2,2-dimethyl-1,3-benzodioxol-4-ol

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: A stirred solution of 0.3 gram (0.00083 mole) of 1,3-dichloro-2-(4-chlorobutoxy)-5-(phenylmethoxy)benzene, 0.17 gram (0.00100 mole) of 2,2-dimethylbenzo[d]1,3-dioxolan-4-ol, and 0.17 gram (0.00125 mole) of potassium carbonate in 10 mL of DMF was heated at 80° C. for about 18 hours. After this time, the reaction mixture was cooled and 30 mL of water was added. The mixture was then extracted with three 20 mL portions of diethyl ether. The combined extracts were washed with 20 mL of an aqueous solution saturated with sodium chloride. The organic layer was dried with sodium sulfate, filtered, and concentrated under reduced pressure to a residue. The residue was purified with column chromatography on silica gel using 1:1 methylene chloride:hexane as an eluant. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.29 gram of the subject compound. The NMR spectrum was consistent with the proposed structure. After this time, the reaction mixture was cooled The mixture was then extracted with three 20 mL portions of diethyl ether The combined extracts were washed with 20 mL of an aqueous solution saturated with sodium chloride The organic layer was dried with sodium sulfate filtered concentrated under reduced pressure to a residue The residue was purified with column chromatography on silica gel using 1:1 methylene chloride concentrated under reduced pressure

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

実験手順: A stirred mixture of 10.0 grams (0.079 mole) of benzene-1,2,3-triol, 20 mL (0.163 mole) of 2,2-dimethoxypropane and 1.0 gram (catalyst) of Amberlite® IR-120 (plus) ion exchange resin in 50 mL of toluene was warmed to 100° C., where it was maintained during an 18 hour period. After this time the reaction mixture was concentrated under reduced pressure to a residual solid. The solid was triturated with three 50 mL portions of methylene chloride. The combined organic extracts were concentrated under reduced pressure to a residual solid, which was then dissolved in methylene chloride and subjected to column chromatography on silical gel. Elution was accomplished with 1:4 ethyl acetate:hexane. A second column chromatography as described above was needed to purify the solid. In each chromatography, the appropriate fractions were combined and concentrated under reduced pressure, ultimately yielding 5.3 grams of the subject compound. The NMR spectrum was consistent with the proposed structure. where it was maintained during an 18 hour period After this time the reaction mixture was concentrated under reduced pressure to a residual solid The solid was triturated with three 50 mL portions of methylene chloride The combined organic extracts were concentrated under reduced pressure to a residual solid, which was then dissolved in methylene chloride Elution to purify the solid concentrated under reduced pressure

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: A mixture of 9.0 g of pyrogallol, 7.5 g of 2,2-dimethoxypropane and 100 ml of toluene was refluxed for 4.5 hours. After cooling, the reaction mixture was worked up in a customary manner and purified by column chromatography to give 2.0 g (yield 17%) of the desired product as a pale yellow solid. was refluxed for 4.5 hours After cooling purified by column chromatography

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

実験手順: The pyrogallol is particularly suitable for reaction with 2,2-dimethoxypropane to form 2,2-dimethyl-4-hydroxy-1,3-benzodioxole, and then reaction of this with methyl isocyanate to produce the pesticide 2,2-dimethyl-1,3-benzodioxol-4-yl methylcarbamate.

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

実験手順: A solution of pyrogallol (63 parts) in 2,2-dimethoxypropane (100 parts) and benzene (100 parts) containing toluenesulphonic acid (0.01 parts) was slowly distilled through a fractionating column during 4 hours, removing liquid (150 parts), boiling point 57°-64°C. A few drops of triethylamine were then added and the mixture thoroughly washed with water, dried and evaporated. Distillation gave 4-hydroxy-2,2-dimethyl-1,3-benzodioxole (36 parts), boiling point 110°C/0.7 mm., which was purified by recrystallisation from carbon tetrachloride. Melting point 88°-90°C. was slowly distilled through a fractionating column during 4 hours removing liquid (150 parts), boiling point 57°-64°C A few drops of triethylamine were then added the mixture thoroughly washed with water dried evaporated Distillation

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

実験手順: 2,2-Dimethyl-4-hydroxy-1,3-benzodioxole (14 parts) in benzene (25 parts) was treated with methyl isocyanate (6 parts) and a few drops of triethylamine with cooling. After standing for 30 minutes, the crystals of 2,2-dimethyl-1,3-benzodioxol-4-yl N-methylcarbamate which formed were filtered off and washed with benzene then with petroleum (boiling point below 40°C.) to yield the pure compound as a white solid, melting point 129°-130°C. (16 parts, 85% yield). with cooling

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

実験手順: A solution of pyrogallol (63 parts) in 2,2-dimethoxypropane (100 parts) and benzene (100 parts) containing toluenesulphonic acid (0.01 parts) was slowly distilled through a fractionating column during 4 hours, removing liquid (150 parts), boiling point 57°-64° C. A few drops of triethylamine were then added and the mixture thoroughly washed with water, dried and evaporated. Distillation gave 4-hydroxy-2,2-dimethyl-1,3-benzodioxole (36 parts), boiling point 110° C/0.7 mm., which was purified by recrystallisation from carbon tetrachloride. Melting point 88°-90° C. was slowly distilled through a fractionating column during 4 hours removing liquid (150 parts), boiling point 57°-64° C A few drops of triethylamine were then added the mixture thoroughly washed with water dried evaporated Distillation

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

実験手順: 2,2-Dimethyl-4-hydroxy-1,3-benzodioxole (14 parts) in benzene (25 parts) was treated with methyl isocyanate (6 parts) and a few drops of triethylamine with cooling. After standing for 30 minutes, the crystals of 2,2-dimethyl-1,3-benzodioxol-4-yl N-methylcarbamate which formed were filtered off and washed with benzene then with petroleum (boiling point below 40° C.) to yield the pure compound as a white solid, melting point 129°-130° C. (16 parts, 85% yield). with cooling