2-异戊烯基-1,4-苯醌 | 5594-02-5

• 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
• 中文名称: 2-异戊烯基-1,4-苯醌
• 英文名称: 2-prenyl-p-benzoquinone
• 英文别名: 2-Prenyl-1,4-benzoquinone；2-(3-methylbut-2-enyl)cyclohexa-2,5-diene-1,4-dione
• CAS: 5594-02-5
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: PJERCKGJJBCWEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  2-异戊烯基-1,4-苯醌 以 乙腈 为溶剂， 反应 24.0h， 以10%的产率得到6-hydroxy-2,2-dimethyl-3‑chromen
  参考文献：
  名称：

  Arnebinones B、D 和 E 的光诱导不可逆分子内质子转移：对苯醌-CH2/CH-π 系统的光烯醇化案例

  摘要：

  已发现Arnebinones B、E 和 D ( 1-3 )对光敏感，在光触发时会产生复杂多样的质子转移产物。1的独特的两步不可逆分子内质子转移产生了五种比例混合物，其中四种具有有趣的双平面手性。通过HPLC监测和DFT计算，首次在同源类二萜中观察和研究了环状双键前所未有的定向差向异构化平衡。A“对苯醌-CH 2结构中的/CH-π”部分是这种光烯醇化反应发生的共同关键特征。分析了这种光诱导的不可逆质子转移反应的产物转化过程和普遍性，并分析了阿尼比酮 B、D 和 E 及其光反应产物的细胞毒活性。

  DOI：

  10.1021/acs.jnatprod.1c00830
• 作为产物：
  描述：

  4-(二甲基氨基甲基)苯酚 在 三异辛胺 disodium hydrogenphosphate 、 sodium dihydrogenphosphate 、 lithium tetrachloropalladate 、 potassium nitrososulfonate 、 氨 、 sodium acetate 、 lithium 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 52.58h， 生成 2-异戊烯基-1,4-苯醌
  参考文献：
  名称：

  Synthesis of prenylated quinones by the oxidative degradation approach. Birch vs vinylogous Birch hydrogenolysis (BIHY vs VIBIHY) in controlling 2.DELTA. stereochemistry of the prenyl chain

  摘要：

  Two novel approaches toward prenylated quinones are described. The first (route A) involves the following three basic operations: (a) construction of a 4-hydroxybenzylamine carrying a tertiary allyl alcohol (cinnamyl alcohol) side chain of appropriate length (C5, C-10, etc), followed by (b) vinylogous Birch reductive cleavage with concomitant isomerization of the double bond (vinylogous Birch hydrogenolysis, VIBIHY) and (c) Fremy's salt oxidative degradation of the resulting prenylated phenolic benzylamines to the corresponding quinones. The required phenolic cinnamyl alcohols were successfully synthesized by means of two alternative routes, namely: (1) cyclopalladation of phenolic benzylamines followed by ketovinylation and treatment of the resulting beta-aryl substituted alpha,beta unsaturated ketone with methyllithium and (2) reaction of the dilithio derivatives of the appropriate phenolic benzylamine with the desired alpha,beta unsaturated aldehyde, followed by acid rearrangement. The key feature of this approach, namely, the so-called vinylogous Birch hydrogenolysis (VIBIHY) takes place very efficiently on the phenolic tertiary cinnamyl alcohol stage, provided that the reaction (Li/NH3) is carried out on its bissilylated derivative. Unfortunately, its stereochemistry cannot be properly controlled, as it leads to the formation of ca 2.5:1 (E/Z) mixture of (DELTA2) alkenes. The second generation approach (route B), which solves this problem, requires the following: (a) preparation of a 4-hydroxybenzylamine carrying a 3-methyl-2-buten-1-ol (dimethylallyl alcohol) side chain, or higher homologue, followed by (b) Birch hydrogenolysis (BIHY) and step c above. The key Birch hydrogenolysis takes place with almost complete control of the stereochemically labile DELTA2 double bond, thereby making this approach the one of choice for the synthesis of isoprenyl benzoquinones.

  DOI：

  10.1021/jo00054a012

文献信息

• [EN] SURFACTANTS<br/>[FR] TENSIOACTIFS
  申请人：AMYRIS INC

  公开号：WO2012103156A1

  公开（公告）日：2012-08-02

  This application relates to derivatives of hydrocarbon terpenes (e.g., myrcene or farnesene), to methods of making the derivatives, and to the use of the derivatives as surfactants.

  这个应用涉及到碳氢化合物萜类化合物（例如，肉豆蔻烯或芬尼烯）的衍生物，制备这些衍生物的方法，以及将这些衍生物用作表面活性剂的用途。
• Catalytic Electrophilic Alkylation of<i>p</i>-Quinones through a Redox Chain Reaction
  作者：Xiao-Long Xu、Zhi Li

  DOI：10.1002/anie.201702885

  日期：2017.7.3

  Allylation and benzylation of p‐quinones was achieved through an unusual redox chain reaction. Mechanistic studies suggest that the existence of trace hydroquinone initiates a redox chain reaction that consists of a Lewis acid catalyzed Friedel–Crafts alkylation and a subsequent redox equilibrium that regenerates hydroquinone. The electrophiles could be various allylic and benzylic esters. The addition

  对苯醌的烯丙基化和苄基化是通过不寻常的氧化还原链反应实现的。机理研究表明，痕量对苯二酚的存在会引发氧化还原链反应，该反应由路易斯酸催化的Friedel-Crafts烷基化反应和随后的氧化还原平衡而重新生成对苯二酚。亲电子试剂可以是各种烯丙基和苄基酯。Hantzsch酯作为引发剂的添加提高了反应效率。
• Structure-activity relationship studies on thiaplidiaquinones A and B as novel inhibitors of Plasmodium falciparum and farnesyltransferase
  作者：Melissa M. Cadelis、Marie-Lise Bourguet-Kondracki、Joëlle Dubois、Marcel Kaiser、Jean Michel Brunel、David Barker、Brent R. Copp

  DOI：10.1016/j.bmc.2017.06.029

  日期：2017.8

  thiaplidiaquinones A and B and their respective non-natural dioxothiazine regioisomers have been shown to inhibit mammalian and protozoal farnesyltransferase (FTase) with the regioisomers exhibiting activity in the nanomolar range. In order to explore the structure-activity relationship (SAR) of this class of marine natural products, analogues of thiaplidiaquinones A and B and their regioisomers were

  海洋类萜，类噻二醌A和B以及它们各自的非天然二氧噻吩嗪区域异构体已显示出抑制哺乳动物和原生动物的法呢基转移酶（FTase），其区域异构体在纳摩尔范围内具有活性。为了探索此类海洋天然产物的结构-活性关系（SAR），合成了噻二苯醌A和B及其区域异构体的类似物，其侧链中存在异戊二烯单元的数目发生变化，从而得到异戊二烯基和法呢基类似物。发现先前报道的香叶基系列化合物是最有效的FTase抑制剂，紧随其后的是新的法呢基系列。异戊二烯系列显示出最有效的抗疟原虫活性，但该系列也具有最强的细胞毒性。全面的，14也表现出低细胞毒性，将其鉴定为值得进一步探索的支架。
• Avarol derivatives as competitive AChE inhibitors, non hepatotoxic and neuroprotective agents for Alzheimer’s disease
  作者：Giuseppina Tommonaro、Nuria García-Font、Rosa Maria Vitale、Boris Pejin、Carmine Iodice、Sixta Cañadas、José Marco-Contelles、María Jesús Oset-Gasque

  DOI：10.1016/j.ejmech.2016.06.036

  日期：2016.10

  inhibitory activity. The multiple pharmacological properties of avarol, thio-avarol and/or their derivatives prompted us to continue the in vitro screening, focusing on their AChE inhibitory and neuroprotective effects. Due to the complex nature of Alzheimer’s disease (AD), there is a renewed search for new, non hepatotoxic anticholinesterasic compounds. This paper describes the synthesis and in vitro biological

  Avarol是一种海洋倍半萜类对苯二酚，以前从海洋海绵Dysidea avara Schmidt（Dictyoceratida）中分离出来，具有抗炎，抗肿瘤，抗氧化剂，抗血小板，抗HIV和抗银屑病的功效。最近的发现表明，一些硫代avarol衍生物表现出乙酰胆碱酯酶（AChE）抑制活性。阿瓦洛尔，硫代avarol和/或其衍生物的多种药理特性促使我们继续进行体外筛选，重点研究其对AChE的抑制和神经保护作用。由于阿尔茨海默氏病（AD）的复杂性质，人们正在重新寻找新的，无肝毒性的抗胆碱酯酶化合物。本文介绍了其合成及体外作用生物学评估的Avarol-3'-thiosalicylate（TAVA）和thiosalycil-prenyl- hydroquinones（TPHs）作为非肝毒性抗胆碱能药物，对寡霉素A /鱼藤酮和冈田霉素诱导的SHSY5Y人神经母细胞瘤细胞活力下降具有良好的神经保护作用。酸
• Allylation of quinones by allylic indium reagents
  作者：Shuki Araki、Nobuhito Katsumura、Yasuo Butsugan

  DOI：10.1016/0022-328x(91)83277-b

  日期：1991.9

  sigmatropic rearrangement. Substituted quinones reacted with allylindium reagent giving excellent yields of allyquinols, whereas with prenylindium and geranylindium reagents, trisubstituted quinones gave diprenylcyclohexene-1,4-diones and 2,3-disubstituted quinones gave mixtures of prenylhydroquinones and diprenylcyclohexene-1,4-diones. In the prenylation of haloquinones, 1,2-addition, [3,3] sigmatropic rearrangement

  研究了烯丙基倍半卤化物对各种醌的烯丙基化作用。未取代的p的反应苯甲酸醌与烯丙基，pre烯丙基和香叶菊醇试剂在用氧化银氧化后，以良好的收率得到相应的烯丙基化的醌。这些反应似乎是通过在γ-碳上添加1,2-烯丙基铟试剂然后进行[3,3]σ重排而进行的。取代的醌与烯丙基dium试剂反应可得到优异的烯丙基醇收率，而与戊炔醇和ger草醇dium试剂反应，三取代醌可生成二戊烯基环己烯-1,4-二酮，2,3-二取代醌可得到异戊二烯基氢醌和二戊烯基环己烯-1,4-二酮的混合物。在卤代醌的异戊烯基化中，依次产生1,2-加成，[3,3]σ重排和消除铟（III）卤化物，生成异戊烯基醌。2-羟基和2-甲氧基-1，