2-Bromopyridine → HCID 21462565, compound

HRID 1940509Notes

Reaction equation

HRID 1940509 reaction equation
[F:1][CH:2]([F:31])[C:3]1([CH:28]([F:30])[F:29])[CH2:8][N:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=2)[C:6]2[CH:15]=[C:16]([S:19]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)(=[O:21])=[O:20])[CH:17]=[CH:18][C:5]=2[O:4]1.FC(F)C1(C(F)F)CNC2C=C(S(C3C=CC=CC=3)(=O)=O)C=CC=2[O:35]1.C(=O)([O-])[O-].[K+].[K+].BrC1C=CC=CN=1>[Cu].ClCCl.C(OCC)(=O)C.O>[F:31][CH:2]([F:1])[C:3]1([CH:28]([F:29])[F:30])[CH2:8][N:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N+:10]=2[O-:35])[C:6]2[CH:15]=[C:16]([S:19]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)(=[O:20])=[O:21])[CH:17]=[CH:18][C:5]=2[O:4]1

Participants

9

Reactant 4

HCID 79732-BromopyridineHCID 11430Potassium CarbonateHCID 21462581HCID 21462581, compoundHCID 21462585HCID 21462585, compound

Product 1

HCID 21462565HCID 21462565, compound

Reagents, catalysts & solvents 4

HCID 23978CopperCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
200 °C

Procedure

2-(2,2-bis(Difluoromethyl)-6-phenylsulfonyl-3,4-dihydro-2H-1,4-benzoxazine-4-yl)pyridine. A mixture of the product of step e. (1 g), potassium carbonate (0.41 g), copper bronze (0125 g,), and 2-bromopyridine (4.3 g) was stirred and heated at 200° C. for 18 hours. The cooled, dark mixture was stirred with water and ethyl acetate:dichloromethane. The mixture was filtered through diatomaceous earth, and the lower organic layer was separated. The organic phase was washed (water), dried, and evaporated. Chromatography, eluting ethyl acetate:hexane (gradient 40% to 60%) gave the pyridine as a pale yellow gum (0.29 g); NMR: 4.31 (s,2), 6.49 (t,2), 7.06 (t,1), 7.21 (d,1), 7.33 (d,1), 7.53 (d,1), 7.60 to 7.70 (m,3), 7.79 (t,1), 7.92 (d,2), 7.94 (s,1), 8.36 (d,1); MS: m/z=453 (M+1).

Workup

  1. filtrationThe mixture was filtered through diatomaceous earth
  2. customthe lower organic layer was separated
  3. washThe organic phase was washed (water)
  4. customdried
  5. customevaporated
  6. washChromatography, eluting ethyl acetate
  7. customhexane (gradient 40% to 60%) gave the pyridine as a pale yellow gum (0.29 g)

Sources & evidence

ORD record
ord-08e8eaa3ed804815b43af0822e72bab3
Source dataset
uspto-grants-1997_12
Patent number
US05700798

Reaction notes

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