diethyl 2-<<(2,2,2-trichloroethoxy)carbonyl>amino>malonate | 97935-38-1

• 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: diethyl 2-<<(2,2,2-trichloroethoxy)carbonyl>amino>malonate
• 英文别名: diethyl (2.2.2-trichloroethoxycarbonyl)aminomalonate；Diethyl 2-(2,2,2-trichloroethoxycarbonylamino)propanedioate
• CAS: 97935-38-1
• 化学式: C₁₀H₁₄Cl₃NO₆
• 分子量: 350.583
• InChiKey: HKYQOLAAELMKIO-UHFFFAOYSA-N

物化性质

• 沸点：
  406.3±45.0 °C(Predicted)
• 密度：
  1.416±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  90.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl 2-<<(2,2,2-trichloroethoxy)carbonyl>amino>malonate 在 N-甲基吗啉 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium 、 三氯化铁 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二氯甲烷 、 xylene 为溶剂， 反应 62.0h， 生成 -(S)-α-<5-oxy>-4-pentenoate>>glycyl>-(R)-alanine methyl ester
  参考文献：
  名称：

  Synthesis of modified partial structures of the bacterial cell wall. 1. Lipopeptides containing nonproteinogenic amino acids

  摘要：

  Two stereoisomeric lipopeptides 1 and 2 which can be regarded as modified peptidoglycans have been synthesized by using three different reaction sequences. The ene reaction of the alpha-allylated dipeptide 12 with butyl glyoxylate was used as a key step. The required enantiomerically pure substrates 9, 10, and 23 were obtained by enzymatic hydrolysis of the corresponding racemic alpha-allylated esters. The absolute configuration of both stereoisomers 1 and 2 was assigned by oxidative cleavage of the double bond in 18 and 19 followed by comparison of the esterified degradation products 28 and 29 with samples of authentic configuration, derived from (R)- and (S)-malic acid.

  DOI：

  10.1021/jo00055a022
• 作为产物：
  描述：

  氨基丙二酸二乙酯盐酸盐 、 氯甲酸-2,2,2-三氯乙酯 在 N-甲基吗啉 作用下， 以 四氢呋喃 为溶剂， 以91.6%的产率得到diethyl 2-<<(2,2,2-trichloroethoxy)carbonyl>amino>malonate
  参考文献：
  名称：

  Synthesis of modified partial structures of the bacterial cell wall. 1. Lipopeptides containing nonproteinogenic amino acids

  摘要：

  Two stereoisomeric lipopeptides 1 and 2 which can be regarded as modified peptidoglycans have been synthesized by using three different reaction sequences. The ene reaction of the alpha-allylated dipeptide 12 with butyl glyoxylate was used as a key step. The required enantiomerically pure substrates 9, 10, and 23 were obtained by enzymatic hydrolysis of the corresponding racemic alpha-allylated esters. The absolute configuration of both stereoisomers 1 and 2 was assigned by oxidative cleavage of the double bond in 18 and 19 followed by comparison of the esterified degradation products 28 and 29 with samples of authentic configuration, derived from (R)- and (S)-malic acid.

  DOI：

  10.1021/jo00055a022

文献信息

• Fluorine containing amino acids and their derivatives. 7. Synthesis and antitumor activity of α- and γ-substituted methotrexate analogs
  作者：Tadahiko Tsushima、Kenji Kawada、Shoichi Ishihara、Naomi Uchida、Osamu Shiratori、Junko Higaki、Masaharu Hirata

  DOI：10.1016/s0040-4020(01)86044-0

  日期：1988.1

  afforded a number of fluorine containing α amino acids such as β-fluorinated-alanines, 2-amino-n,n,n-trifluoroalkanoic acids, and fluorinated glutamic acids as well as other γ-heteroatom substituted glutamic acids. Here, an efficient enzymatic optical resolution using hog kidney acylase was conducted to obtain both optical isomers of 2-amino-n,n,n-trifluoroalkanoic acids. In addition, a novel sulfoxide

  α-取代的丙二酸酯的三种类型的反应，二氟甲基化，与n，n，n-三氟烷基磺酸酯的烷基化以及与2-取代的丙烯酸酯的Michael加成反应，可方便地得到许多含氟的α氨基酸，​​例如β-氟代丙氨酸。 ，2-氨基-n，n，n-三氟链烷酸和氟化谷氨酸以及其他γ-杂原子取代的谷氨酸。在此，进行了使用猪肾酰基转移酶的有效酶促光学拆分，以获得2-氨基-n，n，n-三氟链烷酸的两种旋光异构体。另外，在α-二氟甲基-α-亚磺酰丙二酸二乙酯的碱催化反应中观察到了新的亚砜重排。最后，获得的α-和γ-取代的谷氨酸用于抗肿瘤药甲氨蝶呤的化学修饰，以显示出显着的构效关系。特别是，氟取代对观察到体内抗肿瘤活性。
• Fluorine-containing amino acids and their derivatives. 6. An efficient synthesis of β-fluorinated alanines via fluorohalomethylation of aminomalonates
  作者：Tadahiko Tsushima、Kenji Kawada

  DOI：10.1016/s0040-4039(00)94849-4

  日期：1985.1

  in good yields. These products were successfully converted to various versatile β-fluorinated alanine derivatives, i.e., β,β-difluoroalanine (), N-acyl-β-fluorodehydroalaninate (), and fluoropyruvic acid ().

  Aminomalonates，例如，和，平滑地和二氟chlorofluorocarbene以产生加合物（反应，和以良好产率）。这些产品已成功转化为各种通用的β-氟代丙氨酸衍生物，即β，β-二氟丙氨酸（），N-酰基-β-氟代脱氢丙氨酸盐（）和氟丙酮酸（）。
• Methodology for the Efficient Synthesis of 3,4-Differentially Substituted Indoles. Fluoride Ion-induced Elimination-Addition Reaction of 1-Triisopropylsilylgramine Methiodides
  作者：M Iwao

  DOI：10.1016/00404-0399(50)1197p-

  日期：1995.8.14

  1-Triisopropylsilylgramine methiodide reacted smoothly with a variety of nucleophiles in the presence of tetrabutylammmonium fluoride to give 3-substituted indoles. The 3,4-disubstituted indoles were efficiently synthesized by sequential use of 4-selective lithiation of 1-triisopropylsilylgramine and this new substitution reaction.
• Synthesis of modified partial structures of the bacterial cell wall. 1. Lipopeptides containing nonproteinogenic amino acids
  作者：Helmut Schneider、Gerhard Sigmund、Bettina Schricker、Klaus Thirring、Heinz Berner

  DOI：10.1021/jo00055a022

  日期：1993.1

  Two stereoisomeric lipopeptides 1 and 2 which can be regarded as modified peptidoglycans have been synthesized by using three different reaction sequences. The ene reaction of the alpha-allylated dipeptide 12 with butyl glyoxylate was used as a key step. The required enantiomerically pure substrates 9, 10, and 23 were obtained by enzymatic hydrolysis of the corresponding racemic alpha-allylated esters. The absolute configuration of both stereoisomers 1 and 2 was assigned by oxidative cleavage of the double bond in 18 and 19 followed by comparison of the esterified degradation products 28 and 29 with samples of authentic configuration, derived from (R)- and (S)-malic acid.