trans-isohumulone | 467-72-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: trans-isohumulone
• 英文别名: trans-iso-n-humulone；cis-isohumulone；isohumulone；(4S)-3,4r-dihydroxy-2-isovaleryl-5t-(3-methyl-but-2-enyl)-4-(4-methyl-pent-3-enoyl)-cyclopent-2-enone；(4S)-3,4r-Dihydroxy-2-isovaleryl-5t-(3-methyl-but-2-enyl)-4-(4-methyl-pent-3-enoyl)-cyclopent-2-enon；trans-Isohumolon；(4S,5S)-3,4-dihydroxy-2-(3-methylbutanoyl)-5-(3-methylbut-2-enyl)-4-(4-methylpent-3-enoyl)cyclopent-2-en-1-one
• CAS: 467-72-1
• 化学式: C₂₁H₃₀O₅
• 分子量: 362.466
• InChiKey: QARXXMMQVDCYGZ-QVKFZJNVSA-N

物化性质

• 沸点：
  530.5±50.0 °C(Predicted)
• 密度：
  1.135±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  91.7
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  trans-isohumulone 在 水 作用下， 以 aq. phosphate buffer 、 乙醇 为溶剂， 反应 168.0h， 生成 4-hydroxy-trans-alloisohumulone
  参考文献：
  名称：

  Oxidation of Isohumulones Induces the Formation of Carboxylic Acids by Hydrolytic Cleavage

  摘要：

  The degradation of isohumulones in mechanistic experiments was investigated. Incubation of trans-isohumulone in the presence of L-proline led to the formation of carboxylic acids and their corresponding proline amides. In the context of isohumulones unknown amides were verified first in model incubations and then in beer for the first time by comparison with authentic reference standards via LC-MS analyses. Carboxylic acids and amides were formed preferably under oxidative conditions and increasing pH. Stable isotope experiments excluded the incorporation of molecular oxygen into carboxylic acids, strongly indicating a hydrolytic mechanism via beta-dicarbonyl cleavage. The proposed mechanism includes oxidation and thereby incorporation of molecular oxygen to the isohumulone ring structure followed by hydrolytic cleavage leading to acids and amides.

  DOI：

  10.1021/jf501826h
• 作为产物：
  描述：

  律草酮 以 甲醇 为溶剂， 生成 trans-isohumulone
  参考文献：
  名称：

  Oxidation of Isohumulones Induces the Formation of Carboxylic Acids by Hydrolytic Cleavage

  摘要：

  The degradation of isohumulones in mechanistic experiments was investigated. Incubation of trans-isohumulone in the presence of L-proline led to the formation of carboxylic acids and their corresponding proline amides. In the context of isohumulones unknown amides were verified first in model incubations and then in beer for the first time by comparison with authentic reference standards via LC-MS analyses. Carboxylic acids and amides were formed preferably under oxidative conditions and increasing pH. Stable isotope experiments excluded the incorporation of molecular oxygen into carboxylic acids, strongly indicating a hydrolytic mechanism via beta-dicarbonyl cleavage. The proposed mechanism includes oxidation and thereby incorporation of molecular oxygen to the isohumulone ring structure followed by hydrolytic cleavage leading to acids and amides.

  DOI：

  10.1021/jf501826h

文献信息

• The photochemistry of <i>trans</i>-isohumulone, a bitter flavouring component of beer
  作者：Alan C Weedon、John S Morrison

  DOI：10.1139/v08-072

  日期：2008.8.1

  Methanolic solutions of trans-isohumulone (2), a major bitter flavouring component in beer, were irradiated with UV light of 313 nm wavelength and yielded four primary products containing an enolized cyclic β-triketone moiety: cis-isohumulone (3), humulone (1), dehydro-isohumulone (7), and dehydro-humulinic acid (5). The last of these products results from loss of the 4-methyl-3-pentenoyl side chain of trans-isohumulone. Nine volatile products derived from this side chain were identified and quantitated. The identifications of all photoproducts were confirmed by independent preparation of authentic samples. No evidence of either intramolecular or intermolecular 2+2 cyclo-addition was observed. This work clarifies previous contradictory reports of the products of isohumulone photolysis and provides an example of unexpected photochemistry of an alkenyl-substituted enolized cyclic β-triketone.Key words: trans-isohumulone, photo-degradation, cyclic β-triketone.

  反式-异胡麻酮（2）是啤酒中的一种主要苦味香料成分，其甲醇溶液经波长为 313 纳米的紫外线照射后，产生了四种含有烯醇化环β-三酮分子的初级产品：顺式-异胡麻酮（3）、胡麻酮（1）、脱氢-异胡麻酮（7）和脱氢-胡麻酸（5）。最后一种产品是反式-异胡柚酮的 4-甲基-3-戊烯酰侧链脱落后产生的。从该侧链衍生出的九种挥发性产物已被鉴定和定量。所有光反应产物的鉴定结果都已通过独立制备真实样品得到证实。没有观察到分子内或分子间 2+2 环加成的证据。这项研究澄清了之前关于异胡麻酮光解产物的相互矛盾的报道，并提供了一个烯基取代烯醇化环β-三酮的意想不到的光化学实例。
• METHODS OF SYNTHESIZING ALPHA ACIDS AND SUBSTANTIALLY ENANTIOMERICALLY PURE COMPOSITIONS THEREOF
  申请人：KINDEX PHARMACEUTICALS, INC.

  公开号：US20150197472A1

  公开（公告）日：2015-07-16

  Methods of synthesizing a cis 3,4-dihydroxy-2-(3-methylbutanoyl)-5-(3-methylbutyl)-4-(4-methylpentanoyl)cyclopent-2-en-1-one (“KDT500”) derivative are provided. Such methods may be used to synthesize any desired KDT derivative. In one embodiment, the KDT500 derivative is KDT501.

  提供了合成顺式3,4-二羟基-2-(3-甲基丁酰基)-5-(3-甲基丁基)-4-(4-甲基戊酰基)环戊-2-烯-1-酮（“KDT500”）衍生物的方法。这些方法可用于合成任何所需的KDT衍生物。在一个实施例中，KDT500衍生物是KDT501。
• A Kinetic Study on the Isomerization of Hop α-Acids
  作者：Barbara Jaskula、Pawel Kafarski、Guido Aerts、Luc De Cooman

  DOI：10.1021/jf8004965

  日期：2008.8.1

  In this article, a detailed study on hop alpha-acid isomerization kinetics is presented. Because of the complex wort matrix and interfering interactions occurring during real wort boiling (i.e., trub formation and alpha-acids/iso-alpha-acids complexation), this investigation on alpha-acid isomerization kinetics was performed in aqueous buffer solution as a function of time (0-90 min) and heating temperature

  在本文中，对啤酒花α-酸异构化动力学进行了详细研究。由于麦芽汁基质复杂，并且在真正的麦芽汁煮沸过程中发生干扰相互作用（即t形成和α-酸/异α-酸络合），因此对α-酸异构化动力学的研究是在缓冲水溶液中进行的。时间（0-90分钟）和加热温度（80-100摄氏度）。确定了形成单个异α-酸的速率常数和活化能。发现异α-酸的形成遵循一级动力学和阿累尼乌斯行为。注意到形成反式和顺式异构体的活化能不同，形成反式-α-酸的活化能低大约9 kJmol（-1）。
• Structures of Storage-Induced Transformation Products of the Beer’s Bitter Principles, Revealed by Sophisticated NMR Spectroscopic and LC–MS Techniques
  作者：Daniel Intelmann、Grit Kummerlöwe、Gesa Haseleu、Nina Desmer、Kerstin Schulze、Roland Fröhlich、Oliver Frank、Burkhard Luy、Thomas Hofmann

  DOI：10.1002/chem.200902058

  日期：2009.12.7

  exclusively, not the cis‐iso‐α‐acids, were found to be degraded upon storage of beer, the key transformation products formed exclusively from the trans isomers in beer are not known. In the present study, suitable model experiments followed by LC–MS/MS and sophisticated NMR spectroscopic experiments, including the measurement of residual dipolar couplings (RDCs) in gel‐based alignment media as well as a novel

  除了令人讨厌的香气发生不良变化外，苦味的强度显着降低以及味道转变为挥之不去的刺鼻苦味，长期以来一直被认为是啤酒的货架期限制因素。多项研究表明，啤酒的老化会导致顺式和反式-异α-酸的总量减少，这是众所周知的啤酒苦味原理。尽管发现在啤酒储存时会专门降解反式-异α-酸，而不是顺式异-α-酸，但关键的转化产物完全是由反式形成的啤酒中的异构体未知。在本研究中，进行合适的模型实验，然后进行LC-MS / MS和复杂的NMR光谱实验，包括在基于凝胶的取向介质以及新型宽带和B 1场补偿后的残留偶极耦合（RDC）的测量令人难以置信的自然丰度双量子转移实验（INADEQUATE）脉冲序列使人们得以鉴定出一系列先前未知的反式异特异异α-酸转化产物，分别是三环香豆酚，三环香豆烯，异三环香豆素，四环香豆酚和表四环香豆酚。这些化合物的HPLC-MS / MS分析显示出上述刺鼻的持久苦味并具有5至70μmolL的阈值浓
• Anti-inflammatory cyclooxygenase-2 selective inhibitors
  申请人：——

  公开号：US20040137096A1

  公开（公告）日：2004-07-15

  Disclosed is a novel anti-inflammatory pharmaceutical composition that exhibits potent and selective inhibition of the cycloooxygenase-2 (COX-2) enzyme. The formulation consists of a hops extract that exhibits COX-2 selectivity as defined by dividing the IC50 COX-2/IC50COX-1 concentrations that are determined by testing with the William Harvey Whole Blood Assay (WHMA), and falls in the range of 0.011 to 0.2. Such compositions may also optionally contain high levels of alpha acids and low levels of beta acids, some flavonoid compounds, and virtually no essential oils. Such compositions are useful for treating conditions that manifest as inflammatory pain, or are impacted by the COX-2 enzyme. The recited compositions are particularly beneficial for treating osteoarthritis and rheumatoid arthritis, and can be used for chronic pain with reduced gastric side-effects.

  本发明公开了一种新型抗炎药物组合物，它对环氧化酶-2（COX-2）酶具有强效的选择性抑制作用。该制剂由啤酒花提取物组成，其 COX-2 选择性是通过威廉-哈维全血测定法（WHMA）测试确定的 IC50 COX-2/IC50COX-1 浓度相除来定义的，范围在 0.011 至 0.2 之间。此类组合物还可选择含有高浓度的α酸和低浓度的β酸、一些类黄酮化合物，几乎不含精油。此类组合物适用于治疗表现为炎症性疼痛或受 COX-2 酶影响的病症。所述组合物尤其有利于治疗骨关节炎和类风湿性关节炎，并可用于慢性疼痛，同时减少胃部副作用。