N-(4,4-dicyano-3-phenyl-1,3-butadienyl)-N,2,2-trimethylpropanamide | 244019-35-0

• 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-(4,4-dicyano-3-phenyl-1,3-butadienyl)-N,2,2-trimethylpropanamide
• 英文别名: N-[(1E)-4,4-dicyano-3-phenylbuta-1,3-dienyl]-N,2,2-trimethylpropanamide
• CAS: 244019-35-0
• 化学式: C₁₈H₁₉N₃O
• 分子量: 293.368
• InChiKey: BXTXAGRFOSAMPI-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  67.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  四氢吡咯 、 N-(4,4-dicyano-3-phenyl-1,3-butadienyl)-N,2,2-trimethylpropanamide 以 乙腈 为溶剂， 反应 0.25h， 以73%的产率得到2-(1-phenyl-3-pyrrolidin-1-yl-2-propenylidene)-1,3-propanedinitrile
  参考文献：
  名称：

  The Analogy Between C=O and C=C(CN)2: Structural Properties of 3-(N,N-Dialkylamino)propenones and 4-(N,N-Dialkylamino)-1,1-dicyano-1,3-butadienes.

  摘要：

  The barriers to rotation around the carbon-amino nitrogen bond in (3-(N,N-dimethylamino)-1-phenyl-2-propenylidene)propanedinitrile (1a), (3-N,N-diethylamino)-1-phenyl-2-propenylidene)propanedinitrile (1b), 1-phenyl-[(3-(N-pyrrolidine)-2-propenylidene) propanedinitrile (1c), 3-(N,N-dimethylamino)-1-phenyl-2-propene-1-one (2a), 3-(N,N-diethylamino)-1-phenyl-2-propene-1-one (2b) and 1-phenyl-(3-N-pyrrolidine)-2-propene-1-one (2c) were determined using H-1 NMR spectroscopy. X-Ray crystal structures of 1b, 1c, 2b and 2c were determined, and quantum chemical calculations were carried out for model compounds of 1 and 2 and for the transition state for the rotation process for these models. The measured barriers (by NMR) far compounds 2 were about 10 kJ mol(-1) lower than for compounds 1, results explained by the longer bond distance between the amino nitrogen and the connecting carbon atom in the former compounds, and qualitatively in line with the calculation results. Bond lengths around the C=C(CN)(2) structure element indicate that the conjugation in the chain in 1 does not involve the cyano groups, and that their electronic effect is purely electrostatic; they only exert an inductive effect on the conjugated system.

  DOI：

  10.3891/acta.chem.scand.52-0391
• 作为产物：
  描述：

  N¹,N²,N²-trimethyl-N¹-2,2-dimethylpropionylamidinium trifluoromethanesulfonate 、 2-(1-phenylethylidene)-1,3-propanedinitrile 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-(3-dimethylamino-1-phenyl-2-propenylidene)-1,3-propanedinitrile 、 N-(4,4-dicyano-3-phenyl-1,3-butadienyl)-N,2,2-trimethylpropanamide
  参考文献：
  名称：

  Reactions between 1,1-Dicyano-2-phenylallyl Anion and Some Substituted Trifluoromethanesulfonates. Part 2. Kinetics and Mechanism.

  摘要：

  The reaction between 1,1-dicyano-2-phenylallyl anion (potassium salt) (1) and N-1,N-2,N-2-trimethyl-N-1-(2,2-dimethylpropionyl)amidinium triflate (2a) in acetonitrile was monitored by HPLC. The reaction between the salts was instantaneous, yielding a tetrahedral intermediate (3a) which decomposed within one minute at room temperature, apparently by a first order process, to give N-(4,4-dicyano-3-phenyl-1,3-butadienyl)-N2,2-trimethylpropanamide (5) and dimethylamine (6a). Then, in a higher order process, 5 and 6a react to give 2-(3-dimethylamino-1-phenyl-2-propenylidene)-1,3-propanedinitrile (4a) and N2,2-trimethylpropanamide (7). When the mixture of the two salts (1 and 2a) was quenched (H3O+) immediately after mixing 4a and 7 were the only products. Owing to difficulties in purification and handling of salts 1 and 2, the analytical results of the kinetic runs were considerably scattered. Therefore, the kinetic studies were concentrated on simulation of the latter step, thus the reaction of presynthezised 5 with diethylamine (6b) was used to establish the reaction order. Both conventional and pseudo-first-order kinetics lead to the conclusion that the reaction is of overall third order, first order in amide 5 and second order in diethylamine; the latter molecule adds nucleophilically to the amide to form the Michael adduct, the tetrahedral intermediate 3b, and subsequently acts as a base in the beta-elimination of the adduct.

  DOI：

  10.3891/acta.chem.scand.53-0487

文献信息

• The Analogy Between C=O and C=C(CN)2: Structural Properties of 3-(N,N-Dialkylamino)propenones and 4-(N,N-Dialkylamino)-1,1-dicyano-1,3-butadienes.
  作者：Hege Karlsen、Per Kolsaker、Christian Rømming、Einar Uggerud、Louisa Barré、Ole Hammerich、Inger Søtofte、Bengt Långström

  DOI：10.3891/acta.chem.scand.52-0391

  日期：——

  The barriers to rotation around the carbon-amino nitrogen bond in (3-(N,N-dimethylamino)-1-phenyl-2-propenylidene)propanedinitrile (1a), (3-N,N-diethylamino)-1-phenyl-2-propenylidene)propanedinitrile (1b), 1-phenyl-[(3-(N-pyrrolidine)-2-propenylidene) propanedinitrile (1c), 3-(N,N-dimethylamino)-1-phenyl-2-propene-1-one (2a), 3-(N,N-diethylamino)-1-phenyl-2-propene-1-one (2b) and 1-phenyl-(3-N-pyrrolidine)-2-propene-1-one (2c) were determined using H-1 NMR spectroscopy. X-Ray crystal structures of 1b, 1c, 2b and 2c were determined, and quantum chemical calculations were carried out for model compounds of 1 and 2 and for the transition state for the rotation process for these models. The measured barriers (by NMR) far compounds 2 were about 10 kJ mol(-1) lower than for compounds 1, results explained by the longer bond distance between the amino nitrogen and the connecting carbon atom in the former compounds, and qualitatively in line with the calculation results. Bond lengths around the C=C(CN)(2) structure element indicate that the conjugation in the chain in 1 does not involve the cyano groups, and that their electronic effect is purely electrostatic; they only exert an inductive effect on the conjugated system.
• Reaction between 2-Phenyl-1,1-dicyanoallyl Anion and N-Methyl-2,2-dimethylpropionitrilium and N1,N2,N2-Trimethyl-2,2-dimethylpropionylamidinium Trifluoromethanesulfonates.
  作者：Per Kolsaker、Hege Karlsen、Christian Rømming、Joseph Arukwe、Jo Klaveness、Frode Rise、Kjell Undheim、Connie N. Rosendahl、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0623

  日期：——

  The reaction of 2-phenyl-1,1-dicyanoallyl anion with N-methyl-2,2-dimethyl-propionitrilium ion (2) in acetonitrile solution resulted in formation of [3-(N-methylamino)-4,4-dimethyl-1-phenyl-2-pentenylidene]propanedinitrile (6), which at elevated temperature (25-50 degrees C, depending on the solvent) undergoes a ring closure to 2-(N-methylamino)-3-cyano-4-phenyl-6-tert-butylpyridine (7) or in the presence of aqueous acid to 3-cyano-4-phenyl-6-tert-butyl-2-pyrone (8). Using N,N-dimethylformamide as solvent, in addition to 7, two other compounds are formed, viz. (3-(N,N-dimethylamino)-1-phenyl-2-propenylidene)propanedinitrile (9) and N-(4,4-dicyano-3-phenyl-1, 3-butadienyl)-N,2,2-trimethylpropanamide (10). The latter two compounds are results of a primary reaction of the title nitrilium ion with the solvent to give N-1,N-2,N-2-trimethyl-N-1-2,2-dimethyl-propionylamidinium trifluoromethanesulfonate (11) which in turn reacted with the title allyl anion 2 to give 9 and 10, for which X-ray crystal structures were determined. Strong indications of a tetrahedral mechanism in the reaction of 2 with 11 are presented.
• Reactions between 1,1-Dicyano-2-phenylallyl Anion and Some Substituted Trifluoromethanesulfonates. Part 2. Kinetics and Mechanism.
  作者：Hege Karlsen、Per Kolsaker、Anneli Hase、Vladimir Tolmachev、Bengt Långström、Shi-Ping Yan、Geng-Lin Wang、Xin-Kan Yao、Hong-Gen Wang、J. -P. Tuchagues、Mattias Ögren

  DOI：10.3891/acta.chem.scand.53-0487

  日期：——

  The reaction between 1,1-dicyano-2-phenylallyl anion (potassium salt) (1) and N-1,N-2,N-2-trimethyl-N-1-(2,2-dimethylpropionyl)amidinium triflate (2a) in acetonitrile was monitored by HPLC. The reaction between the salts was instantaneous, yielding a tetrahedral intermediate (3a) which decomposed within one minute at room temperature, apparently by a first order process, to give N-(4,4-dicyano-3-phenyl-1,3-butadienyl)-N2,2-trimethylpropanamide (5) and dimethylamine (6a). Then, in a higher order process, 5 and 6a react to give 2-(3-dimethylamino-1-phenyl-2-propenylidene)-1,3-propanedinitrile (4a) and N2,2-trimethylpropanamide (7). When the mixture of the two salts (1 and 2a) was quenched (H3O+) immediately after mixing 4a and 7 were the only products. Owing to difficulties in purification and handling of salts 1 and 2, the analytical results of the kinetic runs were considerably scattered. Therefore, the kinetic studies were concentrated on simulation of the latter step, thus the reaction of presynthezised 5 with diethylamine (6b) was used to establish the reaction order. Both conventional and pseudo-first-order kinetics lead to the conclusion that the reaction is of overall third order, first order in amide 5 and second order in diethylamine; the latter molecule adds nucleophilically to the amide to form the Michael adduct, the tetrahedral intermediate 3b, and subsequently acts as a base in the beta-elimination of the adduct.