6-bromo-2,2-dimethyl-4H-spiro[chromene-3,1'-cyclopropan]-4-one → 6-bromo-2,2-dimethyl-4-methylene-4H-spiro[chromene-3,1'-cyclopropane]

HRID 594882노트

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HRID 594882 반응식
[CH2:1]([Li])CCC.[Br:6][C:7]1[CH:8]=[C:9]2[C:16](=[CH:17][CH:18]=1)[O:15][C:14]([CH3:20])([CH3:19])[C:11]1([CH2:13][CH2:12]1)[C:10]2=O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[Br:6][C:7]1[CH:8]=[C:9]2[C:16](=[CH:17][CH:18]=1)[O:15][C:14]([CH3:20])([CH3:19])[C:11]1([CH2:13][CH2:12]1)[C:10]2=[CH2:1]

참가 물질

5

반응물 2

HCID 867242776-bromo-2,2-dimethyl-4H-spiro[chromene-3,1'-cyclopropan]-4-oneHCID 178418339Butyllithium

생성물 1

HCID 867242836-bromo-2,2-dimethyl-4-methylene-4H-spiro[chromene-3,1'-cyclopropane]수율 95%

시약·촉매·용매 2

HCID 74505Methyltriphenyliphosphonium bromide촉매HCID 8028Tetrahydrofuran용매

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온도
0 °C

실험 절차

To a suspension of methyl(triphenyl)phosphonium bromide (20.8 g, 58.2 mmol) in tetrahydrofuran (168 ml) was added n-butyllithium (2.69 M solution in hexane, 21.6 ml, 58.2 mmol) under dry ice-acetone bath cooling and argon atmosphere. The mixture was stirred for 1 hour at 0° C. To the mixture was added 6-bromo-2,2-dimethyl-4H-spiro[chromene-3,1′-cyclopropan]-4-one (8.18 g, 29 mmol). The mixture was stirred for 1 hour at 0° C. The reaction was quenched by adding water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The residue was purified by silicagel column chromatography (hexane/ethyl acetate=20:1-10:1) to afford 6-bromo-2,2-dimethyl-4-methylene-4H-spiro[chromene-3,1′-cyclopropane] (7.69 g).

후처리

  1. temperaturecooling
  2. stirringThe mixture was stirred for 1 hour at 0° C
  3. customThe reaction was quenched
  4. additionby adding water
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by silicagel column chromatography (hexane/ethyl acetate=20:1-10:1)

출처 및 근거

ORD 기록
ord-75deb37f810742f692be770eb1477749
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09242973B2

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