Pyridine → 4-[3-(8,8-Dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-3-hydroximino-propenyl]-benzoic Acid

HRID 853194노트

반응식

HRID 853194 반응식
[CH3:1][C:2]1([CH3:38])[C:11]2[CH:10]=[C:9]([C:12](=O)[CH:13]=[CH:14][C:15]3[CH:29]=[CH:28][C:18]([C:19]([O:21]CC[Si](C)(C)C)=[O:20])=[CH:17][CH:16]=3)[CH:8]=[CH:7][C:6]=2[C:5]([C:31]2[CH:36]=[CH:35][C:34]([CH3:37])=[CH:33][CH:32]=2)=[CH:4][CH2:3]1.Cl.[NH2:40][OH:41].N1C=CC=CC=1.[F-]>CCO.CS(C)=O.O>[CH3:1][C:2]1([CH3:38])[C:11]2[CH:10]=[C:9]([C:12](=[N:40][OH:41])[CH:13]=[CH:14][C:15]3[CH:29]=[CH:28][C:18]([C:19]([OH:21])=[O:20])=[CH:17][CH:16]=3)[CH:8]=[CH:7][C:6]=2[C:5]([C:31]2[CH:36]=[CH:35][C:34]([CH3:37])=[CH:33][CH:32]=2)=[CH:4][CH2:3]1

참가 물질

8

반응물 4

HCID 1049PyridineHCID 28179Fluoride IonHCID 443297Hydroxyamine hydrochlorideHCID 688321412-Trimethylsilanyl-ethyl 4-[3-(8,8-dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-3-oxo-propenyl]-benzoate2회

생성물 1

HCID 729541014-[3-(8,8-Dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-3-hydroximino-propenyl]-benzoic Acid수율 42%

시약·촉매·용매 3

HCID 679Dimethyl Sulfoxide용매HCID 702Ethanol용매HCID 962Water용매

실험 절차

To a solution of 2-trimethylsilanyl-ethyl 4-[3-(8,8-dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-3-oxo-propenyl]-benzoate (Compound 6, 240 mg, 0.46 mmol) in 5 mL of EtOH was added hydroxylamine hydrochloride (64 mg, 0.92 mmol) and pyridine (77 mg, 0.97 mmol). The reaction mixture was then heated at reflux for 6 h. After cooling to room temperature, the solvent was removed in vacuo and the residue was taken up in water. The aqueous layer was adjusted to pH=4–5 with 1 N HCl and extracted with ethyl acetate (3×10 mL). The organic layers were combined and washed with water (2×10 mL) and brine (1×10 mL), dried (MgSO4) and concentrated at reduced pressure to obtain a yellow crude oil. This crude product was then dissolved in 2 mL of dimethylsulfoxide (DMSO) and tetraethylammomium fluoride (TEAF) (137 g, 0.92 mmol) was added. After stirring at room temperature for 0.5 h, the mixture was diluted with water (10 mL), extracted with ethyl acetate (3×5 mL), washed with brine (1×5 mL), dried (MgSO4) and concentrated at reduced pressure. Purification by recrystallization with acetonitrile yielded Substance 7c, (a mixture of E/Z isomers, 84 mg, 42% yield).

후처리

  1. temperatureThe reaction mixture was then heated
  2. temperatureat reflux for 6 h
  3. customthe solvent was removed in vacuo
  4. extractionextracted with ethyl acetate (3×10 mL)
  5. washwashed with water (2×10 mL) and brine (1×10 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated at reduced pressure
  8. customto obtain a yellow crude oil
  9. extractionextracted with ethyl acetate (3×5 mL)
  10. washwashed with brine (1×5 mL)
  11. dry with materialdried (MgSO4)
  12. concentrationconcentrated at reduced pressure
  13. customPurification
  14. customby recrystallization with acetonitrile yielded Substance 7c
  15. addition(a mixture of E/Z isomers, 84 mg, 42% yield)

출처 및 근거

ORD 기록
ord-fc26292e6f7a469e91b12c4658dee850
출처 데이터셋
uspto-grants-2007_08
특허 번호
US07253319B2

반응 노트

불러오는 중…