dimethyl (Z)-2-hexenedioate | 16631-58-6

• 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 (Z)-2-hexenedioate
• 英文别名: Dimethyl-cis-α-hydromuconat；dimethyl (Z)-hex-2-enedioate
• CAS: 16631-58-6
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: QPFMISCWBTXLFC-HYXAFXHYSA-N

物化性质

• 沸点：
  101-104 °C(Press: 2 Torr)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  甲醇 、 2,2-二氯-1,3-环己二酮 在 sodium methylate 作用下， 生成 dimethyl (Z)-2-hexenedioate
  参考文献：
  名称：

  Schamp,N., Bulletin des Societes Chimiques Belges, 1967, vol. 76, p. 400 - 406

  摘要：

  DOI：

文献信息

• Expanding the Scope of the Tail-to-Tail Dimerization of Vinyl Compounds Catalyzed by N-Heterocyclic Carbene
  作者：Shin-ichi Matsuoka、Masanori Nakazawa、Masato Suzuki

  DOI：10.1246/bcsj.20150048

  日期：2015.8.15

  The tail-to-tail dimerization of vinyl compounds catalyzed by an N-heterocyclic carbene was found to show a very broad substrate scope and tolerance to various functional groups. The optimization o...

  发现由 N-杂环卡宾催化的乙烯基化合物的尾对尾二聚反应显示出非常广泛的底物范围和对各种官能团的耐受性。优化...
• Dimerization of methyl acrylate by homogeneous transition metal catalysis. Part II. Activation of dihydridoruthenium(II) phosphane complexes by CF3 3H
  作者：Barbara Patzke、Reiner Sustmann

  DOI：10.1016/0022-328x(94)87103-5

  日期：1994.10

  ligand. The basic mechanistic features of the dimerization reaction have been revealed by 2H NMR spectroscopy involving the use of CF3SO3D. The deuterium-labelling studies indicate the intermediate formation of a ruthenium(II) hydride complex. Subsequent olefin insertions in this complex, followed by β-hydride elimination,lead to the linear dimeric products.

  在H 2 Ru（PPh 3）4（1）或H 2（CO）Ru（PPh 3）3（2）和CF 3 SO 3 H存在下，丙烯酸甲酯（MA）的尾到尾二聚给出了线性二聚体的混合物的描述。在85°C的纯丙烯酸甲酯中，反应在20小时内显示300的转换率，在7天内显示640的转换率。机理研究表明，反应的第一步是通过MA还原H 2 Ru（PPh 3）4（1）形成Ru（MA）2（PPh 3）2（5）。用CF 3 SO 3 H活化后，催化活性物质仅包含一种膦配体。通过使用CF 3 SO 3 D的2 H NMR光谱揭示了二聚反应的基本机理。氘标记研究表明氢化钌（II）配合物的中间形成。随后在该络合物中插入烯烃，然后消除β-氢化物，生成线性二聚体产物。
• Design and Study of Rh(III) Catalysts for the Selective Tail-to-Tail Dimerization of Methyl Acrylate
  作者：Elisabeth Hauptman、Sylviane Sabo-Etienne、Peter S. White、Maurice Brookhart、J. Michael Garner、Paul J. Fagan、Joseph C. Calabrese

  DOI：10.1021/ja00097a011

  日期：1994.9

  The development of an efficient, highly selective Rh(III) catalyst system for the tail-to-tail dimerization of methyl acrylate (MA) to dimethyl hexenedioates, precursors to adipic acid, is described. The catalytic cycle is entered by protonation of Cp*Rh(C2H4)(2)l(Cp* = C(5)Me(5)) to yield Cp*Rh(C2H4) (CH2CH2-mu-H)(+) (7) followed by reaction with methylacrylate. The catalyst resting state has been generated by low-temperature protonation of Cp*Rh(CH2CHCO2-CH3)(2)l (15) and identified as Cp*Rd(CH(2)CH(2)COOMe)(eta(2)-CH(2)CHCO(2)Me)(+) (8) by H-1 and C-13 NMR spectroscopy. Investigation of iridium analogs has led to the isolation and X-ray structural characterization of Cp*Ir(CH(2)CH(2)COOMe)(eta(2)-CH(2)CHCO(2)Me)(+) (23a), in which the orientation of the acrylate ligands is that required for tail-to-tail coupling. At -23 degrees C, complex 8 undergoes beta-migratory insertion to give Cp*RhCH(CH(2)COOMe)(CH2-CH(2)COOMe)(+) (10). Complex 10 was independently synthesized by treatment of complex 7 with trans-MeO(2)CCH=CHCH(2)CH(2)CO(2)Me and was characterized by X-ray crystallography. The free energy of activation for the migration reaction is 18.7 kcal/mol and matches that based on the catalytic turnover (TO) frequency (6.6 TO/min at 25 degrees C, Delta G* = 19 kcal/mol).This observation confirms 8 as the resting state and the C-C coupling reaction as the turnover-limiting step. The catalyst deactivates by formal loss of Hz from complex 10 to produce Cp*Rh(eta(3)-CH3OCOCH2CHCHCHCO2CH3)(+) (9). The structure of complex 9 was verified by an X-ray crystallographic study. Exposure of 9 to an atmosphere of H-2 in the presence of MA regenerates the resting state 8, and dimerization proceeds. Second generation catalysts with increased activity and lifetimes have been developed by replacing the C(5)Me(5) ligand by methylated indenyl ligands. Using the catalytic system derived from (1,2,3-trimethylindenyl)Rh(C2H4>(2) (11), conversion of 54 000 equiv of methyl acrylate to dimethyl hexenedioates could be achieved after 68 h at 55 OC under N-2. Details of the mechanism have been elucidated and resemble closely those of the Cp* system. Similar intermediates to 8 and 10 have been characterized by H-1 and C-13 NMR spectroscopy. In contrast, treatment with methyl acrylate of the more electrophilic systems derived from CpRh(C2H4)(2) (25) (Cp = C5H5) and Cp*Rh(C2H4)(2) (30) (Cp* = C-5(CH3)(4)CF3) results in slow dimerization. Low-temperature protonation of CpRh(CH2CHCO2CH3)(2) (27) with H(Et(2)O)(2)BAr'(4) yields a mixture of rhodium species which upon warming to 23 degrees C converge to the bis-chelate complex CpRhCH(CH(2)COOMe)(CH(2)CH(2)COOMe)(+) (28). Exposure of complex 28 to MA generates the unusual bridged species CpRh(CH2CHCOOCH3)H(CH2CHCOOCH3)(+) (29), which serves as the resting state during dimerization. Treatment of complex 30 with H(Et(2)O)(2)BAr'(4) yields Cp*Rh(C2H4)(CH2CH2-mu-H)(+) (31), which upon reaction with MA clearly produces Cp*RhCH(CH(2)COOMe)(CH(2)CH(2)COOMe)(+) (33), and dimerization proceeds. Finally, attempts to catalyze the dimerization of other functionalized olefins including methyl vinyl ketone, methyl crotonate, 2-vinylpyridine, and 1-vinyl-2-pyrrolidinone are presented.
• Brookhart, Maurice; Sabo-Etienne, Sylviane, Journal of the American Chemical Society, 1991, vol. 113, # 7, p. 2777 - 2779
  作者：Brookhart, Maurice、Sabo-Etienne, Sylviane

  DOI：——

  日期：——