تفاعل #72436

معادلة التفاعل

(S)-4-Benzyloxycarbonylamino-2-hydroxybutyric acid

benzyl bromide

Barium oxide

barium oxide

barium hydroxide octahydrate

→

(S)-2-benzyloxy-4-benzyloxycarbonylaminobutyric acid

المذيبات

chloroform

HCl

water

water

acetic acid

N,N-dimethylformamide

chloroform

ethyl acetate

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITIONwas added
2. 2
   workup.WAITAfter 5 min
3. 3
   أخرىwas returned to room temperature
4. 4
   workup.WAITAfter 1.5 hr
5. 5
   workup.ADDITIONwas added
6. 6
   workup.ADDITIONwas added
7. 7
   أخرىfollowed by separation
8. 8
   استخلاصThe water layer was extracted with chloroform (50 mL)
9. 9
   غسيلwere washed with a saturated aqueous NaCl solution
10. 10
    تجفيفThe washed solution was dried over magnesium sulfate
11. 11
    أخرىThe solvent was removed by distillation under the reduced pressure
12. 12
    أخرىthe residue was purified by column chromatography on silica gel (silica gel 60, neutral spheres, 160 g) (chloroform:ethyl acetate=4:1→chloroform:methanol=10:1→chloroform:methanol:acetic acid=10:1:0.1 (600 mL))
13. 13
    أخرىto give (S)-2-benzyloxy-4-benzyloxycarbonylaminobutyrylic acid (2.86 g, 8.34 mmol)

الإجراء التجريبي

(S)-4-Benzyloxycarbonylamino-2-hydroxybutyric acid (5.25 g, 20.7 mmol) synthesized according to the report of Kawaguchi et al. (Journal of Antibiotics, Vol. 25, pp. 695-708 (1972)) was dissolved in 60 mL of N,N-dimethylformamide. Barium oxide (15.9 g, 103.7 mmol) was added under an ice bath. After the elapse of 2 min from the addition of barium oxide, barium hydroxide octahydrate (13.4 g, 42.5 mmol) was added thereto under an ice bath. After 10 min, benzyl bromide (7.5 mL, 63.1 mmol) was added thereto under an ice bath. After 5 min, the reaction solution was returned to room temperature and was vigorously stirred. After 1.5 hr, the completion of the reaction was confirmed by TLC (developing solvent system=chloroform:ethyl acetate:acetic acid=10:5:1), and water (0.5 mL) was added thereto under an ice bath. The mixture was diluted with chloroform (165 ml), and 4 N HCl (70 mL) was added thereto. Further, water (25 mL) was added followed by separation. The water layer was extracted with chloroform (50 mL). The organic layer and the extracted organic layer were combined and were washed with a saturated aqueous NaCl solution. The washed solution was dried over magnesium sulfate. The solvent was removed by distillation under the reduced pressure, and the residue was purified by column chromatography on silica gel (silica gel 60, neutral spheres, 160 g) (chloroform:ethyl acetate=4:1→chloroform:methanol=10:1→chloroform:methanol:acetic acid=10:1:0.1 (600 mL)) to give (S)-2-benzyloxy-4-benzyloxycarbonylaminobutyrylic acid (2.86 g, 8.34 mmol).

المصدر