Hydrochloric Acid → Dimethyl 2-[(4-nitrophenyl)methyl]propanedioate

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Reaction Conditions

Reaction Steps

2-Carbomethoxy-3-(4-nitrophenyl)propenoic acid methyl ester was made from the Knovenagle condensation of dimethylmalonate and p-nitrobenzaldehyde according to the method of J. Chem. Soc., 2125 (1927): Melting point observed (mpobs)=133-134° C. Melting point reported in the literature (mplit)=136-137° C. 2-Carbomethoxy-3-(4-nitrophenyl)propenoic acid methyl ester (23.0 grams (g), 86.7 millimoles (mmole)) was dissolved in 175 milliliters (mL) of methanol (MEOH) under nitrogen and sodium cyanoborohydride (6.0 g, 95.5 mmole) was cautiously added to the stirred solution with cooling. The pH was adjusted to 4.0 with concentrated hydrochloric acid and the solution was stirred at 25° C. overnight. During the first 8 hrs the pH was readjusted from 6 to 4 on several occasions. The yellow methanol solution was poured into 700 mL of water and extracted with 3×200 mL portions of methylene chloride. The combined organic fractions were washed with 400 mL of saturated sodium bicarbonate and 400 mL of water, dried over magnesium sulfate and evaporated to a pale yellow oil on a rotary evaporator. The oil crystallized (mp=82-83° C.) upon standing and gave 2-carbomethoxy-3-(4-nitrophenyl)propanoic acid methyl ester (p-nitrobenzyl malonate dimethyl ester) in 93 percent yield (21.3 g, 81 mmole).

Provenance & Evidence