Dicamba → HCID 57076317, compound

HRID 2166744Notes

Reaction equation

HRID 2166744 reaction equation
[Cl:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[C:7]([O:12][CH3:13])[C:3]=1[C:4]([OH:6])=[O:5].S(Cl)(Cl)=O.[C:18]([O:23][CH2:24][CH3:25])(=[O:22])[CH:19]([CH3:21])O.C(N(CC)CC)C>C1C=CC=CC=1>[Cl:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[C:7]([O:12][CH3:13])[C:3]=1[C:4]([O:6][CH2:21][CH2:19][C:18]([O:23][CH2:24][CH3:25])=[O:22])=[O:5]

Participants

6

Reactant 4

HCID 3030DicambaHCID 7344Ethyl LactateHCID 8471TriethylamineHCID 24386Thionyl Chloride

Product 1

HCID 57076317HCID 57076317, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a 100-milliliter round bottom flask provided with a reflux condenser was charged 20 grams of 2,5-dichloro-6-methoxybenzoic acid (prepared as described in paragraph (a) of this Example) and 30 milliliters (48 grams) of thionyl chloride. The mixture was heated to reflux and maintained at reflux for two hours after which the miture was stripped under vacuum to remove excess thionyl chloride. The oily residue was poured into a separatory funnel along with water and benzene and the contents thoroughly mixed. A small amount of potassium chloride was added to assist phase separation and the benzene layer was washed several times with water. Benzene was then stripped under vacuum and the residue was vacuum distilled. 20.8 grams of a clear oil ws collected, the oil having a boiling point of 82°-84° C. at 0.1 mm Hg. 12 grams of this oil and 75 milliliters of benzene were charged to a 250-milliter round bottom flask provided with a reflux condenser. To this stirred mixture was added, dropwise, 6 milliliters of ethyl lactate and 6 grams of triethylamine in 40 milliliters of benzene. (Some solids formation was noted.) The mixture was then heated to reflux and maintained at reflux for 31/2 hours after which the mixture was cooled and filtered, 1.7 grams of amine hydrochloride solids being collected. 5 milliliters of pyridine was added to the filtrate and the mixture was heated to reflux and maintained at reflux overnight. The mixture was then filtered (3.2 grams of amine hydrochloride solids being collected) and the filtrate was washed consecutively with dilute hydrochloric acid, water, dilute aqueous sodium hydroxide and twice more with water. Benzene was then stripped under vacuum leaving a black oil. The oil was vacuum distilled and 6.7 grams of clear oil was collected at 142°-144° C. and 0.2 mm Hg., which oil was identified by NMR spectroscopy as 2,5-dichloro-6-methoxy-benzoic acid, (ethoxycarbonyl)ethyl ester.

Workup

  1. customTo a 100-milliliter round bottom flask provided with a reflux condenser
  2. customprepared
  3. temperatureThe mixture was heated
  4. temperatureto reflux
  5. temperaturemaintained
  6. temperatureat reflux for two hours after which the miture
  7. customto remove excess thionyl chloride
  8. additionThe oily residue was poured into a separatory funnel along with water and benzene
  9. additionthe contents thoroughly mixed
  10. additionA small amount of potassium chloride was added
  11. customphase separation
  12. washthe benzene layer was washed several times with water
  13. distillationdistilled
  14. custom20.8 grams of a clear oil ws collected
  15. addition12 grams of this oil and 75 milliliters of benzene were charged to a 250-milliter round bottom flask
  16. customprovided with a reflux condenser
  17. additionTo this stirred mixture was added
  18. temperature) The mixture was then heated
  19. temperatureto reflux
  20. temperaturemaintained
  21. temperatureat reflux for 31/2 hours after which the mixture
  22. temperaturewas cooled
  23. filtrationfiltered
  24. custom1.7 grams of amine hydrochloride solids being collected
  25. addition5 milliliters of pyridine was added to the filtrate
  26. temperaturethe mixture was heated
  27. temperatureto reflux
  28. temperaturemaintained
  29. temperatureat reflux overnight
  30. filtrationThe mixture was then filtered
  31. custom(3.2 grams of amine hydrochloride solids being collected)
  32. washthe filtrate was washed consecutively with dilute hydrochloric acid, water, dilute aqueous sodium hydroxide and twice more with water
  33. customleaving a black oil
  34. distillationdistilled
  35. custom6.7 grams of clear oil was collected at 142°-144° C.

Sources & evidence

ORD record
ord-9c0a36f2f2e84309a9b5b0654464dec9
Source dataset
uspto-grants-1983_06
Patent number
US04388473

Reaction notes

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