5-methylbenzene-1,3-diol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Triphenylphoshine (7.86 g; 30 mmol), 3,5-dihydroxytoluene (2.5 g; 20 mmol) and 2-(4-cyanophenyl)ethanol (4.41 g; 30 mmol) were dissolved in THF (50 mL). Diethylazodicarboxylate (5.22 g; 30 mmol; dissolved in THF (10 mL)), was added and the solution was stirred at room temperature overnight. The solvent was removed in vacuo and the white solid residue extracted with Et2O. Purification by flash chromatography (SiO2; toluene:EtOAc (10:1)) afforded 1.85 g (37%) of the sub-title compound as a white solid. The solvent was removed in vacuo the white solid residue extracted with Et2O Purification by flash chromatography (SiO2; toluene:EtOAc (10:1))

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5-methylresorcin (25.0 g), malic acid (26.0 g) and conc.H2SO4 (55 ml) was gently heated with the gaseous development almost ceased. The reaction mixture was then poured with vigorous stirring into a mixture of water and ice (700 ml), and stirred until the gummy mass initially formed was completely dispersed. The precipitate was collected by filtration, washed with water and crystallized twice (Me2CO) producing 5-methyl-7-hydroxycoumarin (I; 15 g; m.p. 256° C.) ##STR4## free from the isomer 5-hydroxy-7-methylcoumarin (II). ##STR5## The reaction mixture was then poured initially formed was completely dispersed The precipitate was collected by filtration washed with water crystallized twice (Me2CO)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The monosodium salt of 5-methylresorcinol prepared in Example 4 and dimethyl formamide (200 ml) were charged under nitrogen gas into a glass reaction vessel equipped with a mechanical stirrer, thermometer and addition funnel. 1-Chloro-2,2-dimethoxyethane (6.25 grams) was added, and the mixture was heated at 85° to 90° C. and stirred for a period of about 221/2 hours. After this time the reaction mixture was cooled to room temperature and was added to 1200 ml of water. The resulting mixture was carefully neutralized and extracted with chloroform. The organic phase was then separated from the aqueous phase and stripped of solvent, leaving a liquid residue. The residue was distilled under reduced pressure to yield a yellow viscous liquid which solidified upon cooling to -10° C. This product was then recrystallized from a methanol-water mixture, was washed with boiling water and dried to yield the desired product 3-(2,2-dimethoxyethoxy)-5-hydroxytoluene as a white solid melting at 73° to 75° C. equipped with a mechanical stirrer thermometer and addition funnel the mixture was heated at 85° to 90° C. extracted with chloroform The organic phase was then separated from the aqueous phase leaving a liquid residue The residue was distilled under reduced pressure to yield a yellow viscous liquid which upon cooling to -10° C This product was then recrystallized from a methanol-water mixture was washed with boiling water dried