Alkyl sulfonic acid esters of phenol

Additives used in final products Fillers calcium carbonate, calcium hydroxide, calcium oxide, carbon black, polymeric beads, polystyrene particles, zinc oxide Plasticizers 1-isobutyrate benzyl phthalate, 2,2,4-tri-methyl-1,3-pentanediol, alkyl sulfonic acid esters of phenol and/or cresol, benzyl butyl phthalate, chlorinated paraffins, hydrogenated perphenyl, isooctyl benzyl phthalate Curatives metal peroxides, oxy salts (e.g., dioxides of lead, manganese, calcium, etc.) ... 

Fast-fusing plasticizers enable the PVC material to be processed faster or at lower temperatures. Generally it is in the area of plasfisol applications where the uses of faster fusing plasticizers are preferred. Examples of fast-fiising plasticizers include butyl benzyl phthalate (BBP), citrates, the epoxidized fatty acid plasticizer methyl epoxy stearate, alkyl sulfonic acid esters of phenol, dibutyl phthalates and tere-phthalates, and dibenzoate esters and benzoate ester blends. It should be noted that the use of BBP in PVC has rapidly declined because of product restrictions, while the use of dibutyl phthalate (DBP) declined in North America and in Europe years ago because of its high volatility. 

Alkyl Sulfonic Acid Esters of Phenol There are two esters in this category, differing in average chain length of the alkyl group. The esters are reported to be used for GP applications in Europe and are often promoted as a phthalate alternative. They are also used in polyurethane sealants. Plasticizing efficiency (SF) is similar to that of... 

Solid esters are easily crystallisable materials. It is important to note that esters of alcohols must be recrystallised either from non-hydroxylic solvents (e.g. toluene) or from the alcohol from which the ester is derived. Thus methyl esters should be crystallised from methanol or methanol/toluene, but not from ethanol, n-butanol or other alcohols, in order to avoid alcohol exchange and contamination of the ester with a second ester. Useful solvents for crystallisation are the corresponding alcohols or aqueous alcohols, toluene, toluene/petroleum ether, and chloroform (ethanol-free)/toluene. Esters of carboxylic acids derived from phenols are more difficult to hydrolyse and exchange, hence any alcoholic solvent can be used freely. Sulfonic acid esters of phenols are even more resistant to hydrolysis they can safely be crystallised not only from the above solvents but also from acetic acid, aqueous acetic acid or boiling n-butanol. Note that sulfonic esters of lower alcohols, e.g. methanol, are good alkylating agents. 

It is possible to prepare esters of phenols with carboxylic acid anhydrides or acid halides, and phenyl ethers by reaction of benzenolate anion with halides, sulfate esters, sulfonates, or other alkyl derivatives that react well by the SN2 mechanism ... 

Mechanisms of Carbon-Oxygen Alkylations. Kinetic studies have been made of reactions between chlorinated hydrocarbons and sodium or potassium alcoholates. The rate data indicate second-order equations between the reactants. Phenol and substituted phenols were alkylated using sulfonic acid esters. The rates of the reactions depend on the substituent on the aromatic ring. The relative velocities were as follows p-creso], 1.58 2-naphthol, 1.46 phenol, 1.0 salicyclic acid, about 0.3 p-chlorophenol, 0.16 and o-cresol, less than 0.12. Electronic considerations are probably the cause of the different reaction rates. 

Sulfonic esters are most frequently prepared by treatment of the corresponding halides with alcohols in the presence of a base. The method is much used for the conversion of alcohols to tosylates, brosylates, and similar sulfonic esters. Both R and R may be alkyl or aryl. The base is often pyridine, which functions as a nucleophilic catalyst, as in the similar alcoholysis of carboxylic acyl halides (10-21). Primary alcohols react the most rapidly, and it is often possible to sulfonate selectively a primary OH group in a molecule that also contains secondary or tertiary OH groups. The reaction with sulfonamides has been much less frequently used and is limited to N,N-disubstituted sulfonamides that is, R" may not be hydrogen. However, within these limits it is a useful reaction. The nucleophile in this case is actually R 0 . However, R" may be hydrogen (as well as alkyl) if the nucleophile is a phenol, so that the product is RS020Ar. Acidic catalysts are used in this case. Sulfonic acids have been converted directly to sulfonates by treatment with triethyl or trimethyl orthoformate HC(OR)3, without catalyst or solvent and with a trialkyl phosphite P(OR)3. ... 

A wide range of anionic surfactants (Fig. 23) has been classified into groups, including alkyl benzene sulfonates (ABS), linear alkyl benzene sulfonates (LAS), alcohol sulfates (AS), alcohol ether sulfates (AES), alkyl phenol ether sulfates (APES), fatty acid amide ether sulfates (FAES), alpha-olefin sulfates (AOS), paraffin sulfonates, alpha sulfonated fatty acids and esters, sulfonated fatty acids and esters, mono- and di-ester sulfosuccinates, sulfosuccinamates, petroleum sulfonates, phosphate esters, and ligno-sulfonates. Of the anionic surfactants, ABS and LAS continue to be the major products of anionic surfactants [314, 324]. Anionic surfactants have been extensively monitored and characterized in various environmental matrices [34,35,45,325-329]. 

Anionic emulsifiers. Typically used anionic emulsifiers are sodium, potassium, or ammonium salts of fatty acids and sulfonic acids alkali salts of alkyl sulfates, ethoxylated and sulfated or sulfonated fatty alcohols alkyl phenols and sulfodicarboxylate esters. These emulsifiers are typically used at levels of 0.2-5 wt% based on monomers. 

Fragmentation Loss of alkyl by fragmentation of the C-O bond with concomitant double H rearrangement to form the protonated sulfonic acid ion (m/z 97 for methanesulfonates), which then loses water. Loss of the alkoxyl residue (fragmentation of the S-O bond). Formation of an alkene ion from the sulfonate alkyl by a McLafferty-type rearrangement. In aryl esters, the phenoxy ion and the phenol radical cations dominate the spectrum. 

Effluents from the manufacture of Pb(CH3)4 can be treated with an alkali metal borohydride, e.g., NaBH4 at pH 8 to 11 to substantially reduce the level of dissolved lead compounds, like [Pb(CH3)3][145, 146]. Zn can also be used [147]. Liquid NH3 and toluene are used to remove solid NH4Clfrom the apparatus for producing Pb(CH3)4 by the NH3- or amine-catalyzed reaction of CH3CI with a PbNa alloy [148]. Stabilization of Pb(CH3)4, and of antiknock fluids containing Pb(CH3)4, is accomplished by addition of compounds, like toluene [149], xylene [141, 150], styrenes [151], naphthalenes [149, 151, 152], anthracenes [152], substituted phenols [141, 152 to 155], olefinic hydrocarbons [152], alcohols [141, 152], amines [155], hydroquinones [156], ethers [141], saturated or unsaturated carboxylic acids [141, 152], esters of phosphoric acid [152], or of sulfuric acid [157], or of sulfonic acids [141], imidazoles [158], alkyl halides and alkyl thiocyanates [141], or tall oil [159] see also Organolead Compounds , Vol. 2, Section 1.1.1.2, to be published. 

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