Hydrochloric Acid → 2-Chloro-6-methylbenzonitrile

HRID 1389507Notes

Reaction equation

HRID 1389507 reaction equation
[C-:1]#[N:2].[Na+].Cl.[Cl:5][C:6]1[C:11](N)=[C:10]([CH3:13])[CH:9]=[CH:8][CH:7]=1.N([O-])=O.[Na+].C(=O)([O-])[O-].[Na+].[Na+]>O.C1(C)C=CC=CC=1>[Cl:5][C:6]1[CH:7]=[CH:8][CH:9]=[C:10]([CH3:13])[C:11]=1[C:1]#[N:2]

Participants

8

Reactant 5

HCID 313Hydrochloric Acid2×HCID 68972-Chloro-6-methylanilineHCID 8929Sodium CyanideHCID 10340Sodium CarbonateHCID 23668193Sodium Nitrite

Product 1

HCID 230532-Chloro-6-methylbenzonitrileYield 4.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

Sodium cyanide (65 g, 1.33 mol) in 100 ml of water is added to cuprous chloride (49.5 g, 0.5 mol) in 200 ml of water while stirring mechanically in a 5 l. 3-necked flask. Evolution of heat resulted and the cuprous chloride dissolves. This is then cooled in an ice bath to 0° C. A milky suspension of cuprous cyanide results. To this is added 100 ml of toluene. 6 N Hydrochloric acid (140 ml) is added slowly to 6-chloro-2-methylbenzenamine (56 g, 0.4 mol) while swirling in a 2 l. erlenmeyer flask and keeping the temperature at 0° C. A solution of sodium nitrite (28 g, 0.4 mol) in 80 ml of water is added dropwise to the hydrochloride suspension. Ice is added, when required, keeping the temperature at 0° C. Anhydrous sodium carbonate is added until the diazonium hydrochloride solution is neutral to pH paper. This is then added slowly to the cold stirring cuprous cyanide suspension, the temperature not being allowed to rise above 5° C. The reaction is then stirred at 0°-5° C. for 0.75 hr, allowed to reach room temperature over a 3 hr period and then heated on the steam bath at 50° C. After remaining at room temperature overnight, the product is steam distilled off. The distillate (3.5 l.) is extracted with benzene, dried and evaporated to give 2.8 g of the title compound, nmr (CDCl3) δ 2.55 (s, 3H) and 7.3 (m, 3H).

Workup

  1. temperatureEvolution of heat
  2. customresulted
  3. customresults
  4. customerlenmeyer flask and keeping
  5. customat 0° C
  6. additionIce is added
  7. customat 0° C
  8. additionThis is then added slowly to the
  9. customto rise above 5° C
  10. stirringThe reaction is then stirred at 0°-5° C. for 0.75 hr
  11. temperatureheated on the steam bath at 50° C
  12. waitAfter remaining at room temperature overnight
  13. distillationdistilled off
  14. extractionThe distillate (3.5 l.) is extracted with benzene
  15. customdried
  16. customevaporated

Sources & evidence

ORD record
ord-b7ff77b118124a96ab1298ff84354626
Source dataset
uspto-grants-1981_01
Patent number
US04244966

Reaction notes

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