Methyl iodide → HCID 18422244, compound

HRID 1281793Notes

Reaction equation

HRID 1281793 reaction equation
[N+:1]([C:4]1[CH:24]=[CH:23][CH:22]=[CH:21][C:5]=1[NH:6][C:7]1[S:11][C:10]2[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=2[C:8]=1[C:16]([O:18][CH2:19][CH3:20])=[O:17])([O-])=O.[CH3:25]C(C)([O-])C.[K+].CI>CN(C)C=O>[NH2:1][C:4]1[CH:24]=[CH:23][CH:22]=[CH:21][C:5]=1[N:6]([C:7]1[S:11][C:10]2[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=2[C:8]=1[C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH3:25]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 18422189HCID 18422189, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 18422244HCID 18422244, compoundYield 55.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

Ethyl 2-(2-nitroanilino)benzo[b]thiophene-3-carboxylate (6.0 g) was dissolved in N,N-dimethylformamide (120 ml) and the mixture was stirred at 0° C., during which potassium tert-butoxide (3.0 g) was added portionwise. Methyl iodide (12.4 g) was added dropwise under ice-cooling and the mixture was stirred at 0° C. for 5 min and heated to room temperature. The reaction mixture was extracted with ethyl acetate, washed with saturated brine and dried over anhydrous magnesium sulfate. After natural filtration, the solvent was evaporated under reduced pressure, and the residue was separated by silica gel column chromatography (hexane:ethyl acetate=4:1) to give crude crystals (2.8 g) of ethyl 2-(N-methyl-2-nitroanilino)benzo[b]thiophene-3-carboxylate. Without purification, the crystals were treated in the same manner as in Starting Material Synthesis Example 21 using ethanol (50 ml), 18% hydrochloric acid (50 ml) and tin(II) chloride-dihydrate (12.6 g) to give ethyl 2-(2-amino-N-methylanilino)benzo[b]thiophene-3-carboxylate (3.2 g).

Workup

  1. additionwas added portionwise
  2. temperaturecooling
  3. temperatureheated to room temperature
  4. extractionThe reaction mixture was extracted with ethyl acetate
  5. washwashed with saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationAfter natural filtration
  8. customthe solvent was evaporated under reduced pressure
  9. customthe residue was separated by silica gel column chromatography (hexane:ethyl acetate=4:1)
  10. customto give crude crystals (2.8 g) of ethyl 2-(N-methyl-2-nitroanilino)benzo[b]thiophene-3-carboxylate
  11. customWithout purification
  12. additionthe crystals were treated in the same manner as
  13. customMaterial Synthesis Example 21 using ethanol (50 ml), 18% hydrochloric acid (50 ml) and tin(II) chloride-dihydrate (12.6 g)

Sources & evidence

ORD record
ord-e3df619f3b0e458294aaab32b8bc3c81
Source dataset
uspto-grants-2002_09
Patent number
US06455521B1

Reaction notes

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