3,5-Dichloro-4-hydroxybenzoic acid → 2,6-Dichloro-4-[[[[3-[[(1,1-dimethylethyl)dimethyl-silyl]oxy]phenyl]methyl]amino]carbonyl]phenol

HRID 393030

反応式

HRID 393030 の反応式
[CH3:1][C:2]([Si:5]([CH3:16])([CH3:15])[O:6][C:7]1[CH:8]=[C:9]([CH2:13][NH2:14])[CH:10]=[CH:11][CH:12]=1)([CH3:4])[CH3:3].[Cl:17][C:18]1[CH:19]=[C:20]([CH:24]=[C:25]([Cl:28])[C:26]=1[OH:27])[C:21](O)=[O:22].CN([P+](ON1N=NC2C=CC=CC1=2)(N(C)C)N(C)C)C.F[P-](F)(F)(F)(F)F.C(N(C(C)C)CC)(C)C>ClCCl>[Cl:17][C:18]1[CH:19]=[C:20]([C:21]([NH:14][CH2:13][C:9]2[CH:10]=[CH:11][CH:12]=[C:7]([O:6][Si:5]([C:2]([CH3:1])([CH3:3])[CH3:4])([CH3:16])[CH3:15])[CH:8]=2)=[O:22])[CH:24]=[C:25]([Cl:28])[C:26]=1[OH:27]

参加物

6

反応物 4

HCID 187493,5-Dichloro-4-hydroxybenzoic acidHCID 81531DiisopropylethylamineHCID 151348Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphateHCID 222661693-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]benzenemethanamine

生成物 1

HCID 226613522,6-Dichloro-4-[[[[3-[[(1,1-dimethylethyl)dimethyl-silyl]oxy]phenyl]methyl]amino]carbonyl]phenol収率 87%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

A solution of 3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]benzenemethanamine (Example 8; 5.80 g, 24.5 mmol) in dry dichloromethane (20 mL) was added to a cooled (0° C.) suspension of 3,5-dichloro-4-hydroxybenzoic acid (4.2 g, 20.4 mmol) and BOP reagent (9.80 g, 22.3 mmol) in dry dichloromethane (50 mL). Diisopropylethylamine (10.6 mL, 60.9 mmol) was added slowly, and the cooling bath was removed. The solution was stirred at room temperature for 5 h, then the solvent was evaporated and the residue was dissolved in ethyl acetate. The solution was washed with 1 M HCl (2×100 mL), saturated aqueous sodium hydrogen carbonate (100 mL), and brine (100 mL), dried (MgSO4), filtered, evaporated, and chromatographed (30% ethyl acetate/hexanes) to give 2,6-dichloro-4-[[[[3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]phenyl]methyl]amino]carbonyl]phenol (7.50 g, 87%) as a white solid.

後処理

  1. temperaturea cooled
  2. customthe cooling bath was removed
  3. customthe solvent was evaporated
  4. dissolutionthe residue was dissolved in ethyl acetate
  5. washThe solution was washed with 1 M HCl (2×100 mL), saturated aqueous sodium hydrogen carbonate (100 mL), and brine (100 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. customchromatographed (30% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-c1bdd17c95d843a9a4633411b80f843c
出典データセット
uspto-grants-2004_10
特許番号
US06803384B2

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