2-acetoxy-2-methoxy-4-methoxycarbonyl-3,5-cyclohexadienone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-acetoxy-2-methoxy-4-methoxycarbonyl-3,5-cyclohexadienone
• 英文别名: Methyl 3-acetyloxy-3-methoxy-4-oxocyclohexa-1,5-diene-1-carboxylate
• 化学式: C₁₁H₁₂O₆
• 分子量: 240.213
• InChiKey: URJPOCMBXFPIJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Z)-1,3-bis(3-chlorophenyl)-3-hydroxyprop-2-en-1-one 、 2-acetoxy-2-methoxy-4-methoxycarbonyl-3,5-cyclohexadienone 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 以96 %的产率得到4-(3-chlorobenzoyl)-3-(3-chlorophenyl)-6-hydroxy-5-methoxy-1H-isochromen-1-one
  参考文献：
  名称：

  通过邻喹诺乙酸酯和软亲核试剂的一锅反应化学和区域选择性构建功能化异香豆素、黄酮和异喹啉二酮

  摘要：

  已经开发出一种通过可切换的 C-芳基化/内酯化或 SNA Ar 反应从各种软亲核试剂和邻羟基乙酸酯合成取代异香豆素、黄酮和异喹啉二酮衍生物的一锅策略。这种碱介导的方案在无过渡金属的条件下进行，并从易于制备或市售的 1,3-二羰基和α -EWG 取代的羰基化合物中选择性地以 13-98% 的产率提供各种杂芳烃。该合成效用在潜在抗HIV 和抗 HIV 药物的合成中得到了进一步证明。-冠状病毒衍生物和COX-2抑制剂。此外，还进行了详细的实验和计算研究，以提供对反应机理的深入理解和有力支持。

  DOI：

  10.1002/adsc.202201291
• 作为产物：
  描述：

  香草酸甲酯 、 溶剂黄146 在 碘苯二乙酸 作用下， 以 硝基甲烷 为溶剂， 反应 0.17h， 以61%的产率得到2-acetoxy-2-methoxy-4-methoxycarbonyl-3,5-cyclohexadienone
  参考文献：
  名称：

  Structural Studies on Bioactive Compounds. 32. Oxidation of Tyrphostin Protein Tyrosine Kinase Inhibitors with Hypervalent Iodine Reagents

  摘要：

  Hydroxylated styrenes (tyrphostins) undergo oxidation by hypervalent iodine oxidants such as [(diacetoxy)iodo]benzene (DAIB) to give a range of products depending on the structure of the phenolic substrate, the solvent, the oxidant stoichiometry, and the purification strategy. Conditions have been developed to modify the phenolic component of the tyrphostin without affecting the appended substituted-vinyl moiety. Novel products include: unstable 2-acyloxy-2-methoxy-4-(substituted-vinyl)cyclohexadienones and their rearrangement products 2-acyloxy-4-hydroxy-3 -methoxy-1-(substituted-vinyl)benzenes; phenyliodoniophenolates and their rearrangement products iodophenoxytyrphostins; and 3,3'-dialkoxy-2,2'-dihydroxy-5,5'-di(substituted-vinyl)biphenyls. None of these oxidation products displayed enhanced activity in vitro in the NCI 60-cell line panel or in a panel of human breast cancer cell lines, compared to their tyrphostin precursors. The inhibitory activity of three representative tyrphostins (3e,n, 28) was not modulated by aerobic/anaerobic conditions in MCF-7 and MDA 468 cells and was independent of EGFR status in clones of ZR75B cells transfected with this receptor. Basal growth of MCF-7 cells was unaffected by co-administration of the growth factors EGF, TGF-alpha, IGF-I, and IGF-II, and the new agents did not inhibit EGFR and c-erbB2 autaphosphorylation in cell lysates from MDA 468 or SkBr3 cells, respectively, suggesting that receptor tyrosine kinases are not targets for these compounds. Growth stimulation by the tyrphostin 3n in the ER+ breast cell lines MCF-7, T47D, and ZR75-1 was abolished by 1 mu M tamoxifen, suggesting that this compound has estrogen agonist activity.

  DOI：

  10.1021/jm990947f

文献信息

• Structural Studies on Bioactive Compounds. 32. Oxidation of Tyrphostin Protein Tyrosine Kinase Inhibitors with Hypervalent Iodine Reagents
  作者：Geoffrey Wells、Angela Seaton、Malcolm F. G. Stevens

  DOI：10.1021/jm990947f

  日期：2000.4.1

  Hydroxylated styrenes (tyrphostins) undergo oxidation by hypervalent iodine oxidants such as [(diacetoxy)iodo]benzene (DAIB) to give a range of products depending on the structure of the phenolic substrate, the solvent, the oxidant stoichiometry, and the purification strategy. Conditions have been developed to modify the phenolic component of the tyrphostin without affecting the appended substituted-vinyl moiety. Novel products include: unstable 2-acyloxy-2-methoxy-4-(substituted-vinyl)cyclohexadienones and their rearrangement products 2-acyloxy-4-hydroxy-3 -methoxy-1-(substituted-vinyl)benzenes; phenyliodoniophenolates and their rearrangement products iodophenoxytyrphostins; and 3,3'-dialkoxy-2,2'-dihydroxy-5,5'-di(substituted-vinyl)biphenyls. None of these oxidation products displayed enhanced activity in vitro in the NCI 60-cell line panel or in a panel of human breast cancer cell lines, compared to their tyrphostin precursors. The inhibitory activity of three representative tyrphostins (3e,n, 28) was not modulated by aerobic/anaerobic conditions in MCF-7 and MDA 468 cells and was independent of EGFR status in clones of ZR75B cells transfected with this receptor. Basal growth of MCF-7 cells was unaffected by co-administration of the growth factors EGF, TGF-alpha, IGF-I, and IGF-II, and the new agents did not inhibit EGFR and c-erbB2 autaphosphorylation in cell lysates from MDA 468 or SkBr3 cells, respectively, suggesting that receptor tyrosine kinases are not targets for these compounds. Growth stimulation by the tyrphostin 3n in the ER+ breast cell lines MCF-7, T47D, and ZR75-1 was abolished by 1 mu M tamoxifen, suggesting that this compound has estrogen agonist activity.
• Chemo‐ and Regioselective Construction of Functionalized Isocoumarin, Flavone, and Isoquinolinedione <i>via</i> a One‐pot Reaction of <i>o</i> ‐Quinol Acetate and Soft Nucleophiles
  作者：Yeong‐Jiunn Jang、Guan‐Yu Chen、Yun‐Lian Jhan、Pei‐Ting Lo、Wei‐Yu Hsu、Ke Wang、Ya‐Ting Hsu、Chia‐Lin Lee、Yu‐Liang Yang、Yang‐Chang Wu

  DOI：10.1002/adsc.202201291

  日期：——

  strategy for the synthesis of substituted isocoumarin, flavone, and isoquinolinedione derivatives through a switchable C-arylation/lactonization or SNAr reaction from a wide range of soft nucleophiles and o-quinol acetates has been developed. This base-mediated protocol proceeds under transition-metal-free conditions and selectively affords various heteroarenes in 13–98% yields from readily prepared or commercially

  已经开发出一种通过可切换的 C-芳基化/内酯化或 SNA Ar 反应从各种软亲核试剂和邻羟基乙酸酯合成取代异香豆素、黄酮和异喹啉二酮衍生物的一锅策略。这种碱介导的方案在无过渡金属的条件下进行，并从易于制备或市售的 1,3-二羰基和α -EWG 取代的羰基化合物中选择性地以 13-98% 的产率提供各种杂芳烃。该合成效用在潜在抗HIV 和抗 HIV 药物的合成中得到了进一步证明。-冠状病毒衍生物和COX-2抑制剂。此外，还进行了详细的实验和计算研究，以提供对反应机理的深入理解和有力支持。