Hydrochloric Acid → HCID 14722454, compound

HRID 1031741Notes

Reaction equation

HRID 1031741 reaction equation
[CH3:1][S:2]([NH:5][C:6]1[C:16]([O:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:15][C:9]2[C:10](=[O:14])[CH2:11][CH2:12][O:13][C:8]=2[CH:7]=1)(=[O:4])=[O:3].C([Li])CCC.[CH3:29][S:30]S(C)(=O)=O.Cl>O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C.O1CCCC1>[CH3:1][S:2]([NH:5][C:6]1[C:16]([O:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:15][C:9]2[C:10](=[O:14])[CH:11]([S:30][CH3:29])[CH2:12][O:13][C:8]=2[CH:7]=1)(=[O:3])=[O:4]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 18064S-Methyl methanethiosulfonateHCID 10806538HCID 10806538, compoundHCID 178418339Butyllithium

Product 1

HCID 14722454HCID 14722454, compoundYield 42.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 86583969tetrahydrofuran HMPASolvent

Procedure

In 10 ml of a mixture of anhydrous tetrahydrofuran-hexamethylphosphoric acid triamide (7:3) was dissolved 1.00 g of 2,3-dihydro-7-methylsulfonylamino-6-phenoxy-4H-1-benzopyran-4-one. To the resulting solution was added 10 ml of a tetrahydrofuran solution of 1,1,1,3, 3,3-hexamethylsilazane lithium salt consisting of 1.17 g of 1,1,1,3,3,3-hexamethylsilazane and 6.6 millimoles of n-butyllithium at -78° C., and the resulting mixture was stirred for 40 minutes, after which 500 mg of methyl methanethiolsulfate was added at the same temperature and the mixture was stirred for 15 minutes. Subsequently, the temperature of the reaction mixture was elevated to room temperature. The reaction mixture was introduced into 80 ml of 2N hydrochloric acid with ice-cooling and the resulting mixture was extracted with two 40-ml portions of ethyl acetate. The extracts were combined and washed with water and saturated aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure and the oily product obtained was purified by a column chromatography (eluant: toluene:ethyl acetate=50:1) to obtain 480 mg (yield: 39.6%) of 2,3-dihydro-7-methylsulfonylamino-3-methylthio-6-phenoxy-4H-1-benzopyran-4-one.

Workup

  1. stirringthe mixture was stirred for 15 minutes
  2. customwas elevated to room temperature
  3. temperaturecooling
  4. extractionthe resulting mixture was extracted with two 40-ml portions of ethyl acetate
  5. washwashed with water and saturated aqueous sodium chloride solution in this order
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent was removed by distillation under reduced pressure
  8. customthe oily product obtained
  9. customwas purified by a column chromatography (eluant: toluene:ethyl acetate=50:1)

Sources & evidence

ORD record
ord-770e66e662204ae7b0be768440f101be
Source dataset
uspto-grants-1990_09
Patent number
US04954518

Reaction notes

Loading…