Acetanilide → HCID 11229794, compound

HRID 1028368Notes

Reaction equation

HRID 1028368 reaction equation
Br[C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[CH:4][C:3]=1[CH3:11].[C:12]1([NH:18][C:19](=O)[CH3:20])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=CC=1.[Cu]I.[Fe]>[CH3:20][C:19]1[N:18]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:2]2[C:3]([CH3:11])=[CH:4][CH:5]=[CH:6][C:7]=2[N:8]=1

Participants

7

Reactant 3

HCID 904AcetanilideHCID 62657Potassium Phosphate, TribasicHCID 2318282-Bromo-3-nitrotoluene

Product 1

HCID 11229794HCID 11229794, compoundYield 41.4%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A reaction tube containing 2-Bromo-3-nitrotoluene (108 mg, 0.5 mmol), N-phenylacetamide (81 mg, 0.6 mmol) and trans-1,2-cyclohexanodiamine (6 μL, 0.05 mmol), potassium phosphate (212 mg, 1 mmol), copper(I) iodide (9.5 mg, 0.05 mmol) in dry toluene (3 mL) was purged with dry argon for 3 min. Then the mixture was heated at 100° C. for 18 h. After cooling, the reaction was hydrolyzed with 3 mL of water and filtered through a Varian cartridge Chem Elut 12198007, rinsing with ethyl acetate. The crude mixture was dissolved in 10 mL of glacial acetic acid and refluxed for 30 min in the presence of iron powder (279 mg, 5 mmol). The acid was removed under reduced pressure and the residue was suspended in saturated sodium bicarbonate solution and extracted with ethyl acetate. The obtained crude was purified by preparative HPLC, affording the title compound as a pale yellow solid (46 mg, 41%). mp 107-109° C. NMR (DMSO) δ 1.83 (s, 3 H), 2.34 (s, 3 H), 7.02 (d, J=7.8 Hz, 1 H), 7.22 (t, J=7.8 Hz, 1 H), 7.53 (d, J=7.8 Hz, 1 H), 7.55-7.63 (m, 5 H); 13C NMR δ 13.3, 17.1, 114.8, 121.7, 123.0, 125.5, 128.6, 129.4, 129.9, 136.0, 144.5, 151.2, 157.2. HRMS (FAB): cal. for C15H15N2 [M+H+]: 223.1235; found: 223.1231.

Workup

  1. customwas purged with dry argon for 3 min
  2. temperatureAfter cooling
  3. filtrationfiltered through a Varian cartridge Chem Elut 12198007
  4. washrinsing with ethyl acetate
  5. dissolutionThe crude mixture was dissolved in 10 mL of glacial acetic acid
  6. customThe acid was removed under reduced pressure
  7. extractionextracted with ethyl acetate
  8. customThe obtained crude
  9. customwas purified by preparative HPLC

Sources & evidence

ORD record
ord-4e264417b609469b8d6bf3526c44260b
Source dataset
uspto-grants-2014_05
Patent number
US08735586B2

Reaction notes

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