2-Bromopyridine → N-(alpha-[2-pyridyl]benzyl)-4-pyridinamine

HRID 1448603Notes

Reaction equation

HRID 1448603 reaction equation
[CH:1](=[N:8][C:9]1[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[Li].BrC1C=CC=CN=1>CCOCC>[N:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[CH:1]([NH:8][C:9]1[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 79732-BromopyridineHCID 6428664-BenzylideneaminopyridineHCID 178506720HCID 178506720, compound

Product 1

HCID 20380317N-(alpha-[2-pyridyl]benzyl)-4-pyridinamineYield 34.7%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

4.55 Grams (0.025 mole) of 4-benzylideneaminopyridine in 50 milliliters of dry ether was added dropwise to a stirred solution of 2-pyridyl lithium (prepared from 0.03 mole of butyl lithium and 4.74 grams [0.03 mole] of 2-bromopyridine) in 100 ml. of hexane-ether cooled to -30° C. under nitrogen. A purple precipitate was formed which was stirred for 4 hours while allowing the product to warm up to room temperature. The mixture was poured onto ice and the organic layer was separated and extracted with 2 N hydrochloric acid. The acid extracts were combined with the aqueous layer and the combined aqueous medium was basified with 5 N sodium hydroxide and extracted into dichloromethane. After drying over magnesium sulphate, the solvent was removed to leave a solid which was recrystallized from a mixture of toluene and light petroleum (b.p. 100°-120° C.) to afford 2.27 grams of the title compound as free base, m.p. 114°-115° C. The base was converted to its colourless dihydrobromide salt, m.p. 230° (decomposition), by dissolution in the minimum quantity of 2-propanol and adding a solution of hydrogen bromide in dry ether.

Workup

  1. customA purple precipitate was formed which
  2. additionThe mixture was poured onto ice
  3. customthe organic layer was separated
  4. extractionextracted with 2 N hydrochloric acid
  5. extractionextracted into dichloromethane
  6. dry with materialAfter drying over magnesium sulphate
  7. customthe solvent was removed
  8. customto leave a solid which
  9. customwas recrystallized from a mixture of toluene and light petroleum (b.p. 100°-120° C.)

Sources & evidence

ORD record
ord-d8a5a23f3c7a441a93bc94e23d85ce9f
Source dataset
uspto-grants-1979_12
Patent number
US04180670

Reaction notes

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