MBC 233.1 Organic Chemistry Dr. Mrs.

Winifred Udeh

Amines, Nitriles, Thiols, Thioethers, Sulphoxides and Sulphones

1. Amines:

Amines are organic compounds that contain nitrogen atoms with a lone pair. Amines
constitute an important class of organic compounds derived by replacing one or more
hydrogen atoms in an ammonia compound by alkyl/aryl group(s). They are basically
derived from ammonia (NH3) in which one or more hydrogen atoms of the ammonia
molecule, is replaced by an alkyl or aryl group, and so they are known as alkylamines and
arylamines respectively.

Classification of Amines
Amines are classified as primary, secondary, or tertiary depending on whether one, two,
or three of the hydrogen atoms of ammonia have been replaced by organic groups. In
chemical notation these three classes are represented as RNH 2, R2NH, and R3N,
respectively.

Amines are classified as primary (1o), secondary (2o) and tertiary (3o) depending upon the
number of hydrogen atoms replaced by alkyl or aryl groups in ammonia molecule. If one
hydrogen atom of ammonia is replaced by R or Ar, we get RNH2 or ArNH2, a primary
amine (1o). If two hydrogen atoms of ammonia or one hydrogen atom of R-NH2 are
replaced by another alkyl/aryl (R’) group, you get R-NHR’, a secondary amine. The second
alkyl/aryl group may be same or different. Replacement of another hydrogen atom by
alkyl/aryl group leads to the formation of tertiary amine.
Amines are said to be ‘simple’ when all the alkyl or aryl groups are the same, and ‘mixed’
when they are different.

Properties of Amines

• Primary amines are liquids at room temperature containing three to four carbon
atoms, whereas higher amines are solids.
• The lower aliphatic amines with a fishy smell are gaseous in nature.
• Aniline and other arylamines are normally colourless, but when stored open due
to atmospheric oxidation, they get painted.
• Lower aliphatic amines can form water molecular hydrogen bonds, making them
water-soluble.
• Increasing the size of the hydrophobic alkyl portion decreases the amine molar
weight, resulting in a decrease in water solubility.
• Lower amines in the soil are insoluble. Organic solvents such as ethanol, benzene,
and ether dissolve amines readily.
 • As a product of hydrogen bonding between the nitrogen and the hydrogen of the
other atom, primary and secondary amines are often involved in the
intermolecular interaction.
• Due to the availability of two hydrogen atoms, the intermolecular association is
more prominent in primary amines compared to secondary. Due to the absence
of a free hydrogen atom for bonding, there is no intermolecular association in
tertiary amines.
• With an increasing molecular mass of the molecule boiling point of the amine
increases. Depending on the intermolecular hydrogen bonding, the boiling point
order of amine is given as; primary amine > secondary amine > tertiary amine.
• Boiling point: 48.60C > 37.00C > 3.5 0C.
• Aliphatic amines are more basic than aromatic amines because in aromatic amines
lone pair of electrons on a nitrogen atom is delocalized and less available for acid.

Structure of Amines
The amine molecule is a derivative of ammonia. Figure 1 compares the molecular amine
structure with the structure of a regular ammonia molecule. Nitrogen is the central atom
in the amine groups; one of its bonds is always preserved for the parent organic carbon
chain, the remaining two bonds can either be with hydrogen atoms or alkyl groups.
R H H H

N N

H H
Amine Group Ammonia

Fig 1. Structure of an amine and ammonia

There are slight differences between amines depending on whether they are primary,
secondary or tertiary (based on number of R groups attached to the N)

Primary amines

• Primary amines have one alkyl group attached to the N.

• The root name is based on the longest chain with the -NH2 attached.
• The chain is numbered so as to give the amine unit the lowest possible number.
• The amine suffix is appended to the appropriate alkyl root or alkana- root.
• Functional group is an amine, therefore suffix = -amine
• Hydrocarbon structure is an alkane therefore -ane
• The longest continuous chain is C4 therefore root = but
• The first point of difference rule requires numbering from
the right as drawn to make the amine group locant 2- CH3CH2CH(NH2)CH3

butan-2-amine or 2-butylamine
(or sec-butylamine)

Secondary amines

• Secondary amines have two alkyl groups attached to the N.

• The root name is based on the longest chain with the -NH attached.
• The chain is numbered so as to give the amine unit the lowest possible number.
• The other alkyl group is treated as a substituent, with N as the locant.
• The N locant is listed before numerical locants, e.g. N,2-dimethyl....
• The amine suffix is appended to the appropriate alkyl root or alkana- root.

• Functional group is an amine, therefore suffix = -amine

• Hydrocarbon structure is an alkane therefore -ane
• The longest continuous chain is C2 therefore root = eth

N-methylethylamine CH3NHCH2CH3
or
N-methylethanamine

Tertiary amines

• Tertiary amines have three alkyl group attached to the N.

• The root name is based on the longest chain with the -N attached.
• The chain is numbered so as to give the amine unit the lowest possible number.
• The other alkyl groups are treated as substituents, with N as the locant.
• The N locant is listed before numerical locants, e.g. N, 2-dimethyl....
• The amine suffix is appended to the appropriate alkyl root or alkana- root

• Functional group is an amine, therefore suffix = -amine

• Hydrocarbon structure is an alkane therefore -ane
• The longest continuous chain is C1 therefore root = meth

Name : N,N-dimethylmethylamine (CH3)3N

or
 N,N-dimethylmethanamine
or
trimethylamine

Common examples of amines

These include amino acids, trimethylamine, and aniline. Some other inorganic ammonia
compounds such as monochloramine (NClH2) are also known as amines. In nature,
amines naturally occur amongst hormones, alkaloids, vitamins, proteins and other
substances.
Synthetic examples of amines include polymers, dye stuffs and drugs. Two biologically
active compounds, namely adrenaline and ephedrine, both containing secondary amino
group, are used to increase blood pressure. Novocain, a synthetic amino compound, is
used as an anesthetic in dentistry while Benadryl, a well-known antihistaminic drug also
contains tertiary amino group.
Quaternary ammonium salts are used as surfactants. Diazonium salts are intermediates
in the preparation of a variety of aromatic compounds including dyes.

Synthesis of Amine
1. From alcohols: Industrially significant alkyl amines are prepared from ammonia
by alkylation with alcohols:

2. From alkyl and aryl halides: Unlike the reaction of amines with alcohols the reaction
of amines and ammonia with alkyl halides is used for synthesis in the laboratory: In such
reactions, which are more useful for alkyl iodides and bromides, the degree of alkylation
is difficult to control such that one obtains mixtures of primary, secondary, and tertiary
amines, as well as quaternary ammonium salts.
Aryl halides are much less reactive toward amines and for that reason are more
controllable. A popular way to prepare aryl amines is the Buchwald-Hartwig reaction.
3. From alkenes: Disubstituted alkenes react with HCN in the presence of strong acids
to give formamides, which can be decarbonylated. This method, the Ritter reaction, is
used industrially to produce tertiary amines such a tert-octylamine.
Hydroamination of alkenes is also widely practiced. The reaction is catalyzed by zeolite-
based solid acids.
4. Reductive routes: Via the process of hydrogenation, unsaturated N-containing
functional groups are reduced to amines using hydrogen in the presence of a nickel
catalyst.
Suitable groups include nitriles, azides, imines, including oximes, amides, and nitro. In
the case of nitriles, reactions are sensitive to acidic or alkaline conditions, which can
cause hydrolysis of the −CN group. LiAlH4 is more commonly employed for the reduction
of these same groups on the laboratory scale.
Many amines are produced from aldehydes and ketones via reductive amination, which
can either proceed catalytically or stoichiometrically.
Aniline (C6H5NH2) and its derivatives are prepared by reduction of the nitroaromatics. In
industry, hydrogen is the preferred reductant, whereas, in the laboratory, tin and iron
are often employed.
Specialized methods of Amine production:
Many methods exist for the preparation of amines, many of these methods being
rather specialized.
Reaction name Substrate Comment

Staudinger reduction This reaction also takes

place with a reducing
Organic azide
agent such as lithium
aluminium hydride.

Schmidt reaction Carboxylic acid

Aza-Baylis–Hillman Imine
Synthesis of allylic amines
reaction

Birch reduction Imine Useful for reactions that

trap unstable imine
intermediates, such
as Grignard
reactions with nitriles.[13]
 Reaction name Substrate Comment

Hofmann degradation Amide This reaction is valid for

preparation of primary
amines only. Gives good
yields of primary amines
uncontaminated with
other amines.

Hofmann elimination Quaternary Upon treatment with

ammonium salt strong base

Leuckart reaction Ketones and aldehydes Reductive

amination with formic
acid and ammonia via
an imine intermediate

Hofmann–Löffler Haloamine
reaction

Eschweiler–Clarke Amine Reductive

reaction amination with formic
acid and formaldehyde via
an imine intermediate

Reactions of Amines
Amines undergo certain reactions such as Alkylation, acylation, sulfonation, etc. Aside
from their basicity, the dominant reactivity of amines is their nucleophilicity. Most
primary amines are good ligands for metal ions to give coordination complexes. Amines
are alkylated by alkyl halides. Acyl chlorides and acid anhydrides react with primary and
secondary amines to form amides (the "Schotten–Baumann reaction").
Similarly, with sulfonyl chlorides, one obtains sulfonamides. This transformation, known
as the Hinsberg reaction, is a chemical test for the presence of amines.
Because amines are basic, they neutralize acids to form the corresponding ammonium
salts R3NH+. When formed from carboxylic acids and primary and secondary amines,
these salts thermally dehydrate to form the corresponding amides. Amines
undergo sulfamation upon treatment with sulfur trioxide or sources thereof:
1. Acid-base reactions: Alkyl amines protonate near pH=7 to give alkyl
ammonium derivative.

2. Diazotization: Amines reacts with nitrous acid to give diazonium salts. The alkyl
diazonium salts are of little importance because they are too unstable. The most
important members are derivatives of aromatic amines such as aniline ("phenylamine")
(A = aryl or naphthyl):
Anilines and naphthylamines form more stable diazonium salts, which can be isolated in
the crystalline form.
Diazonium salts undergo a variety of useful transformations involving replacement of
the N2 group with anions. For example, cuprous cyanide gives the corresponding nitriles:
Aryldiazonium couple with electron-rich aromatic compounds such as a phenol to
form azo compounds. Such reactions are widely applied to the production of dyes
3. Conversion to imines: Imine formation is an important reaction. Primary amines react
with ketones and aldehydes to form imines. In the case of formaldehyde (R' = H), these
products typically exist as cyclic trimers.
Reduction of these imines gives secondary amines:
Similarly, secondary amines react with ketones and aldehydes to form enamines:

An overview of the reactions of amines is given below:

Reaction name Reaction product Comment

Amine alkylation Amines Degree of substitution increases

Schotten–Baumann Amide Reagents: acyl chlorides, acid

reaction anhydrides

Hinsberg reaction Sulfonamides Reagents: sulfonyl chlorides

Amine–carbonyl Imines
condensation

Organic oxidation Nitroso compounds Reagent: peroxymonosulfuric

acid

Organic oxidation Diazonium salt Reagent: nitrous acid

Zincke reaction Reagent: pyridinium salts, with

Zincke aldehyde
primary and secondary amines
 Reaction name Reaction product Comment

Emde degradation Tertiary amine Reduction of quaternary

ammonium cations

Hofmann–Martius Aryl-
rearrangement substituted anilines

von Braun reaction Organocyanamide By cleavage (tertiary amines

only) with cyanogen bromide

Hofmann elimination Alkene Proceeds by β-elimination of less

hindered carbon

Cope reaction Alkene Similar to Hofmann elimination

Carbylamine reaction Isonitrile Primary amines only

Hoffmann's mustard oil Isothiocyanate Carbon

test disulfide CS2 and mercury(II)
chloride HgCl2 are used.
Thiocyanate smells like mustard.

2. NITRILES
Nitriles: These are the organic compounds in organic chemistry which are also called
Cyano Compounds. This class of organic compounds contain cyanide as the functional
group with the formula −C ≡ N. They are called cyano compounds and include any of a
class of organic compounds having molecular structures in which a cyano group (―C ≡
N) is attached to a carbon atom (C). Nitriles are colourless solids or liquids with distinctive
odors.
Acrylonitrile is produced in large quantities by a process called ammoxidation that
depends on the oxidation of propylene in the presence of ammonia and a catalyst.
Acrylonitrile constitutes an important component of several polymeric substances,
including the acrylic textile fibres and synthetic rubbers and thermoplastic resins.
Some nitriles are manufactured by heating carboxylic acids with ammonia in the
presence of catalysts. This process is used to make nitriles from natural fats and oils, the
products being used as softening agents in synthetic rubbers, plastics, and textiles and
for making amines. Nitriles are also formed by heating amides with phosphorous
pentoxide. They can be reduced to primary amines through the action of lithium
aluminum hydride or hydrolyzed to carboxylic acids in the presence of either an acid or
a base.
Properties of Nitriles
The chemical and physical properties of nitriles are given below-

• Nitriles are colourless solids or liquids with unique odours.

• They have boiling points measuring between 82-118 °C.
• Nitriles exhibit strong dipole-dipole movements and also the Van der Waals forces
of dispersion between the molecules.
• They also show high polarity and electronegativity.
• These are said to be highly soluble in water, and the solubility decreases as the
chain length increases.
Reactions of Nitriles
Nitrile undergoes a various set of reactions as shown below-

1. Hydrolysis- The hydrolysis of nitriles in the presence of an acid or a base produces

carboxamides and carboxylic acids efficiently.

2. Reduction- Nitriles are reduced to primary and tertiary amines by treating them
with lithium aluminium hydride. The reduction process occurs in the presence of
some catalysts.

3. Alkylation- The alkylation of nitrile compounds leads to the formation of nitrile

anions.
The other reactions are nucleophilic addition reactions, Friedel–Crafts acylation, etc.

Uses of Nitriles:
Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in
super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory
and medical gloves. Nitrile rubber is also widely used as automotive and other seals since
it is resistant to fuels and oils.
One of the most common occurrences of nitriles is in Nitrile rubber. Nitrile rubber is a
synthetic copolymer of acrylonitrile and butadiene. This form of rubber is highly resistant
to chemicals and is used to make protective gloves, hoses and seals.
Nitrile is used in various medical and industrial applications of which some are listed
below:

• Nitriles are used in the manufacture of nitrile gloves, seals, and hoses as they
exhibit resistance to chemicals.
• They are used as an anti-diabetic drug which is used in the treatment of breast
cancers.
• The compound of nitrile called pericyazine is used in treating opiate dependence
as an antipsychotic.
• This compound is found in many plant and animal sources.

• They are utilized in the applications of oil-resistant substances and also for low-
temperature uses
They are also employed in automotive systems, hydraulic hoses and also in aircraft
systems.

3. Thiols

Thiol, also called mercaptan, is a class of organic chemical compounds similar to the
alcohols and phenols but containing a sulfur atom in place of the oxygen atom. Thiols
can be defined as a sulfur analogue of alcohols. In a simpler way, it is an organic
compound consisting of compounds with a sulfur atom. It is also referred to as
mercaptan. It consists of sulfhydryl group, i.e., Thiol = R-SH. Thiols are among the
odorous principles in the scent of skunks and of freshly chopped onions; their presence
in petroleum and natural gas is objectionable because they have disagreeable odours,
interfere with catalysts used in refining processes, and produce sulfur dioxide upon
combustion.

Properties of Thiols
Many thiols consist of odours that are usually strong which may resemble the scent of
onions and garlic.

Thiols possessing a low molecular weight, consist of a repulsive and strong smell. For
example, consider skunks consisting of the lower molecular weight of thiol and it is easily
detectable by humans.

It is also responsible for some sort of wine faults that have resulted due to some
unintended reactions caused between sulphur and yeast. Note that not all kinds of thiols
have bad odour; there are many other thiols with a pleasant smell. For example, furan-
2-yl methanethiol is responsible for the beautiful aroma of roasted coffee, and
monoterpenoid thiol is responsible for the mesmerizing scent of a grapefruit. One can
find it only at low concentration levels.

Thiols are less likely soluble in water.

Boiling points and solubility: Thioether functional groups possess similar boiling points
and solubility features, but this does not hold true for alcohols. Thiols show little
association by hydrogen bonding, both with water molecules and among themselves.
Hence, they have lower boiling points and are less soluble in water and other polar
solvents than alcohols of similar molecular weight. For this reason also, thiols and their
corresponding sulfide functional group isomers have similar solubility characteristics and
boiling points, whereas the same is not true of alcohols and their corresponding isomeric
ethers.
Volatile thiols can be easily identified due to their distinctive odours.

Reactions of Thiols
Many reactions are exhibited by thiols similar to that of hydroxyl compounds involving
the formation of sulphides and thioesters. Oxidation would affect the sulphur atom in
thiols, whereas in alcohol it would lead to the generation of a new product where it
changes the oxidation state of a carbon atom.
Thioxanthates
Thiolates react with carbon disulphide to produce thioxanthate. Thioxanthates are
organic compounds with the formula RSCS2X. If X is an alkali metal, then thioxanthate is
a salt. IF X is a transition metal, then thioxanthate is a ligand, and if X is an organic group,
then the compounds are called thioxanthate esters.
Metal ion complexation
Thiolates form transition metal thiolate complexes with metal ions.

Redox
Thiols readily oxidize through reagent iodine, in the presence of a base to produce
organic sulphide. The redox reaction of thiol is mentioned below.
2 R–SH + Br2 → R–S–S–R + 2 HBr

Reagents such as hydrogen peroxide or sodium hypochlorite can also produce sulfonic
acids.
R–SH + 3 H2O2 → RSO3H + 3 H2O

In the presence of a catalyst, oxidation can be affected by oxygen.

2 R–SH + 1⁄2 O2 → RS–SR + H2O

Participation of thiols in thiol-disulfide exchange.

RS–SR + 2 R′SH → 2 RSH + R′S–SR′

S-alkylation
Thiols are alkylated to give thioethers.
RSH + R′Br + B → RSR′ + [HB]Br

Acidity
Thiols are more acidic in nature. Thiolate is a conjugate base of thiol. It is obtained from
thiol on treatment with alkali metal hydroxides.

Thiols show many reactions like those of the hydroxyl compounds, such as formation of
thioesters and thioethers (sulfides). Toward oxidation, however, they differ profoundly
from alcohols: that is, whereas oxidation of an alcohol usually leads to a product in which
the oxidation state of a carbon atom has been changed, oxidation of a thiol affects the
sulfur atom. Mild oxidants convert thiols to disulfides, and more vigorous reagents result
in the formation of sulfonic acids. Aliphatic thiols are commonly prepared from alkyl
halides and sodium hydrosulfide or from olefins and hydrogen sulfide, while Aromatic
thiols can be made from the amino compounds by way of the diazonium salts.

A thiol generally has a much lower boiling point than the hydroxyl compound of like
structure; for example, methanethiol boils at 6° C (43° F), methanol at 65° C (149° F). The
lower aliphatic thiols are useful as warning odorants in fuel gases and are somewhat
toxic.

Examples of thiols

• Methanethiol – CH3SH [methyl mercaptan]

• Ethanethiol – C2H5SH [ethyl mercaptan]
• 1-Propanethiol – C3H7SH [n-propyl mercaptan]
• 2-Propanethiol – CH3CH(SH)CH3 [2C3 mercaptan]
• Allyl mercaptan – CH2=CHCH2SH [2-propenethiol]
• Butanethiol – C4H9SH [n-butyl mercaptan]
• tert-Butyl mercaptan – (CH3)3CSH [t-butyl mercaptan]
• Pentanethiols – C5H11SH [pentyl mercaptan]
• Thiophenol – C6H5SH
• Dimercaptosuccinic acid
• Thioacetic acid

Uses of thiols
Thiols are used as odorants to assist in the detection of natural gas
Thiols serve a central role in protein-based and low-molecular-weight redox systems.

Thiol-based antioxidants protect organisms against oxidative stress.

Thiols in antioxidant enzymes can relay oxidative signals to other proteins and
Glutathione represents a tightly balanced compartment-specific reducing currency.

4. Thioethers
Thioether (sulfide): Is a functional group characterized by a sulfur atom flanked by two
carbon atoms of any hybridization. A thioether is a molecule with the group R-S-R. The
first atom in R is a carbon. Thioether take their name from ethers. They have
a sulfur instead of an oxygen atom between the two R.
Thioethers can have very bad smells like thiols. They can also be called sulfides. The C-S-
C bond is at nearly 90 degrees. A thioester is formed between the carboxyl of the
terminal glycine residue of Ubiquitone and a cysteine residue of the activating enzyme,
or E1.
This bond occurs when a carboxylic acid is conjugated with a sulfhydryl group, such as
the one on coenzyme A.
The thiol ester linkage is an important concern to those studying the mechanisms of
action of acetyl-CoA carboxylase, citrate synthase, propionyl-CoA carboxylase, and
HMG-CoA synthase.
Acetyl-CoA carboxylase and propionyl-CoA carboxylase catalyze the condensation of
CO2 with the 2-carbon of the thiol ester substrate. Citrate synthase catalyzes the
condensation of OAA at the 2-carbon of the thiol ester substrate. These condensation
reactions involve attack of an atom with a partial positive charge (the carbon of CO 2 or
the keto group of OAA) on an atom with a negatively charged character (the 2-carbon of
the substrate). Condensation of positively and negatively charged carbons to form a
stable, covalent bond.

Uses of Thioethers
Thioethers are important in biology. The thioester-containing proteins (TEPs) are
accessory proteins of the complement system, homologous to proteins such as C3, C4,
a2M and CD109s. TEPs promote the opsonization of microorganisms and their
elimination by phagocytosis in some invertebrates by activating the Toll signaling
pathway.
They are present in some amino acids. Petroleum has many thioethers in it as well.
Thioethers can be made in the laboratory by the reaction of a thiol with a base and
an electrophile. It is easy to oxidise them to sulfoxides and then sulfones.
Dimethyl sulfide is the simplest thioether. It is used in important reactions like the Swern
oxidation which is used to make aldehydes starting from alcohols.
Examples of a thioether
Some thioethers are named by modifying the common name for the corresponding
ether. For example, C6H5SCH3 is methyl phenyl sulfide, but is more commonly called
thioanisole, since its structure is related to that for anisole, C 6H5OCH3.

5. Sulphoxides

A sulfoxide, also called a sulphoxide, is an organosulfur compound containing

a sulfinyl (>SO) functional group attached to two carbon atoms. It is a polar functional
group. Sulfoxides are oxidized derivatives of sulfides. Examples of important sulfoxides
are alliin, a precursor to the compound that gives freshly crushed garlic its aroma,
and dimethyl sulfoxide (DMSO), a common solvent.

Sulfoxides are typically prepared by oxidation of sulfides, sometimes referred to

as sulfoxidation. Hydrogen peroxide is a typical oxidant used, but periodate has also
been used in some cases. In these oxidation reactions, care is required to avoid over
oxidation to form the sulfone. For example, dimethyl sulfide is oxidized to dimethyl
sulfoxide and then further to dimethyl sulfone.

Aryl sulfoxides
In addition to the oxidation routes, diaryl sulfoxides can be prepared by two Friedel–
Crafts arylations of sulfur dioxide using an acid catalyst:
2 ArH + SO2 → Ar2SO + H2O
Both aryl sulfinyl chlorides and diaryl sulfoxides can be also prepared from arenes
through reaction with thionyl chloride in the presence of Lewis acid catalysts such as
BiCl3, Bi(OTf)3, LiClO4, or NaClO4.

Reactions of Sulfoxides

Deoxygenation and oxygenation

Sulfoxides undergo deoxygenation to give sulfides. Typically metal complexes are used
to catalyze the reaction, using hydrosilanes as the stoichiometric reductant. The
deoxygenation of dimethylsulfoxide is catalyzed by DMSO reductase, a molybdoenzyme:
 OSMe2 + 2 e- + 2 H+ → SMe2 + H2O
Acid-base reactions
The α-CH groups of alkyl sulfoxides are susceptible to deprotonation by strong bases,
such as sodium hydride:
CH3S(O)CH3 + NaH → CH3S(O)CH2Na + H2
In the Pummerer rearrangement, alkyl sulfoxides react with acetic anhydride to give
migration of the oxygen from sulfur to the adjacent carbon as an acetate ester. The first
step of the reaction sequence involves the sulfoxide oxygen acting as a nucleophile:

Elimination reactions
Sulfoxide undergo thermal elimination via an Ei mechanism to yield
[16][17]
vinyl alkenes and sulfenic acids.
CH3S(O)CH2CH2R → CH3SOH + CH2=CHR
The acids are powerful antioxidants, but lack long-term stability. Some parent sulfoxides
are therefore marketed as antioxidant polymer stabilisers. Structures based on
thiodipropionate esters are popular. The reverse reaction is possible.
Coordination chemistry
Sulfoxides, especially DMSO, form coordination complexes with transition metals.
Depending on the hard-soft properties of the metal, the sulfoxide binds through either
the sulfur or the oxygen atom. The latter is particularly common.

6. Sulphones
A Sulphone also called a sulfone, is an organosulfur compound containing a sulfonyl
functional group attached to two carbon atoms. The central hexavalent sulfur atom
is double-bonded to each of two oxygen atoms and has a single bond to each of two
carbon atoms, usually in two separate hydrocarbon substituents.

Examples of sulfones in pharmacology include dapsone, a drug formerly used as an

antibiotic to treat leprosy, dermatitis herpetiformis, tuberculosis, or pneumocystis
pneumonia (PCP).

By oxidation of thioethers and sulfoxides

Sulfones are typically prepared by organic oxidation of thioethers, often referred to
as sulfides. Sulfoxides are intermediates in this route. For example, dimethyl
sulfide oxidizes to dimethyl sulfoxide and then to dimethyl sulfone.
From SO2
Sulfur dioxide is a convenient and widely used source of the sulfonyl functional group.
Specifically, Sulfur dioxide participates in cycloaddition reactions with dienes.[3] The
industrially useful solvent sulfolane is prepared by addition of sulfur dioxide to buta-1,3-
diene followed by hydrogenation of the resulting sulfolene.

Synthesis of sulfolane by hydrogenation of sulfolene.

Sulfur dioxide is a convenient and widely used source of the sulfonyl functional group.
Specifically, Sulfur dioxide participates in cycloaddition reactions with dienes.[3] The
industrially useful solvent sulfolane is prepared by addition of sulfur dioxide to buta-1,3-
diene followed by hydrogenation of the resulting sulfolene. [4]
From sulfonyl and sulfuryl halides
Sulfones are prepared under conditions used for Friedel–Crafts reactions using sources
of RSO+2 derived from sulfonyl halides and sulfonic acid anhydrides. Lewis acid catalysts
such as AlCl3 and FeCl3 are required.

Sulfones have been prepared by nucleophilic displacement of halides by sulfinates/

Reactions of Sulphones
Sulfone is a relatively inert functional group, being weakly basic (compared to sulfoxides).
They are non-oxidizing. In the Ramberg–Bäcklund reaction and the Julia olefination,
sulfones are converted to alkenes by the elimination of sulfur dioxide.

Applications or uses of Sulphones

Sulfolane is used to extract valuable aromatic compounds from petroleum.

Polymers
Some polymers containing sulfone groups are useful engineering plastics. They exhibit
high strength and resistance to oxidation, corrosion, high temperatures, and creep under
stress. For example, some are valuable as replacements for copper in domestic hot water
plumbing. Precursors to such polymers are the sulfones bisphenol S and 4,4′-
dichlorodiphenyl sulfone.
Pharmacology
Examples of sulfones in pharmacology include dapsone, a drug formerly used as
an antibiotic to treat leprosy, dermatitis herpetiformis, tuberculosis, or pneumocystis
pneumonia (PCP). Several of its derivatives, such as promin, have similarly been studied
or actually been applied in medicine, but in general, sulfones are of far less prominence
in pharmacology than the sulfonamides for example.