N,N'-di-tert-butyl-3-tert-butyl-1,4-diazabut-1-ene | 84814-13-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N'-di-tert-butyl-3-tert-butyl-1,4-diazabut-1-ene
• 英文别名: 1,3,4-tri-tert-butyl-1,4-diazabut-1-ene；N-tert-butyl-1-tert-butylimino-3,3-dimethylbutan-2-amine
• CAS: 84814-13-1
• 化学式: C₁₄H₃₀N₂
• 分子量: 226.406
• InChiKey: JGOYTKAXQWMSOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  铝-三甲胺络合物 、 N,N'-di-tert-butyl-3-tert-butyl-1,4-diazabut-1-ene 以 正己烷 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  Hydroalumination of 1,4-Diazabut-1-enes and 4-Lithio-1,4-diazabut-1-enes: Synthesis of Amidoaluminum Hydride, Lithium Aluminum Hydride, and Lithium Diamidoaluminum Hydride Complexes

  摘要：

  Treatment of the dimeric alkyl-substituted (E)-4-lithio-1,4-diazabut-1-ene [cis-{Li[mu-N(t-Bu)CH(t-Bu)CHN(t-Bu)]}(2)], 1, With 2 equiv of AlH3 . NMe(3) results in hydroalumination yielding a tetrameric lithium diamidoaluminum hydride complex [{Li[N(t-Bu)CH(t-Bu)CH2N(t-Bu)]AlH2}(4)], 4, which is associated through both mono- and dibridging hydrides forming a complex Li4Al2H6 12-membered macrocycle. Treatment of the (E)-1,4-diazabut-1-ene HN(t-Bu)CH(t-Bu)CHN(t-Bu), 2, with 2 equiv of AlH3 . NMe(3) in hexane or 1 equiv of AlH3 in Et(2)O yields the monomeric internally coordinated secondary amine complexed aminoalane [{HN(t-Bu)CH(t-Bu)CH2N(t-Bu)}-AlH2], 5, which is stable with respect to loss of hydrogen under reflux in benzene. Treatment of 2 with LiAlH4 gives the imine-secondary amine adduct 2 . LiAlH4, 3, which decomposes by hydrometalation and metalation on heating to 120 degrees C in benzene to give 4. Compound 4 is not accessible via lithiation of 5 by MeLi in Et(2)O. Crystals of 4 are triclinic, of space group (No. 2), with a 15.664(6) Angstrom, b = 15.723(7) Angstrom c = 16.408(6) Angstrom, alpha = 69.65(3)degrees, beta = 84.98(3)degrees, gamma = 84.22(3)degrees, V = 3763(3) Angstrom(3), and Z = 2. Crystals of 5 are monoclinic, of space group P2(1)/n (No. 14), with a = 9.426(9) Angstrom, b = 12.389(1) Angstrom, c = 15.42(1) A, beta = 103.04(4)degrees, V= 1754(2) Angstrom(3), and Z = 4.

  DOI：

  10.1021/ic00122a023
• 作为产物：
  描述：

  N,N'-二丁基-1,2-乙二亚胺 、 magnesium,2-methylpropane,bromide 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 N,N'-di-tert-butyl-3-tert-butyl-1,4-diazabut-1-ene
  参考文献：
  名称：

  Steuerung DER Ñ -奥德Ç -alkylierung冯CN-systemen MIT锂，镁- UND aluminiumorganylen

  摘要：

  二氮杂二烯（DAD）型共轭偶氮甲碱（RN = CR'-CR'= NR）形成铜（I）络合物（DAD）CuCl，与乙基格氏试剂和醇解反应后生成N-乙基化的还原产物VIII和IX产量低。可以从DAD I和正丁基锂，​​乙基溴化镁或三乙基铝在极性溶剂中直接以优异的收率直接获得相同的β-氨基亚胺（VIII）或互变异构二胺（IX）。仲和叔烷基卤化镁仅产生C-烷基化的X。用正丁基锂进行的溶剂研究表明，“正态” C-烷基化仅在非极性溶剂中和较高的温度下才有利。添加极性溶剂（THF），络合剂（TMEDA）或降低温度会增加N-烷基化。在将格氏试剂加到I之后，中间体VIIIg也可以用卤代烷作为亲电子试剂处理，得到烯二胺XIII和XIV。产品的不寻常立体化学已经通过1 H和13 C NMR光谱进行了研究。具有非平面NRR”基团的顺式构型似乎是对二胺VIII和XIV的典型特征。[t-Bu（CH 3）N]和[t-Bu（C

  DOI：

  10.1016/0022-328x(84)80715-9

文献信息

• Synthesis and Crystal Structure of an Oligomeric Lithium Bis(amido)hydridooxidoaluminate Cluster, [{Li(C14H30N2)AlHO1/2}4]
  作者：Michael G. Gardiner、Colin L. Raston

  DOI：10.1002/zaac.200700468

  日期：2008.3

  bis(amido)hydridooxidoaluminate cluster [Li(C14H30N2)AlHO1/2}4] has been synthesized during systematic metallation/hydrometallation studies of a series of 1,4-diazabut-1-enes with lithium aluminiumhydride. Formation of the complex is presumably derived from partial hydrolysis of the related lithium bis(amido)dihydridoaluminate and has been characterized using single crystal X-ray diffraction. The complex crystallizes

  双（酰氨基）氢化氧化铝酸锂簇 [Li(C14H30N2)AlHO1/2}4] 是在一系列 1,4-二氮杂丁-1-烯与氢化铝锂的系统金属化/氢金属化研究中合成的。复合物的形成可能源自相关的双（酰氨基）二氢铝酸锂的部分水解，并已使用单晶 X 射线衍射进行表征。配合物在单斜空间群 C2/c (No. 15) 中结晶，a = 25.012(2)A°, b = 10.673(2)A°, c = 28.673(3)A°, β = 115.855(7) °，V = 6887(1)A°3，Z = 4。该配合物表现出晶体学 C2 对称性的低聚结构，由广泛的金属、氢化物、氧化物和配体桥接相互作用产生的复杂多环单元组成。这些关联产生边缘融合，
• Hydroalumination of 1,4-Diazabut-1-enes and 4-Lithio-1,4-diazabut-1-enes: Synthesis of Amidoaluminum Hydride, Lithium Aluminum Hydride, and Lithium Diamidoaluminum Hydride Complexes
  作者：Michael G. Gardiner、Stacey M. Lawrence、Colin L. Raston

  DOI：10.1021/ic00122a023

  日期：1995.8

  Treatment of the dimeric alkyl-substituted (E)-4-lithio-1,4-diazabut-1-ene [cis-Li[mu-N(t-Bu)CH(t-Bu)CHN(t-Bu)]}(2)], 1, With 2 equiv of AlH3 . NMe(3) results in hydroalumination yielding a tetrameric lithium diamidoaluminum hydride complex [Li[N(t-Bu)CH(t-Bu)CH2N(t-Bu)]AlH2}(4)], 4, which is associated through both mono- and dibridging hydrides forming a complex Li4Al2H6 12-membered macrocycle. Treatment of the (E)-1,4-diazabut-1-ene HN(t-Bu)CH(t-Bu)CHN(t-Bu), 2, with 2 equiv of AlH3 . NMe(3) in hexane or 1 equiv of AlH3 in Et(2)O yields the monomeric internally coordinated secondary amine complexed aminoalane [HN(t-Bu)CH(t-Bu)CH2N(t-Bu)}-AlH2], 5, which is stable with respect to loss of hydrogen under reflux in benzene. Treatment of 2 with LiAlH4 gives the imine-secondary amine adduct 2 . LiAlH4, 3, which decomposes by hydrometalation and metalation on heating to 120 degrees C in benzene to give 4. Compound 4 is not accessible via lithiation of 5 by MeLi in Et(2)O. Crystals of 4 are triclinic, of space group (No. 2), with a 15.664(6) Angstrom, b = 15.723(7) Angstrom c = 16.408(6) Angstrom, alpha = 69.65(3)degrees, beta = 84.98(3)degrees, gamma = 84.22(3)degrees, V = 3763(3) Angstrom(3), and Z = 2. Crystals of 5 are monoclinic, of space group P2(1)/n (No. 14), with a = 9.426(9) Angstrom, b = 12.389(1) Angstrom, c = 15.42(1) A, beta = 103.04(4)degrees, V= 1754(2) Angstrom(3), and Z = 4.
• Steuerung der N- oder C-alkylierung von CN-systemen mit lithium-, magnesium- und aluminiumorganylen
  作者：Lutz Stamp、Heindirk tom Dieck

  DOI：10.1016/0022-328x(84)80715-9

  日期：1984.12

  which give, after reaction with ethyl Grignard reagent and alcoholysis, the N-ethylated reduction products VIII and IX in low yield. The same β-amino-imines (VIII) or tautomeric en-diamines (IX) can be obtained directly in excellent yields from DAD I and n-butyllithium, ethyl magnesium bromide or triethylaluminium in polar solvents. Secondary and tertiary alkyl magnesium halides give only the C-alkylated

  二氮杂二烯（DAD）型共轭偶氮甲碱（RN = CR'-CR'= NR）形成铜（I）络合物（DAD）CuCl，与乙基格氏试剂和醇解反应后生成N-乙基化的还原产物VIII和IX产量低。可以从DAD I和正丁基锂，​​乙基溴化镁或三乙基铝在极性溶剂中直接以优异的收率直接获得相同的β-氨基亚胺（VIII）或互变异构二胺（IX）。仲和叔烷基卤化镁仅产生C-烷基化的X。用正丁基锂进行的溶剂研究表明，“正态” C-烷基化仅在非极性溶剂中和较高的温度下才有利。添加极性溶剂（THF），络合剂（TMEDA）或降低温度会增加N-烷基化。在将格氏试剂加到I之后，中间体VIIIg也可以用卤代烷作为亲电子试剂处理，得到烯二胺XIII和XIV。产品的不寻常立体化学已经通过1 H和13 C NMR光谱进行了研究。具有非平面NRR”基团的顺式构型似乎是对二胺VIII和XIV的典型特征。[t-Bu（CH 3）N]和[t-Bu（C