溴丁烷-D2 | 55724-40-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 中文名称: 溴丁烷-D2
• 英文名称: 1-Brombutan-2,2-d(2)
• 英文别名: 1-Bromobutane-2,2-D2；1-bromo-2,2-dideuteriobutane
• CAS: 55724-40-8
• 化学式: C₄H₉Br
• 分子量: 139.004
• InChiKey: MPPPKRYCTPRNTB-SMZGMGDZSA-N

物化性质

• 溶解度：
  可溶于氯仿（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  5
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  溴丁烷-D2 在 lithium hydroxide 、 ammonium hydroxide 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以0.51 g的产率得到
  参考文献：
  名称：

  Mechanisms of Catalyst Poisoning in Palladium-Catalyzed Cyanation of Haloarenes. Remarkably Facile C−N Bond Activation in the [(Ph₃P)₄Pd]/[Bu₄N]⁺ CN^- System

  摘要：

  Reaction paths leading to palladium catalyst deactivation during cyanation of haloarenes (eq 1) have been identified and studied. Each key step of the catalytic loop (Scheme 1) can be disrupted by excess cyanide, including ArX oxidative addition, X/CN exchange, and ArCN reductive elimination. The catalytic reaction is terminated via the facile formation of inactive [(CN)(4)Pd](2-), [(CN)(3)PdH](2-), and [(CN)(3)PdAr](2-). Moisture is particularly harmful to the catalysis because of facile CN- hydrolysis to HCN that is highly reactive toward Pd(0). Depending on conditions, the reaction of [(Ph3P)(4)Pd] with HCN in the presence of extra CN- can give rise to [(CN)(4)Pd](2-) and/or the remarkably stable new hydride [(CN)(3)PdH](2-) (NMR, X-ray). The X/CN exchange and reductive elimination steps are vulnerable to excess CN- because of facile phosphine displacement leading to stable [(CN)(3)PdAr](2-) that can undergo ArCN reductive elimination only in the absence of extra CN-. When a quaternary ammonium cation such as [Bu4N](+) is used as a phase-transfer agent for the cyanation reaction, C-N bond cleavage in the cation can occur via two different processes. In the presence of trace water, CN- hydrolysis yields HCN that reacts with Pd(0) to give [(CN)(3)PdH)(2-). This also releases highly active OH- that causes Hofmann elimination of [Bu4N](+) to give Bu3N, 1-butene, and water. This decomposition mode is therefore catalytic in H2O. Under anhydrous conditions, the formation of a new species, [(CN)(3)PdBu](2-), is observed, and experimental studies suggest that electron-rich mixed cyano phosphine Pd(0) species are responsible for this unusual reaction. A combination of experimental (kinetics, labeling) and computational studies demonstrate that in this case C-N activation occurs via an S(N)2-type displacement of amine and rule out alternative 3-center C-N oxidative addition or Hofmann elimination processes.

  DOI：

  10.1021/ja078298h
• 作为产物：
  描述：

  丁酸-D2 在 lithium aluminium tetrahydride 、 三溴化磷 作用下， 生成 溴丁烷-D2
  参考文献：
  名称：

  A McLafferty rearrangement in an even-electron system: C3H6 elimination from the α-cleavage product of tri-n-butylamine

  摘要：

  AbstractIt is shown by deuterium labelling, linked‐scan measurements and collision activation that the [M‐C3H7˙]+ (α‐cleavage) ion in the electron impact ionization spectrum of tributylamine loses C3H6 with transfer of one hydrogen specifically from the γ‐position. The experimental data point towards a mechanism which involves the intermediate formation of a distonic diradical ion from an excited α‐cleavage ion which then eliminates the neutral alkene.

  DOI：

  10.1002/oms.1210260808

文献信息

• Intermediacy of ion neutral complexes in the fragmentation of short-chain dialkyl sulfides
  作者：G. Filsak、H. Budzikiewicz

  DOI：10.1002/(sici)1096-9888(199906)34:6<601::aid-jms811>3.0.co;2-8

  日期：1999.6

  The main fragmentation processes after electron ionization of butyl methyl and butyl ethyl sulfides are rationalized by the intermediacy of the ion neutral complex [RSH . methylcyclopropane](+.) as demonstrated by extensive labeling and collision activation studies. Copyright (C) 1999 John Wiley & Sons, Ltd.
• The formation of [CH3CH2C(OH)CH2]+˙ from 1-hepten-3-ol
  作者：David J. McAdoo、Charles E. Hudson

  DOI：10.1002/oms.1210160704

  日期：1981.7

  AbstractThe [C4H8O]+˙ ion in the mass spectrum of 1‐hepten‐3‐ol is shown to be \documentclassarticle}\pagestyleempty}\begindocument}$ \rmCH}}_\rm3}} \rmCH}}_\rm2}} \rmC(= }}\mathop \rmO}}\limits^\rm + }} \rmH}})\mathop \rmC}}\limits^\rm.}} \rmH}}_\rm2}} $\enddocument} by collisional activation spectra, appearance energies and comparison of the ratios of the intensities of metastable decompositions. [C4H8O]+˙ appears to be formed by rearrangement of ionized 1‐hepten‐3‐ol to \documentclassarticle}\pagestyleempty}\begindocument}$ \rmCH}}_\rm3}} \mathop \rmC}}\limits^\rm.}} \rmHC(= }}\mathop \rmO}}\limits^\rm + }} \rmH)CH}}_\rm2}} \rmCH}}_\rm2}} \rmCH}}_\rm2}} \rmCH}}_\rm3}} $\enddocument} followed by γ‐hydrogen rearrangement‐β‐cleavage.
• β-Hydrogen Elimination of Ionic Butylzinc Complexes
  作者：Konrad Koszinowski、Christina Müller、Harald Brand、Julia E. Fleckenstein

  DOI：10.1021/om300698b

  日期：2012.10.22

  Gas-phase experiments on deuterium-labeled BuZn-(TMEDA)(+) (TMEDA = N,N,N',N'-tetramethylethylenediamine) prove that the loss of butene from this species corresponds to a beta-H elimination. Quantum-chemical calculations corroborate this finding and furthermore predict that the fragmentations of related cationic butylzinc complexes as well as of Bu3Zn- follow similar mechanisms.
• DANNHARDT G.; OBERGRUSBERGER R., ARCH. PHARM., 1979, 312, NO 6, 498-507
  作者：DANNHARDT G.、 OBERGRUSBERGER R.

  DOI：——

  日期：——
• Mechanisms of Catalyst Poisoning in Palladium-Catalyzed Cyanation of Haloarenes. Remarkably Facile C−N Bond Activation in the [(Ph₃P)₄Pd]/[Bu₄N]⁺ CN^- System
  作者：Stefan Erhardt、Vladimir V. Grushin、Alison H. Kilpatrick、Stuart A. Macgregor、William J. Marshall、D. Christopher Roe

  DOI：10.1021/ja078298h

  日期：2008.4.1

  Reaction paths leading to palladium catalyst deactivation during cyanation of haloarenes (eq 1) have been identified and studied. Each key step of the catalytic loop (Scheme 1) can be disrupted by excess cyanide, including ArX oxidative addition, X/CN exchange, and ArCN reductive elimination. The catalytic reaction is terminated via the facile formation of inactive [(CN)(4)Pd](2-), [(CN)(3)PdH](2-), and [(CN)(3)PdAr](2-). Moisture is particularly harmful to the catalysis because of facile CN- hydrolysis to HCN that is highly reactive toward Pd(0). Depending on conditions, the reaction of [(Ph3P)(4)Pd] with HCN in the presence of extra CN- can give rise to [(CN)(4)Pd](2-) and/or the remarkably stable new hydride [(CN)(3)PdH](2-) (NMR, X-ray). The X/CN exchange and reductive elimination steps are vulnerable to excess CN- because of facile phosphine displacement leading to stable [(CN)(3)PdAr](2-) that can undergo ArCN reductive elimination only in the absence of extra CN-. When a quaternary ammonium cation such as [Bu4N](+) is used as a phase-transfer agent for the cyanation reaction, C-N bond cleavage in the cation can occur via two different processes. In the presence of trace water, CN- hydrolysis yields HCN that reacts with Pd(0) to give [(CN)(3)PdH)(2-). This also releases highly active OH- that causes Hofmann elimination of [Bu4N](+) to give Bu3N, 1-butene, and water. This decomposition mode is therefore catalytic in H2O. Under anhydrous conditions, the formation of a new species, [(CN)(3)PdBu](2-), is observed, and experimental studies suggest that electron-rich mixed cyano phosphine Pd(0) species are responsible for this unusual reaction. A combination of experimental (kinetics, labeling) and computational studies demonstrate that in this case C-N activation occurs via an S(N)2-type displacement of amine and rule out alternative 3-center C-N oxidative addition or Hofmann elimination processes.