4-Toluenesulfonyl chloride → HCID 18369347, compound

HRID 1699775Notes

Reaction equation

HRID 1699775 reaction equation
C1(C)C=CC(S(Cl)(=O)=O)=CC=1.[CH3:12][O:13][C:14]1[CH:19]=[CH:18][C:17]([C:20]2[C:25]([C:26]3[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=3)=[N:24][N:23]([CH2:34][CH2:35]O)[C:22](=[O:37])[CH:21]=2)=[CH:16][CH:15]=1.[CH3:38][N:39]1[CH2:44][CH2:43][NH:42][CH2:41][CH2:40]1.[K+].[Br-]>N1C=CC=CC=1.O>[CH3:12][O:13][C:14]1[CH:15]=[CH:16][C:17]([C:20]2[C:25]([C:26]3[CH:27]=[CH:28][C:29]([O:32][CH3:33])=[CH:30][CH:31]=3)=[N:24][N:23]([CH2:34][CH2:35][N:42]3[CH2:43][CH2:44][N:39]([CH3:38])[CH2:40][CH2:41]3)[C:22](=[O:37])[CH:21]=2)=[CH:18][CH:19]=1

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 531671-MethylpiperazineHCID 253877Potassium BromideHCID 9906490HCID 9906490, compound

Product 1

HCID 18369347HCID 18369347, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1049PyridineSolvent2×

Procedure

To a solution of para-toluenesulfonyl chloride (357 mg, 4 eq) in pyridine (0.5 ml), a solution of 5,6-bis(4-methoxyphenyl)-2-(2-hydroxyethyl)-2H-pyridazin-3-one (165 mg, 0.47 mmol) in pyridine (1.0 ml) was added, followed by stirring at room temperature for 2 hours. The reaction mixture was poured into ice water, followed by extraction with ethyl acetate. The organic layer was washed successively with water and a brine, and was then dried over anhydrous sodium sulfate. The solvent was distilled off, and N-methylpiperazine (0.15 ml, 3 eq) was added to the residue. The resulting mixture was stirred at 90-100° C. for 2 hours. After water was added to the reaction mixture, the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and a brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off, and ethanol was added to the residue. The resulting mixture was azeotropically boiled three times with ethanol to drive off water. The thus-obtained residue (256 mg) was separated and purified by chromatography on a silica gel column [silica gel: 8 g, chloroform/methanol (20/1)], whereby a yellow oil (165 mg, 81%) was obtained. The oil was left over in a refrigerator. Precipitated crystals were washed with a mixed solvent of methanol and diethyl ether, whereby the title compound (65 mg, 32%) was obtained as pale yellow prisms. Melting point: 109.7-110.8° C. 1H-NMR (CDCl3) δ: 2.29(3H,s), 2.46(4H,brs), 2.64(4H,brs), 2.87(2H,t,J=6.83 Hz), 3.80(3H,s), 3.81(3H,s), 4.40(2H,t,J=6.84 Hz), 6.79(2H,d,J=9.03 Hz), 6.81(2H,d,J=8.78 Hz), 6.87(1H,s), 7.02(2H,d,J=8.79 Hz), 7.12(2H,d,J=9.03 Hz). IR (KBr) cm−1: 1659,1608,1513,1295,1250,1177,1013.

Workup

  1. extractionfollowed by extraction with ethyl acetate
  2. washThe organic layer was washed successively with water
  3. dry with materiala brine, and was then dried over anhydrous sodium sulfate
  4. distillationThe solvent was distilled off
  5. stirringThe resulting mixture was stirred at 90-100° C. for 2 hours
  6. extractionthe mixture was extracted with ethyl acetate
  7. washThe organic layer was washed successively with water
  8. dry with materiala brine, and then dried over anhydrous sodium sulfate
  9. distillationThe solvent was distilled off
  10. additionethanol was added to the residue
  11. customThe thus-obtained residue (256 mg) was separated
  12. custompurified by chromatography on a silica gel column [silica gel: 8 g, chloroform/methanol (20/1)], whereby a yellow oil (165 mg, 81%)
  13. customwas obtained
  14. waitThe oil was left over in a refrigerator
  15. customPrecipitated crystals
  16. washwere washed with a mixed solvent of methanol and diethyl ether, whereby the title compound (65 mg, 32%)
  17. customwas obtained as pale yellow prisms

Sources & evidence

ORD record
ord-3ab2e79d92804667b41b609dbbbbff73
Source dataset
uspto-grants-2002_02
Patent number
US06348468B1

Reaction notes

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