Sulfones olefination

Analysis of sulfonic acid species in sulfonated olefins. Kupfer and Kuenzler [108] reported the determination of acid species following partition between a 6.5% hydrochloric acid solution in 40% ethanol and a 1 1 (v/v) propan-2-ol-hexane mixture. The organic fraction contains alkenesulfonic and hydroxy-alkanesulfonic acids and the aqueous phase disulfonic acids and sulfato-sulfonates. The monosulfonic acids were converted to methyl esters and separated by column chromatography. To determine sulfatosulfonates the aqueous fraction was hydrolyzed and then partitioned and chromatographed. The separation is controlled using IR spectroscopy. 

A variety of barium sulfonates have found use in antifriction lubricants for high speed bearing applications. Calcium and sodium salts of sulfonated olefins, esters, or oils are used for the enhancement of extreme pressure properties of grease and gear lubricants,... 

Resins carrying the guanidine function have been patented as catalyst[128] for the preparation of organic disulfides and polysulfides11291 and the preparation of sulfonated olefins.[130]... 

If the central sulfur atom of the hydrophilic group is directly bonded to a carbon atom, the resulting compound is called a sulfonate. Because aromatic ring systems will easily react with sulfuric acid or sulfur trioxide, alkylbenzene sulfonates were one of the earliest types of surface-active compounds to be produced. The sulfonate group is the hydrophilic part in many surfactants in the trade. Besides alkylbenzene sulfonates, alkane sulfonates, olefine sulfonates, of-sulfo fatty acid methyl esters, taurates and isothionates should also be mentioned. 

Anionic surfactant Alkylbenzene sulfonate, paraffin sulfonate, olefin sulfonate, secondary alkane sulfonate, alkyl sulfonate, dialkyldiphenylether disulfonate 0-3... 

A wide range of dithioester RAFT agents has been reported. Common examples of mono-RAFT agents and their application are provided in Tables 11 (Z = aryl) and 13 (Z = alkyl or aralkyl). RAFT agents can contain various unprotected functionality on the R fragment of dithiobenzoate including hydroxy, carboxylic acid/carboxylate, sulfonic acid/sulfonate, olefin, and siloxane. Examples of bis- and multi-dithioester RAFT agents (Z=aryl) that may be used for triblock or star synthesis are shown in Tables 12 and 22, respectively. Bis-dithioesters can be used to synthesize triblock copolymers in a two-step process. 

For chemical processes, some examples are the elimination of aromatics by sulfonation, the elimination of olefins by bromine addition on the double bond (bromine number), the elimination of conjugated diolefins as in the case of the maleic anhydride value (MAV), and the extraction of bases or acids by contact with aqueous acidic or basic solutions. 

The Julia-Lythgoc olefination operates by addition of alkyl sulfone anions to carbonyl compounds and subsequent reductive deoxysulfonation (P. Kocienski, 1985). In comparison with the Wittig reaction, it has several advantages sulfones are often more readily available than phosphorus ylides, and it was often successful when the Wittig olefination failed. The elimination step yields exclusively or predominantly the more stable trans olefin stereoisomer. 

Alpha olefins Alpha-olefin sulfonates Alphaprodine [77-20-3]... 

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

A.lpha-Olefm Sulfonates. Sulfonation of alpha-olefins yields a mixture of alkene sulfonates, hydroxyalkane sulfonates, and some amount of various disulfonates. These detergents are excellent foamers with good detergency properties. They are unaffected ia hard water and thek effects are considered superior to the alkyl ether sulfates (9). 

The synthesis of 2,4-dihydroxyacetophenone [89-84-9] (21) by acylation reactions of resorcinol has been extensively studied. The reaction is performed using acetic anhydride (104), acetyl chloride (105), or acetic acid (106). The esterification of resorcinol by acetic anhydride followed by the isomerization of the diacetate intermediate has also been described in the presence of zinc chloride (107). Alkylation of resorcinol can be carried out using ethers (108), olefins (109), or alcohols (110). The catalysts which are generally used include sulfuric acid, phosphoric and polyphosphoric acids, acidic resins, or aluminum and iron derivatives. 2-Chlororesorcinol [6201-65-1] (22) is obtained by a sulfonation—chloration—desulfonation technique (111). 1,2,4-Trihydroxybenzene [533-73-3] (23) is obtained by hydroxylation of resorcinol using hydrogen peroxide (112) or peracids (113). 

In the manufacture of 2-naphthalenol, 2-naphthalenesulfonic acid must be converted to its sodium salt this can be done by adding sodium chloride to the acid, and by neutralizing with aqueous sodium hydroxide or neutralizing with the sodium sulfite by-product obtained in the caustic fusion of the sulfonate. The cmde sulfonation product, without isolation or purification of 2-naphthalenesulfonic acid, is used to make 1,6-, 2,6-, and 2,7-naphthalenedisulfonic acids and 1,3,6-naphthalenetrisulfonic acid by further sulfonation. By nitration, 5- and 8-nitro-2-naphthalenesulfonic acids, [89-69-1] and [117-41-9] respectively, are obtained, which are intermediates for Cleve s acid. All are dye intermediates. The cmde sulfonation product can be condensed with formaldehyde or alcohols or olefins to make valuable wetting, dispersing, and tanning agents. 

All lnaphthalenesulfonic Acids. The aLkyLnaphthalenesulfonic acids can be made by sulfonation of aLkyLnaphthalenes, eg, with sulfuric acid at 160°C, or by alkylation of naphthalenesulfonic acids with alcohols or olefins. These products, as the acids or their sodium salts, are commercially important as textile auxiUaries, surfactants (qv), wetting agents, dispersants (qv), and emulsifying aids, eg, for dyes (qv), wettable powder pesticides, tars, clays (qv), and hydrotropes. 

Primary nitroparaffins react with two moles of formaldehyde and two moles of amines to yield 2-nitro-l,3-propanediamines. With excess formaldehyde, Mannich bases from primary nitroparaffins and primary amines can react further to give nitro-substituted cycHc derivatives, such as tetrahydro-l,3-oxa2iaes or hexahydropyrimidines (38,39). Pyrolysis of salts of Mannich bases, particularly of the boron trifluoride complex (40), yields nitro olefins by loss of the amine moiety. Closely related to the Mannich reaction is the formation of sodium 2-nitrobutane-1-sulfonate [76794-27-9] by warming 1-nitropropane with formaldehyde and sodium sulfite (41). 

Commercial Olefin Reactions. Some of the more common transformations involving a-olefins ia iadustrial processes iaclude the oxo reaction (hydroformylation), oligomerization and polymerization, alkylation reactions, hydrobromination, sulfation and sulfonation, and oxidation. 

Sulfation and Sulfonation. a-Olefin reactions involving the introduction of sulfur-containing functional groups have commercial importance. As with many derivatives of olefins, several of these products have appHcations in the area of surfactants (qv) and detergents. Typical sulfur reagents utilized in these processes include sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, and sodium bisulfite. 

In addition, and 2(S-is CC-olefins can be directly sulfonated to produce a-olefin sulfonate (AOS). AOS was formerly used as an efficient,... 

Benzene is alkylated with C g and C20+ olefins and subsequently sulfonated and neutralized with a dibasic salt such as calcium, magnesium, or barium. These so-called overbased sulfonates are used ia crankcase additive packages. 

Additioaal uses for higher olefias iaclude the productioa of epoxides for subsequeat coaversioa iato surface-active ageats, alkylatioa of benzene to produce drag-flow reducers, alkylation of phenol to produce antioxidants, oligomeriza tion to produce synthetic waxes (qv), and the production of linear mercaptans for use in agricultural chemicals and polymer stabilizers. Aluminum alkyls can be produced from a-olefias either by direct hydroalumination or by transalkylation. In addition, a number of heavy olefin streams and olefin or paraffin streams have been sulfated or sulfonated and used in the leather (qv) iadustry. 

Ozonation of Aromatics. Aromatic ring unsaturation is attacked much slower than olefinic double bonds, but behaves as if the double bonds in the classical Kekule stmctures really do exist. Thus, benzene yields three moles of glyoxal, which can be oxidized further to glyoxyUc acid and then to oxahc acid. Substituted aromatics give mixtures of aUphatic acids. Ring substituents such as amino, nitro, and sulfonate are cleaved during ozonation. 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

Gravity override of low density steam leads to poor volumetric sweep efficiency and low oil recovery in steam floods. Nonchemical methods of improving steam volumetric sweep efficiency include completing the injection well so steam is only injected in the lower part of the oil-bearing zone (181), alternating the injection of water and steam (182), and horizontal steam injection wells (183,184). Surfactants frequently are used as steam mobihty control agents to reduce gravity override (185). Field-proven surfactants include alpha-olefin sulfonates (AOS), alkyltoluene sulfonates, and neutralized... 

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