Ethanethiol → Diethyl 2-hydroxyethylthiomethylphosphonate

HRID 1031069Notes

Reaction equation

[H-].[Na+].[CH3:3][CH2:4][SH:5].[CH2:6]([O:8][P:9]([CH2:14]Cl)(=[O:13])[O:10][CH2:11][CH3:12])[CH3:7].[O:16]1CCCC1>[I-].[K+]>[OH:16][CH2:3][CH2:4][S:5][CH2:14][P:9](=[O:13])([O:10][CH2:11][CH3:12])[O:8][CH2:6][CH3:7]

Participants

Conditions

Temperature: 80 °C

Procedure

Sodium hydride (1.5g, 80%, 50 mmol) was added in portions to a stirred solution of thioethanol (3.9 g, 50 mmol) in dry tetrahydrofuran (50 ml) at room temperature. The mixture was stirred for 0.5 hours then freshly ground and dried potassium iodide (0.5 g, 3.0 mmol) was added, followed by diethylchloromethylphosphonate (9.3 g, 50 mmol) in dry tetrahydrofuran (25 ml) over 5 minutes (exothermic reaction, temperature rose to 50° C.). The reaction mixture was then stirred and heated at 80° C. for 18 hours. The cooled reaction was evaporated to dryness in vacuo, and the residue was purified by column chromatography on silica gel eluting with chloroform, to give the title compound as an oil (8.0 g, 79%); υmax (Film) 3380, 2980, 2900, 2860, 1475 and 1440 cm-1 ; δH (CDCl3) 1.35 (6H, t, J 7Hz, 2 × CH3), 2.80 (2H, d, J 13Hz, PCH2S), 2.87 (2H, t, J 5Hz, SCH2CH2), 3.8 (2H, br s, CH2OH), 3.92 (lH, br s, D2O exchangeable, OH), 4.2 (4H, m, 2 × CH2OP),

Workup

custom(exothermic reaction, temperature rose to 50° C.)
stirringThe reaction mixture was then stirred
customThe cooled reaction
customwas evaporated to dryness in vacuo
customthe residue was purified by column chromatography on silica gel eluting with chloroform

Sources & evidence

ORD record: ord-becdc5b70c4d450bb77a284bc2a54ca6
Source dataset: uspto-grants-1992_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05108994

Reaction notes

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