Acetonitrile → 2-(3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-6-chloro-8-methyl-4H-benzo[d][1,3]oxazin-4-one

HRID 251905

Reaction equation

HRID 251905 reaction equation
[Br:1][C:2]1[CH:6]=[C:5]([C:7]([OH:9])=O)[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1.C(#N)C.CS(Cl)(=O)=O.[NH2:25][C:26]1[C:34]([CH3:35])=[CH:33][C:32]([Cl:36])=[CH:31][C:27]=1[C:28](O)=[O:29]>C(N(CC)CC)C>[Br:1][C:2]1[CH:6]=[C:5]([C:7]2[O:9][C:28](=[O:29])[C:27]3[CH:31]=[C:32]([Cl:36])[CH:33]=[C:34]([CH3:35])[C:26]=3[N:25]=2)[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 31297Methanesulfonyl chloride2×HCID 115875353-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acidHCID 116440442-Amino-5-chloro-3-methylbenzoic acid

Product 1

HCID 102533072-(3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-6-chloro-8-methyl-4H-benzo[d][1,3]oxazin-4-oneYield 14.9%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent2×

Procedure

To a mixture of 0.44 g of 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid, 6 ml of acetonitrile and 0.20 g of triethylamine was added 0.125 ml of methanesulfonyl chloride. After the resulting mixture was stirred at room temperature for 15 minutes, 0.27 g of 2-amino-5-chloro-3-methylbenzoic acid was added and the mixture was stirred at room temperature for 20 minutes. To the mixture, 0.40 ml of triethylamine was added. After the mixture was stirred at room temperature for 20 minutes, 0.13 ml of methanesulfonyl chloride was added and the mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered and the filter cake was washed with methyl tert-butyl ether. The resulting filter cake was dissolved in ethyl acetate, washed successively with water and an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.098 g of 2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one. In addition, the filtrate was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to obtain 0.093 g of 2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one of the formula:

Workup

  1. stirringthe mixture was stirred at room temperature for 20 minutes
  2. stirringAfter the mixture was stirred at room temperature for 20 minutes
  3. stirringthe mixture was stirred at room temperature for 16 hours
  4. filtrationThe reaction mixture was filtered
  5. washthe filter cake was washed with methyl tert-butyl ether
  6. filtrationThe resulting filter cake
  7. dissolutionwas dissolved in ethyl acetate
  8. washwashed successively with water
  9. dry with materialan aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-780960cf4f784562b8e6dbf60d402b9a
Source dataset
uspto-grants-2011_01
Patent number
US07867949B2

Linked notes

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