CN106008349A - Crystallization treating technology for pyraclostrobin - Google Patents

Abstract

The invention discloses a crystallization treating technology for pyraclostrobin. The treating technology is characterized by comprising the following steps that 1, a pyraclostrobin crude solution is rectified, filtered and washed and then is transferred to a liquid storage device on a metering pump, the flow speed of the metering pump is set, the flowing-out solution is subjected to column separation through a silicagel column, column separation is repeatedly carried out for 3-4 times, and the separated solution is collected for high-pressure suction filtration; 2, an isopropanol solvent and normal heptane are used for crystallizing filtrate obtained after high-pressure suction filtration in the step 1; 3, centrifugal mother liquor is recycled, centrifugal solid is washed with water and dried, and therefore the purified pyraclostrobin can be obtained. By carrying out column separation on the roughly-treated filtrate, the purity of pyraclostrobin can be improved; the flow speed needed during column separation is controlled through the metering pump, and therefore the product purity is further improved; isopropanol and normal heptane are added during crystallization operation, and a crystallized crystal nucleus of pyraclostrobin can be formed at normal temperature.

Description

A kind of crystallization treatment technique of pyraclostrobin

Technical field

The present invention relates to the crystallization treatment technique of a kind of pyraclostrobin.

Background technology

Pyraclostrobin is the methoxy acrylic bactericide having pyrrazole structure concurrently, 1993 Year is found by BASF Aktiengesellschaft, and calendar year 2001 registers and lists, and has been used for more than 100 at present Plant on crop.2009, its sales volume reached 7.35 hundred million dollars, was only second to Fluoxastrobin, became For world's second largest antibacterial.Pyraclostrobin wide spectrum, efficiently, toxicity low, raw to non-target Thing safety, friendly to user and environment all safety, it is market in strobilurin series bactericidal agent The staple product that prospect is preferable, patent will be expired.

Sum up to get up to be divided into two to the synthetic route of pyraclostrobin the most both at home and abroad:

Article 1, route is by ortho-methylnitrobenzene, first obtains adjacent nitrobenzyl through Benzylphosphonium Bromide Bromine, o-nitrobenzyl bromide is condensed to yield 2-[(N-4-chlorobenzene with 1-(4-chlorphenyl)-3-hydroxypyrazoles Base)-3-pyrazoles epoxide methyl] Nitrobenzol, then obtain N-hydroxy-n-2-[(N-4-through reduction Chlorphenyl)-3-pyrazoles epoxide methyl]-aniline, then with methylchloroformate reaction obtains N-hydroxyl -N-2-[(N-rubigan)-3-pyrazoles epoxide methyl] carbanilate, last and sulphuric acid Dimethyl ester reaction obtains pyraclostrobin.

Article 2 route, by ortho-methylnitrobenzene, obtains o-methyl-phenyl-azanol through reduction, Obtain N-hydroxy-n-toluidino methyl formate with methylchloroformate reaction again, then with sulphuric acid two Methyl ester reaction obtains N-methoxy-. N-methyl phenylcarbamate.N-methoxyl group-N-first Base phenylcarbamate obtains pyrazoles pyrazoles ether with 1-(4-chlorphenyl)-3-hydroxypyrazoles again Bacterium ester.

The traditional method of mix reagent crystallization is when solvent degree is fine in certain solvent for Organic substance, First carrying out heating for dissolving with this solvent of minimum, the another kind reheating dissolubility slightly worse is molten Agent, reduces this organic dissolubility, and then cooling separates out crystal.Or at reflux state Lower with the solvent of minimal amount of favorable solubility by product dissolve, then add molten from condensing tube The solvent that solution property is relatively low, to solution Hun Chi, then backflow is dripped clear, and cooling separates out.But this side Method can make product crystallization not exclusively, and solvent recovery is not thorough, thus affects the yield of product, increases Add post processing cost.

Summary of the invention

For the deficiencies in the prior art, the invention provides the crystallization treatment of a kind of pyraclostrobin Technique.

The present invention can be achieved through the following technical solutions:

A kind of crystallization treatment technique of pyraclostrobin, it is characterised in that process technique include with Lower step:

(1) pretreatment: by the pyraclostrobin crude product solution of 1 weight portion through rectification, filtration, After washing, transferring in the device for storing liquid on dosing pump, the flow velocity arranging dosing pump is 10mL/min, the solution of outflow carried out post through silicagel column and separated, repeated post and separate 3-4 Secondary, regather the solution after separation and carry out high pressure sucking filtration；

(2) crystallization: the filtrate after step 1 high pressure sucking filtration is transferred to the knot of enamel material In brilliant still, then it is slowly added dropwise isopropanol solvent, carries out stirring at normal temperature, when filtrate no longer presents oil Shape, continues dropping isopropanol, and system is that yellow is muddy, then it is clear to drip several normal heptane backflows droplet, Stopping stirring, stand and make system layering, upper strata is red, transparent liquid, and lower floor is yellow crystal Solid；

(3) it is fully transferred in centrifuge be centrifuged by the material after layering in step 2, Centrifuge mother liquor recycles in being transferred to disposing mother liquor still, and centrifugal solids is after washing and drying, i.e. Available pyraclostrobin after purification.

The invention have the benefit that 1) divide by the filtrate after preliminary treatment was carried out post From, the purity of pyraclostrobin can be improved；2) flow velocity during post was controlled by dosing pump, The more thorough of magazins' layout can be made, thus improve product purity further；3) crystallization operation Time, by adding isopropanol and normal heptane, the crystallization that can form pyraclostrobin under room temperature is brilliant Core；4) disposing mother liquor still is used can to reclaim various solvent, it is achieved recycling of resource, Cost-effective, the most environmentally friendly.

Detailed description of the invention:

By embodiment, the detailed description of the invention of the present invention is made an explanation below.

Embodiment

A kind of crystallization treatment technique of pyraclostrobin, it is characterised in that process technique include with Lower step: (1) by the pyraclostrobin crude product solution of 1 weight portion through rectification, filter, wash After, to transfer in the device for storing liquid on dosing pump, the flow velocity arranging dosing pump is 10mL/min, The solution flowed out carried out post through silicagel column and separated, and repeated post and separates 3-4 time, at regulation stream Speed descended post to separate, and can make the more thorough of magazins' layout, thus improve product pyraclostrobin Purity, regather the solution after separation and carry out high pressure sucking filtration；(2) by step 1 high pressure sucking filtration After filtrate be transferred in the crystallization kettle of enamel material, then be slowly added dropwise isopropanol solvent, enter Row stirring at normal temperature, when filtrate no longer presents oily, continues dropping isopropanol, and system is that yellow is muddy Turbid, then drip several normal heptane, stopping stirring, stand and make system layering, upper strata is red saturating Prescribed liquid, lower floor is yellow crystalline solid；(3) material after layering in step 2 is all turned Moving to be centrifuged in centrifuge, centrifuge mother liquor recycles in being transferred to disposing mother liquor still, from Heart solid, after washing and drying, i.e. can get pyraclostrobin after purification.

The invention have the benefit that 1) divide by the filtrate after preliminary treatment was carried out post From, the purity of pyraclostrobin can be improved；2) flow velocity during post was controlled by dosing pump, The more thorough of magazins' layout can be made, thus improve product purity further；3) crystallization operation Time, by adding isopropanol and normal heptane, the crystallization that can form pyraclostrobin under room temperature is brilliant Core；4) disposing mother liquor still is used can to reclaim various solvent, it is achieved recycling of resource, Cost-effective, the most environmentally friendly.

Claims (1)

1. the crystallization treatment technique of a pyraclostrobin, it is characterised in that process technique bag Include following steps:

(1) pretreatment: by the pyraclostrobin crude product solution of 1 weight portion through rectification, filtration, After washing, transferring in the device for storing liquid on dosing pump, the flow velocity arranging dosing pump is 10mL/min, the solution of outflow carried out post through silicagel column and separated, repeated post and separate 3-4 Secondary, regather the solution after separation and carry out high pressure sucking filtration；

(2) crystallization: the filtrate after step 1 high pressure sucking filtration is transferred to the knot of enamel material In brilliant still, then it is slowly added dropwise isopropanol solvent, carries out stirring at normal temperature, when filtrate no longer presents oil Shape, continues dropping isopropanol, and system is that yellow is muddy, then drips several normal heptane, stops stirring Mixing, stand and make system layering, upper strata is red, transparent liquid, and lower floor is yellow crystalline solid；

(3) it is fully transferred in centrifuge be centrifuged by the material after layering in step 2, Centrifuge mother liquor recycles in being transferred to disposing mother liquor still, and centrifugal solids is after washing and drying, i.e. Available pyraclostrobin after purification.