Anthranilic Acid → 2-(4-Chloro-2-nitroanilino)benzoic acid

HRID 1701125노트

반응식

HRID 1701125 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[C:12]([OH:21])(=[O:20])[C:13]1[C:14](=[CH:16][CH:17]=[CH:18][CH:19]=1)[NH2:15].CCCCCO.C(=O)([O-])[O-].[K+].[K+]>[Cu]>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([NH:15][C:14]2[C:13](=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:12]([OH:21])=[O:20])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

참가 물질

6

반응물 4

HCID 227Anthranilic AcidHCID 62761-PentanolHCID 11430Potassium CarbonateHCID 27949042-Bromo-5-chloronitrobenzene

생성물 1

HCID 120423912-(4-Chloro-2-nitroanilino)benzoic acid수율 83%

시약·촉매·용매 1

HCID 23978Copper촉매

실험 절차

In a 3 liter, three necked round bottom flask, provided with a mechanical stirrer, reflux condenser and thermometer (to 200° C.) was placed 300 g. (1.25 m.) 1-bromo-4-chloronitrobenzene, 140 g. (1.02 m.) anthranilic acid, and 130 ml. n-amyl alcohol. The mixture was heated in an oil bath. After most of the chemicals were dissolved (80°-90° C.) the stirrer was started. Then, 1.3 gm. copper powder and 140 gm. (1.02 m.) potassium carbonate were added all at once. A yellow voluminous froth formed but no heat of reaction. As the reaction temperature rose from 80° to 120°, a red reaction mixture became more solid and hindered further stirring. The reflux condenser was replaced to distill off the formed water and amyl alcohol. Meanwhile, the temperature of the oil bath was steadily increased and finally kept at 200°-210° for 3 hours. The oil bath was replaced by a steam bath and the excess bromochloronitrobenzene was removed by steam distillation. After removal of bromochloronitrobenzene was completed, the solution was filtered and water added making the total volume of dark red solution about 2.5 liters. The solution was cooled to room temperature overnight, and filtered. Dilute HCl (1:1) was carefully added to the filtrate until it was just acid to Congo red litmus paper. The ochre-colored precipitate was removed by filtration and washed with water (750 ml.). The product was dried in vacuo at 70°. The original dark-red filter cake was digested with hot water several times and then treated as described above to extract all the desired product. Obtained: 247 grams (83% yield) of crude N-(4-chloro-2-nitrophenyl)anthranilic acid; orange granular powder; m.p. 235°-247° C.

후처리

  1. customIn a 3 liter, three necked round bottom flask, provided with a mechanical stirrer
  2. temperaturereflux condenser
  3. customthermometer (to 200° C.)
  4. temperatureThe mixture was heated in an oil bath
  5. dissolutionAfter most of the chemicals were dissolved (80°-90° C.) the stirrer
  6. customA yellow voluminous froth formed
  7. temperatureno heat of reaction
  8. customrose from 80° to 120°
  9. distillationto distill off the formed water and amyl alcohol
  10. temperatureMeanwhile, the temperature of the oil bath was steadily increased
  11. customThe oil bath was replaced by a steam bath
  12. customthe excess bromochloronitrobenzene was removed by steam distillation
  13. customAfter removal of bromochloronitrobenzene
  14. filtrationthe solution was filtered
  15. additionwater added
  16. filtrationfiltered
  17. additionDilute HCl (1:1) was carefully added to the filtrate until it
  18. customThe ochre-colored precipitate was removed by filtration
  19. washwashed with water (750 ml.)
  20. customThe product was dried in vacuo at 70°
  21. additiontreated
  22. extractionto extract all the desired product
  23. customObtained

출처 및 근거

ORD 기록
ord-ad46416b40594ec5bdb903ea60cf5bf4
출처 데이터셋
uspto-grants-1980_03
특허 번호
US04191760

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