Sodium Iodide → 1-Bromo-7-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]heptane

HRID 1588145Notes

Reaction equation

HRID 1588145 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([O:9][CH2:10][O:11][CH3:12])[C:6]([O:13][CH3:14])=[CH:5][C:4]=1[O:15][CH2:16][O:17][CH3:18].C([Li])(CC)C.[Br:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31]Br.[I-].[Na+]>O1CCCC1.C1C=CC=CC=1.C(OCC)C.CN(C)P(=O)(N(C)C)N(C)C>[Br:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:5]1[C:4]([O:15][CH2:16][O:17][CH3:18])=[C:3]([O:2][CH3:1])[CH:8]=[C:7]([O:9][CH2:10][O:11][CH3:12])[C:6]=1[O:13][CH3:14]

Participants

8

Reactant 4

HCID 5238Sodium IodideHCID 783091,7-DibromoheptaneHCID 10061046HCID 10061046, compoundHCID 178418400CID 53628100

Product 1

HCID 100030781-Bromo-7-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]heptaneYield 72%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 12679HexamethylphosphoramideSolventHCID 22174802Benzene etherSolvent

Conditions

Temperature
-78 °C

Procedure

5 Grams of 1,4-dimethoxy-2,5-bis(methoxymethoxy)benzene was dissolved in 140 ml of tetrahydrofuran, then the solution was cooled to -78° C. under argon gas stream condition, in a dry ice-acetone bath. Then 18 ml of sec-butyllithium (1.3 mole cyclohexane solution) was added dropwise thereto and stirred for 30 minutes. To the reaction mixture was added dropwise 10 g (6.7 ml) of 1,7-dibromoheptane, next 6 g of sodium iodide and 10 ml of hexamethylphosphoric triamide were added to the reaction mixture. The cooling bath was removed from the reaction apparatus, and the reaction mixture was stirred at room temperature for 12-14 hours. Tetrahydrofuran was removed by evaporation under reduced pressure, the residue obtained was dissolved in 500 ml of a mixed solvent benzene-diethyl ether (1:1). The organic layer was washed with 100 ml of water in 4 times, and with 100 ml of saturated sodium chloride aqueous solution in 4 times, and dried over anhydrous magnesium sulfate. After the removal of the solvent by evaporating under reduced pressure, the residue obtained was treated by means of a silica gel column chromatography (diameter 5 cm×length 30 cm, adsorbent: "Wakol-C200") and developed and eluted with 20%-ethyl acetate-n-hexane to obtain 6.06 g (yield=72%) of 1-bromo-7-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]heptane. Colorless oily substance.

Workup

  1. additionwere added to the reaction mixture
  2. customThe cooling bath was removed from the reaction apparatus
  3. stirringthe reaction mixture was stirred at room temperature for 12-14 hours
  4. customTetrahydrofuran was removed by evaporation under reduced pressure
  5. customthe residue obtained
  6. washThe organic layer was washed with 100 ml of water in 4 times
  7. dry with materialwith 100 ml of saturated sodium chloride aqueous solution in 4 times, and dried over anhydrous magnesium sulfate
  8. customAfter the removal of the solvent
  9. customby evaporating under reduced pressure
  10. customthe residue obtained
  11. additionwas treated by means of a silica gel column chromatography (diameter 5 cm×length 30 cm, adsorbent: "Wakol-C200")
  12. washeluted with 20%-ethyl acetate-n-hexane

Sources & evidence

ORD record
ord-9791e426b5be44d599464f02b83d08b2
Source dataset
uspto-grants-1993_06
Patent number
US05220042

Reaction notes

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