Trimethyl phosphite → Methyl (Dimethoxyphosphinyl)thioformate

HRID 1278949

Reaktionsgleichung

Reaktionsgleichung von HRID 1278949
Cl[C:2]([O:4][CH3:5])=[S:3].[P:6]([O:11]C)([O:9][CH3:10])[O:7][CH3:8]>C1(C)C=CC=CC=1>[CH3:5][O:4][C:2]([P:6]([O:9][CH3:10])([O:7][CH3:8])=[O:11])=[S:3]

Komponenten

4

Edukt 2

HCID 8472Trimethyl phosphiteHCID 554404Methyl chloromethanethioate

Produkt 1

HCID 9794069Methyl (Dimethoxyphosphinyl)thioformateAusbeute 56,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel2×

Versuchsvorschrift

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: δ1 (ppm)2.5 (d, 1JCP=223 Hz, PC), 59.1 (d, 2JCP=8 Hz, POCH3), 54.8 (d, 3JCP=6 Hz, COCH 3); 31P NMR {H}: δ(ppm) −1.14 (s); 31 P NMR: δ (ppm) −1.14 (m, 3JPH=11 Hz); HRMS: 185.0031 (MH+, Found); 185.0037 (MH+, Calcd).

Aufarbeitung

  1. customThe solvent was rotary-evaporated
  2. distillationthe residue distilled in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-327f4673a7534fa085e4b0e6fa85c08c
Quelldatensatz
uspto-grants-2002_09
Patentnummer
US06444837B1

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