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 1159437Notes

Reaction equation

HRID 1159437 reaction equation
[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]

Participants

5

Reactant 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

Product 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

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

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].

Workup

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

Sources & evidence

ORD record
ord-dda9839fe4964b47825498b457896cdf
Source dataset
uspto-grants-2010_10
Patent number
US07812051B2

Reaction notes

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