Hydrochloric Acid → 6,7-Dimethyl-1,4-di-cyanonaphthalene

HRID 2071702Notes

Reaction equation

HRID 2071702 reaction equation
[CH3:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([CH2:9][C:10]#[N:11])=[C:4]([CH2:12][C:13]#[N:14])[CH:3]=1.O.[CH:16]([CH:18]=O)=O.C(C=O)=O.[OH-].[K+].Cl>CO>[CH3:8][C:7]1[CH:6]=[C:5]2[C:4](=[CH:3][C:2]=1[CH3:1])[C:12]([C:13]#[N:14])=[CH:18][CH:16]=[C:9]2[C:10]#[N:11]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7860GlyoxalHCID 14797Potassium Hydroxide2×HCID 3051422-[2-(Cyanomethyl)-4,5-dimethylphenyl]acetonitrileHCID 21880647Glyoxal hydrate

Product 1

HCID 202940746,7-Dimethyl-1,4-di-cyanonaphthaleneYield 34%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

17 parts of 4,5-dimethyl-1,2-bis-cyanomethyl-benzene and 7.8 parts of glyoxal hydrate (trimer) (3C2H2O2.2H2O) containing 80% of glyoxal to be liberated, are stirred in 100 parts by volume of methanol. The reaction mixture is treated at 0° to 5° C, with stirring and under nitrogen, with 10.5 parts of powdered potassium hydroxide added by small amounts. After the addition of potassium hydroxide, stirring is continued for a further 5 hours at 0° to 5° C under nitrogen. The slightly brown coloured reaction mixture is subsequently neutralised with dilute hydrochloric acid, freed from methanol in vacuo and extracted with methylene chloride. The methylene chloride extract is washed neutral with water, dried over sodium sulphate and concentrated to dryness in vacuo. Yield: 18 parts of a brown oil which is chromatographed over aluminium oxide. Elution with chlorobenzene yields 6.5 parts (34% of theory) of 6,7-dimethyl-1,4-di-cyanonaphthalene of formula ##STR46## in the form of white crystals with a melting point of 212°-220° C. Two recrystallisations from alcohol yield small white needles with a melting point of 225°-227° C.

Workup

  1. additionThe reaction mixture is treated at 0° to 5° C
  2. additionadded by small amounts
  3. extractionextracted with methylene chloride
  4. extractionThe methylene chloride extract
  5. washis washed neutral with water
  6. dry with materialdried over sodium sulphate
  7. concentrationconcentrated to dryness in vacuo
  8. customYield: 18 parts of a brown oil which is chromatographed over aluminium oxide
  9. washElution with chlorobenzene

Sources & evidence

ORD record
ord-e3686e01075e4b5289354b4ae4654082
Source dataset
uspto-grants-1977_09
Patent number
US04048212

Reaction notes

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