Hexamethylphosphoramide → HCID 21519201, compound

HRID 1283002Notes

Reaction equation

HRID 1283002 reaction equation
C([N:8]1[CH2:13][CH2:12][O:11][CH:10]([CH2:14][NH:15][C:16]2[CH:21]=[CH:20][CH:19]=[C:18]([S:22][CH3:23])[CH:17]=2)[CH2:9]1)C1C=CC=CC=1.CN(C)P(N(C)C)(N(C)C)=O.Cl[C:36]([O:38][C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)=[O:37]>C1(C)C=CC=CC=1>[CH3:23][S:22][C:18]1[CH:17]=[C:16]([CH:21]=[CH:20][CH:19]=1)[NH:15][CH2:14][CH:10]1[O:11][CH2:12][CH2:13][N:8]([C:36]([O:38][C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)=[O:37])[CH2:9]1

Participants

5

Reactant 3

HCID 12679HexamethylphosphoramideHCID 15891Phenyl chloroformateHCID 21519198HCID 21519198, compound

Product 1

HCID 21519201HCID 21519201, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 4-benzyl-2-(3-methylthioanilino)methylmorpholine (1.7 g.) in toluene (50 ml.) is added hexamethylphosphoramide (1 ml.) and then phenyl chloroformate (1.5 ml.). The mixture is heated under reflux for 18 hours, the toluene is then removed under reduced pressure, the oily residue is dissolved in ether and the ethereal solution is washed successively with sodium hydroxide solution, water, hydrochloric acid and water before drying over anhydrous magnesium sulphate. Evaporation of the dried filtered ethereal solution gives yellow oil (2.4 g.) or 2-(3-methylthioanilino)methyl-4-phenoxycarbonylmorpholine, which is dissolved in dimethylsulphoxide (20 ml.) and this solution is added to a solution of sodium methylsulphinylmethide [prepared in the usual way from sodium hydride (2.4 g.) and dimethylsulphoxide (50 ml.) ]. Water (1.8 ml.) is then added when the temperature of the mixture rises to about 60°C. The solution is stirred for 1 hour and then poured into water containing ice and the mixture extracted with ether (3 × 100 ml.). The ethereal solution is washed with water, dried (MgSO4) and filtered and the filtrate is treated with an ethereal solution of oxalic acid to precipitate 2-(3-methylthioanilino)methylmorpholine oxalate, m.p. 114°-115°C. after recrystallisation from acetone.

Workup

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 18 hours
  3. customthe toluene is then removed under reduced pressure
  4. dissolutionthe oily residue is dissolved in ether
  5. washthe ethereal solution is washed successively with sodium hydroxide solution, water, hydrochloric acid and water
  6. dry with materialbefore drying over anhydrous magnesium sulphate
  7. customEvaporation of the dried
  8. filtrationfiltered ethereal solution

Sources & evidence

ORD record
ord-ed3daee9f83e4eaabb6f0fd59166d411
Source dataset
uspto-grants-1976_08
Patent number
US03974156

Reaction notes

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