Names | |||
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Preferred IUPAC name Hexafluorobenzene | |||
Other names Perfluorobenzene | |||
Identifiers | |||
3D model (JSmol) | |||
Abbreviations | HFB | ||
1683438 | |||
ChEBI | |||
ChemSpider | |||
ECHA InfoCard | 100.006.252 | ||
EC Number |
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101976 | |||
PubChem CID | |||
UNII | |||
CompTox Dashboard (EPA) | |||
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Properties | |||
C6F6 | |||
Molar mass | 186.056 g·mol−1 | ||
Appearance | Colorless liquid | ||
Density | 1.6120 g/cm3 | ||
Melting point | 5.2 °C (41.4 °F; 278.3 K) | ||
Boiling point | 80.1 °C (176.2 °F; 353.2 K) | ||
Refractive index (nD) | 1.377 | ||
Viscosity | cP (1.200 mPa•s) (20 °C) | ||
0.00 D (gas) | |||
Hazards [1] | |||
GHS labelling: | |||
Warning | |||
H225 | |||
P210, P233, P240, P241, P242, P243 | |||
Flash point | 10 °C (50 °F; 283 K) [2] | ||
Related compounds | |||
Related compounds | Benzene Hexachlorobenzene Polytetrafluoroethylene Perfluorotoluene | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Hexafluorobenzene, HFB, C
6F
6, or perfluorobenzene is an organofluorine compound. In this derivative of benzene, all hydrogen atoms have been replaced by fluorine atoms. The technical uses of the compound are limited, although it has some specialized uses in the laboratory owing to distinctive spectroscopic properties.
Hexafluorobenzene stands somewhat aside in the perhalogenbenzenes. When counting for bond angles and distances it is possible to calculate the distance between two ortho fluorine atoms. Also the non bonding radius of the halogens is known. The following table presents the results: [3]
Formula | Name | Calculated inter-halogen distance, aromatic ring assumed planar | Twice nonbonding radius | Consequent symmetry of the benzene |
---|---|---|---|---|
C6F6 | hexafluorobenzene | 279 | 270 | D6h |
C6Cl6 | hexachlorobenzene | 312 | 360 | D3d |
C6Br6 | hexabromobenzene | 327 | 390 | D3d |
C6I6 | hexaiodobenzene | 354 | 430 | D3d |
Hexafluorobenzene is the only perhalobenzene being planar, the other perhalobenzene species exhibiting buckling. As a consequence, in C6F6 the overlap between the p-orbitals is optimal versus the other perhalobenzenes, resulting in lower aromaticity of those compounds compared to C6F6.
The direct synthesis of hexafluorobenzene from benzene and fluorine has not been useful. Instead it is prepared by the reaction of alkali-fluorides with halogenated benzene: [4]
Most reactions of hexafluorobenzene proceed with displacement of fluoride. One example is its reaction with sodium hydrosulfide to afford pentafluorothiophenol: [5]
The reaction of pentafluorophenyl derivatives has been long puzzling for its mechanism. Independent of the substituent, they all exhibit a para directing effect. The new introduced group too has no effect on the directing behaviour. In all cases, a 1,4-disubstituted-2,3,5,6-tetrafluorobenzene derivative shows up. Finally, the clue is found not in the nature of the non-fluorine substituent, but in the fluorines themselves. The π-electropositive effect introduces electrons into the aromatic ring. The non-fluorine substituent is not capable of doing so. As charge accumulates at the ortho and para positions relative to the donating group, the ortho and para-positions relative to the non-fluorine substituent receive less charge, so are less negative or more positive. Furthermore, the non-fluorine substituent in general is more bulky than fluorine, so its ortho-positions are sterically shielded, leaving the para-position as the sole reaction site for anionic entering groups.
UV light causes gaseous HFB to isomerize to hexafluoro derivative of Dewar benzene. [6]
Hexafluorobenzene has been used as a reporter molecule to investigate tissue oxygenation in vivo. It is exceedingly hydrophobic, but exhibits high gas solubility with ideal liquid gas interactions. Since molecular oxygen is paramagnetic it causes 19F NMR spin lattice relaxation (R1): specifically a linear dependence R1= a + bpO2 has been reported. [7] HFB essentially acts as molecular amplifier, since the solubility of oxygen is greater than in water, but thermodynamics require that the pO2 in the HFB rapidly equilibrates with the surrounding medium. HFB has a single narrow 19F NMR signal and the spin lattice relaxation rate is highly sensitive to changes in pO2, yet minimally responsive to temperature. HFB is typically injected directly into a tissue and 19F NMR may be used to measure local oxygenation. It has been extensively applied to examine changes in tumor oxygenation in response to interventions such as breathing hyperoxic gases or as a consequence of vascular disruption. [8] MRI measurements of HFB based on 19F relaxation have been shown to correlate with radiation response of tumors. [9] HFB has been used as a gold standard for investigating other potential prognostic biomarkers of tumor oxygenation such as BOLD (Blood Oxygen Level Dependent), [10] TOLD (Tissue Oxygen Level Dependent) [11] and MOXI (MR oximetry) [12] A 2013 review of applications has been published. [13]
HFB has been evaluated as standard in fluorine-19 NMR spectroscopy. [14]
Hexafluorobenzene may cause eye and skin irritation, respiratory and digestive tract irritation and can cause central nervous system depression per MSDS. [15] The National Institute for Occupational Safety and Health (NIOSH) lists it in its Registry of Toxic Effects of Chemical Substances as neurotoxicant.
Aromatic compounds, also known as "mono- and polycyclic aromatic hydrocarbons", are organic compounds containing one or more aromatic rings. The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were understood. The current definition of aromatic compounds does not have any relation with their odor.
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In electrophilic aromatic substitution reactions, existing substituent groups on the aromatic ring influence the overall reaction rate or have a directing effect on positional isomer of the products that are formed. An electron donating group (EDG) or electron releasing group is an atom or functional group that donates some of its electron density into a conjugated π system via resonance (mesomerism) or inductive effects —called +M or +I effects, respectively—thus making the π system more nucleophilic. As a result of these electronic effects, an aromatic ring to which such a group is attached is more likely to participate in electrophilic substitution reaction. EDGs are therefore often known as activating groups, though steric effects can interfere with the reaction.
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Kenneth Kin Man Kwong is a Hong Kong-born American nuclear physicist. He is a pioneer in human brain imaging. He received his bachelor's degree in Political Science in 1972 from the University of California, Berkeley. He went on to receive his Ph.D. in physics from the University of California, Riverside studying photon-photon collision interactions.
Herbert Sander Gutowsky was an American chemist who was a professor of chemistry at the University of Illinois Urbana-Champaign. Gutowsky was the first to apply nuclear magnetic resonance (NMR) methods to the field of chemistry. He used nuclear magnetic resonance spectroscopy to determine the structure of molecules. His pioneering work developed experimental control of NMR as a scientific instrument, connected experimental observations with theoretical models, and made NMR one of the most effective analytical tools for analysis of molecular structure and dynamics in liquids, solids, and gases, used in chemical and medical research, His work was relevant to the solving of problems in chemistry, biochemistry, and materials science, and has influenced many of the subfields of more recent NMR spectroscopy.
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