Toluene → 2-benzenesulfonyl-4-methylpyridine

HRID 1700813Notes

Reaction equation

HRID 1700813 reaction equation
[CH:1](=O)[CH:2]=[C:3]([CH3:5])[CH3:4].[C:7]1([S:13]([C:16]#[N:17])(=[O:15])=[O:14])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C1(C)C=CC=CC=1.B(O)(O)O>C(O)CCC>[C:7]1([S:13]([C:16]2[CH:4]=[C:3]([CH3:5])[CH:2]=[CH:1][N:17]=2)(=[O:14])=[O:15])[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 7628Boric AcidHCID 610203-Methyl-2-butenalHCID 10313279Benzenesulfonyl cyanide

Product 1

HCID 98375592-benzenesulfonyl-4-methylpyridineYield 72.9%

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent

Conditions

Temperature
119 °C

Procedure

First, 9.00 g (107 mmol) of senecialdehyde (3-methyl-2-butenal) and 8.35 g (50.0 mmol) of benzenesulfonyl cyanide were introduced to the same reaction vessel as in Example 1. Toluene (15 ml) as the solvent and butanol (1.5 ml) were added, and 0.30 g (4.85 mmol) boric acid were added. Then the mixture was heated under reflux for 3 hours while agitating at an internal temperature of 119° C. in a nitrogen atmosphere, separating and removing water that was produced. After this solution was cooled to room temperature, the low-boiling components, such as solvent, etc., were removed under reduced pressure and the resulting concentrate was cooled in an ice bath to precipitate crystals. The crystals were filtered with a glass filter and washed with 10 ml of toluene that had been cooled to 5° C. or lower. Then the crystals were dried for 2 hours in vacuo to give 8.50 g of 2-benzenesulfonyl-4-methylpyridine with the following properties as colorless crystals (purity of 99%, yield of 72% based on benzenesulfonyl cyanide).

Workup

  1. temperatureThen the mixture was heated
  2. temperatureunder reflux for 3 hours
  3. customseparating
  4. customremoving water that
  5. customwas produced
  6. temperatureAfter this solution was cooled to room temperature
  7. customthe low-boiling components, such as solvent, etc., were removed under reduced pressure
  8. concentrationthe resulting concentrate
  9. temperaturewas cooled in an ice bath
  10. customto precipitate crystals
  11. filtrationThe crystals were filtered with a glass
  12. filtrationfilter
  13. washwashed with 10 ml of toluene that
  14. temperaturehad been cooled to 5° C.
  15. customThen the crystals were dried for 2 hours in vacuo

Sources & evidence

ORD record
ord-da454b7857a94cebab9f74fa10489cd7
Source dataset
uspto-grants-2002_02
Patent number
US06350876B2

Reaction notes

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