Triethylamine → (2,2-dimethyl-5-oxo-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2'-[1,3]dioxolan]-4'-yl)methyl methanesulfonate

HRID 1159437노트

반응식

HRID 1159437 반응식
[OH:1][CH2:2][CH:3]1[CH2:7][O:6][C:5]2([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[C:14]3[O:13][C:12]([CH3:22])([CH3:21])[CH2:11][CH2:10][C:9]=3[C:8]2=[O:23])[O:4]1.[CH3:24][S:25](Cl)(=[O:27])=[O:26].C(N(CC)CC)C>ClCCl>[CH3:24][S:25]([O:1][CH2:2][CH:3]1[CH2:7][O:6][C:5]2([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[C:14]3[O:13][C:12]([CH3:21])([CH3:22])[CH2:11][CH2:10][C:9]=3[C:8]2=[O:23])[O:4]1)(=[O:27])=[O:26]

참가 물질

5

반응물 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 595143894'-(hydroxymethyl)-2,2-dimethyl-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2'-[1,3]dioxolan]-5-one

생성물 1

HCID 59514394(2,2-dimethyl-5-oxo-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2'-[1,3]dioxolan]-4'-yl)methyl methanesulfonate

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a solution of 4′-(hydroxymethyl)-2,2-dimethyl-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2′-[1,3]dioxolan]-5-one (316 mg, 1.0 mmol) in dichloromethane (2 mL) is added methanesulfonyl chloride (0.095 mL, 1.3 mmol) and triethylamine (0.163 mL, 1.24 mmol). The mixture is stirred at room temperature for 2 hours. The reaction mixture is washed with water (2×1.0 mL), dried over sodium sulfate and concentrated to provide (2,2-dimethyl-5-oxo-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2′-[1,3]dioxolan]-4′-yl)methyl methanesulfonate as a white solid (99% by LC/MS, UV 254 nm). The (2,2-dimethyl-5-oxo-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2′-[1,3]dioxolan]-4′-yl)methyl methanesulfonate (197 mg, 0.5 mmol) is dissolved in DMF (2 mL) followed by the addition of sodium azide (97 mg, 1.5 mmol). The reaction is heated at 80° C. for 24 hour and 100° C. for 12 h. The mixture is diluted with CH2Cl2 (4 mL), washed with water (2 ml) and concentrated. The organic layer is dried with sodium sulfate, concentrated under reduced pressure and purified by flash column chromatography (SiO2, 30% EtOAc in hexane) to provide 4′-(azidomethyl)-2,2-dimethyl-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2′-[1,3]dioxolan]-5-one (25 mg, 15%) as a white solid. 400 MHz 1H NMR (CDCl3) δ: 7.78-7.56 (m, 1H), 7.60-7.57 (m, 1H), 7.44-7.40 (m, 2H), 4.68-4.62 (m, 1H), 4.46-4.42 (m, 1H), 4.23 (t, J=8 Hz, 1H). 3.96-3.91 (m, 1H), 3.54-3.49 (m, 1H), 2.48-2.42 (m, 2H), 1.79 (t, J=6.8 Hz, 2H), 1.42 (d, J=3.2 Hz, 6H); LCMS: 342 [M+H].

후처리

  1. washThe reaction mixture is washed with water (2×1.0 mL)
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated

출처 및 근거

ORD 기록
ord-dda9839fe4964b47825498b457896cdf
출처 데이터셋
uspto-grants-2010_10
특허 번호
US07812051B2

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