Potassium tert-butoxide → tert-Butyl 5-ethyl-7,8-dihydropyrido[3,4-b]pyrazine-6(5H)-carboxylate

HRID 132867ノート

反応式

HRID 132867 の反応式
[CH3:1][C:2]([CH3:5])([O-:4])[CH3:3].[K+].[CH2:7]([CH:9]1[C:14]2=[N:15][CH:16]=[CH:17][N:18]=[C:13]2[CH2:12][CH2:11][N:10]1[C:19](OC1C=CC=CC=1)=[O:20])[CH3:8]>O1CCCC1>[CH2:7]([CH:9]1[C:14]2=[N:15][CH:16]=[CH:17][N:18]=[C:13]2[CH2:12][CH2:11][N:10]1[C:19]([O:4][C:2]([CH3:5])([CH3:3])[CH3:1])=[O:20])[CH3:8]

参加物

4

反応物 2

HCID 23665647Potassium tert-butoxideHCID 69182558Phenyl 5-ethyl-7,8-dihydropyrido[3,4-b]pyrazine-6(5H)-carboxylate

生成物 1

HCID 69184558tert-Butyl 5-ethyl-7,8-dihydropyrido[3,4-b]pyrazine-6(5H)-carboxylate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-25 °C

実験手順

Potassium tert-butoxide (11.0M in tetrahydrofuran, 0.7 mL, 0.7 mmol) was added over 3 min to a solution of phenyl 5-ethyl-7,8-dihydropyrido[3,4-b]pyrazine-6(5H)-carboxylate (91 mg, 0.32 mmol) in tetrahydrofuran (1.8 mL) cooled in a −20 to −30° C. bath. After 30 min, the bath was removed and stirring was continued for 75 min. The mixture was added to saturated aqueous sodium bicarbonate solution (10 mL) which was then extracted with two portions of ethyl acetate (35 mL and 15 mL). The organic layers were washed in succession with saturated aqueous brine (10 mL), dried over sodium sulfate, decanted, and evaporated. Purification by flash column chromatography (silica gel, 15% ethyl acetate/hexanes) gave the title compound as a colorless oil. 1H NMR (500 MHz, CD3OD) δ 8.43 (d, 1H, J=2 Hz), 8.40 (d, 1H, J=2 Hz), 5.17-5.02 (bm, 1H), 4.40-4.25 (bm, 1H), 3.37-3.20 (bm, 1H), 3.04 (ddd, 1H, J=17, 12, 6 Hz), 2.90 (dd, 1H, J=17, 4 Hz), 2.10-2.00 (m, 1H), 1.87-1.76 (m, 1H), 1.49 (s, 9H), 1.04 (bt, 3H). LC/MS 208 (M+1-56).

後処理

  1. customthe bath was removed
  2. waitwas continued for 75 min
  3. additionThe mixture was added to saturated aqueous sodium bicarbonate solution (10 mL) which
  4. extractionwas then extracted with two portions of ethyl acetate (35 mL and 15 mL)
  5. washThe organic layers were washed in succession with saturated aqueous brine (10 mL)
  6. dry with materialdried over sodium sulfate
  7. customdecanted
  8. customevaporated
  9. customPurification by flash column chromatography (silica gel, 15% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-f3997b5b3f1e43d3af4130f7e8fce403
出典データセット
uspto-grants-2008_06
特許番号
US07388019B2

反応ノート

読み込み中…