Phenylhydrazine → HCID 53785654, compound

HRID 597666Notes

Reaction equation

HRID 597666 reaction equation
[CH3:1][S:2][C:3]1[CH:11]=[CH:10][C:6]([C:7]([OH:9])=O)=[CH:5][CH:4]=1.S(Cl)(Cl)=O.[C:16]1([NH:22][NH2:23])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>N1C=CC=CC=1>[C:16]1([NH:22][NH:23][C:7](=[O:9])[C:6]2[CH:5]=[CH:4][C:3]([S:2][CH3:1])=[CH:11][CH:10]=2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 7516PhenylhydrazineHCID 24386Thionyl ChlorideHCID 832304-(Methylthio)benzoic acid

Product 1

HCID 53785654HCID 53785654, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
31 °C

Procedure

A mixture consisting of 21.88 g. (0.130 mole) p-(methylthio)benzoic acid and 25 ml. thionyl chloride was heated at the reflux temperature until evolution of gas ceased and a clear solution was obtained. After removing the excess thionyl chloride on a rotary evaporator and then under substantially complete vacuum, the solid residue that remained was dissolved in 35 ml. dioxane. The dioxane solution was mixed with a solution consisting of 14.06 g. (0.130 mole) phenylhydrazine in 100 ml. pyridine initially at 5° to 10° C. Inadvertently, about one third of the acid chloride was added rapidly and the mixture was heated to 31° C. by the exothermic reaction. The reaction mixture was set aside at 25° C. with continuous stirring for 3 days. It was then poured into 1.5 l. water in order to precipitate the desired p-(methylthio)benzoic acid 2-phenylhydrazide. The precipitate was collected on a filter, washed with water, washed with 1N hydrochloride acid, and finally washed with water. The washed filter cake was then recrystallized from 3A alcohol to give 23.2 g. (69% yield) of p-(methylthio)benzoic acid 2-phenylhydrazide having a melting point at 165.5° to 167.5° C. Recrystallization from 250 ml. ethyl acetate gave the compound melting at 167° to 168° C. (shrinks at 162° C.). Two further recrystallizations from ethyl acetate gave the compound melting at 167° to 168.5° C. with shrinkage at 161.5° C.

Workup

  1. customa clear solution was obtained
  2. customAfter removing the excess thionyl chloride
  3. customon a rotary evaporator
  4. dissolutionunder substantially complete vacuum, the solid residue that remained was dissolved in 35 ml
  5. additionThe dioxane solution was mixed with a solution
  6. custominitially at 5° to 10° C
  7. customwas set aside at 25° C.
  8. additionIt was then poured into 1.5 l
  9. customwater in order to precipitate the desired p-(methylthio)benzoic acid 2-phenylhydrazide
  10. customThe precipitate was collected on a filter
  11. washwashed with water
  12. washwashed with 1N hydrochloride acid
  13. washfinally washed with water
  14. filtrationThe washed filter cake
  15. customwas then recrystallized from 3A alcohol
  16. customto give 23.2 g

Sources & evidence

ORD record
ord-70c7b2a000e04041b29db660fed6f39b
Source dataset
uspto-grants-1977_03
Patent number
US04014932

Reaction notes

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