[go: up one dir, main page]

CN1401646A - Insecticidal compound and production process thereof - Google Patents

Insecticidal compound and production process thereof Download PDF

Info

Publication number
CN1401646A
CN1401646A CN 02100296 CN02100296A CN1401646A CN 1401646 A CN1401646 A CN 1401646A CN 02100296 CN02100296 CN 02100296 CN 02100296 A CN02100296 A CN 02100296A CN 1401646 A CN1401646 A CN 1401646A
Authority
CN
China
Prior art keywords
thiazolylmethyl
ylamine
solvent
chloro
compound according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 02100296
Other languages
Chinese (zh)
Inventor
吴桂秀
施永兵
马英高
陈锦军
张万忠
王志敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangshan Pesticides & Chemical Co Ltd Nantong
Original Assignee
Jiangshan Pesticides & Chemical Co Ltd Nantong
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangshan Pesticides & Chemical Co Ltd Nantong filed Critical Jiangshan Pesticides & Chemical Co Ltd Nantong
Priority to CN 02100296 priority Critical patent/CN1401646A/en
Publication of CN1401646A publication Critical patent/CN1401646A/en
Pending legal-status Critical Current

Links

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

A nitromethylene compound as insecticide, its preparing process, and the insecticide composition containing said compound as active component are disclosed.

Description

Insecticidal compound and production method thereof
Technical Field
The invention relates to a novel pesticide nitromethylene compound, a synthetic method and a pesticide composition thereof. The compounds of the present invention have the following structure:
wherein R is1Represents hydrogen, halogen element, CH3O-、C1-C12Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, aryl, heterocyclyl. R2Represents oxygen, N-CH, N-CN, CH-CN, N-NO2、CH-NO2。
Background
The existing nitromethylene systemic insecticide such as imidacloprid (imidacloprid) is an action body of nicotinic acid acetylcholinesterase receptor, and can be used for preventing and controlling piercing-sucking mouthpart pests such as aphids, leafhoppers, plant hoppers, thrips, whiteflies and various lepidoptera pests.
Furthermore, DE 4417742 a1 and DE 3712307 a1 patent applications disclose methods for the synthesis of nitromethylene compounds similar in structure to the present application. However, the preferred compounds of the present application, as well as methods for their synthesis and pesticidal compositions, are not disclosed in the above-mentioned applications.
Disclosure of Invention
The invention provides a novel pesticide nitromethylene compound, which has the following general formula:
wherein R is1Represents hydrogen, halogen element, CH3O-、C1-C12Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, aryl, heterocyclyl. R2Represents oxygen, N-CN, CH-CN, N-NO2、CH-NO2. It is preferred that R is1Represents a chlorine or bromine atom, R2Represents N-NO2. Most preferred is the compound 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
Preferred compounds of the invention are 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine, 5-thiazolylmethyl-N-nitroimidazolidin-2-ylamine, 1- (2-bromo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine, 1- (2-fluoro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine, 1- (2-iodo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine, 1- (2-chloro-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine, and the like, 1- (2-bromo-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine, 1- (2-iodo-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine, 1- (2-chloro-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine, 1- (2-bromo-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine, 1- (2-iodo-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine, 1- (2-chloro-5-thiazolylmethyl) -2-cyanomethylimidazolidin-2-ylamine, and pharmaceutically acceptable salts thereof, 1- (2-bromo-5-thiazolylmethyl) -2-cyanomethylidene imidazolidin-2-ylamine, 1- (2-iodo-5-thiazolylmethyl) -2-cyanomethylidene imidazolidin-2-ylamine. The physicochemical properties of the compound of general formula (I) 11- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidine-2-ylamine M.p.146.8-147.8 deg.C
B.p.208 ℃/0.8kpa 25-Thiazolylmethyl-N-nitroimidazolidin-2-ylamine M.p.134.2-135.4 ℃ 31- (2-bromo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine M.p.158.8-161.4 ℃ 41- (2-fluoro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine M.p.132.6-134.1 ℃ 51- (2-iodo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine M.p.173.2-174.6 ℃ 61- (2-chloro-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine M.p.139.1-140.3 ℃ 71- (2-bromo-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine Amine M.p.145.8-146.9 ℃ 81- (2-iodo-5-thiazolylmethyl) -N-cyanoimidazolidinylidene-2-ylamine M.p.159.2-160.5 ℃ 91- (2-chloro-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine M.p.142.3-143.8 ℃ 101- (2-bromo-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine M.p.149.2-150.4 ℃ 111- (2-iodo-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine M.p.168.2-169.1 ℃ 121- (2-chloro-5-thiazolylmethyl) -2-cyanomethylideneimidazolidin-2-ylamine M.p.141.2-142.5 ℃ 2- (2-bromo-5- Thiazolylmethyl) -2-cyanomethylidene imidazolidin-2-ylamine M.p.148.6-149.9 deg.C 141- (2-iodo-5-thiazolylmethyl) -2-cyanomethylidene imidazolidin-2-ylamine M.p.162.6-164.1 deg.C
The compounds of the present application can be synthesized by various conventional methods in the chemical field, and the present inventors have made extensive studies and, as a result, have preferred the following synthesis methods.
The synthesis of the compounds of general formula (I) is as follows:
1、
2、
Figure A0210029600071
in the above reaction formula 1, one or more of acetonitrile, ethyl acetate, dichloroethane, dichloromethane, toluene, chlorobenzene, acetone, water, petroleum ether, ethanol, dimethylformamide and the like may be selected as a solvent, and the amount of the solvent used is 0.5 to 10 times the weight of 2, 3-dichloropropene; thiocyanates include alkali metal salts such as sodium thiocyanate and potassium thiocyanate, alkaline earth metal salts such as calcium thiocyanate, magnesium thiocyanate, and ammonium thiocyanate, and the amount of thiocyanate used is 1 to 1.5 moles per mole of 2, 3-dichloropropene; the reaction may be carried out in the presence of a phase transfer catalyst comprising a quaternary ammonium salt and a quaternary phosphonium salt, the amount of the phase transfer catalyst being from 0.001 to 0.01 mole per mole of 2, 3-dichloropropene; the reaction temperature is 30-150 ℃; the reaction time is 3-9 hours.
The preferable solvent can be one or a mixed solvent of acetonitrile, ethanol, dichloroethane, toluene, water and the like, and the amount of the solvent used is 2 to 3 times of the weight of 2, 3-dichloropropene; the thiocyanate is preferably sodium thiocyanate; the phase transfer catalyst is preferably a tetraalkylammonium halide such as tetramethylammonium chloride, benzyltrimethylammonium chloride and tetrabutylammonium chloride; the reaction temperature is in the range of 20 to 80 ℃; the reaction time varies depending on the reaction conditions, but is generally suitably 1 to 4 hours.
In the above reaction 2, the reaction may be carried out in the presence of a solvent or in the absence of a solvent. Toluene, xylene, propionitrile, dimethylformamide, diisopropyl ether, carbon tetrachloride and the like can be used as a solvent, the amount of the solvent is 1 to 50 times of the weight of 2-chloro-1-thiocyanato-2-propene, the reaction temperature is between 0 and 200 ℃, and the reaction time is between 0.5 and 8 hours.
The solvent is preferably used in an amount of 4 to 20 times the weight of 2-chloro-1-thiocyanato-2-propene, the reaction temperature is 100 to 150 ℃ and the reaction time varies depending on the reaction conditions, but it is usually preferably 1 to 5 hours.
In the above reaction 3, the reaction may be carried out in the presence of a solvent or in the absence of a solvent. One or more of acetonitrile, ethyl acetate, dichloroethane, dichloromethane, toluene, chlorobenzene, acetone, water, petroleum ether, ethanol, dimethylformamide and the like can be selected as a solvent, and the amount of the solvent is 0.5 to 10 times of the weight of 2-chloroallyl isothiocyanate; the chlorinating agent can be one of chlorine, sulfuryl chloride, phosphorus pentachloride, phosphorus oxychloride and the like, and the amount of the chlorinating agent is 1.0 to 1.5 equivalent of the weight of the 2-chloroallyl isothiocyanate; the reaction temperature is between-20 and 150 ℃ and the reaction time is 3 to 9 hours.
One or more of acetonitrile, ethyl acetate, dichloromethane, toluene, chlorobenzene, dimethylformamide and the like can be preferably used as the solvent, and the amount of the solvent is 2 to 3 times of the weight of 2-chloroallyl isothiocyanate; the chlorinating agent is preferably sulfuryl chloride, the reaction temperature is between 10 and 60 ℃, the reaction time is different according to different reaction conditions, but 4 to 5 hours are suitable.
In the above reaction 4, the reaction may be carried out in the presence of a solvent or in the absence of a solvent. One or more of acetonitrile, ethyl acetate, dichloroethane, dichloromethane, toluene, chlorobenzene, acetone, water, petroleum ether, ethanol, dimethylformamide, dimethyl sulfoxide and the like can be selected as a solvent, and the amount of the solvent used is 0.5 to 10 times of the weight of 2-chloro-5-chloromethylthiazole; the acid-binding agent is one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate and the like, the amount of the acid-binding agent is 1 to 2 times of the weight of 2-chloro-5-chloromethylthiazole, the amount of the imidazolidine is 1 to 1.5 times of the weight of 2-chloro-5-chloromethylthiazole, quaternary ammonium salts such as tetramethylammonium chloride, benzyltrimethylammonium chloride and tetrabutylammonium chloride can be selected as catalysts, and the amount of the phase transfer catalyst is 0.001 to 0.01 mole per mole of 2-chloro-5-chloromethylthiazole; the reaction temperature is 10-150 ℃; the reaction time is 7 to 32 hours.
One or more of acetonitrile, chlorobenzene, dimethylformamide, dimethyl sulfoxide and the like can be preferably used as a solvent, and the amount of the solvent is 2 to 3 times of the weight of 2-chloroallyl isothiocyanate; preferably, the catalyst is tetrabutylammonium chloride, the reaction temperature is between 15 and 40 ℃ and the reaction time varies depending on the reaction conditions, but generally 8 to 12 hours are suitable.
The compounds of the present invention may be applied directly to pests or may be formulated for use as conventional pesticidal compositions using techniques conventional in the art. The composition is a solution, missible oil, cocoa wet powder, wet seed dressing agent, water suspension, suspension seed coating agent, suspension emulsion, aqueous emulsion or microemulsion, water dispersible granule and dry suspension agent containing an effective amount of active compound. The preparation can also be added with penetrant to form corresponding hypertonic preparation.
These formulations are prepared using art-recognized surfactants, adjuvants and/or carriers by art-recognized methods of formulating formulations, such as dissolving the active ingredient in a liquid emulsion or suspending in a liquid solvent, or by premixing with a solid carrier, pulverizing, and mixing, during which surfactants (including emulsifying and dispersing agents, wetting agents), stabilizers (including anti-decomposition agents, anti-freezing agents, preservatives, etc.), binders, viscosity modifiers and suspending agents, film formers, dyes, penetrants or other synergists are added.
The compound of the general formula (I) is an effector of nicotinic acid acetylcholinesterase receptor, and is used for preventing and treating piercing-sucking mouthpart pests, such as aphids, leafhoppers, plant hoppers, thrips, whiteflies and resistant strains thereof. Because of its excellent systemic property, it is specially suitable for seed treatment and root application, and can be used for early-stage control of pests on wheat, corn, rice, potato, beet and cotton, and the later-stage control of pests of the above-mentioned crops and citrus, deciduous fruit tree, tea tree and vegetable, etc. can be implemented by leaf surface spray control. The foliar spray has excellent control effects on leafhoppers, plant hoppers, aphids and thrips, and is also effective on whiteflies, rice stem borers, rice mud worms and rice weevils.
The present invention is specifically described below by way of examples, but it should be kept in mind that the present invention is not limited to the following examples.
EXAMPLE 1 Synthesis of Compounds
Example 1.1
100 g of sodium thiocyanate were dissolved in 150ml of water, and to the resulting solution 100 g of 2, 3-dichloropropene and 2.5 g of tetrabutylammonium chloride were added, followed by heating at 65 ℃ for 4 hours, cooling the reaction mixture to room temperature and pouring into 100ml of water, followed by extraction once with 200ml of toluene. The organic layer was washed with 300ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 98.6 g of 2-chloroallyl thiocyanate.
The yield is 81.7 percent
The purity is 97.5 percent
Boiling point of 82-87 deg.C/5 mmHg
Example 1.2
100 g of sodium thiocyanate were dissolved in 600ml of acetonitrile, 140 g of 2, 3-dichloropropene and 2.46 g of tetrabutylammonium chloride were added to the resulting solution, which was then heated at the reflux temperature of acetonitrile (80-82 ℃ C.) for 3.5 hours, the reaction mixture was cooled to room temperature and the acetonitrile was distilled off under reduced pressure, 800ml of water was added to the residue, and extraction was carried out once with 800ml of ethyl acetate. The organic layer was washed with 800ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 144.7 g of 2-chloroallyl thiocyanate.
The yield is 88.5 percent
The purity is 97.8 percent
Boiling point 83-88 deg.C/5 mmHg
Example 1.3
100 g of sodium thiocyanate were dissolved in 600ml of acetonitrile, 260 g of 2, 3-dibromopropene and 2.46 g of tetrabutylammonium bromide were added to the resulting solution, which was then heated at the reflux temperature of acetonitrile (80-82 ℃ C.) for 3.5 hours, the reaction mixture was cooled to room temperature and the acetonitrile was distilled off under reduced pressure, 800ml of water was added to the residue, and extraction was carried out once with 800ml of ethyl acetate. The organic layer was washed with 800ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 240.8 g of 2-bromoallyl thiocyanate.
The yield is 90.5 percent
The purity is 98.2 percent
Boiling point of 102-
Example 1.4
100 g of sodium thiocyanate were dissolved in 600ml of ethanol, 140 g of 2, 3-dichloropropene were added to the resulting solution, which was then heated at the reflux temperature of ethanol (78-80 ℃) for 3.5 hours, the reaction mixture was cooled to room temperature and the ethanol was removed under reduced pressure, 800ml of water was added to the residue, and extraction was carried out once with 800ml of ethyl acetate. The organic layer was washed with 800ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was subjected to distillation under reduced pressure to obtain 140.2 g of 2-chloroallyl thiocyanate.
The yield is 86.4 percent
The purity is 97.6 percent
Boiling point 83-88 deg.C/5 mmHg
Example 1.5
100 g of sodium thiocyanate were dissolved in 600ml of acetone, 140 g of 2, 3-dichloropropene were added to the resulting solution, which was then heated at the reflux temperature of acetone (55-58 ℃ C.) for 6 hours, the reaction mixture was cooled to room temperature and the acetone was removed under reduced pressure, 800ml of water was added to the residue, and extraction was carried out once with 800ml of ethyl acetate. The organic layer was washed with 800ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 146.3 g of 2-chloroallyl thiocyanate.
The yield is 83.7 percent
The purity is 98.2 percent
Boiling point 83-88 deg.C/5 mmHg
Example 1.6
250ml of toluene were added to 50 g of 2-bromoallyl thiocyanate, the reaction was stirred at reflux temperature for 2 hours, and the reaction mixture was cooled to room temperature. The toluene was evaporated by concentration under reduced pressure to obtain 47.2 g of 2-bromoallyl isothiocyanate.
The yield is 92.6 percent
The purity is 98.1 percent
Boiling point 95-103 deg.C/5 mmHg
Example 1.7
250ml of toluene were added to 50 g of 2-chloroallyl thiocyanate, the reaction was stirred at reflux temperature for 2 hours, and the reaction mixture was cooled to room temperature. The toluene was evaporated by concentration under reduced pressure to obtain 46.3 g of 2-chloroallyl isothiocyanate.
The yield is 90.2 percent
The purity is 97.4 percent
Boiling point of 70-75 deg.C/5 mmHg
Example 1.8
50 g of 2-chloroallyl thiocyanate are reacted at a temperature of 145 to 150 ℃ for 1.5 hours with stirring, and the reaction mixture is cooled to room temperature. Distillation under reduced pressure gave 40.7 g of 2-chloroallyl isothiocyanate.
The yield is 78.4 percent
The purity is 98.2 percent
Boiling point of 60-70 deg.C/5 mmHg
Example 1.9
To 26.9 g of 2-chloroallyl isothiocyanate was added 100ml of acetonitrile, followed by cooling to 15 ℃. 28.6 g of sulphuryl chloride are added dropwise over 2 hours to the resulting mixture. After completion of the dropwise addition, the temperature was raised to 50 to 60 ℃ and heated at the same temperature for 3 hours. After the solvent was distilled off under reduced pressure, the mixture was washed with 100ml of a 10% aqueous solution of sodium carbonate, and the mixture was extracted twice with 200ml of ethyl acetate, dried over anhydrous sodium sulfate, andthen the solvent was distilled off by concentration under reduced pressure to obtain 25.6 g of 2-chloro 5-chloromethylthiazole.
The yield is 72.5 percent
The purity is 94.2 percent
Boiling point 90-98 deg.C/10 mmHg
Example 1.9
100ml of methylene chloride was added to 26.9 g of 2-chloroallyl isothiocyanate, followed by cooling to 0 ℃. 28.5 g of sulfonyl chloride were added dropwise over 1 hour to the resulting mixture. After completion of the dropwise addition, the temperature was raised to 70 to 80 ℃ and heated at the same temperature for 5 hours. After the solvent was distilled off under reduced pressure, the mixture was washed with 100ml of a 10% aqueous solution of sodium carbonate, and the mixture was extracted once with 200ml of ethyl acetate, dried over anhydrous sodium sulfate, and then the solvent was distilled off by concentration under reduced pressure to obtain 26.5 g of 2-chloro-5-chloromethylthiazole.
The yield is 75.1 percent
The purity is 93.7 percent
Boiling point 88-95 deg.C/10 mmHg
Example 1.10
100ml of methylene chloride was added to 26.9 g of 2-bromoallyl isothiocyanate, followed by cooling to 0 ℃. To the resulting mixture was added dropwise over 1 hour, 30.6 g of sulfuryl chloride was added. After completion of the dropwise addition, the temperature was raised to 70 to 80 ℃ and heated at the same temperature for 5 hours. After the solvent was distilled off under reduced pressure, the mixture was washed with 100ml of a 10% aqueous solution of sodium carbonate, and the mixture was extracted once with 200ml of ethyl acetate, dried over anhydrous sodium sulfate, and then the solvent was distilled off by concentration under reduced pressure to obtain 26.3g of 2-bromo-5-chloromethylthiazole.
The yield is 77.2 percent
The purity is 94.1 percent
Boiling point 95-103 deg.C/10 mmHg
Example 1.11
100 g of imidazolidine are dissolved in 600ml of acetonitrile, 46.8 g of sodium hydroxide are added to the resulting solution, 130.8 g of 2-chloro-5-chloromethylthiazole solution are added dropwise at a temperature of from 50 to 60 ℃ and heating is continued at the reflux temperature (80 to 82 ℃) of acetonitrile for 25 hours. The reaction mixture was cooled to room temperature and acetonitrile was distilled off under reduced pressure, and 1000ml of water was added to the residue, followed by extraction once with 800ml of ethyl acetate. The organic layer was washed with 1000ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 112.5 g of 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
The yield is 54.4 percent
The purity is 93.7 percent
Example 1.12
100 g of imidazolidine are dissolved in 600ml of dimethylformamide, 45.3 g of potassium hydroxide and 3 g of tetrabutylammonium chloride are added to the resulting solution, 130.8 g of 2-chloro-5-chloromethylthiazole solution are added dropwise at a temperature of from 50 to 60 ℃ and heating is continued for 15 hours at a temperature of from 50 to 60 ℃. The reaction mixture was cooled to room temperature and dimethylformamide was distilled off under reduced pressure, and 1000ml of water was added to the residue, followed by extraction once with 800ml of ethyl acetate. The organic layer was washed with 1000ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 130.5 g of 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
The yield is 63.5 percent
The purity is 95.2 percent
Example 1.13
100 g of imidazolidine are dissolved in 600ml of dimethylformamide, 45.3 g of potassium hydroxide and 3 g of tetrabutylammonium chloride are added to the resulting solution, 155.5 g of 2-bromo-5-chloromethylthiazole solution are added dropwise at a temperature of from 50 to 60 ℃ and heating is continued for 15 hours at a temperature of from 50 to 60 ℃. The reaction mixture was cooled to room temperature and dimethylformamide was distilled off under reduced pressure, and 1000ml of water was added to the residue, followed by extraction once with 800ml of ethyl acetate. The organic layer was washed with 1000ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 158.6 g of 1- (2-bromo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
The yield is 68.2 percent
The purity is 96.3 percent
Example 1.14
100 g of imidazolidine are dissolved in 600ml of dimethyl sulfoxide, 45.3 g of potassium hydroxide and 3 g of tetrabutylammonium chloride are added to the resulting solution, 130.8 g of 2-chloro-5-chloromethylthiazole solution are added dropwise at a temperature of from 10 to 20 ℃ and heating is continued for 14 hours at a temperature of from 50 to 60 ℃. The reaction mixture was cooled to room temperature and the dimethyl sulfoxide was distilled off under reduced pressure, and 1000ml of water was added to the residue, followed by extraction once with 800ml of ethyl acetate. The organic layer was washed with 1000ml of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 142.7 g of 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
The yield is 67.4 percent
The purity is 90.1%
Example 2 precise virulence determination of Myzus persicae
The tested insect source is collected in an insect breeding observation nursery, and is raised indoors to 4-5-year-old Aphis pyriformis at the raising temperature of 25 +/-1 ℃ and the illumination of 12L: 12D. And (3) carrying out virulence determination by adopting an immersion method. Accurately weighing a certain amount of the compound of the general formula (1), dissolving the compound with 2ml of acetone and 8ml of xylene, adding 1ml of emulsifier to prepare missible oil, and then adding water to dilute the missible oil into 5 different concentrations to be used as test liquid medicine. The treatment of 100 heads of red peach aphids with each concentration of the liquid medicine is repeated three times. Cutting cabbage leaves with red peach aphids into proper sizes, removing lower-age nymphs and adult aphids, and keeping 30-40 heads of 4-5-age nymphs in each leaf to enable the ages of the processed aphids to be consistent. Dipping the cabbage leaves with the pink aphids in the test liquid medicine for 5s, taking out the cabbage leaves, putting the cabbage leaves into a culture dish with the diameter of 12mm, and covering the culture dish after the liquid medicine is dried. The blank control is a test solution diluted by 40000 times by acetone and dimethylbenzene, and the pink aphid is treated by the same immersion method. Mortality was checked after 24h and 48 h.
TABLE 11 virulence Effect of- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine on Nepeta persicae
Concentration of (ppm) Logarithmic value of concentration (x) 24 hours 48 hours
Correcting mortality (％) Probability of mortality Value (y) Correcting mortality (％) Probability of mortality Value (y)
25 1.3979 90 6.2816 98 7.0537
12.5 1.0969 82 5.9154 87 6.1264
6.25 0.7959 60 5.2533 65 5.3853
3.125 0.4949 32 4.5323 39 4.7207
1.5626 0.1938 18 4.0846 19 4.1221

Claims (28)

1. A nitromethylene compound as an insecticide, the structure of which is a compound having the following general formula:
wherein R is1Represents hydrogen, halogen element, CH3O-、C1-C12Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, aryl, heterocyclyl, R2Represents oxygen, N-CH, N-CN, CH-CN, N-NO2、CH-NO2。
2. A compound according to claim 1 which is 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
3. A compound according to claim 1 which is 5-thiazolylmethyl-N-nitroimidazolidin-2-ylamine.
4. A compound according to claim 1 which is 1- (2-bromo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
5. The compound according to claim 1 which is 1- (2-fluoro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine
6. A compound according to claim 1 which is 1- (2-iodo-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine.
7. A compound according to claim 1 which is 1- (2-chloro-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine.
8. A compound according to claim 1 which is 1- (2-bromo-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine.
9. A compound according to claim 1 which is 1- (2-iodo-5-thiazolylmethyl) -N-cyanoimidazolidin-2-ylamine.
10. The compound according to claim 1 which is 1- (2-chloro-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine.
11. A compound according to claim 1 which is 1- (2-bromo-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine.
12. The compound according to claim 1 which is 1- (2-iodo-5-thiazolylmethyl) -2-nitromethyleneimidazolidin-2-ylamine.
13. A compound according to claim 1 which is 1- (2-chloro-5-thiazolylmethyl) -2-cyanomethylimidazolidin-2-ylamine, a compound according to claim 1.
14. A compound according to claim 1 which is 1- (2-bromo-5-thiazolylmethyl) -2-cyanomethylidene imidazolidin-2-ylamine.
15. The compound according to claim 1 which is 1- (2-iodo-5-thiazolylmethyl) -2-cyanomethylidene imidazolidin-2-ylamine.
16. A method for the synthesis of a compound according to claims 1, 2, characterized in that: firstly, synthesizing allyl thiocyanate from 2, 3-dichloropropene, thiocyanate and a solvent directly or under the action of a catalyst; the allyl thiocyanate is then converted into allyl isothiocyanate directly or in the presence of a solvent; synthesizing 2-chloro-5-chloromethylthiazole from allyl isothiocyanate and a chlorinating agent directly or in the presence of a solvent; finally condensing with imidazolidine, acid binding agent and solvent directly or under the action of catalyst to obtain the invented product.
17. The method according to claim 16, wherein the allyl thiocyanate is synthesized using one or more solvents selected from acetonitrile, ethyl acetate, dichloroethane, dichloromethane, toluene, chlorobenzene, acetone, water, petroleum ether, ethanol, and N, N-dimethylformamide in an amount of 0.5 to 10 times by weight of 2, 3-dichloropropene.
18. The method of claim 16, wherein the allyl thiocyanate comprises an alkali metal salt, an alkaline earth metal salt and ammonium thiocyanate, and the amount of thiocyanate used is from 1 to 1.5 moles per mole of 2, 3-dichloropropene.
19. The process of claim 16 wherein the allyl thiocyanate synthesis is carried out directly or/and in the presence of a phase transfer catalyst comprising a quaternary ammonium salt and a quaternary phosphonium salt, the phase transfer catalyst being used in an amount of 0.001 to 0.01 mole per mole of 2, 3-dichloropropene; the reaction temperature is 30-150 ℃; the reaction time is 3-9 hours.
20. The process according to claim 16, wherein the process for the synthesis of allyl isothiocyanate is carried out in the presence of a solvent and in the absence of a solvent. Toluene, xylene, propionitrile, dimethylformamide, diisopropyl ether, carbon tetrachloride and the like can be used as solvents, the amount of the solvents is 1 to 50 times of the weight of allyl isothiocyanate, the reaction temperature is between 0 and 200 ℃, and the reaction time is between 0.5 and 8 hours.
21. The process according to claim 16, wherein the 2-chloro-5-chloromethylthiazole can be synthesized in the absence of a solvent, in the presence of a solvent, wherein one or more solvents selected from acetonitrile, ethyl acetate, dichloroethane, dichloromethane, toluene, chlorobenzene, acetone, water, petroleum ether, ethanol, and N, N-dimethylformamide are used as the solvent, and the amount of the solvent is 0.5 to 10 times the weight of allyl isothiocyanate.
22. The method according to claim 16, wherein in the synthesis of 2-chloro-5-chloromethylthiazole, the chlorinating agent can be selected from one of chlorine, sulfuryl chloride, phosphorus pentachloride, phosphorus oxychloride and the like, and the amount of the chlorinating agent used is between 1.0 and 1.5 equivalents of allyl isothiocyanate; the reaction temperature is between-20 and 150 ℃ and the reaction time is 3 to 9 hours.
23. The method according to claims 16-22, wherein the synthesis can be carried out in the presence of a solvent or in the absence of a solvent, and one or more solvents selected from acetonitrile, ethyl acetate, dichloroethane, dichloromethane, toluene, chlorobenzene, acetone, water, petroleum ether, ethanol, dimethylformamide, and dimethylsulfoxide can be used as the solvent in an amount of 0.5 to 10 times the weight of 2-chloro-5-chloromethylthiazole.
24. The method according to claim 16-22, wherein one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and sodium bicarbonate is used as an acid-binding agent, and the amount of the acid-binding agent is 1 to 2 times of the weight of 2-chloro-5-chloromethylthiazole.
25. The synthesis method according to claim 16-22, wherein the amount of imidazolidine used is 1 to 1.5 times the weight of 2-chloro-5-chloromethylthiazole, and the reaction temperature is between 10 and 150 ℃; the reaction time is 7 to 32 hours.
26. The process according to claims 16-22, wherein 1- (2-chloro-5-thiazolylmethyl) -N-nitroimidazolidin-2-ylamine is synthesized using a catalyst selected from quaternary ammonium salts such as tetramethylammonium chloride, benzyltrimethylammonium chloride and tetrabutylammonium chloride in an amount of 0.001 to 0.01 mole per mole of 2-chloro-5-chloromethylthiazole
27. A method of synthesis according to claims 16-26, wherein a catalyst may or may not be added.
28. A pesticidal composition comprising the compound of claims 1 to 15 as an active ingredient.
CN 02100296 2001-08-08 2002-01-18 Insecticidal compound and production process thereof Pending CN1401646A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 02100296 CN1401646A (en) 2001-08-08 2002-01-18 Insecticidal compound and production process thereof

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN01127099 2001-08-08
CN01127099.3 2001-08-08
CN 02100296 CN1401646A (en) 2001-08-08 2002-01-18 Insecticidal compound and production process thereof

Publications (1)

Publication Number Publication Date
CN1401646A true CN1401646A (en) 2003-03-12

Family

ID=25740480

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02100296 Pending CN1401646A (en) 2001-08-08 2002-01-18 Insecticidal compound and production process thereof

Country Status (1)

Country Link
CN (1) CN1401646A (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007080903A1 (en) * 2006-01-13 2007-07-19 Sumitomo Chemical Company, Limited Method for producing thiazole compound
WO2012146569A1 (en) 2011-04-26 2012-11-01 Bayer Intellectual Property Gmbh Method for producing 2-chloroallyl thiocyanate and 2-chloroallyl isothiocyanate
CN103741163A (en) * 2013-12-20 2014-04-23 哈尔滨理工大学 Synthesis method of 2-chloro-5-chloromethyl-1,3-thiazole
CN104016941A (en) * 2014-03-17 2014-09-03 江苏辉腾生物医药科技有限公司 Preparation method of 2-chlorine-5-chloromethylthiazole
CN104119291A (en) * 2014-06-30 2014-10-29 绍兴文理学院 Method for preparing 2-chlorine-5 chloromethyl thiazole
CN105145615A (en) * 2015-09-30 2015-12-16 河南科技学院 Imidaclothiz-and-chlorfluazuron-containing pest killing composition and application thereof
CN105175298A (en) * 2015-08-04 2015-12-23 山东省农药科学研究院 Synthesis and refining method of thiamethoxam intermediate 2-chloroallyl isothiocyanate
CN106029658A (en) * 2014-05-28 2016-10-12 龙灯农业化工国际有限公司 Method for preparing thiamethoxam
CN107235970A (en) * 2017-06-29 2017-10-10 南通天泽化工有限公司 A kind of synthetic method of imidaclothiz
WO2017211594A1 (en) * 2016-06-06 2017-12-14 Bayer Cropscience Aktiengesellschaft Method for producing heterocyclic compounds
CN107935960A (en) * 2017-12-28 2018-04-20 湖南化工研究院有限公司 The preparation method of 2 chlorine, 5 5-chloromethyl thiazole
CN108484524A (en) * 2018-06-21 2018-09-04 岳阳景嘉化工有限公司 A kind of synthetic method of chloromethyl sulphur pyrolle
CN108892630A (en) * 2018-06-21 2018-11-27 岳阳景嘉化工有限公司 A kind of synthetic method of 1- isothiocyanic acid base -2- chloro-2-propene
CN112480023A (en) * 2020-12-09 2021-03-12 怀仁市普惠生物科技有限公司 Method for synthesizing dichloro pentachloromethyl thiazole
CN112778295A (en) * 2021-01-28 2021-05-11 南通江山农药化工股份有限公司 Preparation method and application of imidaclothiz
CN113121465A (en) * 2021-05-28 2021-07-16 安徽海顺化工有限公司 Synthesis process of 2-chloro-5-chloromethyl thiazole
CN113620902A (en) * 2021-09-23 2021-11-09 邯郸市瑞田农药有限公司 Preparation of 2-chloro-5-chloro-methylthiazole by tower reactor
CN113754609A (en) * 2021-10-11 2021-12-07 邯郸市瑞田农药有限公司 2-chloro-5-chloromethyl thiazole prepared by aqueous phase method and synthesis process thereof

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8304558B2 (en) 2006-01-13 2012-11-06 Sumitomo Chemical Company, Limited Method for producing thiazole compound
CN101370795B (en) * 2006-01-13 2011-12-14 住友化学株式会社 Method for producing thiazole compound
WO2007080903A1 (en) * 2006-01-13 2007-07-19 Sumitomo Chemical Company, Limited Method for producing thiazole compound
US8785673B2 (en) 2011-04-26 2014-07-22 Bayer Intellectual Property Gmbh Method for producing 2-chloroallyl thiocyanate and 2-chloroallyl isothiocyanate
CN103502210A (en) * 2011-04-26 2014-01-08 拜耳知识产权有限责任公司 Process for the preparation of 2-chloroallyl thiocyanate and 2-chloroallyl isothiocyanate
WO2012146569A1 (en) 2011-04-26 2012-11-01 Bayer Intellectual Property Gmbh Method for producing 2-chloroallyl thiocyanate and 2-chloroallyl isothiocyanate
CN103741163A (en) * 2013-12-20 2014-04-23 哈尔滨理工大学 Synthesis method of 2-chloro-5-chloromethyl-1,3-thiazole
CN103741163B (en) * 2013-12-20 2016-06-29 哈尔滨理工大学 A kind of synthetic method of 2-chloro-5-chloromethyl-1,3-thiazole
CN104016941A (en) * 2014-03-17 2014-09-03 江苏辉腾生物医药科技有限公司 Preparation method of 2-chlorine-5-chloromethylthiazole
CN106029658A (en) * 2014-05-28 2016-10-12 龙灯农业化工国际有限公司 Method for preparing thiamethoxam
CN106029658B (en) * 2014-05-28 2019-08-16 龙灯农业化工国际有限公司 Method for preparing thiamethoxam
CN104119291A (en) * 2014-06-30 2014-10-29 绍兴文理学院 Method for preparing 2-chlorine-5 chloromethyl thiazole
CN105175298A (en) * 2015-08-04 2015-12-23 山东省农药科学研究院 Synthesis and refining method of thiamethoxam intermediate 2-chloroallyl isothiocyanate
CN105145615A (en) * 2015-09-30 2015-12-16 河南科技学院 Imidaclothiz-and-chlorfluazuron-containing pest killing composition and application thereof
WO2017211594A1 (en) * 2016-06-06 2017-12-14 Bayer Cropscience Aktiengesellschaft Method for producing heterocyclic compounds
TWI750181B (en) * 2016-06-06 2021-12-21 德商拜耳作物科學股份有限公司 Process for producing heterocyclic compounds
CN109311866A (en) * 2016-06-06 2019-02-05 拜耳作物科学股份公司 Process for preparing heterocyclic compounds
JP2019517535A (en) * 2016-06-06 2019-06-24 バイエル・クロップサイエンス・アクチェンゲゼルシャフト Method for producing heterocyclic compound
CN109311866B (en) * 2016-06-06 2022-12-09 拜耳作物科学股份公司 Process for preparing heterocyclic compounds
US11161840B2 (en) 2016-06-06 2021-11-02 Bayer Cropscience Aktiengesellschaft Process for producing heterocylic compounds
CN107235970A (en) * 2017-06-29 2017-10-10 南通天泽化工有限公司 A kind of synthetic method of imidaclothiz
CN107935960B (en) * 2017-12-28 2020-01-17 湖南化工研究院有限公司 Preparation method of 2-chloro-5-chloromethyl thiazole
CN107935960A (en) * 2017-12-28 2018-04-20 湖南化工研究院有限公司 The preparation method of 2 chlorine, 5 5-chloromethyl thiazole
CN108484524A (en) * 2018-06-21 2018-09-04 岳阳景嘉化工有限公司 A kind of synthetic method of chloromethyl sulphur pyrolle
CN108892630A (en) * 2018-06-21 2018-11-27 岳阳景嘉化工有限公司 A kind of synthetic method of 1- isothiocyanic acid base -2- chloro-2-propene
CN112480023A (en) * 2020-12-09 2021-03-12 怀仁市普惠生物科技有限公司 Method for synthesizing dichloro pentachloromethyl thiazole
CN112778295A (en) * 2021-01-28 2021-05-11 南通江山农药化工股份有限公司 Preparation method and application of imidaclothiz
CN113121465A (en) * 2021-05-28 2021-07-16 安徽海顺化工有限公司 Synthesis process of 2-chloro-5-chloromethyl thiazole
CN113620902A (en) * 2021-09-23 2021-11-09 邯郸市瑞田农药有限公司 Preparation of 2-chloro-5-chloro-methylthiazole by tower reactor
CN113620902B (en) * 2021-09-23 2023-08-18 邯郸市瑞田农药有限公司 Preparation of 2-chloro-5-chloro-methylthiazole in tower reactor
CN113754609A (en) * 2021-10-11 2021-12-07 邯郸市瑞田农药有限公司 2-chloro-5-chloromethyl thiazole prepared by aqueous phase method and synthesis process thereof

Similar Documents

Publication Publication Date Title
CN1401646A (en) Insecticidal compound and production process thereof
CN1033805C (en) Herbicide compositions containing novel substituted pyrazolylpyrazoles and their preparation and use
CN1270593A (en) Pyrimidin-4-one and pyrimidin-4-thione as fungicide
JPH0184A (en) Picolinate derivatives and herbicides
CN101337940A (en) Nitrogen heterocyclic ring dichloro allyl ether compound with insecticidal activity
TW200911754A (en) Novel fungicides
CN1328561A (en) Pyrimidin-4-enamine as fungicide
CN1053233A (en) N-phenylpyrazole derivatives as sterilant
CN1039905C (en) Triazole derivatives and insecticides
JP2514823B2 (en) Methods and agents for protecting plants from disease
CN1097545A (en) With replacing De oxadiazole and thiadiazole compound control insect
AU2014222637B2 (en) Plant growth regulating compounds
JPS5920285A (en) 5-dibasic acid ester derivative of milbemycin d and its salt
DK164912B (en) MILBEMYCIN-5 CARBONATE DERIVATIVES, AND ANTHELMINTIC, ACARACIDE AND INSECTICIDES WITH CONTENTS
EP0387195B1 (en) Agents for the protection of plants against diseases
CN88100536A (en) 2-imino--1,3-dithio-cyclobutane compounds and preparation method thereof and as the application of sterilant
CN1066717C (en) 1-Arylpyrazole insecticides
CN1075490C (en) O-benzyl oxime ether derivatives and their use in crop protection compositions
CN1223584C (en) Pyrrolecarboxamides for use as fungicides
CN1134934A (en) Herbicidal 1-alkenyl tetrazolinone
CN111620867A (en) Mesoionic insecticides
CN1229352C (en) Herbicide 2-(5-isoxazolinylmethoxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives
CN1018922B (en) Process for preparing 3-perfluoroalkyl-5-substd-oxy-isoxazole derivs
CN1288459A (en) Organic nitrile derivatives and their use as pesticides
CN1045391A (en) The substituted 2-propenyl derivatives of nitrogen heterocyclic

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication