E-3-methyl-2-penten-4-ynal | 74336-72-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: E-3-methyl-2-penten-4-ynal
• 英文别名: 3-methylpent-2-en-4-ynal；(E)-3-methyl-pent-2-en-4-ynal；3-methyl-pent-2-en-4-ynal；3-Methyl-pent-2-en-4-inal；(E)-3-methylpent-2-en-4-ynal
• CAS: 74336-72-4
• 化学式: C₆H₆O
• 分子量: 94.113
• InChiKey: IFWPFCCGBZEOPS-GQCTYLIASA-N

物化性质

• 沸点：
  127.8±23.0 °C(Predicted)
• 密度：
  0.921±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  E-3-methyl-2-penten-4-ynal 在 sodium carbonate 、 硫酸肼 作用下， 以 乙醇 为溶剂， 生成 bis-(3-methyl-pent-2-en-4-ynylidene)-hydrazine
  参考文献：
  名称：

  The Synthesis of Tetrakisdehydrotetraazaannulenes. Tetramethyl[32]-,[40]-, and Tetrabenzo[32]annulene

  摘要：

  含有末端乙炔的共轭醛分别转化为相应的共轭吖嗪6a-c和8a-c。尝试了这些吖嗪的氧化偶联。吖嗪6b、6c和8b分别提供相应的环状二聚体9、10和11。 1H NMR 谱的检查表明四氮杂环烯是阿托性的。

  DOI：

  10.1246/bcsj.51.2112
• 作为产物：
  描述：

  5-乙炔基-5-甲基-2,3-二氢-1,4-二氧杂卓 在 盐酸 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以50%的产率得到E-3-methyl-2-penten-4-ynal
  参考文献：
  名称：

  A Novel Aldol Condensation Alternative:α,β-Unsaturated Aldehydes from 3-Hydroxy-1-alkynes via Dihydrodioxepins

  摘要：

  The controlled aldol condensation between an aliphatic ketone and an acetaldehyde equivalent remains a challenge. One solution to this evergreen problem consists of the nucleophilic addition of acetylene to the ketone and the subsequent isomerization of the resulting 3-hydroxy-1-alkyne to the corresponding 2-alkenal. So far, however, the latter step could only be executed with acid-insensitive substrates. We now present a milder, three-step method which extends the scope of the procedure considerably. In the first step, the 3-hydroxy-1-alkynes are converted into 2-propynyl ethylene glycol monoethers; these then undergo base-catalyzed cyclization to give the dihydro-1,4-dioxepins, which are hydrolyzed in acidic medium in the third and final step.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1738::aid-chem1738>3.0.co;2-p

文献信息

• Synthesis of C6 Acetylenic Alcohols
  作者：Shuai Pu、Ai Gui Zhang、Shao Feng Zhang、Yu Liang Wang

  DOI：10.14233/ajchem.2015.17094

  日期：——

  C6 acetylenic alcohols are important intermediates in the synthesis of Vitamin A and carotenoids. New synthesis methods of the C6 acetylenic alcohols and their four derivatives are reported. These designed synthesis methods are useful improvement to the present methodologies. Structures of these compounds are confirmed by 1H NMR, IR and mass spectra analysis.

  C6炔醇是合成维生素A和类胡萝卜素的重要中间体。报道了C6炔醇及其四种衍生化合物的新的合成方法。这些设计的合成方法对当前的方法学是有益的改进。通过1H NMR、IR和质谱分析确认了这些化合物的结构。
• Synthesen in der Carotinoid-Reihe. 11. Mitteilung. α,β-Ungesättigte Carbonylverbindungen aus Allylhalogeniden mittels Nitroparaffinen
  作者：M. Montavon、H. Lindlar、R. Marbet、R. Rüegg、G. Ryser、G. Saucy、P. Zeller、O. Isler

  DOI：10.1002/hlca.19570400516

  日期：——

  Starting with linaloöl, citral has been prepared by reacting a geranyl halide with alkali salts of nitro paraffines. By the same method other α,β-unsaturated carbonyl compounds were obtained, which are useful intermediates for the synthesis of carotenoids.

  从利那洛尔开始，柠檬醛是通过使香叶基卤化物与硝基石蜡的碱金属盐反应制得的。通过相同的方法，获得了其他α，β-不饱和羰基化合物，它们是合成类胡萝卜素的有用中间体。
• Synthesis and Rearrangement of 3-Methyl-1,4-pentadiyne-3-ol
  作者：Dominik Buser、Horst Pauling、Andreas Thum、Werner Bonrath

  DOI：10.3390/70300341

  日期：——

  An efficient synthesis and rearrangement of 3-methyl-1,4-pentadiyne-3-ol (1) using perrhenate- and Mo(VI)-catalysts is reported. The by-products 3,6-dimethyl-1,4,7-octatriyne-3,6-diol (2) and 3-ethynyl-5-methyl-1,6-heptadiyne-3,5-diol (3) were isolated and spectroscopically characterized. A possible reaction mechanism for the formation of the byproducts is discussed.

  报道了一种使用过铼酸盐和钼（VI）催化剂对3-甲基-1,4-戊二炔-3-醇（1）进行高效合成和重排的方法。分离并光谱表征了副产物3,6-二甲基-1,4,7-辛三炔-3,6-二醇（2）和3-乙炔基-5-甲基-1,6-庚二炔-3,5-二醇（3）。讨论了副产物形成的可能反应机理。
• Oxovanadium Complex-Catalyzed Aerobic Oxidation of Propargylic Alcohols
  作者：Yasunari Maeda、Nobuyuki Kakiuchi、Satoshi Matsumura、Takahiro Nishimura、Takashi Kawamura、Sakae Uemura

  DOI：10.1021/jo025918i

  日期：2002.9.1

  A catalytic system consisting of vanadium oxyacetylacetonate [VO(acac)(2)] and 3 A molecular sieves (MS3A) in acetonitrile works effectively for the aerobic oxidation of propargylic alcohols [R(1)CH(OH)Ctbd1;CR(2)] to the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Although the reactivity of alpha-acetylenic alkanols (R(1) = alkyl) is lower compared to that of

  乙腈中由氧乙酰丙酮钒[VO（acac）（2）]和3 A分子筛（MS3A）组成的催化体系可有效地进行丙醇的需氧氧化[R（1）CH（OH）Ctbd1; CR（2）在分子氧的大气压下将其转化为相应的羰基化合物。尽管与R（1）=芳基，烯基和炔基的醇相比，α-炔属烷醇（R（1）=烷基）的反应性较低，但使用VO（hfac）（2）作为催化剂在这些情况下，添加六氟乙酰丙酮可提高产品收率。对于这种氧化，已经提出了涉及钒（V）醇化物和从中消除β-氢的催化循环。
• Regio- and Stereoselective Synthesis of Vinylallenes by 1,5-(SN′′)-Substitution of Enyne Acetates and Oxiranes with Organocuprates
  作者：Martin Purpura、Norbert Krause

  DOI：10.1002/(sici)1099-0690(199901)1999:1<267::aid-ejoc267>3.0.co;2-v

  日期：1999.1

  substitution patterns react with organocuprates regioselectively under 1,5-(SN2′′)-substitution to provide vinylallenes 11 and 12. With lithium dimethylcuprate, reduced vinylallenes originating from a (formal) transfer of a hydride ion to the substrate are formed in some cases. The products are usually obtained as mixtures of (E/Z)isomers; however, pure (E)-vinylallenes are formed occasionally. The 1,5-substitutions

  具有不同取代模式的烯炔乙酸酯 2、4、6 和 8 以及烯炔环氧乙烷 10 在 1,5-(SN2'')-取代下与有机铜酸盐区域选择性地反应以提供乙烯基丙二烯 11 和 12。使用二甲基铜酸锂，还原在某些情况下，会形成源自氢化物离子（正式）转移到基材上的乙烯基丙二烯。产品通常以 (E/Z) 异构体的混合物形式获得；然而，偶尔会形成纯 (E)-乙烯基丙二烯。1,5-取代也可以用催化量的铜试剂进行。手性醋酸烯炔(S)-2a与tBu2CuLi·LiCN的反应对映选择性地进行，使这种转化构成了远程立体控制的新案例。