CN104402837B - A kind of preparation method of herbicide hexazinone - Google Patents
A kind of preparation method of herbicide hexazinone Download PDFInfo
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- CN104402837B CN104402837B CN201410806020.8A CN201410806020A CN104402837B CN 104402837 B CN104402837 B CN 104402837B CN 201410806020 A CN201410806020 A CN 201410806020A CN 104402837 B CN104402837 B CN 104402837B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract
The present invention is directed to existing herbicide hexazinone preparation method exists side reaction and problem that side reaction is difficult to suppress; disclose a kind of new hexazinone preparation method; including: the first step; N; the N dimethyl N ' methyl N ' alkoxy acyl guanidine and cyclohexylamine reaction, N, N dimethyl N ' methyl N ' ester group on alkoxy acyl guanidine is by amine solution; generate intermediate N, N dimethyl N ' methyl N ' cyclohexylamine acylguanidines；Second step, this intermediate N, N dimethyl N ' methyl N ' cyclohexylamine acylguanidines with phosgene under acid binding agent effect, intermediate N, N dimethyl N ' methyl N ' cyclohexylamine acylguanidines cyclization, generates hexazinone；3rd step, cools to room temperature, filtering and washing by the mixture that second step reacts, and mother solution washes with water, and reduce pressure precipitation, adds petroleum ether crystallization, filters, dries, obtain hexazinone crystal.Preparation method step of the present invention is simple, occurs without side reaction, and yield is high, uses this method to prepare hexazinone low cost, and can obtain high-purity hexazinone.
Description
Technical field
The invention belongs to herbicide technology field, be specifically related to the preparation method of a kind of herbicide hexazinone.
Background technology
Hexazinone is contact three pyridines after a kind of interior suction selectivity, the bud developed by du pont company for 1974
Type herbicides, owing to it is strong to the lethality of weeds and shrub, obtains in many countries such as the U.S., Australia, New Zealand
To being widely applied, it it is a kind of eco-friendly herbicide of high-efficiency low-toxicity.
The domestic and international synthetic method of hexazinone is referring especially to United States Patent (USP) US4178448, US4150225 at present, its synthesis three
Piperazine ring all uses highly basic to exchange with the dimethylamino of hexazinone as cyclization catalyst, the alcohol that such cyclization generates, and generates
Cyclization side reaction product, affects yield.This two patents is pointed out: suppress this side reaction by two kinds of approach: one is to be passed through
Dimethylamine suppression dimethylamine more than equivalent comes off；Another kind is that the alcohol that reaction is generated removes in time, prevents side reaction from sending out
Raw.Both schemes all possess a drawback: the gas dimethylamine being passed through in the first scheme to add water removal, and the waste water produced increases
Environmental protection pressure, and there is potential safety hazard, it addition, the program can not completely inhibit side reaction, Shang You in the use of dimethylamine
The side reaction of about 10% occurs；First scheme is relatively strict to the requirement of equipment, and operating flexibility narrow range too increases life
Produce cost.
The following is general hexazinone synthetic route:
Ring-closure reaction custom catalysts has inorganic strong alkali, Organic Alcohol metal overbase etc., and the ethanol that this reaction generates is at highly basic
Come off in the presence of catalyst reversible exchange side reaction with cyclised products hexazinone generation dimethylamino, and reaction equation is as follows:
Based on above-mentioned consideration, we have selected a new synthetic route, can avoid the generation of cyclization side reaction, step
Simply, more environmentally-friendly, yield is higher.
Summary of the invention
The present invention provides the preparation method of a kind of new herbicide hexazinone, occurs without side reaction, it is possible to ring is greatly improved
The synthesis yield of piperazine ketone, and more environmentally-friendly, and the requirement to equipment is the highest.Its concrete preparation method is:
The first step, adds solvent in reaction vessel, adds the N that mol ratio is 1:1～1.05, N-dimethyl-N '-first
Base-N '-alkoxy acyl guanidine (I) and cyclohexylamine, stirring, reaction 1.5～4h at 55～110 DEG C, N, N-dimethyl-N '-methyl-
Ester group on N '-alkoxy acyl guanidine (I), by amine solution, generates intermediate N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines
(II) and alcohol, the alcohol that reaction generates is removed in rectification, obtains intermediate N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines (II)
Thin liquid；
Second step, at intermediate N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines (II) thin liquid that the first step obtains
Middle addition solvent, adds acid binding agent, stirs and makes temperature be down to-20～5 DEG C, being passed through and N, and N-dimethyl-N '-methyl-N '-
The phosgene of the amount of alkoxy acyl guanidine (I) commaterial, in-20～5 DEG C of insulation reaction 0.5～5h, after be warming up to 55～110 DEG C, add
Enter acid binding agent, reaction 1～4h, intermediate N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines (II) cyclization, generate ring piperazine
Ketone (III)；
3rd step, cools to room temperature, filtering and washing by the mixture that second step reaction obtains, and mother solution washes with water, decompression
Precipitation, adds petroleum ether crystallization, filters, dry, obtain hexazinone crystal.
Reacting the later stage in the described first step, the alcohol that reaction generates is removed in rectification under vacuum, can further improve reaction yield, increases
Add intermediate N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines yield.
Described solvent is the aromatic solvent such as benzene,toluene,xylene, Benzene Chloride or the chloro alkanes such as chloroform, dichloroethanes
Solvent.
Described acid binding agent is in sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium acetate, triethylamine, tri-n-butylamine or pyridine
A kind of.
The concrete reaction equation of this preparation method is as follows:
The first step: amine solution
If this step aminolysis reaction removes the alcohol generated from reaction system in time, reaction yield is up to 99%.
Second step: photochemical cyclization
Second step reacts in two stages, and reaction equation is as follows:
Second step reaction yield is up to 97-98%, and two-step reaction total recovery is up to more than 96%.
Compared to the prior art, the invention have the benefit that the present invention provides the conjunction of a kind of new herbicide hexazinone
Becoming route, the synthetic route method of the present invention is simple, and cyclization side reaction will not occur, and requires the highest to consersion unit, is one
Plant the hexazinone preparation method of novel high yield.
Detailed description of the invention
Below by detailed description of the invention, the present invention will be further described in detail.
Embodiment 1
R=ethyl in the reactant that the present embodiment uses, molecular weight is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Reaction bulb adds 800g toluene, N, toluene solution 346g (wherein N, the N-of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The mass content 50% of dimethyl-N '-methyl-N '-alkoxy acyl guanidine, N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The amount of material is 1mol) and cyclohexylamine 100g (1mol), react 2h at 65～70 DEG C, then under vacuum 200mmHg, decompression essence
Evaporate the ethanol that reaction generates, sample analysis in distillation process, treat that N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine is complete
After portion converts, stopping rectification, the toluene obtaining midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines is dilute
Liquid.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 1800g toluene and above-mentioned reaction obtain-cyclohexylamine acylguanidines toluene thin liquid, adds
102g (1mol) triethylamine, stirs and cools to 0 DEG C, is passed through phosgene 99g (1mol), and during logical phosgene, temperature controls at 0～5 DEG C,
Have friendly relations after phosgene, 0～5 DEG C of insulation reaction 2h, be then slowly ramped to 70 DEG C, drip 102g (1mol) triethylamine, and control
Temperature is at 70～75 DEG C, after dripping off triethylamine, 70～75 DEG C of insulation reaction 1h, then cools to room temperature, filtering and washing, reclaims
Triethylamine hydrochloride.Mother solution 100mL water washs, and reduce pressure precipitation, adds the crystallization of 700g petroleum ether, filters, dries, obtain hexazinone
247g, content 99%, yield 98%.
Embodiment 2
R=ethyl in reactant N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine that the present embodiment uses, molecular weight
It is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Reaction bulb adds 800g benzene, N, benzole soln 346g (wherein N, the N-diformazan of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The mass content 50% of base-N '-methyl-N '-alkoxy acyl guanidine, the material of N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
Amount be 1mol) and cyclohexylamine 102g (1.02mol), react 3h at 70～80 DEG C, then under vacuum 200mmHg, decompression essence
Evaporate the ethanol that reaction generates, sample analysis in distillation process, treat that N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine is complete
After portion converts, stop rectification, obtain the benzene thin liquid of midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 1800g benzene and above-mentioned reaction obtain-cyclohexylamine acylguanidines benzene thin liquid, adds 84g
(1mol) sodium bicarbonate, stirs and cools to-10 DEG C, is passed through phosgene 99g (1mol), and during logical phosgene, temperature controls-10～0
DEG C, after phosgene of having friendly relations ,-10～0 DEG C of insulation reaction 1h, then it is slowly ramped to 70 DEG C, drips 84g (1mol) sodium bicarbonate,
And control temperature at 70～75 DEG C, after dripping off sodium bicarbonate, 70～75 DEG C of insulation reaction 4h, then cool to room temperature, sucking filtration
Washing, reclaims sodium chloride salt.Mother solution 200mL water washs, and reduce pressure precipitation, adds the crystallization of 700g petroleum ether, filters, dries, obtain ring
Piperazine ketone 243g, content 99.3%, yield 96.4%.
Embodiment 3
R=ethyl in reactant N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine that the present embodiment uses, molecular weight
It is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Reaction bulb adds 1400g chloroform, N, chloroformic solution 346g (wherein N, the N-of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The mass content 50% of dimethyl-N '-methyl-N '-alkoxy acyl guanidine, N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The amount of material is 1mol) and cyclohexylamine 105g (1.05mol), react 4h at 55～60 DEG C, then azeotropic distillation removes reaction life
The ethanol become, sample analysis in distillation process, after treating that N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine all converts, stops
Only rectification, obtains the chloroform thin liquid of midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 3000g chloroform and above-mentioned reaction obtain-cyclohexylamine acylguanidines chloroform thin liquid, adds 40g
(1mol) sodium hydroxide, stirs and cools to-20 DEG C, is passed through phosgene 99g (1mol), and during logical phosgene, temperature controls-20～-10
DEG C, after phosgene of having friendly relations ,-20～-10 DEG C of insulation reaction 0.5h, then it is slowly ramped to 55 DEG C, drips 40g (1mol) hydroxide
Sodium, and control temperature at 55～60 DEG C, after dripping off sodium hydroxide, 55～60 DEG C of insulation reaction 4h, then cool to room temperature, take out
Filter washing, reclaims sodium chloride salt.Mother solution 100mL water washs, and reduce pressure precipitation, adds the crystallization of 750g petroleum ether, filters, dries,
Hexazinone 249g, content 99.1%, yield 98.8%.
Embodiment 4
R=ethyl in reactant N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine that the present embodiment uses, molecular weight
It is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Reaction bulb adds 800g toluene, N, toluene solution 346g (wherein N, the N-of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The mass content 50% of dimethyl-N '-methyl-N '-alkoxy acyl guanidine, N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
The amount of material is 1mol) and cyclohexylamine 103g (1.03mol), react 2.5h at 90～100 DEG C, then under vacuum 200mmHg,
The ethanol that reaction generates, sample analysis in distillation process are removed in rectification under vacuum, treat N, N-dimethyl-N '-methyl-N '-alcoxyl acyl
After base guanidine all converts, stop rectification, obtain midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines
Toluene thin liquid.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 1800g toluene and above-mentioned reaction obtain-cyclohexylamine acylguanidines toluene thin liquid, adds 82g
(1mol) sodium acetate, stirs and cools to 0 DEG C, is passed through phosgene 99g (1mol), and during logical phosgene, temperature controls, at 0～5 DEG C, to have friendly relations
After phosgene, 0～5 DEG C of insulation reaction 5h, then it is slowly ramped to 90 DEG C, drips 82g (1mol) sodium acetate, and control temperature and exist
90～100 DEG C, after dripping off sodium acetate, 90～100 DEG C of insulation reaction 2h, then cool to room temperature, filtering and washing, reclaim chlorination
Sodium salt.Mother solution 150mL water washs, and reduce pressure precipitation, adds the crystallization of 700g petroleum ether, filters, dries, obtain hexazinone 242g, content
99%, yield 96%.
Embodiment 5
R=ethyl in reactant N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine that the present embodiment uses, molecular weight
It is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Adding 800g dimethylbenzene, N in reaction bulb, the xylene solution 346g of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine is (wherein
The mass content 50% of N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine, N, N-dimethyl-N '-methyl-N '-alkoxy acyl
The amount of the material of guanidine is 1mol) and cyclohexylamine 100g (1mol), react 1.5h at 100～110 DEG C, then in vacuum 200mmHg
Under, the ethanol that reaction generates, sample analysis in distillation process are removed in rectification under vacuum, treat N, N-dimethyl-N '-methyl-N '-alcoxyl
After acylguanidines all converts, stop rectification, obtain midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines
Dimethylbenzene thin liquid.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 1800g dimethylbenzene and above-mentioned reaction obtain-cyclohexylamine acylguanidines dimethylbenzene thin liquid, then add
Enter 186g (1mol) tri-n-butylamine, stir and cool to-15 DEG C, be passed through phosgene 99g (1mol), during logical phosgene temperature control-
15～-5 DEG C, after phosgene of having friendly relations ,-15～-5 DEG C of insulation reaction 3h, then it is slowly ramped to 100 DEG C, dropping 186g (1mol)
Tri-n-butylamine, and control temperature at 100～110 DEG C, after dripping off tri-n-butylamine, 100～110 DEG C of insulation reaction 2.5h, then
Cool to room temperature, filtering and washing, reclaim tri-n-butylamine hydrochlorate.Mother solution 100mL water washs, and reduce pressure precipitation, adds 750g oil
Ether crystallizes, and filters, and dries, obtains hexazinone 245g, content 99.1%, yield 97.2%.
Embodiment 6
R=ethyl in reactant N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine that the present embodiment uses, molecular weight
It is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Reaction bulb adds 1200g dichloroethanes, N, the dichloroethane solution 346g of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine
(mass content 50% of wherein N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine, N, N-dimethyl-N '-methyl-N '-alkane
The amount of the material of oxygen acylguanidines is 1mol) and cyclohexylamine 100g (1mol), react 2h at 70～75 DEG C, then in vacuum
Under 200mmHg, rectification under vacuum remove reaction generate ethanol, sample analysis in distillation process, treat N, N-dimethyl-N '-methyl-
After N '-alkoxy acyl guanidine all converts, stop rectification, obtain midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine
The dichloroethanes thin liquid of acylguanidines.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 2600g dichloroethanes and above-mentioned reaction obtain-cyclohexylamine acylguanidines dichloroethanes thin liquid,
Add 80g (1mol) pyridine, stir and cool to-5 DEG C, be passed through phosgene 99g (1mol), during logical phosgene temperature control-5～
0 DEG C, after phosgene of having friendly relations ,-5～0 DEG C of insulation reaction 4h, then it is slowly ramped to 70 DEG C, drips 80g (1mol) pyridine, and control
Temperature processed is at 70～75 DEG C, after dripping off pyridine, 70～75 DEG C of insulation reaction 2h, then cools to room temperature, filtering and washing, reclaims
Pyridine hydrochloride.Mother solution 100mL water washs, and reduce pressure precipitation, adds the crystallization of 700g petroleum ether, filters, dries, obtain hexazinone
244g, content 99.2%, yield 96.8%.
Embodiment 7
R=ethyl in reactant N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine that the present embodiment uses, molecular weight
It is 173.
Equipped with mechanical agitation, thermometer and internal diameter 15mm, the 2000mL of length 300mm built-in triangle stainless steel helices tower
Adding 1000g Benzene Chloride, N in reaction bulb, the Benzene Chloride solution 346g of N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine is (wherein
The mass content 50% of N, N-dimethyl-N '-methyl-N '-alkoxy acyl guanidine, N, N-dimethyl-N '-methyl-N '-alkoxy acyl
The amount of the material of guanidine is 1mol) and cyclohexylamine 102g (1.02mol), react 2.5h at 80～85 DEG C, then in vacuum 200mmHg
Under, the ethanol that reaction generates, sample analysis in distillation process are removed in rectification under vacuum, treat N, N-dimethyl-N '-methyl-N '-alcoxyl
After acylguanidines all converts, stop rectification, obtain midbody compound N, N-dimethyl-N '-methyl-N '-cyclohexylamine acylguanidines
Benzene Chloride thin liquid.
5000mL reaction bulb equipped with mechanical agitation, thermometer, addition funnel, logical light pipe and condenser adds
N, N-dimethyl-N '-methyl-N ' that 2300g Benzene Chloride and above-mentioned reaction obtain-cyclohexylamine acylguanidines Benzene Chloride thin liquid, then add
Entering 53g (0.5mol) sodium carbonate, stir and cool to-10 DEG C, be passed through phosgene 99g (1mol), during logical phosgene, temperature controls-10
～0 DEG C, after phosgene of having friendly relations ,-10～0 DEG C of insulation reaction 2.5h, then it is slowly ramped to 80 DEG C, drips 53g (0.5mol) carbon
Acid sodium, and control temperature at 80～85 DEG C, after dripping off sodium carbonate, 80～85 DEG C of insulation reaction 1.5h, then cool to room temperature,
Filtering and washing, reclaims sodium chloride salt.Mother solution 200mL water washs, and reduce pressure precipitation, adds the crystallization of 700g petroleum ether, filters, dries,
Obtain hexazinone 247g, content 99.1%, yield 98%.
Above-described embodiment is only the explanation to product of the present invention, and the present invention not makes any pro forma restriction,
Within the scope of technical scheme, any technology contents utilizing the disclosure above make simple transformation etc. Tongfang
Case, all belongs to protection scope of the present invention.
Claims (7)
1. the preparation method of a herbicide hexazinone, it is characterised in that including:
The first step, N, N-dimethyl-N'-methyl-N'-alkoxy acyl guanidine and cyclohexylamine reaction, N, N-dimethyl-N'-methyl-
Ester group on N'-alkoxy acyl guanidine, by amine solution, generates intermediate N, N-dimethyl-N'-methyl-N'-cyclohexylamine acylguanidines；
Second step, this intermediate N, N-dimethyl-N'-methyl-N'-cyclohexylamine acylguanidines and phosgene under acid binding agent effect, in
Mesosome N, N-dimethyl-N'-methyl-N'-cyclohexylamine acylguanidines cyclization, generates hexazinone,
Wherein, the structural formula of N, N-dimethyl-N'-methyl-N'-alkoxy acyl guanidine is formula I:
R is ethyl；
The structural formula of N, N-dimethyl-N'-methyl-N'-cyclohexylamine acylguanidines is formula II:
The structural formula of hexazinone is formula III:
The preparation method of herbicide hexazinone the most according to claim 1, it is characterised in that react in the described first step
In, described N, N-dimethyl-N'-methyl-N'-alkoxy acyl guanidine and cyclohexylamine rate of charge are mol ratio 1:1～1.05, reaction temperature
Spend 55～110 DEG C, the response time 1.5～4h.
The preparation method of herbicide hexazinone the most according to claim 1, it is characterised in that described two-step reaction uses
Solvent is aromatic solvent or alkyl chloride kind solvent.
The preparation method of herbicide hexazinone the most according to claim 1, it is characterised in that described acid binding agent is carbonic acid
One in sodium, sodium bicarbonate, sodium hydroxide, sodium acetate, triethylamine, tri-n-butylamine or pyridine.
The preparation method of herbicide hexazinone the most according to claim 1, it is characterised in that the reaction of described second step is divided into
Low temperature and two stages of reaction of high temperature, the temperature in low-temp reaction stage controls at-20～5 DEG C, the response time 0.5～5h, high temperature
The temperature of the stage of reaction controls at 55～110 DEG C, the response time 1～4h.
The preparation method of herbicide hexazinone the most according to claim 1, it is characterised in that in the described first step is reacted
Also include: the alcohol that reaction generates is removed in rectification.
The preparation method of herbicide hexazinone the most according to claim 1, it is characterised in that also include the 3rd step: by
The mixture that two step reactions obtain cools to room temperature, filtering and washing, and mother solution washes with water, and reduce pressure precipitation, adds petroleum ether crystallization, mistake
Filter, dries, obtains hexazinone crystal.
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| CN108689954A (en) * | 2018-05-29 | 2018-10-23 | 安徽广信农化股份有限公司 | A kind of hexazinone cleanly production technique |
| CN110172041B (en) * | 2019-05-20 | 2022-09-09 | 江苏蓝丰生物化工股份有限公司 | Novel method for synthesizing hexazinone |
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| US4178448A (en) * | 1975-05-05 | 1979-12-11 | E. I. Du Pont De Nemours And Company | Process for preparing herbicidal triazines |
| US4150225A (en) * | 1977-03-14 | 1979-04-17 | E. I. Du Pont De Nemours And Company | Process for preparing herbicidal triazines |
| CN103755654B (en) * | 2013-12-26 | 2015-10-28 | 安徽广信农化股份有限公司 | A kind of synthesis technique of hexazinone |
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