3-Hydroxypyridine → 2-[(Pyridin-3-yloxy)methyl]-2,3-dihydronaphtho[1,2-b][1,4]oxathiine-5,6-dione

HRID 563123노트

반응식

HRID 563123 반응식
[OH:1][CH2:2][CH:3]1[O:8][C:7]2[C:9]3[C:14]([C:15](=[O:18])[C:16](=[O:17])[C:6]=2[S:5][CH2:4]1)=[CH:13][CH:12]=[CH:11][CH:10]=3.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N:38]1[CH:43]=[CH:42][CH:41]=[C:40](O)[CH:39]=1.N(/C(OCC)=O)=N/C(OCC)=O>O1CCCC1>[N:38]1[CH:43]=[CH:42][CH:41]=[C:40]([O:1][CH2:2][CH:3]2[O:8][C:7]3[C:9]4[C:14]([C:15](=[O:18])[C:16](=[O:17])[C:6]=3[S:5][CH2:4]2)=[CH:13][CH:12]=[CH:11][CH:10]=4)[CH:39]=1

참가 물질

6

반응물 4

HCID 79713-HydroxypyridineHCID 11776TriphenylphosphineHCID 5354216Diethyl azodicarboxylate, (Z)-HCID 577754892-(Hydroxymethyl)-2,3-dihydronaphtho[1,2-b][1,4]oxathiine-5,6-dione

생성물 1

HCID 252638612-[(Pyridin-3-yloxy)methyl]-2,3-dihydronaphtho[1,2-b][1,4]oxathiine-5,6-dione수율 14.3%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of 2-(hydroxymethyl)-2,3-dihydronaphtho[1,2-b][1,4]oxathiine-5,6-dione (0.35 g, 1.34 mmol) in tetrahydrofuran (10.0 mL) was added triphenylphosphine (1.4 g, 5.34 mmol) and pyridin-3-ol (0.507 g, 5.34 mmol) followed by diethyl (Z)-diazene-1,2-dicarboxylate (0.53 mL, 3.34 mmol). The reaction mixture was stirred at room temperature for 8 hours. The reaction was quenched by addition of water (30 mL). The aqueous layer was extracted with dichloromethane (2×20 mL). The organic extracts were combined and extracted thrice with 1.0N HCl (10 mL). The HCl extracts were combined and its pH adjusted to 9 with a saturated sodium carbonate solution. The aqueous layer was extracted with dichloromethane (2×20 mL), extracts combined, dried with sodium sulfate and concentrated under reduced pressure. The crude mixture was purified by flash column chromatography (SiO2, 50% EtOAc in hexanes to 80% EtOAc in hexanes) to give the product as a purple solid (0.065 g, 14%). M.p.=153-155° C.; 400 MHz 1H NMR (CDCl3) δ: 8.43-8.35 (m, 1H), 8.33-8.24 (m, 1H), 8.05-7.94 (m, 1H), 7.72-7.56 (m, 2H), 7.56-7.4 (m, 2H), 7.33-7.2 (m, 1H), 4.98-4.86 (m, 1H), 4.54-4.34 (m, 2H), 3.34-3.16 (m, 2H); LCMS: 340 [M+H].

후처리

  1. customThe reaction was quenched by addition of water (30 mL)
  2. extractionThe aqueous layer was extracted with dichloromethane (2×20 mL)
  3. extractionextracted thrice with 1.0N HCl (10 mL)
  4. extractionThe aqueous layer was extracted with dichloromethane (2×20 mL)
  5. dry with materialdried with sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe crude mixture was purified by flash column chromatography (SiO2, 50% EtOAc in hexanes to 80% EtOAc in hexanes)

출처 및 근거

ORD 기록
ord-5f895a788ea94f99ae165009994de6b8
출처 데이터셋
uspto-grants-2011_11
특허 번호
US08067459B2

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