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Esterification of Monomethyl Fumarate; Ethyl Methyl Fumarate

SyntheticPage 959
Submitted Aug 03, 2022, published Oct 05, 2022
Ramesha Ramakrishna (ramesha63@hotmail.com), Sayyed Mudassar (), Bishwajit Chakraborthy ()
A contribution from ramesha


			Reaction Scheme: Esterification of Monomethyl Fumarate

Chemicals Used

1. Monomethylfumaric acid: Prepared as per patent No: WO2021/053476A1

2. Dichloromethane: Commercial

3. Ethylchloroformate: Aldrich

4. Sodium sulfate: SD Fine Chem

5. Triethylamine: SD Fine Chem

 

Procedure

In a 500 mL RB flask fitted with mechanical stirrer, nitrogen inlet and addition flask, dichloromethane (150 mL) was charged followed by mono methylfumaric acid (25 g, 0.192 mol) at room temperature followed by triethylamine (29.2 g, 0.288 mole). Reaction mixture was cooled to about 2-3 degree centigrade under nitrogen atmosphere. At this temperature, ethylchloroformate (23 g, 0.211 mole) in 50 mL dichloromethane was slowly added keeping the temperature below 5 oC. After 1 h of stirring, cooling was removed and allowed to come to RT in 2h. TLC (7:3, ethyl acetate: cyclohexane, Rf:~0.8), showed complete conversion of monomethyl fumarate to ethyl methyl fumarate . Slowly added the reaction mixture to water 200 mL and separate dichloromethane layer. Water wash 2 times (2x 100 mL) and evaporated the dichloromethane layer to get ethyl methyl fumarate (30 g, 98.7 %) which is pure by NMR.

Author's Comments

1. Dry condition is required for succesful reaction.  2. Product is almost pure by NMR (attached). 3. 1H NMR and 13C NMR attached

Data

1H NMR (CDCl3, delta): 6.86(2H, Singlet), 4.28-4.23(2H, Quartet), 3.80(3H, Singlet), 1.33-1.30 (3H, Triplet)

13C NMR (CDCl3, delta): 165.12, 164.59, 133.63, 132.28, 61.06, 51.97, 13.79

 


Lead Reference

Patent No: WO2021/053476A1

Supplementary Information

13C NMR (13 C NMR of Ethyl Methyl fumerate.png)
1H NMR (1H NMR Ethyl methyl Fumerate.png)

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Get structure file (.cdx, .sk2, .mol)

Keywords: addition, carboxylic acids, electrophilic, Esterification, esters, Ethyl, Ethyl chloroformate, Fumarate, insertion, Methyl

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