lithium;acetonitrile;cyanide | 799829-66-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: lithium;acetonitrile;cyanide
• CAS: 799829-66-6
• 化学式: CN*C₂H₃N*Li
• 分子量: 74.0112
• InChiKey: FJYHZUWGYXWIQG-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  lithium;acetonitrile;cyanide 、 cyanoborane 在 C₄H₈O₂ 作用下， 以 further solvent(s) 为溶剂， 以77%的产率得到lithium dicyanodihydroborate*dioxane
  参考文献：
  名称：

  硼烷和四氢硼酸根阴离子的新型氰基和异氰基衍生物的制备和性质

  摘要：

  NaBH 3 CN与HCl在THF中的反应主要得到NaBH 3 CNBH 2 CN，而在Me 2 S中观察到BH 2 CN的定量形成。在二甲基硫醚中，BH 2 CN以单体或二聚体形式作为Me 2 S络合物与低聚物平衡存在。这些化合物被胺以几乎定量的产率转化为BH 2 CN络合物，并用氰化锂处理得到LiBH 2（CN）2。相应的溴硼烷的Me 2 S配合物与AgCN的反应生成异氰硼酸酯AgBH n（NC）4- n（n＝ 1，2），其可以容易地转化为钠盐，通过热异构化将其转化为氰基硼酸盐。二-和tricyanohydroborates是对酸非常稳定，并且BH 3 CNBH 2 CN -离子显著比BH更稳定的3 CN -离子。在N碱存在下进行溴氧化时，LiBH 2（CN）2得到N-碱·BH（CN）2络合物和LiBH 2（CN）CNBH（CN）2。NaBH（NC）3转化为C 5 N 5 N·BH（NC）2

  DOI：

  10.1016/0022-328x(83)80169-7
• 作为产物：
  描述：

  乙腈 、 Lithium cyanide tetrahydrofuran 以 乙腈 为溶剂， 生成 lithium;acetonitrile;cyanide
  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