Hydrochloric Acid → HCID 55080110, compound

HRID 2074462Notes

Reaction equation

HRID 2074462 reaction equation
[N+:1]([C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[NH:13][CH:14]1[CH2:19][CH2:18][N:17]([CH3:20])[CH2:16][CH2:15]1)([O-])=O.O.Cl>CCO>[CH3:20][N:17]1[CH2:18][CH2:19][CH:14]([NH:13][C:5]2[C:4]([NH2:1])=[CH:9][C:8]([N+:10]([O-:12])=[O:11])=[CH:7][CH:6]=2)[CH2:15][CH2:16]1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 962WaterHCID 59799760HCID 59799760, compound

Product 1

HCID 55080110HCID 55080110, compoundYield 25.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
65 °C

Procedure

(2,4-Dinitro-phenyl)-(1-methyl-piperidin-4-yl)-amine 51 (1.50 g, 5.352 mmol) was dissolved in anhydrous EtOH (20 mL) in a 2 neck 250 mL argon purged flask. The reaction vessel was fitted with a condenser and dropping funnel and heated in an oil bath to 65° C. H2O (20 mL), EtOH (40 mL) and aqueous (NH4)2S (50 wt %, 2.55 g, 18.73 mmol) were charged to the dropping funnel and added to the hot reaction mixture dropwise over 30 minutes. The reaction was heated at 75° C. for 2 hours then cooled to room temperature overnight. Mixture was acidified by the addition of aqueous 4M HCl to adjust pH to 2. The reaction mixture was filtered to remove any insoluble material and the filtrate was concentrated under reduced pressure to remove EtOH. The resulting aqueous solution was basified by the addition of aqueous 2M ammonium hydroxide solution to adjust pH to 10. The aqueous solution was diluted with dichloromethane and transferred to a separatory funnel and the organic layer collected. The aqueous layer was further extracted with dichloromethane and the combined organic layers were washed with H2O, brine, and dried over magnesium sulphate, filtered and concentrated to afford a dark red oil. The product was purified using silica gel dry column chromatography with a solvent system of 5% 2M NH3 in methanol/95% dichloromethane to afford an orange solid 52 N1-(1-Methyl-piperidin-4-yl)-4-nitro-benzene-1,2-diamine Yield: 0.342 grams (25.5%). 1H NMR (DMSO) δ: 1.42-1.55 (m, 2H), 1.89-1.93 (m, 2H), 1.97-2.05 (m, 2H), 2.17 (s, 3H), 2.70-2.81 (m, 2H), 3.30-3.42 (m, 1H), 5.20 (br s, 2H), 5.63 (br d, 1H, J=7.4), 6.53 (d, 1H, J=9.0), 7.39 (d, 1H, J=2.9), 7.49 (dd, 1H, J=8.9, 2.7); MS (ESI): 251 (MH+, 100%).

Workup

  1. customThe reaction vessel was fitted with a condenser
  2. additionadded to the hot reaction mixture dropwise over 30 minutes
  3. temperatureThe reaction was heated at 75° C. for 2 hours
  4. temperaturethen cooled to room temperature overnight
  5. filtrationThe reaction mixture was filtered
  6. customto remove any insoluble material
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customto remove EtOH
  9. additionThe resulting aqueous solution was basified by the addition of aqueous 2M ammonium hydroxide solution
  10. additionThe aqueous solution was diluted with dichloromethane
  11. customtransferred to a separatory funnel
  12. customthe organic layer collected
  13. extractionThe aqueous layer was further extracted with dichloromethane
  14. washthe combined organic layers were washed with H2O, brine
  15. dry with materialdried over magnesium sulphate
  16. filtrationfiltered
  17. concentrationconcentrated
  18. customto afford a dark red oil
  19. customThe product was purified
  20. dry with materialdry column chromatography with a solvent system of 5% 2M NH3 in methanol/95% dichloromethane

Sources & evidence

ORD record
ord-ba6af52b3d504a5bbe42cc28361ff4c9
Source dataset
uspto-grants-2011_04
Patent number
US07919510B2

Reaction notes

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