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3-Methylpyridine → 2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]-8-methyl-4-oxo-4H-3,1-benzoxazine-6-carbonitrile

HRID 1178694
Notes
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Reaction equation

HRID 1178694 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:17]([C:19]1[CH:30]=[C:29]([CH3:31])[C:22]2[NH:23]C(=O)[O:25][C:26](=O)[C:21]=2[CH:20]=1)#[N:18].N1C=CC=C(C)C=1.CS(Cl)(=O)=O>C(#N)C.O>[Br:1][C:2]1[CH:6]=[C:5]([C:7]2[O:9][C:26](=[O:25])[C:21]3[CH:20]=[C:19]([C:17]#[N:18])[CH:30]=[C:29]([CH3:31])[C:22]=3[N:23]=2)[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 79703-MethylpyridineHCID 31297Methanesulfonyl chlorideHCID 115875353-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acidHCID 578871986-cyano-8-methyl-1H-benzo[d][1,3]oxazine-2,4-dione

Product 1

HCID 666945472-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]-8-methyl-4-oxo-4H-3,1-benzoxazine-6-carbonitrileYield 82%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
-5 °C

Procedure

A mixture of 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid (97.9% purity, 3.09 g, 10.0 mmol), 6-cyano-8-methyl-1H-benzo[d][1,3]oxazine-2,4-dione (96.3% purity, 2.10 g, 10.0 mmol) and 3-picoline (3.30 mL, 3.16 g, 34 mmol) in acetonitrlle (65 mL) was cooled to about −5° C. Then methanesulfonyl chloride (1.0 mL, 1.5 g, 13 mmol) in acetonitrile (3 mL) was added dropwise at −5 to 0° C. After 15 minutes at −5 to 0° C., the reaction mixture was heated to 50° C. for 4 hours. The reaction mixture was then cooled to room temperature, water (4 mL) was added dropwise, and the reaction mixture was stirred 15 minutes. The mixture was filtered, and the solids were washed sequentially with 4:1 acetonitrile-water (2×2 mL) and acetonitrile (3×2 mL), and dried under nitrogen to afford the title product as a pale green powder, 3.71 g (94.2% purity by HPLC, 82.0% yield calculated based on the purity), melting at 263-267° C.

Workup

  1. temperaturethe reaction mixture was heated to 50° C. for 4 hours
  2. temperatureThe reaction mixture was then cooled to room temperature
  3. filtrationThe mixture was filtered
  4. washthe solids were washed sequentially with 4:1 acetonitrile-water (2×2 mL) and acetonitrile (3×2 mL)
  5. customdried under nitrogen

Sources & evidence

ORD record
ord-f2a6c4c5037c4722b182d69effdff4b3
Source dataset
uspto-grants-2007_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07276601B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes