Dimethyl <2,3-2H2>maleate | 41411-75-0

• 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: Dimethyl <2,3-2H2>maleate
• 英文别名: [2H2]-dimethyl maleate；2,3-Dideutero-maleinsaeure-dimethylester；2,3-dideuterio-maleic acid dimethyl ester；dimethyl (Z)-2,3-dideuteriobut-2-enedioate
• CAS: 41411-75-0
• 化学式: C₆H₈O₄
• 分子量: 146.111
• InChiKey: LDCRTTXIJACKKU-KKLCAENNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.11
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Dimethyl <2,3-2H2>maleate 在 [Rh(COD)(DPPB)]BF₄ 氢气 作用下， 以 丙酮 为溶剂， 生成 dimethyl (2,3-(2)H2)succinate
  参考文献：
  名称：

  Polarization transfer from para-hydrogen to heteronuclei: Effect of H/D substitution. The case of AA′X and spin systems

  摘要：

  Upon hydrogenation from para-hydrogen (p-H-2), hyperpolarization transfer toward a heteronucleus may be possible even if the two protons are chemically equivalent in the final product (but not magnetically equivalent), provided that J couplings with the heteronucleus exist. It is however shown (theoretically and experimentally) that this transfer effectively occurs if the spin system in the hydrogenated molecule is of the type AA'X (A and A' denoting the two protons originating from p-H-2 and X the heteronucleus) but does not occur for a spin system of the AA'X type. A theory has been worked out for assessing the details of the X spectrum (multiplet patterns) in the case of ALTADENA and PASADENA experiments. Experimental verifications are provided. (c) 2005 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jmr.2005.09.008
• 作为产物：
  描述：

  丁炔二酸二甲酯 在 C₅₆H₅₂Fe₂OP₄S₂ 、 氘 作用下， 以 四氢呋喃 为溶剂， 生成 Dimethyl <2,3-2H2>maleate
  参考文献：
  名称：

  末端氢化物在二硫代二铁上的新反应

  摘要：

  生物和受生物启发的二氢活化和生产机制通常会调用二硫代二铁二氢化物的中间体。这种 Fe2(SR)2H2 物质的第一个例子是由复合物 [(term-H)(μ-H)Fe2(pdt)(CO)(dppv)2] ([H1H](0)) 提供的。光谱和计算研究表明 [H1H](0) 包含一个桥连氢化物和一个末端氢化物，特别是占据了一个基础位点。合成从 [(μ-H)Fe2(pdt)(CO)2(dppv)2](+) ([H1(CO)](+)) 开始，经过取代得到 [(μ-H)Fe2 (pdt)(CO)(NCMe)(dppv)2](+) ([H1(NCMe)](+))。用硼氢化物盐处理 [H1(NCMe)](+) 后，MeCN 配体被置换得到 [H1H](0)。该复合物的 DNMR (EXSY, SST) 实验表明，末端和桥连氢化物配体在 -40 °C 下以 1 s(-1) 的速率进行分子内交换。该化合物与 D2

  DOI：

  10.1021/ja501366j

文献信息

• Chemistry in water - Part VI Catalytic isomerization and stereochemistry of reduction of acetylenics mediated by water-soluble phosphines
  作者：Chantal Larpent、Gérard Meignan

  DOI：10.1016/s0040-4039(00)79342-7

  日期：1993.7

  Reaction of water-soluble phosphines with disubstituted electrodeficient alkynes in H2O (D2O) gives rise either to mixtures of cis and trans (dideuterated) olefins or specifically to trans (dideuterated) olefins, by simple control of the phosphine amount. A cis-trans olefin isomerization catalyzed by sulfonated phosphines occurs in water and allows the obtention of specifically trans disubstituted

  通过简单地控制膦的量，水溶性膦与H 2 O（D 2 O）中的双取代电有效炔烃的反应产生了顺式和反式（去氘代）烯烃的混合物，或者特别是反式（去氘代）烯烃的混合物。磺化膦催化的顺-反烯烃异构化反应在水中发生，可从相应的顺式异构体中获得特定的反式二取代烯烃。
• Microwave Spectra and Molecular Structures of (<i>Z</i>)-Pent-2-en-4-ynenitrile and Maleonitrile
  作者：Robert J. Halter、Ryan L. Fimmen、Robert J. McMahon、Sean A. Peebles、Robert L. Kuczkowski、John F. Stanton

  DOI：10.1021/ja011195t

  日期：2001.12.1

  Accurate equilibrium structures have been determined for (Z)-pent-2-en-4-ynenitrile (8) and maleonitrile (9) by combining microwave spectroscopy data and ab initio quantum chemistry calculations. The microwave spectra of 10 isotopomers of 8 and 5 isotopomers of 9 were obtained using a pulsed nozzle Fourier transform microwave spectrometer. The ground-state rotational constants were adjusted for vibration-rotation

  通过结合微波光谱数据和 ab initio 量子化学计算，已经确定了 (Z)-pent-2-en-4-炔腈 (8) 和马来腈 (9) 的准确平衡结构。使用脉冲喷嘴傅里叶变换微波光谱仪获得了 8 种同位素的 10 种和 9 种同位素的 5 种的微波光谱。基态旋转常数根据从 ab initio 计算获得的力场计算的振动-旋转相互作用效应进行了调整。所得的平衡旋转常数用于确定与从高级 ab initio 计算 (CCSD(T)/cc-pVTZ) 获得的结构非常一致的结构。8和9中的几何参数非常相似；它们也与全碳类似物 (Z)-hex-3-ene-1,5-diyne (7) 没有显着差异，伯格曼环化的母体分子。观察到 7-9 和几个相关物种的炔烃和氰基键的线性偏差很小，其中有准确的平衡参数可用。7-9 的数据应该对射电天文学感兴趣，并且可以提供对不饱和物质（如氰基多炔）的形成和星际化学的见解。
• New insight into the pyruvate decarboxylase-catalysed formation of lactaldehyde from H–D exchange experiments: a ‘water proof’ active site
  作者：Mario Lobell、David H. G. Crout

  DOI：10.1039/p19960001577

  日期：——

  Pyruvate decarboxylase from Saccharomyces cerevisiae catalyses the formation of lactaldehyde from sodium glyoxylate and acetaldehyde. By using deuteriated sodium glyoxylate (sodium [2-H-2] glyoxylate monohydrate) as a substrate it was verified that the lactaldehyde formed retains the deuterium atom. The implications of the observed result for the enzyme mechanism are discussed in the light of conclusions derived from recent molecular modelling studies.