Pyridine → HCID 136062499, compound

HRID 2192747Notes

Reaction equation

HRID 2192747 reaction equation
[OH:1][CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][C:7]([N:10]=[N:11][C:12]2[CH:17]=[C:16]([CH3:18])[CH:15]=[CH:14][C:13]=2[OH:19])=[CH:6][CH:5]=1.COC1C=CC(O)=CC=1.N1C=CC=CC=1.[C:35](Cl)(=[O:39])[C:36]([CH3:38])=[CH2:37]>C1COCC1>[C:35]([O:1][CH2:2][CH2:3][C:4]1[CH:5]=[CH:6][C:7]([N:10]=[N:11][C:12]2[CH:17]=[C:16]([CH3:18])[CH:15]=[CH:14][C:13]=2[OH:19])=[CH:8][CH:9]=1)(=[O:39])[C:36]([CH3:38])=[CH2:37]

Participants

6

Reactant 4

HCID 1049PyridineHCID 90154-MethoxyphenolHCID 13528Methacryloyl chlorideHCID 136062500HCID 136062500, compound

Product 1

HCID 136062499HCID 136062499, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

In a 250 ml 3-neck round bottom flask equipped with a magnetic stirrer and gas inlet was dissolved 8.21 g (32.0 mmol) 2-((4-(2-hydroxyethyl)phenyl)diazenyl)-4-methylphenol in 200 ml anhydrous THF. ˜50 mg 4-Methoxyphenol (50 mg, Aldrich) was added followed by 20.1 g (254 mmol) anhydrous pyridine. The reaction mixture was cooled to −20° C. and 4.75 g (45.4 mmol) methacryloyl chloride was added dropwise. The reaction mixture was stirred for 1 hour at −20° C. and 20 hours at ambient temperature. The solid was filtered and 200 ml diethyl ether was added to the filtrate. Ethyl acetate (100 ml) was also added to aid in the separation. The organic layer was washed with 0.5 N HCl, and then dried over magnesium sulfate and then filtered. The solvent was removed under removed pressure and the crude product was recrystallized in ethanol to give an orange solid which was rinsed with cold ethanol and dried overnight under high vacuum at room temperature to afford 3.1 g (30%). 1H NMR (CDCl3) delta: 12.67 (s, 1H, Ar—OH), 7.82 (d, 2H, Ar—H), 7.73 (s, 1H, Ar—H), 7.38 (d, 2H, Ar—H), 7.15 (d, 1H, Ar—H), 6.93 (d, 1H, Ar—H), 6.08 (s, 1H, vinyl-H), 5.56 (s, 1H, vinyl-H), 4.41 (m, 2H, CH2OCO), 3.07 (m, 2H, Ar—CH2), 2.38 (s, 3H, Ar—CH3), 1.93 (s, 3H, C═C—CH3).

Workup

  1. customIn a 250 ml 3-neck round bottom flask equipped with a magnetic stirrer and gas inlet
  2. filtrationThe solid was filtered
  3. addition200 ml diethyl ether was added to the filtrate
  4. additionEthyl acetate (100 ml) was also added to aid in the separation
  5. washThe organic layer was washed with 0.5 N HCl
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customThe solvent was removed
  9. customunder removed pressure
  10. customthe crude product was recrystallized in ethanol
  11. customto give an orange solid which
  12. washwas rinsed with cold ethanol
  13. customdried overnight under high vacuum at room temperature
  14. customto afford 3.1 g (30%)

Sources & evidence

ORD record
ord-0d33db42e91c47adae4d9d1cce7e6bb3
Source dataset
uspto-grants-2012_12
Patent number
US08329775B2

Reaction notes

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