Hydrochloric Acid → 3-{4-chloro-2-[2-chloro-2-(ethoxycarbonyl)ethyl]-6-fluoro-3-methoxyphenyl}-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

HRID 277439

反応式

HRID 277439 の反応式
N[C:2]1[C:7]([O:8][CH3:9])=[C:6]([Cl:10])[CH:5]=[C:4]([F:11])[C:3]=1[N:12]1[C:17](=[O:18])[CH:16]=[C:15]([C:19]([F:22])([F:21])[F:20])[N:14]([CH3:23])[C:13]1=[O:24].[C:25]([O:29][CH2:30][CH3:31])(=[O:28])[CH:26]=[CH2:27].N(OC(C)(C)C)=O.[ClH:39]>C(#N)C.[Cu](Cl)Cl>[Cl:10][C:6]1[CH:5]=[C:4]([F:11])[C:3]([N:12]2[C:17](=[O:18])[CH:16]=[C:15]([C:19]([F:21])([F:20])[F:22])[N:14]([CH3:23])[C:13]2=[O:24])=[C:2]([CH2:27][CH:26]([Cl:39])[C:25]([O:29][CH2:30][CH3:31])=[O:28])[C:7]=1[O:8][CH3:9]

参加物

7

反応物 4

HCID 313Hydrochloric AcidHCID 8821Ethyl AcrylateHCID 10906Tert-Butyl nitriteHCID 183145373-(2-Amino-4-chloro-6fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)pyrimidinedione

生成物 1

HCID 865859093-{4-chloro-2-[2-chloro-2-(ethoxycarbonyl)ethyl]-6-fluoro-3-methoxyphenyl}-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

試薬・触媒・溶媒 2

HCID 24014Cupric Chloride触媒HCID 6342Acetonitrile溶媒2 回

実験手順

A solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)pyrimidinedione (0.94 g, 2.56 mmol) in acetonitrile (3 ml) was slowly added to an acetonitrile (9 ml) solution of ethyl acrylate (6 ml), tert-butyl nitrite (0.41 g, 3.97 mmol), and copper (II) chloride (0.42 g, 3.12 mmol) at −20° C. After stirred for 16 hr (−20° C. to room temperature), the mixture was poured into cold 5% hydrochloric acid (30 ml) and extracted with ethyl acetate (20 ml ×3), the organic phase was washed with cold 5% NaHCO3 and brine, dried over Na2SO4. Column chromatography was used for purification (silica gel, hexane/ether=9/1) which also isolated two isomers. Yield: isomer-1 (eluted earlier), 0.23 g, 0.47 mmol; isomer-2 (eluted later), 0.14 g, 0.29 mmol.

後処理

  1. extractionextracted with ethyl acetate (20 ml ×3)
  2. washthe organic phase was washed with cold 5% NaHCO3 and brine
  3. dry with materialdried over Na2SO4
  4. customColumn chromatography was used for purification (silica gel, hexane/ether=9/1) which
  5. customalso isolated two isomers
  6. washYield: isomer-1 (eluted earlier), 0.23 g, 0.47 mmol
  7. washisomer-2 (eluted later), 0.14 g, 0.29 mmol

出典と根拠

ORDレコード
ord-c61bf01a734b445590057c2dceb0950b
出典データセット
uspto-grants-2002_03
特許番号
US06355799B1

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