Formation of a diacid; 3-(2-carboxymethyl-4-methoxy-6-tolyl)-propionic acid

lisa frost (kafs4@sussex.ac.uk),
A contribution from the Caddick Group, Sussex

Chemicals Used
3-(2-cyanomethyl-4-methoxy-6-tolyl)-acrylic acid ethyl ester [SyntheticPage 173] magnesium turnings (Avocado) Methanol (distilled from Mg) water

Procedure
A mixture of 3-(2-cyanomethyl-4-methoxy-6-tolyl)-acrylic acid ethyl ester (9.0 g, 35 mmol, 1 equiv) and magnesium turnings (3.38 g, 139 mmol, 4 equiv)was stirred at 0 ^oC in methanol (200 mL). Initiation of the reaction was achieved by the addition of 1 crystal of iodine to the solution. Stirring was continued for 6 h at 0 ^oC. To the resulting grey/green solution was added NaOH (6.94 g, 173 mmol, 5 equiv) and water (200 mL) and the reaction heated at 130 ^oC for 36 h. The resulting grey solid was acidified to pH 1 with conc HCl and the organics extracted into DCM (c.a. 1L). The organics were then washed with 6N NaOH (400 mL). The combined NaOH extracts were acidified to pH 1 and extracted with DCM (2 x 500 mL), dried (MgSO₄), filtered and concentrated in vacuo yielding a fawny white solid (6.56 g, 75%)

Author's Comments
This reaction works really well and provides material that does not need further purification. One word of caution, it is important to fully reduce the double bond before addition of the NaOH solution. Tlc analysis will verify whether the reaction has gone to completion.

Data
1H nmr (300 mHz, CDCl₃) 6.70 (1H, d, J = 2.2 Hz), 6.58 (1H, d, J = 2.2 Hz), 3.77 (5H, s), 2.94 (2H, t, J = 7.9 Hz), 2.56 (2H, t, J = 7.9 Hz), 2.31 (3H, s).

Lead Reference
Rucker, Mark; Brueckner, Reinhard; Syn.Lett.; 10; 1997; 1187-1189.

Other References

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