N,N'-bis(tert-butyl)-2-bromo-1,3,2-diazaborole | 64486-89-1

• 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: N,N'-bis(tert-butyl)-2-bromo-1,3,2-diazaborole
• 英文别名: 1,3-Di-t-butyl-2-brom-Δ⁴-1,3,2-diazaborolin；2-bromo-1,3-di-t-butyl-1,3,2-diazaborole；2-bromo-1,3-bis(tert-butyl)-2,3-dihydro-1H-1,3,2-diazaborole；1,3-di-tert-butyl-2-bromo-2,3-dihydro-1H-1,3,2-diazaborole；2-bromo-1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole；2-bromo-1,3-(ert-butyl)-1,3,2-diazaboroline；2-Bromo-1,3-di-t-butyl-1,3,2-diazaborol；(S)-tBuN(a)CHCHN(b)(tBu)B-Br(N(a)-B)；tBuNCH=CHN(tBu)BBr；2-bromo-1,3-ditert-butyl-1,3,2-diazaborole
• CAS: 64486-89-1
• 化学式: C₁₀H₂₀BBrN₂
• 分子量: 258.997
• InChiKey: QGDZCLVHYKUTHM-UHFFFAOYSA-N

物化性质

• 沸点：
  251.0±23.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  N,N'-bis(tert-butyl)-2-bromo-1,3,2-diazaborole 在 nitrosyl hexafluorophosphate 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 以88%的产率得到
  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：

  dibromo-(N,N'-di-tert-butyl-ethanediylidenediamine-N,N')-boron(1+); bromide 在 Na-Hg 作用下， 以 正己烷 为溶剂， 以85%的产率得到N,N'-bis(tert-butyl)-2-bromo-1,3,2-diazaborole
  参考文献：
  名称：

  Reaction of 1,3‐Dialkyl‐4,5‐dimethylimidazol‐2‐ylidenes with 2‐Bromo‐2,3‐dihydro‐1 H ‐1,3,2‐diazaboroles (Alkyl= i Pr and t Bu)

  摘要：

  Abstract2‐Bromo‐2,3‐dihydro‐1H‐1,3,2‐diazaboroles (3a–c) were synthesized by cyclocondensation of dilithiated 1,4‐diazabutadienes (5a–c) with boron tribromide in hexane. 3a was also obtained by sodium amalgam reduction was conducted in ether solvents, diboroxane (2) resulted as the main product. Compound 3a and 1,3‐dialkyl‐4,5‐dimethylimidazol2‐ylidenes (6a, b) underwent halide displacement to afford the borolylimidazolium salts 7a, b. Compounds 2, 3a–c, and 7a, b were characterized by elemental analyses and spectroscopic methods (1H, 11B, 13C NMR; Ir; MS). The molecular structures of 2 and 7a were established by single‐crystal X‐ray diffraction analyses.

  DOI：

  10.1002/cber.19971300606

文献信息

• Synthesis and Structure of 2-Hydro-, 2-Alkyl-, 2-Alkynyl-, and 2-Stannyl-2,3-dihydro-1H-1,3,2-diazaboroles
  作者：Lothar Weber、Eckhard Dobbert、Hans-Georg Stammler、Beate Neumann、Roland Boese、Dieter Bläser

  DOI：10.1002/(sici)1099-0682(199903)1999:3<491::aid-ejic491>3.0.co;2-9

  日期：1999.3

  the compound 3a serves as an η1 ligand towards the [Cr(CO)5] unit via the cyano group. These novel compounds were characterized by 1H-, 11B-, 13C-, and 119Sn-NMR spectroscopy, as well as by X-ray structure analyses of 4b, 8a, and 9a.

  1,3-二叔丁基-2,3-二氢-1H-1,3,2-二氮杂硼(4a)和1,3-双(2,6-二甲基苯基)-2,3-二氢-1H- 1,3,2-二氮杂硼 (4b) 是由相应的 2-溴或 2-碘衍生物 1a 和 2b 与 LiAlH4 反应形成的。用正丁基锂处理 1a 得到 2-n-丁基-1,3-二叔丁基-2,3-二氢-1H-1,3,2-二氮杂硼 (5a)，而 1,3-二-叔丁基-2-氰基-2,3-二氢-1H-1,3,2-二氮杂硼(3a)转化为2-叔丁基衍生物6a或2-乙炔基-1,3,2-二氮杂硼7a通过叔丁基锂或通过乙炔化锂的乙二胺加合物。类似地，1,3-二叔丁基-2-三甲基甲锡烷基-2,3-二氢-1H-1,3,2-二氮杂硼(8a)和1,3-双(2,6-二甲基苯基)-2-三甲基锡基-2,3-二氢-1H-1,3,2-二氮杂硼 (8b) 可从 1a 或 2b 和三甲基锡基锂获得。在配合物9a中，化合物
• Synthesis, structure, and properties of luminescent diazaborole and indole systems
  作者：Lothar Weber、Daniel Eickhoff、Anna Chrostowska、Clovis Darrigan、Hans-Georg Stammler、Beate Neumann

  DOI：10.1007/s10593-017-2021-0

  日期：2017.1

  Thiophenes and phenylacetylenes, decorated with 1-methylindol-2-yl, 1,3,2-benzodiazaborol-2-yl, 1,3,2-diazaborol-2-yl, or 1,3,2-diazaborolidinyl groups at one end and dimesitylborolyl or CN substituents at the opposite end of the molecules, were synthesized. Upon UV irradiation, these push-pull systems in THF solution gave rise to bright-blue emission with Stokes shifts ranging from 4100 to 9300 cm–1

  噻吩和苯乙炔，在一个末端被1-甲基吲哚-2-基，1,3,2-苯并二氮杂硼醇-2-基，1,3,2-二氮杂硼醇-2-基或1,3,2-二氮杂硼烷炔基修饰合成了在分子的相反端的二甲硅烷基硼烯丙基或CN取代基。在紫外线照射下，这些在THF溶液中的推挽系统产生了亮蓝色发射，斯托克斯位移范围为4100至9300 cm –1，量子效率高达0.99。因此，分子内的电荷从吲哚基或硼烯丙基荧光团的HOMO发生转移到LUMO，主要集中在吸电子氰基或二聚异戊二烯基上。
• Synthese, Struktur und Reaktivität von 2-Amino- und 2-Imino-2,3-dihydro-1H-1,3,2-diazaborolen / Synthesis, Structure and Reactivity of 2-Amino- and 2-Imino-2,3-dihydro-1H-1,3,2-diazaboroles
  作者：Lothar Weber、Eckhard Dobbert、Andreas Rausch、Hans-Georg Stammler、Beate Neumann

  DOI：10.1515/znb-1999-0312

  日期：1999.3.1

  The 2-halo-2,3-dihydro-1H-1,3,2-diazaboroles (1a′: R = tBu, X = Br; 1b: R = 2,6-Me₂C₆H_3; X = I) were converted into the 2-amino-2,3-dihydro-1H-1,3,2- diazaboroles (2a: R = tBu; 2b: 2,6-Me₂C₆H₃) by treatment with dry gaseous ammonia. Similarly reaction of 1a′ with 2,6-dimethylaniline or tBuNH₂ afforded the corresponding derivates (3; R¹ = 2,6-Me₂C₆H₃; 4; R¹ = tBu). The treatment of 1a′ with the ethylene diamine adduct of lithium acetylide led to the formation of (5). Lithiation of 2 a and subsequent silylation gave 6 (R¹ = SiMe₃), which was transformed to the diborolylamine (7) upon exposure to 1a′. Borolylketimine (8 ) and borolylcarbodiimide (9) resulted from 1a′ and Ph₂C=NSiMe₃ or Me₃SiN=C=NSiMe₃, respectively. All the new compounds were characterized by elemental analyses as well as spectroscopic data (IR, ¹H, ¹¹B, ¹³C NMR, MS). Heterocycle 5 was also subjected to an X-ray diffraction analysis.

  2-卤代-2,3-二氢-1H-1,3,2-二氮硼烷（1a′: R = tBu, X = Br; 1b: R = 2,6-Me₂C₆H_3; X = I）经干燥氨气处理转化为2-氨基-2,3-二氢-1H-1,3,2-二氮硼烷（2a: R = tBu; 2b: 2,6-Me₂C₆H₃）。类似地，1a′与2,6-二甲基苯胺或tBuNH₂反应生成相应的衍生物（3; R¹ = 2,6-Me₂C₆H₃; 4; R¹ = tBu）。1a′与乙炔二胺配合物反应形成了（5）。2a的锂化及随后的硅烷化反应得到6（R¹ = SiMe₃），暴露于1a′后转化为二硼杂氨基（7）。Borolylketimine（8）和borolylcarbodiimide（9）分别由1a′和Ph₂C=NSiMe₃或Me₃SiN=C=NSiMe₃形成。所有新化合物均通过元素分析和光谱数据（IR，¹H，¹¹B，¹³C NMR，MS）进行表征。杂环化合物5还进行了X射线衍射分析。
• 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。
• 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