反応 #417301

反応方程式

beta-benzyl-N-benzyloxycarbonyl-L-aspartyl-D-alanine

triethylamine

tetrahydrofuran

ethyl chloroformate

→

vanillin

反応条件

後処理

1. 1
   その他three-necked flask fitted with a stopper
2. 2
   その他thermometer, drying tube and magnetic stirring bar
3. 3
   workup.ADDITIONwas added 4.28 g
4. 4
   温度cooled to -35° C.
5. 5
   workup.ADDITION(0.010 mole) of dicyclcpropylcarbinylamine added
6. 6
   温度to warm slowly to room temperature
7. 7
   workup.STIRRINGstirred overnight
8. 8
   workup.ADDITIONThe mixture was poured into 150 ml
9. 9
   抽出water, extracted with 250 ml
10. 10
    洗浄of ethyl acetate and the organic phase washed with 5% aqueous sodium bicarbonate (2×75 ml.), 3M hydrochloric acid (2×75 ml.), brine (1×100 ml.)
11. 11
    乾燥dried over anhydrous magnesium sulfate
12. 12
    抽出The dried extract
13. 13
    その他was evaporated to dryness in vacuo
14. 14
    その他to provide a colorless solid which
15. 15
    その他was recrystallized from 75 ml
16. 16
    その他of boiling ethyl acetate to obtain 3.78 g
17. 17
    洗浄Thin-layer chromatography (TLC) on silica gel, eluting with 1:1 ethyl acetate/hexane

実験手順

To a 250 ml. three-necked flask fitted with a stopper, thermometer, drying tube and magnetic stirring bar was added 4.28 g. (0.010 mole) of beta-benzyl-N-benzyloxycarbonyl-L-aspartyl-D-alanine, 75 ml. tetrahydrofuran and 1.53 ml. (0.011 mole) triethylamine. The mixture was cooled to -10° C., 1.05 ml. (0.011 mole) ethyl chloroformate was added, stirred for 20 minutes, cooled to -35° C. and 1.11 g. (0.010 mole) of dicyclcpropylcarbinylamine added. The reaction mixture was allowed to warm slowly to room temperature and stirred overnight. The mixture was poured into 150 ml. water, extracted with 250 ml. of ethyl acetate and the organic phase washed with 5% aqueous sodium bicarbonate (2×75 ml.), 3M hydrochloric acid (2×75 ml.), brine (1×100 ml.) and dried over anhydrous magnesium sulfate. The dried extract was evaporated to dryness in vacuo to provide a colorless solid which was recrystallized from 75 ml. of boiling ethyl acetate to obtain 3.78 g. (72%) of diblocked amide, M.P. 164°-165° C. Thin-layer chromatography (TLC) on silica gel, eluting with 1:1 ethyl acetate/hexane gave a single spot, Rf 0.40 with vanillin spray reagent. An additional 0.65 g. was recovered from the mother liquors. C. To a slurry of 2.58 g. (4.9 mmole) of the product obtained in Part B in 250 ml. of methanol was added 0.60 g. of 5% palladium-on-carbon catalyst (50% wet) and the mixture hydrogenated for one hour at an initial pressure of 71 psi (5.0 kg./cm.2). The catalyst was removed by filtration and the methanol evaporated at reduced pressure to afford 1.47 g. (100%) of colorless product, M.P. 190°-191° C. TLC in

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