1,8-Diazabicyclo(5.4.0)undec-7-ene → 3-(Azidomethyl)-5-chloro-2-methylpyridine

HRID 2071030Notes

Reaction equation

HRID 2071030 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9]O)[C:5]([CH3:8])=[N:6][CH:7]=1.C1(P([N:25]=[N+:26]=[N-:27])(C2C=CC=CC=2)=O)C=CC=CC=1.N12CCCN=C1CCCCC2>C1(C)C=CC=CC=1>[N:25]([CH2:9][C:4]1[C:5]([CH3:8])=[N:6][CH:7]=[C:2]([Cl:1])[CH:3]=1)=[N+:26]=[N-:27]

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 66961492(5-Chloro-2-methylpyridin-3-yl)methanol

Product 1

HCID 866474243-(Azidomethyl)-5-chloro-2-methylpyridine

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

To a stirring solution of 399 mg (2.55 mmol) of (5-chloro-2-methylpyridin-3-yl)methanol in 10 mL of toluene at r.t. was added 660 μL (3.06 mmol) of DPPA (diphenylphosphoryl azide). The solution was cooled to 0° C. and 450 μL of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) was added. The ice bath was removed and stirring was continued with warming to r.t. After 16 h, 1 N HCl was added to a pH=8. Water was added and the aqueous layer was extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (45% EtOAc/hexanes) provided 3-(azidomethyl)-5-chloro-2-methylpyridine as a yellow oil in quantitative yield.

Workup

  1. customThe ice bath was removed
  2. temperaturewith warming to r.t
  3. addition1 N HCl was added to a pH=8
  4. additionWater was added
  5. extractionthe aqueous layer was extracted with EtOAc
  6. washThe organic layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by flash silica gel chromatography (45% EtOAc/hexanes)

Sources & evidence

ORD record
ord-d42a839719bc4f12ab3b671dc2b2b436
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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