N,N-diethyl-2'-methylbiphenyl-4-carboxamide

• 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,N-diethyl-2'-methylbiphenyl-4-carboxamide
• 英文别名: N,N-diethyl-4-(2-methylphenyl)benzamide
• 化学式: C₁₈H₂₁NO
• 分子量: 267.371
• InChiKey: QGDCXPIMEXBWTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  邻甲苯基溴化镁 在 C₃₈H₃₄Br₂N₄Ni₂P₂ 、 lithium chloride 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 为溶剂， 反应 12.0h， 生成 N,N-diethyl-2'-methylbiphenyl-4-carboxamide
  参考文献：
  名称：

  Mono- and Dinuclear Pincer Nickel Catalyzed Activation and Transformation of C–Cl, C–N, and C–O Bonds

  摘要：

  Condensation of 2-NH2C6H4P(Et)Ph (2) with pyrrole-2-carboxaldehyde generated 2-(C4H4N-2'-CH-N)C6H4P(Et)Ph (3). Treatment of 3 with NaH and followed by (DME)NiX2 (X = Cl, Br) afforded mononuclear pincer nickel complexes [Ni{2-(C4H3N-2'-CH-N)C6H4P(Et)Ph}X] (4a, X = Cl; 4b, X = Br). Reaction of [2-NH2C6H4P(Ph)](2)(CH2)(n) (5a, n = 3; 5b, n = 4) with pyrrole-2-carboxaldehyde or 5-tert-butyl-1H-pyrrole-2-carbaldehyde formed [2-(C4H4N-2'-CH-N)C6H4P(Ph)](2)(CH2)(n) (6a, n = 3; 6b, n = 4) and [2-(5'-tBuC(4)H(3)N-2'-CH-N)C6H4P(Ph)](2)(CH2)(4) (6c). Respective treatment of 6ac with NaH followed by (DME)NiX2 (X = Cl, Br) gave the dinuclear nickel complexes [Ni{2-(5'-RC4H2N-2'-CH-N)C6H4P(Ph)}X](2)(CH2)(n) (7a, R = H, X = Cl, n = 3; 7b, R = H, X = Cl, n = 4; 7c, R = H, X = Br, n = 4; 7d, R = tBu, X = Cl, n = 4). Catalysis of the complexes for the activation and transformation of CCl, CN, and CO bonds was evaluated. Complex 7c exhibited excellent catalytic activity in the cross-coupling of aryl chlorides or aryltrimethylammonium iodides with arylzinc reagents as well as of aryl sulfamates with aryl Grignard reagents. The dinuclear nickel complexes 7bd showed higher catalytic activity than the mononuclear complexes in each type of reaction.

  DOI：

  10.1021/om500452c

文献信息

• Efficient Cross-Coupling of Aryl Chlorides with Arylzinc Reagents Catalyzed by Amido Pincer Complexes of Nickel
  作者：Li Wang、Zhong-Xia Wang

  DOI：10.1021/ol701927g

  日期：2007.10.1

  The nickel-catalyzed Negishi cross-coupling reaction of aryl chlorides with arylzinc compounds was investigated. The nickel complexes with the amido pincer type of ligands exhibited high catalytic activity and good functional group tolerance.

  研究了芳基氯化物与芳基锌化合物的镍催化Negishi交叉偶联反应。具有酰胺钳型配体的镍配合物表现出高催化活性和良好的官能团耐受性。
• P,N,N-Pincer nickel-catalyzed cross-coupling of aryl fluorides and chlorides
  作者：Dan Wu、Zhong-Xia Wang

  DOI：10.1039/c4ob01041h

  日期：——

  were synthesized and their catalysis toward the Kumada or Negishi cross-coupling reaction of aryl fluorides and chlorides was evaluated. Complex 3a effectively catalyzes the cross-coupling of (hetero)aryl fluorides with aryl Grignard reagents at room temperature. Complex 3a also catalyzes the cross-coupling of (hetero)aryl chlorides and arylzinc reagents at 80 °C with low catalyst loadings and good

  P，N，N-镍镍配合物[Ni（Cl）N（2-R 2 PC 6 H 4）（2'-Me 2 NC 6 H 4）}]（R = Ph，3a ; R = Pr i，合成了3b； R ＝ Cy，3c），并评估了它们对芳基氟化物和氯化物的Kumada或Negishi交叉偶联反应的催化作用。在室温下，配合物3a有效催化（杂）芳基氟化物与芳基格氏试剂的交叉偶联。复杂3a 它还在低催化剂负载和良好的官能团相容性下，于80°C催化（杂）芳基氯和芳基锌试剂的交叉偶联。
• Room-temperature nickel-catalysed cross-couplings of aryl chlorides with arylzincs
  作者：Ning Liu、Li Wang、Zhong-Xia Wang

  DOI：10.1039/c0cc03064c

  日期：——

  P,N,O-chelate nickel complexes efficiently catalyse the cross-coupling reaction of aryl chlorides with arylzinc reagents in a 1:1 THF-NMP mixture. The reactions proceed at room temperature with low catalyst loading.

  P，N，O-螯合物镍络合物可有效催化芳基氯化物与芳基锌试剂在1：1 THF-NMP混合物中的交叉偶联反应。反应在室温下以低催化剂负载进行。
• Nickel complexes supported by quinoline-based ligands: synthesis, characterization and catalysis in the cross-coupling of arylzinc reagents and aryl chlorides or aryltrimethylammonium salts
  作者：Qiang Zhang、Xue-Qi Zhang、Zhong-Xia Wang

  DOI：10.1039/c2dt30886j

  日期：——

  Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph2PNHR (R = p-MeC6H4, But) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph2)N(8-C9H6N) (1a, R = p-MeC6H4; 1b, R = But. C9H6N = quinolyl)). Reaction of 1a with (DME)NiCl2 generates a nickel complex [NiCl2N(8-C9H6N)P(Ph2)NH(p-MeC6H4)}] (2a). Treatment of 1b with (DME)NiCl2 and following with NaH produces [NiCl(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl2 with [Li(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH2P(Ph2)N(8-C9H6N) (6, Py = pyridyl) and PhNC(Ph)CH2P(Ph2)N(8-C9H6N) (8), respectively, with (DME)NiCl2 yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl22-PyCH2P(Ph2)N(8-C9H6N)}] (7) and [NiCl2PhNC(Ph)CH2P(Ph2)N(8-C9H6N)}] (9). Similar reaction between Ph2PCH2P(Ph2)N(8-C9H6N) (10) and (DME)NiCl2 results in five-coordinate N,N,P-chelate nickel complex [NiCl2Ph2PCH2P(Ph2)N(8-C9H6N)}] (11). Treatment of [(8-C9H6N)NP(Ph2)]2CH2 (12) [prepared from (Ph2P)2CH2 and 2 equiv. of 8-azidoquinoline] with LiBun and (DME)NiCl2 successively affords [NiCl(8-C9H6N)NP(Ph2)}2CH] (13). The new compounds were characterized by 1H, 13C and 31P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.

  含喹啉基配体的锂和镍配合物已被合成和表征。8-叠氮喹啉与Ph2PNHR(R = p-MeC6H4, But)反应得到N-(8-喹啉基)亚氨基膦烷RNHP(Ph2)N(8-C9H6N)(1a, R = p-MeC6H4; 1b, R = But. C9H6N = 喹啉基))。1a与(DME)NiCl2反应生成镍配合物[NiCl2N(8-C9H6N)P(Ph2)NH(p-MeC6H4)}] (2a)。1b与(DME)NiCl2反应后，再用NaH处理得到[NiCl(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (4)。配合物4也可通过(DME)NiCl2与[Li(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (5)反应得到，后者是通过1b的锂化制备的。2-吡啶基甲基P(Ph2)N(8-C9H6N)(6, Py = 吡啶基)和PhNC(Ph)CH2P(Ph2)N(8-C9H6N)(8)分别与(DME)NiCl2反应，得到两个五配位的N,N,N-螯合镍配合物[NiCl22-PyCH2P(Ph2)N(8-C9H6N)}] (7)和[NiCl2PhNC(Ph)CH2P(Ph2)N(8-C9H6N)}] (9)。Ph2PCH2P(Ph2)N(8-C9H6N)(10)与(DME)NiCl2的类似反应生成五配位的N,N,P-螯合镍配合物[NiCl2Ph2PCH2P(Ph2)N(8-C9H6N)}] (11)。[(8-C9H6N)NP(Ph2)]2CH2(12)[由(Ph2P)2CH2和2当量的8-叠氮喹啉制备]依次与LiBun和(DME)NiCl2反应得到[NiCl(8-C9H6N)NP(Ph2)}2CH] (13)。新化合物通过1H、13C和31P NMR光谱(对于抗磁性化合物)、IR光谱(对于镍配合物)和元素分析进行表征。配合物2a、4、7、9、11和13还通过单晶X射线衍射技术进行表征。这些镍配合物被评估用于芳基锌试剂与芳基氯和芳基三甲基铵盐的交叉偶联反应的催化活性。在催化芳基锌试剂与芳基氯或芳基三甲基溴化铵的反应中，配合物7显示出最高的活性。
• Mono- and Dinuclear Pincer Nickel Catalyzed Activation and Transformation of C–Cl, C–N, and C–O Bonds
  作者：Xia Yang、Zhong-Xia Wang

  DOI：10.1021/om500452c

  日期：2014.10.27

  Condensation of 2-NH2C6H4P(Et)Ph (2) with pyrrole-2-carboxaldehyde generated 2-(C4H4N-2'-CH-N)C6H4P(Et)Ph (3). Treatment of 3 with NaH and followed by (DME)NiX2 (X = Cl, Br) afforded mononuclear pincer nickel complexes [Ni2-(C4H3N-2'-CH-N)C6H4P(Et)Ph}X] (4a, X = Cl; 4b, X = Br). Reaction of [2-NH2C6H4P(Ph)](2)(CH2)(n) (5a, n = 3; 5b, n = 4) with pyrrole-2-carboxaldehyde or 5-tert-butyl-1H-pyrrole-2-carbaldehyde formed [2-(C4H4N-2'-CH-N)C6H4P(Ph)](2)(CH2)(n) (6a, n = 3; 6b, n = 4) and [2-(5'-tBuC(4)H(3)N-2'-CH-N)C6H4P(Ph)](2)(CH2)(4) (6c). Respective treatment of 6ac with NaH followed by (DME)NiX2 (X = Cl, Br) gave the dinuclear nickel complexes [Ni2-(5'-RC4H2N-2'-CH-N)C6H4P(Ph)}X](2)(CH2)(n) (7a, R = H, X = Cl, n = 3; 7b, R = H, X = Cl, n = 4; 7c, R = H, X = Br, n = 4; 7d, R = tBu, X = Cl, n = 4). Catalysis of the complexes for the activation and transformation of CCl, CN, and CO bonds was evaluated. Complex 7c exhibited excellent catalytic activity in the cross-coupling of aryl chlorides or aryltrimethylammonium iodides with arylzinc reagents as well as of aryl sulfamates with aryl Grignard reagents. The dinuclear nickel complexes 7bd showed higher catalytic activity than the mononuclear complexes in each type of reaction.