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

HRID 1658551Notes

Reaction equation

HRID 1658551 reaction equation
CNC(NC)=O.[P:7]([O:22]C1C=CC=CC=1)([O:15]C1C=CC=CC=1)[O:8]C1C=CC=CC=1.CCCC=S.[CH3:34][N:35]1[C:39](=[O:40])[N:38]([CH3:41])[CH:37]([CH2:42][CH2:43][S:44][CH3:45])P1(=O)OC1C=CC=CC=1.C1(O)C=CC=CC=1>C1(C)C=CC=CC=1>[CH3:41][N:38]([CH:37]([P:7](=[O:8])([OH:15])[OH:22])[CH2:42][CH2:43][S:44][CH3:45])[C:39]([NH:35][CH3:34])=[O:40]

Participants

7

Reactant 5

HCID 996PhenolHCID 7293N,N'-DimethylureaHCID 7540Triphenyl phosphiteHCID 12463483ButanthialHCID 21527952HCID 21527952, compound

Product 1

HCID 215012441-(1,3-Dimethylureido)-3-(methylthio)propylphosphonic acid

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

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 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-diazaphospholidin-5-one-2-oxide. The above product is then employed in a toluene solution from which byproduct phenol is removed by stripping to 110° /1 mm, 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 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).

Workup

  1. temperatureis warmed to 75°
  2. temperaturethe temperature increases rapidly to 120°
  3. temperatureAfter further warming at 105° for 1 hr
  4. customis removed
  5. customby stripping to 110°
  6. dissolutionafter which one-third of the residue is dissolved in 75ml of acetonitrile
  7. temperature10g of water, and this solution is refluxed for 3 hr
  8. customto evaporate to dryness
  9. extractionthe residue is extracted with ether
  10. customwith hot acetonitrile and recrystallized twice from acetic acid
  11. customto give a white solid

Sources & evidence

ORD record
ord-4a1ba50c8e9743918bb921f852396a38
Source dataset
uspto-grants-1976_06
Patent number
US03965127

Reaction notes

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