Toluene → 1-(1,3-Dimethylureido)-3-(methylthio)propylphosphonic acid
Reaction equation
[CH3:1][NH:2][C:3]([NH:5][CH3:6])=[O:4].[P:7]([O:22]C1C=CC=CC=1)([O:15]C1C=CC=CC=1)[O:8]C1C=CC=CC=1.C[CH2:30][CH2:31][CH:32]=[S:33].[C:34]1(C)C=CC=CC=1>>[CH3:1][N:2]([CH:30]([P:7](=[O:8])([OH:15])[OH:22])[CH2:31][CH2:32][S:33][CH3:34])[C:3]([NH:5][CH3:6])=[O:4]Participants
Procedure
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 solution has a 31P nmr signal only at -28.2 ppm. After the solvent and most of the byproduct phenol are removed by stripping to 110°/1mm, 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 δ9.6 (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).
Workup
- temperatureis warmed to 75°
- temperaturethe temperature increases rapidly to 120°
- temperatureAfter further warming at 105° for 1 hr
- customAfter the solvent and most of the byproduct phenol are removed
- customby stripping to 110°
- dissolutionis dissolved in 75ml of acetonitrile
- temperature10g of water, and this solution is refluxed for 3 hr
- customto evaporate to dryness
- extractionthe residue is extracted with ether
- customwith hot acetonitrile and recrystallized twice from acetic acid
- customto give a white solid
Sources & evidence
- ORD record
- ord-69adae23bb3a4cf08751a9fd6a660665
- Source dataset
- uspto-grants-1976_09
- Patent number
- US03980618
Reaction notes
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