6-溴-3,3-二苯基-2-苯并呋喃-1-酮 | 60573-65-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 中文名称: 6-溴-3,3-二苯基-2-苯并呋喃-1-酮
• 英文名称: 6-bromo-3,3-diphenyl-3H-isobenzofuran-1-one
• 英文别名: 6-bromo-3,3-diphenyl-phthalide；6-Brom-3,3-diphenyl-phthalid；5-Brom-1,1-diphenylphthalid；6-Bromo-3,3-diphenyl-2-benzofuran-1(3H)-one；6-bromo-3,3-diphenyl-2-benzofuran-1-one
• CAS: 60573-65-1
• 化学式: C₂₀H₁₃BrO₂
• 分子量: 365.226
• InChiKey: YZMJLJWCRFJSLM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,5-二溴苯甲酸 在 sodium hydroxide 、 氯化亚砜 、 苯基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 11.5h， 生成 6-溴-3,3-二苯基-2-苯并呋喃-1-酮
  参考文献：
  名称：

  Selectivities in reactions of organolithium reagents with aryl bromides which bear proton-donating groups

  摘要：

  Studies of substrates which offer an acidic hydrogen and an aryl bromide for reaction with an organolithium reagent have been carried out with a series of benzene bromo amides and bromo anilides as well as selected benzene bromo carboxylic acids, bromoanilines, and bromobenzylamines. A representative example is the reaction of N-ethyl-N-deutero-o-bromobenzamide (6-d) with 1-lithio-3-phenylpropane to give N-ethyl-o-deuterobenzamide (46%, 94%-d) (7-d), N-ethyl-o-bromobenzamide (6)(49%), 3-deutero-1-phenylpropane(51%, 92%-d), and 1-bromo-3-phenylpropane (48%). Product formation in this and related cases is explained by the operation of a two step sequence in which an initial deprotonation is followed by a bromine-lithium exchange which is accelerated with respect to mixing. Such a sequence is consistent with the results of deuterium labeling and with changes in product ratios on different mixing and with differently aggregated organolithium reagents. Support is provided for the operation of two pathways for the expedited bromine-lithium exchange reactions. In one pathway a high local concentration of the organolithium reagent promotes rapid reaction and in the second the exchange reaction occurs within an initially formed complex. The selectivity for removal of a bromine ortho to a lithiated carboxamide is found to be 5-8 with n-butyllithium, and satisfactory synthetic ortho selectivity is obtained for N-ethyl-2,5-dibromobenzamide with phenyllithium.

  DOI：

  10.1021/jo00078a007

文献信息

• Facile Synthesis of Phthalides from Methyl <i>ortho</i>-Iodobenzoates and Ketones via an Iodine–Magnesium Exchange Reaction Using a Silylmethyl Grignard Reagent
  作者：Yu Nakamura、Suguru Yoshida、Takamitsu Hosoya

  DOI：10.1246/cl.170211

  日期：2017.6.5

  Phthalides have been easily prepared by the treatment of methyl o-iodobenzoates with a silylmethyl Grignard reagent in the presence of ketones. The electron-withdrawing ester moiety of methyl o-iodobenzoates and the low nucleophilicity of the silylmethyl Grignard reagent prompted a smooth iodine–magnesium exchange reaction, at room temperature, without affecting the ester moiety or resulting in an

  在酮的存在下，用甲硅烷基甲基格氏试剂处理邻碘苯甲酸甲酯很容易制备邻苯二甲酸酯。邻碘苯甲酸甲酯的吸电子酯部分和甲硅烷基甲基格氏试剂的低亲核性促使碘-镁交换反应在室温下顺利进行，不会影响酯部分或导致与亲电酮发生不希望的反应。这种简单的方法不需要对反应温度进行特殊控制，可以合成各种苯酞，包括酚酞衍生物。
• Oxidative lactonization of C(sp3)-H bond in methyl aromatic alcohols enabled by proton-coupled electron transfer
  作者：Shanyi Chen、Qihong Lai、Chao Liu、Hui Liu、Mingqiang Huang、Shunyou Cai

  DOI：10.1007/s11426-022-1283-7

  日期：2022.8

  Direct functionalization of inert C(sp3)-H bonds in pharmaceutically significant compounds is very important in modern synthetic organic chemistry. In this article, we disclose a practical and efficient method for the oxidative lactonization of benzylic C(sp3)-H bonds enabled by the synergistic interactions of organic dye-type rose bengal, n-Bu4N·Br, O2 and Na2HPO4 under visible light irradiation.

  在药学上显着的化合物中惰性 C(sp 3 )-H 键的直接官能化在现代合成有机化学中非常重要。在本文中，我们公开了一种通过有机染料型玫瑰红、n -Bu 4 N·Br、O 2和 Na的协同作用实现苄基 C(sp 3 )-H 键氧化内酯化的实用且有效的方法。 2高压氧4在可见光照射下。该反应不需要过渡金属催化剂或强氧化剂。已经合成了一系列结构多样的苯酞，具有优异的选择性和高官能团相容性。该反应在制备结构复杂的苯酞的后期应用证明了其合成效用。
• Stephens, Journal of the American Chemical Society, 1921, vol. 43, p. 1952
  作者：Stephens

  DOI：——

  日期：——
• Selectivities in reactions of organolithium reagents with aryl bromides which bear proton-donating groups
  作者：Peter Beak、Timothy J. Musick、Chao Liu、Thomas Cooper、Donald J. Gallagher

  DOI：10.1021/jo00078a007

  日期：1993.12

  Studies of substrates which offer an acidic hydrogen and an aryl bromide for reaction with an organolithium reagent have been carried out with a series of benzene bromo amides and bromo anilides as well as selected benzene bromo carboxylic acids, bromoanilines, and bromobenzylamines. A representative example is the reaction of N-ethyl-N-deutero-o-bromobenzamide (6-d) with 1-lithio-3-phenylpropane to give N-ethyl-o-deuterobenzamide (46%, 94%-d) (7-d), N-ethyl-o-bromobenzamide (6)(49%), 3-deutero-1-phenylpropane(51%, 92%-d), and 1-bromo-3-phenylpropane (48%). Product formation in this and related cases is explained by the operation of a two step sequence in which an initial deprotonation is followed by a bromine-lithium exchange which is accelerated with respect to mixing. Such a sequence is consistent with the results of deuterium labeling and with changes in product ratios on different mixing and with differently aggregated organolithium reagents. Support is provided for the operation of two pathways for the expedited bromine-lithium exchange reactions. In one pathway a high local concentration of the organolithium reagent promotes rapid reaction and in the second the exchange reaction occurs within an initially formed complex. The selectivity for removal of a bromine ortho to a lithiated carboxamide is found to be 5-8 with n-butyllithium, and satisfactory synthetic ortho selectivity is obtained for N-ethyl-2,5-dibromobenzamide with phenyllithium.