2-iodo-3,4-dimethyl-1-nitrobenzene | 909135-23-5

• 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-iodo-3,4-dimethyl-1-nitrobenzene
• 英文别名: 3-iodo-1,2-dimethyl-4-nitrobenzene
• CAS: 909135-23-5
• 化学式: C₈H₈INO₂
• 分子量: 277.062
• InChiKey: YJEXTEWJBCPDAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-iodo-3,4-dimethyl-1-nitrobenzene 在 potassium phosphate 、 palladium on activated charcoal 、 氢气 、 palladium diacetate 、 potassium carbonate 、 对甲苯磺酸 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 作用下， 以 1,4-二氧六环 、 N-甲基吡咯烷酮 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.0h， 生成 (6-((5-chloro-2-((2-methoxy-5-(1-methyl-1H-pyrazol-4-yl)-4-(4-(2,7-diazaspiro[3.5]nonyl-7-yl))phenyl)amino)pyrimidin-4-yl)amino)-2,3-dimethylphenyl)phosphine oxide
  参考文献：
  名称：

  EGFR Inhibitor, Composition, and Preparation Method Therefor

  摘要：

  本发明涉及公式I的化合物，使用该化合物作为EGFR抑制剂的方法，以及包含这些化合物的药物组合物。这些化合物可用于治疗、预防或改善癌症或感染等疾病或疾病。

  公开号：

  US20220259235A1
• 作为产物：
  描述：

  2,3-二甲基-6-硝基苯胺 在 亚硝酸特丁酯 、 甲烷磺酸 、 四丁基碘化铵 作用下， 以 乙腈 为溶剂， 反应 0.37h， 生成 2-iodo-3,4-dimethyl-1-nitrobenzene
  参考文献：
  名称：

  使用苯胺作为掩蔽的交叉偶联伙伴：伸缩三步流重氮化，碘化二重氮化，交叉偶联工艺的设计

  摘要：

  通过使用伸缩的三反应器流动重氮化/碘化重氮化/交叉偶联工艺，可以将市售苯胺转化为联芳基和联芳基乙炔产品。通过使用由内部定制软件控制的特别设计的连续流装置，将在桑德梅尔序列中由除气产生的分段流动流恢复到反应溶液的连续塔中。然后将生成的芳基碘化物与交叉偶联溶液流合并，将其送入最终反应器中。该系统被证明是通用的，因为可以快速进行重氮化/碘化重氮化序列的修饰，以考虑到任何底物特异性（例如，溶解性问题），从而导致了Suzuki–Miyaura和Sonogashira交叉偶联产物的广泛底物范围。

  DOI：

  10.1002/chem.201603626

文献信息

• Copper-Catalyzed Asymmetric Ring-Opening of Cyclic Diaryliodonium with Benzylic and Aliphatic Amines
  作者：Shibo Xu、Kun Zhao、Zhenhua Gu

  DOI：10.1002/adsc.201800637

  日期：2018.10.18

  A Cu‐catalyzed asymmetric ring‐opening reaction between cyclic diaryliodonium and benzylic or aliphatic amines has been developed. At low concentration of the amines, realized by either mixing the amines with Lewis acid or slow addition of the amines, the reaction afforded the products in high enantioselectivity.

  已开发出环状二芳基碘鎓与苄基或脂肪族胺之间的Cu催化不对称开环反应。在低浓度的胺下，通过将胺与路易斯酸混合或缓慢加入胺来实现，该反应提供了高对映选择性的产物。
• Enhanced Reactivity by Torsional Strain of Cyclic Diaryliodonium in Cu-Catalyzed Enantioselective Ring-Opening Reaction
  作者：Kun Zhao、Longhui Duan、Shibo Xu、Julong Jiang、Yao Fu、Zhenhua Gu

  DOI：10.1016/j.chempr.2018.01.017

  日期：2018.3

  asymmetric ring-opening amination reaction of cyclic diaryliodoniums. Increasing the torsional strain of these cyclic compounds significantly improved the reactivity of cyclic diaryliodoniums. Computational investigation indicated that the two conformers of the cyclic diaryliodoniums had a low rotational barrier, and generally the reaction achieved high yields and high enantioselectivity (up to >99%

  阻转异构体是由于绕单键旋转受限而产生的立体异构体。特别地，联芳基阻转异构体代表一类重要的化合物，因为它们广泛存在于天然产物，配体和药物分子中。然而，在温和条件下制备结构多样的联芳基阻转异构体是一项重大挑战。在这里，我们描述了一个铜-双（恶唑啉基）吡啶催化的环状二芳基碘鎓的不对称开环胺化反应。增加这些环状化合物的扭转应变可显着提高环状二芳基碘鎓的反应性。计算研究表明，环状二芳基碘鎓的两个构象异构体具有较低的旋转势垒，并且通常该反应实现了高收率和高对映选择性（高达> 99％ee）。此外，与涉及二芳基碘鎓的传统反应相比，这种开环胺化反应还具有较高的原子经济性。最后，我们提出了一个催化循环和一个机制模型，用于解释所观察到的对映选择性。
• A Versatile Method for Kinetic Resolution of Protecting‐Group‐Free BINAMs and NOBINs through Chiral Phosphoric Acid Catalyzed Triazane Formation
  作者：Wei Liu、Qianwen Jiang、Xiaoyu Yang

  DOI：10.1002/anie.202009395

  日期：2020.12.21

  azodicarboxylates. A series of mono‐N‐protected and unprotected BINAMs, diphenyl diamines and NOBIN derivatives could be kinetically resolved with excellent performances (with s factor up to 420). The gram‐scale reactions and facile derivatizations of the chiral products demonstrate the potential of these methods in the asymmetric synthesis of chiral catalysts and ligands.

  通过手性磷酸与偶氮二羧酸酯催化三氮烷的形成，已实现了无保护基的BINAM和NOBIN的通用动力学拆分。一系列具有单-N-保护和未保护的BINAM，二苯二胺和NOBIN衍生物可以动力学拆分，并具有出色的性能（系数高达420）。手性产物的克级反应和易衍生化证明了这些方法在手性催化剂和配体的不对称合成中的潜力。
• OPTICALLY ACTIVE AMMONIUM SALT COMPOUND, PRODUCTION INTERMEDIATE THEREOF, AND PRODUCTION METHOD THEREOF
  申请人：Maruoka Keiji

  公开号：US20100041881A1

  公开（公告）日：2010-02-18

  An optically active quaternary ammonium salt compound represented by formula ( 1 ), wherein R 1 represents a halogen, a C 1-8 alkyl which is optionally substituted and which is linear, branched, or cyclic, a C 2-8 alkenyl which is optionally substituted, a C 2-8 alkynyl which is optionally substituted, a C 6-14 aryl which is optionally substituted, a C 3-8 heteroaryl which is optionally substituted, a C 1-8 alkoxy which is optionally substituted and which is linear, branched, or cyclic, or a C 7-16 aralkyl which is optionally substituted; R 2 and R 21 each independently represents hydrogen, halogen, nitro, a C 1-8 alkyl which is optionally substituted and which is linear, branched, or cyclic, a C 2-8 alkenyl which is optionally substituted, a C 2-8 alkynyl which is optionally substituted, a C 6-14 aryl which is optionally substituted, a C 1-8 alkoxy which is optionally substituted and which is linear, branched, or cyclic, or a C 7-16 aralkyl which is optionally substituted; one of combinations of R 1 and R 21 , and R 2 and R 21 , may bond to form a C 1-6 alkylene which is optionally substituted, a C 1-6 alkylenemonooxy which is optionally substituted, or a C 1-6 alkylenedioxy which is optionally substituted; R 3 and R 4 each independently represents hydrogen, a C 6-14 aryl which is optionally substituted, a C 3-8 heteroaryl which is optionally substituted, or a C 7-16 aralkyl which is optionally substituted, with a proviso that R 3 and R 4 are not hydrogen at the same time; R 5 represents hydrogen, halogen, a C 1-8 alkyl which is optionally substituted and which is linear, branched, or cyclic, a C 1-8 alkoxy which is optionally substituted and which is linear, branched, or cyclic, a C 2-8 alkenyl which is optionally substituted, or a C 2-8 alkynyl which is optionally substituted; R 6 represents halogen, a C 1-8 alkyl which is optionally substituted and which is linear, branched, or cyclic, a C 1-8 alkoxy which is optionally substituted and which is linear, branched, or cyclic, a C 2-8 alkenyl which is optionally substituted, or a C 2-8 alkynyl which is optionally substituted, and R 5 and R 6 may bond to form an aromatic ring which is optionally substituted; ring A and ring B do not have a same substituent at the same time; symbols * and ** represent an optical activity having an axial chirality; and X −1 represents an anion.

  一种光学活性的季铵盐化合物，其化学式表示为（1），其中R1代表卤素，C1-8烷基（可选择性取代，线性、支链或环状），C2-8烯基（可选择性取代），C2-8炔基（可选择性取代），C6-14芳基（可选择性取代），C3-8杂环芳基（可选择性取代），C1-8烷氧基（可选择性取代，线性、支链或环状）或C7-16芳基烷基（可选择性取代）；R2和R21各自独立地表示氢，卤素，硝基，C1-8烷基（可选择性取代，线性、支链或环状），C2-8烯基（可选择性取代），C2-8炔基（可选择性取代），C6-14芳基（可选择性取代），C1-8烷氧基（可选择性取代，线性、支链或环状）或C7-16芳基烷基（可选择性取代）；R1和R21的组合之一，以及R2和R21的组合之一，可以结合形成C1-6烷基（可选择性取代），C1-6烷基单氧（可选择性取代）或C1-6烷基二氧（可选择性取代）；R3和R4各自独立地表示氢，C6-14芳基（可选择性取代），C3-8杂环芳基（可选择性取代）或C7-16芳基烷基（可选择性取代），但R3和R4不能同时为氢；R5表示氢，卤素，C1-8烷基（可选择性取代，线性、支链或环状），C1-8烷氧基（可选择性取代，线性、支链或环状），C2-8烯基（可选择性取代）或C2-8炔基（可选择性取代）；R6表示卤素，C1-8烷基（可选择性取代，线性、支链或环状），C1-8烷氧基（可选择性取代，线性、支链或环状），C2-8烯基（可选择性取代）或C2-8炔基（可选择性取代），且R5和R6可以结合形成一个芳环（可选择性取代）；环A和环B在同一时间不具有相同的取代基；符号*和**表示轴手性的光学活性；X^-1表示阴离子。
• Optically active ammonium salt compound, production intermediate thereof, and production method thereof
  申请人：Maruoka Keiji

  公开号：US08367820B2

  公开（公告）日：2013-02-05

  Disclosed is an optically active quaternary ammonium salt compound represented by the formula (1) below. Also disclosed are a production intermediate of such an optically active quaternary ammonium salt compound, and a method for producing such an optically active quaternary ammonium salt compound. (1) (In the formula, R1, R2, R21, R3 and R4 respectively represent an alkyl group, an aryl group or the like; R5 and R6 respectively represent an alkyl group, an alkoxy group or the like; and X− represents an anion.)

  本发明揭示了一种光学活性的季铵盐化合物，其化学式如下所示（1）。本发明还揭示了这种光学活性季铵盐化合物的制备中间体以及制备这种光学活性季铵盐化合物的方法。（在式中，R1、R2、R21、R3和R4分别表示烷基、芳基或类似物；R5和R6分别表示烷基、烷氧基或类似物；X-表示阴离子。）