Ethanol → Chlorfenapyr

HRID 1657193

Reaction equation

HRID 1657193 reaction equation
[H-].[Na+].[Br:3][C:4]1[C:5]([C:20]#[N:21])=[C:6]([C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=2)[NH:7][C:8]=1[C:9]([F:12])([F:11])[F:10].Br[CH2:23]Cl.[CH2:25]([OH:27])[CH3:26]>O1CCCC1>[Br:3][C:4]1[C:5]([C:20]#[N:21])=[C:6]([C:13]2[CH:14]=[CH:15][C:16]([Cl:19])=[CH:17][CH:18]=2)[N:7]([CH2:23][O:27][CH2:25][CH3:26])[C:8]=1[C:9]([F:12])([F:11])[F:10]

Participants

6

Reactant 4

HCID 702EthanolHCID 6333BromochloromethaneHCID 24758Sodium hydrideHCID 183559Tralopyril

Product 1

HCID 91778ChlorfenapyrYield 91.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A stirred mixture of sodium hydride (26.5 g, 1.105 mol) in tetrahydrofuran, under nitrogen, is treated slowly with a solution of 4-bromo-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (1.00 g, 0.273 mol) in tetrahydrofuran at ≤60° C. When the addition is complete, the reaction mixture is treated with bromochloromethane (93.0 g, 0.718 mol), heated to 63°-65° C., treated dropwise with absolute ethanol (39.5 g, 0.859 mol) over a 5.5 hour period, stirred at 63°-65° C. for another 3 hours and concentrated in vacuo. The concentrate is dispersed in a mixture of water and methylene chloride. The aqueous phase is separated and washed with methylene chloride. The organic phases are combined and concentrated. The concentrate is dispersed in hexane, cooled to 5°-10° C. and filtered. The filtercake is washed with heptane and dried to give the title product as a white solid, 111.6 g, (91.3% yield) and 91.2% purity by HPLC analysis.

Workup

  1. additionWhen the addition
  2. temperatureheated to 63°-65° C.
  3. concentrationconcentrated in vacuo
  4. additionThe concentrate is dispersed in a mixture of water and methylene chloride
  5. customThe aqueous phase is separated
  6. washwashed with methylene chloride
  7. concentrationconcentrated
  8. additionThe concentrate is dispersed in hexane
  9. temperaturecooled to 5°-10° C.
  10. filtrationfiltered
  11. washThe filtercake is washed with heptane
  12. customdried

Sources & evidence

ORD record
ord-a5e336248f944df8bcc4865c83f293de
Source dataset
uspto-grants-1993_10
Patent number
US05256796

Linked notes

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