Dimethyl Sulfoxide → 2-[2-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl] pyridine-5-carboxaldehyde

HRID 1886085Notes

Reaction equation

HRID 1886085 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH3:11][C:12]1([CH3:34])[CH2:21][CH2:20][C:19]([CH3:23])([CH3:22])[C:18]2[CH:17]=[C:16]([C:24]#[C:25][C:26]3[CH:31]=[CH:30][C:29]([CH2:32][OH:33])=[CH:28][N:27]=3)[CH:15]=[CH:14][C:13]1=2.C(N(CC)CC)C>C(Cl)Cl>[CH3:11][C:12]1([CH3:34])[CH2:21][CH2:20][C:19]([CH3:22])([CH3:23])[C:18]2[CH:17]=[C:16]([C:24]#[C:25][C:26]3[CH:31]=[CH:30][C:29]([CH:32]=[O:33])=[CH:28][N:27]=3)[CH:15]=[CH:14][C:13]1=2

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 193728362-[2-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl]-5-hydroxymethylpyridine

Product 1

HCID 152955542-[2-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl] pyridine-5-carboxaldehyde

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-60 °C

Procedure

A solution of 1.396 g (11 mmol) of freshly distilled oxalyl chloride in 25 ml of methylene chloride is placed in a 4-necked flask equipped with a stirrer, a thermometer and two pressure-equalizing addition funnels fitted with drying tubes. The solution is cooled to -60° C. and then treated dropwise with a solution of 1.875 g (24 mmol) of dimethyl sulfoxide (distilled from calcium hydride) in 5 ml of methylene chloride over a five minute period. The reaction mixture is then stirred at -60° C. for an additional 10 minutes. A solution of 3.195 g (10 mmol) of 2-[2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphth-2-yl)ethynyl]-5-hydroxymethylpyridine in 10 ml of methylene chloride is then added to the reaction mixture over a period of 5 minutes. The mixture is stirred for a further minutes and is then treated with 5.06 g (50 mmol) of triethylamine. The cooling bath is then removed and the mixture is allowed to warm to room temperature. Thirty ml of water is then added to the mixture and stirring is continued for a further 10 minutes. The organic layer is then separated and the aqueous layer is extracted with 20 ml of methylene chloride. The organic layers are then combined and washed successively with dilute HCl, water and dilute Na2CO3 solution and then dried (MgSO4) The solution is then filtered and concentrated in vacuo and the residue is purified by chromatography followed by recrystallization to give the title compound.

Workup

  1. customequipped with a stirrer
  2. additiona thermometer and two pressure-equalizing addition funnels
  3. customfitted with drying tubes
  4. stirringThe mixture is stirred for a further minutes
  5. customThe cooling bath is then removed
  6. temperatureto warm to room temperature
  7. additionThirty ml of water is then added to the mixture
  8. stirringstirring
  9. waitis continued for a further 10 minutes
  10. customThe organic layer is then separated
  11. extractionthe aqueous layer is extracted with 20 ml of methylene chloride
  12. washwashed successively with dilute HCl, water and dilute Na2CO3 solution
  13. dry with materialdried (MgSO4) The solution
  14. filtrationis then filtered
  15. concentrationconcentrated in vacuo
  16. customthe residue is purified by chromatography
  17. customfollowed by recrystallization

Sources & evidence

ORD record
ord-676f5fc408e74385b424667832cc9258
Source dataset
uspto-grants-1992_09
Patent number
US05149705

Reaction notes

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