Sulfuric Acid and Its Derivatives

Ammonium sulfate is a compound with weak herbicidal action. Applied at high rates on the leaves of dicotyledons it has a contact action. Its phytotoxic action can be attributed mainly to the ammonium ions. Ammonia rapidly penetrates to the acid-buffered cell sap, making it alkaline, thus rapidly destroying the cells (Harvey, 1911). Bokomy (1915) assumed that ammonia formed complexes with cell proteins. 

Ferrosulfate heptahydrate (FeSO 7HjO) is another compound with weak herbicidal action. Applied as an aqueous solution at rates of 6-12 kg/ha, it has been used for the postemergence control of dicotyledonous weeds in cereals. At rates of 100 kg/ha (in the form of a 10% aqueous solution) it can be used for the control of moss in turf. 

The salts of heavy metals, namely iron and copper salts, are general enzyme poisons and protein coagulants. Iron sulfate causes plasmolysis, though Aberg (1948), on killing Sinapis plants with 5% iron sulfate solution, found no plasmolysis in the plants or damage to the chloroplasts. 

Copper sulfate pentahydrate (CuSO 7H2O) is used today only as an algicide in hsh ponds and in industrial water basins at 1 ppm concentration. 

Of the sulfuric acid derivatives the most efficient herbicide is ammonium sulfamate, AMS, introduced in 1945 in the USA. 

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Cationic polymerization of cyclosiloxanes is well known but used much less frequently than anionic reactions. The most widely used catalysts include sulfuric acid and its derivatives, alkyl and aryl sulfonic acids and trifluoroacetic acid1 2,1221. Due to their ease of removal, in industrial applications acid catalysts are generally employed on supports such as bentonite clay or Fuller s earth. 

Next, we consider ammonia and its derivatives in the top 50 chemicals. We have completed a study of the number one inorganic chemical sulfuric acid and its derivatives and have also studied industrial gases from which ammonia is made. Ammonia is in the top 10 chemicals and some important ammonia derivatives are listed in the top 50 ammonium nitrate, nitric acid, urea, and ammonium sulfate. Most ammonia eventually ends up in fertilizers of one type or another. The manufacturing chemistry for these chemicals is outlined below. 

A. THE REACTION OF SULFURIC ACID AND ITS DERIVATIVES WITH AROMATIC HYDROCARBONS... 

R. may be cyclized by reaction with sulfuric acid and its derivatives. It is used in printing inks and - coatings. 

Acetaldehyde Cyanohydrin. This cyanohydrin, commonly known as lactonitnle, is soluble in water and alcohol, but insoluble in diethyl ether and carbon disulfide. Lactonitnle is used chiefly to manufacture lactic acid and its derivatives, primarily ethyl lactate. Lactonitnle [78-97-7] is manufactured from equimolar amounts of acetaldehyde and hydrogen cyanide containing 1.5% of 20% NaOH at —10 20 ° C. The product is stabili2ed with sulfuric acid (28). Sulfuric acid hydroly2es the nitrile to give a mixture of lactic acid [598-82-3] and ammonium bisulfate. 

Benzoic acid and its derivatives are among the most widely used antimicrobial agents these, together with the propionates, sulfur dioxide, nitrates, nitrites and sorbic add, account for the bulk of food preservatives. A number of other compounds find use, however, in various miscellaneous applications, including 3-acetyl-6-methyl-3f/-pyran-2,4-dione (67)... 

Nitrophthalic acid80 can be reduced in dilute sulfuric acid at a platinum cathode in high yield to 4-carboxy-benzisoxazolone. Benzisoxazolones are formed in the reduction of o-nitrobenzoic acid and its derivatives at a mercury cathode in acid solution at 60°C. 

Methods for the preparation of organic sulfur compounds by alteration of sulfur-containing groups already present include reduction, oxidation, and cleavage. The preparation of thiocarbonic acid and its derivatives is treated at the end of the present Chapter. For the rearrangement of sulfur compounds see the Section on p. 1074. 

Chemical. In addition to its intrinsic interest, sulfur serves as a starting point for the synthesis of many labeled molecules. Digestion of sulfur in aqueous sulfites yields thiosulfates, which when heated with iodine lead to tetra-thionates and trithionates. Digestion of sulfur in alcoholic cyanide solutions yields thiocyanates, thence thiocyanogen and thiourea with its derivatives and coordination complexes. Oxidation of sulfur to sulfur dioxide is a potential route to labeled sulfamic acid and its derivatives and to labeled sulfuryl chloride. The intermediate sodium sulfide readily yields hydrogen sulfide and metallic sulfides. 

Ascorbic acid and its derivatives Hydrogensulfites, sulfur dioxide... 

Table 12.4 shows the rich variety of oxoanions of sulfur that are possible. In fact, few of these oxoacids are known in the undissociated state. Apart from some of the polythionic acids, no oxoacid in which sulfur has an oxidation number <6 is stable, even in concentrated aqueous solution, and only sulfuric acid and its dimer disulfuric acid exist as free acids at room temperature. The derivative, obtained by replacing one of the —OH groups of sulfuric acid by an —SH group, thiosulfuric acid, is stable only below 0 °C. 

The derivatives used in corrosion inhibitor formulations for down-hole use constitute a significant industrial appHcation for polyamines. Again, mono- and bisarnidoamines, imidazolines, and polyamides made from the higher polyamines are the popular choices. The products made from DETA and fatty acids have been widely used (308). A wide variety of other polyamine-based, corrosion inhibiting derivatives have been developed, generally incorporating some form of oil-soluble or od-dispersible residue. Sulfur and its derivatives are also used in these polyamine-based corrosion inhibitors on... 

Esterification. The formation of an ester from an acid (or its derivative) and an alcohol is of limited appHcation siace carboxyUc esters are comparatively rare substitueats ia dyes. Esters of A/-(3-hydroxyethylaniLiaes are important iatermediates for azo disperse dyes for polyester. Another example is methyl anthranilate, formed by the classical esterification of anthranilic acid usiag methanol and sulfuric acid. 

The range of preparatively useful electrophilic substitution reactions is often limited by the acid sensitivity of the substrates. Whereas thiophene can be successfully sulfonated in 95% sulfuric acid at room temperature, such strongly acidic conditions cannot be used for the sulfonation of furan or pyrrole. Attempts to nitrate thiophene, furan or pyrrole under conditions used to nitrate benzene and its derivatives invariably result in failure. In the... 

Benzanthrone has been prepared by three general methods, the first of which is generally regarded as the best (i) by heating a reduction product of anthraquinone with sulfuric acid and glycerol,1 or with a derivative of glycerol, or with acrolein. The anthraquinone is usually reduced in sulfuric acid solution, just prior to the reaction, by means of aniline sulfate, iron, , or copper. It has also been prepared (2) by the action of aluminum or ferric chloride on phenyl-a-naphthyl ketone, and (3) from i-phenylnaphthalene-2-carboxylic acid. ... 

Because phenols are weak acids, they can be freed from neutral impurities by dissolution in aqueous N sodium hydroxide and extraction with a solvent such as diethyl ether, or by steam distillation to remove the non-acidic material. The phenol is recovered by acidification of the aqueous phase with 2N sulfuric acid, and either extracted with ether or steam distilled. In the second case the phenol is extracted from the steam distillate after saturating it with sodium chloride (salting out). A solvent is necessary when large quantities of liquid phenols are purified. The phenol is fractionated by distillation under reduced pressure, preferably in an atmosphere of nitrogen to minimise oxidation. Solid phenols can be crystallised from toluene, petroleum ether or a mixture of these solvents, and can be sublimed under vacuum. Purification can also be effected by fractional crystallisation or zone refining. For further purification of phenols via their acetyl or benzoyl derivatives (vide supra). 

Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

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