trimethylamine-bromo(methoxycarbonyl)boranes | 159095-45-1

• 英文名称: trimethylamine-bromo(methoxycarbonyl)boranes
• 英文别名: trimethylamine-bromo(methoxycarbonyl)borane
• CAS: 159095-45-1
• 化学式: C₅H₁₃BBrNO₂
• 分子量: 209.879
• InChiKey: ZJPOMWPWDZWPPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  trimethylamine-bromo(methoxycarbonyl)boranes 以 乙腈 为溶剂， 生成 N-methylmorpholine-cyano(methoxycarbonyl)borane
  参考文献：
  名称：

  Synthesis and examination of amine-cyanocarboxyboranes, the boron analogues of α-cyanocarboxylic acids: X-ray structural study of the first lactam containing a boron atom in the lactam ring

  摘要：

  The first representatives of chiral boron atom-containing amine-cyanomethoxycarbonyl boranes (A . BH(CN)COOMe) have been synthesized either from the corresponding amine-bromocyanomethoxycarbonylborane complexes with [BU4N]CN or from Me3N.BH(CN)COOMe and an amine in a base-exchange reaction. Acid hydrolyses of methyl esters generated the free acids (A.BH(CN)COOH), which are isoelectronic to the alpha-cyano carboxylic acids. Their pK(a) values and hydrolysis half-lives in acidic medium (that is rate of proton reduction) have been determined. Similarly to the alpha cyano carboxylic acids, the cyano group attached to the boron (in alpha position to the COOH group) increased the acid strength of carboxy boranes with 2.0-2.5 orders of magnitude. Independently from the type of the amine, pK(a) values of the amine-cyanocarboxyhoranes (6.34-5.82) decrease consistently with the increase of pK(b) values of the amines. Hydrolytic decomposition rate of the alkylamine complexes increases with increasing pKb values of the amines while the opposite was found for pyridine base complexes. When considering both types of the amines, hydrolysis half-lives of the complexes range over several orders of magnitude from 0.005 to 400 h. Based on these observations protonation of the amine nitrogen atom appears to be the rate determining step in the hydrolysis process. With loss of methanol, 2-NH2-py.BH(CN)COOMe transformed into a five membered lactam derivative. X-ray diffraction revealed that the pyridine ring is coplanar with the five membered lactam ring. In the crystal two molecules are connected in a head to tail arrangement by strong intermolecular H-bonds between N(2)-H and the carbonyl oxygen (01) with a donor and acceptor distance of 2.867(3) A. Three new cyanomethoxycarbonylborates having the composition of K[BHn(CN)(3-n)COOMe] (n = 1, 2) and K[B(OH)(CN)(2-) COOMe] have also been synthesized and their properties examined. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.06.066
• 作为产物：
  描述：

  N-溴代丁二酰亚胺(NBS) 、 (甲氧基羰基)三甲基硼胺 以 甲醇 为溶剂， 以87%的产率得到trimethylamine-bromo(methoxycarbonyl)boranes
  参考文献：
  名称：

  Synthesis and examination of amine-cyanocarboxyboranes, the boron analogues of α-cyanocarboxylic acids: X-ray structural study of the first lactam containing a boron atom in the lactam ring

  摘要：

  The first representatives of chiral boron atom-containing amine-cyanomethoxycarbonyl boranes (A . BH(CN)COOMe) have been synthesized either from the corresponding amine-bromocyanomethoxycarbonylborane complexes with [BU4N]CN or from Me3N.BH(CN)COOMe and an amine in a base-exchange reaction. Acid hydrolyses of methyl esters generated the free acids (A.BH(CN)COOH), which are isoelectronic to the alpha-cyano carboxylic acids. Their pK(a) values and hydrolysis half-lives in acidic medium (that is rate of proton reduction) have been determined. Similarly to the alpha cyano carboxylic acids, the cyano group attached to the boron (in alpha position to the COOH group) increased the acid strength of carboxy boranes with 2.0-2.5 orders of magnitude. Independently from the type of the amine, pK(a) values of the amine-cyanocarboxyhoranes (6.34-5.82) decrease consistently with the increase of pK(b) values of the amines. Hydrolytic decomposition rate of the alkylamine complexes increases with increasing pKb values of the amines while the opposite was found for pyridine base complexes. When considering both types of the amines, hydrolysis half-lives of the complexes range over several orders of magnitude from 0.005 to 400 h. Based on these observations protonation of the amine nitrogen atom appears to be the rate determining step in the hydrolysis process. With loss of methanol, 2-NH2-py.BH(CN)COOMe transformed into a five membered lactam derivative. X-ray diffraction revealed that the pyridine ring is coplanar with the five membered lactam ring. In the crystal two molecules are connected in a head to tail arrangement by strong intermolecular H-bonds between N(2)-H and the carbonyl oxygen (01) with a donor and acceptor distance of 2.867(3) A. Three new cyanomethoxycarbonylborates having the composition of K[BHn(CN)(3-n)COOMe] (n = 1, 2) and K[B(OH)(CN)(2-) COOMe] have also been synthesized and their properties examined. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.06.066

文献信息

• Preparation of Novel Fluoro Derivatives of Amine Cyanoboranes and Amine Carboxyborane Esters
  作者：Eli Shalom、Khuloud Takrouri、Israel Goldberg、Jehoshua Katzhendler、Morris Srebnik

  DOI：10.1021/om050371u

  日期：2005.11.1

  results in rapid incorporation of fluorine by bromine/fluorine exchange to provide the difluoro derivatives of amine cyanoboranes and amine carboxyborane esters, 1−10, in yields of 59−70%. Bromination of the amine monofluorocyanoboranes and amine monofluorocarboxyborane ester derivatives successfully afforded the expected amine bromofluoro derivatives, 11 and 12, in yields of 57−62%. This was confirmed

  胺的单和dibromocarboxyborane酯类或超声处理所述胺的单和与氟快速掺入过量AGF结果由溴/氟交换，以提供胺cyanoboranes和胺carboxyborane酯的二氟衍生物，dibromocyanoboranes 1 - 10，在产量59-70％。胺单氟氰基硼烷酮和胺单氟羧基硼烷酯衍生物的溴化成功提供了预期的胺溴氟衍生物11和12，收率为57-62％。所有化合物的NMR位移均证实了这一点。确定了氟化胺羧基硼烷13的p K a值，发现其为5.15，而对于Me为8.383 N：BH 2 COOH，符合预期。化合物1的分子结构通过X射线晶体学测定。
• Synthesis and properties of bis(amine)carboxyhydroboron(1+) cations
  作者：József Emri、Zoltán Kovács、Béla Györi、István Lázár

  DOI：10.1016/0020-1693(94)03980-1

  日期：1994.8

  Abstract Carboxy- O -methyl, carboxylic and carboxylate groups containing bis(amine)hydroboron(1+) cations, including the boron analogue of tetramethyl-proline, have been synthesized and characterized. The latter is the first representative of those boron compounds which are truly isosteric to the α-amino acids.

  摘要合成并表征了含双（胺）氢硼（1+）阳离子的羧基-O-甲基，羧基和羧酸根，包括四甲基脯氨酸的硼类似物。后者是真正与α-氨基酸等排的那些硼化合物的第一个代表。
• Gyoeri, Bela; Berente, Zoltan; Kiraly, Robert, Journal of the Chemical Society. Perkin Transactions 1 (2001), 2002, # 3, p. 300 - 301
  作者：Gyoeri, Bela、Berente, Zoltan、Kiraly, Robert、Lazar, Istvan

  DOI：——

  日期：——