5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine | 172471-92-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯嗪
• 英文名称: 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine
• 英文别名: 5-Amino-3-imino-3H-pyrrolizine-1,2,6,7-tetracarbonitrile；3-amino-5-iminopyrrolizine-1,2,6,7-tetracarbonitrile
• CAS: 172471-92-0
• 化学式: C₁₁H₃N₇
• 分子量: 233.192
• InChiKey: AYDQYVGXCBODAX-UHFFFAOYSA-N

物化性质

• 熔点：
  270 °C (decomp)
• 沸点：
  731.3±70.0 °C(Predicted)
• 密度：
  1.61±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  150
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine 在 盐酸 作用下， 以 乙腈 为溶剂， 生成 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide
  参考文献：
  名称：

  Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide in Water:  A Completely Sorted out Square Scheme

  摘要：

  A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (H.L) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L'-) in the pH range from -0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from -4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL'. The study has allowed the determination of the acid dissociation constants of HL (pK(a)) and HL' (pK(a)'), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL') and basic (L-/L'(-)) forms. Although L'(-) is the sole species present at pH > ca. 7, species HL and HL' establish an equilibrium favoring the former compound at low pH, with the distribution being ca. 79:21 at pH less than ca. 2. A slow decomposition of HL occurs at low pH via the initial formation of an unobserved and unstable protonated form H2L+. Geometry optimizations of all species at the B3LYP/LAN-L2DZ level, including water solvation energy, afford results in qualitative agreement with the experiment and indicate the structural nature of the new species L- and HL'.

  DOI：

  10.1021/jp011628e
• 作为产物：
  描述：

  2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide sodium salt 在 盐酸 作用下， 以 水 为溶剂， 生成 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine
  参考文献：
  名称：

  Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide in Water:  A Completely Sorted out Square Scheme

  摘要：

  A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (H.L) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L'-) in the pH range from -0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from -4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL'. The study has allowed the determination of the acid dissociation constants of HL (pK(a)) and HL' (pK(a)'), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL') and basic (L-/L'(-)) forms. Although L'(-) is the sole species present at pH > ca. 7, species HL and HL' establish an equilibrium favoring the former compound at low pH, with the distribution being ca. 79:21 at pH less than ca. 2. A slow decomposition of HL occurs at low pH via the initial formation of an unobserved and unstable protonated form H2L+. Geometry optimizations of all species at the B3LYP/LAN-L2DZ level, including water solvation energy, afford results in qualitative agreement with the experiment and indicate the structural nature of the new species L- and HL'.

  DOI：

  10.1021/jp011628e

文献信息

• 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine: synthesis of alkylimino derivatives. X-Ray crystal and molecular structures of the hex-5-enyl, and Langmuir–Blodgett film of the octyl and octadecyl derivatives
  作者：Alberto Flamini、Vincenzo Fares、Aldo Capobianchi、Veronica Valentini

  DOI：10.1039/b103423p

  日期：2001.11.15

  The alkylimino-substituted derivatives of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine, H2N–C7N(CN)4NR, R = hex-5-enyl (1), octyl (2), octadecyl (3), have been synthesized through a nucleophilic substitution reaction on the amino group of the anion 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide, C5N3–C4N(CN)2–NH2− (L′). A sigmatropic rearrangement via a [1,5]-H shift is involved in this synthesis and also in the deprotonation of 1, leading to the anion C5N3–C4N(CN)2–NH(CH2)4CHCH2− (1′) isolated as the tetraphenylarsonium salt, AsPh4·1′. All the new compounds have been characterized by elemental analysis and IR, UV–VIS and 1H NMR spectroscopy. The X-ray crystal and molecular structure of 1 has been determined. Langmuir–Blodgett (LB) films from 2 and 3 have been deposited and characterized by polarised optical absorption spectroscopy.

  合成了5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine的烷基氨基取代衍生物H2N–C7N(CN)4NR，其中R = hex-5-enyl (1)、octyl (2)、octadecyl (3)，通过在阴离子2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide, C5N3–C4N(CN)2–NH2− (L′)的氨基上进行亲核取代反应合成。这一合成过程涉及通过[1,5]-H迁移的σ-转移重排，以及对1的脱质子化，导致阴离子C5N3–C4N(CN)2–NH(CH2)4CHCH2− (1′)的形成，该阴离子以四苯砷盐AsPh4·1′的形式被分离。所有新化合物均通过元素分析、红外光谱、紫外-可见光谱和^1H NMR光谱进行了表征。化合物1的X射线晶体结构和分子结构已被确定。已从2和3沉积并表征了Langmuir–Blodgett (LB)薄膜，采用了偏振光吸收光谱技术。
• On the Spectral Similarities between 1,2,6,7-Tetracyano-3,5-dihydro-3,5-diiminopyrrolizinato Complexes and Phthalocyanines – X-ray Crystal and Molecular Structure of Two Mixed Monopyrrolizinato Nickel(II) Complexes with the 2,4-tert-Butylacetylacetonide Ligand
  作者：Alberto Flamini、Vincenzo Fares、Augusto Pifferi

  DOI：10.1002/(sici)1099-0682(200003)2000:3<537::aid-ejic537>3.0.co;2-z

  日期：2000.3
• Reductive Condensation of Tetracyanoethylene on a Metal Center. Synthesis and Characterization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine
  作者：Vincenzo Fares、Alberto Flamini、Nicola Poli

  DOI：10.1021/ja00151a024

  日期：1995.11
• Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide in Water:  A Completely Sorted out Square Scheme
  作者：Edmond Collange、Alberto Flamini、Rinaldo Poli

  DOI：10.1021/jp011628e

  日期：2002.1.1

  A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (H.L) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L'-) in the pH range from -0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from -4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL'. The study has allowed the determination of the acid dissociation constants of HL (pK(a)) and HL' (pK(a)'), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL') and basic (L-/L'(-)) forms. Although L'(-) is the sole species present at pH > ca. 7, species HL and HL' establish an equilibrium favoring the former compound at low pH, with the distribution being ca. 79:21 at pH less than ca. 2. A slow decomposition of HL occurs at low pH via the initial formation of an unobserved and unstable protonated form H2L+. Geometry optimizations of all species at the B3LYP/LAN-L2DZ level, including water solvation energy, afford results in qualitative agreement with the experiment and indicate the structural nature of the new species L- and HL'.