4-甲基吗啉硼烷络合物 | 15648-16-5

• 物质功能分类: 化学试剂 - 有机试剂 - 硼烷
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 中文名称: 4-甲基吗啉硼烷络合物
• 中文别名: 硼烷N-甲基吗啉络合物；4-甲基吗啉-硼烷；N-甲基吗啉硼烷络合物；硼烷 N-甲基吗啉络合物
• 英文名称: borane 4-methylmorpholine complex
• 英文别名: N-methylmorpholine-borane；borane-4-methylmorpholine；borane-N-methylmorpholine；4-methylmorpholine-borane；4-methylmorpholine - borane (1/1)；4-methylmorpholine borane complex；5-Chloro-1,3-dimethyl-1H-pyrazole-4-sulfonicacid；(4-methylmorpholin-4-ium-4-yl)boranuide
• CAS: 15648-16-5
• 化学式: C₅H₁₄BNO
• 分子量: 114.983
• InChiKey: HEOFHMZUMVDLFB-UHFFFAOYSA-N

物化性质

• 熔点：
  42-45 °C (lit.)
• 闪点：
  151 °F

计算性质

• 辛醇/水分配系数(LogP)：
  -1.26
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险等级：
  4.1
• 危险品标志：
  Xn,F
• 安全说明：
  S16,S23,S26,S33,S36
• 危险类别码：
  R20/21/22,R36/37/38,R11
• WGK Germany：
  3
• 包装等级：
  III
• 危险类别：
  4.1
• 危险标志：
  GHS02,GHS07
• 危险品运输编号：
  UN 1325
• 危险性描述：
  H228,H302 + H312 + H332,H315,H319,H335
• 危险性防范说明：
  P210,P261,P280,P305 + P351 + P338

反应信息

• 作为反应物：
  描述：

  4-甲基吗啉硼烷络合物 在 ethanol 作用下， 以 乙醇 为溶剂， 生成 氢气
  参考文献：
  名称：

  使用胺-硼烷加合物的醇解作为还原体系，温和有效地进行rh催化的terminal烯末端转移氢化

  摘要：

  [ReBr 2（NO）（CH 3 CN）（PTA）2 ]（PTA = 1，3，5-三氮杂-7-磷金刚烷）催化氨-硼烷和胺-硼烷的醇解以及各种末端的催化转移加氢反应烯烃。使用t BuOK作为助催化剂，在70°C的异丙醇中获得优异的收率，TOF值高达396 h -1。

  DOI：

  10.1016/j.jorganchem.2011.01.027
• 作为产物：
  描述：

  N-甲基吗啉盐酸盐 、 sodium tetrahydroborate 在 18-冠醚-6 作用下， 以 乙醚 为溶剂， 以75%的产率得到4-甲基吗啉硼烷络合物
  参考文献：
  名称：

  冠醚催化的胺·甲硼烷和胺加合物trideuterioborane的合成从加入NaBH 4 NaBD 4在乙醚

  摘要：

  通过R 3 N·HCl与NaBH 4和NaBD 4在醚中的冠醚催化反应，可以高产率获得胺基硼烷和胺基三氘代硼烷加合物。通过Me 3 N·BD 3的IR和11 B和2 H核磁共振谱证明了与NaBD 4的反应中没有同位素交换。

  DOI：

  10.1016/0022-328x(94)80072-3
• 作为试剂：
  描述：

  刺五加苷 在 4-甲基吗啉硼烷络合物 、 三氟乙酸 作用下， 以 水 为溶剂， 反应 1.08h， 生成 葡萄糖
  参考文献：
  名称：

  Potent AChE and BChE inhibitors isolated from seeds of Peganum harmala Linn by a bioassay-guided fractionation

  摘要：

  Ethnopharmacological relevance: Seeds of Peganum harmala Linn are traditionally used as folk medical herb in Uighur medicine in China to treat disorders of hemiplegia and amnesia. Previously studies have proved that dominating alkaloids in P. harmala show significant inhibitory activities on the cholinesterase.Aim of the study: The aim of the present study is to isolate trace ingredients from seeds of P. harmala and evaluate its inhibitory activities on acetylcholinesterase (AChE) and butyrylcholinesterase (BChE).Materials and methods: For sake of screening effective cholinesterase inhibitors, trace compounds were isolated from seeds of P. harmala through a bioassay-guided fractionation and their structures were determined via detailed spectral analysis. The inhibitory activities on AChE and BChE were assessed using an improved Ellman method by UPLC-ESI-MS/MS to determine the common final product choline.Results: The activity-guided fractionation led to the isolation of two new alkaloids 2-aldehyde-tetrahydroharmine (10), 2-carboxyl-3,4-dihydroquinazoline (19), one syringin structure analog 1-O-beta-D-xylopyranose sinapyl alcohol (22), and along with 19 known compounds. Compounds acetylnorharmine (6), harmic acid methy ester (7), harmine N-oxide (13), 6-methoxyindoline (14), syringin (21) were first found from genus Peganum and compounds 3-hydroxylated harmine (4), 1-hydroxy-7-methoxy-beta-carboline (5) were new natural products. The results showed that the 2-aldehyde-tetrahydroharmine (10) has a potential inhibitive effect on both AChE and BChE with IC50 values of 1235 +/- 0.24 and 5.51 +/- 033 mu M, respectively. Deoxyvasicine (15) and vasicine (16) showed the strongest BChE inhibitory activity with IC50 values of 0.04 +/- 0.01 and 0.1 +/- 0.01 mu M. The analysis of the structure-activity relationship indicated that the saturation of pyridine ring and the presence of substitution at indole ring, C-1, C-3, C-7 and N-2, for beta-carbolines, were essential for effective inhibition of both AChE and BChE and the five-membered ring between C-2 and N-3 as well as the substituent groups sited at C-4 and C-9, for quinazolines, were important to both the AChE/BChE-inhibitory activity.Conclusions: Bioassay-guided fractionation has led to the isolation of AChE and BChE inhibitors from the seeds of P. harinala. These results are in agreement with the traditional uses of the seeds of P. harmala. (C) 2015 Elsevier Ireland Ltd. All rights reserved.

  DOI：

  10.1016/j.jep.2015.03.070

文献信息

• Dirhodium‐Catalyzed Enantioselective B−H Bond Insertion of <i>gem</i> ‐Diaryl Carbenes: Efficient Access to <i>gem</i> ‐Diarylmethine Boranes
  作者：Yu‐Tao Zhao、Yu‐Xuan Su、Xiao‐Yu Li、Liang‐Liang Yang、Ming‐Yao Huang、Shou‐Fei Zhu

  DOI：10.1002/anie.202109447

  日期：2021.11.2

  We report highly enantioselective dirhodium-catalyzed B−H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance.

  我们报告了以二芳基重氮甲烷作为卡宾前体的高对映选择性二铑催化的 B-H 键插入反应。这些反应以高产率（高达 99 % 的产率）、高活性（高达 14 300 的转化率）、高对映选择性（高达 99 % ee）提供了手性 gem-二芳基次甲基硼烷化合物，并显示出前所未有的广泛官能团耐受性。
• Deuteration of boranes: catalysed versus non-catalysed processes
  作者：David J. Nelson、Jonathan D. Egbert、Steven P. Nolan

  DOI：10.1039/c3dt33045a

  日期：——

  A dichotomy in the reactivity of B–H bonds is reported. A bis(N-heterocyclic carbene)-ligated iridium(III) complex can effect rapid deuteration of boronate esters at room temperature with low catalyst loadings; however, borane and 9-BBN both undergo deuteration in the absence of catalyst, and do not react with the iridium complexes. This is proposed to result from the inductive electron-withdrawing properties of the boronic ester substituents. Deuterated boronic esters can be accessed rapidly at room temperature with only very low loadings of iridium catalyst.

  据报道，B-H 键的反应性存在二分法。双（N-杂环碳烯）配位铱（III）络合物可以在室温下以较低的催化剂负载量实现硼酸酯的快速氘化；然而，硼烷和 9-BBN 在没有催化剂的情况下都会发生氘化，并且不会与铱络合物发生反应。据推测，这是由于硼酸酯取代基具有感应式电子吸收特性。只需极低的铱催化剂负载量，就能在室温下快速获得氚代硼酸酯。
• Synthesis of Propargyl Boranes via Silver Catalyzed Insertion of Alkynyl Carbene into B‐H Bond
  作者：Mengtian Huo、Yongquan Ning、Xudong Zheng、Xinyue Han、Swastik Karmakar、Jing Sun、Xihe Bi

  DOI：10.1002/cctc.202201381

  日期：2023.1.20

  insertion reaction of alkynyl carbenes, derived in situ by decomposition of alkynyl N-nosylhydrazones, into a B−H bond emerges as a straightforward synthesis protocol for various propargylic boron compounds with up to 95 % yield. Deuterium labelling experiments and DFT studies show that the reaction proceeds via insertion of alkynyl Ag-carbene into the B−H bond and generation of silver carbene occurs

  通过炔基N -nosylhydrazone原位分解得到的炔基卡宾，通过银催化插入反应生成 B-H 键，作为各种炔丙基硼化合物的直接合成方案，收率高达 95%。氘标记实验和 DFT 研究表明，反应通过将炔基 Ag-卡宾插入 B-H 键进行，并在决速步骤中生成银卡宾。
• Photocatalyzed H2-Acceptorless Dehydrogenative Borylation by Using Amine Borane
  作者：Hao-Wen Jiang、Wan-Lei Yu、Dong Wang、Peng-Fei Xu

  DOI：10.1021/acscatal.4c00401

  日期：2024.6.7

  merger of photoredox/HAT/cobalt catalysis, thereby circumventing the necessity for noble metals, sacrificial hydrogen acceptors, and high temperatures. This method employs stable and cost-effective amine borane reagents as feedstocks, resulting in the sole byproduct of H2. This dehydrogenative borylation methodology facilitates the conversion of a diverse array of functionalized alkenes into valuable organoboron

  烯烃的催化脱氢硼基化可以说是合成烯基硼酸酯的最直接的方法，因为它消除了对烯烃或硼烷预官能化的需要。虽然过渡金属催化通常用于这种转化，但竞争性副反应，包括氢硼化、过度硼化和区域异构体形成，始终存在。在这项研究中，我们提出了一种催化脱氢硼基化的激进方法，涉及光氧化还原/HAT/钴催化的协同合并，从而避免了对贵金属、牺牲氢受体和高温的需要。该方法采用稳定且具有成本效益的胺硼烷试剂作为原料，产生唯一的副产物H 2 。这种脱氢硼化方法有利于将多种官能化烯烃转化为有价值的有机硼试剂。此外，复杂分子的后期硼化表现出高水平的位点选择性。
• Brown, Herbert C.; Murray, Leo T., Inorganic Chemistry, 1984, vol. 23, # 18, p. 2746 - 2753
  作者：Brown, Herbert C.、Murray, Leo T.

  DOI：——

  日期：——