3-Bromopyridine → HCID 67731667, compound

HRID 375087Notes

Reaction equation

HRID 375087 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][C:5]([CH2:6][C:7]#[N:8])=[CH:4][CH:3]=1.Br[C:12]1[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=1.[OH-].[K+]>CS(C)=O>[F:1][C:2]1[CH:10]=[CH:9][C:5]([CH:6]([C:12]2[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=2)[C:7]#[N:8])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 122863-BromopyridineHCID 14797Potassium Hydroxide2×HCID 68016Benzeneacetonitrile, 4-fluoro-

Product 1

HCID 67731667HCID 67731667, compoundYield 49.4%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

In a 1 liter 3 neck round bottomed flask was charged 20.0 g. of 4-fluorobenzyl cyanide (1.0 eq., 0.15 moles), in 300 ml. dimethylsulfoxide (DMSO) (dried over molecular sieves), and 46.8 g. of 3-bromopyridine (2.0 eq., 0.30 moles) while stirring under N2. The reaction mixture was heated to 60° C. at which time 12.4 g of KOH (1.5 eq., 0.22 moles) as powdered pellets was added neat. The reaction exotherms to 80° C. and was monitored by GLC. After 30 min., an additional 2.4 g. of potassium hydroxide (KOH) was added (0.3 eq., 0.043 moles) and 1 hr. later GLC showed 6% unreacted nitrile. The reaction was quenched by the addition of 500 ml. of water and then extracted with 1 liter of ether. The organic phase was washed 3 times 250 ml. H2O, dried over MgSO4 and concentrated to give 50 g. of oil. The crude product was distilled under vacuum to give 15.7 g. of oil (49.4% yield) bp 160°-170° C. @1-2 min. Hg.

Workup

  1. additionwas added neat
  2. customexotherms to 80° C.
  3. customThe reaction was quenched by the addition of 500 ml
  4. extractionof water and then extracted with 1 liter of ether
  5. washThe organic phase was washed 3 times 250 ml
  6. dry with materialH2O, dried over MgSO4
  7. concentrationconcentrated
  8. customto give 50 g
  9. distillationThe crude product was distilled under vacuum
  10. customto give 15.7 g

Sources & evidence

ORD record
ord-239d0af56dc2435ebbd866d0f7f8291e
Source dataset
uspto-grants-1996_01
Patent number
US05484787

Reaction notes

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