Sulphur, alkylation

Alkylation The addition of an alkyl group, to a carbon (C-alkylation), nitrogen (/V-alkylation), oxygen (O-alkylation), or sulphur (//-alkylation) atom. 

On acetylation it gives acetanilide. Nitrated with some decomposition to a mixture of 2-and 4-nitroanilines. It is basic and gives water-soluble salts with mineral acids. Heating aniline sulphate at 190 C gives sulphanilic add. When heated with alkyl chlorides or aliphatic alcohols mono- and di-alkyl derivatives are obtained, e.g. dimethylaniline. Treatment with trichloroethylene gives phenylglycine. With glycerol and sulphuric acid (Skraup s reaction) quinoline is obtained, while quinaldine can be prepared by the reaction between aniline, paraldehyde and hydrochloric acid. 

CH OfiSj, H2C(S03H)2- a colourless, crystalline solid which readily absorbs water vapour decomposes on distillation. The potassium salt is prepared by heating methylene chloride with an aqueous solution of potassium sulphite under pressure at 150-I60" C. The free acid is obtained by decomposing the sparingly soluble barium salt with sulphuric acid. The aryl esters are very stable, but the alkyl esters decompose on heating to give ethers. Resembles malonic acid in some of its reactions. 

This method has the great advantage over method (A) in that it can be applied in particular to those aromatic nitriles in which the aryl group is readily sulphonated clearly, it can also be applied to nitriles in which the alkyl or aryl portion contains groups which are in any other way affected by concentrated sulphuric acid, or by concentrated aqueous alkalis. 

Cold concentrated sulphuric acid will remove unsaturated hydrocarbons present in saturated hydrocarbons, or alcohols and ethers present in alkyl halides. In the former case soluble sulphonated products are formed, whilst in the latter case alkyl hydrogen sulphates or addition complexes, that are soluble in the concentrated acid, are produced. 

Alkyl nitrites. By the interaction at 0° of the alcohol with sodium nitrite in the presence of excess of concentrated sulphuric acid, for example ... 

Alkyl sulphates. The dimethyl and diethyl esters may be prepared infer alia by the interaction of chlorosulphonic acid with the anhydrous alcohol, followed by distillation of the resulting alkyl sulphuric acid under diminished pressure, for example ... 

For those nitriles which yield water-insoluble amides e.g., the higher alkyl cyanides), hydrolysis to the amide often leads to a satisfactory derivative. The hydration is eflfected by warming a solution of the nitrile in concentrated sulphuric acid for a few minutes, cooling and pouring... 

If only the monocarboxybc acid is required, the ester after hydrolysis with potash may be strongly acidified with sulphuric acid and the mixture heated under reflux the mineral acid promotes decarboxylation at a temperature just above 100°. The net result is the replacement of the halogen atom of the alkyl halide by —CH COOH thus in the above example ... 

Mercaptans (or thio-alcohols or thiols), the sulphur analogues of the alcohols, were formerly prepared by the interaction of an alkyl halide and sodium hydrosulphide in alcoholic solution ... 

The alkyl sulphides or thioethers, the sulphur analogues of the ethers, are conveniently obtained by boiling alkyl halides with anhydrous sodium sulphide in alcoholic solution, for example ... 

Oxidation of side chains. Aromatic nitro compounds that contain a side chain (e.g., nitro derivatives of alkyl benzenes) may be oxidised to the corresponding acids either by alkahne potassium permanganate (Section IV,9, 6) or, preferably, with a sodium dichromate - sulphuric acid mixture in which medium the nitro compound is more soluble. 

It has been tentatively suggested that one mechanism underlies the Willgerodt reaction and the Kindler modification of it. A labile intermediate is first formed which has a carbon—carbon bond in the side chain. The scheme is indicated below it postulates a series of steps involving the addition of ammonia or amine (R = H or alkyl), elimination of water, re addition and eUmination of ammonia or amine until the unsaturation appears at the end of the chain then an irreversible oxidation between sulphur and the nitrogen compound may occur to produce a thioamide. 

Nitration in sulphuric acid is a reaction for which the nature and concentrations of the electrophile, the nitronium ion, are well established. In these solutions compounds reacting one or two orders of magnitude faster than benzene do so at the rate of encounter of the aromatic molecules and the nitronium ion ( 2.5). If there were a connection between selectivity and reactivity in electrophilic aromatic substitutions, then electrophiles such as those operating in mercuration and Friedel-Crafts alkylation should be subject to control by encounter at a lower threshold of substrate reactivity than in nitration this does not appear to occur. 

Kinetic data are available for the nitration of a series of p-alkylphenyl trimethylammonium ions over a range of acidities in sulphuric acid. - The following table shows how p-methyl and p-tert-h xty augment the reactivity of the position ortho to them. Comparison with table 9.1 shows how very much more powerfully both the methyl and the tert-butyl group assist substitution into these strongly deactivated cations than they do at the o-positions in toluene and ferf-butylbenzene. Analysis of these results, and comparison with those for chlorination and bromination, shows that even in these highly deactivated cations, as in the nitration of alkylbenzenes ( 9.1.1), the alkyl groups still release electrons in the inductive order. In view of the comparisons just... 

Sulphuric acid (H2SO4) Alkylation reactions inorganic pigments., caprolactam, copper leaching, detergents, explosives, fertilizers, textiles... 

Alkyl sulphides are the sulphur analogues of ethers from which they differ considerably in chemistry. They are unpleasant-smelling oils, insoluble in water but soluble in organic solvents. They tend to be comparatively inert. Mustard gas, CICH2CH2—S—CH2CH2CI, an oily liquid boiling at 216°C with a mustard-like smell, is highly poisonous and a vesicant, and for this reason found use in chemical warfare. 

Sulphur oxides G Sulphur dioxide Sulphur trioxide Coal distillation Combustion of coal and heavy fuel oil Detergents (sulphonation of alkyl benzenes) Electricity generation... 

The presence of sulphur may indicate a sulphate of an organic base, alkyl sulphate, sulphite, sulphide, incrcaptan, sulphonit and, bisulphite unnpound of aldehyde or ketone. 

Sulphur compounds, e.g., thiopropionate esters and metal dithiolates (Table la, AO 16 and 17), decompose hydroperoxides catalytically, i.e., one antioxidant molecule destroys several hydroperoxides through the intermediacy of sulphur acids [19,20]. Scheme 6 shows a simplified scheme for the antioxidant mechanism of simple alkyl sulphides. 

An exception to the lone pair or donor electron requirement of organic inhibitors is provided by the quaternary ammonium compounds. Meakins reports the effectiveness of tetra-alkyl ammonium bromides with the alkyl group having C 10. Comparative laboratory tests of commercial inhibitors of this type have been described . The inhibiting action of tetra-butyl ammonium sulphate for iron in H S-saturated sulphuric acid has been described, better results being achieved than with mono-, di- or tri-butylamines . 

Nitration by nitric acid in sulphuric acid has also been by Modro and Ridd52 in a kinetic study of the mechanism by which the substituent effects of positive poles are transmitted in electrophilic substitution. The rate coefficients for nitration of the compounds Pl CHi NMej (n = 0-3) given in Table 10 show that insertion of methylene groups causes a substantial decrease in deactivation by the NMej group as expected. Since analysis of this effect is complicated by the superimposed activation by the introduced alkyl group, the reactivities of the... 

Arrhenius parameters for nitration of 4-aikylphenyltrimethyiammonium ions in nitric acid-sulphuric acid mixtures (Table 12). It was argued that the observed Baker-Nathan order of alkyl substituent effect was, in fact, the result of a steric effect superimposed upon an inductive order. However, a number of assumptions were involved in this deduction, and these render the conclusion less reliable than one would like it would be useful to have the thermodynamic parameters for nitration of the methyl substituted compound in particular, in order to compare with the data for the /-butyl compound, though experimental difficulties may preclude this. It would not be surprising if a true Baker-Nathan order were observed because it is observed for all other electrophilic substitutions in this medium1. 

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