Benzylthiouronium chloride

Add in turn benzyl chloride (8 3 g., 8 o ml.) and powdered thiourea (5 gm.) to 10 ml. of 95% ethanol in a 100 ml. flask fitted with a reflux condenser. Warm the mixture on the water-bath with gentle shaking until the reaction occurs and the effervescence subsides then boil the mixture under reflux for 30 minutes. Cool the clear solution in ice-water, filter off the crystalline deposit of the benzylthiouronium chloride at the pump, wash it with ice-cold ethyl acetate, and dry in a desiccator. Yield, 11-12 g., m.p. 170-174°. The white product is sufficiently pure for use as a reagent. It is very soluble in cold water and ethanol, but can be recrystallised by adding ethanol dropwise to a boiling suspension in ethyl acetate or acetone until a clear solution is just obtained, and then rapidly cooling. 

Arsonic acids, like carboxylic and sulphonic acids (pp. 349, 353), usually give crystalline benzylthiouronium salts. Add just sufficient dilute aqueous sodium hydroxide dropwise with shaking to a suspension of 0 5 g. of phenylarsonic acid in 10 ml. of water to give a clear solution. Then add 0 5 g. of benzylthiouronium chloride dissolved in 10 ml. of water. Filter off the precipitated benzylthiouronium salt, wash with water and dry m.p. 114-117° it tends to dissociate on attempted recrystallisation. 

A) Benzylthiouronium salts. The sodium salt of an acid in aqueous solution will react with benzylthiouronium chloride ... 

Example. Dissolve 0 3 g. of benzoic acid in a minimum of hot water (about 70 ml.) and add 5% aqueous sodium hydro.xide until the solution is just alkaline to methyl-orange, then add i drop of dilute hydrochloric acid. Pour this solution of the sodium salt into a solution of 0 5 g, of benzylthiouronium chloride in 5 ml. of water, and cool the stirred mixture in ice-water. Filter off the benzylthiouronium salt which has separated, and recrystallise from ethanol con taining 10% of water cream-coloured cr> stals, m.p. i66 . (M.ps., pp. 543 545.)... 

Thiourea. Boil in ethanolic solution with benzyl chloride to prepare the crystalline benzylthiouronium chloride, m.p. lyo i 74" (P- 126). 

Benzylthiouronium salts. Add 0 5 g. of sulphanilic acid to 10 ml. of water and 5 ml. of 10% NaOH solution, zndgently warm the shaken mixture until a clear solution is obtained. Cool, add 1 drop of phenol-phthalein solution, and then add dilute HCl dropwise with shaking until the pink colour is just discharged. Now add very dilute NaOH solution until the pink colour yt/rZ returns. Cool and add with shaking a solution of 0-5 g. of benzylthiouronium chloride in 5 ml. of water. The thiouronium salt rapidly separates filter at the pump, wash with water, drain and recrystallise from ethanol. Colourless crystals, m.p. 185°. (M.ps., p. 548.)... 

Ameta et al. (2012) reported one-pot three-component reactions of chalcones (50) with 5-benzylthiouronium chloride (SBT) (51) and aliphatic heterocyclic secondary amines such as morpholine (52), pyrrolidine (53), and piperidine (54) in the presence of ZnO heterogeneous catalyst to afford 2-substituted-4,6-diarylpyrimidines (55,56, 57) (Scheme 9.13). The method is highly economic, simple, and environmentally friendly in nature. Furthermore, the catalyst showed good reusability up to three successive runs. 

Prepared by drop-wise addition of Bu°Li in ether-pentane to perfluoro-l-iodobicyclo-[2,2,] ]hept-2-ene in ether at room temperature surprisingly, no significant replacement of vinylic fluorine by Bu occurred. fDerivatized with 5 -benzylthiouronium chloride. 

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