1,3-bis(bromomethyl)-2,4-dimethylbenene | 155536-73-5

• 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: 1,3-bis(bromomethyl)-2,4-dimethylbenene
• 英文别名: 1,3-Bis(brommethyl)-2,4-dimethylbenzol；1,3-bis(bromomethyl)-2,4-dimethylbenzene
• CAS: 155536-73-5
• 化学式: C₁₀H₁₂Br₂
• 分子量: 292.013
• InChiKey: XIEKPMVCBXGKJN-UHFFFAOYSA-N

物化性质

• 沸点：
  316.9±37.0 °C(predicted)
• 密度：
  1.613±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.09
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,2-乙二硫醇 、 1,3-bis(bromomethyl)-2,4-dimethylbenene 在 cesium hydroxide 作用下， 以 乙醇 、 苯 为溶剂， 反应 4.0h， 以11%的产率得到8,12-dimethyl-2,5-dithia<6>metacyclophane
  参考文献：
  名称：

  Experimental and Theoretical Study of Dithia[n]metacyclophanes: Syntheses, Chiroptical Properties, and Conformational Analysis

  摘要：

  The synthesis of 8,12-dimethyl-2,5-dithia[6]metacyclophane (3a) has been achieved for the first time by cesium-assisted high dilution methods. Enantiomeric separation was performed by HPLC with enantioselective chromatography using cellulose tris(3,5-dimethylphenyl carbamate). The CD spectra of 3a and the homologous 9,13-dimethyl-2,6-dithia[7]metacyclophan (2a) are reported and compared with results of theoretical AM1/MRD-CI calculations. The geometries of the cyclophanes have been investigated with X-ray and-theoretical AM1 and ab initio SCF methods. Application of all these methods reveals the existence of several energetic low-lying conformers with different orientation of the S-(CH2)(n)-S (n = 3 and 2) chains. Comparison of experimental and theoretical CD data shows that the spectra depend strongly on the varying dihedral angles in these chains. Electronic excitations out of the sulfur 3p lone-pair orbitals are quite important in the theoretical description of the Cotton effects above 200 nm excitation wavelength. The conversion barriers (approximate to 20 kJ/mol for 2a,40-50 kJ/mol for 3a) between the conformers have been determined by temperature dependent NMR-spectroscopy and are found to be in good agreement with theoretical AM1 data.

  DOI：

  10.1021/ja00106a019
• 作为产物：
  描述：

  三聚甲醛 、 2,6-二甲基苄醇 在 氢溴酸 、 溴棕三甲铵 、 溶剂黄146 作用下， 反应 24.0h， 以82%的产率得到1,3-bis(bromomethyl)-2,4-dimethylbenene
  参考文献：
  名称：

  Experimental and Theoretical Study of Dithia[n]metacyclophanes: Syntheses, Chiroptical Properties, and Conformational Analysis

  摘要：

  The synthesis of 8,12-dimethyl-2,5-dithia[6]metacyclophane (3a) has been achieved for the first time by cesium-assisted high dilution methods. Enantiomeric separation was performed by HPLC with enantioselective chromatography using cellulose tris(3,5-dimethylphenyl carbamate). The CD spectra of 3a and the homologous 9,13-dimethyl-2,6-dithia[7]metacyclophan (2a) are reported and compared with results of theoretical AM1/MRD-CI calculations. The geometries of the cyclophanes have been investigated with X-ray and-theoretical AM1 and ab initio SCF methods. Application of all these methods reveals the existence of several energetic low-lying conformers with different orientation of the S-(CH2)(n)-S (n = 3 and 2) chains. Comparison of experimental and theoretical CD data shows that the spectra depend strongly on the varying dihedral angles in these chains. Electronic excitations out of the sulfur 3p lone-pair orbitals are quite important in the theoretical description of the Cotton effects above 200 nm excitation wavelength. The conversion barriers (approximate to 20 kJ/mol for 2a,40-50 kJ/mol for 3a) between the conformers have been determined by temperature dependent NMR-spectroscopy and are found to be in good agreement with theoretical AM1 data.

  DOI：

  10.1021/ja00106a019

文献信息

• Mueller, Bernd; Pischel, Ivo; Nieger, Martin, Chemische Berichte, 1994, vol. 127, # 4, p. 759 - 766
  作者：Mueller, Bernd、Pischel, Ivo、Nieger, Martin、Voegtle, Fritz

  DOI：——

  日期：——
• Experimental and Theoretical Study of Dithia[n]metacyclophanes: Syntheses, Chiroptical Properties, and Conformational Analysis
  作者：S. Grimme、I. Pischel、F. Voegtle、M. Nieger

  DOI：10.1021/ja00106a019

  日期：1995.1

  The synthesis of 8,12-dimethyl-2,5-dithia[6]metacyclophane (3a) has been achieved for the first time by cesium-assisted high dilution methods. Enantiomeric separation was performed by HPLC with enantioselective chromatography using cellulose tris(3,5-dimethylphenyl carbamate). The CD spectra of 3a and the homologous 9,13-dimethyl-2,6-dithia[7]metacyclophan (2a) are reported and compared with results of theoretical AM1/MRD-CI calculations. The geometries of the cyclophanes have been investigated with X-ray and-theoretical AM1 and ab initio SCF methods. Application of all these methods reveals the existence of several energetic low-lying conformers with different orientation of the S-(CH2)(n)-S (n = 3 and 2) chains. Comparison of experimental and theoretical CD data shows that the spectra depend strongly on the varying dihedral angles in these chains. Electronic excitations out of the sulfur 3p lone-pair orbitals are quite important in the theoretical description of the Cotton effects above 200 nm excitation wavelength. The conversion barriers (approximate to 20 kJ/mol for 2a,40-50 kJ/mol for 3a) between the conformers have been determined by temperature dependent NMR-spectroscopy and are found to be in good agreement with theoretical AM1 data.