Dimethyl Sulfate → HCID 86170751, compound

HRID 1489341Notes

Reaction equation

HRID 1489341 reaction equation
[C:1]([CH2:3][CH2:4][CH2:5][CH2:6][CH:7]1[CH2:12][O:11][C:10]([CH3:14])([CH3:13])[O:9][CH2:8]1)#N.[OH-:15].[K+].S(OC)([O:20][CH3:21])(=O)=O>CN(C=O)C.C(O)C.O>[CH3:13][C:10]1([CH3:14])[O:11][CH2:12][CH:7]([CH2:6][CH2:5][CH2:4][CH2:3][C:1]([O:20][CH3:21])=[O:15])[CH2:8][O:9]1

Participants

7

Reactant 3

HCID 6497Dimethyl SulfateHCID 14797Potassium HydroxideHCID 22904252HCID 22904252, compound

Product 1

HCID 86170751HCID 86170751, compoundYield 52%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent

Procedure

The crude nitrile 23 obtained above (79 g, 0.401 mol) is heated under reflux for 24 h with potassium hydroxide (31 g, 0.47 mol), 250 mL ethanol and 100 mL water. 300 mL water is added and most of the ethanol is distilled off. 200 mL n-propanol is added and the mixture is heated under reflux for 2 d. After cooling, 300 mL water is added and the mixture is extracted with 2×250 mL toluene. The toluene layers are washed with 250 mL water. The aqueous layers are evaporated, the last traces of water are removed at 100° C. (0.2 mmHg). The solid residue is stirred for 24 h with 300 mL DMF and 62 mL dimethyl sulfate (0.66 mol). The mixture is evaporated and to the residue there is added 500 mL toluene and 300 mL water. The layers are separated and the toluene layer is washed with 300 mL water. The aqueous layers are extracted with 250 mL toluene. The combined organic layers are dried and evaporated end the residue is purified by bulb-to-bulb distillation to give ester 24 (47.7 g, 0.207 mol, 52%) with bp 120° C. (0.2 mmHg). 1H-NMR (CCl4): δ 1.0-1.9 (m), 1.25 (s) and 1.30 (s) (13H), 2.2 (bt, 2H), 3.2-3.9 (m) and 3.6 (s) (7H).

Workup

  1. temperatureis heated
  2. distillationis distilled off
  3. addition200 mL n-propanol is added
  4. temperaturethe mixture is heated
  5. temperatureunder reflux for 2 d
  6. temperatureAfter cooling
  7. addition300 mL water is added
  8. extractionthe mixture is extracted with 2×250 mL toluene
  9. washThe toluene layers are washed with 250 mL water
  10. customThe aqueous layers are evaporated
  11. customthe last traces of water are removed at 100° C. (0.2 mmHg)
  12. customThe mixture is evaporated and to the residue there
  13. additionis added 500 mL toluene and 300 mL water
  14. customThe layers are separated
  15. washthe toluene layer is washed with 300 mL water
  16. extractionThe aqueous layers are extracted with 250 mL toluene
  17. customThe combined organic layers are dried
  18. customevaporated end the residue
  19. distillationis purified by bulb-to-bulb distillation

Sources & evidence

ORD record
ord-d44e7f74f24545fba730f37198fa82d6
Source dataset
uspto-grants-1997_10
Patent number
US05677432

Reaction notes

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