Iodine → 8-(3-Fluoro-4-iodophenyl)-1,4-dioxaspiro[4.5]decane

HRID 1106376Notes

Reaction equation

HRID 1106376 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:8]2[CH2:17][CH2:16][C:11]3([O:15][CH2:14][CH2:13][O:12]3)[CH2:10][CH2:9]2)[CH:5]=[CH:6][CH:7]=1.CC(C)([O-])C.[K+].C([Li])CCC.[I:29]I.OS([O-])=O.[Na+]>C1COCC1.CCCCCC.O>[F:1][C:2]1[CH:3]=[C:4]([CH:8]2[CH2:17][CH2:16][C:11]3([O:12][CH2:13][CH2:14][O:15]3)[CH2:10][CH2:9]2)[CH:5]=[CH:6][C:7]=1[I:29]

Participants

9

Reactant 5

HCID 807IodineHCID 187879268-(3-Fluorophenyl)-1,4-dioxaspiro[4.5]decaneHCID 23665647Potassium tert-butoxideHCID 23665763Sodium BisulfiteHCID 178418339Butyllithium

Product 1

HCID 187879248-(3-Fluoro-4-iodophenyl)-1,4-dioxaspiro[4.5]decane

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-100 °C

Procedure

121.0 g of 8-(3-fluorophenyl)-1,4-dioxaspiro[4.5]decane and 61.7 g of potassium tert-butoxide in 700 ml of THF were introduced into the apparatus and cooled to -100° C. 335.6 ml of a 15% solution of butyllithium in hexane were then added dropwise with stirring at -100° C., and the mixture was stirred at the same temperature for a further 30 minutes. A solution of 139.6 g of iodine in 300 ml of THF was then added dropwise with stirring at from -90 to -100° C., and the mixture was stirred for a further 30 minutes, allowed to warm to -25° C. and hydrolysed using 500 ml of water. 37% NaHSO3 solution was then added until the mixture became colorless. The organic phase was then separated off, and the aqueous phase was extracted with 2×200 ml of methyl tert-butyl ether. The combined organic extracts were washed once with 200 ml of sodium chloride solution, dried using sodium sulfate, filtered and evaporated to a residue, giving 8-(3-fluoro-4-iodophenyl)-1,4-dioxaspiro[4.5]decane.

Workup

  1. stirringthe mixture was stirred at the same temperature for a further 30 minutes
  2. stirringwith stirring at from -90 to -100° C.
  3. stirringthe mixture was stirred for a further 30 minutes
  4. temperatureto warm to -25° C.
  5. customThe organic phase was then separated off
  6. extractionthe aqueous phase was extracted with 2×200 ml of methyl tert-butyl ether
  7. washThe combined organic extracts were washed once with 200 ml of sodium chloride solution
  8. customdried
  9. filtrationfiltered
  10. customevaporated to a residue

Sources & evidence

ORD record
ord-30dc6c069f144fdeb14f5fffdde64149
Source dataset
uspto-grants-2000_05
Patent number
US06057006

Reaction notes

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