Hydrochloric Acid → HCID 23371775, compound

HRID 1899864Notes

Reaction equation

HRID 1899864 reaction equation
Br[C:2]1[C:3]([CH3:14])=[CH:4][C:5]2[O:10][C:9]([CH3:12])([CH3:11])[CH:8]=[CH:7][C:6]=2[CH:13]=1.[Mg].II.Br[C:19]1[CH:24]=[CH:23][N:22]=[C:21]([CH3:25])[CH:20]=1.Cl>O1CCCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Cl-].[Ni+2]>[CH3:25][C:21]1[CH:20]=[C:19]([C:2]2[C:3]([CH3:14])=[CH:4][C:5]3[O:10][C:9]([CH3:12])([CH3:11])[CH:8]=[CH:7][C:6]=3[CH:13]=2)[CH:24]=[CH:23][N:22]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 807IodineHCID 27628354-Bromo-2-methylpyridineHCID 5462224MagnesiumHCID 23371782HCID 23371782, compound

Product 1

HCID 23371775HCID 23371775, compound

Reagents, catalysts & solvents 2

HCID 84306Bis(triphenylphosphine)nickel(II)chlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
5 °C

Procedure

A solution of the product of step e (7.60 g) in dry tetrahydrofuran (30 ml) is added over 15 min. to a stirred mixture of magnesium turnings (0.85 g) and iodine (0.06 g) in dry tetrahydrofuran (25 ml) at 45° C. under an argon atmosphere. The mixture is heated under reflux for 3 h, cooled to 5° C., treated with bis-(triphenylphosphine)nickel (II) chloride (0.32 g) and a solution of 4-bromopicoline (4.8 g) in dry tetrahydrofuran (50 ml) and stirred at room temperature for 18 h. The mixture is treated with HCl (140 ml, 1M) and extracted with diethyl ether (2×60 ml). The combined ether extracts are washed with HCl . The combined acid solutions are basified to pH 10 with K2CO3, extracted with diethyl ether (3×100 ml), dried (Na2SO4), filtered and the solvent is evaporated off under reduced pressure to yield the crude product. This is purified by chromatography (silica gel, 10% acetone in hexane) to give the title compound as an oil, having the following physical characteristics: 1H-NMR(δ-CDCl3): 1.44 (s,6H), 2.21 (s,3H), 2.59 (s, 3H), 5.60 (d,1H), 6.31 (d,1H), 6.70 (s,1H), 6.82 (s,1H), 7.04 (dd,1H), 7.09 (d,1H) and 8.49 (d,1H).

Workup

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 3 h
  3. extractionextracted with diethyl ether (2×60 ml)
  4. washThe combined ether extracts are washed with HCl
  5. extractionextracted with diethyl ether (3×100 ml)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customthe solvent is evaporated off under reduced pressure
  9. customto yield the crude product
  10. customThis is purified by chromatography (silica gel, 10% acetone in hexane)

Sources & evidence

ORD record
ord-34d08f8bd559453394c99ccbf3516677
Source dataset
uspto-grants-1996_11
Patent number
US05574049

Reaction notes

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