N-(4-iodo-3-methylphenyl)-N,4-dimethylbenzenesulfonamide | 867309-17-9

• 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-iodo-3-methylphenyl)-N,4-dimethylbenzenesulfonamide
• CAS: 867309-17-9
• 化学式: C₁₅H₁₆INO₂S
• 分子量: 401.268
• InChiKey: JAAMQPHQDUUOIN-UHFFFAOYSA-N

物化性质

• 熔点：
  97-98 °C
• 沸点：
  484.8±55.0 °C(Predicted)
• 密度：
  1.594±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(4-iodo-3-methylphenyl)-N,4-dimethylbenzenesulfonamide 、 1-(2-溴乙基)-7-氯-6-氮杂吲哚 在 palladium dichloride 降冰片烯 、 三(2-呋喃基)膦 、 caesium carbonate 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以62%的产率得到1-methyl-3-(N-methyl-N-tosyl)-5,6-dihydro-9-chloro-10-azaindolo[2,1-a]isoquinoline
  参考文献：
  名称：

  A Palladium-Catalyzed Alkylation/Direct Arylation Synthesis of Nitrogen-Containing Heterocycles

  摘要：

  [Graphics]A norbornene-mediated palladium-catalyzed sequence is described in which an alkyl-aryl bond and an aryl-heteroaryl bond are formed in one reaction vessel. The aryl-heteroaryl bond-forming step occurs via a direct arylation reaction. A number of six-, seven-, and eight-membered ring-annulated indoles, pyrroles, pyrazoles, and azaindoles were synthesized from the corresponding bromoalkyl azole and an aryl iodide.

  DOI：

  10.1021/jo702052b
• 作为产物：
  描述：

  4-碘-3-甲基苯胺 在 吡啶 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 N-(4-iodo-3-methylphenyl)-N,4-dimethylbenzenesulfonamide
  参考文献：
  名称：

  通过钯催化串联烷基化/直接芳基化反应制备环化吲哚的途径

  摘要：

  描述了降冰片烯介导的钯催化串联烷基化/CH 官能化序列，其中烷基-芳基键和杂芳基-芳基键在一锅中形成。以溴代烷基吲哚和芳基碘化物为原料，以良好的收率合成了多种高度取代的六元和七元环环化吲哚。

  DOI：

  10.1021/ja054472v

文献信息

• Palladium/Norbornene-Catalyzed <i>ortho</i> Aliphatic Acylation with Mixed Anhydride: Selectivity and Reactivity
  作者：Shibo Xu、Julong Jiang、Linlin Ding、Yao Fu、Zhenhua Gu

  DOI：10.1021/acs.orglett.7b03514

  日期：2018.1.19

  synthesis of functionalized alkyl aryl ketones is reported. Studies on the electronic and steric properties of mixed aryl anhydrides indicated that the cross-coupling favored with the electron-enriched aryl acyl group. DFT calculation on the oxidative addition of Pd(II) with 2,4,6-(Cl)3C6H2CO2C(O)Ph suggested that 2,4,6-(Cl)3C6H2C(O)–O bond cleavage was more kinetically disfavored than that of the PhC(O)–O

  报道了钯/降冰片烯催化的邻位酰化，用于有效合成官能化的烷基芳基酮。对混合的芳基酸酐的电子和空间特性的研究表明，交叉偶联有利于富电子的芳基酰基。用2,4,6-（Cl）3 C 6 H 2 CO 2 C（O）Ph氧化Pd（II）的DFT计算表明2,4,6-（Cl）3 C 6 H 2 C （O）–O键的断裂在动力学上比PhC（O）–O键的断裂更不利于11.7 kJ / mol。
• Decarboxylative Alkynyl Termination of Palladium-Catalyzed Catellani Reaction: A Facile Synthesis of α-Alkynyl Anilines via <i>Ortho</i> C–H Amination and Alkynylation
  作者：Fenggang Sun、Zhenhua Gu

  DOI：10.1021/acs.orglett.5b00830

  日期：2015.5.1

  A palladium-catalyzed synthesis of α-alkynyl anilines is reported. The reaction proceeds via Catellani ortho C–H amination followed by decarboxylative alkynylative amination. Different terminal alkyne precursors were screened, and it was found that alkynyl carboxylic acids were superior over other alkynes, which led to operationally simple reaction conditions (no gradual addition of alkynes) and broad

  报道了钯催化的α-炔基苯胺的合成。反应通过Catellani邻位C-H胺化反应进行，然后进行脱羧炔基化胺化反应。筛选了不同的末端炔烃前体，发现炔基羧酸优于其他炔烃，这导致了操作简单的反应条件（无需逐步添加炔烃）和较宽的底物范围。三种不同组分的反应性很好地匹配。结果，可以使用相对较高的反应温度，从而将反应时间从先前报道的144小时大大缩短到4小时。
• Palladium-Catalyzed Norbornene-Mediated Tandem Amination/Cyanation Reaction: A Method for the Synthesis of <i>ortho</i>-Aminated Benzonitriles
  作者：Bo Luo、Jin-Ming Gao、Mark Lautens

  DOI：10.1021/acs.orglett.6b02249

  日期：2016.9.2

  norbornene-mediated tandem amination/cyanation reaction via Catellani-type C–H functionalization was developed using N-benzoyloxyamines as the amination reagent and Zn(CN)2 as the terminating agent. This transformation, in which one C–N bond and one C–C bond are formed, provides an efficient approach for the synthesis of ortho-aminated benzonitriles in one pot from easily accessible starting materials

  通过使用N-苯甲酰氧基胺作为胺化试剂和Zn（CN）2作为终止剂，开发了通过卡塞拉尼型C–H官能化进行的钯催化，降冰片烯介导的串联胺化/氰化反应。这种形成一个C–N键和一个C–C键的转变，为从容易获得的起始原料在一锅中合成邻氨基苯甲腈提供了一种有效的方法。
• Palladium-Catalyzed Catellani<i>ortho</i>-Acylation Reaction: An Efficient and Regiospecific Synthesis of Diaryl Ketones
  作者：Yunze Huang、Rui Zhu、Kun Zhao、Zhenhua Gu

  DOI：10.1002/anie.201506446

  日期：2015.10.19

  A palladium‐catalyzed, norbornene‐mediated Catellani ortho‐acylation reaction was developed by the use of either acyl chlorides or acid anhydrides as acylation reagents. The addition of more than a stoichiometric amount of H2O is crucial for this transformation when acid chlorides are used, and kinetic studies indicate that the active acylation reagent is possibly an acid anhydride.

  通过使用酰氯或酸酐作为酰化剂，开发了钯催化的降冰片烯介导的卡塞拉尼正酰化反应。当使用酰氯时，添加超过化学计算量的H 2 O对于该转化至关重要，动力学研究表明，活性酰化剂可能是酸酐。
• Synthesis of 2-(1-Alkoxyvinyl)anilines by Palladium/Norbornene-Catalyzed Amination Followed by Termination with Vinyl Ethers
  作者：Jie Wang、Zhenhua Gu

  DOI：10.1002/adsc.201600339

  日期：2016.9.15

  A palladium/norbornene‐catalyzed ortho‐amination and ipso vinyl ether termination reaction of iodoarenes is reported. The benzyl vinyl ether serves as an efficient alternative carbonyl source in palladium/norbornene catalysis for the final ipso termination reaction to give [1‐(benzyloxy)vinyl]arenes, which readily undergo hydrolysis to deliver methyl ketones under aqueous acidic conditions. The final

  钯/降冰片烯催化邻-amination和本位乙烯基醚iodoarenes的终止反应的报道。在钯/降冰片烯催化中，苄基乙烯基醚可作为有效的替代羰基来源，用于最终的ipso终止反应，以生成[1-（苄氧基）乙烯基]芳烃，该芳烃在含水酸性条件下易于水解以生成甲基酮。与乙烯基醚的最终的Heck终止反应具有较高的支链/线性选择性。该反应可耐受多种碘芳烃和O-苯甲酰羟胺底物，为制备邻苯二甲酰胺提供了简便的方法。-乙酰苯胺。简要研究了[1-（苄氧基）乙烯基]芳烃和相应的酮的合成效用。