3-methylbenzene-1,2-diol

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

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

Conditions: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 300 ml of dry dimethylformamide, was dissolved 30 g of 3-methylcatechol and then 100 g of potassium carbonate was added to the solution. This solution was heated to 120 to 130° C. and 136 g of 1,2-dibromoethane was added dropwise in ten and several portions. After stirring for 30 minutes under the same conditions, the mixture was cooled and solid materials were removed by filtration. To the filtrate, was added diethyl ether, and the mixture was washed successively with a 3% sodium hydroxide aqueous solution, water and saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting oily material was purified by silica gel column chromatography to obtain 29.7 g of the titled 5-methyl-1,4-benzodioxane (yield: 82%). the mixture was cooled solid materials were removed by filtration To the filtrate, was added diethyl ether the mixture was washed successively with a 3% sodium hydroxide aqueous solution, water and saturated saline solution dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The resulting oily material was purified by silica gel column chromatography

Conditions: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 300 ml of dry dimethylformamide, was dissolved 30 g of 3-methylcatechol and then 100 g of potassium carbonate was added to the solution. This solution was heated to 120 to 130° C. and 136 g of 1,2-dibromoethane was added dropwise in ten and several portions. After stirring for 30 minutes under the same conditions, the mixture was cooled and solid materials were removed by filtration. To the filtrate, was added diethyl ether, and the mixture was washed successively with a 3% sodium hydroxide aqueous solution, water and saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting oily material was purified by silica gel column chromatography to obtain 29.7 g of the titled 5-methyl-1,4-benzodioxane (yield: 82%). the mixture was cooled solid materials were removed by filtration To the filtrate, was added diethyl ether the mixture was washed successively with a 3% sodium hydroxide aqueous solution, water and saturated saline solution dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The resulting oily material was purified by silica gel column chromatography

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

Procedure: 11.6 g Adogen 464 and 7 mL of dibromomethane were refluxed in 50 mL of H2O for 0.5 hours under argon. 3-Methylcatechol (8.89 g, 71.6 mmol) was added over 2 hours and the mixture refluxed for an additional 1 hour. Distillation of the product from the reaction mixture afforded the title compound as a yellow oil: HRMS m/e 136.0524 (calc'd for C8H8 O2, 136.0524). the mixture refluxed for an additional 1 hour Distillation of the product from the reaction mixture

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

Procedure: Mixtures of 4-hydroxyindole (0.1-10%) and 5-hydroxyindole (0.1-10%), 6-hydroxyindole (0.1-10%), or 7-hydroxyindole (0.1-10%) will give a color range from black to light auburn. 5-Hydroxyindole (0.1-10%) was found to produce progressively darker browns and, eventually, black through the addition of 3-methylcatechol (0.1-10%), 3-methoxycatechol (0.1-10%), or 3,6-dimethylcatechol (0.1-10%) followed by oxidation by sodium periodate (15%). 4-Hydroxyindole (1%) was found to produce progressively lighter colors with increasing red highlights through the addition of dopamine (2-5%) when penetration of precursors was done at high pH (9.2). Therefore a range of colors from light brown to black can be obtained through combinations of 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, and 7-hydroxyindole with each other or various other dye precursors. Similar results were obtained in staining skin in that a range of shades from light to dark brown can be obtained through combinations of hydroxyindoles with various other dye precursors. to produce progressively darker browns to produce progressively lighter colors with increasing red highlights

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

Procedure: Mixtures of 4-hydroxyindole (0.1-10%) and 5-hydroxyindole (0.1-10%), 6-hydroxyindole (0.1-10%), or 7-hydroxyindole (0.1-10%) will give a color range from black to light auburn. 5-Hydroxyindole (0.1-10%) was found to produce progressively darker browns and, eventually, black through the addition of 3-methylcatechol (0.1-10%), 3-methoxycatechol (0.1-10%), or 3,6-dimethylcatechol (0.1-10%) followed by oxidation by sodium periodate (15%). 4-Hydroxyindole (1%) was found to produce progressively lighter colors with increasing red highlights through the addition of dopamine (2-5%) when penetration of precursors was done at high pH (9.2). Therefore a range of colors from light brown to black can be obtained through combinations of 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, and 7-hydroxyindole with each other or various other dye precursors. Similar results were obtained in staining skin in that a range of shades from light to dark brown can be obtained through combinations of hydroxyindoles with various other dye precursors. to produce progressively darker browns to produce progressively lighter colors with increasing red highlights

Conditions: temp:1600.02; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The effluent crackate vapor is separated from particulate solids in a cyclone separator, and the solids containing coke deposits are passed into the upper end of an ordinary or slow fluidized bed combustion zone maintained at about 1600° F. temperature for combustion of coke. Heated air and superheated steam are introduced into the lower end of the slow fluidized bed combustion zone. The hot decoked solids are recycled to the lower end of the fast fluidized bed, and flue gas is withdrawn from the top of the slow bed. The typical product slate that is obtained if secondary reactions are minimized is given in Table 1, with methyl catechol being the principal product. Increased process severity produces more secondary conversion of methyl catechol to catechol, cresol, phenol, toluene, and benzene. In addition, some tar is formed. The effluent crackate vapor is separated from particulate solids in a cyclone separator the solids containing coke deposits Heated air and superheated steam are introduced into the lower end of the is withdrawn from the top of the slow bed The typical product slate that is obtained if secondary reactions Increased process severity

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

Procedure: 400 g of methylene bromide and 50 g of tetrabutylammonium bromide are taken under reflux in a stirred apparatus and a solution of 400 ml of water, 130 g of sodium hydroxide and 200 g of 3-methylpyrocatechol are added dropwise in the course of 5 hours. At the end of the addition, the mixture is subsequently stirred for a further 2 hours, cooled and extracted with methylene chloride. The organic phase is dried and distilled on a column. After first runnings of unreacted methylene bromide, 175 g of 4-methyl-1,3-benzodioxole are obtained. under reflux in a stirred apparatus At the end of the addition cooled extracted with methylene chloride The organic phase is dried distilled on a column

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

Procedure: 400 g of methylene bromide and 50 g of tetrabutylammonium bromide are taken under reflux in a stirred apparatus and a solution of 400 ml of water, 130 g of sodium hydroxide and 200 g of 3-methylpyrocatechol are added dropwise in the course of 5 hours. At the end of the addition, the mixture is subsequently stirred for a further 2 hours, cooled and extracted with methylene chloride. The organic phase is dried and distilled on a column. After first runnings of unreacted methylene bromide, 175 g of 4-methyl-1,3-benzodioxole are obtained. under reflux in a stirred apparatus At the end of the addition cooled extracted with methylene chloride The organic phase is dried distilled on a column

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

Procedure: A 500 ml three-neck flask, equipped with magnetic stirrer, addition funnel and reflux condenser, was charged with 108.0g (1.0 mole) of m-cresol. Sulfuric acid (96.5%), 147.9g was added dropwise during 25 minutes, while the temperature rose to 80°. External heating by mantle raised the temperature to 107° during 15 min. and Sample 1 was withdrawn. The sample was diluted with water, made basic with aqueous sodium hydroxide and the water was evaporated. The resultant salts, 11.0 g. were fused with 25 g. potassium hydroxide for 40 min. at 235°-330° under a nitrogen atmosphere. The mass was diluted with water, acidified with hydrochloric acid to pH 2 and extracted with four portions of 100 ml each of ether. The solvent was boiled off leaving only 0.5 g. of residue. Infrared and nuclear magnetic resonance showed it to contain 36% m-cresol, 26% diethyl ether solvent and 38% aryl carboxylic acids. There was no evidence of orcinol, methylhydroquinone and methylcatechol. Continuous liquid-liquid extraction of the aqueous phase with ether for five hours only produced 0.2 g. of additional product. A repeat fusion on ca. 25 ml of reaction mixture produced 45 g. of salts which were fused with 100 g. of potassium hydroxide for 35 min. at 350° to 360°. Work-up produced only 2.2 g. in which only m-cresol could be identified. The sulfonation resulted in the formation of substantially only m-cresolsulfonic acid isomers wherein the acid group is in ortho and/or para position relative to the hydroxyl group. The failure to obtain methylhydroquinone and/or 4-methylcatechol by fusion from the above m-cresol-sulfonic acids is not surprising in view of Barth and Senhofer's [Ber. 9, 969 (1876)] failure to fuse o- and p- phenolsulfonic acids. A 500 ml three-neck flask, equipped with magnetic stirrer, addition funnel reflux condenser rose to 80° External heating by mantle raised the temperature to 107° during 15 min. Sample 1 was withdrawn The sample was diluted with water the water was evaporated The mass was diluted with water extracted with four portions of 100 ml each of ether leaving only 0.5 g Continuous liquid-liquid extraction of the aqueous phase with ether for five hours only produced 0.2 g A repeat fusion on ca. 25 ml of reaction mixture produced 45 g Work-up produced only 2.2 g

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

Procedure: A 500 ml three-neck flask, equipped with magnetic stirrer, addition funnel and reflux condenser, was charged with 108.0g (1.0 mole) of m-cresol. Sulfuric acid (96.5%), 147.9g was added dropwise during 25 minutes, while the temperature rose to 80°. External heating by mantle raised the temperature to 107° during 15 min. and Sample 1 was withdrawn. The sample was diluted with water, made basic with aqueous sodium hydroxide and the water was evaporated. The resultant salts, 11.0 g. were fused with 25 g. potassium hydroxide for 40 min. at 235°-330° under a nitrogen atmosphere. The mass was diluted with water, acidified with hydrochloric acid to pH 2 and extracted with four portions of 100 ml each of ether. The solvent was boiled off leaving only 0.5 g. of residue. Infrared and nuclear magnetic resonance showed it to contain 36% m-cresol, 26% diethyl ether solvent and 38% aryl carboxylic acids. There was no evidence of orcinol, methylhydroquinone and methylcatechol. Continuous liquid-liquid extraction of the aqueous phase with ether for five hours only produced 0.2 g. of additional product. A repeat fusion on ca. 25 ml of reaction mixture produced 45 g. of salts which were fused with 100 g. of potassium hydroxide for 35 min. at 350° to 360°. Work-up produced only 2.2 g. in which only m-cresol could be identified. The sulfonation resulted in the formation of substantially only m-cresolsulfonic acid isomers wherein the acid group is in ortho and/or para position relative to the hydroxyl group. The failure to obtain methylhydroquinone and/or 4-methylcatechol by fusion from the above m-cresol-sulfonic acids is not surprising in view of Barth and Senhofer's [Ber. 9, 969 (1876)] failure to fuse o- and p- phenolsulfonic acids. A 500 ml three-neck flask, equipped with magnetic stirrer, addition funnel reflux condenser rose to 80° External heating by mantle raised the temperature to 107° during 15 min. Sample 1 was withdrawn The sample was diluted with water the water was evaporated The mass was diluted with water extracted with four portions of 100 ml each of ether leaving only 0.5 g Continuous liquid-liquid extraction of the aqueous phase with ether for five hours only produced 0.2 g A repeat fusion on ca. 25 ml of reaction mixture produced 45 g Work-up produced only 2.2 g