1,3-bis(tert-butyl)-2-methoxy-2,3-dihydro-1H-1,3,2-diazaborole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环化合物
• 英文名称: 1,3-bis(tert-butyl)-2-methoxy-2,3-dihydro-1H-1,3,2-diazaborole
• 英文别名: 1,3-Ditert-butyl-2-methoxy-1,3,2-diazaborole；1,3-ditert-butyl-2-methoxy-1,3,2-diazaborole
• 化学式: C₁₁H₂₃BN₂O
• 分子量: 210.127
• InChiKey: SKHLWAHXVRVIFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  15.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,3-bis(tert-butyl)-2-methoxy-2,3-dihydro-1H-1,3,2-diazaborole 在 nitrosyl hexafluorophosphate 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 168.0h， 以50%的产率得到甲氧基二氟硼烷
  参考文献：
  名称：

  Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

  摘要：

  AbstractOxidation of the 1,3,2‐diazaborole tBuNaCH=CHNb(tBu)BBr(Na–B) (1h) with NO+PF6– afforded the diazaborolium salts [tBuNa=CH–CH=Nb(tBu)BF2(Na–B)]+X– (X = Br–, Br3–, PF6–) (3h) as the result of different oxidation processes. The same product was obtained when the 1,3,2‐diazaborolidine tBuNaCH2CH2Nb(tBu)BBr(Na–B) (2h) was subjected to reaction with NO+PF6–. In contrast to this, oxidation of 1h and 2h with NO+BF4– cleanly furnished [tBuNaCH–CH=Nb(tBu)BFBr(Na–B)]+BF4– (6h). Treatment of the 1,3,2‐diazaboroles tBuNaCH=CHNb(tBu)BR(Na–B) [R = H (1e), CN (1i), C≡CH (1j)] with NO+PF6– under comparable conditions led to the borolium salts [tBuNa=CH–CH=Nb(tBu)BRF(Na–B)]+PF6– [R = H (3e), CN (3i), C≡CH (3j)]. All the borolium salts investigated in this study were reversibly reduced by cyclic voltammetry. The novel products were characterized by elemental analyses and NMR spectra (1H, 11B, 13C, 19F, 31P). The X‐ray structure analysis of 3h reveals two independent planar cations in the asymmetric unit, accompanied by one bromide and one tribromide ion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

  DOI：

  10.1002/ejic.200600006
• 作为产物：
  描述：

  sodium methylate 、 N,N'-bis(tert-butyl)-2-bromo-1,3,2-diazaborole 以 正己烷 为溶剂， 以66%的产率得到1,3-bis(tert-butyl)-2-methoxy-2,3-dihydro-1H-1,3,2-diazaborole
  参考文献：
  名称：

  Alkali metal reduction of 2-halogeno- and 2-thiolato-2,3-dihydro-1H-1,3,2-diazaboroles

  摘要：

  将2-溴-1,3,2-二氮硼烷tBuNCHCH(tBu)BBr (4c)在1,2-二甲氧基乙烷中用钾镜还原，得到了一个不可分离的1∶2∶1混合物，包含化合物tBuNCHCHN(tBu)BH (5)、tBuNCHCHN(tBu)BOCH3 (6)和{tBuNCHCHN(tBu)B}2O (7)。将4c与钾-钠合金在N,N,N′,N′-四甲基乙二胺中反应，主要产物为5。1,3,2-二氮硼烷tBuNCHCHN(tBu)BNMe2 (8)和{tBuNCHCHN(tBu)B}2 (9)被光谱学鉴定为次要产物。用钾-钠合金在存在[15]冠-5的甲苯溶液中处理4c，得到了5和苄基衍生物tBuNCHCHN(tBu)BCH2Ph (12)的1∶1混合物。在甲苯-d8中的相同反应产生了去uterated物种5-d1和12-d7。将tBuNCHCHN(tBu)BSCH3 (15)用钾-钠合金在正己烷中处理，得到了tBuNCHCHN(tBu)BCH3 (17)和1,4-二氮丁二烯(tBuNCH)2 (18)。与此相对，在相似条件下，化合物9是tBuNCHCHN(tBu)BStBu (16)还原的主要产物。1-溴-2-叔丁基-1,2-二氢[1,3,2]二氮硼烷[1,5-a]吡啶(19)的还原顺利产生了相应的二硼烷(4)衍生物(20)，并进行了X射线衍射分析。

  DOI：

  10.1039/b106128n

文献信息

• Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines
  作者：Lothar Weber、Imme Domke、Jan Kahlert、Hans‐Georg Stammler

  DOI：10.1002/ejic.200600006

  日期：2006.9

  AbstractOxidation of the 1,3,2‐diazaborole tBuNaCH=CHNb(tBu)BBr(Na–B) (1h) with NO+PF6– afforded the diazaborolium salts [tBuNa=CH–CH=Nb(tBu)BF2(Na–B)]+X– (X = Br–, Br3–, PF6–) (3h) as the result of different oxidation processes. The same product was obtained when the 1,3,2‐diazaborolidine tBuNaCH2CH2Nb(tBu)BBr(Na–B) (2h) was subjected to reaction with NO+PF6–. In contrast to this, oxidation of 1h and 2h with NO+BF4– cleanly furnished [tBuNaCH–CH=Nb(tBu)BFBr(Na–B)]+BF4– (6h). Treatment of the 1,3,2‐diazaboroles tBuNaCH=CHNb(tBu)BR(Na–B) [R = H (1e), CN (1i), C≡CH (1j)] with NO+PF6– under comparable conditions led to the borolium salts [tBuNa=CH–CH=Nb(tBu)BRF(Na–B)]+PF6– [R = H (3e), CN (3i), C≡CH (3j)]. All the borolium salts investigated in this study were reversibly reduced by cyclic voltammetry. The novel products were characterized by elemental analyses and NMR spectra (1H, 11B, 13C, 19F, 31P). The X‐ray structure analysis of 3h reveals two independent planar cations in the asymmetric unit, accompanied by one bromide and one tribromide ion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Alkali metal reduction of 2-halogeno- and 2-thiolato-2,3-dihydro-1H-1,3,2-diazaboroles
  作者：Lothar Weber、Markus Schnieder、Peter Lönnecke

  DOI：10.1039/b106128n

  日期：2001.12.3

  The reduction of 2-bromo-1,3,2-diazaborole tBuNCHCH(tBu)BBr (4c) with a potassium mirror in 1,2-dimethoxyethane afforded a non-separable 1 ∶ 2 ∶ 1 mixture of the compounds tBuNCHCHN(tBu)BH (5), tBuNCHCHN(tBu)BOCH3 (6) and tBuNCHCHN(tBu)B}2O (7). Reaction of 4c with a potassium–sodium alloy in N,N,N′,N′-tetramethylethylenediamine led to 5 as the major product. 1,3,2-Diazaboroles tBuNCHCHN(tBu)BNMe2 (8) and tBuNCHCHN(tBu)B}2 (9) were spectroscopically identified as minor products. The treatment of 4c with potassium–sodium alloy in toluene solution in the presence of [15]crown-5 yielded a 1 ∶ 1 mixture of 5 and the benzyl derivative tBuNCHCHN(tBu)BCH2Ph (12). The same reaction in toluene-d8 produced the deuterated species 5-d1 and 12-d7. tBuNCHCHN(tBu)BCH3 (17) and 1,4-diazabutadiene (tBuNCH)2 (18) resulted from the treatment of tBuNCHCHN(tBu)BSCH3 (15) with potassium–sodium alloy in n-hexane. In contrast to this, compound 9 was obtained as the main product of the reduction of tBuNCHCHN(tBu)BStBu (16) under similar conditions. The reduction of the 1-bromo-2-tert-butyl-1,2-dihydro[1,3,2]diazaborolo[1,5-a]pyridine (19) smoothly produced the respective diborane(4) derivative (20) which was subjected to X-ray diffraction analysis.

  将2-溴-1,3,2-二氮硼烷tBuNCHCH(tBu)BBr (4c)在1,2-二甲氧基乙烷中用钾镜还原，得到了一个不可分离的1∶2∶1混合物，包含化合物tBuNCHCHN(tBu)BH (5)、tBuNCHCHN(tBu)BOCH3 (6)和tBuNCHCHN(tBu)B}2O (7)。将4c与钾-钠合金在N,N,N′,N′-四甲基乙二胺中反应，主要产物为5。1,3,2-二氮硼烷tBuNCHCHN(tBu)BNMe2 (8)和tBuNCHCHN(tBu)B}2 (9)被光谱学鉴定为次要产物。用钾-钠合金在存在[15]冠-5的甲苯溶液中处理4c，得到了5和苄基衍生物tBuNCHCHN(tBu)BCH2Ph (12)的1∶1混合物。在甲苯-d8中的相同反应产生了去uterated物种5-d1和12-d7。将tBuNCHCHN(tBu)BSCH3 (15)用钾-钠合金在正己烷中处理，得到了tBuNCHCHN(tBu)BCH3 (17)和1,4-二氮丁二烯(tBuNCH)2 (18)。与此相对，在相似条件下，化合物9是tBuNCHCHN(tBu)BStBu (16)还原的主要产物。1-溴-2-叔丁基-1,2-二氢[1,3,2]二氮硼烷[1,5-a]吡啶(19)的还原顺利产生了相应的二硼烷(4)衍生物(20)，并进行了X射线衍射分析。