Methyl morpholine oxide → 2-(4-Chloro-6-(pyridin-2-yl)pyrimidin-5-yl)acetaldehyde

HRID 717571Notes

Reaction equation

HRID 717571 reaction equation
[CH2:1]([C:4]1[C:5]([Cl:16])=[N:6][CH:7]=[N:8][C:9]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][N:11]=1)[CH:2]=C.C[N+]1([O-])CC[O:21]CC1>O1CCOCC1.[Os](=O)(=O)(=O)=O>[Cl:16][C:5]1[C:4]([CH2:1][CH:2]=[O:21])=[C:9]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][N:11]=2)[N:8]=[CH:7][N:6]=1

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 898144745-Allyl-4-chloro-6-(pyridin-2-yl)pyrimidine

Product 1

HCID 898152122-(4-Chloro-6-(pyridin-2-yl)pyrimidin-5-yl)acetaldehydeYield 69.4%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a stirred solution of 5-allyl-4-chloro-6-(pyridin-2-yl)pyrimidine (1 g) in dry dioxane (10 mL), N-methyl morpholine N-oxide (0.75 g) and osmium tetroxide (0.35 mL, 25% solution in water) were added. The reaction mixture was stirred at room temperature for 2 hours before being quenched by solid sodium bisulphate. The reaction mixture was filtered through celite bed and the celite bed was washed with dioxane (5 mL). The combined filtrate was taken into a 100 mL three necked round bottom flask and sodium metaperiodate (2.3 g, in 5 mL water) was added. The reaction mixture was stirred at room temperature for 3 hours and then diluted with water (30 mL). Aqueous layer was extracted with dichloromethane (2×25 mL). The combined organic layer was washed with brine (50 mL) and dried over anhydrous Na2SO4. Evaporation of solvents under reduced pressure gave crude 2-(4-chloro-6-(pyridin-2-yl)pyrimidin-5-yl)acetaldehyde (0.7 g) which was used as was. 1H NMR (DMSO-d6): δ 4.12 (s, 2H), 7.53-7.55 (m, 1H), 7.88-8.01 (m, 2H), 8.66-8.69 (d, 1H), 8.97 (s, 1H), 9.79 (s, 1H).

Workup

  1. custombefore being quenched by solid sodium bisulphate
  2. filtrationThe reaction mixture was filtered through celite bed
  3. washthe celite bed was washed with dioxane (5 mL)
  4. additionwas added
  5. stirringThe reaction mixture was stirred at room temperature for 3 hours
  6. additiondiluted with water (30 mL)
  7. extractionAqueous layer was extracted with dichloromethane (2×25 mL)
  8. washThe combined organic layer was washed with brine (50 mL)
  9. dry with materialdried over anhydrous Na2SO4
  10. customEvaporation of solvents under reduced pressure

Sources & evidence

ORD record
ord-15ae0ef706cc48da9ec268cee24656af
Source dataset
uspto-grants-2015_11
Patent number
US09193725B2

Reaction notes

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