Acetic Acid → Ethyl 4-(4-cyclopropyl-1,4-diazepan-1-yl)benzoate

HRID 16886

反応式

HRID 16886 の反応式
[N:1]1([C:8]2[CH:18]=[CH:17][C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:10][CH:9]=2)[CH2:7][CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.C(O[C:22]1(O[Si](C)(C)C)[CH2:24][CH2:23]1)C.C(O)(=O)C.C([BH3-])#N.[Na+]>O1CCCC1.CO>[CH:22]1([N:4]2[CH2:5][CH2:6][CH2:7][N:1]([C:8]3[CH:18]=[CH:17][C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:10][CH:9]=3)[CH2:2][CH2:3]2)[CH2:24][CH2:23]1

参加物

7

反応物 4

HCID 176Acetic AcidHCID 2734686(1-Ethoxycyclopropoxy)trimethylsilaneHCID 5003444Sodium cyanoborohydrideHCID 18425301Ethyl 4-(1,4-diazepan-1-yl)benzoate

生成物 1

HCID 66589916Ethyl 4-(4-cyclopropyl-1,4-diazepan-1-yl)benzoate収率 118%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

A solution of ethyl 4-(1,4-diazepan-1-yl)benzoate (0.621 g, 2.5 mmol), (1-ethoxycyclopropoxy)trimethylsilane (2.51 mL, 12.50 mmol) and acetic acid (0.286 mL, 5.00 mmol) in tetrahydrofuran (50 mL), methanol (5 mL) was treated with sodium cyanoborohydride (0.393 g, 6.25 mmol) at 20° C. The resulting solution was stirred at 60° C. for 18 h. The reaction mixture was cooled, filtered and evaporated to dryness. 1N HCl (40 ml) and water (60 ml) were added and the solution extracted with ethyl acetate (3×50 ml). The aqueous layer was basified to pH 10 with solid potassium carbonate and extracted with ethyl acetate (4×50 ml). The organic extracts washed with saturated NaCl (50 ml) and dried over MgSO4, filtered and evaporated to dryness. The crude product was purified by silica column chromatography, eluting with a gradient of 0 to 5% MeOH in DCM. Pure fractions were evaporated to dryness to afford ethyl 4-(4-cyclopropyl-1,4-diazepan-1-yl)benzoate (0.849 g, 118%) as a colourless oil.

後処理

  1. temperatureThe reaction mixture was cooled
  2. filtrationfiltered
  3. customevaporated to dryness
  4. addition1N HCl (40 ml) and water (60 ml) were added
  5. extractionthe solution extracted with ethyl acetate (3×50 ml)
  6. extractionextracted with ethyl acetate (4×50 ml)
  7. washThe organic extracts washed with saturated NaCl (50 ml)
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated to dryness
  11. customThe crude product was purified by silica column chromatography
  12. washeluting with a gradient of 0 to 5% MeOH in DCM
  13. customPure fractions were evaporated to dryness

出典と根拠

ORDレコード
ord-5ea8033f01d946058fca533261c3438e
出典データセット
uspto-grants-2010_06
特許番号
US07737149B2

関連ノート

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