反应 #1282

反应方程式

triethylamine

benzylchloroformate

(S)-1,3,4,5-tetrahydro-4-phthalimido-3-oxo-2H-2-benzazepine-2-acetic acid, ethyl ester

ethanol

→

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

溶剂

ethyl acetate

ethyl acetate

toluene

hydrazine hydrate

反应条件

后处理

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

实验过程

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).

来源