Alkyl sulfonates preparation

Alkyl sulfonates are derivatives of sulfonic acids m which the proton of the hydroxyl group is replaced by an alkyl group They are prepared by treating an alcohol with the appropriate sulfonyl chloride usually m the presence of pyridine... 

Alkyl sulfonic acids are prepared by the oxidation of thiols (36,37). This reaction is not quite as simple as would initially appear, because the reaction does not readily go to completion. The use of strong oxidants can result in the complete oxidation of the thiol to carbon dioxide, water, and sulfur dioxide. 

Since sulfonate groups have been used in other ground-water tracers, the goal of this work was to synthesize several N-substi-tuted pyridone alkyl sulfonates which might be less susceptible to adsorption as well as more soluble. Alkyl sulfonates of varying chain lengths would be unique in a water system and separately identifiable by HPLC analysis. Two series of compounds were synthesized (Vla-c and Vlla-c). These compounds could be prepared by treating compounds III and IV with the appropriate lu-bromoalkyl sulfonate. 

Trifluoromethanesulfonates of alkyl and allylic alcohols can be prepared by reaction with trifluoromethanesulfonic anhydride in halogenated solvents in the presence of pyridine.3 Since the preparation of sulfonate esters does not disturb the C—O bond, problems of rearrangement or racemization do not arise in the ester formation step. However, sensitive sulfonate esters, such as allylic systems, may be subject to reversible ionization reactions, so appropriate precautions must be taken to ensure structural and stereochemical integrity. Tertiary alkyl sulfonates are neither as easily prepared nor as stable as those from primary and secondary alcohols. Under the standard preparative conditions, tertiary alcohols are likely to be converted to the corresponding alkene. 

Alkylation of hydroxylamines with secondary alkyl halides and alkyl sulfonates like 10 (equation 7) is one of the most frequently used synthetic approaches, especially to enantiomerically pure hydroxylamines such as 11 (equation 7). The reaction proceeds with inversion of configuration and does not produce appreciable amounts of diaUcyla-tion products. Both hydroxylamine as well as N- and O-alkylhydroxylamines have been successfully used. Alkyl trillates are probably the most useful substrates for these transformations since they can be prepared from a large pool of commercially available enantiomerically pure chiral secondary alcohols. 

Alkyl hydroperoxysilanes, preparation, 783 Alkyl hydrotrioxides, structural chemistry, 132 Alkyl iodides, dioxirane oxidation, 1158 Alkyl methyl sulfonates, alkyl hydroperoxide synthesis, 673... 

Iron-acyl enolates, such as 2, prepared by x-deprotonation of the corresponding acyl complexes with lithium amides or alkyllithiums, are nearly always generated as fs-enolates which suffer stereoselective alkylation while existing as the crmt-conformer which places the carbon monoxide oxygen anti to the enolate oxygen (see Section 1.1.1.3.4.1.). These enolates react readily with strong electrophiles, such as primary iodoalkanes, primary alkyl sulfonates, 3-bromopropenes, (bromomethyl)benzenes and 3-bromopropynes, a-halo ethers and a-halo carbonyl compounds (Houben-Weyl, Volume 13/9 a, p 413) (see Table 6 for examples). 

SCHEME 11. Preparation and uses of alkyd zinc derivatives starting from alkyl sulfonates... 

The composition data obtained for the series of mixed fatty acid-potassium soap systems, prepared by both the ethanol and petroleum ether routes, lend strong support to the formation of 1 to 1 acid-soap complexes. It is of interest to inquire into the phase relationships in these two-component systems. A phase diagram presented by McBain and Field (15) for the lauric acid-potassium laurate system shows that compound formation takes place between the two components at the 1 to 1 molar ratio, but the compound undergoes melting with decomposition at 91.3 °C. [A similar type of phase behavior has been reported by us for the sodium alkyl sulfate-alkyl alcohol (9) and sodium alkyl sulfonate-alkyl alcohol (12) systems, but in these cases the stoichiometry is 2 to 1]. 

Resin-bound 7-keto sulfones, prepared in a straightforward, three-step process comprising alkylation of a resin-bound sulfinate salt, alkylation of a sulfone-supported anion with an epoxide, and Jones oxidation of the 7-hydroxy sulfone, provided a source of structurally diverse three-carbon fragments <2004JC0928>. Reaction with a phenylenediamine to give the 1,5-benzodiazepine presumably occurs via initial imine formation followed by expulsion of the resin-bound sulfone, which acts as a traceless linker (Scheme 73). Yields for this process are a modest 10-38%. 

Coupling of sulfones to alkenes. In the presence of a catalytic amount of Ni(acac), a-anions of allylic sulfones undergo coupling at the a-position with desulfonylation to give 1,3,5-trienes in good yield. The original double bonds of the sulfone retain their configuration, but both isomers of the newly formed double bond are obtained. The reaction is particularly useful for preparation of C20- and C30-polyisoprenoids. Benzyl and w-alkyl sulfones can also be coupled to form symmetrical alkenes in this way.1... 

To prepare alkyl sulfonate esters, sulfonic acids were treated with supported alkyl triazenes (entry 17).21 The acids decompose the triazenes to diazoalkanes, which subsequently alkylate the sulfonates in situ. These supported triazenes avoid the dangerous handling of pure diazoalkanes. 

Alkyl-substituted ruthenocenes, preparation, 6, 635-636 Alkyl sulfonates, cross coupling, and Grignard reactions, 9, 44 Alkyltantalum imido complexes, as catalysts, 5, 193 Alkyl tellurides... 

Another regiospecific preparation of trimethylsilyl enol ethers involves treatment of acyltrimethylsilanes with the lithium anions of alkyl sulfones or nitriles. In this case, the sulfone or nitrile group is eliminated during the silyl alkoxide rearrangement (e.g., 5 — 6). Mixtures of olefin stereoisomers are obtained. Note that 4 and 8 give complementary regiochemical results. 

Here, mixed cuprates prepared from organolithium or organomagnesium compounds serve as a carbanion, while derivatives like alkyl halides, alkyl sulfonates, or alkyl acetates are suitable equivalents for the carbocationic counterpart (Scheme 2.34). 

In dyeing, surfactants are used as wetting agents. They are also used in the formulation of disperse dyes. A stable suspension of the dye is prepared with the help of an anionic surfactant, such as alkyl or aryl alkyl sulfonate. It has been shown that dyeing takes place through the aqueous phase by the slow dissolution of the solid dye particles (61, 62). The presence of the surfactant helps the dissolution of the dye. 

Both electrochemical and chemical oxidation have been used to produce 3-substituted alkylsulfonated pyrroles [106]. Electrochemical polymerisation was achieved using acetonitrile as solvent to form a solid deposit on the electrode. Alternatively, FeCl3 was used as oxidant. Conductivities in the range 0.001-0.500 S cm were obtained, with lower conductivity products obtained from chemical polymerisation. Others [107,108] have prepared homopolymers and copolymers of polypyrroles with alkyl sulfonate groups attached via the N-group. This N-group substitution decreases the polymers inherent conductivity. 

Like alkyl halides, alkyl sulfonates are prepared from alcohols but, as we shall see in Sec. 16.7, the two syntheses differ in one very important way. 

Alkyl sulfonates offer a very real advantage over alkyl halides in reactions where stereochemistry is important this advantage lies, not in the reactions of alkyl sulfonates, but in their preparation. Whether we use an alkyl halide or sulfonate, and whether we let it undergo substitution or elimination, our starting point for the study is almost certainly the alcohol. The sulfonate must be prepared from 4he alcohol the halide nearly always will be. It is at the alcohol stage that any resolution will be carried out, or any diastereomers separated the alcohol is then converted into the halide or sulfonate, the reaction we are studying is carried out, and the products are examined. 

Alkenes are prepared from alcohols either by direct dehydration or by de-hydrohalogenation of intermediate alkyl halides to avoid rearrangement we often select dehydrohalogenation of halides even though this route involves an extra step. (Or, sometimes better, we use elimination from alkyl sulfonates.)... 

From a historical perspective, the a-(dialkylamino)nitrile anions were the first acyl anion equivalents to undergo systematic investigation. More recent studies indicate that anions of a-(dialkylamino)nitriles derived from aliphatic, aromatic or heteroaromatic aldehydes intercept an array of electrophiles including alkyl halides, alkyl sulfonates, epoxides, aldehydes, ketones, acyl chlorides, chloroformates, unsaturated ketones, unsaturated esters and unsaturated nitriles. Aminonitriles are readily prepared and their anions are formed with a variety of bases such as sodium methoxide, KOH in alcohol, NaH, LDA, PhLi, sodium amide, 70% NaOH and potassium amide. Regeneration of the carbonyl group can be achieved... 

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