Dimethyl Sulfoxide → 4-Nitropicolinaldehyde

HRID 600264Notes

Reaction equation

HRID 600264 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[N+:11]([C:14]1[CH:19]=[CH:18][N:17]=[C:16]([CH2:20][OH:21])[CH:15]=1)([O-:13])=[O:12].C(N(CC)CC)C>C(Cl)Cl.[Cl-].[Na+].O>[N+:11]([C:14]1[CH:19]=[CH:18][N:17]=[C:16]([CH:20]=[O:21])[CH:15]=1)([O-:13])=[O:12]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 14761455(4-Nitropyridin-2-yl)methanol

Product 1

HCID 145789294-Nitropicolinaldehyde

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
-78 °C

Procedure

To cooled solution of oxalyl chloride (0.533 g, 4.18 mmol) in DCM (2 mL) at −78° C. under nitrogen was added dimethyl sulfoxide (0.593 mL, 8.37 mmol) dropwise. After 30 minutes (4-nitro-pyridin-2-yl)-methanol (17)(0.129, 0.837 mmol) in DCM (2 mL) was added dropwise maintaining temperature at −78° C. After 2 hours the mixture was warmed to −55° C. Triethylamine (1.74 mL, 12.55 mmol) was then added and the mixture allowed to warm to room temperature over 2 hours. Brine (10 mL) was then added and the mixture extracted with DCM (4×10 mL). The combined organics were then dried over MgSO4 and concentrated in vacuo to an oil. The material was used directly without need for purification assuming quantitative conversion.

Workup

  1. temperatureAfter 2 hours the mixture was warmed to −55° C
  2. temperatureto warm to room temperature over 2 hours
  3. extractionthe mixture extracted with DCM (4×10 mL)
  4. dry with materialThe combined organics were then dried over MgSO4
  5. concentrationconcentrated in vacuo to an oil
  6. customThe material was used directly without need for purification

Sources & evidence

ORD record
ord-1e9d636496704bfaac3c279886c4075c
Source dataset
uspto-grants-2011_03
Patent number
US07902193B2

Reaction notes

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