N-(2-chlorobenzylidene)-N,N'-dimethylethylenediamine | 137708-23-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(2-chlorobenzylidene)-N,N'-dimethylethylenediamine
• 英文别名: 2-C6H4Cl2CHNCH2CH2NMe2；2-[(2-chlorophenyl)methylideneamino]-N,N-dimethylethanamine
• CAS: 137708-23-7
• 化学式: C₁₁H₁₅ClN₂
• 分子量: 210.706
• InChiKey: MKHXVUFTJHWFQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(2-chlorobenzylidene)-N,N'-dimethylethylenediamine 以 丙酮 、 苯 为溶剂， 生成
  参考文献：
  名称：

  钯（II）与C，N，N '齿状席夫碱供体配体的环金属化配合物。芳基氯键与钯（O）的氧化加成

  摘要：

  的治疗ñ - （2-氯亚苄基） - N，N'二甲基乙二胺，2-CLC 6 ħ 4 C（H）NCH 2 CH 2 NME 2，用三（二亚苄基丙酮）（0）的氯仿，得到氧化加成环金属化产物Me 2 }（Cl）]（1），其中钯原子键合到C，N，N '齿状给体配体上。用叔单膦处理1得到环金属化的配合物CH 2 CH 2 NMe 2 }（Cl）（L）]（2：LPPh 3 ; 3：LPEtPh 2; 4：LPET 2 Ph值; 5：LPET 3），其中，所述膦配体是任何反式的苯基碳原子（2，3）或反式的亚胺氮原子（4，5）。用高氯酸银处理1，然后与叔单膦反应，得到环金属化的配合物Me 2 }（L）] [ClO 4 ]（6：LPPh 3； 7：LPEtPh 2； 8：LPEt 2 Ph; 9：LPET 3）。1与乙酰丙酮th反应生成环金属化配合物CH 2 CH 2 NMe 2 }（H 3

  DOI：

  10.1016/s0022-328x(96)06800-3

文献信息

• Oxidative addition of aryl–halogen bonds to platinum(<scp>II</scp>) and the structure of a complex formed by aryl–fluoride oxidative addition
  作者：Craig M. Anderson、Richard J. Puddephatt、George Ferguson、Alan J. Lough

  DOI：10.1039/c39890001297

  日期：——

  The complexes [PtMe2(Me2NCH2CH2NCHAr)] react by oxidative addition of the aryl–halogen bond when Ar = 2-BrC6H4, 2-CIC6H4, or C6F5 but by ortho-metallation when Ar = 2-FC6H4 or C6H5, and in the case where Ar = C6F5, the oxidative addition product adds acetone across the imine bond and the complex formed has been characterized crystallographically as a hydrogen-bonded dimer; the reactivity to oxidative

  当Ar = 2-BrC 6 H 4，2 -CIC 6 H 4或C 6 F 5时，配合物[PtMe 2（Me 2 NCH 2 CH 2 N CHAr）]通过芳基-卤素键的氧化加成反应，但通过Ar = 2-FC 6 H 4或C 6 H 5时，以及Ar = C 6 F 5时，进行邻位金属化，氧化加成产物通过亚胺键加成丙酮，形成的络合物在晶体学上被表征为氢键二聚体。与氧化加成反应的反应性可能与C–X键能相关。
• Preparation of Five-Membered Nickelacycles with Anionic C−N−N‘ Terdentate Ligands. X-ray Crystal Structure of [NiCl{2-(CHNCH₂CH₂NMe₂)-3-ClC₆H₃}]
  作者：Rosa M. Ceder、Jaume Granell、Guillermo Muller、Mercè Font-Bardía、Xavier Solans

  DOI：10.1021/om960309k

  日期：1996.10.15

  imines derived from N,N-dimethylethylenediamine, C6RnH5-nCH NCH2CH2NMe2 to [Ni(COD)2]. The molecular structure of [NiCl2-(CHNCH2CH2NMe2)-3-ClC6H3}] has been determined by a single-crystal X-ray crystallographic study. Some ionic compounds [Ni(C−N−N‘)L]BF4 (L = NCMe, heterocyclic amines) were also obtained. The NiC bond of these complexes is inert toward insertion reactions of ethylene or PhC⋮CPh. The action

  五元金属环[Ni（C-N-N'）X]是通过氧化添加衍生自N，N-二甲基乙二胺，C 6 R n H 5 - n CH NCH 2 CH的邻卤代亚胺制备的2 NMe 2至[Ni（COD）2 ]。通过单晶X射线晶体学研究确定了[NiCl 2-（CH NCH 2 CH 2 NMe 2）-3-ClC 6 H 3 }]的分子结构。一些离子化合物[Ni（C-N'N'）L] BF 4（L ＝ NCMe，杂环胺）也被获得。这些配合物的Ni C键对乙烯或PhC⋮CPh的插入反应呈惰性。[Ni（COD）2 ]对二胺C 6 R n H 5 - n CH 2 N（Me）CH 2 CH 2 NMe 2的作用提供了高度不溶的有机镍衍生物，其通过与芳族胺（L）反应TlBF 4的存在导致离子衍生物[Ni（C- N'N '）L] BF 4。使用CuCl 2稳定有机金属Ni（III）化合物因为没有达到氧化剂。配位化合物[NiClBr（N'-N）]，其中N-N'=
• Preparation of molybdenum(II) η2-vinyl complexes via sequential CCl activation and alkyne insertion
  作者：Jaqueline L. Kiplinger、Thomas G. Richmond

  DOI：10.1016/0277-5387(96)00311-7

  日期：1997.1

  (η6-C6H5CH3)Mo(CO)3 2 resulted in the formation of the seven-coordinate molybdenum(II) metallacycle, 3, by oxidative addition of the strong aromatic CCl bond at molybdenum(0). The metallacycle 3 undergoes migratory insertion with electron-deficient internal acetylenes to afford novel η2-vinyl complexes 4, resulting in net replacement of a CCl bond by a CC bond.

  摘要由2-氯苯甲醛和N，N-二甲基乙二胺与（η6-C6H5CH3）Mo（CO）3 2缩合制备的席夫碱配体1形成了七配位的钼（II）金属环， 3，通过在钼（0）处氧化加成强芳族CCl键来实现。金属环3与电子不足的内部乙炔进行迁移插入，得到新颖的η2-乙烯基络合物4，导致C 3 Cl键被C 3 C键净取代。
• Competition between intramolecular oxidative addition and ortho metalation in organoplatinum(II) compounds: activation of aryl-halogen bonds
  作者：Craig M. Anderson、Margarita Crespo、Michael C. Jennings、Alan J. Lough、George Ferguson、Richard J. Puddephatt

  DOI：10.1021/om00054a031

  日期：1991.8

  The ligands 2-XC6H4CH = NCH2CH2NMe2 (1) react with [Pt2Me4(mu-SMe2)2] (2) to give [PtMe2(2-XC6H4CH = NCH2CH2NMe2)] (3), which then react either by ortho metalation to give CH4 and [PtMe-(2-XC6H3CH = NCH2CH2NMe2)] (4) or undergo oxidative addition of the C-X bond to give [PtXMe2-(C6H4CH = NCH2CH2NMe2)] (5). These complexes, and related compounds with modified aryl substituents, have been characterized by NMR spectroscopy, and the derivative [PtClMe2(ClC6H3CH = NCH2CH2NMe2)] (7b) has been characterized crystallographically. The complex [PtMe(C6H4CH = NCH2CH2NMe2)] reacts with CD3Br or MeI to give [PtBrMe(CD3)(C6H4CH = NCH2CH2NMe2)] or [PtIMe2(C6H4CH = NCH2CH2NMe2)], respectively, initially by trans oxidative addition. The ligands 2-XC6H4CH = NR (R = Ph, Pr) react with [Pt2Me4(mu-SMe2)2] to give similar products of ortho metalation, [PtMe(2-XC6H3CH = NR)(SMe2)], or oxidative addition, [PtXMe2(C6H4CH = NR)(SMe2)]. The kinetics of the reaction of 3 to give 4 or 5 have been studied, and the reactions each follow first-order kinetics. The activation parameters for both types of reaction are similar, and since the ortho metalation is presumed to occur by concerted C-H oxidative addition followed by rapid reductive elimination of methane, it is suggested that the oxidative addition of aryl-bromide or aryl-chloride bonds also occurs by a concerted mechanism. The rates of reaction are C-Br > C-Cl > C-H, and internal competition reactions give the sequence C-Cl > C-H > C-F. Hence, the overall reactivity series is C-Br > C-Cl > C-H > C-F, the series of increasing C-X bond energies. These are the first examples of aryl-halogen bond activation by platinum(II) complexes.
• Preparation of Metallacycles with Anionic Terdentate [C,N,N‘] Ligands by Intramolecular Oxidative Addition of C−X (X = Br, Cl) Bonds to [Pt(dba)₂]. An Unexpected Effect of Chloro Substituents
  作者：Margarita Crespo、Jaume Granell、Xavier Solans、Mercè Font-Bardia

  DOI：10.1021/om020532j

  日期：2002.11.1

  The reactions of [Pt(dba)(2)] with ligands C6RnH5-nCHNCH2CH2NMe2 (1a, R = 2-Br; 1b, R = 2,3,4,5,6-Cl-5; 1c, R = 2,3,6-Cl-3, and 1d, R = 2,6-Cl-2) produce the corresponding [CNN'] cyclometalated platinum(H) compounds [PtXC6RnH4-nCHNCH2CH2NMe2}] (2a-d) via intramolecular oxidative addition of C-Br or C-Cl bonds. All the new compounds were characterized by elemental analyses and mass and NMR spectroscopy, and [PtBr(Me2NCH2CH2NCHC6H4)] (2a) and [PtCl(M(e)2NCH(2)CH(2)NC(H)(3,5-C6H2Cl2)] (2f) were also characterized crystallographically.