Water → HCID 21831366, compound

HRID 977632Notes

Reaction equation

HRID 977632 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]([CH2:40][F:41])([CH2:38][F:39])[N: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:41][CH2:40][C:27]1([CH2:38][F:39])[N: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 21831354HCID 21831354, compoundHCID 178418244HCID 178418244, compound

Product 1

HCID 21831366HCID 21831366, compound

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To 3 ml of anhydrous tetrahydrofuran solution of 0.21 ml of 2-bromopyridine was added dropwise 1.38 ml of 1.68M n-butyllithium hexane solution at -78° C. under nitrogen atmosphere. After 30 minutes, 4.26 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. To the mixture were added under ice-cooling 65 mg of tetrakis(triphenylphosphine)palladium (0) and 330 mg of 4-trifluoromethanesulfonyloxy-2,2-bisfluoromethyl-6-nitro-2H-1,3-benzoxazine. The mixture was warmed to room temperature and was stirred for additional 36 hours. Water was added to the reaction mixture which was then extracted with ethyl acetate and dried. The solvent was distilled off and the resultant residue was purified using column chromatography (developing solution, AcOEt:hexane=1:5) to obtain 110 mg of oily 2,2-bisfluoromethyl-6-nitro-4-(2-pyridyl)-2H-1,3-benzoxazine represented by the following formula.

Workup

  1. temperaturecooling for 15 minutes
  2. additionTo the mixture were added under ice-
  3. temperatureThe mixture was warmed to room temperature
  4. stirringwas stirred for additional 36 hours
  5. extractionwas then extracted with ethyl acetate
  6. customdried
  7. distillationThe solvent was distilled off
  8. customthe resultant residue was purified

Sources & evidence

ORD record
ord-093efc0a2a444983bf7bf398b2d1f72b
Source dataset
uspto-grants-1997_03
Patent number
US05614633

Reaction notes

Loading…