Thiophosphoryl chloride
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| UN number | 1837 |
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| Template:Longitem | Template:Chem2 |
| Molar mass | Template:Chem molar mass |
| Appearance | Colorless liquid |
| Density | 1.67 g/cm3 |
| Melting point | Template:Chembox CalcTemperatures |
| Boiling point | Template:Chembox CalcTemperatures |
| Solubility | Soluble in benzene, chloroform, [[Carbon disulfide|Template:Chem2]] and [[Carbon tetrachloride|Template:Chem2]]. |
| Template:Longitem | Tetrahedral at the P atom |
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Thiophosphoryl chloride is an inorganic compound with the chemical formula Template:Chem2.[1] It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.
Synthesis
Thiophosphoryl chloride can be generated by several reactions starting from phosphorus trichloride. The most common and practical synthesis, hence used in industrial manufacturing, is directly reacting phosphorus trichloride with excess sulfur at 180 °C.[2]
Using this method, yields can be very high after purification by distillation. Catalysts facilitate the reaction at lower temperatures, but are not usually necessary. Alternatively, it is obtained by combining phosphorus pentasulfide and phosphorus pentachloride.[3]
Structure
Thiophosphoryl chloride has tetrahedral molecular geometry and C3v molecular symmetry, with the structure Template:Chem2. According to gas electron diffraction, the phosphorus–sulfur bond length is 189 pm and the phosphorus–chlorine bond length is 201 pm, while the Template:Chem2 bond angle is 102°.[4]
Reactions
Template:Chem2 is soluble in benzene, carbon tetrachloride, chloroform, and carbon disulfide.[1] However, it hydrolyzes rapidly in basic or hydroxylic solutions, such as alcohols and amines, to produce thiophosphates.[2] In water Template:Chem2 reacts, and contingent on the reaction conditions, produces either phosphoric acid, hydrogen sulfide, and hydrochloric acid or dichlorothiophosphoric acid and hydrochloric acid.[5]
An intermediate in this process appears to be tetraphosphorus nonasulfide.[6]
Template:Chem2 is used to thiophosphorylate organic compounds (to add thiophosphoryl group, P=S, with three free valences at the P atom, to organic compounds).[2] This conversion is widely applicable for amines and alcohols, as well as aminoalcohols, diols, and diamines.[1] Industrially, Template:Chem2 is used to produce insecticides, like parathion.[5]
Template:Chem2 reacts with tertiary amides to generate thioamides.[1] For example:
When treated with methylmagnesium iodide, it give tetramethyldiphosphine disulfide Template:Chem2.[7]
References
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- ↑ a b c d Spilling, C. D. "Thiophosphoryl Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, Weinheim, 2001 Script error: No such module "CS1 identifiers".. Article Online Posting Date: April 15, 2001
- ↑ a b c Script error: No such module "citation/CS1".
- ↑ Martin, D. R.; Duvall, W. M. “Phosphorus(V) Sulfochloride” Inorganic Syntheses, 1953, Volume IV, p73. Script error: No such module "CS1 identifiers"..
- ↑ Script error: No such module "Citation/CS1".
- ↑ a b Fee, D. C.; Gard, D. R.; Yang, C. “Phosphorus Compounds” Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons: New York, 2005 Script error: No such module "CS1 identifiers".
- ↑ Script error: No such module "citation/CS1".
- ↑ G. W. Parshall "Tetramethylbiphosphine Disulfide" Org. Synth. 1965, volume 45, p. 102. Script error: No such module "CS1 identifiers".
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