Reactions in fused salts, acid-base

F.R. Duke and S. Yamamoto, Acid-Base Reactions in Fused Salts. I. The Dichromate-Nitrate Reaction, J. Am. Chem. Soc. 80 (1958) 5061-5063. 

The subject is also closely related to fuel-ash corrosion which in most cases is caused by a layer of fused salts such as sulphates and chlorides Attention has been focused on the electrochemistry of this type of corrosion and the relevant thermodynamic data summarised in the form of diagrams . Fluxing and descaling reactions also resemble in some respects reactions occurring during the corrosion of metals in fused salts. A review of some of the more basic concepts underlying corrosion by fused salts (such as acid-base concepts and corrosion diagrams) has appeared. ... 

The key intermediate 21 is in principle accessible in any of several ways. Thus reaction of thiophenecarbox-aldehyde with amninoacetal would lead to the Schiff base 20 treatment with acid would result in formation of the fused thiophene-pyridine ring (21). Alkylation of that intermediate with benzyl chloride gives the corresponding ternary imini urn salt 23. Treatment with sodium borohydride leads to reduction of the quinolinium ring and thus formation of ticlopidine (24). ... 

A broader definition than that confined to solutions is demanded in some fields of chemistry (e.g., in high temperature reactions of acids, bases, and salts). In the foimation of metallulgical slags, at furnace tempeiatuies, calcium oxide is used as base and silicon oxide and aluminum oxide as acids calcium aluminosilicate is produced as a fused salt. Sodium carbonate and silicon oxide when fused react to form the salt sodium silicate with the evolution of carbon dioxide. In this sense ... 

Thiete structures have been suggested as fragmentation products in the mass spectra of a thietane fused to a 3-lactam, an ortho disulfide of a thiolbenzoate ester, -propanethiol, thiirane carboxylic acid esters, isothiazoles, thiazoles, 1,3-dithiole 2-thiones, 1,3-dithiolene-2-ones, S-ethyl thio-benzoate, and thianaphthene sulfones. Tetramethylthiete may have been formed on thermolysis of the p-toluenesulfonyl-hydrazone of 2,2,4,4-tetramethyl-3-thietanone. " Thiete 2-thione may be an intermediate in the decomposition of 1,2-ditholium salts by the action of bases. " 2,2-Diphenyl-2H-thiete is suggested as an intermediate in the reaction of diphenyldiazomethane with 1,2,3-benzo-thiadiazole which yields 9-phenylthioxanthene and three other products. ... 

The condensation of 1-hydrazinophthalazine with polycarbonyl compounds can give a variety of products (open chain, fused cyclic, and nonfused cyclic) depending in particular on the presence of acid <83JHC123I> and this has led to some inconsistencies in the literature. This type of reaction has now been studied in detail and, for example, the hydrochloride salt of hydralazine with acetylacetone has been shown to give l-(3,5-dimethylpyrazolyl)phthalazine, while the free base reacts (Scheme 61) to give a triazolo[3,4-a]phthalazine <87H(26)ll77,87H(26)1277,87H(26)1853>. 

Pyridine is a tertiary amine its aqueous solution shows an alkaline reaction and precipitates the hydroxides of metals, some of which are soluble in an excess of the amine. Salts of pyridine like those of other amines form characteristic double salts with metallic halides. The ferrocyanide of pyridine and the addition-product of pyridine and mercuric chloride are difficultly soluble in water these compounds are used in the purification of the base. Pyridine is a very stable compound it can be heated with nitric acid or chromic acid without undergoing change but at 330° it is converted by a mixture of nitric acid and fuming sulphuric acid into nitropyridine, a colorless compound that melts at 41° and boils at 216°. At a high temperature pyridine is converted into a sulphonic acid by sulphuric acid. Chlorine and bromine form addition-products, e.g., C5H5N.CI2, at the ordinary temperature when these are heated to above 200°, substitution-products are formed. The hydroxyl derivative of pyridine is made by fusing the sulphonic acid with sodium hydroxide it resembles phenol in chemical properties. The three possible carboxyl derivatives of pyridine are known. The a-acid is called picolinic acid, the jS-acid nicotinic acid (664), and the 7-acid isonicotinic acid. 

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