CN105693611A - Green synthesis technology for 3-(2-nitrobenzene methoxy)-1-(4-chlorphenyl)-1H-pyrazole - Google Patents
Green synthesis technology for 3-(2-nitrobenzene methoxy)-1-(4-chlorphenyl)-1H-pyrazole Download PDFInfo
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
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- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention provides a green synthesis technology for 3-(2-nitrobenzene methoxy)-1-(4-chlorphenyl)-1H-pyrazole. The synthesis technology includes the following steps that firstly, an intermediate 1 is synthesized; secondly, an intermediate 2 is synthesized; thirdly, an intermediate 3 is synthesized; fourthly, 3-(2-nitrobenzene methoxy)-1-(4-chlorphenyl)-1H-pyrazole is synthesized. The synthesis technology is simple in process route and simple in synthesis device, synthesis raw materials in use and the synthesis technology are environmentally friendly, synthesis cost is low, the product yield is high, production cost is effectively reduced, energy conservation and consumption reduction are achieved, and economic benefits of enterprises are improved easily.
Description
Technical field
The present invention relates to the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles。
Background technology
3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles also has called after: 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] Nitrobenzol or 1-(4-chlorphenyl)-3-[(2-nitrobenzophenone) methoxyl group]-1H-pyrazoles, is the important intermediate producing pyraclostrobin。The quality of its synthetic effect and the height of combined coefficient, directly will produce existing major effect to the bactericidal effect of pyraclostrobin。
Pyraclostrobin is a kind of methoxy acrylic new type bactericide, and for New-type wide-spectrum antibacterial, the mechanism of action is mitochondrial respiratory inhibitor, makes mitochondrion can not produce and provide the energy needed for cell homergy, ultimately results in cell death。
It can suppress fungus-caused most of diseases such as crop Ascomycetes, Basidiomycetes, deuteromycetes, Oomycete。The growth of spore germination and mycelia there is is very strong inhibitory action, there is protection and therapeutic activity。Having permeability and local systemic activity, the lasting period is long, resistance of rainwater washing against。It is widely used in the disease on preventing and treating Semen Tritici aestivi, Oryza sativa L., Semen arachidis hypogaeae, Fructus Vitis viniferae, vegetable, Rhizoma Solani tuber osi, Fructus Musae, Fructus Citri Limoniae, coffee, fruit tree, Semen Juglandis, Camellia sinensis, Nicotiana tabacum L. and ornamental plant, lawn and other field crop。
This antibacterial not only toxicity is low, to non-target organism safety, and also user and environment all safety is friendly, it is classified as " Candidate Agents reducing risk " by U.S. EPA Environmental Protection Agency。
Crop can be produced positive physiological regulatory action by pyraclostrobin, the generation of its energy ethene suppressing, crop so can be helped to have longer time deposit bio-energy to guarantee Maturity, can significantly improve the activity of the nitrated reductase of crop。
Through field control effectiveness test result, pyraclostrobin cream shows that powdery mildew of cucumber, downy mildew and banana freckle, leaf spot, sclerotiniose etc. are had good prevention effect。Prevent and treat powdery mildew of cucumber, the dosage of downy mildew is effective ingredient 75 ~ 150g/hm2(being converted into cream commodity amount is 20-40mL/667m2)。In their early stage even spraying after dilute. general spray medicine 3 ~ 4 times. interval 7d sprays 1 medicine。Prevent and treat banana freckle, the effective ingredient concentration of leaf spot is 83.3-250mg/kg (extension rate is 1000-3000 times), starts spraying in their early stage. general spray medicine 3 times, interval 10d sprays 1 medicine。Spray medicine number of times is depending on the state of an illness。To Fructus Cucumidis sativi, Fructus Musae safety, have no poisoning and occur。
And it is also comparatively rare for the synthesis technique of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles at present。
Summary of the invention
For solving above-mentioned Problems existing, it is an object of the invention to provide the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles, described synthesis technique process route is simple, synthesizer is simple, and synthesis material used and synthesis technique are environmentally friendly, and synthesis cost is low, product yield is high, effectively reduce production cost, energy-saving and cost-reducing, be conducive to enterprise economic benefit。
For reaching above-mentioned purpose, the technical scheme is that
The green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles, comprises the steps:
1. synthetic intermediate 1
1a) in dehydrating kettle, extract toluene 900 ~ 1100kg, add 200 ~ 240kg p-hydrochloride and obtain mixed liquor, stirring, heat up, reflux dewatering, it is warming up to 100 ~ 120 DEG C, continues reflux dewatering, to mixed liquor, moisture is qualified, proceeds to synthesis reactor；
1b) it is cooled to 50 ~ 55 DEG C, open tail gas adsorption, add 90 ~ 110kg solid sodium methylate, stirring and dissolving, within the scope of 50 ~ 70 DEG C, add 120 ~ 140kg acrylamide, stirring is to dissolving, being warmed up to 80 ~ 90 DEG C, insulation, to without backflow, is cooled to 65 ~ 75 DEG C, add water 900 ~ 1100kg, then with the salt acid for adjusting pH value of 180 ~ 220kg to 6 ~ 6.5；
1c) heating azeotropic backflow and separate toluene, stirring is cooled to 18 ~ 23 DEG C, centrifuge dehydration, washing, and centrifugal drying obtains intermediate 1；
2. synthetic intermediate 2
2a) take reactor, put into 550 ~ 650kg dimethylformamide, 200 ~ 300kg step 1c) gained intermediate 1, stirring and dissolving, add 3 ~ 7kg ferric chloride as catalyst；
2b) it is warming up to 30 ~ 35 DEG C, passes into pure oxygen, sample analysis, to intermediate 1 content less than 1wt%, obtain qualified oxidation material；
2c) separately take reactor, add 1300 ~ 1500kg water, the lower addition 15 ~ 25kg32% hydrochloric acid of stirring, by step 2b) in the qualified oxidation material of gained be added to the water, stirring 50 ~ 70min, being cooled to less than 20 DEG C, after insulation 50 ~ 60min, filtration is washed, is centrifuged, dries, weighs, is obtained intermediate 2；
3. synthetic intermediate 3
3a) take reactor, add 700 ~ 900kg chlorobenzene, 250 ~ 260kg48 chlorine bromic acid addition 8 ~ 12kg azo diisobutylene nitrile as catalyst, stirring, be heated to 90 ~ 95 DEG C；
3b) in the high-order reservoir of reactor one, add 180 ~ 220kg ortho-methylnitrobenzene, stand-by；
3c) in another high-order reservoir of reactor, add 160 ~ 180kg hydrogen peroxide, stand-by；
When 3d) question response temperature in the kettle rises to 90 DEG C, open step 3b) and step 3c) in two high-order reservoirs, in still, drip ortho-methylnitrobenzene and hydrogen peroxide simultaneously, rate of addition keeps synchronizing, the stirring of dropping limit, limit, dropping temperature 90 ~ 95 DEG C；
3e) after completion of dropwise addition, at 90 ~ 95 DEG C, it is incubated 4 ~ 6h, stops stirring, stand more than 1 hour, layering, separate organic layer, intermediate 3 of weighing to obtain；
4. synthesis 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles
4a) take reactor, add 100 ~ 140kg step 2c) gained intermediate 2,760 ~ 800kg step 3e) gained intermediate 3, add 3 ~ 5kg tetrabutyl ammonium bromide as catalyst, stirring, heat temperature raising；
4b) in reactor dropping bath, add 25% potassium hydroxide solution 210 ~ 220kg, stand-by；
4c) when temperature in the kettle rises to 75 ~ 80 DEG C, open dropping bath, in still, drip described 25% potassium hydroxide solution；
4d) after completion of dropwise addition, at 80 ~ 85 DEG C, insulation, sample analysis, intermediate 2 content is qualified less than 1wt%, being incubated 1.5 ~ 2.5h again, with salt acid for adjusting pH value to 6 ~ 6.5, add water 150 ~ 250kg, stirring, it is cooled to 13 ~ 16 DEG C, is incubated 50 ~ 70min, centrifugal drying material, obtains crude product；
4e) add 300 ~ 500kg methanol, carry out temperature rising reflux 20 ~ 40min, be cooled to 10 ~ 15 DEG C, centrifugal drying, obtain described 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles。
Further, described step 1a) in, in mixed liquor, moisture content is qualified less than 0.1wt%。
Separately, described step 1b) in, if there being backflow to occur, then it is incubated 2 ~ 3h to without backflow。
Separately have, described step 1c) in washing water consumption be 550 ~ 650kg, washing times is 2 ~ 3 times。
Again, described step 2b) in pure oxygen intake be 22 ~ 25kg。
Further, described step 4d) in insulation duration before sample analysis be 50 ~ 70min。
And, described step 3d) in, ortho-methylnitrobenzene rate of addition is 60kg/h。
Separately, described step 3d) in, hydrogen peroxide rate of addition 50kg/h。
Again, described step 4e) in, it is warmed up to 70 DEG C of backflows。
The beneficial effects of the present invention is:
Described synthesis technique process route is simple, synthesizer simple (several reactors can complete synthesis), synthesis material used and synthesis technique are environmentally friendly, synthesis cost is low, be conducive to enterprise economic benefit, gained 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles yield up to 70 ~ 80%, high purity more than 98%。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail。Following example will assist in those skilled in the art and are further appreciated by the present invention, but do not limit the present invention in any form。It should be pointed out that, to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement。These broadly fall into protection scope of the present invention。
The green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles of the present invention, comprises the steps:
1. synthetic intermediate 1
1a) in dehydrating kettle, extract toluene 900 ~ 1100kg, add 200 ~ 240kg p-hydrochloride and obtain mixed liquor, stirring, heat up, reflux dewatering, it is warming up to 100 ~ 120 DEG C, continues reflux dewatering, to mixed liquor, moisture is qualified, proceeds to synthesis reactor；
1b) it is cooled to 50 ~ 55 DEG C, open tail gas adsorption, add 90 ~ 110kg solid sodium methylate, stirring and dissolving, within the scope of 50 ~ 70 DEG C, add 120 ~ 140kg acrylamide, stirring is to dissolving, being warmed up to 80 ~ 90 DEG C, insulation, to without backflow, is cooled to 65 ~ 75 DEG C, add water 900 ~ 1100kg, then with the salt acid for adjusting pH value of 180 ~ 220kg to 6 ~ 6.5；
1c) heating azeotropic backflow and separate toluene, stirring is cooled to 18 ~ 23 DEG C, centrifuge dehydration, washing, and centrifugal drying obtains intermediate 1；
2. synthetic intermediate 2
2a) take reactor, put into 550 ~ 650kg dimethylformamide, 200 ~ 300kg step 1c) gained intermediate 1, stirring and dissolving, add 3 ~ 7kg ferric chloride as catalyst；
2b) it is warming up to 30 ~ 35 DEG C, passes into pure oxygen, sample analysis, to intermediate 1 content less than 1wt%, obtain qualified oxidation material；
2c) separately take reactor, add 1300 ~ 1500kg water, the lower addition 15 ~ 25kg32% hydrochloric acid of stirring, by step 2b) in the qualified oxidation material of gained be added to the water, stirring 50 ~ 70min, being cooled to less than 20 DEG C, after insulation 50 ~ 60min, filtration is washed, is centrifuged, dries, weighs, is obtained intermediate 2；
3. synthetic intermediate 3
3a) take reactor, add 700 ~ 900kg chlorobenzene, 250 ~ 260kg48 chlorine bromic acid addition 8 ~ 12kg azo diisobutylene nitrile as catalyst, stirring, be heated to 90 ~ 95 DEG C；
3b) in the high-order reservoir of reactor one, add 180 ~ 220kg ortho-methylnitrobenzene, stand-by；
3c) in another high-order reservoir of reactor, add 160 ~ 180kg hydrogen peroxide, stand-by；
When 3d) question response temperature in the kettle rises to 90 DEG C, open step 3b) and step 3c) in two high-order reservoirs, in still, drip ortho-methylnitrobenzene and hydrogen peroxide simultaneously, rate of addition keeps synchronizing, the stirring of dropping limit, limit, dropping temperature 90 ~ 95 DEG C；
3e) after completion of dropwise addition, at 90 ~ 95 DEG C, it is incubated 4 ~ 6h, stops stirring, stand more than 1 hour, layering, separate organic layer, intermediate 3 of weighing to obtain；
4. synthesis 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles
4a) take reactor, add 100 ~ 140kg step 2c) gained intermediate 2,760 ~ 800kg step 3e) gained intermediate 3, add 3 ~ 5kg tetrabutyl ammonium bromide as catalyst, stirring, heat temperature raising；
4b) in reactor dropping bath, add 25% potassium hydroxide solution 210 ~ 220kg, stand-by；
4c) when temperature in the kettle rises to 75 ~ 80 DEG C, open dropping bath, in still, drip described 25% potassium hydroxide solution；
4d) after completion of dropwise addition, at 80 ~ 85 DEG C, insulation, sample analysis, intermediate 2 content is qualified less than 1wt%, being incubated 1.5 ~ 2.5h again, with salt acid for adjusting pH value to 6 ~ 6.5, add water 150 ~ 250kg, stirring, it is cooled to 13 ~ 16 DEG C, is incubated 50 ~ 70min, centrifugal drying material, obtains crude product；
4e) add 300 ~ 500kg methanol, carry out temperature rising reflux 20 ~ 40min, be cooled to 10 ~ 15 DEG C, centrifugal drying, obtain described 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles。
Further, described step 1a) in, in mixed liquor, moisture content is qualified less than 0.1wt%。
Separately, described step 1b) in, if there being backflow to occur, then it is incubated 2 ~ 3h to without backflow。
Separately have, described step 1c) in washing water consumption be 550 ~ 650kg, washing times is 2 ~ 3 times。
Again, described step 2b) in pure oxygen intake be 22 ~ 25kg。
Further, described step 4d) in insulation duration before sample analysis be 50 ~ 70min。
And, described step 3d) in, ortho-methylnitrobenzene rate of addition is 60kg/h。
Separately, described step 3d) in, hydrogen peroxide rate of addition 50kg/h。
Again, described step 4e) in, it is warmed up to 70 DEG C of backflows。
The concrete operations mode of the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles provided by the present invention is as follows:
One, the synthesis of intermediate 1
1, taking out toluene 1000Kg in 2000L dehydrating kettle, open manhole cover and throw p-hydrochloride 220Kg, open stirring temperature rising reflux and slough moisture content, be dewatered to temperature and reach 110 DEG C, at this moment water is substantially de-clear, is further continued for reflux dewatering clear to toluene。Check that moisture content is qualified less than 0.1%, turn and expect in synthesis reactor；
2, cool to 50-55 DEG C, open tail gas adsorption system operating。It is initially added into solid sodium methylate 100KG, stirring and dissolving。In 50-70 DEG C of temperature, add acrylamide 130KG, stir to acrylamide dissolving。When being warmed up to 80-90 DEG C, when having backflow, sample after reacting 2 hours。Defective continuation insulation is to qualified；
3, after qualified。Cooling about 70 DEG C, add water 1000KG, then adjusts PH6 ~ 6.5 with the hydrochloric acid of about 200KG；
4, the backflow of heating azeotropic separates toluene, and stirring cools to about 20 DEG C, and centrifuge dehydration is used 600KG water, washed twice, centrifugal drying。Assay, obtains intermediate 1；
Two, the synthesis of intermediate 2
1, in 2000L reactor, DMF(dimethylformamide is put into) 600KG, intermediate 1250KG, stirring and dissolving, add catalyst (ferric chloride) 5KG；
2, controlling temperature and slowly pass into pure oxygen at 30-35 degree, pass into pure oxygen when being about 22-25KG, sample analysis, intermediate 1 content is qualified less than 1%；
3, in 3000L reactor, add the hydrochloric acid that the stirring of 1400KG clean water adds 20KG32%, the oxidation material after qualified for upper step is added to the water, stirs and cool to less than 20 degree in 1 hour。Filter after keeping 1 hour, washing, from doing, dry, weigh, detection level, obtain intermediate 2。
Three, the synthesis of intermediate 3
1, adding 800KG chlorobenzene in 3000L reactor, the chlorine bromic acid of 255KG48%, catalyst (azo diisobutylene nitrile) 10KG agitating heating is warmed up to 90 ~ 95 DEG C；
2, in the high-order reservoir of reactor one, ortho-methylnitrobenzene 200KG is added；
3, in another high-order reservoir of reactor, hydrogen peroxide 170KG is added；
4, opening the dropping of ortho-methylnitrobenzene and the dropping of hydrogen peroxide when temperature to 90 DEG C, rate of addition keeps synchronizing, and ortho-methylnitrobenzene rate of addition is 60kg/h, hydrogen peroxide rate of addition 50kg/h。Keep 90-95 DEG C of dropping temperature；
5, dropping process heat release, controls rate of addition well, and temperature controls at 90-95 degree；
6, after completion of dropwise addition 90-95 DEG C be incubated 5 hours, stop stirring, stand more than 1 hour, be layered, separate organic layer and weigh to obtain intermediate 3。
Four, 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl) synthesis of-1H-pyrazoles
1. adding intermediate 3780KG, intermediate 2120KG, catalyst (tetrabutyl ammonium bromide) 4KG in the reactor of 3000L, stirring heats up；
2. in dropwise adding tank, suction has configured 25% potassium hydroxide aqueous solution 215KG；
3. material stirring is warmed up to 75-80 when spending, and opens dropping 25% potassium hydroxide aqueous solution；
4. completion of dropwise addition is incubated control in sampling in 1 hour at 80-85 degree, and intermediate 2 content is qualified less than 1%。Adjusting pH value to add water 200KG to 6 ~ 6.5 with hydrochloric acid after being incubated 2 hours again after qualified, stirring cools to centrifugal drying material after about 15 degree insulations 1 hour, obtains crude product；
5. refining: in a collection of suction 2000L reactor of crude product, to add methanol 400KG, it is warmed up to 70 DEG C and refluxes half an hour。10-15 DEG C of centrifugal drying of rear cooling obtains 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles。
Described synthesis technique process route is simple, synthesizer simple (several reactors can complete synthesis), synthesis material used and synthesis technique are environmentally friendly, synthesis cost is low, be conducive to enterprise economic benefit, gained 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles yield up to 70 ~ 80%, high purity more than 98%。
It should be noted that above example is only in order to illustrate technical scheme and unrestricted。Although the present invention being described in detail with reference to preferred embodiment, it will be understood by those within the art that, the technical scheme of invention can being modified or equivalent replacement, without deviating from the scope of technical solution of the present invention, it all should be encompassed in scope of the presently claimed invention。
Claims (9)
1. the green synthesis process of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles, it is characterised in that comprise the steps:
Synthetic intermediate 1
1a) in dehydrating kettle, extract toluene 900 ~ 1100kg, add 200 ~ 240kg p-hydrochloride and obtain mixed liquor, stirring, heat up, reflux dewatering, it is warming up to 100 ~ 120 DEG C, continues reflux dewatering, to mixed liquor, moisture is qualified, proceeds to synthesis reactor；
1b) it is cooled to 50 ~ 55 DEG C, open tail gas adsorption, add 90 ~ 110kg solid sodium methylate, stirring and dissolving, within the scope of 50 ~ 70 DEG C, add 120 ~ 140kg acrylamide, stirring is to dissolving, being warmed up to 80 ~ 90 DEG C, insulation, to without backflow, is cooled to 65 ~ 75 DEG C, add water 900 ~ 1100kg, then with the salt acid for adjusting pH value of 180 ~ 220kg to 6 ~ 6.5；
1c) heating azeotropic backflow and separate toluene, stirring is cooled to 18 ~ 23 DEG C, centrifuge dehydration, washing, and centrifugal drying obtains intermediate 1；
Synthetic intermediate 2
2a) take reactor, put into 550 ~ 650kg dimethylformamide, 200 ~ 300kg step 1c) gained intermediate 1, stirring and dissolving, add 3 ~ 7kg ferric chloride as catalyst；
2b) it is warming up to 30 ~ 35 DEG C, passes into pure oxygen, sample analysis, to intermediate 1 content less than 1wt%, obtain qualified oxidation material；
2c) separately take reactor, add 1300 ~ 1500kg water, the lower addition 15 ~ 25kg32% hydrochloric acid of stirring, by step 2b) in the qualified oxidation material of gained be added to the water, stirring 50 ~ 70min, being cooled to less than 20 DEG C, after insulation 50 ~ 60min, filtration is washed, is centrifuged, dries, weighs, is obtained intermediate 2；
Synthetic intermediate 3
3a) take reactor, add 700 ~ 900kg chlorobenzene, 250 ~ 260kg48% chlorine bromic acid addition 8 ~ 12kg azo diisobutylene nitrile as catalyst, stirring, be heated to 90 ~ 95 DEG C；
3b) in high-order reservoir, add 180 ~ 220kg ortho-methylnitrobenzene, stand-by；
3c) in another high-order reservoir, add 160 ~ 180kg hydrogen peroxide, stand-by；
When 3d) question response temperature in the kettle rises to 90 DEG C, open step 3b) and step 3c) in two high-order reservoirs, in still, drip ortho-methylnitrobenzene and hydrogen peroxide, the stirring of dropping limit, limit, dropping temperature 90 ~ 95 DEG C simultaneously；
3e) after completion of dropwise addition, at 90 ~ 95 DEG C, it is incubated 4 ~ 6h, stops stirring, stand more than 1 hour, layering, separate organic layer, intermediate 3 of weighing to obtain；
Synthesis 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles
4a) take reactor, add 100 ~ 140kg step 2c) gained intermediate 2,760 ~ 800kg step 3e) gained intermediate 3, add 3 ~ 5kg tetrabutyl ammonium bromide as catalyst, stirring, heat temperature raising；
4b) in reactor dropping bath, add 25% potassium hydroxide solution 210 ~ 220kg, stand-by；
4c) when temperature in the kettle rises to 75 ~ 80 DEG C, open dropping bath, in still, drip described 25% potassium hydroxide solution；
4d) after completion of dropwise addition, at 80 ~ 85 DEG C, insulation, sample analysis, intermediate 2 content is qualified less than 1wt%, being incubated 1.5 ~ 2.5h again, with salt acid for adjusting pH value to 6 ~ 6.5, add water 150 ~ 250kg, stirring, it is cooled to 13 ~ 16 DEG C, is incubated 50 ~ 70min, centrifugal drying material, obtains crude product；
4e) add 300 ~ 500kg methanol, temperature rising reflux 20 ~ 40min, it is cooled to 10 ~ 15 DEG C, centrifugal drying, obtain described 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles。
2. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 1a) in, in mixed liquor, moisture content is qualified less than 0.1wt%。
3. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 1b) in, if there being backflow to occur, then it is incubated 2 ~ 3h to without backflow。
4. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterized in that, described step 1c) in washing water consumption be 550 ~ 650kg, washing times is 2 ~ 3 times。
5. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 2b) in pure oxygen intake be 22 ~ 25kg。
6. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 4d) in insulation duration before sample analysis be 50 ~ 70min。
7. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 3d) in, ortho-methylnitrobenzene rate of addition is 60kg/h。
8. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 3d) in, hydrogen peroxide rate of addition 50kg/h。
9. the green synthesis process of a kind of 3-(2-Nitrobenzol methoxyl group)-1-(4-chlorphenyl)-1H-pyrazoles according to claim 1, it is characterised in that described step 4e) in, it is warmed up to 70 DEG C of backflows。
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| CN106866531A (en) * | 2017-04-17 | 2017-06-20 | 安徽广信农化股份有限公司 | A kind of synthesis technique of pyraclostrobin intermediate pyrazole alkanone |
| CN106977456A (en) * | 2017-04-17 | 2017-07-25 | 安徽广信农化股份有限公司 | A kind of synthesis system of pyraclostrobin intermediate pyrazole alkanone |
| CN107935931A (en) * | 2017-12-23 | 2018-04-20 | 杨向党 | 1‑（4 chlorphenyls）3 ketone of pyrazolidine, which does not purify, directly produces 1（4 chlorphenyls）3 pyrazoles alcohol |
| CN111454208A (en) * | 2020-05-29 | 2020-07-28 | 安徽国星生物化学有限公司 | Production method of 2- [ (N-p-chlorophenyl) -3-pyrazolyloxymethyl ] nitrobenzene |
| CN114369029A (en) * | 2022-01-05 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of o-nitrobenzyl bromide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106866531A (en) * | 2017-04-17 | 2017-06-20 | 安徽广信农化股份有限公司 | A kind of synthesis technique of pyraclostrobin intermediate pyrazole alkanone |
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| CN107935931A (en) * | 2017-12-23 | 2018-04-20 | 杨向党 | 1‑（4 chlorphenyls）3 ketone of pyrazolidine, which does not purify, directly produces 1（4 chlorphenyls）3 pyrazoles alcohol |
| CN111454208A (en) * | 2020-05-29 | 2020-07-28 | 安徽国星生物化学有限公司 | Production method of 2- [ (N-p-chlorophenyl) -3-pyrazolyloxymethyl ] nitrobenzene |
| CN114369029A (en) * | 2022-01-05 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of o-nitrobenzyl bromide |
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