Acetonitrile → 3,4-Bis-(1,1-dimethyl-prop-2-ynyloxy)-xanthen-9-one

HRID 734184Notes

Reaction equation

HRID 734184 reaction equation
[OH:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[O:17])[C:7]3[C:12]([O:13][C:14]=2[C:15]=1[OH:16])=[CH:11][CH:10]=[CH:9][CH:8]=3.Cl[C:19]([CH3:23])([CH3:22])[C:20]#[CH:21].N12CCCN=[C:30]1[CH2:29][CH2:28][CH2:27]CC2.[C:35](#N)C>>[CH3:22][C:19]([CH3:23])([O:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[O:17])[C:7]3[C:12]([O:13][C:14]=2[C:15]=1[O:16][C:29]([CH3:30])([CH3:35])[C:28]#[CH:27])=[CH:11][CH:10]=[CH:9][CH:8]=3)[C:20]#[CH:21]

Participants

5

Reactant 4

HCID 6342AcetonitrileHCID 706791-Butyne, 3-chloro-3-methyl-HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 57483823,4-Dihydroxy-xanthone

Product 1

HCID 593560783,4-Bis-(1,1-dimethyl-prop-2-ynyloxy)-xanthen-9-oneYield 25%

Conditions

Temperature
75 °C

Procedure

A solution of 3,4-dihydroxy-xanthen-9-one (1.25 g, 5.47 mmol), cupric chloride (30.2 mg, 0.225), 3-chloro-3-methyl-1-butyne (3.36 mL, 29.9 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (2.00 mL, 13.3 mmol), and acetonitrile (100 mL) was stirred at room temperature for 11 h under argon. The solution was then heated at 75° C. for 2 h and cooled to room temperature. The solution was partitioned between ethyl acetate (100 mL) and water (75 mL). The ethyl acetate layer was dried over sodium sulfate and was concentrated by rotary evaporation. The product was purified by flash column chromatography (10:1 hexanes/ethyl acetate) to yield 496 mg (25%) of the title compound as a light yellow solid. 1H NMR (CDCl3, 300 MHz): δ 8.33 (dd, J1=7.97 Hz, J2=1.65, 1H), 8.07 (d, J=9.06 Hz, 1H), 7.71 (ddd, J1=8.18 Hz, J2=7.08, J3=1.58, 1H), 7.65 (d, J=9.06 Hz, 1H), 7.52 (dd, J1=8.52 Hz, J2=0.55, 1H), 7.38 (m, 1H), 2.66 (s, 1H), 2.30 (s, 1H), 1.84 (s, 6H), 1.77 (s, 6H).

Workup

  1. temperaturecooled to room temperature
  2. customThe solution was partitioned between ethyl acetate (100 mL) and water (75 mL)
  3. dry with materialThe ethyl acetate layer was dried over sodium sulfate
  4. concentrationwas concentrated by rotary evaporation
  5. customThe product was purified by flash column chromatography (10:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-d7f4fc90fad34e528c2636322cc83446
Source dataset
uspto-grants-2009_09
Patent number
US07592143B2

Reaction notes

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