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Baylis-Hillman reaction of 4-pyridinecarboxaldehyde and methyl acrylate; methyl 2-(hydroxy(pyridin-4-yl)methyl)acrylate

SyntheticPage 827
DOI: 10.1039/SP827
Submitted Jun 16, 2017, published Jun 21, 2017
Steven M. Kennedy (Steven.Kennedy@millersville.edu), Jevica Salim (jev340@gmail.com)
A contribution from Kennedy Group, Millersville University


			Reaction Scheme: <IMG src="/images/empty.gif">Baylis-Hillman reaction of <SPAN id=csm1498055411899 class=csm-chemical-name title=4-pyridinecarboxaldehyde grpid="1">4-pyridinecarboxaldehyde</SPAN> and <SPAN id=csm1498055419437 class=csm-chemical-name title="methyl acrylate" grpid="2">methyl acrylate</SPAN><IMG src="/images/empty.gif">

Chemicals Used

4-Pyridinecarboxaldehyde (98%, Acros Organics)
Methyl acrylate (99%, stabilized with MEHQ, TCI America)
1,4-Diazabicyclo[2.2.2]octane (DABCO, 98%, TCI America)
Dichloromethane (99.5%, stabilized with amylene, Alfa Aesar)

Procedure

4-pyridinecarboxaldehyde (0.38 mL, 4.0 mmol), then methyl acrylate (0.48 mL, 5.2 mmol), were both added to a 2 dram (7.5 mL) reaction vial. The mixture was stirred rapidly with a magnetic stir bar prior to adding 1,4-Diazabicyclo[2.2.2]octane (45 mg, 0.40 mmol). The reaction mixture was stirred at 23 °C for 45 min; at which time, 4 mL of dichloromethane was added, prior to breaking up the solid with a metal spatula. The solid was collected via vacuum filtration using a hirsch filter. Recrystallization from a minimum amount of ethanol provided methyl 2-(hydroxy(pyridin-4-yl)methyl)acrylate (0.60 g, 3.1 mmol, 78% yield).

Author's Comments

Methyl acrylate is extremely volatile and very toxic. This reaction was carried out in a fume hood.

Data

1H NMR (400 MHz, CDCl3): δ 8.56 (d, 2H), 7.32 (d, 2H), 6.39 (s, 1H), 5.87 (s, 1H), 5.52 (s, 1H), 3.75 (s, 3H).
13C NMR (100 MHz, CDCl3): δ 166.62, 150.38, 149.84, 140.75, 127.39, 121.31, 72.42, 52.20.
M.p.
142-143°C (lit. 143–144 ºC)


Lead Reference

R.D. Crouch and T.D. Nelson, J. Chem. Ed. 1995, 72 (1), A6. DOI: 10.1021/ed072pA6

Other References

Y. Jeong and J.S. Ryu, J. Org. Chem. 2010, 75 (12), 4183. DOI: 10.1021/jo100618d

Supplementary Information

 
13C_NMR_Full_methyl 2-(hydroxy (CNMR_Full.pdf)
1H_NMR_Full_methyl 2-(hydroxy( (HNMR_Full.pdf)
1H_NMR_Zoom_methyl 2-(hydroxy( (HNMR_Zoom.pdf)

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

Keywords: addition, aldehydes, alkenes, elimination, nucleophilic

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