Dichloromethane → HCID 11381978, compound

HRID 989453Notes

Reaction equation

HRID 989453 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:17]([OH:19])=O)[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:20]([Cl:22])[Cl:21].C([N-]C(C)C)(C)C.[Li+].[Cl-].[NH4+]>O1CCCC1.CCCCCCC.C(C1C=CC=CC=1)C>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:10][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)[C:17](=[O:19])[CH:20]([Cl:22])[Cl:21])=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 25517Ammonium ChlorideHCID 77857L-Phenylalanine, N-[(1,1-dimethylethoxy)carbonyl]-HCID 2724682Lithium diisopropylamide

Product 1

HCID 11381978HCID 11381978, compoundYield 36%

Reagents, catalysts & solvents 3

HCID 7500EthylbenzeneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8900HeptaneSolvent

Conditions

Temperature
-78 °C

Procedure

Methyl ester (1.4 g) of N-tert-butoxycarbonyl-L-phenylalanine (1.4 g) was dissolved in dehydrated tetrahydrofuran (20 ml), and the obtained solution was cooled to −78° C. Methylene chloride (0.64 ml) and then 2 M solution (7.5 ml) of lithium diisopropylamide in heptane, tetrahydrofuran and ethylbenzene were added thereto, and they were stirred for 1 hour. A saturated aqueous ammonium chloride solution (20 ml) was added to the reaction mixture to terminate the reaction. The temperature was elevated to room temperature. After the extraction with ethyl acetate and water, the obtained solution in ethyl acetate was analyzed by HPLC to find that the intended (3S)-3-tert-butoxycarbonylamino-1,1-dichloro-4-phenyl-2-butanone (0.86 g) was obtained in a yield of 52%. The obtained solution in ethyl acetate was dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off. The solvent was evaporated under reduced pressure. Ethyl acetate was added to the residue to form a slurry. The crystals thus formed were separated from the slurry and dried to obtain the intended (3S)-3-tert-butoxycarbonylamino-1,1-dichloro-4-phenyl-2-butanone (0.65 g) in a yield of 36%.

Workup

  1. customto terminate
  2. customthe reaction
  3. customwas elevated to room temperature
  4. extractionAfter the extraction with ethyl acetate and water
  5. customwas obtained in a yield of 52%
  6. dry with materialThe obtained solution in ethyl acetate was dried over anhydrous magnesium sulfate
  7. filtrationMagnesium sulfate was filtered off
  8. customThe solvent was evaporated under reduced pressure
  9. additionEthyl acetate was added to the residue
  10. customto form a slurry
  11. customThe crystals thus formed
  12. customwere separated from the slurry
  13. customdried

Sources & evidence

ORD record
ord-c7c969b510fc478ea29bc75d75b74b6e
Source dataset
uspto-grants-2003_10
Patent number
US06639094B2

Reaction notes

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