m-Chlorophenylhydrazine hydrochloride → HCID 58345406, compound

HRID 1877974Notes

Reaction equation

HRID 1877974 reaction equation
[CH2:1]([O:3][C:4](=[O:20])[C:5](=O)/[CH:6]=[C:7](/[C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=1)\[O-])[CH3:2].[Li+].Cl.[Cl:23][C:24]1[CH:25]=[C:26]([NH:30][NH2:31])[CH:27]=[CH:28][CH:29]=1>C(O)C>[Cl:23][C:24]1[CH:25]=[C:26]([N:30]2[C:7]([C:9]3[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=3)=[CH:6][C:5]([C:4]([O:3][CH2:1][CH3:2])=[O:20])=[N:31]2)[CH:27]=[CH:28][CH:29]=1

Participants

4

Reactant 2

HCID 75331m-Chlorophenylhydrazine hydrochlorideHCID 58277291HCID 58277291, compound

Product 1

HCID 58345406HCID 58345406, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

631.5 mg (2.15 mmol) of lithium (1Z)-4-ethoxy-3,4-dioxo-1-[3-(trifluoromethyl)phenyl]but-1-en-1-olate from example 1A are suspended in 15 ml of ethanol, 522.7 mg (2.92 mmol) of 3-chlorophenylhydrazine hydrochloride are added and the mixture is stirred for 48 hours at room temperature. The reaction mixture is concentrated by evaporation to approx. 5 ml and the precipitated solid is collected by suction filtration. After drying the crystals, they are taken up in 15 ml of acetic acid and stirred for 12 hours under reflux. The mixture is added to ethyl acetate, and washed with water, a saturated sodium bicarbonate solution and a sodium chloride solution. The organic phase is dried over sodium sulfate and concentrated on a rotary evaporator. The residue obtained is purified on a silica gel flash (mobile phase: cyclohexane/ethyl acetate 3:1) and then crystallized from diethyl ether/pentane. 528 mg (1.5 mmol, 62% yield of theory) of product are obtained.

Workup

  1. concentrationThe reaction mixture is concentrated by evaporation to approx. 5 ml
  2. filtrationthe precipitated solid is collected by suction filtration
  3. customAfter drying the crystals, they
  4. stirringstirred for 12 hours
  5. temperatureunder reflux
  6. additionThe mixture is added to ethyl acetate
  7. washwashed with water
  8. dry with materialThe organic phase is dried over sodium sulfate
  9. concentrationconcentrated on a rotary evaporator
  10. customThe residue obtained
  11. customis purified on a silica gel flash (mobile phase: cyclohexane/ethyl acetate 3:1)
  12. customcrystallized from diethyl ether/pentane
  13. custom528 mg (1.5 mmol, 62% yield of theory) of product are obtained

Sources & evidence

ORD record
ord-42c9b73a61c64ffdbc6ec5588d9887da
Source dataset
uspto-grants-2012_11
Patent number
US08314089B2

Reaction notes

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