CN113651771A - Synthesis method of combined buprofezin - Google Patents
Synthesis method of combined buprofezin Download PDFInfo
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- CN113651771A CN113651771A CN202110915440.XA CN202110915440A CN113651771A CN 113651771 A CN113651771 A CN 113651771A CN 202110915440 A CN202110915440 A CN 202110915440A CN 113651771 A CN113651771 A CN 113651771A
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- stirring
- distillation
- buprofezin
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- 239000005885 Buprofezin Substances 0.000 title claims abstract description 30
- PRLVTUNWOQKEAI-VKAVYKQESA-N buprofezin Chemical compound O=C1N(C(C)C)\C(=N\C(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-VKAVYKQESA-N 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 22
- NUJIXNWAWRCFKV-UHFFFAOYSA-N n-(chloromethyl)-n-phenylcarbamoyl chloride Chemical compound ClCN(C(Cl)=O)C1=CC=CC=C1 NUJIXNWAWRCFKV-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZFWFRTVIIMTOLY-UHFFFAOYSA-N 2-isothiocyanato-2-methylpropane Chemical compound CC(C)(C)N=C=S ZFWFRTVIIMTOLY-UHFFFAOYSA-N 0.000 claims abstract description 18
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims abstract description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000019253 formic acid Nutrition 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- JKZGKJJRHXYLRI-UHFFFAOYSA-N 1-tert-butyl-3-propan-2-ylthiourea Chemical compound CC(C)NC(=S)NC(C)(C)C JKZGKJJRHXYLRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 102
- 238000001816 cooling Methods 0.000 claims description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000000498 cooling water Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003466 welding Methods 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- ABIKNLOWSFHUPA-UHFFFAOYSA-N tert-butyl thiocyanate Chemical compound CC(C)(C)SC#N ABIKNLOWSFHUPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 206010003497 Asphyxia Diseases 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- -1 N-methylformamido Chemical group 0.000 abstract 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 241000238631 Hexapoda Species 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 241000238876 Acari Species 0.000 description 1
- 235000009024 Ceanothus sanguineus Nutrition 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 240000003553 Leptospermum scoparium Species 0.000 description 1
- 235000015459 Lycium barbarum Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SOYKEARSMXGVTM-UHFFFAOYSA-N chlorphenamine Chemical compound C=1C=CC=NC=1C(CCN(C)C)C1=CC=C(Cl)C=C1 SOYKEARSMXGVTM-UHFFFAOYSA-N 0.000 description 1
- 229960003291 chlorphenamine Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000974 larvacidal effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000026267 regulation of growth Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
- C07D285/16—Thiadiazines; Hydrogenated thiadiazines
- C07D285/34—1,3,5-Thiadiazines; Hydrogenated 1,3,5-thiadiazines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/02—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in boilers or stills
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of combined buprofezin, relates to the technical field of synthesis methods of buprofezin, and aims to solve the problem that the existing combined buprofezin usually uses a phosgene crop organic intermediate for reaction in the synthesis process, phosgene is severe asphyxia poison gas, and the phosgene can cause harm to human bodies after being inhaled by people. Adding N-methylaniline and formic acid into a reaction kettle to prepare N-methylformamido, adding the prepared N-methylformamido, carbon tetrachloride and benzoyl peroxide into a distillation kettle, introducing chlorine gas to prepare N-chloromethyl-N-phenylcarbamoyl chloride solution, then preparing tert-butyl isothiocyanate, then preparing N-tert-butyl-N' -isopropylthiourea solution, and finally adding the prepared N-chloromethyl-N-phenylcarbamoyl chloride solution, tert-butyl isothiocyanate, acetone, dimethylformamide and potassium hydroxide into the reaction kettle for reaction, thereby preparing the buprofezin crystal.
Description
Technical Field
The invention relates to the technical field of a synthesis method of buprofezin, in particular to a synthesis method of combined buprofezin.
Background
Buprofezin, also known as chlorpheniramine, belongs to an insect growth regulation pesticide, can be used as a selective insect growth regulator for inhibiting the synthesis of insect chitin, has the advantages of strong pest selectivity, high killing power, long residual effect period, low toxicity and the like, is mainly used for controlling pests of crops such as rice, fruit trees, tea trees, vegetables and the like, and has persistent larvicidal activity on coleoptera, partial homoptera and acarina, thereby effectively protecting crops.
However, in the synthesis process of the existing combined buprofezin, carbonyl chloride which is a severe asphyxia toxic gas is generally used as an organic intermediate for crop reaction, and is harmful to human bodies after being inhaled by people, so that a synthesis method of the combined buprofezin is urgently needed in the market to solve the problems.
Disclosure of Invention
The invention aims to provide a synthesis method of a combined buprofezin, which aims to solve the problem that the existing combined buprofezin in the background art usually uses a phosgene crop organic intermediate for reaction in the synthesis process, and phosgene is severe asphyxia toxic gas which can cause harm to human bodies after being inhaled by people.
In order to achieve the purpose, the invention provides the following technical scheme: a synthetic method of the combined buprofezin comprises the following steps:
step 1: adding 100g of N-methylaniline and 60g of formic acid into a reaction kettle, wherein the molar ratio of the N-methylaniline to the formic acid is 1:1.2, heating the reaction kettle to enable liquid in the reaction kettle to be in a heating state, gradually heating the reaction kettle to enable the temperature in the reaction kettle to rise to 200 ℃, enabling gas generated in the reaction kettle to enter a cooling tank for cooling, stopping reaction when no steam is generated in the liquid in the reaction kettle, cooling distilled steam through the cooling tank, and generating a brown oily substance after cooling, wherein the generated oily substance is 120g of N-methylformamide;
step 2: adding 120g of prepared N-methylformamide, 400ml of carbon tetrachloride and 6.2g of benzoyl peroxide into a distillation still, then introducing chlorine, raising the temperature in the distillation still to 60 ℃ through the distillation still, carrying out reaction tracking by using a gas chromatograph in the reaction process, stopping introducing the chlorine when N-chloromethyl-N-phenylcarbamoyl chloride is generated in the distillation still, then introducing nitrogen, thus discharging residual carbon tetrachloride and generated hydrogen chloride in the distillation still, then extracting the gas in the distillation still again by using a vacuum pump, enabling the interior of the distillation still to be in a relatively vacuum environment, then heating the heating still to 100 ℃, evaporating the solution in the distillation still for 30-40 minutes to evaporate the solvent in the solution, thus, the produced N-chloromethyl-N-phenyl carbamyl chloride solution can be purified, and the concentration of the produced N-chloromethyl-N-phenyl carbamyl chloride solution is higher;
wherein, the distillation kettle comprises a distillation kettle body, a mounting frame is installed below the distillation kettle body, supporting legs are installed below the mounting frame, a mounting plate is installed on one side of each supporting leg, a mounting seat is arranged at the upper end of the distillation kettle body, a speed reducer is installed above the mounting seat, a stirring motor is installed above the speed reducer, a stirring shaft is installed below the speed reducer, stirring blades are installed on two sides of the outer wall of the stirring shaft and are welded with the stirring shaft, a feed opening is arranged at the lower end of the distillation kettle body, a feed opening is arranged on one side of the mounting seat, a steam outlet is arranged on the other side of the mounting seat, a connecting pipeline is installed above the steam outlet, a cooling storage tank is installed at one end of the connecting pipeline, and a gas inlet is arranged at one end of the distillation kettle body, an electromagnetic valve is installed on one side of the gas inlet, a connecting seat is arranged at the other end of the distillation kettle body, a vacuumizing tube is installed on one side of the connecting seat, and a vacuumizing pump is installed at one end of the vacuumizing tube;
and step 3: adding 90g of ammonium thiocyanate and 1200ml of water into a stirring device, opening the stirring device to start stirring by the stirring device, thus, ammonium thiocyanate and water can be dissolved, 50g of tertiary butanol is added after the ammonium thiocyanate and the water are dissolved, the stirring is continued for 30 minutes, then the temperature in the stirring equipment is reheated to 80-100 ℃ by slowly heating the stirring equipment, then dropping 120ml of hydrogen chloride solution at a constant speed under the condition of stirring, stopping stirring, reducing the temperature in the stirring equipment to 50 ℃, standing the solution for 5 hours, layering the solution, then discharging the acid wastewater, adding anhydrous sodium sulfate into the upper oil layer, heating the stirring equipment to raise the internal temperature of the stirring equipment to 120 ℃, distilling the solution in the stirring equipment, and filtering out insoluble substances after distillation to obtain 110g of tert-butyl isothiocyanate;
and 4, step 4: adding chlorobenzene into a stirring device containing tert-butyl isothiocyanate, wherein the specific gravity of chlorobenzene to tert-butyl isothiocyanate is 6:1, opening the stirring device, stirring the stirring device for 30 minutes, simultaneously reducing the temperature inside the stirring device to 20-30 ℃, and then dropwise adding 60g of isopropylamine in the stirring process, wherein the molar ratio of the isopropylamine to tert-butyl thiocyanate is 1:1, finishing the dropwise addition of the isopropylamine within about 1 hour, continuously maintaining the temperature inside the stirring equipment at 20-30 ℃ after the dropwise addition of the isopropylamine is finished, and reacting the solution inside the stirring equipment for 4 hours to obtain an N-tert-butyl-N' -isopropylthiourea solution;
and 5: adding N-chloromethyl-N-phenyl carbamyl chloride solution, tert-butyl isothiocyanate, acetone, dimethylformamide and potassium hydroxide into a reaction kettle, reacting for 6 hours at room temperature, adding 500ml of water into a reacted object after the reaction is finished, then adding 300ml of benzene, extracting the reacted object through the benzene, repeatedly extracting for three times, removing the solvent benzene, and recrystallizing the liquid by using isopropanol, thus obtaining the buprofezin crystal.
Preferably, the number of the supporting feet is four, and the four supporting feet are symmetrical about a vertical center line of the mounting frame.
Preferably, the lower extreme of speed reducer is provided with the fixing base, pass through fixing bolt fixed connection between fixing base and the mount pad.
Preferably, the upper end of cooling holding vessel is provided with the stiff end, through fastening bolt fixed connection between the one end of connecting tube and the stiff end, through fastening bolt fixed connection between the other end of connecting tube and the steam outlet.
Preferably, the lower extreme of cooling holding vessel one side is provided with the cooling water inlet port, the top of cooling water inlet port is provided with the cooling water backward flow mouth, the lower extreme of cooling holding vessel is provided with the liquid outlet.
Preferably, the vacuum pumping pump is located above the mounting plate and is connected with the mounting plate in a welding mode.
Preferably, the connecting pipe is arranged obliquely.
Preferably, the distillation kettle body is connected with the mounting frame in a welded mode, and the cooling storage tank is connected with the mounting frame in a welded mode.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the synthesis method of the combined buprofezin, the N-chloromethyl-N-phenyl carbamyl chloride solution can be conveniently prepared through the arranged distillation kettle body, so that the concentration of the prepared N-chloromethyl-N-phenyl carbamyl chloride solution is better, and the quality of the produced buprofezin is better.
2. The formic acid is used in the synthesis method of the combined buprofezin, so that the phenomenon that the carbonyl chloride crop organic intermediate is used for reaction in the preparation process can be avoided, the carbonyl chloride has toxicity, when the carbonyl chloride is directly introduced for reaction, the body of a worker is easily injured when leakage occurs, and the harm to the body of the worker can be well avoided through the formic acid.
Drawings
FIG. 1 is a front view of a still body of the present invention;
FIG. 2 is a chemical reaction equation of step 1 of the present invention;
FIG. 3 is a chemical reaction equation of step 2 of the present invention;
FIG. 4 is a chemical reaction equation of step 3 of the present invention;
FIG. 5 is the chemical reaction equation of step 4 of the present invention;
FIG. 6 shows the chemical reaction equation of step 5 of the present invention.
In the figure: 1. a distillation kettle body; 101. a feed inlet; 102. a steam outlet; 103. a feeding port; 104. a connecting seat; 2. a mounting frame; 3. supporting legs; 4. mounting a plate; 5. a mounting seat; 6. a speed reducer; 601. a fixed seat; 7. a stirring motor; 8. fixing the bolt; 9. a stirring shaft; 10. stirring blades; 11. connecting a pipeline; 12. cooling the storage tank; 1201. a cooling water inlet port; 1202. a cooling water return port; 1203. a fixed end; 1204. a liquid outlet; 13. fastening a bolt; 14. a gas inlet; 15. an electromagnetic valve; 16. vacuumizing a tube; 17. and (4) vacuumizing the pump.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1-6, an embodiment of the present invention is shown: a synthetic method of the combined buprofezin comprises the following steps:
step 1: adding 100g of N-methylaniline and 60g of formic acid into a reaction kettle, wherein the molar ratio of the N-methylaniline to the formic acid is 1:1.2, heating the reaction kettle to enable liquid in the reaction kettle to be in a heating state, gradually heating the reaction kettle to enable the temperature in the reaction kettle to rise to 200 ℃, enabling gas generated in the reaction kettle to enter a cooling tank for cooling, stopping reaction when no steam is generated in the liquid in the reaction kettle, cooling distilled steam through the cooling tank, and generating a brown oily substance after cooling, wherein the generated oily substance is 120g of N-methylformamide;
step 2: adding 120g of prepared N-methylformamide, 400ml of carbon tetrachloride and 6.2g of benzoyl peroxide into a distillation still, then introducing chlorine, raising the temperature in the distillation still to 60 ℃ through the distillation still, carrying out reaction tracking by using a gas chromatograph in the reaction process, stopping introducing the chlorine when N-chloromethyl-N-phenylcarbamoyl chloride is generated in the distillation still, then introducing nitrogen, thus discharging residual carbon tetrachloride and generated hydrogen chloride in the distillation still, then extracting the gas in the distillation still again by using a vacuum pump, enabling the interior of the distillation still to be in a relatively vacuum environment, then heating the heating still to 100 ℃, evaporating the solution in the distillation still for 30-40 minutes to evaporate the solvent in the solution, thus, the produced N-chloromethyl-N-phenyl carbamyl chloride solution can be purified, and the concentration of the produced N-chloromethyl-N-phenyl carbamyl chloride solution is higher;
wherein, the distillation kettle comprises a distillation kettle body 1, a mounting frame 2 is arranged below the distillation kettle body 1, a supporting leg 3 is arranged below the mounting frame 2, a mounting plate 4 is arranged on one side of the supporting leg 3, a mounting seat 5 is arranged at the upper end of the distillation kettle body 1, a speed reducer 6 is arranged above the mounting seat 5, a stirring motor 7 is arranged above the speed reducer 6, a stirring shaft 9 is arranged below the speed reducer 6, stirring blades 10 are arranged on both sides of the outer wall of the stirring shaft 9, the stirring blades 10 are welded with the stirring shaft 9, a discharging port 103 is arranged at the lower end of the distillation kettle body 1, a charging port 101 is arranged on one side of the mounting seat 5, a steam outlet 102 is arranged on the other side of the mounting seat 5, a connecting pipeline 11 is arranged above the steam outlet 102, a cooling storage tank 12 is arranged at one end of the connecting pipeline 11, and a gas inlet 14 is arranged at one end of the distillation kettle body 1, an electromagnetic valve 15 is installed on one side of the gas inlet 14, a connecting seat 104 is arranged at the other end of the distillation kettle body 1, a vacuumizing tube 16 is installed on one side of the connecting seat 104, and a vacuumizing pump 17 is installed at one end of the vacuumizing tube 16;
and step 3: adding 90g of ammonium thiocyanate and 1200ml of water into a stirring device, opening the stirring device to start stirring by the stirring device, thus, ammonium thiocyanate and water can be dissolved, 50g of tertiary butanol is added after the ammonium thiocyanate and the water are dissolved, the stirring is continued for 30 minutes, then the temperature in the stirring equipment is reheated to 80-100 ℃ by slowly heating the stirring equipment, then dropping 120ml of hydrogen chloride solution at a constant speed under the condition of stirring, stopping stirring, reducing the temperature in the stirring equipment to 50 ℃, standing the solution for 5 hours, layering the solution, then discharging the acid wastewater, adding anhydrous sodium sulfate into the upper oil layer, heating the stirring equipment to raise the internal temperature of the stirring equipment to 120 ℃, distilling the solution in the stirring equipment, and filtering out insoluble substances after distillation to obtain 110g of tert-butyl isothiocyanate;
and 4, step 4: adding chlorobenzene into a stirring device containing tert-butyl isothiocyanate, wherein the specific gravity of chlorobenzene to tert-butyl isothiocyanate is 6:1, opening the stirring device, stirring the stirring device for 30 minutes, simultaneously reducing the temperature inside the stirring device to 20-30 ℃, and then dropwise adding 60g of isopropylamine in the stirring process, wherein the molar ratio of the isopropylamine to tert-butyl thiocyanate is 1:1, finishing the dropwise addition of the isopropylamine within about 1 hour, continuously maintaining the temperature inside the stirring equipment at 20-30 ℃ after the dropwise addition of the isopropylamine is finished, and reacting the solution inside the stirring equipment for 4 hours to obtain an N-tert-butyl-N' -isopropylthiourea solution;
and 5: adding N-chloromethyl-N-phenyl carbamyl chloride solution, tert-butyl isothiocyanate, acetone, dimethylformamide and potassium hydroxide into a reaction kettle, reacting for 6 hours at room temperature, adding 500ml of water into a reacted object after the reaction is finished, then adding 300ml of benzene, extracting the reacted object through the benzene, repeatedly extracting for three times, removing the solvent benzene, and recrystallizing the liquid by using isopropanol, thus obtaining the buprofezin crystal.
Further, the four supporting legs 3 are arranged, and the four supporting legs 3 are symmetrical about the vertical center line of the mounting frame 2, so that the stability of the mounting frame 2 can be improved.
Further, the lower extreme of speed reducer 6 is provided with fixing base 601, passes through fixing bolt 8 fixed connection between fixing base 601 and the mount pad 5, and what can be convenient installs fixedly between fixing base 601 and the mount pad 5.
Further, the upper end of cooling holding vessel 12 is provided with stiff end 1203, passes through fastening bolt 13 fixed connection between the one end of connecting tube 11 and stiff end 1203, passes through fastening bolt 13 fixed connection between the other end of connecting tube 11 and steam outlet 102, can be convenient be connected fixedly to cooling holding vessel 12 and connecting tube 11, can be convenient to install fixedly between connecting tube 11 and the steam outlet 102.
Further, the lower extreme of cooling holding vessel 12 one side is provided with cooling water inlet 1201, and the top of cooling water inlet 1201 is provided with cooling water backward flow mouth 1202, and the lower extreme of cooling holding vessel 12 is provided with liquid outlet 1204, can conveniently let in the inside of the inner wall of cooling holding vessel 12 with cooling water, then recycles, makes the cooling effect of cooling holding vessel 12 can be better like this.
Further, the vacuum pump 17 is located above the mounting plate 4, the vacuum pump 17 is connected with the mounting plate 4 in a welding mode, and the vacuum pump 17 and the mounting plate 4 can be conveniently and fixedly mounted.
Further, the connection pipe 11 is disposed obliquely, so that the steam entering the connection pipe 11 can enter the cooling storage tank 12 along the connection pipe 11 after being condensed.
Further, the distillation still kettle body 1 is connected with the mounting frame 2 in a welding mode, and the cooling storage tank 12 is connected with the mounting frame 2 in a welding mode, so that the firmness of installation between the distillation still kettle body 1 and the cooling storage tank 12 and the mounting frame 2 can be improved.
The working principle is as follows: when the preparation method is used, 100g of N-methylaniline and 60g of formic acid are added into a reaction kettle, the molar ratio of the N-methylaniline to the formic acid is 1:1.2, the reaction kettle is heated to enable liquid in the reaction kettle to be in a heating state, then the reaction kettle is gradually heated to enable the temperature in the reaction kettle to rise to 200 ℃, gas generated in the reaction kettle enters a cooling tank to be cooled, the reaction is stopped when no steam is generated in the liquid in the reaction kettle, then the distilled steam is cooled through the cooling tank to generate a brown oily substance after cooling, the generated oily substance is 120g of the N-methylformamide, 120g of the prepared N-methylformamide, 400ml of carbon tetrachloride and 6.2g of benzoyl peroxide are added into the distillation kettle, then chlorine is introduced, the temperature in the distillation kettle is raised to 60 ℃ through the distillation kettle, a gas chromatograph is adopted for reaction tracking in the reaction process, when N-chloromethyl-N-phenyl carbamoyl chloride is generated in a distillation kettle, the introduction of chlorine is stopped, then nitrogen is introduced, so that residual carbon tetrachloride and generated hydrogen chloride in the distillation kettle can be discharged, then the gas in the distillation kettle is extracted again through a vacuum pump, the interior of the distillation kettle is in a relatively vacuum environment, then the heated distillation kettle is heated to 100 ℃, the solution in the distillation kettle is evaporated for 30-40 minutes, so that the solvent in the solution is evaporated, the produced N-chloromethyl-N-phenyl carbamoyl chloride solution can be purified, the concentration of the produced N-chloromethyl-N-phenyl carbamoyl chloride solution is higher, adding 90g of ammonium thiocyanate and 1200ml of water into stirring equipment, opening the stirring equipment, starting stirring by the stirring equipment, dissolving the ammonium thiocyanate and the water, adding 50g of tert-butyl alcohol after dissolving, continuing stirring for 30 minutes, heating the stirring equipment slowly to 80-100 ℃ again, dripping 120ml of hydrogen chloride solution at a constant speed under stirring, stopping stirring, reducing the temperature in the stirring equipment to 50 ℃, standing the solution for 5 hours, layering the solution, discharging acidic wastewater, adding anhydrous sodium sulfate into an upper oil layer, heating the stirring equipment to 120 ℃, distilling the solution in the stirring equipment, filtering out insoluble substances after distillation to obtain 110g of tert-butyl isothiocyanate, adding chlorobenzene into a stirring device containing tert-butyl isothiocyanate, wherein the specific gravity of chlorobenzene to tert-butyl isothiocyanate is 6:1, opening the stirring device, stirring the stirring device for 30 minutes, simultaneously reducing the temperature inside the stirring device to 20-30 ℃, and then dropwise adding 60g of isopropylamine in the stirring process, wherein the molar ratio of the isopropylamine to tert-butyl thiocyanate is 1:1, dropwise adding isopropylamine for about 1 hour, keeping the temperature inside a stirring device to be 20-30 ℃ after dropwise adding isopropylamine, reacting the solution inside the stirring device for 4 hours to obtain an N-tert-butyl-N' -isopropylthiourea solution, adding the N-chloromethyl-N-phenylcarbamoyl chloride solution, tert-butyl isothiocyanate, acetone, dimethylformamide and potassium hydroxide into a reaction kettle, reacting for 6 hours at room temperature, adding 500ml of water into the reacted object after the reaction is finished, adding 300ml of benzene into the reacted object, extracting the reacted object through benzene, repeatedly extracting for three times, removing the solvent benzene, and recrystallizing the liquid by using isopropanol, thus obtaining the buprofezin crystal.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A synthetic method of the combined buprofezin is characterized by comprising the following steps:
step 1: adding 100g of N-methylaniline and 60g of formic acid into a reaction kettle, wherein the molar ratio of the N-methylaniline to the formic acid is 1:1.2, heating the reaction kettle to enable liquid in the reaction kettle to be in a heating state, gradually heating the reaction kettle to enable the temperature in the reaction kettle to rise to 200 ℃, enabling gas generated in the reaction kettle to enter a cooling tank for cooling, stopping reaction when no steam is generated in the liquid in the reaction kettle, cooling distilled steam through the cooling tank, and generating a brown oily substance after cooling, wherein the generated oily substance is 120g of N-methylformamide;
step 2: adding 120g of prepared N-methylformamide, 400ml of carbon tetrachloride and 6.2g of benzoyl peroxide into a distillation still, then introducing chlorine, raising the temperature in the distillation still to 60 ℃ through the distillation still, carrying out reaction tracking by using a gas chromatograph in the reaction process, stopping introducing the chlorine when N-chloromethyl-N-phenylcarbamoyl chloride is generated in the distillation still, then introducing nitrogen, thus discharging residual carbon tetrachloride and generated hydrogen chloride in the distillation still, then extracting the gas in the distillation still again by using a vacuum pump, enabling the interior of the distillation still to be in a relatively vacuum environment, then heating the heating still to 100 ℃, evaporating the solution in the distillation still for 30-40 minutes to evaporate the solvent in the solution, thus, the produced N-chloromethyl-N-phenyl carbamyl chloride solution can be purified, and the concentration of the produced N-chloromethyl-N-phenyl carbamyl chloride solution is higher;
wherein, the distillation kettle comprises a distillation kettle body (1), a mounting frame (2) is installed below the distillation kettle body (1), supporting legs (3) are installed below the mounting frame (2), a mounting plate (4) is installed on one side of the supporting legs (3), a mounting seat (5) is arranged at the upper end of the distillation kettle body (1), a speed reducer (6) is installed above the mounting seat (5), a stirring motor (7) is installed above the speed reducer (6), a stirring shaft (9) is installed below the speed reducer (6), stirring blades (10) are installed on two sides of the outer wall of the stirring shaft (9), the stirring blades (10) are welded with the stirring shaft (9), a feed opening (103) is arranged at the lower end of the distillation kettle body (1), and a feed inlet (101) is arranged on one side of the mounting seat (5), a steam outlet (102) is formed in the other side of the mounting seat (5), a connecting pipeline (11) is installed above the steam outlet (102), a cooling storage tank (12) is installed at one end of the connecting pipeline (11), a gas inlet (14) is formed in one end of the distillation kettle body (1), an electromagnetic valve (15) is installed at one side of the gas inlet (14), a connecting seat (104) is arranged at the other end of the distillation kettle body (1), a vacuumizing pipe (16) is installed at one side of the connecting seat (104), and a vacuumizing pump (17) is installed at one end of the vacuumizing pipe (16);
and step 3: adding 90g of ammonium thiocyanate and 1200ml of water into a stirring device, opening the stirring device to start stirring by the stirring device, thus, ammonium thiocyanate and water can be dissolved, 50g of tertiary butanol is added after the ammonium thiocyanate and the water are dissolved, the stirring is continued for 30 minutes, then the temperature in the stirring equipment is reheated to 80-100 ℃ by slowly heating the stirring equipment, then dropping 120ml of hydrogen chloride solution at a constant speed under the condition of stirring, stopping stirring, reducing the temperature in the stirring equipment to 50 ℃, standing the solution for 5 hours, layering the solution, then discharging the acid wastewater, adding anhydrous sodium sulfate into the upper oil layer, heating the stirring equipment to raise the internal temperature of the stirring equipment to 120 ℃, distilling the solution in the stirring equipment, and filtering out insoluble substances after distillation to obtain 110g of tert-butyl isothiocyanate;
and 4, step 4: adding chlorobenzene into a stirring device containing tert-butyl isothiocyanate, wherein the specific gravity of chlorobenzene to tert-butyl isothiocyanate is 6:1, opening the stirring device, stirring the stirring device for 30 minutes, simultaneously reducing the temperature inside the stirring device to 20-30 ℃, and then dropwise adding 60g of isopropylamine in the stirring process, wherein the molar ratio of the isopropylamine to tert-butyl thiocyanate is 1:1, finishing the dropwise addition of the isopropylamine within about 1 hour, continuously maintaining the temperature inside the stirring equipment at 20-30 ℃ after the dropwise addition of the isopropylamine is finished, and reacting the solution inside the stirring equipment for 4 hours to obtain an N-tert-butyl-N' -isopropylthiourea solution;
and 5: adding N-chloromethyl-N-phenyl carbamyl chloride solution, tert-butyl isothiocyanate, acetone, dimethylformamide and potassium hydroxide into a reaction kettle, reacting for 6 hours at room temperature, adding 500ml of water into a reacted object after the reaction is finished, then adding 300ml of benzene, extracting the reacted object through the benzene, repeatedly extracting for three times, removing the solvent benzene, and recrystallizing the liquid by using isopropanol, thus obtaining the buprofezin crystal.
2. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the four supporting legs (3) are symmetrical about the vertical center line of the mounting frame (2).
3. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the lower extreme of speed reducer (6) is provided with fixing base (601), pass through fixing bolt (8) fixed connection between fixing base (601) and mount pad (5).
4. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the upper end of cooling holding vessel (12) is provided with stiff end (1203), pass through fastening bolt (13) fixed connection between one end of connecting tube (11) and stiff end (1203), pass through fastening bolt (13) fixed connection between the other end of connecting tube (11) and steam outlet (102).
5. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the lower extreme of cooling storage tank (12) one side is provided with cooling water inlet port (1201), the top of cooling water inlet port (1201) is provided with cooling water backward flow mouth (1202), the lower extreme of cooling storage tank (12) is provided with liquid outlet (1204).
6. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the vacuum pumping pump (17) is located above the mounting plate (4), and the vacuum pumping pump (17) is connected with the mounting plate (4) in a welding mode.
7. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the connecting pipeline (11) is obliquely arranged.
8. The method for synthesizing the combined buprofezin according to claim 1, characterized in that: the distillation still kettle body (1) is connected with the mounting rack (2) in a welding mode, and the cooling storage tank (12) is connected with the mounting rack (2) in a welding mode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114573487A (en) * | 2022-03-11 | 2022-06-03 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing butylpropylthiourea |
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