Water → 5-(2-Methyl-2-nitropropoxy)salicylamide

HRID 1462376Notes

Reaction equation

HRID 1462376 reaction equation
CC1(C)[NH:7][C:6](=[O:8])[C:5]2[CH:9]=[C:10]([OH:13])[CH:11]=[CH:12][C:4]=2[O:3]1.[CH3:15][C:16]([N+:24]([O-:26])=[O:25])([CH3:23])[CH2:17]OS(C)(=O)=O.C(=O)([O-])[O-].[K+].[K+].O>COCCOCCOC>[CH3:15][C:16]([N+:24]([O-:26])=[O:25])([CH3:23])[CH2:17][O:13][C:10]1[CH:9]=[C:5]([C:6]([NH2:7])=[O:8])[C:4]([OH:3])=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 137543316-hydroxy-2,2-dimethyl-3,4-dihydro-2H-1,3-benzoxazin-4-oneHCID 20452658HCID 20452658, compound

Product 1

HCID 137544245-(2-Methyl-2-nitropropoxy)salicylamide

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Procedure

A mixture of 84.3 g of 2,3-dihydro-2,2-dimethyl-6-hydroxy-4H-1,3-benzoxazin-4-one, 144.2 g of methanesulfonic acid-(2-methyl-2-nitropropyl)-ester and 121 g of anhydrous potassium carbonate in 440 ml of diethylene glycol dimethyl ether is stirred for 9 hours in a bath at about 150°. The reaction mixture is cooled, poured into 4000 ml of water, and extracted with 3000 ml of ethyl acetate. The oil, obtained by concentrating the organic phase by evaporation, is dissolved in 250 ml of dioxane, and about 750 ml of 2N hydrochloric acid is added until an acid reaction occurs. The solution is held for 11/2 hours at 80°-100°; it is then concentrated under reduced pressure to half its volume, and extracted three times with 500 ml of ethyl acetate each time. The combined organic phases are washed with 200 ml of water, then with saturated sodium bicarbonate solution, and finally with saturated sodium chloride solution; they are subsequently dried over magnesium sulfate and concentrated by evaporation. The dark brown oil thus obtained is chromatographed on 500 g of silica gel. Elution with ether yields crystalline 5-(2-methyl-2-nitropropoxy)-salicylamide, m.p. 145°-148°.

Workup

  1. temperatureThe reaction mixture is cooled
  2. extractionextracted with 3000 ml of ethyl acetate
  3. customThe oil, obtained
  4. concentrationby concentrating the organic phase
  5. customby evaporation
  6. dissolutionis dissolved in 250 ml of dioxane
  7. additionabout 750 ml of 2N hydrochloric acid is added until an acid reaction
  8. custom2 hours
  9. customat 80°-100°
  10. concentrationit is then concentrated under reduced pressure to half its volume
  11. extractionextracted three times with 500 ml of ethyl acetate each time
  12. washThe combined organic phases are washed with 200 ml of water
  13. dry with materialthey are subsequently dried over magnesium sulfate
  14. concentrationconcentrated by evaporation
  15. customThe dark brown oil thus obtained
  16. customis chromatographed on 500 g of silica gel
  17. washElution with ether

Sources & evidence

ORD record
ord-d7b2bc34de0048779933e4d4a7977dcd
Source dataset
uspto-grants-1984_07
Patent number
US04460580

Reaction notes

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