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Baylis-Hillman reaction of ethyl acrylate with ethyl 2-methylene-5-oxopentanoate;  Diethyl 3-hydroxy-2,6-dimethyleneheptanedioate

SyntheticPage 804
DOI: 10.1039/SP804
Submitted Nov 06, 2015, published Nov 11, 2015
RAJU THOMBAL (rthombal@gmail.com)
A contribution from Dr.V.H.JADHAV'S GROUP


			Reaction Scheme: <IMG src="/images/empty.gif">Baylis-Hillman reaction of <SPAN id=csm1447325310009 class=csm-chemical-name title="ethyl acrylate" grpid="1">ethyl acrylate</SPAN> with <SPAN id=csm1447325323219 class=csm-chemical-name title="ethyl 2-methylene-5-oxopentanoate" grpid="2">ethyl 2-methylene-5-oxopentanoate</SPAN><IMG src="/images/empty.gif">

Chemicals Used

 

1)      Ethyl 2-methylene-5-oxopentanoate

2)      Ethyl Acrylate

3)      DABCO

4)      1, 4-dioxane.

Procedure

To a solution of ethyl 2-methylene-5-oxopentanoate (1.0 g, 6.40 mmol) in 1, 4 dioxane-H2O (1:1, 25 mL) was added DABCO (0.71 g, 6.40 mmol) and ethyl acrylate (2.05 mL, 19.21mmol) at 30 ο C. Reaction mixture was stirred for 48 h and quenched by adding saturated NH4Cl solution. The solution was extracted with ethyl acetate (50 mL), and ethyl acetate was evaporated to give crude product. Purification by column chromatography (n-hexane/ethyl acetate = 9/1) gave the pure product as colourless oil (1.35 g, 82 %).

Author's Comments

Reation proceeds smoothly, no side products were observed.

Data

1H NMR (400 MHz, CDCl3) δ 6.25 (d, J= 1.5 Hz, 1H), 6.17 (d, J= 1.6 Hz, 1H), 5.83 (t, J= 1.14 Hz, 1H), 5.59 (d, J= 1.5 Hz, 1H), 4.49-4.40 (m, 1H), 4.28-4.13 (m, 4H), 2.91 (bs, 1H), 2.49-2.31 (m, 2H), 1.91-1.68 (m, 3H), 1.35-1.22 (m, 6H).

13C NMR (100 MHz, CDCl3) δ 167.3, 166.5, 142.2, 140.1, 125.1, 124.9, 70.5, 60.8, 34.9, 28.0, 14.0.


Lead Reference

V. H. Jadhav, O. P. Bande, R. V. Pinjari, S. P. Gejji, V. G. Puranik, D. D. Dhavale, J. Org. Chem. 2009, 74, 6486-6494.

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Keywords: alcohols, aldehydes, alkenes, esters, nucleophilic