N,N'-Dimethylethylenediamine → HCID 66790319, compound

HRID 1929442Notes

Reaction equation

HRID 1929442 reaction equation
[NH2:1][C:2]1[CH:14]=[CH:13][C:5]2[NH:6][C:7](=[O:12])[C:8]([CH3:11])([CH3:10])[O:9][C:4]=2[CH:3]=1.Br[C:16]1[CH:17]=[CH:18][C:19]([Cl:23])=[C:20]([CH3:22])[CH:21]=1.C(=O)([O-])[O-].[K+].[K+].CNCCNC>[Cu]I.O.C1(C)C=CC=CC=1>[NH2:1][C:2]1[CH:14]=[CH:13][C:5]2[N:6]([C:16]3[CH:17]=[CH:18][C:19]([Cl:23])=[C:20]([CH3:22])[CH:21]=3)[C:7](=[O:12])[C:8]([CH3:10])([CH3:11])[O:9][C:4]=2[CH:3]=1

Participants

8

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 6098995-Bromo-2-chlorotolueneHCID 136655467-Amino-2,2-dimethyl-2H-1,4-benzoxazin-3(4H)-one

Product 1

HCID 66790319HCID 66790319, compoundYield 39.6%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 7-amino-2,2-dimethyl-2H-1,4-benzoxazin-3(4H)-one (compound obtained in Reference Example 3(1); 150 mg), 5-bromo-2-chlorotoluene (321 mg), copper(I) iodide (37 mg), potassium carbonate (216 mg), N,N′-dimethylethylenediamine (40 μL) and toluene (8 mL) was heated at 110° C. overnight under argon atmosphere. After cooling, to the reaction mixture was added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel (solvent; n-hexane/ethyl acetate=4/1→1/1) to give 7-amino-4-(4-chloro-3-methylphenyl)-2,2-dimethyl-2H-1,4-benzoxazin-3(4H)-one (98 mg) as a pale orange powder.

Workup

  1. temperatureAfter cooling, to the reaction mixture
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by column chromatography on silica gel (solvent; n-hexane/ethyl acetate=4/1→1/1)

Sources & evidence

ORD record
ord-abc09fe762814c80b2fea48782bc874c
Source dataset
uspto-grants-2012_05
Patent number
US08188073B2

Reaction notes

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