methyl 2-methyl-3-butenoate | 51747-33-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 2-methyl-3-butenoate
• 英文别名: methyl methacrylate；methylbutene-3-oate；2-Methyl-Δ³-butensaeure-methylester；2-Methylbut-3-ensaeuremethylester；3-Acetoxy-1-buten；methyl 2-methylbut-3-enoate
• CAS: 51747-33-2
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: MXUWGYXCKWBYRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 2-methyl-3-butenoate 在 六甲基磷酰三胺 、 zinc(II) chloride 、 lithium diisopropyl amide 作用下， 以 乙酸乙酯 为溶剂， 反应 1.0h， 生成 methyl 2-methyl-4-<<(p-nitrophenyl)sulfonyl>oxy>-2-butenoate
  参考文献：
  名称：

  Regiochemical control in the preparation of 2-(nosyloxy) .beta.,.gamma.-unsaturated esters and 4-(nosyloxy) .alpha.,.beta.-unsaturated esters from 1-[(trimethylsilyl)oxy]-1-alkoxy 1,3-dienes

  摘要：

  A series of 1-[(trialkylsilyl)oxy]-1-alkoxy 1,3-dienes 1a-i were found to react with p-nitrobenzenesulfonyl peroxide in the presence of sodium methoxide or zinc chloride to give alkyl 2-[[(p-nitrophenyl)sulfonyl]oxy] beta-gamma-unsaturated esters 3 and alkyl 4-[[(p-nitrophenyl)sulfonyl]oxy] alpha,beta-unsaturated esters 4 which are readily separable. The regioselectivity is determined by kinetic versus thermodynamic control. When positions 2 or 4 of the diene are unsubstituted, the 2-isomer is the major product and is the kinetically fastest formed product. It can be thermally rearranged to the more stable 4-isomer. When alkyl substituents are present at either the 2- or 4-positions, only the 4-isomer is obtained. Substitution for nosylate by amine nucleophiles occurs by an S(N)2 process. Thus 2-amino beta,gamma-unsaturated esters and 4-amino alpha,beta-unsaturated esters can be prepared from the appropriate starting nosylate.

  DOI：

  10.1021/jo00003a022
• 作为产物：
  描述：

  惕各酸甲酯 生成 methyl 2-methyl-3-butenoate
  参考文献：
  名称：

  酯的光化学。非环状和环状共轭酯之间反应性的对比

  摘要：

  DOI：

  10.1016/s0040-4039(01)87364-0
• 作为试剂：
  描述：

  benzyl 3-iodopropyl thioether 在 sodium tetrahydroborate 、 偶氮二异丁腈 、 methyl 2-methyl-3-butenoate 、 三丁基氯化锡 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以25%的产率得到methyl 6-benzylthiohexanoate
  参考文献：
  名称：

  Foubelo, Francisco; Gutierrez, Ana Maria, Anales de Quimica, 1996, vol. 92, # 5, p. 280 - 284

  摘要：

  DOI：

文献信息

• METHOD FOR PRODUCING 1,3-BUTADIENE FROM 1,4-BUTANEDIOL
  申请人：IFP Energies nouvelles

  公开号：US20180037519A1

  公开（公告）日：2018-02-08

  A method for producing 1,3-butadiene from a 1,4-butanediol feedstock: One step for esterification of 1,4-butanediol, One step for pyrolysis of 1,4-butanediol diester, producing butadiene.

  从1,4-丁二醇原料生产1,3-丁二烯的方法：一步骤用于1,4-丁二醇的酯化，一步骤用于1,4-丁二醇二酯的热解，产生丁二烯。
• ?-Cleavage of Bis(homoallylic) Potassium Alkoxides. Two-Step Preparation of Propenyl Ketones from Carboxylic Esters. Synthesis ofar-Turmerone, ?-Damascone, ?-Damascone, and ?-Damascenone
  作者：Roger L. Snowden、Simon M. Linder、Bernard L. Muller、Karl H. Schulte-Elte

  DOI：10.1002/hlca.19870700721

  日期：1987.11.4

  The transformation of 36 bis(homoallylic) alcohols VII to alkenones IX and Xvia β-cleavage of their potassium alkoxides VIIa in HMPA has been investigated (cf. Scheme 2). These studies have established an order of β-cleavage for 2-propenyl, 1-methyl-2propenyl, 2-methyl-2-propenyl, 1,1-dimethyl-2propenyl, and benzyl groups in alkoxides 49a–56a and have allowed a comparison between the β-cleavege reaction

  已经研究了在HMPA中通过36个双（均烯丙基）醇VII的醇钾VIIa的β裂解转化为烯酮IX和X的方法（参见方案2）。这些研究建立了醇盐49a – 56a中2-丙烯基，1-甲基-2丙烯基，2-甲基-2-丙烯基，1,1-二甲基-2丙烯基和苄基的β裂解顺序，并允许进行比较β裂解反应与烷氧化物74a – 83a中的氧化Cope重排之间的关系。作为示例性的合成应用，丙烯醛的两步制备15 –42从羧酸酯中描述，用合成在一起AR -turmerone（48），α二氢大马酮（（ë） - 71），β大马酮（（ë） - 109），和β大马酮（（ë） - 111）。
• Engineering the Promiscuous Racemase Activity of an Arylmalonate Decarboxylase
  作者：Robert Kourist、Yusuke Miyauchi、Daisuke Uemura、Kenji Miyamoto

  DOI：10.1002/chem.201001924

  日期：2011.1.10

  Variant G74C of arylmalonate decarboxylase (AMDase) from Bordatella bronchoseptica has a unique racemising activity towards profens. By protein engineering, variant G74C/V43A with a 20‐fold shift towards promiscuous racemisation was obtained, based on a reduced activity in the decarboxylation reaction and a two‐fold increase in the racemisation activity. The mutant showed an extended substrate range

  支气管败血波氏杆菌中的芳基丙二酸脱羧酶（AMDase）G74C变体对profens具有独特的消旋作用。通过蛋白质工程，基于脱羧反应的活性降低和消旋活性的两倍提高，获得了向混杂消旋化20倍的变体G74C / V43A。该突变体显示出扩大的底物范围，对酮洛芬的反应速率提高了30倍。分子动力学模拟和消旋酶的底物特征表明，底物结构的空间和极性效应在催化方面比单纯的动力学α-质子酸度起着更大的作用。β，γ-不饱和羧酸的转化不会导致重排形成其α，β异构体的观察结果表明，这是一个协调的机制，而不是逐步的机制。有趣的是，
• Ring-closing metathesis, Kharasch addition and enol ester synthesis catalysed by a novel class of ruthenium(II) complexes
  作者：Bob De Clercq、Francis Verpoort

  DOI：10.1016/s0040-4039(01)01952-9

  日期：2001.12

  addition of carbon tetrachloride across olefins with high yields which markedly depended on the catalyst and the substrate used. In addition, ring-closing metathesis of some representative diolefins was carried out. The best catalytic system III is able to form tri- and tetrasubstituted double bond products. Finally, dependent of the catalytic system and the reaction conditions used, these systems can catalyse

  钌席夫碱配合物I – III以高收率介导了四氯化碳在烯烃中的Kharasch加成反应，这明显取决于所用的催化剂和底物。另外，进行了一些代表性二烯烃的闭环易位。最佳的催化体系III能够形成三取代和四取代的双键产物。最后，取决于所使用的催化体系和反应条件，这些体系可以以优异的产率催化烯醇酯或烯炔的立体选择形成。
• Reactions of ketene acetals-14 The use of simple mixed vinylketene acetals in the annulation of quinones
  作者：Jacques Savard、Paul Brassard

  DOI：10.1016/s0040-4020(01)91496-6

  日期：1984.1

  α,β- β, γ-unsaturated esters can be converted by strong base and chlorotrimethylsilane to the corresponding mixed vinylketene acetals which are shown to be particularly useful and generally applicable reagents for the regiospecific annulation of halogenoquinones. The reaction proceeds readily with a variety of substrates including benzoquinones.

  α，β-β，γ-不饱和酯可通过强碱和三甲基氯硅烷转化为相应的混合乙烯酮缩醛，这对于卤代醌的区域特异性环合而言是特别有用和普遍适用的试剂。该反应在包括苯醌在内的多种底物下容易进行。