Benzoxazole → HCID 86755592, compound

HRID 1871166Notes

Reaction equation

HRID 1871166 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:7]([C:9]1([CH2:36][CH3:37])[C:21]2[CH:20]=[C:19]([N:22]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[CH:18]=[CH:17][C:16]=2[C:15]2[C:10]1=[CH:11][C:12](Br)=[CH:13][CH:14]=2)[CH3:8].O1C2C=CC=CC=2N=C1.[I-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:67]1([C:73]2O[C:75]3[CH:81]=[CH:80][CH:79]=[CH:78][C:76]=3[N:77]=2)C=CC=CC=1>C1(C)C=CC=CC=1.[Cu].C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C=O)C>[CH2:7]([C:9]1([CH2:36][CH3:37])[C:21]2[CH:20]=[C:19]([N:22]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[CH:18]=[CH:17][C:16]=2[C:15]2[C:10]1=[CH:11][C:12]([C:73]1[NH:77][C:76]3[CH:75]=[CH:81][CH:80]=[CH:79][C:78]=3[CH:67]=1)=[CH:13][CH:14]=2)[CH3:8]

Participants

11

Reactant 6

HCID 9228BenzoxazoleHCID 10796Cesium carbonateHCID 11776TriphenylphosphineHCID 30165Iodide IonHCID 70030Benzoxazole, 2-phenyl-HCID 18694816HCID 18694816, compound

Product 1

HCID 86755592HCID 86755592, compoundYield 65%

Reagents, catalysts & solvents 4

HCID 23978CopperCatalystHCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of cesium carbonate (6.5 g. 20 mmol, dried at 190° C. under 1 mm), 9,9-diethyl-N,N-diphenyl-7-bromo-2-fluoreneamine (7.4 g., 16 mmol), benzoxazole (2.4 g., 20 mmol), copper(l) iodide (0.38 g., 2 mmol), palladium (II) acetate (0.075 g., 0.334 mmol), triphenyl phosphine (0.15 g., 0.6 mmol) and DMF (30 ml) was kept at 115° C. for 18 hours under an atmosphere of nitrogen, then cooled, diluted with toluene and filtered. The filtrate was washed with water, dried and concentrated. The residue was chromatographed on alumina. Earlier fractions gave 0.25 g., m.p. 102-104° C., identified as 2-phenyl benzoxazole (m/z 195). Elution with heptane-toluene (3:1), followed by crystallization, gave 5.14 g. (65% yield) of bright yellow crystals, m.p. 193-194° C. A sample for analysis was obtained by sublimation under 0.5 mm vacuum at a bath temperature of 210° C. Mass Spec: mlz 506 (M+). Analysis: Calculated for C36H30N2O: C, 85.34; H, 5.97; N, 5.53. Found: C, 85.25; H, 5.97; N, 5.55.

Workup

  1. temperaturecooled
  2. filtrationfiltered
  3. washThe filtrate was washed with water
  4. customdried
  5. concentrationconcentrated
  6. customThe residue was chromatographed on alumina
  7. customEarlier fractions gave 0.25 g
  8. washElution with heptane-toluene (3:1)
  9. customfollowed by crystallization
  10. customgave 5.14 g

Sources & evidence

ORD record
ord-284b77fb431a421fa620db81bb87b670
Source dataset
uspto-grants-2000_08
Patent number
US06100405

Reaction notes

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