Hydrogen Peroxide → HCID 118038105, compound

HRID 587910Notes

Reaction equation

HRID 587910 reaction equation
[OH:1][C:2]1[C:9]([CH3:10])=[C:8]([O:11][CH2:12][O:13][CH3:14])[CH:7]=[CH:6][C:3]=1C=O.[OH-:15].[Na+].OO>O>[CH3:14][O:13][CH2:12][O:11][C:8]1[C:9]([CH3:10])=[C:2]([OH:1])[C:3]([OH:15])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 14798Sodium Hydroxide2×HCID 58439048HCID 58439048, compound

Product 1

HCID 118038105HCID 118038105, compoundYield 95.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
42.5 °C

Procedure

Into a 2.0 L, 4-Necked, RB flask equipped with two addition funnels, thermometer socket and a pH meter was charged 800 mL of DM water. The contents were kept under nitrogen atmosphere. 2-Hydroxy-4-(methoxymethoxy)-3-methylbenzaldehyde (100 g) was added to the reaction mass under stirring. Aqueous sodium hydroxide (0.5 mL, dissolve 24.6 g of sodium hydroxide in 82.0 mL of DM Water) was added to the reaction mass to get a pH of 7.0-8.0. Reaction mass was heated to 40-45° C. Simultaneous addition of aqueous sodium hydroxide and hydrogen peroxide to, the reaction was started using two addition funnels. During the addition pH of the reaction mass was maintained at 7.8-8.4 and the temperature at 40-45° C. After the completion of addition, maintained the reaction mass at 40-45° C. for 4.0 h. The reaction mass was cooled to 25-30° C. and extracted with 3×500 mL of ethyl acetate. Combined organic layer was washed with 500 mL of saturated NaCl solution, treated with 20 g of activated carbon, dried with sodium sulphate, and distilled of solvent under vacuum to get 90 g of crude 4-(methoxymethoxy)-3-methylbenzene-1,2-diol as thick syrup. HPLC purity of sample is about 85%. The material is directly used in next stage. A small sample is purified by column chromatography for characterization purpose. M.R.: 60.5-61.5° C. IR (neat): 3487, 3200, 2969, 2942, 1630, 1621, 1488, 1443, 1405, 1378, 1307, 1290, 1242, 1150, 1086, 1042, 1007, 987, 904, 881, 806, 735, 660, 606 cm−1. 1H-NMR (CDCl3, 400 MHz): δ 8.79 (s, 1H, exchangeable with D2O, OH), 8.19 (s, 1H, exchangeable with D2O, OH), 6.51 (d, J=8.4 Hz, 1H, Ar. H), 6.34 (d, J=8.8 Hz, 1H, Ar. H), 5.02 (s, 2H, OCH2O), 3.36 (s, 3H, OMe), 2.01 (s, 3H, ArCH3). 13C-NMR (CDCl3, 100 MHz): δ 148.45 (C-4), 143.92 (C-2), 139.95 (C-1), 114.64 (C-3), 111.77 (C-6), 105.60 (C-5), 95.16 (OCH2O), 55.49 (OMe), 9.17 (ArCH3). Mass (EI-MS): 184.46 (M), 183.3 (M−1)

Workup

  1. customInto a 2.0 L, 4-Necked, RB flask equipped with two addition funnels, thermometer socket
  2. customto get a pH of 7.0-8.0
  3. customReaction mass
  4. additiontwo addition funnels
  5. temperatureDuring the addition pH of the reaction mass was maintained at 7.8-8.4
  6. customat 40-45° C
  7. additionAfter the completion of addition
  8. temperaturemaintained the reaction mass at 40-45° C. for 4.0 h
  9. temperatureThe reaction mass was cooled to 25-30° C.
  10. extractionextracted with 3×500 mL of ethyl acetate
  11. washCombined organic layer was washed with 500 mL of saturated NaCl solution
  12. additiontreated with 20 g of activated carbon
  13. dry with materialdried with sodium sulphate
  14. distillationdistilled of solvent under vacuum

Sources & evidence

ORD record
ord-8c3c106ff3184b04bed56b6ef537daca
Source dataset
uspto-grants-2016_01
Patent number
US09227948B2

Reaction notes

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