Benzyl chloroformate → Boc-dap(Z)-OH

HRID 1055259

반응식

HRID 1055259 반응식
[NH:1]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[C@H:2]([C:5]([OH:7])=[O:6])[CH2:3][NH2:4].C([O-])([O-])=O.[K+].[K+].[OH-].[K+].[CH:23]1[CH:28]=[CH:27][C:26]([CH2:29][O:30][C:31](Cl)=[O:32])=[CH:25][CH:24]=1>O.C1COCC1>[NH:1]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[C@H:2]([C:5]([OH:7])=[O:6])[CH2:3][NH:4][C:31]([O:30][CH2:29][C:26]1[CH:27]=[CH:28][CH:23]=[CH:24][CH:25]=1)=[O:32]

참가 물질

7

반응물 4

HCID 10387Benzyl chloroformateHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 2755946Boc-Dap-OH

생성물 1

HCID 2755950Boc-dap(Z)-OH수율 94%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매

반응 조건

온도
-5 °C

실험 절차

A stirring mixture of the N-Boc-Dap-OH 1 (10.00 g, 49.02 mmol), THF (90 mL), water (30 mL), K2CO3 (13.53 g, 98.04 mmol) and KOH (2.75 g, 49.02 mmol) was cooled to −5° C. Cbz-Cl solution (50 wt % in toluene, 25 mL, 73.53 mmol) was then added dropwise over a period of an hour. The mixture was allowed to stir for 8 h before being concentrated under reduced pressure to remove the THF. The aqueous residue was extracted with diethyl ether (50 mL), acidified to pH 4 by solid citric acid and the resulting precipitate was extracted by CH2Cl2 (2 50 mL). Combined organic layers were dried (Na2SO4) and evaporated to furnish the free acid 2 (15.57 g, 94% yield) as a gummy white solid which was used without further purification. 1H NMR (300 MHz, CDCl3) δ10.76 (1H), 7.25 (5H), 6.24, 5.67 (2H), 5.85 (1H), 5.08, 5.02 (2H), 4.36-4.23 (1H), 3.63-3.35 (2H), 1.38 (9H); 13C NMR (75 MHz, CDCl3)δ 173.5, 157.5, 156.2, 136.4, 128.6, 128.2, 80.6, 67.3, 54.4, 42.9, 28.6.

후처리

  1. concentrationbefore being concentrated under reduced pressure
  2. customto remove the THF
  3. extractionThe aqueous residue was extracted with diethyl ether (50 mL)
  4. extractionthe resulting precipitate was extracted by CH2Cl2 (2 50 mL)
  5. dry with materialCombined organic layers were dried (Na2SO4)
  6. customevaporated

출처 및 근거

ORD 기록
ord-2cb57f19cf16490488ec1898174ca183
출처 데이터셋
uspto-grants-2016_07
특허 번호
US09394338B2

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