Alkyl sulfates with aromatic rings

Aromatic EC5-EC9 Fraction. As indicated by studies with humans and animals exposed to individual BTEXs, compounds in this fraction may be expected to be metabolized via cytochrome P-450 oxidases, either at carbons in the aromatic ring or in alkyl side groups, to metabolic intermediates that can be conjugated with glucuronides, sulfates, glutathione, or amino acids (e.g.,... 

Cations can be formed from alcohols, and they add to aromatic rings in the usual manner. Sulfuric acid is a common catalyst for alcohols, forming an alkyl sulfate that then reacts with the aromatic substrate. 120 Alcohols are more reactive than halides, although large quantities of the Lewis acid are usually required for Friedel-Crafts reactions.I2l Alcohols form a complex with aluminum chlorides [R(H)0— A1C13], and a complicating side reaction is loss of HCl and formation of an alkyl chloride.122 a full equivalent of the Lewis acid... 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

The alkylation of aromatic 1,2,4-triazines has been studied by various groups.251 -259 Alkylation with iodomethane affords the red 1-methyl-1,2,4-triazinium salts 4c-j predominantly and in a few cases yields the colorless 2-methyl-l,2,4-triazinium salts 5. The best results are obtained when nitromethane is used as the solvent for the alkylation. Similar results are obtained when trialkyloxonium tetrafluoroborates or dialkyl sulfates are used as alkylation agents. The formation of either the 1- or the 2-isomers depends on the substituents bound to the 1,2,4-triazine ring. In cases with a bulky substituent in the 3-position, alkylation occurs exclusively at Nl, in other cases mixtures of N1 and N2 alkylated triazinium salts are obtained. Introduction of a more bulky substituent, such as isopropyl or aryl substituents, in the 6-posi-tion hinders quaternization at Nl. 

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