4-Methyl-6-methylidenetetrahydro-2-pyranone | 92911-99-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 4-Methyl-6-methylidenetetrahydro-2-pyranone
• 英文别名: 4-Methyl-6-methylideneoxan-2-one
• CAS: 92911-99-4
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: HFBGMHKUPOMHPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-Methyl-5-hexynoic acid 在 Hg(II) trifluoroacetate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.5h， 以85%的产率得到4-Methyl-6-methylidenetetrahydro-2-pyranone
  参考文献：
  名称：

  New approaches to the synthesis of alkyl-substituted enol lactone systems, inhibitors of the serine protease elastase

  摘要：

  We have synthesized a series of alkyl-substituted enol lactones designed to act as mechanism-based inhibitors of human neutrophil elastase (HLE). General methods were developed for the preparation of alpha- and beta-alkyl-substituted 5-hexynoic acids by the bromoform reaction on the corresponding alkynoic methyl ketone, prepared by an Eschenmoser-Tanabe fragmentation sequence from a suitably substituted cyclohexenone. By this method, beta-methyl- and beta,beta-dimethyl-5-hexynoic acids were synthesized from commercially available isophorone and 3,5-dimethyl-2-cyclohexen-1-one, respectively. Alpha-Substituted 5-hexynoic acids were prepared from 3-ethoxy-2-cyclohexen-1-one, using a novel ZnCl2-mediated alkylation that we developed; this method gives high yields of alpha'-alkylation products, even with secondary halides. The most efficient method for the preparation of alpha-substituted 5-hexynoic acids involved a four-reaction sequence-alkylation of the alpha-substituted ester with 1,4-dibromobutane, elimination, bromination and bisdehydrobromination-that proceeded in high overall yield. Protio enol lactonizations were performed with mercury(II) catalysis in CH2Cl2 or CH2Cl2-H2O. Stereo-selective Z-bromo enol lactonization was carried out by Br+-induced lactonization in the presence of Ag+. E-Bromo enol lactonization with N-bromosuccinimide in CH2Cl2 in the presence of a small amount of water gave better yields and shorter reaction times than the traditional anhydrous conditions. In studies of the inhibitory activity of these lactones toward several proteases (reported in full elsewhere), we found that the alpha-alkyl-substituted protio and bromo enol lactones 1-3 were very good inhibitors of HLE, with k(a)/K(i) values ranging from 14 500 to 37 500 M-1 s-1; the beta-alkyl-substituted enol lactones 5-8 showed only moderate inhibition of HLE.

  DOI：

  10.1021/jo00059a049

文献信息

• [EN] KINETIC RESOLUTION<br/>[FR] RÉSOLUTION CINÉTIQUE
  申请人：TRINITY COLLEGE DUBLIN

  公开号：WO2011070028A1

  公开（公告）日：2011-06-16

  Whilst methodologies for the Kinetic Resolution of alcohols are well established, no analogous direct methods exist for the highly selective, direct catalytic Kinetic Resolution of thiols (i.e., R-SH). The present invention relates to a method for resolving stereoisomeric mixtures of thiols. In particular, the present invention relates to purely organocatalytic mediated resolution of enantiomeric mixtures of thiols without the need for enzymes. Also disclosed are some novel catalysts. Such catalysts may comprise a cinchona alkaloid-derived moiety.

  尽管醇的动力学分辨方法已经得到很好的建立，但并不存在类似的高度选择性、直接催化的巯基（即R-SH）的动力学分辨方法。本发明涉及一种用于分离巯基立体异构体混合物的方法。具体来说，本发明涉及纯有机催化介导的巯基对映体混合物的分辨，无需酶。还披露了一些新型催化剂。这些催化剂可能包括奎宁生物碱衍生基团。
• Obtention de δ-methylene δ-lactones et de δ-lactones γ-ethyleniques
  作者：Abdelkébir Jellal、Jacques Grimaldi、Maurice Santelli

  DOI：10.1016/s0040-4039(01)91002-0

  日期：1984.1
• JELLAL, A.;GRIMALDI, J.;SANTELLI, M., TETRAHEDRON LETT., 1984, 25, N 30, 3179-3182
  作者：JELLAL, A.、GRIMALDI, J.、SANTELLI, M.

  DOI：——

  日期：——
• CANNABIDINOID DERIVATIVES
  申请人：SUTTER WEST BAY HOSPITALS

  公开号：US20130209483A1

  公开（公告）日：2013-08-15

  The disclosure relates to cannabinoid derivative compounds, pharmaceutical compositions made thereof, and methods for treating various diseases and disorders including cancer.
• US7531662B2
  申请人：——

  公开号：US7531662B2

  公开（公告）日：2009-05-12