2-Bromopyrimidine → 3-((e)-2-(Pyrimidin-2-yl)vinyl)-5,5,8,8,-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde

HRID 1836913노트

반응식

HRID 1836913 반응식
Br[C:2]1[C:3]([CH:16]=[O:17])=[CH:4][C:5]2[C:6]([CH3:15])([CH3:14])[CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]=2[CH:11]=1.C([Sn](C[CH2:43][CH2:44][CH3:45])(CCCC)/C=C/[Sn](CCCC)(CCCC)CCCC)CCC.BrC1[N:52]=[CH:51][CH:50]=[CH:49][N:48]=1>C1(C)C=CC=CC=1.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>[N:48]1[CH:49]=[CH:50][CH:51]=[N:52][C:43]=1/[CH:44]=[CH:45]/[C:2]1[C:3]([CH:16]=[O:17])=[CH:4][C:5]2[C:6]([CH3:15])([CH3:14])[CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]=2[CH:11]=1

참가 물질

6

반응물 3

HCID 783452-BromopyrimidineHCID 5378370trans-1,2-Bis(tri-n-butylstannyl)ethyleneHCID 177898873-Bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde

생성물 1

HCID 234988743-((e)-2-(Pyrimidin-2-yl)vinyl)-5,5,8,8,-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde수율 27%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매2회HCID 1140Toluene용매2회

실험 절차

A solution of 0.874 g (2.96 mmol) of 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde, 1.886 g (3.11 mmol) of trans-1,2-bis(tri-n-butylstannyl)ethylene and 0.068 g (0.059 mmol) of tetrakis(triphenylphosphine)palladium in 20 ml toluene was heated to reflux under argon for 1.75 hour. The reaction was cooled slightly and 0.518 g (3.26 mmol) of 2-bromopyrimidine and 0.068 g (0.059 mmol) of tetrakis(triphenylphosphine)palladium was added in 3.5 ml toluene. The reaction was heated at reflux for 3 hours. The reaction was cooled to room temperature, quenched with 5% potassium fluoride and diluted with ethyl acetate. The two phases were stirred vigorously for 16 hours. The mixture was filtered through celite and the organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude material was purified by flash chromatography (gradient elution with 20% ethyl acetate/hexane-25% ethyl acetate/hexane) to afford 0.254 g (27%) of 3-((E)-2-(pyrimidin-2-yl)vinyl)-5,5,8,8,-tetramethyl-5,6,7,8-tetrahydro-2-naphthaldehyde (M+1=321).

후처리

  1. temperatureto reflux under argon for 1.75 hour
  2. temperatureThe reaction was cooled slightly
  3. temperatureThe reaction was heated
  4. temperatureat reflux for 3 hours
  5. customquenched with 5% potassium fluoride
  6. additiondiluted with ethyl acetate
  7. filtrationThe mixture was filtered through celite
  8. washthe organic layer was washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated in vacuo
  11. customThe crude material was purified by flash chromatography (gradient elution with 20% ethyl acetate/hexane-25% ethyl acetate/hexane)

출처 및 근거

ORD 기록
ord-fb9e110f1f6d4e1fa68c255be40b133b
출처 데이터셋
uspto-grants-2004_08
특허 번호
US06777418B2

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