Ethyl bromoacetate → Ethyl acetate methanol ammonia

HRID 488849

반응식

HRID 488849 반응식
[N-:1]=[N+]=[N-].[Na+].[C:5]([O:8][C@@H:9]1C[C@H](O)C=[CH:10]1)(=[O:7])[CH3:6].[H-].[Na+].BrC[C:19](OCC)=[O:20].[Cl-].[NH4+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O.O1CCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:5]([O:8][CH2:9][CH3:10])(=[O:7])[CH3:6].[CH3:19][OH:20].[NH3:1]

참가 물질

10

반응물 6

HCID 7748Ethyl bromoacetateHCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 33557Sodium AzideHCID 10154103rac-(1R,4S)-4-hydroxycyclopent-2-en-1-yl acetate

생성물 1

HCID 21873639Ethyl acetate methanol ammonia

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매2회HCID 8028Tetrahydrofuran용매5회

반응 조건

온도
20 °C

실험 절차

A solution of sodium azide (4.70 g) in degassed water (25 ml) was added to a solution of (1R,4S)-4-hydroxy-2-cyclopenten-1-yl acetate (9.99 g) in tetrahydrofuran (60 ml) and stirred for 10 min. Tetrakis(triphenylphosphine)palladium(0) (365 mg) was added and stirred for 10 min. The aqueous layer was separated and extracted twice with ethyl acetate. The combined organic layers were dried (MgSO4), concentrated and purified on a short column (SiO2, ethyl acetate:isohexane 1:2 as eluant) to afford a yellow oil. This was dissolved in tetrahydrofuran (25 ml) and slowly added to a suspension of sodium hydride (2.94 g, 60% dispersion in oil) in tetrahydrofuran (60 ml) at −78° C. A solution of ethyl bromoacetate (8.2 ml) in tetrahydrofuran (5 ml) was added and the mixture was allowed to warm to 20° C. and stirred for 30 min. Aqueous ammonium chloride solution was added and the mixture was extracted with ether. The organic layers were dried (MgSO4), concentrated and purified (SiO2, ether:isohexane 1:5 as eluant) to afford a colourless oil. A solution of this oil and triphenylphosphine (17.89 g) in tetrahydrofuran (90 ml) was stirred for 10 min. Water (15 ml) was added and the solution was stirred for 18 hours. The solvent was removed in vacuo and the residue azeotroped with toluene then purified (SiO2, ethyl acetate then ethyl acetate-methanol-ammonia (90:9:1) as eluant) to afford a pale yellow oil (7.14 g).

후처리

  1. stirringstirred for 10 min
  2. customThe aqueous layer was separated
  3. extractionextracted twice with ethyl acetate
  4. dry with materialThe combined organic layers were dried (MgSO4)
  5. concentrationconcentrated
  6. custompurified on a short column (SiO2, ethyl acetate:isohexane 1:2 as eluant)
  7. customto afford a yellow oil
  8. stirringstirred for 30 min
  9. extractionthe mixture was extracted with ether
  10. dry with materialThe organic layers were dried (MgSO4)
  11. concentrationconcentrated
  12. custompurified (SiO2, ether:isohexane 1:5 as eluant)
  13. customto afford a colourless oil
  14. stirringthe solution was stirred for 18 hours
  15. customThe solvent was removed in vacuo
  16. customthe residue azeotroped with toluene
  17. customthen purified (SiO2, ethyl acetate

출처 및 근거

ORD 기록
ord-201d2c581b65438383b2dccbaace6b75
출처 데이터셋
uspto-grants-2005_12
특허 번호
US06974868B2

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