Hydrochloric Acid → 1,1-Dimethylethyl 4-[(5-amino-2-chlorophenyl)methyl]-1-piperazinecarboxylate

HRID 1750883Notes

Reaction equation

HRID 1750883 reaction equation
Cl.[Cl:2][C:3]1[CH:22]=[CH:21][C:20]([N+:23]([O-])=O)=[CH:19][C:4]=1[CH2:5][N:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8][CH2:7]1>[Fe].C(O)C.O>[NH2:23][C:20]1[CH:21]=[CH:22][C:3]([Cl:2])=[C:4]([CH:19]=1)[CH2:5][N:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])[CH2:8][CH2:7]1

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 57678518HCID 57678518, compound

Product 1

HCID 576785351,1-Dimethylethyl 4-[(5-amino-2-chlorophenyl)methyl]-1-piperazinecarboxylateYield 86.2%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 19096565Water ethanolSolvent

Procedure

Iron (1.7 g, 26.7 mmol) and concentrated hydrochloric acid (0.2 mL) were added to ethanol/water (45 mL/45 mL), and refluxed for 1 hour. The mixed reaction solution was added with tert-butyl 4-(2-chloro-5-nitrobenzyl)piperazine-1-carboxylate (1.9 g, 5.34 mmol) obtained in <Step 1> above, and further refluxed for 1 hour. The reaction mixture was filtered through a Celite pad under reduced pressure, and washed with ethanol and chloroform/2-propanol=3/1 (v/v). The resulting filtrate was distilled under reduced pressure and dissolved in ethanol and chloroform/2-propanol=3/1 (v/v). The organic layer was washed with an aqueous solution of sodium bicarbonate and brine. The obtained organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The concentrated compound was purified using silica gel chromatography (chloroform:methanol=30:1 (v/v)) to obtain the title compound (1.5 g, 86%).

Workup

  1. temperaturerefluxed for 1 hour
  2. customThe mixed reaction solution
  3. customobtained in <Step 1> above, and
  4. temperaturefurther refluxed for 1 hour
  5. filtrationThe reaction mixture was filtered through a Celite pad under reduced pressure
  6. washwashed with ethanol and chloroform/2-propanol=3/1 (v/v)
  7. distillationThe resulting filtrate was distilled under reduced pressure
  8. dissolutiondissolved in ethanol
  9. washThe organic layer was washed with an aqueous solution of sodium bicarbonate and brine
  10. dry with materialThe obtained organic layer was dried over anhydrous sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure
  13. customThe concentrated compound was purified

Sources & evidence

ORD record
ord-8a8299b459db4dec9799b04f8afd3e9f
Source dataset
uspto-grants-2015_10
Patent number
US09156852B2

Reaction notes

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