dibenzyl ethylmalonate | 74254-53-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dibenzyl ethylmalonate
• 英文别名: dibenzyl 2-ethylpropanedioate
• CAS: 74254-53-8
• 化学式: C₁₉H₂₀O₄
• 分子量: 312.365
• InChiKey: CTCBQXVDAITWDZ-UHFFFAOYSA-N

物化性质

• 沸点：
  190 °C(Press: 2 Torr)
• 密度：
  1.144±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dibenzyl ethylmalonate 在 palladium on activated charcoal 氢气 、 potassium hydride 作用下， 以 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 22.0 ℃ 、101.33 kPa 条件下， 反应 2.5h， 生成 (-)-(S)-methyl 3,3-dicarboxy-2-methylvalerate
  参考文献：
  名称：

  Leeuwen, F. F. van; Noordam, A.; Maat, L., Recueil des Travaux Chimiques des Pays-Bas, 1980, vol. 99, # 3, p. 96 - 99

  摘要：

  DOI：
• 作为产物：
  描述：

  乙基丙二酸二乙酯 、 苯甲醇 在 sodium methylate 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以92%的产率得到dibenzyl ethylmalonate
  参考文献：
  名称：

  Leeuwen, F. F. van; Noordam, A.; Maat, L., Recueil des Travaux Chimiques des Pays-Bas, 1980, vol. 99, # 3, p. 96 - 99

  摘要：

  DOI：

文献信息

• Design of Sulphate Modified Solid Acid Catalysts for Transesterification of Diethyl Malonate with Benzyl Alcohol
  作者：K. U Minchitha、H. N Hareesh、K Venkatesh、M Shanty、N Nagaraju、N Kathyayini

  DOI：10.1166/jnn.2018.14567

  日期：2018.1.1

  and n-butyl amine titration methods. Catalytic activity of these materials was investigated in liquid phase transesterification of diethyl malonate with benzyl alcohol. Effect of various reaction parameters on product yield as well as recyclability of the catalysts was investigated. Kinetics of the reactions was studied and activation energy was evaluated. All the catalysts investigated in this reaction

  通过湿法浸渍法制备了硫酸根离子改性的多壁碳纳米管（S-CNT），中孔碳（S-MC），氧化锆（S-ZrO2），氧化铝（S-Al2O3）和二氧化硅（S-SiO2）。通过粉末XRD，BET表面积和SEM-EDS分析研究了所制备材料的理化性质。使用TPD-NH3和正丁胺滴定法分析了材料的表面酸度。在丙二酸二乙酯与苯甲醇的液相酯交换反应中研究了这些材料的催化活性。研究了各种反应参数对产物收率和催化剂可回收性的影响。研究了反应的动力学并评估了活化能。发现该反应中研究的所有催化剂均具有催化活性，但S-Al2O3，用于形成酯交换产物；丙二酸苄基乙酯（BEM）和丙二酸二苄基酯（DBM）。S-ZrO2和S-MC产生的总酯交换产物的收率很好（分别为70％和73％），而S-CNTs仅对BEM的形成具有100％的选择性。发现具有中等酸强度的酸位对于酯交换反应具有催化活性。除S-MC外，这些催化剂可循环使用多达5次，
• Lithium Binaphtholate-Catalyzed Michael Reaction of Malonates with Maleates and Its Application to the Enantioselective Synthesis of Tricarboxylic Acid Derivatives
  作者：Midori Sakamoto、Tetsuya Kaneko、Yuya Orito、Yasushi Shimoda、Makoto Nakajima

  DOI：10.1248/cpb.c18-00993

  日期：2019.5.1

  The Michael reaction of malonates with maleates afforded the corresponding adducts in high yields with high enantioselectivities (up to 98% enantiomeric excess (ee)) by using dilithium 3,3'-dichlorobinaphtholate as a catalyst. The obtained Michael adducts could be converted to optically active tricarboxylic acid (TCA) derivatives via the Krapcho reaction.

  通过使用3，3′-二氯联萘二酸二锂作为催化剂，丙二酸酯与马来酸酯的迈克尔反应以高收率和高对映选择性（高达98％对映体过量（ee））提供了相应的加合物。所获得的迈克尔加合物可以通过Krapcho反应转化为光学活性三羧酸（TCA）衍生物。
• METHOD FOR PRODUCING a-SUBSTITUTED CYSTEINE OR SALT THEREOF OR SYNTHETIC INTERMEDIATE OF a-SUBSTITUTED CYSTEINE
  申请人：API Corporation

  公开号：US20160083341A1

  公开（公告）日：2016-03-24

  According to the present invention, it becomes possible to perform a process for converting into an α-substituted cysteine represented by general formula (1) or a salt thereof at low cost and on an industrial scale by employing a process that is routed through a compound represented by general formula (3) to a compound represented by general formula (6). Particularly, by employing a process that is routed through a compound represented by general formula (7-2), it becomes possible to detach a tert-butyl protection group in a simple manner and to produce the compound represented by general formula (1) with high purity. Furthermore, by employing a process that is routed through tert-butylthiomethanol or a process that is routed through a compound represented by general formula (9), it becomes possible to produce a compound represented by general formula (2) without generating bischloromethylether that is an oncogenic substance. In the production of an α-substituted-D-cysteine or a salt thereof, it becomes possible to perform a process for converting the compound represented by general formula (2) into a compound represented by general formula (3S) in one step by allowing an enzyme or the like to act on the compound represented by general formula (2).

  根据本发明，通过采用经由一种化合物（通式（3）表示）到一种通式（6）表示的化合物的过程，可以以低成本和工业化规模进行将其转化为通式（1）表示的α-取代半胱氨酸或其盐的过程。特别是，通过采用经由一种通式（7-2）表示的化合物的过程，可以简单地去除叔丁基保护基，并以高纯度生产通式（1）表示的化合物。此外，通过采用经由叔丁基硫代甲醇或经由一种通式（9）表示的化合物的过程，可以生产通式（2）表示的化合物，而不产生致癌物质双氯甲醚。在生产α-取代-D-半胱氨酸或其盐时，可以通过允许酶或类似物作用于通式（2）表示的化合物，一步将其转化为通式（3S）表示的化合物。
• Enantioselective Michael Addition of a Malonic Ester to a Maleic Ester Catalyzed by Lithium Binaphtholate
  作者：Makoto Nakajima、Midori Sakamoto、Tetsuya Kaneko、Yuya Orito

  DOI：10.1055/s-0035-1562691

  日期：——

  Lithium 3,3′-chlorobinaphtholate was found to catalyze the enantioselective Michael addition of a malonic ester to a maleic ester. High enantioselectivities (>90% ee) were observed, especially in the reactions of 2-alkylmalonic esters and maleic esters.

  发现 3,3'-氯联萘酸锂催化丙二酸酯与马来酸酯的对映选择性迈克尔加成。观察到高对映选择性 (>90% ee)，特别是在 2-烷基丙二酸酯和马来酸酯的反应中。
• Stereoselective synthesis of the imidazole alkaloids (+)-pilocarpine and (+)-isopilocarpine. (Imidazole chemistry, Part IX)
  作者：A. Noordam、L. Maat、H. C. Beyerman

  DOI：10.1002/recl.19811001202

  日期：——

  A novel synthesis of (+)-pilocarpine (10a) is described. L-Histidine is converted into methyl (R)-2-bromo-3-(l-methyl-5-imidazolyl)propionate (5) in which the configuration has been inverted. Alkylation of dibenzyl ethylmalonate with 5 yields the imidazole compound 6, again with inversion. Finally, 6 is converted into a mixture of (+)-pilocarpine (10a) and (+)-isopilocarpine (10b), the separation of

  描述了（+）-pilocarpine（10a）的新型合成。L-组氨酸被转化成（R）-2-溴-3-（1-甲基-5-咪唑基）丙酸甲酯（5），其构型已被反转。丙二酸乙基二苄酯与5的烷基化反应再次生成咪唑化合物6。最后，6被转化成（+）的混合物-毛果芸香碱（10A）和（+） - isopilocarpine（10B），其中所述分离是公认的。