Sulfuric Acid → HCID 74057421, compound

HRID 1835019Notes

Reaction equation

HRID 1835019 reaction equation
[C:1]1([CH3:10])[CH:6]=[CH:5][C:4]([CH2:7][C:8]#[N:9])=[CH:3][CH:2]=1.[OH-].[Na+].[N:13](OC)=[O:14].OS(O)(=O)=O.N([O-])=O.[Na+]>CO.O>[OH:14][N:13]=[C:7]([C:8]#[N:9])[C:4]1[CH:5]=[CH:6][C:1]([CH3:10])=[CH:2][CH:3]=1

Participants

8

Reactant 5

HCID 1118Sulfuric AcidHCID 12231Methyl nitriteHCID 14798Sodium HydroxideHCID 76280p-TolylacetonitrileHCID 23668193Sodium Nitrite

Product 1

HCID 74057421HCID 74057421, compoundYield 83.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent2×

Conditions

Temperature
2.5 °C

Procedure

131.2 g (1 mol) of p-tolylacetonitrile are placed in a sulfonation flask and charged with 40 g (1 mol) of sodium hydroxide, dissolved in 325 ml of methanol. This solution is cooled in an ice bath to 0-5° C. At this temperature, 1 mol of gaseous methyl nitrite (prepared in situ by addition of 31.5 ml of conc. H2SO4, dissolved in 65 ml of water, to a solution of 83 g of NaNO2 in 50 ml of water and 53 ml of methanol (see Org. Synthesis 1979, 59, 95)) is introduced, with stirring, over 3 hours. The ice bath is then removed and the red solution is stirred overnight at room temperature. The methanol is distilled off on a rotary evaporator and the orange residue is then charged with water and toluene. The aqueous phase is separated, washed twice with toluene and acidified with conc. HCl. The resulting orange emulsion is extracted three times with ethyl acetate, the extracts are washed with water and dried over magnesium sulfate. After filtration, the solvent is distilled off and a yellowish-orange oil is obtained which solidifies upon standing. Recrystallisation from toluene gives 133.6 g (83% of theory) of α-hydroxyimino-4-methylbenzylcyanide as a beige solid having a melting point of 110.5-114.5° C. The 1H-NMR spectrum is consistent with the proposed structure.

Workup

  1. additionis introduced
  2. customThe ice bath is then removed
  3. stirringthe red solution is stirred overnight at room temperature
  4. distillationThe methanol is distilled off on a rotary evaporator
  5. additionthe orange residue is then charged with water and toluene
  6. customThe aqueous phase is separated
  7. washwashed twice with toluene
  8. extractionThe resulting orange emulsion is extracted three times with ethyl acetate
  9. washthe extracts are washed with water
  10. dry with materialdried over magnesium sulfate
  11. filtrationAfter filtration
  12. distillationthe solvent is distilled off
  13. customa yellowish-orange oil is obtained which
  14. customRecrystallisation from toluene

Sources & evidence

ORD record
ord-4a08f9f68f4b491a8fe7642aeac1baac
Source dataset
uspto-grants-2004_08
Patent number
US06770420B2

Reaction notes

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