Triphenylphosphine → HCID 11587463, compound

HRID 1937758Notes

Reaction equation

HRID 1937758 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[O:10])[O:8][C:6](=[O:7])[C:5]2=[CH:11][CH:12]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.C1C=CC=CC=1.[C:45]([C:47]1[C:56]2[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=2)[CH:50]=[CH:49][CH:48]=1)#[CH:46]>C1C=CC=CC=1.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>[C:47]1([C:45]#[C:46][C:2]2[CH:3]=[C:4]3[C:9](=[O:10])[O:8][C:6](=[O:7])[C:5]3=[CH:11][CH:12]=2)[C:56]2[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=2)[CH:50]=[CH:49][CH:48]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 665904-Bromophthalic anhydrideHCID 1233571-EthynylnaphthaleneHCID 23508724HCID 23508724, compound

Product 1

HCID 11587463HCID 11587463, compoundYield 36.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 241BenzeneSolvent

Procedure

To a solution of 4-bromophthalic anhydride (4.54 g, 20.0 mmol), triphenylphosphine (520 mg, 2.0 mmol), cuprous iodide (190 mg, 1.0 mmol), bis(triphenylphosphine)palladium dichloride (280 mg, 0.4 mmol) in 2:1 triethylamine/benzene (75 mL) was added 1-ethynylnaphthalene (4.94 g, 32.5 mmol) in benzene (25 mL) by cannula transfer and the mixture was heated at reflux for 2 h. The cooled solution was filtered and the precipitate was added to water (150 mL), filtered and washed with water (3×5 mL). The crude yellow solid was recrystallized from toluene, filtered and washed with hexanes (3×5 mL). The product was then added to 0.15 M NaHCO3(aq), stirred vigorously for 1 h and filtered. The yellow solid was dried at reduced pressure to constant weight to yield 4-(1-naphthylethynyl)phthalic anhydride (2.16 g, 36.2%). mp 220-222° C.; 1H NMR (CDCl3, 300 MHz) δ7.48-7.68 (m, 3H), 7.82 (d, J=7.2 Hz, 1H), δ7.92 (t, J=8.1 Hz, 2H), δ7.99 (d, J=7.8 Hz, 1H), δ8.07 (d, J=8.0 Hz, 1H), δ8.20 (s, 1H), δ8.35 (d, J8.1 Hz, 1H); 13 C NMR (CDCl3, 300 MHz) δ92.0, 94.6, 119.3, 125.5, 125.8, 125.9, 127.0, 127.6, 128.4, 128.8, 129.7, 130.6, 131.7, 131.9, 132.2, 133.3, 133.4, 138.7, 162.3, 162.3. Anal. Calcd for C20H10O3: C, 80.53;H, 3.38. Found: C, 80.37;H, 3.36.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 2 h
  3. filtrationThe cooled solution was filtered
  4. additionthe precipitate was added to water (150 mL)
  5. filtrationfiltered
  6. washwashed with water (3×5 mL)
  7. customThe crude yellow solid was recrystallized from toluene
  8. filtrationfiltered
  9. washwashed with hexanes (3×5 mL)
  10. additionThe product was then added to 0.15 M NaHCO3(aq)
  11. filtrationfiltered
  12. customThe yellow solid was dried at reduced pressure to constant weight

Sources & evidence

ORD record
ord-89829f890447404eb4c4616109c05c99
Source dataset
uspto-grants-2002_05
Patent number
US06395907B1

Reaction notes

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