Water → HCID 21831312, compound

HRID 1601417Notes

Reaction equation

HRID 1601417 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.CCCCCC.C([Li])CCC.FC(F)(F)S(O[C:25]1[C:30]2[CH:31]=[C:32]([N+:35]([O-:37])=[O:36])[CH:33]=[CH:34][C:29]=2[O:28][C:27]([C:42]([F:45])([F:44])[F:43])([C:38]([F:41])([F:40])[F:39])[CH:26]=1)(=O)=O.O>O1CCCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:44][C:42]([F:43])([F:45])[C:27]1([C:38]([F:39])([F:41])[F:40])[CH:26]=[C:25]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=2)[C:30]2[CH:31]=[C:32]([N+:35]([O-:37])=[O:36])[CH:33]=[CH:34][C:29]=2[O:28]1

Participants

8

Reactant 4

HCID 962WaterHCID 79732-BromopyridineHCID 21831321HCID 21831321, compoundHCID 178418244HCID 178418244, compound

Product 1

HCID 21831312HCID 21831312, compound

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

To 5 ml of dry tetrahydrofuran solution containing 0.16 ml of 2-bromopyridine was added dropwise 1.0 ml of 1.61M n-butyllithium hexane solution under nitrogen atmosphere at -78° C. After 30 minutes, 3.2 ml of solution of 0.5M zinc chloride in dry tetrahydrofuran was added thereto and the mixture was stirred at -78° C. for 15 minutes and under ice-cooling for 15 minutes. Then, the solution of 50 mg of tetrakis(triphenylphosphine)palladium (O) and 300 mg of 4-trifluoromethanesulfonyloxy-2,2-bistrifluoromethyl-6-nitro-2H-1-benzopyran dissolved in 5 ml of dry tetrahydrofuran was added under ice-cooling to the mixture obtained above. The resultant mixture was warmed to room temperature and stirred for additional 15 hours. Water was added to the reaction mixture which was then extracted with ethyl acetate. The organic layer was washed with water and dried. The solvent was distilled off and the resultant residue was purified using silica gel column chromatography (developing solution, CH2Cl2 :hexane=1:1) to obtain 200 mg of 2,2-bistrifluoromethyl-6-nitro-4-(2-pyridyl)-2H-1-benzopyran represented by the following formula having a melting point of 105-107° C.

Workup

  1. temperaturecooling for 15 minutes
  2. additionwas added under ice-
  3. temperaturecooling to the mixture
  4. customobtained above
  5. stirringstirred for additional 15 hours
  6. extractionwas then extracted with ethyl acetate
  7. washThe organic layer was washed with water
  8. customdried
  9. distillationThe solvent was distilled off
  10. customthe resultant residue was purified

Sources & evidence

ORD record
ord-d0c860a8c2054594ad992edbe8b38d3e
Source dataset
uspto-grants-1999_11
Patent number
US05977167

Reaction notes

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