Cesium fluoride → 1,4-Dimethyl-2-nitro-5-vinylbenzene

HRID 536396ノート

反応式

HRID 536396 の反応式
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH3:12].[CH:13](B(OCCCC)OCCCC)=[CH2:14].[F-].[Cs+]>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.COCCOC.CO>[CH3:8][C:6]1[CH:7]=[C:2]([CH:13]=[CH2:14])[C:3]([CH3:12])=[CH:4][C:5]=1[N+:9]([O-:11])=[O:10]

参加物

6

反応物 3

HCID 25953Cesium fluorideHCID 236543Dibutyl Vinylboronate (stabilized with Phenothiazine)HCID 8258081-Bromo-2,5-dimethyl-4-nitrobenzene

生成物 1

HCID 671554491,4-Dimethyl-2-nitro-5-vinylbenzene

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 86595564Dimethoxyethane methanol溶媒

反応条件

温度
130 °C

実験手順

To a microwave reaction vessel was added a mixture of 1-bromo-2,5-dimethyl-4-nitrobenzene (1.15 g, 5.0 mmol), dibutyl vinylboronate (1.16 g, 6.3 mmol), Pd(PPh3)4(289 mg, 0.25 mmol), CsF (2.28 g, 15 mmol) and a mixed solvent (1,2-dimethoxyethane/MeOH=2:1, 15 mL). The mixture was degassed and sealed with N2. The reaction vessel was then heated to 130° C. in a microwave reactor for 15 min. After opening the reaction vessel, the mixture was poured into saturated NH4Cl aqueous solution (30 mL) and extracted with EtOAc (3×50 mL). The combined organic layers were washed with brine and dried (MgSO4). After removing the drying agent by filtration, the filtrate was concentrated and purified by flash column chromatography (silica gel, 0-30% EtOAc in hexanes gradient) to provide 1,4-dimethyl-2-nitro-5-vinylbenzene as needlelike crystals; ESMS m/z 178.1 (M+H+).

後処理

  1. customTo a microwave reaction vessel
  2. additionwas added
  3. customThe mixture was degassed
  4. customsealed with N2
  5. additionthe mixture was poured into saturated NH4Cl aqueous solution (30 mL)
  6. extractionextracted with EtOAc (3×50 mL)
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried (MgSO4)
  9. customAfter removing the drying agent
  10. filtrationby filtration
  11. concentrationthe filtrate was concentrated
  12. custompurified by flash column chromatography (silica gel, 0-30% EtOAc in hexanes gradient)

出典と根拠

ORDレコード
ord-10698b50dd2f488aab6c0a01cc4b2397
出典データセット
uspto-grants-2014_10
特許番号
US08859574B2

反応ノート

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