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Hydrochloric Acid → cis-Methyl 4-(3-ethoxy-3-oxopropanoyl)-2-(2-fluoro-4-(trifluoromethyl)phenyl)piperidine-1-carboxylate

HRID 1963476
ノート
印刷プレビュー

反応式

HRID 1963476 の反応式
[F:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][C:3]=1[CH:12]1[CH2:17][CH:16]([C:18]([OH:20])=O)[CH2:15][CH2:14][N:13]1[C:21]([O:23][CH3:24])=[O:22].N1(C(N2C=CN=C2)=O)C=CN=C1.[CH2:37]([O:39][C:40](=[O:45])[CH2:41]C([O-])=O)[CH3:38].[K+].[Cl-].[Mg+2].[Cl-].Cl>CN1C2C(N=C(N)NC=2NCC1CNC1C=CC(C(NC(C(O)=O)CCC(O)=O)=O)=CC=1)=O.O.CC(OC)(C)C>[CH2:37]([O:39][C:40](=[O:45])[CH2:41][C:18]([C@H:16]1[CH2:15][CH2:14][N:13]([C:21]([O:23][CH3:24])=[O:22])[C@@H:12]([C:3]2[CH:4]=[CH:5][C:6]([C:8]([F:11])([F:10])[F:9])=[CH:7][C:2]=2[F:1])[CH2:17]1)=[O:20])[CH3:38]
参加物実験手順後処理出典と根拠反応ノート

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 682631,1'-CarbonyldiimidazoleHCID 3446434Potassium ethyl malonateHCID 5360315Magnesium ChlorideHCID 667315582-(2-Fluoro-4-(trifluoromethyl)phenyl)-1-(methoxycarbonyl)piperidine-4-carboxylic acid

生成物 1

HCID 131730431
cis-Methyl 4-(3-ethoxy-3-oxopropanoyl)-2-(2-fluoro-4-(trifluoromethyl)phenyl)piperidine-1-carboxylate
収率 49%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 15413tert-Butyl methyl ether溶媒HCID 178479889HCID 178479889、化合物溶媒2 回

実験手順

2-(2-fluoro-4-(trifluoromethyl)phenyl)-1-(methoxycarbonyl)piperidine-4-carboxylic acid (4.82 g, 13.80 mmol) was dissolved in methyl THF (120 mL), then di(1H-imidazol-1-yl)methanone (4.03 g, 24.84 mmol) was added. The mixture was stirred at room temperature under nitrogen for 5 h (flask 1). In a separate flask potassium 3-ethoxy-3-oxopropanoate (4.23 g, 24.84 mmol) was suspended in methyl THF (120 mL), then magnesium chloride (2.365 g, 24.84 mmol) was added. The suspension was stirred at 50° C. under nitrogen for 5 h using a large magnetic stirring bar (flask 2). The contents of flask 1 was transferred into flask 2. The resulting white suspension was stirred under nitrogen at room temperature overnight. The mixture was acidified to pH 1 with 3.8 M HCl, then MTBE (50 mL) and water (50 mL) was added. The phases were separated and the organic layer was washed with water, satd NaHCO3 and brine. The organic layer was dried over Na2SO4, filtered and evaporated leaving a slightly yellow oil. The residue was purified by chromatography on silica (Biotage (340 g) with a 1 CV EtOAc in heptane (20%) followed by a gradient of 20-60% EtOAc in n-heptane (8 CV). The column was conditioned at 20% EtOAc in -n-heptane (1 CV)). Trans-methyl 4-(3-ethoxy-3-oxopropanoyl)-2-(2-fluoro-4-(trifluoromethyl)phenyl) piperidine-1-carboxylate (413 mg, 7%) and cis-methyl 4-(3-ethoxy-3-oxopropanoyl)-2-(2-fluoro-4-(trifluoromethyl)-phenyl)piperidine-1-carboxylate (2.83 g, 49%) were isolated. Cis-isomer: 1H NMR (400 MHz, cdcl3) δ 1.22-1.32 (m, 3H), 1.81-1.96 (m, 2H), 2.06-2.18 (m, 1H), 2.27-2.36 (m, 1H), 2.87-2.97 (m, 1H), 3.34-3.51 (m, 3H), 3.58-3.66 (m, 3H), 4.14-4.23 (m, 3H), 5.15 (dd, 1H), 7.25-7.40 (m, 3H). MS m/z 420 (M+H)+. Trans-isomer: 1H NMR (400 MHz, cdcl3) δ 1.18-1.31 (m, 3H), 1.58-1.72 (m, 1H), 1.87-2.06 (m, 2H), 2.40-2.60 (m, 2H), 3.17 (dt, 1H), 3.45 (s, 2H), 3.73 (s, br., 3H), 4.08-4.23 (m, 2H), 4.34 (s, br., 1H), 5.75 (s, br., 1H), 7.22-7.43 (m, 3H). MS m/z 420 (M+H)+

後処理

  1. stirringThe suspension was stirred at 50° C. under nitrogen for 5 h
  2. customThe contents of flask 1 was transferred into flask
  3. stirringThe resulting white suspension was stirred under nitrogen at room temperature overnight
  4. customThe phases were separated
  5. washthe organic layer was washed with water
  6. dry with materialThe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. customevaporated
  9. customleaving a slightly yellow oil
  10. customThe residue was purified by chromatography on silica (Biotage (340 g) with a 1 CV EtOAc in heptane (20%)

出典と根拠

ORDレコード
ord-09e87f18510e45e5ab220a836deb76de
出典データセット
uspto-grants-2013_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08415378B2

反応ノート

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