p-Toluenesulfonic acid monohydrate → N'-(4-azido-1-phenylbutylidene)-5-chloro-2-methyl benzohydrazide

HRID 270523Notes

Reaction equation

HRID 270523 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:12])=[C:6]([CH:11]=1)[C:7]([NH:9][NH2:10])=[O:8].[N:13]([CH2:16][CH2:17][CH2:18][C:19]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=O)=[N+:14]=[N-:15].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1.CCOC(C)=O>[N:13]([CH2:16][CH2:17][CH2:18][C:19](=[N:10][NH:9][C:7](=[O:8])[C:6]1[CH:11]=[C:2]([Cl:1])[CH:3]=[CH:4][C:5]=1[CH3:12])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[N+:14]=[N-:15]

Participants

6

Reactant 3

HCID 521998p-Toluenesulfonic acid monohydrateHCID 108779184-AzidobutyrophenoneHCID 131576295-Chloro-2-methylbenzohydrazide

Product 1

HCID 86604839N'-(4-azido-1-phenylbutylidene)-5-chloro-2-methyl benzohydrazideYield 59.4%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 5-chloro-2-methylbenzohydrazide (2.70 g, 14.62 mmol) prepared as in Example 1, Step B, in toluene (100 mL) was added 4-azido-1-phenylbutan-1-one (3.04 g, 16.1 mmol) prepared as in Example 70, Step A, followed by p-toluenesulfonic acid monohydrate (0.28 g, 1.46 mmol). The reaction was heated to reflux and stirred under a Dean-Stark trap for 16 hours. The cooled mixture was diluted with EtOAc (300 mL) and washed with NaHCO3 (100 mL). The aqueous layer was extracted with EtOAc (100 mL) and the combined organics were washed with brine (100 mL), dried over Na2SO4 and concentrated. The residue was triturated with ether and filtered to afford the product (3.09 g, 59%) as a tan solid.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux
  3. washwashed with NaHCO3 (100 mL)
  4. extractionThe aqueous layer was extracted with EtOAc (100 mL)
  5. washthe combined organics were washed with brine (100 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe residue was triturated with ether
  9. filtrationfiltered

Sources & evidence

ORD record
ord-96468bcf6b4644da860f53fe8bcb7cc2
Source dataset
uspto-grants-2008_11
Patent number
US07449486B2

Reaction notes

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