Chloroform → Methyl 5-nitro-2-(2-methoxy-6-methoxymethoxyphenyl)-benzoate

HRID 1358126ノート

反応式

HRID 1358126 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([O:9][CH2:10][O:11][CH3:12])[CH:4]=1.C([Li])CCC.[CH3:18][O:19][C:20](=[O:31])[C:21]1[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=1Br.C(Cl)(Cl)Cl>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cl-].[Zn+2].[Cl-]>[N+:27]([C:25]1[CH:24]=[CH:23][C:22]([C:4]2[C:5]([O:9][CH2:10][O:11][CH3:12])=[CH:6][CH:7]=[CH:8][C:3]=2[O:2][CH3:1])=[C:21]([CH:26]=1)[C:20]([O:19][CH3:18])=[O:31])([O-:29])=[O:28]

参加物

8

反応物 4

HCID 6212ChloroformHCID 245494Methyl 2-Bromo-5-nitrobenzoateHCID 5426211-Methoxy-3-(methoxymethoxy)benzeneHCID 178418339Butyllithium

生成物 1

HCID 18189455Methyl 5-nitro-2-(2-methoxy-6-methoxymethoxyphenyl)-benzoate

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 178418476HCID 178418476、化合物溶媒

反応条件

温度
25 °C

実験手順

A solution of 1-methoxy-3-methoxymethoxy benzene (3.62 g., 21.55 mmole), prepared as described in J. Med. Chem. 1995, 38, 1437-1445, in THF (15 mL) at −30° C. was treated with n-butyllithium (8.28 ml. of 2.5M in hexane, 20.69 mmole), stirred for 1 hour at 25° C., cooled to 0° C., treated with anhydrous zinc chloride beads (3.5 g, 25.67 mmole), stirred for 2 hours at 25° C., treated with a solution of methyl-2-bromo-5-nitrobenzoate (5.0 g, 19.23 mmol) in THF (20 mL) and bis(triphenylphosphine)palladium dichloride (600 mg), stirred it 65° C. for 15 hours, cooled, and treated with chloroform and aqueous KHCO3. The precipitated zinc salts were filtered, and the water layer was removed, and the organic layer dried over (Na2SO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 8% ethyl acetate in dichloromethane to provide the desired product. MS (ESI(−)Q1MS) m/z 346 (M−H)−.

後処理

  1. temperaturecooled to 0° C.
  2. stirringstirred for 2 hours at 25° C.
  3. stirringstirred it 65° C. for 15 hours
  4. temperaturecooled
  5. filtrationThe precipitated zinc salts were filtered
  6. customthe water layer was removed
  7. dry with materialthe organic layer dried over (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe concentrate was purified by flash column chromatography on silica gel with 8% ethyl acetate in dichloromethane

出典と根拠

ORDレコード
ord-d5132172fe0b4164922555b46eadfa86
出典データセット
uspto-grants-2003_07
特許番号
US06593480B2

反応ノート

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