Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes (50,000 short tons) per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons. Thionyl chloride is sometimes confused with sulfuryl chloride, SO2Cl2, but the properties of these compounds differ significantly. Sulfuryl chloride is a source of chlorine whereas thionyl chloride is a source of chloride ions.
Production The major industrial synthesis involves the reaction of sulfur trioxide and sulfur dichloride. This synthesis can be adapted to the laboratory by heating oleum to slowly distill the sulfur trioxide into a cooled flask of sulfur dichloride.
SO3 + SCl2 → SOCl2 + SO2 Other methods include syntheses from:
Phosphorus pentachloride: SO2 + PCl5 → SOCl2 + POCl3 Chlorine and sulfur dichloride: SO2 + Cl2 + SCl2 → 2 SOCl2 SO3 + Cl2 + 2SCl2 → 3 SOCl2 Phosgene: SO2 + COCl2 → SOCl2 + CO2 The second of the above five reactions also affords phosphorus oxychloride (phosphoryl chloride), which resembles thionyl chloride in many of its reactions. They may be separated by distillation, since thionyl chloride boils at a much lower temperature than phosphoryl chloride.
Properties and structure
SOCl2 adopts a trigonal pyramidal molecular geometry with Cs molecular symmetry. This geometry is attributed to the effects of the lone pair on the central sulfur(IV) center. In the solid state SOCl2 forms monoclinic crystals with the space group P21/c.
Stability Thionyl chloride has a long shelf life, however "aged" samples develop a yellow hue, possibly due to the formation of disulfur dichloride. It slowly decomposes to S2Cl2, SO2 and Cl2 at just above the boiling point. Thionyl chloride is susceptible to photolysis, which primarily proceeds via a radical mechanism. Samples showing signs of ageing can be purified by distillation under reduced pressure, to give a colourless liquid.
Reactions Thionyl chloride is mainly used in the industrial production of organochlorine compounds, which are often intermediates in pharmaceuticals and agrochemicals. It usually is preferred over other reagents, such as phosphorus pentachloride, as its by-products (HCl and SO2) are gaseous, which simplifies purification of the product. Many of the products of thionyl chloride are themselves highly reactive and as such it is involved in a wide range of reactions.
With water and alcohols Thionyl chloride reacts exothermically with water to form sulfur dioxide and hydrochloric acid:
SOCl2 + H2O → 2 HCl + SO2 By a similar process it also reacts with alcohols to form alkyl chlorides. If the alcohol is chiral the reaction generally proceeds via an SNi mechanism with retention of stereochemistry; however, depending on the exact conditions employed, stereo-inversion can also be achieved. Historically the use of SOCl2 with pyridine was called the Darzens halogenation, but this name is rarely used by modern chemists.
Reactions with an excess of alcohol produce sulfite esters, which can be powerful methylation, alkylation and hydroxyalkylation reagents.
SOCl2 + 2 R−OH → (R−O)2SO + 2 HCl For example, the addition of SOCl2 to amino acids in methanol selectively yields the corresponding methyl esters.
With carboxylic acids Classically, it converts carboxylic acids to acyl chlorides:
SOCl2 + R−COOH → R−COCl + SO2 + HCl The reaction mechanism has been investigated:
With nitrogen species With primary amines, thionyl chloride gives sulfinylamine derivatives (RNSO), one example being N-sulfinylaniline. Thionyl chloride reacts with primary formamides to form isocyanides and with secondary formamides to give chloroiminium ions; as such a reaction with dimethylformamide will form the Vilsmeier reagent. By an analogous process, secondary amides will react with thionyl chloride to form imidoyl chlorides, with tertiary amides giving chloroiminium ions. These species are highly reactive and can be used to catalyse the conversion of carboxylic acids to acyl chlorides; they are also exploited in the Bischler–Napieralski reaction as a means of forming isoquinolines.
Primary amides will continue on to form nitriles if heated (Von Braun amide degradation). Thionyl chloride has also been used to promote the Beckmann rearrangement of oximes.
With sulfur species Thionyl chloride will transform sulfinic acids into sulfinyl chlorides Sulfonic acids react with thionyl chloride to produce sulfonyl chlorides. Sulfonyl chlorides have also been prepared from the direct reaction of the corresponding diazonium salt with thionyl chloride. Thionyl chloride can be used in variations of the Pummerer rearrangement.
With phosphorus species Thionyl chloride converts phosphonic acids and phosphonates into phosphoryl chlorides. It is for this type of reaction that thionyl chloride is listed as a Schedule 3 compound, as it can be used in the "di-di" method of producing G-series nerve agents. For example, thionyl chloride converts dimethyl methylphosphonate into methylphosphonic acid dichloride, which can be used in the production of sarin and soman.
With metals As SOCl2 reacts with water it can be used to dehydrate various metal chloride hydrates, such magnesium chloride (MgCl2·6H2O), aluminium chloride (AlCl3·6H2O), and iron(III) chloride (FeCl3·6H2O). This conversion involves treatment with refluxing thionyl chloride and follows the following general equation:
MCln·xH2O + x SOCl2 → MCln + x SO2 + 2x HCl If an excess of SOCl2 is used to dehydrate aluminium trichloride, it will form an adduct (1 molecule of thionyl chloride for each molecule of the aluminium trichloride dimer).
… excerpt ends here. Continue reading the full article.
