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Toluene → Methyl 3-(Boc-amino)-2-(4-chlorophenyl)propanoate

HRID 1675888
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HRID 1675888 반응식
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:13]C(OC(C)(C)C)=O)[C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.[C:21]([OH:27])(C(F)(F)F)=[O:22].C1(P([N:42]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.C(N(CC)CC)C.[N-]=[N+]=[N-].[C:55]1([CH3:61])[CH:60]=CC=C[CH:56]=1>C(Cl)Cl.C(O)(C)(C)C.Cl[Sn](Cl)(Cl)Cl>[C:55]([O:27][C:21]([NH:42][CH2:13][CH:8]([C:5]1[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=1)[C:9]([O:11][CH3:12])=[O:10])=[O:22])([CH3:61])([CH3:60])[CH3:56]
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참가 물질

10

반응물 6

HCID 1140TolueneHCID 6422Trifluoroacetic acidHCID 8471TriethylamineHCID 33558AzideHCID 199401P,P-Diphenylphosphinic azideHCID 666183864-Tert-butyl 1-methyl 2-(4-chlorophenyl)succinate

생성물 1

HCID 66617917
Methyl 3-(Boc-amino)-2-(4-chlorophenyl)propanoate
수율 79%

시약·촉매·용매 3

HCID 24287Tin tetrachloride촉매HCID 6344Dichloromethane용매HCID 6386tert-Butanol용매

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온도
0 °C

실험 절차

A solution of 4-tert-butyl 1-methyl 2-(4-chlorophenyl)succinate (14.3 g, 47.7 mmol) in DCM (75 mL) was treated with neat TFA (75 mL) at room temperature. The mixture was stirred for five hours to completion, after which the reaction mixture was concentrated and dried in vacuo overnight to afford a white solid. The solid was suspended in toluene (160 mL), cooled to 0° C., and treated successively with diphenylphosphoryl azide (11.2 mL, 52.1 mmol) and triethylamine (13.2 mL, 94.7 mmol). The reaction mixture (homogeneous) was allowed to warm to room temperature and stirred for four hours to completion. The solution was quenched with 1% citric acid solution and extracted with EtOAc (3×). The combined organics were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to give a light brown oil. The crude azide was dissolved in tert-butanol (160 mL), treated with neat SnCl4 (1.0M solution, 2.37 mL, 2.37 mmol), and carefully heated to 90° C. with evolution of nitrogen. The mixture was stirred at 90° C. for 2.5 hours and cooled to room temperature. The solution was quenched with saturated NaHCO3 solution and then concentrated. The oily mixture was extracted with EtOAc (3×), and the combined organics were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by on silica gel (4:1 hexanes:EtOAc) to afford the methyl 3-(tert-butoxycarbonylamino)-2-(4-chlorophenyl)propanoate as a pale yellow oil (11.7 g, 79%). 1H NMR (CDCl3, 400 MHz) δ 7.31 (d, J=8.0 Hz, 2H), 7.20 (d, J=8.0 Hz, 2H), 4.86 (br s, 1H), 3.88 (m, 1H), 3.69 (s, 3H), 3.58 (m, 1H), 3.49 (m, 1H), 1.42 (s, 9H).

후처리

  1. concentrationafter which the reaction mixture was concentrated
  2. customdried in vacuo overnight
  3. customto afford a white solid
  4. temperatureto warm to room temperature
  5. stirringstirred for four hours to completion
  6. customThe solution was quenched with 1% citric acid solution
  7. extractionextracted with EtOAc (3×)
  8. washThe combined organics were washed with brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customto give a light brown oil
  13. temperaturecarefully heated to 90° C. with evolution of nitrogen
  14. stirringThe mixture was stirred at 90° C. for 2.5 hours
  15. temperaturecooled to room temperature
  16. customThe solution was quenched with saturated NaHCO3 solution
  17. concentrationconcentrated
  18. extractionThe oily mixture was extracted with EtOAc (3×)
  19. washthe combined organics were washed with brine
  20. dry with materialdried over MgSO4
  21. filtrationfiltered
  22. concentrationconcentrated in vacuo
  23. customThe residue was purified by on silica gel (4:1 hexanes:EtOAc)

출처 및 근거

ORD 기록
ord-3c7b41ff35d3498aa270035112b756e4
출처 데이터셋
uspto-grants-2011_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08003651B2

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