Tributyltin Chloride → 7Hydroxyiminomethyl-2-(tri-n-butylstannyl)imidazo[5,1-b]thiazole

HRID 989811Notes

Reaction equation

HRID 989811 reaction equation
[OH:1][N:2]=[CH:3][C:4]1[N:5]=[CH:6][N:7]2[CH:11]=[CH:10][S:9][C:8]=12.C([Li])CCC.CCCCCC.[CH2:23]([Sn:27](Cl)([CH2:32][CH2:33][CH2:34][CH3:35])[CH2:28][CH2:29][CH2:30][CH3:31])[CH2:24][CH2:25][CH3:26].[Cl-].[NH4+]>C1COCC1.CN(C)P(N(C)C)(N(C)C)=O>[OH:1][N:2]=[CH:3][C:4]1[N:5]=[CH:6][N:7]2[CH:11]=[C:10]([Sn:27]([CH2:28][CH2:29][CH2:30][CH3:31])([CH2:32][CH2:33][CH2:34][CH3:35])[CH2:23][CH2:24][CH2:25][CH3:26])[S:9][C:8]=12

Participants

7

Reactant 4

HCID 15096Tributyltin ChlorideHCID 25517Ammonium ChlorideHCID 857694057-Hydroxyiminomethylimidazo[5,1-b]thiazoleHCID 178418244HCID 178418244, compound

Product 1

HCID 857694067Hydroxyiminomethyl-2-(tri-n-butylstannyl)imidazo[5,1-b]thiazole

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-40 °C

Procedure

7-Hydroxyiminomethylimidazo[5,1-b]thiazole (a low-polarity geometrical isomer) (831 mg) was dissolved in 25 ml of THF and 5 ml of hexamethylphosphoramide (HMPA). A 1.55 N n-butyllithium/n-hexane solution (7.67 ml) was dropwise added in an argon atmosphere at −70° C. to the solution. The mixture was stirred at the same temperature for 40 min. Tri-n-butylstannyl chloride (1.84 ml) was added thereto. The mixture was stirred for 1.5 hr while raising the temperature to −40° C. An ammonium chloride solution was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography on silica gel (hexane:ethyl acetate=3:1 to 1:1) to give 680 mg of 7hydroxyiminomethyl-2-(tri-n-butylstannyl)imidazo[5,1-b]thiazole (a geometrical isomer derived from a starting compound as a low-polarity oxime isomer).

Workup

  1. stirringThe mixture was stirred for 1.5 hr
  2. extractionfollowed by extraction with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. customThe solvent was removed by distillation under the reduced pressure
  7. customThe residue was purified by column chromatography on silica gel (hexane:ethyl acetate=3:1 to 1:1)

Sources & evidence

ORD record
ord-1eeebb371f774c8296e0e0e96baec152
Source dataset
uspto-grants-2002_10
Patent number
US06458780B1

Reaction notes

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