Tetrahydrofuran → 4-(2-Vinyl-benzooxazol-5-yl)-benzonitrile

HRID 10406

Reaction equation

HRID 10406 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]([CH:10]=[CH2:11])=[N:7][C:6]=2[CH:12]=1.[C:13]([C:15]1[CH:20]=[CH:19][C:18](B(O)O)=[CH:17][CH:16]=1)#[N:14].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.O1CCCC1>CCCCCC>[CH:10]([C:8]1[O:9][C:5]2[CH:4]=[CH:3][C:2]([C:18]3[CH:19]=[CH:20][C:15]([C:13]#[N:14])=[CH:16][CH:17]=3)=[CH:12][C:6]=2[N:7]=1)=[CH2:11]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 27343264-Cyanophenylboronic acidHCID 219800995-Bromo-2-ethenyl-1,3-benzoxazole

Product 1

HCID 219800914-(2-Vinyl-benzooxazol-5-yl)-benzonitrileYield 78%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Conditions

Temperature
23 °C

Procedure

A mixture of 224 mg (1 mmol) of 5-bromo-2-vinyl-benzooxazole, 191 mg (1.3 mmol) of 4-cyanophenylboronic acid, 55 mg (0.03 mmol) of tris-(dibenzylidineacetone)dipalladium (0) (CAS #52409-22-0), 0.2 mL (0.06 mmol) of a 10% solution of tri-tert-butylphosphine in hexane, and 1.5 mL of tetrahydrofuran was stirred at 23° C. for 24 hours. It was then heated at 65° C. for 0.5 hour, then cooled. The mixture was suction filtered to remove particulates, then partitioned between 80 mL of water and a mixture of 30 mL of ethyl acetate and 10 mL of hexane. The organic phase was collected, dried over Na2SO4, and purified by flash chromatography on silica gel (eluting with 1:1 hexane:dichloromethane) to give 4-(2-vinyl-benzooxazol-5-yl)-benzonitrile (192 mg, 78%) as a white solid: mp 143–144° C.; 1H NMR (300 MHz, CDCl3) δ 7.90 (d, J=1.8 Hz, 1 H), 7.76 (d, J=8.4 Hz, 2 H), 7.70 (d, J=8.4 Hz, 2 H), 7.62 (d, J=7.5 Hz, 1 H), 7.55 (dd, J=7.5, 1.8 Hz, 1 H), 6.79 (dd, J=17.4, 10.5 Hz, 1 H), 6.52 (d, J=17.4 Hz, 1 H), 5.91 (d, J=10.5 Hz, 1 H); Mass spectrum: [M+H]+ 247.1.

Workup

  1. temperatureIt was then heated at 65° C. for 0.5 hour
  2. temperaturecooled
  3. filtrationfiltered
  4. customto remove particulates
  5. custompartitioned between 80 mL of water
  6. additiona mixture of 30 mL of ethyl acetate and 10 mL of hexane
  7. customThe organic phase was collected
  8. dry with materialdried over Na2SO4
  9. custompurified by flash chromatography on silica gel (eluting with 1:1 hexane:dichloromethane)

Sources & evidence

ORD record
ord-28e2094b51fe4314ac393822d96728b9
Source dataset
uspto-grants-2006_08
Patent number
US07094790B2

Linked notes

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