Formaldehyde → HCID 19072254, compound

HRID 1955759Notes

Reaction equation

HRID 1955759 reaction equation
[CH:1]1([N:4]2[C:13]3[C:8](=[CH:9][C:10]([F:33])=[C:11]([CH2:16][C:17]([O:19][CH:20]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)=[O:18])[C:12]=3[O:14][CH3:15])[C:7](=[O:34])[C:6]([C:35]([O:37][CH2:38][CH3:39])=[O:36])=[CH:5]2)[CH2:3][CH2:2]1.C=O.[C:42](=O)([O-])O.[Na+].C(OCC)(=O)C>CS(C)=O.O>[CH:1]1([N:4]2[C:13]3[C:8](=[CH:9][C:10]([F:33])=[C:11]([C:16]([C:17]([O:19][CH:20]([C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)=[O:18])=[CH2:42])[C:12]=3[O:14][CH3:15])[C:7](=[O:34])[C:6]([C:35]([O:37][CH2:38][CH3:39])=[O:36])=[CH:5]2)[CH2:2][CH2:3]1

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 8857Ethyl AcetateHCID 516892Sodium BicarbonateHCID 19072265HCID 19072265, compound

Product 1

HCID 19072254HCID 19072254, compoundYield 1,462.5%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

2.64 g of ethyl 1-cyclopropyl-7-diphenylmethoxycar-bonylmethyl-6-fluoro-8-methoxy-1,4-dihydro-4-oxo-3-quino-linecarboxylate was suspended in 20 ml of dimethylsulfoxide. Then 0.85 g of a 35% aqueous solution of formaldehyde and 21 mg of sodium hydrogencarbonate were added thereto and the mixture was stirred at 50° C. for 1.5 hours. To the reaction mixture, 100 ml of ethyl acetate and 50 ml of water were added and then the organic layer was collected. The organic layer thus collected was successively washed with water and a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the obtained residue was dissolved in 25 ml of methylene chloride. Under ice-cooling, 0.57 g of methanesulfonyl chloride and 1.0 mg of triethylamine were successively dropped thereinto slowly and the resulting mixture was stirred at room temperature for 3 hours. 20 ml of water was added to the reaction mixture and the pH value of the mixture was regulated to 1 with 2N hydrochloric acid. Then the organic layer was collected, successively washed with water and a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the oily product thus obtained was crystallized by adding ethanol and the crystals were collected by filtration. Thus 1.98 g of ethyl 1-cyclopropyl-7-(1-diphenylmethoxycarbonylvinyl)-6-fluoro-8-methoxy-1,4-dihydro-4-oxo-3-quinolinecarboxylate was obtained (yield: 73.1%).

Workup

  1. customthe organic layer was collected
  2. customThe organic layer thus collected
  3. washwas successively washed with water
  4. dry with materiala saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate
  5. customAfter removing the solvent under reduced pressure
  6. dissolutionthe obtained residue was dissolved in 25 ml of methylene chloride
  7. temperatureUnder ice-cooling
  8. addition0.57 g of methanesulfonyl chloride and 1.0 mg of triethylamine were successively dropped
  9. stirringslowly and the resulting mixture was stirred at room temperature for 3 hours
  10. addition20 ml of water was added to the reaction mixture
  11. customThen the organic layer was collected
  12. washsuccessively washed with water
  13. dry with materiala saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate
  14. customAfter removing the solvent under reduced pressure
  15. customthe oily product thus obtained
  16. customwas crystallized
  17. additionby adding ethanol
  18. filtrationthe crystals were collected by filtration

Sources & evidence

ORD record
ord-6cd1f124582e4d02833564d0ecc501c0
Source dataset
uspto-grants-1998_07
Patent number
US05776948

Reaction notes

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