Hydrochloric Acid → HCID 59799755, compound

HRID 2074453Notes

Reaction equation

HRID 2074453 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][CH2:14][CH2:15][CH:16]1[CH2:20][CH2:19][CH2:18][N:17]1[CH3:21])([O-])=O.O.Cl>CCO>[CH3:21][N:17]1[CH2:18][CH2:19][CH2:20][CH:16]1[CH2:15][CH2:14][NH:13][C:5]1[C:4]([NH2:1])=[CH:9][C:8]([N+:10]([O-:12])=[O:11])=[CH:7][CH:6]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 962WaterHCID 59799764HCID 59799764, compound

Product 1

HCID 59799755HCID 59799755, compoundYield 45.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
65 °C

Procedure

(2,4-Dinitro-phenyl)-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-amine 31 (0.979 g, 3.329 mmol) was dissolved in anhydrous EtOH (16 mL) in a 2 neck 100 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 (16 mL), EtOH (32 mL) and aqueous (NH4)2S (50 wt %, 1.59 g, 11.652 mmol) were charged to the dropping funnel and added to the hot reaction mixture dropwise over 45 minutes. The reaction was heated at 65-70° 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 10% 2M NH3 in methanol/90% dichloromethane) to afford an orange-red oil/solid 32 N1-[2-(1-Methyl-pyrrolidin-2-yl)-ethyl]-4-nitro-benzene-1,2-diamine Yield: 0.396 grams (45.1%). 1H NMR (DMSO) δ: 1.39-1.69 (m, 5H), 1.86-1.98 (m, 2H), 2.01-2.10 (m, 1H), 2.10-2.16 (m, 1H), 2.22 (s, 3H), 2.91-2.98 (m, 1H), 3.16-3.24 (m, 2H), 5.11 (br s, 2H), 5.92-5.98 (m, 1H), 6.46 (d, 1H, J=8.8), 7.40 (d, 1H, J=2.5), 7.52 (dd, 1H, J=8.9, 2.5); MS (ESI): 265 (MH+, 100%).

Workup

  1. customThe reaction vessel was fitted with a condenser
  2. additionadded to the hot reaction mixture dropwise over 45 minutes
  3. temperatureThe reaction was heated at 65-70° 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 to 10% 2M NH3 in methanol/90% dichloromethane)

Sources & evidence

ORD record
ord-169a5ab460a9472288fd161c71d03f5f
Source dataset
uspto-grants-2011_04
Patent number
US07919510B2

Reaction notes

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