1,1-双-(4-氟苯基)-1,3-丁二烯 | 3888-61-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,1-双-(4-氟苯基)-1,3-丁二烯
• 英文名称: 4,4'-(buta-1,3-diene-1,1-diyl)bis(fluorobenzene)
• 英文别名: 1,1-Bis(4-fluorophenyl)-buta-1,3-diene；1-fluoro-4-[1-(4-fluorophenyl)buta-1,3-dienyl]benzene
• CAS: 3888-61-7
• 化学式: C₁₆H₁₂F₂
• 分子量: 242.268
• InChiKey: JTACHUIAXFOWNK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2903999090

反应信息

• 作为反应物：
  描述：

  4-羟基-N-甲基-2-喹啉 、 1,1-双-(4-氟苯基)-1,3-丁二烯 在 manganese(III) triacetate dihydrate 作用下， 以 溶剂黄146 为溶剂， 反应 3.0h， 以58%的产率得到2-[2,2-bis(4-fluorophenyl)ethenyl]-3,5-dihydro-5-methylfuro[3,2-c]quinolin-4(2H)-one
  参考文献：
  名称：

  Mn(III)-based reaction of alkenes with quinolinones. Formation of peroxyquinolinones and quinoline-related derivatives

  摘要：

  The reactions of 1,1-disubstituted alkenes with 4-hydroxyquinolin-2(1H)-ones under both Mn(III)-catalyzed aerobic oxidation conditions at room temperature and Mn(III)-mediated oxidation conditions at reflux temperature are described. The Mn(III)-catalyzed aerobic oxidation afforded bis(hydroperoxyethyl)quinolinones and azatrioxa[4.431propellanes, while the oxidation with Mn(OAc)(3)center dot 2H(2)O produced furo[3,2-c]quinolin-4-one analogues. The existence of a substituent at the 3-position of the 4-hydroxyquinolin-2(1H)-ones prevented a double reaction with the alkenes, and (endoperoxy)quinolinones and/or (hydroperoxyethyl)quinolinones were obtained under the Mn(III)-catalyzed aerobic conditions, while furo[3,2-c]quinolinone hemiacetals and vinylquinolinones were selectively produced under the Mn(III)-mediated oxidation conditions depending on the reaction temperature and times. Cyclic assembly of quinolinone-related 1,3-dicarbonyl compounds such as dihydropyridinones, pyranones, and dimedone derivatives was also examined under elevated temperature conditions. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.01.013
• 作为产物：
  描述：

  4,4'-二氟二苯甲酮 在 manganese(IV) oxide 、 potassium tert-butylate 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 1,1-双-(4-氟苯基)-1,3-丁二烯
  参考文献：
  名称：

  可见光驱动的 1,3-二烯与有机卤化物和 CO2 的区域选择性碳羧化

  摘要：

  利用光将二氧化碳 (CO 2 ) 转化为增值精细化学品是一种有吸引力的合成策略。在此，我们报道了一种前所未有的可见光驱动的 1,3-二烯与 CO 2的区域选择性碳羧化反应。在温和条件下使用芳基卤化物和烷基卤化物以及低成本甲酸钾 (HCOOK) 来产生二氧化碳自由基阴离子，作为具有挑战性的有机卤化物还原的有效还原剂。用 1,1-二芳基取代的 1,3-二烯实现了高度的 3,4-区域选择性碳羧化，而用受阻较小的单芳基取代的 1,3-二烯获得了主要的 1,4-碳羧化产物。该协议提供了一种从容易获得的 1,3-二烯和具有 CO 2的有机卤化物中生产复杂 β、γ-不饱和羧酸的快速方法。

  DOI：

  10.1039/d2gc01256a

文献信息

• Pd(0)-catalyzed cross-coupling of allyl halides with α-diazocarbonyl compounds or N-mesylhydrazones: synthesis of 1,3-diene compounds
  作者：Kang Wang、Shufeng Chen、Hang Zhang、Shuai Xu、Fei Ye、Yan Zhang、Jianbo Wang

  DOI：10.1039/c6ob00454g

  日期：——

  With palladium catalysis, allyl bromides or chlorides react with α-diazocarbonyl compounds or N-mesylhydrazones to afford 1,3-diene derivatives. The reaction represents a novel and efficient method for the synthesis of 1,3-butadiene derivatives. Mechanistically, the reaction is proposed to follow a pathway involving the formation of a π-allylic palladium carbene complex and subsequent migratory insertion

  在钯催化下，烯丙基溴或氯化物与α-重氮羰基化合物或N-甲磺酰基hydr反应生成1，3-二烯衍生物。该反应代表了一种新颖且有效的合成1,3-丁二烯衍生物的方法。从机理上讲，建议该反应遵循包括形成π-烯丙基钯卡宾配合物和随后的迁移插入的途径。
• Cyclopropylmethyl Palladium Species from Carbene Migratory Insertion: New Routes to 1,3-Butadienes
  作者：Lei Zhou、Fei Ye、Yan Zhang、Jianbo Wang

  DOI：10.1021/ol2034405

  日期：2012.2.3

  Cyclopropylmethyl palladium species can be accessed by Pd-catalyzed reaction of either cyclopropyl N-tosylhydrazone with halide or N-tosylhydrazone with cyclopropyl halide. In both approaches migratory insertion of Pd carbene is the key process. These transformations constitute new approaches toward 1,3-butadiene derivatives.

  环丙基甲基钯物质可通过环丙基N-甲苯磺酰to与卤化物或N-甲苯磺酰with与环丙基卤化物的Pd催化反应获得。在这两种方法中，Pd卡宾的迁移插入都是关键过程。这些转变构成了针对1,3-丁二烯衍生物的新方法。
• Cooperative N-Heterocyclic Carbene/Nickel-Catalyzed Hydroacylation of 1,3-Dienes with Aldehydes in Water
  作者：Hao Liu、You-Feng Han、Zhong-Hua Gao、Chun-Lin Zhang、Congyang Wang、Song Ye

  DOI：10.1021/acscatal.1c05517

  日期：2022.2.4

  carbene/nickel-catalyzed redox-neutral hydroacylation of 1,3-dienes with aldehydes in water was reported. A wide range of aliphatic and aromatic aldehydes were directly coupled with 1,3-dienes, providing synthetically useful β,γ-unsaturated ketones or the corresponding ketones after hydrogenation in moderate to high yields and high atom economy. This protocol first demonstrated the compatibility of NHC catalysis

  报道了1,3-二烯与醛在水中的协同N-杂环卡宾/镍催化的氧化还原中性氢化酰化。多种脂肪族和芳香族醛与 1,3-二烯直接偶联，以中等至高产率和高原子经济性提供合成有用的β,γ-不饱和酮或氢化后的相应酮。该协议首先证明了 NHC 催化与镍催化的相容性。水被用作唯一的溶剂，这在协同金属/有机催化体系中很少被报道。
• Synthesis of Structurally Diverse Allylsilanes via Copper-Catalyzed Regiodivergent Hydrosilylation of 1,3-Dienes
  作者：Zi-Lu Wang、Ying Wang、Jian-Lin Xu、Meng Zhao、Kai-Yang Dai、Cui-Cui Shan、Yun-He Xu

  DOI：10.1021/acs.orglett.1c01455

  日期：2021.6.18

  hydrosilylation reactions of substituted 1,3-dienes with hydrosilanes have been developed. The 1,2- and 1,4-hydrosilylations of 1-(hetero)aryl-substituted 1,3-dienes were highly selectively controlled via variation of the catalytic systems. Meanwhile, the 1,4-hydrosilylation reaction of 2-aryl-substituted 1,3-dienes with diphenylsilane was also successfully realized for the first time. These methods provide convenient

  已经开发了取代 1,3-二烯与氢硅烷的前所未有的铜催化区域发散氢化硅烷化反应。1-（杂）芳基取代的 1,3-二烯的 1,2- 和 1,4-氢化硅烷化反应通过催化系统的变化被高度选择性地控制。同时，2-芳基取代的1,3-二烯与二苯基硅烷的1,4-氢化硅烷化反应也首次成功实现。这些方法为合成结构多样的烯丙基硅烷提供了方便和有效的方法。
• Selective C–C Bond Activation of 2-Aryl-1-methylenecyclopropanes Promoted by Ir(I) and Rh(I) Hydrido Complexes. Mechanism of Ring-Opening Isomerization of the Strained Molecules
  作者：Yasushi Nishihara、Chikako Yoda、Masumi Itazaki、Kohtaro Osakada

  DOI：10.1246/bcsj.78.1469

  日期：2005.8

  [IrH(CO)(PPh3)3] promotes ring opening of 2-phenyl-1-methylenecyclopropane at room temperature to produce the Ir complex with a chelating 2-phenyl-3-butenyl ligand, [Irη2-CH2CH(Ph)CH=CH2-κC1}(CO)(PPh3)2] (1). The reaction of excess 2-phenyl-1-methylenecyclopropane with [IrH(CO)(PPh3)3] at 50 °C yields [Irη2-(o-C6H4)CH(Me)CH=CH2-κC1}(CO)(PPh3)2] (2), accompanied by the formation of 1-phenyl-1,3-butadiene and 2-phenyl-1,3-butadiene. 2,2-Diphenyl-1-methylenecyclopropane reacts with [IrH(CO)(PPh3)3] to afford [Irη2-CH2CPh2CH=CH2-κC1}(CO)(PPh3)2] (3) at 50 °C and [Irη2-(o-C6H4)CMe(Ph)CH=CH2-κC1}(CO)(PPh3)2] (4) at 100 °C. Heating a solution of 3 at 100 °C also forms 4 quantitatively. X-ray crystallography of 3 reveals a penta-coordinated structure around the Ir center bonded to a chelating 2,2-diphenyl-3-butenyl ligand. The reactions of 2,2-diphenyl-1-methylenecyclopropane and of 2,2-di(4-fluorophenyl)-1-methylenecyclopropane with [RhH(CO)(PPh3)3] at room temperature yield [Rhη2-CH2CAr2CH=CH2-κC1}(CO)(PPh3)2] (5a: Ar = Ph, 5b: Ar = C6H4-F-4). The reactions at 50 °C cause ring opening of the substrate and orthometalation of the phenyl group to afford [Rhη2-(o-C6H4)CMe(Ph)CH=CH2-κC1}(CO)(PPh3)2] (6a) and [Rhη2-(o-C6H3-F-4)CMe(C6H4-F-4)CH=CH2-κC1}(CO)(PPh3)2] (6b), respectively. Formation of 1,1-diaryl-1,3-butadiene is observed during the reaction. Heating a solution of 5a at 50 °C produces 1,1-diphenyl-1,3-butadiene and an allylrhodium complex, 8, rather than 6a, although the reaction of excess 2,2-diphenyl-1-methylenecyclopropane with 5a at 50 °C affords 6a in 60%. The mechanisms of the above reactions are discussed based on the products and reaction rates. Coordination of P(OMe)3 to the Rh center of 5a causes insertion of the CO ligand into the Rh–C bond to afford [Rhη2-CO-CH2CPh2CH=CH2-κC1}(P(OMe)3)3] (7).

  [IrH(CO)(PPh3)3] 可促进 2-苯基-1-亚甲基环丙烷在室温下开环，生成带有 2-苯基-3-丁烯基螯合配体的 Ir 复合物 [Irη2-CH2CH(Ph)CH=CH2-κC1}(CO)(PPh3)2] (1)。过量的 2-苯基-1-亚甲基环丙烷与[IrH(CO)(PPh3)3]在 50 °C下反应生成[Irη2-(o-C6H4)CH(Me)CH=CH2-κC1}(CO)(PPh3)2](2)，同时生成 1-苯基-1,3-丁二烯和 2-苯基-1,3-丁二烯。2,2-二苯基-1-亚甲基环丙烷与[IrH(CO)(PPh3)3]反应，在 50 °C 时生成[Irη2-CH2CPh2CH=CH2-κC1}(CO)(PPh3)2](3)，在 100 °C 时生成[Irη2-(o-C6H4)CMe(Ph)CH=CH2-κC1}(CO)(PPh3)2](4)。在 100 °C 下加热 3 的溶液也能定量生成 4。3 的 X 射线晶体学显示，围绕与 2,2-二苯基-3-丁烯基螯合配体成键的 Ir 中心，存在五配位结构。室温下，2,2-二苯基-1-亚甲基环丙烷和 2,2-二（4-氟苯基）-1-亚甲基环丙烷与[RhH(CO)(PPh3)3]反应生成[Rhη2-CH2CAr2CH=CH2-κC1}(CO)(PPh3)2]（5a：Ar = Ph，5b：Ar = C6H4-F-4）。在 50 °C下反应会导致底物开环和苯基正金属化，分别生成[Rhη2-(o-C6H4)CMe(Ph)CH=CH2-κC1}(CO)(PPh3)2](6a)和[Rhη2-(o-C6H3-F-4)CMe(C6H4-F-4)CH=CH2-κC1}(CO)(PPh3)2](6b)。在反应过程中观察到 1,1-二芳基-1,3-丁二烯的形成。在 50 °C下加热 5a 的溶液会生成 1,1-二苯基-1,3-丁二烯和烯丙基铑络合物 8，而不是 6a，不过在 50 °C下将过量的 2,2-二苯基-1-亚甲基环丙烷与 5a 反应会生成 60%的 6a。根据产物和反应速率对上述反应的机理进行了讨论。P(OMe)3 与 5a 的 Rh 中心配位，导致 CO 配体插入 Rh-C 键，生成 [Rhη2-CO-CH2CPh2CH=CH2-κC1}(P(OMe)3)3] (7)。