反応 #1282

ord-6edcc2e8e3744c608ae582a2c614eb39

反応方程式

CCN(CC)CC
triethylamine
O=C(Cl)OCc1ccccc1
benzylchloroformate
CCOC(=O)CN1Cc2ccccc2C[C@H](N2C(=O)c3ccccc3C2=O)C1=O
(S)-1,3,4,5-tetrahydro-4-phthalimido-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester
CCO
ethanol
CCOC(=O)CN1Cc2ccccc2C[C@H](NC(=O)OCc2ccccc2)C1=O
(S)-1,3,4,5-Tetrahydro-4-[[(phenylmethoxy)carbonyl]amino]-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester

反応条件

温度
0°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    ろ過filtered
  2. 2
    その他filtrate evaporated to dryness
  3. 3
    その他again evaporated to dryness
  4. 4
    その他placed in an ice bath
  5. 5
    その他the mixture was partitioned between ethyl acetate-5% potassium bisulfate
  6. 6
    洗浄The organic phase was washed successively with 5% potassium bisulfate, saturated sodium bicarbonate and saturated sodium chloride solutions
  7. 7
    乾燥dried (sodium sulfate)
  8. 8
    その他evaporated to dryness
  9. 9
    その他Purification of the crude product by flash chromatography on silica gel (Whatmann LPS-1)
  10. 10
    洗浄eluting with ethyl acetate:hexane (1:2)
  11. 11
    その他gave 1.0747 g
  12. 12
    その他A sample crystallized from hexane
  13. 13
    その他[α]D =+87.2° (C=0.53, chloroform)

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).

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US05723457uspto-grants-1998_03