Ammonia → HCID 18428309, compound

HRID 1279420Notes

Reaction equation

HRID 1279420 reaction equation
[OH:1][CH2:2][C:3]1[O:4][C:5]([CH2:18]O)=[CH:6][C:7](=[O:17])[C:8]=1[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[OH-].[Na+].S([O:27][CH3:28])(OC)(=O)=O.N.Cl[CH2:31]Cl>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O.CCOC(C)=O>[CH3:31][O:1][CH2:2][C:3]1[O:4][C:5]([CH2:18][O:27][CH3:28])=[CH:6][C:7](=[O:17])[C:8]=1[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

9

Reactant 5

HCID 222AmmoniaHCID 6344Dichloromethane2×HCID 6497Dimethyl Sulfate2×HCID 14798Sodium HydroxideHCID 18428308HCID 18428308, compound

Product 1

HCID 18428309HCID 18428309, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (3) (26.2 g, 100 mmol, 1 eq.) in 150 ml dichloromethane was added 350 mg of tetrabutylammonium hydrogen sulphate, 50% (w/w) aqueous sodium hydroxide (from 24 g of sodium hydroxide and 24 g of water), and the mixture stirred vigorously for 30 min. The flask was cooled in an ice-water bath and 38 g (300 mmol, 3 eq) of dimethyl sulphate was added dropwise over a period of 1 hour. The mixture was stirred vigorously at room temperature for 6 hours until TLC analysis (EtOAc) revealed that the reaction was completed. 15 ml of concentrated aqueous ammonia was added and stirred for a further 30 min at room temperature to decompose excess dimethyl sulphate. The reaction mixture was poured into water, added 350 ml of dichloromethane. The dichloromethane layer was washed with water, dried (Na2SO4), and concentrated in vacuo to yield the crude product as orange oil. Further purfication by column chromatography on silica gel (eluant: EtOAc) furnished the pure product as a bright yellow oil (23.5 g, 81%). 1H-NMR (CDCl3) δ: 3.2 (s, 3H, OCH3), 3.4 (s, 3H, OCH3), 4.15 (s, 4H, 2,6-CH2OCH3), 5.1 (s, 2H, CH2Ph), 6.3 (s, 1H, 5-H(pyranone)), 7.26 (s, 5H, Ar).

Workup

  1. temperatureThe flask was cooled in an ice-water bath
  2. stirringstirred for a further 30 min at room temperature
  3. washThe dichloromethane layer was washed with water
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customto yield the crude product as orange oil

Sources & evidence

ORD record
ord-bff258e4d52443b6902921433ee3dabc
Source dataset
uspto-grants-2002_09
Patent number
US06448273B1

Reaction notes

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