Hydrochloric Acid → (1R)-N-(4-nitrophenyl)-1,8,8-trimethyl-2,4-dioxobicyclo[3.2.1]octane-3-carboxamide

HRID 349781ノート

反応式

HRID 349781 の反応式
[CH3:1][C@:2]12[C:9]([CH3:11])([CH3:10])[CH:6]([CH2:7][CH2:8]1)[C:5](=[O:12])[CH2:4][C:3]2=[O:13].C(N(CC)CC)C.[N+:21]([C:24]1[CH:29]=[CH:28][C:27]([N:30]=[C:31]=[O:32])=[CH:26][CH:25]=1)([O-:23])=[O:22].Cl>CN(C)C1C=CN=CC=1.ClCCl>[N+:21]([C:24]1[CH:25]=[CH:26][C:27]([NH:30][C:31]([CH:4]2[C:5](=[O:12])[CH:6]3[C:9]([CH3:10])([CH3:11])[C@@:2]([CH3:1])([CH2:8][CH2:7]3)[C:3]2=[O:13])=[O:32])=[CH:28][CH:29]=1)([O-:23])=[O:22]

参加物

7

反応物 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 66012Benzene, 1-isocyanato-4-nitro-HCID 58805524(1R)-1,8,8-trimethylbicyclo[3.2.1]octane-2,4-dione

生成物 1

HCID 11624341(1R)-N-(4-nitrophenyl)-1,8,8-trimethyl-2,4-dioxobicyclo[3.2.1]octane-3-carboxamide収率 30%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
30 °C

実験手順

To an ice-cooled solution of (1R)-1,8,8-trimethylbicyclo[3.2.1]octane-2,4-dione (0.36 g, 2.0 mmole), triethylamine (0.20 g, 2.0 mmole) and 4-(dimethylamino)pyridine (0.24 g, 2.0 mmole) in dry dichloromethane (25 mL) was added a solution of 4-nitrophenyl isocyanate (0.33 g, 2.0 mmole) in dry dichloromethane (5 mL). The resulting mixture was allowed to stir overnight under a nitrogen atmosphere, during which time it came up to room temperature, and then was heated at 30° C. for 24 hours. The reaction mixture was treated with 2N aqueous HCl and the layers separated. The acidic aqueous layer was extracted with two additional portions of dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and concentrated on a rotary evaporator to give a yellow oil, which was purified by chromatography on silica gel (10% ethyl acetate/hexane) to yield an orange oil, which was crystallized from 95% ethanol to yield the title compound as an off-white solid (0.20 g, 30% yield), mp=168–170° C.; MS (−) ESI m/z=343 (M−H)−; [α]D25=+29.4° (c=1, DMSO).

後処理

  1. customcame up to room temperature
  2. customthe layers separated
  3. extractionThe acidic aqueous layer was extracted with two additional portions of dichloromethane
  4. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  5. concentrationconcentrated on a rotary evaporator
  6. customto give a yellow oil, which
  7. customwas purified by chromatography on silica gel (10% ethyl acetate/hexane)
  8. customto yield an orange oil, which
  9. customwas crystallized from 95% ethanol

出典と根拠

ORDレコード
ord-e0fd581e89874e7a8632da32c57c36a2
出典データセット
uspto-grants-2007_02
特許番号
US07179943B2

反応ノート

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