Sulfuric Acid → alpha-Methyl-4'-(methoxy)[1,1'-biphenyl]-4-acetic acid, ethyl ester

HRID 2380162ノート

反応式

HRID 2380162 の反応式
[CH3:1]OC1C=CC(C2C=CC(CC(O)=O)=CC=2)=CC=1.S(=O)(=O)(O)O.[CH3:24][O:25][C:26]1[CH:31]=[CH:30][C:29]([C:32]2[CH:37]=[CH:36][C:35]([CH2:38][C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:34][CH:33]=2)=[CH:28][CH:27]=1.C([N-]C(C)C)(C)C.[Li+].CI>O1CCCC1.O.C(O)C>[CH3:1][CH:38]([C:35]1[CH:36]=[CH:37][C:32]([C:29]2[CH:28]=[CH:27][C:26]([O:25][CH3:24])=[CH:31][CH:30]=2)=[CH:33][CH:34]=1)[C:39]([O:41][CH2:42][CH3:43])=[O:40]

参加物

9

反応物 5

HCID 1118Sulfuric AcidHCID 6328Methyl iodideHCID 13937004-Biphenyl-(4'-methoxy)acetic acidHCID 2724682Lithium diisopropylamideHCID 15733994Ethyl 4-(4-methoxyphenyl)phenylacetate

生成物 1

HCID 86746941alpha-Methyl-4'-(methoxy)[1,1'-biphenyl]-4-acetic acid, ethyl ester収率 69.6%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

The known starting material, 4'-methoxy-4-biphenylacetic acid (J. Chem. Soc. 1959, 557) is first converted to its ethyl ester by Fisher esterification with ethanol and concentrated sulfuric acid. To a solution of 4'-methoxy-4-biphenylacetic acid, ethyl ester (30.0 g, 0.110 mol) in tetrahydrofuran (400 mL) at -78° C. is added slowly, 2.01 M lithium diisopropylamide (63 mL). The mixture is stirred for 30 minutes and then methyl iodide (30 mL) is added rapidly. The reaction mixture is warmed to 0° C. for 30 minutes, then at room temperature for 3 hours. The mixture is poured into water (2 L) and is extracted with ethyl acetate (3×1 L). The combined ethyl acetate extract is washed with 1N HCl (1 L), water (1 L) and brine (1 L), dried over MgSO4 and is concentrated under reduced pressure to give 48 g of crude yellow oil. Purification of the product by column chromatography (12% ethyl acetate in hexane) gives 22.0 g (69.6 %) of crystalline material, m.p. 52°-54° C.

後処理

  1. waitat room temperature for 3 hours
  2. extractionis extracted with ethyl acetate (3×1 L)
  3. extractionThe combined ethyl acetate extract
  4. washis washed with 1N HCl (1 L), water (1 L) and brine (1 L)
  5. dry with materialdried over MgSO4
  6. concentrationis concentrated under reduced pressure
  7. customto give 48 g of crude yellow oil
  8. customPurification of the product by column chromatography (12% ethyl acetate in hexane)

出典と根拠

ORDレコード
ord-50e66714aa6e4eb3b5c32452b20d0914
出典データセット
uspto-grants-1994_11
特許番号
US05364944

反応ノート

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