Hydrochloric Acid → HCID 178496276、化合物

HRID 1805459ノート

反応式

HRID 1805459 の反応式
[N:1]([O-])=O.[Na+].[F:5][CH:6]([F:15])[O:7][C:8]1[CH:14]=[CH:13][CH:12]=[CH:11][C:9]=1[NH2:10].Cl.[CH3:17][O:18][CH2:19][C:20](=[O:26])[CH2:21][C:22]([O:24][CH3:25])=[O:23].CC([O-])=O.[Na+]>O.CO>[F:5][CH:6]([F:15])[O:7][C:8]1[CH:14]=[CH:13][CH:12]=[CH:11][C:9]=1[NH:10][N:1]=[C:21]([C:20](=[O:26])[CH2:19][O:18][CH3:17])[C:22]([O:24][CH3:25])=[O:23]

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 123500Methyl 4-methoxyacetoacetateHCID 517045Sodium AcetateHCID 9346202-(Difluoromethoxy)anilineHCID 23668193Sodium Nitrite

生成物 1

HCID 178496276HCID 178496276、化合物収率 96%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 962Water溶媒

反応条件

温度
0 °C

実験手順

A solution of NaNO2 (2.378 g, 34.5 mmol) in H2O (10 mL) was added dropwise at 0° C. to a solution of 2-(difluoromethoxy)aniline (3.59 mL, 28.7 mmol) in 6 M HCl aqueous solution (28.7 mL, 172 mmol). After stirring for 15 min, the resulting aqueous solution was added to a suspension of methyl 4-methoxyacetoacetate (3.72 mL, 28.7 mmol) and NaOAc (14.14 g, 172 mmol) in MeOH (50 mL) pre-cooled at 0° C. The precipitate was collected by filtration, washed with water, and dissolved in AcOEt. The organic solution was washed with water, saturated NaHCO3 aqueous solution and brine, dried over MgSO4, and concentrated under reduced pressure. The residue was washed with hexane/AcOEt (3/1) to give the title compound (8.70 g, 96% yield) as yellow crystals: 1H NMR (300 MHz, CDCl3): δ ppm 3.51 (3H, s), 3.89 (3H×0.5, s), 3.94 (3H×0.5, s), 4.68 (1H×0.5, s), 4.70 (1H×0.5, s), 6.63 (1H×0.5, t, J=72.7 Hz), 6.66 (1H×0.5, t, J=72.3 Hz), 7.10-7.34 (4H, m), 7.67 (1H×0.5, dd, J=8.3, 1.5 Hz), 7.90 (1H×0.5, dd, J=8.3, 1.5 Hz), 13.14 (1H×0.5, s), 14.96 (1H×0.5, br s).

後処理

  1. filtrationThe precipitate was collected by filtration
  2. washwashed with water
  3. dissolutiondissolved in AcOEt
  4. washThe organic solution was washed with water, saturated NaHCO3 aqueous solution and brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated under reduced pressure
  7. washThe residue was washed with hexane/AcOEt (3/1)

出典と根拠

ORDレコード
ord-21d4b9d1c5964067a963d95a3f89d6ed
出典データセット
uspto-grants-2013_01
特許番号
US08354411B2

反応ノート

読み込み中…