Iodine → HCID 18183624, compound

HRID 1429278Notes

Reaction equation

HRID 1429278 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([C:9]2[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][CH3:17])=[CH:11][CH:10]=2)[CH:5]=[C:6]([F:8])[CH:7]=1.C1COCC1.C([Li])CCC.[I:28]I>C1(C)C=CC=CC=1>[F:1][C:2]1[CH:3]=[C:4]([C:9]2[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][CH3:17])=[CH:11][CH:10]=2)[CH:5]=[C:6]([F:8])[C:7]=1[I:28]

Participants

6

Reactant 4

HCID 807IodineHCID 8028Tetrahydrofuran2×HCID 156387533,5-Difluoro-4'-propyl-1,1'-biphenylHCID 178418339Butyllithium

Product 1

HCID 18183624HCID 18183624, compoundYield 77.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a reaction vessel under a nitrogen atmosphere, 3,5-difluoro-4′-propylbiphenyl (T-4) (18.0 g) and THF (200 ml) were added, and cooling was carried out to −74° C. Thereto, a n-butyllithium (1.57 M) n-hexane solution (56.4 ml) was added dropwise in a temperature range of −74° C. to −70° C., and stirring was carried out for another 1 hour. Subsequently, a THF (150 ml) solution of iodine (24.6 g) was added dropwise in a temperature range of −75° C. to −70° C., and stirring was carried out for 6 hours while returning to room temperature. The resultant reaction mixture was poured into ice water (400 ml), and mixing was carried out. Toluene (300 ml) was added to separate layers into an organic layer and an aqueous layer, and an extraction operation was performed. The resultant organic layer was sequentially washed with an aqueous solution of sodium thiosulfate and water, and drying over anhydrous magnesium sulfate was carried out. The resultant solution was concentrated under reduced pressure, and a residue was purified by means of column chromatography (silica gel; heptane), and further purified by recrystallization from Solmix A-11, and thus 3,5-difluoro-4-iodo-4′-propylbiphenyl (T-5) (21.4 g) was obtained. The yield based on compound (T-4) was 77%.

Workup

  1. temperaturecooling
  2. customwas carried out to −74° C
  3. stirringstirring
  4. waitwas carried out for 6 hours
  5. customwhile returning to room temperature
  6. customThe resultant reaction mixture
  7. additionmixing
  8. customto separate layers into an organic layer
  9. washThe resultant organic layer was sequentially washed with an aqueous solution of sodium thiosulfate and water
  10. dry with materialdrying over anhydrous magnesium sulfate
  11. concentrationThe resultant solution was concentrated under reduced pressure
  12. customa residue was purified by means of column chromatography (silica gel; heptane)
  13. customfurther purified by recrystallization from Solmix A-11

Sources & evidence

ORD record
ord-7ec49470d20f42418fdb239725c1becd
Source dataset
uspto-grants-2015_01
Patent number
US08940185B2

Reaction notes

Loading…