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Synlett 2008(20): 3121-3124  
DOI: 10.1055/s-0028-1087362
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© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of O,O-Diethyl Arylthiophosphonate from O-Aryl-O,O-diethylthiophosphate

Thierno Dienga, Aurore Fraixa, Jean-Yves Salaüna, Isabelle Dezb, Robertus J. M. Klein Gebbinkc, Gerard van Kotenc, Paul-Alain Jaffrès*a
a Fédération de Recherche ScInBios, CNRS UMR 6521 CEMCA, Université de Brest, Université Européenne de Bretagne, 6 Avenue Le Gorgeu, 29238 Brest, France
Fax: +33(298)017001; e-Mail: pjaffres@univ-brest.fr;
b LCMT, UMR CNRS 6507, ENSICAEN, Université de Caen, 6 Boulevard du Maréchal Juin, 14050 Caen cedex, France
c Chemical Biology and Organic Chemistry, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
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Publication History

Received 30 June 2008
Publication Date:
24 November 2008 (online)

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Abstract

The synthesis of O,O-diethyl 2-hydroxyarylthiophosphonate is reported by using a [1,3]-rearrangement. This method is achieved in high yield from ortho-bromophenols derivatives by a two-step process

Key words

phosphorylation - metallation - phenols - rearrangement

    References and Notes

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13

Preparation of Thiophosphates 1a-i Represented by the Preparation of O , O- Diethyl 6-Bromo-2-(diethoxythio-phosphinyl)-4-methylphenylthiophosphonate (1g): A solution of the phenolic derivative 2c (3.70 g, 8.85 mmol), triethylamine (1.48 mL, 10.6 mmol, 1.2 equiv) and DMAP (0.108 g, 0.88 mmol, 0.1 equiv) in THF (36 mL) was slowly added (15 min) to a solution of O,O-diethylchlorothio-phosphate (1.67 g, 8.85 mmol) in THF (10 mL). The solution was then stirred overnight. The obtained suspension was filtered on celite and washed with Et2O. The filtrate was concentrated and redissolved in Et2O (80 mL). The organic phase was washed with H2O (2 × 20 mL) and brine (15 mL), dried over MgSO4, filtered and concentrated. The obtained crude product was purified by column chromatography over silica gel (70-230 mesh; pentane-EtOAc, 100:5) to produce 1g (87% yield) as a colorless solid; mp 81 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 1.33, 1.40 (2 × t, ³ J HH = 7.0 Hz, 12 H, CH 3CH2O), 2.34 (s, 3 H, Me), 4.14, 4.31 (2 × m, 8 H, CH3CH 2O), 7.57 (d, 5 J HP = 1.8 Hz, 1 H, H5), 7.92 (d, ³ J HP = 19.0 Hz, 1 H, H3). ³¹P (81.03 MHz, CDCl3): δ = 62.2 (d, 4 J PP = 2.7 Hz), 83.5 (d, 4 J PP = 2.7 Hz). ¹³C (75.48 MHz, CDCl3): δ = 16.0 (m, CH2 CH3), 20.7 (s, Me), 63.3 (d, ³ J HP = 5 Hz, OCH2CH3), 65.2 (m, OCH2CH3), 117.6 (dd, ³ J CP = 12 Hz, ³ J CP = 5 Hz, CBr), 127.6 (dd, ¹ J CP = 143 Hz, ³ J CP = 5 Hz, CArP), 136.0-136.42 (m, 2 × CAr), 139.0 (s, CArH), 147.3 (m, CArO). IR (neat): 709, 735, 790, 889, 927, 966, 1018, 1245, 1432, 2979 cm-¹. Anal. Calcd for C15H25BrO5P2S2: C, 36.67; H, 5.13; S, 13.05. Found: C, 36.74; H, 5.10; S, 13.02.

14

Synthesis of Thiophosphonate 2-2i from Thiophosphate Represented by the Preparation of O , O -Diethyl 6-Hydroxy-2-pyridinylthiophosphonate (2f):
n-Butyllithium (1.5 M in n-hexane, 2.25 mL, 3.38 mmol, 1.1 equiv) was added dropwise to a solution of 1f (1 g, 3.07 mmol) in THF (10 mL) previously cooled to -78 ˚C. At the end of the addition, the solution was left to warm slowly. Then an aqueous solution of ammonium chloride was added (10 mL). The aqueous phase was extracted with Et2O (3 × 30 mL). The combined organic phases were washed with H2O and dried over MgSO4. After filtration and concentration the crude product was purified by column chromatography over silica gel (PE-EtOAc, 5:1) to produce the pure compound 2f as a white solid in 85% yield; mp 70 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 1.37 (t, ³ J HH = 7.0 Hz, 6 H, OCH2CH 3), 4.26 (m, 4 H, OCH 2CH3), 7.31 (dd, ³ J HH = 7.0 Hz, ³ J HP = 1.0 Hz, 1 H, C4-H), 7.36 (m, 1 H, C5-H), 8.34 (dt, ³ J HH = 5.0 Hz, 4 J HP = 1.0 Hz, 1 H, C6-H), 9.65 (s, 1 H, OH). ³¹P NMR (81.03 MHz, CDCl3): δ = 69.7. ¹³C NMR (75.48 MHz, CDCl3): δ = 16.0 (d, ³ J CP = 7 Hz, OCH2 CH3), 63.6 (d, ² J CP = 6 Hz, OCH2CH3), 126.4 (d, ³ J CP = 10 Hz, C4), 128.4 (d, 4 J CP = 4 Hz, C5), 135.4 (d, ¹ J CP = 188 Hz, C2), 141.9 (d, ³ J CP = 20 Hz, C6), 158.3 (d, ² J CP = 27 Hz, C3). Anal. Calcd for C9H14NO3PS: C, 43.72; H, 5.71; N, 5.66; S, 12.87. Found: C, 44.19; H, 5.90; N, 5.30; S, 12.66. HRMS (ES-TOF): m/z
[M + H] calcd for C9H15NO3PS: 248.0505; found: 248.0510. IR (neat): 953, 1009, 1306, 1455, 1570, 2733, 2927 cm-¹.