Aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution. This page guides you through the mechanism for the electrophilic substitution reaction between benzene and sulphuric acid or sulphur. Electrophilic aromatic sulfonation of benzene with sulfur trioxide is studied with ab initio molecular dynamics. Jancar institute of materials chemistry, faculty of chemistry, technical university, cz637 00 brno received 2 april 1996 the experimental details of homogeneous sulfonation of polystyrene in solution of dichloroethane. These reactions produce a variety of products, including derivate polysulfones. Important sulfonation procedures include the reaction of aromatic hydrocarbons with sulfuric acid, sulfur trioxide, or chlorosulfuric acid. Mechanistic insight into ruthenium catalysed metasulfonation. The reaction of sulfur trioxide is with an alkyl benzene whereby the sulfonated alkyl benzene is obtained. Aryl sulfonic acids are used as detergents, dye, and drugs. If you want this mechanism explained to you in detail, there is a link at the bottom of the page. Sulfonation reaction kinetics of polyether ketone ketone. We report herein structural and mechanistic studies of the meta sulfonation of phenylpyridine using ruthenium complexes. The sulfonic acids are among the most important of the organosulfur compounds.
These groups may be situated on either a carbon or a nitrogen atom. The esters are commonly prepared by treating an alcohol with sulfuric acid, sulfur trioxide, chlorosulfuric acid, or sulfamic acid. Elimination reactions just as there are two mechanisms of substitution s n 2 and s n 1, there are two mechanisms of elimination e2 and e1. What is sulfation or sulfonation biosynthesis, inc. During this process, product distributions and sulfonation reaction rate in the sulfonation of phenol are determined by different sulfonating agents, such as fuming sulfuric acid, concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide so 3 and its complexes kucera and jancar, 1998. Sulfonationsulfation processing technology for anionic. Hgbased catalysts have been used at elevated temperature 200450 c for methane sul.
Sulfonation of alkyl phenyl ether selfassembled monolayers. Sulfonation is similar to nitration because in general, we create the electrophile by protonating the so3 with h2so4 to make a stronger electrophile. Organic lecture series 16 friedelcrafts alkylation friedelcrafts alkylation forms a new cc bond between an aromatic ring and an. Preliminary study of sulfonation of polystyrene by. Protodemetallation studies suggest that a concerted ch activationdemetallation process may be involved. So 3 which can be formed by the loss of water from the sulfuric acid. The reaction rate rises with an increase of s o 3 content. Conclusions in the process of sulfonation with sulfuric acid or oleum the reaction mixture contains a residue of sulfuric acid. Synthesis of sucrosebased surfactants through regioselective. Oleum is concentrated sulfuric acid enriched with sulfur trioxide s o 3. Concentrated sulphuric acid contains traces of so 3 due to slight dissociation of the acid. Sulfonation of a low molecular weight linear alkyl benzene lab commercial cut with so 3 air mixtures was conducted in a corrugated wall falling film reactor cwffr.
In contrast to many other electrophilic aromatic substitution reactions, aromatic sulfonation is reversible, in other words it is an equilibrium. Sulfonation may also be carried out the application of s o 3 in an inert solvent. Sulfonation reaction kinetics of polyether ketone ketone pekk using a mixture of concentrated and fuming sulfuric acid steven swier, jeffrey gasa, montgomery t. Reaction of lithium diethylamide with an alkyl bromide and alkyl benzenesulfonate. Prototropic tautomerism was used as a tool for the reductive dehalogenation of heteroaryl bromides and iodides, or dehalogenative sulfonation of heteroaryl chlorides and fluorides, using sodium sulfite as the sole reagent in an aqueous medium. In the menu at the top, select view make sure thumbnails is checked in the dropdown menu. Sulfonation of polystyrene ps has been at tempted by a number of. A chemical reaction which introduces the sulfonic acid functional group so 3 h into a molecule. Chemically sulfation refers to the conversion of a molecule into a sulfate. Illustrated glossary of organic chemistry sulfonation. Catalyzed sulfonation of methane to methanesulfonic acid. Conformational changes and anticoagulant activity of chondroitin sulfate following its osulfonation1 tomohiro maruyama a, toshihiko toida a, toshio imanari a, guyong yu b, robert j.
Draw the mechanism of electrophilic aromatic substitution. Linhardt division of medicinal andnatural productschemistry, anddepartment of chemical andbiochemical. Pdf study of the sulfonation of expanded polystyrene. Because the sulfonation reaction stops when the acid concentration in the reaction mixture drops to less than approximately 90%, sulfonation of detergent feedstocks with sulfuric acid is not normally practiced. This protocol does not require a metal or phase transfer cata. Sulfonation alters the chemical structure of a polymeric substrate by introducing sulfonic groups on its surface region. The mechanism can then proceed as an electrophilic aromatic substitution reaction.
Weiss polymer science program and department of chemical engineering, university of. Sulfonation definition of sulfonation by the free dictionary. And so we would form benzene sulfonic acid and also water as a byproduct. Sulfuric anhydride reacts easily with delocalized electronic densities as those present in aromatics groups or alkenes in general. Weiss polymer science program and department of chemical engineering, university of connecticut, storrs, connecticut 0626936.
Study of the sulfonation of expanded polystyrene waste and of properties of the products obtained. Pdf sulfonationsulfation processing technology for anionic. They are nonvolatile compounds produced by sulfonation. Conformational changes and anticoagulant activity of.
Introduction the sulfonation process relates to the sulfur trioxide sulfonation of long chain and branched chain aliphatic alcohols such as fatty alcohols, and to the sulfonation of the aromatic nucleus of alkyl aromatic compounds. Experimental reactions were carried out in a 100cm3 highpressure autoclave parr instruments, 3000psig maximum constructed of hastelloy b. Greener methods for batch sulfonation 2011 4 by anuja sawant list of figures figure no. There is also a large increase in viscosity associated with sulfonation of lab. Origins of alkylation, elimination, and sulfonation lekha gupta, antonio ramrez, and david b. In the case study presented here, alkylbenzenes are contacted with sulfur trioxide in a short residence time falling film reactor following which the liquid reaction product mixture is. Patents and patent applications class 56298 filed with the uspto. Unlike the other electrophilic aromatic substitution reactions. Sulfonation may be defined as any chemical process by which the sulfonic acid group so. Principles of our sulfonation process sulfo technologies. If your open pdf has more than a single page, select a thumbnail in the lefthand side where you want to insert another pdf file. Water is a byproduct of the reaction so spent acid is inevitable.
Sulfonation of plastics is a process of treating the surface region with sulfur trioxide gas and various neutralization agents to modify the molecular structure of the surface region of the plastic. We have recently reported success in the pdcucatalyzed sulfonation of methane with so2 in presence of molecular o2 9. Organic chemistry ii chem 252 chapter 15 reactions of. Organic chemistry specific name reactions class xii sandmeyer reaction the cl, br and cn nucleophiles can easily be introduced in the benzene ring of benzene diazonium salt in the presence of cui ion.
Reductive dehalogenation and dehalogenative sulfonation of. The reaction free energy profiles for electrophilic substitution of benzene, nitrobenzene at the meta position. Sulfonation with sulfuric acid is a special case of oleum sulfonation. Reactions of aromatic compounds overall chemgapedia. Furthermore, we disclose that the catalytically active species does not require the presence of a. Preliminary study of sulfonation of polystyrene by homogeneous and heterogeneous reaction f. The reaction runs considerably more rapidly, when oleum is applied instead of concentrated sulfuric acid. Pdf study of the sulfonation of expanded polystyrene waste. Sulfonationsulfation processing technology for anionic surfactant manufacture. Pdf conventional sulfonation processes generate large volumes of waste, which becomes increasingly an important issue. Heating the benzene sulfonyl compound in aqueous acid removes the sulfonyl group and replaces it with a proton. Overall, this study provides fundamental insight into the metasulfonation phenylpyridine reaction pathway and uncovers new reaction intermediates that will guide the design of new catalytic systems for remote metafunctionalization.
The product distribution and kinetics of this process were studied by ultraviolet, infrared, and photoelectron. In contrast to the usual interpretations, the results provide clear evidence that in nonpolar media and in the absence of catalysts the mechanism of aromatic sulfonation with a single so3 is concerted and does not. The temperature of desulfonation correlates with the ease of the sulfonation. In organic chemistry, the desulfonation reaction is the hydrolysis of sulfonic acids. Unlike the other electrophilic aromatic substitution reactions, sulfonation is reversible. Sulfonation scheme in a falling film reactor ffr 4. Sulfonic acid, any of a class of organic acids containing sulfur and having the general formula rso3h, in which r is an organic combining group. After completion of the reaction, the reaction mixture was concentrated using rotary evaporator and. How to combine pdf files into one document lifewire. Explaining the mechanism for the sulphonation of benzene an electrophilic substitution reaction between benzene and sulphuric acid to make benzenesulphonic acid. First, a h 2 so 4 molecule generates a so 3 and a h 2 o molecule through a hydroxyloxygen protonation completed by another h 2 so 4 molecule. Jan 04, 2010 the sulfonation of phenyl ether decorated selfassembled monolayers sams was studied with an eye toward creating surfaces with a particularly high negative charge density based on a closepacked array of phenyl rings with more than one sulfonic acid group per molecule. The aim of the study was to compare the performance of this reactor with that of a conventional smooth wall falling film reactor swffr of. However, the sulfonation reaction is highly exothermic, higher feeding rate leads to more reaction heat and thus higher reaction temperature in inner of the reaction system, which is prone to the formation of byproducts.
Direct sulfonation of methane to methanesulfonic acid by. Use a pasteur pipette to slowly add the aniline sulfonic acid suspension to the hcl solution with constant stirring using a glass rod. Search for sulfonation utilizing sulfur trioxide or oleum e. Sulfonation of benzene benzene will react with sulfur trioxide, and in the presence of an acid, aryl sulfonic acids are produced. Today sulfuric acid sulfonation is principally used for. Thermodynamic vs kinetic sulphonation of naphthalene. A process for the sulfonation of an aromatic compound wherein the aromatic compound and sulfonating agent. Peek particles were first dried in a vacuum oven at 100. Production of linear alkyl benzene sulphonic acid labsa. The aim of the study was to compare the performance of this reactor with that of a conventional smooth wall falling film reactor swffr of the same le. The chemistry of benzene and its derivatives solutions to intext problems 16.
Chapter reactions of arenes electrophilic aromatic. Institute of chemical technology greener methods for batch. Heating a sulfonic acid with aqueous sulfuric acid can result be the reverse reaction, desulfonation. A higher feeding rate of concentrated sulfuric acid favored for forward reaction and increased the rate of the sulfonation reaction, which led to the increase of the formation rate of phbsa. Organic lecture series 16 friedelcrafts alkylation friedelcrafts alkylation forms a new cc bond between an aromatic ring and an alkyl group cl alcl3. Reaction of lithium diethylamide with an alkyl bromide and. In conclusion, we have demonstrated a synthetic approach for the direct, liquidphase sulfonation of methane with so2. Today, our customers use chemithon airso3 sulfonation systems to produce surfactants used in a wide variety of consumer and industrial products, as well as oil additives. Reactions that use raw materials those are easily available. So over here we have benzene, and to that we add some sulfuric acid. Pdf sulfonation chemistry more sustainable approaches.
Removal of water from the system favours the formation of the sulfonation product. The most characteristic reaction of aromatic compounds is electrophilic aromatic substitution, in which one of the ring hydrogens is substituted by a halogen, nitro group, sulfonic acid group, alkyl or acyl group. Principles of our sulfonation process sulfo technologies, llc. Mechanical properties of sulfonated poly ether ether.
Under the best reaction conditions, 22% conversion of so2 to msa was achieved after 26 h of reaction. Pdf sulfonationsulfation processing technology for. Linhardt b a faculty of pharmaceutical sciences, chiba uni. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. The mechanism by which ce catalyzes the sulfonation. Then 10 g of peek was dissolved gradually in 400 ml of 96% sulfuric acid in a threeneck flask under. Products of the reaction of sulfonation conducted at 60 c for a period longer than. Direct sulfonation of methane to methanesulfonic acid with so. Sulfonation process used for the manufacturing of anionic surfactants sulfonation reactions can be carried out in different configurations, either liquidliquid contact, or gasliquid contact reactors, and a di versity of sulfonating reagents can be applied. To change the order of your pdfs, drag and drop the files as you want. Kinetics of sulfonation of dodecylbenzene by sulfurtrioxide. Reactions of aromatic compounds rutgers university. Since this reaction is at equilibrium, we can shift the equilibrium by using the different concentrations of.
Merge pdf files combine pdfs in the order you want with the easiest pdf merger available. Study on phenol sulfonation by concentrated sulfuric acid. Although sulphur trioxide isnt ionic, it is highly polar. Mechanical properties of sulfonated poly ether ether ketone nanocomposite membranes. Sulfonation of linear alkyl benzene lab in a corrugated. The more stable this cation intermediate, the faster the ratedetermining step and the faster the overall reaction. Rearrange individual pages or entire files in the desired order.
Sulfonation with sulfur trioxide and sulfuric acid converts benzene into benzene sulfonic acid. Synthesis of sucrosebased surfactants through regioselective sulfonation of acylsucrose and the nucleophilic opening of a sucrose cyclic sulfate he. Sulfonation of linear alkylbenzenes by reaction with sulfur trioxide is the predominant route to anionic surfactants other than soap. The electrophile is sulphur trioxide, and this arises in one of two ways depending on which sort of acid you are using. Explaining the sulphonation of benzene electrophilic. Kinetic and catalysis, reaction engineering and materials science.
Since this reaction is at equilibrium, we can shift the equilibrium by using the different concentrations of sulfuric acid. Request pdf on jan 1, 2015, monica pica and others published sulfonation reaction find, read and cite all the research you need on researchgate. E2 mechanism bimolecular elimination e1 mechanism unimolecular elimination the e2 and e1 mechanisms differ in the timing of bond cleavage and bond formation, analogous to the s n 2and s n 1. More specifically, it is the addition of a sulfate group as an ester group to a target molecule such as a hydroxyl group connected to a hydrophobic moiety. The largest chemithon division emerged from the companys invention of the continuous oleum sulfonation process in the mid1950s. King chapter 18 electrophilic aromatic substitution i. Optimisation of the linear alkyl benzene sulfonation. The reaction applied to aryl and naphthylsulfonic acids. Preliminary study of sulfonation of polystyrene by homogeneous. Linear alkyl benzene sulfonic acid are complex mixtures of homologues of different alkyl chain lengths c10 to c or c14 and phenyl positional isomers of 2 to 5phenyl in proportions dictated by the starting materials and reaction conditions, each containing an aromatic ring sulfonated. Preliminary information on manufacturing, processing. Sulfonation, also spelled sulphonation, in chemistry, any of several methods by which sulfonic acids are prepared.
The catalytic metafunctionalization of arenes has emerged as an important synthetic methodology in the last decade. Sulfonation of benzene benzene will react with sulfur trioxide, and in the presence of an acid, aryl sulfonic. Sulfation, in chemistry, any of several methods by which esters or salts of sulfuric acid sulfates are formed. Electrophilic aromatic substitution the most characteristic reaction of aromatic compounds is electrophilic aromatic substitution, in which one of the ring hydrogens is substituted by a halogen, nitro group, sulfonic acid group, alkyl or acyl group. Aims of green batch sulfonation reactions that can be carried out at room temperature and consume less energy. Relative rates of sulfonation of linear and branched longchain.
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