Diethyl Malonate → Diethyl 3-(benzyloxy)cyclobutane-1,1-dicarboxylate

HRID 399103ノート

反応式

HRID 399103 の反応式
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Cl[CH2:15][CH:16]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH2:17]Br>O1CCOCC1>[CH2:20]([O:19][CH:16]1[CH2:17][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])([C:3]([O:11][CH2:12][CH3:13])=[O:10])[CH2:15]1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

参加物

5

反応物 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydride2 回HCID 3468282(((1-Bromo-3-chloropropan-2-yl)oxy)methyl)benzene

生成物 1

HCID 12815110Diethyl 3-(benzyloxy)cyclobutane-1,1-dicarboxylate収率 85%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒2 回

実験手順

To a stirred slurry of 4.6 g (0.19 mol) sodium hydride in 115 mL of dry dioxane was added dropwise 30.4 (0.10 mol) of diethyl malonate over a 30 min period. After this addition was complete, 50.0 g (0.19 mol) of 1-chloro-2-benzyloxy-3-bromopropane 3 was added dropwise in 30 min (St mixture was heated at reflux for 44 hr, cooled to room ##STR5## temperature, and 4.6 g (0.19 mol) of sodium hydride in 50 mL of dioxane was added in portions. The mixture was heated at reflux for an additional 120 hr. The solvent was partially removed under reduced pressure and the mixture was treated with 100 mL of water. The organic layer was extracted into ether. The ether extracts were dried and concentrated and the residue was distilled under reduced pressure. Distillation through a 12-in Vigreux column yielded 49.0 g (85%) of diethyl 3-benzyloxycyclobutane-1, 1-dicarboxylate 4 bp 174°-176° C. (0.9 mm); 1H NMR(CDCl3) δ1.23 (t, J=7 Hz, 6H, CH3), 4.0-4.7 (m, 1H OCH), 4.34 (s, 2H OCH2), 4.13 (q, J=7 Hz, 4H, OCOCH2), 7.23 (s, 5H, phenyl).

後処理

  1. additionAfter this addition
  2. temperaturewas heated
  3. temperatureat reflux for 44 hr
  4. additionwas added in portions
  5. temperatureThe mixture was heated
  6. temperatureat reflux for an additional 120 hr
  7. customThe solvent was partially removed under reduced pressure
  8. additionthe mixture was treated with 100 mL of water
  9. extractionThe organic layer was extracted into ether
  10. dry with materialThe ether extracts were dried
  11. concentrationconcentrated
  12. distillationthe residue was distilled under reduced pressure
  13. distillationDistillation through a 12-in Vigreux column

出典と根拠

ORDレコード
ord-09b8476876734dd0955105f13082224f
出典データセット
uspto-grants-1998_10
特許番号
US05817776

反応ノート

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