Hydrochloric Acid → HCID 89668260, compound

HRID 1482207Notes

Reaction equation

HRID 1482207 reaction equation
[C:1](Cl)(=[O:17])[O:2][CH2:3][C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([O:12][CH3:13])=[CH:6][C:5]=1[N+:14]([O-:16])=[O:15].[NH2:19][C@@H:20]([CH2:24][S:25][S:26][C:27]([CH3:30])([CH3:29])[CH3:28])[C:21]([OH:23])=[O:22].C(=O)([O-])[O-].[Na+].[Na+].Cl.Br[CH2:39][C:40]#[N:41].C(N(C(C)C)C(C)C)C.[Cl-].[NH4+]>O1CCOCC1.O.CN(C=O)C>[C:27]([S:26][S:25][CH2:24][C@H:20]([NH:19][C:1]([O:2][CH2:3][C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([O:12][CH3:13])=[CH:6][C:5]=1[N+:14]([O-:16])=[O:15])=[O:17])[C:21]([O:23][CH2:39][C:40]#[N:41])=[O:22])([CH3:30])([CH3:29])[CH3:28]

Participants

11

Reactant 7

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 11534BromoacetonitrileHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 3084878((Nitroveratryl)oxy)chlorocarbamateHCID 7006457s-tert-Butylmercapto-L-cysteine2×

Product 1

HCID 89668260HCID 89668260, compoundYield 98%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Procedure

4,5-Dimethoxy-2-nitrobenzyl carbonochloridate (694 mg, 2.52 mmol) was added to a solution of (R)-2-amino-3-(tert-butyldisulfanyl)propanoic acid (Compound 2f-E, 500 mg, 2.29 mmol) and sodium carbonate (534 mg, 5.04 mmol) in dioxane (5 ml) and water (5 ml), and the mixture was stirred at room temperature for 30 minutes. The reaction solution was then adjusted to pH 2 by adding 1 N hydrochloric acid, and was extracted by adding ethyl acetate. The organic extract was dried over magnesium sulfate and concentrated under reduced pressure. 2-Bromoacetonitrile (0.284 ml, 4.08 mmol) and N-ethyl-N-isopropylpropan-2-amine (0.285 ml, 1.63 mmol) were added to a solution of the resulting residue in DMF (6 ml), and the mixture was stirred at room temperature for 20 minutes. A saturated aqueous ammonium chloride solution (3 ml) was added to the reaction mixture, after which the mixture was extracted with ethyl acetate and the organic layer was washed with water. The organic extract was then dried over magnesium sulfate. Following concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→60/40) to afford (R)-cyanomethyl 3-(tert-butyldisulfanyl)-2-((((4,5-dimethoxy-2-nitro benzyl)oxy)carbonyl)amino)propanoate (Compound 21-E) (653 mg, 98%).

Workup

  1. extractionwas extracted
  2. additionby adding ethyl acetate
  3. extractionThe organic extract
  4. dry with materialwas dried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. stirringthe mixture was stirred at room temperature for 20 minutes
  7. extractionafter which the mixture was extracted with ethyl acetate
  8. washthe organic layer was washed with water
  9. extractionThe organic extract
  10. dry with materialwas then dried over magnesium sulfate
  11. concentrationconcentration under reduced pressure
  12. customthe resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→60/40)

Sources & evidence

ORD record
ord-e473ca4f1ca5411a9e1a212f2c1c4027
Source dataset
uspto-grants-2016_08
Patent number
US09409952B2

Reaction notes

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