Methyl Nicotinate → 1,4-Dihydro-1-ethoxycarbonyl-4-(4'-fluorophenyl)-3-methoxycarbonylpyridine

HRID 1723473ノート

反応式

HRID 1723473 の反応式
Cl[C:2]([O:4][CH2:5][CH3:6])=[O:3].[C:7]([O:15][CH3:16])(=[O:14])[C:8]1[CH:13]=[CH:12][CH:11]=[N:10][CH:9]=1.[F:17][C:18]1[CH:23]=[CH:22][C:21]([Mg]Br)=[CH:20][CH:19]=1.[Cl-].[NH4+].N>O1CCCC1.C(OCC)(=O)C>[CH2:5]([O:4][C:2]([N:10]1[CH:11]=[CH:12][CH:13]([C:21]2[CH:22]=[CH:23][C:18]([F:17])=[CH:19][CH:20]=2)[C:8]([C:7]([O:15][CH3:16])=[O:14])=[CH:9]1)=[O:3])[CH3:6]

参加物

7

反応物 4

HCID 7151Methyl NicotinateHCID 10928Ethyl chloroformateHCID 86743336Ammonia ammonium chlorideHCID 178418676HCID 178418676、化合物

生成物 1

HCID 110558661,4-Dihydro-1-ethoxycarbonyl-4-(4'-fluorophenyl)-3-methoxycarbonylpyridine収率 93%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

Ethyl chloroformate (3.5 ml) was added to a stirred suspension of cuprous chloride (0.33 g) in dry tetrahydrofuran (100 ml) under nitrogen. After cooling to 0°, a solution of methyl nicotinate (5.0 g) in tetrahydrofuran (10 ml) was added slowly followed by the addition of 4-fluorophenyl magnesium bromide solution [from 4-bromo-fluorobenzene (4.4 ml) and magnesium (0.93 g) in tetrahydrofuran (25 ml)]. After stirring for 20 minutes, the mixture was diluted with ethyl acetate and decomposed by the addition of a saturated ammonium chloride/ammonia solution (1:1, 100 ml). The organic phase was washed with dilute acid and brine and dried over anhydrous sodium sulphate. Evaporation of the solvent gave 1,4-dihydro-1-ethoxycarbonyl-4-(4'-fluorophenyl)-3-methoxycarbonylpyridine as an off-white solid (10.37 g, 93%). A sample crystallised from ethyl acetate had m.p. 83-85°.

後処理

  1. temperatureAfter cooling to 0°
  2. washThe organic phase was washed
  3. additionwith dilute acid and brine
  4. dry with materialdried over anhydrous sodium sulphate
  5. customEvaporation of the solvent

出典と根拠

ORDレコード
ord-1fc0179dcc2a4147a7abb961f3e26e7b
出典データセット
uspto-grants-1989_08
特許番号
US04861893

反応ノート

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