O-Alkylation of carboxylates

3 real reactions from the literature, on carboxylic acids and benzylic alkyl chlorides. Each scheme shows starting materials, conditions and products, with the yield and reference where the source reports them.

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1. Carboxylate alkylation: 4-nitrobenzyl chloride (a benzylic alkyl chloride) with NaOAc; AcOH, Δ gives (4-nitrophenyl)methyl acetate (the ester).

   Carboxylate alkylationOrg. Synth. Coll. Vol. 3, p. 650

2. Carboxylate alkylation: 5-(4-methoxy-phenyl)-5-oxo-pentanoic acid (a carboxylic acid) with Br2; Et2O gives 5-(4-methoxybenzoyl)oxolan-2-one (the five-membered lactone). 87% yield.

   Carboxylate alkylationJ. Chem. Soc., Chem. Commun. 1969, 1479

3. Carboxylate alkylation: 2-bromopropane (a secondary alkyl bromide) and 3-hydroxy-2,2-dimethylpropionic acid (a carboxylic acid) with Cs2CO3; DMF gives methylethyl 3-hydroxy-2,2-dimethylpropanoate (the ester).

   Carboxylate alkylationPCT Int. Appl. WO2009033061