2-(phenylethynyl)-1,3-diethyl-1,3,2-benzodiazaborole | 951020-55-6

• 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: 2-(phenylethynyl)-1,3-diethyl-1,3,2-benzodiazaborole
• 英文别名: 2-phenylethynyl-1,3-diethyl-2,3-dihydro-1H-1,3,2-benzodiazaborole；2-Phenylethinyl-1,3-diethyl-2,3-dihydro-1H-1,3,2-benzodiazaborol；1,3-Diethyl-2-(2-phenylethynyl)-1,3,2-benzodiazaborole；1,3-diethyl-2-(2-phenylethynyl)-1,3,2-benzodiazaborole
• CAS: 951020-55-6
• 化学式: C₁₈H₁₉BN₂
• 分子量: 274.173
• InChiKey: DWUKCWIJBMRCIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.43
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  2-(phenylethynyl)-1,3-diethyl-1,3,2-benzodiazaborole 、 bis(cyclohexanyl)borane 以 乙醚 为溶剂， 反应 4.0h， 生成 (Z)-2-(2-(dicyclohexylboraneyl)-2-phenylvinyl)-1,3-diethyl-2,3-dihydro-1H-benzo[d][1,3,2]diazaborole 、 (Z)-2-(1-(dicyclohexylboraneyl)-2-phenylvinyl)-1,3-diethyl-2,3-dihydro-1H-benzo[d][1,3,2]diazaborole
  参考文献：
  名称：

  Hydroboration of Alkyne‐Functionalized 1,3,2‐Benzodiazaboroles

  摘要：

  AbstractReactions of equimolar amounts of dicyclohexylborane (DCB) with a series of 2‐alkynyl‐1,3‐diethyl‐1,3,2‐benzodiazaboroles R–C≡C–B(NEt)2C6H4 (1: R = nBu, 2: R = tBu, 3: R = Ph, 4: R = p‐Me2NC6H4, 5: R = p‐MeOC6H4) regioselectively afforded the 1,1‐diborylalkenes (Z)‐R(H)C=C{(B{NEt}2C6H4)B(c‐C6H11)2} (7a–11a) as the result of a cis‐addition of the BH bond of the borane to the C≡C triple bond in compounds 1 to 5. In contrast to this, reaction of Me3Si–C≡C–B(NEt)2C6H4 (6) with HB(c‐C6H11)2 yielded a 2.5:1 mixture of the 1,2‐diborylated alkene (Z)‐Me3Si{(c‐C6H11)2B}C=CHB(NEt)2C6H4 (12b) and the 1,1‐regioisomer (Z)‐Me3Si(H)C=C{B(NEt)2C6H4}{B(c‐C6H11)2} (12a). These results were rationalized by the differing π‐acceptor qualities of the benzodiazaborolyl and trimethylsilyl substituents at the C≡C triple bond in compounds 1 to 6. The novel products 7–12 were characterized by elemental analysis, mass spectrometry and NMR spectroscopy (1H, 11B, and 13C NMR). The molecular structures of 9b and 12b were substantiated by single‐crystal X‐ray diffraction analysis.

  DOI：

  10.1002/ejic.201201489
• 作为产物：
  描述：

  2-bromo-1,3-diethyl-1,3,2-benzodiazaborole 、 苯乙炔 在 n-BuLi 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 以84%的产率得到2-(phenylethynyl)-1,3-diethyl-1,3,2-benzodiazaborole
  参考文献：
  名称：

  Synthese, Struktur, Elektrochemie und optische Eigenschaften von alkinylfunktionalisierten 1,3,2-Diazaborolen und 1,3,2-Diazaborolidin

  摘要：

  炔官能化 1,3,2-二氮杂硼和 1,3,2-二氮杂硼烷的合成、结构、电化学和光学性质 2-溴-1,3-二叔丁基-2,3-二氢-1H-的反应1,3,2-二氮杂硼 (3) 与锂化的叔丁基-乙炔和锂化的苯乙炔得到 2-炔基官能化的 1,3,2-二氮杂硼 4 和 5，为不耐热的无色油 (4) 或固体 (5 ）。类似地，2-溴-1,3-二乙基-2,3-二氢-1H-1,3,2-苯并二氮杂硼(6)转化为结晶2-炔基-苯并-1,3,2-二氮杂硼7和8通过分别用 LiC≡C–tBu 或 LiC≡CPh 处理。2-Ethynyl-1,3-ditert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (2) 用叔丁基锂金属化，随后与 2-bromo-1,3 偶联， -二叔丁基-2,3-二氢-1H-1,3,2-二氮杂硼(3)得到双(1,3-二叔丁基-2,3-二氢-1H-1,3, 2-diazaborol-2-yl)乙炔

  DOI：

  10.1002/zaac.200600351

文献信息

• Synthese, Struktur, Elektrochemie und optische Eigenschaften von alkinylfunktionalisierten 1,3,2-Diazaborolen und 1,3,2-Diazaborolidinen
  作者：L. Weber、A. Penner、I. Domke、H.-G. Stammler、B. Neumann

  DOI：10.1002/zaac.200600351

  日期：2007.4

  Syntheses, Structures, Electrochemistry and Optical Properties of Alkyne-Functionalized 1,3,2-Diazaboroles and 1,3,2-Diazaborolidenes The reaction of 2-bromo-1,3-ditert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (3) with lithiated tert-butyl-acetylene and lithiated phenylacetylene affords the 2-alkynyl-functionalized 1,3,2-diazaboroles 4 and 5 as a thermolabile colorless oil (4) or a solid (5). Similarly

  炔官能化 1,3,2-二氮杂硼和 1,3,2-二氮杂硼烷的合成、结构、电化学和光学性质 2-溴-1,3-二叔丁基-2,3-二氢-1H-的反应1,3,2-二氮杂硼 (3) 与锂化的叔丁基-乙炔和锂化的苯乙炔得到 2-炔基官能化的 1,3,2-二氮杂硼 4 和 5，为不耐热的无色油 (4) 或固体 (5 ）。类似地，2-溴-1,3-二乙基-2,3-二氢-1H-1,3,2-苯并二氮杂硼(6)转化为结晶2-炔基-苯并-1,3,2-二氮杂硼7和8通过分别用 LiC≡C–tBu 或 LiC≡CPh 处理。2-Ethynyl-1,3-ditert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (2) 用叔丁基锂金属化，随后与 2-bromo-1,3 偶联， -二叔丁基-2,3-二氢-1H-1,3,2-二氮杂硼(3)得到双(1,3-二叔丁基-2,3-二氢-1H-1,3, 2-diazaborol-2-yl)乙炔
• UV-Photoelectron Spectroscopic Studies on 2-Arylethynyl-1,3,2-benzodiazaboroles
  作者：Anna Chrostowska、Małgorzata Maciejczyk、Alain Dargelos、Patrick Baylère、Lothar Weber、Vanessa Werner、Daniel Eickhoff、Hans-Georg Stammler、Beate Neumann

  DOI：10.1021/om100352c

  日期：2010.11.8

  Gas-phase He 1 photoelectron spectra of a series of 2-arylethynyl-1,3,2-benzodiazaboroles BEP-X [1 (X = H), 2 (X = Me), 3 (X = OMe), 4 (X = SMe), 5 (X = NMe2), 6 (X = Br)] have been recorded and assessed by density functional theory calculations. The first ionization energies of these benzodiazaboroles are in the order 5 (7.0 eV) < 3 (7.15 eV) < 2 (7.2 eV) < 1 = 4 = 6 (7.3 eV). As an important result of this study it was disclosed that in contrast to the remaining diazaboroles the frontier orbitals of the amino derivative 5 lack contributions from the diazaborole part of the molecule. In keeping with this, the dipole moment of the ground state (5.51 D) is only slightly changed, to 6.60 D, upon electronic excitation. This also rationalizes the low Stokes shift of 2600 cm(-1) in comparison to the other diazaboroles in this study (5900-7300 cm(-1)).
• Hydroboration of Alkyne‐Functionalized 1,3,2‐Benzodiazaboroles
  作者：Lothar Weber、Daniel Eickhoff、Johannes Halama、Stefanie Werner、Jan Kahlert、Hans‐Georg Stammler、Beate Neumann

  DOI：10.1002/ejic.201201489

  日期：2013.5.6

  AbstractReactions of equimolar amounts of dicyclohexylborane (DCB) with a series of 2‐alkynyl‐1,3‐diethyl‐1,3,2‐benzodiazaboroles R–C≡C–B(NEt)2C6H4 (1: R = nBu, 2: R = tBu, 3: R = Ph, 4: R = p‐Me2NC6H4, 5: R = p‐MeOC6H4) regioselectively afforded the 1,1‐diborylalkenes (Z)‐R(H)C=C(BNEt}2C6H4)B(c‐C6H11)2} (7a–11a) as the result of a cis‐addition of the BH bond of the borane to the C≡C triple bond in compounds 1 to 5. In contrast to this, reaction of Me3Si–C≡C–B(NEt)2C6H4 (6) with HB(c‐C6H11)2 yielded a 2.5:1 mixture of the 1,2‐diborylated alkene (Z)‐Me3Si(c‐C6H11)2B}C=CHB(NEt)2C6H4 (12b) and the 1,1‐regioisomer (Z)‐Me3Si(H)C=CB(NEt)2C6H4}B(c‐C6H11)2} (12a). These results were rationalized by the differing π‐acceptor qualities of the benzodiazaborolyl and trimethylsilyl substituents at the C≡C triple bond in compounds 1 to 6. The novel products 7–12 were characterized by elemental analysis, mass spectrometry and NMR spectroscopy (1H, 11B, and 13C NMR). The molecular structures of 9b and 12b were substantiated by single‐crystal X‐ray diffraction analysis.