2-bromo-1,3-di-tert-butyl-1,3,2-diazaborolidine | 869309-50-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2-bromo-1,3-di-tert-butyl-1,3,2-diazaborolidine
• 英文别名: (tBuEn)B-Br；tBuNCH2CH2N(tBu)BBBr；(t)BuNCH2CH2N((t)Bu)BBr；2-Bromo-1,3-di-t-butyl-1,3,2-diazaborolidine；2-bromo-1,3-ditert-butyl-1,3,2-diazaborolidine
• CAS: 869309-50-2
• 化学式: C₁₀H₂₂BBrN₂
• 分子量: 261.013
• InChiKey: NBBYNLXQGWSKNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.58
• 重原子数：
  14
• 可旋转键数：
  2
• 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：

  2-bromo-1,3-di-tert-butyl-1,3,2-diazaborolidine 在 nitrosyl hexafluorophosphate 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 生成
  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：

  1,2-双(叔丁基氨基)乙烷 、 三溴化硼 在 triethylamine 作用下， 以 正己烷 为溶剂， 以84%的产率得到2-bromo-1,3-di-tert-butyl-1,3,2-diazaborolidine
  参考文献：
  名称：

  Synthetic, Cyclovoltammetric, and UV-Photoelectron Spectroscopic Studies of 2,3-Dihydro-1H-1,3,2-diazaboroles and 1,3,2-Diazaborolidines

  摘要：

  The oxidation potentials E-ox of a series of 2,3-dihydro-1H-1,3,2-diazaboroles (BuNCH)-Bu-t=CHN(Bu-t)BR (1a-i) and of the corresponding saturated 1,3,2-diazaborolidines 2a (R = NH2)2b (OMe), 2c (Me), 2d (NMe2), 2e (H), 2f (SMe), 2g (SnMe3) 2h (Br), 2i (CN) were determined by cyclovoltammetry in CH2Cl2 solution. The potentials E-ox of the irreversible electrochemical oxidations range from E-ox = -288 mV (1a) to 752 mV (1i). In contrast to this, E-ox of the corresponding diazaborolidines are anodically shifted by 260 mV (1d, 2d) to 752 mV (1b, 2b) and vary from 280 mV (2a) to 1164 mV (2i). Gas-phase photoelectron spectra of representatives of both series of compounds were recorded and assessed by density functional calculations. The first ionization potentials of the 2,3-dihydro-1H-1,3,2-diazaboroles range in the series 1c (7.1 eV) < If (7.3 eV) < 1e = 1h (7.4 eV) < 1i (7.7 eV). They differ by less than 0.3 eV from the first ionization potentials determined for the saturated analogues [1st IP for 2c (7.3 eV) < 2e = 2f (7.4 eV) < 2h (7.7 eV)].

  DOI：

  10.1021/om0580304

文献信息

• Unsymmetrical diborane(4) derivatives by copper mediated B–B coupling
  作者：W. Oschmann、C. Borner、C. Kleeberg

  DOI：10.1039/c8dt00627j

  日期：——

  A novel, versatile and modular route to unsymmetrical diborane(4) derivatives bearing either two different diol moieties or one diol and one diamine moiety is presented. Utilising the very basic approach of reacting a boron nucleophile with a boron electrophile to establish the B–B bond allows a simple variation of the two individual boron moieties. The copper(I) boryl complexes used as nucleophilic

  提出了一种新颖，通用和模块化的途径，可制得带有两个不同二醇部分或一个二醇和一个二胺部分的不对称乙硼烷（4）衍生物。利用使亲核硼与亲电硼反应以建立BB键的最基本方法，可以简单地改变两个单独的硼部分。可以从市售的对称二硼烷（4）衍生物中轻松获得用作亲核硼源的铜（I）硼基络合物，而同样容易获得的卤化硼衍生物用作亲电子试剂。获得了七个以前无法获得的乙硼烷（4）衍生物，并进行了全面表征，包括单晶X射线结构测定，从而说明了该方法的广泛范围。
• 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, 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
• Elusive Phosphine Copper(I) Boryl Complexes: Synthesis, Structures, and Reactivity
  作者：Corinna Borner、Lisa Anders、Kai Brandhorst、Christian Kleeberg

  DOI：10.1021/acs.organomet.7b00775

  日期：2017.12.26

  We report the first isolation of phosphine copper boryl complexes—species pivotal to numerous copper-catalyzed borylation reactions. The reaction of diboron(4) derivatives with copper tert-butoxide complexes of phosphine ligands allows the isolation of the dimeric μ-boryl-bridged Cu(I) complexes [(iPr3P)Cu–Bdmab]2 (4) and [(C6H4(Ph2P)2)Cu–Bpin]2 (6) with Cu···Cu distances of 2.24–2.27 Å (dmab = (NMe)2C6H4

  我们报道了首次分离出磷化氢铜硼酸酯配合物-对许多铜催化的硼酸酯化反应至关重要的物种。Diboron（4）衍生物与膦配体的叔丁醇铜配合物的反应可分离出二聚体μ-硼基桥接的Cu（I）配合物[（i Pr 3 P）Cu–Bdmab] 2（4）和[ （C 6 H 4（Ph 2 P）2）Cu–Bpin] 2（6），Cu···Cu距离为2.24–2.27Å（dmab =（NMe）2 C 6 H 4，pin =（OCMe 2）2个））。在空间上要求更高的硼基配体提供了空前的多核铜硼基络合物[（i Pr 3 P）2 Cu 8（B（i PrEn））3（O t Bu）3 ]（5），是一种潜在的中间体分解。初始的Cu（I）硼基络合物（i PrEn =（N i Pr）2 C 2 H 4）。所有配合物均通过单晶X射线衍射，NMR光谱和元素分析进行​​表征。DFT计算支持这些独特复合物的性质，并深入了解其电子结构。