Barium hydroxide, monohydrate → 3-Hydroxymethyl-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acid

HRID 2262416Notes

Reaction equation

HRID 2262416 reaction equation
C[O:2][C:3]([C:5]1[CH:16]=[CH:15][C:8]2[O:9][CH2:10][CH:11]([CH2:13][OH:14])[O:12][C:7]=2[C:6]=1[CH3:17])=[O:4].O.[OH-].[Ba+2].[OH-]>CO>[OH:14][CH2:13][CH:11]1[CH2:10][O:9][C:8]2[CH:15]=[CH:16][C:5]([C:3]([OH:4])=[O:2])=[C:6]([CH3:17])[C:7]=2[O:12]1

Participants

4

Reactant 2

HCID 17749100Barium hydroxide, monohydrateHCID 687788313-Hydroxymethyl-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acid methyl ester

Product 1

HCID 687762923-Hydroxymethyl-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acidYield 80%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a round bottom flask equipped with magnetic stirring was added 3-hydroxymethyl-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acid methyl ester (6.40 g, 26.9 mmol), barium hydroxide monohydrate (25.44 g, 134.3 mmol), and methanol (108 mL). This mixture was stirred at room temperature for 24 hours. The methanol was evaporated. The resulting slurry was taken up in water and washed once with ether. The aqueous layer was acidified by pouring into iced concentrated HCl. This was extracted (vice with ethyl acetate. The ethyl acetate extracts were combined, dried over magnesium sulfate, filtered and evaporated to give a yellow solid, 3-hydroxymethyl-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acid, (4.82 g, 21.5 mmol) in 80% yield. 1H-NMR (300 MHz, CD3COCD3) δ (ppm): 2.45 (s, 3H), 3.85 (m, 2H), 4.12 (m, 1H), 4.24 (m, 1H), 4.41 (m, 1H), 6.76 (d, 1H), 7.51 (d, 1H); TLC: Rf=0.32 (1:1 ethyl acetate/hexane).

Workup

  1. customTo a round bottom flask equipped
  2. stirringThis mixture was stirred at room temperature for 24 hours
  3. customThe methanol was evaporated
  4. washwashed once with ether
  5. additionby pouring into iced concentrated HCl
  6. extractionThis was extracted (vice with ethyl acetate
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated

Sources & evidence

ORD record
ord-24dd7c429ba7427b890d6b81740c2eaf
Source dataset
uspto-grants-2010_12
Patent number
US07851220B2

Reaction notes

Loading…