Dimethyl Sulfoxide → 4-(Azidopropoxy)-2,6-diformyl-pyridine

HRID 411863Notes

Reaction equation

HRID 411863 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[N:11]([CH2:14][CH2:15][CH2:16][O:17][C:18]1[CH:23]=[C:22]([CH2:24][OH:25])[N:21]=[C:20]([CH2:26][OH:27])[CH:19]=1)=[N+:12]=[N-:13].C(N(CC)CC)C>C(Cl)Cl>[N:11]([CH2:14][CH2:15][CH2:16][O:17][C:18]1[CH:23]=[C:22]([CH:24]=[O:25])[N:21]=[C:20]([CH:26]=[O:27])[CH:19]=1)=[N+:12]=[N-:13]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 543426824-(3-Azidopropoxy)-2,6-dihydroxymethylpyridine

Product 1

HCID 223237004-(Azidopropoxy)-2,6-diformyl-pyridine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

DMSO (1.21 mL, 17.1 mmol) was diluted with CH2Cl2 (approximately 25 mL) and cooled to −78° C. Oxalyl chloride (0.745 mL, 8.45 mmol) was added dropwise and the reaction mixture was stirred for 15 minutes. 4-(3-azidopropoxy)-2,6-dihydroxymethylpyridine (1 g, 4.27 mmol) dissolved in CH2Cl2 (10 mL) was added slowly to the cooled reaction mixture. After 0.5 hour triethylamine (2.77 mL, 19.70 mmol) was added dropwise to the reaction mixture. The dry ice/acetone bath was removed and the reaction mixture was warmed to room temperature for approximately 40 minutes. The reaction mixture was partitioned between CH2Cl2 and water and extracted several times with CH2Cl2. The CH2Cl2 layers were combined, dried (MgSO4) and concentrated in vacuo. The resulting residue was purified by silica gel flash column chromatography to give the title compound. 1H NMR (DMSO) δ2.02 (m, 2H, CH2), 3.52 (t, 2H, CH2), 4.31 (t, 2H, CH2), 7.64 (s, 2H, 2× Ar), 10.01 (s ,2H, CHO). 13C NMR (DMSO) δ27.61 (CH2), 47.40 (CH2), 66.22 (CH2), 111.58 (Ar), 154.40 (quaternary, Ar), 166,50 (quaternary, Ar), 192.44 (CHO).

Workup

  1. additionwas added slowly to the cooled reaction mixture
  2. customThe dry ice/acetone bath was removed
  3. temperaturethe reaction mixture was warmed to room temperature for approximately 40 minutes
  4. customThe reaction mixture was partitioned between CH2Cl2 and water
  5. extractionextracted several times with CH2Cl2
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo
  8. customThe resulting residue was purified by silica gel flash column chromatography

Sources & evidence

ORD record
ord-708da7f2ef5543cfbddddbdf9ed4037d
Source dataset
uspto-grants-2003_05
Patent number
US06559303B1

Reaction notes

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