Sodium Carbonate → 1-Methyl-5-nitro-4-propoxy-2-vinyl-benzene

HRID 1850911ノート

反応式

HRID 1850911 の反応式
Cl[C:2]1[CH:7]=[C:6]([O:8][CH:9]([CH3:11])C)[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][C:3]=1[CH3:15].[CH2:16](OB(C=C)OCCCC)[CH2:17]CC.[C:29](=O)([O-])[O-].[Na+].[Na+]>C1COCC1.O>[CH3:15][C:3]1[CH:4]=[C:5]([N+:12]([O-:14])=[O:13])[C:6]([O:8][CH2:9][CH2:11][CH3:29])=[CH:7][C:2]=1[CH:16]=[CH2:17]

参加物

5

反応物 3

HCID 10340Sodium CarbonateHCID 236543Dibutyl Vinylboronate (stabilized with Phenothiazine)HCID 457903241-Chloro-5-isopropoxy-2-methyl-4-nitrobenzene2 回

生成物 1

HCID 670710261-Methyl-5-nitro-4-propoxy-2-vinyl-benzene

試薬・触媒・溶媒 1

HCID 21881883Oxolane--water (1/1)溶媒

反応条件

温度
90 °C

実験手順

To a mixture of 1-chloro-2-methyl-4-nitro-5-isopropoxy-benzene (Intermediate 4, 870 mg, 3.77 mmol), vinylboronic acid dibutyl ester (1.24 mL, 5.6 mmol), and sodium carbonate (2.8 g, 26.4 mmol) in THF/H2O (20/5 mL) is added dichlorobis(triphenylphosphine) palladium (II) (132 mg, 5% mmol). The reaction tube is sealed, the mixture is purged with N2 for 3 min and then heated at 90° C. under N2 for overnight. The reaction is cooled to room temperature and poured into saturated aqueous ammonia chloride solution. The crude reaction mixture is extracted with ethyl acetate (3×100 mL). The organic extracts are combined, washed with brine and concentrated. The crude product is purified with silica gel column chromatography (10% ethyl acetate in hexanes) to afford 1-methyl-5-nitro-4-propoxy-2-vinyl-benzene as a yellow solid. 1-Methyl-5-nitro-4-propoxy-2-vinyl-benzene obtained from the previous step (360 mg, 1.63 mmol) is dissolved in DCM (20 mL) and is cooled to −78° C. O3 (g) is bubbled into the solution until the solution's color turns blue/gray. The solution is then purged with N2 (g) until the blue color disappears. The solution is warmed to room temperature and treated with triphenylphosphine resin (2 g) pre-swelled in DCM (30 mL). After 30 min, the mixture is filtered, and the filtrate is concentrated to afford 2-methyl-4-nitro-5-propoxy-benzaldehyde as yellow solid.

後処理

  1. customThe reaction tube is sealed
  2. customthe mixture is purged with N2 for 3 min
  3. temperatureThe reaction is cooled to room temperature
  4. additionpoured into saturated aqueous ammonia chloride solution
  5. customThe crude reaction mixture
  6. extractionis extracted with ethyl acetate (3×100 mL)
  7. washwashed with brine
  8. concentrationconcentrated
  9. customThe crude product is purified with silica gel column chromatography (10% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-41280a79c48a40719295074faf4062a2
出典データセット
uspto-grants-2015_02
特許番号
US08957081B2

反応ノート

読み込み中…