Toluene → Prop-2-ynyl-(2,2,3,3-tetrafluoro-2,3-dihydro-benzo[1,4]dioxin-6-yl)-amine

HRID 2245362Notes

Reaction equation

[F:1][C:2]1([F:15])[O:7][C:6]2[CH:8]=[CH:9][C:10]([NH2:12])=[CH:11][C:5]=2[O:4][C:3]1([F:14])[F:13].[CH2:16](Br)[C:17]#[CH:18].C1(C)C=CC=CC=1>FC1C=CC=CC=1>[CH2:18]([NH:12][C:10]1[CH:9]=[CH:8][C:6]2[O:7][C:2]([F:1])([F:15])[C:3]([F:13])([F:14])[O:4][C:5]=2[CH:11]=1)[C:17]#[CH:16]

Participants

Conditions

Temperature: 50 °C

Procedure

2,2,3,3-Tetrafluoro-6-aminobenzodioxane (6.694 g, 30.0 mmol) and Aldrich basic alumina (activated, Brockmann 1, 150 mesh, CAS #1344-28-1) (51 g) were mixed in fluorobenzene (100 mL) and then treated with 80% propargyl bromide in toluene (2.56 mL, 23.0 mmol). The resulting mixture was thoroughly stirred and heated at 50° C. for 17 hours. The mixture was cooled to ambient temperature and filtered. The alumina was rinsed thoroughly with dichloromethane (150 mL), the filtrate was reduced in volume under reduced pressure, washed with concentrated aqueous NH4OH (5 mL), dried (Na2SO4), concentrated and chromatographed on silica eluting with 0-10% EtOAc/hexanes to provide the titled compound. 1H NMR (CDCl3) δ ppm 2.24 (t, 1H), 3.92 (m, 2H), 3.96 (m, 1H), 6.43 (d, 1H), 6.45 (dd, 1H), 6.96 (d, 1H); MS (DCI) 262 (M+H).

Workup

temperatureThe mixture was cooled to ambient temperature
filtrationfiltered
washThe alumina was rinsed thoroughly with dichloromethane (150 mL)
washwashed with concentrated aqueous NH4OH (5 mL)
dry with materialdried (Na2SO4)
concentrationconcentrated
customchromatographed on silica eluting with 0-10% EtOAc/hexanes

Sources & evidence

ORD record: ord-8bbac60a72c848b98dfd112f0b69cfdd
Source dataset: uspto-grants-2010_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07683084B2

Reaction notes

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