1,3-Propanedithiol → Diethyl vinylphosphonate

Participants

Reaction Conditions

Reaction Steps

A sample of 60% NaH in mineral oil (95 mmol) was placed in a 2-neck round bottom flask and charged with dry hexane (20 mL). This solution was allowed to stir for ten minutes, after which the hexane-mineral oil layer was completely removed. The flask was then charged with dry tetrahydrofuran (100 mL), followed by dropwise addition of HS(CH2)3SH (46 mmol) with constant stirring. The resulting solution was cooled at 0° C. and BrCH2CH2P(O)(OC2H5)2 (95 mmol) was added dropwise with constant stirring over a period of 30 minutes. Excess NaH was quenched by addition of 50 mL of deionized water. The solution was extracted from ethyl acetate (3×50 mL) and washed with a saturated sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate. Upon filtering, the solvent was removed in vacuo to afford compound 5 in 90% yield along with a trace amount of diethyl vinylphosphonate. The compounds were separated on a silica gel column (20 cm; 60 mesh) using 90:10 ethyl acetate to hexane solvent mixture. Removal of the solvent in vacuo, afforded compound 5 as a viscous, yellow-green oil with an overall yield of 88%. High resolution FAB/MS Anal. Calcd. for C15H34O6P2S2 : 436.1272; Found: [M+H+ ], m/z=437.1350. 1H NMR (CDCl3): δ 1.34 (t, 3JHH =9.0 Hz, 12H, OCH2CH3), 1.87 (qn, 2H, CH2CH2CH2), 2.03 (m, 4H, PCH2CH2), 2.65 (t, 3JHH =9.0 Hz, 4H, CHCH2CH2), 2.74 (m, 4H, PCH2CH2), 4.11 (m, 8H, OCH2CH3). 13C NMR (CHCl3): δ 16.3 (d, 3JPC =4.5 Hz, OCH2CH3), 24.8 (d, 2JPC =3.0 Hz, PCH2CH2), 26.6 (d, 1JPC =136.6 Hz, PCH2CH2), 28.5 (s, CH2CH2CH2), 30.5 (s, CH2CH2CH2), 61.6 (d, 2JPC= 6.0 Hz OCH2CH3). 31P NMR (CDCl3): δ 29.1 (s).

Provenance & Evidence