2,3,6-trimethylphenol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: methylating meta-cresol and para-cresol in the ortho position by reacting the meta-cresol and para-cresol with methanol, dimethyl ether or a mixture thereof at a temperature of 270° to 450° C., at a pressure of atmospheric to 100 bar and in the presence of a catalyst bed without a residence time of 0.01 to 10 seconds, whereby a mixture of 2,3,6-trimethylphenol and 2,4,6-trimethylphenol is produced;

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: methylating meta-cresol and para-cresol in the ortho position by reacting the meta-cresol and para-cresol with methanol, dimethyl ether or a mixture thereof at a temperature of 270° to 450° C., at a pressure of atmospheric to 100 bar and in the presence of a catalyst bed without a residence time of 0.01 to 10 seconds, whereby a mixture of 2,3,6-trimethylphenol and 2,4,6-trimethylphenol is produced;

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,3,6-trimethylphenol (1.6 g, 11.8 mmol) was disolved in 50 mL of anhydrous methanol which had been deoxygenated by bubbling with nitrogen. Ammonium thiocyanate (2.2 g, 28,9 mmol) was added to this solution which was then cooled to 0° C. and bubbled with chlorine gas. The initially colorless homogeneous solution becomes pink and then green with the formation of a white precipitate. The solution was stirred for 1 h at 0° C. and then for a further hour at 20° C. The dissolved chlorine was removed by bubbling with nitrogen and the precipitate removed by filtration. Evaporation of the filtrate under reduced pressure followed by drying under high vacuum (0.1 torr) yielded 2.20 g (97%) of 2,3,5-Trimethyl-4-hydroxyphenylthiocyanate in a form pure enough for the next step in the synthesis. An analytical sample was recrystallized from hexanes: white crystals, mp 100.3° C. 1H NMR (CDCl3) δ 7.2 (s, 1H), 5.0 (s, 1H) 2.4 (s, 3H), 2.2 (s, 6H). had been deoxygenated by bubbling with nitrogen bubbled with chlorine gas for a further hour at 20° C The dissolved chlorine was removed by bubbling with nitrogen the precipitate removed by filtration Evaporation of the filtrate under reduced pressure by drying under high vacuum (0.1 torr)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,3,6-trimethylphenol (1.6 g, 11.8 mmol) was disolved in 50 mL of anhydrous methanol which had been deoxygenated by bubbling with nitrogen. Ammonium thiocyanate (2.2 g, 28,9 mmol) was added to this solution which was then cooled to 0° C. and bubbled with chlorine gas. The initially colorless homogeneous solution becomes pink and then green with the formation of a white precipitate. The solution was stirred for 1 h at 0° C. and then for a further hour at 20° C. The dissolved chlorine was removed by bubbling with nitrogen and the precipitate removed by filtration. Evaporation of the filtrate under reduced pressure followed by drying under high vacuum (0.1 torr) yielded 2.20 g (97%) of 2,3,5-Trimethyl-4-hydroxyphenylthiocyanate in a form pure enough for the next step in the synthesis. An analytical sample was recrystallized from hexanes: white crystals, mp 100.3° C. 1H NMR (CDCl3) δ 7.2 (s, 1H), 5.0 (s, 1H) 2.4 (s, 3H), 2.2 (s, 6H). had been deoxygenated by bubbling with nitrogen bubbled with chlorine gas for a further hour at 20° C The dissolved chlorine was removed by bubbling with nitrogen the precipitate removed by filtration Evaporation of the filtrate under reduced pressure by drying under high vacuum (0.1 torr)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 10 g (71 mmol) of 2,3,6-trimethylphenol are initially introduced in a solvent mixture consisting of 250 ml of dichloromethane and 190 ml of methanol, and 35.4 g (72 mmol) of tetrabutylammonium tribromide in 170 ml of dichloromethane and 130 ml of methanol are added. After 5 h at room temperature, the batch is evaporated in a rotary evaporator, and the residue remaining is taken up in MTB. The organic solution is washed three times with water, dried over sodium sulfate and evaporated in a rotary evaporator. The crystalline residue obtained is employed in the next step without further work-up. are added the batch is evaporated in a rotary evaporator The organic solution is washed three times with water dried over sodium sulfate evaporated in a rotary evaporator The crystalline residue obtained

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Oxygen was passed into a solution of 0.68 g (2 mmol) of iron 5,14-dihydrodibenzo[b,i][5,9,14,18]tetraaza[14]annulene in 150 ml of 85% by weight aqueous acetic acid and, during this, a solution of 13.6 g (100 mmol) of 2,3,6-trimethylphenol and 0.5 g of concentrated sulfuric acid in 75 ml of 85% by weight acetic acid was added dropwise while stirring vigorously at 40° C. After oxygen uptake ceased, the mixture was subjected to a steam distillation. The distillate was extracted with tert-butyl methyl ether. The organic phase was shaken with aqueous sodium bicarbonate solution and then with water, separated from the aqueous phase, dried over magnesium sulfate, filtered and evaporated to dryness to yield 12.0 g (80%) of 2,3,5-trimethylbenzoquinone in the form of yellow oily crystals. the mixture was subjected to a steam distillation The distillate was extracted with tert-butyl methyl ether The organic phase was shaken with aqueous sodium bicarbonate solution with water, separated from the aqueous phase dried over magnesium sulfate filtered evaporated to dryness

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 13.6 g (100 mmol) of 2,3,6-trimethylphenol in 40 ml of acetic acid and a solution of 73.7 g (240 mmol) of 50% by weight potassium peroxomonosulfate in 320 ml of water were simultaneously added dropwise to a stirred solution of 0.68 g (2.0 mmol) of iron 5,14-dihydrodibenzo[b,i][5,9,14,18]tetraaza[14]annulene and 0.5 ml of concentrated sulfuric acid in 50 ml of acetic acid at room temperature with cooling. The reaction mixture was then subjected to steam distillation. The distillate was extracted by shaking with methylene chloride. The organic phase was shaken with aqueous sodium bicarbonate solution and then with water, separated from the aqueous phase, dried over magnesium sulfate, filtered and concentrated to a yellow oil, which slowly solidifed. 11.1 g (74%) of 2,3,5-trimethyl-p-benzoquinone were obtained in the form of yellow oily crystals. with cooling The reaction mixture was then subjected to steam distillation The distillate was extracted The organic phase was shaken with aqueous sodium bicarbonate solution with water, separated from the aqueous phase dried over magnesium sulfate filtered concentrated to a yellow oil, which

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 13.6 g (100 mmol) of 2,3,6-trimethylphenol in 40 ml of acetic acid and a solution of 32.3 g (250 mmol) of 70% by weight aqueous tert-butyl hydroperoxide in 20 ml of acetic acid were simultaneously added dropwise to a stirred solution of 0.68 g (2.0 mmol) of iron 5,14-dihydrodibenzo[b,i][5,9,14,18]tetraaza[14]annulene and 0.5 ml of concentrated sulfuric acid in 50 ml of acetic acid at 40° C. with cooling. The reaction mixture was then subjected to steam distillation. The distillate was extracted by shaking with methylene chloride. The organic phase was shaken with aqueous sodium bicarbonate solution and then with water, separated from the aqueous phase, dried over magnesium sulfate, filtered and concentrated to a yellow oil, which slowly solidifed. 14.0 g (93%) of 2,3,5-trimethyl-p-benzoquinone were obtained in the form of yellow oily crystals. with cooling The reaction mixture was then subjected to steam distillation The distillate was extracted The organic phase was shaken with aqueous sodium bicarbonate solution with water, separated from the aqueous phase dried over magnesium sulfate filtered concentrated to a yellow oil, which

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 13.6 g (100 mmol) of 2,3,6-trimethylphenol in 40 ml of acetic acid and a solution of 32.3 g (250 mmol) of 70% by weight aqueous tert-butyl hydroperoxide in 20 ml of acetic acid were simultaneously added dropwise to a stirred solution of 0.68 g (2.0 mmol) of iron 5,14-dihydrodibenzo[b,i][5,9,14,18]tetraaza[14]annulene and 0.5 ml of concentrated sulfuric acid in 50 ml of acetic acid at 40° C. with cooling. The reaction mixture was then subjected to steam distillation. The distillate was extracted by shaking with methylene chloride. The organic phase was shaken with aqueous sodium bicarbonate solution and then with water, separated from the aqueous phase, dried over magnesium sulfate, filtered and concentrated to a yellow oil, which slowly solidifed. 14.0 g (93%) of 2,3,5-trimethyl-p-benzoquinone were obtained in the form of yellow oily crystals. with cooling The reaction mixture was then subjected to steam distillation The distillate was extracted The organic phase was shaken with aqueous sodium bicarbonate solution with water, separated from the aqueous phase dried over magnesium sulfate filtered concentrated to a yellow oil, which

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 13.6 g (100 mmol) of 2,3,6-trimethylphenol in 40 ml of acetic acid and 62.3 g (550 mmol) of 30% by weight aqueous hydrogen peroxide were simultaneously added dropwise to a stirred solution of 0.68 g (2.0 mmol) of iron 5,14-dihydrodibenzo[b,i][5,9,14,18]tetraaza[14]annulene, 2.52 g (2.0 mmol) of a 40% by weight aqueous solution of a pentasodiumdiethylenetriaminepentaacetate and 0.5 ml of concentrated sulfuric acid in 50 ml of acetic acid at 40° C. with cooling. The reaction mixture was then subjected to steam distillation. The distillate was extracted by shaking with methylene chloride. The organic phase was shaken with aqueous sodium bicarbonate solution and then with water, separated from the aqueous phase, dried over magnesium sulfate, filtered and concentrated to a yellow oil, which slowly solidifed. 12.6 g (84%) of 2,3,5-trimethyl-p-benzoquinone were obtained in the form of yellow oily crystals. with cooling The reaction mixture was then subjected to steam distillation The distillate was extracted The organic phase was shaken with aqueous sodium bicarbonate solution with water, separated from the aqueous phase dried over magnesium sulfate filtered concentrated to a yellow oil, which