Triphenylphosphine → Silane, (9-anthracenylethynyl)trimethyl-

HRID 1937759Notes

Reaction equation

HRID 1937759 reaction equation
Br[C:2]1[C:3]2[C:8]([CH:9]=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[CH:11]3)=[CH:7][CH:6]=[CH:5][CH:4]=2.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.C1C=CC=CC=1.[CH3:48][Si:49]([C:52]#[CH:53])([CH3:51])[CH3:50]>C(OCC)C.[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:14]1[C:15]2[C:10](=[CH:9][C:8]3[C:3]([C:2]=2[C:53]#[C:52][Si:49]([CH3:51])([CH3:50])[CH3:48])=[CH:4][CH:5]=[CH:6][CH:7]=3)[CH:11]=[CH:12][CH:13]=1

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 740629-BromoanthraceneHCID 23508724HCID 23508724, compound

Product 1

HCID 10978683Silane, (9-anthracenylethynyl)trimethyl-

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolvent

Procedure

To a solution of 9-bromoanthracene (1.35 g, 5.25 mmol), triphenylphosphine (138 mg, 0.53 mmol), copper iodide (50 mg, 0.26 mmol), and bis(triphenylphosphine)palladium dichloride (74 mg, 0.11 mmol) in 1:1 triethylamine/benzene (35 mL) was added trimethylsilylacetylene (1.11 mL, 7.85 mmol) and the solution was heated at reflux 1 h. The cooled solution was diluted with ethyl ether (100 mL) and filtered. The organic was washed with H2O (3×100 mL), dried over Na2SO4, and filtered. Solvents were removed under reduced pressure to yield crude 9-anthracenyltrimethylsilylacetylene. The crude oil was dissolved in methanol (150 mL) and 3.5 M KOH(aq) (2 mL) was added and stirred 1 h. The reaction was quenched with H2O (150 mL) and the product was extracted with hexane (3×100 mL). The combined organic layers were dried over Na2SO4, filtered, and solvents were removed under reduced pressure to yield crude 9-anthracenylacetylene. The crude oil was dissolved in benzene (10 mL) and added to a solution of 4-bromophthalic anhydride (0.908 g, 4.0 mmol), triphenylphosphine (105 mg, 0.40 mmol), copper iodide (39 mg, 0.20 mmol), and bis(triphenylphosphine)palladium dichloride (56 mg, 0.08 mmol) in 2:1 triethylamine/benzene (30 mL) by cannula transfer and heated at reflux 1 h. The cooled solution was filtered and the precipitate was diluted with 0.5 M NaHCO3(aq) (100 mL) and stirred vigorously 1 h. The mixture was diluted with acetone (50 mL) and filtered. The crude product was recrystallized from toluene and dried under reduced pressure to yield 4-(9-anthracenylethynyl)phthalic anhydride (1.03 g, 73.8%) as a deep red solid. 1H NMR (DMSO-d6, 300 MHz) δ7.77 (t, J=7.1 Hz, 2H), 7.88 (t, J=7.2 Hz, 2H), 8.29-8.34 (m, 3H), 8.56 (d, 7.8 Hz, 1H), 8.75 (s, 1H), 8.83 (d, J=8.7 Hz, 2H), 8.92 (s, 1H).

Workup

  1. temperaturethe solution was heated
  2. temperatureat reflux 1 h
  3. filtrationfiltered
  4. washThe organic was washed with H2O (3×100 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customSolvents were removed under reduced pressure

Sources & evidence

ORD record
ord-79e03f56ffde4083b3249f0403fe829c
Source dataset
uspto-grants-2002_05
Patent number
US06395907B1

Reaction notes

Loading…