Dibromodifluoromethane → HCID 86698189, compound

HRID 623944Notes

Reaction equation

HRID 623944 reaction equation
O1CCCC1.Br[C:7](Br)([F:9])[F:8].CN(C)P(=O)(N(C)C)N(C)C.[CH3:22][O:23][C:24]1[CH:58]=[CH:57][C:27]([CH2:28][O:29][C:30]2[CH:35]=[CH:34][C:33]([C:36]3[N:41]=[CH:40][C:39]([C:42]4[N:43]([CH2:49][O:50][CH2:51][CH2:52][Si:53]([CH3:56])([CH3:55])[CH3:54])[CH:44]=[C:45]([CH:47]=O)[N:46]=4)=[CH:38][CH:37]=3)=[CH:32][CH:31]=2)=[CH:26][CH:25]=1>O.C(OCC)(=O)C>[F:8][C:7]([F:9])=[CH:47][C:45]1[N:46]=[C:42]([C:39]2[CH:38]=[CH:37][C:36]([C:33]3[CH:34]=[CH:35][C:30]([O:29][CH2:28][C:27]4[CH:57]=[CH:58][C:24]([O:23][CH3:22])=[CH:25][CH:26]=4)=[CH:31][CH:32]=3)=[N:41][CH:40]=2)[N:43]([CH2:49][O:50][CH2:51][CH2:52][Si:53]([CH3:54])([CH3:55])[CH3:56])[CH:44]=1

Participants

7

Reactant 4

HCID 6382DibromodifluoromethaneHCID 8028Tetrahydrofuran2×HCID 12679HexamethylphosphoramideHCID 86698190HCID 86698190, compound

Product 1

HCID 86698189HCID 86698189, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a tetrahydrofuran (70 mL) solution containing dibromodifluoromethane (5.09 g) was added dropwise hexamethyl phosphoric triamide (8.81 mL) at −78° C. The temperature of the mixture was returned to room temperature, and the mixture was stirred for 30 minutes. The mixture was cooled to −78° C., and a tetrahydrofuran (20 mL) solution of 2-(6-{4-[(4-methoxybenzyl)oxy]phenyl}pyridin-3-yl)-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-imidazol-4-carbaldehyde (1.25 g) was added dropwise thereto. The temperature of the mixture was returned to room temperature, and the mixture was stirred for 3 hours. To the mixture were added ethyl acetate, water and a saturated aqueous sodium bicarbonate solution, and the liquids were separated. The organic layer was separated, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=85:15 to 55:45) to obtain 5-[4-(2,2-difluoroethenyl)-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-imidazol-2-yl]-2-{4-[(4-methoxybenzyl)oxy]phenyl}pyridine (0.84 g).

Workup

  1. customwas returned to room temperature
  2. customwas returned to room temperature
  3. stirringthe mixture was stirred for 3 hours
  4. customa saturated aqueous sodium bicarbonate solution, and the liquids were separated
  5. customThe organic layer was separated
  6. washwashed with saturated brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe obtained residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=85:15 to 55:45)

Sources & evidence

ORD record
ord-3f812c1057f64d9a884c30f26488a20c
Source dataset
uspto-grants-2016_04
Patent number
US09302996B2

Reaction notes

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