Acetonitrile → N-4-Thiazolyl-L-alanine

HRID 1589053Notes

Reaction equation

HRID 1589053 reaction equation
ClC[C:3]([CH2:5]Cl)=O.[C:7]([O-:10])([O-])=[O:8].[Ca+2].[CH:12]([NH2:14])=[S:13].[CH3:15][C:16]#[N:17]>>[S:13]1[CH:15]=[C:16]([NH:17][C@H:5]([C:7]([OH:10])=[O:8])[CH3:3])[N:14]=[CH:12]1

Participants

5

Reactant 4

HCID 6342AcetonitrileHCID 10112Calcium CarbonateHCID 107931,3-DichloroacetoneHCID 3005587Methanethioamide

Product 1

HCID 53261258N-4-Thiazolyl-L-alanineYield 71%

Procedure

To a solution of the above compound [36a] (40.3 g, 144.1 mmol) in MeCN (160 ml) are added CaCO3 (28 g, 280 mmol, 1.9 eq) and thioformamide (HCSNH2, 14 g, 229.1 mmol, 1.6 eq) and the mixture is stirred at room temperature for 18 hours under nitrogen atmosphere. Insoluble materials are filtered off and the filtrate is concentrated to dryness in vacuo The residue is dissolved in dichloromethane, subsequently washed with 7% aqueous sodium bicarbonate, 1N NaOH, and water, two times each, to remove non-reacted thioformamide. The dichloromethane layer is dried over MgSO4, concentrated to dryness in vacuo, and subjected to silica gel chromatography (SiO2 : 370 g, MeCN CH2Cl2 =1:7) to obtain (4-thiazolyl)alanine derivative [37a] (29.15 g, 71%) as an oil.

Workup

  1. filtrationInsoluble materials are filtered off
  2. concentrationthe filtrate is concentrated to dryness in vacuo The residue
  3. dissolutionis dissolved in dichloromethane
  4. washsubsequently washed with 7% aqueous sodium bicarbonate, 1N NaOH, and water, two times each,
  5. customto remove non-reacted thioformamide
  6. dry with materialThe dichloromethane layer is dried over MgSO4
  7. concentrationconcentrated to dryness in vacuo

Sources & evidence

ORD record
ord-15f3fdd031a546f4bbc4c15d0457df49
Source dataset
uspto-grants-1993_06
Patent number
US05223615

Reaction notes

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