Water → HCID 54107824, compound

HRID 990140Notes

Reaction equation

HRID 990140 reaction equation
[CH3:1][O:2][C:3](=[O:31])[C@H:4]([CH2:21][C:22]1[CH:27]=[CH:26][C:25]([N+:28]([O-])=O)=[CH:24][CH:23]=1)[NH:5][C:6]([C:8]1([CH2:13][CH2:14][CH2:15][CH2:16][S:17]([CH3:20])(=[O:19])=[O:18])[CH2:12][CH2:11][CH2:10][CH2:9]1)=[S:7].C1COCC1.[Cl-].[NH4+].O>CO.[Zn]>[CH3:1][O:2][C:3](=[O:31])[C@H:4]([CH2:21][C:22]1[CH:27]=[CH:26][C:25]([NH2:28])=[CH:24][CH:23]=1)[NH:5][C:6]([C:8]1([CH2:13][CH2:14][CH2:15][CH2:16][S:17]([CH3:20])(=[O:19])=[O:18])[CH2:12][CH2:11][CH2:10][CH2:9]1)=[S:7]

Participants

7

Reactant 4

HCID 962Water2×HCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 53714300HCID 53714300, compound

Product 1

HCID 54107824HCID 54107824, compoundYield 98.4%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 887MethanolSolvent

Procedure

The poorly soluble N-[[1-[4-(methylsulfonyl)butyl]cyclopentyl]thioxomethyl]-4-nitro-L-phenylalanine methyl ester (19.3 mmol, 9.07 g) was dissolved in methanol (150 mL) and THF (20 mL) by gentle heating with a heat gun. To this solution, zinc dust (˜325 mesh, 193 mmol, 12.62 g, 10 equiv.) and ammonium chloride (289.5 mmol, 15.5 g, 15 equiv.) were added followed by water (75 mL) at room temperature. After the addition of water, an exothermic reaction ensued and the temperature rose to 45 to 50° C. The suspension was stirred for 1 h, at which time TLC analysis of the mixture indicated the absence of starting material. The reaction mixture was filtered and the filter cake was washed with methanol (200 mL) and THF (100 mL). The volatiles were removed under vacuum and the organic residue was extracted into ethyl acetate (2×200 mL). The combined extracts were washed brine (250 mL) then were dried (MgSO4), filtered and evaporated to dryness to give 8.37 g (98%) of 4-amino-N-[[1-[4-(methylsulfonyl)butyl]cyclopentyl]thioxomethyl)-L-phenylalanine methyl ester as a colorless gum which was used directly for next step. HRMS: Obs. mass, 441.1884. Calcd. mass, 441.1882 (M+H).

Workup

  1. customan exothermic reaction
  2. customrose to 45 to 50° C
  3. filtrationThe reaction mixture was filtered
  4. washthe filter cake was washed with methanol (200 mL) and THF (100 mL)
  5. customThe volatiles were removed under vacuum
  6. extractionthe organic residue was extracted into ethyl acetate (2×200 mL)
  7. washThe combined extracts were washed brine (250 mL)
  8. dry with materialthen were dried (MgSO4)
  9. filtrationfiltered
  10. customevaporated to dryness

Sources & evidence

ORD record
ord-91f0869e6e0342d5b878ae5ef6a0ee07
Source dataset
uspto-grants-2002_10
Patent number
US06458844B2

Reaction notes

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