甲基丙二酸二苯酯 | 33697-58-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 中文名称: 甲基丙二酸二苯酯
• 英文名称: diphenyl 2-methylmalonate
• 英文别名: diphenyl methylmalonate；methyl-malonic acid diphenyl ester；Methyl-malonsaeure-diphenylester；Methylmalonsaeure-bis-phenylester；Methylmalonsaurediphenylester；diphenyl 2-methylpropanedioate
• CAS: 33697-58-4
• 化学式: C₁₆H₁₄O₄
• 分子量: 270.285
• InChiKey: WJOTZDLRNBMLQD-UHFFFAOYSA-N

物化性质

• 熔点：
  50 °C(Solv: water (7732-18-5); ethanol (64-17-5))
• 沸点：
  407.9±28.0 °C(Predicted)
• 密度：
  1.196±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  甲基丙二酸二苯酯 生成 4-羟基-3-甲基色烯-2-酮
  参考文献：
  名称：

  Zur Chemie des 4-Hydroxy-cumarins

  摘要：

  DOI：

  10.1007/bf00903604
• 作为产物：
  描述：

  2-methyl-malonic acid monophenyl ester 生成 甲基丙二酸二苯酯
  参考文献：
  名称：

  Eine einfache Synthese von Malonsäure-mono- und -bis-phenylestern¹

  摘要：

  DOI：

  10.1055/s-1976-24041

文献信息

• Selective Sulfenylative Desulfonylation or Decarbalkoxylation of <font>α</font>-Sulfonyl Malonates with DABCO or Bu₃N: Reactivity and Conformational Analysis
  作者：Claudio L. Donnici、Elaine Henriques Teixeira Pereira、Júlio C. Dias Lopes、Liliana Marzorati、Blanka Wladislaw

  DOI：10.1080/00397910902962852

  日期：2010.1.14

  reactivity of several α-substituted α-sulfonyl malonates toward 1,4-diazabicyclo[2.2.2]octane (DABCO) and Bu3N is described. The reactivity with DABCO revealed the possible competition between decarbalkoxylation and unexpected desulfonylation, depending on the α-substituent, because of sterical hindrance around the electrophilic centers (SO2 and CO2R). The derivatives with crowded α-substituents suffer

  描述了几种 α-取代的 α-磺酰基丙二酸酯对 1,4-二氮杂双环 [2.2.2] 辛烷 (DABCO) 和 Bu3N 的反应性研究。由于亲电子中心（SO2 和 CO2R）周围的空间位阻，与 DABCO 的反应性揭示了脱羧基化和意外脱磺酰化之间可能存在竞争，这取决于 α-取代基。具有拥挤的α-取代基的衍生物会发生选择性脱磺酰化，因此可以提出一种新颖有效的脱磺酰化方法。通过构象分析（Macromodel/MM2* 和 Mopac/MP3）证实了 α-磺酰基丙二酸酯的反应性对亲电子中心周围空间位阻的依赖性。由于相应的质子化、氘化、通过加入相应的亲电试剂得到亚磺酰化产物。Bu3N 本身是一种新型的选择性脱羧基试剂，可用于任何 α-取代的 α-磺酰基丙二酸酯。
• 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。
• Rhodium-catalyzed arylative cyclization of alkynyl malonates by 1,4-rhodium(<scp>i</scp>) migration
  作者：Luke O’Brien、Somnath Narayan Karad、William Lewis、Hon Wai Lam

  DOI：10.1039/c9cc05205d

  日期：——

  The synthesis of functionalized 1-tetralones by the rhodium(I)-catalyzed reaction of alkynyl malonates with arylboronic acids is described. These arylative cyclizations proceed via an alkenyl-to-aryl 1,4-Rh(I) migration as a key step. Preliminary results of an enantioselective variant of these reactions are also presented.

  描述了通过铑（I）催化的丙二酸炔基酯与芳基硼酸的反应合成官能化的1-四氢萘酮。这些芳基环化是通过烯基至芳基的1，4-Rh（I）迁移进行的，这是关键步骤。还提供了这些反应的对映选择性变体的初步结果。
• Retro-ene reactions in heterocyclic synthesis.<b>IV</b>. A new synthetic method for 6-hydroxypyrimidin-4(3<i>H</i>)-ones and 1,3,5-triazine-2,4(1<i>H</i>,3<i>H</i>)-diones
  作者：Kunio Ito、Shingo Miyajima

  DOI：10.1002/jhet.5570360107

  日期：1999.1

  N-t-Butylbenzamidines 1 reacted with diphenyl phenylmalonate or diphenyl methylmalonate to give 6-hydroxypyrimidin-4(3H)-ones 4 or 5. Amidines 1 on reaction with diphenyl imidodicarboxylate afforded 1,3,5-triazine-2,4(1H, 3H)-diones 8.

  N-吨-Butylbenzamidines 1与碳酸二苯苯基丙二或二苯基甲基丙反应，得到6-羟基嘧啶-4-（3 H ^） -酮4或5脒1上，得到与碳酸二苯imidodicarboxylate反应-1,3,5-三嗪-2,4（ 1 H，3 H）-二酮8。
• Zur Chemie des 4-Oxy-cumarins
  作者：E. Ziegler、H. Junek

  DOI：10.1007/bf00899270

  日期：——