Thiophenol

From Wikipedia, the free encyclopedia
Jump to: navigation, search
Thiophenol
Skeletal formula
Ball-and-stick model
Names
Preferred IUPAC name
Benzenethiol
Other names
Thiophenol (no longer recommended[1])
Phenyl mercaptan
Mercaptobenzene
Identifiers
3D model (Jmol)
ChEBI
ChemSpider
ECHA InfoCard 100.003.306
RTECS number DC0525000
UNII
Properties
C6H6S
Molar mass 110.19 g/mol
Appearance colorless liquid, with unpleasant odour.
Density 1.0766 g/mL
Melting point −15 °C (5 °F; 258 K)
Boiling point 169 °C (336 °F; 442 K)
0.08% in water, 25°C[2]
Solubility Most organic solvents; aqueous base
Vapor pressure 1 mmHg (18°C)[2]
Acidity (pKa) 6.62 (H2O),[3] 10 (DMSO)[4]
-70.8·10−6 cm3/mol
Hazards
Main hazards Toxic
R-phrases (outdated) R10 R24/25 R26 R41
S-phrases (outdated) S23 S26 S28 S36/37/39 S45
Flash point 56 °C; 132 °F; 329 K[2]
US health exposure limits (NIOSH):
PEL (Permissible)
none[2]
REL (Recommended)
C 0.1 ppm (0.5 mg/m3) [15-minute][2]
IDLH (Immediate danger)
N.D.[2]
Related compounds
Related thiols
1,2-Benzenedithiol
Benzenemethanethiol
Related compounds
Phenol
Benzeneselenol
Diphenyl disulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
YesY verify (what is YesYN ?)
Infobox references

Thiophenol is an organosulfur compound with the formula C6H5SH, sometimes abbreviated as PhSH. This foul-smelling colourless liquid is the simplest 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, in the case of 'thiol' that the alcohol 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 the medicine thiomersal is a thiophenol.

Synthesis[edit]

There are several methods of synthesis for thiophenol and related compounds, although thiophenol itself is usually purchased for laboratory operations. Methods are the reduction of benzenesulfonyl chloride with zinc.[5] and the action of elemental sulfur on phenyl magnesium halide or phenyllithium followed by acidification.

Via the Newman–Kwart rearrangement, phenols (1) can be converted to the thiophenols (5) by conversion to the O-aryl dialkylthiocarbamates (3), followed by heating to give the isomeric S-aryl derivative (4).[6] Phenols-to-thiophenols-via-NKR-2D-skeletal.png

In the Leuckart thiophenol reaction the starting material is an aniline through the diazonium salt (ArN2X) and the xanthate (ArS(C=S)OR) [7][8]

Thiophenol can be manufactured from chlorobenzene and hydrogen sulfide over alumina at 700 to 1,300 °F (371 to 704 °C). The disulfide is the primary byproduct.[9] The reaction medium is corrosive and requires ceramic or similar reactor lining.

Properties[edit]

Acidity[edit]

Thiophenol has appreciably greater acidity than does phenol. Thiophenol has a pKa of 6 vs 10 for 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).

Alkylation[edit]

The thiophenolate is highly nucleophilic, which translates to a high rate of alkylation.[10] 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 via Michael addition.

Oxidation[edit]

Thiophenols, especially in the presence of base are easily 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.

Chlorination[edit]

Phenylsulfenyl chloride, a blood-red liquid (b.p. 41–42 °C, 1.5 mm Hg), can be prepared by the reaction of thiophenol with chlorine (Cl2).[11]

Coordination to metals[edit]

Metal cations form thiophenolates, some of which are polymeric. One example is "C6H5SCu," obtained by treating copper(I) chloride with thiophenol.[12]

Safety[edit]

Thiophenol is an irritant and toxic by ingestion, absorption through skin, or inhalation. This chemical is also flammable. The US National Institute for Occupational Safety and Health has established a recommended exposure limit at a ceiling of 0.1 ppm (0.5 mg/m3), and exposures not greater than 15 minutes.[13]

References[edit]

  1. ^ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 97, 698. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4. 
  2. ^ a b c d e f "NIOSH Pocket Guide to Chemical Hazards #0050". National Institute for Occupational Safety and Health (NIOSH). 
  3. ^ Cox, Brian G. Acids and Bases: Solvent Effects on Acid-base Strength. 1st ed. Oxford, UK: Oxford UP, 2013.
  4. ^ Arnett, E.M., Venkatasubremanian, K.G., J. Org. Chem., 1983, 48, 1569.
  5. ^ Adams, R.; C. S. Marvel, C. S. "Thiophenol". Org. Synth. ; Coll. Vol., 1, p. 504 .
  6. ^ Melvin S. Newman and Frederick W. Hetzel (1990). "Thiophenols from Phenols: 2-Naphthalenethiol". Org. Synth. ; Coll. Vol., 6, p. 824 
  7. ^ Leuckart, J. prakt. Chem., [2] 41, 189 (1890).
  8. ^ D. S. Tarbell and D. K. Fukushima "m-Thiocresol" Org. Synth. 1947, volume 27, p. 81. doi: 10.15227/orgsyn.027.0081
  9. ^ US Patent 2,490,257, Duncan J. Crowley & Alvin L Kosak, "Mono- and Polyalkyl Mono- and Polynuclear Mercaptans", issued 1949-12-06, assigned to Socony-Vacuum Oil Co. 
  10. ^ Campopiano, O. "Thiophenol" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289.
  11. ^ Barrett, A. G. M.; Dhanak, D.; Graboski, G. G.; Taylor, S. J. (1993). "(Phenylthio)nitromethane". Org. Synth. ; Coll. Vol., 8, p. 550 
  12. ^ 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, p. 248 
  13. ^ CDC - NIOSH Pocket Guide to Chemical Hazards