2,6-bis(dimethylaminomethyl)phenyllithium | 313963-74-5

• 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: 2,6-bis(dimethylaminomethyl)phenyllithium
• 英文别名: 2,6-bis<(dimethylamino)methyl>phenyllithium
• CAS: 313963-74-5
• 化学式: C₁₂H₁₉LiN₂
• 分子量: 198.237
• InChiKey: GAXURNHUDNEMIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.23
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-bis(dimethylaminomethyl)phenyllithium 以 乙醚 、 甲苯 为溶剂， 反应 120.0h， 生成 t-4-dimethylamino-8-(dimethylaminomethyl)-1,c-3-diphenyl-r-1-[bis(trimethylsilyl)methyl]-2-oxa-1-sila-1,2,3,4-tetrahydronaphthalene
  参考文献：
  名称：

  Intramolecularly donor-stabilized silenes: Part 6. The synthesis of 1-[2,6-bis(dimethylaminomethyl)phenyl]silenes and their reaction with aromatic aldehydes

  摘要：

  The intramolecularly donor-stabilized silenes (ArRSi)-Si-1=C(SiMe3)(2) (3a-d) (3a: R-1 = Me; 3b: R-1 = t-Bu; 3c: R-1 = Ph; 3d: R-1 = SiMe3; Ar = 2,6-(Me2NCH2)(2)C6H3) were prepared by treatment of the (dichloromethyl)oligosilanes (Me3Si)(2)R-1 Si-CHCl2 (la-l), with 2,6-bis(dimethylaminomethyl)phenyllithium (molar ratio 1:2). For 3c and 3d, X-ray structural analyses were performed indicating that only one dimethylamino group of the tridentate ligand is coordinated to the electrophilic silene silicon atoms, i.e., the central silicon atoms are tetracoordinated. The N -> Si donation leads to pyramidalization at the silene silicon atoms; the configuration at the silene carbon atoms is planar. For a chemical characterization 3a and 3c were treated with water to give the silanols (ArRSi)-Si-1(OH)-CH(SiMe3)(2) (5a,c). Studies of the reactions of 3a and 3c with benzaldehyde, 4-chlorobenzaldehyde or 4-methoxybenzaldehyde, respectively, revealed an unexpected reaction path leading to the substituted 2-oxa-1-sila-1,2,3,4-tetrahydronaphthalenes 12a, 12c, 13 and 14. Both 12a and 12c were structurally characterized by X-ray analyses. The formation of these six-membered cyclic compounds, which is discussed in detail, gives support to a dipolar mechanism for the general reaction of silenes with carbonyl derivatives. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.02.049
• 作为产物：
  描述：

  1,3-双(二甲氨基甲基)苯 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 24.0h， 生成 2,6-bis(dimethylaminomethyl)phenyllithium
  参考文献：
  名称：

  含有2,6-（Me 2 NCH 2）2 C 6 H 3配体钳的卤化 有机硒（ii）–实验和理论研究† •

  摘要：

  新有机硒（II类型）的卤化物[的RSe] + X - [R = 2,6-（ME 2 NCH 2）2 C ^ 6 ħ 3 ; X = Cl（2），Br（3），I（4）]的制备方法是：用SO 2 Cl 2裂解R 2 Se 2（1）中的Se-Se键，然后用氯化氢处理有机硒，然后进行卤素交换。 NaBr或KI。之间的反应2和R' 2的MC1 Ñ导致新离子[的RSe] + [R'2 MCl n +1 ] - [R'= 2-（Me 2 NCH 2）C 6 H 4， n = 1，M = Sb（ 5），Bi（ 6）；R'= Ph，M = Sb， n = 1（ 7）或n = 3（ 8）]种。所有新化合物均通过多核NMR光谱法（ 1 H， 13 C， 77 Se，2D实验）和质谱法在溶液中进行研究。电导率研究证实了2和锑酸根离子的离子性质。[{2,6-（Me2 NCH 2） 2 C ^ 6 ħ 3 }硒] +氯-

  DOI：

  10.1039/c3dt52886c

文献信息

• Quest for triorganotin(IV) compounds containing three C,N- and N,C,N-chelating ligands
  作者：Aleš Růžička、Zdeňka Padělková、Petr Švec、Vladimír Pejchal、Lenka Česlová、Jaroslav Holeček

  DOI：10.1016/j.jorganchem.2013.02.018

  日期：2013.5

  tetraorganotin(IV) compounds of general formula L3SnR [where i) L is LCN 2-(N,N-dimethylaminomethyl)phenyl- and R = n-Bu (1), Ph (2); and ii) L is LNCN 2,6-bis-(N,N-dimethylaminomethyl)phenyl- with R = n-Bu (3)] were synthesized. These species were used as potential precursors for the target preparation of some triorganotin(IV) species of general formula L3SnX [where i) L is LNCN with X = OH (4), and

  三种通式为L 3 SnR [ i ] L的新颖的四有机锡化合物（IV）为L CN 2-（N，N-二甲基氨基甲基）苯基-，R =  n -Bu（1），Ph（2）；和II）L-为L NCN 2,6-二- （Ñ，Ñ二甲基氨基甲基）苯基- ，其中R =  Ñ -Bu（3）]的合成。这些物质被用作一些三有机锡（IV）的制备目标潜在的前体一般式L的物种3 SNX [其中我）L-为L NCN其中X = OH（4），并且ii）L是L CN，X = Br（5），F（5b），Cl（5c）]。几种方法可用于达到目标L 3 SnX分子，包括1或2与溴，碘或氢卤酸在各种介质中的反应，科切什科夫反应或与HgCl 2的金属转移，但所有反应混合物的组成均不能令人满意。目标。化合物4具有带有经由H桥与一个氮原子相互作用的OH基的单体结构。目标化合物5 由三个当量的反应制得 L.第四名C。ñSn与SnBr 4的结合，然后根据
• An intramolecularly base-stabilized monomeric organoaluminum dihydride
  作者：Leopoldo Contreras、Alan H. Cowley、François P. Gabbaï、Richard A. Jones、Carl J. Carrano、Marcus R. Bond

  DOI：10.1016/0022-328x(94)05132-u

  日期：1995.3

  The intramolecularly base-stabilized arylaluminum dihydride [2,6-(Me2NCH2)2C6H3]AlH2 (1) has been prepared by the metathesis reaction of the corresponding lithium aryl with AlH2Cl·NMe3. Alternative methods for the synthesis of 1 are transmetalation or reduction reactions of [2,6-(Me2NCH2)2C6H3]MCl2 (M = Al (2), Ga (3), In (4)) with LiAlH4. The x-ray crystal structures of 1 and 2 have been determined:

  通过相应的芳基锂与AlH 2 Cl·NMe 3的复分解反应，制备了分子内碱稳定的芳基二氢化铝[2,6-（Me 2 NCH 2）2 C 6 H 3 ] AlH 2（1）。合成1的替代方法是[2,6-（Me 2 NCH 2）2 C 6 H 3 ] MCl 2（M = Al（2），Ga（3），In（4））的金属转移或还原反应与LiAlH 4。已经确定了1和2的X射线晶体结构：1，正交，Pbca，具有；2，单斜，，用。化合物1和2为固态单体。
• Organohydridosilanes containing Y,C,Y-chelating ligands: Reactivity and vapour pressure studies
  作者：Miroslav Novák、Libor Dostál、Zdenka Padělková、Klaus Jurkschat、Christina Dietz、Květoslav Růžička、Michal Fulem、Antonín Lyčka、Roman Jambor

  DOI：10.1016/j.jorganchem.2014.08.020

  日期：2014.12

  formula PhL1-3SiH2 (1, L1 = C6H3(CH2OtBu)2-2,6; 2, L2 = C6H3(CH2OtBu)-2-(CH2NMe2)-6; 3, L3 = C6H3(CH2NMe2)2-2,6) are reported. The reactivity of compounds 1–3 towards elemental sulphur and selenium was studied. It depends on the identity of the donor atoms. While the ether-substituted organohydridosilane PhL1SiH2 (1) does not react, the amino-substituted organohydridosilanes PhL2SiH2 (2) and PhL3SiH2

  含有通式PhL 1-3 SiH 2（1，L 1  = C 6 H 3（CH 2 O t Bu）2 -2.6; 2，L 2  = C的Y，C，Y螯合配体的有机氢化硅烷的合成6 ħ 3（CH 2 ö吨丁基）-2-（CH 2 NME 2）-6; 3，L 3  = C 6 H ^ 3（CH 2 NME 2）2-2.6）。化合物的反应性1 - 3向元素硫和硒进行了研究。这取决于给体原子的身份。尽管醚取代的有机氢化硅烷PhL 1 SiH 2（1）不反应，但氨基取代的有机氢化硅烷PhL 2 SiH 2（2）和PhL 3 SiH 2（3）提供了N→Si配位的硅氢化物PhL 2 SiS（4）），PhL 3 SiS（6）和甲硅烯酮PhL 2 SiSe（5），PhL 3 SiSe（7）分别包含末端Si-E键（E  = S，Se）。化合物1和2在环境温度下不与水反应，而3的水解则产生二有机硅烷二醇PhL 3 Si（OH）2（8）。该化合物的特征在于1
• Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation
  作者：Alexey V. Chuchuryukin、Rubin Huang、Ernst E. van Faassen、Gerard P. M. van Klink、Martin Lutz、John C. Chadwick、Anthony L. Spek、Gerard van Koten

  DOI：10.1039/c1dt10482a

  日期：——

  Transmetallation of 4,4′-bis(2,6-bis[(dimethylamino)methyl]phenylgold)diphenyl-phosphino}biphenyl (3) with MCl4 (M = Ti, NbCl, V) in benzene gave the corresponding transition metal pincer complexes (4) and insoluble 4,4′-bis[P-(chloro gold(I))diphenylphosphino]biphenyl (2), which can be quantitatively recovered and recycled. Interestingly, 3 did not react with TiCl3. However, reaction of 2,6-bis[

  4,4'-双（2,6-双[（二甲基氨基）甲基]苯基金）二苯基膦基}联苯（3）与MCl 4（M = Ti，NbCl，V）的金属转移苯得到相应的过渡金属钳配合物（4）和不溶的4,4'-双[ P-（氯金（I））二苯基膦基]联苯（2），可以定量回收和再循环。有趣的是，3没有与TiCl 3反应。但是，反应2,6-双[（二甲氨基）甲基]苯基锂（1）用TiCl 4 3导致形成新diaryltitanium（的IV）化合物5（16％产率），其包括一个Ñ，Ç，N-二聚体结合NCN-钳配体和被第二NCN-钳配体重排从1,2,6-异构体变成1,2,4一个。后者的NCN配体为双阴离子，并且是双齿键；的CH中的一个2 NME 2取代基（对位到C'本位）是非配位，而第二个CH 2 NME 2基团，CH活化我基团之一的后，是η 2 - Ç，Ñ π-键结合到钛中心反至C本位所述的聚体-NCN配体。固定在MgCl 2基上后，得到了新的NCN-钳金属配合物2
• A new, easily recyclable arylating agent based on a diphosphino-digold(i) complex
  作者：Marianne Stol、Dennis J. M. Snelders、Huub Kooijman、Anthony L. Spek、Gerard P. M. van Klink、Gerard van Koten

  DOI：10.1039/b701271c

  日期：——

  The synthesis of two organogold(I) complexes, [(Au(NCN))2(dppbp)] (6) and [(Au(Phebox))2(dppbp)] (9), and their application in subsequent transmetalating reactions are described. A trinuclear organogold(I) complex, [(AuCl)3(tdpppb)] (4) is also reported, which exhibits a surprisingly high solubility in dichloromethane. It was found that 6 and 9 can cleanly transfer the anionic NCN-([C6H3(CH2NMe2)2-2,6]−) or Phebox-([2,6-bis(oxazolinyl)phenyl]−) moiety to TiIV and PdII centers, respectively. The coproduct [(AuCl)2(dppbp)] (3, dppbp is [4-Ph2PC6H4]2 (1)) formed during this transmetalation reaction, precipitates almost quantitatively from the reaction mixture (toluene) and can thus be separated by simple filtration. In comparison, [AuCl(PPh3)], formed as the coproduct in the transmetalation reaction of [Au(NCN)(PPh3)] with metal salts, has a higher solubility in apolar solvents and thus is more difficult to separate from the resultant organometallic complex. Digold complex 6 has been characterized by NMR spectroscopy and crystallographic analyses. These analyses show that the two gold units are essentially independent. The formation of a dimetallic transmetalating agent based on gold(I) had no effect on its transmetalating properties.

  本文介绍了两种有机金（I）配合物 [(Au(NCN))2(dppbp)] (6) 和 [(Au(Phebox))2(dppbp)] (9) 的合成及其在随后的反金属化反应中的应用。报告还介绍了一种三核有机金（I）配合物[(AuCl)3(tdpppb)] (4)，它在二氯甲烷中的溶解度之高令人惊讶。研究发现，6 和 9 可以分别将阴离子 NCN-（[C6H3(CH2NMe2)2-2,6]-）或 Phebox-（[2,6-双（恶唑啉基）苯基]-）分子干净地转移到 TiIV 和 PdII 中心。在这一跨金属化反应中形成的副产物[(AuCl)2(dppbp)]（3，dppbp 为 [4-Ph2PC6H4]2 (1)）几乎定量地从反应混合物（甲苯）中析出，因此只需简单过滤即可分离。相比之下，在[Au(NCN)(PPh3)]与金属盐的反金属反应中形成的副产物[AuCl(PPh3)]在非极性溶剂中的溶解度较高，因此更难从生成的有机金属复合物中分离出来。Digold 复合物 6 已通过核磁共振光谱和晶体学分析进行了表征。这些分析表明，两个金单元基本上是独立的。以金（I）为基础形成的二金属透金属剂对其透金属特性没有影响。