Reaktion #1816933

Reaktionsgleichung

phenol

1,3-dimethylurea

triphenyl phosphite

3-methylthiopropionaldehyde

→

1-(1,3-Dimethylureido)-3-(methylthio)propylphosphonic acid

Lösungsmittel

toluene

toluene

—

100g

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturis warmed to 75°
2. 2
   Temperaturthe temperature increases rapidly to 120°
3. 3
   TemperaturAfter further warming at 105° for 1 hr the resulting yellow product
4. 4
   Sonstigein removed
5. 5
   Sonstigeby stripping to 110°
6. 6
   workup.DISSOLUTIONis dissolved in 75ml of acetonitrile
7. 7
   Temperatur10g of water, and this solution is refluxed for 3 hr
8. 8
   Sonstigeto evaporate to dryness
9. 9
   Extraktionthe residue is extracted with ether
10. 10
    Sonstigewith hot acetonitrile and recrystallized twice from acetic acid
11. 11
    Sonstigeto give a white solid

Vorschrift

When a mixture of 0.5 mole each of 1,3-dimethylurea, triphenyl phosphite, and 3-methylthiopropionaldehyde in 100g of toluene is warmed to 75°, a reaction is initiated and the temperature increases rapidly to 120°. After further warming at 105° for 1 hr the resulting yellow product has a 31P nmr signal at -28.2 ppm for the cyclic ester, 1,4-dimethyl-3-(2-methylthioethyl)-2-phenoxy-1,4,2-diazophospholidin-5-one-2-oxide. The above product is then employed in a toluene solution from which by product phenol in removed by stripping to 110°/1mm after which one-third of the residue is dissolved in 75ml of acetonitrile and 10g of water, and this solution is refluxed for 3 hr. The reaction mixture is allowed to evaporate to dryness, and the residue is extracted with ether and then with hot acetonitrile and recrystallized twice from acetic acid to give a white solid: mp 164.5°-167°; 31P nmr (DMSO-d6) -21.4 ppm; 1H nmr δ 9.6 (broad, 2, OH), 4.5 (m, 1, PCH), 2.8 (s, NCH3), 2.6 (s, NCH3), 2.0 (s, SCH3), 1.9-2.6 (m, CH2CH2S).

Quelle