Thiophenol
From Wikipedia, the free encyclopedia
| Thiophenol | |
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| IUPAC name | Thiophenol |
| Other names | Benzenethiol |
| Identifiers | |
| CAS number | [108-98-5] |
| RTECS number | DC0525000 |
| SMILES | c1ccccc1S |
| Properties | |
| Molecular formula | C6H6S |
| Molar mass | 110.19 g/mol |
| Appearance | colorless liquid |
| Density | 1.0766 g/mL |
| Melting point |
-15 °C |
| Boiling point |
169 °C |
| Hazards | |
| Main hazards | Toxic |
| R-phrases | R10 R24/25 R26 R41 |
| S-phrases | S23 S26 S28 S36/37/39 S45 |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references |
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Thiophenol is a chemical compound with the formula C6H5SH, and sometimes abbreviated as PhSH. The foul-smelling liquid is the principal aromatic thiol. The chemical structures of thiophenols are analogous to phenols except the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring is replaced by a sulfur atom. The prefix thio- implies a sulfur-containing compound and when used before a root word name for a compound which would normally contain an oxygen atom, thio- commonly means that the oxygen atom is replaced by a sulfur atom.
Thiophenols also describes a class of compounds formally derived from thiophenol itself. All have a sulfhydryl group (-SH) covalently bonded to an aromatic ring. The organosulfur ligand in medicine merthiolate is a thiophenol.
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[edit] Synthesis
Many ways exist to generate thiophenol and related compounds, although thiophenol is usually purchased for laboratory operations.
- Reduction of benzenesulfonyl chloride with zinc.[1]
- Action of elemental sulfur on phenyl magnesium halide or phenyllithium followed by acificiation.
[edit] Properties
[edit] Acidity
Thiophenol has appreciably greater acidity than does phenol. A similar pattern is seen for H2S vs. H2O and all thiols vs. the corresponding alcohols. Treatment of PhSH with strong base such as sodium hydroxide (NaOH) or sodium metal affords the salt sodium thiophenolate (PhSNa). Such salts are readily oxidized.
[edit] Alkylation
The thiophenolate is highly nucleophilic, which translates to an high rate of alkylation.[2] Thus, treatment of C6H5SH with methyl iodide in the presence of a base gives methyl phenyl sulfide, C6H5SCH3, a thioether. Such reactions are fairly irreversible. C6H5SH also adds to α,β-unsaturated carbonyls.
[edit] Oxidation
A substantial difference between sulfur and oxygen is that thiophenolate is oxidized to diphenyl disulfide:
- 2 C6H5SH + 1/2 O2 → C6H5S-SC6H5 + H2O
The disulfide can be reduced back the thiol using sodium borohydride followed by acidification. This redox reaction is also exploited in the use of C6H5SH as a source of H atoms. Of course free H atoms are almost never observed in solution, but C6H5SH delivers the equivalent result by adding H atoms to various substrates.
[edit] Chlorination
Phenylsulfenyl chloride, a blood-red liquid (b.p. 41–42 °C), can be prepared by the reaction of thiophenol with chlorine (Cl2).[3]
[edit] Coordination to metals
Metal cations form thiophenolates, some of which are polymeric. One example is "C6H5SCu," obtained by treating copper(I) chloride with thiophenol.[4]
[edit] Safety
Thiophenol is highly toxic.
[edit] References
- ^ Adams, R.; C. S. Marvel, C. S.. "Thiophenol". Org. Synth.; Coll. Vol. 1: 504.
- ^ Campopiano, O. "Thiophenol" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
- ^ Barrett, A. G. M.; Dhanak, D.; Graboski, G. G.; Taylor, S. J. (1993). "(Phenylthio)nitromethane". Org. Synth.; Coll. Vol. 8: 550.
- ^ Posner, G. H.; Whitten, C. E.. "Secondary and Tertiary Alkyl Ketones from Carboxylic Acid Chlorides and Lithium Phenylthio(alkyl)cuprate Reagents: tert-Butyl Phenyl Ketone". Org. Synth.; Coll. Vol. 6: 248.
