CN107629015A - One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 - Google Patents
One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 Download PDFInfo
- Publication number
- CN107629015A CN107629015A CN201710788143.7A CN201710788143A CN107629015A CN 107629015 A CN107629015 A CN 107629015A CN 201710788143 A CN201710788143 A CN 201710788143A CN 107629015 A CN107629015 A CN 107629015A
- Authority
- CN
- China
- Prior art keywords
- cln
- reaction
- triazole
- methyl
- ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses one kind synthesis 1 (2, 4 dichlorophenyls) 3 methyl, 4 difluoromethyl 1, 2, the method of the ketone of 4 triazole 5, using parachloroanilinum as raw material, pass through diazotising, reduction, p-hydrochloride is synthesized into salt, neutralize to obtain to chlorophenyl hydrazine through alkali, to chlorophenyl hydrazine under conditions of the tert-butyl alcohol is solvent, and acetaldehyde, Zassol, sodium hypochlorite is by condensation, cyclisation and oxidation reaction generation 1 rubigan 3 methyl 1H 1, 2, the ketone of 4 triazole 5, the methyl 1H 1 of 1 rubigan 3, 2, the ketone of 4 triazole 5 passes through into salt again, fluorine potassium and chlorination reaction obtain 1 (2, 4 dichlorophenyls) 3 methyl, 4 difluoromethyl 1, 2, the ketone of 4 triazole 5 (sulfentrazone intermediate).The synthetic method of the present invention, using parachloroanilinum as raw material, only need chlorination reaction to can be achieved, and can make that the steric hindrance of synthetic intermediate is small, and impurity is low, so as to improve yield；Raw material needed for this other synthetic route is easy to get and cost is low, mild condition, easy to operate, safe, is advantageously implemented industrialized production.
Description
Technical field
The present invention relates to herbicide preparing technical field, is specially a kind of synthesis 1- (2,4- dichlorophenyl) -3- methyl -4-
Difluoromethyl -1,2, the method for 4- triazole -5- ketone.
Background technology
Sulfentrazone is a kind of low toxicity herbicide for belonging to difluoromethyl triazolineone, and contact killing type cauline leaf process agent is special
It is not that the weeds resistant to sulfonylurea have special efficacy, succession crop safety, broad weed-killing spectrum, dosage is few, herbicide speed is fast, is suitable to
The various crop such as corn and soybean, sorghum, peanut, sunflower field, 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyl -1,
2,4- triazole -5- ketone are the intermediates for synthesizing sulfentrazone, and chemical structural formula is as follows：
1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2,4- triazole -5- ketone are among synthesis sulfentrazone
Body, the synthetic route that current domestic prior art has been announced have a variety of.Wherein using phenylhydrazine as initiation material, first synthesize 1- phenyl-
3- methyl -4- difluoromethyls -1,2,4- triazole -5- ketone, then intermediate is obtained by chlorination reaction twice, but such a mode due to
Need two chlorine on phenyl ring, reaction is realized relatively difficult, and impurity is high, and yield is low；In addition can also 2,4- dichloroanilines be
Raw material is played, but due to existing two chlorine on phenyl ring, synthesis steric hindrance is larger, and yield is low.It is domestic at present prior art discloses on
1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 are prepared, the process route of 4- triazole -5- ketone mainly has several.
Zhang Yuanyuan et al. discloses synthesis (synthesis of herbicide sulfentrazone, Zhang Yuanyuan etc., the agriculture of herbicide sulfentrazone
Medicine is studied and application, the 1st phase, 2008) technique, the synthetic method, for initial feed, through diazotising, contracts with 2,4- dichloroanilines
Conjunction, N- are alkylated to obtain sulfentrazone intermediate difluoromethyl Triazolinones, and beneficial effects of the present invention are embodied in：Reaction raw materials
The cost that is easy to get is low, and reaction is gentle, is advantageous to commercial introduction；But there is the shortcomings that certain in the synthesis：It is original with 2,4- dichloroanilines
Easily there is steric hindrance in material, intermediate product, and impurity is high, and product yield is low.
Patent CN106478532A discloses a kind of method for synthesizing difluoromethyl Triazolinones：With adjacent chlorophenylhydxazine hydrochloride
For initiation material, neutralize to obtain adjacent chlorophenyl hydrazine by alkali, organic phase is after dichloromethane extracts, with trimethyl orthoacetate and cyanogen
Sour nak response obtains 1- Chloro-O-Phenyl -3- methyl isophthalic acids H-1,2,4- triazole -5- ketone, 1- Chloro-O-Phenyl -3- methyl isophthalic acids H-1, and 2,4-
Triazole -5- ketone is alkylated through N- again, chlorination obtains 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, and 4- triazoles -
5- ketone.Beneficial effects of the present invention are embodied in：Using adjacent chlorophenylhydxazine hydrochloride, make the steric hindrance of intermediate product small, high income, but should
The shortcomings that certain be present in method：Reaction raw materials trimethyl orthoacetate and potassium cyanate are not easy to obtain and price is high, increase production cost；And
And dichloromethane low boiling point, recovery loss are big.
The content of the invention
It is an object of the invention to provide one kind to synthesize 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2,4-
The method of triazole -5- ketone, using parachloroanilinum as raw material, p-hydrochloride is synthesized by diazotising, reduction, into salt, through alkali
Neutralization is obtained to chlorophenyl hydrazine, and to chlorophenyl hydrazine under conditions of the tert-butyl alcohol is solvent, and acetaldehyde, Zassol, sodium hypochlorite are by contracting
Conjunction, cyclisation and oxidation reaction generation 1- rubigan -3- methyl isophthalic acids H-1,2,4- triazole -5- ketone, 1- rubigan -3- methyl -
1H-1,2,4- triazole -5- ketone into salt, fluorine potassium and chlorination reaction again by obtaining 1- (2,4- dichlorophenyl) -3- methyl -4- two
Methyl fluoride -1,2,4- triazole -5- ketone (sulfentrazone intermediate), to solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides following technical scheme：One kind synthesis 1- (2,4- dichlorophenyl) -3- first
Base -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone, using parachloroanilinum as raw material, synthesized by diazotising, reduction, into salt
P-hydrochloride, neutralize to obtain to chlorophenyl hydrazine through alkali, to chlorophenyl hydrazine under conditions of the tert-butyl alcohol is solvent, and acetaldehyde, cyanogen
Sour sodium, the condensation of sodium hypochlorite process, cyclisation and oxidation reaction generation 1- rubigan -3- methyl isophthalic acids H-1,2,4- triazole -5- ketone,
1- rubigan -3- methyl isophthalic acids H-1,2,4- triazole -5- ketone into salt, fluorine potassium and chlorination reaction again by obtaining 1- (2,4- bis-
Chlorphenyl) -3- methyl -4- difluoromethyls -1,2,4- triazole -5- ketone (sulfentrazone intermediate).
The further technical scheme of the present invention, comprises the following steps：
(1) p-hydrochloride synthesizes
Parachloroanilinum is added in the reactor equipped with quantitative hydrochloric acid, reaction temperature is kept at -30-5 DEG C, then to reaction
Add sodium nitrite solution in kettle, with natrium nitrosum diazo-reaction occurs for parachloroanilinum, afterwards with ammonium sulfite and sulfurous acid
Hydrogen ammonium reacts, and generates p-hydrochloride, and reaction terminates dropwise addition sodium hydroxide solution in backward reactor and neutralized, dissociated
To chlorophenyl hydrazine, generate intermediate 1, whole diazotising, reduction, carry out at ambient pressure into salt and neutralization reaction.
Wherein, the intermediate 1 is C6H7ClN2, product C6H7ClN2With water H2O；C6H7ClN2With water H2O mass ratio
For 142: 18.
(2) into hydrazone reaction
Into using the tert-butyl alcohol as solvent, with acetaldehyde condensation reaction occurs for intermediate 1 in hydrazone reaction kettle under normal temperature, temperature is controlled
Quantitative acetaldehyde is added dropwise at -5-10 DEG C, control temperature, generation intermediate 2 was treated in next step instead for -5-10 DEG C of insulated and stirreds 15 minutes
Should.
Wherein, the intermediate 2 is C8H9ClN2, product C8H9ClN2, water H2O；C8H9ClN2, water H2O mass ratio be
168∶18。
(3) cyclization
Above-mentioned intermediate 2 adds quantitative Zassol and quantitative hydrochloric acid, controls temperature in acid condition as -5-10 DEG C of insulations
Reaction 2.5 hours, reaction end obtain intermediate 3, treat the next step.
Wherein, the intermediate 3 is C9H10ClN3O, product C9H10ClN3O and sodium chloride nacl；C9H10ClN3O and chlorine
The mass ratio for changing sodium NaCl is 422: 117.
(4) oxidation reaction
Intermediate 3 is added in oxidizing reactor, control temperature is middle into kettle that the hypochlorous acid quantitatively prepared is added dropwise at 5-30 DEG C
Sodium solution, it is added dropwise, 5-30 DEG C is incubated 30 minutes, and reaction end obtains intermediate 4, treats the next step.
Wherein, the intermediate 4 is C9H8ClN3O, product C9H8ClN3O and sodium chloride nacl, water H2O；C9H8ClN3O
With sodium chloride nacl, water H2O mass ratio is 418: 117: 36.
(5) salt-forming reaction
Quantitative DMF and quantitative intermediate 4 are put into reactor, is stirred 0.5 hour, it is fixed then to be put under normal temperature condition
Potassium carbonate is measured, 160-165 DEG C is warming up to, insulation reaction 0.5 hour, generates intermediate 5, treats to react in next step.
Wherein, the intermediate 5 is KC9H7ClN3O, product KC9H7ClN3O and carbon dioxide CO2, water H2O；
KC9H7ClN3O and carbon dioxide CO2, water H2O mass ratio is 247: 44: 18.
(6) fluorine potassiumization is reacted
Salt-forming reaction rises to 180-190 DEG C after dehydration, by temperature of reaction kettle, is passed through quantitative F-22, protects
Temperature reaction 15 minutes, is cooled to 80 DEG C, turns material to crystallization kettle and cools, after centrifugal filtration sylvite, desolvation, obtains intermediate 6,
Treat to react in next step.
Wherein, the intermediate 6 is C10H8ClN3OF2, product C10H8ClN3OF2And potassium chloride (KCl)；C10H8ClN3OF2
Mass ratio with potassium chloride (KCl) is 518: 149.
(7) chlorination reaction
Quantitative acid DMF and fluorine potassium the reaction product intermediate 6 of input in reactor, opens air inducing and is passed through quantitative chlorine,
50-60 DEG C of temperature control, lead to chlorine, be incubated 1 hour, obtain 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyl -1,
2,4- triazole -5- ketone (sulfentrazone intermediate).
Preferably, in step (1), the parachloroanilinum C6H6NCl, hydrochloric acid HCl, natrium nitrosum NaNO2, ammonium sulfite
(NH4)2SO3, ammonium bisulfite NH4HSO3, sodium hydroxide NaOH mass ratio be 254: 73: 138: 232: 198: 80.
Preferably, in step (2), the intermediate 1 is to chlorophenyl hydrazine C6H7ClN2, acetaldehyde C2H4O mass ratio is 142:
44。
Preferably, in step (3), the C of intermediate 28H9ClN2, Zassol NaOCN, hydrochloric acid HCl mass ratio be
336∶130∶73。
Preferably, in step (4), the C of intermediate 39H10ClN3O, sodium hypochlorite NaClO mass ratio is 422:
149。
Preferably, in step (5), the C of intermediate 49H8ClN3O, potassium carbonate K2CO3Mass ratio be 209: 138.
Preferably, in step (6), the KC of intermediate 59H7ClN3O, F-22 HCF2Cl mass ratio is
494∶173。
Preferably, in step (7), the C of intermediate 610H8ClN3OF2, chlorine Cl2Mass ratio be 259: 71.
Preferably, in step (1-7), p-hydrochloride synthesis, into hydrazone reaction, cyclization, oxidation reaction, into
The conversion ratio of reactant salt, the reaction of fluorine potassium and chlorination reaction is all higher than 97%.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, present invention synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone,
Using parachloroanilinum as initiation material, one-step chlorination reaction is only needed, can make that the steric hindrance of synthetic intermediate is small, and side reaction is few, so as to
Improve yield.
2nd, present invention synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone,
P-hydrochloride obtains free to chlorophenyl hydrazine after being neutralized with sodium hydroxide solution, it is not necessary to extracted by organic solvent,
It can enter and react in next step, it is easy to operate.
3rd, present invention synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone,
Reaction raw materials acetaldehyde and the Zassol market price are low and be easy to get, and advantageously reduce production cost.
4th, present invention synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone,
Chlorine does not need catalyst to carry out on phenyl ring, and problem is reclaimed in the absence of catalyst.
5th, present invention synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone,
Chlorination reaction directly can so far walk reaction by recovery with DMF solvent by simple distillation, easy to operate.
6th, present invention synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone,
It is few to react step number, and each step process mild condition, safe, easy to operate, raw material is cheap and easy to get, and reaction is gentle, operation letter
Just, it is advantageously implemented large-scale production.
Brief description of the drawings
Fig. 1 is the sulfentrazone intermediate synthetic reaction equation of the present invention；
The p-hydrochloride that Fig. 2 is the present invention synthesizes equation；
Fig. 3 is to be of the invention into hydrazone reaction equation；
Fig. 4 is the cyclization equation of the present invention；
Fig. 5 is the oxidation equation formula of the present invention；
Fig. 6 is the salt-forming reaction equation of the present invention；
Fig. 7 is the fluorine potassium reaction equation of the present invention；
Fig. 8 is the chlorination reaction equation of the present invention；
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Referring to Fig. 1, a kind of synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2,4- triazole -5- ketone
Method, using parachloroanilinum as raw material, p-hydrochloride is synthesized by diazotising, reduction, into salt, neutralizes to obtain pair through alkali
Chlorophenyl hydrazine, to chlorophenyl hydrazine under conditions of the tert-butyl alcohol is solvent, and acetaldehyde, Zassol, sodium hypochlorite are by condensation, cyclisation and oxygen
Change reaction generation 1- rubigan -3- methyl isophthalic acids H-1,2,4- triazole -5- ketone, 1- rubigan -3- methyl isophthalic acids H-1,2,4- tri-
Azoles -5- ketone passes through into salt, fluorine potassium and chlorination reaction again obtains 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2,
4- triazole -5- ketone (sulfentrazone intermediate).
The further technical scheme of the present invention, comprises the following steps：
(1) p-hydrochloride synthesizes
Parachloroanilinum is added in the reactor equipped with quantitative hydrochloric acid, reaction temperature is kept at -30-5 DEG C, then to reaction
Add sodium nitrite solution in kettle, with natrium nitrosum diazo-reaction occurs for parachloroanilinum, afterwards with ammonium sulfite and sulfurous acid
Hydrogen ammonium reacts, and generates p-hydrochloride, and reaction terminates dropwise addition sodium hydroxide solution in backward reactor and neutralized, dissociated
To chlorophenyl hydrazine, generate intermediate 1, whole diazotising, reduction, carry out at ambient pressure into salt and neutralization reaction.
Wherein, the intermediate 1 is C6H7ClN2, product C6H7ClN2With water H2O；C6H7ClN2With water H2O mass ratio
For 142: 18.
Wherein, the parachloroanilinum C6H6NCl, hydrochloric acid HCl, natrium nitrosum NaNO2, ammonium sulfite (NH4)2SO3, sulfurous acid
Hydrogen ammonium NH4HSO3, sodium hydroxide NaOH mass ratio be 254: 73: 138: 232: 198: 80.
(2) into hydrazone reaction
Into using the tert-butyl alcohol as solvent, with acetaldehyde condensation reaction occurs for intermediate 1 in hydrazone reaction kettle under normal temperature, temperature is controlled
Quantitative acetaldehyde is added dropwise at -5-10 DEG C, control temperature, generation intermediate 2 was treated in next step instead for -5-10 DEG C of insulated and stirreds 15 minutes
Should.
Wherein, the intermediate 2 is C8H9ClN2, product C8H9ClN2, water H2O；C8H9ClN2, water H2O mass ratio be
168∶18。
Wherein, the intermediate 1 is to chlorophenyl hydrazine C6H7ClN2(142), acetaldehyde C2H4O (44) mass ratio is 142: 44.
(3) cyclization
Above-mentioned intermediate 2 adds quantitative Zassol and quantitative hydrochloric acid, controls temperature in acid condition as -5-10 DEG C of insulations
Reaction 2.5 hours, reaction end obtain intermediate 3, treat the next step.
Wherein, the intermediate 3 is C9H10ClN3O, product C9H10ClN3O and sodium chloride nacl；C9H10ClN3O and chlorine
The mass ratio for changing sodium NaCl is 422: 117.
Wherein, the C of intermediate 28H9ClN2, Zassol NaOCN, hydrochloric acid HCl mass ratio be 336: 130: 73.
(4) oxidation reaction
Intermediate 3 is added in oxidizing reactor, control temperature is middle into kettle that the hypochlorous acid quantitatively prepared is added dropwise at 5-30 DEG C
Sodium solution, it is added dropwise, 5-30 DEG C is incubated 30 minutes, and reaction end obtains intermediate 4, treats the next step.
Wherein, the intermediate 4 is C9H8ClN3O, product C9H8ClN3O and sodium chloride nacl, water H2O；C9H8ClN3O
With sodium chloride nacl, water H2O mass ratio is 418: 117: 36.
Wherein, the C of intermediate 39H10ClN3O, sodium hypochlorite NaClO mass ratio is 422: 149.
(5) salt-forming reaction
Quantitative DMF and quantitative intermediate 4 are put into reactor, is stirred 0.5 hour, it is fixed then to be put under normal temperature condition
Potassium carbonate is measured, 160-165 DEG C is warming up to, insulation reaction 0.5 hour, generates intermediate 5, treats to react in next step.
Wherein, the intermediate 5 is KC9H7ClN3O, product KC9H7ClN3O and carbon dioxide CO2(44), water H2O；
KC9H7ClN3O and carbon dioxide CO2, water H2O mass ratio is 247: 44: 18.
Wherein, the C of intermediate 49H8ClN3O, potassium carbonate K2CO3Mass ratio be 209: 138.
(6) fluorine potassiumization is reacted
Salt-forming reaction rises to 180-190 DEG C after dehydration, by temperature of reaction kettle, is passed through quantitative F-22, protects
Temperature reaction 15 minutes, is cooled to 80 DEG C, turns material to crystallization kettle and cools, after centrifugal filtration sylvite, desolvation, obtains intermediate 6,
Treat to react in next step.
Wherein, the intermediate 6 is C10H8ClN3OF2, product C10H8ClN3OF2And potassium chloride (KCl)；C10H8ClN3OF2
Mass ratio with potassium chloride (KCl) is 518: 149.
Wherein, the KC of intermediate 59H7ClN3O, F-22 HCF2Cl mass ratio is 494: 173.
(7) chlorination reaction
Quantitative acid DMF and fluorine potassium the reaction product intermediate 6 of input in reactor, opens air inducing and is passed through quantitative chlorine,
50-60 DEG C of temperature control, lead to chlorine, be incubated 1 hour, obtain 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyl -1,
2,4- triazole -5- ketone (sulfentrazone intermediate).
Wherein, the C of intermediate 610H8ClN3OF2(259), chlorine Cl2Mass ratio be 259: 71.
In step (1-7), p-hydrochloride synthesis, into hydrazone reaction, cyclization, oxidation reaction, salt-forming reaction,
The conversion ratio of the reaction of fluorine potassium and chlorination reaction is all higher than 97%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. one kind synthesis 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2, the method for 4- triazole -5- ketone, its feature
It is, using parachloroanilinum as raw material, synthesizes p-hydrochloride by diazotising, reduction, into salt, neutralize to obtain to chlorine through alkali
Phenylhydrazine, to chlorophenyl hydrazine under conditions of the tert-butyl alcohol is solvent, and acetaldehyde, Zassol, sodium hypochlorite are by condensation, cyclisation and oxidation
Reaction generation 1- rubigan -3- methyl isophthalic acids H-1,2,4- triazole -5- ketone, 1- rubigan -3- methyl isophthalic acids H-1,2,4- triazoles -
5- ketone into salt, fluorine potassium and chlorination reaction again by obtaining 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2,4-
Triazole -5- ketone (sulfentrazone intermediate).
2. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 1,4- triazole -5- ketone
Synthetic method, it is characterised in that：Synthetic method comprises the following steps：
(1) p-hydrochloride synthesizes
Parachloroanilinum is added in the reactor equipped with quantitative hydrochloric acid, reaction temperature is kept at -30-5 DEG C, then into reactor
Add sodium nitrite solution, diazo-reaction occurs for parachloroanilinum and natrium nitrosum, afterwards with ammonium sulfite and ammonium bisulfite
Reaction, p-hydrochloride is generated, reaction terminates dropwise addition sodium hydroxide solution in backward reactor and neutralized, and obtains free pair
Chlorophenyl hydrazine, intermediate 1 is generated, whole diazotising, reduction, is carried out at ambient pressure into salt and neutralization reaction.
Wherein, the intermediate 1 is C6H7ClN2, product C6H7ClN2With water H2O；C6H7ClN2With water H2O mass ratio is 142
∶18。
(2) into hydrazone reaction
Into using the tert-butyl alcohol as solvent, condensation reaction occurs for intermediate 1 and acetaldehyde in hydrazone reaction kettle under normal temperature, control temperature-
5-10 DEG C is added dropwise quantitative acetaldehyde, and control temperature, generation intermediate 2 treated that next step is reacted for -5-10 DEG C of insulated and stirreds 15 minutes.
Wherein, the intermediate 2 is C8H9ClN2, product C8H9ClN2, water H2O；C8H9ClN2, water H2O mass ratio be 168:
18。
(3) cyclization
Above-mentioned intermediate 2 adds quantitative Zassol and quantitative hydrochloric acid, and it is -5-10 DEG C of insulation reactions to control temperature in acid condition
2.5 hours, reaction end obtained intermediate 3, treats the next step.
Wherein, the intermediate 3 is C9H10ClN3O, product C9H10ClN3O and sodium chloride nacl；C9H10ClN3O and sodium chloride
NaCl mass ratio is 422: 117.
(4) oxidation reaction
Intermediate 3 is added in oxidizing reactor, for control temperature at 5-30 DEG C, the sodium hypochlorite that middle dropwise addition quantitatively prepares into kettle is molten
Liquid, it is added dropwise, 5-30 DEG C is incubated 30 minutes, and reaction end obtains intermediate 4, treats the next step.
Wherein, the intermediate 4 is C9H8ClN3O, product C9H8ClN3O and sodium chloride nacl, water H2O；C9H8ClN3O and chlorination
Sodium NaCl, water H2O mass ratio is 418: 117: 36.
(5) salt-forming reaction
Quantitative DMF and quantitative intermediate 4 are put into reactor, stirs 0.5 hour, quantitative carbon is then put under normal temperature condition
Sour potassium, 160-165 DEG C is warming up to, insulation reaction 0.5 hour, generates intermediate 5, treat to react in next step.
Wherein, the intermediate 5 is KC9H7ClN3O, product KC9H7ClN3O and carbon dioxide CO2(44), water H2O；
KC9H7ClN3O and carbon dioxide CO2, water H2O mass ratio is 247: 44: 18.
(6) fluorine potassiumization is reacted
Salt-forming reaction rises to 180-190 DEG C after dehydration, by temperature of reaction kettle, is passed through quantitative F-22, and insulation is anti-
Answer 15 minutes, be cooled to 80 DEG C, turn material to crystallization kettle and cool, after centrifugal filtration sylvite, desolvation, obtain intermediate 6, treat down
Single step reaction.
Wherein, the intermediate 6 is C10h8ClN3OF2, product C10H8ClN3OF2And potassium chloride (KCl)；C10h8ClN3OF2And chlorine
The mass ratio for changing potassium KCl is 518: 149.
(7) chlorination reaction
Quantitative acid DMF and fluorine potassium the reaction product intermediate 6 of input in reactor, opens air inducing and is passed through quantitative chlorine, temperature
50-60 DEG C of control, chlorine is led to, has been incubated 1 hour, obtains 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2,4-
Triazole -5- ketone (sulfentrazone intermediate).
3. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (1), the parachloroanilinum C6H6NCl, hydrochloric acid HCl, natrium nitrosum NaNO2, sulfurous
Sour ammonium (NH4)2SO3, ammonium bisulfite NH4HSO3, sodium hydroxide NaOH mass ratio be 254: 73: 138: 232: 198: 80.
4. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (2), the intermediate 1 is to chlorophenyl hydrazine C6H7ClN2, acetaldehyde C2H4O mass ratio is
142∶44。
5. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (3), the C of intermediate 28H9ClN2, Zassol NaOCN, hydrochloric acid HCl quality
Than for 336: 130: 73.
6. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (4), the C of intermediate 39H10ClN3O, sodium hypochlorite NaClO mass ratio is
422∶149。
7. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (5), the C of intermediate 49H8ClN3O, potassium carbonate K2CO3Mass ratio be 209:
138。
8. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (6), the KC of intermediate 59H7ClN3O, F-22 HCF2Cl matter
Amount is than being 494: 173.
9. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (7), the intermediate 6C10h8ClN3OF2, chlorine Cl2Mass ratio be 259:
71。
10. 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyls -1,2 according to claim 2,4- triazole -5- ketone
Synthetic method, it is characterised in that：In step (1-7), p-hydrochloride synthesis, into hydrazone reaction, cyclization, oxidation
Reaction, salt-forming reaction, the conversion ratio of the reaction of fluorine potassium and chlorination reaction are all higher than 97%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710788143.7A CN107629015A (en) | 2017-08-23 | 2017-08-23 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710788143.7A CN107629015A (en) | 2017-08-23 | 2017-08-23 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107629015A true CN107629015A (en) | 2018-01-26 |
Family
ID=61100075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710788143.7A Pending CN107629015A (en) | 2017-08-23 | 2017-08-23 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107629015A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125859A (en) * | 2019-06-25 | 2020-12-25 | 帕潘纳(北京)科技有限公司 | Method for preparing sulfentrazone intermediate |
| CN112225705A (en) * | 2020-11-20 | 2021-01-15 | 湖南海利常德农药化工有限公司 | Preparation method of 3-methyl-1-phenyl-1H-1,2, 4-triazole-5 (4H) -ketone |
| CN114149342A (en) * | 2021-11-02 | 2022-03-08 | 浙大宁波理工学院 | N- (2, 4-dichloro-5-hydrazinophenyl) acetamide compound and synthesis method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110683A (en) * | 1993-12-16 | 1995-10-25 | Fmc有限公司 | Process for the selective chlorination of 4,5-dihydro-1-phenyl-1h-1,2,4-triazol-5-one |
| CN103965124A (en) * | 2014-04-29 | 2014-08-06 | 安徽苏启化工有限公司 | Synthetic method for triazoline-ketone |
-
2017
- 2017-08-23 CN CN201710788143.7A patent/CN107629015A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110683A (en) * | 1993-12-16 | 1995-10-25 | Fmc有限公司 | Process for the selective chlorination of 4,5-dihydro-1-phenyl-1h-1,2,4-triazol-5-one |
| CN103965124A (en) * | 2014-04-29 | 2014-08-06 | 安徽苏启化工有限公司 | Synthetic method for triazoline-ketone |
Non-Patent Citations (1)
| Title |
|---|
| YAN TAO ET AL.: "Design, Synthesis and Biological Activities of Novel Benzoyl Hydrazines Containing Pyrazole", 《CHIN. J. CHEM.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125859A (en) * | 2019-06-25 | 2020-12-25 | 帕潘纳(北京)科技有限公司 | Method for preparing sulfentrazone intermediate |
| CN112125859B (en) * | 2019-06-25 | 2022-02-08 | 帕潘纳(北京)科技有限公司 | Method for preparing sulfentrazone intermediate |
| CN112225705A (en) * | 2020-11-20 | 2021-01-15 | 湖南海利常德农药化工有限公司 | Preparation method of 3-methyl-1-phenyl-1H-1,2, 4-triazole-5 (4H) -ketone |
| CN112225705B (en) * | 2020-11-20 | 2022-06-07 | 湖南海利常德农药化工有限公司 | Preparation method of 3-methyl-1-phenyl-1H-1,2, 4-triazole-5 (4H) -ketone |
| CN114149342A (en) * | 2021-11-02 | 2022-03-08 | 浙大宁波理工学院 | N- (2, 4-dichloro-5-hydrazinophenyl) acetamide compound and synthesis method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107629015A (en) | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 | |
| CN110799503A (en) | Synthesis of mecamitocainide | |
| CN107698529A (en) | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 | |
| KR100529856B1 (en) | Process for melamine manufacture | |
| CN105218472B (en) | A kind of preparation method of triazinone | |
| CN113754647B (en) | Synthesis method of sulfuryl pyraflufen-ethyl and intermediate thereof | |
| CN109796419B (en) | Preparation method of sulfentrazone through catalytic coupling of copper reagent | |
| JP4119842B2 (en) | Method and apparatus for producing hydrazodicarbonamide using urea as a starting material | |
| CN108558830B (en) | A kind of synthetic method of nicosulfuron raw medicine | |
| CN108047208A (en) | A kind of method for reducing Losartan dimer impurity | |
| CN108610290B (en) | Preparation method of fluxapyroxad | |
| KR20130013652A (en) | Process for preparing amino-triazolinone | |
| CN108997203B (en) | Efficient purification method of 2, 3-dichloro-5-trifluoromethylpyridine | |
| US4335260A (en) | Process for the preparation of N-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline having a low content of nitrosamines | |
| CN108912043A (en) | A kind of synthetic method of 2,3,5- trichloropyridine | |
| TWI564292B (en) | For the preparation of N-substituted pyrazole compounds | |
| CA2075805C (en) | Novel process for producing semicarbazide | |
| CN106565560A (en) | Synthesis process of mesotrione | |
| CN107556254A (en) | A kind of synthetic method of sulfentrazone | |
| JP2006503889A (en) | A novel method for preparing synthetic intermediates for pesticides | |
| CN107021936B (en) | A kind of method of coproduction BIT and MBIT | |
| CN110835323A (en) | Production method of important intermediate for synthesizing mesotrione | |
| CN109293591A (en) | A kind of preparation method of triazinone | |
| KR100473333B1 (en) | Method and apparatus for preparing hydrazodicarbonamide using urea as starting material | |
| US6133447A (en) | Process for the preparation of substituted pyridines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180126 |