Amides from Esters smuv - 9-5-2009 at 20:59 Preface To further research amidations in molten urea, the synthesis of benzamide

from m ethyl benzoate performed. Methyl Benzoate This is straight from vogel... 30g Benzoic acid 100 mL Methanol ~3 mL Sulfuric acid Refluxed 4.5 hours. Allowed to stand overnight. Separated ester, extracted aqueo us phase w/ CH2Cl2. Combined Organics, washed with bicarbonate and water. Dried over CaCl2. Removed solvent via distillation. Obtained 10.9g of a clear just slightly yellow oil. Benzamide 10.9g Methyl benzoate 11g Urea .75g Boric Acid Mixed everything, heated in oil bath for 2 hours. Oil bath temp was increased fr om 140c to 170c over course of rxn. At first yellow plates precipitated but with further heating heating a lot of brownish colored trash precipitated. By end 2h only ca. 4mL of molten stuff remained, the rest was solid. The melt was allowed to cool and 125mL of 10% NH3 solution was added. Solution was boiled with stirr ing for ~10min and allowed to cool in a water bath. About 3mL of oily methyl ben zoate remained unreacted. The solution was vac filtered and obtained off-white p owder was dried in oven. Yield 2.95g (30%) of a fairly clean product. Discussion The yields of the esterification are probably low because the sulfuric acid used was drain cleaner, and likely contained a fair bit of water. For the amidation, in the future more urea should be used, because a lot of meth yl benzoate was left unreacted, and would have had no chance to react if the rxn was extended longer because most of the urea was decomposed after 2h. Also less ammonia solution should be used in work-up as the solubility of benzamide in wa ter is 1g /~75mL. Additionally unreacted methyl benzoate could have dissolved so me of the benzamide as well. Despite these shortcomings, the purpose was to determine if esters react well in this reaction, it appears with some subtle modifications, this process can be a pplied to esters if so desired. Of course there are other ways of making amides from esters, some are more convenient. However, this is just one more choice for the amateur chemist. [Edited on 5-10-2009 by smuv]