Triethylamine → 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate

HRID 1691504

Reaction equation

HRID 1691504 reaction equation
[F:1][C:2]1[CH:21]=[CH:20][C:5]2=[N:6][N:7]([C:9]3[CH:14]=[C:13]([O:15][CH3:16])[CH:12]=[C:11]([CH2:17][OH:18])[C:10]=3[OH:19])[N:8]=[C:4]2[CH:3]=1.C(N(CC)CC)C.[C:29](Cl)(=[O:33])[C:30]([CH3:32])=[CH2:31]>C1COCC1>[C:29]([O:18][CH2:17][C:11]1[CH:12]=[C:13]([O:15][CH3:16])[CH:14]=[C:9]([N:7]2[N:6]=[C:5]3[CH:20]=[CH:21][C:2]([F:1])=[CH:3][C:4]3=[N:8]2)[C:10]=1[OH:19])(=[O:33])[C:30]([CH3:32])=[CH2:31]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 13528Methacryloyl chlorideHCID 669077462-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenol

Product 1

HCID 593174003-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-5 °C

Procedure

The esterification was carried out using the product. In a 250 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 5.06 g (17.5 mmol) 2-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenol in 60 ml anhydrous THF. Triethylamine (8.7 ml, 62 mmol)) was added and the mixture was cooled to −10-0° C. Methacryloyl chloride (2.26 g, 21.6 mmol) was added dropwise and the mixture was stirred for 1 hr at −10° C. followed by 20 hours at ambient temperature. The salts were filtered and rinsed with 100 ml THF (≧99.9%, anhydrous containing inhibitor, Aldrich). Diethyl ether (100 ml) was added to the filtrate, which was washed with 1N HCl and water, dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to give the desired product, which was recrystallized in ethanol to give 2.5 g (40%) of a yellow solid. 1H NMR (CDCl3) delta: 11.03 (s, 1H, phenol OH), 7.94 (m, 1H, Ar—H benzotriazole ring), 7.87 (s, 1H, Ar—H phenol ring), 7.53 (m, 1H, Ar—H benzotriazole ring), 7.29 (m, 1H, Ar—H benzotriazole ring), 7.05 (s, 1H, Ar—H phenol ring), 6.21 (s, 1H, C═C—H trans), 5.61 (s, 1H, C═C—H cis), 5.39 (s, 2H, Ar—CH2), 3.89 (s, 3H, Ar—OCH3), 2.01 (s, 3H, C═C—CH3).

Workup

  1. customIn a 250 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet
  2. waitfollowed by 20 hours at ambient temperature
  3. filtrationThe salts were filtered
  4. washrinsed with 100 ml THF (≧99.9%, anhydrous containing inhibitor, Aldrich)
  5. additionDiethyl ether (100 ml) was added to the filtrate, which
  6. washwas washed with 1N HCl and water
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record
ord-a81c620b41554dd8a97e439c64eb01aa
Source dataset
uspto-grants-2012_04
Patent number
US08153703B2

Linked notes

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