2-甲基戊二醛 | 7420-87-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-甲基戊二醛
• 英文名称: 2-methylpentanedial
• 英文别名: 2-methyl-pentanedial；2-methyl-glutaraldehyde；2-Methyl-glutaraldehyd；2-methylglutaraldehyde
• CAS: 7420-87-3
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: IQKPRZPVTQHVOY-UHFFFAOYSA-N

物化性质

• 沸点：
  86-88 °C(Press: 17 Torr)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-甲基戊二醛 以 二氯甲烷 为溶剂， 生成 3-methyl-4H-pyran
  参考文献：
  名称：

  Isomerization and fragmentation of methylfuran ions and pyran ions in the gas phase

  摘要：

  AbstractThe mutual interconversion of the molecular ions [C5H6O]+ of 2‐methylfuran (1), 3‐methylfuran (2) and 4H‐pyran (3) before fragmentation to [C5H5O]+ ions has been studied by collisional activation spectrometry, by deuterium labelling, by the kinetic energy release during the fragmentation, by appearance energles and by a MNDO calculation of the minimum energy reaction path. The electron impact and collisional activation mass spectra show clearly that the molecular ions of 1–3 do not equilibrate prior to fragmentation, but that mostly pyrylium ions [C5H5O]+ arise by the loss of a H atom. This implies an irreversible isomerization of methylfuran ions 1 and 2 into pyran ions before fragmentation, in contrast to the isomerization of the related systems toluene ions/cycloheptatriene ions. Complete H/D scrambling is observed in deuterated methylfuran ions prior to the H/D loss that is associated with an iostope effect kH/kD = 1.67–2.16 for metastable ions. In contrast, no H/D scrambling has been observed in deuterated 4H‐pyran ions. However, the loss of a H atom from all metastable [C5H5O]+ ions gives rise to a flat‐topped peak in the mass‐analysed ion kinetic energy spectrum and a kinetic energy release (T50) of 26 ± 1.5 kJ mol−1. The MNDO calculation of the minimum energy reaction path reveals that methylfuran ions 1 and 2 favour a rearrangement into pyran ions before fragmentation into furfuryl ions, but that the energy barrier of the first rearrangement step is at least of the same height as the barrier for the dissociation of pyran ions into pyrylium ions. This agrees with the experimental results.

  DOI：

  10.1002/oms.1210210803
• 作为产物：
  描述：

  2-ethoxy-3-methyl-3,4-dihydro-2H-pyran 在 盐酸 作用下， 生成 2-甲基戊二醛
  参考文献：
  名称：

  685.还原的环状化合物。第五部分。5：6-二氢-3-甲基-4 H-吡喃的制备及其转化为4-甲基-己基-反式-4-烯-1-醇

  摘要：

  DOI：

  10.1039/jr9580003388

文献信息

• Synthesis, complexation behavior and catalytic performance of chelating bisphosphite ligands based on 9,10-brigded 9,10-dihydroanthracenes in Rh catalyzed hydroformylation of 4-pentenal
  作者：Bojan P. Bondžić、Frank Rominger、Peter Hofmann

  DOI：10.1016/j.molcata.2016.07.049

  日期：2016.11

  technique. Modular synthesis route was established allowing for a variety of ligands to be synthesized in a standard procedure The new ligands were tested in the hydroformylation of 4-pentenal under optimized conditions to give adipic aldehyde a promising starting material for the polyamide nylon-6,6. Ligand L3 showed the best selectivity towards adipic aldehyde with selectivity of 10.2/1 n/iso aldehyde

  摘要 在目前的工作中，提出了基于 9,10-桥 9,10-二氢蒽作为配体骨架的新型螯合双亚磷酸酯配体的模块化合成。研究了这些配体在铑金属配合物中的络合行为以及铑催化加氢甲酰化的预形成步骤的机理研究。已使用基于 NMR 的计算技术确定了这些配体的 Rh 配合物中配位异构体的比例。建立了模块化合成路线，允许在标准程序中合成各种配体。在优化的条件下，在 4-戊烯醛的加氢甲酰化中测试了新的配体，使己二醛成为聚酰胺尼龙 6,6 的有希望的起始材料。配体 L3 对己二醛的选择性最好，选择性为 10。
• Butadiene hydroformylation to adipaldehyde with Rh-based catalysts: Insights into ligand effects
  作者：Si-min Yu、William K. Snavely、Raghunath V. Chaudhari、Bala Subramaniam

  DOI：10.1016/j.mcat.2019.110721

  日期：2020.3

  CO/H2 = 1) pressure in a batch reactor. Specifically, the effects of operating conditions and eight commercially available ligands on activity and selectivity were systematically investigated. It was found that the adipaldehyde selectivity is independent of the ligand/Rh ratio, rhodium concentration, butadiene concentration and syngas pressure, but significantly dependent on the type of ligand used. For

  丁二烯经Rh催化加氢甲酰化成己二醛是生产有价值的C 6化合物（如己二酸和六亚甲基二胺）的有前途的替代途径。在80°C和14 bar合成气（CO / H 2摩尔比）下，从时间浓度分布图和在Rh配合物上丁二烯加氢甲酰化的原位ReactIR研究获得了旨在提高己二醛收率的反应途径的基本见解。 = 1）分批反应器中的压力。具体而言，系统地研究了操作条件和八种市售配体对活性和选择性的影响。发现己二醛的选择性与配体/ Rh比，铑浓度，丁二烯浓度和合成气压力无关，但显着取决于所用配体的类型。例如，当DIOP配体以丁二烯为底物可提供约40％的己二醛产率，而6-DPPon配体以4-戊烯为底物可提供约93％的最大己二醛产率。此外，己二醛的选择性与各种配体的自然咬合度密切相关。的ReactIR研究表明，优先形成稳定的铑η 3-巴豆基配合物与各种Rh配合物可能是导致己二醛选择性低的主要原因。
• Toward the Rhodium-Catalyzed Bis-Hydroformylation of 1,3-Butadiene to Adipic Aldehyde
  作者：Stuart E. Smith、Tobias Rosendahl、Peter Hofmann

  DOI：10.1021/om200334g

  日期：2011.7.11

  of all of these reaction parameters, except for ligand structure. However, the reaction parameters do have a substantial effect on the selectivity for the products, resulting from the branched addition of the rhodium hydride to the carbon–carbon double bond. The optimum reaction parameters and ligand have resulted in a so far unprecedented maximum selectivity of 50% for adipic aldehyde.

  在铑催化的1,3的低压羰基化反应中，研究了12种最合理的产物对配体与金属比，温度，合成气压力，H 2和CO的分压以及新的配体结构的影响。 -丁二烯。对于所需的线性二氢甲酰基化产物1，6-己二醛（己二醛）的选择性，除配体结构外，基本上与所有这些反应参数无关。但是，由于氢化铑支链加成到碳-碳双键上，反应参数确实对产物的选择性有很大影响。最佳的反应参数和配体导致对己二醛的前所未有的最大选择性达到50％。
• [EN] HETEREOCYCLIC AGENT AS CATALYTIC STABILIZING AGENT IN A HYDROFORMYLATION PROCESS<br/>[FR] AGENT HÉTÉROCYCLIQUE COMME AGENT DE STABILISATION CATALYTIQUE DANS UN PROCÉDÉ D'HYDROFORMYLATION
  申请人：DOW TECHNOLOGY INVESTMENTS LLC

  公开号：WO2014149915A1

  公开（公告）日：2014-09-25

  A heterocyclic nitrogen stabilizing agent is employed to reduce the rate of catalyst deactivation in a hydroformylation process.

  在氢甲酰化过程中，使用杂环氮稳定剂来降低催化剂失活的速率。
• Evidence for isomerizing hydroformylation of butadiene. A combined experimental and computational study
  作者：Tapan Maji、Camina H. Mendis、Ward H. Thompson、Jon A. Tunge

  DOI：10.1016/j.molcata.2016.08.021

  日期：2016.12

  selectivities for formation of adipaldehyde, which is useful for the synthesis of nylon. Herein, isomerizing hydroformylation is shown to be a mechanism that is partially responsible for this selectivity and density functional theory studies are used to reveal the detailed pathway for the requisite alkene isomerization.

  摘要 （DIOP）铑催化的丁二烯加氢甲酰化反应对生成己二醛的选择性最高，可用于尼龙的合成。在此，异构化加氢甲酰化被证明是一种部分负责这种选择性的机制，密度泛函理论研究用于揭示所需烯烃异构化的详细途径。