Hydrochloric Acid → 2-(2-Diphenylmethylaminoanilin-5-yl)benzoxazole

HRID 74271Notes

Reaction equation

HRID 74271 reaction equation
F[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[O:9][C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[N:12]=2)=[CH:4][C:3]=1[N+:17]([O-])=O.[C:20]1([CH:26]([NH2:33])[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C(N(CC)CC)C.Cl>C(#N)C.O1CCCC1.C(OCC)C.[Fe].C(O)(=O)C.O>[C:20]1([CH:26]([NH:33][C:2]2[CH:7]=[CH:6][C:5]([C:8]3[O:9][C:10]4[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=4[N:12]=3)=[CH:4][C:3]=2[NH2:17])[C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

11

Reactant 4

HCID 313Hydrochloric AcidHCID 7036BenzhydrylamineHCID 8471TriethylamineHCID 219909702-(4-Fluoro-3-nitrophenyl)benzoxazole

Product 1

HCID 674980322-(2-Diphenylmethylaminoanilin-5-yl)benzoxazoleYield 20.2%

Reagents, catalysts & solvents 6

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of 2-(4-fluoro-3-nitrophenyl)benzoxazole (see Working Example 15-2) (0.50 g, 1.9 mmol) in acetonitrile (10 mL) was added diphenylmethylamine (0.39 g, 2.1 mmol) and triethylamine (0.29 g, 2.4 mmol), and this was heated to reflux for 10 hours. After the reaction was complete, this was cooled to room temperature, water was added, and the precipitated crystals were filtered, washed with water and then dried. To the residue obtained was added iron powder (0.33 g, 5.8 mmol), and aqueous acetic acid (50 mL), and this was heated to reflux for 2 hours. After cooling the reaction solution, filtration through Celite and concentration, the residue obtained was purified by silica gel column chromatography. The oil obtained was dissolved in tetrahydrofuran (3 mL), and to this was added a 1M solution of hydrogen chloride in diethyl ether (1 mL). The precipitated crystals were filtered, and after washing with tetrahydrofuran, they were dried to yield the title compound (0.15 g, 20% yield) as a light brown solid.

Workup

  1. temperaturethis was heated
  2. temperatureto reflux for 10 hours
  3. filtrationthe precipitated crystals were filtered
  4. washwashed with water
  5. customdried
  6. customTo the residue obtained
  7. temperaturethis was heated
  8. temperatureto reflux for 2 hours
  9. temperatureAfter cooling
  10. filtrationthe reaction solution, filtration
  11. concentrationthrough Celite and concentration
  12. customthe residue obtained
  13. customwas purified by silica gel column chromatography
  14. customThe oil obtained
  15. filtrationThe precipitated crystals were filtered
  16. washafter washing with tetrahydrofuran, they
  17. customwere dried

Sources & evidence

ORD record
ord-5ec0fe8685bf42c8bac102a8755bcb9f
Source dataset
uspto-grants-2014_09
Patent number
US08829035B2

Reaction notes

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