3-溴-2,5-二苯基呋喃 | 1487-09-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃
• 中文名称: 3-溴-2,5-二苯基呋喃
• 英文名称: 3-Bromo-2,5-diphenylfuran
• 英文别名: 3-bromo-2,5-diphenyl-furan；3-Brom-2,5-diphenyl-furan
• CAS: 1487-09-8
• 化学式: C₁₆H₁₁BrO
• 分子量: 299.167
• InChiKey: WUBRVLIZSPCIBS-UHFFFAOYSA-N

物化性质

• 熔点：
  77 °C(Solv: methanol (67-56-1))
• 沸点：
  358.8±37.0 °C(Predicted)
• 密度：
  1.366±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  13.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-溴-2,5-二苯基呋喃 在 氯化亚砜 、 乙醚 、 magnesium 作用下， 生成 2,5-diphenyl-furan-3-carbonyl chloride
  参考文献：
  名称：

  抗疟药；2,5-二苯基-3-呋喃基氨基酮和醇。

  摘要：

  DOI：

  10.1021/ja01184a022
• 作为产物：
  描述：

  4-nitro-1,4-diphenyl-butan-1-one 在 溴 、 sodium methylate 、 溶剂黄146 作用下， 生成 3-溴-2,5-二苯基呋喃
  参考文献：
  名称：

  Allen; Bridgess, Journal of the American Chemical Society, 1929, vol. 51, p. 2155

  摘要：

  DOI：

文献信息

• Zirconium-redox-shuttled cross-electrophile coupling of aromatic and heteroaromatic halides
  作者：Ting-Feng Wu、Yue-Jiao Zhang、Yue Fu、Fang-Jie Liu、Jian-Tao Tang、Peng Liu、F. Dean Toste、Baihua Ye

  DOI：10.1016/j.chempr.2021.06.007

  日期：2021.7

  palladium-catalyzed processes. The zirconaaziridine-mediated palladium (ZAPd)-catalyzed reaction shows excellent compatibility with various functional groups and diverse heteroaromatic scaffolds. In accord with density functional theory (DFT) calculations, a redox transmetallation between the oxidative addition product and the zirconaaziridine is proposed as the crucial elementary step. Thus, cross-coupling selectivity

  过渡金属催化的交叉亲电偶联 (XEC) 是锻造 C(sp 2 )–C(sp 2 ) 的有力工具) 联芳基分子中来自丰富芳族卤化物的键。虽然通过多金属 XEC 合成不对称联芳基化合物具有很高的合成价值，但两种杂芳族卤化物的选择性 XEC 仍然难以捉摸且具有挑战性。在这里，我们报告了一种均相 XEC 方法，该方法依赖于锆氮丙啶配合物作为双钯催化过程的穿梭。锆氮丙啶介导的钯 (ZAPd) 催化反应显示出与各种官能团和各种杂芳族支架的良好相容性。根据密度泛函理论 (DFT) 计算，氧化加成产物和锆氮丙啶之间的氧化还原金属转移被认为是关键的基本步骤。因此，使用单一过渡金属催化剂的交叉偶联选择性由 Pd(0) 氧化加成到芳族卤化物的相对速率控制。总体而言，组合还原剂和金属转移剂的概念为过渡金属还原偶联催化的发展提供了机会。
• One-step synthesis of 5-acylisothiazoles from furans
  作者：Jérôme Guillard、Christelle Lamazzi、Otto Meth-Cohn、Charles W. Rees、Andrew J. P. White、David J. Williams

  DOI：10.1039/b101157j

  日期：——

  Premixed ethyl carbamate, thionyl chloride and pyridine (which generate thiazyl chloride, NSCl) in boiling benzene or toluene convert 2,5- and 2,3,5-substituted furans into 5-acylisothiazoles regiospecifically. The reactions are much faster and generally higher yielding in boiling chlorobenzene with more thionyl chloride and with pyridine or isoquinoline as base. Under the more vigorous conditions, even fully substituted 3-bromofurans give isothiazoles, with the displacement of bromine. Deactivated furans, with electron-withdrawing groups such as ester, cyano, benzoyl and phenylsulfonyl in the α-position, react under the more vigorous conditions to give 5-acylisothiazoles with the electronegative group in the 3-position. The ‘activated’ 2-methyl-5-phenyl- and 5-phenyl-2-phenylthio-furans react analogously, with the more electron-releasing group becoming part of the 5-acyl substituent, exclusively or predominantly. These results are explained by initial electrophilic attack of the furan ring to give a β-thiazyl derivative which spontaneously ring-opens and closes to the isothiazole. The X-ray structures of five of the differently substituted isothiazole compounds are reported. All have very similar patterns of bonding within their isothiazole rings that appear to be independent of the electron-withdrawing or -donating nature of the substituents. Three of the compounds (8a, 8g and 13) have loosely linked chain structures in the solid state, adjacent molecules being connected by combinations of hydrogen bonding and π–π stacking interactions.

  预混的乙基氨基甲酸、亚硫酰氯和吡啶（生成噻唑氯，NSCl）在沸腾的苯或甲苯中能够进行区域特异性地将2,5-和2,3,5-取代的呋喃转化为5-酰基异噻唑。在沸腾的氯苯中，反应更快，产率普遍更高，且使用了更多的亚硫酰氯及吡啶或异喹啉作为碱。在更激烈的反应条件下，甚至完全取代的3-溴呋喃也能与溴发生取代反应生成异噻唑。对于那些带有电子吸引基团（如酯、氰、苯甲酰和苯磺酰）且位于α位的非活性呋喃，在较为激烈的条件下也能反应，生成5-酰基异噻唑，其中电负性基团位于3位。这些“活化”型的2-甲基-5-苯基和5-苯基-2-苯硫基呋喃也表现出类似的反应，其中电子供给基团会独占或主导成为5-酰基取代基。其结果可以通过呋喃环的初始亲电攻击解释，生成β-噻唑衍生物，随后自发环打开并闭合成异噻唑。报告了五种不同取代异噻唑化合物的X射线结构，所有化合物在其异噻唑环内的键合模式非常相似，似乎与取代基的电子吸引或供给特性无关。三种化合物（8a、8g和13）在固态下具有松散联接的链结构，邻近的分子通过氢键和π–π堆叠相互作用相连。
• Reaction of furans with trithiazyl trichloride: a new synthesis of isothiazoles
  作者：Xiao-Lan Duan、Ross Perrins、Charles W. Rees

  DOI：10.1039/a700358g

  日期：——

  Trithiazyl trichloride 1 converts 2,5-diphenylfuran into 5-benzoyl-3-phenylisothiazole 2 regiospecifically and in high yield. This is a new ring opening of furans and a new synthesis of isothiazoles. 2,5-Bis(4-methylphenyl)furan, 3-bromo-2,5-diphenylfuran, 2,3,5-triphenylfuran, 2,5-di-tert-butylfuran and its 3-chloro and 3-bromo derivatives react in an entirely analogous manner to give the corresponding isothiazoles (55–85%) in synthetically useful, one-pot, conversions. 2,5-Diphenylthiophene reacts more slowly with the trimer 1 to give the same product, 2, as the corresponding furan, probably by oxidation of the analogous thiobenzoyl compound by the reagent, which is shown to oxidise thiobenzophenone to benzophenone very rapidly. Tetraphenylcyclopentadienone 8 reacts rapidly with the trimer to give 3,4,5,6-tetraphenyl-2(1H)-pyridone 10 (56%). Possible mechanisms in which the monomer, Cl–SN, is the reacting species are proposed for all of these reactions.

  三氮化氯化物1使2,5-二苯基呋喃转化为具有区域选择性和高得率的5-苯甲酰-3-苯基异噻唑2。这是呋喃的新环开化和异噻唑的新合成。2,5-双(4-甲基苯基)呋喃、3-溴-2,5-二苯基呋喃、2,3,5-三苯基呋喃、2,5-二叔丁基呋喃及其3-氯和3-溴衍生物以完全类似的方式反应，生成相应的异噻唑（55-85%），实现合成上有用的一锅法转化。2,5-二苯基噻吩与三聚物1的反应速度较慢，生成相同的产物2，可能是由于该试剂对类似的噻苯乙酰化合物的氧化，已证明其能迅速将噻苯基酮氧化为苯基酮。四苯基环戊二烯酮8与三聚物迅速反应，生成3,4,5,6-四苯基-2(1H)-吡啶酮10（56%）。对于所有这些反应，提出了单体Cl–SN作为反应物种的可能机制。
• Reaction of furans with trithiazyl trichloride: new synthesis of isothiazoles
  作者：Xiao-Lan Duan、Charles W. Rees、Tai-Yuen Yue

  DOI：10.1039/a608345e

  日期：——

  Trithiazyl trichloride 1 converts 2,5-disubstituted furans into isothiazoles (e.g. 3, 6, 7) regiospecifically and in good yield, providing a new, one-step synthesis of isothiazoles, for which a novel mechanism involving formation and ring-opening of a β-thiazylfuran 4 is proposed.

  三噻唑三氯化物 1 可将 2,5 二甲基呋喃转化为异噻唑（如 3、6、7），且具有区域特异性和良好的收率，为异噻唑的一步法合成提供了一种新方法。
• The Ready Conversion of 2,5-Disubstituted Furans into Isothiazoles
  作者：Sean M. Laaman、Otto Meth-Cohn、Charles W. Rees

  DOI：10.1055/s-1999-3480

  日期：1999.5

  Various 2,5-disubstituted furans are very readily and efficiently transformed into 5-acyl-3-substituted isothiazoles by the action of ethyl carbamate, thionyl chloride and pyridine.

  在氨基甲酸乙酯、亚硫酰氯和吡啶的作用下，各种 2,5-二取代呋喃很容易高效地转化为 5-酰基-3-取代异噻唑。