N,N'-Dimethylethylenediamine → HCID 70980214, compound

HRID 1749080Notes

Reaction equation

HRID 1749080 reaction equation
[CH3:1][O:2][C:3]1[CH:21]=[C:20]([O:22][CH3:23])[CH:19]=[CH:18][C:4]=1[CH2:5][NH:6][C:7]1[CH:8]=[CH:9][C:10]2[NH:15][C:14](=[O:16])[CH2:13][O:12][C:11]=2[N:17]=1.I[C:25]1[CH:30]=[CH:29][C:28]([Cl:31])=[CH:27][CH:26]=1.CNCCNC.[F-].[Cs+]>CC#N.[Cu]I>[Cl:31][C:28]1[CH:29]=[CH:30][C:25]([N:15]2[C:14](=[O:16])[CH2:13][O:12][C:11]3[N:17]=[C:7]([NH:6][CH2:5][C:4]4[CH:18]=[CH:19][C:20]([O:22][CH3:23])=[CH:21][C:3]=4[O:2][CH3:1])[CH:8]=[CH:9][C:10]2=3)=[CH:26][CH:27]=1

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 125101-Chloro-4-iodobenzeneHCID 25953Cesium fluorideHCID 70980205HCID 70980205, compound

Product 1

HCID 70980214HCID 70980214, compoundYield 87.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

6-(2,4-Dimethoxy-benzylamino)-1H-pyrido[2,3-b][1,4]oxazin-2-one (3.76 g, 11.9 mmol), 4-iodo-chlorobenzene (3.4 g, 14.3 mmol), N,N′-dimethylethylenediamine (1.27 mL, 11.9 mmol), and CsF (4.5 g, 29.7 mmol) were suspended in MeCN (100 mL) and sparged with nitrogen. CuI (238 mg, 1.19 mmol) was then added and the mixture stirred at 80° C. for 16 hours. The mixture was allowed to cool and was then concentrated in vacuo. The residue was partitioned between EtOAc and aqueous potassium hydrogenphosphate solution. The EtOAc layer was then washed with saturated aqueous ammonium chloride solution, brine, dried over MgSO4, filtered and then concentrated in vacuo. The residue was purified using SiO2 chromatography (20-70% EtOAc/Petrol) to give 1-(4-chloro-phenyl)-6-(2,4-dimethoxybenzylamino)-1H-pyrido[2,3-b][1,4]oxazin-2-one (4.42 g) as a pale yellow crystalline solid. MS: [M+H]+=426.

Workup

  1. customsparged with nitrogen
  2. temperatureto cool
  3. concentrationwas then concentrated in vacuo
  4. customThe residue was partitioned between EtOAc and aqueous potassium hydrogenphosphate solution
  5. washThe EtOAc layer was then washed with saturated aqueous ammonium chloride solution, brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified

Sources & evidence

ORD record
ord-440eb019f01946db917527e87d38a543
Source dataset
uspto-grants-2015_10
Patent number
US09155743B2

Reaction notes

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