Facile Synthesis of Phosphonates via Catalyst-Free Multicomponent Reactions in Water

Abstract

Stable derivatives of phosphonates were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate with 1-(6-hydroxy-2-isopropenyl-1-benzofuran-yl)-1-ethanone or 4-hydroxycoumarin in the presence of trimethyl or triphenyl phosphite in water in good yields.

Key words

phosphonates - triphenyl phosphate - trimethyl phosphate - triethyl phosphate

• References and Notes

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• 17 General Procedure for the Preparation of Compounds 4 To a magnetically stirred solution of dialkyl acetylenedicarboxylate 2 (2 mmol) and 1-(6-hydroxy-2-isopropenyl-1-benzofuran-yl)-1-ethanone (1, 2 mmol) in H₂O was added trimethyl or triphenyl phosphite 3 (2 mmol). The reaction mixture was stirred for 6 h, and, after completion of reaction (monitored by TLC), the mixture was purified by silica gel column chromatography (Merck 230–400 mesh) using n-hexane–EtOAc as eluent to give compound 4. Representative Analytical Data for Compound 4a White powder; mp 138–140 °C; yield: 0.81 g (87%). IR (KBr): ν_max = 3225, 1740, 1735, 1724, 1678, 1587, 1128 cm^–1. Anal. Calcd (%) for C₂₁H₂₅O₁₀P (468.39): C, 53.85; H, 5.38. Found: C, 53.92; H, 5.47. ¹H NMR (500 MHz, CDCl₃): δ = 2.12 (3 H, s, Me), 2.58 (3 H, s, Me), 2.87 (3 H, d ³ J _HP = 11.2 Hz, MeO), 3.72 (3 H, s, MeO), 3.78 (3 H, d ³ J _HP = 11.2 Hz, OMe), 3.84 (3 H, s, MeO), 3.94 (1 H, dd ² J _HP = 20.4 Hz, ³ J _HH = 12.0 Hz, CH), 4.78 (1 H, d, ² J = 3.5 Hz, CH), 5.15 (1 H, dd, ³ J _HH = 12.0 Hz, ³ J _HP = 8.7 Hz, CH), 5.30 (1 H, s, CH), 5.73 (1 H, d, ² J = 3.5 Hz, CH), 7.82 (1 H, s, CH), 8.22 (1 H, s, OH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 18.6 (Me), 27.3 (Me), 44.2 (CH), 48.5 (d, ¹ J _PC = 134.4 Hz, CH), 52.0 (OMe), 52.8 (d, ² J _PC = 8.2 Hz, MeO), 53.6 (MeO), 54.6 (d, ² J _PC = 8.2 Hz, MeO), 110.8 (d, ³ J _PC = 5.8 Hz, C), 111.4 (CH), 112.3 (CH₂), 117.5 (C), 121.0 (C), 122.4 (CH), 137.5 (C), 154.2 (C), 157.4 (C), 159.2 (C), 167.5 (d, ² J _PC = 5.4 Hz, C=O), 172.6 (d, ³ J _PC = 22.4 Hz, C=O), 192.8 (C=O). ³¹P NMR (202 MHz, CDCl₃): δ = 18.6. MS: m/z (%) = 468 (10) [M⁺], 359 (56), 109 (100), 31 (86)
• 18 General Procedure for the Preparation of Compounds 6 To a magnetically stirred solution of dialkyl acetylenedicarboxylate 2 (2 mmol) and 4-hydroxycoumarin (5, 2 mmol) in H₂O was added trimethyl or triphenyl phosphite 3 (2 mmol). The reaction mixture was then stirred for 5 h. After completion of reaction (monitored by TLC), the mixture was purified by silica gel column chromatog-raphy (Merck 230–400 mesh) using n-hexane–EtOAc as eluent to give compound 6. Representative Analytical Data for Compound 6a Colorless crystals; mp 185–187 °C; yield 0.70 g (85%). IR (KBr): ν_max = 3235, 1754, 1740, 1732 cm^–1. Anal. Calcd (%) for C₁₇H₁₉O₁₀P (414.30): C, 49.28; H, 4.62. Found: C, 49.36; H, 4.74. ¹H NMR (500 MHz, CDCl₃): δ = 2.92 (3 H, d, ³ J _HP = 11.2 Hz, MeO), 3.65 (3 H, s, MeO), 3.72 (3 H, d, ³ J _HP = 11.2 Hz, OMe), 3.85 (3 H, s, MeO), 3.92 (1 H, dd, ² J _HP = 20.4 Hz, ³ J _HH = 11.7 Hz, CH), 5.12 (1 H, dd, ³ J _HH = 11.7 Hz, ³ J _HP = 8.7 Hz, CH), 6.95–7.92 (4 H, m, 4 CH), 8.12 (1 H, s, OH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 43.8 (CH), 48.2 (d, ¹ J _PC = 134.4 Hz, CH), 51.8 (OMe), 52.3 (d, ² J _PC = 8.2 Hz, MeO), 53.4 (MeO), 54.0 (d, ² J _PC = 8.2 Hz, MeO), 115.4 (C), 122.4 (CH), 123.8 (C), 125.4 (CH), 126.8 (CH), 127.5 (C), 132.6 (CH), 149.6 (C), 165.2 (C=O), 167.5 (d, ² J _PC = 5.4 Hz, C=O), 172.6 (d, ³ J _PC = 21.5 Hz, C=O). ³¹P NMR (202 MHz, CDCl₃): δ = 18.6. MS: m/z (%) = 414 (20) [M⁺], 252 (48), 162 (86), 31 (100)
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