Diketene → 4-Methyl-6-chloro-7-aminoquinolone

HRID 857430

Reaction equation

HRID 857430 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[CH:4][C:3]=1[NH2:9].[CH2:10]=[C:11]1O[C:13](=[O:14])[CH2:12]1>C1(C)C=CC=CC=1>[CH3:10][C:11]1[C:6]2[C:5](=[CH:4][C:3]([NH2:9])=[C:2]([Cl:1])[CH:7]=2)[NH:8][C:13](=[O:14])[CH:12]=1

Participants

4

Reactant 2

HCID 12661DiketeneHCID 212094-Chloro-M-phenylenediamine

Product 1

HCID 111951454-Methyl-6-chloro-7-aminoquinoloneYield 92%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
30 °C

Procedure

28.6 g of 4-chloro-1,3-phenylendiamine are suspended at 22° C. in 400 ml of toluene. 17.6 g of diketene in 100 ml of toluene are added to the grey suspension in the course of 30 minutes at 25±2° C., the suspension briefly passing into solution before the mono-diketenisation product is precipitated in the form of a beige solid. Stirring is then carried out for 6 h at 22° C. Then 5 g of pyridinium para-toluenesulfonate (PPTS) are added and the mixture is boiled under reflux for 16 h. The yellow suspension is cooled to 30° C., with stirring, and then at 30° C. 30 ml of 1 N NaOH are added. A further 100 ml of water are then added. The crude product is filtered at 22° C., washed neutral with H2O and dried overnight at 60° C. in vacuo. 38.5 g (yield: 92%, isomeric ratio of 4-methyl-6-chloro-7-aminoquinolone to 4-methyl-5-amino-6-chloroquinolone>95:5) of a beige solid having a melting point of 350° C. are obtained.

Workup

  1. customis precipitated in the form of a beige solid
  2. additionThen 5 g of pyridinium para-toluenesulfonate (PPTS) are added
  3. temperatureunder reflux for 16 h
  4. stirringwith stirring
  5. customat 30° C
  6. addition30 ml of 1 N NaOH are added
  7. additionA further 100 ml of water are then added
  8. filtrationThe crude product is filtered at 22° C.
  9. washwashed neutral with H2O
  10. customdried overnight at 60° C. in vacuo
  11. customare obtained

Sources & evidence

ORD record
ord-5272b2e9b7384f5c9b0cedefa6e3f25a
Source dataset
uspto-grants-2006_12
Patent number
US07144993B2

Linked notes

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