Dabco → HCID 12853035, compound

HRID 2057991Notes

Reaction equation

HRID 2057991 reaction equation
[Cl:1][C:2]([Cl:12])=[CH:3][C@@H:4]1[C@H:6]([C:7]([OH:9])=[O:8])[C:5]1([CH3:11])[CH3:10].[OH-].[Na+].Br[CH2:16][C:17]1[C:18]([F:30])=[C:19]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH:20]=[CH:21][C:22]=1[F:23].N12CCN(CC1)CC2>CCCCCCC.O.C(#N)C>[Cl:1][C:2]([Cl:12])=[CH:3][CH:4]1[CH:6]([C:7]([O:9][CH2:16][C:17]2[C:18]([F:30])=[C:19]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[CH:20]=[CH:21][C:22]=2[F:23])=[O:8])[C:5]1([CH3:10])[CH3:11]

Participants

8

Reactant 4

HCID 9237DabcoHCID 14798Sodium HydroxideHCID 41507Cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acidHCID 128530343-(Bromomethyl)-2,4-difluoro-1,1'-biphenyl

Product 1

HCID 12853035HCID 12853035, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8900HeptaneSolvent

Procedure

To a mixture of cis-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid (2.2 g, 0.11 mole) in 75 ml of heptane was added sodium hydroxide (0.42 g, 0.011 mole) in 5 ml of water. The mixture was shaken until the acid dissolved. The water was then removed by distillation, the volume of the reaction mixture being reduced to 50 ml. To the reaction mixture was added 3-bromomethyl-2,4-difluoro[1,1'-biphenyl] (3.0 g, 0.011 mole) and 0.1 gram of 1,4-diazabicyclo[2.2.2]octane in 35 ml of acetonitrile. The mixture was heated under reflux for 3 hours. The solvent was then removed by evaporation under reduced pressure, and the residue was partitioned between water and diethyl ether. The ether phase was washed with two portions of aqueous 2% hydrochloric acid, two portions of water, two portions of aqueous 10% sodium carbonate, two portions of water and one portion of aqueous saturated sodium chloride solution in that order. The washed ethereal solution was dried over magnesium sulfate, and the ether was evaporated under reduced pressure. The oily residue was purified by column chromatography on silical gel, elution with hexane. This afforded (2,4-difluoro-[1,1'-biphenyl]-3-yl)methyl cis-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate (1.8 g), Example XIV in Table 1.

Workup

  1. dissolutiondissolved
  2. customThe water was then removed by distillation
  3. temperatureThe mixture was heated
  4. temperatureunder reflux for 3 hours
  5. customThe solvent was then removed by evaporation under reduced pressure
  6. customthe residue was partitioned between water and diethyl ether
  7. washThe ether phase was washed with two portions of aqueous 2% hydrochloric acid, two portions of water, two portions of aqueous 10% sodium carbonate, two portions of water and one portion of aqueous saturated sodium chloride solution in that order
  8. dry with materialThe washed ethereal solution was dried over magnesium sulfate
  9. customthe ether was evaporated under reduced pressure
  10. customThe oily residue was purified by column chromatography on silical gel, elution with hexane

Sources & evidence

ORD record
ord-5a151bd0c3e648d89f3b8c1c12708473
Source dataset
uspto-grants-1980_07
Patent number
US04214004

Reaction notes

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