Ammonium Chloride → 2-(3,5-dichloropyridine-4-yl)-1-(7-methoxy-2',3',5',6'-tetrahydro-spiro[1,3-benzodioxole-2,4'-(4H)-pyran]-4-yl)ethanone

HRID 2196090노트

반응식

HRID 2196090 반응식
[CH3:1][O:2][C:3]1[C:8]2[O:9][C:10]3([O:16][C:7]=2[C:6]([C:17](OC)=[O:18])=[CH:5][CH:4]=1)[CH2:15][CH2:14][O:13][CH2:12][CH2:11]3.[Cl:21][C:22]1[CH:23]=[N:24][CH:25]=[C:26]([Cl:29])[C:27]=1[CH3:28].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[NH4+].[Cl-]>O1CCCC1>[Cl:21][C:22]1[CH:23]=[N:24][CH:25]=[C:26]([Cl:29])[C:27]=1[CH2:28][C:17]([C:6]1[C:7]2[O:16][C:10]3([CH2:11][CH2:12][O:13][CH2:14][CH2:15]3)[O:9][C:8]=2[C:3]([O:2][CH3:1])=[CH:4][CH:5]=1)=[O:18]

참가 물질

6

반응물 4

HCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 109538273,5-Dichloro-4-methylpyridineHCID 59286723methyl 7-methoxy-2',3',5',6'-tetrahydro-spiro[1,3-benzodioxole-2,4'-(4H)-pyran]-4-carboxylate

생성물 1

HCID 250044922-(3,5-dichloropyridine-4-yl)-1-(7-methoxy-2',3',5',6'-tetrahydro-spiro[1,3-benzodioxole-2,4'-(4H)-pyran]-4-yl)ethanone수율 72.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

A solution of methyl 7-methoxy-2′,3′,5′,6′-tetrahydro-spiro[1,3-benzodioxole-2,4′-(4H)-pyran]-4-carboxylate (1.80 g, 6.42 mmol) and 3,5-dichloro-4-picoline (1.46 g, 8.99 mmol) in tetrahydrofuran (33 mL) was cooled to 0° C. A 1.0 M solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran (19.3 mL, 19.3 mmol) was added and the reaction mixture was allowed to reach room temperature overnight. Saturated aqueous NH4Cl (70 mL) was added. The aqueous phase was extracted with dichloromethane (3×100 mL). The combined organic phase was washed with water (50 mL), dried over MgSO4 and evaporated to dryness under reduced pressure. Standard silica gel column chromatography followed by recrystallization from isopropanol afforded 2-(3,5-dichloropyridine-4-yl)-1-(7-methoxy-2′,3′,5′,6′-tetrahydro-spiro[1,3-benzodioxole-2,4′-(4H)-pyran]-4-yl)ethanone (1.90 g, 71%). 13C NMR (DMSO) δ 189.1, 148.2, 147.7, 147.0, 141.2, 134.5, 132.8, 122.0, 118.0, 113.0, 107.8, 64.4, 56.3, 43.5, 35.2.

후처리

  1. extractionThe aqueous phase was extracted with dichloromethane (3×100 mL)
  2. washThe combined organic phase was washed with water (50 mL)
  3. dry with materialdried over MgSO4
  4. customevaporated to dryness under reduced pressure
  5. customStandard silica gel column chromatography followed by recrystallization from isopropanol

출처 및 근거

ORD 기록
ord-5114aa416b8b492889950fb0cede67a4
출처 데이터셋
uspto-grants-2012_12
특허 번호
US08338431B2

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