CN105859625A - Synthetic method for preparing pyraclostrobin intermediate from o-nitrobenzyl chloride - Google Patents
Synthetic method for preparing pyraclostrobin intermediate from o-nitrobenzyl chloride Download PDFInfo
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- CN105859625A CN105859625A CN201610396769.9A CN201610396769A CN105859625A CN 105859625 A CN105859625 A CN 105859625A CN 201610396769 A CN201610396769 A CN 201610396769A CN 105859625 A CN105859625 A CN 105859625A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
Abstract
The invention discloses a synthetic method for preparing a pyraclostrobin intermediate from o-nitrobenzyl chloride. The synthetic method includes the following steps that a catalyst is added into o-nitrotoluene, heating and stirring are carried out, chlorine is slowly introduced, o-nitrotoluene is recycled after the reaction is finished, and o-nitrobenzyl chloride is obtained; o-nitrobenzyl chloride and 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole are subjected to an etherification reaction, and 2-[(N-4-chlorphenyl)-3-pyrazolyloxymethyl]nitrobenzene is obtained. According to the synthetic method, o-nitrobenzyl chloride is substituted for o-nitrobenzyl bromide to react with 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole, the pyraclostrobin intermediate 2-[(N-4-chlorphenyl)-3-pyrazolyloxymethyl]nitrobenzene is obtained, the defects of an existing synthetic method using o-nitrobenzyl bromide are overcome, and the etherification product with the content larger than or equal to 98% and the yield larger than or equal to 90% can be prepared.
Description
Technical field
The present invention is a kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride, is specifically related to by adjacent nitre
Base benzyl chloride prepares the synthesis technique of pyraclostrobin intermediate 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene, belongs to
Synthesis field in organic compound.
Background technology
Pyraclostrobin, since within 2002, being released by BASF AG, has received significant attention and has applied.Pyraclostrobin
As one effective broad spectrum type bactericide, the disease causing the true pathogen of all classes all has preferable prevention effect.Example
As: potato and the early blight of tomato, late blight, leaf hardship disease, powdery mildew, rust etc., have preventing and treating the effect cured.
Adjacent nitro benzyl bromide is the important synthetic intermediate of New-type wide-spectrum bactericide pyraclostrobin, can with 1-(4-chlorine
Phenyl) reaction of-3-pyrazoles alcohol, prepare pyraclostrobin intermediate 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene.
As important synthetic intermediate, the production technology of adjacent nitrobenzyl bromine is more, such as: patent document CN104496905A(2-
The preparation method of [(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene, 2014.12.29), patent document
CN105111148A(2-[(N-rubigan)-3-pyrazoles epoxide methyl] nitrobenzene and preparation method and application,
2015.08.10) etc..Being proven, existing synthetic method has several important shortcoming, the most importantly bromine
Or the bromine source such as hydrobromic acid is expensive, not readily transportable, and there is the Environmental assessment technology requirements such as bromine source recovery.
The chemical molecular formula of adjacent nitro benzyl chloride is C7H6ClNO2, the molecular structural formula of adjacent nitro benzyl chloride is, its
Its title has: 2-nitro benzyl chloride, adjacent nitro benzyl chloride, 2-nitrobenzene methyl chloride, 2-nitrobenzyl chlorine, adjacent nitro benzyl chloride.This change
The fusing point of compound is 51 DEG C, and molecular weight is 171.58 g/mol, white crystalline powder.
It is known that adjacent nitro benzyl chloride has identical chemical property compared with adjacent nitro benzyl bromide, can be as adjacent nitro
The important replacement of cylite.But the method that existing nitrotoleune replaces chlorination mainly has two kinds: thermal chlorination and luminescence method
(" Hubei Chemical ", the 4th phase in 1997, " adjacent nitro benzyl chloride new technique for synthesizing ").Thermal chlorination method productivity is low, and general productivity is less than
5%.And on the one hand illumination chloridising is illumination in-convenience in use, be on the other hand that accessory substance is many, reaction effect is the best.Therefore, mesh
Front adjacent nitro benzyl chloride not yet has a low cost, the efficient synthesis of economic serviceability.
Summary of the invention
It is an object of the invention to provide a kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride, this
Synthetic method is replaced adjacent nitro benzyl bromide with adjacent nitro benzyl chloride and is reacted with 1-(4-chlorphenyl)-3-pyrazoles alcohol, prepares pyrazoles ether
Bacterium ester intermediate 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene, it is to avoid existing use adjacent nitro benzyl bromide to close
In one-tenth method, etherate is difficult to purify and content is relatively low, bromine price height enterprise causes cost high and produces sodium bromide needs time
The defects such as receipts, can prepare content >=98%, the etherification product of productivity >=90%.
The present invention is achieved through the following technical solutions: a kind of synthesis being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride
Method, comprises the following steps:
A, in ortho-methylnitrobenzene, add catalyst, add thermal agitation, and be slowly introducing chlorine, after question response terminates, reclaim adjacent nitre
Base toluene, it is thus achieved that adjacent nitro benzyl chloride；
B, neighbour's nitro benzyl chloride and 1-(4-chlorphenyl)-3-pyrazoles alcohol are carried out etherification reaction, it is thus achieved that 2-[(N-4-chlorphenyl)-
3-pyrazoles epoxide methyl] nitrobenzene.
Synthetic method of the present invention carries out etherification reaction with adjacent nitro benzyl chloride with 1-(4-chlorphenyl)-3-pyrazoles alcohol, prepares pyrrole
Azoles kresoxim-methyl intermediate 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene, wherein, adjacent nitro benzyl chloride is with adjacent nitro first
Benzene and chlorine are reaction raw materials, and under the effect of catalyst, reaction generates adjacent nitro benzyl chloride, and its productivity is apparently higher than thermal chlorination
The thermal chlorination caused with initiator, from the point of view of course of reaction, its synthesis step is substantially better than light chlorination process, therefore, the present invention
Method also includes a kind of effective, synthetic method of the simply adjacent nitro benzyl chloride of synthesis step.
In described step A, count in mass ratio, ortho-methylnitrobenzene: catalyst=1:(0.01～0.2), preferably 1:(0.05
～0.10).
In described step A, catalyst includes: the activated carbon of 50～200 mesh, bromine, iodine, azodiisobutyronitrile,
One or more in ABVN, phosphorus pentachloride, phosphorus trichloride, benzoyl peroxide, hyperis, DMF
Mixture.
In described step A, heating and temperature control is at 100～180 DEG C, and stir speed (S.S.) controls at >=200r/min.
In described step A, in course of reaction, use gas-chromatography to follow the tracks of byproduct of reaction neighbour's nitro benzal chloride and reach
4～6%, stop reaction.
In described step A, after reaction terminates, at vacuum is less than 120 DEG C higher than-0.095Mpa, temperature, decompression is steamed
Evaporating, reclaim ortho-methylnitrobenzene, the ortho-methylnitrobenzene of recovery can continue cycling through chlorination and utilize, and reduces production cost.
In described step A, reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that white crystal
The adjacent nitro benzyl chloride pressed powder of shape.
In described step B, etherification reaction includes: the adjacent nitro prepared to 1-(4-chlorphenyl)-3-pyrazoles alcohol, step A
The organic solution of benzyl chloride, phase transfer catalyst mixed solution in, the lower aqueous solution dripping alkali of stirring, controlling reaction temperature is
0～100 DEG C, react 1～6 hour, after question response terminates, through extraction, recycling design, purifying after drying, obtain 2-[(N-4-chlorine
Phenyl)-3-pyrazoles epoxide methyl] nitrobenzene.
Can be summarized as follows further at the etherification reaction that the present invention relates to: in container, add 1-(4-chlorphenyl)-3-pyrrole
The organic solution of the adjacent nitro benzyl chloride that azoles alcohol, step A prepare and phase transfer catalyst, it is thus achieved that mixed solution；Quickly under stirring
The aqueous solution of alkali, preferable reaction temperature 20～60 DEG C, reaction time 2～4 hours is dripped in container；Reaction solution is taken
Sample, with HPLC detection sampling sample, when amount≤1% of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol, stops reaction；Regulation solution
PH value is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide
Methyl] nitrobenzene.
The concentration of organic solution of described adjacent nitro benzyl chloride is 10～40%, in described mixed solution, 1-(4-chlorphenyl)-
3-pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:(1.02～1.50): (1.05～1.6).
In described chlorobenzene solution, adjacent nitro benzyl chloride controls at 1:(0.01～0.20 with the mass ratio of phase transfer catalyst).
In the etherification reaction that the present invention relates to, it is organic that the organic solution of the adjacent nitro benzyl chloride that step A prepares uses
Solvent is selected from halogenated aliphatic hydrocarbon, such as dichloromethane, dichloroethanes, chloroform, carbon tetrachloride etc., aromatic hydrocarbon such as chlorobenzene, toluene,
Dimethylbenzene etc.；Also selected from fatty ether, such as THF, Di Iso Propyl Ether, methyl tertiary butyl ether(MTBE), dioxane, anisole etc.；Also may be used
Selected from acid amides, such as DMF, DMA or NMP, alcohol such as methyl alcohol, ethanol, propyl alcohol, isopropanol, butanol, the tert-butyl alcohol etc., or selected from ketone such as third
Ketone, methyl ethyl ketone etc.；And DMSO, acetonitrile and the mixture of above-mentioned solvent, wherein, preferably dichloroethanes, chlorobenzene and acetone
And mixture.
In the etherification reaction that the present invention relates to, alkali is selected from alkali and alkaline earth metal ions oxide, such as lithia, oxidation
Sodium, potassium oxide, magnesia and calcium oxide etc.；Also selected from alkali and alkaline earth metal ions hydroxide, such as lithium hydroxide, hydroxide
Sodium, potassium hydroxide and calcium hydroxide etc.；Also selected from alkali and alkaline earth metal ions carbonate and bicarbonate, such as sodium carbonate, carbon
Acid potassium, calcium carbonate, sodium acid carbonate and saleratus etc.；Or selected from organic base, such as triethylamine, trimethylamine, N-methyl piperidine and pyrrole
Pyridine etc., wherein, the preferred NaOH of alkali.
Can be at the aqueous solution by alkali and alkaline earth metal ions hydroxide or carbonate at the etherification reaction that the present invention relates to
The two-phase system formed with organic phase (such as aromatic hydrocarbon or/and halogenated hydrocarbons etc.) is carried out.In the case, suitable catalysis is added
The PTC of amount is favourable to reaction, and PTC is selected from ammonium halide, such as benzyltriethylammoinium chloride, TBAB, benzyl three
Butylammonium bromide, tetrabutylammonium chloride, cetyl trimethylammonium bromide etc., it is possible to selected from polyethylene glycol, as PEG400,
PEG600 and PEG800 etc., it is possible to selected from crown ether, such as 18-crown-6,15-crown-5 etc., or selected from tetrabutyl ammonium tetrafluoroborate etc., its
In, the particularly preferred benzyltriethylammoinium chloride of PTC.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) synthetic method of the present invention uses cheap chlorine and ortho-methylnitrobenzene chlorination to generate adjacent nitro benzyl chloride, substitutes
Existing pyraclostrobin production process carries out etherification reaction with adjacent nitro benzyl bromide and 1-(4-chlorphenyl)-3-pyrazoles alcohol, one
Aspect, is avoided that use bromine or the adjacent nitro benzyl bromide of hydrobromic acid preparation, reduces environmental protection pressure, on the other hand, uses price low
The bromine of honest and clean chlorine fictitious hosts costliness or hydrobromic acid, can reduce production cost.
(2) synthesis technique of the present invention is simple, and the synthesis of adjacent nitro benzyl chloride uses ortho-methylnitrobenzene and chlorine former for reaction
Material, and the mass ratio controlling ortho-methylnitrobenzene and catalyst is 1:(0.01～0.2) react, sampled and use gas-chromatography
When method detecting and tracking ortho-methylnitrobenzene conversion ratio is about 40%, i.e. stopping reaction, distillation of reducing pressure the most again, residue is through petroleum ether
After crystallization, i.e. available adjacent nitro benzyl chloride crystal, the adjacent nitro benzyl chloride product of purity >=99% and productivity >=80% can be realized
Yield (in terms of the ortho-methylnitrobenzene of actual consumption), far above the product of the thermal chlorination 5% that thermal chlorination 1.9% and initiator cause
Product yield.
(3) in step A that synthesis technique of the present invention relates to, for preparing the ortho-methylnitrobenzene of adjacent nitro benzyl chloride, in reaction
After end, unreacted ortho-methylnitrobenzene can be recycled by the way of decompression is distilled, can realize reclaiming 90～about 95% adjacent
The circulation chlorination of nitrotoleune utilizes, the beneficially control of production cost.
(4) in step A of the present invention, the mixture of one or both compositions in the preferred bromine of catalyst, phosphorus trichloride, tool
It is improved selectivity, accelerates the effect of reaction speed, use the mass ratio 1:(0.01～0.2 of ortho-methylnitrobenzene and catalyst),
Particularly 1:(0.05～0.10), be conducive to controlling the consumption of catalyst, the most cost-effective, also allow for post processing.
(5) in step A of the present invention, before being passed through chlorine, by control heating-up temperature 100～180 DEG C and stir speed (S.S.) >=
200r/min, is conducive to being smoothed out of reaction, temperature is controlled at optimum range, it is to avoid occur that temperature low reaction process is slow,
The many situations about even decomposing of temperature height side reaction；The absorption dispersion controlling to be conducive to leading to chlorine of stir speed (S.S.), adds fast response and enters
Journey.
(6) etherification reaction that the inventive method relates to is 10～the organic solution of adjacent nitro benzyl chloride of 40%, 1-with concentration
(4-chlorphenyl)-3-pyrazoles alcohol is main, then is aided with the phase transfer catalyst of appropriate ratio and the aqueous solution of alkali, controls 1-(4-chlorine
Phenyl)-3-pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali control at 1.0:(1.02～1.50): (1.05～1.6), adjacent nitre
The mass ratio of base benzyl chloride and phase transfer catalyst is 1:(0.01～0.2) in the case of carry out etherification reaction, content can be obtained
>=98%, the etherification product of productivity >=90%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Example 1 below～10 relates to the synthesis of adjacent nitro benzyl chloride.
Embodiment 1:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
Adding catalyst (activated carbons of 50 mesh) in ortho-methylnitrobenzene, ortho-methylnitrobenzene controls 1 with the mass ratio of catalyst:
It is stirred and heated to 100 DEG C under 0.01,200r/min speed, is slowly introducing chlorine, follow the tracks of byproduct of reaction by gas-chromatography adjacent
Nitro benzal chloride reaches 4%, and ortho-methylnitrobenzene conversion ratio 39.7%, stopping is reacted；After question response terminates, vacuum-
Decompression distillation at 0.097Mpa, temperature 110 DEG C, reclaims ortho-methylnitrobenzene, continues cycling through chlorination and utilizes；After reclaiming ortho-methylnitrobenzene
Residue petroleum ether recrystallization purifying, it is thus achieved that the adjacent nitro benzyl chloride pressed powder of white crystalline.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.3% and productivity 83.7% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 2:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
Catalyst (mass ratio is the activated carbon of 2:1200 mesh and the mixture of DMF composition), adjacent nitre is added in ortho-methylnitrobenzene
Base toluene controls, at 1:0.2, to be stirred and heated to 180 DEG C, be slowly introducing chlorine under 400r/min speed with the mass ratio of catalyst
Gas, follows the tracks of byproduct of reaction neighbour's nitro benzal chloride by gas-chromatography and reaches 6%, and ortho-methylnitrobenzene conversion ratio 41%, stopping is reacted；
After question response terminates, decompression distillation at vacuum-0.098Mpa, temperature 100 DEG C, reclaim ortho-methylnitrobenzene, continue cycling through chlorine
Change and utilize；Reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that the adjacent nitro chlorination of white crystalline
Benzyl pressed powder.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.6% and productivity 80.0% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 3:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
(mass ratio is 1:1:2 bromine, azodiisobutyronitrile and ABVN composition to add catalyst in ortho-methylnitrobenzene
Mixture), the mass ratio of ortho-methylnitrobenzene and catalyst controls, at 1:0.15, to be stirred and heated under 300r/min speed
130 DEG C, being slowly introducing chlorine, follow the tracks of byproduct of reaction neighbour's nitro benzal chloride by gas-chromatography and reach 5%, ortho-methylnitrobenzene turns
Rate 40.2%, stops reaction；After question response terminates, decompression distillation at vacuum-0.097Mpa, temperature 115 DEG C, reclaim neighbour
Nitrotoleune, continues cycling through chlorination and utilizes；Reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that white
The adjacent nitro benzyl chloride pressed powder of lenticular.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.0% and productivity 82.9% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 4:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
Catalyst (mass ratio is 2:1 bromine, the mixture of ABVN composition), adjacent nitro is added in ortho-methylnitrobenzene
Toluene controls, at 1:0.05, to be stirred and heated to 140 DEG C, be slowly introducing chlorine under 315r/min speed with the mass ratio of catalyst
Gas, follows the tracks of byproduct of reaction neighbour's nitro benzal chloride by gas-chromatography and reaches 4%, and ortho-methylnitrobenzene conversion ratio 40.1%, stopping is anti-
Should；After question response terminates, decompression distillation at vacuum-0.098Mpa, temperature 110 DEG C, reclaim ortho-methylnitrobenzene, continue cycling through
Chlorination utilizes；Reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that the adjacent nitroxyl chloride of white crystalline
Change benzyl pressed powder.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.2% and productivity 86.0% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 5:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
Adding catalyst (hyperis) in ortho-methylnitrobenzene, ortho-methylnitrobenzene controls with the mass ratio of catalyst
It is stirred and heated to 155 DEG C under 1:0.9,305r/min speed, is slowly introducing chlorine, follow the tracks of byproduct of reaction by gas-chromatography adjacent
Nitro benzal chloride reaches 5%, and ortho-methylnitrobenzene conversion ratio 40.6%, stopping is reacted；After question response terminates, vacuum-
Decompression distillation at 0.095Mpa, temperature 118 DEG C, reclaims ortho-methylnitrobenzene, continues cycling through chlorination and utilizes；After reclaiming ortho-methylnitrobenzene
Residue petroleum ether recrystallization purifying, it is thus achieved that the adjacent nitro benzyl chloride pressed powder of white crystalline.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.2% and productivity 85.2% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 6:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
Adding catalyst (ABVN) in ortho-methylnitrobenzene, ortho-methylnitrobenzene controls 1 with the mass ratio of catalyst:
It is stirred and heated to 160 DEG C under 0.84,345r/min speed, is slowly introducing chlorine, follow the tracks of byproduct of reaction by gas-chromatography adjacent
Nitro benzal chloride reaches 6%, and ortho-methylnitrobenzene conversion ratio 42%, stopping is reacted；After question response terminates, vacuum-
Decompression distillation at 0.098Mpa, temperature 112 DEG C, reclaims ortho-methylnitrobenzene, continues cycling through chlorination and utilizes；After reclaiming ortho-methylnitrobenzene
Residue petroleum ether recrystallization purifying, it is thus achieved that the adjacent nitro benzyl chloride pressed powder of white crystalline.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.4% and productivity 83.8% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 7:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
In four mouthfuls of round-bottomed flasks of 1000ml, add 288.72g ortho-methylnitrobenzene and quantitative catalyst (mass ratio is 3:1:
The mixture of 2:1 phosphorus pentachloride, elemental iodine, hyperis, DMF composition), ortho-methylnitrobenzene and the mass ratio of catalyst
Control to be stirred and heated to 135 DEG C under 1:0.72,350r/min speed, be slowly introducing chlorine, sample after two hours, use gas phase
Chromatogram tracking byproduct of reaction neighbour's nitro benzal chloride reaches 6%, and ortho-methylnitrobenzene conversion ratio 40.4%, stopping is reacted；Question response
After end, decompression distillation at vacuum-0.095Mpa, temperature 115 DEG C, reclaim ortho-methylnitrobenzene, continue cycling through chlorination and utilize；
Reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that the adjacent nitro benzyl chloride solid powder of white crystalline
End.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.6% and productivity 85.8% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 8:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
In four mouthfuls of round-bottomed flasks of 1000ml, (mass ratio is 10:1 for addition 312.56g ortho-methylnitrobenzene and quantitative catalyst
Bromine and the mixture of iodine composition), ortho-methylnitrobenzene controls at 1:0.08 with the mass ratio of catalyst, 235r/min speed
Under be stirred and heated to 140 DEG C, be slowly introducing chlorine, after two hours sample, with gas-chromatography follow the tracks of byproduct of reaction neighbour's nitro
Benzal chloride reaches 5%, and ortho-methylnitrobenzene conversion ratio 41%, stopping is reacted；After question response terminates, in vacuum-0.098Mpa, temperature
Decompression distillation at spending 109 DEG C, reclaims ortho-methylnitrobenzene, continues cycling through chlorination and utilizes；Reclaim the residue after ortho-methylnitrobenzene to use
Petroleum ether recrystallization purifying, it is thus achieved that the adjacent nitro benzyl chloride pressed powder of white crystalline.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.2% and productivity 86.1% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 9:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
In four mouthfuls of round-bottomed flasks of 1000ml, add 296.34g ortho-methylnitrobenzene and quantitative catalyst (azo two isobutyl
Nitrile), ortho-methylnitrobenzene controls, at 1:0.05, to be stirred and heated to 120 DEG C under 300r/min speed with the mass ratio of catalyst, slow
Slowly it is passed through chlorine, samples after two hours, follow the tracks of byproduct of reaction neighbour's nitro benzal chloride by gas-chromatography and reach 4%, adjacent nitro first
Benzene conversion ratio 40.3%, stops reaction；After question response terminates, decompression distillation at vacuum-0.099Mpa, temperature 118 DEG C, return
Receive ortho-methylnitrobenzene, continue cycling through chlorination and utilize；Reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that
The adjacent nitro benzyl chloride pressed powder of white crystalline.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.4% and productivity 85.2% (with actual consumption
Ortho-methylnitrobenzene meter).
Embodiment 10:
In the present embodiment, the building-up process of adjacent nitro benzyl chloride is as follows:
In four mouthfuls of round-bottomed flasks of 1000ml, add 286.84g ortho-methylnitrobenzene and quantitative catalyst (mass ratio is 1:2:
The mixture of 1 phosphorus pentachloride, phosphorus trichloride, benzoyl peroxide composition), ortho-methylnitrobenzene controls with the mass ratio of catalyst
Be stirred and heated to 140 DEG C under 1:0.10,320r/min speed, be slowly introducing chlorine, after two hours sample, with gas-chromatography with
Track byproduct of reaction neighbour's nitro benzal chloride reaches 5%, and ortho-methylnitrobenzene conversion ratio is 40.9%, stops reaction；Question response terminates
After, decompression distillation at vacuum-0.096Mpa, temperature 115 DEG C, reclaim ortho-methylnitrobenzene, continue cycling through chlorination and utilize；Reclaim
Residue after ortho-methylnitrobenzene petroleum ether recrystallization purifying, it is thus achieved that the adjacent nitro benzyl chloride pressed powder of white crystalline.
The present embodiment can realize the production effect of adjacent nitro benzyl chloride purity 99.5% and productivity 84.5% (with actual consumption
Ortho-methylnitrobenzene meter).
Example 1 below 1～20 is that the adjacent nitro benzyl chloride synthesized with embodiment 1～8 is prepared in pyraclostrobin for raw material
The etherification reaction process of mesosome.
Embodiment 11:
The etherification reaction process that the present embodiment relates to is as follows:
To the organic solution of 1-(4-chlorphenyl)-3-pyrazoles alcohol, the prepared adjacent nitro benzyl chloride of embodiment 1, (organic solvent is optional
From halogenated aliphatic hydrocarbon, such as dichloromethane, dichloroethanes, chloroform, carbon tetrachloride etc.), phase transfer catalyst (be selected from halogenation
Ammonium, such as benzyltriethylammoinium chloride, TBAB, benzyl tributyl ammonium bromide, tetrabutylammonium chloride, cetyl front three
Base ammonium bromide etc.) mixed solution in, drip alkali under stirring and (be selected from alkali and alkaline earth metal ions oxide, such as lithia, oxygen
Change sodium, potassium oxide, magnesia and calcium oxide etc.) the aqueous solution, controlling reaction temperature is 0 DEG C, reacts 6 hours, and question response terminates
After, through extraction, recycling design, purifying after drying, obtain etherification product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitro
Benzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 40%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.02:1.05；Adjacent nitro benzyl chloride and phase transfer in organic solution
The mass ratio of catalyst controls at 1:0.01.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 98.0%, productivity
The production effect of 90.0%.
Embodiment 12:
The etherification reaction process that the present embodiment relates to is as follows:
To the organic solution of 1-(4-chlorphenyl)-3-pyrazoles alcohol, the prepared adjacent nitro benzyl chloride of embodiment 2, (organic solvent is optional
From aromatic hydrocarbon, such as chlorine benzene,toluene,xylene etc.), phase transfer catalyst (be selected from polyethylene glycol, such as PEG400, PEG600 and
PEG800 etc.) mixed solution in, drip under stirring alkali (be selected from alkali and alkaline earth metal ions hydroxide, as lithium hydroxide,
NaOH, potassium hydroxide and calcium hydroxide etc.) the aqueous solution, control reaction temperature be 100 DEG C, react 1 hour, question response knot
Shu Hou, through extraction, recycling design, purifying after drying, obtains etherification product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitre
Base benzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 10%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.50:1.6；In organic solution, adjacent nitro benzyl chloride is urged with phase transfer
The mass ratio of agent controls at 1:0.20.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 99.0%, productivity
The production effect of 91.8%.
Embodiment 13:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 3 (has
Machine solvent is selected from acid amides, such as DMF, DMA or NMP etc.) and phase transfer catalyst (be selected from crown ether, such as 18-crown-6,15-crown-5
Deng), it is thus achieved that mixed solution；In container, quickly drip alkali under stirring (be selected from alkali and alkaline earth metal ions carbonate and carbonic acid
Hydrogen salt, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium acid carbonate and saleratus etc.) the aqueous solution, reaction temperature is 20 DEG C, reaction
4 hours time；Reaction solution is sampled, with HPLC detection sampling sample, when wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol
When amount is 0.8%, stop reaction；Regulation solution ph is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherificate product
Product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 20%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.11:1.20；Adjacent nitro benzyl chloride and phase transfer in organic solution
The mass ratio of catalyst controls at 1:0.08.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 98.5%, productivity
The production effect of 92.2%.
Embodiment 14:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 4 (has
Machine solvent is selected from alcohol, such as methyl alcohol, ethanol, propyl alcohol, isopropanol, butanol, the tert-butyl alcohol etc.) and phase transfer catalyst (be selected from four
Fluoboric acid TBuA etc.), it is thus achieved that mixed solution；In container, quickly drip alkali under stirring (be selected from organic base, such as three second
Amine, trimethylamine, N-methyl piperidine and pyridine etc.) the aqueous solution, reaction temperature is 60 DEG C, 2 hours reaction time；To reaction solution
It is sampled, with HPLC detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol is 0.9%, stops reaction；
Regulation solution ph is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-[(N-4-chlorphenyl)-3-
Pyrazoles epoxide methyl] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 30%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.30:1.52；Adjacent nitro benzyl chloride and phase transfer in organic solution
The mass ratio of catalyst controls at 1:0.12.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 98.7%, productivity
The production effect of 92.5%.
Embodiment 15:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 5 (has
Machine solvent is acetone) and phase transfer catalyst (benzyltriethylammoinium chloride), it is thus achieved that mixed solution；Quickly under stirring in container
The aqueous solution of dropping alkali (NaOH), reaction temperature is 40 DEG C, 3 hours reaction time；Reaction solution is sampled, uses
HPLC detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol is 1%, stops reaction；Regulation solution ph
To 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide first
Base] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 35%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.4:1.2；In organic solution, adjacent nitro benzyl chloride is urged with phase transfer
The mass ratio of agent controls at 1:0.1.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 99.5%, productivity
The production effect of 92.7%.
Embodiment 16:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 6 (has
Machine solvent is mass ratio 2:1:1 dichloroethanes, chlorobenzene and the mixture of acetone) and phase transfer catalyst (TBAB),
Obtain mixed solution；Quickly dripping the aqueous solution of alkali (NaOH) under stirring in container, reaction temperature is 50 DEG C, during reaction
Between 4 hours；Reaction solution is sampled, with HPLC detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol
When being 0.5%, stop reaction；Regulation solution ph is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product
2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 25%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.2:1.2；In organic solution, adjacent nitro benzyl chloride is urged with phase transfer
The mass ratio of agent controls at 1:0.15.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 99.3%, productivity
The production effect of 93.0%.
Embodiment 17:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 7 (has
Machine solvent is chlorobenzene) and phase transfer catalyst (benzyltriethylammoinium chloride), it is thus achieved that mixed solution；Quickly under stirring in container
The aqueous solution of dropping alkali (potassium hydroxide), reaction temperature is 50 DEG C, 2 hours reaction time；Reaction solution is sampled, uses
HPLC detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol is 0.6%, stops reaction；Regulation pH value of solution
Value is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide first
Base] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 40%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.50:1.46；Adjacent nitro benzyl chloride and phase transfer in organic solution
The mass ratio of catalyst controls at 1:0.16.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 98.6%, productivity
The production effect of 92.4%.
Embodiment 18:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 8 (has
Machine solvent is dichloroethanes) and phase transfer catalyst (PEG400), it is thus achieved that mixed solution；In container, quickly drip alkali under stirring
The aqueous solution of (NaOH), reaction temperature is 60 DEG C, 3 hours reaction time；Reaction solution is sampled, detects with HPLC
Detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol is 0.8%, stops reaction；Regulation solution ph is extremely
3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl]
Nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 30%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.08:1.30；Adjacent nitro benzyl chloride and phase transfer in organic solution
The mass ratio of catalyst controls at 1:0.10.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 99.0%, productivity
The production effect of 92.5%.
Embodiment 19:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 9 (has
Machine solvent is mass ratio 1:2 dichloroethanes, the mixture of chlorobenzene) and phase transfer catalyst (benzyltriethylammoinium chloride), it is thus achieved that
Mixed solution；Quickly dripping the aqueous solution of alkali (sodium acid carbonate) under stirring in container, reaction temperature is 45 DEG C, the reaction time 4
Hour；Reaction solution is sampled, with HPLC detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol is
When 0.5%, stop reaction；Regulation solution ph is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-
[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 38%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.2:1.15；In organic solution, adjacent nitro benzyl chloride is urged with phase transfer
The mass ratio of agent controls at 1:0.16.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 99.4%, productivity
The production effect of 91.5%.
Embodiment 20:
The etherification reaction process that the present embodiment relates to is as follows:
Add 1-(4-chlorphenyl)-3-pyrazoles alcohol in container, the organic solution of the prepared adjacent nitro benzyl chloride of embodiment 10 (has
Machine solvent is mass ratio 1:1 dichloroethanes and the mixture of acetone) and phase transfer catalyst (benzyltriethylammoinium chloride), it is thus achieved that
Mixed solution；Quickly dripping the aqueous solution of alkali (NaOH) under stirring in container, reaction temperature is 35 DEG C, the reaction time 4
Hour；Reaction solution is sampled, with HPLC detection sampling sample, when the amount of wherein 1-(4-chlorphenyl)-3-pyrazoles alcohol is
When 1%, stop reaction；Regulation solution ph is to 3, then dried through extraction, recycling design, purifying, it is thus achieved that etherification product 2-
[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene.
In said process, the concentration of organic solution of adjacent nitro benzyl chloride is 26%, in mixed solution, and 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:1.24:1.18；Adjacent nitro benzyl chloride and phase transfer in organic solution
The mass ratio of catalyst controls at 1:0.06.
The present embodiment can realize 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] nitrobenzene 98.7%, productivity
The production effect of 91.8%.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every depends on
Any simple modification of being made above example according to the technical spirit of the present invention, equivalent variations, each fall within the protection of the present invention
Within the scope of.
Claims (10)
1. the synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride, it is characterised in that: comprise the following steps:
A, in ortho-methylnitrobenzene, add catalyst, add thermal agitation, and be slowly introducing chlorine, after question response terminates, reclaim adjacent nitre
Base toluene, it is thus achieved that adjacent nitro benzyl chloride；
B, neighbour's nitro benzyl chloride and 1-(4-chlorphenyl)-3-pyrazoles alcohol are carried out etherification reaction, it is thus achieved that 2-[(N-4-chlorphenyl)-
3-pyrazoles epoxide methyl] nitrobenzene.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levy and be: in described step A, count in mass ratio, ortho-methylnitrobenzene: catalyst=1:(0.01～0.2).
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levy and be: in described step A, catalyst includes: the activated carbon of 50～200 mesh, bromine, iodine, azodiisobutyronitrile, idol
One or more in the different heptonitrile of nitrogen two, phosphorus pentachloride, phosphorus trichloride, benzoyl peroxide, hyperis, DMF
Mixture.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levying and be: in described step A, heating and temperature control is at 100～180 DEG C, and stir speed (S.S.) controls at >=200r/min.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levy and be: in described step A, in course of reaction, use gas-chromatography to follow the tracks of byproduct of reaction neighbour's nitro benzal chloride and reach 4
～6%, stop reaction.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levying and be: in described step A, after reaction terminates, at vacuum is less than 120 DEG C higher than-0.095Mpa, temperature, decompression is steamed
Evaporate, reclaim ortho-methylnitrobenzene.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levy and be: in described step A, reclaim the residue petroleum ether recrystallization purifying after ortho-methylnitrobenzene, it is thus achieved that white crystal
The adjacent nitro benzyl chloride pressed powder of shape.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 1, it is special
Levy and be: in described step B, etherification reaction includes: the adjacent nitroxyl chloride prepared to 1-(4-chlorphenyl)-3-pyrazoles alcohol, step A
Changing in the mixed solution of the organic solution of benzyl, phase transfer catalyst, the lower aqueous solution dripping alkali of stirring, controlling reaction temperature is 0
～100 DEG C, react 1～6 hour, after question response terminates, through extraction, recycling design, purifying after drying, obtain 2-[(N-4-chlorobenzene
Base)-3-pyrazoles epoxide methyl] nitrobenzene.
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 8, it is special
Levy and be: the concentration of organic solution of described adjacent nitro benzyl chloride is 10～40%, in described mixed solution, 1-(4-chlorphenyl)-3-
Pyrazoles alcohol, adjacent nitro benzyl chloride, the mol ratio of alkali are 1.0:(1.02～1.50): (1.05～1.6).
A kind of synthetic method being prepared pyraclostrobin intermediate by adjacent nitro benzyl chloride the most according to claim 8, it is special
Levy and be: in described organic solution, adjacent nitro benzyl chloride controls at 1:(0.01～0.20 with the mass ratio of phase transfer catalyst).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883178A (en) * | 2017-04-13 | 2017-06-23 | 安徽广信农化股份有限公司 | The synthesis technique of 2 [(chlorphenyls of the N 4) yloxymethyl of 1H pyrazoles 3] nitrobenzene |
| CN106928145A (en) * | 2017-04-17 | 2017-07-07 | 安徽广信农化股份有限公司 | A kind of synthesis system of pyraclostrobin Intermediate nitro benzene |
| CN109651111A (en) * | 2018-12-25 | 2019-04-19 | 新昌县泰如科技有限公司 | A kind of preparation method of p-chlorobenzaldehyde |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154692A (en) * | 1994-07-06 | 1997-07-16 | 巴斯福股份公司 | 2-[(dihydro) pyrazolyl-3'-oxymethyene]-anilides, prepn. method and use thereof |
| CN104211641A (en) * | 2014-08-19 | 2014-12-17 | 山东康乔生物科技有限公司 | Synthetic technology for pyraclostrobin |
| CN104370746A (en) * | 2014-10-29 | 2015-02-25 | 河南师范大学 | Cost-saving preparation method of p-nitrobenzyl alcohol |
-
2016
- 2016-06-07 CN CN201610396769.9A patent/CN105859625A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154692A (en) * | 1994-07-06 | 1997-07-16 | 巴斯福股份公司 | 2-[(dihydro) pyrazolyl-3'-oxymethyene]-anilides, prepn. method and use thereof |
| CN104211641A (en) * | 2014-08-19 | 2014-12-17 | 山东康乔生物科技有限公司 | Synthetic technology for pyraclostrobin |
| CN104370746A (en) * | 2014-10-29 | 2015-02-25 | 河南师范大学 | Cost-saving preparation method of p-nitrobenzyl alcohol |
Non-Patent Citations (3)
| Title |
|---|
| 刘鸿: "邻苯二甲醛合成新工艺", 《精细化工中间体》 * |
| 李和平: "《含氯精细化学品》", 31 August 2010 * |
| 蒋笃孝等: "邻氨基苄胺的新法合成与表征", 《化学试剂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883178A (en) * | 2017-04-13 | 2017-06-23 | 安徽广信农化股份有限公司 | The synthesis technique of 2 [(chlorphenyls of the N 4) yloxymethyl of 1H pyrazoles 3] nitrobenzene |
| CN106928145A (en) * | 2017-04-17 | 2017-07-07 | 安徽广信农化股份有限公司 | A kind of synthesis system of pyraclostrobin Intermediate nitro benzene |
| CN109651111A (en) * | 2018-12-25 | 2019-04-19 | 新昌县泰如科技有限公司 | A kind of preparation method of p-chlorobenzaldehyde |
| CN109651111B (en) * | 2018-12-25 | 2021-11-12 | 新昌县泰如科技有限公司 | Preparation method of p-chlorobenzaldehyde |
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