Diphenyl diselenide

Diphenyl diselenide
Names
	IUPAC name 1,1′-Diselanediyldibenzene
	Other names Phenyl diselenide
Identifiers
CAS Number	1666-13-3 ;
3D model (JSmol)	Interactive image;
ChemSpider	14710 ;
ECHA InfoCard	100.015.256
EC Number	216-780-2;
PubChem CID	15460;
RTECS number	JM9152500;
UNII	9ATU3Z459Q ;
CompTox Dashboard (EPA)	DTXSID6061864 ;
	InChI InChI=1S/C12H10Se2/c1-3-7-11(8-4-1)13-14-12-9-5-2-6-10-12/h1-10H Key: YWWZCHLUQSHMCL-UHFFFAOYSA-N ; InChI=1/C12H10Se2/c1-3-7-11(8-4-1)13-14-12-9-5-2-6-10-12/h1-10H Key: YWWZCHLUQSHMCL-UHFFFAOYAK;
	SMILES c1ccc(cc1)[Se][Se]c2ccccc2;
Properties
Chemical formula	C12H10Se2
Molar mass	312.154 g·mol−1
Appearance	Yellow crystals
Density	1.84 g/cm3
Melting point	59 to 61 °C (138 to 142 °F; 332 to 334 K)
Solubility in water	Insoluble
Solubility in other solvents	Dichloromethane, THF, hot Hexane
Structure
Coordination geometry	90° at Se; C2 symmetry
Dipole moment	0 D
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H301, H331, H373, H410
Precautionary statements	P260, P261, P264, P270, P271, P273, P301+P310, P304+P340, P311, P314, P321, P330, P391, P403+P233, P405, P501
Related compounds
Related compounds	Ph2S2,; C6H5SeH
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Diphenyl diselenide is the chemical compound with the formula (C₆H₅)₂Se₂, abbreviated Ph₂Se₂. This orange-coloured solid is the oxidized derivative of benzeneselenol. It is used as a source of the PhSe unit in organic synthesis.

Preparation and properties

Ph₂Se₂ is prepared by the oxidation of benzeneselenoate, the conjugate base of benzeneselenol which is generated via the Grignard reagent:[1]

PhMgBr + Se → PhSeMgBr

2 PhSeMgBr + Br₂ → Ph₂Se₂ + 2 MgBr₂

The molecule has idealized C₂-symmetry, like hydrogen peroxide and related molecules. The Se-Se bond length of 2.29 Å the C-Se-Se-C dihedral angle is 82° and the C-Se-Se angles are near 110°.[2]

Medical applications

Diphenyl diselenide alleviates methylmercury poisoning in grass carp.[3]

Reactions

A reaction characteristic of Ph₂Se₂ is its reduction:

Ph₂Se₂ + 2 Na → 2 PhSeNa

PhSeNa is a useful nucleophile used to introduce the phenylselenyl group by nucleophilic substitution of alkyl halides, alkyl sulfonates (mesylates or tosylates) and epoxides. The example below was taken from a synthesis of morphine.[4]

Another characteristic reaction is chlorination:

Ph₂Se₂ + Cl₂ → 2 PhSeCl

PhSeCl is a powerful electrophile, used to introduce PhSe groups by reaction with a variety of nucleophiles, including enolates, enol silyl ethers, Grignard reagents, organolithium reagents, alkenes and amines. In the sequence below (early steps in the synthesis of Strychnofoline), a PhSe group is introduced by reaction of a lactam enolate with PhSeCl.[5] This sequence is a powerful method for the conversion of carbonyl compounds to their α,β-unsaturated analogs.[6]

Diphenyl diselenide itself is also a source of a weakly electrophilic PhSe group in reactions with relatively powerful nucleophiles like Grignard reagents, lithium reagents and ester enolates (but not ketone enolates or weaker nucleophiles). PhSeCl is both more reactive, and more efficient, since with Ph₂Se₂ half of the selenium is wasted.

Ph₂Se₂ + Nu⁻ → PhSeNu + PhSe⁻

N-Phenylselenophthalimide (N-PSP) can be used if PhSeCl is too strong and diphenyl diselenide is too weak or wasteful.[7]

References

Reich, H. J.; Cohen, M. L.; Clark, P. S. (1979). "Reagents for Synthesis of Organoselenium Compounds: Diphenyl Diselenide and Benzeneselenenyl Chloride". Organic Syntheses. 59: 141.; Collective Volume, vol. 6, p. 533
Marsh, R. E. (1952). "The Crystal Structure of Diphenyl Diselenide". Acta Crystallographica. 5 (4): 458–462. doi:10.1107/S0365110X52001349.
Baldissera, Matheus D.; Souza, Carine F.; da Silva, Aleksandro S.; Henn, Alessandra S.; Flores, Erico M. M.; Baldisserotto, Bernardo (2020). "Diphenyl diselenide dietary supplementation alleviates behavior impairment and brain damage in grass carp (Ctenopharyngodon idella) exposed to methylmercury chloride". Comparative Biochemistry and Physiology. Toxicology & Pharmacology. 229: 108674. doi:10.1016/j.cbpc.2019.108674. ISSN 1532-0456. PMID 31760078. S2CID 208274623.
Taber, D. F.; Neubert, T. D.; Rheingold, A. L. (2002). "Synthesis of (−)-Morphine". Journal of the American Chemical Society. 124 (42): 12416–12417. doi:10.1021/ja027882h. PMID 12381175.
Lerchner, A.; Carreira, E. M. (2002). "First Total Synthesis of (±)-Strychnofoline via a Highly Selective Ring-Expansion Reaction". Journal of the American Chemical Society. 124 (50): 14826–14827. doi:10.1021/ja027906k. PMID 12475306.
Reich, H. J.; Wollowitz, S. (1993). "Preparation of α,β-Unsaturated Carbonyl Compounds and Nitriles by Selenoxide Elimination". Organic Reactions. 44: 1–296. doi:10.1002/0471264180.or044.01. ISBN 0471264180.
Barrero, A. F.; Alvarez-Manzaneda, E. J.; Chahboun, R.; Corttés, M.; Armstrong, V. (1999). "Synthesis and Antitumor Activity of Puupehedione and Related Compounds". Tetrahedron. 55 (52): 15181–15208. doi:10.1016/S0040-4020(99)00992-8.

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[1] Reich, H. J.; Cohen, M. L.; Clark, P. S. (1979). "Reagents for Synthesis of Organoselenium Compounds: Diphenyl Diselenide and Benzeneselenenyl Chloride". Organic Syntheses. 59: 141.; Collective Volume, vol. 6, p. 533

[2] Marsh, R. E. (1952). "The Crystal Structure of Diphenyl Diselenide". Acta Crystallographica. 5 (4): 458–462. doi:10.1107/S0365110X52001349.

[3] Baldissera, Matheus D.; Souza, Carine F.; da Silva, Aleksandro S.; Henn, Alessandra S.; Flores, Erico M. M.; Baldisserotto, Bernardo (2020). "Diphenyl diselenide dietary supplementation alleviates behavior impairment and brain damage in grass carp (Ctenopharyngodon idella) exposed to methylmercury chloride". Comparative Biochemistry and Physiology. Toxicology & Pharmacology. 229: 108674. doi:10.1016/j.cbpc.2019.108674. ISSN 1532-0456. PMID 31760078. S2CID 208274623.

[4] Taber, D. F.; Neubert, T. D.; Rheingold, A. L. (2002). "Synthesis of (−)-Morphine". Journal of the American Chemical Society. 124 (42): 12416–12417. doi:10.1021/ja027882h. PMID 12381175.

[5] Lerchner, A.; Carreira, E. M. (2002). "First Total Synthesis of (±)-Strychnofoline via a Highly Selective Ring-Expansion Reaction". Journal of the American Chemical Society. 124 (50): 14826–14827. doi:10.1021/ja027906k. PMID 12475306.

[6] Reich, H. J.; Wollowitz, S. (1993). "Preparation of α,β-Unsaturated Carbonyl Compounds and Nitriles by Selenoxide Elimination". Organic Reactions. 44: 1–296. doi:10.1002/0471264180.or044.01. ISBN 0471264180.

[7] Barrero, A. F.; Alvarez-Manzaneda, E. J.; Chahboun, R.; Corttés, M.; Armstrong, V. (1999). "Synthesis and Antitumor Activity of Puupehedione and Related Compounds". Tetrahedron. 55 (52): 15181–15208. doi:10.1016/S0040-4020(99)00992-8.