Sodium Hydroxide → 1-Bromo-3-methyl-5-nitro-2-vinylbenzene

HRID 1468705ノート

反応式

HRID 1468705 の反応式
FC(F)(F)S(O[C:7]1[C:12]([CH3:13])=[CH:11][C:10]([N+:14]([O-:16])=[O:15])=[CH:9][C:8]=1[Br:17])(=O)=O.[CH2:20](C([Sn])=C(CCCC)CCCC)[CH2:21]CC.[Li+].[Cl-].[OH-].[Na+]>CN(C=O)C>[Br:17][C:8]1[CH:9]=[C:10]([N+:14]([O-:16])=[O:15])[CH:11]=[C:12]([CH3:13])[C:7]=1[CH:20]=[CH2:21]

参加物

6

反応物 4

HCID 14798Sodium HydroxideHCID 433294Lithium ChlorideHCID 53438229Tri(butyl)vinyltinHCID 866997872-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate

生成物 1

HCID 866997861-Bromo-3-methyl-5-nitro-2-vinylbenzene収率 30%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
70 °C

実験手順

The reaction mixture of 2-bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate (65B) (10.1 g, 27.7 mmol), tributylvinyltin (8.18 ml, 27.7 mmol), LiCl (1.4 g, 33.2 mmol), PdCl2dppf (607 mg, 0.83 mmol) in DMF (50 ml) was reacted at 70° C. for 3 h. Then 2N NaOH was added and stirred at 70° C. for 5 min. The reaction mixture was cooled down, washed by sat. NaHCO3, extracted by EtOAc, dry over MgSO4, filtered, concentrated down and purified by silica gel column, eluting by 0-100% EtOAc in Hexanes to give 65C (1.9 g, 30%). 1H-NMR: 400 MHz, (CDCl3) δ: 8.30 (d, J=0.8 Hz, 1H), 8.03 (d, J=1 Hz, 1H), 6.71-6.64 (dd, J=18, 12 Hz, 1H), 5.77-5.74 (d, J=12 Hz, 1H), 5.51-5.46 (d, J=18 Hz, 1H), 2.48 (s, 3H).

後処理

  1. customwas reacted at 70° C. for 3 h
  2. temperatureThe reaction mixture was cooled down
  3. washwashed by sat. NaHCO3
  4. extractionextracted by EtOAc
  5. dry with materialdry over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated down
  8. custompurified by silica gel column
  9. washeluting by 0-100% EtOAc in Hexanes

出典と根拠

ORDレコード
ord-1faa7832bde9447dbb9d270b9b89cf1e
出典データセット
uspto-grants-2015_04
特許番号
US09006229B2

反応ノート

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