Dichloromethane → (S)-2-((tert-butoxycarbonyl)amino)-3-(2-nitrophenoxy)propanoic acid

HRID 1187

반응식

HRID 1187 반응식
[CH3:1][C:2]([CH3:14])([O:4][C:5]([NH:7][C@H:8]([C:11]([OH:13])=[O:12])[CH2:9][OH:10])=[O:6])[CH3:3].[H-].[Na+].F[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[N+:24]([O-:26])=[O:25].C(Cl)Cl>CN(C)C=O.C(O)(=O)C.CO>[CH3:3][C:2]([CH3:14])([O:4][C:5]([NH:7][C@H:8]([C:11]([OH:13])=[O:12])[CH2:9][O:10][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[N+:24]([O-:26])=[O:25])=[O:6])[CH3:1]

참가 물질

8

반응물 4

HCID 6344DichloromethaneHCID 24758Sodium hydrideHCID 738951-Fluoro-2-nitrobenzeneHCID 98766N-[tert-butoxycarbonyl]-L-serine

생성물 1

HCID 18599736(S)-2-((tert-butoxycarbonyl)amino)-3-(2-nitrophenoxy)propanoic acid

시약·촉매·용매 3

HCID 176Acetic Acid용매HCID 887Methanol용매HCID 6228Dimethylformamide용매2회

실험 절차

A solution of N-[(1,1-dimethylethoxy)carbonyl]-L-serine (24.3 g., 0.118 mole) in dry dimethylformamide (25 ml.) was added dropwise over a period of 1.0 hour to a cooled (0°, ice-salt bath) suspension of 60% sodium hydride (10.1 g., 0.25 mole) in dry dimethylformamide (200 ml.) and stirring was continued at 0° until the frothing subsided (about 2.0 hours). The reaction mixture was treated dropwise with 1-fluoro-2-nitrobenzene (14.3 ml., 0.13 mole) over a period of 20 minutes, stirred at 0° under argon for 4.0 hours then poured into ice-water (750 ml.) and extracted with ethyl acetate (2×100 ml.). The aqueous phase was brought to pH 1.0 with 6N hydrochloric acid (70 ml.), extracted with ethyl acetate (3×500 ml.) and the combined organic extracts were washed with brine (100 ml.), dried (anhydrous sodium sulfate), filtered, evaporated to dryness and dried in vacuo. The crude product mixture was chromatographed on a silica gel column (Merck), eluting the column with methylene chloride:methanol:acetic acid (100:5:0.2) to give 27.22 g. of product as a thick yellow syrup; Rf =0.27 (methylene chloride:methanol:acetic acid, 100:5:0.5).

후처리

  1. temperaturea cooled
  2. customwas continued at 0° until the frothing
  3. custom(about 2.0 hours)
  4. stirringstirred at 0° under argon for 4.0 hours
  5. extractionextracted with ethyl acetate (2×100 ml.)
  6. extractionextracted with ethyl acetate (3×500 ml.)
  7. washthe combined organic extracts were washed with brine (100 ml.)
  8. dry with materialdried (anhydrous sodium sulfate)
  9. filtrationfiltered
  10. customevaporated to dryness
  11. customdried in vacuo
  12. customThe crude product mixture was chromatographed on a silica gel column (Merck)
  13. washeluting the column with methylene chloride:methanol:acetic acid (100:5:0.2)
  14. customto give 27.22 g

출처 및 근거

ORD 기록
ord-c2956910e6964c68a222931d19fd2abc
출처 데이터셋
uspto-grants-1998_03
특허 번호
US05723457

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