Amberlyst-15 as a Heterogeneous Reusable Catalyst for the Synthesis of α-Hydroxy Phosphonates in Water

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.

α-hydroxy phosphonates - Abramov reaction - water - Amberlyst-15 - nucleophilic addition

References and Notes

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27

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).

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