The Reaction of Alkylenecyclopropanes and Diethyl Phosphite: A Novel ­Method for the Preparation of Diethyl 3,4-Dihydro-2-naphthylphosphonates and 3-Butenyl Ethyl Phosphates

Abstract

AIBN-mediated addition of alkylidenecyclopropanes to diethyl phosphite produces diethyl-3,4-dihydro-2-naphthylphosphonates in moderate yields. When the reaction was carried out without AIBN in the presence of 5% water, 3-butenyl ethyl phosphites were obtained.

phosphates - phosphorus - radicals - radical reactions - methylenecyclopropanes

References

For the preparation of the MCPs, see:

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Diethyl 3,4-Dihydro-2-naphthylphosphonates 3; Typical Procedure. A soln of AIBN (0.049 g, 0.3 mmol) in diethyl phosphate (2 mL) was added very slowly (1 h) into(diphenylmethylene)cyclopropane (1a, 0.062 g, 0.3 mmol) at 130 °C under a nitrogen atmosphere. After the addition of AIBN, the mixture was heated for an extra 30 min at the same temperature. The excess diethyl phosphite was evaporated under vacuum and recovered, the residue was subjected to preparative TLC (petroleum ether-EtOAc, 3:1) to afford 3a (0.075g, 73%). Other diethyl 3,4-dihydro-2-naphthylphosphonates were prepared in a similar way.
Oil. IR (KBr): 2892, 1239, 1053, 1027, 820 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.35-7.41 (m, 3 H), 7.24-7.26 (m, 2 H), 7.19-7.20 (m, 2 H), 7.04-7.06 (m, 1 H), 6.67 (d, J = 7.6 Hz, 1 H), 3.721-3.862 (m, 4 H), 2.90 (t, J = 8.0 Hz, 2 H), 2.69-2.75 (m, 2 H), 1.13 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 16.1 (d, ³ J _P-C = 6.7 Hz), 25.1 (d, ³ J _P-C = 10.1 Hz), 27.8 (d, ² J _P-C = 6.9 Hz), 61.3 (d, ² J _P-C = 6.6 Hz), 124.5 (d, ¹ J _P-C = 184.3 Hz), 126.4, 127.2, 127.5, 127.7, 127.8, 128.1, 128.9, 129.6, 129.7, 135.5 (d, ³ J _P-C = 19.1 Hz), 137.0, 138.8 (d, ² J _P-C = 7.9 Hz), 149.9 (d, ³ J _P-C = 10.0 Hz). MS (70 eV, EI): m/z (%) = 342 (M⁺, 16.8), 341 (M⁺ - 1, 100.0).

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3-Butenyl Ethyl Phosphite 4a. Under a nitrogen atmosphere (diphenylmethylene)cyclopropane (1a, 0.062 g, 0.3 mmol) in diethyl phosphite (2 mL) and H₂O (0.1 mL) was heated at 150 °C. The reaction was monitored by TLC (petroleum ether-EtOAc, 2:1). After 1 h, excess diethyl phosphite was evaporated under vacuum and recovered, the residue was subjected to preparative TLC (petroleum ether-EtOAc, 3:1) to afford 4a (0.060 g, 63%). Other 3-butenyl ethyl phosphites were prepared in a similar way.
Oil. IR (KBr): 2982, 1258, 1034, 976, 766, 701 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.81 (d, J = 695.6 Hz, 1 H), 7.16-7.40 (m, 10 H), 6.09 (t, J = 7.2 Hz, 1 H), 4.09-4.15 (m, 4 H), 2.50-2.55 (m, 2 H), 1.33 (t, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 16.2 (d, ³ J _P-C = 6.3 Hz), 30.9 (d, ³ J _P-C = 6.4 Hz), 61.8 (d, ² J _P-C = 6.2 Hz), 65.1 (d, ² J _P-C = 5.8 Hz), 123.5, 127.2, 127.3, 128.1, 128.3, 129.7, 139.5, 142.0, 144.7. MS (70 eV, EI): m/z (%) = 316 (M⁺, 2.0), 207 (100.0), 206 (79.3).

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