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

HRID 349781노트

반응식

HRID 349781 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 142844-(Dimethylamino)pyridine촉매HCID 6344Dichloromethane용매2회

반응 조건

온도
30 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-e0fd581e89874e7a8632da32c57c36a2
출처 데이터셋
uspto-grants-2007_02
특허 번호
US07179943B2

반응 노트

불러오는 중…