Hexane → 1-(2-Methyl-allyl)-4-(4-amino-phenyl)-piperazine

HRID 37872Notes

Reaction equation

HRID 37872 reaction equation
O.O.[Sn](Cl)Cl.[CH3:6][C:7](=[CH2:24])[CH2:8][N:9]1[CH2:14][CH2:13][N:12]([C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-])=O)=[CH:17][CH:16]=2)[CH2:11][CH2:10]1.CCCCCC>C(OCC)(=O)C>[CH3:24][C:7](=[CH2:6])[CH2:8][N:9]1[CH2:14][CH2:13][N:12]([C:15]2[CH:20]=[CH:19][C:18]([NH2:21])=[CH:17][CH:16]=2)[CH2:11][CH2:10]1

Participants

5

Reactant 3

HCID 8058HexaneHCID 61436Stannous chloride dihydrateHCID 399755471-(2-Methyl-allyl)-4-(4-nitrophenyl)-piperazine

Product 1

HCID 668514031-(2-Methyl-allyl)-4-(4-amino-phenyl)-piperazineYield 74%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Tin (II) chloride dihydrate (67.0 g, 297 mmol) was added in portions to a solution of 1-(2-methyl-allyl)-4-(4-nitro-phenyl)-piperazine (prepared as described in Reference Example 40, 13 g, 50 mmol) in ethyl acetate (200 mL) at room temperature. The mixture was heated to reflux for 4 hours then the solvent was evaporated under reduced pressure. The resulting residue was diluted with water and basified with 10% sodium hydroxide solution to pH ˜10 then extracted with ethyl acetate (4×100 mL). The combined organic layers were washed twice with saturated brine then dried over sodium sulfate. Filtration and concentration in vacuo gave a gummy mass which was washed repeatedly with small volumes of 1:3 ether/hexane to afford a solid. This was slurried with hexane, filtered and dried under vacuum at room temperature to afford 1-(2-methyl-allyl)-4-(4-amino-phenyl)-piperazine (8.5 g, 74%) as light yellow solid.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 4 hours
  3. customthe solvent was evaporated under reduced pressure
  4. additionThe resulting residue was diluted with water and basified with 10% sodium hydroxide solution to pH ˜10
  5. extractionthen extracted with ethyl acetate (4×100 mL)
  6. washThe combined organic layers were washed twice with saturated brine
  7. dry with materialthen dried over sodium sulfate
  8. filtrationFiltration and concentration in vacuo
  9. customgave a gummy mass which
  10. washwas washed repeatedly with small volumes of 1:3 ether/hexane
  11. customto afford a solid
  12. filtrationfiltered
  13. customdried under vacuum at room temperature

Sources & evidence

ORD record
ord-3cdad19d5f634517a4a6ebfcc683e1c1
Source dataset
uspto-grants-2013_09
Patent number
US08524705B2

Reaction notes

Loading…