Chlorotrimethylsilane → (4-Methoxy-dibenzofuran-1-yl)-acetonitrile

HRID 2383973Notes

Reaction equation

HRID 2383973 reaction equation
[CH3:1][O:2][C:3]1[C:8]2[O:9][C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[C:7]=2[C:6]([CH:16]=O)=[CH:5][CH:4]=1.[Li+].[Br-].[Si](Cl)(C)(C)C.C[SiH](C)O[SiH](C)C.[C-:32]#[N:33].[Na+]>C(#N)C.C(Cl)Cl>[CH3:1][O:2][C:3]1[C:8]2[O:9][C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[C:7]=2[C:6]([CH2:16][C:32]#[N:33])=[CH:5][CH:4]=1

Participants

8

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 8929Sodium CyanideHCID 186591,1,3,3-Tetramethyl-disiloxaneHCID 82050Lithium BromideHCID 574316924-Methoxy-dibenzofuran-1-carbaldehyde

Product 1

HCID 57431693(4-Methoxy-dibenzofuran-1-yl)-acetonitrile

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4-methoxy-dibenzofuran-1-carbaldehyde (13.5 g, 0.059 mol) in acetonitrile (200 ml) was added LiBr (9.8 g, 0.13 mol) and TMS chloride (11.5 ml, 0.089 mol) at room temperature under stirring. The reaction mass was cooled to 0° C., and at 0° C., 1,1,3,3-tetramethyl disiloxane (17 ml, 0.096 mol) was added drop wise. The reaction mass was allowed slowly to come to room temperature and was stirred for 4 hrs at room temperature. Once TLC confirmed the absence of starting material, the reaction mass was diluted with DCM (300 ml), and filtered through Hyflow. The filtrate was concentrated under vacuum and again dissolved in DCM and filtered. To the brown colored compound DMF (150 ml) was added and the reaction mass was stirred for 10 min, until it dissolved. To the solution NaCN (6.44 g, 0.131 mol) was added and the reaction mass was allowed to stir for 4 hrs at room temperature. The reaction mass was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine, dried with sodium sulfate and concentrated under vacuum to get (4-methoxy-dibenzofuran-1-yl)-acetonitrile, Yield 12 g (85%) 1H-NMR (300 MHz, CDCl3) 7.9 (d, J=7.2, 1H); 7.67 (d, J=8.2, 1H); 7.55 (ddd, J=1.2, 7.3, 8.5, 1H); 7.43 (ddd, J=1, 7.8, 8.5, 1H), 7.29 (d, J=8.2, 1H), 6.98 (d, J=8.2, 1H); 4.15 (s, 2H), 4.0 (s, 3H)

Workup

  1. customto come to room temperature
  2. stirringwas stirred for 4 hrs at room temperature
  3. filtrationfiltered through Hyflow
  4. concentrationThe filtrate was concentrated under vacuum
  5. dissolutionagain dissolved in DCM
  6. filtrationfiltered
  7. additionTo the brown colored compound DMF (150 ml) was added
  8. stirringthe reaction mass was stirred for 10 min, until it
  9. dissolutiondissolved
  10. stirringto stir for 4 hrs at room temperature
  11. customThe reaction mass was quenched with water
  12. extractionextracted with ethyl acetate
  13. washThe organic layer was washed with brine
  14. dry with materialdried with sodium sulfate
  15. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-972a1efa971c47849c527dd61e7700c0
Source dataset
uspto-grants-2012_09
Patent number
US08263648B2

Reaction notes

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