Pyridine → 2-(6,11-Dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetaldoxime

HRID 357257노트

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HRID 357257 반응식
[O:1]=[C:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH2:6][O:5][C:4]2[CH:13]=[CH:14][C:15]([CH2:17][C:18](Cl)=O)=[CH:16][C:3]1=2.C(O[AlH-](OC(C)(C)C)OC(C)(C)C)(C)(C)C.[Li+].N1C=CC=CC=1.Cl.[NH2:45][OH:46]>COCCOCCOC>[O:1]=[C:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH2:6][O:5][C:4]2[CH:13]=[CH:14][C:15]([CH2:17][CH:18]=[N:45][OH:46])=[CH:16][C:3]1=2

참가 물질

6

반응물 4

HCID 1049PyridineHCID 443297Hydroxyamine hydrochlorideHCID 134570082-(6,11-Dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetyl chlorideHCID 16684435Lithium tritertbutoxyaluminohydride

생성물 1

HCID 867533622-(6,11-Dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetaldoxime

시약·촉매·용매 1

HCID 8150Diglyme용매2회

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온도
-78 °C

실험 절차

A solution of 2-(6,11-dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetyl chloride (15.00 g) in 150 ml of dry diglyme was stirred at -78° C. under nitrogen as lithium tri-tert-butoxyaluminohydride (104.6 ml of a 0.5M solution in diglyme) was added slowly dropwise over one hour. The reaction was stirred ten minutes at -78° C. and then quenched with 3 ml of glacial acetic acid added slowly dropwise. After warming the reaction to room temperature 50 ml of pyridine and 2 equiv. of hydroxylamine hydrochloride (7.27 g) was added and the slurry stirred at 50° C. for two hours. The solvent was evaporated using high vacuum and the residue taken up in chloroform and 1N HCl. The layers were separated and the aqueous phase extracted with chloroform. The combined organic phases were dried (MgSO4), filtered, and evaporated. The residue was purified by flash chromatography (silica; 5:2 hex-EtOAc) and recrystallized from ethyl acetate-hexane to give 2-(6,11-dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetaldoxime, as crystals, m.p. 132°-134° C.

후처리

  1. additionwas added slowly dropwise over one hour
  2. customquenched with 3 ml of glacial acetic acid
  3. additionadded slowly dropwise
  4. temperatureAfter warming
  5. additionwas added
  6. stirringthe slurry stirred at 50° C. for two hours
  7. customThe solvent was evaporated
  8. customThe layers were separated
  9. extractionthe aqueous phase extracted with chloroform
  10. dry with materialThe combined organic phases were dried (MgSO4)
  11. filtrationfiltered
  12. customevaporated
  13. customThe residue was purified by flash chromatography (silica; 5:2 hex-EtOAc)
  14. customrecrystallized from ethyl acetate-hexane

출처 및 근거

ORD 기록
ord-638b2cea1bab42afae356a3ee1753fe0
출처 데이터셋
uspto-grants-1998_11
특허 번호
US05840749

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