Pivalaldehyde → Methyl (Z)-2-[(tert-butoxycarbonyl)amino]-4,4-dimethylpent-2-enoate

HRID 658134노트

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HRID 658134 반응식
[CH:1](=O)[C:2]([CH3:5])([CH3:4])[CH3:3].[C:7]([O:11][C:12]([NH:14][CH:15](P(OC)(OC)=O)[C:16]([O:18][CH3:19])=[O:17])=[O:13])([CH3:10])([CH3:9])[CH3:8]>C1COCC1>[C:7]([O:11][C:12]([NH:14]/[C:15](=[CH:1]\[C:2]([CH3:5])([CH3:4])[CH3:3])/[C:16]([O:18][CH3:19])=[O:17])=[O:13])([CH3:10])([CH3:9])[CH3:8]

참가 물질

4

반응물 2

HCID 12417PivalaldehydeHCID 397380Methyl ((tert-butoxy(hydroxy)methylidene)amino)(dimethoxyphosphoryl)acetate

생성물 1

HCID 59302433Methyl (Z)-2-[(tert-butoxycarbonyl)amino]-4,4-dimethylpent-2-enoate

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-70 °C

실험 절차

Pivalaldehyde (303.2 g, 3.41 mol, 10 eq.) and methyl {[(tert-butoxy)carbonyl]amino}-(dimethoxyphosphoryl)acetate (101.5 g, 0.341 mol, 1.0 eq.) are dissolved in THF (800 ml) and cooled to −70° C. At −70° C., TMG (78.7 g, 0.683 mmol, 6.95 ml, 2.0 eq.) is slowly added dropwise and the mixture is then stirred at −70° C. for 4 h and subsequently at RT for 4 days. The reaction mixture is concentrated and then extracted by shaking with ethyl acetate (twice 500 ml) and water, and the combined org. phases are washed with a sat. sodium chloride solution (100 ml) and dried over sodium sulfate. After concentration the crude product is chromatographed (1.5 kg of silica gel, eluent: cyclohexane/ethyl acetate 5:1). 67 g (76% of theory) of the title compound are obtained.

후처리

  1. additionAt −70° C., TMG (78.7 g, 0.683 mmol, 6.95 ml, 2.0 eq.) is slowly added dropwise
  2. concentrationThe reaction mixture is concentrated
  3. extractionextracted
  4. stirringby shaking with ethyl acetate (twice 500 ml) and water
  5. washphases are washed with a sat. sodium chloride solution (100 ml)
  6. dry with materialdried over sodium sulfate
  7. concentrationAfter concentration the crude product
  8. customis chromatographed (1.5 kg of silica gel, eluent: cyclohexane/ethyl acetate 5:1)

출처 및 근거

ORD 기록
ord-aae22c08ce45473791dac7f143857499
출처 데이터셋
uspto-grants-2011_12
특허 번호
US08076285B2

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