Trimethyl phosphite → dimethyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl phosphate

HRID 384577

반응식

HRID 384577 반응식
[P:1]([O:6]C)([O:4][CH3:5])[O:2][CH3:3].[CH2:8]1[O:12][C@@H:11]2[C@H:13]([O:16][N+:17]([O-:19])=[O:18])[CH2:14][O:15][C@@H:10]2[C@H:9]1[OH:20].C(Br)(Br)(Br)Br>N1C=CC=CC=1>[P:1]([O:20][C@H:9]1[CH2:8][O:12][C@@H:11]2[C@H:13]([O:16][N+:17]([O-:19])=[O:18])[CH2:14][O:15][C@H:10]12)([O:4][CH3:5])([O:2][CH3:3])=[O:6]

참가 물질

5

반응물 3

HCID 8472Trimethyl phosphiteHCID 11205Carbon tetrabromideHCID 27661Isosorbide Mononitrate

생성물 1

HCID 86652099dimethyl (3S,3aS,6R,6aS)-6-(nitrooxy)hexahydrofuro[3,2-b]furan-3-yl phosphate

시약·촉매·용매 1

HCID 1049Pyridine용매

실험 절차

Trimethyl phosphite (2.95 mL, 25.0 mmol) was added dropwise over ca. 1 hour to a stirred 0° C. mixture of isosorbide-5-mononitrate (3.82 g, 20.0 mmol) and carbon tetrabromide (7.30 g, 22.0 mmol) in pyridine (10 mL), and the mixture was stirred at room temperature for 3 hours. The reaction was partitioned between 1M hydrochloric acid and diethyl ether/ethyl acetate (1:1). The aqueous phase was extracted with diethyl ether. The combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate and brine, dried (sodium sulfate), filtered and concentrated in vacuo. Chromatography over silica eluting with 50-100% ethyl acetate/hexane afforded the title compound as an orange solid. 1H NMR (500 MHz, CD3OD) δ 5.46 (td, J=5.5, 2.2 Hz, 1H), 5.02 (t, J=5.3 Hz, 1H), 4.82 (dd, J=6.8, 2.7 Hz, 1H), 4.58 (d, J=5.1 Hz, 1H), 4.10 (d, J=10.7 Hz, 1H), 3.99 (dd, J=11.5, 2.1 Hz, 1H), 3.91 (dd, J=11.4, 5.2 Hz, 1H), 3.88 (dt, J=11.0, 2.4 Hz, 1H), 3.80 (d, J=2.7 Hz, 3H), 3.78 (d, J=2.7 Hz, 3H); LC-MS: m/z 300.0 (M+H).

후처리

  1. customThe reaction was partitioned between 1M hydrochloric acid and diethyl ether/ethyl acetate (1:1)
  2. extractionThe aqueous phase was extracted with diethyl ether
  3. washThe combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate and brine
  4. dry with materialdried (sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-660a2ae073184d109cdd086d47109875
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08367711B2

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