Ethanol → (S)-1,3,4,5-tetrahydro-4-[[(phenylmethoxy)carbonyl]amino]-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester

HRID 1318

반응식

HRID 1318 반응식
[C:1]1(=[O:29])[N:5]([C@H:6]2[CH2:12][C:11]3[CH:13]=[CH:14][CH:15]=[CH:16][C:10]=3[CH2:9][N:8]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:7]2=[O:23])C(=O)C2=CC=CC=C12.C(O)C.C(N(CC)CC)C.[CH2:40]([O:47]C(Cl)=O)[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1>O.NN.C(OCC)(=O)C.C1(C)C=CC=CC=1>[C:41]1([CH2:40][O:47][C:1]([NH:5][C@H:6]2[CH2:12][C:11]3[CH:13]=[CH:14][CH:15]=[CH:16][C:10]=3[CH2:9][N:8]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:7]2=[O:23])=[O:29])[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

참가 물질

8

반응물 4

HCID 702EthanolHCID 8471TriethylamineHCID 10387Benzyl chloroformateHCID 86751053(S)-1,3,4,5-tetrahydro-4-phthalimido-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester

생성물 1

HCID 86749789(S)-1,3,4,5-tetrahydro-4-[[(phenylmethoxy)carbonyl]amino]-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester

시약·촉매·용매 3

HCID 1140Toluene용매HCID 8857Ethyl Acetate용매2회HCID 24654Hydrazine hydrate (1:1)용매

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온도
0 °C

실험 절차

A solution of (S)-1,3,4,5-tetrahydro-4-phthalimido-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester (1.67 g., 4.26 mmol.) in 1.0M hydrazine hydrate in ethanol (9.0 ml., 9.0 mmol.) was stirred at room temperature under argon for 36 hours. The mixture was diluted with an equal volume of ethyl acetate, filtered and filtrate evaporated to dryness. The residue was taken up in toluene and again evaporated to dryness. The colorless, semi-solid residue (1.81 g.) was taken up in dry methylene chloride (20 ml.), placed in an ice bath and treated successively with triethylamine (0.80 ml., 5.8 mmol.) and benzylchloroformate (0.77 ml., 5.4 mmol.). After stirring at 0° C. for 2 hours, the mixture was partitioned between ethyl acetate-5% potassium bisulfate. The organic phase was washed successively with 5% potassium bisulfate, saturated sodium bicarbonate and saturated sodium chloride solutions, dried (sodium sulfate), and evaporated to dryness. Purification of the crude product by flash chromatography on silica gel (Whatmann LPS-1) eluting with ethyl acetate:hexane (1:2) gave 1.0747 g. of product as a colorless foam; Rf =0.52 (ethyl acetate:toluene, 3:7). A sample crystallized from hexane had m.p. 80°-82° C.; [α]D =+87.2° (c=0.53, chloroform).

후처리

  1. filtrationfiltered
  2. customfiltrate evaporated to dryness
  3. customagain evaporated to dryness
  4. customplaced in an ice bath
  5. customthe mixture was partitioned between ethyl acetate-5% potassium bisulfate
  6. washThe organic phase was washed successively with 5% potassium bisulfate, saturated sodium bicarbonate and saturated sodium chloride solutions
  7. dry with materialdried (sodium sulfate)
  8. customevaporated to dryness
  9. customPurification of the crude product by flash chromatography on silica gel (Whatmann LPS-1)
  10. washeluting with ethyl acetate:hexane (1:2)
  11. customgave 1.0747 g
  12. customA sample crystallized from hexane
  13. custom[α]D =+87.2° (c=0.53, chloroform)

출처 및 근거

ORD 기록
ord-32bc0b3ba19f4eee8fecd0b31789e6b2
출처 데이터셋
uspto-grants-1998_03
특허 번호
US05723602

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