N-[(diisopropylamino)methylene]benzamide

• 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-[(diisopropylamino)methylene]benzamide
• 英文别名: N'-benzoyl-N,N-diisopropylformamidine
• 化学式: C₁₄H₂₀N₂O
• 分子量: 232.326
• InChiKey: JTUPWKYSCPYXDV-XNTDXEJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.97
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  32.67
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N-[(diisopropylamino)methylene]benzamide 、 仲丁胺 在 氯化锆(IV) 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 以56.7 mg的产率得到N-仲-丁基苯甲酰胺
  参考文献：
  名称：

  Efficient Transamidation of Primary Carboxamides by in Situ Activation with N,N-Dialkylformamide Dimethyl Acetals

  摘要：

  Two protocols for the transamidation of primary amides with primary and secondary amines, forming secondary and tertiary amides, respectively, are described. Both processes employ N,N-dialkylformamide dimethyl acetals for primary amide activation, producing N'-acyl-N,N-dialkylformamidines as intermediates, as widely documented in the literature. Although the latter intermediates react irreversibly with amines by amidinyl transfer, we show that in the presence of certain Lewis acid additives efficient acyl transfer occurs, providing new and useful methods for amide exchange. In one protocol for transamidation, the N'-acyl- N,N-dialkylformamidine intermediates are purified by flash-column chromatography and the purified intermediates are then treated with an amine (typically, 2.5 equiv) in the presence of scandium triflate (10 mol %) in ether to form in high yields the products of transamidation. In a second procedure, N'-acyl-N,N-dialkylformamidines are generated in situ and, without isolation, are subjected to transamidation in the presence of zirconium chloride (0.5 equiv) and an amine (typically 2 equiv). A variety of different primary amides and amines are found to undergo efficient transamidation using the methods described.

  DOI：

  10.1021/ja066728i
• 作为产物：
  描述：

  N,N-二异丙基甲酰胺 在 5A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 113.0h， 生成 N-[(diisopropylamino)methylene]benzamide
  参考文献：
  名称：

  Efficient Transamidation of Primary Carboxamides by in Situ Activation with N,N-Dialkylformamide Dimethyl Acetals

  摘要：

  Two protocols for the transamidation of primary amides with primary and secondary amines, forming secondary and tertiary amides, respectively, are described. Both processes employ N,N-dialkylformamide dimethyl acetals for primary amide activation, producing N'-acyl-N,N-dialkylformamidines as intermediates, as widely documented in the literature. Although the latter intermediates react irreversibly with amines by amidinyl transfer, we show that in the presence of certain Lewis acid additives efficient acyl transfer occurs, providing new and useful methods for amide exchange. In one protocol for transamidation, the N'-acyl- N,N-dialkylformamidine intermediates are purified by flash-column chromatography and the purified intermediates are then treated with an amine (typically, 2.5 equiv) in the presence of scandium triflate (10 mol %) in ether to form in high yields the products of transamidation. In a second procedure, N'-acyl-N,N-dialkylformamidines are generated in situ and, without isolation, are subjected to transamidation in the presence of zirconium chloride (0.5 equiv) and an amine (typically 2 equiv). A variety of different primary amides and amines are found to undergo efficient transamidation using the methods described.

  DOI：

  10.1021/ja066728i

文献信息

• <i>N</i>-Acyl- and<i>N</i>-Sulfonylformamidines from Cyanamides and Carbodiimides by Hydroalumination and Subsequent Treatment with Electrophiles
  作者：Johannes Hellmann、Ines Rhotert、Hauke Westenberg、Roland Fröhlich、Birgit Wibbeling、Werner Uhl、Ernst-Ulrich Würthwein

  DOI：10.1002/ejoc.201300208

  日期：2013.6

  react with dialkylaluminium hydrides R2AlH (R = tBu, iBu) to give compounds 9 in which one C=N bond of the carbodiimide is reduced to form an amidinate ligand and a second molecule of the hydride is coordinated through an Al–N and an Al–H–Al bond. Treatment of 9 with acyl chlorides yields N,N′-disubstituted N-acylformamidines 10, whereas reaction with sulfonyl chlorides gives the corresponding N-sulfonylformamidines

  氰胺 1 与二（异丁基）氢化铝的加氢铝化得到中间体化合物 3，其在固态下具有二聚结构，具有四元 Al2N2 杂环和环外 N=C 双键。3 与酰氯反应生成 N',N'-二取代 N-酰基甲脒 5，而与磺酰氯反应生成相应的 N-磺酰甲脒 7。相反，碳二亚胺 8 与二烷基氢化铝反应 R2AlH (R = tBu, iBu)得到化合物 9，其中碳二亚胺的一个 C=N 键被还原形成脒配体，并且氢化物的第二个分子通过 Al-N 和 Al-H-Al 键配位。用酰氯处理 9 产生 N,N'-二取代的 N-酰基甲脒 10，而与磺酰氯反应得到相应的 N-磺酰甲脒 11。
• Efficient Transamidation of Primary Carboxamides by in Situ Activation with <i>N</i>,<i>N</i>-Dialkylformamide Dimethyl Acetals
  作者：Thomas A. Dineen、Matthew A. Zajac、Andrew G. Myers

  DOI：10.1021/ja066728i

  日期：2006.12.1

  Two protocols for the transamidation of primary amides with primary and secondary amines, forming secondary and tertiary amides, respectively, are described. Both processes employ N,N-dialkylformamide dimethyl acetals for primary amide activation, producing N'-acyl-N,N-dialkylformamidines as intermediates, as widely documented in the literature. Although the latter intermediates react irreversibly with amines by amidinyl transfer, we show that in the presence of certain Lewis acid additives efficient acyl transfer occurs, providing new and useful methods for amide exchange. In one protocol for transamidation, the N'-acyl- N,N-dialkylformamidine intermediates are purified by flash-column chromatography and the purified intermediates are then treated with an amine (typically, 2.5 equiv) in the presence of scandium triflate (10 mol %) in ether to form in high yields the products of transamidation. In a second procedure, N'-acyl-N,N-dialkylformamidines are generated in situ and, without isolation, are subjected to transamidation in the presence of zirconium chloride (0.5 equiv) and an amine (typically 2 equiv). A variety of different primary amides and amines are found to undergo efficient transamidation using the methods described.