Patents

Manufacturing method of proPiconazole

Abstract
CN102225935B
The invention discloses a manufacturing method of proPiconazole. The manufacturing method
China
comprises that 2,4-dichloroacetophenone and 1,2-pentanediol undergo a cyclization reaction, and
then bromine and the reaction products of the cyclization reaction undergo a bromination reaction to
form 2-bromomethyl-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane. The manufacturing method is Download PDF Find Prior Art Similar
characterized in that solid heteropolyacid catalysts are utilized in the cyclization reaction, and are
filtered and recycled after the cyclization reaction is finished; then the bromination reaction is Other languages: Chinese
caused and the 2-bromomethyl-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane, 1,2,4-triazole and
Inventor: 刘在成, 张春华, 范丰梅, 李金艳
potassium carbonate undergo a condensation reaction to form the proPiconazole after the
bromination reaction is finished. Through the manufacturing method, new impurities which can be Current Assignee : SHANDONG WEIFANG SHUANGXING
introduced because catalysts take part in a bromination reaction are reduced. In the invention, PESTICIDES CO Ltd
because a potassium triazole preparation process, a condensation reaction process and a solvent
removing process are carried out simultaneously during a condensation reaction, problems of long
Worldwide applications
reaction time and adhesion of 1,2,4-triazole on a kettle are solved, and a reaction time and a
production cost are reduced. 2011 CN

Images (1) Application CN201110106714.7A events

2011-04-27 Application filed by SHANDONG WEIFANG

SHUANGXING PESTICIDES CO Ltd

2011-04-27 Priority to CN201110106714.7A

2011-10-26 Publication of CN102225935A

2014-04-02 Application granted

2014-04-02 Publication of CN102225935B

Classifications Status Active

2031-04-27 Anticipated expiration

Y02P20/584 Recycling of catalysts

Info: Patent citations (3), Non-patent citations (2), Cited by (8),

Legal events, Similar documents, Priority and Related
Applications

External links: Espacenet, Global Dossier, Discuss

Claims (2) Hide Dependent

1. the production method of a propiconazole, adopt 2, 4-dichloroacetophenone and 1, 2-pentanediol carries out cyclisation, then carry out bromination with bromine and
generate 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane, it is characterized in that: during described cyclization, add solid heteropoly acid class
catalyzer, described solid heteropoly acid class catalyzer is phospho-molybdic acid, phospho-wolframic acid, described 2, 4-dichloroacetophenone, 1, 2-pentanediol, the
ratio of the amount of solid heteropoly acid class catalyzer is 1:1.07～1.20:0.02～0.1, described cyclization finishes rear described catalyzer to be carried out to filtered
and recycled, then carry out bromination reaction, described bromination reaction temperature is 35～37 ℃, and bromine dropwise adding speed is 18～20Kg/h, after
bromination reaction finishes, keep 0.3～0.5Mpa to stir 1～2h, reclaim bromize hydrogen gas, desolventizing obtains 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-
bis-Evil pentane, described bromination reaction completes afterwards described 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane and 1, 2, 4-triazole,
salt of wormwood carries out condensation reaction and prepares described propiconazole, described condensation reaction is with salt of wormwood and 1, 2, 4-
triazole is done reactant, with 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, the dimethyl sulfoxide (DMSO) that 3-bis-Evil pentane quality is 2～5 times is solvent, at
140～180 ℃, under the continuous negative pressure condition of-0.02～-0.08MPa, desolventizing reaction 4～9h, after reaction, add 2-brooethyl-(2, 4-dichlorophenyl)-4-
propyl group-1, the dissolve with methanol crude product that 3-bis-Evil pentane quality is 4～6 times, remove by filter bromination sylvite, separating methanol obtains
the thick product of propiconazole, after being added to oxidation inhibitor four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the thick
product of described propiconazole adopt the molecular distillation of 30～200Pa to obtain described propiconazole product.

2. the production method of a kind of propiconazole as claimed in claim 1, it is characterized in that: described 2-brooethyl-(2,4 dichloro benzene base)-4-propyl group-
1,3-bis-Evil pentane, described 1, the ratio of the amount of 2,4-triazole and described salt of wormwood is 1:1.2～1.5:1.2～1.5.

Description

A kind of production method of propiconazole

Technical field

The present invention relates to technical field of pesticide, relate in particular to a kind of production method of propiconazole.

Background technology

A kind of SSF109 class systemic fungicide of Wocosin 50TK (proPiconazole) Shi You Switzerland Qi Bayijia base company exploitation, the chemical name of Wocosin
50TK: along anti-1 one " 2 one (2; 4 one dichlorophenyls) one 4 one propyl group 1; 3 dioxolane one 2 one ylmethyls) 1H 1; 2; 4 one triazoles, be sterol demethylation
preparation, there is wide spectrum, interior absorption.Former medicine outward appearance is faint yellow sticky silk fabric liquid, 180 ℃ of boiling points (13.3Pa),
vapour pressure (ZOoC) 0.133mPa, proportion 1.279/cm during 1.5468,20 ℃ of refractive index 3.In water, solubleness is 110mg/L, is soluble in organic solvent.320 ℃
following stable, more stable to light, is hydrolyzed not obvious.More stable in acid, alkaline medium, corroding metal not.Package stability 3 years.Former medicine is to
rat acute LD50 of passing through mouth >1517mg/kg, acute through skin LD50>4000mg/kg.Rabbit eyes and skin are had to slight hormesis.

Propiconazole affects the formation of fungal cell wall by hindering the biosynthesizing of fungi ergosterol; most fungal diseases to damage to crops growth all have
good prevention effect; there is certain plant growth regulating activity simultaneously; by suppressing the synthetic of plant materials inner gibberellin; eliminate plant
apical dominance; there is volume increase, precocity, the several functions such as resistant to lodging; it is a kind of interior absorption triazole bactericidal agent with
provide protection and therapeutic action; can be absorbed by root, stem, leaf portion, and can be very soon in plant on conduction.Wocosin 50TK can be prevented and
treated the microbial diseases of cause of disease such as ascus capsule bacterium, basidiomycetes and imperfect fungi, as take-all, root rot, Powdery Mildew, rice
bakanae disease etc. are had to good prevention effect, to uncinula necator, anthrax, the leaf spot of peanut and banana etc. also has preventive effect, also can prevent
and treat the multiple fungal diseases such as leaf blight, rust, the black disease of raw meat.Its disperse means are used for the control of plastic greenhouse
vegetables, melon, fruit disease evil, safe ready, and the lasting period is for 3 months.Orchard crop storage anti-corrosive fresh-keeping is also had to positive effect, the
particularly storage of the main fruit such as citrus, apple kind.

Currently used technique be mainly with intermediate 2,4 one dichloroacetophenones, pentanediol, bromine, triazole etc. for main raw material, through cyclisation,
bromination, condensation, purification, form, be total to four-step reaction, total recovery exists) 70% left and right, former medicine content 95%, light yellow viscous
liquid.

In the general production method adopting, there is following shortcoming at present: after bromination reaction, need to wash and remove impurity, reversible reaction
easily occurs during washing; Synthesizing triazazole sylvite the reaction time is long, is difficult for dehydration, and material is clamminess; Long at condensation
reaction time, reaction after washing by product is difficult for reclaiming, and produces a large amount of waste water; Nitrated salify when product is purified, not easy
to operate, quality product fluctuation is large; During high vacuum rectification, there is partial oxidation, the refining yield of impact.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of bromination condensation without the production method of the propiconazole that waste water,
product are easily purified, refining yield is high.

For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of production method of propiconazole, adopt 2, 4-
dichloroacetophenone and 1, 2-pentanediol carries out cyclisation, then carry out bromination with bromine and generate 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-
1, 3-bis-Evil pentane, during described cyclization, add solid heteropoly acid class catalyzer, described cyclization finishes rear described catalyzer to be carried out to
filtered and recycled, then carry out bromination reaction, described bromination reaction completes afterwards described 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl
group-1, 3-bis-Evil pentane and 1, 2, 4-triazole, salt of wormwood carries out condensation reaction and prepares described propiconazole.

Before bromination reaction, filtering recovering catalyst, reduces because catalyzer participates in bromination reaction and introduces new impurity, and the catalyzer
after recovery can recycle.

During cyclisation, reaction formula is as follows:

As preferred technical scheme, described solid heteropoly acid class catalyzer is preferably phospho-molybdic acid, phospho-wolframic acid, described 2,4 dichloro
benzene ethyl ketone, 1, and the ratio of the amount of 2-pentanediol, solid heteropoly acid class catalyzer is 1:1.07～1.20:0.02～0.1.

As preferred technical scheme, described bromination reaction temperature is 35～37 ℃, and bromine dropwise adding speed is 18～20Kg/h, after bromination reaction
finishes, keep 0.3～0.5Mpa to stir 1～2h, reclaim bromize hydrogen gas, desolventizing obtains 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane,
described bromination reaction adopts P-TOLUENE SULFO ACID 99 to make catalyzer, accurate measurement bromine consumption, finally reach and improve
bromination reaction yield, do not wash the object of producing high-quality bromide, bromide transformation efficiency is up to 98%, bromide content is more than 98%,
after bromination, adopt micro-negative pressure to reclaim hydrogen bromide, solve hydrogen bromide and entered the reluctant problem of waste water, to reducing
environmental pollution, reduce discharge of wastewater and played positive effect.

Bromination reaction formula is as follows:

As preferred technical scheme, described 2-brooethyl-(2,4 dichloro benzene base)-4-propyl group-1,3-bis-Evil pentane, described 1,2, the ratio of the amount of 4-triazole
and described salt of wormwood is 1:1.2～1.5:1.2～1.5.

As the improvement to technique scheme, described condensation reaction is with salt of wormwood and 1, 2, 4-triazole is done reactant, with 2-brooethyl-(2, 4-
dichlorophenyl)-4-propyl group-1, the dimethyl sulfoxide (DMSO) that 3-bis-Evil pentane quality is 2～5 times is solvent, at 140～180 ℃, under the continuous negative
pressure condition of-0.02～-0.08MPa, desolventizing reaction 4～9h, , after reaction, add 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, the dissolve with methanol
crude product that 3-bis-Evil pentane quality is 4～6 times, cross filtering Potassium Bromide salt, separating methanol obtains the thick product of propiconazole,
triazole potassium preparation like this, condensation reaction and desolventizing three step process carry out simultaneously, old explained hereafter triazole potassium
and condensation reaction proceed step by step long reaction time have been solved, triazole potassium material is clamminess, the problem of sticky still, technique is
simple, easy to operate, shortened reaction time, to reducing costs, there is significant economic benefit, condensation again after stepwise reaction production triazole
potassium, need 20～26h reaction, after adopting technique of the present invention, total reaction time shortens to 6～8h, adopt dissolve with methanol after product
condensation reaction after, remove by filter bromination sylvite, the treatment process of separating methanol again, can solve after washing extraction again causes by
product to be difficult to reclaim and the high problem of condensation waste water processing costs, saved solvent and wastewater treatment expense for extraction,
reclaim by product simultaneously and can be used as product sale, there is distinct economic and environmental benefit.

The reaction formula of condensation is as follows:

As the improvement to technique scheme, the thick product of described propiconazole is added and carries out high vacuum after oxidation inhibitor and purify and
obtain described propiconazole product, add oxidation inhibitor as product stablizer, reduce the loss of Wocosin 50TK high temperature oxidation, improved refining yield
and product quality.

As preferred technical scheme, described high vacuum purification is to adopt the molecular distillation of 30～200Pa 16～20 hours, has reduced the time oxidational
losses of high temperature rectifying, avoids using nitric acid salify, the solvent loss expense that then sodium hydroxide alkaline hydrolysis WATER-WASHING METHOD
causes.

As preferred technical scheme, described oxidation inhibitor is four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester preferably.

A kind of production instance of prior art below:

In reactor, add 2, 4-dichloroacetophenone 210Kg, under solvent hexanaphthene 800L and catalyzer p-methyl benzenesulfonic acid 10～20Kg condition with 1 of 1126Kg,
2-pentanediol back flow reaction, constantly divide and anhydrate, obtain the cyclohexane solution containing cyclisation thing, when wherein 2, 4-dichloroacetophenone
mass content is lower than 1.0% rear (liquid chromatography, L-150ITlln～250ITlln, T-40 ℃, wavelength 205nm～220nm, moving phase is a certain proportion of methyl
alcohol and water mixed solvent), cool to 20～80 ℃, filtering recovering catalyst, within standing minute, go excessive 1, 2-pentanediol.Lift temperature to after 50 ℃,
add bromine and cause, cooling, drips bromine at about 36 ℃, drip off rear insulation 0.5～3.0 hour, add and be washed to neutrality, pressure reducing and steaming
hexanaphthene, bromide 2-brooethyl-(2,4 dichloro benzene base)-4-propyl group-1 of high-content, 3-bis-Evil pentane will be obtained.

Use tosic acid to do catalyzer bromination, continuous five batch reaction results are as table 1, and following per-cent is mass percent:

Batch Ketone Ketone monobromo thing % Ketone dibromo thing % Cyclisation thing % Bromide % 1 0.63 2.01 2.00 0.13 93.23
2 0.54 2.05 2.34 0.27 92.88 3 0.75 3.03 1.97 0.33 91.03
4 0.80 3.22 2.37 0.53 92.07 5 0.62 2.31 1.77 0.09 93.58

Table 1.

Filtered and recycled after the cyclisation of use solid heteropoly acid class catalyzer, the continuous five batch reaction results of bromination are as table 2 afterwards,
and following per-cent is mass percent:

Batch Ketone Ketone monobromo thing % Ketone dibromo thing % Cyclisation thing % Bromide % 1 0.09 0.33 0.26 0.11 98.22
2 0.17 0.51 0.14 0.22 98.02 3 0.26 0.44 0.12 0.31 97.93
4 0.55 0.23 0.34 0.10 98.30 5 0.43 0.11 0.46 0.09 98.44

Table 2.

The result of table 1 and table 2 shows: use filtered and recycled after the cyclisation of solid heteropoly acid class catalyzer, and bromination afterwards, bromination
stability improves, and bromide transformation efficiency can reach more than 98%.

Prior art first produce triazole first the more continuous five batch reaction results of condensation as table 3:

Batch Process time Content in crude product Condensation yield 1 19.5 76.5% 83.1%
2 20.2 74.6% 80.5% 3 18．8 77.3% 79.7%
4 12 75.5% 82.6% 5 21.6 77.5% 80.2%

Table 3.

Add solid heteropoly acid class catalyzer, the preparation of triazole potassium, condensation, desolventizing carry out simultaneously, and continuous five batch
reaction results are as table 4:

Batch Process time Content in crude product Condensation yield 1 8.2 80.5% 90.4%
2 9.1 82.5% 91.2% 3 8.6 83.4% 88.9%
4 8.8 82.9% 91.3% 5 9.5 80.7% 90.8%

Table 4.

The result of table 3 and table 4 shows: add solid heteropoly acid class catalyzer, the continuous production of condensation reaction can be shortened the process time
more than 10 hours, and content in crude product yield obviously improves.

Add oxidation inhibitor, the continuous five batches of results of high vacuum rectification, as table 5:

Batch Fine work yield Fine work content Product Status 1 85.3% 98.1% Faint yellow transparent thick liquid
2 86.2% 97.5% Faint yellow transparent thick liquid 3 86.0% 97.8% Faint yellow transparent thick liquid
4 85.8% 98.3% Faint yellow transparent thick liquid 5 87.5% 98.2% Faint yellow transparent thick liquid
Table 5.

Do not add the continuous five batches of results of oxidation inhibitor high vacuum rectification, as table 6:

Batch Fine work yield Fine work content Product Status 1 82.2% 95.5% The translucent thick liquid of deep yellow
2 83.5% 95.1% The translucent thick liquid of deep yellow 3 82.7% 94.8% The translucent thick liquid of deep yellow
4 81.9% 95.6% The translucent thick liquid of deep yellow 5 83.1% 95.3% The translucent thick liquid of deep yellow

Table 6.

The continuous five batches of results of nitrated salify, as table 7:

Batch Fine work yield Fine work content Product Status 1 73.5% 94.4% Reddish-brown thick liquid
2 74.2% 95.0% Reddish-brown thick liquid 3 71.3% 93.8% Reddish-brown thick liquid
4 71.9% 95.1% Reddish-brown thick liquid 5 72.1% 93.9% Reddish-brown thick liquid

Table 7.

The result of table 5, table 6 and table 7 shows: adopt the technique of vacuum distilling, the yield of product is not had to too much influence, and nitric acid salifying
process handicraft product appearance poor, content, yield are lower, and consumes about 400L during every batch of toluene distillation.Add oxidation inhibitor
distillation, product content, yield obviously improves.

Owing to having adopted technique scheme, a kind of production method of propiconazole, adopt 2, 4-dichloroacetophenone and 1, 2-pentanediol carries out cyclisation,
then carry out bromination with bromine and generate 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane, during described cyclization, add solid
heteropoly acid class catalyzer, described cyclization finishes rear described catalyzer to be carried out to filtered and recycled, then carry out bromination reaction,
described bromination reaction completes afterwards described 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane and 1, 2, 4-triazole, salt of
wormwood carries out condensation reaction and prepares described propiconazole, before bromination reaction, catalyzer is added in filtration, minimizing is introduced
new impurity because catalyzer participates in bromination reaction, accurate measurement bromine consumption, finally reach and improve bromination reaction yield,
do not wash the object of producing high-quality bromide, bromide transformation efficiency is up to 98%, bromide content is more than 98%, after bromination, adopt
micro-negative pressure to reclaim hydrogen bromide, solve hydrogen bromide and entered the reluctant problem of waste water, to reducing environmental pollution,
reduce discharge of wastewater and played positive effect, when carrying out condensation reaction, adopt the preparation of triazole potassium, condensation reaction,
the method that desolventizing carries out simultaneously, solved long reaction time, the problem of the sticky still of triazole potassium, shortened the reaction times,
effectively reduce production cost, after condensation, adopt the method for dissolve with methanol filtered and recycled bromination sylvite, after having solved
washing, toluene extracts, solvent load is large, the unmanageable problem of waste water, raising to the yield of product and quality, positively effect has been played in
the reduction of production cost, and environmental protection more, when purifying, product molecular distillation adds oxidation inhibitor as product stablizer, reduce
the loss of Wocosin 50TK high temperature oxidation, refining yield and product quality have been improved.

Accompanying drawing explanation

Accompanying drawing is the collection of illustrative plates of system when bromination reaction finishes in Wocosin 50TK product building-up process of the present
invention;

Wherein, bromide appearance time is: 14.365～15.798min, cyclisation thing appearance time is: 12.232～13.565min, ketonates appearance time is: 2.89Omin.

Embodiment

Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of
the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present
invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range
equally.

Embodiment mono-:

According to the ratio 2 of amount of substance, 4-dichloroacetophenone: 1, 2-pentanediol: the ratio that catalyzer phospho-molybdic acid is 1:1.07:0.02, by 2, 4-
dichloroacetophenone and 1, 2-pentanediol the effect of catalyzer phospho-molybdic acid next time stream carry out cyclization, now temperature is 86 ℃, reaction
times is 8 hours, after cyclization finishes, after filtering recovering catalyst phospho-molybdic acid, carry out bromination reaction, described bromination reaction
temperature is 35 ℃, and bromine dropwise adding speed is 18Kg/h, after bromination reaction finishes, keep 0.3Mpa to stir 1h, reclaim bromize hydrogen gas,
desolventizing obtains 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane, in the present invention, synthetic cyclisation thing is first reclaimed and
removes catalyzer phospho-molybdic acid, carry out again bromination reaction, more than bromide yield can reach 98%wt, bromide quality content is more than 98%,
minimizing produces monobromide and the dibromide of ketone because cyclisation thing decomposes again, finally reach the object that improves bromide quality.

Afterwards by described 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane and 1, 2, 4-triazole, salt of wormwood carries out condensation reaction,
described 2, 4-dichloroacetophenone and 1, 2, 4-triazole, the amount of substance of salt of wormwood compares 1:1.35:1.35, with 2-brooethyl-(2, 4-dichlorophenyl)-4-
propyl group-1, the dimethyl sulfoxide (DMSO) that 3-bis-Evil pentane quality is 2 times is solvent, at 140 ℃, under the continuous negative pressure condition of-
0.02MPa, desolventizing reaction 4h, after reaction, add 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, the dissolve with methanol crude product that 3-bis-Evil
pentane quality is 4 times, cross filtering Potassium Bromide salt, separating methanol obtains the thick product of propiconazole, add afterwards oxidation inhibitor four
[methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, in vacuum tightness, be that under 30Pa, molecular distillation obtains product
propiconazole for 16 hours.

Embodiment bis-:

According to the ratio 2 of amount of substance, 4-dichloroacetophenone: 1, 2-pentanediol: the ratio that catalyzer phospho-molybdic acid is 1:1.13:0.06, by 2, 4-
dichloroacetophenone and 1, 2-pentanediol the effect of catalyzer phospho-molybdic acid next time stream carry out cyclization, now temperature is 83～88 ℃, reaction
times is 8 hours, after cyclization finishes, after filtering recovering catalyst phospho-molybdic acid, carry out bromination reaction, described bromination reaction
temperature is 36 ℃, and bromine dropwise adding speed is 19Kg/h, after bromination reaction finishes, keep 0.4Mpa to stir 1.5h, reclaim bromize hydrogen gas,
desolventizing obtains 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane, in the present invention, synthetic cyclisation thing is first reclaimed and
removes catalyzer phospho-molybdic acid, carry out again bromination reaction, more than bromide yield can reach 98%wt, bromide quality content is more than 98%,
minimizing produces monobromide and the dibromide of ketone because cyclisation thing decomposes again, finally reach the object that improves bromide quality.

Afterwards by described 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane and 1, 2, 4-triazole, salt of wormwood carries out condensation reaction,
described 2, 4-dichloroacetophenone and 1, 2, 4-triazole, the amount of substance of salt of wormwood compares 1:1.45:1.45, with 2-brooethyl-(2, 4-dichlorophenyl)-4-
propyl group-1, the dimethyl sulfoxide (DMSO) that 3-bis-Evil pentane quality is 4 times is solvent, at 160 ℃, under the continuous negative pressure condition of-
0.04MPa, desolventizing reaction 5h, after reaction, add 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, the dissolve with methanol crude product that 3-bis-Evil
pentane quality is 5 times, cross filtering Potassium Bromide salt, separating methanol obtains the thick product of propiconazole, add afterwards oxidation inhibitor four
[methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, in vacuum tightness, be that under 140Pa, molecular distillation obtains product
propiconazole for 18 hours.

Embodiment tri-:

According to the ratio 2 of amount of substance, 4-dichloroacetophenone: 1, 2-pentanediol: the ratio that phosphate-tungstic acid is 1:1.20:0.1, by 2, 4-
dichloroacetophenone and 1, 2-pentanediol phosphate-tungstic acid effect next time stream carry out cyclization, now temperature is 85～89 ℃, reaction times is 4～8
hours, after cyclization finishes, after filtering recovering catalyst phospho-molybdic acid, carry out bromination reaction, described bromination reaction temperature is
37 ℃, and bromine dropwise adding speed is 20Kg/h, after bromination reaction finishes, keep 0.5Mpa to stir 2h, reclaim bromize hydrogen gas, desolventizing obtains 2-
brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane, in the present invention, synthetic cyclisation thing is first reclaimed and removes catalyzer phospho-
molybdic acid, carry out again bromination reaction, more than bromide yield can reach 98%wt, bromide quality content is more than 98%, minimizing produces
monobromide and the dibromide of ketone because cyclisation thing decomposes again, finally reach the object that improves bromide quality.

Afterwards by described 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, 3-bis-Evil pentane and 1, 2, 4-triazole, salt of wormwood carries out condensation reaction,
described 2, 4-dichloroacetophenone and 1, 2, 4-triazole, the amount of substance of salt of wormwood compares 1:1.5:1.5, with 2-brooethyl-(2, 4-dichlorophenyl)-4-
propyl group-1, the dimethyl sulfoxide (DMSO) that 3-bis-Evil pentane quality is 5 times is solvent, at 180 ℃, under the continuous negative pressure condition of-
0.08MPa, desolventizing reaction 6～9h, after reaction, add 2-brooethyl-(2, 4-dichlorophenyl)-4-propyl group-1, the methyl alcohol that 3-bis-Evil pentane quality is 6 times,
dissolve crude product, cross filtering Potassium Bromide salt, separating methanol obtains the thick product of propiconazole, add afterwards oxidation inhibitor four
[methyl-β-(3 that account for quality of material 0.2～1%, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, in vacuum tightness, it is molecular
distillation 20 hours under 200Pa, temperature reaches 185 ℃, fraction in starting to collect, collect Wocosin 50TK fine work in 185～205 ℃ of fractions, distillation again
after front and back fraction is concentrated 7～10 batches, obtain product propiconazole, distillation residue are concentrated and are sent to burning.

More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry
should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just
illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and
modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending
claims and equivalent thereof .

Patent Citations (3)

Publication number Priority date Publication date Assignee Title

US4925842A * 1986-03-06 1990-05-15 Ciba-Geigy Microbicides

Corporation

US4940799A * 1987-07-20 1990-07-10 Ciba-Geigy Preparation of the diastereomeric mixture 2R,4S-1-[2-(2,4-dichlorophenyl)-4-n-propyl-

Corporation 1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole

CN101781290A * 2010-03-19 2010-07-21 利民化工股份有限 New method for producing propiconazole

公司

Family To Family Citations

* Cited by examiner, † Cited by third party

Non-Patent Citations (2)

Title

李贵贤，等.Keggin型多元杂多酸催化合成苯乙酮环乙二缩酮.《分子催化》.2010,第24卷(第02期),129-134. *

王珊,等.丙环唑的合成及表征.《应用化工》.2009,第38卷(第04期),517-519. *

* Cited by examiner, † Cited by third party

Cited By (8)

Publication number Priority date Publication date Assignee Title

Family To Family Citations

CN102584802A * 2012-01-07 2012-07-18 浙江禾本科技有限公司 Preparation method for propiconazole serving as bactericide

CN102775395A * 2012-07-12 2012-11-14 江苏七洲绿色化工股份有限公 Preparation method of propiconazole and propiconazole intermediate
司

CN109879862A * 2019-03-30 2019-06-14 长沙鑫本药业有限公司 A kind of synthesis technology of propiconazole

CN110127727B * 2019-05-06 2021-08-13 浙江禾本科技股份有限公司 Production process of byproduct potassium bromide in propiconazole
synthesis

CN110105341B * 2019-05-10 2020-10-09 浙江禾本科技股份有限公司 Recycling process of excessive triazole potassium in propiconazole
synthesis

CN110105322B * 2019-05-31 2020-08-07 浙江禾本科技股份有限公司 Improved process for ketal reaction in propiconazole synthesis

CN113444077A * 2020-03-27 2021-09-28 江苏扬农化工股份有限公司 Process method for synthesizing propiconazole

CN114671860B * 2022-04-22 2023-08-15 浙江禾本科技股份有限公司 Purification method of high-content propiconazole

 * Cited by examiner, † Cited by third party, ‡ Family to family citation

Similar Documents

Publication Publication Date Title

CN102225935B 2014-04-02 Manufacturing method of proPiconazole

CN101781290B 2011-11-09 New method for producing propiconazole

EP1858903B1 2008-10-08 Diarylphenoxy aluminum compounds

CN102060850B 2012-12-05 Preparing and refining methods of difenoconazole

CN101899040B 2012-07-11 Preparation process of difenoconazole

EP2059493B1 2016-11-16 Recovery of phenol ligands during the production of isopulegol

CN101624357A 2010-01-13 Method for producing 2-hydroxyl-4-methoxybenzophenone-5-sulfonic acid

CN112707799A 2021-04-27 Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer

CN102898422A 2013-01-30 Method for preparing difenoconazole

CN102584740B 2013-11-27 Synthesis method for 4-methyl-5-(2-ethoxyl)-thiazole

CN113444077A 2021-09-28 Process method for synthesizing propiconazole

CN103130657A 2013-06-05 Synthetic method of 2-chloro-4-aminophenol

CN102432600A 2012-05-02 Purification method of difenoconazole

CN112321434A 2021-02-05 Preparation method of salicylate green synthesis process

CN109232452B 2020-11-24 Preparation method of high-quality prothioconazole

CN106699522A 2017-05-24 Production process of high-quality trimethyl orthoacetate

CN115197056A 2022-10-18 Method for preparing 3, 5-dichloro-2-pentanone by one-pot method

CN102964252A 2013-03-13 Technology for preparing propyl gallate by utilizing mixed catalyst

CN112645815A 2021-04-13 Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent

CN111269190A 2020-06-12 Method for synthesizing triazoline thioketone compound by one-pot method

CN111116507A 2020-05-08 Synthetic process of indoxacarb

CN109833916B 2021-08-27 Composite catalyst for propiconazole cyclization reaction and preparation method thereof

CN110105322A 2019-08-09 The improvement technique of ketal reaction in a kind of synthesis of propiconazole

CN110606801A 2019-12-24 Method for continuously preparing vanillin and syringaldehyde

CN113896653B 2023-10-27 Synthesis and purification method of 2-chloro-6-fluorobenzonitrile

Priority And Related Applications

Priority Applications (1)

Application Priority date Filing date Title

CN201110106714.7A 2011-04-27 2011-04-27 Manufacturing method of proPiconazole

Applications Claiming Priority (1)

Application Filing date Title

CN201110106714.7A 2011-04-27 Manufacturing method of proPiconazole

Legal Events

Date Code Title Description

2011-10-26 C06 Publication

2011-10-26 PB01 Publication

2011-12-07 C10 Entry into substantive examination

2011-12-07 SE01 Entry into force of request for substantive examination

2014-04-02 C14 Grant of patent or utility model

2014-04-02 GR01 Patent grant

About Send Feedback Public Datasets Terms Privacy Policy Help