Phosphonium, (2-methoxy-2-oxoethyl)triphenyl-, bromide (1:1) → methyl (E)-3-[3-bromo-5-(1-cyanocyclopropyl)phenyl]prop-2-enoate

HRID 1920860

반응식

HRID 1920860 반응식
[Br-].[CH3:2][O:3][C:4](=[O:25])[CH2:5][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[Br:36][C:37]1[CH:38]=[C:39]([C:45]2([C:48]#[N:49])[CH2:47][CH2:46]2)[CH:40]=[C:41]([CH:43]=O)[CH:42]=1>C1COCC1>[Br:36][C:37]1[CH:42]=[C:41](/[CH:43]=[CH:5]/[C:4]([O:3][CH3:2])=[O:25])[CH:40]=[C:39]([C:45]2([C:48]#[N:49])[CH2:47][CH2:46]2)[CH:38]=1

참가 물질

5

반응물 3

HCID 2733211Phosphonium, (2-methoxy-2-oxoethyl)triphenyl-, bromide (1:1)HCID 2733832Lithium HexamethyldisilazideHCID 57969743HCID 57969743, 화합물

생성물 1

HCID 86636473methyl (E)-3-[3-bromo-5-(1-cyanocyclopropyl)phenyl]prop-2-enoate수율 97.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매3회

반응 조건

온도
-25 °C

실험 절차

To a suspension of (2-methoxy-2-oxo-ethyl)-triphenyl-phosphonium bromide (1.502 g, 3.618 mmol) in THF (15 mL) under nitrogen at room temperature was added LHMDS in THF (3.358 mL of 1 M, 3.358 mmol) dropwise. The mixture was stirred for 10 mins then cooled to −25° C. 1-(3-bromo-5-formyl-phenyl)cyclopropane-1-carbonitrile (500 mg, 1.999 mmol) was dissolved in 1 mL of THF and added to the reaction. The reaction was allowed to warm to room temperature over 1 hour. The reaction was quenched with MeOH (2 mL) and then partitioned between ethyl acetate and brine. The aqueous was extracted with ethyl acetate and dried, filtered and concentrated. The crude product was purified on silica (Companion, 24 g) eluting with 1-20% EtOAc:Petrol ether to give methyl (E)-3-[3-bromo-5-(1-cyanocyclopropyl)phenyl]prop-2-enoate as a yellow solid (594 mg, 97%).

후처리

  1. additionadded to the reaction
  2. temperatureto warm to room temperature over 1 hour
  3. customThe reaction was quenched with MeOH (2 mL)
  4. custompartitioned between ethyl acetate and brine
  5. extractionThe aqueous was extracted with ethyl acetate
  6. customdried
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified on silica (Companion, 24 g)
  10. washeluting with 1-20% EtOAc

출처 및 근거

ORD 기록
ord-65b330ad44924c08be48c7f91ca5f2d5
출처 데이터셋
uspto-grants-2012_05
특허 번호
US08173635B2

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