Water → 4-(Methanesulfonylmethyl)-2-methoxyaniline

HRID 1014236ノート

反応式

HRID 1014236 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[N+:11]([O-])=O)[CH2:6]Cl.[Na+].[CH3:15][S:16]([O-:18])=[O:17].O>C(O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH2:6][S:16]([CH3:15])(=[O:18])=[O:17])[CH:8]=[CH:9][C:10]=1[NH2:11]

参加物

5

反応物 3

HCID 962WaterHCID 2733271Sodium methanesulfinateHCID 220516194-(Chloromethyl)-2-methoxy-1-nitrobenzene

生成物 1

HCID 594419624-(Methanesulfonylmethyl)-2-methoxyaniline収率 83.4%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
80 °C

実験手順

To a solution of 3-methoxy-4-nitrobenzyl chloride (2.76 g, 13.7 mmol) in 20 mL of absolute ethanol was added methanesulphinic acid sodium salt (1.0 g, 27.4 mmol). The reaction was heated to 80° C. for 16 h. The reaction was cooled to room temperature and poured into water and the aqueous layer was extracted with ethyl acetate. Combined organics were dried over anhydrous MgSO4, filtered, concentrated onto silica gel and purified by flash chromatography with ethyl acetate/hexanes as the eluent. The fractions containing the desired product were concentrated to dryness, then redisolved in absolute ethanol and 10% Palladium on carbon (500 mg) was added and the reaction was placed on the Fischer-Porter hydrogenation apparatus and treated with 50 psi of H2 gas overnight to afford 2-(methyloxy)-4-[(methylsulfonyl) methyl]aniline (2.46 g, 83%). 1H NMR (400 MHz, CDCl3) δ ppm 6.80 (d, J=1.7 Hz, 1H), 6.68 (d, J=8.0, 1.6 Hz, 1H), 6.57 (d, J=8.1, 1H), 4.82 (s, 2H), 4.21 (s, 2H), 3.72 (s, 3H).

後処理

  1. temperatureThe reaction was cooled to room temperature
  2. extractionthe aqueous layer was extracted with ethyl acetate
  3. dry with materialCombined organics were dried over anhydrous MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated onto silica gel
  6. custompurified by flash chromatography with ethyl acetate/hexanes as the eluent
  7. additionThe fractions containing the desired product
  8. concentrationwere concentrated to dryness
  9. addition10% Palladium on carbon (500 mg) was added
  10. additiontreated with 50 psi of H2 gas overnight

出典と根拠

ORDレコード
ord-d861e61e119e421da429d29f62f6c54f
出典データセット
uspto-grants-2011_07
特許番号
US07981903B2

反応ノート

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