N-tosyl-6-isopropyl-3-methyl-1,4-benzoquinone monoimine

• 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-tosyl-6-isopropyl-3-methyl-1,4-benzoquinone monoimine
• 英文别名: N-tosyl-5-isopropyl-2-methyl-1,4-benzoquinone monoimine；4-methyl-N-(2-methyl-4-oxo-5-propan-2-ylcyclohexa-2,5-dien-1-ylidene)benzenesulfonamide
• 化学式: C₁₇H₁₉NO₃S
• 分子量: 317.409
• InChiKey: YQCGNLFNNVNLAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  72
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-tosyl-6-isopropyl-3-methyl-1,4-benzoquinone monoimine 在 氯 作用下， 以 氯仿 为溶剂， 以73%的产率得到2-isopropyl-5-methyl-4-tosylimino-5,6-dichloro-2-cyclohexen-1-one
  参考文献：
  名称：

  Halogenation of N-substituted para-quinone monoimine and para-quinone monooxime esters: V. Chlorination and bromination of N-arylsulfonyl-1,4-benzoquinone monoimines dialkyl-substituted in the quinoid ring

  摘要：

  The direction of halogen addition to N-arylsulfonyl-1,4-benzoquinone monoimines dialkyl-substituted in the quinoid ring is governed by the steric factors: the size and position of the substituent, the halogen volume, and the position of the substituent at the nitrogen. The first stage of halogenation of N-arylsulfonyl-4-aminophenols with two alkyl substituents in the phenylsulfonyl ring largely occurs as electrophilic substitution.

  DOI：

  10.1134/s1070428006050058
• 作为产物：
  描述：

  百里酚 在 吡啶 、 盐酸 、 [N,N'-bis(salicylidene)ethane-1,2-diaminato]cobalt(II) 、 盐酸羟胺 、 氧气 、 sodium acetate 、 tin(ll) chloride 、 silver(l) oxide 作用下， 以 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 23.5h， 生成 N-tosyl-6-isopropyl-3-methyl-1,4-benzoquinone monoimine
  参考文献：
  名称：

  对苯醌氮衍生物的狄尔斯-阿尔德反应：实验和理论研究

  摘要：

  对对苯醌和三种氮衍生物的狄尔斯-阿尔德反应的比较反应性和选择性进行了实验和理论研究。单肟衍生物在所测试的反应条件下不反应，而甲苯磺酸化的单肟反应缓慢。然而，单N-甲苯磺酰基亚胺显示出优异的反应性，并且优于母体对-苯醌。DFT计算支持这些实验结果。

  DOI：

  10.1016/j.tet.2014.07.088

文献信息

• Symmetry in Cascade Chirality-Transfer Processes: A Catalytic Atroposelective Direct Arylation Approach to BINOL Derivatives
  作者：Jin-Zheng Wang、Jin Zhou、Chang Xu、Hongbin Sun、László Kürti、Qing-Long Xu

  DOI：10.1021/jacs.6b01458

  日期：2016.4.27

  disclose a scalable organocatalytic direct arylation approach for the regio- and atroposelective synthesis of non-C2-symmetric 2,2'-dihydroxy-1,1'-binaphthalenes (BINOLs). In the presence of catalytic amounts of axially chiral phosphoric acids, phenols and naphthols are coupled with iminoquinones via a cascade process that involves sequential aminal formation, sigmatropic rearrangement, and rearomatization

  在此，我们公开了一种可扩展的有机催化直接芳基化方法，用于非 C2 对称 2,2'-二羟基-1,1'-联萘 (BINOL) 的区域选择性和阻转选择性合成。在催化量的轴向手性磷酸存在下，苯酚和萘酚通过级联过程与亚氨基醌偶联，该级联过程涉及连续的氨基形成、sigmatropic 重排和重构化，以提供对映体富集的 BINOL 衍生物，收率良好至极好。我们的研究表明，最初形成的氨基中间体的（局部）对称性对最终产品中的对映体诱导水平具有显着影响。具有对称平面的 Aminals 产生 BINOL 衍生物，其对映体过量明显低于具有立体中心的不对称衍生物。据推测，sigmatropic 重排步骤中的不对称诱导比无性形成过程中更具挑战性。对映体富集的氨基的Sigmatropic重排和随后的重构化以高保真度将中心手性转化为轴向手性。
• Reaction of N-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted hydrazines
  作者：S. A. Konovalova、A. P. Avdeenko、S. A. Goncharova、V. V. D’yakonenko、S. V. Shishkina

  DOI：10.1134/s1070428016050055

  日期：2016.5

  Reaction direction of N-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted hydrazines depends on the redox potential of the quinone imine and on the basicity of the hydrazine. Aryl (alkyl)hydrazines of high basicity favor the reduction of quinone monoimine. In reactions with less basic aroylhydrazones N'-(4-oxocyclohexa-2,5-dienylidene)aroylhydrazides were obtained only from the alkylsubstituted

  1,4-苯醌单亚胺的N-磺酰基衍生物与取代的肼的反应方向取决于醌亚胺的氧化还原电势和肼的碱性。高碱性的芳基（烷基）肼有助于减少醌单亚胺。在与碱性较低的芳酰基hydr的反应中，仅从具有较低氧化还原电势的N-磺酰基衍生物的喹啉环中取代的烷基获得N ′-（4-氧代环己二-2，5-二烯基）芳酰基酰肼。
• Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids
  作者：A. P. Avdeenko、S. A. Konovalova、D. A. Roman’kov、O. N. Ludchenko、I. L. Marchenko

  DOI：10.1134/s1070428009030063

  日期：2009.3

  Reactions of N-aroyl-, N-arylsulfonyl-, and N-(N-arylsulfonylbenzimidoyl)-2,5-dialkyl-1,4-benzoquinone imines with sodium arenesulfinates in acetic acid gave the corresponding 1,4-, 6,1-, and 1,6-addition products. Variation of the size and donor power of substituents in positions 2 and 5 of the quinoid ring almost does not affect the ratio of the addition products, which is determined mainly by the nature of substituent on the nitrogen atom.
• The Diels–Alder reactions of para-benzoquinone nitrogen-derivatives: an experimental and theoretical study
  作者：Marciana P. Uliana、Bruno M. Servilha、Olga Alexopoulos、Kleber T. de Oliveira、Cláudio F. Tormena、Marco A.B. Ferreira、Timothy J. Brocksom

  DOI：10.1016/j.tet.2014.07.088

  日期：2014.9

  An experimental and theoretical study of the comparative reactivity and selectivity of the Diels–Alder reactions of para-benzoquinones and three nitrogen derivatives have been performed. The mono-oximes derivatives do not react under the tested reaction conditions, whereas the tosylated mono-oximes react slowly. However, the mono N-tosyl imines show excellent reactivity, and superior to the parent

  对对苯醌和三种氮衍生物的狄尔斯-阿尔德反应的比较反应性和选择性进行了实验和理论研究。单肟衍生物在所测试的反应条件下不反应，而甲苯磺酸化的单肟反应缓慢。然而，单N-甲苯磺酰基亚胺显示出优异的反应性，并且优于母体对-苯醌。DFT计算支持这些实验结果。
• Halogenation of N-substituted para-quinone monoimine and para-quinone monooxime esters: V. Chlorination and bromination of N-arylsulfonyl-1,4-benzoquinone monoimines dialkyl-substituted in the quinoid ring
  作者：A. P. Avdeenko、S. A. Konovalova

  DOI：10.1134/s1070428006050058

  日期：2006.5

  The direction of halogen addition to N-arylsulfonyl-1,4-benzoquinone monoimines dialkyl-substituted in the quinoid ring is governed by the steric factors: the size and position of the substituent, the halogen volume, and the position of the substituent at the nitrogen. The first stage of halogenation of N-arylsulfonyl-4-aminophenols with two alkyl substituents in the phenylsulfonyl ring largely occurs as electrophilic substitution.