3-Bromo-4,4-dimethoxy-2,5-cyclohexadien-1-one | 72054-82-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Bromo-4,4-dimethoxy-2,5-cyclohexadien-1-one
• 英文别名: 3-bromo-4,4-dimethoxycyclohexa-2,5-dien-1-one；3-bromo-4,4-dimethoxycyclohexa-2,5-dienone；2,5-Cyclohexadien-1-one, 3-bromo-4,4-dimethoxy-
• CAS: 72054-82-1
• 化学式: C₈H₉BrO₃
• 分子量: 233.062
• InChiKey: BMNNRIBGSKUTMH-UHFFFAOYSA-N

物化性质

• 沸点：
  303.6±42.0 °C(Predicted)
• 密度：
  1.52±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Bromo-4,4-dimethoxy-2,5-cyclohexadien-1-one 在 叔丁基过氧化氢 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 以46%的产率得到4-Bromo-5,5-dimethoxy-7-oxabicyclo[4.1.0]hept-3-en-2-one
  参考文献：
  名称：

  Synthesis of bromoxone

  摘要：

  A short synthetic route to the natural product bromoxone is reported (5 steps, 15% overall yield), involving regioselective monoepoxidation of an electrolytically-derived quinone monoketal followed by stereoselective ketone reduction.

  DOI：

  10.1016/s0040-4039(00)78490-5
• 作为产物：
  描述：

  1-溴-3,3,6,6-四甲氧基环己-1,4-二烯 在 溶剂黄146 作用下， 以 丙酮 为溶剂， 以71%的产率得到3-Bromo-4,4-dimethoxy-2,5-cyclohexadien-1-one
  参考文献：
  名称：

  Synthesis of bromoxone

  摘要：

  A short synthetic route to the natural product bromoxone is reported (5 steps, 15% overall yield), involving regioselective monoepoxidation of an electrolytically-derived quinone monoketal followed by stereoselective ketone reduction.

  DOI：

  10.1016/s0040-4039(00)78490-5

文献信息

• [EN] COMPOSITIONS AND METHODS FOR THE PREPARATION OF 4-OXY-2-CYCLOHEXENONE AND 6-OXY-2-CYCLOHEXENONE COMPOUNDS<br/>[FR] COMPOSITIONS ET PROCÉDÉS POUR LA PRÉPARATION DE COMPOSÉS 4-OXY-2-CYCLOHEXÉNONE ET 6-OXY-2-CYCLOHEXÉNONE
  申请人：UNIV NAT TAIWAN

  公开号：WO2016011130A1

  公开（公告）日：2016-01-21

  The present invention relates to a new synthetic route to 4-oxy-2-cyclohexenone and 6-oxy-2- cyclohexenone compounds useful for treatment of cancers and/or diseases, and the intermediates thereto. Examples of these cyclohexenone compounds include, but not limited to, A. cinnamomea active medicinal substances such as antroquinonol, antroquinonol B, antroquinonol C, and antroquinonol D. The intermediates include the compounds of formulae (I), (II) and (III), and the cyclohexenone compounds have the structures of formulae (IV), (V), (VI) and (VII).

  本发明涉及一种用于治疗癌症和/或疾病的新的合成路线，用于制备4-氧基-2-环己烯酮和6-氧基-2-环己烯酮化合物，以及这些化合物的中间体。这些环己烯酮化合物的示例包括但不限于A.桂枝活性药物成分，如antroquinonol，antroquinonol B，antroquinonol C和antroquinonol D。这些中间体包括式(I)、(II)和(III)的化合物，环己烯酮化合物具有式(IV)、(V)、(VI)和(VII)的结构。
• Direct synthesis of anilines and nitrosobenzenes from phenols
  作者：A. H. St. Amant、C. P. Frazier、B. Newmeyer、K. R. Fruehauf、J. Read de Alaniz

  DOI：10.1039/c6ob00073h

  日期：——

  A one-pot synthesis of anilines and nitrosobenzenes from phenols has been developed using an ipso-oxidative aromatic substitution (iSOAr) process. The products are obtained in good yields under mild and metal-free conditions. The leaving group effect on reactions that proceed through mixed quionone monoketals has also been investigated and a predictive model has been established.

  已经使用ipso-氧化性芳族取代（i S O Ar）方法开发了一种从苯酚一锅合成苯胺和亚硝基苯的方法。在温和且不含金属的条件下，可以以高收率获得产品。还研究了离去基团对通过混合的醌酮单缩酮进行的反应的影响，并建立了预测模型。
• Sporolide B: synthetic studies
  作者：Jeffery A. Gladding、James P. Bacci、Scott A. Shaw、Amos B. Smith

  DOI：10.1016/j.tet.2011.04.094

  日期：2011.9

  Studies directed toward the synthesis of the architecturally complex marine natural product sporolide B are described. Synthetic analysis suggested advanced hydroquinone and benzodiquinane fragments, which upon elaboration were successfully united via an ester linkage. Macrocyclization studies were then carried out, and although a novel macrocyclization product was obtained, subsequent studies revealed

  描述了针对结构复杂的海洋天然产物孢子内酯 B 合成的研究。合成分析表明，先进的氢醌和苯二喹烷碎片在精心设计后通过酯键成功结合。然后进行了大环化研究，虽然获得了一种新的大环化产品，但随后的研究表明，C(6) 和 C(10) 处的叔羟基在空间上受阻，无法参与成功的大环化以提供孢子内酯 B。
• Ph₃P-mediated highly selective C(α)–P coupling of quinone monoacetals with R₂P(O)H: convenient and practical synthesis of <i>ortho</i>-phosphinyl phenols
  作者：Ruwei Shen、Ming Zhang、Jing Xiao、Chao Dong、Li-Biao Han

  DOI：10.1039/c8gc02918k

  日期：——

  A highly selective Ph3P-mediated C(α)–P coupling reaction of quinone monoacetals with secondary phosphine oxides is developed to provide an effective method for the synthesis of a wide array of ortho-phosphinylphenols in good to excellent yields. This protocol can be adopted for scale-up synthesis directly from cheap and abundant phenols, and the products can be easily obtained in high yields by simple

  已开发出一种高选择性的Ph 3 P介导的醌单缩醛与仲氧化膦的C（α）-P偶联反应，为合成多种正膦基苯酚提供了一种有效的方法，收率好至极好。该方案可直接用于由廉价和丰富的苯酚进行大规模合成，并且无需使用有机萃取或色谱法即可通过简单的过滤轻松轻松地以高收率获得产物。
• A Variation of the Fischer Indolization Involving Condensation of Quinone Monoketals and Aliphatic Hydrazines
  作者：Jinzhu Zhang、Zhiwei Yin、Patrick Leonard、Jing Wu、Kate Sioson、Che Liu、Robert Lapo、Shengping Zheng

  DOI：10.1002/anie.201207533

  日期：2013.2.4

  new twist: A one‐pot nitrous acid free, diazonium‐free, and transition‐metal‐free variation of the Fischer indole synthesis has been developed. Condensation of quinone monoketals and aliphatic hydrazine hydrochlorides afforded indoles via intermediate alkylaryldiazenes. This method will complement the classical Fischer indole synthesis by providing indoles in two steps from widely available phenols

  一个新的转折：已开发出Fischer吲哚合成的一锅无亚硝酸，无重氮和无过渡金属的变体。醌单缩酮和脂族肼盐酸盐的缩合通过中间体烷基芳基二氮烯得​​到吲哚。该方法将在温和的条件下从两步制得的苯酚中分两步提供吲哚，从而补充了经典的Fischer吲哚合成方法。