Potassium Cyanide → 6-Amino-2-cyanobenzothiazole

HRID 2113066Notes

Reaction equation

HRID 2113066 reaction equation
[C-:1]#[N:2].[K+].Cl[C:5]1[S:6][C:7]2[CH:13]=[C:12]([NH2:14])[CH:11]=[CH:10][C:8]=2[N:9]=1.C(OCC)(=O)C.CCCCCC.P([O-])(O)(O)=O.[K+]>CS(C)=O.C(OCC)C>[C:1]([C:5]1[S:6][C:7]2[CH:13]=[C:12]([NH2:14])[CH:11]=[CH:10][C:8]=2[N:9]=1)#[N:2]

Participants

7

Reactant 4

HCID 9032Potassium CyanideHCID 516951Monobasic potassium phosphateHCID 109212032-Chloro-1,3-benzothiazol-6-amineHCID 21226206Ethyl acetate hexane

Product 1

HCID 141571126-Amino-2-cyanobenzothiazoleYield 54%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
135 °C

Procedure

Potassium cyanide (1.29 g, 19.7 mmol) was added to dimethyl sulfoxide (DMSO, 150 mL). After argon substitution, the mixture was refluxed overnight at 135° C. with stirring. The temperature was lowered to 120° C., and Compound 3 (1.02 g, 5.55 mmol) dissolved in DMSO (20 mL) was added. After disappearance of the starting materials was confirmed by thin layer chromatography (developing solvent: ethyl acetate/n-hexane=2/1), the reaction mixture was poured into a mixed solution of 1.0 mol/L potassium dihydrogenphosphate solution (100 mL) and diethyl ether, (150 mL), and the diethyl ether layer was separated. The aqueous layer was extracted 5 times with ethyl acetate, the organic layer was mixed with the diethyl ether layer, and this organic solvent layer was washed twice with purified water and twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane=1/4 to 1/2) to obtain Compound 4 as yellow solid (521 mg, 54% yield).

Workup

  1. customwas lowered to 120° C.
  2. additionwas added
  3. customthe diethyl ether layer was separated
  4. extractionThe aqueous layer was extracted 5 times with ethyl acetate
  5. additionthe organic layer was mixed with the diethyl ether layer
  6. washthis organic solvent layer was washed twice with purified water and twice with saturated brine
  7. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane=1/4 to 1/2)

Sources & evidence

ORD record
ord-f7de2d01612043cc97bef0be7dd929a2
Source dataset
uspto-grants-2009_04
Patent number
US07524876B2

Reaction notes

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