(E)-3-甲基-4-氧代-2-丁烯酸 | 54168-84-2

• 物质功能分类: 生物化工 - 生化试剂 - 胺、酸和盐
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: (E)-3-甲基-4-氧代-2-丁烯酸
• 中文别名: (E)-3-甲基-4-氧-2-丁烯酸
• 英文名称: (E)-3-methyl-4-oxo-2-butenoic acid
• 英文别名: trans-β-formyl crotonic acid；β-Formyl-cis-croton-saeure；3-Methyl-4-oxo-crotonic acid；(E)-3-methyl-4-oxobut-2-enoic acid
• CAS: 54168-84-2
• 化学式: C₅H₆O₃
• 分子量: 114.101
• InChiKey: VXAWORVMCLXEKH-DUXPYHPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-甲基-4-氧代-2-丁烯酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 14.33h， 生成 (1aα,3aα,5aα,5bβ,7aβ,7bβ,8α,10bR*,10cα)-(+/-)-8-ethenyl-1,1a,2,3,3a,5a,5b,7a,7b,8,9,10c-dodecahydro-3a,8-dimethylcyclopropa<4,4a>phenanthro<9,8-bc:10,1-b'c'>difuran-4,7-dione
  参考文献：
  名称：

  Total Synthesis of (.+-.)-Myrocin C

  摘要：

  A stereoselective total synthesis of racemic myrocin C (1) has been achieved. Initial investigations produced cyclopropane-containing AB sector 22 via intramolecular ester-tethered Diels-Alder reaction of quinone 14 followed by internal alkylation of bromide 19. Although the natural product was not to be obtained through this route, the information garnered from this impetus provided the basis for a strategically improved and ultimately successful synthesis of 1. Thus, intermolecular Diels-Alder reaction of p-benzoquinone with cyclic diene 39 gave endo cycloadduct 41 which could be elaborated to cyclopropane precursors 52 and 99. While a plethora of intramolecular alkylation reactions of derivatives of 52 failed to afford cyclopropane-containing products, a novel organolithium-induced cyclization reaction of 99 did indeed provide key compound 96 via postulated intermediate 100. The resultant functionality in 96 paved the way for a directed intramolecular Diels-Alder annulation of the C-ring and concomitant introduction of the remote quaternary C13 stereocenter (cf. 96 --> 107 --> 108). The tertiary hydroxyl group at C9 was then introduced via epoxidation of 119 followed by overall eliminative ring-opening (123 --> 125 --> 5). The incorporation of the C6 tertiary hydroxyl group was accomplished via oxidation of the enolate derived from 6-desoxymyrocin C (5), yielding racemic 1. Studies on the bioactivation process of 5 and 1 led to support for a hypothesis which emphasized the importance of the C6 hydroxyl group in facilitating cyclopropane-ring-opening possibly through the intermediacy of quinone homomethide 134.

  DOI：

  10.1021/ja00104a002
• 作为产物：
  描述：

  ethyl 4,4-diethoxy-3-methylbut-2-enoate 生成 (E)-3-甲基-4-氧代-2-丁烯酸
  参考文献：
  名称：

  DE1068709

  摘要：

  公开号：

文献信息

• Carotenoids and related compounds. Part XVIII. Synthesis of cis- and di-cis-polyenes by reactions of the Wittig type
  作者：Gerald Pattenden、B. C. L. Weedon

  DOI：10.1039/j39680001984

  日期：——

  Some claims to have achieved “cis-olefination” have been re-examined.

  对已经实现“顺式-烯烃化”的一些主张进行了重新审查。
• Stereospecific synthesis process for tretinoin compounds
  申请人：Deng Qingjun

  公开号：US08835680B1

  公开（公告）日：2014-09-16

  A stereospecific synthesis process for tretinoin compounds comprises the following steps: using substituted triphenyl phosphine salt and β-formyl crotonic acid as raw material to carry out WITTIG reaction under the action of alkali; then adjusting the pH of the reaction liquid to 5-10; adding palladium compound or rhodium compound to carry out isomerization directly and obtain tretinoin compounds with desired configuration. The product yield of the process is high and the intermediate product in the reaction dose not need to be separated. The process is easy to operate and can save the production cost and as well is suitable for industrial production.

  一种用于合成维甲酸类化合物的立体选择性合成过程包括以下步骤：使用取代三苯基膦盐和β-甲酰丙烯酸作为原料，在碱的作用下进行威特希格反应；然后将反应液的pH值调整为5-10；添加钯化合物或铑化合物进行直接异构化，获得具有期望构型的维甲酸类化合物。该过程的产物收率高，反应中间体无需分离。该过程操作简便，可节省生产成本，适用于工业生产。
• A C6, C7 Oxygen Functionalized Intermediate for the Synthesis of Forskolin: Stereochemical Control in an Intramolecular Diels-Alder Reaction
  作者：Frederick E. Ziegler、Burton E. Jaynes、Manohar T. Saindane

  DOI：10.1016/s0040-4039(00)98284-4

  日期：1985.1

  Stereospecific intramolecular Diels-Alder reactions of aldehydes 3a and 3b afford lactones 4 and 5, respectively. The mechanism of the reactions is considered. Lactone 4 is elaborated further to provide acetonide 14b, an important intermediate in an approach to the synthesis of forskolin (1).

  醛3a和3b的立体特异性分子内Diels-Alder反应分别得到内酯4和5。考虑反应的机理。进一步详细说明内酯4，以提供丙酮化物14b，它是合成毛喉素（1）的重要中间体。
• 一种阿维A的中间体的制备方法及其应用
  申请人：重庆华邦胜凯制药有限公司

  公开号：CN114105737A

  公开（公告）日：2022-03-01

  本发明属于化学合成技术领域，具体涉及一种阿维A的中间体的制备方法及其应用。所述制备方法包括：将式V所示的化合物V与卤代乙烯镁反应得式VII所示的阿维A的中间体a，然后将所述化合物VII与三苯基膦及含卤酸、含硫酸、含磷酸的酸中的一种或多种酸反应得到式VIII式的阿维A的中间体b，然后由中间体b制得阿维A。该方法反应过程中使用了乙炔、镁等易燃易爆炸的化学品，也避免了使用贵重金属钯炭，避免使用了毒性较大的溶剂如苯，因此，利于环境保护、人员的健康、安全，而且反应条件温和，反应时间短，收率高。
• STEREOSPECIFIC SYNTHESIS PROCESS FOR TRETINOIN COMPOUNDS
  申请人：Chongqing Huabangshengkai Pharm. Co., Ltd

  公开号：EP2708530B1

  公开（公告）日：2016-08-10