Triphenylphosphine → 1-Azido-2-(benyloxycarbonylamino)-2-methylbutane

HRID 5556

반응식

HRID 5556 반응식
[CH2:1]([O:8][C:9]([NH:11][C:12]([CH3:17])([CH2:15][CH3:16])[CH2:13]O)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:37]=[N+:38]=[N-:39].[O-]S([O-])(=O)=O.[Mg+2].N(C(OC(C)C)=O)=NC(OC(C)C)=O.[N-]=[N+]=[N-]>C(Cl)Cl.CCOC(C)=O.CCCCCC>[N:37]([CH2:13][C:12]([NH:11][C:9]([O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:10])([CH3:17])[CH2:15][CH3:16])=[N+:38]=[N-:39]

참가 물질

9

반응물 6

HCID 11776TriphenylphosphineHCID 24083Sulfuric acid magnesium salt (1:1)HCID 24530Hydrazoic acidHCID 33558AzideHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 15235183Benzyl (1-hydroxy-2-methylbutan-2-yl)carbamate

생성물 1

HCID 152351841-Azido-2-(benyloxycarbonylamino)-2-methylbutane

시약·촉매·용매 2

HCID 6344Dichloromethane용매2회HCID 21226206Ethyl acetate hexane용매

반응 조건

온도
0 °C

실험 절차

2-(Benyloxycarbonylamino)-2-methyl-1-butanol (1.358 g, 5.722 mmol) and triphenylphosphine (1.800 g, 6.86 mmol) were dissolved in 10 mL CH2Cl2, and the resulting solution was cooled to 0° C. A solution of hydrazoic acid (prepared from sodium azide (1.30 g, 20.0 mmol), 0.533 mL concentrated sulfuric acid and 1.3 mL water) in 20 mL CH2Cl2 was passed through a plug of MgSO4, the filtrate was added to the above alcohol solution, then diisopropyl azodicarboxylate (1.35 mL, 1.40 g, 6.91 mmol) was added dropwise over 3 min. The reaction mixture was stirred at 0° C. for 1 h, then at room temperature for 5 h. The mixture was concentrated in vacuo, and the residue was applied to 300 g of silica gel in a fritted disc funnel and eluted with 3×500 mL of 10% EtOAc-hexane. The second fraction contained pure desired azide (0.822 g, 3.13 mmol, 55%) as a colorless oil: Rf 0.17 (10% EtOAc-hexane); 1H NMR (CDCl3) δ 1.33 (s, 6 H), 2.02 (bt, J=7.5 Hz, 2 H), 3.32 (bt, J=7.5 Hz, 2 H), 4.74 (br s, 1 H), 5.05 (s, 2 H), 7.3-7.4 (m, 5 H); MS m/e 263 ((M+H)+), 280 (M+NH4)+).

후처리

  1. waitat room temperature for 5 h
  2. concentrationThe mixture was concentrated in vacuo
  3. customthe residue was applied to 300 g of silica gel in a fritted disc funnel
  4. washeluted with 3×500 mL of 10% EtOAc-hexane

출처 및 근거

ORD 기록
ord-622c30d078094a8eb9dec49e03627d22
출처 데이터셋
uspto-grants-1993_09
특허 번호
US05244910

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