Hydrochloric Acid → (3aR*,10aS*)-9-Benzyl-4-(2-phthalimidoethyl)-2,3,3a,4,9,10a-hexahydrobenzo[b]cyclopenta[e][1,4]-diazepin-10(1H)-one

HRID 356158

反応式

HRID 356158 の反応式
C(O[CH:4](OCC)[CH2:5][N:6]1[C:10](=[O:11])[C:9]2=[CH:12][CH:13]=[CH:14][CH:15]=[C:8]2[C:7]1=[O:16])C.Cl.[CH2:21]([N:28]1[C:34](=[O:35])[C@H:33]2[CH2:36][CH2:37][CH2:38][C@H:32]2[NH:31][C:30]2[CH:39]=[CH:40][CH:41]=[CH:42][C:29]1=2)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(O)(=O)C.O.ClCCl>[CH2:21]([N:28]1[C:34](=[O:35])[C@H:33]2[CH2:36][CH2:37][CH2:38][C@H:32]2[N:31]([CH2:4][CH2:5][N:6]2[C:7](=[O:16])[C:8]3=[CH:15][CH:14]=[CH:13][CH:12]=[C:9]3[C:10]2=[O:11])[C:30]2[CH:39]=[CH:40][CH:41]=[CH:42][C:29]1=2)[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 3152862-Phthalimidoacetaldehyde Diethyl AcetalHCID 5049666Sodium triacetoxyborohydrideHCID 70109795(3aR*,10aS*)-9-benzyl-2,3,3a,4,9,10a-hexahydrobenzo[b]cyclopenta [e][1,4]diazepin-10(1H)-one

生成物 1

HCID 70110111(3aR*,10aS*)-9-Benzyl-4-(2-phthalimidoethyl)-2,3,3a,4,9,10a-hexahydrobenzo[b]cyclopenta[e][1,4]-diazepin-10(1H)-one収率 57.3%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
50 °C

実験手順

To a solution of phthalimidoacetaldehyde diethyl acetal (790 mg, 3.0 mmol) in acetic acid (2.5 mL) was added conc.HCl (0.1 mL). The mixture was stirred for 80 minutes at 50° C. The reaction mixture was cooled to room temperature, to which was added (3aR*,10aS*)-9-benzyl-2,3,3a,4,9,10a-hexahydrobenzo[b]cyclopenta [e][1,4]diazepin-10(1H)-one (877 mg, 3.0 mmol), and the mixture was stirred for 25 minutes at room temperatures. To this solution was added, sodium triacetoxyborohydride (805 mg, 3.9 mmol) portionwise, and the mixture was stirred for 40 minutes at 45° C. The reaction mixture was cooled to room temperatures, to which were added dichloromethane (10 mL) and water (10 mL). The aqueous layer was separated, and the organic layer was washed with water and a saturated aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate and subjected to filtration. The filtrate was concentrated under reduced pressure. The concentrate was purified by silica-gel column chromatography (chloroform-methanol 20:1), followed by crystallization from ethanol-hexane to give 0.80 g (yield 57%) the titled compound. The sample for analytical experiment was prepared by recrystallization from dichloromethane-ethanol-hexane. m.p. 142.0°-142.6° C.

後処理

  1. temperatureThe reaction mixture was cooled to room temperature, to which
  2. stirringthe mixture was stirred for 25 minutes at room temperatures
  3. additionTo this solution was added
  4. temperatureThe reaction mixture was cooled to room temperatures, to which
  5. customThe aqueous layer was separated
  6. washthe organic layer was washed with water
  7. dry with materiala saturated aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate
  8. filtrationsubjected to filtration
  9. concentrationThe filtrate was concentrated under reduced pressure
  10. customThe concentrate was purified by silica-gel column chromatography (chloroform-methanol 20:1)
  11. customfollowed by crystallization from ethanol-hexane

出典と根拠

ORDレコード
ord-6162d9ee8e4347b3a3b0c9716fa815fe
出典データセット
uspto-grants-1998_11
特許番号
US05834463

関連ノート

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