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DCC mediated esterification of 2,4-dinitrophenol; (S)-2’,4’-Dinitrophenyl 2-methylbutanoate

SyntheticPage 705
DOI: 10.1039/SP705
Submitted Nov 25, 2013, published Dec 03, 2013
Sergey Vatsadze (zurabych@gmail.com), Alexey Medved'ko (lexeym@gmail.com), Gregory Kazankov (gkazankov@hotmail.com), Sergey Kurzeev (kurzeev@gmail.com)
A contribution from Vatsadze Group, Moscow State University


			Reaction Scheme: <IMG src="/images/empty.gif"><IMG src="/images/empty.gif"><IMG src="/images/empty.gif"><SPAN id=csm1397728869488 class=csm-chemical-name title=DCC grpid="5">DCC</SPAN> mediated esterification of <SPAN id=csm1397728686872 class="csm-chemical-name csm-not-validated" title=2,4-dinitrophenol grpid="2">2,4-dinitrophenol</SPAN><IMG src="/images/empty.gif"><IMG src="/images/empty.gif"><IMG src="/images/empty.gif">

Chemicals Used

2,4-dinitrophenol (Labteh)
(S)-2-methylbutanoic acid (Sigma)
N,N-dicyclohexylcarbodiimide DCC (Sigma)
Ethyl acetate (Irea)
Petroleum ether 40-60°C (Irea)
Dichloromethane (Irea)
Silica gel

Procedure

2,4-dinitrophenol (0.4484 g, 2.44 mmol) and (S)-2-methylbutanoic acid (0.265 ml, 2.43 mmol) of  were dissolved in dry ethyl acetate (4 ml) and cooled in ice bath. DCC (0.5074 g, 2.46 mmol) of was dissolved in dry ethyl acetate (4 ml) and was added to above solution in one portion under vigorous stirring. The reaction mixture was stirred for 1 h with cooling and 19 h at room temperature. The precipitated N,N-dicyclohexylurea was filtered off and the solvent was removed from the filtrate on rotary evaporator. The yellow oil thus obtained was purified with column chromatography. Eluent: petroleum ether:DCM:ethyl acetate 5:1:1. Product obatained as yellow oil that slowly solidifies in refrigerator. Yield 100% (650.1 mg).

Author's Comments

2,4-Dinitrophenyl ester elutes as the first yellow band, prior to 2,4-dinitrophenol.

Data

Yellow solid.
[α]d20 +16.6° (c 0.54, EtOAc).
1H-NMR (400MHz, CDCl3, δ, ppm): 1.05 (t, 3H, J 7.4Hz), 1.36 (d, 3H, 3J = 7Hz), 1.66 (dt, 1H, 3J = 14.1Hz, 3J = 7Hz), 1.9 (dt, 1H, 3J = 14.1 Hz, 3J = 7.2Hz), 2.75 (sext, 1H, 3J = 6.9Hz), 7.46 (d, 1H, 3J = 8.9Hz), 8.51 (dd, 1H, 3J = 8.9Hz, 3J = 2.7Hz), 8.94 (d, 1H, 3J = 2.6Hz).

Lead Reference

V. K. Kibirev, A. A. Gershkovich Sintez peptidov. Reagenty i metody (in Russian) // Kiev, 1987, p. 59.

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Keywords: alcohols, carboxylic acids, esters, nucleophilic, substitution