2-tert-butylamino-3-chloroquinoxaline | 478628-67-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 2-tert-butylamino-3-chloroquinoxaline
• 英文别名: N-tert-butyl-3-chloroquinoxalin-2-amine
• CAS: 478628-67-0
• 化学式: C₁₂H₁₄ClN₃
• 分子量: 235.716
• InChiKey: RQDAYOYZKBKGOH-UHFFFAOYSA-N

物化性质

• 沸点：
  341.1±37.0 °C(Predicted)
• 密度：
  1.234±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  37.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  二苯基膦 、 2-tert-butylamino-3-chloroquinoxaline 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以74%的产率得到3-(tert-butylamino)quinoxalin-2-yldiphenylphosphine oxide
  参考文献：
  名称：

  Comparison of the reactivity of 2-amino-3-chloro- and 2,3-dichloroquinoxalines towards Ph2PH and Ph2PLi and of the properties of diphenylphosphanyl-quinoxaline P,N and P,P ligands

  摘要：

  The synthesis of quinoxaline P,N ligands by monoamination of 2,3-dichloroquinoxaline (1) to 2-amino-3-chloroquinoxalines 2a,b and the subsequent substitution of chlorine by a diphenylphosphanyl group was studied. Whereas the reaction of 2a,b with Ph2PH in the presence (or absence) of catalytic amounts of palladium acetate furnished only minor amounts of the expected ligands in favor of tetraphenyldiphosphane and dechlorinated quinoxalines, the coupling with Ph2PLi in ether provided the novel NH-functional P,N hybrid ligands 3a,b with a quinoxaline scaffold in moderate to good yields. 3a is slightly and 3b somewhat more sensitive to air oxidation, leading to the P-oxides 4a,b. The more reactive 1 forms with Ph2PH only a small amount of 2-chloro-3-diphenylphosphanylquinoxaline 5 and traces of the quinoxaline-bis(phosphane) 6. The main products are 2,2'-bis(quinoxaline) and Ph2PCl, which converts residual Ph2PH into tetraphenyldiphosphane. The coupling with Ph2PLi in diethyl ether, however, gave in a fast reaction high yields of 6, exceeding those of 3a,b, with interfering NH functions. Semi-empirical quantum chemical calculations (PM6) illuminate the background of the air sensitivity of 3a,b, whereas the recently reported 6 is air stable. Preliminary studies for use of the ligands in catalysis with the air-stable 6, showed moderate to good yields in the Pd-catalyzed C-N cross coupling of 2-bromopyridine with mesityl amine. Complex formation was confirmed by isolation of the Pd complex 7. The structure elucidation of the new compounds is based on conclusive NMR data and crystal structure analyses for 2b, 3a, 4a and 4b. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.08.089
• 作为产物：
  描述：

  2,3-二氯喹喔啉 、 叔丁胺 反应 2.0h， 以92%的产率得到2-tert-butylamino-3-chloroquinoxaline
  参考文献：
  名称：

  二氨基卡宾的同系物：显示亲电子锗中心的第一个二氨基锗烯LiCl加合物的合成和晶体结构

  摘要：

  2-氯-3-叔丁基氨基喹喔啉 1，准备2,3-二氯喹喔啉 和 叔丁胺在升高的温度和压力下，用BuLi两个当量和GeCl的semimolar量进行反应2（二恶烷），以形成一个新的环状二氨基锗烯-的LiCl加合物2通过在溶剂化的晶体二恶烷 和两个分子 甲苯。氯离子的在双重喹喔啉的锗的接合稠合八元N-戈-N杂环，通过X射线晶体结构分析示出2，表示电特性，并因此极性转换由电子的通常的亲核diaminogermylene结构单元的撤消举证和不明确的性质卡宾。每个喹喔啉环系统通过其之一进行配位氮原子 到锂 阳离子，固定在 聚合物Li + –二恶烷主链，增强了电子吸收作用。

  DOI：

  10.1039/b205902a

文献信息

• Quinoxaline-anellated N,N´-dialkylimidazolium salts and iPr2quinox-NHC-Pd halide complexes
  作者：Saravanakumar Shanmuganathan、Carola Schulzke、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1016/j.jorganchem.2020.121487

  日期：2020.11

  imidazolium salts as precursors for quinoxaline-anellated imidazolin-2-ylidene transition metal complexes. The bulky tert-butylamine replaces only one chlorine atom and opens, via a second amination step, a route to unsymmetrically N,N´-substituted diaminoquinoxalines as potential precursors to quinox-NHCs with different N,N´-substituents. A convenient high-yield access to the new trans-(iPr2quinoxImy)2PdX2

  过量的异丙基或新戊胺与二氯喹喔啉反应成相应的二氨基喹喔啉，并进一步与原甲酸三乙酯反应成喹喔啉修饰的咪唑啉盐，作为喹喔啉修饰的咪唑啉-2-亚烷基过渡金属配合物的前体。庞大的叔丁胺仅取代一个氯原子，并通过第二步胺化步骤，开辟了一条路线，使不对称的N，N'-取代的二氨基喹喔啉成为具有不同N，N'-取代基的喹喔啉-NHC的潜在前体。方便获得新反式-（i Pr 2 quinoxImy）2 PdX 2的高产率（X = Cl，I）配合物，通过PdCl 2 / NaOAc或Pd（OAc）2 / 2KI与i Pr的反应提供了对第一种喹喔啉-NHC-Rh（COD）Cl和Ag配合物的早期通讯的补充。2 quinoxImyH + PF 6 -经由与醋酸CH酸性前体盐的去质子化。化合物通过NMR数据（通过2D和质子耦合的13 C NMR光谱分配）和/或晶体结构分析进行表征。CMe 2 -H···Pd和Pd-Cl····C
• Phosphonylation of 2-Amino- and 2-Amido-3-bromopyridines and 2-Amino-3-chloroquinoxalines with Triethyl Phosphite
  作者：M. Shaker S. Adam、Markus K. Kindermann、Martin Köckerling、Joachim W. Heinicke

  DOI：10.1002/ejoc.200900698

  日期：2009.9

  the N atoms towards the reaction site. The advantage of the Tavs reaction is the easy optimization because neither auxiliary ligands are required nor a base to trap the halide or a solvent. Triethyl phosphite itself acts as ligand and forms Pd0P(OEt)3}n in the initial phase of the reaction. The structures of the products and the expected intramolecular N–H···O=P hydrogen bridging bonds were proven

  2-氨基-和2-酰氨基-3-溴吡啶1和2与亚磷酸三乙酯在乙酸钯或氯化物存在下的Tavs反应允许合成2-氨基-和2-酰氨基-3-膦酸酯3和4。第二个环氮原子引起强烈的活化，并导致 2-氨基-3-氯喹喔啉的膦酰化产生极好的收率。2,3-二氯喹喔啉不需要催化剂，在 Michaelis-Becker 条件下与二乙基亚磷酸钠发生双膦酰化反应。结果显示了吡啶氮 (-M) 的活化影响和氨基 (+M) 的失活影响。将Tavs偶联中1和2的反应性与3-NH-2-溴吡啶位置异构体和2-溴苯胺的反应性进行了比较，并从吡啶和氨基（酰氨基）氮的相反作用和不同位置的方面进行了讨论。 N 原子朝向反应位点。Tavs 反应的优点是易于优化，因为既不需要辅助配体，也不需要碱来捕获卤化物或溶剂。亚磷酸三乙酯本身作为配体并在反应的初始阶段形成 Pd0P(OEt)3}n。通过溶液核磁共振和单晶 3c 的 X 射线晶体结构分析证明了产物的结构和预期的分子内
• Novel highly electron-deficient quinoxaline-annulated 1,3,2-diazagermol- and diazastannol-2-ylidenes, stabilized as LiCl adducts
  作者：Farman Ullah、Olaf Kühl、Wajid Rehman、Peter G. Jones、Joachim Heinicke

  DOI：10.1016/j.poly.2009.12.014

  日期：2010.2

  Reaction of 2,3-bis(neopentylamino)quinoxaline ( 1 ) with n BuLi and GeCl 4 or GeCl 2 ·(dioxane) (molar ratio 1:2:1) in THF furnished highly moisture-sensitive Ge(IV) and Ge(II) heterocycles 2a and 3a , respectively. The quinoxaline-annulated N -heterocyclic germylene (quinNHGe) 3a is stable only in the presence of Li(THF) x and exhibits electrophilic properties associated with the strongly electron-withdrawing

  2,3-双（新戊基氨基）喹喔啉（1）与n BuLi和GeCl 4或GeCl 2·（二恶烷）（摩尔比为1：2：1）在THF中的反应提供了高度湿敏的Ge（IV）和Ge（IV II）分别为杂环2a和3a。喹喔啉环化的N-杂环亚二甲基（quinNHGe）3a仅在Li（THF）x存在下才稳定，并且表现出与强吸电子环化相关的亲电性能。如在双（喹喔啉）环化的八元NHGe LiCl加合物的晶体中发现的，假定Ge（II）处的氯化物与N处的Li +发生配位。如对于卡宾供体原子的NMR信号的强下场配位位移所表明的，二烯戊基-苯并咪唑-2-亚烷基（bnNHC）的添加提供了不稳定的bnNHC-quinNHGe加合物4。试图生长单晶导致卡宾分解和质子化，从而与Li 2（THF）2 Cl 4 2-阴离子形成双（苯并咪唑鎓）盐5。将2-甲氧基乙基或2-二甲基氨基乙基侧链作为螯合官能团引入二氨基喹喔啉6和7中，然后与2 n
• Diaminocarbene homologues: synthesis and crystal structure of the first diaminogermylene LiCl adduct displaying an electrophilic germanium centre
  作者：Olaf Kühl、Peter Lönnecke、Joachim Heinicke

  DOI：10.1039/b205902a

  日期：——

  2-Chloro-3-tert-butylaminoquinoxaline 1, prepared from 2,3-dichloroquinoxaline and tert-butylamine under elevated temperatures and pressure, reacts with two equivalents of BuLi and a semimolar amount of GeCl2(dioxane) to form a novel cyclic diamino germylene–LiCl adduct 2 solvated in the crystals by dioxane and two molecules of toluene. The bonding of the chloride ion at germanium of the twofold quinoxaline

  2-氯-3-叔丁基氨基喹喔啉 1，准备2,3-二氯喹喔啉 和 叔丁胺在升高的温度和压力下，用BuLi两个当量和GeCl的semimolar量进行反应2（二恶烷），以形成一个新的环状二氨基锗烯-的LiCl加合物2通过在溶剂化的晶体二恶烷 和两个分子 甲苯。氯离子的在双重喹喔啉的锗的接合稠合八元N-戈-N杂环，通过X射线晶体结构分析示出2，表示电特性，并因此极性转换由电子的通常的亲核diaminogermylene结构单元的撤消举证和不明确的性质卡宾。每个喹喔啉环系统通过其之一进行配位氮原子 到锂 阳离子，固定在 聚合物Li + –二恶烷主链，增强了电子吸收作用。
• Comparison of the reactivity of 2-amino-3-chloro- and 2,3-dichloroquinoxalines towards Ph2PH and Ph2PLi and of the properties of diphenylphosphanyl-quinoxaline P,N and P,P ligands
  作者：Mohamed Shaker S. Adam、Ahmad Desoky Mohamad、Peter G. Jones、Markus K. Kindermann、Joachim W. Heinicke

  DOI：10.1016/j.poly.2012.08.089

  日期：2013.2

  The synthesis of quinoxaline P,N ligands by monoamination of 2,3-dichloroquinoxaline (1) to 2-amino-3-chloroquinoxalines 2a,b and the subsequent substitution of chlorine by a diphenylphosphanyl group was studied. Whereas the reaction of 2a,b with Ph2PH in the presence (or absence) of catalytic amounts of palladium acetate furnished only minor amounts of the expected ligands in favor of tetraphenyldiphosphane and dechlorinated quinoxalines, the coupling with Ph2PLi in ether provided the novel NH-functional P,N hybrid ligands 3a,b with a quinoxaline scaffold in moderate to good yields. 3a is slightly and 3b somewhat more sensitive to air oxidation, leading to the P-oxides 4a,b. The more reactive 1 forms with Ph2PH only a small amount of 2-chloro-3-diphenylphosphanylquinoxaline 5 and traces of the quinoxaline-bis(phosphane) 6. The main products are 2,2'-bis(quinoxaline) and Ph2PCl, which converts residual Ph2PH into tetraphenyldiphosphane. The coupling with Ph2PLi in diethyl ether, however, gave in a fast reaction high yields of 6, exceeding those of 3a,b, with interfering NH functions. Semi-empirical quantum chemical calculations (PM6) illuminate the background of the air sensitivity of 3a,b, whereas the recently reported 6 is air stable. Preliminary studies for use of the ligands in catalysis with the air-stable 6, showed moderate to good yields in the Pd-catalyzed C-N cross coupling of 2-bromopyridine with mesityl amine. Complex formation was confirmed by isolation of the Pd complex 7. The structure elucidation of the new compounds is based on conclusive NMR data and crystal structure analyses for 2b, 3a, 4a and 4b. (C) 2012 Elsevier Ltd. All rights reserved.