SULFONATION AND
SULFATION
Group 1
12/21/2018 1
PRESENTED BY:
• Hira Meraj (2016-CH-217)
• Roshaan Akhtar (2016-CH-239)
• Faqeeha Fatima Haq (2016-CH-251)
• Tayyaba Yousaf (2016-CH-261)
• Fatima Amir (2016-CH-287)
• Maria Hameed (2016-CH-299)
12/21/2018 2
INTRODUCTION
Sulfonation and sulfation are major industrial chemical processes used to make a diverse
range of products, including dyes and color intensifiers, pigments, pesticides and organic
intermediates. Additionally, almost 500,000 metric tons per year of lignin sulfonates are
produced as a by-product from paper pulping. Petroleum sulfonates are widely used as
detergent additives in lubricating oils
12/21/2018 3
SULFONATION
• “Sulfonation involves the introduction of sulfonic acid group or corresponding salt like
sulfonyl halide group into an organic compound”
12/21/2018 4
TYPES OF SULFONATION
Particular types of sulfonation includes:-
• Sulfochlorination
• Halosulfonation
• Sulfoxidation
• Sulfoalkylation
• Sulfoacylation
• Sulfoarylation
12/21/2018 5
GENERAL INTRODUCTION
• Desulfonationation
• Formation of sulfonation product
• Electrophile
• Highly exothermic reaction
12/21/2018 6
SULFATION
PRESENTED BY:
ROSHAAN AKTHAR
12/21/2018 7
DEFINITION
• The process of becoming sulfated or sulfating
• Placement of the -OSO2OH group on carbon, yielding an acid sulfate (R-OSO2O-R), or
of the –SO4- group between two carbons becoming the sulfate ROSO2OR
• The replacement of a hydrogen atom of an organic compound with a sulfate (-
OSO2OH) functional group, or the replacement of the hydrogen atoms of two molecules
to form a sulfate (R-OSO2O-R)
12/21/2018 8
SULFATOALKYLATION
• Introduction of a sulfated alkyl group into an organic compound
• For example, production of dimethyl sulfate (CH3)2 SO4
12/21/2018 9
CLASSIFICATION OF SULFONATES
• Four main types
• Aliphatic and alicyclic sulfonates
• Aromatic sulfonates
• Heterocyclic sulfonates
• N-sulfonates
12/21/2018 10
OTHER TYPES OF SULFONATES
DERIVED FROM
• petroleum fractions
• lignin
• fatty oils
12/21/2018 11
CLASSIFICATION OF SULFATES
• Sulfates may be classified as
• Sulfated alkenes
• Alcohol sulfates
• Cyclic sulfates
• Sulfated carbohydrates
• Sulfated nitrogenous polysacchrides
12/21/2018 12
MECHANISM OF
SULFONATION
PRESENTED BY :
Faqeeha Fatima Haq (2016-CH-251)
12/21/2018 13
SULFONATION OF BENZENE
• Sulfonation of benzene is a process of heating benzene with fuming sulfuric
acid (H2SO4 +SO3) to produce benzene sulfonic acid. The reaction is
reversible in nature.
12/21/2018 14
MECHANISM
• Due to higher electronegativity, oxygen present in sulfuric acid pulls an electron towards
itself, generating an electrophile. This attacks the benzene ring, leading to the formation
of benzene sulfonic acid.
There are four main steps of sulfonation reaction
• Formation of electrophile
• Attacking the benzene ring
• Rearrangement
• Regeneration of Catalyst
12/21/2018 15
Formation of Electrophile
• The sulfur trioxide electrophile arises in one of two ways depending on which sort of acid
you are using.
• Concentrated sulfuric acid contains traces of SO3 due to slight dissociation of the acid.
• Fuming sulfuric acid, H2S2O7, can be thought of as a solution of SO3 in sulfuric acid -
and so is a much richer source of the SO3.
• Sulfur trioxide is an electrophile because it is a highly polar molecule with a fair amount
of positive charge on the sulfur atom. It is this which is attracted to the ring electrons.
12/21/2018 16
Formation of Electrophile
• Sulfur trioxide SO3, in fuming sulfuric acid is the electrophile.
12/21/2018 17
Attacking the Benzene Ring
• The electrophile attack the benzene ring as follows:
12/21/2018 18
MECHANISM FOR SULFONATION OF
BENZENE
Step 1:
• The p electrons of the aromatic C=C act as a nucleophile, attacking the electrophilic S,
pushing charge out onto an electronegative O atom. This destroys the aromaticity giving the
cyclohexadienyl cation intermediate.
Step 2:
• Loss of the proton from the sp3 C bearing the sulfonyl- group reforms the C=C and the
aromatic system.
Step 3:
• Protonation of the conjugate base of the sulfonic acid by sulfuric acid produces the sulfonic
acid.
12/21/2018 19
Rearrangement and Regeneration of Catalyst
• The benzene ring is rearranged in order to stabilize the delocalized pi
electrons.
12/21/2018 20
The electrophilic substitution reaction between
benzene and sulfuric acid
There are two equivalent ways of sulfonating benzene:
• Heat benzene under reflux with concentrated sulfuric acid for several hours.
• Warm benzene under reflux at 40°C with fuming sulfuric acid for 20 to 30 minutes.
12/21/2018 21
MECHANISM OF
SULFATION
PRESENTED BY:
Fatima Amir (2016-CH-287)
12/21/2018 22
Preparation
For the preparation of sulfates the methods of interest are
• Treatment of organic compound with SO3
• Condensation Process
• Polymerization
12/21/2018 23
Reaction with SO3
• SO3 is the most efficient sulfonating and sulfating agent
• Direct addition of SO3 is involved
• SO3 is the active reagent in all reactions
RH + SO3 RSO3H
ROH + SO3 ROSO3H
12/21/2018 24
Sulfation of Alkenes and Alcohols
• Sulfation of alkenes or alcohols with conc. acid
• Produces both dialkyl and monoalkyl sulfates
ROH +H2SO4 ROSO2H + H2O
2ROSO2H (RO)2SO2 + H2SO4
RCH CH2 + H2SO4 RCH(CH2)OSO3H
12/21/2018 25
Sulfation of Ethers
• Dimethyl sulfate, used as a methylating agent, is manufactured in excellent
yield and purity by continuous reaction of dimethyl ether with SO3
(CH3)2O + SO3 (CH3)2SO4
12/21/2018 26
Endogenous Compounds
12/21/2018 27
Nucleophilic Attack
12/21/2018 28
Function of Sulfation
• Sulfation plays role in strengthening protein–protein interactions. Types of human
proteins known to undergo tyrosine sulfation include adhesion molecules, G-protein-
coupled receptors, coagulation factors, serine protease inhibitors, extracellular matrix
proteins, and hormones. Tyrosine O-sulfate is a stable molecule and is excreted in urine in
animals. No enzymatic mechanism of tyrosine sulfate desulfation is known to exist. By
knock-out of TPST genes in mice, it may be observed that tyrosine sulfation has effects
on the growth of the mice, such as body weight, fecundity, and postnatal viability.
12/21/2018 29
USES OF
SULFONATION
PRESENTED BY:
Tayyaba Yousaf (2016-CH-261)
12/21/2018 30
USES OF SULFONATION
• DMS (dimethyl sulfate) is mostly act as a sulfonating agent.
• Catalyst:
• pyrolysis reactions
• alkylation of phenol.
• Polymerization
12/21/2018 31
USES OF SULFONATION
• Solvent
• It has been used as a solvent in research on Lewis acid-aromatic hydrocarbon complexes
Electroplating process.
• Stabilizer
• a stabilizer against insecticides.
• ground wood pulp brightness stability
12/21/2018 32
USES OF SULFONATION
• Commercial Uses
• Quaternary Amine
• Ethers
• Prevent corrosion
• Sunneborn’sodium sulfonates provide excellent emulsion quality and corrosion
resistance.
12/21/2018 33
USES OF SULFONATION
• Fuel Additives
Highly overbased magnesium sulfonates often used as fuel oil additives.
• Detergents
sodium dodecylbenzenesulfonate is especially particular component in detergents
12/21/2018 34
USES OF SULFATION
PRESENTED BY:
Maria Hameed (2016-CH-299)
12/21/2018 35
USES OF SULFATION
• Conjugates toxins to sulfur compounds
• Sulfation requires sulfates and its limited by the amount present in the body
• Sulfates may be injected from food
• Sulfoxidation , a final stage of methylation, transforms toxic sulfites into
sulfates
• Sulfites are used to preserve food and can cause respiratory problem in some
people
12/21/2018 36
USES OF SULFATES
• Sulfates are generally used as a preservative. They keep harmful bacterial or fungal
organisms from growing in food products.
• They also act as antioxidants in dried fruit and wine to prevent the product from turning
to a brownish color.
• In wine they prevent the wine from turning to vinegar.
• They extend the shelf-life of many products and are widely used in agricultural ways.
• Sometimes trace amounts can be found in products because of the indirect ways sulfites
are used.
12/21/2018 37
DIFFERENCE BETWEEN
SULFATION SULFONATION
• Sulfation is the replacement of a • Sulfonation is the replacement of a
hydrogen atom of an organic compound hydrogen atom of an organic
with a sulfate (-OSO2OH) functional compound with a sulfonic acid (-
group, or the replacement of the SO3H) functional group, often by
hydrogen atoms of two molecules to reaction with sulfuric acid at high
form a sulfate (R-OSO2O-R). temperatures.
• Sulfation involves the formation of a C- • Sulfonation involves the formation of
O-S bond a C-S bond.
12/21/2018 38
12/21/2018 39
