1-(dimethylamino)-1-aza-2,5-disilacyclopentane | 170999-54-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-(dimethylamino)-1-aza-2,5-disilacyclopentane
• 英文别名: N,N-Dimethyl-1,2,5-azadisilolidin-1-amine
• CAS: 170999-54-9
• 化学式: C₄H₁₄N₂Si₂
• 分子量: 146.34
• InChiKey: SBABCWSGUZFAAS-UHFFFAOYSA-N

物化性质

• 沸点：
  123.0±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.22
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  硼烷四氢呋喃络合物 、 1-(dimethylamino)-1-aza-2,5-disilacyclopentane 以 四氢呋喃 为溶剂， 以91%的产率得到(1-aza-2,5-disila-1-cyclopentyl)dimethylamine-borane
  参考文献：
  名称：

  Cyclic Silylhydrazines and Their Borane Adducts

  摘要：

  A series of five-, six-, and seven-membered cyclic silylhydrazines have been prepared from the reactions of 1,2-bis(bromosilyl)ethane and 1,3-bis(bromosilyl)propane with 1,1-dimethylhydrazine [leading to 1-(dimethylamino)-1-aza-2,5-disilacyclopentane (3) and 1-(dimethylamino)-1-aza-2,6-disilacyclohexane (4)] and 1,2-dimethylhydrazine [leading to 1,2-dimethyl-1,2-diaza-3,6-disilacyclohexane (7) and 1,2-dimethyl-1,2-diaza-2,7-disilacycloheptane (8)] in the presence of triethylamine, respectively. The compounds with endocyclic Si-N-Si units (3, 4) are found to be stable for long periods of time, while those with Si-N-N-Si units (7, 8) decompose within a few days at ambient temperature. Compounds 3 and 4 have been reacted with the Lewis acid BH3 to give the dimethylamine-borane adducts 5 and 6. All compounds have been fully characterized by spectroscopic data [IR, MS, NMR (H-1, C-13, N-15, Si-29)]. Single crystals of 5 [6] grown from the melt and studied by low-temperature X-ray diffraction analyses are orthorhombic, space group Pbca (No. 61), with a = 11.385(1) [13.300 (1)] Angstrom, b = 9.938(1) [9.837(1)] Angstrom, c = 17.156(1) [16.364(1)] Angstrom, d(calc) = 1.096 (1.081) g cm(-3), and Z = 8 [8]. In both compounds, the BH3 unit is bound to the nonsilylated nitrogen atom, indicating the reduction of the basicity of nitrogen by Si substitution. The silylated nitrogen atoms show planar coordination, while the borylated amine unit is tetrahedrally coordinated. From a comparison of the ring geometries of 5 and 6 with known open-chain structures, it appears that the C2Si2N ring system of 5 is clearly more strained than that of 6 (C3Si2N) This argument also offers an explanation for the preferred formation of the compounds 1,6-diaza-2,5,7,10-tetrasila-[4.4.0]bicyclodecane (1) and bi(1-aza-2,6-disilacyclohexyl) (2) as compared to their isomers with different ring sizes. The relative stabilities of these isomers in question have been quantified by ab initio (MP2(fc)/6-31G*) calculations of geometries and energies of the systems [(CH2)(n)(SiH2)]N-N[(SiH2)(CH2)(n)] versus the annelated molecules (CH2)(n)(SiH2)N-2(CH2)(n)(SiH2) with n = 1-3. These results show the annelated isomers (ring enlarged) to be lower in energy for n = 1 and 2, while for n = 3 the N-N bridged nonannelated isomer is preferred.

  DOI：

  10.1021/ic00123a019

文献信息

• Cyclic Silylhydrazines and Their Borane Adducts
  作者：Norbert W. Mitzel、Matthias Hofmann、Klaus Angermaier、Annette Schier、Paul von Rague Schleyer、Hubert Schmidbaur

  DOI：10.1021/ic00123a019

  日期：1995.9

  A series of five-, six-, and seven-membered cyclic silylhydrazines have been prepared from the reactions of 1,2-bis(bromosilyl)ethane and 1,3-bis(bromosilyl)propane with 1,1-dimethylhydrazine [leading to 1-(dimethylamino)-1-aza-2,5-disilacyclopentane (3) and 1-(dimethylamino)-1-aza-2,6-disilacyclohexane (4)] and 1,2-dimethylhydrazine [leading to 1,2-dimethyl-1,2-diaza-3,6-disilacyclohexane (7) and 1,2-dimethyl-1,2-diaza-2,7-disilacycloheptane (8)] in the presence of triethylamine, respectively. The compounds with endocyclic Si-N-Si units (3, 4) are found to be stable for long periods of time, while those with Si-N-N-Si units (7, 8) decompose within a few days at ambient temperature. Compounds 3 and 4 have been reacted with the Lewis acid BH3 to give the dimethylamine-borane adducts 5 and 6. All compounds have been fully characterized by spectroscopic data [IR, MS, NMR (H-1, C-13, N-15, Si-29)]. Single crystals of 5 [6] grown from the melt and studied by low-temperature X-ray diffraction analyses are orthorhombic, space group Pbca (No. 61), with a = 11.385(1) [13.300 (1)] Angstrom, b = 9.938(1) [9.837(1)] Angstrom, c = 17.156(1) [16.364(1)] Angstrom, d(calc) = 1.096 (1.081) g cm(-3), and Z = 8 [8]. In both compounds, the BH3 unit is bound to the nonsilylated nitrogen atom, indicating the reduction of the basicity of nitrogen by Si substitution. The silylated nitrogen atoms show planar coordination, while the borylated amine unit is tetrahedrally coordinated. From a comparison of the ring geometries of 5 and 6 with known open-chain structures, it appears that the C2Si2N ring system of 5 is clearly more strained than that of 6 (C3Si2N) This argument also offers an explanation for the preferred formation of the compounds 1,6-diaza-2,5,7,10-tetrasila-[4.4.0]bicyclodecane (1) and bi(1-aza-2,6-disilacyclohexyl) (2) as compared to their isomers with different ring sizes. The relative stabilities of these isomers in question have been quantified by ab initio (MP2(fc)/6-31G*) calculations of geometries and energies of the systems [(CH2)(n)(SiH2)]N-N[(SiH2)(CH2)(n)] versus the annelated molecules (CH2)(n)(SiH2)N-2(CH2)(n)(SiH2) with n = 1-3. These results show the annelated isomers (ring enlarged) to be lower in energy for n = 1 and 2, while for n = 3 the N-N bridged nonannelated isomer is preferred.