“Thionyl chloride”的意思、由来-开放百科全书

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 {{convert|45,000|t|ST}} per year being produced during the early 1990s.^[5] 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:^[6]

Other methods include syntheses from phosphorus pentachloride, chlorine and sulfur dichloride, or phosgene:

The first of the above four reactions also affords phosphorus oxychloride (phosphoryl chloride), which resembles thionyl chloride in many of its reactions.

Properties and structure

SOCl₂ adopts a trigonal pyramidal molecular geometry with C_s 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.^[7]

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.^[6]^[8] Thionyl chloride is susceptible to photolysis, which primarily proceeds via a radical mechanism.^[9] Samples showing signs of ageing can be purified by distillation under reduced pressure, to give a colourless liquid.^[10]

Reactions

Thionyl chloride is mainly used in the industrial production of organochlorine compounds, which are often intermediates in pharmaceuticals and agrichemicals. 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 oxygen species

Thionyl chloride reacts exothermically with water to form sulfur dioxide and hydrochloric acid:

By a similar process it also reacts with alcohols to form alkyl chlorides. If the alcohol is chiral the reaction generally proceeds via an S_Ni mechanism with retention of stereochemistry;^[11] however, depending on the exact conditions employed, stereo-inversion can also be achieved. Historically the use of SOCl₂ in combination with a tertiary amine such as 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.^[12]

For example, the addition of SOCl₂ to amino acids in methanol selectively yields the corresponding methyl esters.^[13]

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^[17] and with secondary formamides to give chloroiminium ions; as such a reaction with dimethylformamide will form the Vilsmeier reagent.^[18]

By an analogous process primary amides will react with thionyl chloride to form imidoyl chlorides, with secondary amides also 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).^[19]

Thionyl chloride has also been used to promote the Beckmann rearrangement of oximes.

With sulfur species

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 MgCl₂·6H₂O, AlCl₃·6H₂O, and FeCl₃·6H₂O.^[6] This conversion involves treatment with refluxing thionyl chloride and follows the following general equation:^[25]

Other reactions

Batteries

Thionyl chloride is a component of lithium–thionyl chloride batteries, where it acts as the positive electrode (cathode) with lithium forming the negative electrode (anode); the electrolyte is typically lithium tetrachloroaluminate. The overall discharge reaction is as follows:

These non-rechargeable batteries have many advantages over other forms of lithium battery such as a high energy density, a wide operational temperature range and long storage and operational lifespans. However, their high cost and safety concerns have limited their use. The contents of the batteries are highly toxic and require special disposal procedures; additionally, they may explode if shorted.

Safety

SOCl₂ is a reactive compound that can violently release dangerous gases upon contact with water and other reagents. It is also controlled under the Chemical Weapons Convention and listed as a Schedule 3 substance since it is used in the "di-di" method of producing G-series nerve agents.{{fact|date=August 2018}}

History

In 1849, the French chemists Jean-François Persoz and Bloch, and the German chemist Peter Kremers (1827-?), independently first synthesized thionyl chloride by reacting phosphorus pentachloride with sulfur dioxide.^[29]^[30] However, their products were impure: both Persoz and Kremers claimed that thionyl chloride contained phosphorus,^[31] and Kremers recorded its boiling point as 100°C (instead of 74.6°C). In 1857, the German-Italian chemist Hugo Schiff subjected crude thionyl chloride to repeated fractional distillations and obtained a liquid which boiled at 82°C and which he called Thionylchlorid.^[32] In 1859, the German chemist Georg Ludwig Carius noted that thionyl chloride could be used to make acid anhydrides and acyl chlorides from carboxylic acids and to make alkyl chlorides from alcohols.^[33]

See also

References

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29. ^See* {{cite journal |last1=Persoz |last2=Bloch |title=Des composés binaires formés par les métalloïdes, et, en particulier, de l'action du chloride phosphorique sur les acides sulfureux, sulfurique, phosphorique, chromique, etc. |journal=Comptes rendus |date=1849 |volume=28 |pages=86–88 |url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015035450975;view=1up;seq=96 |trans-title=Binary compounds formed by metalloids and in particular the action of phosphorus pentachloride on sulfurous acid, sulfuric acid, phosphoric acid, chromic acid, etc. |language=French}}* {{cite journal |last1=Persoz |last2=Bloch |title=Addition à une Note précédente concernant les combinaisons du chloride phosphorique avec les acides phosphorique, sulfurique et sulfureux |journal=Comptes rendus |date=1849 |volume=28 |page=389 |url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015035450975;view=1up;seq=401 |trans-title=Addition to a preceding note concerning compounds of phosphorus pentachloride with phosphoric acid, sulfuric acid, and sulfurous acid |language=French}}
30. ^{{cite journal |last1=Kremers |first1=P. |title=Ueber schwefligsaures Phosphorchlorid |journal=Annalen der Chemie und Pharmacie |date=1849 |volume=70 |pages=297-300 |url=https://babel.hathitrust.org/cgi/pt?id=hvd.hx3bh3;view=1up;seq=703 |trans-title=On sulfurous phosphorus pentachloride |language=German}}
31. ^The German chemist Georg Ludwig Carius noted that, when the reaction mixture that produced thionyl chloride was distilled, the crude mixture initially released substantial quantities of gas, so that phosphoryl chloride (POCl₃) was carried into the receiver. {{cite journal |last1=Carius |first1=L. |title=Ueber die Chloride des Schwefels und deren Derivate |journal=Annalen der Chemie und Pharmacie |date=1859 |volume=111 |pages=93–113 |url=https://babel.hathitrust.org/cgi/pt?id=hvd.hx3bhp;view=1up;seq=107 |trans-title=On sulfur chloride and its derivatives |language=German}} From p. 94: " … dabei ist jedoch die Vorsicht zu gebrauchen, … und nie reines Chlorthionyl erhalten wird." ( … however, during that [i.e., the fractional distillation], caution must be used, [so] that one carefully avoids a concentration of hydrogen chloride or excess sulfurous acid in the liquid that is to be distilled, as otherwise, by the evolution of gas that occurs at the start of the distillation, much phosphoryl chloride is transferred and pure thionyl chloride is never obtained.)
32. ^{{cite journal |last1=Schiff |first1=Hugo |title=Ueber die Einwirkung des Phosphorsuperchlorids auf einige anorganische Säuren |journal=Annalen der Chemie und Pharmacie |date=1857 |volume=102 |pages=111–118 |url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015026321813;view=1up;seq=509 |trans-title=On the reaction of phosphorus pentachloride with some inorganic acids |language=German}} The boiling point of thionyl chloride which Schiff observed, appears on p. 112. The name Thionylchlorid is coined on p. 113.
33. ^{{cite journal |last1=Carius |first1=L. |title=Ueber die Chloride des Schwefels und deren Derivate |journal=Annalen der Chemie und Pharmacie |date=1859 |volume=111 |pages=93–113 |url=https://babel.hathitrust.org/cgi/pt?id=hvd.hx3bhp;view=1up;seq=107 |trans-title=On sulfur chloride and its derivatives |language=German}} On p. 94, Carius notes that thionyl chloride can be " … mit Vortheil zur Darstellung wasserfreier Säuren verwenden." ( … used advantageously for the preparation of acid anhydrides.) Also on p. 94, Carius shows chemical equations in which thionyl chloride is used to transform benzoic acid (OC₇H₅OH) into benzoyl chloride (ClC₇H₅O) and to transform sodium benzoate into benzoic anhydride. On p. 96, he mentions that thionyl chloride will transform methanol into methyl chloride (Chlormethyl). Thionyl chloride behaves like phosphoryl chloride: from pp. 94-95: "Die Einwirkung des Chlorthionyls … die Reaction des Chlorthionyls weit heftiger statt." (The reaction of thionyl chloride with [organic] substances containing oxygen proceeds in general parallel to that of phosphoryl chloride; where the latter exerts an effect, thionyl chloride usually does so also, only in nearly all cases the reaction occurs far more vigorously.)