Methanesulfonyl chloride → 3-bromo-5-nitro-4-(4-methoxy-3-(6-oxo-3(1H)-pyridazinylmethyl)phenoxy)benzaldehyde

HRID 1761621Notes

Reaction equation

HRID 1761621 reaction equation
CS(Cl)(=O)=O.[Br:6][C:7]1[CH:8]=[C:9]([CH:12]=[C:13]([N+:16]([O-:18])=[O:17])[C:14]=1[OH:15])[CH:10]=[O:11].[CH3:19][O:20][C:21]1[CH:26]=[CH:25][C:24](O)=[CH:23][C:22]=1[CH2:28][C:29]1[CH:34]=[CH:33][C:32](=[O:35])[NH:31][N:30]=1>N1C=CC=CC=1>[Br:6][C:7]1[CH:8]=[C:9]([CH:12]=[C:13]([N+:16]([O-:18])=[O:17])[C:14]=1[O:15][C:24]1[CH:25]=[CH:26][C:21]([O:20][CH3:19])=[C:22]([CH2:28][C:29]2[CH:34]=[CH:33][C:32](=[O:35])[NH:31][N:30]=2)[CH:23]=1)[CH:10]=[O:11]

Participants

5

Reactant 3

HCID 31297Methanesulfonyl chlorideHCID 14943783-Bromo-4-hydroxy-5-nitrobenzaldehydeHCID 143331384-methoxy-3-(6-oxo-3(1H)-pyridazinylmethyl)phenol

Product 1

HCID 146735223-bromo-5-nitro-4-(4-methoxy-3-(6-oxo-3(1H)-pyridazinylmethyl)phenoxy)benzaldehydeYield 40%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Procedure

Methane sulphonyl chloride (3.6 g) was added to a solution of 3-bromo-4-hydroxy-5-nitrobenzaldehyde (7.7 g) in dry pyridine (100 ml), and the mixture heated at reflux for 10 min. A solution of 4-methoxy-3-(6-oxo-3(1H)pyridazinylmethyl)phenol (prepared as in Example 44(a)) (6.6 g) in dry pyridine (50 ml) was then added and the resultant dark mixture heated at reflx for 1.5 hours, then allowed to cool to room temperature. The solvent was then evaporated and the residue dissolved in dichloromethane (150 ml), washed with aqueous 2N hydrochloride acid (100 ml), water (100 ml), aqueous saturated sodium bicarbonate solution (2×100 ml) and water (4×100 ml), then dried and evaporated to dryness. The orange residue was dissolved in IMS, treated with charcoal and filtered. On addition of water (200 ml) and cooling a precipitate was formed which was filtered off and dried. This solid was recrystallised from ethyl acetate/petroleum spirit to give 3-bromo-5 -nitro-4-(4-methoxy-3-(6-oxo-3(1H)-pyridazinylmethyl)phenoxy)benzaldehyde (5.2 g, 40%) as a yellow solid, m.p. 188°-190°.

Workup

  1. temperaturethe mixture heated
  2. temperatureat reflux for 10 min
  3. temperaturethe resultant dark mixture heated at reflx for 1.5 hours
  4. customThe solvent was then evaporated
  5. dissolutionthe residue dissolved in dichloromethane (150 ml)
  6. washwashed with aqueous 2N hydrochloride acid (100 ml), water (100 ml), aqueous saturated sodium bicarbonate solution (2×100 ml) and water (4×100 ml)
  7. customdried
  8. customevaporated to dryness
  9. dissolutionThe orange residue was dissolved in IMS
  10. additiontreated with charcoal
  11. filtrationfiltered
  12. additionOn addition of water (200 ml)
  13. temperaturecooling a precipitate
  14. customwas formed which
  15. filtrationwas filtered off
  16. customdried
  17. customThis solid was recrystallised from ethyl acetate/petroleum spirit

Sources & evidence

ORD record
ord-839fd11d23d64cbf9986bc06197362be
Source dataset
uspto-grants-1989_05
Patent number
US04826876

Reaction notes

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