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Wittig- Horner Reaction of Triethyl phosphonoacetate with Formaldehyde in Aqueous Medium; Ethyl 2-(hydroxymethyl)acrylate

SyntheticPage 799
DOI: 10.1039/SP799
Submitted Sep 19, 2015, published Sep 21, 2015
A contribution from Dr.V.H.JADHAV'S GROUP

			Reaction Scheme: <IMG src="/images/empty.gif">Wittig- Horner Reaction of <SPAN id=csm1442842283414 class=csm-chemical-name title="Triethyl phosphonoacetate" grpid="1">Triethyl phosphonoacetate</SPAN> with <SPAN id=csm1442842291847 class=csm-chemical-name title=Formaldehyde grpid="2">Formaldehyde</SPAN> in Aqueous Medium<IMG src="/images/empty.gif">

Chemicals Used

1)      triethyl phosphonoacetate

2)      37% aq. Formaldehyde

3)      potassium carbonate


A mixture of triethyl phosphonoacetate (22.4 g, 0.1 mol) and a 37% aqueous solution of formaldehyde (32.4 g, 0.4 mol) were stirred at room temperature. A saturated solution of potassium carbonate (24.15 g, 0.175 mol) was added to the above mixture over 30 min. After addition, the reaction mixture reached 30 – 35 0C. Stirring was continued for an additional 2 h. The reaction was quenched with a saturated solution of ammonium chloride (35 mL). The reaction mixture was then extracted with ethyl ether (3x 12.5 mL). Organic layers were combined and dried over sodium sulfate. The solvent was evaporated using a rotary evaporator, and the product (colourless oil) was purified using flash chromatography using 20% ethyl acetate/hexanes. This purification yielded the pure product as colourless oil (8 g, 70%).

Author's Comments

1) Reaction proceeds smoothly on bulk scale.
2) Slow addition of saturated potassium carbonate is required.


1H NMR (400 MHz, CDCl3) δ 6.24 (s, 1H), 5.82 (s, 1H), 4.3 (s, 2H), 4.24-4.19 (m, 2H), 2.72 (bs, 1H), 1.3 (t, J=7.3Hz, 3H)

13C NMR (100 MHz, CDCl3) δ 166.2, 139.6, 125.3, 62.2, 60.7, 14.0. 

Lead Reference

1) J. Villieras, M. Rambaud, Synthesis 1982, 1982, 924-926.

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Keywords: addition, alcohols, alkenes, elimination, esters, organo phosphorous

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