Ammonia → 4,4'-Di-tert-butyl-2,2'-bipyridyl

HRID 1447708Notes

Reaction equation

HRID 1447708 reaction equation
[NH2-:1].[Na+].N.[C:4]([C:8]1[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=1)([CH3:7])([CH3:6])[CH3:5].[H][H]>O>[C:4]([C:8]1[CH:13]=[CH:12][N:11]=[C:10]([C:12]2[CH:13]=[C:8]([C:4]([CH3:7])([CH3:6])[CH3:5])[CH:9]=[CH:10][N:1]=2)[CH:9]=1)([CH3:7])([CH3:6])[CH3:5]

Participants

6

Reactant 4

HCID 222Ammonia2×HCID 198784-tert-ButylpyridineHCID 24533Sodium amideHCID 178418361HCID 178418361, compound2×

Product 1

HCID 42491874,4'-Di-tert-butyl-2,2'-bipyridylYield 24.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
135 °C

Procedure

In a one-liter, three-neck flask, equipped with a stirrer and dropping funnel, was prepared one mole of sodamide (23.0 g of sodium and iron catalyst) in 700 cc of liquid ammonia. The ammonia was replaced with 589.7 g (4.37 moles) of 4-t-butylpyridine. The mixture was heated to 135° C. at which time the purple reaction mixture began evolving hydrogen. The reaction was continued for 3.1 hours at 135°-149° C. until hydrogen evolution became slow. The reaction mixture was cooled to 100° C. and hydrolyzed with 100 cc of water. The oil layer was separated at 40° C. The aqueous layer was extracted with 50 cc of xylene. The oil layer and xylene extract were charged to a Vigreaux column for distillation. Xylene and about 300 g of unreacted 4-t-butylpyridine were distilled under vacuum. The residue was cooled to room temperature, allowing 4,4'-di-(t-butyl)-2,2'-bipyridyl to crystallize. It was filtered and washed with acetone to give 66.4 g of 4,4'-di-(t-butyl)-2,2'-bipyridyl with a melting point of 159°-160° C.

Workup

  1. customIn a one-liter, three-neck flask, equipped with a stirrer
  2. customThe oil layer was separated at 40° C
  3. extractionThe aqueous layer was extracted with 50 cc of xylene
  4. extractionThe oil layer and xylene extract
  5. additionwere charged to a Vigreaux column for distillation
  6. distillationXylene and about 300 g of unreacted 4-t-butylpyridine were distilled under vacuum
  7. temperatureThe residue was cooled to room temperature
  8. customto crystallize
  9. filtrationIt was filtered
  10. washwashed with acetone

Sources & evidence

ORD record
ord-4f0d35d59fd64853b610293995acc6bd
Source dataset
uspto-grants-1979_12
Patent number
US04177349

Reaction notes

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