N-2-pyrimidinyl oxy-benzyl substituted cyclic amine compound, its preparation process and uses
A technology of pyrimidinyloxybenzyl, compounds, applied in the field of agrochemical herbicides
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example 1
[0050] Synthesis of intermediate 2-methyl-3-chlorophenol (III-1):
[0051] Add 80ml of concentrated sulfuric acid and 400ml of water to the flask, and add 64.5 grams (0.4mol) of 2-methyl-3-chloroaniline under mechanical stirring in an ice bath for about half an hour, then stir for another half an hour, and add 34 grams (0.4 mol) of sodium nitrite and 70ml of water takes about half an hour, and stir at 0°C for 1 hour to obtain a diazonium salt solution. Add 150g of sodium sulfate, 200ml of sulfuric acid and 200ml of water into a 1000ml flask, stir and heat to Reflux (the temperature in the bottle is 130-135°C), keep the temperature, drop the above diazonium salt solution for about 2 hours, and distill out about the same amount of water at the same time, add 500ml of water after the addition, and distill out the same amount of water , cooled, the distillation fraction was extracted with chloroform (100ml*3), the chloroform layer was dried over sodium sulfate and then precipitate...
example 2
[0054] Preparation of intermediate 2-(4,6-dimethoxy-2-pyrimidinyloxy)-6-chlorotoluene (VI-1):
[0055] In a 250mL flask, add 0.1mol of 2-methyl-3-chlorophenol (III-1), 15.0 grams of anhydrous potassium carbonate, 0.1mol4,6-dimethoxy 2-methylsulfonylpyrimidine and 200ml tetrahydrofuran, and reflux for 4 hour, cooling, suction filtration, steaming off tetrahydrofuran, adding 50ml of methanol, stirring to precipitate a white solid, filtering, and drying to obtain intermediate 2-(4,6-dimethoxy-2-pyrimidinyloxy)-6 chlorotoluene ( IV-1), the yield is 86%.
[0056] Using the same method, using different raw materials - 4-D-6-E-2-methylsulfonylpyrimidine can synthesize intermediate 2-(4-D-6-E-2-pyrimidinyloxy)-6-chloro Toluene (IV), (D, E represent other substituents in the structural formula (I)).
example 3
[0058] Preparation of intermediate 2-(4,6-dimethoxy-2-pyrimidinyloxy)-6-chlorobenzyl bromide (V-1):
[0059] In a 150mL flask, add 20mmol 2-(4,6-dimethoxy-2-pyrimidinyloxy)-6 chlorotoluene (IV-1), 20mmol N-bromosuccinimide, 0.3 g of azobis Isobutyronitrile, dry CCl 4 100ml, connect the reflux condenser and drying tube, heat and reflux for 4 hours, cool, filter, desolvate under reduced pressure, add 15ml methanol and stir at room temperature, a white solid precipitates, filter, and dry to obtain the intermediate 2-(4,6-dimethoxy yl-2-pyrimidinyloxy)-6-chlorobenzyl bromide (V-1), the yield was 80.7%.
[0060] In the same way, using a different starting material - 2-(4-D-6-E-2-pyrimidinyloxy)-6-R 1 -Toluene (IV) can synthesize intermediate 2-(4-D-6-E-2-pyrimidinyloxy)-6-R 1 -Benzyl bromide (V), (D, E, R 1 represent other substituents in formula (I)).
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