Tin tetrachloride → 3-Amino-4-chloro-5-ethoxy-benzoic acid methyl ester

HRID 1990862ノート

反応式

HRID 1990862 の反応式
[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[C:8]([N+:10]([O-])=O)[C:7]([Cl:13])=[C:6]([O:14][CH2:15][CH3:16])[CH:5]=1.[Sn](Cl)(Cl)(Cl)Cl>CO.Cl>[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:5]=[C:6]([O:14][CH2:15][CH3:16])[C:7]([Cl:13])=[C:8]([NH2:10])[CH:9]=1

参加物

5

反応物 2

HCID 24287Tin tetrachlorideHCID 686994194-Chloro-3-ethoxy-5-nitro-benzoic acid methyl ester

生成物 1

HCID 686990463-Amino-4-chloro-5-ethoxy-benzoic acid methyl ester

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 887Methanol溶媒

実験手順

To a solution of 4-chloro-3-ethoxy-5-nitro-benzoic acid methyl ester (1.0 g, 3.85 mmol, 1.0 equiv) in methanol (20 mL) was added dropwise under stirring at 0° C. a solution of tin chloride (2.92 g, 15.41 mmol, 4.0 equiv) in 37% HCl (7.5 mL). After the addition was completed the cooling bath was removed and the reaction mixture stirred at rt for 18 h. The solution was concentrated by evaporation under reduced pressure and the solution extracted with ethyl acetate (3×100 mL). The combined organic phases were dried over MgSO4, the solvent removed by evaporation under reduced pressure and the crude material purified by recrystallization from dichloromethane yielding 0.88 g (100%) of the title compound. 1H NMR (300 MHz, DMSO): δ 1.28 (t, J=7.0 Hz, 3H), 3.75 (s, 3H), 4.01 (q, J=7.0 Hz, 2H), 5.57 (br s, 2H), 6.71 (d, J=1.7 Hz, 1H), 7.03 (d, J=1.7 Hz, 1H). 13C NMR (75 MHz, DMSO): δ 14.51, 52.09, 64.31, 100.87, 108.93, 110.33, 128.52, 145.93, 154.51, 166.10. MS (ISP): 230.0 [M+H]+.

後処理

  1. additionAfter the addition
  2. customwas removed
  3. concentrationThe solution was concentrated by evaporation under reduced pressure
  4. extractionthe solution extracted with ethyl acetate (3×100 mL)
  5. dry with materialThe combined organic phases were dried over MgSO4
  6. customthe solvent removed by evaporation under reduced pressure
  7. customthe crude material purified by recrystallization from dichloromethane yielding 0.88 g (100%) of the title compound

出典と根拠

ORDレコード
ord-ba52e64bb49c45258447681b1f53b957
出典データセット
uspto-grants-2010_01
特許番号
US07645753B2

反応ノート

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