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

HRID 853194ノート

反応式

HRID 853194 の反応式
[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

参加物

8

反応物 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]-benzoate2 回

生成物 1

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

試薬・触媒・溶媒 3

HCID 679Dimethyl Sulfoxide溶媒HCID 702Ethanol溶媒HCID 962Water溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-fc26292e6f7a469e91b12c4658dee850
出典データセット
uspto-grants-2007_08
特許番号
US07253319B2

反応ノート

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