N,N'-dimethyl-N,N'-diphenylmalonamide | 36949-57-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N,N'-dimethyl-N,N'-diphenylmalonamide
• 英文别名: N¹,N³-dimethyl-N¹,N³-diphenylmalonamide；N,N'-dimethyl-N,N'-diphenylpropanediamide
• CAS: 36949-57-2
• 化学式: C₁₇H₁₈N₂O₂
• 分子量: 282.342
• InChiKey: HFVHOHNNXRSOBQ-UHFFFAOYSA-N

物化性质

• 熔点：
  108 °C
• 沸点：
  424.7±28.0 °C(Predicted)
• 密度：
  1.191±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-dimethyl-N,N'-diphenylmalonamide 在 氯仿 、 硝酸 、 亚硝酰氯 、 sodium nitrite 作用下， 生成 4-methyl-3-oxo-1-oxy-3,4-dihydro-quinoxaline-2-carboxylic acid N-methyl-anilide
  参考文献：
  名称：

  Usherwood; Whiteley, Journal of the Chemical Society, 1923, vol. 123, p. 1082

  摘要：

  DOI：
• 作为产物：
  描述：

  二氧化三碳 、 N-甲基苯胺 在 乙醚 作用下， 生成 N,N'-dimethyl-N,N'-diphenylmalonamide
  参考文献：
  名称：

  Pauw, Recueil des Travaux Chimiques des Pays-Bas, 1936, vol. 55, p. 218

  摘要：

  DOI：

文献信息

• Structural studies of lanthanide complexes with new hydrophobic malonamide solvent extraction agents †
  作者：Peter B. Iveson、Michael G. B. Drew、Michael J. Hudson、Charles Madic

  DOI：10.1039/a905579g

  日期：——

  Two new hydrophobic malonamide ligands butyl-N,N′-dimethyl-N,N′-diphenyl malonamide and ethoxyethyl-N,N′-dimethyl-N,N′-diphenyl malonamide and corresponding lanthanide complexes [Ln(NO3)3(L)2], Ln = Nd or Pr, have been prepared and structurally characterised. The structural studies establish that the alkyl or alkyloxy groups attached to the central carbon atom of the malonamides do not effect the bidentate co-ordination of adjacent carbonyl oxygen atoms. All the metal complexes presented show the lanthanide to be 10-co-ordinate, being bonded to four oxygen atoms of two malonamides and six oxygen atoms of three nitrates. Malonamide ligands with alkyloxy groups have been shown previously to be better extractants for lanthanide(III) and actinide(III) ions than those with just alkyl groups. This solid state evidence seems to suggest that the enhanced extraction performance of ligands with an ether oxygen in the alkyloxy chain is not due to direct co-ordination between the metal ion and the ether oxygen.

  两种新的疏水性丙二酰胺配体丁基-N,N'-二甲基-N,N'-二苯基丙二酰胺和乙氧基乙基-N,N'-二甲基-N,N'-二苯基丙二酰胺及其相应的镧系配合物[Ln(NO3)3(L)2]（Ln=Nd或Pr）已被制备并进行结构表征。结构研究表明，连接在丙二酰胺中心碳原子上的烷基或烷氧基不影响相邻羰基氧原子的双齿配位。所有金属配合物均显示镧系元素为10配位，与两个丙二酰胺的四个氧原子和三个硝酸根的六个氧原子相连。具有烷氧基的丙二酰胺配体此前已被证明对镧系(III)和锕系(III)离子具有更好的萃取性能，而仅含烷基的配体则不然。这种固态证据似乎表明，带有烷氧链中醚氧的配体萃取性能增强的原因并非金属离子与醚氧之间直接配位。
• Electrochemical dehydrogenative cyclization of 1,3-dicarbonyl compounds
  作者：Zheng-Jian Wu、Shi-Rui Li、Hao Long、Hai-Chao Xu

  DOI：10.1039/c8cc02472c

  日期：——

  The intramolecular C(sp3)–H/C(sp2)–H cross-coupling of 1,3-dicarbonyl compounds has been achieved through Cp2Fe-catalyzed electrochemical oxidation. The key to the success of these dehydrogenative cyclization reactions is the selective activation of the acidic α-C–H bond of the 1,3-dicarbonyl moiety to generate a carbon-centered radical.

  1,3-二羰基化合物的分子内C（sp 3）–H / C（sp 2）–H交叉偶联是通过Cp 2 Fe催化的电化学氧化实现的。这些脱氢环化反应成功的关键是选择性激活1,3-二羰基部分的酸性α-C–H键以生成一个以碳为中心的自由基。
• Solvent extraction of metal ions from nitric acid solution using N,N ′-substituted malonamides. Experimental and crystallographic evidence for two mechanisms of extraction, metal complexation and ion-pair formation
  作者：Gabriel Y. S. Chan、Michael G. B. Drew、Michael J. Hudson、Peter B. Iveson、Jan-Olov Liljenzin、Mats Skålberg、Lena Spjuth、Charles Madic

  DOI：10.1039/a605577j

  日期：——

  The solvent extraction of actinides including Am III and Cm III together with some trivalent lanthanides from nitric acid solutions by two newly synthesized malonamides, N,N′-dimethyl-N,N′ -diphenyltetradecylmalonamide (dmptdma) and N,N′-dicyclohexyl-N,N′ -dimethyltetradecylmalonamide (dcmtdma) has been investigated and compared with data for the reference malonamide, N,N′-dibutyl-N,N′ -dimethyloctadecylmalonamide (dbmocma). The dependence of the extraction on the nitric acid and malonamide concentrations together with the probable molecular structure of the extraction species from nitric acid solution suggests that there are two principal mechanisms of extraction. For low nitric acid concentrations (up to 1 mol dm -3 ) a co-ordinative mechanism dominates for the extraction of metal cations, whereas at higher nitric acid concentrations (1–14 mol dm -3 ) an ion-pair mechanism involving the mono- or di-protonated malonamide and the metal anions [M(NO 3 ) 4 ] - or [M(NO 3 ) 5 ] 2- appears to be more important. Crystal structures show that in the protonated, unalkylated species Hdcmma + (dcmma = N,N′-dicyclohexyl-N ,N′-dimethylmalonamide) and in the chelated complexes [Nd(NO 3 ) 3 (dcmma) 2 ], [Nd(NO 3 ) 3 (H 2 O) 2 (dmpma)] and [Yb(NO 3 ) 3 (H 2 O)(dmpma)] (dmpma = N,N′-dimethyl-N ,N′-diphenylmalonamide) the carbonyl oxygens lie cis to each other suggesting that it is the cis form which is involved in extraction. However, crystal structures of the free unalkylated malonamides N,N′-dicyclohexyl-N,N′ -diethylmalonamide and N,N′-dicyclohexyl-N,N′ -diisopropylmalonamide show that the carbonyl amide groups adopt a trans configuration in which the carbonyl oxygens are at maximum separation. By contrast, in the crystal structure of the diphenyl derivative dmpma the carbonyl amide groups adopt a gauche configuration with an OC · · · C O torsion angle of 57.2°. Conformational analysis confirms that the differences in these structures reflect the differences between the lowest-energy gas-phase conformations and are not caused by packing effects.

  研究了两种新合成的丙二酰胺（N,N²-二甲基-N,N²-二苯基十四烷基丙二酰胺（dmptdma）和 N、N,N²-二甲基-N,N²-二苯基十四烷基丙二酰胺（dmptdma）和 N,N²-二环己基-N,N²-二甲基十八烷基丙二酰胺（dbmocma）进行了研究，并与参考丙二酰胺 N,N²-二丁基-N,N²-二甲基十八烷基丙二酰胺（dbmocma）的数据进行了比较。萃取率与硝酸和丙二酰胺浓度的关系以及硝酸溶液中萃取物的可能分子结构表明，萃取主要有两种机制。 在硝酸浓度较低（1 摩尔分米-3 以下）的情况下，金属阳离子的萃取主要采用协同机制，而在硝酸浓度较高（1â14 摩尔分米-3）的情况下，涉及单质子或双质子丙二酰胺和金属阴离子 [M(NO 3 ) 4 ] - 或 [M(NO 3 ) 5 ] 2 - 的离子对机制似乎更为重要。 [Nd(NO 3 ) 3 (H 2 O) 2 (dmpma)]和[Yb(NO 3 ) 3 (H 2 O) (dmpma)]（dmpma = N,N²-二甲基-N,N²-二苯基丙二酰胺）的螯合物中，羰基氧原子互为顺式，表明参与萃取的是顺式。然而，游离的未烷基化丙二酰胺 N,N²-二环己基-N,N²-二乙基丙二酰胺和 N,N²-二环己基-N,N²-二异丙基丙二酰胺的晶体结构显示，羰基酰胺基团采用反式构型，其中羰基氧原子的距离最大。与此相反，在二苯基衍生物 dmpma 的晶体结构中，羰基酰胺基团采用的是 OC Â- Â- Â- C O 扭转角为 57.2°的高扭构型。构象分析证实，这些结构的差异反映了最低能量气相构象之间的差异，而不是由堆积效应引起的。
• Asymmetric Organocatalytic Direct C(sp²)H/C(sp³)H Oxidative Cross-Coupling by Chiral Iodine Reagents
  作者：Hua Wu、Yu-Ping He、Lue Xu、Dong-Yang Zhang、Liu-Zhu Gong

  DOI：10.1002/anie.201309967

  日期：2014.3.24

  An asymmetric organocatalytic direct CH/CH oxidative coupling reaction of N1,N3‐diphenylmalonamides has been well established by using chiral organoiodine compounds as catalysts, wherein four CH bonds were stereoselectively functionalized to give structurally diverse spirooxindoles with high levels of enantioselectivity. More importantly, the findings indicated that chiral hypervalent organoiodine

  不对称的有机催化直接Ç  H / C  ħ氧化偶联反应Ñ 1，Ñ 3 -diphenylmalonamides已经很好地利用建立手性有机碘化合物作为催化剂，其特征在于，四号丙 H键被立体选择性地官能化以得到具有高结构多样spirooxindoles对映选择性水平。更重要的是，这些发现表明，手性高价有机碘试剂可作为替代催化剂，用于创建无活性CH键的对映选择性官能化。
• SEPARATION REAGENT OF PLATINUM GROUP METAL, METHOD FOR SEPARATING AND RECOVERING PLATINUM GROUP METAL, AND AMIDE-CONTAINING TERTIARY AMINE COMPOUND
  申请人：NARITA Hirokazu

  公开号：US20100095807A1

  公开（公告）日：2010-04-22

  The present invention provides a novel separation reagent capable of obtaining a high extraction % of rhodium in a chlorine-based acid solution, which has never existed heretofore, and a method for separating and recovering a platinum group metal using the same. An organic phase composed of an amide-containing tertiary amine separation reagent represented by the structural formula shown below is brought into contact with an acid solution containing a platinum group metal, thereby extracting rhodium, platinum and palladium with the organic phase. Among the metals extracted with the organic phase, rhodium is selectively back-extracted with a highly-concentrated hydrochloric acid solution, while palladium and platinum are back-extracted with a highly-concentrated nitric acid solution: wherein at least one of R 1 , R 2 and R 3 represents an amide group represented by: R 1 to R 3 other than the amide group and R 4 to R 6 represent a group selected from an optionally branched chain hydrocarbon group of 1 to 18 carbon atoms, an alicyclic hydrocarbon group of 1 to 10 carbon atoms, and an aromatic hydrocarbon group of 1 to 14 carbon atoms.

  本发明提供了一种新型分离试剂，能够在含氯酸溶液中获得高萃取率的铑，此前从未存在过，以及使用该试剂分离和回收铂族金属的方法。将由下式表示的含酰胺的三级胺分离试剂组成的有机相与含铂族金属的酸性溶液接触，从而用有机相萃取铑、铂和钯。在从有机相中萃取的金属中，铑选择性地被高浓度盐酸溶液回萃，而钯和铂则被高浓度硝酸溶液回萃：其中，R1、R2和R3中的至少一个表示由下式表示的酰胺基：R1到R3除了酰胺基外，R4到R6表示选自1到18个碳原子的可选支链烃基、1到10个碳原子的脂环烃基和1到14个碳原子的芳香烃基的基团。