Trifluoroacetic acid → 3-Dipropylamino-5-nitrochroman

HRID 264991Notes

Reaction equation

HRID 264991 reaction equation
[CH2:1]([N:4]([CH2:16][CH2:17][CH3:18])[CH:5]1[CH2:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][C:12]=2N)[O:7][CH2:6]1)[CH2:2][CH3:3].FC(F)(F)C(O)=O.[N:26]([O-:28])=[O:27].[Na+].C(=O)([O-])[O-].[Ca+2]>O.S([O-])([O-])(=O)=O.[Cu+2].[Cu-]=O>[CH2:16]([N:4]([CH2:1][CH2:2][CH3:3])[CH:5]1[CH2:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][C:12]=2[N+:26]([O-:28])=[O:27])[O:7][CH2:6]1)[CH2:17][CH3:18]

Participants

8

Reactant 4

HCID 6422Trifluoroacetic acidHCID 10112Calcium CarbonateHCID 190281333-Dipropylamino-5-aminochromanHCID 23668193Sodium Nitrite2×

Product 1

HCID 190281923-Dipropylamino-5-nitrochroman

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 178419072HCID 178419072, compoundCatalystHCID 962WaterSolvent4×

Procedure

3-Dipropylamino-5-aminochroman (Example 14; 0.050 g, 0.20 mmol) was dissolved in a mixture of trifluoracetic acid (0.080 ml, 1.0 mmol) in water (5 ml). The clear solution was cooled to 0°-4° C. Sodium nitrite (0.017 g, 2.5 mmol) in water (1.0 ml), was added dropwise with good stirring. The solution was stirred for 15 minutes and neutralized with calcium carbonate. A solution of sodium nitrite (0.50 g, 7.2 mmol) in water (1.0 ml) was added followed by a mixture of copper sulfate (0.10 g, 0.62 mmol) and copper (1) oxide in water (1.0 ml). The solution was stirred at 0° C. for 20 minutes and then at ambient temperature for 2 hours. The solution was extracted with diethyl ether. The organic phase was dried with sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel by elution with ethyl acetate/hexane 1:9 to give the title compound. Mp 150°-151° C. (hydrochloride).

Workup

  1. temperatureThe clear solution was cooled to 0°-4° C
  2. stirringThe solution was stirred at 0° C. for 20 minutes
  3. waitat ambient temperature for 2 hours
  4. extractionThe solution was extracted with diethyl ether
  5. dry with materialThe organic phase was dried with sodium sulfate
  6. customevaporated to dryness
  7. customThe residue was purified by flash chromatography on silica gel by elution with ethyl acetate/hexane 1:9

Sources & evidence

ORD record
ord-69b2847a6f514134b41a0c903d0a66df
Source dataset
uspto-grants-1997_07
Patent number
US05646309

Reaction notes

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