Thionyl chloride is an
inorganic compound
In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemi ...
with the
chemical formula
In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...
. It is a moderately
volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a
chlorinating reagent, with approximately 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
A chemical weapon (CW) is a specialized munition that uses chemicals formulated to inflict death or harm on humans. According to the Organisation for the Prohibition of Chemical Weapons (OPCW), this can be any chemical compound intended as ...
.
Thionyl chloride is sometimes confused with
sulfuryl chloride, , but the properties of these compounds differ significantly. Sulfuryl chloride is a source of
chlorine
Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is ...
whereas thionyl chloride is a source of
chloride
The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride s ...
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
Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is ...
and
sulfur dichloride:
*:
SO2 + Cl2 + SCl2 -> 2 SOCl2
*:
SO3 + Cl2 + 2 SCl2 -> 3 SOCl2
*
Phosgene
Phosgene is the organic chemical compound with the formula COCl2. It is a toxic, colorless gas; in low concentrations, its musty odor resembles that of freshly cut hay or grass. Phosgene is a valued and important industrial building block, es ...
:
*:
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
SOCl
2 adopts a
trigonal pyramidal molecular geometry with C
s molecular symmetry
Molecular symmetry in chemistry describes the symmetry present in molecules and the classification of these molecules according to their symmetry. Molecular symmetry is a fundamental concept in chemistry, as it can be used to predict or explain ...
. This geometry is attributed to the effects of the
lone pair on the central sulfur(IV) center.
In the solid state SOCl
2 forms
monoclinic
In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in the orthorhombic ...
crystals with the
space group
In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it ...
P2
1/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 agrichemicals. It usually is preferred over other reagents, such as
phosphorus pentachloride, as its by-products (HCl and ) 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
Sulfur dioxide ( IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic ...
and
hydrochloric acid
Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the dig ...
:
:
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 with
pyridine
Pyridine is a basic (chemistry), basic heterocyclic compound, heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakl ...
was called the
Darzens halogenation
Darzens halogenation is the chemical synthesis of alkyl halides from alcohols via the treatment upon reflux of a large excess of thionyl chloride or thionyl bromide (SOX2) in the presence of a small amount of a nitrogen base, such as a tertiary ...
, but this name is rarely used by modern chemists.
Reactions with an excess of alcohol produce
sulfite ester
A sulfite ester (also known as an organosulfite) is a functional group with the structure (RO)(R'O)SO. They adopt a trigonal pyramidal molecular geometry due to the presence of lone pairs on the sulphur atom.
When substituents R and R' differ, ...
s, which can be powerful
methylation
In the chemical sciences, methylation denotes the addition of a methyl group on a substrate, or the substitution of an atom (or group) by a methyl group. Methylation is a form of alkylation, with a methyl group replacing a hydrogen atom. These t ...
,
alkylation
Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effectin ...
and hydroxyalkylation reagents.
:
SOCl2 + 2 R-OH -> (R-O)2SO + 2 HCl
For example, the addition of to
amino acid
Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although hundreds of amino acids exist in nature, by far the most important are the alpha-amino acids, which comprise proteins. Only 22 alpha ...
s in methanol selectively yields the corresponding methyl esters.
With carboxylic acids
Classically, it converts
carboxylic acid
In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxyl ...
s to
acyl chloride
In organic chemistry, an acyl chloride (or acid chloride) is an organic compound with the functional group . Their formula is usually written , where R is a side chain. They are reactive derivatives of carboxylic acids (). A specific example ...
s:
:
SOCl2 + R-COOH -> R-COCl + SO2 + HCl
The reaction mechanism has been investigated:
:
With nitrogen species
With primary amines, thionyl chloride gives
sulfinylamine
153 px, ''N''-Sulfinylaniline is a common sulfinylamine.
Sulfinylamines (formerly ''N''-sulfinyl amines) are organosulfur compounds with the formula RNSO where R = an organic substituent. These compounds are, formally speaking, derivatives of H ...
derivatives (RNSO), one example being ''N''-
sulfinylaniline
''N''-Sulfinylaniline is the organosulfur compound with the formula C6H5NSO. It is a straw-colored liquid. ''N''-Sulfinylaniline is an example of a sulfinylamine. It is a dienophile and a ligand in organometallic chemistry.
Synthesis and struc ...
. Thionyl chloride reacts with primary
formamides to form
isocyanide
An isocyanide (also called isonitrile or carbylamine) is an organic compound with the functional group –. It is the isomer of the related nitrile (–C≡N), hence the prefix is ''isocyano''.IUPAC Goldboo''isocyanides''/ref> The organic fra ...
s and with secondary formamides to give chloro
iminium ions; as such a reaction with
dimethylformamide will form the
Vilsmeier reagent.
By an analogous process primary
amide
In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula , where R, R', and R″ represent organic groups or hydrogen atoms. The amide group is called a peptide bond when it is ...
s will react with thionyl chloride to form
imidoyl chlorides, with secondary amides also giving chloro
iminium 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
The Bischler–Napieralski reaction is an intramolecular electrophilic aromatic substitution reaction that allows for the cyclization of β-arylethylamides or β-arylethylcarbamates. It was first discovered in 1893 by August Bischler and , in affil ...
as a means of forming
isoquinolines.
Primary amides will continue on to form
nitriles if heated (
Von Braun amide degradation
The von Braun amide degradation is the chemical reaction of a monosubstituted amide with phosphorus pentachloride or thionyl chloride to give a nitrile and an organohalide. It is named after Julius Jacob von Braun, who first reported the reaction. ...
).
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 agent
Nerve agents, sometimes also called nerve gases, are a class of organic chemicals that disrupt the mechanisms by which nerves transfer messages to organs. The disruption is caused by the blocking of acetylcholinesterase (AChE), an enzyme that ...
s. For example, thionyl chloride converts
dimethyl methylphosphonate into
methylphosphonic acid dichloride
Methylphosphonyl dichloride (DC) or dichloro is an organophosphorus compound. It has a number of commercial uses but is most notable as being a precursor to several chemical weapons agents. It is a white crystalline solid that melts slightly above ...
, which can be used in the production of
sarin
Sarin (NATO designation GB G-series, "B"">Nerve_agent#G-series.html" ;"title="hort for Nerve agent#G-series">G-series, "B" is an extremely toxic synthetic organophosphorus compound.[soman
Soman (or GD, EA 1210, Zoman, PFMP, A-255, systematic name: ''O''-pinacolyl methylphosphonofluoridate) is an extremely toxic chemical substance. It is a nerve agent, interfering with normal functioning of the mammalian nervous system by inhibiti ...]
.
With metals
As reacts with water it can be used to dehydrate various metal chloride hydrates, such
magnesium chloride (),
aluminium chloride (), and
iron(III) chloride ().
This conversion involves treatment with refluxing thionyl chloride and follows the following general equation:
:
MCl_\mathit\! .\! \mathit\ H2O + \mathit\ SOCl2 -> MCl_\mathit + \mathit\ SO2 + 2\! \mathit\ HCl
Other reactions
* Thionyl chloride can engage in a range of different electrophilic addition reactions. It adds to alkenes in the presence of 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 or the presence of catalysts such as , , or .
* In the laboratory, a reaction between thionyl chloride and an excess of
anhydrous
A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achi ...
alcohol can be used to produce anhydrous alcoholic solutions of
HCl.
* Thionyl chloride undergoes halogen exchange reactions to give compounds such as
antimony trifluoride
Antimony trifluoride is the inorganic compound with the formula SbF3. Sometimes called Swarts' reagent, is one of two principal fluorides of antimony, the other being SbF5. It appears as a white solid. As well as some industrial applications, i ...
and
antimony trichloride:
*:
3 SOCl2 + 2 SbF3 -> 3 SOF2 + 2 SbCl3
* or
hydrogen bromide and hydrogen chloride:
*:
SOCl2 + 2 HBr -> SOBr2 + 2 HCl
Batteries
Thionyl chloride is a component of lithium–thionyl chloride
batteries
Battery most often refers to:
* Electric battery, a device that provides electrical power
* Battery (crime), a crime involving unlawful physical contact
Battery may also refer to:
Energy source
*Automotive battery, a device to provide power t ...
, where it acts as the positive electrode (in batteries:
cathode
A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction i ...
) with
lithium
Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid ...
forming the negative electrode (
anode
An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemoni ...
); the
electrolyte is typically
lithium tetrachloroaluminate. The overall discharge reaction is as follows:
:
4 Li + 2 SOCl2 -> 4 LiCl + 1/8 S8 + SO2
These non-rechargeable batteries had many advantages over other forms of lithium batteries such as a high energy density, a wide operational temperature range, and long storage and operational lifespans. However, their high cost, non-rechargeability, 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. The technology was used on the
Sojourner Mars rover.
Safety
SOCl
2 is highly reactive and can violently release hydrochloric acid upon contact with water and alcohols. It is also a controlled substance under the
Chemical Weapons Convention, where it is listed as a
Schedule 3 substance, since it is used in the "di-di" method of producing G-series
nerve agent
Nerve agents, sometimes also called nerve gases, are a class of organic chemicals that disrupt the mechanisms by which nerves transfer messages to organs. The disruption is caused by the blocking of acetylcholinesterase (AChE), an enzyme that ...
s and the Meyer and Meyer–Clarke methods of producing
sulfur-based mustard gases.
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
Sulfur dioxide ( IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic ...
. However, their products were impure: both Persoz and Kremers claimed that thionyl chloride contained phosphorus, and Kremers recorded its boiling point as 100 °C (instead of 74.6 °C). In 1857, the German-Italian chemist
Hugo Schiff
Hugo (Ugo) Schiff (26 April 1834 – 8 September 1915) was an Italian naturalized chemist. The son of a Jewish businessman and brother of the physiologist Moritz Schiff was German by nationality. He discovered Schiff bases and other imines, ...
subjected crude thionyl chloride to repeated fractional distillations and obtained a liquid which boiled at 82 °C and which he called ''Thionylchlorid''. In 1859, the German chemist
Georg Ludwig Carius noted that thionyl chloride could be used to make
acid anhydrides and
acyl chloride
In organic chemistry, an acyl chloride (or acid chloride) is an organic compound with the functional group . Their formula is usually written , where R is a side chain. They are reactive derivatives of carboxylic acids (). A specific example ...
s from
carboxylic acid
In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxyl ...
s and to make
alkyl chlorides from
alcohols.
[
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
Benzoyl chloride, also known as benzenecarbonyl chloride, is an organochlorine compound with the formula . It is a colourless, fuming liquid with an irritating odour, and consists of a benzene ring () with an acyl chloride () substituent. It i ...
(ClC7H5O) and to transform sodium benzoate into benzoic anhydride
Benzoic anhydride is the organic compound with the formula (C6H5CO)2O. It is acid anhydride of benzoic acid and the simplest symmetrical aromatic acid anhydride. It is a white solid.
Preparation and reactions
It is usually prepared by the dehydra ...
. 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 rganicsubstances 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.)
See also
*
Oxalyl chloride
*
Phosphorus pentachloride
*
Phosgene
Phosgene is the organic chemical compound with the formula COCl2. It is a toxic, colorless gas; in low concentrations, its musty odor resembles that of freshly cut hay or grass. Phosgene is a valued and important industrial building block, es ...
*
Sulfur dichloride
*
Thionyl bromide
References
{{DEFAULTSORT:Thionyl Chloride
Thionyl compounds
Sulfur(IV) compounds
Sulfur oxohalides
Oxychlorides
Reagents for organic chemistry
Lachrymatory agents
Foul-smelling chemicals
Inorganic solvents