1-fluorocyclobutene | 53661-90-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 1-fluorocyclobutene
• 英文别名: Fluorocyclobutene
• CAS: 53661-90-8
• 化学式: C₄H₅F
• 分子量: 72.0821
• InChiKey: RLMMCBZQTSRCHJ-UHFFFAOYSA-N

物化性质

• 沸点：
  29.5±19.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  cyclopropylfluorocarbene 生成 1-fluorocyclobutene
  参考文献：
  名称：

  Kinetics of alkylhalocarbene rearrangements: modulation by fluorine substituents

  摘要：

  Rate constants were measured by laser flash photolytic methods for hydrogen and carbon 1,2-migrations in four different alkylchlorocarbenes and in the analogous alkylfluorocarbenes. The carbenes, products, and rate constants (s-1) were as follows: phenoxymethylchlorocarbene to (Z)- and (E)-1-chloro-2-phenoxyethene (Z/E approximately 4/1), k = 3.6 x 10(7); phenoxymethylfluorocarbene to (Z)-1-fluoro-2-phenoxyethene (Z/E > 10/1), k = 1.3 x 10(7); neopentylchlorocarbene to (Z)- and (E)-1-tert-butyl-2-chloroethene (Z/E = 1/12), k = 1.4 x 10(7); neopentylfluorocarbene to (Z)- and (E)-1-tert-butyl-2-fluoroethene (Z/E = 1/2.5), k = 2.6 X 10(6); cyclobutylchlorocarbene to 1-chlorocyclopentene (C migration) and chloromethylenecyclobutane (H migration), k(c) = 4.6 X 10(7), k(H) = 2.1 X 10(7); cyclobutylfluorocarbene to 1-fluorocyclopentene (C migration) and fluoromethylenecyclobutane (H migration), k(c) = 1.8 x 10(6), k(H) = 5.3 x 10(5); cyclopropylchlorocarbene to 1-chlorocyclobutene, k = 9 x 10(5); cyclopropylfluorocarbene to 1-fluorocyclobutene, k = 1.4 x 10(5). Activation energies for several of these processes were in the range of 2-4 kcal/mol, with A approximately 10(8)-10(9) s-1.

  DOI：

  10.1021/ja00029a025

文献信息

• Selective Copper Complex-Catalyzed Hydrodefluorination of Fluoroalkenes and Allyl Fluorides: A Tale of Two Mechanisms
  作者：Nicholas O. Andrella、Nancy Xu、Bulat M. Gabidullin、Christian Ehm、R. Tom Baker

  DOI：10.1021/jacs.9b03101

  日期：2019.7.24

  synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalkenes using silanes. In this work it is shown that copper hydride complexes of tertiary phosphorus ligands (L) can be tuned to achieve selective multiple HDF of fluoroalkenes. In one example, HDF of the hexafluoropropene

  向更经济友好的小链氟化基团的转变导致氟烯烃的合成和反应性重新兴起。获得各种商业相关氢氟烯烃的一种通用方法涉及使用硅烷对氟烯烃进行催化加氢脱氟 (HDF)。在这项工作中，表明可以调整叔磷配体 (L) 的氢化铜配合物以实现氟烯烃的选择性多重 HDF。在一个实例中，六氟丙烯二聚体的 HDF 提供了七氟-2-甲基戊烯的单一异构体，其中五个氟已被氢选择性取代。DFT 计算研究表明 L2CuH（双齿或大单齿膦）和 L3CuH（小锥角单齿膦）催化剂具有不同的 HDF 机制，
• A new synthesis of 3-fluoro- and 3-chlorocyclobutenes from dihalocyclobutanes. The five isomers of chlorofluorocyclobutane
  作者：Norman C. Craig、Steven S. Borick、Michael A. Fisher、Thomas R. Tucker、Yong-Zhuang Xiao

  DOI：10.1016/s0022-1139(00)82413-6

  日期：1992.11

  3-Fluorocyclobutene (1) and 3-chlorocyclobutene (2) have been obtained by simpler syntheses and in higher yield than previously reported. One of the synthetic steps involves a three-phase-transfer-catalysis technique that could be of wider utility. New examples are cited of applying AgF2, an underutilized reagent, as a fluorinating agent near room temperature. Compounds 1 and 2 have been characterized by mass, NMR and vibrational spectroscopies. The NMR spectra have been fully analyzed. Useful group frequencies in the vibrational spectra of halocyclobutenes have been identified. The five monochloro-monofluorocyclobutane precursors of fluorocyclobutenes have also been separated and characterized. From NMR coupling constants, conformer mixtures have been identified for three of the isomers.
• Vibrational spectra and assignments for 1-fluoro- and 1-chlorocyclobutenes: revised assignment for cyclobutene
  作者：Norman C. Craig、Steven S. Borick、Thomas R. Tucker、Yong Zhuang Xiao

  DOI：10.1021/j100162a023

  日期：1991.5

  Gas-phase infrared spectra and liquid-phase Raman spectra are presented for 1-chlorocyclobutene and 1-fluorocyclobutene. Complete assignments of vibrational fundamentals are proposed for these molecules of C(s) symmetry. For 1-chlorocyclobutene (cm-1): (a') 3090, 2947, 2940, 1595, 1452, 1434, 1250, 1197, 1165, 1120, 916, 891, 869, 493, 299; (a") 2980, 2966, 1140, 1070, 1016, 854, 751, 395, 211. For 1-fluorocyclobutene (cm-1): (a') 3111, 2954, 2948, 1667, 1464, 1437, 1306, 1214, 1189, 1154, 972, 911, 866, 651, 412; (a") 2982, 2969, 1142, 1076, 1020, 855, 764, 436, 264. Frequencies of CH-rich modes correlate closely for these isotopomer-like molecules. These results along with a Raman spectrum of liquid cyclobutene near -100-degrees-C have provided evidence for assigning five unsettled vibrational fundamentals of cyclobutene. These modes in cm-1 are (a2) nu-9 = 2944, nu-11 = 1011, and nu-12 = 846 and (b1) nu-19 = 903 and nu-20 = 888. Ring-puckering frequencies for a variety of halogen-substituted cyclobutenes are compared and found to follow an understandable pattern.
• Kinetics of alkylhalocarbene rearrangements: modulation by fluorine substituents
  作者：Robert A. Moss、Guo Jie Ho、Weiguo Liu

  DOI：10.1021/ja00029a025

  日期：1992.1

  Rate constants were measured by laser flash photolytic methods for hydrogen and carbon 1,2-migrations in four different alkylchlorocarbenes and in the analogous alkylfluorocarbenes. The carbenes, products, and rate constants (s-1) were as follows: phenoxymethylchlorocarbene to (Z)- and (E)-1-chloro-2-phenoxyethene (Z/E approximately 4/1), k = 3.6 x 10(7); phenoxymethylfluorocarbene to (Z)-1-fluoro-2-phenoxyethene (Z/E > 10/1), k = 1.3 x 10(7); neopentylchlorocarbene to (Z)- and (E)-1-tert-butyl-2-chloroethene (Z/E = 1/12), k = 1.4 x 10(7); neopentylfluorocarbene to (Z)- and (E)-1-tert-butyl-2-fluoroethene (Z/E = 1/2.5), k = 2.6 X 10(6); cyclobutylchlorocarbene to 1-chlorocyclopentene (C migration) and chloromethylenecyclobutane (H migration), k(c) = 4.6 X 10(7), k(H) = 2.1 X 10(7); cyclobutylfluorocarbene to 1-fluorocyclopentene (C migration) and fluoromethylenecyclobutane (H migration), k(c) = 1.8 x 10(6), k(H) = 5.3 x 10(5); cyclopropylchlorocarbene to 1-chlorocyclobutene, k = 9 x 10(5); cyclopropylfluorocarbene to 1-fluorocyclobutene, k = 1.4 x 10(5). Activation energies for several of these processes were in the range of 2-4 kcal/mol, with A approximately 10(8)-10(9) s-1.