methyl (E)-4,4-dimethoxy-2-butenoate | 32815-00-2

• 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 (E)-4,4-dimethoxy-2-butenoate
• 英文别名: methyl (E)-4,4-dimethoxybut-2-enoate；2-Butenoic acid, 4,4-dimethoxy-, methyl ester
• CAS: 32815-00-2
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: CWHHPNNHJKOQQV-SNAWJCMRSA-N

物化性质

• 沸点：
  84-86 °C(Press: 10 Torr)
• 密度：
  1.038±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (E)-4,4-dimethoxy-2-butenoate 在 正丁基锂 、 硫酸 、 盐酸羟胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 叔丁醇 为溶剂， 反应 96.5h， 生成 (2R,3R)-(-)-3-(dimethoxymethyl)-5-oxo-2-pyrrolidinecarboxylate
  参考文献：
  名称：

  Asymmetric Michael Addition of theN-Alkylidene Derivative of an α-Amino Ester to Methyl (E)-3-[(3R,7aS)-2-Phenylperhydropyrrolo[1,2-c]imidazol-3-yl]propenoate

  摘要：

  报道了锂化的甲基N-(2,2-二甲基丙叉)甘氨酸酯与甲基(E)-3-[(3R,7aS)-2-苯基全氢吡咯[1,2-c]咪唑-3-基]丙烯酸酯之间的专一性立体选择性不对称迈克尔加成反应。在这种反应中，受体的烯丙酸酯的同侧平伏构象参与反应，其中受体分子的re面被锂化中间体的re(β)面攻击。

  DOI：

  10.1246/bcsj.64.2739
• 作为产物：
  描述：

  甲醇 、 4,4-二甲氧基-2-丁烯醛 在 manganese(IV) oxide 、 氰化钠 、 溶剂黄146 作用下， 反应 24.0h， 以82%的产率得到methyl (E)-4,4-dimethoxy-2-butenoate
  参考文献：
  名称：

  Ovanesyan; Garibyan; Badanyan, Russian Journal of Organic Chemistry, 2000, vol. 36, # 7, p. 951 - 954

  摘要：

  DOI：

文献信息

• Asymmetric Cycloaddition of<i>N</i>-Metalated Azomethine Ylides with the Optically Active α,β-Unsaturated Esters Derived from α-Amino Acids
  作者：Shuji Kanemasa、Hidetoshi Yamamoto、Eiji Wada、Tosio Sakurai、Kunio Urushido

  DOI：10.1246/bcsj.63.2857

  日期：1990.10

  α,β-Unsaturated esters bearing a chiral oxazolidine or perhydropyrrolo[1,2-c]imidazole auxiliary at the β-position have been prepared and applied to the cycloadditions with N-metalated azomethine ylides derived from α-(benzylideneamino) esters. These reactions are found to proceed with an exclusively high diastereofacial selectivity to give 2,4-pyrrolidinedicarboxylates with four consecutive chiral

  已经制备了在 β 位带有手性恶唑烷或全氢吡咯并 [1,2-c] 咪唑助剂的 α,β-不饱和酯，并将其应用于与衍生自 α-（亚苄基氨基）酯的 N-金属化偶氮甲碱叶立德的环加成反应。发现这些反应以独特的高非对映选择性进行，在去除手性助剂后得到具有四个连续手性中心的 2,4-吡咯烷二羧酸盐。讨论了过渡态的详细立体化学。
• Stereoselective radical-mediated cyclization of norephdrine derived α-iodoamides: synthesis of enantiopure pyrrolidines and trandition state modelling1
  作者：Laura Belvisi、Cesare Gennari、Giovanni Poli、Carlo Scolastico、Barbara Salom、Marco Vassallo

  DOI：10.1016/s0040-4020(01)88474-x

  日期：1992.1

  Radical-mediated cyclization of norephedrine derived α-iodoamides 1 was found to be highly stereoselective (≥97:3) favouring diastereoisomer 2. Bicyclic lactams 2 were transformed in high yields into enantiomerically pure pyrrolidines 10. Transition state modelling with a force developed ad hoc nicely predicts the stereochemical results.

  自由基介导的去甲肾上腺素衍生的α-碘酰胺1的环化具有高度立体选择性（≥97：3），有利于非对映异构体2。双环内酰胺2以高收率转化为对映体纯的吡咯烷10。临时开发的力进行的过渡态建模可以很好地预测立体化学结果。
• Macrocyclisation of Macrodiolide with Dimethylaluminium Methaneselenolate
  作者：Liu-Lan Shen、Han-Seo Mun、Jin-Hyun Jeong

  DOI：10.1002/ejoc.201001201

  日期：2010.12

  Dimethylaluminium methaneselenolate (Me 2 AlSeMe, 1) acts as an acyl transfer agent for esterification. In cases of direct macrolactonisation (n = 10-12), this selenium-aluminium complex preferentially creates symmetric macrodiolides rather than macrolides. The factors determining macrodilactonisation were investigated and applied toward the total synthesis of norpyrenophorin, which result in a macrodilactonisation

  二甲基硒化铝 (Me 2 AlSeMe, 1) 作为酯化的酰基转移剂。在直接大环内酯化（n = 10-12）的情况下，这种硒铝复合物优先产生对称的大二内酯而不是大环内酯。研究了决定大内酯化的因素并将其应用于去甲肾上腺素的全合成，这导致了 64% 的大内酯化产率。
• Novel process for preparation of 1-furenyl-2,2-dimethyl-cyclopropane
  申请人：Roussel Uclaf

  公开号：US04642372A1

  公开（公告）日：1987-02-10

  A process for the preparation of cyclopropane carboxylic acid derivatives of the formula ##STR1## wherein Z is selected from the group consisting of --CN, --COOH and --COOR.sub.1, R.sub.1 is alkyl of 1 to 6 carbon atoms and R.sub.2 and R.sub.3 are alkyl of 1 to 4 carbon atoms or taken together with the carbon atom to which they are attached form a carbon homocycle of 3 to 6 carbon atoms comprising reacting at low temperatures in a solvent in the presence of a strong base a compound of the formula ##STR2## wherein Z has the above definitions and R is alkyl of 1 to 6 carbon atoms or together form a polymethylene of 2 to 3 carbon atoms with a sulfone of the formula ##STR3## wherein R.sub.2 and R.sub.3 have the above definitions and Y is an aromatic group followed by aqueous treatment to obtain a compound of the formula ##STR4## wherein Y, R, R.sub.2, R.sub.3 and Z have the above definitions, reacting the latter at a low temperature in a solvent with a strong base while letting the temperature rise to obtain a compound of the formula ##STR5## wherein R, R.sub.2, R.sub.3 and Z have the above definitions of the cis/trans configuration richer in the trans isomer and either reacting the latter when Z is --CN or --COOR.sub.1 with a strong base in an aqueous media followed by acidification to obtain a compound of the formula ##STR6## wherein R, R.sub.2 and R.sub.3 have the above definitions having the same configuration as the compound of formula V or reacting the compound of formula V or Va with an acid agent in an aqueous media to obtain the corresponding compound of formula I with the same configuration as the compound of formula V or Va and optionally treating the latter with a weak base at room temperature to obtain the compound of formula I with a trans configuration which are valuable intermediates for the preparation of esters of cyclopropane carboxylic acid having elevated insecticidal activity.

  一种制备环丙烷羧酸衍生物的方法，其化学式为##STR1##其中Z选自--CN、--COOH和--COOR.sub.1的群，R.sub.1为1至6个碳原子的烷基，R.sub.2和R.sub.3为1至4个碳原子的烷基或与它们所附着的碳原子形成3至6个碳原子的碳同环，包括在强碱存在下，在溶剂中低温反应化合物##STR2##其中Z具有上述定义，R为1至6个碳原子的烷基或与它们一起形成2到3个碳原子的聚亚甲基，与公式##STR3##其中R.sub.2和R.sub.3具有上述定义，Y是芳香族基，在水处理后得到公式##STR4##其中Y、R、R.sub.2、R.sub.3和Z具有上述定义，在溶剂中低温反应后，让温度升高以得到公式##STR5##其中R、R.sub.2、R.sub.3和Z具有上述定义的顺反异构体，富含反异构体，如果Z是--CN或--COOR.sub.1，则与强碱在水介质中反应，然后酸化以得到公式##STR6##其中R、R.sub.2和R.sub.3具有上述定义，具有公式V的化合物的相同构型，或者与酸剂在水介质中反应，以得到具有公式V或Va相同构型的相应公式I化合物，可选择性地在室温下用弱碱处理后得到具有反构型的公式I化合物，这些化合物是制备具有升高杀虫活性的环丙烷羧酸酯的有价中间体。
• Generation of 2,3-dimethylene-2,3-dihydropyrrole derivatives; intermediates in intra- and inter-molecular Diels–Alder reactions
  作者：Frederik R. Leusink、Ronald ten Have、Kiempe J. van den Berg、Albert M. van Leusen

  DOI：10.1039/c39920001401

  日期：——

  Three different approaches are described for the generation of derivatives of 2,3-dimethylene-2,3-dihydropyrrole 2, which are reactive intermediates in Diels–Alder cycloaddition reactions; one of the intramolecular cycloadditions provides a new tricyclo[3.2.1.02,7]octane compound 8.

  本文介绍了生成 2,3-二亚甲基-2,3-二氢吡咯 2 衍生物的三种不同方法，这些衍生物是 DielsâAlder 环加成反应中的活性中间体；其中一种分子内环加成反应提供了一种新的三环[3.2.1.02,7]辛烷化合物 8。