9-Bromo-2,2,4,4-tetrachloro-9-nitro-7,11-dioxa-1,3,5-triaza-2lambda5,4lambda5,6lambda5-triphosphaspiro[5.5]undeca-1(6),2,4-triene | 1257063-64-1

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 9-Bromo-2,2,4,4-tetrachloro-9-nitro-7,11-dioxa-1,3,5-triaza-2lambda5,4lambda5,6lambda5-triphosphaspiro[5.5]undeca-1(6),2,4-triene
• 英文别名: 9-bromo-2,2,4,4-tetrachloro-9-nitro-7,11-dioxa-1,3,5-triaza-2λ5,4λ5,6λ5-triphosphaspiro[5.5]undeca-1(6),2,4-triene
• CAS: 1257063-64-1
• 化学式: C₃H₄BrCl₄N₄O₄P₃
• 分子量: 474.726
• InChiKey: TXYUDODRYHZKDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  2-溴-2-硝基-1,3-丙二醇 在 吡啶 、 六氯环三磷腈 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 生成 9-Bromo-2,2,4,4-tetrachloro-9-nitro-7,11-dioxa-1,3,5-triaza-2lambda5,4lambda5,6lambda5-triphosphaspiro[5.5]undeca-1(6),2,4-triene
  参考文献：
  名称：

  Effect of gem 2,2′-disubstitution and base in the formation of spiro- and ansa-1,3-propandioxy derivatives of cyclotriphosphazenes

  摘要：

  The gem-dialkyl effect has been investigated in the reactions of cyclotriphosphazene, N3P3Cl6 1, with various 2,2'-derivatives of 1,3-propandiol, CXY(CH2OH)(2), in either THF or DCM to form spiro (6-membered) and ansa (8-membered ring) derivatives. The reactions were made with a number of symmetrically-substituted (X = Y, methyl, ethyl, n-butyl and a malonate ester) and unsymmetrically-substituted (X not equal Y, methyl/H, phenyl/H, methyl/n-propyl, ethyl/n-butyl and Br/NO2) 1,3-propandiols. The products were analysed by H-1 and P-31 NMR spectroscopy and some of the spiro and ansa derivatives were also characterized by X-ray crystallography. Reactions of 1 with unsymmetrically-substituted 1,3-propandiols results in the formation of two structural isomers of ansa-substituted compounds, both isomers (endo and exo) have been structurally-characterized by X-ray crystallography for the ethyl/n-butyl derivative. It is found that the regioselectivity of the reaction is changed when the base is changed. The relative proportions of spiro and ansa compounds formed under different reaction conditions were quantified by P-31 NMR measurements of the reaction mixtures. The results were rationalised mainly in terms of the electronic effect of the substituents, whereas the steric effect has a secondary role in the formation of both spiro and ansa compounds. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.07.005

文献信息

• Effect of gem 2,2′-disubstitution and base in the formation of spiro- and ansa-1,3-propandioxy derivatives of cyclotriphosphazenes
  作者：Aylin Uslu、Simon J. Coles、David B. Davies、Mükremin Esen、Michael B. Hursthouse、Adem Kılıç

  DOI：10.1016/j.ica.2010.07.005

  日期：2010.10

  The gem-dialkyl effect has been investigated in the reactions of cyclotriphosphazene, N3P3Cl6 1, with various 2,2'-derivatives of 1,3-propandiol, CXY(CH2OH)(2), in either THF or DCM to form spiro (6-membered) and ansa (8-membered ring) derivatives. The reactions were made with a number of symmetrically-substituted (X = Y, methyl, ethyl, n-butyl and a malonate ester) and unsymmetrically-substituted (X not equal Y, methyl/H, phenyl/H, methyl/n-propyl, ethyl/n-butyl and Br/NO2) 1,3-propandiols. The products were analysed by H-1 and P-31 NMR spectroscopy and some of the spiro and ansa derivatives were also characterized by X-ray crystallography. Reactions of 1 with unsymmetrically-substituted 1,3-propandiols results in the formation of two structural isomers of ansa-substituted compounds, both isomers (endo and exo) have been structurally-characterized by X-ray crystallography for the ethyl/n-butyl derivative. It is found that the regioselectivity of the reaction is changed when the base is changed. The relative proportions of spiro and ansa compounds formed under different reaction conditions were quantified by P-31 NMR measurements of the reaction mixtures. The results were rationalised mainly in terms of the electronic effect of the substituents, whereas the steric effect has a secondary role in the formation of both spiro and ansa compounds. (C) 2010 Elsevier B.V. All rights reserved.