Benzene, 1,2,4-trichloro-5-methoxy- → HCID 20355612, compound

HRID 371678Notes

Reaction equation

HRID 371678 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([Cl:9])=[CH:4][C:3]=1[O:10][CH3:11].P(Cl)(Cl)(Cl)(Cl)Cl.P(Cl)(Cl)Cl.[S-:22][C:23]#[N:24].[K+]>>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([Cl:9])=[CH:4][C:3]=1[O:10][CH2:11][S:22][C:23]#[N:24]

Participants

5

Reactant 4

HCID 22503Benzene, 1,2,4-trichloro-5-methoxy-HCID 24387Phosphorus trichlorideHCID 24819Phosphorus pentachlorideHCID 516872Potassium thiocyanate

Product 1

HCID 20355612HCID 20355612, compoundYield 71%

Conditions

Temperature
160 °C

Procedure

In a 50 ml. flask equipped with a thermometer, magnetic stirrer, oil bath, and fractionating distillation head place 20.0 g. (0.095 mole) 2,4,5-trichloroanisole and 19.7 g. (0.095 mole) phosphorous pentachloride. The mixture is stirred and heated at 160° C. for 3 hours. As reaction takes place, phosphorous trichloride distills out of the flask. The mixture is heated at 180° C. for 0.5 hour, cooled, and the intermediate product α,2,4,5-tetrachloroanisole is distilled; b. p. 123° C. at 1.5 mm Hg., yield 18.6 g. (81%). This product is dissolved in 120 ml. acetone and 8.1 g. (0.083 mole) dried potassium thiocyanate is added in one portion. The mixture is stirred at ambient temperature for 48 hours, poured into 900 ml. ice water, and extracted with ether. The ether extracts are washed with cold 0.5 N sodium hydroxide and water, dried (MgSO4), and concentrated. The crude product is recrystallized from hexane to give compound (I) 14.5g (71%), as colorless needles, m.p. 103°-105° C. Calcd. for C8H4Cl3NOS: C, 35.78; H, 1.50; Cl, 39.61; N, 5.22; S, 11.94. Found: C, 35.71; H, 1.68; Cl, 39.2; N, 5.14; S, 11.99.

Workup

  1. customflask equipped with a thermometer, magnetic stirrer, oil bath
  2. distillationdistillation head place 20.0 g
  3. customAs reaction
  4. distillationdistills out of the flask
  5. temperatureThe mixture is heated at 180° C. for 0.5 hour
  6. temperaturecooled
  7. distillationthe intermediate product α,2,4,5-tetrachloroanisole is distilled
  8. dissolutionThis product is dissolved in 120 ml
  9. stirringThe mixture is stirred at ambient temperature for 48 hours
  10. additionpoured into 900 ml
  11. extractionice water, and extracted with ether
  12. washThe ether extracts are washed with cold 0.5 N sodium hydroxide and water
  13. dry with materialdried (MgSO4)
  14. concentrationconcentrated
  15. customThe crude product is recrystallized from hexane

Sources & evidence

ORD record
ord-84b046527edd4cbab544a9a63f71456e
Source dataset
uspto-grants-1978_05
Patent number
US04087450

Reaction notes

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