Salt, inner

The presence of certain substituents e.g., the amino group) may markedly affect the solubibty and other properties of the sulphonic acid or carboxylic acid. Thus such sulphonic acids as the aminobenzenesul-phonic acids, pyridine- and quinoline-sulphonic acids exist in the form of inner salts or zwitter-ions that result from the interaction of the basic amino group and the acidic sulphonic acid. Sulphanilic acid, for example, is more accurately represented by formula (I) than by formula (II) ... 

Burgess Reagent (inner salt) JOC, 1973, 38, 26 occurs vis a syn elimination... 

The preparation of these [4-hydroxy-THISs, (1), X = O] by cydization of a-carboxy-N-arylthiobenzimides (5) by treatment with acetic anhydride and triethylamine has been investigated in detail, and the structure has been revised for the compound previously described as 2.3-diphenyl-4-hydroxythiazolium hydroxide inner salt (1, X = 0, R = R = Ph, R = H) (Scheme 5) (3, 10). 4-Hydroxy-THlSs also arise by condensation of gem-dicyanoepoxides with thioamides (Scheme 6) (8). 

Hydroxy-THISs add to the C-C bond of diphenylcyclopropenethione (181. Inner salts without substituents in 5-posnion react similarly with diphenylcyclopropenone (Scheme 10) (4, 18). Pwolysis of the stable adducts (9) leads to rupture of the R-C-CY bond. Subsequent ring closure yields 10. When Y = O. 10 eliminates COS. producing 2-pyridone. When Y = S. 10 is isolated together with its isocyanate extrusion product, a thiopyran-2-thione (18). 

Irradiation of a 2-methvlthio-4-hydroxythiazolium hydroxide inner salt (12) leads to exchange of the carbon atoms located in the 2 and 4 positions, probably via a thiirenium ion (Scheme 13) (5). 

Mercapto- or 4-alkylidenethia2oIium hydroxide inner salts (1) (X = S or CRR ) have not been described. 

Hydroxvthiazolium hydroxide inner salts (2) (X = 0) have been synthesized by an improved acetic-anhydride-triethylamine-caialyzed cyclization of N-substituied N-thiobenzovlalanines (Scheme 15) (23). 

Hydroxy-THISs add regioselectively to the C=N bonds of isocyanates or isothiocyanates. The initially formed cycloadducts eliminate carbonyl sulfide with formation of 4-hydroxy- or 4-mercaptoimidazolium hydroxide inner salts (21) (Scheme 21). 4-Hydroxyimidazolium hydroxide... 

Mercaptothiazolium hydroxide inner salts (2) (X = S) are prepared from 5-hydroxy-oxazolium inner salts and CS (2, 25). The oxazolium inner salts may advantageously be replaced with their precursors, which are N-arylacylalanins (Scheme 23). 

The 5-methylthiothiazolium salts react with methylamine to give 4-mercaptoimidazolium hydroxide inner salts (25) and with aniline to give 26 (Scheme 24) (32). 

Aminothiazolium hydroxide inner salts (2) (X = NR) are only known as N-phenyl (29) or acyl derivatives. (6. 34) or as hydrochlorides (35). 

Mercapto-imida2oliuin inner salts have been reported to rearrange under the influence of hydrochloric acid, producing S-aminothiazolium chlorides (Scheme 25) (36). Their N-acylated derivatives are obtained by cyclization of N-thiobenzoyl alkylaminoacetonitriles, effected with acyl or sulfonyl halides (Scheme 26) (34, 35). 

Besides being useful precursors to pyrroles pyridine-2-ones -4-ones, -4-thiones. and -4-imines 4-alkylidene-dihydropyridines thiophenes 1,2,4-triazoles thiapyrane-2-thiones, isoquinoline-3-ones isoben-zothiophenes and 4-mercaptoimidazolium hydroxide inner salts, mesoionic thiazoles are potentially useful in the construction of molecules with herbicidic (39). central nerve stimulating, and antiinflammatory properties (40,41). Application in dye synthesis has likewise been reported (42). 

The physical properties of a typical amino acid such as glycine suggest that it is a very polar substance much more polar than would be expected on the basis of its formula tion as H2NCH2CO2H Glycine is a crystalline solid it does not melt but on being heated It eventually decomposes at 233°C It is very soluble m water but practically insoluble m nonpolar organic solvents These properties are attributed to the fact that the stable form of glycine is a zwittenon, or inner salt... 

These acid rhodamines are usually used for sHk and wool because they have level dyeing properties and show good fastness to alkaU however, they have poor lightfastness. An improved process for manufacturing 3,6-diaminosubstituted xanthenes is reaction of the inner salts of... 

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