1-Bromo-4-iodobenzene → HCID 57471568, compound

HRID 2100217Notes

Reaction equation

HRID 2100217 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.[CH:9]#[C:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].C(OP([O-])OCC)C>[Pd](Cl)Cl.[Cu]I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:9]([C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1)#[C:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]

Participants

7

Reactant 3

HCID 115221-Bromo-4-iodobenzene3×HCID 129971-Decyne3×HCID 3780918Diethylphosphite

Product 1

HCID 57471568HCID 57471568, compoundYield 98%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 24290Palladium ChlorideCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Conditions

Temperature
55 °C

Procedure

A synthesis protocol was designed to test the modular approach to synthesis of the conductive compositions of the present invention (FIG. 3). The model conductive composition 5b was prepared using 1-iodo-4-bromobenzene as a precursor to the body structure, 1-decyne as the tail group moiety, and diethylphosphite as the head group moiety. To a 500 mL schlenk flask with egg-shaped stirbar under argon, palladium dichloride (1.0 mmol, 0.177 g), copper(I) iodide (2.36 mmol, 0.450 g), and triphenylphosphine (2.0 mmol, 0.525 g) were added in a glovebox under argon. On a schlenk line, 1-iodo-4-bromo-benzene (50 mmol, 14.15 g, compound 1) was added, the vessel was stoppered, and the flask was placed under vacuum and backfilled with argon (3×). The flask was fitted with a septum under positive argon pressure and degassed diisopropyl amine (100 mL) was added via cannula under positive argon pressure with stirring. Next, degassed 1-decyne (50 mmol, 6.91 g, compound 2) was added via syringe under argon. Finally, dry, degassed tetrahydrofuran was added via cannula transfer under argon, the vessel sealed with a glass stopper and allowed to stir at ambient for 16 h followed by heating to 55° C. for one hour. After cooling to ambient temperature, the solvent was removed by roto-evaporation, the residue dissolved in diethyl ether (200 mL) and washed with ammonium chloride (sat. aqueous, 3×100 mL). The organic layer was separated and dried over magnesium sulfate, filtered and the solvent removed by roto-evaporation. The resulting oil was dissolved in hexanes and plugged through silica gel. Removal of the solvent resulted in a yellow oil of 4-decynyl-bromo-benzene 3 (14.34 g, 98% yield).

Workup

  1. customto synthesis of the conductive compositions of the present invention (FIG. 3)
  2. customThe flask was fitted with a septum under positive argon pressure
  3. customdegassed diisopropyl amine (100 mL)
  4. additionwas added via cannula under positive argon pressure
  5. additionwas added via syringe under argon
  6. customFinally, dry
  7. customdegassed tetrahydrofuran
  8. additionwas added via cannula transfer under argon
  9. customthe vessel sealed with a glass stopper
  10. stirringto stir at ambient for 16 h
  11. temperatureAfter cooling to ambient temperature
  12. customthe solvent was removed by roto-evaporation
  13. dissolutionthe residue dissolved in diethyl ether (200 mL)
  14. washwashed with ammonium chloride (sat. aqueous, 3×100 mL)
  15. customThe organic layer was separated
  16. dry with materialdried over magnesium sulfate
  17. filtrationfiltered
  18. customthe solvent removed by roto-evaporation
  19. dissolutionThe resulting oil was dissolved in hexanes
  20. customRemoval of the solvent

Sources & evidence

ORD record
ord-a9a05e1554894aa688bdfbfd99222b91
Source dataset
uspto-grants-2009_08
Patent number
US07572393B2

Reaction notes

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