Sodium Azide → 4'-(azidomethyl)-2,2-dimethyl-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2'-[1,3]dioxolan]-5-one

HRID 1159438Notes

Reaction equation

HRID 1159438 reaction equation
CS(O[CH2:6][CH:7]1[CH2:11][O:10][C:9]2([C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][C:19]=3[C:18]3[O:17][C:16]([CH3:26])([CH3:25])[CH2:15][CH2:14][C:13]=3[C:12]2=[O:27])[O:8]1)(=O)=O.[N-:28]=[N+:29]=[N-:30].[Na+]>CN(C=O)C.C(Cl)Cl>[N:28]([CH2:6][CH:7]1[CH2:11][O:10][C:9]2([C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][C:19]=3[C:18]3[O:17][C:16]([CH3:26])([CH3:25])[CH2:15][CH2:14][C:13]=3[C:12]2=[O:27])[O:8]1)=[N+:29]=[N-:30]

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 59514394(2,2-dimethyl-5-oxo-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2'-[1,3]dioxolan]-4'-yl)methyl methanesulfonate

Product 1

HCID 595143904'-(azidomethyl)-2,2-dimethyl-3,4-dihydro-2H,5H-spiro[benzo[h]chromene-6,2'-[1,3]dioxolan]-5-oneYield 15%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

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. washwashed with water (2 ml)
  2. concentrationconcentrated
  3. dry with materialThe organic layer is dried with sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. custompurified by flash column chromatography (SiO2, 30% EtOAc in hexane)

Sources & evidence

ORD record
ord-b4b028f6b9554148ac76110e1cb90686
Source dataset
uspto-grants-2010_10
Patent number
US07812051B2

Reaction notes

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