Hydrochloric Acid → methyl (S)-(1-benzyl-3-chloro-2-oxo-propyl)carbamate

HRID 2292852Notes

Reaction equation

HRID 2292852 reaction equation
C([Li])CCCCC.[CH3:8][O:9][C:10]([NH:12][C@@H:13]([CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:14]([O:16]C)=O)=[O:11].Cl[Si](C)(C)C.Br[CH2:31][Cl:32].Cl>CCCCCC.O1CCCC1.O>[CH2:18]([C@H:13]([NH:12][C:10](=[O:11])[O:9][CH3:8])[C:14](=[O:16])[CH2:31][Cl:32])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6333BromochloromethaneHCID 6397ChlorotrimethylsilaneHCID 10609905(S)-Methyl 2-((methoxycarbonyl)amino)-3-phenylpropanoateHCID 178506865HCID 178506865, compound

Product 1

HCID 9881533methyl (S)-(1-benzyl-3-chloro-2-oxo-propyl)carbamateYield 70%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

15.4 ml of a 2.6 molar solution of hexyllithium in hexane were added dropwise at -80° C. to a solution of 9.50 g of methyl (S)-2-methoxycarbonylamino-3-phenyl-propionate in 60 ml of tetrahydrofuran. Subsequently, the mixture was treated with 5.60 ml of chlorotrimethylsilane. The resulting suspension was stirred and treated with 3.22 ml of bromochloromethane. Subsequently, 18.4 ml of hexyllithlum solution were added. The solution was treated at -80° C. with 11 ml of 20% methanolic hydrochloric acid, warmed to 220 and diluted with 100 ml of water and 40 ml of tetrahydrofuran. The phases were separated and the organic phase was washed with saturated sodium chloride solution, dried and concentrated. The residue was recrystallized from ethyl acetate and hexane and the crystallizate was dried, there being obtained 7.20 g (70%) of pure methyl (S)-(1-benzyl-3-chloro-2-oxopropyl)-carbamate, m.p. 122°-123° C. IR (KBr): 3336s (NH), 1737s and 1686s (C=O), 1535s (amide II).

Workup

  1. additionSubsequently, 18.4 ml of hexyllithlum solution were added
  2. temperaturewarmed to 220
  3. customThe phases were separated
  4. washthe organic phase was washed with saturated sodium chloride solution
  5. customdried
  6. concentrationconcentrated
  7. customThe residue was recrystallized from ethyl acetate and hexane
  8. customthe crystallizate was dried

Sources & evidence

ORD record
ord-4283e600b56340ec9a6340c69c66f573
Source dataset
uspto-grants-1997_11
Patent number
US05684176

Reaction notes

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