Tris(pyrrolidino)carbenium-chlorid | 73575-64-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: Tris(pyrrolidino)carbenium-chlorid
• 英文别名: 1-(dipyrrolidin-1-ylmethylidene)pyrrolidin-1-ium;chloride
• CAS: 73575-64-1
• 化学式: C₁₃H₂₄N₃*Cl
• 分子量: 257.807
• InChiKey: VVIUFRVNWMLNCJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.66
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  9.49
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Tris(pyrrolidino)carbenium-chlorid 在 sodium perchlorate 作用下， 以 乙腈 为溶剂， 以93%的产率得到Tris(pyrrolidino)carbenium-perchlorat
  参考文献：
  名称：

  Orthoamide. IL. Umsetzungen von Orthoamid-Derivaten mit Schwefel und Selen, Synthesen von 1,3-Thiazol- und 1,3-Selenazolderivaten

  摘要：

  N,N-Dimethylformamide acetal reacts with elemental selenium to give a mixture of selenocarbonic acid derivatives 2 and 3, which can be converted to the pure N,N-dimethylcarbamidic acid Se-methylester 2 by treatment with methyl iodide. Analogously from the orthoformic acid derivatives 5 and 6 and selenium the N,N,N',N'-tetramethyl-selenurea 7 can be prepared. In the reaction of 12 with elemental sulfur and selenium the amidines 14 and 15, respectively, are formed. By treatment of 14 and 15 with alpha-halogenated carbonyl compounds and triethylamine the 1,3-thiazoles 18 and 1,3-selenazoles 19 can be prepared. The synthesis of the propynoic acid orthoamide 26b is described. 26b reacts with the guanidinium salt 24b to give the bis-orthoamide of butynedioic acid 20b. Other orthoamides of butynedioic acid 20b-20e can be synthesized from the orthoamide 20a by transamination. The thiolation of the orthoamides affords the bis-amidinium-dithiolates 21a-c, which can be alkylated to give the bis-amidinium salts 27. By treatment with alpha-halogene carbonyl compounds and triethylamine the dithiolates 21a-e are cyclized to give thieno [3,2b] thiophenes 28a-n. The quadrupoles 21 undergo cycloadditions with dimethyl-butynedioate which afford the bis(3H-thiophene-2 ylidenes) 29a-c. Treatment of 29a with methyl tosylate gives rise to the dithiophene 30a. The dithiophene 30b can be obtained by heating 21b with dimethylbutynedionate.

  DOI：

  10.1002/prac.19963380180
• 作为产物：
  描述：

  1,1’-羰基二吡咯烷 在 COCl₂ 作用下， 以 甲苯 为溶剂， 生成 Tris(pyrrolidino)carbenium-chlorid
  参考文献：
  名称：

  四（氨基）甲烷：其结构和反应性模式对假设的氮化碳构架的影响†

  摘要：

  由于它们可能作为氮化碳C 3 N 4的结构单元的模型化合物，已对（氨基）甲烷的制备，结构化学和一些代表性反应进行了（重新）研究。在晶体中，C（NMe 2）4（1）的分子几何形状接近D 2a对称性是通过使用最新的密度泛函方法进行的理论计算所提出的。与四（氨基）硅烷中几乎为平面的相反，中心碳原子的配位是扭曲的四面体，氮原子的构型是强金字塔形的。四（吡咯烷基）甲烷具有相似的核心结构，其信封构象中的所有杂环取代基在溶液中均呈柔性。由于结构更拥挤，四（哌啶子基）甲烷在溶液中的刚性更高，对六元环的反转换垒更高。1的水解生成MezNH和六甲基胍基氢氧化物，用HAuCl 4（aq）处理1得到晶体[C（NMe 2）3 ] 4 AuCl 4−其结构也已确定。化合物1是强亲核试剂，可以用作胺化剂，将胍基阳离子作为离去基团，例如将卤代硅烷转化为二甲基氨基硅烷。根据有关块状碳氮化物的最新预测讨论了实验结果。

  DOI：

  10.1002/cber.19971301206

文献信息

• Eine einfache Synthese für Tris[dialkylamino]methane
  作者：Willi Kantlehner、Peter Speh、Hans J. Bräuner

  DOI：10.1055/s-1983-30559

  日期：——
• Orthoamide. IL. Umsetzungen von Orthoamid-Derivaten mit Schwefel und Selen, Synthesen von 1,3-Thiazol- und 1,3-Selenazolderivaten
  作者：W. Kantlehner、Michael Hauber、Markus Vettel

  DOI：10.1002/prac.19963380180

  日期：——

  N,N-Dimethylformamide acetal reacts with elemental selenium to give a mixture of selenocarbonic acid derivatives 2 and 3, which can be converted to the pure N,N-dimethylcarbamidic acid Se-methylester 2 by treatment with methyl iodide. Analogously from the orthoformic acid derivatives 5 and 6 and selenium the N,N,N',N'-tetramethyl-selenurea 7 can be prepared. In the reaction of 12 with elemental sulfur and selenium the amidines 14 and 15, respectively, are formed. By treatment of 14 and 15 with alpha-halogenated carbonyl compounds and triethylamine the 1,3-thiazoles 18 and 1,3-selenazoles 19 can be prepared. The synthesis of the propynoic acid orthoamide 26b is described. 26b reacts with the guanidinium salt 24b to give the bis-orthoamide of butynedioic acid 20b. Other orthoamides of butynedioic acid 20b-20e can be synthesized from the orthoamide 20a by transamination. The thiolation of the orthoamides affords the bis-amidinium-dithiolates 21a-c, which can be alkylated to give the bis-amidinium salts 27. By treatment with alpha-halogene carbonyl compounds and triethylamine the dithiolates 21a-e are cyclized to give thieno [3,2b] thiophenes 28a-n. The quadrupoles 21 undergo cycloadditions with dimethyl-butynedioate which afford the bis(3H-thiophene-2 ylidenes) 29a-c. Treatment of 29a with methyl tosylate gives rise to the dithiophene 30a. The dithiophene 30b can be obtained by heating 21b with dimethylbutynedionate.
• Tetra(amino)methanes: Implications of Their Structure and Reactivity Pattern for Hypothetical Carbon Nitride Frameworks
  作者：Alexander Jockisch、Annette Schier、Hubert Schmidbaur

  DOI：10.1002/cber.19971301206

  日期：1997.12

  hexamethylguanidinium hydroxide, and treatment of 1 with HAuCl4(aq) affords crystalline [C(NMe2)3]4 AuCl4− the structure of which has also been determined. Compound 1 is a strong nucleophile and can be used as an aminating agent, converting e.g. halosilanes into dimethylaminosilanes, with the guanidinium cation as the leaving group. The experimental results are discussed in the light of recent predictions

  由于它们可能作为氮化碳C 3 N 4的结构单元的模型化合物，已对（氨基）甲烷的制备，结构化学和一些代表性反应进行了（重新）研究。在晶体中，C（NMe 2）4（1）的分子几何形状接近D 2a对称性是通过使用最新的密度泛函方法进行的理论计算所提出的。与四（氨基）硅烷中几乎为平面的相反，中心碳原子的配位是扭曲的四面体，氮原子的构型是强金字塔形的。四（吡咯烷基）甲烷具有相似的核心结构，其信封构象中的所有杂环取代基在溶液中均呈柔性。由于结构更拥挤，四（哌啶子基）甲烷在溶液中的刚性更高，对六元环的反转换垒更高。1的水解生成MezNH和六甲基胍基氢氧化物，用HAuCl 4（aq）处理1得到晶体[C（NMe 2）3 ] 4 AuCl 4−其结构也已确定。化合物1是强亲核试剂，可以用作胺化剂，将胍基阳离子作为离去基团，例如将卤代硅烷转化为二甲基氨基硅烷。根据有关块状碳氮化物的最新预测讨论了实验结果。