Thionyl chloride

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Thionyl chloride
Thionyl-chloride-2D-dimensions.png
Ball-and-stick model of thionyl chloride
Thionyl chloride 25ml.jpg
Identifiers
CAS number 7719-09-7 YesY
PubChem 24386
ChemSpider 22797 YesY
EC number 231-748-8
UN number 1836
ChEBI CHEBI:29290 YesY
RTECS number XM5150000
Jmol-3D images Image 1
Properties
Molecular formula SOCl2
Molar mass 118.97 g/mol
Appearance clear, colourless liquid (yellows on ageing)
Odor pungent and unpleasant
Density 1.638 g/cm3, liquid
Melting point −104.5 °C (−156.1 °F; 168.7 K)
Boiling point 74.6 °C (166.3 °F; 347.8 K)
Solubility in water reacts
Solubility soluble in most aprotic solvents: toluene, chloroform, diethyl ether
Vapor pressure 384 Pa (-40 °C)
4.7 kPa (0 °C)
15.7 kPa (25 °C)[1]
Refractive index (nD) 1.517 (20 °C) [2]
Viscosity 0.6 cP
Structure
Molecular shape pyramidal
Dipole moment 1.44 D
Thermochemistry
Specific
heat capacity
C
121.0 kJ/mol (liquid)[3]
Std molar
entropy
So298
309.8 kJ/mol (gas)[3]
Std enthalpy of
formation
ΔfHo298
-245.6 kJ/mol (liquid)[3]
Hazards
GHS pictograms The corrosion pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)The exclamation-mark pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)The skull-and-crossbones pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)
GHS signal word Danger
GHS hazard statements H302, H314, H331
GHS precautionary statements P261, P280, P305+351+338, P310
EU Index 016-015-00-0
R-phrases R14, R20/22, R29, R35
S-phrases (S1/2), S26, S30, S36/37/39, S45
Main hazards Toxic
Reacts violently with water to release toxic gas
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 4: Very short exposure could cause death or major residual injury. E.g., VX gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
Flash point Non-flammable
Related compounds
Related thionyl halides Thionyl fluoride
Thionyl bromide
Thionyl iodide
Related compounds Sulfuryl chloride
Selenium oxydichloride
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

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 tons per year being produced during the early 1990s.[4] It is toxic and will react violently with water to produce toxic gases, it is also listed as a Schedule 3 compound, as in addition to its legitimate uses it may be use 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[edit]

The major industrial synthesis involves the reaction of sulfur trioxide and sulfur dichloride:[5]

SO3 + SCl2 → SOCl2 + SO2

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

SO2 + PCl5 → SOCl2 + POCl3
SO2 + Cl2 + SCl2 → 2 SOCl2
SO3 + Cl2 + 2 SCl2 → 3 SOCl2
SO2 + COCl2 → SOCl2 + CO2

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[edit]

Crystal structure of SOCl2

SOCl2 adopts a pyramidal molecular geometry with Cs molecular symmetry. This geometry is attributed to the effects of the lone pairs on the sulfur(IV) centre.

In the solid state SOCl2 forms monoclinic crystals with the space group P21/c.[6]

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.[7][5] Thionyl chloride is susceptible to photolysis, which primarily proceeds via a radical mechanism.[8] Samples showing signs of ageing can by purified by distillation under reduced pressure, to give a clear colourless liquid.[9]

Reactions[edit]

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[edit]

Thionyl chloride reacts with water to form sulfur dioxide and hydrochloric acid. This process is highly exothermic.

SOCl2 + H2O → 2 HCl + SO2

Classically, it converts carboxylic acids to acyl chlorides.[10][11]

SOCl2 + RCO2H → RC(O)Cl + SO2 + HCl

By a similar process it also converts alcohols to alkyl chlorides. If the alcohol is chiral the reaction generally proceeds via an SNi mechanism with retention of stereochemistry;[12] however, depending on the exact conditions employed, stero-inversion can also be achieved.

SNi reaction mechanism.gif

Reactions with an excess of alcohol produce sulfite esters, which can be powerful methylation, alkylation and hydroxyalkylation reagents.[13]

SOCl2 + 2 ROH → (RO)2SO + 2 HCl

For example the addition of SOCl2 to amino acids in methanol selectively yields the corresponding methyl esters.[14] If the same reaction is performed in an unreactive solvent then cyclodehydration takes place to give a cyclic amine.[15]

With nitrogen species[edit]

Thionyl chloride will react with primary formamides to form isocyanides[16] and with secondary formamides to give chloroiminium ions; as such a reaction with dimethylformamide will form the Vilsmeier reagent.[17] 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.

Acyl chloride via amide catalysis.png

Primary amides will continue on to form nitriles if heated.[18] Thionyl chloride has also been used to promote the Beckmann rearrangement of oximes.

With sulphur species[edit]

Pummerer Ex ThionylChloride.png

With phosphorus species[edit]

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[edit]

As SOCl2 reacts vigously with water it can be used to dehydrate various metal chloride hydrates, for example MgCl2⋅6H2O, AlCl3⋅6H2O, FeCl3⋅6H2O etc.[5] This conversion involves treatment with refluxing thionyl chloride and follows the following general equation:[23]

MCln·xH2O + x SOCl2 → MCln + x SO2 + 2x HCl

Other reactions[edit]

  • Thionyl chloride can engage in a range of electrophilic addition reactions. It adds to alkenes in the presence of AlCl3 to form an aluminium complex which can be hydrolysed to form a sulfinic acid. Both aryl sulfinyl chlorides and diaryl sulfoxides can be prepared from arenes through reaction with thionyl chloride in triflic acid[24] or the presence of catalysts such as BiCl3, Bi(OTf)3, LiClO4 or NaClO4.[25][26]
  • In the laboritory, a reaction between thionyl chloride and an excess of anhydrous alcohol can be used to produce anhydrous alcoholic solutions of HCl.
3 SOCl2 + 2 SbF3 → 3 SOF2 + 2 SbCl3
SOCl2 + 2HBr → SOBr2 + 2 HCl

Batteries[edit]

A selection of Lithium/Thionyl chloride 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:

4Li + 2 SOCl2 → 4 LiCl + S + SO2

These 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 diposal procedures, additionally they may explode if shorted.

Safety[edit]

SOCl2 is a reactive compound that can violently and/or explosively release dangerous gases upon contact with water and other reagents. Industrial production of thionyl chloride is controlled under the Chemical Weapons Convention, where it is listed in Schedule 3. Thionyl chloride is used in the "di-di" method of producing G-series nerve agents.

See also[edit]

References[edit]

  1. ^ Thionyl chloride in Linstrom, P.J.; Mallard, W.G. (eds.) NIST Chemistry WebBook, NIST Standard Reference Database Number 69. National Institute of Standards and Technology, Gaithersburg MD. http://webbook.nist.gov (retrieved 2014-05-11)
  2. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  3. ^ a b c Lide, ed.-in-chief David R. (1996). CRC handbook of chemistry and physics (76. ed ed.). Boca Raton, Fla.: CRC Press. p. 5-10. ISBN 0-8493-0476-8. 
  4. ^ Hans-Dietrich Lauss, Wilfried Steffens “Sulfur Halides” in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, Weinheim, 2005.doi:10.1002/14356007.a25_623
  5. ^ a b c Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 694. ISBN 0080379419. 
  6. ^ Mootz, D.; Merschenz-Quack, A. (15 May 1988). "Structures of thionyl halides: SOCl2 and SOBr2". Acta Crystallographica Section C Crystal Structure Communications 44 (5): 926–927. doi:10.1107/S010827018800085X. 
  7. ^ Riley, edited by Georg Brauer ; translated by Scripta Technica, Inc. Translation editor Reed F. (1963). Handbook of preparative inorganic chemistry. Volume 1 (2nd ed. ed.). New York, N.Y.: Academic Press. p. 383. ISBN 978-0121266011. 
  8. ^ Donovan, R. J.; Husain, D.; Jackson, P. T. "Spectroscopic and kinetic studies of the SO radical and the photolysis of thionyl chloride". Transactions of the Faraday Society 65: 2930. doi:10.1039/TF9696502930. 
  9. ^ Friedman, L. and Wetter, W. P., "Purification of Thionyl Chloride", J. Chem. Soc. A, 1967, 36-8.doi:10.1039/J19670000036
  10. ^ Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter (2001). Organic Chemistry (1st ed.). Oxford University Press. p. 295. ISBN 978-0-19-850346-0. 
  11. ^ Allen, C. F. H.; Byers, Jr., J. R.; Humphlett, W. J. (1963), Oleoyl chloride, Org. Synth. ; Coll. Vol. 4: 739 ; Rutenberg, M. W.; Horning, E. C. (1963), 1-Methyl-3-ethyloxindole, Org. Synth. ; Coll. Vol. 4: 620 
  12. ^ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, p. 469, ISBN 0-471-72091-7 
  13. ^ van Woerden, H. F. "Organic Sulfites.". Chemical Reviews 63 (6): 557–571. doi:10.1021/cr60226a001. 
  14. ^ Brenner, M.; Huber, W. "Herstellung von α-Aminosäureestern durch Alkoholyse der Methylester". Helvetica Chimica Acta (in German) 36 (5): 1109–1115. doi:10.1002/hlca.19530360522. 
  15. ^ Feng Xu, Bryon Simmons, Robert A. Reamer, Edward Corley, Jerry Murry, and David Tschaen (2008). "Chlorination/Cyclodehydration of Amino Alcohols with SOCl2: An Old Reaction Revisited". J. Org. Chem. 73 (1): 312–5. doi:10.1021/jo701877h. PMID 18052293. 
  16. ^ Niznik, G. E.; Morrison, III, W. H.; Walborsky, H. M. (1988), 1-d-Aldehydes from organometallic reagents: 2-methylbutanal-1-d, Org. Synth. ; Coll. Vol. 6: 751 
  17. ^ Arrieta, A; Aizpurua, J.M; Palomo, C. "N,N-Dimethylchlorosulfitemethaniminium chloride (SOCl2-DMF) a versatile dehydrating reagent.". Tetrahedron Letters 25 (31): 3365–3368. doi:10.1016/S0040-4039(01)81386-1. 
  18. ^ Krynitsky, J. A.; Carhart, H. W. (1963), 2-Ethylhexanonitrile, Org. Synth. ; Coll. Vol. 4: 436 
  19. ^ Hulce, M.; Mallomo, J. P.; Frye, L. L.; Kogan, T. P.; Posner, G. H. (1990), (S)-(+)-2-(p-toluenesulfinyl)-2-cyclopentenone: Precursor for enantioselective synthesis of 3-substituted cyclopentanones, Org. Synth. ; Coll. Vol. 7: 495 ; Kurzer, F. (1963), p-Toluenesulfinyl chloride, Org. Synth. ; Coll. Vol. 4: 937 
  20. ^ Weinreb, S. M.; Chase, C. E.; Wipf, P.; Venkatraman, S. (2004), 2-Trimethylsilylethanesulfonyl chloride (SES-Cl), Org. Synth. ; Coll. Vol. 10: 707 
  21. ^ Hazen, G. G.; Bollinger, F. W.; Roberts, F. E.; Russ, W. K.; Seman, J. J.; Staskiewicz, S. (1998), 4-Dodecylbenzenesulfonyl azides, Org. Synth. ; Coll. Vol. 9: 400 
  22. ^ Philip J. Hogan and Brian G. Cox (2009). "Aqueous Process Chemistry: The Preparation of Aryl Sulfonyl Chlorides". Org. Process Res. Dev. 13 (5): 875–879. doi:10.1021/op9000862. 
  23. ^ Alfred R. Pray, Richard F. Heitmiller, Stanley Strycker (1990). "Anhydrous Metal Chlorides". Inorganic Syntheses. Inorganic Syntheses 28: 321–323. doi:10.1002/9780470132593.ch80. ISBN 978-0-470-13259-3. 
  24. ^ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, p. 697, ISBN 0-471-72091-7 
  25. ^ Le Roux, C.; Mazières, S. P.; Peyronneau, M.; Roques, N. (2003). "Catalytic Lewis Acid Activationof Thionyl Chloride: Application to the Synthesis of ArylSulfinyl Chlorides Catalyzed by Bismuth(III) Salts". Synlett (5): 0631. doi:10.1055/s-2003-38358.  edit
  26. ^ Bandgar, B. P. and Makone, S. S. (2004). "Lithium/Sodium Perchlorate Catalyzed Synthesis of Symmetrical Diaryl Sulfoxides". Syn. Commun. 34 (4): 743–750. doi:10.1081/SCC-120027723.