Diethyl Oxalate → Ethyl 3-benzyloxy-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate

HRID 346486

反応式

HRID 346486 の反応式
[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2](OCC)=O.[CH2:11]([O:18][CH2:19][C:20]([O:22]CC)=O)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[H-].[Na+].Cl.[NH:28]=[C:29]1[CH2:34][CH2:33][CH2:32][CH2:31][NH:30]1.[O-]CC.[Na+]>O1CCCC1.C(O)C.C(O)(=O)C>[CH2:11]([O:18][C:19]1[C:20](=[O:22])[N:30]2[CH2:31][CH2:32][CH2:33][CH2:34][C:29]2=[N:28][C:2]=1[C:1]([O:8][CH2:9][CH3:10])=[O:7])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

参加物

9

反応物 5

HCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 290299Ethyl 2-(benzyloxy)acetateHCID 2723922Sodium ethoxideHCID 178479080HCID 178479080、化合物

生成物 1

HCID 21080169Ethyl 3-benzyloxy-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate収率 14%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒2 回HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

Diethyl oxalate (7.66 g, 52.4 mmol) and ethyl benzyloxyacetate (10.2 g, 52.5 mmol) in dry tetrahydrofuran (70 ml) were treated at 22° C. with sodium hydride (2.31 g of a 60% dispersion in mineral oil, 57.7 mmol) and ethanol (40 μl). The tetrahydrofuran was then evaporated under reduced pressure and the residue treated with a mixture of 2-iminopiperidine hydrochloride (7.05 g, 52.2 mmol) in a solution of sodium ethoxide (26.0 mmol, prepared from 0.60 g of sodium) in ethanol (70 ml) and the resulting mixture heated at 60° C. for 4 h. Acetic acid (2 ml) was added and the ethanol was evaporated under reduced pressure. The residue was diluted with ethyl acetate washed successively with saturated sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Chromatography on silica gel (elution toluene/ethyl acetate 1:1) gave 2.37 g (14% yield) of the title ester as white crystals; mp 97–99° C. (ethyl acetate-hexane). 1HNMR 400 MHz (CDCl3) δ (ppm): 1.33 (3H, t, J=7.1 Hz, CH3), 1.92 (2H, m, CH2), 2.0 (2H, m, CH2), 2.97 (2H, t, J=6.8 Hz, CH2), 4.02 (2H, t, J=6.3 Hz, NCH2), 4.36 (2H, q, J=7.1 Hz, OCH2), 5.27 (2H, s, OCH2), 7.3–7.51 (5H, m, aromatics). Anal. Calcd for C18H20N2O4: C, 65.84; H, 6.14; N, 8.53. Found: C 65.72, H 6.33, N 8.41.

後処理

  1. customThe tetrahydrofuran was then evaporated under reduced pressure
  2. customthe ethanol was evaporated under reduced pressure
  3. additionThe residue was diluted with ethyl acetate
  4. washwashed successively with saturated sodium bicarbonate and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-9b16c11e56dc43afa955cb6ec061fcd3
出典データセット
uspto-grants-2007_02
特許番号
US07173022B2

関連ノート

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