Reaktion #2393305

Reaktionsgleichung

O-methyl chlorothioformate

trimethyl phosphite

→

yellow oil

Ausbeute 56.5%

Methyl (Dimethoxyphosphinyl)thioformate

Ausbeute 56.5%

Lösungsmittel

toluene

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe solvent was rotary-evaporated
2. 2
   workup.DISTILLATIONthe residue distilled in vacuo

Vorschrift

While cooled externally with cold water, 34 g of the crude oil described above was treated with 9 g of chlorine. The temperature should not exceed 30° C. to avoid over-chlorination. The mixture was heated slowly, then fractionated. The fraction boiling at 84-86° C./760 mm was collected, giving 12.7 g of O-methyl chlorothioformate, Y=72%. 1H NMR: δ (ppm) 4.16. [See, Dieter Martin and Wolfgang Mocke, Chemishe Berichte, 98 (7), 2059 (1965).4] A solution of 0.55 g (5 mmol) of O-methyl chlorothioformate in 8 mL of dry toluene was added over 10 min to a solution of 0.62 g (5 mmol) trimethyl phosphite in 15 mL of dry toluene under N2. The mixture was stirred and left for 2 hr at room temperature. The solvent was rotary-evaporated, and the residue distilled in vacuo, giving 0.52 g of a yellow oil, 80-81° C./100μ, Y=56.5%. 1H NMR: δ (ppm) 4.18 (d, 3H, 4JHP=2 Hz, COCH3), 3.87 (d, 6H, 3JHP=11 Hz POCH3); 13C NMR: δ (ppm) 212.5 (d, 1JCP=223 Hz, PC), 59.1 (d, 2JCP=8 Hz, POCH3), 54.8 (d, 3JCP=6 Hz, COCH3); 31P NMR {H }: δ (ppm) −1.14 (s); 31P NMR: δ (ppm) −1.14 (m, 3JPH=11 Hz); HRMS: 185.0031 (MH+, Found); 185.0037 (MH+, Calcd).

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