Hydrochloric Acid → 1-N-benzyl-5-(4-methylpiperazin-1-yl)benzene-1,2-diamine

HRID 930539Notes

Reaction equation

HRID 930539 reaction equation
[CH2:1]([NH:8][C:9]1[CH:14]=[C:13]([N:15]2[CH2:20][CH2:19][N:18]([CH3:21])[CH2:17][CH2:16]2)[CH:12]=[CH:11][C:10]=1[N+:22]([O-])=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.O1CCOCC1>C1COCC1.CO.[Ni]>[CH2:1]([NH:8][C:9]1[C:10]([NH2:22])=[CH:11][CH:12]=[C:13]([N:15]2[CH2:20][CH2:19][N:18]([CH3:21])[CH2:17][CH2:16]2)[CH:14]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 312751,4-DioxaneHCID 2866378N-benzyl-5-(4-methylpiperazin-1-yl)-2-nitroaniline

Product 1

HCID 901610111-N-benzyl-5-(4-methylpiperazin-1-yl)benzene-1,2-diamine

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

N-Benzyl-5-(4-methylpiperazin-1-yl)-2-nitroaniline E-1.1′ (5.000 g; 15.319 mmol) is dissolved in THF (50.000 ml) and filled into a Büchi autoclave. RaNi (500.000 mg) is added and hydrogenated at 6 bar overnight (pressure after 16 h=0.5 bar). The autoclave is filled again with 6 bar H2 and stirred for 5 hours at rt. The reaction mixture is filtered through a plug of celite and HCl in dioxane (4 M, 4.000 ml; 16.000 mmol) is added. The filtrate is concentrated under reduced pressure to give a residue, which is dissolved in the smallest possible amount of MeOH and sonicated for few minutes. Precipitation of the product occurs and the product is filtered off. The product is washed with a very small amount of MeOH and 50 ml of isopropyl ether and then dried under reduced pressure.

Workup

  1. additionfilled into a Büchi autoclave
  2. customhydrogenated at 6 bar overnight (pressure after 16 h=0.5 bar)
  3. additionThe autoclave is filled again with 6 bar H2
  4. additionis added
  5. concentrationThe filtrate is concentrated under reduced pressure
  6. customto give a residue, which
  7. customsonicated for few minutes
  8. customPrecipitation of the product
  9. filtrationthe product is filtered off
  10. washThe product is washed with a very small amount of MeOH and 50 ml of isopropyl ether
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-b84c0d3bb6f041bdb4f3bb2fdf24ddfa
Source dataset
uspto-grants-2016_03
Patent number
US09296748B2

Reaction notes

Loading…