Tetramethylene bromide reaction with

The formic acid Is distilled off, and the remainder dissolved in warm benzene and washed with a bicarbonate solution to a neutral reaction. After the benzene has been distilled off, the aminomalonic ester xylidide is obtained. This Is treated with an equal quantity of sodium ethylate and boiled with twice the theoretical quantity of tetramethylene bromide in absolute alcohol. 

Uses. Tetramethylene sulfone has high solvent power for aromatics and has been used extensively by Olah and co-workers for Friedel-Crafts type nitrations and for studies of the mechanism of nitronium tetrafluoroborate nitration of alkyl-benzenes and halobenzenes in homogeneous solution. It is a superior solvent for quaternization of tertiary amines with alkyl halides, since it has a high dielectric constant and does not enter into side reactions observed with nitrobenzene and dimethylformamide. For example in the synthesis of the acridizinium salt (3), Bradsher and Parham effected quaternization of (1) with benzyl bromide in tetramethylene sulfone at room temperature in excellent yield. Several other salts analagous to (2) were obtained in good yield and in crystalline form with use of tetramethylene sulfone, whereas with other solvents the products were colored... 

The importance of the solvent, in many cases an excess of the quatemizing reagent, in the formation of heterocyclic salts was recognized early. The function of dielectric constants and other more detailed influences on quatemization are dealt with in Section VI, but a consideration of the subject from a preparative standpoint is presented here. Methanol and ethanol are used frequently as solvents, and acetone,chloroform, acetonitrile, nitrobenzene, and dimethyl-formamide have been used successfully. The last two solvents were among those considered by Coleman and Fuoss in their search for a suitable solvent for kinetic experiments both solvents gave rise to side reactions when used for the reaction of pyridine with i-butyl bromide. Their observation with nitrobenzene is unexpected, and no other workers have reported difficulties. However, tetramethylene sulfone, 2,4-dimethylsulfolane, ethylene and propylene carbonates, and salicylaldehyde were satisfactory, giving relatively rapid reactions and clean products. Ethylene dichloride, used quite frequently for Friedel-Crafts reactions, would be expected to be a useful solvent but has only recently been used for quatemization reactions. ... 

Tetramethylene Telluronium Bromides2 30 g (69 mmol) of aluminum telluride and 67 g (310 mmol) of 1,4-dibromobutane are placed in a 250 ml, round-bottom flask fitted with a reflux condenser and a stirrer. The stirred mixture is heated at 125° when the reaction becomes too vigorous the flask is cooled. When the reaction has subsided the mixture is heated for 2 h, then cooled to 20°. The semi-solid mass is extracted in sequence with carbon tetrachloride, acetone, ethanol, and water. The acetone and ethanol extracts are combined, evaporated, and the residue is recrystallized from ethanol to give white crystals of 4-bromobutyl tetramethylene telluronium bromide. 

The cleavage of tetrahydrofuran and its alkylated derivatives with halogen acids is an excellent method for the preparation of, A-dihalo-alkanes.The reaction of tetrahydrofuran with the less-reactive hydrogen chloride stops at the chlorohydrin stage, whereas the reaction in the presence of zinc chloride catalyst leads to the formation of the dichloride. The crude reaction mixture containing the intermediate chlorohydrin may be treated directly with phosphorus tribromide, yielding tetramethylene chlorobromide. The preparation of dibromides can be accomplished easily with hydrogen bromide or phosphorus and bromine and diiodides, by the action of potassium iodide and orthophosphoric acid. ... 

During preparation of polyelectrolytes from poly(4-vinyl-pyridine) (P-4-VP) and alkyl halides, some puzzling phenomena were observed by Coleman and Fuoss. These authors found quaternization of pyridine, 4-picoline and 4-isopropylpyridine with n-butyl bromide in tetramethylene sulfone followed normal second-order kinetics. Similar results were reported by Hinshelwood and coworkersfor the reaction of pyridine and alkyl halides. However, on quaternization of poly(4-vinylpyridine) under the same conditions, they observed... 

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