2-Bromopyridine → HCID 16678705, compound

HRID 1661219Notes

Reaction equation

HRID 1661219 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.C([Li])CCC.CON(C)[C:16]([C:18]1[N:19]=[CH:20][N:21]([C:23]2[CH:24]=[C:25]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[CH:26]=[CH:27][CH:28]=2)[CH:22]=1)=[O:17].[Cl-].[NH4+]>C1COCC1>[C:25]1([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[CH:26]=[CH:27][CH:28]=[C:23]([N:21]2[CH:22]=[C:18]([C:16]([C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=3)=[O:17])[N:19]=[CH:20]2)[CH:24]=1

Participants

6

Reactant 4

HCID 79732-BromopyridineHCID 25517Ammonium ChlorideHCID 86634426HCID 86634426, compoundHCID 178418339Butyllithium

Product 1

HCID 16678705HCID 16678705, compoundYield 28.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 2-bromopyridine (1.0 g, 6.5 mmol) in THF (20 ml) was stirred at −78° C. in a nitrogen atmosphere. n-Butyllithium (8.1 ml 1.6M solution in hexanes, 13.0 mmol) was added and stirring at −78° C. was continued for 45 min. The resultant mixture was allowed to warm to 0° C. for two hours, in order to ensure completion of anion formation. The mixture was again cooled to −78° C. and compound 12a (0.5 g, 1.6 mmol) was added. After 30 min. the mixture was allowed to warm to 0° C. and saturated, aqueous ammonium chloride was added. The mixture was extracted with ethyl acetate. The combined extracts were dried over magnesium sulfate and concentrated under reduced pressure. The concentrate was purified by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (9:1) as the eluent. This afforded the desired product (0.15 g, 22%) as a yellowish gum. HRMS (ESI+): m/z=326.1305 [M+H]

Workup

  1. temperatureto warm to 0° C. for two hours, in order
  2. temperatureThe mixture was again cooled to −78° C.
  3. waitAfter 30 min. the mixture was allowed
  4. temperatureto warm to 0° C.
  5. extractionThe mixture was extracted with ethyl acetate
  6. dry with materialThe combined extracts were dried over magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe concentrate was purified by column chromatography on silica gel using
  9. additiona mixture of petroleum ether and ethyl acetate (9:1) as the eluent

Sources & evidence

ORD record
ord-d46a78334a1b486a868ec82b691796c8
Source dataset
uspto-grants-2011_10
Patent number
US08030339B2

Reaction notes

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