Citric Acid → [4-(3-Bromo-5-hydroxy-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid Ethyl Acetate

HRID 549544ノート

反応式

HRID 549544 の反応式
[CH2:1]([O:3][C:4](=[O:15])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([SH:13])=[CH:9][C:8]=1[CH3:14])[CH3:2].[Br:16][C:17]1[C:18](Br)=[C:19]([OH:23])[CH:20]=[CH:21][CH:22]=1.C(N(CC)CC)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].CN1C(=O)CCC1>[CH2:1]([O:3][C:4](=[O:15])[CH3:5])[CH3:2].[Br:16][C:17]1[CH:22]=[C:21]([S:13][C:10]2[CH:11]=[CH:12][C:7]([O:6][CH2:5][C:4]([OH:3])=[O:15])=[C:8]([CH3:14])[CH:9]=2)[CH:20]=[C:19]([OH:23])[CH:18]=1

参加物

8

反応物 4

HCID 311Citric AcidHCID 8471TriethylamineHCID 342642,3-DibromophenolHCID 16641178Ethyl (4-mercapto-2-methylphenoxy)acetate

生成物 1

HCID 67024264[4-(3-Bromo-5-hydroxy-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid Ethyl Acetate

試薬・触媒・溶媒 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
105 °C

実験手順

(2-Methyl-4-mercapto-phenoxy)-acetic acid ethyl ester (6 g; 26.51 mmol), dibromo-phenol (8.68 g; 34.47 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.97 g; 1.06 mmol), and 1,1′-bis-(diphenylphosphino)ferrocene (0.88 g; 1.59 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (10.73 mL, 106 mmol) and NMP (20 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 105° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were washed twice with water (30 mL), dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane:ethyl acetate (10:1→7:3). Yield 6.5 g. HPLC-MS: m/z: 397.3 (M+); Rt: 2.33 min.

後処理

  1. extractionwas extracted with ethyl acetate (4×100 mL)
  2. washThe pooled organic phases were washed twice with water (30 mL)
  3. customdried
  4. customevaporated in vacuo
  5. customThe crude reaction product
  6. customwas purified by flash chromatography (heptane:ethyl acetate (10:1→7:3)

出典と根拠

ORDレコード
ord-88c5d72d599d473d9e7bcdb017c413e7
出典データセット
uspto-grants-2011_05
特許番号
US07943669B2

反応ノート

読み込み中…