CN107739341A - A kind of preparation method of climbazole - Google Patents
A kind of preparation method of climbazole Download PDFInfo
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- CN107739341A CN107739341A CN201711047092.9A CN201711047092A CN107739341A CN 107739341 A CN107739341 A CN 107739341A CN 201711047092 A CN201711047092 A CN 201711047092A CN 107739341 A CN107739341 A CN 107739341A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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Abstract
The invention discloses a kind of preparation method of climbazole, this method is insulation reaction 4 hours, then to pass through crystallization, purifying at 100~110 DEG C with toluene, cloroecther ketone, imidazoles and catalyst raw material, alkali cleaning, the climbazole of high purity 99% is prepared the methods of recrystallization.The present invention screens the preparation method of optimal climbazole by many experiments, whole technological design is reasonable, technological operation is simple, efficient, especially filter out optimal reaction condition, including catalyst type, reaction dissolvent, reaction temperature, reaction time and toluene and climbazole crude product react and its steps such as buck is washed, and can greatly improve reaction yield (up to more than 92%), reduce side reaction, reaction rate is improved, significantly lowers production cost, there is good application prospect.
Description
Technical field
The invention belongs to synthesising chemical technology field, and in particular to a kind of preparation method of climbazole.
Background technology
Climbazole, Chinese:1- (4- chloros phenoxy group) -1- (1H- imidazoles -1- bases) -3,3- dimethyl-2-butanones,
Climbazole has broad-spectrum sterilization performance, is mainly used in the hair washing of relieving itching and removing dandruff conditioning-type, hair conditioning shampoo, it can also be used to Antibacterial soaps,
In the high-grade articless for washing such as shower cream, medicated toothpaste, rinse liquid.
Synthetic method in the prior art on climbazole is less, and combined coefficient is less efficient, and yield is low, and reacts bar
Part requires high, and the feature of environmental protection is poor, and the climbazole purity that synthesis obtains is relatively low, and cost is higher.
The content of the invention
Goal of the invention：The invention aims to overcome the deficiencies in the prior art, there is provided a kind of technological design is reasonable, operation
Convenient, cost is low, and combined coefficient is high, and yield is high, the preparation method of the high climbazole of purity.
Technical scheme：In order to solve the above technical problems, the technical scheme that the present invention takes is：
A kind of preparation method of climbazole, it is characterised in that comprise the following steps：
Step 1：
Toluene, cloroecther ketone, imidazoles, catalyst are put into reactor in order, then started to warm up, when heating reaches
Certain temperature, steam off valve, starts insulation reaction, after insulation terminates, is cooled to 80~90 DEG C, adds water, enter water-filling immediately
Wash；Then stir at 50~60 DEG C, then stand, separate water layer, reaction mass then is transferred into crystallization kettle is crystallized, so
Centrifuge is discharged to after cooling afterwards, climbazole crude product is obtained after centrifugation；
Step 2：
Take toluene and climbazole crude product that step 1 is prepared, put into reactor, heating, be incubated 2~4 hours, then
Add alkali and water to carry out alkali cleaning, washing is added water after alkali cleaning, water layer is separated after washing, then receive material press filtration to crystallization with filter press
Kettle, then with cooling water temperature, centrifuge is then discharged to, dries to obtain climbazole.
Preferably, the preparation method of above-described climbazole, comprises the following steps：
Step 1：
Toluene, cloroecther ketone, imidazoles, catalyst are put into reactor in order, then begin to warm to 100~110
DEG C, steam off valve, starts insulation reaction 4 hours immediately after, after insulation terminates, is cooled to 80~90 DEG C, adds water, carries out
Washing；Then stirred at 50~60 DEG C 30 minutes, then stand 30 minutes, separate water layer, reactant is then transferred to crystallization
Kettle is crystallized, and centrifuge is discharged to after then cooling 2 hours, and climbazole crude product sediment is obtained after centrifugation；
Step 2：
Take toluene and climbazole crude product that step 1 is prepared, put into reactor, then heat to 80~90 DEG C, protect
Temperature 2 hours, then plus alkali and water carry out alkali cleaning, and washing is added water after alkali cleaning, water layer is separated after washing, then with filter press by thing
Press filtration is expected to crystallization kettle, is then crystallized with cooling water temperature to 35 DEG C, is then discharged to centrifuge, obtains centrifugation
Thing, dry to obtain climbazole.
Preferably, the preparation method of described climbazole, described catalyst are N, N dimethyl benzyl acid amides.
Preferably, the preparation method of described climbazole, toluene, cloroecther ketone, imidazoles, catalyst in step 1
Weight ratio be 3：3：1.5~1.65：0.25~0.3.The present invention is screened by many experiments, using toluene as reaction dissolvent,
Screen the toluene (1~10) of different weight ratio:Cloroecther ketone (1~10)：The conjunction of imidazoles (1~10) and catalyst (0.1~5)
Into reaction, test result indicates that, when the weight ratio of toluene, cloroecther ketone, imidazoles, catalyst is 3：3：1.65：When 0.26, reaction
Yield reaches as high as more than 92%, and therefore, the part by weight is the optimal raw material weight ratio of the present invention.
Preferably, the preparation method of described climbazole, it is characterised in that toluene and climbazole are thick in step 2
The weight ratio of product is 3：1.
Preferably, the preparation method of described climbazole, it is characterised in that the alkali used in alkali cleaning is hydroxide
Sodium, potassium hydroxide, sodium carbonate, potassium carbonate or organic base.
Craft screening is tested：
1st, catalyst screening is tested：
The present invention, which has screened, does not dose the catalyst catalyst different with addition, by toluene, cloroecther ketone, imidazoles, catalysis
Agent (different catalysts include palladium carbon, platinum, Raney's nickel, N, N dimethyl benzyl acid amides, Methylethyl benzyl acid amides etc.) is by input reactor
In, 100~110 DEG C are then begun to warm to, immediately after steam off valve, start insulation reaction 4 hours.Obtain climbazole
The yield of crude product is respectively such as following table：
Test result indicates that, present invention reaction uses N, and N dimethyl benzyl acid amides is greatly improved as catalyst more than
Reaction rate and raising yield.
2nd, the screening experiment in reaction temperature and reaction time
The present invention has screened different reaction temperatures and reaction time, by toluene, cloroecther ketone, imidazoles, catalyst by suitable
Sequence input reactor in, then begin to warm to 80~150 DEG C, immediately after steam off valve, start insulation reaction 0.5 to
4 hours, the yield for obtaining climbazole crude product was respectively such as following table：
Shown by above screening experiment result, different reaction temperatures and reaction time have to the yield of climbazole crude product
Very big influence, when reaction temperature be 100 to 110 DEG C, react 4 hours, yield highest.Therefore the present invention is preferably 100 to 110
Insulation reaction 4 hours is preferred plan at DEG C.
In step 2, add alkali and water to carry out alkali cleaning, washing is added water after alkali cleaning, can remove the impurity components such as parachlorophenol, carry
High-purity and yield.
The present invention screens the synthesis technique of cloroecther ketone by many experiments, and specific synthetic reaction step is：
The preparation of (1) one chlorine pinacolone：Pinacolone is pumped into pinacolone head tank, it is stand-by；It is high-order that methanol is pumped into methanol
Groove is stand-by；
Liquid chlorine by liquid chlorine cylinder after vaporizer vaporizes (40 DEG C), into Chlorine Buffer Vessel (0.35~0.45MPa), through turning
After the control of subflow gauge.Chlorination post is passed through, while opens the baiting valve of pinacolone head tank and methanol head tank, condensed device mixes
After conjunction, be passed through chlorination post and chlorination reaction occur for the chlorine that is passed through, Stress control in 0.09MPa or so, temperature control -5 to
10℃.Accumulator still is flowed into through overchlorinated pinacolone methanol solution, then after sending condenser cooling back to transfering material pump, then passes through chlorination
Post carries out second of chlorination, until chlorination obtains a chlorine pinacolone methanol solution completely.By a chlorine pinacolone methanol solution by turning material
Pump squeezes into distillation still, is evaporated under reduced pressure under negative pressure (- 0.08MPa), and solvent methanol steams recovery at 50 DEG C, will be stayed after precipitation
The chlorine pinacolone barrelling of product one in kettle is stand-by.
Chlorine inlet pipeline is equipped with stop valve；Overtemperature alarm, temperature and the interlocking of chlorine feed pipeline stop valve.Methanol distills
Kettle sets overtemperature alarm；Distillation still sets overtemperature alarm, temperature and the interlocking of steam pipe line stop valve.Pinacolone and chlorine mol ratio
For 1:1.1.
(2) preparation of cloroecther ketone：
It is stand-by that toluene is squeezed into toluene head tank, stand-by, the Xiang Shuigao that is pumped into a chlorine pinacolone to a chlorine pinacolone head tank
It is stand-by that process water is added in the groove of position, it is stand-by to be pumped into chlorosulfuric acid to chlorosulfuric acid head tank.
The inlet valve of toluene head tank is opened, the toluene measured is put into ether ketone kettle, puts into parachlorophenol, carbon again successively
Sour potassium, stirring are warming up to 68 DEG C, instill a quantitative chlorine pinacolone to its back flow reaction 8 hours, and prepared by " ether ketone " terminates, and cools
Sylvite water point is removed after adding washing sylvite, waste water decontamination water process, ether ketone is pumped into chlorination tank, under 30 DEG C~35 DEG C stirrings, beaten
The baiting valve of chlorosulfuric acid head tank is opened, quantitative chlorosulfuric acid is instilled into chlorination tank in 6 hours, is incubated 3 hours at 35 DEG C, insulation knot
Beam, part toluene recovery is steamed at -0.08MPa, 80 DEG C and is applied mechanically, and the material of chlorination tank is transferred into crystallization kettle, cold at 0-5 DEG C
But crystallize, product cloroecther ketone is dried to obtain by centrifuge；The toluene mixture recovery being centrifuged out.One chlorine pinacolone：
Parachlorophenol：The mol ratio of chlorosulfuric acid is 1:1~1.2：1~1.2.
Chlorosulfuric acid drop tube is traditional thread binding stop valve, and chlorination tank sets overtemperature alarm, and stop valve connection is added dropwise in temperature and chlorosulfuric acid
Lock；Temperature and the interlocking of chlorination tank steam pipe line stop valve.
Key reaction equation：
One chlorine pinacolone and into equation：
Condensation
Chloride
Beneficial effect：The present invention screens the preparation method of optimal climbazole by many experiments, and whole technological design is closed
Reason, technological operation is simple, efficient, especially filters out optimal reaction condition, including catalyst type, reaction dissolvent, reaction
Temperature, reaction time and toluene and climbazole crude product react and its steps such as buck is washed, and it is (reachable can greatly to improve reaction yield
More than 92%) side reaction, is reduced, reaction rate is improved, significantly lowers production cost, there is good application prospect.The present invention
Agricultural chemicals and medication chemistry can be used for add the preparation of agent etc. in the climbazole being prepared.
Brief description of the drawings
Fig. 1 is the synthetic reaction flow chart of the present invention.
Embodiment
In the following embodiments, illustrations are carried out to the present invention by way of examples.Tool described by embodiment
Material proportion, process conditions and its result of body are merely to illustrate the present invention, without should be also without limitation in claims
The present invention described in detail.
Embodiment 1：The preparation method of climbazole, it comprises the following steps：
Step 1：The preparation of cloroecther ketone
The preparation of one chlorine pinacolone:
Pinacolone is pumped into pinacolone head tank, it is stand-by；It is stand-by that methanol is pumped into methanol head tank；
Liquid chlorine by liquid chlorine cylinder after vaporizer vaporizes (40 DEG C), into Chlorine Buffer Vessel (0.35~0.45MPa), through turning
After the control of subflow gauge.Chlorination post is passed through, while opens the baiting valve of pinacolone head tank and methanol head tank, condensed device mixes
After conjunction, be passed through chlorination post and chlorination reaction occur for the chlorine that is passed through, Stress control in 0.09MPa or so, temperature control -5 to
10℃.Accumulator still is flowed into through overchlorinated pinacolone methanol solution, then after sending condenser cooling back to transfering material pump, then passes through chlorination
Post carries out second of chlorination, until chlorination obtains a chlorine pinacolone methanol solution completely.By a chlorine pinacolone methanol solution by turning material
Pump squeezes into distillation still, is evaporated under reduced pressure under negative pressure (- 0.08MPa), and solvent methanol steams recovery at 50 DEG C, will be obtained after precipitation
(MS shows that the mass spectrometric data of product is 134.6 to one chlorine pinacolone product, and high resolution mass spectrum shows that its molecular formula is C6H11ClO)；
Chlorine inlet pipeline is equipped with stop valve；Overtemperature alarm, temperature and the interlocking of chlorine feed pipeline stop valve.Methanol distills
Kettle sets overtemperature alarm；Distillation still sets overtemperature alarm, temperature and the interlocking of steam pipe line stop valve.Pinacolone and chlorine mol ratio
For 1:1.1.
(2) preparation of cloroecther ketone：
It is stand-by that toluene is squeezed into toluene head tank, stand-by, the Xiang Shuigao that is pumped into a chlorine pinacolone to a chlorine pinacolone head tank
It is stand-by that process water is added in the groove of position, it is stand-by to be pumped into chlorosulfuric acid to chlorosulfuric acid head tank；
The inlet valve of toluene head tank is opened, the toluene measured is put into ether ketone kettle, puts into parachlorophenol, carbon again successively
Sour potassium, stirring are warming up to 68 DEG C, instill a quantitative chlorine pinacolone to its back flow reaction 8 hours, " ether ketone " reaction preparation and terminate
Afterwards, sylvite water point is removed after cooling plus washing sylvite, waste water decontamination water process, ether ketone is pumped into chlorination tank, stirred at 30 DEG C~35 DEG C
Mix down, open the baiting valve of chlorosulfuric acid head tank, quantitative chlorosulfuric acid is instilled into chlorination tank in 6 hours, 3 hours are incubated at 35 DEG C,
Insulation terminates, and part toluene recovery is steamed at -0.08MPa, 80 DEG C and is applied mechanically, and the material of chlorination tank is transferred into crystallization kettle, in 0-5
Crystallisation by cooling at DEG C, by centrifuge, obtaining product cloroecther ketone, (MS shows that the mass spectrometric data of product is 261, high resolution mass spectrum
It is C to show its molecular formula12H14Cl2O2)；The toluene mixture recovery being centrifuged out.
Chlorosulfuric acid drop tube is traditional thread binding stop valve, and chlorination tank sets overtemperature alarm, and stop valve connection is added dropwise in temperature and chlorosulfuric acid
Lock；Temperature and the interlocking of chlorination tank steam pipe line stop valve.The step 1 chlorine pinacolone：Parachlorophenol：The mol ratio of chlorosulfuric acid is
1:1.2:1.2。
Step 2：As shown in figure 1, by 300kg toluene, cloroecther ketone 300Kg, imidazoles 165Kg, 26Kg catalyst (N, N bis-
Methyl benzyl acid amides) once put into reactor, it is noted that feeding sequence, is started to warm up during feeding intake, when temperature in the kettle reaches
At 100~110 DEG C, steam off valve, starts to be incubated (overtemperature emergency processing immediately：Valve is closed, stops stirring, opens safety
Valve exhaust, to set point of temperature closing valve, it is incubated), 4 hours are incubated, after insulation terminates, 80~90 DEG C is cooled to, adds water
250Kg, washed.Then stirred 30 minutes at 50~60 DEG C, stand 30 minutes, divide water, reaction product is then transferred to knot
Brilliant kettle is crystallized, and is cooled 2 hours, is discharged to centrifuge, and climbazole crude product, yield 91%, purity 85% are obtained after centrifugation.
Step 3：900Kg toluene and step 1 are prepared in 296Kg climbazoles crude product input reactor, are warming up to 80
~90 DEG C, it is incubated 2 hours.It is hydrogenated with sodium oxide molybdena 15Kg, water 200Kg and carries out alkali cleaning, divides water after alkali cleaning plus after water 200Kg washings, so
Receive material press filtration to crystallization kettle with filter press afterwards, centrifuge be discharged to 35 DEG C with cooling water temperature, centrifuge climbazole (MS shows
The mass spectrometric data for showing product is 292.76, and high resolution mass spectrum shows that its molecular formula is C15H17ClN2O2), drying both obtains (yield
91%, purity 99%).
The preparation method of the climbazole of comparative example 1, it comprises the following steps：
Step 1：300kg toluene, cloroecther ketone 300Kg, imidazoles 165Kg are once put into reactor, in the process of feeding intake
In it is noted that feeding sequence, is started to warm up, when temperature in the kettle is up to 100~110 DEG C, steam off valve, starts to be incubated immediately,
Insulation 4 hours, after insulation terminates, 80~90 DEG C are cooled to, adds water 250Kg, is washed.Then 30 points are stirred at 50~60 DEG C
Clock, 30 minutes standing, divides water, reaction product then is transferred into crystallization kettle is crystallized, and is cooled 2 hours, is discharged to centrifuge, from
Climbazole crude product, yield 64%, purity 75% are obtained after the heart.
Step 2：296Kg climbazoles are prepared in step 1 and slightly receive material press filtration to crystallization kettle with filter press, use cooling water
It is cooled to 35 DEG C and is discharged to centrifuge, centrifuge to obtain climbazole, drying both obtained (yield 81%, purity 86%).
The preparation method of the climbazole of comparative example 2, it comprises the following steps：
Step 1：By 300kg toluene, cloroecther ketone 300Kg, imidazoles 165Kg, 26Kg catalyst (N, N dimethyl benzyl acid amides)
Once put into reactor, it is noted that feeding sequence, is started to warm up during feeding intake, when temperature in the kettle is up to 100~110 DEG C
When, steam off valve, starts to be incubated (overtemperature emergency processing immediately：Valve is closed, stops stirring, safe valve exhaust is opened, to rule
Constant temperature degree closing valve, is incubated), 4 hours are incubated, after insulation terminates, 80~90 DEG C is cooled to, adds water 250Kg, enter water-filling
Wash.Then stirring 30 minutes at 50~60 DEG C, stand 30 minutes, divide water, reaction product then is transferred into crystallization kettle is crystallized,
Cooling 2 hours, is discharged to centrifuge, and climbazole crude product, yield 92%, purity 85% are obtained after centrifugation.
Step 2：Step 2：296Kg climbazoles are prepared in step 1 and slightly receive material press filtration to crystallization kettle with filter press, are used
Cooling water temperature is discharged to centrifuge to 1 DEG C, centrifuges to obtain climbazole, drying both (yield 82%, purity 90%).
The preparation method of the climbazole of comparative example 3, it comprises the following steps：
Step 1：By 300kg toluene, cloroecther ketone 300Kg, imidazoles 165Kg, 26Kg catalyst (N, N dimethyl benzyl acid amides)
Once put into reactor, it is noted that feeding sequence, is started to warm up during feeding intake, when temperature in the kettle is up to 100~110 DEG C
When, steam off valve, starts to be incubated (overtemperature emergency processing immediately：Valve is closed, stops stirring, safe valve exhaust is opened, to rule
Constant temperature degree closing valve, is incubated), 4 hours are incubated, after insulation terminates, 80~90 DEG C is cooled to, adds water 250Kg, enter water-filling
Wash.Then stirring 30 minutes at 50~60 DEG C, stand 30 minutes, divide water, reaction product then is transferred into crystallization kettle is crystallized,
Cooling 2 hours, is discharged to centrifuge, and climbazole crude product, yield 90%, purity 85% are obtained after centrifugation.
Step 2：900Kg toluene and step 1 are prepared in 296Kg climbazoles crude product input reactor, are warming up to 80
~90 DEG C, it is incubated 2 hours.Add water 200Kg to divide water after washing, then receive material press filtration to crystallization kettle with filter press, use cooling water
It is cooled to 35 DEG C and is discharged to centrifuge, centrifuge to obtain climbazole, drying both obtained (yield 89%, purity 93%).
The preparation method of the climbazole of comparative example 4, it comprises the following steps：
Step 1：By 160kg ethanol, cloroecther ketone 300Kg, imidazoles 165Kg, 26Kg catalyst (N, N dimethyl benzyl acid amides)
Once put into reactor, it is noted that feeding sequence, is started to warm up during feeding intake, when temperature in the kettle is up to 100~110 DEG C
When, steam off valve, starts to be incubated (overtemperature emergency processing immediately：Valve is closed, stops stirring, safe valve exhaust is opened, to rule
Constant temperature degree closing valve, is incubated), 4 hours are incubated, after insulation terminates, 80~90 DEG C is cooled to, adds water 250Kg, enter water-filling
Wash.Then stirring 30 minutes at 50~60 DEG C, stand 30 minutes, divide water, reaction product then is transferred into crystallization kettle is crystallized,
Cooling 2 hours, is discharged to centrifuge, and climbazole crude product, yield 89%, purity 84% are obtained after centrifugation.
Step 2：900Kg toluene and step 1 are prepared in 296Kg climbazoles crude product input reactor, are warming up to 80
~90 DEG C, it is incubated 2 hours.It is hydrogenated with sodium oxide molybdena 15Kg, water 200Kg and carries out alkali cleaning, divides water after alkali cleaning plus after water 200Kg washings, so
Material press filtration is received to crystallization kettle with filter press afterwards, is discharged to centrifuge to 35 DEG C with cooling water temperature, is centrifuged to obtain climbazole, dry
Both (yield 89%, purity 98%) was obtained.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of climbazole, it is characterised in that comprise the following steps：
Step 1：
Toluene, cloroecther ketone, imidazoles, catalyst are put into reactor in order, then started to warm up, when heating reaches certain
Temperature, start insulation reaction, after insulation terminates, be cooled to 80~90 DEG C, add water, washed；Then stirred at 50~60 DEG C
Mix, then stand, separate water layer, reaction mass then is transferred into crystallization kettle is crystallized, and centrifuge is discharged to after then cooling,
Climbazole crude product is obtained after centrifugation；
Step 2：
Then plus alkali take toluene and climbazole crude product that step 1 is prepared, put into reactor, heating, be incubated 2~4 hours,
Alkali cleaning is carried out with water, washing is added water after alkali cleaning, water layer is separated after washing, then with filter press receipts material press filtration to crystallization kettle,
Then cooling water temperature is used, is then discharged to centrifuge, dries to obtain climbazole.
2. the preparation method of climbazole according to claim 1, it is characterised in that comprise the following steps：
Step 1：
Toluene, cloroecther ketone, imidazoles, catalyst are put into reactor in order, then begin to warm to 100~110 DEG C, so
Steam off valve immediately afterwards, starts insulation reaction 4 hours, after insulation terminates, is cooled to 80~90 DEG C, adds water, washed；
Then stirred at 50~60 DEG C 30 minutes, then stand 30 minutes, separate water layer, reactant then is transferred into crystallization kettle is carried out
Crystallization, centrifuge is discharged to after then cooling 2 hours, climbazole crude product sediment is obtained after centrifugation；
Step 2：
Take toluene and climbazole crude product that step 1 is prepared, put into reactor, then heat to 80~90 DEG C, insulation 2 is small
When, then plus alkali and water carry out alkali cleaning, and washing is added water after alkali cleaning, water layer is separated after washing, then with filter press by material pressure
Then filter is crystallized to 35 DEG C with cooling water temperature, is then discharged to centrifuge, obtains centrifugal sediment to crystallization kettle,
Dry to obtain climbazole.
3. the preparation method of climbazole according to claim 1 or 2, it is characterised in that described catalyst is N, N diformazans
Base benzyl acid amides.
4. the preparation method of climbazole according to claim 3, it is characterised in that toluene, cloroecther ketone, miaow in step 1
Azoles, the weight ratio of catalyst are 3：3：1.5~1.65：0.25~0.3.
5. the preparation method of climbazole according to claim 4, it is characterised in that toluene and climbazole crude product in step 2
Weight ratio be 3：1.
6. the preparation method of climbazole according to claim 5, it is characterised in that alkali used in alkali cleaning is sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate or organic base.
7. the preparation method of climbazole according to claim 6, it is characterised in that the preparation method of cloroecther ketone include with
Lower step：
The preparation of (1) one chlorine pinacolone：
Pinacolone is pumped into pinacolone head tank, it is stand-by；It is stand-by that methanol is pumped into methanol head tank；
By liquid chlorine by liquid chlorine cylinder after vaporizer vaporizes, into Chlorine Buffer Vessel, after spinner flowmeter controls, be passed through chlorination
Post；Open the baiting valve of pinacolone head tank and methanol head tank simultaneously, after condensed device mixing, be passed through chlorination post and be passed through
Chlorination reaction occurs for chlorine, and Stress control is in 0.09~0.1MPa or so, and temperature control is at -5 to 10 DEG C；Through overchlorinated frequency that
Ketone methanol solution flow into accumulator still, then with transfering material pump send back to condenser cooling after, then by chlorination post carry out second of chlorination, directly
A chlorine pinacolone methanol solution is obtained completely to chlorination；One chlorine pinacolone methanol solution is squeezed into distillation still by transfering material pump, in negative pressure
Lower vacuum distillation, solvent methanol steam recovery, obtain a chlorine pinacolone；
(2) preparation of cloroecther ketone：
The chlorine frequency that toluene is stand-by, is prepared to chlorine pinacolone head tank suction step (1) is squeezed into toluene head tank
Ketone is stand-by, and process water is added into water head tank, stand-by, and it is stand-by to be pumped into chlorosulfuric acid to chlorosulfuric acid head tank；
The inlet valve of toluene head tank is opened, the toluene measured is put into ether ketone kettle, puts into parachlorophenol, carbonic acid again successively
Potassium, stirring are warming up to 65~70 DEG C, instill a quantitative chlorine pinacolone to its back flow reaction 6~8 hours, after reaction terminates, drop
Divide after temperature plus washing sylvite and remove sylvite water, waste water decontamination water process, reaction product is pumped into chlorination tank, in 30 DEG C~35 DEG C stirrings
Under, the baiting valve of chlorosulfuric acid head tank is opened, quantitative chlorosulfuric acid is instilled into chlorination tank, 2~3 hours are incubated at 30~35 DEG C,
Insulation terminates, and steams part toluene recovery and applies mechanically, and the material of chlorination tank is transferred into crystallization kettle, the crystallisation by cooling at 0-5 DEG C, by from
Product cloroecther ketone is dried to obtain in scheming centrifugation；The toluene mixture recovery being centrifuged out.
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| CN114890951A (en) * | 2022-05-09 | 2022-08-12 | 山东汉峰新材料科技有限公司 | Synthesis method of Ganbaosu |
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| US4229580A (en) * | 1977-03-29 | 1980-10-21 | Bayer Aktiengesellschaft | Preparation of 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones |
| US20050107454A1 (en) * | 2003-11-17 | 2005-05-19 | Symrise Gmbh & Co. Kg. | Process for the purification of climbazole |
| CN101020663A (en) * | 2007-03-20 | 2007-08-22 | 盐城市绿叶化工有限公司 | Synthesis method of climbazole |
| CN104418813A (en) * | 2013-09-03 | 2015-03-18 | 青岛好利特生物农药有限公司 | Preparation method of triazolone |
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- 2017-10-31 CN CN201711047092.9A patent/CN107739341A/en active Pending
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|---|---|---|---|---|
| US4229580A (en) * | 1977-03-29 | 1980-10-21 | Bayer Aktiengesellschaft | Preparation of 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones |
| US20050107454A1 (en) * | 2003-11-17 | 2005-05-19 | Symrise Gmbh & Co. Kg. | Process for the purification of climbazole |
| CN101020663A (en) * | 2007-03-20 | 2007-08-22 | 盐城市绿叶化工有限公司 | Synthesis method of climbazole |
| CN104418813A (en) * | 2013-09-03 | 2015-03-18 | 青岛好利特生物农药有限公司 | Preparation method of triazolone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114890951A (en) * | 2022-05-09 | 2022-08-12 | 山东汉峰新材料科技有限公司 | Synthesis method of Ganbaosu |
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