Pyridine → 2-Hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzyl methacrylate

HRID 222451Notes

Reaction equation

HRID 222451 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[C:7]([CH3:9])[CH:6]=[C:5]([N:10]=[N:11][C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=2)[C:4]=1[OH:20].COC1C=CC(O)=CC=1.N1C=CC=CC=1.[C:36](Cl)(=[O:40])[C:37]([CH3:39])=[CH2:38]>C1COCC1>[C:36]([O:1][CH2:2][C:3]1[CH:8]=[C:7]([CH3:9])[CH:6]=[C:5]([N:10]=[N:11][C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=2)[C:4]=1[OH:20])(=[O:40])[C:37]([CH3:39])=[CH2:38]

Participants

6

Reactant 4

HCID 1049PyridineHCID 90154-MethoxyphenolHCID 13528Methacryloyl chlorideHCID 1359935832-(Hydroxymethyl)-6-((4-methoxyphenyl)-diazenyl)-4-methylphenol

Product 1

HCID 1359935782-Hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzyl methacrylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

In a 500 ml round bottom flask equipped with a magnetic stirrer and gas inlet was dissolved 8.75 g (32.1 mmol) of 2-(hydroxymethyl)-6-((4-methoxyphenyl)-diazenyl)-4-methylphenol in 300 ml anhydrous THF. ˜50 mg 4-methoxyphenol (MEHQ) was added followed by 16.5 g (209 mmol) anhydrous pyridine. The reaction mixture was cooled to −20° C. and 4.91 g (47.0 mmol) methacryloyl chloride was added dropwise. The reaction mixture was stirred for 1 hour at −20° C. and then 20 hours at ambient temperature. The solid was filtered and diethyl ether (200 ml) and ethyl acetate (200 ml) were added to the filtrate. The organic layer was washed with 0.5 N HCl, and then dried over magnesium sulfate. The solvent was removed under removed pressure and the crude product was recrystallized in methanol to give an orange solid which was rinsed with cold ethanol and then for 20 hours under vacuum (0.1 mm Hg) at room temperature to afford 7.0 g (64%). 1H NMR (CDCl3) delta: 13.12 (s, 1H, Ar—OH), 7.84 (m, 2H, Ar—H), 7.68 (s, 1H, Ar—H), 7.23 (s, 1H, Ar—H), 7.02 (m, 2H, Ar—H), 6.16 (s, 1H, vinyl-H), 5.58 (s, 1H, vinyl-H), 5.31 (s, 2H, Ar—CH2), 3.89 (s, 3H, CH3O—Ar), 2.38 (s, 3H, Ar—CH3), 1.98 (s, 3H, C═C—CH3).

Workup

  1. customIn a 500 ml round bottom flask equipped with a magnetic stirrer and gas inlet
  2. custom20 hours
  3. customat ambient temperature
  4. filtrationThe solid was filtered
  5. additiondiethyl ether (200 ml) and ethyl acetate (200 ml) were added to the filtrate
  6. washThe organic layer was washed with 0.5 N HCl
  7. dry with materialdried over magnesium sulfate
  8. customThe solvent was removed
  9. customunder removed pressure
  10. customthe crude product was recrystallized in methanol
  11. customto give an orange solid which
  12. washwas rinsed with cold ethanol
  13. customfor 20 hours under vacuum (0.1 mm Hg) at room temperature to afford 7.0 g (64%)

Sources & evidence

ORD record
ord-8947efe9306f4e61981cbed10fa77750
Source dataset
uspto-grants-2012_06
Patent number
US08207244B2

Reaction notes

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