L-Alanine → HCID 53955669, compound

HRID 1903020Notes

Reaction equation

HRID 1903020 reaction equation
[NH2:1][C@H:2]([C:4]([OH:6])=[O:5])[CH3:3].C(=O)(O)[O-].[Na+].[C:12]([CH2:20][CH:21]([CH3:25])[C:22]([OH:24])=O)(=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.BrBr.[C:28]([O-:31])(=[S:30])[CH3:29].[K+]>C(#N)C.C(O)(=O)C.O1CCCC1.O1CCOCC1.O>[C:28]([S:30][CH:20]([C:12](=[O:19])[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[CH:21]([CH3:25])[C:22]([NH:1][C@H:2]([C:4]([OH:6])=[O:5])[CH3:3])=[O:24])(=[O:31])[CH3:29]

Participants

11

Reactant 5

HCID 5950L-AlanineHCID 24408BromineHCID 744922-Methyl-4-oxo-4-phenylbutanoic acidHCID 516892Sodium BicarbonateHCID 23670855Potassium ethanethioate

Product 1

HCID 53955669HCID 53955669, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 4.64 g. (0.052 mol) of L-alanine and 9.24 g. (0.11 mol) of sodium bicarbonate in 100 ml. of water there was added 10.4 g. (0.036 mol) of 3-benzoyl-2-methylpropionic acid, N-hydroxysuccinimide ester. Dioxane (50 ml.) and tetrahydrofuran (50 ml.) were added and the mixture stirred at room temperature for 2 days. The mixture was concentrated in vacuo and the residue partitioned between dichloromethane and dilute hydrochloric acid. The organic layer was separated and dried over anhydrous sodium sulfate. The solvent was removed in vacuo to give 10.0 g. of a yellow gum. The gum was chromatographed on silica gel with ethyl acetate-hexane-acetic acid (75:25:1) as solvent to give 4.4 g. of a solid intermediate compound. The solid was reprecipitated from hexane-ether to give a white solid. To the preceding compound (0.01 mol) in 25 ml. of acetic acid there can be added (0.01 mol) of bromine. After stirring 18 hours, the solvent can be removed and the residue reacted with 0.01 mol of potassium thioacetate in acetonitrile for 24 hours. The solvent can be removed in vacuo to obtain N-[3-acetylthio-3-(benzoyl)-2-methylpropionyl]-L-alanine as a glass.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. customthe residue partitioned between dichloromethane and dilute hydrochloric acid
  3. customThe organic layer was separated
  4. dry with materialdried over anhydrous sodium sulfate
  5. customThe solvent was removed in vacuo
  6. customto give 10.0 g
  7. customThe gum was chromatographed on silica gel with ethyl acetate-hexane-acetic acid (75:25:1) as solvent
  8. customto give 4.4 g
  9. customThe solid was reprecipitated from hexane-ether
  10. customto give a white solid
  11. stirringAfter stirring 18 hours
  12. customthe solvent can be removed
  13. customThe solvent can be removed in vacuo

Sources & evidence

ORD record
ord-9b6d685e1ab34bc19034f8126ee33778
Source dataset
uspto-grants-1984_03
Patent number
US04435329

Reaction notes

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