HClO₄-SiO₂ as a Novel and Recyclable Catalyst for the Phospha-Michael Addition of Phosphorous Nucleophiles to α,β-Unsaturated Malonates

Abstract

An efficient synthesis of β-phosphono malonates via phospha-Michael addition of phosphorous nucleophiles to α,β-unsaturated malonates in the presence of HClO₄-SiO₂ as a new and ­recyclable catalyst is described.

Key words

silica-supported perchloric acid - phospha-Michael addition - β-phosphono malonates

References and Notes

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24

General Procedure for the Synthesis of β-Phosphono Malonates (2a-t): HClO₄-SiO₂ (0.03 mmol, 0.057 g, 0.52 mmol/g) was added to a mixture of α,β-unsaturated malonates 1a-t (1 mmol) and P(OEt)₃ (1 mmol). The mixture was stirred and monitored by TLC. After completion of the reaction, the reaction mixture was diluted with EtOAc and filtered. Evaporation of the solvent under reduced pressure gave the crude products. The pure products, 2a-t, were obtained by chromatography on silica, eluting with n-hexane-EtOAc (1:1).

(1-Phenyl-2,2-dicyanoethyl) Phosphonic Acid Diethyl Ester (2a)
^¹H NMR (CDCl₃): δ = 1.11 (t, 3 H, ^³ J _HH = 6.8 Hz), 1.33 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.65 (dd, 1 H, ^³ J _HH = 8.0, ^² J _HP = 21.0 Hz), 3.91-4.21 (m, 4 H), 4.55 (t, 1 H, ^³ J _HH = 8.3 Hz), 7.43 (s, 5 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.6 Hz), 16.2 (d, ^³ J _CP = 5.6 Hz), 25.5, 44.6 (d, ^¹ J _CP = 144.0 Hz), 63.4 (d, ^² J _CP = 7.5 Hz), 64.4 (d, ^² J _CP = 7.0 Hz), 111.1 (d, ^³ J _CP = 12.5 Hz), 111.3 (d, ^³ J _CP = 10.0 Hz), 129.2, 129.3, 129.4, 129.8. ^³¹P NMR (CDCl₃): δ = 20.04. MS (70 eV): m/z = 292 [M⁺], 155 [M⁺ - P(O)(OEt)₂].
[1-(2-Chlorophenyl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2b)
^¹H NMR (CDCl₃): δ = 1.11 (t, 3 H, ^³ J _HH = 7.0 Hz), 1.36 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.75-4.30 (m, 4 H), 4.46 (dd, 1 H, ^³ J _HH = 8.2, ^² J _HP = 21.2 Hz), 4.61 (t, 1 H, ^³ J _HH = 8.5 Hz), 7.35 (d, 2 H, ^³ J _HH = 4.0 Hz), 7.47 (s, 1 H), 7.75 (d, 1 H, ^³ J _HH = 5.3 Hz). ^¹³C NMR (CDCl₃): δ = 16.0 (d, ^³ J _CP = 6.3 Hz), 16.2 (d, ^³ J _CP = 5.6 Hz), 24.9, 39.4 (d, ^¹ J _CP = 144.6 Hz), 63.6 (d, ^² J _CP = 7.5 Hz), 64.4 (d, ^² J _CP = 6.9 Hz), 110.9 (d, ^³ J _CP = 5.6 Hz), 111.1, 127.8, 128.6, 129.6, 130.6, 135.1. ^³¹P NMR (CDCl₃): δ = 19.47. MS (70 eV): m/z = 326 [M⁺], 328 [M⁺ + 2], 189 [M⁺ - P(O)(OEt)₂], 191 [(M⁺ + 2) - P(O)(OEt)₂].
[1-(4-Chlorophenyl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2d)
^¹H NMR (CDCl₃): δ = 1.16 (t, 3 H, ^³ J _HH = 7.0 Hz), 1.33 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.62 (dd, 1 H, ^³ J _HH = 7.5 Hz, ^² J _HP = 21.5 Hz), 3.82-4.19 (m, 4 H), 4.55 (t, 1 H, ^³ J _HH = 7.7 Hz), 7.42 (s, 4 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.0 Hz), 16.2 (d, ^³ J _CP = 5.6 Hz), 25.5, 43.9 (d, ^¹ J _CP = 144.7 Hz), 63.5 (d, ^² J _CP = 7.0 Hz), 64.4 (d, ^² J _CP = 7.0 Hz), 111.0 (d, ^³ J _CP = 11.9 Hz), 111.2 (d, ^³ J _CP = 11.3 Hz), 128.8, 129.6, 130.7, 135.7. ^³¹P NMR (CDCl₃): δ = 19.42. MS (70 eV): m/z = 326 [M⁺], 328 [M⁺ + 2], 189 [M⁺ - P(O)(OEt)₂], 191 [(M⁺ + 2) - P(O)(OEt)₂].
[1-(Naphthalen-2-yl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2j)
^¹H NMR (CDCl₃): δ = 1.08 (t, 3 H, ^³ J _HH = 7.0 Hz), 1.36 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.65-4.22 (m, 5 H), 4.66 (t, 1 H, ^³ J _HH = 8.5 Hz), 7.52-7.58 (m, 3 H), 7.87-7.96 (m, 4 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.6 Hz), 16.2 (d, ^³ J _CP = 6.2 Hz), 25.7, 44.8 (d, ^¹ J _CP = 144.0 Hz), 63.4 (d, ^² J _CP = 7.5 Hz), 64.4 (d, ^² J _CP = 7.0 Hz), 111.2 (d, ^³ J _CP = 13.2 Hz), 111.3 (d, ^³ J _CP = 8.2 Hz), 125.9, 126,9, 127.2, 127.6, 127.7, 127.8, 128.2, 129.2, 129.4, 133.3. ^³¹P NMR (CDCl₃): δ = 19.95.
[1-(Furan-2-yl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2k)
^¹H NMR (CDCl₃): δ = 1.24-1.37 (m, 6 H), 3.87 (dd, 1 H, ^³ J _HH = 6.5 Hz, ^² J _HP = 22.7 Hz), 3.98-4.23 (m, 4 H), 4.51 (t, 1 H, ^³ J _HH = 8.7 Hz), 6.44 (s, 1 H), 6.62 (s, 1 H), 7.49 (s, 1 H).
^¹³C NMR (CDCl₃): δ = 16.1, 16.2, 24.3, 39.1 (d, ^¹ J _CP = 147.1 Hz), 63.9 (d, ^² J _CP = 6.9 Hz), 64.2 (d, ^² J _CP = 6.9 Hz), 110.9 (d, ^³ J _CP = 9.4 Hz), 111.1 (d, ^³ J _CP = 11.9 Hz), 111.3, 111.7, 143.2, 144.0. ^³¹P NMR (CDCl₃): δ = 19.88. MS (70 eV): m/z = 282 [M⁺], 145 [M⁺ -P(O)(OEt)₂].
[1-(Pyridin-3-yl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2m)
^¹H NMR (CDCl₃): δ = 1.18 (t, 3 H, ^³ J _HH = 6.8 Hz), 1.33 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.65 (dd, 1 H, ^³ J _HH = 6.8 Hz, ^² J _HP = 21.6 Hz), 3.92-4.21 (m, 4 H), 4.63 (t, 1 H, ^³ J _HH = 8.5 Hz), 7.39 (t, 1 H, ^³ J _HH = 6.5 Hz), 7.95 (d, 1 H, ^³ J _HH = 6.5 Hz), 8.67 (s, 2 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.0 Hz), 16.2 (d, ^³ J _CP = 5.0 Hz), 25.3, 42.1 (d, ^¹ J _CP = 144.6 Hz), 63.8 (d, ^² J _CP = 7.0 Hz), 64.5 (d, ^² J _CP = 7.0 Hz), 110.8 (d, ^³ J _CP = 10.7 Hz), 111.0 (d, ^³ J _CP = 11.9 Hz), 124.0, 126,7, 136.5, 150.5, 150.8. ^³¹P NMR (CDCl₃): δ = 19.03. MS (70 eV): m/z = 293 [M⁺], 156 [M⁺ - P(O)(OEt)₂].