TW307763B - - Google Patents

Description

Printed by the Ministry of Economic Affairs, Central Standards Bureau Staff Consumer Cooperative A7 V. Description of the invention (1) Scope of the invention · The present invention relates to the replacement of chlorinated two crops, this compound unexpectedly has the required pesticidal activity 'including insecticides and Acaricide. In other respects, the invention relates to pesticidal compositions containing these compounds, and methods of using these compounds and / or compositions to control pests. BACKGROUND OF THE INVENTION: The damage caused by insects and insects has caused serious problems for agriculture. Many types of crops need to be protected from mites and / or insects. Such economic crops include soybeans, corn, peanuts, cotton, alfalfa, and tobacco. In addition, vegetables such as tomatoes, yam potatoes, peas, beets, carrots, etc., as well as fruits, nuts, decorative plants and nursery crops such as apples, peaches, pine orange fruits, almonds and grapes may also require protection. And other harmful organisms. Ismail et al., Pestic. Biochem. Physiol. 47, 1-7 (1 9 9 3) describe some diarrhea and two cultivators and their use as acaricides. Dekeyser et al., J. Econ. Entomol. 86 (5); 1 3 3 9 -1343 (1993) describe certain dihydropyrazine and its use as insecticides. Dekeyser et al., Pestic. Sci. 38: 309-314 (1993)) illustrate the design and synthesis of certain dihydropyridiums. Dekeyser et al., J. Agric Food Chem. 41: 1 329- 1 33 1 (1993)) describe the synthesis of certain dihydropyridine two crops and the activity of acaricides and insecticides. J. Med_ Chem. 1966, 753-758 talked about the different 2-substituted 4H-1,3,4-Bao II '• and, allegedly having antispasmodic activity on mice. U.S. Patent 3,4 2 0,8 2 6 discusses some of the paper standards are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page)

, 1T 307763 V. Description of the invention (2 A7 B7 2,4,6-replaces 4H 1, Μ, 3,4-Qi second spray, allegedly used as a sedative, anti-convulsive agent and as a base offender &horse; Pesticides and other uses, especially against nematodes, plants, and fungi. Geff National Patent No. 3,42〇, 825 mentions methods for preparing their compounds. Summary of the invention: The present invention relates to compounds of the following formula: where: Z is (a-(CH2);

(Please read the note Ϋ on the back before filling in this page) Ding,-'° or where x is an integer from 0 to 4, η is an integer from 0 to 5 and R is defined as follows (b) -ch2o

Printed by the Central Bureau of Economics of the Ministry of Economic Affairs, the Negative Workers ’Cooperative Society where η is an integer from 0 to 5 and R is defined as follows; R is selected from the following groups: hydrogen, C ^ -Ca alkyl, CpC group, tooth Nitro, phenyl, cyano, phenoxy, fluorenyloxy, -yl, C "C4 dialkylamino, C" C4 alkylthio, C "C4 haloalkoxy, Ci-C4 southern alkyl , And the standard of gas or paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). V. Description of the invention (Μ Β7 R1 is in addition to gaseous alkyl (: 1- <: 4 haloalkyl, to C ^ -C4 fluoroalkyl is better 'or the following academic difficulties:-

-CO-NH

Among them R4 is hydrogen, halogen, Ci-C4. Halogen pit base or 匸! -^ Halopitoxy & groups of the following formula are preferred: -CO-HH — wherein ruler 4 is halogen, 〇1. ≪: 4fluoroalkyl or 〇1 _ (: 4fluoroalkoxy, is- C1 '_CFS or-0CF3 is better; and its physiologically acceptable salts but the limitation is that when X is 0, R1 is not (^ -dagger halogen pit group. The composition of the present invention comprises (A)-or A number of compounds with the structure of formula I 'above and (B)-a suitable carrier "This suitable carrier may be a solid or liquid in nature. The compounds and compositions of the present invention have pesticidal activity, especially against insects And mites. Description of the invention_ · The compound of the present invention can be obtained by the following formula 111: (Please read the precautions on the back before filling in this page) <

, Printed by 1T Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

CONHNH, (where R is as defined above) and 1-bromo-2-fluoroethane are prepared in the presence of a base. Such bases include eyelid metal hydroxides, and preferred bases include sodium or sodium hydroxide. The preparation of the composition of the present invention can be printed by one or more compounds of the present invention and the appropriate paper size in accordance with the Chinese National Standard (CNS) A4 (2 丨 0X297mm) A7 B7 printed by the Beigong Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs. 3. Description of the invention (4) It is made of extravagant carrier, such as liquid or solid carrier. Suitable liquid carriers may include water, alcohol, ketones, phenol, toluene and xylene. In these formulations, additives conventionally used in the related art, such as one or more surfactants and / or inert diluents, can be used to facilitate handling and application of the final pesticidal composition. Or 'when using a liquid carrier, this pesticidal compound can be used as a liquid or spray, such as a solution in a compatible solvent such as acetone, benzene, toluene, kerosene, or evenly dispersed in the Non-solvent media such as water. The pesticidal composition may also contain a solid carrier in the form of dusting, granules, wettable powders, pastes, aerosols, emulsions, emulsifiable concentrates, and water-soluble solids. For example, when the pesticidal compound of the present invention is mixed with or adsorbed on a powdered solid carrier such as mineral crushed salt such as mica, talc, pyrophyllite and clay, it can be used as a powdering agent and a surface active dispersant Wet powder is then used directly on the area to be treated. Alternatively, the powdered solid carrier mixed with the compound can be dispersed in water to form a suspension application form. The granular formulation of the compound is more suitable for field treatment and suitable for spreading, fertilizing, mixing soil or treating seeds, and it is appropriate to use a granular or pellet carrier such as granular clay, vermiculite, charcoal or corn cob preparation. This biocide is dissolved in a solvent and sprayed onto an inert mineral carrier such as attapulgite particles (10-100 mesh), followed by evaporation of the solvent. The content of the pesticidal agent in this granular composition accounts for 2 to 25% of the carrier plus the pesticidal agent, preferably 3 to 15%. In addition, the paper standard for killing harmful organisms is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back before filling out this page), τ B7 5. Invention description (5) The agent can also be mixed into a polymer carrier, such as polyethylene, polypropylene butylene-styrene, styrene-acrylonitrile resin, polyamidoamine, poly (ethylene acetate), etc. When embedded, the pesticidal agent has the advantage of being released after a very long period of time, and has a longer extended effect than when it is not embedded. 0 Another method of applying to the treatment site is aerosol treatment, which It is to dissolve the compound in an aerosol carrier that is gas at normal temperature (eg, 20 ° C) under normal pressure but liquid under pressure. Aerosol formulations can also be prepared by first dissolving the compound in a less volatile solvent, and then mixing the resulting solution with a highly volatile liquid aerosol carrier. When used for pesticidal treatment of plants (this term includes plant parts), the compounds of the present invention are preferably applied in the form of aqueous emulsions containing nonionic, cationic or anionic surfactants. Suitable surfactants are known to those skilled in the art and include those disclosed in US Patent No. 2,547,724 (columns 3 and 4). The compound of the present invention can be mixed with these surface-active dispersants' with or without an organic solvent to form a concentrate, and water is added to produce an aqueous suspension of the compound of the desired concentration. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back and fill in this 1) In addition, the compounds can have pesticidal activity with themselves, such as insecticides, snailicides, fungicides and Use bactericides and other gifts. Xian understands that the amount of the pesticidal active compound in a specific formulation will depend on the specific pest to be controlled, as well as the specific chemical composition and compound formulation used, the method of applying the compound / formulation and the site to be treated However, the pesticidal effective amount of the compound may vary widely. However, it is generally 'used as a -8-' ^ zhang standard in pesticidal formulations _ China National Standards (〇 called into 4 threats (21〇 father 297 mm) ':-307763 A7 economy Printed by the Ministry of Central Standards Bureau Beigong Consumer Cooperative B7 V. Description of the invention (6) The compound concentration of the active ingredient can be from about 0.1 to 95% by weight./. Spray diluent can be as low as a few ppm, On the contrary, the full-effect concentrate of the compound can be applied by ultra-low volume technology. When the plant is to be treated, the concentration per unit area ranges from about 0.01 to about 50 pounds per acre , Preferably at a concentration of about 0.1 to about 10 pounds per acre, can be applied to crops such as corn, tobacco and rice, etc. When controlling pests, the compound spray can be applied to any suitable site , Such as direct application to pests and / or plants that they ingest or inhabit. This pesticidal active formulation can also be applied to soil or other vectors where pests appear. Harmful insects and mites attack many types of plants, including Both decorative and agricultural plants, It is harmed by edible roots and / or leaves, absorbing liquid from plants, secreting poisons, and often infectious diseases, etc. The compounds of the present invention can be advantageously used to minimize or prevent such damage. The choice and concentration of these compounds will of course vary according to these environments such as geographical area, climate, terrain, plant tolerance, etc. Under certain circumstances, relevant technical experts can determine suitable compounds, concentrations and Method. The compound of the present invention is particularly suitable for the application of insecticides and acaricides on the leaves. This compound is particularly effective for controlling insects such as Spodoptera litura and mites such as spider mites and rust mites. The following examples are used only To illustrate the field of the present invention. The present invention is not limited by the examples provided "Example 1 2- (4-bromophenyl) -4H-1,3,4-dihydrazine Preparation of this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling in this page) Order A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (7 ) · Take a solution of 2.9 g (0.07 mol) of sodium oxyhydroxide dissolved in 10 ml of water at room temperature and add dropwise to 6.5 g (0.03 mol) of 4-bromophenhydrazine and 40 g (0.03 mol) Ear) 1-Han-2-Fluoroethane is dissolved in a mixture of 25 ml of ethanol. The resulting solution is refluxed-another one-half hour. The mixture is cooled to room temperature, diluted with 150 ml of water and diluted with ether ( 100 ml) extracted several times. After separation and dehydration on anhydrous sodium sulfate, the solution was filtered and evaporated under reduced pressure, leaving 4-6 g of oil (yield 63.6%), which was purified by distillation. The product was purified Identification by infrared light and nuclear magnetic resonance spectroscopy.

Example 1 A 2- (4-bromophenyl) -5,6-dihydro-N-[(4-trifluoromethyl) phenyl] _4H-1,3,4-sakizide-4-urea ( Preparation of Compound 12) 1 g of 2- (4-xiphenyl) -5,6-dihydro-4H-1,3,4- > * f · dihydrazine was dissolved in 40 ml of Bichai, stirring and dropping After adding 2 drops of triethylamine, add 1 gram of 4- (trifluoromethyl) phenylisocyanate and remove it for 1 hour at room temperature. The solvent was evaporated under reduced pressure, and the resulting solid was washed with hexane and air-dried to prepare 2- (4-mophenyl) -5,6-dihydro-N-[(4-trifluoromethyl) phenyl]- 4H-1,3,4-humodihydrazine-4-urea, melting point 146-148 ° C (yield 50%). Other compounds can be prepared according to the above method. These compounds and their bactericidal and insecticidal activities are summarized in Tables I and 11. The NMR data of compounds 1 to 12 are summarized in Table III. Example 2 Preparation of formulations The following examples are related to the pesticidal use of the compounds of the present invention. In all these examples, the compound mother solution is made into a concentrated 3,000 pprn _ -10- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -------- Kunyi ------ 1T ------ 1 (please read the precautions on the back before filling in this page) A7 B7 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention Instructions (8) Degree: Take 0.3 g of the test compound is dissolved in 10 ml of acetone, 90 ml of distilled water and 4 drops of ethoxylated sorbitan monolaurate, or similar suitable wetting agent are added. In each of the following examples, this mother solution was used to make each specific dilution. "All the tests discussed below involve treatment with the compound of the present invention at a concentration of 3,000 to 500 ppm, and repeated with the control group (ie. Treatment with active compounds), compare and calculate the percentage of prevention. Example 3 End-killing adult insecticide and end-feeding egg / larvicide test On the day before the treatment, the structure of the bottom of the "8" shaped tree tangles was added to two primary plants of two bovine plants planted in the same pot. On a leaf among the leaves. In each gill shape, the circle closer to the stem is designated for the acaricide / larvicide test, and the circle farther away from the stem is designated for the adult acaricide test. On the day before the treatment, a group of adult mites (Tetranychu urticae koch) were transferred to the ovipositor circle, and the female snails were allowed to print until they were removed one hour before the treatment. The plants were sprayed with a solution diluted from 3,000 ppm of the mother solution to 1000 ρ p m until they flowed down. After one day of treatment, about 25 adult snails were sent to the insecticide ring. After 5 days, these rings were checked for mites remaining on the leaves. Calculate the percentage of control based on the number of mites surviving on the tested plants. After 9 days of treatment, eggs hatched and viable immature mites in the eggicide / larvicide ring were examined. Percentage control is based on the number of immature mites that hatch and survive on the tested plants. When the processing effect is against insect marks, the control process is called ovipositivity (O); when the processing effect is against immature snails, control-U- ^ (please read the precautions on the back before filling out this page) This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210 × 297 mm) A7 B7 printed by the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) The treatment is called larvicidal (L). (MI) and Ovicide / larvicide (MIOVL) test results are shown in Tables I and II »Example 4 Rice fly chaos leaf test was diluted from a mother solution with a concentration of 3000 ppm to 1000ppnl. One pot contains Approximately 20 rice seedlings of the Mars variety were treated with a sprayer for each formulation. After one day of treatment, they were covered with a tubular cage and fed into 20 adult rice worms (Sogatocles orizicola). Each cage. After being fed for 5 days, calculate the rice planthoppers living in each pot and calculate the control percentage. The results of the rice planthopper (RPH) test whip are shown in Table I and π. Example 5 The test uses a mother solution with a roll of 3000 ppm. Each compound Take 0.2 ml of each drop on the surface of 5 feeding troughs, spread them all over the surface and air-dry for 2 hours. Then introduce the second instar larvae of the tobacco budworm (Heiicoverpa virescens) into each trough. After 14 days Calculate the number of surviving larvae and the control percentage of each treatment and calibrate it with Abbott's formula. The test results of tobacco budworm (TB) are shown in Table I and II. In 2 ml of acetone, add 13 ml _; _-12- _ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm); ------ 11 "〒_ (please read the back first (Notes to fill out this page)

、 1T 307763 A7 A7 B7 V. Description of the invention (10) 豢 Steamed water and 1 drop of ethoxylated sorbitol and lauric acid vinegar to prepare a 100 ppm solution. 1 to 2 days before the treatment, thin cotton cloth with eggs is cut into small pieces each containing 40 to 80 eggs. Immerse these small pieces in the solution for one minute. After 5 days, calculate the number of hatched and unhatched eggs and decide the adjusted percentage. The results are shown under the heading TBOV in Tables I and II. -------- "installed-(please read the notes beforehand) and fill in the Qin Benyin", 1T ^ 1 piece of paper and 1 copy of the CN standard mark printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Home country I

I Ligong 97 2 X V. Description of the invention (11) A7 B7 table

RXB! Ml MIOVL RPH TB TBOV 1 Η C0NHCeH4CI 0 100 (01 30 0 0 2 4-CH30 COHNCeH, CI 0 70 (L) 100 40 100 3 2,4-CI ch7o CONHCeH5 0 70IL1 100 0 56 4 4-CH3S CONHCeH4CI 50 10010) 0 0 100 5 4-Βγ conhc8h4ci 0 100 (0) 50 60 100 6 2f4CH3 CONHCeH4CI 0 100 (0) 0 0 100 7 2CI-CONHCeH4CI 0 100 (0) 0 0 6 8 4.CF3 conhc6h4ci 0 100 ( 0) 0 100 100 9 2CeH5CH20 C0NHCbH4CI 50 70 (0) 45 32 48 10 2,4-CI conhcbh, ci 0 0 100 0 100 --------- (袭 ------ ， 玎- -------1. (Please read the precautions on the back before filling out this page) The paper standard printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs uses the Chinese National Standard (CNS) A4 specification (210X297 mm)

T 307763 Α7 Β7 5. Description of the invention (η)

-k I I

IY il: y 編 馬 Ε! R! M! MIOVL RPH IB TBOV 11 4, BrCeH4 C0NHCeH4-4 * 0CF3 0 0 0 100 5 12 4-BrC8H4 C0NHC6H4-4-0CF3 30 0 0 100 1 13 3-BrCeH4 C0NHC9H4 -40CF3 0 0 0 100 0 14 4-C! C6H4 C0NHC8H4-4-0CF3 0 0 0 100 0 15 4〇CF3CeH4 C0NHC8H4-4-0CF3 0 0 0 100 0 16 3-Br, 4 CICflH, C0NHCflH4-40CF3 0 0 0 100 0 17 3-N02CeH4 C0NHCeH44-0CF3 0 0 0 100 0 18 2-CI5-C5H, N C0NHC8H4 4 0CF3 0 0 0 100 0 19 3IC.H, C0NHC8H4-4-0CF3 0 0 0 100 0 20 4ICeH4 C0NHCbH4- 40CF3 0 0 0 100 0 21 3,4-CIC6H4 C0NHCeH4-4-0CF3 0 0 0 100 0 22 4-N02CeH, CONHC8H4-4-OCF3 0 0 0 100 0 (， —Binding ^ •-(Please read the back first (Notes to fill out this page) Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -15 · This paper is printed in China National Standard (CNS) A4 (210X297mm) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (l3) Extravagance

Table III 01 m⑵ 4 .〇; m (2) 4 • 5; m (9) 7. 3- 8.1; s (1) 9.2 02 m (2) 3 • 1; s (3) 3 • 7; m (2) 4.3; m (8) 6.9-7.7 03 m (2) 3.0.0; m (2) 4 • 2; s (2) 4.6./ m (7) 7.0-7. 5 04 s (3) 2, 5; s (1) 8 • 8; m (2) 3. 〇; m (2) 4.4; m (4) 7 .1-7.7 05 m (2) 3 '• 1; m (2) 4 • 4; m (8) 7. 0- 7.7 06 s (3) 2, 3; s (3) 2 4; m (2) 3. 〇; m (2) 4.4; m (7) 7 .0-7.5 s (1) 8, .Ί 0 7 m (2) 3. • 〇; m (2) 4 .4; m (8) 7. 0- 7.6 08 m (2) 3 _ _ 1; m (2) 4. .4; m (8) 7. 0- 7.8 09 m (2) 3., 0; m (2) 4 _ • 4; s (2) 5.0; m ( 14) 7.0-7.5 10 m (2) 4 · 〇; m (2) 4.5; m (7) 7.1-7.6; s (1) 8.5 11 m (2) 3.7-4.0; m ^ (2) 4 .4-4 .7 tm (8) 7.2-8. 2 / s (1) 9.4 12 m (2) 3 .7- 4.0; m 丨 (2) 4 .4-4 .7 ; m (8) 7.6-8. 2; s (1) 9.5 -------- ^ d ------ IT ------ 1 * * (Please read the notes on the back first Please fill in this page again) -16- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm)

Claims (1)

i.—a compound of the formula: where Z is (a) -(CH2) Where x is an integer of 0, a is 0 to 5 (b) The integer JL R is defined as follows; or -------- (-I 丨-(please read the precautions on the back before filling this page) • CH.0 Let η be an integer from 0 to 5 and R is defined as follows; R is selected from the following groups: hydrogen, Ci-C4 alkyl, Ci_c alkoxy, halogen, nitro, phenyl, cyano, benzene Oxy group, benzyloxy group, fluorenyl group, CVC4 dialkylamine group, Cl-c4 slope thio group, Ci_c4 letter hole ^ group 'or (^-(^ halo burning group, and R1 is in addition to gas alkyl ;: 1-(: 4 haloalkyl, or the following formula-based sleep-CO-HH The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) / Printed by Beigong Consumer Cooperative of the Central Bureau of Industry and Commerce, Ministry of Economy Where R is moxibustion, autopigment, Cj-C # draw pit group or oxyalkyl group, or its physiologically acceptable discs, but its limitation is that when \ is 0, R1 is not a self-alkyl group. 2. According to the i-th compound of the patent application, the good is option (a), 1 or 2 and X is 〇. 3. The compound according to item 1 of the patent application scope, where R 1 is the following formula group • CO-NH Where R4 is hydrogen, halogen, CrCj alkyl or Cl_c haloalkoxy compound according to item 3 of the patent application, where… is the following formula (please first «read the precautions on the back and then fill in this education). Ministry of Economic Affairs, Central Standards Bureau, Beigong Consumer Cooperation Duin ¾, where R4 is Yusu, c "C4 fluoroalkyl or c" c4 fluoroalkoxy. The compound according to item 3 of the patent application, where R is hydrogen C _ C alkyl, alkoxy, isocyanide, Cl_c4 haloalkoxy or alkylthio. 6. The compound according to item 3 of the patent application, where R4 is gas, trimethyl or trifluoromethoxy 7. A kind of insecticidal or acaricidal combination '", which contains: (a) an effective amount of the compound according to item 1 of the patent application scope, and (b) an appropriate carrier. Sexual or mothicidal composition, which contains. (A) An effective amount of the compound according to item 3 of the patent application scope, and this paper wave scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) i ·%? 4 * · ΛΒ8 · '307763 Announcement π, patent application scope (b) Appropriate carrier》 9_ — 种 控 昆Or mite method, which includes applying an effective amount of the compound according to item 1 of the patent application scope to the site to be protected. 10. A method for controlling insects or mites, which includes applying an effective amount of the compound according to the patent application scope The compound of item 3 is applied to the area to be protected. -------- Install ------ order ----- ~ line (please read the precautions on the back before filling this page)-I The size of the paper printed by the Consumer Labor Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 grid (210X297 mm)