Dichloromethane → HCID 59349482, compound

HRID 415054Notes

Reaction equation

HRID 415054 reaction equation
[Cl-].[NH4+].C[NH:4][C:5]1[CH:10]=[CH:9][C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=2)=[CH:7][C:6]=1[N+:19]([O-:21])=[O:20].C(OCC)(=O)C.ClCCl>CO.[Fe]>[N+:19]([C:6]1[CH:7]=[C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=2)[CH:9]=[CH:10][C:5]=1[NH2:4])([O-:21])=[O:20].[N:16]1[CH:17]=[CH:18][C:13]([CH2:12][O:11][C:8]2[CH:7]=[C:6]([NH2:19])[C:5]([NH2:4])=[CH:10][CH:9]=2)=[CH:14][CH:15]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 8857Ethyl AcetateHCID 25517Ammonium Chloride2×HCID 66623516HCID 66623516, compound

Product 2

HCID 59349482HCID 59349482, compoundHCID 59349546HCID 59349546, compound

Reagents, catalysts & solvents 2

HCID 23925IronCatalyst2×HCID 887MethanolSolvent2×

Procedure

A single necked 50 ml flask fitted with a Teflon stirrer, Claisen head fitted with a rubber septa and reflux condenser was charged with iron powder (Aldrich, 6.2 mmoles, 3 equivalents, 0.358 g) and an aqueous solution of ammonium chloride (10.70 mmoles, 5 equivalents, 0.573 g). The slurry was rapidly stirred and a solution of 2-nitro-4-(pyridin-4-ylmethoxy)aniline (2.14 mmoles, 0.525 g) in methanol (10 ml, 5 ml./mmole of nitro compound) was prepared with gentle heating to ensure complete dissolution. The methanolic solution of methyl 2-nitro-4-(pyridin-4-ylmethoxy)aniline was added over a period of 10 minutes using a syringe and needle. Upon completion of addition the reaction mixture was brought to a gentle reflux and the progress of the reaction was monitored by TLC (silica, 100% ethyl acetate or dichloromethane, visualizing by UV). After 1.5 hours, additional iron powder (Aldrich, 6.2 mmoles, 3 equivalents, 0.358 g), ammonium chloride (10.70 mmoles, 5 equivalents, 0.573 g) and methanol (10 ml) was added. The reaction was found to be complete after 2.5 hours. A sintered filtered funnel (60 ml, medium grade sintered) was packed with Celite (20 mm thick) and connected to a Buchner flask. The hot reaction mixture was filtered through the pad of Celite, the flask rinsed with hot methanol (2×25 ml), filtered and the filtered pad washed with more hot methanol (2×40 ml). The combined filtrate was evaporated to dryness. The recovered material was dissolved in 50 ml cold water and 100 ml dichloromethane and allowed to separate. The dichloromethane layer was dried over sodium sulfate, filtered and evaporated under reduced pressure to give 0.497 of 4-(pyridin-4-ylmethoxy)benzene-1,2-diamine which was used in the next step without any further purification. 1H-NMR (400 MHz, DMSO-d6) 10.50 (br s, 4H), 7.68 (d, 2H), 7.42 (m, 2H), 6.60 (d, 1H), 6.41 (s, 1H), 6.22 (d, 1H), 5.12 (s, 2H). (MS (EI): 216 (MH+).

Workup

  1. customA single necked 50 ml flask fitted with a Teflon stirrer
  2. customClaisen head fitted with a rubber septa
  3. temperaturereflux condenser
  4. temperaturewith gentle heating
  5. dissolutiondissolution
  6. additionUpon completion of addition the reaction mixture
  7. temperaturea gentle reflux
  8. waitto be complete after 2.5 hours
  9. customA sintered filtered funnel (60 ml, medium grade sintered) was packed with Celite (20 mm thick)
  10. filtrationThe hot reaction mixture was filtered through the pad of Celite
  11. washthe flask rinsed with hot methanol (2×25 ml)
  12. filtrationfiltered
  13. washthe filtered pad washed with more hot methanol (2×40 ml)
  14. customThe combined filtrate was evaporated to dryness
  15. dissolutionThe recovered material was dissolved in 50 ml cold water
  16. customto separate
  17. dry with materialThe dichloromethane layer was dried over sodium sulfate
  18. filtrationfiltered
  19. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-928ba8706e2543d4a5a78f9c38d9a173
Source dataset
uspto-grants-2012_01
Patent number
US08088767B2

Reaction notes

Loading…