Hydrazine → 1-Hydrazinyl-3,4-dihydroisoquinoline

HRID 436429

반응식

HRID 436429 반응식
C(O[C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH2:7][CH2:6][N:5]=1)C.[NH2:14][NH2:15]>C(O)C>[NH:14]([C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH2:7][CH2:6][N:5]=1)[NH2:15]

참가 물질

4

반응물 2

HCID 9321HydrazineHCID 123490381-Ethoxy-3,4-dihydroisoquinoline

생성물 1

HCID 123490411-Hydrazinyl-3,4-dihydroisoquinoline

시약·촉매·용매 1

HCID 702Ethanol용매2회

실험 절차

A solution of 3,4-dihydroisocarbostyril (IV: Y=Y'=Z=Z'=H) (64.3 g.) in dried methylene dichloride was added to a methylene dichloride (250 ml.) solution of triethyloxonium fluoborate, prepared from boron trifluoride etherate (227 g.), epichlorohydrin (74 g.) and absolute ether (600 ml.) After being stirred (for about 16 hr. at 25° C.), the mixture was treated with potassium carbonate solution (50%, 75 ml.) and water (25 ml.), stirred (for 1-1/2 hr.) and filtered. The solid material was washed thoroughly with methylene dichloride and dissolved in hot water. The solution was filtered and extracted three times with chloroform. 1-Ethoxy-3,4-dihydroisoquinoline fluoborate (10.5 g.) obtained in an earlier run was dissolved in potassium carbonate solution and the solution was extracted three times with methylene dichloride. The combined methylene dichloride washing, chloroform extract and methylene dichloride extract were stripped of solvents and distilled under reduced pressure, affording 1-ethoxy-3,4-dihydroisoquinoline (III: Q=C2H5, Y=Y'=Z=Z'=H) (68.4 g., b.p. 110°-137° C./16 mm. Hg), part (10.82 g.) of which was a center cut (b.p. 129°-131° C./16 mm. Hg). B. A solution of 1-ethoxy-3,4-dihydroisoquinoline (2.0 g.) in ethanol (10 ml.) was added dropwise with stirring to a solution (at 80° C.) of hydrazine (95%, 1.83 g.) in ethanol (5 ml.). The solution was concentrated, diluted with chloroform, washed with water, dried and concentrated. The residue (1.6 g.) was crystalized from ether in three crops (0.7 g., 0.5 g., 0.3 g.). Recrystallization of the first crop from ether-pentane afforded 1-hydrazino-3,4-dihydroisoquinoline (V: Y=Y'=Z=Z') (m.p. 55°-57° C.).

후처리

  1. concentrationThe solution was concentrated
  2. additiondiluted with chloroform
  3. washwashed with water
  4. customdried
  5. concentrationconcentrated
  6. customThe residue (1.6 g.) was crystalized from ether in three crops (0.7 g., 0.5 g., 0.3 g.)
  7. customRecrystallization of the first crop from ether-pentane

출처 및 근거

ORD 기록
ord-0d59e96df1984c649b8b4d6a35f2752f
출처 데이터셋
uspto-grants-1977_02
특허 번호
US04009170

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