Pyridine → HCID 14029083, compound

HRID 986824Notes

Reaction equation

HRID 986824 reaction equation
[OH:1][C:2]1[C:7]([C:8]([CH3:11])([CH3:10])[CH3:9])=[CH:6][C:5]([O:12][CH2:13][CH2:14][CH2:15][OH:16])=[CH:4][C:3]=1[N:17]1[N:21]=[C:20]2[CH:22]=[CH:23][C:24]([O:26][CH3:27])=[CH:25][C:19]2=[N:18]1.N1C=CC=CC=1.[C:34](Cl)(=[O:38])[C:35]([CH3:37])=[CH2:36]>C1(C)C=CC=CC=1>[OH:1][C:2]1[C:7]([C:8]([CH3:11])([CH3:10])[CH3:9])=[CH:6][C:5]([O:12][CH2:13][CH2:14][CH2:15][O:16][C:34](=[O:38])[C:35]([CH3:37])=[CH2:36])=[CH:4][C:3]=1[N:17]1[N:21]=[C:20]2[CH:22]=[CH:23][C:24]([O:26][CH3:27])=[CH:25][C:19]2=[N:18]1

Participants

5

Reactant 3

HCID 1049PyridineHCID 13528Methacryloyl chlorideHCID 14029082HCID 14029082, compound

Product 1

HCID 14029083HCID 14029083, compoundYield 99.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

In a 2 L flask equipped with a mechanical stirrer, a thermometer and an addition funnel which was protected from moisture with a drying tube were placed 37.16 g (0.1 mol) of the benzotriazole of Example 3, 800 mL of dry toluene and 17 mL (0.21 mol) of dry pyridine. A solution of 13 mL (0.128 mol) of methacryloyl chloride (freshly distilled) in 10 mL of toluene was added to the mixture over 30 minutes. The reaction mixture was stirred overnight at room temperature (<25° C.). A white precipitate (pyridinium chloride) was separated by filtration and washed with toluene. The filtrate and washings were combined, washed with 1N hydrochloric acid, water, aqueous sodium bicarbonate and water successively, then dried with anhydrous sodium sulfate and evaporated. The residue (ca. 41 g) was dissolved in a mixture of 1 L of methanol and 500 mL of methylene chloride by heating in a water bath at 45° C. The resulting solution was filtered to remove a small amount of insoluble materials and diluted with 250 mL of methanol. The solution was cooled slowly at room temperature, in a refrigerator and finally then placed in a freezer where the temperature was reduced to about -5° C. The resulting crystals were separated by filtration, washed with 250 mL of cold methanol/methylene chloride (90/10 v/v) and dried in vacuo to give 38.4 g of 99.7% pure product m.p. 114°-116° C.

Workup

  1. customIn a 2 L flask equipped with a mechanical stirrer
  2. customa thermometer and an addition funnel which was protected from moisture with a drying tube
  3. additionwas added to the mixture over 30 minutes
  4. customA white precipitate (pyridinium chloride) was separated by filtration
  5. washwashed with toluene
  6. washwashed with 1N hydrochloric acid, water, aqueous sodium bicarbonate and water successively
  7. dry with materialdried with anhydrous sodium sulfate
  8. customevaporated
  9. dissolutionThe residue (ca. 41 g) was dissolved in a mixture of 1 L of methanol and 500 mL of methylene chloride
  10. temperatureby heating in a water bath at 45° C
  11. filtrationThe resulting solution was filtered
  12. customto remove a small amount of insoluble materials
  13. additiondiluted with 250 mL of methanol
  14. temperatureThe solution was cooled slowly at room temperature, in a refrigerator
  15. customwas reduced to about -5° C
  16. customThe resulting crystals were separated by filtration
  17. washwashed with 250 mL of cold methanol/methylene chloride (90/10 v/v)
  18. customdried in vacuo

Sources & evidence

ORD record
ord-3780b9a07b48458ba0968e77b32899ce
Source dataset
uspto-grants-1987_12
Patent number
US04716234

Reaction notes

Loading…