fumarylacetone | 62966-21-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: fumarylacetone
• 英文别名: Fumarylaceton；(E)-4,6-dioxohept-2-enoic acid
• CAS: 62966-21-6
• 化学式: C₇H₈O₄
• 分子量: 156.138
• InChiKey: MQVQZTWTXUPFFC-NSCUHMNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  71.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (Z)-4-acetonylidene-2-butenolide 在 sodium hydroxide 作用下， 生成 fumarylacetone
  参考文献：
  名称：

  Synthesis of model compounds for maleylacetoacetic acid. Maleylacetone

  摘要：

  DOI：

  10.1021/jo00835a075

文献信息

• Synthesis and antimicrobial activity of some 2-acetylcyclopent-4-ene-1,3-diones
  作者：O. P. Shestak、V. L. Novikov、S. I. Stekhova、I. A. Gorshkova

  DOI：10.1007/bf02508410

  日期：1999.1

  3-diones (II). This series of compounds offer an interesting object for investigation because they are closely related to the relatively rare group of natural cyciopentene 13,13'triketones [ 1 3] and can be used as multipurpose reagents for the synthesis of various carboand heterocyclic compounds. Indeed, even the simplest representative of this series contains 10 (sic!) reactive centers, which is explained

  正如已知的 [1 -3] ，乙酸甲基乙烯酯与马来酸酐 (1) 的酰化产生 2-乙酰环戊-4 烯-1,3-二酮 (II)。这一系列化合物提供了一个有趣的研究对象，因为它们与相对稀有的天然环戊烯13,13'三酮[ 1 3 ] 密切相关，可用作合成各种碳杂环化合物的多用途试剂。事实上，即使是这个系列中最简单的代表也包含 10 个（原文如此！）反应中心，这是通过对互变异构的敏感性来解释的。II 结构中共轭双 4(5) 键的存在使这些化合物能够作为受体参与涉及生物分子的 Michaelis 亲核加成反应。y-羟基-13-en-t-one 片段（乙烯基羧基）的存在赋予这些化合物相对于生物底物的酰化能力。最后，烯醇化的 13,13'-三酮基团的存在允许这些化合物通过结合控制金属依赖性酶活性的微量元素的离子形成螯合物。然而，尽管潜力巨大，但三酮 II 的化学和生物学特性几乎仍未得到研究。有两种可能的方法来
• Stereochemical studies. 46. Studies on the synthesis of 4-acetoxy-cyclopentane-1,3-dione derivatives.
  作者：MUTSUYOSHI KITAMOTO、SHIRO TERASHIMA、SHUNICHI YAMADA

  DOI：10.1248/cpb.25.41

  日期：——

  As methods for preparing 4-acetoxy-cyclopentane-1, 3-dione derivatives (1), two synthetic schemes were examined. While the successive catalytic reduction and acetylation of cyclopentane-1, 3, 4-triones (2) according to the reported procedure gave the desired 1, the acid-catalyzed condensation of O-acetyl malic anhydride (3) with isopropenyl acetate (4a) and diethyl ketone enol acetate (4b) gave 2-carboxymethyl-5-methyl-3-oxo-2, 3-dihydrofuran (6a) and its 4-methyl derivative (6b), respectively, as the sole isolable product. The structures of 6a and 6b were elucidated from their chemical and spectroscopic behavior. Plausible formation mechanism for the compounds was also proposed.

  作为制备 4-乙酰氧基环戊烷-1, 3-二酮衍生物（1）的方法，我们研究了两种合成方案。根据已报道的程序，环戊烷-1，3，4-三酮（2）通过连续催化还原和乙酰化得到了所需的 1、在酸催化下，O-乙酰基苹果酸酐（3）与乙酸异丙烯酯（4a）和乙酸二乙酮烯醇酯（4b）缩合，分别得到 2-羧甲基-5-甲基-3-氧代-2，3-二氢呋喃（6a）及其 4-甲基衍生物（6b），作为唯一可分离的产物。6a 和 6b 的结构是从它们的化学和光谱行为中阐明的。还提出了这些化合物的合理形成机制。
• Alkylation and Inactivation of Human Glutathione Transferase Zeta (hGSTZ1-1) by Maleylacetone and Fumarylacetone
  作者：Hoffman B. M. Lantum、Daniel C. Liebler、Philip G. Board、M. W. Anders

  DOI：10.1021/tx025503s

  日期：2002.5.1

  variants were incubated with MA or FA in the presence of S-methyl glutathione. These data indicate that MA and FA are substrate and product inactivators of hGSTZ1-1 and covalently modify hGSTZ1-1 at the active-site cysteine residue in the absence of glutathione. The observation that inactivation was blocked by glutathione indicates that binding of glutathione to the active site prevents reaction of MA

  谷胱甘肽转移酶ζ（GSTZ1-1）分别催化顺丁烯二酰乙酰乙酸酯或顺丁烯二酰丙酮（MA）顺式-反式异构化为富马酰乙酰乙酸酯或富马酰丙酮（FA）。GSTZ1-1还催化各种α-卤代酸（包括二氯乙酸）的谷胱甘肽依赖性生物转化。这项研究的目的是研究MA和FA使hGSTZ1-1失活的机制，并确定在存在和不存在谷胱甘肽的情况下MA和FA对hGSTZ1-1的共价修饰。MA和FA（0.01-1 mM）以浓度和时间依赖性方式灭活所有hGSTZ1-1多态性变体，并且谷胱甘肽阻止了这种失活。hGSTZ1c-1c的C16A突变体被MA和FA部分灭活。电喷雾电离串联质谱法和hGSTZ1多态性变体的胰蛋白酶消化物的SALSA（光谱分析评分算法）分析显示，hGSTZ1-1的活性位点（SSCSWR）和C端（LLVLEAFQVSHPCR）半胱氨酸残基已被MA和Mg共价修饰。 F A。MA和FA的加合导致修饰肽离子及其MS-M
• Kinetics of the Biotransformation of Maleylacetone and Chlorofluoroacetic Acid by Polymorphic Variants of Human Glutathione Transferase Zeta (hGSTZ1-1)
  作者：Hoffman B. M. Lantum、Philip G. Board、M. W. Anders

  DOI：10.1021/tx010095y

  日期：2002.7.1

  Glutathione transferase zeta (GSTZ1-1) catalyzes the cis-trans isomerization of maleylacetoacetate and the biotransformation of a range of alpha-haloacids. The objective of this study was to determine the kinetics of the biotransformation of maleylacetone (MA), an analogue of the natural substrate maleylacetoacetate, and chlorofluoroacetic acid (CFA) by polymorphic variants of recombinant hGSTZ1-1. The k(cat) of the four variants of hGSTZ1-1 with MA as the substrate followed the order: 1c-1c > 1b-1b > 1d-1d > 1a-1a whereas the kcat for the biotransformation of CFA followed the order: similar to1a-1a > 1b-1b 1c-1c similar to 1d-1d. The turnover rates of Nu were much higher than those of CFA for each variant and ranged from 22-fold (1a-1a) to 980-fold differences (1c-1c). The catalytic efficiencies of hGSTZ1-1 variants with MA as the substrate were much greater than those with CFA as the substrate, but little difference among the polymorphic variants was observed. MA was a mixed inhibitor of all variants with CFA as substrate: the mean competitive inhibition constant (K-ic(MA)) for all variants was about 100 muM, and the mean uncompetitive inhibition constant (K-iu(MA)) was about 201 muM. Hence, MA and alpha-haloacids apparently compete for the same active site on the enzyme. DCA-induced inactivation of the four variants showed that the inactivated enzymes show markedly reduced isomerase activities. The residual activities were different for each variant: 1a-1a (12%) > 1b-1b similar to 1c-1c similar to 1d-1d (<5%). This is the first kinetic analysis of polymorphic variants of hGSTZ1-1, and the similarity of the kinetic constants for hGSTZ1-1 variants with either MA or CFA as substrates indicates that few differences in DCA-induced perturbations of tyrosine metabolism would likely be observed in humans.
• Mechanism of cis-trans isomerization about carbon-carbon double bonds catalyzed by silver(I)
  作者：Richard A. Johnson、Stanley. Seltzer

  DOI：10.1021/ja00798a042

  日期：1973.8