Pyridine → 1-(2-Fluoro-6-chlorobenzoyl)-2-methyl-2-[(4-methylphenyl)sulfonyl] hydrazine

HRID 850036Notes

Reaction equation

HRID 850036 reaction equation
[CH3:1][N:2]([S:4]([C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1)(=[O:6])=[O:5])[NH2:3].N1C=CC=CC=1.C(#N)C.[F:23][C:24]1[CH:32]=[CH:31][CH:30]=[C:29]([Cl:33])[C:25]=1[C:26](Cl)=[O:27]>CN(C)C1C=CN=CC=1.C(Cl)Cl>[F:23][C:24]1[CH:32]=[CH:31][CH:30]=[C:29]([Cl:33])[C:25]=1[C:26]([NH:3][N:2]([CH3:1])[S:4]([C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1)(=[O:6])=[O:5])=[O:27]

Participants

7

Reactant 4

HCID 1049PyridineHCID 6342AcetonitrileHCID 280433N,4-dimethylbenzenesulfonohydrazideHCID 27365472-Chloro-6-fluorobenzoyl chloride

Product 1

HCID 211853791-(2-Fluoro-6-chlorobenzoyl)-2-methyl-2-[(4-methylphenyl)sulfonyl] hydrazineYield 34.7%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
10 °C

Procedure

Into a 100 mL three necked round bottom flask equipped with a magnetic stirrer, thermometer, and condenser, under an atmosphere of nitrogen, was added 2-methyl-2-[(4-methylphenyl)sulfonyl] hydrazine (9.5 g, 47.4 mmol), pyridine (3.75 g, 3.83 mL, 47.4 mmol), 4-dimethylaminopyridine (0.30 g, 2.4 mmol) and acetonitrile (50 mL). The resulting mixture was cooled to 10° C. and 2-fluoro-6-chlorobenzoyl chloride (8.99 g, 45.2 mmol) dropwise at a rate such that the temperature did not rise above 10° C. The cooling bath was removed and the mixture was allowed to stir at RT overnight. The solvent was removed from the reaction mixture in vacuo to give an off white solid and the solid was diluted with methylene chloride and extracted with 1N HCl (20 mL), saturated sodium chloride solution (20 mL), dried (Na2SO4), and the solvent removed in vacuo to give an off-white solid. This material was recrystallized from ethyl acetate to give 5.6 g (34.7% yield) of 1-(2-fluoro-6-chlorobenzoyl)-2-methyl-2-[(4-methylphenyl)sulfonyl] hydrazine as a crystalline solid: mp 135-136° C.; 1H NMR (CDCl3) δ 7.6-7.8 (m, 3H), 7.0-7.4 (m, 5H), 3.4 and 3.0 (singlets combined for 3H), 2.4 and 2.45 (singlets combined for 3H); 13C (CDCl3) 160.2, 144.7, 133.6, 132.7, 132.6, 132.1, 131.9, 130.2, 129.6, 129.0, 128.7, 125.7, 114.6, 114.3, 37.7, 21.7. Anal. Calcd. For C15H14ClFN2O3S: C, 50.49; H, 3.95; N, 7.85. Found: C, 50.55; H, 3.89: N. 7.81.

Workup

  1. customdid not rise above 10° C
  2. customThe cooling bath was removed
  3. customThe solvent was removed from the reaction mixture in vacuo
  4. customto give an off white solid
  5. extractionextracted with 1N HCl (20 mL), saturated sodium chloride solution (20 mL)
  6. dry with materialdried (Na2SO4)
  7. customthe solvent removed in vacuo
  8. customto give an off-white solid
  9. customThis material was recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-ca297a3104f84f00a531743abe05bc75
Source dataset
uspto-grants-2000_01
Patent number
US06015826

Reaction notes

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