N′-(4-iodophenyl)benzamidine | 24967-77-9

• 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′-(4-iodophenyl)benzamidine
• 英文别名: N-<4-Jod-phenyl>-benzamidin；N-(4-iodo-phenyl)-benzamidine；N-(4-Jod-phenyl)-benzamidin；N-p-Jodphenylbenzamidin；N'-(4-iodophenyl)benzenecarboximidamide
• CAS: 24967-77-9
• 化学式: C₁₃H₁₁IN₂
• 分子量: 322.148
• InChiKey: HUEDYYCAVRRADD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N′-(4-iodophenyl)benzamidine 以 四氢呋喃 、 乙腈 为溶剂， 反应 5.0h， 生成 2-[1-(4-iodophenyl)-5-imino-2-phenyl-1H-imidazol-4(5H)-ylidene]malononitrile
  参考文献：
  名称：

  Reactions of Tetracyanoethylene with N′-Arylbenzamidines: A Route to 2-Phenyl-3H-imidazo[4,5-b]quinoline-9-carbonitriles

  摘要：

  Eight 2-phenyl-3H-imidazo[4,5-b]quinoline-9-carbonitriles 15 are prepared in four steps from N'-arylbenzamidines 11 and tetracyanoethylene (TCNE) in similar to 70-90% yields. The transformation involves the initial formation of N-aryl-N'-(1,2,2-tricyanovinyl)benzamidines 12 in 87-99% yields, which in MeCN undergo a 5-exodig cyclization to give the 2[1-aryl-5-imino-2-phenyl-1H-imidazol-4(5H)-ylidene]malononitriles 13 in 84-92% yields, while in MeOH the (Z)-2[2-phenyl-4-(arylimino)-1H-imidazol-5(4H)-ylidene]malononitriles 14 are formed in 85-94% yields. The imidazoles 14 can also be prepared directly from imidazoles 13 via a Dimroth rearrangement in either neat MeOH or in DCM with DBU. Subsequent thermolysis of imidazoles 14 in diphenyl ether affords 2-phenyl-3H-imidazo[4,5-b]quinoline-9-carbonitriles 15 in near quantitative yields. Mechanistic rationale is provided for all transformations.

  DOI：

  10.1021/jo4013699
• 作为产物：
  描述：

  (E)-1-benzylidene-2-(4-iodophenyl)hydrazine 在 sodium amide 作用下， 生成 N′-(4-iodophenyl)benzamidine
  参考文献：
  名称：

  Robew; Sumerska, Doklady Bolgarskoi Akademii Nauk, 1959, vol. 12, p. 137,139

  摘要：

  DOI：

文献信息

• Direct Synthesis of 3-Acylindoles through Rhodium(III)-Catalyzed Annulation of<i>N</i>-Phenylamidines with α-Cl Ketones
  作者：Jianhui Zhou、Jian Li、Yazhou Li、Chenglin Wu、Guoxue He、Qiaolan Yang、Yu Zhou、Hong Liu

  DOI：10.1021/acs.orglett.8b03383

  日期：2018.12.7

  versatile 3-acylindoles through Rh(III)-catalyzed C–H activation and annulation cascade of N-phenylamidines with α-Cl ketones was developed, in which α-Cl ketones serve as unusual one-carbon (sp3) synthons. This strategy features high regioselectivity, efficiency, wide substrate tolerance, and mild reaction conditions, which further underscore its synthetic utility in drug molecule synthesis.

  在本研究中，开发了一种新的合成策略，可通过Rh（III）催化的C–H活化和N-苯基am与α-Cl酮的环合级联反应直接生产通用的3-acylindoles ，其中α-Cl酮用作不寻常的一碳（sp 3）合成子。该策略具有较高的区域选择性，效率，宽的底物耐受性和温和的反应条件，这进一步强调了其在药物分子合成中的合成效用。
• Reinvestigating the synthesis of N-arylbenzamidines from benzonitriles and anilines in the presence of AlCl3
  作者：Panayiotis A. Koutentis、Styliana I. Mirallai

  DOI：10.1016/j.tet.2010.04.103

  日期：2010.7

  conditions, allowing for the higher yielding synthesis of N-phenylbenzamidine 3a (83%). Using these modified conditions several N-(4-substituted phenyl)benzamidines can be prepared including the N-(4-methoxyphenyl)benzamidine 3b (93%) and the previously unobtainable 2-amino-N-(4-methoxyphenyl)benzamidine 3l (56%). All new compounds are fully characterised.

  的制备ñ -phenylbenzamidine 3a中从苄腈之间的反应1A中的AlCl的存在和苯胺3被重新调查相对于试剂加入，反应温度，路易斯酸催化的模式。在添加苯胺之前预形成腈-路易斯酸络合物可以实现较温和的反应条件，从而可以实现更高收率的N-苯基苯甲m 3a的合成（83％）。使用这些修饰的条件，可以制备几种N-（4-取代的苯基）苯甲m，包括N-（4-甲氧基苯基）苯甲m3b（93％）和先前无法获得的2-氨基-N-（4-甲氧基苯基）苯甲m 3l（56％）。所有新化合物均具有完整特征。
• Synthesis and properties of imidazolo-fused benzotriazinyl radicals
  作者：Andrey A. Berezin、Christos P. Constantinides、Styliana I. Mirallai、Maria Manoli、Levy L. Cao、Jeremy M. Rawson、Panayiotis A. Koutentis

  DOI：10.1039/c3ob41169a

  日期：——

  1,3-Diphenylbenzo[e][1,2,4]triazin-7(1H)-one, the oxidation product of 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl (Blatter's radical), reacts with N′-arylbenzamidines in PhMe at ca. 100 °C in the presence of N,N-diisopropylethylamine (Hünig's base) (1 equiv.) to give N′-aryl-N-(1,7-dihydro-7-oxo-1,3-diphenylbenzo[e][1,2,4]triazin-6-yl)benzimidamides in 49–95% yield. In neat AcOH heated at ca. 120 °C, N′–aryl-N-(1,7-dihydro-7-oxo-1,3-diphenylbenzo[e][1,2,4]triazin-6-yl)benzimidamides cyclodehydrate to give the novel 8-substituted 1,3,7-triphenyl-4,8-dihydro-1H-imidazo[4,5-g][1,2,4]benzotriazin-4-yls in 13–81% yield. During the optimization of this cyclodehydration an additional oxazole fused benzotriazinyl radical 1,3,7-triphenyl-1,4-dihydro[1,3]oxazolo[4,5-g][1,2,4]benzotriazin-4-yl was isolated as a side product and characterized. The CV and EPR data of the imidazolo- and oxazolo-fused radicals are presented as well as single crystal X-ray structures of 1,3,7-triphenyl-1,4-dihydro-[1,3]oxazolo[4,5-g][1,2,4]benzotriazin-4-yl and 1,3,7,8-tetraphenyl-4,8-dihydro-1H-imidazo[4,5-g][1,2,4]benzotriazin-4-yl.

  1,3-二苯基苯并[e][1,2,4]三嗪-7(1H)-酮，即1,3-二苯基-1,4-二氢-1,2,4-苯并三嗪-4-基（Blatter自由基）的氧化产物，在N,N-二异丙基乙胺（Hünig碱）（1当量）存在下，于约100°C的甲苯中与N'-芳基苯甲脒反应，以49-95%的产率生成N'-芳基-N-(1,7-二氢-7-氧代-1,3-二苯基苯并[e][1,2,4]三嗪-6-基)苯并咪唑胺。在纯乙酸中加热至约120°C时，N'–芳基-N-(1,7-二氢-7-氧代-1,3-二苯基苯并[e][1,2,4]三嗪-6-基)苯并咪唑胺环化脱水，以13-81%的产率生成新型8-取代的1,3,7-三苯基-4,8-二氢-1H-咪唑并[4,5-g][1,2,4]苯并三嗪-4-基。在优化这一环化脱水过程中，还分离出了一种副产物——噁唑并苯并三嗪自由基1,3,7-三苯基-1,4-二氢[1,3]噁唑并[4,5-g][1,2,4]苯并三嗪-4-基，并对其进行了表征。同时提供了咪唑并和噁唑并自由基的CV和EPR数据，以及1,3,7-三苯基-1,4-二氢-[1,3]噁唑并[4,5-g][1,2,4]苯并三嗪-4-基和1,3,7,8-四苯基-4,8-二氢-1H-咪唑并[4,5-g][1,2,4]苯并三嗪-4-基的单晶X射线结构。
• Base-Mediated Amination of Alcohols Using Amidines
  作者：Chunyan Zhang、Zehua Li、Jianbin Chen、Shuo Qi、Yanchen Fang、Sheng Zhang、Chaoyu Ren、Fenghong Lu、Zuyu Liang、Shaohua Jiang、Xiaofei Jia、Shuangming Yu、Guoying Zhang

  DOI：10.1021/acs.joc.0c00281

  日期：2020.6.19

  Novel and efficient base-mediated N-alkylation and amidation of amidines with alcohols have been developed, which can be carried out in one-pot reaction conditions, which allows for the synthesis of a wide range of N-alkyl amines and free amides in good to excellent yields with high atom economy. In contrast to borrowing hydrogen/hydrogen autotransfer or oxidative-type N-alkylation reactions, in which

  已经开发出新颖且有效的碱介导的alcohol基N-烷基化和of与醇的酰胺化反应，该反应可以在一锅法反应条件下进行，从而可以很好地合成各种N-烷基胺和游离酰胺。在高原子经济的情况下达到出色的产量。与借用氢/氢自转移或氧化型N-烷基化反应（其中醇通过过渡金属催化的或氧化的有氧脱氢作用而活化）相反，使用am提供了胺的有效替代。这避免了氧化剂或催化剂被配体稳定化的N-烷基化的内在必要性。
• Direct Synthesis of Quinazolines through Copper-Catalyzed Reaction of Aniline-Derived Benzamidines
  作者：Yusuke Ohta、Yusuke Tokimizu、Shinya Oishi、Nobutaka Fujii、Hiroaki Ohno

  DOI：10.1021/ol1016756

  日期：2010.9.3

  A novel synthesis of 2-phenyl-4-[(triisopropylsilyl)methyl]quinazolines from monosubstituted arenes has been developed. Treatment of N-phenylbenzamidines with 5-nitro-1-[(triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one and K2CO3 in the presence of a catalytic amount of CuBr in benzene gives 2-phenyl-4-[(triisopropylsilyl)methyl]quinazolines in moderate to good yields.

  已开发了由单取代的芳烃合成2-苯基-4-[（三异丙基甲硅烷基）甲基]喹唑啉的新方法。在催化量的CuBr在苯中的存在下，用5-硝基-1-[（三异丙基甲硅烷基）乙炔基] -1,2-苯并恶多酚-3（1 H）-one和K 2 CO 3处理N-苯基苯甲m ，得到2 -苯基-4-[（三异丙基甲硅烷基）甲基]喹唑啉的产率中等至良好。