(2Z,12Z)-22,22-dichloro-2,7,7,12,17,17-hexaethyl-21,23,24,25-tetraza-22-stannahexacyclo[9.9.3.13,6.113,16.08,23.018,21]pentacosa-1(20),2,4,6(25),8,10,12,14,16(24),18-decaene | 245491-68-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: (2Z,12Z)-22,22-dichloro-2,7,7,12,17,17-hexaethyl-21,23,24,25-tetraza-22-stannahexacyclo[9.9.3.13,6.113,16.08,23.018,21]pentacosa-1(20),2,4,6(25),8,10,12,14,16(24),18-decaene
• CAS: 245491-68-3
• 化学式: C₃₂H₃₈Cl₂N₄Sn
• 分子量: 668.297
• InChiKey: GELWIUYZXVXGBU-AWPRATMQSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.01
• 重原子数：
  39
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  34.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  SnCl4*2THF 、 7,7,12,12,17,17,24,24-octaethyl-2,22,23,25-tetraza-1-stannaoctacyclo[11.9.1.11,8.13,21.02,6.016,23.018,22.011,25]pentacosa-3,5,8,10,13,15,18,20-octaene;oxolane 以 甲苯 为溶剂， 以53%的产率得到(2Z,12Z)-22,22-dichloro-2,7,7,12,17,17-hexaethyl-21,23,24,25-tetraza-22-stannahexacyclo[9.9.3.13,6.113,16.08,23.018,21]pentacosa-1(20),2,4,6(25),8,10,12,14,16(24),18-decaene
  参考文献：
  名称：

  The Porphyrinogen−Porphodimethene Relationship Leading to Novel Synthetic Methodologies Focused on the Modification and Functionalization of the Porphyrinogen and Porphodimethene Skeletons

  摘要：

  The general synthetic methods presented in this paper make available, on a preparative scale, unprecedented porphyrinogen-derived skeletons, including their functionalization at the meso positions. The stepwise dealkylation of meso-octaalkylporphyrinogen R8N4H4 [R = Et, 1; R = Bu-n, 2] was chemically, mechanistically, and structurally followed until the formation of porphomethene and porphodimethene derivatives 5-13, obtained with a sequential use of SnCl4. In particular, the porphodimethene derivative [(Et6N4)SnCl2], 9, was reductively transmetalated using Li metal to Et6N4Li2. 14, subsequently hydrolyzed to Et6N4H2, 15. The porphodimethene-nickel complex [(Et6N4)Ni], 16, was used for studying the reactivity and the ligand modification of the porphodimethene skeleton. The reactivity of 16 toward nucleophiles led to otherwise inaccessible meso-substituted-meso-functionalized porphyrinogens [(Et6N4R2)NiLi2], [R = H, 18; R = Bu-n, 19; R = CH2CN, 20], thus exemplifying a general methodology to meso-functionalized porphyrinogens. In addition, when [NMe2](-) was used as the nucleophile, 16 was converted into mono- and bis-vinylideneporphyrinogen derivatives [{Et-4(=CHMe)N-4}NiLi] 21, and [{Et-5(=CHMe)(2)N-4}NiLi2], 22, through the intermediacy of meso-(dimethylamino)-porphyrinogens undergoing an alpha-II elimination from the meso positions. Such intermediates were isolated and characterized in the stepwise reaction of 14 with LiNMe2 leading to [{Et-6(NMe2)(2)N-4}Li-4], 23, and [{Et-5(NMe2)(=CHMe)N-4}Li-4], 25. Both compounds, as a function of the reaction solvent, undergo the thermal elimination of HNMe2 with the formation of [{Et-4(=CHMe)(2)N-4}Li-4], 24, which is then protonated to [{Et-4(=CHMe)(2)N-4}H-4], 27. Transmetalation from 23 to 24 can be used as the methodology for the synthesis of a remarkable variety of meso-substituted and functionalized porphyrinogen complexes. The deprotonation of 16 is reversible, therefore 22 and 23 can be protonated back to their starting materials. We took advantage of the nucleophilicity of the vinylidene carbon in 21 and 22 fur establishing a general synthetic method to produce meso-functionalized porphodimethenes. This approach was exemplified with the alkylation and the benzoylation of 22 and 21 leading to [{(E4Pr2N4)-N-i)Ni], 28, [Et-4{CH(Me)(PhCO)}(2)N4Ni], 29, and [Et-5{CH(Me)(PhCO)}N4Ni], 30, respectively. Complex 21 displays a bifunctional behavior, as shown by the formation of 30, whereas in the reaction with LiBu, led to [{Et-5(Bu-n)(=CHMe)N-4}NiLi2], 31.

  DOI：

  10.1021/ja000253s

文献信息

• Porphomethenes and Porphodimethenes Synthesized by the Two- and Four-Electron Oxidation of themeso-Octaethylporphyrinogen
  作者：Jean-Marc Benech、Lucia Bonomo、Euro Solari、Rosario Scopelliti、Carlo Floriani

  DOI：10.1002/(sici)1521-3773(19990712)38:13/14<1957::aid-anie1957>3.0.co;2-1

  日期：1999.7.12

  Stepwise dealkylation of meso-octaethylporphyrinogen 1 yields porphomethene 2 and porphodimethene 3, providing access to large quantities of these valuable intermediates. The synthetic sequence relies on SnCl4⋅2 THF, Li, and H2O; the extent of dealkylation depends on the amount of SnCl4⋅2 THF employed.
• The Porphyrinogen−Porphodimethene Relationship Leading to Novel Synthetic Methodologies Focused on the Modification and Functionalization of the Porphyrinogen and Porphodimethene Skeletons
  作者：Lucia Bonomo、Euro Solari、Rosario Scopelliti、Carlo Floriani、Nazzareno Re

  DOI：10.1021/ja000253s

  日期：2000.6.1

  The general synthetic methods presented in this paper make available, on a preparative scale, unprecedented porphyrinogen-derived skeletons, including their functionalization at the meso positions. The stepwise dealkylation of meso-octaalkylporphyrinogen R8N4H4 [R = Et, 1; R = Bu-n, 2] was chemically, mechanistically, and structurally followed until the formation of porphomethene and porphodimethene derivatives 5-13, obtained with a sequential use of SnCl4. In particular, the porphodimethene derivative [(Et6N4)SnCl2], 9, was reductively transmetalated using Li metal to Et6N4Li2. 14, subsequently hydrolyzed to Et6N4H2, 15. The porphodimethene-nickel complex [(Et6N4)Ni], 16, was used for studying the reactivity and the ligand modification of the porphodimethene skeleton. The reactivity of 16 toward nucleophiles led to otherwise inaccessible meso-substituted-meso-functionalized porphyrinogens [(Et6N4R2)NiLi2], [R = H, 18; R = Bu-n, 19; R = CH2CN, 20], thus exemplifying a general methodology to meso-functionalized porphyrinogens. In addition, when [NMe2](-) was used as the nucleophile, 16 was converted into mono- and bis-vinylideneporphyrinogen derivatives [Et-4(=CHMe)N-4}NiLi] 21, and [Et-5(=CHMe)(2)N-4}NiLi2], 22, through the intermediacy of meso-(dimethylamino)-porphyrinogens undergoing an alpha-II elimination from the meso positions. Such intermediates were isolated and characterized in the stepwise reaction of 14 with LiNMe2 leading to [Et-6(NMe2)(2)N-4}Li-4], 23, and [Et-5(NMe2)(=CHMe)N-4}Li-4], 25. Both compounds, as a function of the reaction solvent, undergo the thermal elimination of HNMe2 with the formation of [Et-4(=CHMe)(2)N-4}Li-4], 24, which is then protonated to [Et-4(=CHMe)(2)N-4}H-4], 27. Transmetalation from 23 to 24 can be used as the methodology for the synthesis of a remarkable variety of meso-substituted and functionalized porphyrinogen complexes. The deprotonation of 16 is reversible, therefore 22 and 23 can be protonated back to their starting materials. We took advantage of the nucleophilicity of the vinylidene carbon in 21 and 22 fur establishing a general synthetic method to produce meso-functionalized porphodimethenes. This approach was exemplified with the alkylation and the benzoylation of 22 and 21 leading to [(E4Pr2N4)-N-i)Ni], 28, [Et-4CH(Me)(PhCO)}(2)N4Ni], 29, and [Et-5CH(Me)(PhCO)}N4Ni], 30, respectively. Complex 21 displays a bifunctional behavior, as shown by the formation of 30, whereas in the reaction with LiBu, led to [Et-5(Bu-n)(=CHMe)N-4}NiLi2], 31.