CN106496215B - High-yield green environment-friendly synthetic method of thiamethoxam - Google Patents
High-yield green environment-friendly synthetic method of thiamethoxam Download PDFInfo
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- CN106496215B CN106496215B CN201610979438.8A CN201610979438A CN106496215B CN 106496215 B CN106496215 B CN 106496215B CN 201610979438 A CN201610979438 A CN 201610979438A CN 106496215 B CN106496215 B CN 106496215B
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- 239000005941 Thiamethoxam Substances 0.000 title claims abstract description 16
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 title claims abstract description 16
- 238000010189 synthetic method Methods 0.000 title description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 32
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- LETVJWLLIMJADE-UHFFFAOYSA-N pyridazin-3-amine Chemical compound NC1=CC=CN=N1 LETVJWLLIMJADE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- VRMUIVKEHJSADG-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CN=C(Cl)S1 VRMUIVKEHJSADG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 239000012452 mother liquor Substances 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 2
- GAYLOVDFGKQKCJ-UHFFFAOYSA-N n-(3-methyl-2,6-dihydro-1,3,5-oxadiazin-4-yl)nitramide Chemical group CN1COCN=C1N[N+]([O-])=O GAYLOVDFGKQKCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 19
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000006228 supernatant Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 abstract 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 12
- 238000007654 immersion Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 210000003169 central nervous system Anatomy 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 1
- 229960004373 acetylcholine Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003993 organochlorine pesticide Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- -1 potassium halide Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种噻虫嗪的高收率且绿色环保合成方法：A、称取亚氨基二嗪0.5‑1.5份、2‑氯‑5‑氯甲基噻唑0.5‑1.5份、二甲基甲酰胺0.2‑2份、丁酮0.2‑2份、甲苯0.2‑2份、碳酸钾0.5‑1.5份、催化剂0.001‑0.01份，投入到合成釜中并混匀，搅拌反应；B、步骤A所得产物升温到30‑70℃加入浸洗剂进行浸洗，随后离心过滤获得盐分作为副产品，有机上清液送入到结晶釜，冷冻结晶，离心得噻虫嗪固体，离心母液送到溶剂回收塔蒸馏回用。本发明通过改进反应原料的选择和配比以及对合成工艺路线的创新设计和精确控制，达到了较高的产品收率且不产生额外的有害废料。The invention discloses a high-yield and green and environment-friendly synthesis method for thiamethoxam: A. Weigh 0.5-1.5 parts of iminodiazine, 0.5-1.5 parts of 2-chloro-5-chloromethylthiazole, and dimethyl 0.2-2 parts of formamide, 0.2-2 parts of butanone, 0.2-2 parts of toluene, 0.5-1.5 parts of potassium carbonate, and 0.001-0.01 parts of catalysts were put into the synthesis kettle and mixed, and stirred for reaction; B, obtained in step A The product is heated to 30-70°C and soaked with a dipping agent, followed by centrifugal filtration to obtain salt as a by-product, the organic supernatant is sent to a crystallization kettle, frozen and crystallized, centrifuged to obtain thiamethoxam solid, and the centrifugal mother liquor is sent to a solvent recovery tower Distillation for reuse. The present invention achieves higher product yield and does not generate additional harmful waste by improving the selection and proportioning of reaction raw materials and the innovative design and precise control of the synthesis process route.
Description
Technical Field
The invention relates to the technical field of drug synthesis, in particular to an environment-friendly and energy-saving thiamethoxam green synthesis process method.
Background
Thiamethoxam is a neonicotinoid insecticide developed by Nowa company in 1991, has a mechanism similar to imidacloprid, can selectively inhibit nicotinic acetylcholine esterase receptors of central nervous systems of insects, further blocks normal conduction of the central nervous systems of the insects, and causes death of the insects when paralysis occurs. The pesticide has the characteristics of contact poisoning, stomach toxicity and systemic activity, higher activity, better safety, wider insecticidal spectrum, high action speed, long lasting period and the like, and is a better variety for replacing organophosphorus, carbamate and organochlorine pesticides which have high toxicity to mammals and have residue and environmental problems. In the synthesis process of thiamethoxam, DMF is mainly used as a solvent and potassium carbonate is used as an acid-binding agent at the present stage, after the reaction is finished, water with the volume of 5-10 times that of the product is added to separate out the product, then the product is centrifuged and dried, and is recrystallized by using a methanol solvent, wherein the content of the product is 93-96%. The method has the advantages of simple process, untreated DMF, excessive potassium carbonate and the like, large wastewater quantity, particularly high COD and salt content, huge environmental protection pressure, and low yield (76%) caused by the fact that the wastewater contains a small amount of thiamethoxam finished products.
(chemical synthesis equation)
At present, the domestic thiamethoxam wastewater treatment method mainly comprises an incineration method and a three-effect evaporation method, and has the disadvantages of high energy consumption, high cost, large waste residue generation amount and increased incineration cost.
Disclosure of Invention
The invention aims to overcome various defects in the prior art, and provides a high-yield green environment-friendly synthetic method of thiamethoxam by improving selection and proportion of reaction raw materials and innovative design and accurate control of a synthetic process route, so that high yield can be achieved and no additional harmful waste is generated.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
The high-yield green environment-friendly synthetic method of thiamethoxam comprises the following steps:
A. and (3) synthesis reaction: weighing the following reaction raw materials in parts by weight: 0.5-1.5 parts of iminodiazine, 0.5-1.5 parts of 2-chloro-5-chloromethyl thiazole, 0.2-2 parts of dimethylformamide, 0.2-2 parts of butanone, 0.2-2 parts of toluene, 0.5-1.5 parts of potassium carbonate and 0.001-0.01 part of catalyst are put into a synthesis kettle and are uniformly mixed, the pressure of the synthesis kettle is controlled to be open and normal pressure, and the temperature is set between 32 ℃ and 50 ℃, and the mixture is stirred and reacted for 3-6 hours;
B. and (3) post-synthesis treatment: and C, heating the product obtained in the step A to 30-70 ℃, adding an immersion agent for immersion cleaning, then carrying out centrifugal filtration to obtain salt as a byproduct, feeding the organic supernatant into a crystallization kettle, carrying out freezing crystallization at-10-5 ℃, centrifuging to obtain thiamethoxam solid, feeding the centrifugal mother liquor into a solvent recovery tower for distillation and recycling, and recovering toluene, dichloroethane, dimethylformamide, butanone and the like for reuse through rectification.
As a preferable technical scheme of the invention, in the step A, the weight ratio of the dimethyl formamide to the butanone to the toluene is 1 (1-3) to (2-4).
In a preferred embodiment of the present invention, in step a, potassium halide is used as the catalyst, and potassium iodide is preferably used.
In a preferred embodiment of the present invention, in step B, dichloroethane, butanone or a mixture of the dichloroethane and the butanone is used as the immersion cleaning agent.
In a preferred embodiment of the present invention, in step B, the weight ratio of the pickling agent to the iminodiazine is (1-5): 1.
As a preferred technical scheme of the invention, the method comprises the following steps:
A. and (3) synthesis reaction: weighing the following reaction raw materials in parts by weight: 1 part of iminodiazine, 1 part of 2-chloro-5-chloromethyl thiazole, 0.5 part of dimethylformamide, 1 part of butanone, 1-1.5 parts of toluene, 1 part of potassium carbonate and 0.004 part of catalyst are put into a synthesis kettle and uniformly mixed, the pressure of the synthesis kettle is controlled to be open and normal pressure, the temperature is set to be 45 ℃, and the mixture is stirred and reacted for 5 hours;
B. and (3) post-synthesis treatment: and C, heating the product obtained in the step A to 35-60 ℃, adding an immersion agent for immersion cleaning, then carrying out centrifugal filtration to obtain salt as a byproduct, feeding the organic supernatant into a crystallization kettle, carrying out freezing crystallization at-3 ℃, centrifuging to obtain thiamethoxam solid, feeding the centrifugal mother liquor into a solvent recovery tower for distillation and recycling, and recovering toluene, dichloroethane, dimethylformamide, butanone and the like for reuse through rectification.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
the invention utilizes different solubilities of the thiamethoxam in the organic solvent, the solubility of the thiamethoxam is obviously improved by the combined addition of multiple solvents, the use amount of an acid-binding agent is saved, the reaction conversion rate is improved, the product yield is obviously improved to more than 91 percent (about 76 percent in the prior art), and the product purity is kept to more than 98 percent (about 95 percent in the prior art). The combination and the dosage ratio of the multiple solvents have little influence on the purity of the product, but the single use or the ratio imbalance has great influence on the yield of the product, for example, the single use of toluene has the product purity close to 97 percent, but the yield falls about the level of the prior art.
Meanwhile, under the combined treatment of multiple solvents, the salt slag is basically insoluble in organic solvents, and can be sold as a byproduct after being dried by a rake dryer through one-time centrifugal separation; the invention adopts effective treatment processes of synthesis, dissolution filtration, crystallization and the like, and realizes zero discharge of wastewater in the reaction process.
In conclusion, the process improves the reaction yield and the product content through the comprehensive application of multiple solvents and matched technical means, and simultaneously, the generation of waste water is thoroughly solved, and the problem of environmental pollution is solved from the source.
The invention has larger one-time investment in the actual production process, but can improve the production efficiency, particularly effectively reduce the waste water discharge, and still has high popularization value from the aspects of long-term productivity, particularly environmental protection and ecological value.
Detailed Description
The following examples illustrate the invention in detail. The raw materials and various devices used in the invention are conventional commercially available products, and can be directly obtained by market purchase.
Example 1
The specific process steps of the preferred embodiment of the invention are as follows:
1) adding 400kg of iminodiazine, 200kg of dimethylformamide, 400kg of butanone, 400kg of toluene, 400kg of potassium carbonate and O.5kg of potassium iodide into a dried 3000L enamel kettle, dropwise adding 400kg of 2-chloro-5-chloromethyl thiazole, opening a steam valve, and heating, wherein the temperature is controlled to be 45 ℃;
2) after 5 hours of reaction, adding 1000-1200kg of an isometric mixture of dichloroethane and butanone, slowly heating to 60 ℃, preserving heat for 1 hour, opening a bottom valve, separating the materials in a full-automatic centrifuge, protecting with nitrogen, and transferring filter residues to a rake dryer for drying to obtain a salt byproduct; putting the filtrate into a crystallization kettle, cooling and crystallizing, keeping the temperature at minus 3 to 3 ℃ for one hour, putting the filtrate into a full-automatic centrifuge for separation, protecting nitrogen, drying solid materials by using a vacuum double cone, condensing a solvent, and recycling toluene, dichloroethane, dimethylformamide, butanone and the like by rectification; the mother liquor is concentrated and crystallized to obtain 16kg of product, the yield is improved to 91 percent compared with the yield of 76 percent in the prior art, and the purity is 98 percent; meanwhile, the discharge of waste water is reduced from 15 tons of high-concentration waste water per ton of products to 0.3 ton of low-concentration waste water, and the waste water is mainly from flushing waste water of a workshop and the like.
By contrast, another process step implemented in the development of the present invention is as follows, which has a relatively low yield, but the environmental protection value is still significant:
1) synthesizing: adding 400kg of iminodiazine, 800kg of butanone, 400kg of potassium carbonate and O.5Kg of catalyst into a dried 3000L enamel kettle, dropwise adding 400kg of 2-chloro-5-chloromethyl thiazole, opening a steam valve, and heating at the controlled temperature of 45 ℃;
2) dissolving and crystallizing: after 5 hours of reaction, adding 800kg of butanone, slowly heating to 60 ℃, preserving heat for 1 hour, opening a bottom valve, separating the materials in a full-automatic centrifuge, protecting with nitrogen, and transferring filter residues to a rake dryer for drying; and (3) putting the filtrate into a crystallization kettle, cooling and crystallizing, keeping the temperature at minus 3 to 5 ℃ for one hour, putting the filtrate into a full-automatic centrifuge for separation, protecting the filtrate with nitrogen, and drying the materials by using a vacuum double cone to obtain 15kg of products. After the post-treatment, the yield is about 81, and the discharge of the waste water is reduced to 0.3 ton of low-concentration waste water.
This example shows the most effective embodiment of the present invention, wherein the ratio of each process step and the components can be adjusted finely, all of which are within the protection scope of the present invention.
Claims (1)
1. The synthesis method of thiamethoxam is characterized by comprising the following steps: the method comprises the following steps:
1) adding 400kg of iminodiazine, 200kg of dimethylformamide, 400kg of butanone, 400kg of toluene, 400kg of potassium carbonate and O.5kg of potassium iodide into a dried 3000L enamel kettle, and dropwise adding 400kg of 2-chloro-5-chloromethyl thiazole; opening a steam valve for heating, and controlling the temperature to be 45 ℃; the iminodiazine is 3-methyl-4-nitroiminotetrahydro-1, 3, 5-oxadiazine;
2) after 5 hours of reaction, adding 1000-1200kg of an isometric mixture of dichloroethane and butanone, slowly heating to 60 ℃, preserving heat for 1 hour, opening a bottom valve, separating the materials in a full-automatic centrifuge, protecting with nitrogen, and transferring filter residues to a rake dryer for drying to obtain a salt byproduct; putting the filtrate into a crystallization kettle, cooling and crystallizing, keeping the temperature at minus 3 to 3 ℃ for one hour, putting the filtrate into a full-automatic centrifuge for separation, protecting nitrogen, drying solid materials by using a vacuum double cone, condensing a solvent, and recycling toluene, dichloroethane, dimethylformamide and butanone by rectification; the mother liquor is concentrated and crystallized.
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| CN108822098A (en) * | 2018-06-29 | 2018-11-16 | 湖北犇星农化有限责任公司 | A kind of preparation method of Diacloden |
| CN111036158A (en) * | 2019-12-28 | 2020-04-21 | 邯郸市瑞田农药有限公司 | 2 chlorine-5 chloromethyl thiazole synthesis reaction system |
| CN115286624A (en) * | 2022-08-04 | 2022-11-04 | 内蒙古犇星化学有限公司 | Preparation method of thiamethoxam |
| CN116836126A (en) * | 2023-07-04 | 2023-10-03 | 宁夏东吴农化股份有限公司 | Method for extracting oxadiazine through oxadiazine wastewater |
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|---|---|---|---|---|
| CN1084171A (en) * | 1992-07-22 | 1994-03-23 | 希巴-盖吉股份公司 | The oxadiazine derivative |
| WO1997010226A1 (en) * | 1995-09-11 | 1997-03-20 | Novartis Ag | Process for preparing a 2-chloro-5-chloromethyl-thiazole compound |
| CN102372702A (en) * | 2011-11-17 | 2012-03-14 | 安徽省化工研究院 | Preparation method for thiamethoxam |
| CN105175407A (en) * | 2014-05-28 | 2015-12-23 | 龙灯农业化工国际有限公司 | Thiamethoxam and application thereof |
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2016
- 2016-11-08 CN CN201610979438.8A patent/CN106496215B/en active Active
Patent Citations (4)
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|---|---|---|---|---|
| CN1084171A (en) * | 1992-07-22 | 1994-03-23 | 希巴-盖吉股份公司 | The oxadiazine derivative |
| WO1997010226A1 (en) * | 1995-09-11 | 1997-03-20 | Novartis Ag | Process for preparing a 2-chloro-5-chloromethyl-thiazole compound |
| CN102372702A (en) * | 2011-11-17 | 2012-03-14 | 安徽省化工研究院 | Preparation method for thiamethoxam |
| CN105175407A (en) * | 2014-05-28 | 2015-12-23 | 龙灯农业化工国际有限公司 | Thiamethoxam and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and Properties of Thiamethoxam and Related Compounds;Maienfisch，等;《Zeitschrift fuer Naturforschung, B: Chemical Sciences》;20061231;第61卷(第4期);第353-359页 * |
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