dimethyl (hydroxymethylene)malonate | 27931-91-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl (hydroxymethylene)malonate
• 英文别名: hydroxymethylenemalonic acid dimethyl ester；dimethyl 2-(hydroxymethylidene)propanedioate
• CAS: 27931-91-5
• 化学式: C₆H₈O₅
• 分子量: 160.127
• InChiKey: JMHZOSZGGDSKNP-UHFFFAOYSA-N

物化性质

• 熔点：
  41-44 °C
• 沸点：
  184.0±40.0 °C(Predicted)
• 密度：
  1.276±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl (hydroxymethylene)malonate 在 五氯化磷 作用下， 生成 dimethyl 2-chloroethylene-1,1-dicarboxylate
  参考文献：
  名称：

  Rappoport,Z.; Topol,A., Journal of the Chemical Society. Perkin transactions II, 1972, p. 1823 - 1831

  摘要：

  DOI：
• 作为产物：
  描述：

  diethyl 2-(ethoxymethylene)malonate 在 水 、 溶剂黄146 作用下， 生成 dimethyl (hydroxymethylene)malonate
  参考文献：
  名称：

  Synthesis of Dithiolethiones and Identification of Potential Neuroprotective Agents via Activation of Nrf2-Driven Antioxidant Enzymes

  摘要：

  Oxidative stress is implicated in the pathogenesis of a wide variety of neurodegenerative disorders, and accordingly, dietary supplement of exogenous antioxidants or/and upregulation of the endogenous antioxidant defense system are promising for therapeutic intervention or chemoprevention of neurodegenerative diseases. Nrf2, a master regulator of the cellular antioxidant machinery, cardinally participates in the transcription of cytoprotective genes against oxidative/electrophilic stresses. Herein, we report the synthesis of 59 structurally diverse dithiolethiones and evaluation of their neuroprotection against 6-hydroxydopamine- or H2O2 -induced oxidative damages in PC12 cells, a neuron-like rat pheochromocytoma cell line. Initial screening identified compounds 10 and 11 having low cytotoxicity but conferring remarkable protection on PC12 cells from oxidative-mediated damages. Further studies demonstrated that both compounds upregulated a battery of antioxidant genes as well as corresponding genes' products. Significantly, silence of Nrf2 expression abolishes cytoprotection of 10 and 11, indicating targeting Nrf2 activation is pivotal for their cellular functions. Taken together, the two lead compounds discovered here with potent neuroprotective functions against oxidative stress via Nrf2 activation merit further development as therapeutic or chemopreventive candidates for neurodegenerative disorders.

  DOI：

  10.1021/acs.jafc.9b06360
• 作为试剂：
  描述：

  3-三甲基甲硅烷基-2-噁唑烷酮 在 三氟甲磺酸 作用下， 以 四氯化碳 、 dimethyl (hydroxymethylene)malonate 为溶剂， 生成 dimethyl trimethylsilyloxymethylenemalonate
  参考文献：
  名称：

  A new organosilylpolyphosphoric reagent, its preparation and application to the process of synthesis of 3-carboxyquinolones or azaquinolones and their salts

  摘要：

  一种制备新的有机硅聚磷酸酯的方法，通过磷五氧化物与硅氧烷或烷氧基硅烷的反应得到溶液中的试剂，其组成为[P₂O₅]N[SILANE]，其中1 < N < 10，N是温度、反应时间和溶剂的函数，用于调节N-取代氨基亚甲基丙二酸酯的环化反应，形成喹啉酮或氮代喹啉酮。N-取代氨基亚甲基丙二酸酯是通过苯胺与二烷基三甲基硅氧基亚甲基丙二酸酯的反应制备的。

  公开号：

  EP0376870A1

文献信息

• An efficient method for α-monofluorination of carbonyl compounds with molecular fluorine: Use of α-hydroxymethylene substituent as directing and activating groups
  作者：Hiroshi Kamaya、Masayuki Sato、Chikara Kaneko

  DOI：10.1016/s0040-4039(96)02378-7

  日期：1997.1

  Molecular fluorine efficiently reacts with α-hydroxymethylene carbonyl compounds to give α-fluoro-α-formyl compounds in a highly site-specific manner. The fluorinated compounds mostly isolated as their hemiacetals with methanol are readily deformylated just by treatment with weak bases affording α-monofluorinated carbonyl compounds. In this fluorination method, the hydroxymethylene group serves not

  分子氟与α-羟基亚甲基羰基化合物有效反应，以高度位点特异性的方式得到α-氟-α-甲酰基化合物。仅通过用甲醇提供α-单氟化羰基化合物的弱碱处理，就可以容易地将大部分以半缩醛形式与甲醇分离的氟化化合物变形。在该氟化方法中，羟甲基不仅用作氟的羰基化合物的导向基团，而且用作活化基团。通过这种方法，以高收率合成了包括酯在内的一系列α-氟代羰基化合物。
• Method for the preparation of alkoxymethylene compounds of acetic esters
  申请人：Dynamit Nobel AG

  公开号：US04665218A1

  公开（公告）日：1987-05-12

  Disclosed is a method for preparation of alkoxymethylene compounds, especially methoxymethylene compounds, from substituted or unsubstituted acetic acid alkyl esters, especially methyl esters, from the corresponding hydroxymethylene compounds or their alkali salts, by reaction with excess alkanol, especially methanol, in the presence of HCl and a water-binding agent. Preferred are water-binding agents which form stable reaction products with water.

  公开了一种制备烷氧甲基化合物的方法，特别是从取代或未取代的乙酸烷基酯，特别是甲酯，制备甲氧甲基化合物，从相应的羟甲基化合物或其碱盐，通过与过量的烷醇，特别是甲醇，在HCl和水结合剂的存在下反应。首选与水形成稳定反应产物的水结合剂。
• Enantioselective Total Synthesis of (−)-Vinigrol: The Evolution of a Transannular Diels–Alder Strategy
  作者：Xuerong Yu、Lianghong Xiao、Tuoping Luo

  DOI：10.1021/acs.joc.3c02407

  日期：2024.2.2

  a structurally and stereochemically complex diterpenoid that displays various potent pharmacological activities. Two generations of synthetic routes were designed and pursued based on a transannular Diels–Alder (TADA) cycloaddition strategy. An intramolecular [2 + 2]photocycloaddition in the presence of the chelating Lewis acid (MgBr2·Et2O) was first discovered to enable the reaction of sterically challenging

  Vinigrol 是一种结构和立体化学复杂的二萜类化合物，具有多种有效的药理活性。基于跨环狄尔斯-阿尔德（TADA）环加成策略设计和探索了两代合成路线。首次发现在螯合路易斯酸 (MgBr 2 ·Et 2 O) 存在下的分子内 [2 + 2] 光环加成能够实现空间挑战性底物的反应，随后进行 [2 + 2] 环化回复以提供 α-与10元环稠合的吡喃酮。最终，开发了一种新的、可扩展的 (−)-vinigrol 合成路线，并提供了超过 600 mg 的材料，体现了大环立体控制和 TADA 反应的力量。
• .alpha.-Alkoxyallylation of activated carbonyl compounds. A novel variant of the Michael reaction
  作者：Robert M. Coates、Steven J. Hobbs

  DOI：10.1021/jo00175a030

  日期：1984.1
• Über die Farbreaktion nachOgston On Ogston's Colour Test
  作者：Hans-Dietrich Stachel、Thomas Zoukas

  DOI：10.1002/ardp.19913240214

  日期：——