Diphenyl disulfide

Diphenyl disulfide

Names
Preferred IUPAC name 1,1′-Disulfanediyldibenzene
Other names Disulfanyldibenzene Diphenyl disulfide Phenyl disulfide 1,2-Diphenyldisulfane (not recommended)
Identifiers
CAS Number	882-33-7  Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:174102
ChEMBL	ChEMBL462861  Y
ChemSpider	12861  Y
ECHA InfoCard	100.011.752
EC Number	212-926-4
PubChem CID	13436
RTECS number	SS6825000
UNII	7P54H519IJ  Y
CompTox Dashboard (EPA)	DTXSID6022131
InChI InChI=1S/C12H10S2/c1-3-7-11(8-4-1)13-14-12-9-5-2-6-10-12/h1-10H Y Key: GUUVPOWQJOLRAS-UHFFFAOYSA-N Y InChI=1/C12H10S2/c1-3-7-11(8-4-1)13-14-12-9-5-2-6-10-12/h1-10H Key: GUUVPOWQJOLRAS-UHFFFAOYAY
SMILES c1ccc(cc1)SSc2ccccc2
Properties
Chemical formula	C12H10S2
Molar mass	218.33 g·mol−1
Appearance	Colorless crystals
Melting point	61 to 62 °C (142 to 144 °F; 334 to 335 K)
Solubility in water	Insoluble
Solubility in other solvents	Soluble in diethyl ether, benzene, carbon disulfide, and THF
Structure
Dipole moment	0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	Flammable
GHS labelling: [1]
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	P261, P264, P271, P273, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P391, P403+P233, P405, P501
Related compounds
Related compounds	Thiophenol, Dimethyl disulfide, Diphenyl diselenide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Y  verify  (what is  YN ?) Infobox references

Diphenyl disulfide is the chemical compound with the formula (C₆H₅S)₂. This colorless crystalline material is often abbreviated Ph₂S₂. It is one of the more commonly encountered organic disulfides in organic synthesis. Minor contamination by thiophenol is responsible for the disagreeable odour associated with this compound.

Preparation and structure

Diphenyl disulfide is usually prepared by the oxidation of thiophenol:

2 PhSH + I₂ → Ph₂S₂ + 2 HI

Hydrogen peroxide can also be used as the oxidant. ^[2] Ph₂S₂ is rarely prepared in the laboratory because it is inexpensive, and the precursor has a disagreeable odour.

Like most organic disulfides, the C–S–S–C core of Ph₂S₂ is non-planar with a dihedral angle approaching 85°. ^[3]

Ball-and-stick model of diphenyl disulfide. The S-S bond distance is 2.03 Å.

Reactions

Ph₂S₂ is mainly used in organic synthesis as a source of the PhS substituent. ^[4] A typical reaction entails the formation of PhS-substituted carbonyl compounds via the enolate:

RC(O)CHLiR' + Ph₂S₂ → RC(O)CH(SPh)R' + LiSPh

Reduction

Ph₂S₂ undergoes reduction, a reaction characteristic of disulfides:

Ph₂S₂ + 2 M → 2 MSPh (M = Li, Na, K)

Hydride reagents such as sodium borohydride and super hydride can also be used as reductants. The salts PhSM are sources of the potent nucleophile PhS⁻. Most alkyl halides, RX (X = halide) convert it to the thioethers with the general formula RSPh. Analogously, protonation of MSPh gives thiophenol:

PhSM + HCl → HSPh + MCl

Halogenation

Ph₂S₂ reacts with chlorine to give phenylsulfenyl chloride PhSCl (Zincke disulfide cleavage). This species is usually generated and used in situ . With xenon difluoride, Ph₂S₂ reacts to give phenylsulfur pentafluoride. ^[5]

Catalyst for photoisomerization of alkenes

Ph₂S₂ catalyzes the cis-trans isomerization of alkenes under UV-irradiation. ^[6]

Oxidation

Oxidation of Ph₂S₂ with lead(IV) acetate (Pb(OAc)₄) in methanol affords the sulfinite ester PhS(O)OMe. ^[7]

References

1. "Diphenyl disulfide". pubchem.ncbi.nlm.nih.gov. Retrieved 13 December 2021.
2. Ravikumar,K. S.; Kesavan, V.; Crousse, B.; Bonnet-Delpon, D.; Bégué, J.-P. (2003). "Mild and Selective Oxidation of Sulfur Compounds in Trifluoroethanol: Diphenyl Disulfide and Methyl Phenyl Sulfoxide". Organic Syntheses . 80: 184. doi:10.15227/orgsyn.080.0184 .
3. Lee, J. D.; Bryant, M. W. R. (1969). "The Crystal Structure of Diphenyl Disulphide". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 25 (10): 2094–2101. Bibcode:1969AcCrB..25.2094L. doi:10.1107/S0567740869005188.
4. Byers, J. H. (2004). "Diphenyl Disulfide". In L. Paquette) (ed.). Encyclopedia of Reagents for Organic Synthesis. New York: J. Wiley & Sons. doi:10.1002/047084289X. hdl:10261/236866. ISBN   9780471936237..
5. Sergeeva, Tatiana A.; Dolbier, William R. (2004-07-01). "A New Synthesis of Pentafluorosulfanylbenzene" . Organic Letters. 6 (14): 2417–2419. doi:10.1021/ol0491991. ISSN   1523-7060. PMID   15228293.
6. Thalmann, A.; Oertle, K.; Gerlach, H. (1990). "Ricinelaidic Acid Lactone". Organic Syntheses ; Collected Volumes, vol. 7, p. 470.
7. Field, L.; Locke, J. M. (1973). "Methyl Benzenesulfinate". Organic Syntheses ; Collected Volumes, vol. 5, p. 723.