Carbon Tetrachloride → HCID 22320175, compound

HRID 497969Notes

Reaction equation

HRID 497969 reaction equation
[NH2:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[C:3]=1[C:4]([OH:6])=[O:5].[CH2:12]=[C:13]1[O:17][C:15](=O)[CH2:14]1.C(Cl)(Cl)(Cl)Cl.C(OC(=O)C)(=O)C>CC(C)=O>[CH3:11][C:7]1[C:3]2[C:4](=[O:6])[O:5][C:15]([CH2:14][C:13](=[O:17])[CH3:12])=[N:1][C:2]=2[CH:10]=[CH:9][CH:8]=1

Participants

6

Reactant 4

HCID 5943Carbon TetrachlorideHCID 7918Acetic AnhydrideHCID 12661DiketeneHCID 1512106-Methylanthranilic acid

Product 1

HCID 22320175HCID 22320175, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of 2-amino-6-methylbenzoic acid (20 g, 0.132 mol) in acetone (100 mL), diketene (15.3 mL, 0.198 mol) was added dropwise at room temperature, and the mixture was stirred overnight at room temperature. The reaction solvent and excess diketene was evaporated under reduced pressure. To the residue, carbon tetrachloride (80 mL) and subsequently acetic anhydride (27 g, 0.265 mol) were added, and the mixture was heated under reflux for 3 hours. The reaction solvent and excess acetic anhydride were evaporated and concentrated under reduced pressure, and the resulting powder was collected by filtration and washed with diethylether to give crude 5-methyl-2-(2-oxopropyl)-4H-3,1-benzoxazin-4-one (13.75 g, 48% yield). A solution of the compound (12.99 g, 0.06 mol) and 2-hydrazinopyridine (7.18 g, 0.066 mol) in ethanol (100 mL) was heated under reflux for 1 hour. The reaction solution was allowed to cool to room temperature, and the reaction solvent was evaporated and concentrated under reduced pressure. A solution of the residue in phosphorous oxychloride (45.8 g, 0.3 mol) was heated and stirred at 100° C. for 1 hour. After the reaction solution was cooled to room temperature, the reaction solvent was evaporated and concentrated under reduced pressure, and the residue was poured into iced water, which was made basic by the addition of a sodium hydroxide solution, and organic matter was extracted with chloroform. The extract was washed with saturated brine and water, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by silica gel column chromatography (ethyl acetate:methanol=98:2) to give the title compound (4.4 g, 24% yield).

Workup

  1. customThe reaction solvent and excess diketene was evaporated under reduced pressure
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for 3 hours
  4. customThe reaction solvent and excess acetic anhydride were evaporated
  5. concentrationconcentrated under reduced pressure
  6. filtrationthe resulting powder was collected by filtration
  7. washwashed with diethylether

Sources & evidence

ORD record
ord-4dd46bfcc6834644bd61d81a7fbdd303
Source dataset
uspto-grants-2005_09
Patent number
US06949648B2

Reaction notes

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