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DOI: 10.1055/s-2007-985595
Amberlyst-15 as a Heterogeneous Reusable Catalyst for the Synthesis of α-Hydroxy Phosphonates in Water
Publikationsverlauf
Publikationsdatum:
22. August 2007 (online)
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Abstract
An efficient and simple synthesis of α-hydroxy phosphonates has been achieved via reaction of aldehydes with trimethylphosphite in the presence of Amberlyst-15 in water. The reaction is highly selective with excellent yields under mild conditions.
Key words
α-hydroxy phosphonates - Abramov reaction - water - Amberlyst-15 - nucleophilic addition
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References and Notes
Typical Procedure
A solution of benzaldehyde (0.107 g, 1 mmol), trimethyl-phosphite (0.136 g, 1.1 mmol), and Amberlyst-15 (0.1 g) in H2O (2 mL) was placed in a round-bottomed flask equipped with a magnetic stirrer and was heated at 50 °C. The stirring was continued for 1.5 h. After completion of the reaction as indicated by TLC, the reaction mixture was treated with aq sat. NaHCO3 solution followed by brine and the product was extracted three times with 5 mL CH2Cl2, dried over anhyd MgSO4, and concentrated to give an oily residue, which was crystallized to give 0.216 g (95%) of dimethyl 1-hydroxy-1-phenylmethylphosphonate.
Spectral Data for Selected ProductsDimethyl 1-Hydroxy-1-phenylmethylphosphonate
[19]
(Table 1, Entry 1)
IR: 3260 (OH) cm-1. 1H NMR (500 MHz, CDCl3): δ = 3.6 (d, J = 10.3 Hz, 3 H), 3.6 (d, J = 10.3 Hz, 3 H), 5.0 (d, 1 H, J = 13.2 Hz), 6.0 (s, OH), 7.3-7.5 (m, 5 H). 13C NMR (125 MHz, CDCl3): δ = 53.7 (d, J
CP = 7.5 Hz), 54.2 (d, J
CP = 7.5 Hz), 69.1 (d, J
CP = 164.0 Hz), 128.8, 129.4, 131.1, 133.8 (d, J
CP = 2.9 Hz).
Dimethyl 1-Hydroxy-1-(4-chlorophenyl)methyl-phosphonate
[19]
(Table 1, Entry 3)
IR: 3290 (OH) cm-1. 1H NMR (500 MHz, CDCl3): δ = 3.6-3.7 (m, 6 H), 5.1 (d, J = 13.4 Hz, 1 H), 6.2 (s, OH), 7.4 (d, J = 8.5 Hz, 2 H), 7.5 (d, J = 8.5 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 53.7 (d, J
CP = 7.1 Hz), 54.2 (d, J
CP = 7.5 Hz), 69.1 (d, J
CP = 161.1 Hz), 128.8, 129.4, 133.1 (d, J
CP = 3.9 Hz), 138.2.
Dimethyl 1-Hydroxy-3-phenyl-2-propenylphosphonate
[28]
(Table 1, Entry 4)
IR: 3255 (OH) cm-1. 1H NMR (500 MHz, CDCl3): δ = 3.8 (d, J
PH = 10.3 Hz, 3 H), 3.8 (d, J
PH = 10.3 Hz, 3 H), 4.7 (s, OH), 6.4 (d, J = 15.9, 6.2 Hz, J
PH = 5.6 Hz, 1 H), 6.8 (d, J = 15.6, 1.5 Hz, J
PH = 4.9 Hz, 1 H), 7.3-7.2 (m, 3 H), 7.4-7.4 (m, 2 H). 13C NMR (500 MHz, CDCl3): δ = 53.7 (d, J
PC = 7.4 Hz), 53.9 (d, J
PC = 7.1 Hz), 69.2 (d, J
PC = 161.0 Hz), 128.4, 127.8, 126.5, 123.5 (d, J
PC = 4.3 Hz), 132.2 (d, J
PC = 13.0 Hz), 136.1 (d, J
PC = 2.9 Hz).
Dimethyl 1-Hydroxybutylphosphonate
[17]
(Table 1, Entry 11)
IR: 3312 (OH) cm-1. 1H NMR (90 MHz, CDCl3): δ = 1.0 (t, 3 H), 1.8-1.1 (m, 4 H), 2.7 (m, 1 H), 3.7 (d, 3
J
PH = 5.4 Hz, 3 H), 3.8 (d, 3
J
PH = 5.4 Hz, 3 H), 3.9 (s, OH). 13C NMR (22.5 MHz, CDCl3): δ = 13.8 (d, 4
J
PC = 19.1 Hz, CH3), 19.9 (d, 3
J
PC = 11.8 Hz, CH2), 29.0 (d, 2
J
PC = 7.4 Hz, CH2), 51.1 (d, 2
J
PC = 7.3 Hz, OCH3), 52.2 (d, 2
J
PC = 7.3 Hz, OCH3), 56.8 (d, 1
J
PC = 136.8 Hz, OCH3).
Dimethyl 1-Hydroxy-2-methylpropylphosphonate
[17]
(Table 1, Entry 13)
IR: 3313 (OH) cm-1. 1H NMR (90 MHz, CDCl3): δ = 0.8 (m, 3 H), 1.9 (m, 1 H), 3.6 (m, 1 H), 3.6 (d, 3
J
PH = 4.4 Hz, 3 H), 3.7 (d, 3
J
PH = 4.4 Hz, 3 H), 4.8 (s, O H). 13C NMR (22.5 MHz, CDCl3): δ = 17.4 (d, 4
J
PC = 7.0 Hz, CH3), 19.4 (d, 3
J
PC = 9.5 Hz, CH2), 29.9 (d, 2
J
PC = 8.0, CH), 52.4 (2
J
PC = 6.5 Hz, OCH3), 52.6 (2
J
PC = 6.5 Hz, OCH3), 73.2 (1
J
PC = 148.4 Hz, CH).
Dimethyl 1-Hydroxy-1-furylmethylphosphonate
[17]
(Table 1, Entry 14)
1H NMR (90 MHz, CDCl3): δ = 1.3 (s, OH), 3.7 (d, 3
J
PH = 5.8 Hz, 3 H), 3.9 (d, 3
J
PH = 5.8 Hz, 3 H), 5.0 (d, 2
J
PH = 13.5 Hz, 1 H), 6.4-6.6 (m, 2 H), 7.4 (s, 1 H). 13C NMR (22.5 MHz, CDCl3): δ = 53.6 (d, 2
J
PC = 2.7 Hz, OCH3), 53.9 (d, 2
J
PC = 2.7 Hz, OCH3), 64.2 (d, 1
J
PC = 167.8 Hz, CH), 109.3 (d, 3
J
PC = 6.4 Hz, C), 110.7 (s, CH), 142.8 (d, 3
J
PC = 1.8 Hz, CH), 149.9 (s, CH).