Na(1+)(1-)CMe(CN)2 | 81709-97-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Na(1+)(1-)CMe(CN)2
• 英文别名: Sodium;2-methylpropanedinitrile
• CAS: 81709-97-9
• 化学式: C₄H₃N₂*Na
• 分子量: 102.071
• InChiKey: BRZFOVCFEDRRLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.37
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Na(1+)(1-)CMe(CN)2 、 N-methyl-2-phenyl-1,3-oxazolinium triflate 以 四氢呋喃 为溶剂， 反应 1.0h， 以75%的产率得到N-methyl, N-(3,3-dicyanobutyl)benzamide
  参考文献：
  名称：

  1,3-恶唑啉鎓盐与稳定碳原子的反应路径

  摘要：

  稳定的碳负离子与三氟甲磺酸3-甲基-2-苯基-1,3-恶唑啉鎓的反应在C 5和C 2处均发生，其区域选择性部分取决于空间效应。在C 2位点的反应可以导致形成1，4-氧杂ze庚因衍生物。

  DOI：

  10.1016/s0040-4039(00)97535-x
• 作为试剂：
  描述：

  9,10-Dibromo-9,10-ethano-9,10-dihydroanthracene 在 copper(II) nitrate 、 Na(1+)(1-)CMe(CN)2 作用下， 以 六甲基磷酰三胺 、 乙酸酐 为溶剂， 反应 93.0h， 生成 9-bromo-2-nitro-9,10-dihydro-9,10-ethanoanthracene
  参考文献：
  名称：

  Reduction of Bridgehead Halogens by an Intramolecular Electron Transfer Radical Mechanism

  摘要：

  Reactions of 9,10-dibromo- and 9,10-diiodo-2-nitro-9,10-ethano-9,10-dihydroanthracene (10 and 11, respectively) with the tertiary carbanions, 1, 3, 5, and 7-9, proceed exclusively by reduction at the bridgehead with no substitution products being observed. It is proposed that the reduction process occurs by a radical chain mechanism including an intramolecular electron transfer step and beta-hydrogen abstraction from alkyl substituents on the participating carbanions. These ethanoanthracenes contain halogens at bridgehead positions that are meta- and para-benzylic relative to an aromatic nitro group, thus allowing the determination of the relative reactivities of the two benzylic sites within the same molecule. Quantitative studies on the reaction of 11 with sodium salts of 2-ethylmalononitrile and diethyl 2-ethylmalonate reveal that the reduction process is regioselective, with reduction occurring more readily at the benzylic bridgehead position para to the nitro group than at the corresponding meta-benzylic position. The ratio of meta:para reduction products, determined for the reaction of the diiodide 11 with several carbanions, was in the range 1:(1.6 +/- 0.2). This ratio contrasts with the differences in rate constants (approximately 2 orders of magnitude) determined for other nitrobenzylic systems, known to undergo S(RN)1 substitution reactions with the same nucleophiles. These differences in the ratio of rate constants of regioselective reduction compared with those observed for substitution reactions is discussed in terms of the C-X bond at a bridgehead position lying orthogonal to the plane of the nitroaryl group. As a result of this geometry, the rate of intramolecular electron transfer is significantly reduced and the ratio of para-benzylic to meta-benzylic reactivity differs only by a factor of less than 2.

  DOI：

  10.1021/jo00122a030

文献信息

• Reaction paths of 1,3-oxazolinium saltz with stabilized carbanions
  作者：Martine Dreme、Pierre Le perchec、Jacques Garapon、Bernard Sillion

  DOI：10.1016/s0040-4039(00)97535-x

  日期：1982.1

  Reaction of stabilized carbanions with 3-methyl-2-phenyl-1,3-oxazolinium triflate occurs at both C5 and C2 sites with a regioselectivity depending partially on steric effects. The reaction at C2 site can result in the formation of 1,4-oxazepin derivatives.

  稳定的碳负离子与三氟甲磺酸3-甲基-2-苯基-1,3-恶唑啉鎓的反应在C 5和C 2处均发生，其区域选择性部分取决于空间效应。在C 2位点的反应可以导致形成1，4-氧杂ze庚因衍生物。
• Steric and electronic limitations of the SRN1 reaction between p-nitrobenzylic substrates and tertiary carbanions
  作者：Bruce D Jacobs、Soon-Jae Kwon、Leslie D Field、Robert K Norris、David Randles、Karen Wilson、Timothy A Wright

  DOI：10.1016/s0040-4039(00)98673-8

  日期：1985.1
• A new alkylamidation reaction
  作者：M Dreme、S Brunel、P Le Perchec、J Garapon、B Sillion

  DOI：10.1016/s0040-4020(01)91331-6

  日期：1984.1