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

HRID 1186

反応式

HRID 1186 の反応式
[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

参加物

8

反応物 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

生成物 1

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

試薬・触媒・溶媒 3

HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒2 回HCID 24654Hydrazine hydrate (1:1)溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-6edcc2e8e3744c608ae582a2c614eb39
出典データセット
uspto-grants-1998_03
特許番号
US05723457

関連ノート

読み込み中…