Hydrochloric Acid → (S,S)-1-Benzyloxycarbonyl-2-(1-aminoethyl)-4-tert-butyloxycarbonylpiperazine

HRID 429296Notes

Reaction equation

HRID 429296 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][C@H:12]1[C@@H:24]([N:26]=[N+]=[N-])[CH3:25])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl>C1COCC1.O.C(Cl)Cl>[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:21])([CH3:22])[CH3:23])=[O:18])[CH2:13][C@H:12]1[C@@H:24]([NH2:26])[CH3:25])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 86757593HCID 86757593, compound

Product 1

HCID 70212142(S,S)-1-Benzyloxycarbonyl-2-(1-aminoethyl)-4-tert-butyloxycarbonylpiperazineYield 40.6%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21881883Oxolane--water (1/1)Solvent

Conditions

Temperature
75 °C

Procedure

(S,S)-1-Benzyloxycarbonyl-2-(1-azidoethyl)-4-tert-butyloxycarbonylpiperazine (8.1 g) was dissolved in 255 mL of 9:1 THF-water and triphenylphosphine (10.9 g) was added. The mixture was heated to 75° C. and stirred at this temperature overnight. The reaction mixture was cooled, diluted with 286 mL of CH2Cl2, poured into 250 mL of 1N HCl, and extracted with 750 mL of CH2Cl2. The aqueous phase was basified to pH>10 by addition of 5N NaOH, then extracted with 5×750 mL of EtOAc. The combined organic extracts were washed with 750 mL of brine, dried over Na2SO4, and concentrated. The residue was purified by flash chromatography using 90:10 ethyl acetate-methanol to yield 3.07 g of the title compound. Mass spectrum (ESI) 308.3 (M−55).

Workup

  1. temperatureThe reaction mixture was cooled
  2. extractionextracted with 750 mL of CH2Cl2
  3. additionThe aqueous phase was basified to pH>10 by addition of 5N NaOH
  4. extractionextracted with 5×750 mL of EtOAc
  5. washThe combined organic extracts were washed with 750 mL of brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-915a2e8281d44621a23b5b061406f60e
Source dataset
uspto-grants-2001_11
Patent number
US06316444B1

Reaction notes

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