Sulfonates nitrile synthesis

Crosslinked sulfonated poly(phenylene sulfide sulfone nitrile) has been prepared for its potential use for direct methanol fuel cell membrane applications [91]. The monomers and the synthesis are shown in Figure 5.9. 

Phu DS, Lee CH, Park CH, Lee SY, Lee YM. Synthesis of crosslinked sulfonated poly(phenylene sulfide sulfone nitrile) for direct methanol fuel cell applications. Macro-mol Rap Commun 2009 30(l) 64—8. 

Nitdles may be prepared by several methods (1). The first nitrile to be prepared was propionitdle, which was obtained in 1834 by distilling barium ethyl sulfate with potassium cyanide. This is a general preparation of nitriles from sulfonate salts and is referred to as the Pelou2e reaction (2). Although not commonly practiced today, dehydration of amides has been widely used to produce nitriles and was the first commercial synthesis of a nitrile. The reaction of alkyl hahdes with sodium cyanide to produce nitriles (eq. 1) also is a general reaction with wide appHcabiUty ... 

Other Applications. Hydroxylamine-O-sulfonic acid [2950-43-8] h.2is many applications in the area of organic synthesis. The use of this material for organic transformations has been thoroughly reviewed (125,126). The preparation of the acid involves the reaction of hydroxjlamine [5470-11-1] with oleum in the presence of ammonium sulfate [7783-20-2] (127). The acid has found appHcation in the preparation of hydra2ines from amines, aUphatic amines from activated methylene compounds, aromatic amines from activated aromatic compounds, amides from esters, and oximes. It is also an important reagent in reductive deamination and specialty nitrile production. 

Wade and coworkers have found that a-nitro sulfones are useful reagents in organic synthesis because they are converted into nitroalkanes, nitriles, or carboxylic acids (see Eq. 5.52).76... 

A large part of the usefulness of the Michael reaction in organic synthesis derives from the fact that almost any activated alkene can serve as an acceptor7—a, 3-unsaturated ketones, esters, aldehydes, amides, acids, lactones, nitriles, sulfoxides, sulfones, nitro compounds, phosphonates, phosphoranes, quinones,... 

The conjugate addition of heteronucleophiles to activated alkenes has been used very often in organic synthesis to prepare compounds with heteroatoms [3 to various activating functional groups, e.g. ketones, esters, nitriles, sulfones, sulfoxides and nitro groups. As in the Michael reaction, a catalytic amount of a weak base is usually used in these reactions (with amines as nucleophiles, no additional base is added). 

Supercritical carbon dioxide with a minute co-solvent addition is an effective medium for the 1,3-dipolar cycloaddition of azomethine ylides with DMAD to produce substituted pyrroles.67 The 1,3-dipolar cycloaddition of nitrile ylides [e.g. benzonitrile (4-nitrobenzylide) and 4-nitrobenzonitrile(benzylide)] with acrylamides provided a synthesis of 3,4-dihydro-2//-pyrroles with moderate to good yields.68 The Pt(II)-or Au(III)-catalysed 3 + 2-cycloaddition of the transition metal-containing azomethine ylide (63) with electron-rich alkenes provided a carbene complex (64), which yields tricyclic indoles (65) having a substituent at 3-position (Scheme 17).69 The 1,3-dipolar cycloadditions of azomethine ylides with aryl vinyl sulfones are catalysed by Cu(MeCN)4C104-Taniaphos with nearly complete exo- selectivity and enantioselec-tivities up to 85% ee.10 The 3 + 2-cycloaddition of benzol/>]thiophene 1,1-dioxide... 

In 1991, Goff et al reported synthesis and activity testing of monoquatemary imidazole derivatives with various substituents sueh as ether, silicone, nitrile, ester, halogen, nitro, sulfone or amino group (Goff et al, 1991). Published literature reveals that syntheses started from 1-methyl-imidazole (Figure 66.5). 

Olefin synthesis. Condensation of aldehyde tosylhydrazones with stabilized carbanions affords alkenes by an addition-fragmentation process. The overall sequence is formulated in equation (I). Functional groups such as sulfides, sulfones, thioacetals, hemithioacetals, and nitriles can serve as Y, the anion stabilizing group in 2 and the leaving group in 3. When Y = SO2R, the anions 1 and 2 are conveniently prepared by treatment of a mixture of the tosylhydrazone and sulfone with LDA in... 

Tabic 5. Stereoselective Synthesis of ( )-y-Hydroxy-a,/l-Unsaturated Esters, Nitriles and Sulfones... 

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