3-Fluormethyl-crotonsaeure-ethylester

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-Fluormethyl-crotonsaeure-ethylester
• 英文别名: ethyl 4-fluoro-3-methylbut-2-enoate
• 化学式: C₇H₁₁FO₂
• 分子量: 146.162
• InChiKey: PALGNMVCQVXMGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  10.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-Fluormethyl-crotonsaeure-ethylester 在 palladium on activated charcoal 氢气 作用下， 以 乙醚 为溶剂， 生成 异戊酸乙酯
  参考文献：
  名称：

  Machleidt,H.; Grell,W., Justus Liebigs Annalen der Chemie, 1965, vol. 690, p. 79 - 97

  摘要：

  DOI：
• 作为产物：
  描述：

  3-甲基-2-丁烯酸乙酯 在 potassium fluoride 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 生成 3-Fluormethyl-crotonsaeure-ethylester
  参考文献：
  名称：

  Synthesis of ()-β-fluoromethyleneglutamic acid

  摘要：

  DOI：

  10.1016/s0040-4039(00)89300-4

文献信息

• Fluorinated Isopentenyladenines: Synthesis and Cytokinin Activity
  作者：Laurence Marival-Hodebar、Marc Tordeux、Claude Wakselman、Marylène Dias、René Mornet、Michel Laloue

  DOI：10.1002/ijch.199900020

  日期：——

  Analogs of N6-isopentenyladenine bearing one or two fluorine atoms at the allylic position were synthesized from simple fluorinated ketones. The monofluoro analog was found to be more active than N6-isopentenyladenine and equivalent to the more potent zeatin, another natural plant growth hormone. The difluoro analog was even more powerful than zeatin.

  由简单的氟化酮合成了在烯丙基位置带有一个或两个氟原子的N 6-异戊烯腺嘌呤的类似物。发现单氟类似物比N 6-异戊烯腺嘌呤更具活性，并且与更有效的玉米素（另一种天然植物生长激素）相当。二氟类似物甚至比玉米蛋白更有效。
• Synthesis of [1-13C] and stereo-specifically [1-2H] labeled fluorinated substrate analogues of IspH enzyme in the deoxyxylulose phosphate pathway
  作者：Youli Xiao、Pinghua Liu

  DOI：10.1016/j.tetlet.2008.10.151

  日期：2009.1

  IspH in the deoxyxylulose phosphate (DXP) pathway catalyzes the reductive dehydration of (E)-4-hydroxy-3-methyl-2-butenyl diphosphate (HMBPP) to isopentenyl diphosphate (IPP) and its isomer dimethylallyl diphosphate (DMAPP), which are the starting materials for the synthesis of thousands of isoprenoids. Several models have been proposed in the literature to account for this unique transformation, and

  磷酸脱氧木酮糖（DXP）路径中的IspH催化（E的还原脱水）-4-羟基-3-甲基-2-甲基-2-丁烯基二磷酸（HMBPP）生成异戊烯基二磷酸酯（IPP）及其异构体二甲基烯丙基二磷酸酯（DMAPP），它们是合成数千种类异戊二烯的起始原料。文献中已经提出了几种模型来解释这种独特的转变，并且大多数模型都涉及烯丙基自由基中间体的形成。为便于在IspH催化的反应中捕获和表征拟议的中间体，在本工作中，我们报道了四种同位素标记的IspH底物类似物的合成。这些同位素标记的机械探针将在未来用于通过结合生物有机方法和生物物理方法来表征拟议的IspH反应中间体。
• Machleidt,H. et al., Justus Liebigs Annalen der Chemie, 1963, vol. 667, p. 35 - 47
  作者：Machleidt,H. et al.

  DOI：——

  日期：——
• Dimethylallyltryptophan synthase. An enzyme-catalyzed electrophilic aromatic substitution
  作者：John C. Gebler、Andrew B. Woodside、C. Dale Poulter

  DOI：10.1021/ja00045a004

  日期：1992.9

  Dimethylallyltryptophan (DMAT) synthase catalyzes the alkylation of L-tryptophan at C(4) by dimethylallyl diphosphate (DMAPP) in the first pathway-specific step in the biosynthesis of ergot alkaloids. The mechanism of the reaction was studied with analogs of both substrates. Five 7-substituted derivatives of N-acetyltryptophan (2, Z = OCH3, CH3, F, CF3, and NO2) were synthesized. The L enantiomers of the free amino acids were obtained by selective hydrolysis of the racemate using aminoacylase from Aspergillus. In addition, the E and Z fluoromethyl and difluoromethyl analogs of DMAPP (1, Y = CH3, CH2F, CHF2) were prepared. Rates of the enzyme-catalyzed reactions were measured for the dimethylallyl derivatives with L-tryptophan and for the L-tryptophan derivatives with DMAPP. In addition, the relative reactivities of the methanesulfonate derivatives of the DMAPP analogs were determined for solvolysis in aqueous acetone. A Hammett plot for the tryptophan analogs gave a good linear correlation with rho = -2.0. In addition, a Hammett plot of the logarithms of the relative rates of solvolysis and enzyme-catalyzed alkylation gave a positive linear correlation. These results indicate that the prenyl-transfer reaction catalyzed by DMAT synthase is an electrophilic aromatic substitution and is mechanistically similar to the electrophilic alkylation catalyzed by farnesyl diphosphate synthase.