Structure of 220368-29-6
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CAS No. : | 220368-29-6 |
Formula : | C16H12ClN3O3 |
M.W : | 329.74 |
SMILES Code : | O=[N+](C1=CC=CC=C1COC2=NN(C3=CC=C(Cl)C=C3)C=C2)[O-] |
MDL No. : | MFCD17170084 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319 |
Precautionary Statements: | P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P312+P330 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.7% | With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide; In water; acetone; at 40℃; for 3h; | Adding the container 1 - (4-chlorophenyl) - 3- the pyrazole is mellow, embodiment 5 of an organic solution of ortho-nitro benzyl chloride (organic solvent is acetone) and a phase transfer catalyst (benzyl triethyl ammonium chloride), to obtain the mixed solution; drop alkalizing under stirring, to the aqueous solution (sodium hydroxide), the reaction temperature is 40 °C, reaction time 3 hours; the reaction solution for sampling, sampling sample for detection HPLC, when the wherein the 1 - (4-chlorophenyl) - 3- the pyrazole is mellow amount is 1percent of the, stop reaction; pH of the solution is adjusted to the value 3, then by extraction, and recovering the solvent, purification after drying, obtain etheration product 2 - [(N-4-chlorophenyl) - 3- pyrazole oxygen radical methyl] nitrobenzene. In the above-mentioned process, an organic solution of ortho-nitro benzyl chloride concentration is 35percent, in the mixed solution, 1 - (4-chlorophenyl) - 3- the pyrazole is mellow, ortho-nitro benzyl chloride, alkali molar ratio of 1.0: 1.4 : 1.2; ortho-nitro benzyl chloride in organic solution with the phase transfer catalyst in the control of the mass ratio of 1 : 0.1. The embodiment can realize 2 - [(N-4-chlorophenyl) - 3- pyrazole oxygen radical methyl] nitrobenzene content 99.5percent, yield 92.7percent production effect. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.5% | With tetrabutylammomium bromide; potassium hydroxide; In methanol; at 50℃; for 2h;Large scale; | (1) Condensation: 1 Add 1500 kg of methanol, 362 kg of potassium hydroxide and 10 kg of tetrabutylammonium bromide to the reaction vessel, start stirring, and increase the temperature to 50°C and then add 300 kg of 1-(4-chlorophenyl)-3- pyrazoleol, and 900kg of o-nitrobenzylbromide was added dropwise, and the reaction was carried out at 50°C for 2 hours, followed by cooling down to 15°C and centrifugation to obtain 450kg of the centrifuged solid as a crude condensate; 2). After adding 450kg of crude condensate to 500kg of methanol, wash it and cool it to 15°C filter, Filter cake at -0.08 Mpa, 60 °C drying 10 hours to give 360 kg condensation product, a purity of 98.5percent, a yield of 96.5percent; |
70% | In dimethyl sulfoxide; at 25℃; for 1h; | Using the same flask as used in the preparation of 1-(4-chlorophenyl)-3- hydroxy-1H-pyrazole, a dropping funnel filled with 2-nitrobenzyl bromide of formula (IV) was connected. The ratio of 2-nitrobenzyl bromide to the <strong>[76205-19-1]1-(4-chlorophenyl)-3-hydroxy-1H-pyrazole</strong> present in the flask 1.7: 1 While being kept at a temperature of 25°C, the solution of 2-nitrobenzyl bromide was dropped into the flask at a rate of 0.5 ml/minute. After all of the 2-nitrobenzyl bromide was added to the flask, the reaction was mixed for 1 hour, until all of the <strong>[76205-19-1]1-(4-chlorophenyl)-3-hydroxy-1H-pyrazole</strong> was consumed. A small amount of NaOH 15percent was then added to the solution and the solution was then stirred for 30 minutes at 30°C. A small amount of H2O was added to the mixture in order to precipitate the crude product. The crude product was recrystallized using MCB. The product was dried in a vacuum oven at 25 mbar at 70°C. Yield of 1-(4-chlorophenyl)-3-[(2-nitrophenyl)methoxy]-1H-pyrazole: 70percent with a purity of 99.1percent. |
With sodium hydroxide; In water; at 48℃; for 1.6h; | First of all, to the condensation kettle containing o-nitrobenzyl bromobenzene solution into the solid1- (4-chlorophenyl) -3-pyrazole alcohol, wherein 1- (4-chlorophenyl) -3-pyrazole alcohol andNitrobenzyl bromide molar ratio of 1: 1.7; then heated to 48 ° C dropwise aqueous sodium hydroxide solution,The concentration of sodium hydroxide aqueous solution is 20percent; and then after the completion of the dropwise addition to cool to room temperature,And then incubated 1.6h crystallized, centrifuged; and then into the centrifuge after the solid was refined into refined kettle; and then into the above refining kettle methanol was heated to 49 ° C reflux 5 hours;Then then the aforementioned refining kettle material was cooled to room temperature, and then incubated 1.8h crystallization,Centrifuged; Finally, the centrifuged solid was dried to obtain pure product2 - [(N-4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] nitrobenzene.Which before adding the catalyst and DMF in the condensation reactor before heating, pass into the oxygen,The temperature was raised to 50 dropping sodium hydroxide solution, the reaction time was 20h. |
362 kg | With 1-bromo-butane; sodium hydroxide; at 80 - 82℃; for 2h;pH >= 13;Green chemistry; Large scale; | In the second step, in the 5m3 reactor, the initial raw material is 350 kg of p-chloroaniline, which is subjected to salt formation, diazotization, acidification, extraction, cyclization and oxidation.After the reaction of 1-(4-chlorophenyl)pyrazol-3-one to 1-(4-chlorophenyl)-3-pyrazolol,When 1-(4-chlorophenyl)pyrazol-3-one <2percent, liquid chromatography analysis at this time:P-chlorophenylhydrazine hydrochloride: 1.562percent;1-(4-chlorophenyl)pyrazol-3-one: 0.687percent;1-(4-Chlorophenyl)-3-pyrazolol: 95.832percent; high boiler (aldehyde): 1.919percent.All the o-nitrobenzyl bromide prepared in the above batch is put into the 1-(4-chlorophenyl)-3-pyrazolol solution, and an appropriate amount of sodium hydroxide solution is added to adjust the pH to 13 or more;Then, 0.2 kg of 4-butyl bromide catalyst with a purity of 99percent was added to the reaction vessel, and the temperature was raised to 80 ° C to 82 ° C, and the temperature was kept for 2 hours.Liquid chromatography analysis of 1-(4-chlorophenyl)-3-pyrazol <1percent was acceptable, stood still for 1 hour, layered, and cooled to 3 °C. In the third step, the lower layer was centrifuged and dried in a dryer to obtain 362 kg of 2-{(N-4-chlorophenyl)-3-pyrazoloxymethyl}nitrobenzene.Chromatographic purity:p-Chlorobenzoquinone hydrochloride: 0.315percent; 1-(4-chlorophenyl)pyrazol-3-one 0.112percent; o-nitrobenzyl bromide: 0.124percent,1-(4-Chlorophenyl)-3-pyrazol: 0.673percent; 2-{(N-4-chlorophenyl)-3-pyrazoloxymethyl}nitrobenzene:98.124percent. High boiler (aldehyde): 0.652percent. |
With potassium carbonate; In acetone; for 3h;Reflux; | 1-(4-chlorophenyl)-3-pyrazol,Acetone and potassium carbonate are added to the reaction flask,After heating to reflux, a solution of o-nitrobenzyl bromide in acetone is added dropwise.After the completion of the dropwise addition, the reflux reaction is carried out for at least 3 hours.The acetone was concentrated and removed, and then methanol was refluxed for at least 20 min, cooled to room temperature, allowed to stand for at least 30 min, and filtered.Obtaining 2-[(N-p-chlorophenyl)-3-pyrazoloxymethyl]nitrobenzene for use; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tetrabutylammomium bromide; sodium hydroxide; In 1,2-dichloro-ethane; chlorobenzene; at 50℃; for 4h; | A solution of 1- (4-chlorophenyl) -3-pyrazolol prepared in Example 22 in o-nitrochlorobenzyl prepared in Example 30 was added to a container (the organic solvent was a mass ratio 2: 1: 1 mixture of dichloroethane, chlorobenzene and acetone) and a phase transfer catalyst (tetrabutylammonium bromide) to obtain a mixed solution; dropping an aqueous solution of an alkali (sodium hydroxide) , The reaction temperature was 50 ° C and the reaction time was 4 hours. The reaction solution was sampled and the sample was detected by HPLC. When the amount of 1-(4-chlorophenyl) -3-pyrazolol was 0.5percent, the reaction was stopped 2 - [(N-4-chlorophenyl) -3-pyrazolyloxymethyl] nitrobenzene was obtained after adjusting the pH value of the solution to 3 and then extracting, recovering the solvent and purifying and drying.In the above process, the organic solution concentration of o-nitrochlorobenzyl chloride was 25percent, and the molar ratio of 1- (4-chlorophenyl) -3-pyrazolol, o-nitrochlorobenzyl chloride and base in the mixed solution was 1.0: 1.2: 1.2. The mass ratio of o-nitrochlorobenzyl chloride to the phase transfer catalyst in the organic solution was controlled at 1: 0.15.In this example, the production effect of 2-[(N-4-chlorophenyl)-3-pyrazolyloxymethyl]-1-nitrobenzene with 99.3percent content and 93.0percent yield was achieved |
Tags: 220368-29-6 synthesis path| 220368-29-6 SDS| 220368-29-6 COA| 220368-29-6 purity| 220368-29-6 application| 220368-29-6 NMR| 220368-29-6 COA| 220368-29-6 structure
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