、Stephanie Metz、Yehuda Mazur

  DOI：10.1007/bf00810076

  日期：——