JPS63500037A - Insecticide polyhaloalkene derivatives - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] It is also used to control nematodes infesting soil and plant systems, especially crops. to combat plant-killing diseases caused entirely or partially by nematodes. Take time to use them. The invention further relates to anthelmintic uses of the compounds.

U.S. Patent No. 3,513,172 and its divisional patents for Propp (B “0 ke”) is the expression %formula%) [wherein R included some heterocycles such as 2-thio-4-alkylthiazolyl] Nematicide trifluorobutenyl derivative 11 selected from various substituents: It's clear.

These patents, as well as pond patents, are designed to protect agricultural products to combat nematodes and nematode-induced plant diseases. Discover and commercialize drugs and thereby reduce the considerable economic losses resulting from the spread of nematodes. This reflects continued efforts by industry and government to reduce the number of deaths.

A new class of polyhaloalkene derivatives with high nematicidal activity and good soil mobility It has now been discovered that there is more. In addition, the compounds have been shown to control various nematodes and some Case-2 shows the activity of the entire system. Compounds are also indicators of anthelmintic activity in animals It is effective against the landlord.

The novel nematicidal compounds of the present invention are polyhaloalkene derivatives of formula (I).

In the formula, × is sulfur, oxygen, nitrogen or methylene, and Yl and Y2 independently represent fluorine, salt Z is hydrogen or l/I, same as Y2, n is 1-4 , preferably 1 or 2, provided that the following conditions apply.

(A) When X is sulfur, R is thiazolyl, optionally substituted chenyl, optional thianaphthyl substituted, optionally substituted thiazolinyl, optionally substituted thiadiazolyl, optionally substituted oxadiazolyl, or 3,4.4-) Fluoro-3-atenyloxy is luponylmethyl.

(B) When X is oxygen, R is C(0)R+, where R1 is perfluorinated. loalkyl, optionally substituted phenyl, optionally substituted chenyl, optionally substituted substituted furanyl, optionally substituted pyrrolyl or dihydrothiazolylthiomethyl It is le.

(C) When X is nitrogen, R taken together with nitrogen is isothiocyanate, sulfur It is a cinimide or saccharin group.

(D) When X is methylene, R is hydroxy.

Other aspects of the invention include methods for controlling nematode populations, nematodes and nematodes and polyhaloalkene induction. This includes nematicidal and erecticidal formulations based on the class. controlled according to the present invention Typical nematode species include root-knot nematodes, atrophic nematodes, lesion nematodes, cyst nematodes, and C. elegans nematode.

In Subclasses A and B of Formula I Compounds Above, Heterocycles Other than Thiazolyl Can Be Used The carbon atom may be substituted with any group that does not destroy the nematicidal or insecticidal main activity of the compound. can.

Typical substituents include aliphatic, aromatic and heterocyclic groups, halo, nitro, cyal, koxy, alkylthio, haloalkyl, haloalkoxy, halo, nitro, silyl ano- or alkoxy-substituted phenyl, polyhaloalkenylthio, phenyl Nylalkylthio, phenylthioalkylthio, propargylthio, cycloal including kylmethylthio and the like, as well as straight and branched structures and a variety of such substituents. It includes isomers of.

Throughout this specification, alkyl, alkenyl and alkynyl groups are 1-116 or more. contains more carbon atoms and can be straight or branched. The cycloalkyl group is 3 - May contain 8 or more carbon atoms. alkyl, alkenyl, alkini and alkoxy are lower alkyl, lower alkynyl, lower alkynyl or lower alkynyl, Lukoxy is preferred. That is, if these groups contain 1-8 carbon atoms, It means to have. 1-4 like methyl, propenyl, and methoxy It is even more preferred that the carbon atoms contain 5 carbon atoms. Halo or Haloken is fluorine, salt means chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine . Aromatic substituents include phenyl, naphthyl, anthra7ane, diphenyl, etc. .

Representative compounds of formula (1) are shown in the attached Tables 1, 1a, 1b and 1a.

Preferred compounds of formula I are of subclass A, where R is defined as be done.

(1) R is structure has a thiadiazolyl group, R2 is uni and R2 is 3,4,4-)refluoro-3-butyl thenyl, phenylmethyl or phenylthiomethyl group, each optionally containing a halogen or substituted with nitro. The R25- group is 3 of the 1,2,4-thiadiazole ring. - or 5-positions.

(2) R is a thiadiazolyl group as in (1) above, but iodine is used instead of R2S. It has a code.

(3) R is structure thiadiazolyl group, where R3 is aryl, arylalkyl, aryl Roxyalkyl, alkylthio, haloalkylthio, cyanoalkylthio, ali alkylthio, aryloxyalkylthio, arylthioalkylthio, Terocycloalkylthio, alkenylthio, haloalkenylthio, halocycloa alkylalkenylthio or amino group, which is alkyl, alkylcarbonyl , haloalkylcarbonyl, aryl, arylaminocarbonyl, aryl alkylcarbonyl, arylalkoxycarbonyl, and 3-(2,2-dichloro independently selected from loethinyl)-2,2-dimethylcyclopropanecarbonyl; It is mono- or di-substituted with a ro group.

(4) R is structure is an oxadiazolyl group of 5, where R4 is aryl or arylalkyl. and the following substituents: chloro, fluoro, alkyl, haloalkyl, a R' group which is substituted with rukoxy or nitro is 1゜2.4-oxadi It can be in the 3- or 5-position of the azole ring.

(5) R is structure oxadiazole ring, and R5 is alkyl, haloalkyl, aryl , arylalkyl, aryloxyalkyl, arylthioalkyl, heterosyl Chloalkyl, arylalkenyl or alkynyl (C20, alkyl, ha One selected from loalkyl, alkoxy, cyano, nitro and phenyl7)1 Substitute as desired based on the above. Aryl and heterocycle described in (5) above:, t, German Halogen, alkyl, alkoxy, nitro, amino, hydroxy, acetyl substituted with one or more groups selected from xy and alkylaminocarbonyloxy be done.

(6) R is a thiazolyl group.

[Synthetic Co. Compounds of formula ■ are made by known methods. For example, 4-70 motor 1.1.2-tri Fluoro-1-7tene was mercured in a reaction solvent medium containing sodium ethoxide. Putothiazole (reaction of thiazole with sulfur element produces ￥AI or mercaptothiazole) When reacted with zoline, thiazine or thiothiazoline derivatives of polyhaloalkenes give rise to a body. Examples 1, 2.8-14.16 and 17r below, subclassification of formula ■ Representative examples of this and other reaction systems for the synthesis of compounds of A (X = sulfur) It is. Formula I compounds (subclass B) where X is oxygen are described in Examples 3 and 4. Made as described. Similarly, subclass C (x=nitrogen) and subclass D (X=nitrogen) -CH2-) compounds are described in Examples 5 and 6 (subclass C) and 7 (subclass D). Made as described.

Other polyhaloalkenes can be used to make other Formula I compounds by known methods. 0 For example, trifluoroethylene is chain-extended with methyl tribromide, then 1.3- Reacting the dibromo-1,1,2-)lifluoropropane product with a mercaptan The thio intermediate is obtained. The intermediate is then converted into the Tarrant below. and Tandon + J-Org.

Chem, Vol. 34 (No. 4), p. 864 (1969), Subject to hydrogenation treatment. In the formula, BP is benzoyl peroxide and OEU is 1.8 -diazabicyclo[5,4,0oundec-7-ene catalyst.

C) 12Br2 + F2C = (JIF-1111-ra BrCH2CHFC F2BrBLI Special edition Showa 63-500037 (6) Dihalopropene derivatives within formula I are made by the following general reaction. child The trowels Yl and Y2 are as defined above, and one of Yl and Y2 can also be an ice bag. I can do it.

Trihalopropene derivatives can also be treated using the same methods and reactions as the talant and tantone series. and where Yl, Y2, and Z are as defined by the formula Other compounds are obtained.

Prope compounds useful in the present invention for preparing compounds of formula Preparation of alkenes, butenes, and other alkenes is described by M.R. Liligis) ( M.R.

(Ph.D.) thesis, University of Florida (1955) ) 9, 39, pages 59 and 60. Thus, making compounds of formula I Polyhaloalkenes and heterocycles or other compounds used in It will be clear that the compound is a compound or can be synthesized by known procedures.

The following examples further describe methods for preparing compounds of the invention. I have nothing else to pay attention to All parts and percentages in the examples are by weight, and all temperatures are in °C. Example 1- The products of No. 9 correspond to compounds 1-9 listed in Tables 1 and 1b. fruit Examples 10-17 each describe the compounds in the relevant table.

Example 1 2-(3,4,4-trifluoro-3-butenylthio)-4°5-di hydrothiazole In 30 ml of absolute ethanol, 0.25 g (0,011 mol) of sodium metal Sodium ethoxide was made by stirring. In addition, 2-mail 1.2 g (0.01 mol) of lucafutthiazoline was added. 1 of the reaction mixture Stir for an hour and remove excess ethanol under reduced pressure. Dilute the residue with methyl ethyl chloride. 4-bromo-1+1+2-trifluoro-1-butene 2 ．． Og (0.01 mol) was added. The reaction mixture was stirred at ambient temperature for 4 hours; It was then concentrated under reduced pressure to a residue. Dissolve the residue in 501 parts of toluene and 25 parts each of water. I washed it 13 times. The organic phase was dried over sodium chloride and filtered. Filter the filtrate under reduced pressure Vp, condensation gives 2-(3,4,4-trifluoro-3-butenylthio)-4 , 5-dihydrothiazole as an oil. NMR and IR spectra was consistent with the structure of the proposal.

Example 25-Methylthio-2-(3,4,4-trifluoro-3-butenylthio )-1,3,4-thiadiazole 2-mercapto-5 in 25 ml of distilled acetone -Methylthio-1゜3.4-thiadiazole 2.0 g (0,012 mol) solution 0.84 g (0,006 mol) of potassium carbonate in 25 ml of distilled acetone and 0.2 g (0,001 mol) of potassium iodide. . While continuing to stir, add 4-bromo-1,1,2-)refluoro-1-butene. 2.2 g (0,012 mol) were added dropwise. After the addition is complete, the reaction mixture is brought to reflux. Heated for 4 hours. Cool the reaction mixture, filter, and concentrate the filtrate under reduced pressure to a residue. did. The residue was dissolved in diethyl ether and washed with 5z aqueous sodium hydroxide solution. Ta. The organic phase was dried over magnesium sulfate and filtered. When the filtrate is compressed 8 times under reduced pressure, , 5-methylthio-2-(3,4,4-)lifluoro-3-butenylthio)-1 , 3,4-ctor was consistent with the proposed structure.

(A) In 50 ml of water, 7 fluorobutyric acid 2.6 ff1f (0,02 mol) was added. After the addition was complete, the reaction mixture temperature was brought to 50-60'C for 2 hours. held. The reaction mixture was allowed to cool to ambient temperature before it was filtered. Reduce pressure on filtrate Concentration to the bottom yielded 6.4 g of the silver salt of heptafluorobutyric acid as a solid.

(B) 3.2 g of hebutafluorobutyric acid silver salt in diethyl ether 401 (0,0 4-bromo-1 in 10 ml of diethyl ether to a stirred mixture of 1.9 g (0.01 mol) of 1,2-trifluoro-1-butene were added dropwise. Attachment After the addition was complete, the reaction mixture was stirred at ambient temperature for 2 hours and then heated under reduced pressure for 1 hour. Ta. The ether solvent was removed by distillation and the residual oil was distilled under reduced pressure to give (3, 1.0 g of 4,4-)lifluoro-3-butenyl)hebutafluorobutyrate occured. Boiling point 25℃/4.0mIIl) Ig* NMR spectrum shows the proposed structure It was consistent with

Example 4 (3,4,4-)lifluoro-3-butenyl)4-chlorobenzoate to 1.6 g (0.01 mol) of 4-chlorobenzoic M in 35 ml of acetonitrile Stir the solution overnight and add 1,8-diazabicyclo[5,4,0]-undec-7- Nin 1.51Ill (0,01% k) ni continuation 4-b0mo1゜1.2-) 1.9 g (0.01 mol) of refluoro-1-butene were added.

The reaction mixture was heated under reflux for 4 hours and then allowed to cool to ambient temperature. water 251 and the reaction mixture was extracted with 2013 portions of diethyl ether. − The combined extract was mixed with 2511 doses of water and 25 m12 each of 5z sodium hydroxide aqueous solution. It was rinsed one after another with 1 batches and finally 11 batches of 25 ml of water.

The organic phase was dried over sodium sulfate and filtered. When the filtrate is concentrated under reduced pressure, (3 , 1.2 g of 4,4-)lifluoro-3-butenyl) 4-chlorobenzoate was added to the oil. Arose as. NMR and IR spectra were consistent with the proposed structure.

Example ON -(3+4.4-)refluoro-3-butenyl)succinimi de This compound contains 1.1 g (0.0 °C mol) of succinimide, 4-bromo-1, 1,2-)lifluoro-1-butene 1.9 g (0.01 mol) sodium metal 0.25 g (0.01 mol), 30 ml of absolute ethanol and dimethylform It was prepared in the same manner as in Example 1 using 20 ml of amide. N-(3,4 The yield of ,4-)lifluoro-3-butenyl)succinimide was 0.3% as an oil. It was g.

NMR and IR spectra were consistent with the proposed structure.

Example 6 (3,4,4-)lifluoro-3-butenyl)isothiocyanate (A) 4-bromo-1,1,2-triflu in 50 ml of dimethylformamide A commercially available 10.4 g of phthalimide potassium salt (stirred for 0.056 min. Reaction mixture was allowed to cool and 59 ml of chloroform was added. Pour the mixture into 200ml of water is. The aqueous layer was separated and extracted with 12 portions of 50 ml each of chloroform. -Are you with me? Wash machine N with 12 times each of 50ml of 5χ sodium hydroxide solution and 11 times of 50ml of water. It was. The filtrate was concentrated under reduced pressure to give N-(3,4°4-trifluoro-3-butene. This yielded 4.8 g of nyl)phthalimide as an oil. NMR spectrum shows the proposed structure It was consistent with

(B) N-(3,4,4-)lifluoro-3-butenyl in 50 ml of methanol ) 4.2 g (0,016 mol) of phthalimide and 1.2 g (0.016 mol) of anhydrous hydrazine. Oml( The stirred solution of 0.032 mol) was heated under reflux for 1 hour. Release the reaction mixture. Cooled and solvent removed under reduced pressure. Take up the residue in 25 ml of water and 30 ml of concentrated hydrochloric acid. Raised. The reaction mixture was heated under reflux for 2 hours, then cooled to 0°C.

Solids were removed from the reaction mixture by filtration. The filtrate was concentrated under reduced pressure to remove the residue. Ta. The residue was taken up in 50 ml of water and made basic with 10x aqueous sodium hydroxide solution. I made it. The mixture was extracted with 12 portions of 25 ml each of diethyl ether. -were together The extract was dried with sodium sulfate and filtered. When the filtrate is concentrated under reduced pressure, 4- Amino-1,1,2-trifluoro-! - 0.4 g of butene was produced as an oil. I The R spectrum was consistent with the proposed structure.

(C) 4-amino-1,1,2-tri in 25 ml of diethyl ether in gaseous form Saturated with hydrochloric acid. The reaction mixture was concentrated under reduced pressure to give 4-amino-1,1,2- 0.48 of trifluoro-1-butene hydrochloride was produced as a solid. NMR spec Toll was consistent with the structure of the proposal.

(0) 4-amino-1,1,2-)refluoro-1- in 15 ml of chloroform To a stirred mixture of 0.4 g (0,0027 mol) of butene, 0.0 ．． 3 g (0,003 mol) followed by 0.7 ml (0,00 mol) of triethylamine 9 mol) was added. After the addition was complete, the reaction mixture was stirred at ambient temperature for 3 hours.

Next, the reaction mixture was mixed with 11 portions of 25 ml of water and 25 ml each of 5z sodium hydroxide aqueous solution. Washed 12 times and finally with one 25 ml portion of water. Sodium sulfate organic layer and filtered. Concentrating the filtrate under reduced pressure yields (3,4,4-)refluorinated This yielded 0.3 g of -3-butenyl)isothiocyanate as an oil. IR Spec Toll was consistent with the structure of the proposal.

Example 7 4,5.5-) Refluoro-4-penten-1-ol (A) Die 2.4 g (0.1 mol) of magnesium shavings in 100 ml of chill ether Add 4-bromo-1,1,2-trifluoro-! to the stirred mixture. -Butene 18 ．． 98 (0 mol) was added.

After the addition was complete, the reaction mixture was heated under reflux until the end of the reaction. The reaction mixture was heated to 0°C. 9.0 g (0.2 mol) of carbon dioxide gas was gradually passed through. After the addition is complete, Stir the reaction mixture for 1 hour, then add 100 ml of this 2 oz aqueous solution of hydrochloric acid and filter. The remainder was extracted 4013 times each. - Cool the combined extract and add 25% sodium hydroxide. 40 ml of thorium aqueous solution was gradually added. Separate the organic layer and add sodium 251 hydroxide. The mixture was extracted with 40 ml of an aqueous solution of aluminum. - Combined base layer with 2oz hydrochloric acid aqueous solution Carefully acidify. The mixture was extracted with 12 portions of 100 ml each of diethyl ether. Ta. - The combined extracts were dried over sodium sulfate and filtered. Concentrate the filtrate under reduced pressure. Upon condensation, 6.9 g of 4,5.5-trifluoro-4-pentenoic acid was produced as an oil. Ta. NMR and IR spectra were consistent with the proposed structure.

(8) 0.4 g of lithium aluminum hydride in 20 mI of diethyl ether (0.01 mol) in 30 ml of diethyl ether. 5.5-) A solution of 1.5 g (0.01 mol) of refluoro-4-pentenoic acid Added dropwise. After the addition was complete, the reaction mixture was stirred at ambient temperature for 1 hour, then added with 2 On of water. +I was added carefully. The mixture is filtered and the filtrate is compressed under reduced pressure. 4.5. 5-) 0.8 g of refluoro-4-penten-1-ol was produced as an oil.

NMR and IR spectra show the proposed structure ruthio)-1,2,4-thiadiazole (A) dipotassium cyanoimidithiocarbonate in 19 if acetone and 22 ml water M [El Nis Laila Tempertsk (L.

S., Wittenbrook) et al., J. Org, Chem, Volume 38 (3 No.), page 465 (1973)] 5. Og (0,026 mol ) Nogaki special costume Showa 63-500037 (8) The mixed solution was cooled to 0°C, and 4-bromo-1°1.2- ) 4.9 g (0,026 mol) of refluoro-1-butene were added dropwise. Addition completed Afterwards, the reaction mixture was warmed to ambient temperature and stirred for 16 hours. Reaction mixture under reduced pressure Concentrated to residual solid. The solid was dissolved in ethyl acetate and filtered. Filter the filtrate under reduced pressure and the remaining solid was dried in a vacuum oven. Dry solids in hot chloroform/acetic acid Dissolved in ethyl and filtered.

The filtrate was concentrated under reduced pressure and the remaining solid was dried in a vacuum oven to give (3,4,4-tritri) This yielded 4.4 g of potassium fluoro-3-butenyl)cyanoimide dithiocarbonate.

The NMR spectrum was consistent with the proposed structure.

(B) (3,4,4-trifluoro-3-butenyl in 10 ml of chloroform) ) 2.0 g (0,008 mol) of potassium cyanoimide dithiocarbonate was stirred. The solution was cooled to 0°C and 1.2 g (0,009 mol) of sulfuryl chloride was added dropwise. . After the addition was complete, the reaction mixture was kept at 0 °C for 1 h, refluxed for 4 h, then brought to ambient temperature. Warmed at temperature for 16 hours. Stirring was continued for the last 21 hours.

The reaction mixture was filtered and the filtrate was concentrated under reduced pressure. diethyl ether as eluent A concentration method was used and passed through silica gel. Filter the ether eluent and vacuum the filtrate It was concentrated down to the residual oil. Drying the oil in a vacuum oven yields 3-chloro-5-(3 ,4,4-)rifluoro0-3-atenylthio)-1,2,4-thiadiazole0 ．． Yielded 9g. NMR and IR spectra were consistent with the proposed structure.

Example 93-Bromo-5-(3,4,4-trifluoro-3-butenylthio)- 1,2,4-thiadiazole (3,4,4-)lifluoro-3-bu in water 251 cyanoimidopotassium dithiocarbonate (prepared in Example 80 Step A) ) A stirred solution of 3.0 g (0,011 mol) of bromine was cooled to 0°C, and 2. 2 g (0,014 mol) were added dropwise under positive pressure of gaseous nitrogen. After addition, mix the reaction The temperature was held at 0°C for 1 hour, then warmed to ambient temperature and stirred for 16 hours. Zeta. Sodium thiosulfate was added to the reaction mixture, which was then chased with chloroform. and water. Separate the chloroform layer and dry with magnesium sulfate. Ta. The mixture was filtered and the residual oil was concentrated under reduced pressure. 4:1 hexane/diet The oil was passed through silica gel using thyl ether as eluent. Eluent under reduced pressure When concentrated to 3-bromo-5-(3,4°4-trifluoro-3-butenylthi e) 1.1 g of -1,2,4-thiadiazole is produced as an oil. NMR spectrum was consistent with the structure of the proposal.

Example 10 (Compound 25) 3,5-di(3,4,4-trifluoro-3-butene Nilthio) l+2+4-thiadiazole (A) Shea in 425 ml of methanol Dipotassium neumidodithiocarbonate (made in Example 8, Step A) 16.0 A mixed solution of 2.6 g (0.08 mol) and 2.6 g (0.08 mol) of sulfur was released. After cooling, it was concentrated under reduced pressure to a residual solid. When the solid is dried under reduced pressure, 3, Dipotassium salt of 5-dimercapto-1,2,4-thiadiazole is, + g occured.

(B) 3,5-dimercapto-1°2.4- in 35 ml of methyl ethyl ketone Stir a solution of 1.03 (0,004 mol) of dipotassium salt of thiadiazole, 4-Bromo-1,1,2-)refluoro-1-butene 1.7 g (0,009 mole ) was added. The reaction mixture was heated under reduced pressure for 2 hours and then allowed to cool to ambient temperature. I stirred this for 18 hours. The reaction mixture was concentrated under reduced pressure to a residue.

The residue was stirred in 25 ml of water, and the mixture was poured into two portions of 25 ml each of toluene. Extracted. The organic N was dried with sodium sulfate and filtered. The filtrate was condensed under reduced pressure. Then, 3,5-°di(3,4,4-)lifluoro-3-butenylthio)-1 , 1.1 g of 2,4-thiadiazole were produced as a liquid. The NMR spectrum is It was consistent with the structure of the proposal.

Example I+ (Compound 26) 3-(4-nitrophenylmethylthio)-5-( 3,4,4-trifluoro-3-butenylthio)-1゜2.4-thiadiazole (A) 3,5-dimercapto-1,2,4-thiadiazole in 200 ml of water (Prepared in Example 10, Step A) 24.7 g (0,1 The stirred solution of 0.09 mol) was acidified with concentrated hydrochloric acid. The resulting solids are removed by filtration. When collected, wet 5-amino-1,2,4-dithiazole-3-thione 17.3 g was produced.

Melting point 21? -220℃.

(B) 2.2 g of sodium hydroxide (0, 5-amino-1,2,4-dithiazole-3- 4.0 g (0,027 mol) of thione was added in small portions. 5-amino intermediate Once everything is dissolved, add 4.7 g (0,027 mol) of 4-nitrophenylmethyl chloride. ) was added dropwise. After the addition was complete, the reaction mixture was stirred at ambient temperature for 16 hours. reaction The mixture was concentrated under reduced pressure to a residue. Dissolve the residue in 20 ml of water and then Extraction was performed with two portions of 25 ml each of diethyl ether. Acidify the aqueous layer with concentrated hydrochloric acid and a gummy solid formed. Extract the solid from the aqueous layer with two 25 ml portions of ethyl acetate each. did. - The combined extracts were dried over sodium sulfate and filtered. Filter the filtrate under reduced pressure Concentration yielded a gummy solid. Dissolve the solid in methylene chloride and remove a small amount of insoluble Filtered to remove material. The filtrate was concentrated under reduced pressure to give 3-(4-nitrophenium). Nylmethylthio)-5-mercap)-1,2,4-thiadiazole 2.88 Occurred as a solid. The NMR spectrum was consistent with the proposed structure.

(C) 0.25 g (0,011 mol) of sodium in 35 ml of ethanol Stir the solution and add 3-(4-nitrophenylmethylthio)-5-mercapto-1 , 2.7 g (0,0095 mol) of 2,4-thiadiazole were added. Addition completed Afterwards, the reaction mixture was stirred at ambient temperature for 1 hour. Remove ethanol solvent under reduced pressure did. The residue was dissolved in 35 ml of methyl ethyl ketone and 4-bromo-1,1.

1.6 g (0,085 mol) of 2-trifluoro-1-butene was added.

After the addition was complete, the reaction mixture was stirred for 16 hours, then the pressure was reduced and 251.5 z of water was added. Washed with two 25 ml doses each of sodium oxide aqueous solution α and 25 ml of water. organic layer was dried with sodium Vtate and filtered. The filtrate is concentrated under reduced pressure to remove residual oil. occured. The oil was dissolved in methylene chloride and passed through a silica gel column. Evacuate the eluent Concentrating down gives 3-(4-nitrophenylmethylthio)-5-(3+L4-t yielded 2.1 g of refluoro-3-butenylthio)-1,2,4-thiadiazole. Ta. The NMR spectrum was consistent with the proposed structure.

Example 12 (Compound 30) 2-(+-methylethylthio)-5-(3,4°4 -trifluoro-3-butenylthio)-1,3,4-thiadiazole 2,5-dimercapto 1,3°4-thia in 200 ml of tetrahydrofuran Stir a solution of 22.5 g (0.15 mol) of diazole, add triethylamine 21 ml (0.15 mol) was lubricated. After the addition is complete, let the reaction mixture stand at ambient temperature. Stir for 15 minutes, then 4-B D%-1,112-F Leaf Ruollow 1-B 4 g (0.15 mol) of 2B was lubricated with oil. After the addition is complete, the reaction mixture is Heated under reflux for 2 hours. The cooled reaction mixture was concentrated to a residue under reduced pressure. . Stir the residue in 250 ml of diethyl ether and add 10% potassium hydroxide. The aqueous solution was extracted twice with 100 ml each.

- The combined extracts were acidified with 1 inch aqueous hydrochloric acid solution, then 100 ml each of diethyl ether Extracted in 2 ml batches. - Dry the combined ether extracts with sodium sulfate. and filtered.

(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole This yielded 35.6 g of solid. The NMR spectrum is consistent with the proposed structure. was.

(B) 2-Mercapto-5-(3,4,4 -trifluoro-3-butenylthio)-1,3,4-thiadiazole 1.3 g (0,005 mol), 2-iodopropane 0.5 ml (0,005 mol), and Sodium O, 15g (0,007 mol) was added to 35ml of ethanol and methyl ether. The mixture was heated to react under reduced pressure in Chilketone 351 for 5 hours, then Stir at temperature for 16 hours. 2-(+-methylethylthio)-5-(3,4,4 The yield of -trifluoro-3-butenylthio)-1,3,4-thiadiazole is It was 1.3X as an iα body. The NMR spectrum is consistent with the proposed structure. Ta.

Example 13 (Compound 37) 2-(4-chlorophenyl)-5-(3,4,4- Trifluoro-3-butenylthio)-1,3,4-thiadiazole (A) 4-chlorobenzoic acid hydrazide in triethyl orthoformate 3001 8.1 A stirred solution of g (0,048 mol) α) was heated under reflux for 16 hours. excess The triethyl orthoformic acid was removed by distillation and the remaining solids were combined with petroleum ether. When mixed with garlic, 2-(4-chlorophenyl)-1,3,4-oxadiazole 7.78. Melting point: 129°C. The NMR spectrum is consistent with the proposed structure. Ta.

Stir a solution of 17 g (0,084 mol) of phosphorus to obtain 2-(4-chlorophenyl) -1,3,4-oxadiazole 7.6 g (0,042 mol) was added. Attachment After the addition was complete, the reaction mixture was heated under reflux for 30 hours. Cool the reaction mixture and add 1 part water 00 it was lubricated. Pass the mixture through diatomaceous earth to separate the organic and aqueous phases. Filtered. The organic phase (filtrate) was extracted with loz potassium hydroxide aqueous solution. extract liquid Acidification with 5z aqueous hydrochloric acid and then concentration under reduced pressure yields 2-(4-chlorophenylphenyl). This yielded 0.3 g of mercapto-1,3,4-thiadiazole)-5-mercapto-1,3,4-thiadiazole. Melting point 1 78℃.

(C) In the same manner as in Example 2, 2-(4-chlorophenyl)-"5-mercap 0.3 g (0,0015 mol) of tho-1,3,4-thiadiazole, 4-bromo -1,1,2-trifluoro-1-butene 0.4 g (0,002 mol), carbonic acid Measuring 0.2 g (0,0015 mol) of potassium and 0.05 g of potassium iodide The reaction was carried out in 9 ml of thyl ethyl ketone. 2-(4-chlorophenyl)-5- (3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole The yield was 0.18.

Melting point 68-69°C. The NMR spectrum was consistent with the proposed structure.

Example 14 (Compound 39) 3-(4-chlorophenyl)-5-(3,4,4- Trifluoro-3-butenylthio)-1,2,4-oxadiazole (A) 4-chlorobenzonitrile 4 in 10 ml water and 100 ml ethanol ．． 1 g (0.03 mol) of hydroxylamine hydrochloride, the stirred solution α is reduced. Heated under flow for 16 hours. The reaction mixture was cooled and 501 liters of water was added. ethanol The solvent is removed under reduced pressure, the concentrate is cooled in a water bath, and the resulting solid is removed by filtration. collected. When the solid is dried, N-hydroxyiodo-4-chlorobenzamide 4 ．． Yielded 4g. Melting point 122-130°C.

(B) N-hydroxyimido-4-chlorobenz in 50 ml of diethyl ether Stir a solution of 4.4 g (0,028 mol) of amide and 0.55 g (0.55 mol) of thiophosgene. ml (0,007 mol) was prepared. After the addition is complete, the reaction mixture is heated at ambient temperature for 1 Stir for 5 minutes, then under reflux for 1 hour. The reaction mixture was cooled, filtered and ．． 0'-thiocarbonyl (4-chloro-N=hydroxybenzenecarboximide amide) was collected. A 100X yield was assumed.

(C) Dissolution of 10.0 g (0.25% l) of sodium hydroxide in 90 mI of water Stir the night, Bis 0. Ol-thiocarbonyl (4-chloro (0.14 mol) Added. After the addition was complete, the reaction mixture was heated under reflux for 1 hour. Cool the reaction mixture The mixture was cooled and extracted with two 50 ml portions of diethyl ether. Acidify the aqueous layer with concentrated hydrochloric acid It became. The resulting precipitate is collected by filtration, washed with water, and dried. lorophenyl)-5-mercapto-1,2,4-oxadiazole t,og occured. Melting point +39-156°C (decomposition).

The NMR spectrum was consistent with the proposed structure.

(D) In the same manner as in Example 2, 3-(4-chlorophenyl)-5- 500037 (10) Mercapto-1,2,4-oxadiazole 0.7 g (0,003 mol), 4 -bromo-1,1,2-)refluoro-1-butene 0.6 g (0,003 mol ), potassium carbonate 0.2 g (0,0015 mol), and potassium iodide 0.I g was reacted in 40 I+Il of distilled acetone. 3-(4-chlorophenyl )-5-(3,4,4-)lifluoro-3-butenylthio)-1,2,4-ox Thadiazole yield was 0.38. Melting point 49-52°C. The NMR spectrum is It was consistent with the structure of the proposal.

Example +5 (Compound 43) 5-(3,4,4-)lifluoro-3-butenyl thio)-1,3,4-oxadiazole (A) in 250 ml of acetonitrile Stir 25 g (0,147 mol) of 4-chlorophenylacetic acid and 15.0 g (0,0147 mol) of lomoethane followed by 1,8-diazabicyclo[ 5,4,O cholandec-7-ene22. Og (0,147 mol) was added. Attachment After the addition was complete, the reaction mixture was stirred for 18 hours while cooling in a water bath.

The reaction mixture was concentrated to half volume under reduced pressure and then added to 50 ml of water. mixture Extracted with two portions of diethyl ether.

- The combined extracts were dried over magnesium sulfate and filtered. The filtrate was condensed under reduced pressure. This produced 18.2 g of ethyl (4-chlorophenyl)acetate.

(B) 18.2 ethyl (4-chlorophenyl)acetate in 10 ml ethanol A stirred solution of g (0,091 mol) and 10 if of hydrazine hydrate was heated under reflux. Heated for 1 hour, during which time a solid precipitated. Collect solids by filtration and dry Tora 16 pi C, 8 when drying (C) 4-chlorophenylacetic acid hydride in 10 ml of water and 200 ml of ethanol Radide 7, 0 g (0.038 mol), carbon triseptide 3.08 (0.039 mol) A stirred solution of 2.8 g (0.050 mol) of potassium hydroxide was refluxed. The mixture was heated for 4 hours. Ethanol was removed under reduced pressure. Take the concentrate into water, The mixture was washed with diethyl ether. The aqueous layer was acidified with 5z aqueous hydrochloric acid and then diluted with dichloromethane. Extracted with ethyl ether. The extract was dried with magnesium sulfate and filtered. reactor Concentrating the solution under reduced pressure yields 2-(4-chlorophenylmethyl)-5-mercapto. -1.

3.98° of 3,4-oxadiazole was produced. Melting point: 115°C. NMR spectrum was consistent with the structure of the proposal.

(D) 2-(4-chlorophenylmethyl)-5-merca in the same manner as in Example 2. 2.4 g (0.011 mol) of prop-1.3.4-oxadiazole, 4-bro Mo-1.1.2-) Riff Jl, O0-1-Boor”/2, 0z (0.011 mol ), 1.5 g (0.011 mol) of potassium carbonate and 0.5 g of potassium iodide. The reaction was carried out in 45 ml of acetone. 2-(4-chlorophenylmethyl)-5-( 3,4,4-)Lifluoro-3-butenylthio)-1.3.4-oxadi The azole yield was 1.58 as a liquid. The NMR spectrum is of the proposed structure. It was consistent with the construction.

Example 16 (Compound 230) 2-(3,4.4-)lifluoro-3-butenyl Synthesis of thio)thiazole A stirred solution of 2.0 g (0.024 mol) of azole was cooled to -65°C. , 16 ml of 1.55 mol n-butyllithium. After the addition is complete, mix the reaction. Stir the mixture for 45 minutes and add 0.8 g (0.024 mol) of elemental sulfur little by little. do. The reaction mixture was stirred for another hour, then the temperature was adjusted to -60°C and the 4-build Romo-1.1.

Lubricate with 4.5 g (0.024 mol) of 2-trifluoro-1-butene.

After the addition was complete, the reaction mixture was stirred for 3 hours, during which time the mixture was allowed to warm to ambient temperature. Ru. The solvent is removed under reduced pressure.

Dissolve the residue in diethyl ether and make two portions of an aqueous solution saturated with sodium chloride. wash with Dry the organic layer with magnesium sulfate and filter. Remove the remaining half of the filtrate under reduced pressure. I even solid! l! Shrink. Semi-solids are subjected to column chromatography on silica gel. Let's go. Elution is carried out with 1:1 hexane/diethyl ether. appropriate fraction are combined and concentrated under reduced pressure to yield 2-(3,4.4-)lifluoro-3-butyl 0.4 of thiazole (tenylthio)thiazole is produced as an oil. NMR and IR spectra was consistent with the structure of the proposal.

Example 17 (Compound 23+) 2-(2,3.3-trifluoro-2-prope nilthio) thiazole bone twin (A) 50 g of trifluoroethylene (0.6 mole) in a stainless steel autoclave. ), 300 g (1.7 mol) of dibromomethane, and 5 g of benzoyl peroxide. (0.02 mol). The reaction mixture was stirred and heated at 100°C for 6 hours, Then cool to -70'C. When appropriate fractions are combined, 1,3-bromo -1,1,2-) yields refluoropropane.

(B) Thiazole 20 in 300 ml of dry tetrahydrofuran under nitrogen atmosphere The stirred solution of g (0,024 mol) was cooled to -65°C, and 1.55 mol 0 - Add 16o1 of butyllithium dropwise.

After the addition was complete, the reaction mixture was stirred for 45 minutes and 8.0 g (0,024 mol) of elemental sulfur was added. ) is added little by little. After the addition was complete, the reaction mixture was stirred for an additional 1 hour, at -60 1,3-dibromo-1,1,2-trifluoropropane is added dropwise at <0>C. End of addition After completion, the reaction mixture is warmed to ambient temperature and stirred here for 3 hours. Reduce reaction mixture Concentrate under pressure to a residue. Dissolve the residue in diethyl ether and dilute with sodium chloride. Wash twice with aqueous solution. Dry the organic layer with magnesium sulfate and filter.

Concentrate the filtrate under reduced pressure to a residue. Purify the residue by column chromatography. , 2-(3-bromo-2,3,3-trifluoropropylthio)thiazole will occur.

(C) 2-(3-bromo-2,3,3-)refluoro in 40 ml of toluene 2.9 g (0.01 mol) of propylthio)thiazole and i,s-diazabisic Ro[5,4,O] undeku-7-nin l-5g (o, o, imo/l, ) oysters Heat the combined solution under reflux for 2 hours. The solvent is removed by distillation and the residue is filtered. Purification by ram chromatography yields 2-(2,3,3-)refluoro- This yields 1.1 g of 2-propenylthio)thiazole.

It lists the compounds that are produced in Table 18 and lc are used as starting materials for synthesis. 4-Bromo-1,1,2-)Refluoro-l-butene Formula ■Compounds used (wherein Y1. Y2 and 2 are fluoro).

[Use as an insecticide] The compounds of the present invention can be used against a variety of pests that attack plants and animals. Agriculture They are used as nematicides, especially for plant-parasitic nematodes and "independent-living" nematodes, all Thus, it is useful against nematodes that are not dependent on a particular plant or other host.

An example of the latter is the nematode Caenorhabditis elegans (Caenorhabditis elegans), which feeds on microorganisms. Caenorhabd i-Ns elegans), this nematode is found in the large intestine. It feeds on bacteria such as E. coli and is used as an agricultural and veterinary nematocide or dewormer. Used for selection of drugs.

As an anthelmintic, for example, Ascaris lumbricoides When used in the veterinary treatment of porcine roundworms, the compounds are Although it can be used alone orally, parenterally or topically to provide a suitable dosage, It is usually administered in addition to a pharmaceutically acceptable carrier. Such a carrier is Solid (e.g. tablets or capsules) or liquid (e.g. solution, suspension or emulsion) One or more of water, gelatin, sugar, starch, stearic acid or citric acid for administration as Organic acids and their salts, talc, vegetable fats and substances are preservatives, stabilizers, and humectants. The compositions, which may also contain emulsifiers, emulsifiers, buffers, salts, and other therapeutic agents, can be prepared in a conventional manner. Depending on the method, about 5 to 95 weight tX, preferably about 25 to 75 weight tx of deworming Can be formulated to contain compounds. Anthelmintic action and treatment using the compounds of the present invention Further guidance on treatment methods can be found in the Kirkkoosmer Encyclopedia. Field of Chemical Technology” (3rd edition, Vol. 5, pp. 451-468) ``Chemotherapy, anthelmintics'' and the articles cited therein, as well as U.S. Pat. No. 76.892, column 3, lines 29-56, etc. Available from publications.

In order to use the compounds of the present invention as agricultural nematicides, the compounds must be As with medicines, maximum strength is generally not applied, and the formulation and method of application of the poison is dependent on the material. Usually used to facilitate the dispersion of the active ingredients, acknowledging that scales may affect activity. In addition to the agriculturally acceptable carriers used and various additives, and optionally other It is formulated with active ingredients. The compounds can be applied as powders or liquids, for example. However, the choice of application depends on the nematode species present in a particular infested area and environmental factors. change. For this reason, compounds can be prepared as granules, powders, wettable powders, emulsions, solutions, suspensions, controlled It can be formulated as a composition for release, etc.

Typical formulations contain active ingredients, depending on the particular drug used, excipients, carriers, or mode of application. The concentration changes significantly. With proper consideration of these factors, the activity of typical formulations The ingredients may suitably be present, for example, in a concentration of about 0.5 to 99.5% by weight of the formulation. Ru. If a surfactant is used in the formulation, it may be present in various concentrations, from 1 to 3 It may be present in any suitable range of 0 weight 2.

Powders contain the active ingredient and a finely divided solid carrier and/or fillers such as talc, natural clay, clay, etc. - sergar, leaf shortstone, chalk, diatomaceous earth, calcium phosphate, calcium carbonate and mag In mixtures with nesium, sulfur, lime, flour, and other organic and inorganic solid carriers be. These finely divided formulations generally have a size of about 50 microns (325 mesh, US standard sieve system). In most cases, the active ingredient is 1-15", sometimes present in the powder formulation in a concentration ranging from 1z to about 3(H); The remainder of the composition typically contains one or more agriculturally acceptable auxiliaries, carriers, or fillers. Contains inert materials that can be used.

The nematocide of the present invention can also be formulated as a hydrating powder. These formulations are made of finely ground particles. form, which easily disperses in water or other liquid vehicles. Hydrating agents are the best The final application is as a dry powder or as a dispersion in water or other liquid. hydration Typical carriers for the agent are Fuller's earth, kaolin clay, silica, and highly absorbent This will depend on the other inorganic properties and the absorption layer of the carrier. Liquids and low melting point solids (10 (melting point below 0°C) is suitable at a concentration range of 5 to 50% by weight21, usually 10 to 301%. properly prescribed. High melting point (melting point greater than 100°C) solids are 5 to 95% by weight It is usually prescribed in the range of 50 to 85 degrees. Facilitates wetting, dispersion and suspension an agriculturally acceptable carrier or filler often containing small amounts of surfactants to agents make up the remainder of the formulation.

Microcapsule formulations and other controlled release formulations are also suitable for administering the compounds according to the invention. used for

Emulsions are homogeneous liquid compositions containing active ingredients usually dissolved in a liquid carrier. Commonly used overnight carriers are xylene, heavy aromatic naphtha, isophorone, and other non-volatile or semi-volatile organic solvents. When using nematicides, These emulsions are dispersed in water or other liquid vehicles to form emulsions and are typically processed. Applied as a spray to the area. The essential active ingredient concentration in the emulsion depends on the method of application of the composition. Methods vary, but generally the active ingredient is 0.5 to 95 tX, often 10 Ishi80ju II! The remaining 99.5 to 5 parts are the surfactant and liquid carrier. It is.

Flowing agents are similar to emulsions, but 2. However, the ingredients are suspended in a liquid carrier, generally water.

Like emulsions, flow agents also include small amounts of surfactants, ranging from 0.5 to 95% of the composition. i*z, often containing in the range of 10 to 50 parts by weight of active ingredient. application Special clothes Showa 63-500037 (12) For this purpose, the flow agent is diluted with water or other liquid vehicle and is typically used as a propellant. Applied to the treatment area.

Typical wetting agents, dispersing agents or emulsifying agents used in these formulations include sulfonic acids. and alkyl and alkylaryl sulfates, and their sodium or calci salts; alkylaryl polyether alcohols; sulfated higher alcohols class; polyethylene oxide; sulfated animal and vegetable oil; sulfonated petroleum oil; polyhydric alkaline Fatty acid esters of coals and ethylene oxide addition of such esters products; addition products of long-chain mercaptans and ethylene oxide; and nonylphenol adducts of alkylphenols such as ethylene oxide and many others. A variety of useful surfactants are commercially available. When using a surfactant, this usually contains 1 to 15 parts by weight of the nematocidal composition.

Other useful formulations include corn oil, kerosene, propylene glycol or other It includes a simple solution of the active ingredient in a relatively non-volatile solvent such as a solvent. this shape Formulations of the formula are particularly useful for very small volume applications.

The active ingredient concentration at the working dilution is usually in the range of about 2z to about 0.1z.

This technology does not apply to spray, dispersion, and controlled or slow release compositions. Various modifications may be made to the compositions known or obvious in the art to modify the compositions to other compositions. Including nematicides, insecticides, acaricides, fungicides, plant conditioners, herbicides, fertilizers, etc. It can be formulated and applied together with other suitable active ingredients.

When applying the above chemicals, the active ingredient, sometimes referred to as the “nematicidal dose,” Must be applied in an effective amount to control nematodes. Application rate depends on compound selection, formulation and Application methods, plant species to be protected, and planting vary widely depending on density, but appropriate The usage rate is 0.5 to 25 J/ha, preferably 1 to about 20 kg/ha It can be in the range of

The compounds of the present invention can be used at the location or planned location of planting plants or crops, i.e. It is applied by mixing the formulation into the soil where the problem occurs. to do this planting compounds by mixing them into the soil or by spraying prescription chemicals into the area or planned area. or a small area around the roots where the plant is planted or planned to be planted. Limit application to bands. When using the latter method, the nematicidal amount, i.e. soil It will be obvious that the nematicidal concentration in the medium must be applied to the root zone. this purpose The concentration ranges from 0.1 to about 50 parts by weight of the compound of the invention per million parts of soil. It is in.

However, in a significant aspect of the invention, certain polyhaloalkene derivatives of the invention It was found to be an effective nematode agent when applied to nematodes. This aspect is illustrated below. do.

The following are specific examples of formulations that can be utilized in accordance with the present invention. These prescription drugs The percentage is 1/νt.

1. Typical powder formulation Test compound 5z Base 95% 96z Atsuta Clay 2z High purity sodium lignosulfonate (1004) 2χ powder alkyl naphthalene Sodium sulfonate (75X) 2. Typical emulsion (A) Test compound 5. O1 Emulsifier A4.0% Emulsifier 8 0.4% Emulsifier CO, 8! Emulsifier D 1.3Z Purified xylene solvent 88.5X Emulsifier A is an anionic calcium salt of dodecylbenzene sulfonate. emulsification Agent B is an anionic low-molar ethylene oxide condensation product of nonylphenol. Ru. Emulsifier C is an ethylene oxide condensation of 30 moles of nonylphenol anion. It is a product. The emulsifier is a nonionic thickening agent made of tooz polyalkylene glycol. It is.

(B) Test compound 21.3% Emulsifier-A 4.8 Emulsifier B O, 5m Emulsifier C0,9Z Emulsifier D 1.4X Purified xylene solvent 71.7” (C) Test compound 5.0! Emulsifier E 4.0: Emulsifier F 3. O! Emulsifier G 3.0% dormant spray oil solvent (Non-volatile) 85.0! Emulsifier E is Polio, which is commercially available under the trade name and designation "T Mars 808 A". It is an oil-soluble, non-ionic formulation of xyethylene ethers. Emulsifier F is A formulated non-ionic emulsion marketed under the trade name and designation ``LOMO 200-4'' It is. Emulsifier G is commercially available under the trade name and designation ``Gafac RE-410''. It is an anionic free acid of a complex organic phosphate ester.

3. Typical granule formulation (A) Test compound (industrial use) 5. Of Niatsutapulgite carrier/filler 9 5.0% carrier/extender is volatile vIJ quality oligoluminium with 2z free moisture. It is.

(B) Test compound (industrial use) 5.0! Ground corn cob, 1’4/40m Tsushiyu 95.0: (C) Test compound (above emulsion 2 (B) and T') 23. 5 niatutapulgite carrier/filler [Top) 3(A)] 1e, 5X 4. Typical solution formulation Test compound 0.3z [Biological test code] Powders (initial and residual activity) and acetone/water formulations (total systematic activity) of compounds of the invention. The nematicidal and anthelmintic activities (as sex) were tested as follows. Prescription drugs are listed above. It is as follows.

1. Initial root-killing nematode activity The activity against Meloidogyne incognita is as follows: Rates ranging from 1011 pm to 0.078 ppm of compounds in nematode infested soil It was measured by mixing the compound of the present invention. In soil infested with nematodes, I planted several tomato or cucumber seedlings. Two weeks after planting, examine the test pot, Check the degree of root gall (swelling) on the plant as an indicator of control by the test chemical.

The average values are shown in the attached Table 2. The hump index is a number used in determining evaluation, and is based on the following It also has meaning.

ζEyu soil 15 〇　Complete control without expansion.

1. 75% less swelling than control plants.

2. Swells 5 oz less than control plants.

3. 25% less swelling than control plants.

4 Almost the same as the control plant.

The control rate is related to the gall index as follows.

When the Koff index is between O and 1, the control rate is close to 75cm or 10oz. In order to show this, it is further subdivided as follows.

ζL Dwarf J Swimming 1 0.8 80 0.5 90 0.1-0.4 95-99 This result shows that the compounds of the present invention are highly effective against root-knot nematodes at the application rates tested. It has been proven that it is effective.

2. Residual root-killing nematode activity The nematicidal compounds of the invention prevent the spread of root-knot nematodes in the soil during the post-treatment period. The ability was evaluated by observation.

Test compound (5χ) powder was applied to soil samples at test compound application rates of 5 and 10 ppm. mixed into. Next, treated soil samples were inoculated with nematodes at one-week intervals, cultured, and soil samples were tested. The gall index and control rate of seedlings planted in the soil were measured. Specifically, treatment with a test compound The soil was placed in a fiber pot with a diameter of 7.6 cm and stored in a greenhouse. treatment One, two, and four weeks later, appropriate numbers of pots were fed with root-knot nematode eggs and larvae.

Plant cucumber or tomato seedlings in each pot and examine them approximately 2 weeks after the nematode infestation of the soil. As a result, the test results listed in the attached Tables 3 and 33 were obtained. Data are nematode inoculation compared to when seedlings were planted in untreated control soil (seedlings showed no nematode control). Overall, most test compounds showed substantial residual activity at the application rates tested. .

3. Atrophy nematode test Hand 111m is substantially the same as the initial root-killing nematode test described above, except that the formulation The application rate of the compound was 2.5 and 5 ppm in the soil where the corn seedlings were planted, Subsequently, the soil was inoculated with a combination of larval and adult nematodes. Approximately 4 weeks after inoculating the sample It was observed and evaluated. The results (attached Tables 4 and 43) show no control at all. Compared to the untreated sample, the difference in the average number of nematodes between the test fertilizer and the treated sample is It is divided by the number of worms and multiplied by 100.

4. Lesion nematode test The procedure was essentially the same as the wilt nematode test, except that pea seedlings were used. Conclusion fruit (Table 5 attached) showed a higher rate of change at the test application rate compared to untreated samples (no control). The compound shows good control. "Control rate" is defined as follows.

The procedure was essentially the same as the atrophy test, except that a die surface was used. "Control rate ” as defined by the atrophy test results. The data are mostly based on test application rates. Which compounds showed good control.

6. Soil mobility The ability of the nematicidal compounds of the present invention to move through soil infested with nematodes and control nematodes. We considered power. At a rate of 30 ppm in pots with root-knot nematode infested soil. A series of two series containing untreated nematode-infested soil were prepared by pouring the test compound into the soil. This water flowed into more than one pot. Specifically, the pot has a diameter of 8 In a 111° plastic pot, place 10 cm3 on a coarse filter paper disc. It contains a layer of sand. Fill the sand with soil and place a second filter paper on top of the soil.

Untreated soil infested with nematodes on top of sand and filter paper disks described for treated soil pots Place each test compound-treated pot on top of a series of two or more pots containing soil. I fell asleep. Gradually drip 15 cm of water into the upper pot and leave the pot for 16-18 hours. Excess water was removed by letting it flow down from the drain. Next, remove the top filter of each pot. Cucumber or tomato seedlings were planted in pots. Observe and evaluate the seedlings about two weeks after planting. The results shown in the attached Tables 7 and 7a were obtained. The data shows that nematode control is showed good soil mobility and nematode control at test application rates compared to untreated systems that showed no are doing. The “knot index” and “control rate” were defined in the initial root-killing nematode test above. That's right.

8. Overall activity The compounds of the present invention were tested for basic systemic activity against root-knot nematodes. this exam Now, we will use a 10-inch diameter container filled with steam-sterilized soil mixture (5 oz soil, 5 oz sand). Grow tomato seedlings in 2 cm fiber pots until 4-6 true leaves appear. let Three pots are placed on a rotary table in the spray foot and sprayed. During spraying, soil loss Cover the soil surface to prevent dispersion. After treatment, the seedlings in the pot are placed in a drying room with lighting. Next, grow the seedlings in a growth chamber at 25°C for 3 days, then place them on top of the soil in the pot. Inoculate standard nematode culture medium by mixing seed nematodes. Seedlings for about 2 weeks Return to the grow room and allow the pots to dry until the seedlings begin to wilt at this point. roots Dig them out of the soil and compare the degree of galls (swelling) with those of untreated control seedlings. Conclusion The gall index and control rate defined by the initial root-killing nematode activity listed in Table 2 It is expressed as Attached Table 8 lists the test results.

Many of the compounds showed good overall efficacy at test application rates compared to untreated plants that did not show nematicidal activity. Data indicate that it exhibits physical nematicidal activity. Substantial degree of systemic killing The insect activity is exceptional and desirable and cannot be obtained from any commercially available nematocide. Not possible.

9. Selection test and evaluation of C. elegans nematode Caenorhabditis nematode Elegance (Caen.

This in vitro test using rhabditis elegans Simpkin and Coles, J., Chem, Tec. h.

Test developed in Tiotechnol, Vol. 31, p. 66.69 (1981) It is a law changing law. In this test, food sources (E. coli) and 5.0 to 0.156 A suspension of C. elegans nematodes in a medium containing a candidate nematicide at a test rate of ppm The nematicidal activity is examined by adding . Ampere per 100 ml of buffer solution 5 mg of picillin, 10,000 units of mycostatin, and 1 part of a concentrated suspension of E. coli Pipette 0 ml of test medium into each hole of a 24-large microtiter plate. I entered. 2. Candidate nematicide suspended in dimethyl sulfoxide at an appropriate concentration. 5 μm aliquots were added to each well. Each application rate was repeated 2-3 times. Complete the contents of each hole. After thoroughly mixing, add 50-100 μm of the nematode suspension to each hole. 10-15 nematodes were allowed to enter. Add the nematodes, then add the microtiter plate. The cells were cultured at 20°C for 5-6 days.

The effects of candidate nematicides on C. elegans survival and Pa reproduction were It is evaluated by comparing the number of worms with the number of nematodes in untreated holes. Decrease in the number of chicken eggs and Note if specific effects on nematode population development, such as skin disruption, are apparent. . Attached Table 9.10 shows the high activity of many compounds of the invention at the test application rates. I will show you the test results.

-] L1 4 0 4-Chlorobenzoyl CL LH8CIF 3o27 CH20HC 3) 17F30 ffl (Continued) Compound Ippon'', (Continued) ] Dan-X 19 . -C(0)CF2CF3°(CH3"H2)20C11"14FB03 25 -CH2CH2CF =CF2 Cl0HBF6N253 Liquid 264-Nitrophenylmethyl CL3HIOF3"3025327 -5CH2 CH2F CBHBF4N2S3 Liquid 2B -5CH2CH2C MiN CgHBF3N3S3 liquid 29 -9C3H7CgH11F3N2S3 liquid 30 -5CH ( CH3)2 CgH11F3N2s3 liquid 3l-SCH2CH=CI(2CgHgF3N2S3 liquid 32 -9CH2dl C13HLLF3N2S3 liquid - Table"j (continued) Compound 37 -φ, 4-ChloOCl2HBCIF3N2S2S (68-69) 38 -〇(2φ , 4-fluoro C138LOF4N2O5 liquid 39 -φ, 4-RIOOCl2HBCIF3N20SS (49-52) 40 -4.4-Nitro C12HBF3U303SS (61-64) Table 44 -CH21,2-fluoroCt3HIOF4'2os liquid 45 CH2φ, 4- 7 Luo I: 2 CL3HLOF4N2O5 liquid 48 -φ, 3-ChloOCl2HBCIF3N20SS (55) 49 -(II, 4-7 (II MoCl2HBBrF3N20SS (5B -61) Table 1" J- Compound ld - Main fraud + 2-( 3,4,4-trifluoro-3-butenylthio)-4,5-dihydrothiazole 22-methylthio-5-(3,4,4-trifluoro-3-butenylthio)~1.3.4-thiadiazole 3 ( (3,4,4-)lifluoro-3-butenyl) butafluorobutyrate 4 (3,4,4-)lifluoro-3-butenyl)4-chlorobenzoate 5 N-<3.4.4-trifluoro- 3-butenyl)succinimide 6 (3,4,4-)lifluoro-3-butenyl)isothiocyanate? 4,5.5-)Lifluoro-4-penten-1-ol83-chloro-5-(3,4,4-)lifluoro-3-butenylthio)-1,2,4-thiadiazole 93-bromo-5-(3,4,4-trifluoro-3-butenylthio)1,2,4-thiadiazole 10 2-(3,4,4-)lifluoro-3-butenylthio)thiophene 1]L (continued) Compound -(and--each 1- +1 2-(3,4,4-)lifluoro-3-butenylthiomethyl)-thianaf Thene 12 2-(+,1,3.3-tetramethylbutylthio)-5-(3゜4.4-trifluoro-3-butenylthio)・1,3.4-theacyazole 13 2.5-di( 3,4,4-)lifluoro-3-butenylthio)-1,3,4-thiadiazole 142-propargylthio-5-(3,4,4-)lifluoro-3-butenylthio e)-1,3,4-thiadiazole+5 2-cyclopropylmethylthio-5- (3,4,4-)refluoro-0-3-butenylthione to 1,3,4-thiadiazole 162-Phenyl-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole 17 2-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole 17 Fluoro-3-butenylthio)-1,3,4-oxadiazole 18 (3,4,4-)lifluoro-3-butenyl)(3,4,4,-trifluor Oro-3-butenylthio)acetate - Table n (continued) Compound 1i--M1-19 (3,4,4-)lifluoro-3-butenyl)pentafluoropropione monodiethyl etherate 20 (3,4,4-)lifluoro-3-butenyl)2-thiophenecarboxylate 21 (3,4,4-)lifluoro-3-butenyl)5-nitro-2-furanka Ruboxylate 22 (3,4,4-trifluoro-3-butenyl)2-virolcarboxylate 23 (3,4,4-trifluoro-3-butenyl)[2-(4,5-dihydrothiazolyl)thio]acetate 24)I-(3,4,4-trifluoro-3-butenyl)saccharin 25 3,5-di(3,4,4-)trifluoroU1-3-butenylthio)-1,2,4-thiadiazole 26 3-(4-nitrophenylmethylthio)-5-(3,4,4-trifluoro) 2-(2-Fluoroethylthio)-5-(3,4,4-tridiazole) Table 1 j Fluoro-3-butenylthio)-1,3,4-thiadiazole 28 2-(2-cyanoethylthio)-5-(3,4,4-)lifluoro-3-butenylthio)-1,3,4-thiadiazole 292- Propylthio-5-(3,4,4-)lifluoro-3-butenylthio)-1,3,4-thiadiazole 30 2-(1-methylethylthio)-5-(3,4,4-)lifluoro-3 -butenylthio)-1,3,4-thiadiazole 31 2-(2-propenylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole thenylthio)-1,3,4-thiadiazole322-phenylmethylthio-5-(3,4,4-)lifluoro-3-butenylthio)-1,3,4-thiadiazole 33 2-(4-bromophenylmethylthio)-5-(3,4,4-trifluor Oro-3-butenylthio)-1,3,4-thiadiazole 34 2-(2-fluorophenylmethylthio)-5-(3,4゜4-triflu Oro-3-butenylthio)-1,3,4-thiadiazole! (continued) 35 2-(4-nitrophenylmethylthio)-5-(3,4,4-trifluoro lo-3-butenylthio)-1,3,4-thiadiazole 36 2-(2-thenylmethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole 37 2-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butyl thenylthio)-1,3,4-thiadiazole 38 3-(4-fluorophenyl methyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-oxadiazole 39 3- (4-chlorophenyl)-5-(3,4,4-trifluoro-3-butyl thenylthio)-1,2,4-oxadiazole 40 3-(4-nitrophenyl)-5-(3,4,4-)lifluoro-3-bu thenylthio)-1,2,4-oxadiazole 41 2-propyl-5-(3,4,4-)lifluoro-3-butenylthio)- 1,3,4-oxadiazole 422-phenylmethyl-5- (3,4,4-)Lifluoro-3-butenylthio)-1,3,4-oxadiazole-Table 1 (continued) Compound -IL No.--Shudanichi 43 2-(4-chlorophenylmethyl)-5 -(3,4,4-)lifluoro-3-butenylthio)-1,3,4-oxadiazole 44 2-(2-fluorophenylmethyl)-5-(3,4,4-)lifluoro-3- butenylthio) -1,,3,4-oxadiazole 45 2-(4-fluorophenylmethyl)-5-(3,4,4-trifluoro-3-butenylthiol 1,3,4-oxadiazole 46 2 -(2,4-difluorophenylmethyl)-5-(3,4゜4-trif fluoro-3-butenylthio)-1,3,4-oxadiazole 47 2-(2-phenylethyl)-5-(3,4,4-)lifluoro-3-butenylthio)-1,3,4-oxadiazole thenylthio)-1,3,4-oxadiazole 48 2-(3-chlorophenyl)-5-(3,4,4-)lifluoro-3-bu thenylthio)-1,3,4-oxadiazole 49 2-(4-bromophenyl)-5-(3,4,4-trifluoro-3-butyl thenylthio)-1,3,4-oxadiazole 3<Continued) Compound 11 and--Main 50 2-(4-fluorophenyl)-5-(3,4,4-)lifluoro-3-butenylthio )-1,3,4-oxadiazole 230 2-(3,4,44lifluoro-3-butenylthio)thiazole 231 2-(2,3,3-)lifluoro-2-propenylthio)thiazole 232 2-( 4,4-difluoro-3-butenylthio>thiazole 233 2-(3,3-difluoro-2-propenylthio)thiazole 234 2-(4,4-dichloro-3-butynylthio)thiazole 235 2-(3,3- Dichloro0-2-propenylthio)thiazole 236 2-(4,4-dibromo-3-butenylthio)thiazole 237 2-(3,3-dibromo-2-propenylthio)thiazole 238 2-(2,3,3- Trichloro-2-propenylthio)thiazole -J] (continued) 239 2-(3,4,4-)dichloro-3-butenylthio)thiazole 240 2-(2,3,3-)ribucomo-2-propenylthio)thiazole 241 2-(3,4,4-tribromo-3-butenylthio)thiazole fshi 81.1shi/・pa・Ishi4 51 Phenylmethyl-Liquid 524-Chlorophenylmethyl-Liquid 534-Chlorophenylthiomethyl-Liquid i Punishment (Control) 564-Chlorophenylmethyl Liquid 57 -5CH2CH3 Liquid 58 -5CH2CF3 Liquid 59 -5C4H9 Liquid 60 -5CH(C)+3)C2H5 Liquid 61 -5CToCH(CH3)2 Liquid 62 -5(CH2)2cclFcBrFz Liquid 63 - 5(CH2hC H3 liquid 64 -5(C)12)Inc)+3 liquid65 -5(CH2hC)l=cH2liquid66 -5C)1(C113)CI(:CH2liquid67 -5CH2C(C)13)" CH2 in alpha form 68 -5CH2CI (=CHCH:+ liquid 69 -5 (CH2) 3CICCH2 liquid 70 -5CI (2cH=c(C)+3)2 liquid?+ -5C82C(CI)2CH2 liquid?2 -5CH2C( 8rCC Hz Liquid 73 -5GHzCH=C(Br)2 Liquid-Table' Engineering (continued) Compound Engineering FL--NOL Rei L D 74 -5 (fj12)2CH=C(CI)-Solid (55℃) 75 -5CH2C=N Solid (69℃) 76 -5(C)12>3C:N Liquid? ? -5(CH2)tc=N Liquid 79 2.4-Dimethylphenoxythiru Liquid 803-Chlorophenylmethylene 81 4-chlorophenylmethylthio-solid (38°C) 82 3.4-dichlorophenylmethylthio-liquid 832, dichlorophenyl methylthio-liquid 842-bromophenylmethylthio-liquid 853-bromophenyl Nylmethylthio-Liquid 86 3.5-Dibromophenylmethylthio-Liquid 873 -Fluorophenylmethylthio-Liquid 884-Fluorophenylmethylthio-Liquid Body 89 2,4-difluorophenylmethylthio-90 2,5-difluorof phenylmethylthio-iα body-table's (continued) Compound 11 R 3 Keikai Eco 91 3,4-difluorophenylmethylthio-liquid 92 2,6-cyfluoro Phenylmethylthio liquid 93 2,3,4,5.6-pentafluoro liquid fluoro Phenylmethylthio- 942-Chloro-6-Fluoro Liquid Phenylmethylthio- 952-Iodophenylmethylthio- Liquid 962-Methylphenylmethylthio- Liquid 973-Methylphenylmethylthio- Liquid 98 2-) Refluoromethyl Liquid Phenylmethylthio- 99 3- ) Lifluoromethyl Liquid Phenylmethylthio +00 4-) Lifluoromethyl Overnight Phenylmethylthio 101 3-Methoxyphenylmethylthio Liquid 1024-Methoxyphenyl Methylthio Solid (42-44°C) +03 4-) Lifluoromethoxy Liquid phenylmethylthio- +042-cyanophenylmethylthio- Liquid-1 and (continued) 1053-cyanophenylmethylthio- Liquid 1064-cyanophenylmethylthio- Thio- Solid (51-57°C) 1072-Nitrophenylmethylthio- Liquid 1083-Nitrophenylmethyl Thio- Liquid 109 2-Chloro-nitrophenyl Liquid Methylthio- +10 4-Chloro-2-nitrophenyl Risk Methylthio- 1112-Fluoro-4-nitrophenylic Liquid Methylthio- 1122-Methyl-3-nitrophenyl Liquid Methylthio- +13 2-Nitro- 5-methylphenyl liquid methylthio- 1142-methoxy-5-nitrophenyl liquid methylthio- 115 3,5-dinitrophenylmethylthio- liquid 116 4-phenyl phenyl Phenylmethylthio Solid (62℃) 1172-Methyl-3-phenylphenyl Solid Methylthio 118 Anthracen-9-ylmethylthio Liquid 1195-Chlorothiene 2-ylmethylthio) α form 1202-Methylthiazole-4- liquid liquid Chilthio- 121 2,6-cyclopyridin-4-yl overnight methylthio 122 1,3-benzodioxole-5- liquid ylmethylthio- +23 phenylthiomethylthio-) α-isomer 1241-phenylethylthio- liquid +25 2-(4-nitrophenyl)ethylthio- liquid 1263-pheno Xypro and Lucio Liquid +27 -N[C(0)CF3][C2) 15 pieces Liquid 1 bottle +28 -N[:C(0)CH3][CH3] Liquid+29 -N[C(0)C)+3 pieces [ 4-Trifluoro solid methylphenylco 130 1,2-bis(4-chlorophenyl) solid urea- +31 -N[C(0)CF3co[4-methoxyphenyl] solid 11 (continued) Compound One silkworm bean-R31! li=α 1324-trifluoromethyl solid phenylamino- 1334-methoxyphenylamino-solid 1344-chlorophenylamino-solid body +36 1-(4-)lifluoromethylphenyl) solid -2-(4-chlorophenyl) (phenyl) urea-1371-methyl-2-(4-chlorophenyl) Solid urea -(+41-2°C) +38 -N[:C(0)CH3][4-chlorophenyl] Solid (84-85°C) 139 - N[C(0)CH3][4-fluorophenyl] solid 1414-ni Trophenylamino-solid 1421-ethyl-2-(4-chlorophenyl) solid Body urea - Table 1 (continued) Compound -l and -R', IL0n 143 -N[C(0)C)+3co[4-methoxyphenyl] Solid +44 + -(4-fluorophenyl)-2- (4-Solid chlorophenyl)urea- +45 -NHC2H5 solid 1464-fluorophenylamino-solid +47 -NEC)13][2,4-dichlorophenyl liquid methylcarbonylco 1494-bromophenylamino-solid trifluoromethylphenylco +51 -NEC2H5 ][Phenylmethoxy solid carbonyl] +52 -N[C(0)CH3][C2)15 liquid 153 70 momethylthi O Liquid 154 -N[C(0)CH3][4-bromophenyl] Solid i Punishment (continued) Compound 11 and -R3u ■ Nitrophenyl] Fluorophenyl] +57 -5(CH2)3C1 (2CI Semisolid +58 -5C112C1 liquid +59 -5(C)12)4C1 liquid 160 -5(CH2)2CH2CI liquid +61 -5(C)12)3cH2 8r solid 1624-chlorophenylmethyl-liquid 1634-methylphenyl- liquid -table (continued) ) Compound 11-R4 Rei Lc 1662-chlorophenyl-liquid 1673-chlorophenyl-solid (48-51'C) +68 3-) Lifluoromethylphenyl-solid (41-44°C) 1694-methoxyphenylmethyl- Liquid l703-Nitrophenyl-Solid Compound +73 -CH(CI+3)2 Liquid 174 -C)12cH(C)+3)2 Liquid+75 -C(CH3)3 Liquid 176 (C)12)<C1h Liquid +77 -(CH2) +eCH3 solid (45℃) +78 -C= C(CH'2)4C)13 M body - Table "S (continued) Compound" - -Furnace-1, = αD 179 -CH3CN(CH3)CF3 liquid +80 2- Chlorophenylmethy 812-Bromophenylmethyl-Liquid 1824-Bromophenylmethy -Solid (38-40°C) 1832-Methylphenylmethyl-Liquid 184 3-, fflTylphenylmethyl liquid 1852-bromo-4,5-dimethoxy solid phenylmethyl (54 -59°C) 1862-nitrophenylmethyl-nitrogen 1874-nitrophenylmethyl liquid Body 188 Chassis 2-ylmethyl-liquid 189 1,4-benzodioxane-6-,ylmethyl liquid 190 1.3-benzodioxole solid-5-ylmethyl Chill (69-71°C) 1921-Phenylethyl-liquid 193 2-(4-nitrophenyl)ethyl-liquid-table (continued) Compound -bean-R51L 195 2-(4-bromophenyl)ethynyl -Liquid 196 2-(2-fluoro Lophenyl) Ethynyl - Liquid 1973-Phenylpropyl - Liquid 1984-Phenylbutyl - Liquid 1994-Chlorphenoxymethyl - Liquid 2004-Methylphenoxymethyl - Liquid 201 3-Methyl-4-chlorophenoxy Liquid Methyl - 2024-Nitrophenylmethyl - Liquid 203 1-(4-chlorophenoxy)ethyl-liquid 204 +-(4-methylphenoxy)ethyl-liquid 205 2-(4-chlorophenylthio)ethyl-solid (54-59°C) 206 +-(4-chlorophenoxy) ) Propyl-Liquid 2072-Chloropheny Leu-Liquid 2082-Bromophenyl-Liquid 209 2.5-Dichlorophenyl-Liquid 2+0 4-(1-Methylethyl)F phenyl-liquid 2112-methoxyphenyl-liquid 2123-methoxyphenyl-liquid -] Shiha (Continued) Compound 11yo L-R5 SHI Meng Eco 214 3.4-dimethoxyphenyl-solid (51°C) 2154-nitrophenyl- Solid (94-96°C) 2162-Aminophenyl-Solid (57-61°C) 2174-Hydroxyphenyl-Solid (96-1ot°C) 2184-Acetyloxyphenyl-Solid (63-66°C) 219 4-(Methylamino carbonyloxy) solid 7 m -1 (+0 8-111°C) 2204-phenylphenyl-solid (49-52°C) 221 naphth-2-yl-solid (70-72°C) 222 naphth-1-yl- Solid (68℃) 223 Chassis 2-yl-Liquid 224 Furan-2-yl-Liquid -Table"S (continued) Compound -1"L--Tamato-Xko 2254-Methyl-1,2,3- Thiadeazole Liquid-5-yl-226 2-(4-chlorophenyl)ethyl-solid (43-45°C) 227 2-(2-chlorophenyl)ethyl-liquid 228 2-(4-fluorophenyl)ethyl-liquid 229 Phenylmethyl Liquid -Table 11 (Continued) Hi-halo Nire-NI Lum Compound One Silkworm Bean n 'Ru1=α 2302 Liquid 23+ 1 Liquid -Table 22 (Continued) -J Shito- Ni・"lIL- Compound Common % 0.625 100 0.313 99 0.625 100 0.078 56 -Table 2 (continued) -Table 2 (continued) Compound Application % -Table 2 continued) Compound Application % -Table 2 (continued) Compound Application Application % - Table 2 2 (Continued) Compound Application % - 衷ゆ (Continued) Compound Usage % -1 bean--warigo) and 0- -carriage l--'1 yu1 Residual activity against seed layer nematodes Inoculation Compound Application After treatment % 吏 3 z (Camellia 〈 ) -Table-13 (continued) Compound Inoculation % -1 and--Luri1- -Sara Koichi 41 1 week 97 2 weeks 63 4 weeks 6 42 1 week 99 2 weeks 97 4 weeks 0 431 weeks 100 2 weeks 100 4 weeks 100 44 1 week 100 2 weeks 100 4 weeks 100 451 weeks 99 2 weeks 100 4 weeks 98 1 point (continued) Compound Inoculation % -Silkworm!--Basic 1- -Blood plate 1 46 1 week 99 2 weeks 100 4 weeks 99 47 1 week 96 2: Between A 25 4 Week 0 48 1 week 97 2 weeks 97 4 weeks 69 Initial activity against dwarf disease nematode Compound % -] Shul Initial activity against dwarf disease nematode Application rate + 5 ppm Compound % Compound % Slight phytotoxicity fΣ- Lesion nematode Initial activity against Compound % 10 2.5 33 5° per day 21 2.5 54 25 2.5 77 28 2.5 45 29 2.5 68 32 2.5 2B 33 2.5 46 35 2.5 52 2 .5 78 - Compound % 2.5 18 1] Shidan Initial activity against cyst nematodes Compound % 2 ηmu m - 扼l- 1 Whole cysts were used rather than homogenized cysts. It was done.

-Table 1- Root P! Evaluation of soil mobility against nematodes test Compound % of common container Chubu 95 Lower part 85 10 1 (Top) 100 5 Upper part 100 Chubu 98 Lower part 99 2.5 Upper 100 Chubu 100 Lower part 100 -11 (continued) test Compound Application Container % Ichiban 1 1 - 劃" 1 UD - Blood! --Yuichi 1.25 Upper part 100 Chubu 99 Lower part 96 0.625 Upper 97 Chubu 98 Lower part 77 0.313 Upper 77 Chubu 75 Lower part 25 2 30 Upper part 42 Chubu 33 Lower part 25 8 5 Upper part +00 Chubu +00 Lower part 96 Table 1 2 2 (continued) test Compound Application Container % -13--Kaiji Kofuji -Wataru--Yuichi 1830 Upper part 33 Chubu 25 Lower part 25 2130 Upper 100 Chubu 96 Lower part 99 -” [ni l Evaluation of soil mobility against root-knot nematodes - 5% powder: Application rate: 5 ppm Compound % of test container Chubu 69 Lower part 8 27 Upper part 99 Chubu 100 Lower part +00 Lower part 68 29 Upper part 98 Chubu 81 Lower part 50 30 Upper part 99 Chubu 100 Lower part 17 One fold two L” 2 (continued) Compound % of test container -No.1--Blood! --Keiichi 31 Upper part 98 Chubu 86 Lower part 5゜ 32 Upper part 99 Lower part 25 35 Upper part 99 Chubu 5゜ Lower part 0 Lower part 0 - Table 2 Otsu” 5 (Continued) Compound % of test container Lower part 0 Lower part 8 42 Upper part +00 Chubu 100 Lower part +00 Lower part 81 Lower part 96 1 Table 2 Otsu” 2 (continued) Compound % of test container -lヱ　-taten,　-JmJJ２ 45 Upper part 98 46 Upper part 96 Chubu 97 Lower part 78 47 Upper part 98 Chubu 96 Lower part 58 Lower part 0 Lower part 42 1 Table 2 L” 4 (continued) Compound % of test container -Silkworm! ---Leave! --Koichi Sara 49 Upper part 99 Chubu 71 Lower part 8 50 Upper part 98 Some plant toxicity One side”- Systemic activity against root Fl nematodes Compound application test % 1000 42, 95 4B 2000 50 -4L1”L- C.Evaluation of elegance compound reproductive 2.5 too 10O L, 25 100 100 1.25 100 100 1.25 100 100 37 5 too lo.

2.5 100 100 1.25 100 100 2.5 100 100 2.5 too 100 1.25 100 67 1.2S 100 5B 2.5 100 100 1.25 100 100 43 5 1 (X) 83 48　5　1cI:l　1o.

−Table”− C. Screen for elegance -Ratio: 5ppm compound reproductive 32 too 100 International 1Iil inspection carp lost Inl@l+j+・・・−＾D−・・・・den−””tr’l’/lTs8610 1284PCT/US86101284 Attachment Se0210 Parsee.

IPC (4) AOIN 31102.　37102.37/10. 43/7 8. 43/82US, C1,260/454.548/129.130.13 2.136.142.144.182°187, 210. 531. 545 549/49. 62. 79. 481. 484560/111. 219 ．． 227 568/843.849 514/361.363.364.369.373.423.425.443° 445, 448. 514. 544. 549.　550. 739

Claims (1)

[Claims] 1. A polyhydric compound characterized by the formula F2C=CF(CH2)nXR [wherein X is sulfur, oxygen or nitrogen, and n is 1-4] Roalkene compounds. However, (A) when X is sulfur, R is thiazolyl, optionally Thienyl, which may be substituted, Thianafuthi, which may be optionally substituted. optionally substituted thiazolinyl, optionally substituted optionally substituted thiadiazolyl, optionally substituted oxadiazolyl, or is 3,4,4-trifluoro-3-butenyloxycarbonylmethyl. (B) When X is oxygen, R is C(O)R1, where R1 is perfluoroalkyl, optionally substituted phenyl, optionally substituted thienyl, optional furanyl which may be substituted with , pyrrolyl or dihydrothiazolylthiomethyl which may be optionally substituted. (C) When X is nitrogen, R taken together with nitrogen is isothiocyanate, sulfur cinimide or saccharin group. 2. Compounds of the formula according to claim 1, characterized in that X is sulfur. 3. A compound of the formula according to claim 1, characterized in that X is sulfur and R is a thiazolyl group. 4.2-(3,4,4-trifluoro-3-butenylthio)thiazole or 2-(2,3,3-trifluoro-2-propenylthio)theazole. A compound according to item 3 of the desired scope. 5. thiadiazolyl or oxadiazole in which X is sulfur and R is substituted on the nuclear carbon atom Compounds of the formula according to claim 1, characterized in that they are zolyl groups. 6. the substituent is R2S, and R2 is phenylmethyl optionally substituted with 3,4,4-trifluoro-3-butenyl, halogen or nitro, or halogen or nitro; The substituted thiadiazolyl compounds according to claim 5, which are phenylthiomethyl optionally substituted with thoro. 7. Substituted thia according to claim 3, characterized in that the substituent is iodo. Diazolyl compounds. 8. Aryl, aralkyl, aryloxyal in which substituent R3 is optionally substituted Kyl, alkylthio, haloalkylthio, cyanoalkylthio, arylalkyl ruthio, aryloxyalkylthio, arylthioalkylthio, optionally substituted Heterocycloalkylthio, alkenylthio, haloalkenylthio, halosi chloroalkylalkenylthio, or amino group independently alkyl, alkylcarbo Nyl, haloalkylcarbonyl, optionally substituted aryl, arylaminocarbonyl It is characterized by being mono- or di-substituted with a group selected from carbonyl, arylalkylcarbonyl, arylalkoxycarbonyl, and 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl. , Patent Claim 5: Substituted thiadiazolyl compounds. 9. The substituted oxadiazolyl compound according to claim 5, wherein the substituent R4 is an optionally substituted aryl or arylalkyl group substituted with chloro, fluoro, alkyl, haloalkyl, alkoxy or nitro. Kind. 10. Substituent R5 is alkyl, haloalkyl, optionally substituted aryl, aryl The substituted oxadiazolyl compounds according to claim 5, which are arylalkyl, aryloxyalkyl, arylthioalkyl, optionally substituted heterocycloalkyl, arylalkenyl or alkynyl. 11. Compounds according to claim 2 selected from the following compounds. 2-(3,4,4-trifluoro-3-butenylthio)thiophene, 2-(3,4,4-trifluoro-3-butenylthio)-4,5-dihydrothiazole, 2-methylthio-5-(3 ,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole, 2-(1,1,3,3-tetramethylbutylthio)-5-(3,4,4-triph fluoro-3-butenylthio)-1,3,4-thiadiazole, 2,5-di(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole, 2-cyclopropylmethylthio-5 -(3,4,4-trifluoro-3-butenyl ruthio)-1,3,4-thiadiazole, 3-chloro-5-(3,4,4-trifluoro-3-butynylthio)-1,2,4-thiadiazole, 2-(4-chlorophenyl)-5- (3,4,4-trifluoro-3-butenyl thio)-1,3,4-oxadiazole, 3,5-di(3,4,4-trifluoro) lo-3-butenylthio)-1,2,4-thiadiazole, 3-(4-nitrophenylmethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-thiadiazole, 2-(2-fluoroethylthi e)-3-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thi Asiazole, 2-(2-cyanoethylthio)-5-(3,4,4-trifluoro lo-3-butenylthio)-1,3,4-thiadiazole, 2-propylthio-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole 2-(1-methylethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole, 2-(2-propenylthio)-5-( 3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadias sol, 2-phenylmethylthio-5-(3,4,4-trifluoro-3-butene Nylthio)-1,3,4-thiadiazole, 2-(4-bromophenylmethylthio) E)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thi Diazole, 2-(2-fluorophenylmethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole, 2-(4-nitrophenylmethylthio)-5- (3,4,4-trifluoro-3-butenyl thio)-1,3,4-thiadiazole, 2-(2-thienylmethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole 2-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butene nylthio)-1,3'4-thiadiazole, 3-(4-fluorophenylmethyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-ox Thadiazole, 3-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-oxadiazole, 3-(4-nitrophenyl) Nyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-oxadiazole, 2-propyl-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-oxadiazole nylthio)-1,3,4-oxadiazole, 2-phenylmethyl-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole, 2-(4- chlorophenylmethyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole, 2-(2-fluorophenylmethyl-5-(3,4,4-trifluoro- Fluoro-3-butenylthio)-1,3,4-oxadiazole, 2-(4-fluorophenylmethyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4- Oxadiazole, 2-(2,4-difluorophenylmethyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole, 2-(2-phenylethyl) )-5-(3,4,4-trifluoro-3-butenyl thio)-1,3,4-oxadiazole, 2-(3-chlorophenyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole 2-(4-bromophenyl)-5-(3,4,4-trifluoro-3-butene nylthio)-1,3,4-oxadiazole, 2-(4-fluorophenyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole, 2- (3,4,4-trifluoro-3-butenylthio)thiazole, and 2-(2,3,3-trifluoro-2-butenylthio)thiazole. 12. Compounds of the formula according to claim 1, characterized in that X is oxygen. 13. Compounds according to claim 12 selected from the following. (3,4,4-trifluoro-3-butenyl)bentafluoropropionate mono Nodiethyl etherate, (3,4,4-trifluoro-3-butenyl)hebutafluorobutyrate, (3,4,4-trifluoro-3-butenyl)4-chlorobenzoate, (3,4,4 -trifluoro-3-butenyl)2-thiophenecarboxylate, (3,4,4-trifluoro-3-butenyl)5-nitro-2-furancarboxylate sylate, (3,4,4-trifluoro-3-butenyl)2-pyrrolecarboxylate, and (3,4,4-trifluoro-3-butenyl)[2-(4,5-dihydrothiazo lyl)thio]acetate. 14. Compounds of the formula according to claim 1, characterized in that X is nitrogen. 15. Compounds according to claim 14 selected from the following. (3,4,4-trifluoro-3-butenyl)isothiocyanate, N-(3,4,4-trifluoro-3-butenyl)succinimide, and N-(3,4,4-trifluoro-3- butenyl) saccharin. 16. A method for controlling nematodes, which comprises applying a nematicidally effective amount of the compound according to claim 1 to a place to be controlled. 17. A method for controlling nematodes, comprising applying a nematicidally effective amount of the compound according to claim 2 to a place to be controlled. 18. A method for controlling nematodes, which comprises applying a grain nematode-effective amount of the compound according to claim 3 to a place to be controlled. 19. A method for controlling nematodes, which comprises applying a nematicidally effective amount of the compound according to claim 4 to a place to be controlled. 20. A method for controlling nematodes, which comprises applying a nematicidally effective amount of the compound according to claim 5 to a place to be controlled. 21. A method for controlling nematodes, comprising applying a nematicidally effective amount of the compound according to claim 6 to a place to be controlled. 22.・A nematocidal effective amount of the compound of claim 8 is applied to the area to be controlled. A nematode control method characterized by using 23. A method for controlling nematodes, comprising applying a nematicidally effective amount of the compound according to claim 9 to a place to be controlled. 24. A nematicidally effective amount of the compound of claim 10 is applied to the area to be controlled. A nematode control method characterized by using 25. A nematicidally effective amount of at least one compound of claim 11 is used to prevent A nematode control method that is characterized by applying it to the area you want to eliminate. 26. A nematicidally effective amount of the compound of claim 12 is applied to the area to be controlled. A nematode control method characterized by using 27. A nematicidally effective amount of the compound of claim 13 is applied to the area to be controlled. A nematode control method characterized by using 28. A nematicidally effective amount of the compound of claim 14 is applied to the area to be controlled. A nematode control method characterized by using 29. A nematicidally effective amount of the compound of claim 15 is applied to the area to be controlled. A nematode control method characterized by using 30. A method for controlling nematodes, which comprises applying a nematicidally effective amount of a compound of the formula F2C=CF(CH2)nCH2OH [in the formula, n is 1-4] to a place to be controlled. 31. A nematicidally effective amount of a compound of the formula F2C=CFCH2CH2CH2OH controls A nematode control method characterized by applying it to the desired location. 32. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 1 in an agriculturally acceptable carrier. 33. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 2 in an agriculturally acceptable carrier. 34. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 3 in an agriculturally acceptable carrier. 35. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 4 in an agriculturally acceptable carrier. 36. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 5 in an agriculturally acceptable carrier. 37. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 6 in an agriculturally acceptable carrier. 38. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 8 in an agriculturally acceptable carrier. 39. A nematicidal composition characterized by a nematicidal effective amount of a compound of claim 9 in an agriculturally acceptable carrier. 40. Nematicidal presence of the compound of claim 10 in an agriculturally acceptable carrier A nematicidal composition characterized by an effective dose. 41. Nematicidal presence of the compound of claim 11 in an agriculturally acceptable carrier A nematicidal composition characterized by an effective dose. 42. Nematicidal presence of the compound of claim 12 in an agriculturally acceptable carrier A nematicidal composition characterized by an effective dose. 43. Nematicidal presence of the compound of claim 13 in an agriculturally acceptable carrier A nematicidal composition characterized by an effective dose. 44. Nematicidal presence of the compound of claim 14 in an agriculturally acceptable carrier A nematicidal composition characterized by an effective dose. 45. Nematicidal presence of the compound of claim 15 in an agriculturally acceptable carrier A nematicidal composition characterized by an effective dose. 46. characterized in that an anthelmintic amount of the compound according to claim 1 is administered to an animal. A method to exterminate worms that infect animals. 47. characterized in that an anthelmintic amount of the compound according to claim 2 is administered to an animal. A method to exterminate worms that infect animals. 48. characterized in that an anthelmintic amount of the compound according to claim 3 is administered to an animal. A method to exterminate worms that infect animals. 49. characterized in that an anthelmintic amount of the compound according to claim 4 is administered to an animal. A method to exterminate worms that infect animals. 50. characterized in that an anthelmintic amount of the compound according to claim 5 is administered to an animal. A method to exterminate worms that infect animals. 51. characterized in that an anthelmintic amount of the compound according to claim 6 is administered to an animal. A method to exterminate worms that infect animals. 52. characterized in that an anthelmintic amount of the compound according to claim 8 is administered to an animal. A method to exterminate worms that infect animals. 53. characterized in that an anthelmintic amount of the compound according to claim 9 is administered to an animal. A method to exterminate worms that infect animals. 54. A method for exterminating helminths infecting animals, which comprises administering to the animal an anthelmintic amount of the compound according to claim 10. 55. A method for exterminating helminths infecting animals, which comprises administering to the animal an antiparasitic amount of the compound according to claim 11. 56. An anthelmintic composition characterized by an effective amount of a compound of claim 1 in combination with a pharmaceutically acceptable carrier. 57. Anthelmintic composition characterized by an effective amount of a compound of claim 2 in combination with a pharmaceutically acceptable carrier. 58. Anthelmintic composition characterized by an effective amount of a compound of claim 3 in combination with a pharmaceutically acceptable carrier. 59. Anthelmintic composition characterized by an effective amount of a compound of claim 4 in combination with a pharmaceutically acceptable carrier. 60. An anthelmintic composition characterized by an effective amount of a compound of claim 5 in combination with a pharmaceutically acceptable carrier. 61. An anthelmintic composition characterized by an effective amount of a compound of claim 6 in combination with a pharmaceutically acceptable carrier. 62. An anthelmintic composition characterized by an effective amount of a compound of claim 8 in combination with a pharmaceutically acceptable carrier. 63. Anthelmintic composition characterized by an effective amount of a compound of claim 9 in combination with a pharmaceutically acceptable carrier. 64. An anthelmintic composition characterized by an effective amount of a compound of claim 10 in combination with a pharmaceutically acceptable carrier. 65. An anthelmintic composition characterized by an effective amount of a compound of claim 11 in combination with a pharmaceutically acceptable carrier.