methylbromamine | 10218-87-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methylbromamine
• 英文别名: N-bromomethylamine；Methanamine, N-bromo-；N-bromomethanamine
• CAS: 10218-87-8
• 化学式: CH₄BrN
• 分子量: 109.953
• InChiKey: GCZPGFDPWJHDIY-UHFFFAOYSA-N

物化性质

• 熔点：
  152.3-166.5 °C
• 沸点：
  47-48 °C
• 密度：
  1.640±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  methylbromamine 、 苄基甲基硫醚 以 甲醇 、 乙醇 为溶剂， 反应 0.17h， 生成
  参考文献：
  名称：

  Direct Access to N-Alkylsulfoximines from Sulfides by a Sequential Imidation/Oxidation Procedure

  摘要：

  Synthetically relevant N-alkyl-substituted sulfoximines are directly prepared from sulfides by an unprecedented one-pot imidation/oxidation sequence. In situ generated N-bromoalkylamines serve as readily accessible imidating agents leading to N-alkylsulfiliminium bromides that are subsequently oxidized providing the corresponding N-alkylsulfoximines. In this manner, gram quantities of the products can be obtained in a short period of time avoiding the use of toxic and cumbersome to handle alkylating reagents.

  DOI：

  10.1055/s-0034-1380536
• 作为产物：
  描述：

  甲胺 在 溴 作用下， 以 水 为溶剂， 生成 methylbromamine
  参考文献：
  名称：

  1,2-二烷基二氮丙啶形成机制的动力学和量子化学研究

  摘要：

  首次采用紫外光谱法研究了水介质中1,2-二烷基二氮丙啶形成反应中AlkNHBr消耗的规律。由于中间体亚胺阳离子的胺化以及中间体的平行卤化，从形成 1,2-二烷基二氮丙啶前体 N-卤代氨基的可能性开始估计反应的特定步骤的速率常数。二胺。对化合物的空间和电子结构以及键的局域反应性和全局亲电性指数进行了量子化学计算（DFT、B3LYP、6-31++G(d,p) 和 3-21G 基组）反应的中间体。计算结果使我们能够解释使用 EtNHBr 代替 MeNHBr 时反应的延迟。

  DOI：

  10.1007/s11172-012-0152-0
• 作为试剂：
  描述：

  1-己烯 、 N-溴-N-甲基甲胺 、 N,N-二氯-N-甲胺 、 N-bromo-N-methylacetamide 在 三氟化硼乙醚 1-氯哌啶 、 1-溴哌啶 、 methylbromamine 、 氯二甲基胺 、 N,N-dibromomethylamine 、 (CH₃)NBr 、 盐酸甲胺 作用下， 以 二氯甲烷 为溶剂， 生成 1-溴-2-氟己烷 、 1-Chloro-2-fluorohexane
  参考文献：
  名称：

  三氟化硼促进正卤代亲电子体与烯烃的反应

  摘要：

  N-卤代亲电子试剂在氟氟化硼醚化物的存在下与烯烃反应，生成卤代氟化物和N-卤代加合物。

  DOI：

  10.1016/s0040-4039(00)94744-0

文献信息

• The study of the formation mechanism of 1,2,3-trialkyldiaziridines by kinetic and quantum chemistry methods
  作者：V. V. Kuznetsov、V. V. Seregin、D. V. Khakimov、T. S. Pivina、M. D. Vedenyapina、A. A. Vedenyapin、N. N. Makhova

  DOI：10.1007/s11172-014-0691-7

  日期：2014.9

  Using UV spectrometry, we studied for the first time the regularities of AlkNHBr consumption in two variations of the formation of 1,2,3-trialkyldiaziridines in aqueous media: by mixing acetaldehyde and AlkNHBr in excess of AlkNH2 (method 1) and by the reaction of MeCH=NEt with EtNHBr in excess of EtNH2 (method 2). We determined the rate constants of the individual stages of the reaction. Using quantum chemistry methods (DFT/B3LYP/3-21G), we performed calculations of spatial and electronic structures of the reacting compounds, indices of local reactivity, and global electrophilicity of atoms of the individual reaction intermediates, based on which we explained the decrease in the reaction rate when using EtNHBr instead of MeNHBr in method 1. In method 2, the formation of 1,2-diethyl-3-methyldiaziridine occurs exclusively through the intermediate iminium cation.

  利用紫外光谱法，我们首次研究了在水介质中形成 1,2,3-三烷基二氮杂环丁烷的两种变化过程中 AlkNHBr 消耗的规律性：乙醛和 AlkNHBr 在 AlkNH2 过量的情况下混合（方法 1），以及 MeCH=NEt 与 EtNHBr 在 EtNH2 过量的情况下反应（方法 2）。我们测定了反应各个阶段的速率常数。我们使用量子化学方法（DFT/B3LYP/3-21G）计算了反应化合物的空间结构和电子结构、局部反应性指数以及各个反应中间体原子的全局亲电性，并据此解释了在方法 1 中使用 EtNHBr 而不是 MeNHBr 时反应速率降低的原因。在方法 2 中，1,2-二乙基-3-甲基二氮丙啶的生成完全通过中间体亚氨基阳离子进行。
• Schmitz, Ernst; Pagenkopf, Ingeborg, Journal fur praktische Chemie (Leipzig 1954), 1985, vol. 327, # 6, p. 998 - 1006
  作者：Schmitz, Ernst、Pagenkopf, Ingeborg

  DOI：——

  日期：——
• Sahasrabudhey et al., Journal of the Indian Chemical Society, 1953, vol. 30, p. 652
  作者：Sahasrabudhey et al.

  DOI：——

  日期：——
• Risk-Ouaini, R.; Tremblay-Goutaudier, C.; Cohen-Adad, M. T., Journal de Chimie Physique et de Physico-Chimie Biologique, 1993, vol. 90, # 3, p. 579 - 594
  作者：Risk-Ouaini, R.、Tremblay-Goutaudier, C.、Cohen-Adad, M. T.

  DOI：——

  日期：——
• Electrophilic bromination of gaseous aromatic compounds: Mechanism and linear free energy effects on reaction rates
  作者：Olga Bortolini、Sheng Sheng Yang、R. G. Cooks

  DOI：10.1002/oms.1210281105

  日期：1993.11

  AbstractElectrophilic bromination of monosubstituted aromatic compounds is effected in a pentaquadrupole mass spectrometer using BrCO+ and CH3NH2Br+ as mass‐selected reagent ions. Reaction normally occurs at the ring and the brominated product can be mass selected in turn and caused to dissociate by Br˙ loss upon collision‐induced dissociation. Linear free energy correlations with Brown substituent σ+ constants describe the extent of gas‐phase bromine cation addition under the non‐equilibrium, low‐pressure and solvent‐free conditions which pertain in quadruple collision cells. The electrophilic addition reaction proceeds via a σ‐complex to the ring as suggested by MS3 spectra, except in the case of nitrobenzene, where substituent bromination is suggested by the occurrence of a competitive process in which the nitrosubstituent is displaced by bromine. The reactivity parameters ρ are −0.23 and −0.56 for the gaseous reagents, BrCO+ and CH3NH2Br+, respectively. Both values are much less negative than corresponding values for bromination in solution. The greater reactivity of BrCO+ is evident by the fact that it reacts even with the strongly deactivated substrates and this is consistent with a weak BrCO bond. Competitive protonation occurs in the case of CH3NH2Br+ and, unlike bromination, the rate of this reaction does not correlate with σ+ values. This is suggested to be a consequence of protonation at the ring in some cases and at the substituent in others, including acetophenone and benzonitrile. Evidence for this is that, in contrast to its lack of correlation with substituent constants, the rate of protonation correlates linearly with proton affinity.