Chlorophenyl Salicylate

Submitted by Norman G. Gaylord and P. M. Kamath.1 Checked by R. T. Arnold and J. John Brezinski. 

To a mixture of 138.1 g. (1 mole) of salicyclic acid and 128.6 g. (1 mole) of -chlorophenol in a 2-1. round-bottomed flask fitted with a thermometer reaching to the bottom of the flask and a reflux condenser with a drying tube (Note 1) is added 58.3 g. (0.38 mole) of phosphorus oxychloride. The mixture is heated with occasional swirling, and the temperature is maintained at 75-80°. At the end of 4 hours the reactants have been reduced to a molten mass, and this is poured slowly, with vigorous stirring, into a solution of 120 g. of sodium carbonate in 800 ml. of water. The precipitated ester is collected on a filter and washed with four 200-ml. portions of water. The yield of crude, air-dried, p-chloro-phenyl salicylate is 174-189 g. (70-76%) m.p. 65-66°. Recrystallization from absolute ethanol yields 136-154 g. (55-62%) of pure product m.p. 69.5-70.5°. A second crop may be obtained by concentration of the filtrate from the first crop or by the addition of water (Note 2). 

It is advisable to attach the drying tube to a water trap 2 in order to prevent the escape of hydrogen chloride into the atmosphere. 

The above method has been used in the preparation of other substituted phenyl salicylates to give the following yields of recrystallized products with the indicated melting points. 

These esters, with the exception of the / -nitrophenyl derivative, can be recrystallized from absolute ethanol. The nitro compound is recrystallized from dioxane. 

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CHLOROPHENYL SALICYLATE (Salicylic acid, j -chlorophenyl ester)... 

Preparation by hydrolysis of 2-chloro-4-salicyloylphenyl salicylate [346], a secondary product obtained by Fries rearrangement of o-chlorophenyl salicylate at 180-183° for 3 h (20%) [506]. 

Also obtained by UV light irradiation of p-chlorophenyl salicylate in methanol for 8 h [1290]. 

C9H10O3 ethyl salicylate 118-61-6 20.00 1.1326 1 16855 C9H11CIN202 3-(4-chlorophenyl)-1 -methoxy-1 -methyl urea 1746-81-2 25.00 1.2664 2... 

FIGURE 14.10 Comparison between observed and calculated adsorbed amounts of three organic acids (2,4-d, 2-4-dichloro-phenoxy acetic acid salicylic acid, and clofencet, 2 -(chlorophenyl)-3-ethyl-2,5-dihydro-5-oxopyridazine-4-carboxylic acid) on several Cambisols and Ferralsols at their native soil pH. The bars indicate the confidence limits (0.05). (Reprinted from Calvet, R., Eur. J. Soil Sci., 58, 3, 609-624. Copyright 2007, with permission from John Wiley and Sons.)... 

Acids such as stearic acid, salicylic acid, and p-chlorophenyl-substituted fatty acids. 

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