Hydrogen Bromide → 2-Bromo-3-((trifluoromethyl)thio)pyridine

HRID 224782Notes

Reaction equation

HRID 224782 reaction equation
[BrH:1].[C:2]([C:4]([S:10][C:11]([F:14])([F:13])[F:12])=[CH:5][CH:6]=[CH:7]OC)#[N:3].C([O-])([O-])=O.[Na+].[Na+]>CC(O)=O>[Br:1][C:2]1[C:4]([S:10][C:11]([F:14])([F:13])[F:12])=[CH:5][CH:6]=[CH:7][N:3]=1

Participants

5

Reactant 3

HCID 260Hydrogen BromideHCID 10340Sodium CarbonateHCID 539202191-Cyano-1-trifluoromethylthio-4-methoxy-1,3-butadiene

Product 1

HCID 125137492-Bromo-3-((trifluoromethyl)thio)pyridine

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Conditions

Temperature
55 °C

Procedure

A solution of 30% HBr, AcOH (70 mL) was added dropwise with stirring at 40° C. to a solution of 4-cyano-4-trifluoromethylthio-3-butenealdehydedimethylacetal and 1-cyano-1-trifluoromethylthio-4-methoxy-1,3-butadiene (8.8 g) in AcOH (40 mL). After the addition, the solution was heated at 55° C. for 2 hours, poured onto ice and neutralized with solid Na2CO3. The solution was extracted with CH2Cl2 (3x) and the CH2Cl2 extracts dried, filtered and concentrated to dryness. The residual oil was distilled at 68°-71° C. at 0.3 mm of yield 4.0 g (16%) of 2-bromo-3-trifluoromethylthiopyridine 1H NMR (CDCL3) δ7.35 (1H, dd, J=4 and 8), 8.05 (1H, dd, J=2 and 8), 8.45 (1H, dd, J=3 and 4); 19F NFR (CDCl3)+40.7 (s).

Workup

  1. additionAfter the addition
  2. extractionThe solution was extracted with CH2Cl2 (3x)
  3. dry with materialthe CH2Cl2 extracts dried
  4. filtrationfiltered
  5. concentrationconcentrated to dryness
  6. distillationThe residual oil was distilled at 68°-71° C. at 0.3 mm of yield 4.0 g (16%) of 2-bromo-3-trifluoromethylthiopyridine 1H NMR (CDCL3) δ7.35 (1H, dd, J=4 and 8), 8.05 (1H, dd, J=2 and 8), 8.45 (1H, dd, J=3 and 4)

Sources & evidence

ORD record
ord-ff65b31cef944f7c9278d4a7cd2530c9
Source dataset
uspto-grants-1980_11
Patent number
US04234590

Reaction notes

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