JPS5953241B2 - How to control ticks or pests - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for controlling certain arthropods using certain substituted thiophenes.

Arthropods that can be controlled by the method of the present invention include
These include in particular plant-feeding mites (vites) and mites and ticks that plague humans and animals (tiCk), as well as harmful insects.

Plant-feeding mites cause enormous damage to agricultural crops in a world suffering from constant food scarcity.

Crops such as alpha alpha, apple, corn,
Cotton, grapes, oranges, corn, corn, peanuts and many other crops are completely destroyed by these small pests. Other species, such as the pruritus mite, cause severe skin diseases in animals such as dogs, cats, rabbits, horses, cows, and pigs. Ticks and some tick species feed on human and animal blood.

In addition to the added pain, numerous animal diseases are transmitted by this method of food acquisition. Very feared diseases, such as Lotsky spotted fever, relapsing fever, and tularemia, are transmitted by biting ticks. During the last three decades, numerous drugs have been utilized to protect humans and human food and fiber from damage by mites and ticks, as well as insects.

There is a continuing need for new, effective, and safe drugs to accomplish this task. It has now been discovered by the present invention that certain substituted thiophenes are useful in controlling arthropods.

In the method of the present invention, the substituted thiophene used for controlling arthropods has the formula: (wherein, X is hydrogen, chlorine, bromine, CF
、． C, 1C, alkyl, rhenyl, methoxy or methylthio, a is 1 or 2, Y is hydrogen, phenylthio, phenylsulfono, nitrophenylthio, nitro or chlorophenylthio, z is hydrogen or 7-enyl ).

Some compounds within the above formulas, namely 2-(.p-methylthiophenyl)thiophene, 2-(dan-biphenylyl)thiophene, 2-(3,4-xylyl)thiophene, and where Y is nitro, arylthio or arylsulfono compounds are new drugs.

It is thought that Compounds useful in this invention can be prepared by a variety of methods.

In this way, 2-monosubstituted thiophenes can be prepared using the Gomberg-Bachmann free radical arylation reaction (M. GOrnbergaIxiW.
E. Bshame Hmaln, J. A. Chem. SOc. ，
46, 2339 [1924]). n-Butyl nitrite can be used as the diazotizing agent, and a 20- to 25-fold excess of thiophene serves as a solvent and as a diluent to reduce the degree of disubstitution. Free radical arylation of thiophenes proceeds approximately 25% at the d-1 position. Distilled or recrystallized arylthiophenes are generally 98,911 or more pure. Reaction times are 3-7 days at room temperature and yields are mainly in the upper half of the 20-50% range. Similarly, phenylthio-substituted arylthiophenes are prepared by Friedel-Kratzf substitution using benzenesulfenyl chloride as the electrophile (T. Fujisawa, T. Copoly, N. Otsuka,
and G. Tsuchihashi, Tetr. Letters, ▲4
95117 [1968]).

The above new compounds include 2-(J!-methylthiophenyl)thiophene, 2-(.!!-biphenylyl)thiophene,
2-<<3,4-xylyl)thiophene. and Y is nitro. A compound that is phenylthio or phenylsulfono.

Representative drugs useful in the present invention include, but are not limited to, the following:
2-(3-nitrophenyl)-5-phenylthiophene 2-(4-nitrophenyl)-5-phenylthiophene 2-(3-chlorophenylthio)-5●Phenylthiophene 2-(4- Chlorphenylthio)-5-phenylthiophene 2-(4-anisyl)-5-phenylthiophene 2-(4-nitrophenylthio)-5-phenylthiophene 2-(1-naphthyl) -5-phenylthiophene 2-(2-naphthyl)-5-phenylthiophene 2-(
1-anthryl)-5-phenylthiophene 2-(9-
phenanthryl)-5-phenylthiophene 2-(3-
nitrophenyl)-5-(J! monotril)thiophene 2
-(p-promphenyl)-3,5-diphenylthiophene 2-(Jll-nitrophenyl)-5-(phenylthio)thiophene 2-(j-ethoxyphenyl)-5-
(3-Chlorphenylthio)thiophene 2-(4-anisyl)-5-(''-butylphenylthio.)theophene 3,5●diphenyl-2-(dan-propylphenyl)thiophene 2-(1- naphthyl)-5-(m-nitrophenyl)thiophene 5-(J-chlorophenyl)-2-(
2-naphthyl)-3-phenylthiophene 2-(1-anthryl)-5-(dan-trichloromethylphenyl)thiophene 2-(4-chlorophenylthio)-5-(J!
-tolyl)thiophene2-(p-biphenylyl)-5-
(p-tolyl)thiophene 2-(3-nitrophenyl)
-5-phenylthiothiophene 2-(4-nitrophenyl)-5-phenylthiothiophene 2-(3-methylthiophenyl)-5-phenylthiophenyl 2-(4-methylthiophenyl) -5-phenylthiophene 2-(2
-anisyl)-5-phenylthiothiophene 2-(3-
Chlorphenyl)-5-phenylthiothiophene 2-(
1-naphthyl)-5-phenylthiothiophene 2-(2
-naphthyl)-5-phenylthiothiophene 2-(1-
anthryl)-5-phenylthiothiophene 2-(9-
phenanthryl)-5-phenylthiothiophene 2-(
3-Nitrophenyl)-5-(p-tolylthio)thiophene 2-(4-nitrophenyl)-5-(p-chlorophenylthio)thiophene 2-(3-nitrophenylthio)-3,5-diphenylthio Phene 3,5-diphenyl-2(p-tolylthio)thiophene 2-(4-anisyl)-3,5-diphenylthiophene 2-(2-naphthyl)-4-phenyl-5-phenylthiothiophene 2-(
4)-5-phenylsulfonylthiophene 2
-Phenylsulfonyl-5-(3,4-xylyl)thiophene 2-(4-chlorophenyl)-5-phenylsulfonylthiophene 2-(P.-methoxyphenylsulfonyl)-5-phenylthiophene 2- (p-chlorophenylsulfonyl)-3,5-diphenylthiophene 2-
Phenyl-5-(p-tolylsulfonyl)thiophene 2
-(1-naphthyl)-4-phenylthiophene 2-(2
-naphthyl)-4-phenylthiophene 2-(1-anthryl)-4-phenylthiophene 2-(9-phenanthryl)-4-phenylthiophene 2-chloro-3-(
4-Nitrophenyl)-5-(p-tolyl)thiophene 2-(4-nitrophenylthio)-3,5-diphenylthiophene 2-bromo-3,5-bis(p-propyloxyphenyl)thiophene 2-(p-Tert-butylphenylthio)-5-(p-chlorophenyl)thiophene 2-(4-nitrophenylthio)-5-(3,5-xylyl)thiophene 2-(4-chlorophenyl) Lucio)
5-(3,4-methylenedioxylphenyl)thiophene 4-(1-naphthyl)-2-(p-trifluoromethylphenyl)thiophene 2-(0-ethylthiophenyl)-5-(4- nitrophenylthio)thiophene 2-(
p-biphenylyl)-5-(4-chlorophenylthio)
Thiophene 2-(2-nitrophenylthio)-3,5-
Diphenylthiophene 2-(P.-trifluoromethylphenyl)-3,5-diphenylthiophene 2-(p-
Chlorphenylthio)-3,5-diphenylthiophene 2-(.J!-methoxyphenylthio)-3,5-diphenylthiophene 2-(dish-trifluoromethylphenyl)-3,5 -diphenylthiophene 2,4-diphenyl-5-(1-naphthyl)thiophene 2,4-diphenyl-5-(2-naphthyl)thiophene 5-(1-anthryl)-2,4-diphenylthiophene 2 ,4-diphenyl-5-(9-phenanthryl)thiophene3,5-
Bis(.I!-chlorophenyl)-2-phenylthiothiophene 2-phenylthio-3,5-pis-(dan-tolyl)thiophene 3,5-bis(.I!-promphenyl)-2-phenyl[ Thiophene 3,5-di-1-anisyl-2-phenylthiothiophene 3,5-di-anisyl-2-(.p-chlorophenylthio)thiophene 2-(.p- Chlorphenylthio)-3,5-diphenylthiophene 2-(m-chlorophenylthio)-3,5
-Diphenylthiophene The present invention relates to certain arthropods,
It is carried out by applying an effective amount of an acaricidal or insecticidal amount of a drug of the type described to areas susceptible to attack by ticks or insects.

Frequently, the site is either a plant, such as crops such as alfa, apples, corn, cotton, grapes, oranges, potato, corn, peanuts, etc., or an animal, including humans. The drug may be applied alone to the area to be protected against dust mites, etc., or together with carriers that enhance the effectiveness of the active agent or facilitate handling.6 Powdered solid carriers, such as various mineral silicates, may be used. When mixed with or absorbed onto salts such as micas, talc, phyllite and clays, it may be dissolved in a suitable solvent such as acetone, benzene or kerosene, either as a powder or in a liquid carrier. When dissolved in Alternatively, when dispersed in a suitable non-solvent, such as water,
It can be applied as a liquid or spray. To protect plants (this term includes parts of plants) susceptible to attack by stiff pests, the drug of the invention may be combined with a surface-active dispersant (
It is preferably applied as an aqueous emulsion containing anionic, nonionic or cationic surfactants. Such surfactants are well known, and reference is made to J.N.A. Patent No. 512,908 for a detailed example.

The drug according to the present invention is. Such surface-active dispersants can be mixed with such surface-active dispersants as a miticide concentrate for subsequent addition of water to create an aqueous suspension of drug at the desired concentration, with or without an organic solvent. The drug according to the invention can be mixed with a powdered solid carrier, for example a mineral silicate, together with a surface-active dispersant to obtain a wettable powder, which is effective against dust mites etc. It can be applied directly to the area to be protected, or it can be mixed with water to form a suspension of the drug (and powdered solid carrier) in water (applied in this form). The drug of the present invention can be applied to areas to be protected from mites or insects by an aerosol method. Solutions for aerosol treatment. Either by directly dissolving the drug in an aerosol carrier that is liquid under pressure but gaseous at room temperature (e.g., 20°C) or pressure, or by first dissolving the drug in a low-volatility solvent and then dissolving the solution. Aerosol solutions can be created by mixing with highly volatile liquid aerosol carriers. Carriers that are themselves active, e.g. other insecticides, acaricides,
This drug can be used in combination with fungicides or fungicides. Actual formulations typically contain 1 to 95% active ingredient.

Spray dilutions range in concentration of drug per acre from a few ppm to undiluted concentrates applied in ultra-low volume techniques, which vary depending on many factors, but are typically 0.1 ppm.
or 10 pounds. In one aspect, the invention comprises a substituted thiophene drug as described in combination with a drug therefor in an acaricidal or insecticidal effective amount. The present invention is directed to novel compositions useful for controlling certain arthropods.

The following examples illustrate the present invention in detail.

Example 1 2';-(P-Methylthiophenyl)thiophene Into a 4t Erlenmeyer flask, 4-(methylthio,)ar-
Charge 69.5r (0.400 mol) of phosphorus hydrochloride, 500m2 of thiophene and 40.5f of triethylamine.

Stir the mixture for 10 minutes at room temperature. Thiophene (20
00 m2, total 31.8 mol) and n-butyl nitrite 6
Add 5 m2 (0.58 mol). The mixture is then stirred at room temperature (23°C) for 14 days. Divide the reaction mixture into two equal parts and wash each part three times with 500 ml of water.

The residue is then concentrated by evaporation of unreacted thiophene. The concentrated residue was then distilled under reduced pressure to 19t (2
3%) of 2-(p-methylthiophenyl)thiophene,
Boiling point 135-146o (0.1!!0, 108-110
A yellow solid, which melts in water, is obtained. Analysis C,,H,OS,
Calculation for: C, 64. O4; H, 4.89.

Actual measurement: C, 64.44; H, 4.82.

Example 2 2-(0-biphenylyl)thiophene In a 4t Erlenmeyer flask, o-aminobiphenyl (PfalzandBauer), melting point 49-51E, 100r (0.600 mol), thiophene 3000m
2 (38.2 mol) and n-butyl nitrite 90me (
0.80 mol).

The mixture is stirred well and then left at room temperature for 8 days. Unreacted thiophene is distilled off. The residue was distilled under reduced pressure to obtain 49.41 (34.8%) 2-(0-biphenylyl)thiophene boiling point 138-155 ((0.1 m0Nt
We get 1.6465. Example 3 2-phenyl-5-(phenylthio)thiophene 500
m2 flask, add 36.9f of 2-phenylthiophene (
0.23 mol), 200 m2 of reagent grade carbon tetrachloride, 36.9 r (0.26 mol) of benzenesulfenyl chloride, and 0.2 r of iron powder.

The reaction mixture is left at room temperature for 4 days. Distillation of carbon tetrachloride gave a crystalline residue and the residue was diluted first with ethanol monoethyl acetate (9:1) and then with ethyl acetate-pentane (1:1).
When recrystallized from 9). 2- of 10.6f7 (17%)
Phenyl-5-(phenylthio)thiophene, melting point 72
．． 5-74.5e is obtained. Analysis C,,H,,S,
Calculation for: C, 7l. 6O; H, 4.5l: S, 2
3.9O.

Actual measurement: C, 7O. 98:H, 4.47: S, 23.6l.

The infrared spectrum is 761 cm-1 and 744 cm-1
The absorption maximum at , indicated the presence of both phenyl and phenylthio groups.

Example 4 A solution of 2.68 f (10 mmol) of 2-phenyl-5-(phenylthio)thiophene in 30 me acetic acid was prepared at 30%
Treat with 4 m2 (40 mmol) of hydrogen peroxide and leave for 16 hours.

Separate 1.70 t of initial product by filtration. 4 filtrate
Cool well and filter again to obtain a second product, 0.33V, mp 115-116.5. The total yield of 2.037 is 68% of theory based on 2-phenylsulfonyl)thiophene. Analysis Calculation for C,6H,2O2S2: C, 63.97; H, 4. O3:S, 2l. 36.

Actual measurement: C, 64. O2; H3.93; S, 2O. 52.

sulfone group in the product (rather than two sulfoxide groups)
The presence of 1320 cm-1 (s
This is demonstrated by two strong infrared absorption maxima at 1150 cm-1 (s-0 symmetric vibration) and 1150 cm-1 (s-0 antisymmetric vibration).

The fact that oxidation occurred preferentially to the phenylthiosulfur to the thiophene ring sulfur is shown by proton magnetic resonance spectroscopy. This spectrum shows two ortho protons of the phenylsulfonyl group at 7.97-8.17[delta] and ten other protons each and upfield (7.19-7.67[delta]). Example 5 2-phenylthio-5-p-tolylthiophene 500m
1 reagent grade carbon tetrachloride, 2-p-tolylthiophene 6
1t (0.35 mol) benzenesulfenyl hexachloride 41
m2 (51r, 0.35 mol), and iron powder 0.057
Add.

The reaction mixture is left at room temperature for 4 days, then the carbon tetrachloride is distilled off and the 45 t residue is washed with a mixture of 80 ml of ether and 250 m2 of petroleum ether. 3 solids after washing
When recrystallized from 00 m2 of ethanol, 28y (29
%) of 2-phenylthio-5-p-tolylthiophene,
A melting point of 85-86o is obtained. Analysis Calculation for Cl, H, 4S2: C, 72.3O; H, 5. OO;S, 22.
7l.

Actual measurement: C, 72.53: H, 4.97: S, 22. O2.

The structure is 3 aliphatic protons (as a methyl group, 2.34δ)
This is corroborated by proton magnetic resonance spectra showing a ratio of 1 to 11 aromatic protons (7.11-7.49 δ).

Example 6 2-(P-isopropylphenyl)-5-(phenylthio)thiophene reagent grade carbon tetrachloride 150112, 2-
(P-isopropylphenyl)thiophene 29r (0.
143 mol), benzenesulfenyl chloride 17 mt (2
1r, 0.145 mol) and 0.05 P of iron powder are added.

At the end of 4 days, the gas phase chromatogram of the reaction mixture showed the presence of diphenyl disulfide, unreacted 2-(p-isopropylphenyl)thiophene and the desired product.

Add another 4mt (5r, 0.035 mol) of benzenesulfenyl chloride and 0.05r of iron powder. The mixture is left at room temperature for a further 4 days. Evaporate carbon tetrachloride to obtain a residue. The stiffness is recrystallized twice from 250 me each of petroleum ether. 16r (36%) of 2-(P-isopropylphenylene)-5-(phenylthio)thiophene, melting point 61
*Get Jl3(.

Analysis Calculation for C,,H,,S:C,73.5O
; H, 5.85; S, 2O. 65.

Actual measurement: , C, 73.22; H, 5.75; r- Old.
20. -59.

Example 11VJl 2-(m-chlorophenyl)-5-(phenylthio)thiophene 2-(m-chlorophenyl)thiophene 89V
(0.46 mol), reagent grade carbon tetrachloride 40011te,
．． Benzenesulfenyl chloride 54111t (67p,0
．． 46 mol) and 0.05 t of iron powder,
Leave at room temperature for 4 days.

Furthermore, 12 m2 (15P, .0.10 mol) of benzenesulfenyl chloride and 0.05r of iron powder are added. After 4 days, g'' of carbon tetrachloride is distilled off.

The residue was distilled under reduced pressure to give 30f (22%) of 2-(m
-chlorophenyl)-5-(phenylthio)thiophene, boiling point 200-205'' (0.15n) is obtained. Analysis
Calculation for C,6H,,ClS,: C,63.46:
H, 3.66; Cl, ll. 7l; S, 2l. l8.

Actual measurement: C, 63.2O; H, 3.65: ．． Cl, l2. O4:S, 2l. 37.

Experimental Box 8 2-Fuenyldio-5-(m-trifluoromethylphenyl)thiophene 2-(m-trifluoromethylphenyl)thiophene 29.7r (0.13 mol), reagent grade carbon tetrachloride 200m2, chloride Benzenesulfenyl 15
．． 511t (18.81, 0.13mol) and iron powder 0
．． The mixture consisting of 05f is left at room temperature for 4 days.

The reaction mixture was found by gas phase chromatography to contain approximately equal amounts of 2-(m-trifluoromethylphenyl)thiophene, diphenyl disulfide, and the desired disubstituted thiophene. Furthermore, 12.7m2 (
0.11 mol) of benzenesulfenyl chloride and 0.05
You can chase the iron powder of f. The mixture is stirred at room temperature for 2 hours and then at reflux for 1 hour. The carbon tetrachloride solvent is distilled off. The residue was distilled under reduced pressure to give 17r (39%) of 2
-Phenylthio-5-(m-trifluoromethylphenyl)thiophene, boiling point 172-210T (0.04wt
0, N2l=1.6329:1.6330 is obtained. Analysis Calculation for C,,H,,F,S:C,6O. 7O
:H, 3.3O; S, 19. O6.

Actual measurement: C, 59.39; H, 3.35; S, l8.73.

The low values found for carbon. Quantitative determination of the resistance of trifluoromethyl groups to carbon dioxide under possibly combustion analysis conditions
This is probably due to the difficulty of conversion. Implementation Crocodile Number 2-C87-・4-xylyl) Thiophenthi F7l-3
3,4-ψmedefunirin (
Melting point 49-51)) A solution of 182r (150 mol),
Treat with n-butyl nitrite 226me (200 mol).

Leave the solution at room temperature for one week. Unreacted thiophene is distilled off using a steam bath. The residue was distilled under reduced pressure to yield 75t (2
7%) of 2-(3,4-xylyl)thiophene, boiling point 1
07-1224 (0.0811) is obtained. Gas phase chromatography showed the presence of approximately 2% of xylidine starting material (first twice with 100 molar portions of 10% hydrochloric acid, then with 15
(was removed by washing twice with 0 m2 of distilled water). Analysis Calculation for C,, Hl, S: C, 76.55; H
, 6.43:S, l7. O3.

Actual measurement: C, 76. ll;H, 6.5l: S, l5.26.

Example 10 2-phenylthio-5-(3,4-xylyl)thiophene 2-(3,4-xylyl)thiophene 37t (0.1
97 mol), 200 m2 of reagent grade carbon tetrachloride, 29 m2 (367, 0.249 mol) of benzenesulfenyl chloride and 0.05 y of iron powder is left at room temperature for 2 days.

The gas phase chromatogram of the mixture shows that all 2-(3,4
-xylyl)thiophene was consumed. Carbon tetrachloride was distilled off and the residue was recrystallized from ethanol to give 62-phenylthio-5-(3,4-xylyl)thiophene, mp 783,17y (29%) as the first product. Ta. Analysis Calculation for C, 8H, 6S2:
C, 72.93; H, 5.44: Actual measurement: C, 73. l7
:H, 5.33: S: 22.18.

The proton magnetic resonance spectrum shows 6 methyl protons (2.26δ
) to 10 aromatic protons (7.06-7,33δ).

Example 11 2-nitro-3,5-diphenylthiophene acetic anhydride 1
2,4-diphenylthiophene 2.04V in 50m2 (
0.010 mol) is cooled to 5 f and treated with 2.4 f (0.010 mol) of cupric acetate during 5 minutes.

The temperature of the reaction mixture is maintained at 10-150 °C for 1 hour. Next 1
The mixture is warmed to 28 hours, then poured onto 120 tons of crushed ice and diluted to 1 t. The mixture is extracted three times with 25 m2 portions of chloroform. Chloroform is removed from the combined extracts by evaporation. The residue is recrystallized from ethanol to give 1.5 V (53%) of 2-nitro-3,5-diphenylthiophene, mp 100-104.
Analysis Calculation for C,6H,]NO,S: C,68.
3l; H, 3.94; N, 4.98: S, ll. 4O.

Actual measurement: C, 67.63; H, 3.69: N, 5. l4; S, lO. 96.

The proton magnetic resonance spectrum contains 10 aromatic protons (7.41
−7.82δ) to one thiophene proton (7.21δ).

Example 12 3,5-Diphenyl-2-(phenylthio)thiophene A solution of 17.7 V (75 mmol) of 2,4-diphenylthiophene in 300 m2 of carbon tetrachloride was added to 8.7 m2 (10.8 t) of benzenesulfenyl chloride. , 75 mmol) and left for one week.

The solvent is removed by evaporation. Wash the residue with ether and
14 t of crude product was obtained and the residue was recrystallized from ethyl acetate. 10.57 (41%) of 3,5-diphenylene-21 (
phenylthio)thiophene, yielding point 96-972.

Analysis Calculation for C22H, 6S2: C, 76.7O
; H, 4.68; S, l8.6l.

Actual measurement: C, 76.7O:H, 4.56; S, l8.27.

Example 13 2-(p-promphenyl)-5-(m-nitrophenylthio)thiophene 2-p- to a solution of 21.27 (0.112 mol) of m-nitrobenzenesulfenyl chloride in 160 me of carbon tetrachloride. Promphenyl)thiophene 24.
Add 5r (0.103 mol) and 0.1r iron powder.

The reaction mixture is left at room temperature for one week. The solvent was evaporated and the residue was recrystallized from 140 m2 of ethyl acetate to give 1
7.67 (44%) of 2-(J!-promphenyl)-
5-(m-nitrophenylthio)thiophene, melting point 12
0-122 f is obtained. Analysis C, 6H, OBrNO
Calculation for 2S2; C, 48.99: H, 2.57:
Br, 2O. 37; N, 3.59: S, l6.35.

Actual measurement: C, 48.87: H, 2.54: Br, 2O. 5O; N, 3.95; S, l6. O4.

Example 14 2-p-anisyl-5-(phenylthio)thiophene 2-p-anisylthiophene 34 in 500 me carbon tetrachloride
A solution of V (0.179 mol) is treated with 23 m2 of benzenesulfenyl chloride (28.5 V, 0.197 mol) and 0.17 iron powder.

The mixture is left at room temperature for 8 days. Filter the mixture to remove small amounts of solids. Evaporate the filtrate to obtain 67t of crude solid product. Recrystallization of 2201!1t from ethyl acetate yielded 15.4V (2p-anisyl-51 of 29(F6))
phenylthio)thiophene, giving a melting point of 92-93.

Analysis Calculation for C,,H,4OS,:C,6&42
:H, 4.73; S, 2l. 49.

Actual measurement: C, 69. O9:H, 4.73: S, 2O. 93.

Example 15 2-(p-chlorophenylthio)-5-phenylthiophene 2-phenylthiophene 4 in 200 mt of carbon tetrachloride
A solution of Of (0.250 mol) is treated with P-chlorobenzenesulfenyl chloride 45r (0.252 mol) at room temperature.

Iron powder (0.1r) is added and the reaction mixture is left at room temperature for 7 days to remove small amounts of insoluble material. Evaporate the filtrate to obtain the crude product. 79.8 V, melting point 85-87, is obtained as a residue. This residue was recrystallized from 400 g of absolute ethanol to yield 40P (53%) of 2-(p-chlorophenylthio)-5-phenylthiophene, mp 101-10.
35 is obtained. Analysis Calculation for C, 6HlClS,: C, 63.46: H, 3.66: Cl, ll. 7l:S, 2l. l8.

Actual measurement: C, 63.65; H, 3.79: Cl,ll. 55; S, 2O. 52.

EXAMPLE 16 Mite Contact Test This test involved second main stage cotton [GOSSyP] grown in 2 oz.
lUin. ．． ] ] 11U Kaya Um. 3>. B. ]Use the one-sided stonebill (StOnevlle・) 21-3]. One plant per pot (two main leaves) is used for each duplicate experiment, and two duplicate experiments are used for each test drug.

The mites are trapped on the upper leaf surface using a 1 inch diameter ring of wood tanglefoot, a sticky, non-toxic formulation.
Approximately 25 two-spotted spider mites (Tw
O-SpOttedspidermite) (Tetr
aTvchusurticae) were treated with 24
Transfer to each test plant before the hour. , 3 test compounds were dissolved in a small amount of acetone-i] By adding a rumored lubricant, 1000 offshore IC! A solution (or suspension) of 6 grams of the compound in 10 m2 of acetate is prepared for spraying at a concentration of .
2 drops of TritOn-XlOO (trademark)
Add a wetting agent (octylphenoxypolyethoxyethanol with 9-10 mole percent polyethylene oxide) and suspend the stiffness in 100 mt of water to 6000 p.
Make a pm suspension.

Next, a portion was further diluted with distilled water to obtain a drug concentration of 1000p.
Set to Fn. Infested plants are sprayed with this dispersion using a small sprayer for 6 minutes until the leaves are well wetted. The plants are brought to room temperature, where they are kept for 6 days. After this period, examine the plants for live adult dams remaining on the leaves. Percent control is determined based on the calculation criteria and in comparison to the number of live mites on control plants. The data of the tick contact test are presented in Table 1.

Here, drugs 1 to 14 are Examples 1 to 1, respectively.
It corresponds to the compound made in 4. Drugs 16 to 24
The name is as follows. 16.2-phenylthiophene 17.2,5-diphenylthiophene 18.2-(p-isopropylphenyl)thiophene 1
9.2-(!n-chlorophenyl)thiophene 20.2
-(p-methoxyphenyl)thiophene21.2-(p
-nitrophenyl)thiophene 22. 2,4-diphenylthiophene 23. 2-prom-3,5-diphenylthiophene 24. 2,3,5-triyphenylthiophene In a similar test, the general formula However, the known drug 2,5-bis(phenylthio)-thiophene (T. Fujisawa et al., cited above) has shown acaricidal activity but is toxic as evidenced by reduction in new growth. .

Known drug 3,4-diphenylthiophene [H. J. Hacker (B5ker) and W. Stephens (Ste
venB), Rec. trav. chim. ,59,4
23 (1940)) does not fit the above general formula and does not exhibit acaricidal activity. A known acaricide 2-(p-3-butylphenoxy)cyclohexyl-2-provinyl sulfide (0mite, trademark) was used at 80ppn1 and 16pp for comparison of mite control in a similar test.
It was used in m. The LD95 of this drug is. 20 to 100p depending on environmental factors such as light intensity, temperature and humidity
over pm. EXAMPLE 17 One-day Mite Residue Test This test tested cotton at the second main leaf stage (GOssypi) grown in 12 oz cups under greenhouse conditions at 70-75°C.
umirsutumL. , Variant Stonebill 213)
Use.

One plant per pot (two main leaves) is used for each duplicate experiment, and two duplicate experiments are used for each concentration of drug tested. The test compound was prepared by dissolving drug 5077V in acetone 1me,
Commercially available surface active dispersant, EmulfOr
719 (trade mark, polyoxyethylated vegetable oil) and suspended in 50 m2 of water to a concentration of 1000 ppm (parts per million).

A portion is further diluted with distilled water to the test concentration. Spray the plant with the drug dispersion using a small sprayer until the leaves are well wetted.

One day after treatment, a ring of wood tanglefoot is placed on the upper surface of the treated leaf to trap the adult mites therein.

The number of these mites is counted immediately after confinement and again 6 days later. AbbOtt'SfOrmul
a) is used to compensate for the reference standard mortality rate.

The adjusted percent control is obtained from the following formula: where A is the adjusted % control, C is the % live mites on the control plants, and T is the % live mites on the treated plants: 1-day mite residue test. The data obtained from is presented in a table.

Here, the test drug has the number assigned previously. Example
18 Mosquito Larvae Test The drug is prepared by dissolving 30 mf of the drug in 10 ml of acetone.

10 pI] N2: Dilute to 1 ppm with water.

Two 25 ml portions of each concentration are placed in test tubes and 10 to 25 fourth instar larvae of the yellow fever mosquito (Aedesaegypti) are added to this. The tubes are kept in the dark at 20°C for 72 hours.

At the end of this time the control percentage is determined. The medicinal efficacy of mono-, di- and tri-substituted thiophenes is shown in the table.

Here, the test drugs were numbered as before. The present invention includes the following aspects.

(1) The method according to claim 1, wherein the substituted thiophene is applied to plants.

(2) The pest is a tick, the substituted thiophene is applied in an acaricidal amount, and the pest is an alkyl, halogen, or halogen in which X has 1 to 3 carbon atoms. nitro, haloalkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, alkylthio or phenyl having 1 to 3 carbon atoms; a is 0,1 or 2; Y is hydrogen, halogen, Process according to claim 1, characterized in that the substituted thiophene is nitro, phenyl, phenylthio or phenylsulfono and Z is hydrogen or phenyl.

(3) The site to which the substituted thiophene is applied is a plant, and the mites to be controlled are mites.
) method. (4) The pests are ticks, substituted thiophenes are applied in carcidal amounts, and these include 2-(p-methylthiophenyl)thiophene, 2-(0-pifnia thiophene, 2-(p-methylthiophenyl)thiophene, The method of claim 1, characterized in that it is (3,4-xyl.3yl)thiophene and a compound in which Y is nitro, aryl"thio, or arylsulfono.

(5) The method according to claim 1, wherein Y is hydrogen and z is phenyl.

(6) The method according to claim 1, wherein Y is phenyl 6Z is phenyl.

(7) The pest is a mite, and the substituted thiophene is 2-(p-
methylthiophenyl)thiophene, 2-(0-biphenylyl)thiophene. ．． 2-phenyl-3-(phenylthio)thiophene, 2-phenyl-5-(phenylsulfonyl)thiophene, 2-phenylthio-5-p-tolylthiophene, 2-(p-isopropylphenyl)-5-
(Phenylthio)thiophene, 2-(m-chlorophenyl)-5-(phenylthio)thiophene, 2-phenylthio-5-(m-trifluoromethylphenyl)thiophene, 2-(3,4-xylyl)thiophene, 2- Phenylthio-5-(3,4-xylyl)thiophene, 2-nitro-3,5-diphenylthiophene, 3,5-diphenyl-2-(phenylthio)thiophene, 3-(p-
p-chlorophenyl)-5-(!nnitrophenyl)thiophene, 2-p-a[■■(p-chlorophenylthio)
-5-phenylthiophene, 2-phenylthiophene,
2,5-diphenylthiophene, 2-(p-isopropylphenyl)thiophene, 2-(m-chlorophenyl)
Thiophene, 2-(p-methoxyphenyl)thiophene. selected from the group consisting of 2-(p-nitrophenyl)thiophene, 2,4-diphenylthiophene, 2-bromo-3,5-diphenylthiophene, and 2,3,5-triphenylthiophene. A method according to claim 1, characterized in:

(8) Substituted thiophene is alkyne, halogen, nitro, haloalkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, alkylthio or phenyl having 1 to 3 carbon atoms; a is 0, 1 or 2; Y is hydrogen, halogen, nitro, phenyl, phenylthio, or phenylsulfono; and z is hydrogen or phenyl. The acaricidal or insecticidal composition of item 2.

(9) The acaricidal composition according to claim 3, wherein the substituted thiophene is 2,3,5-triphenylthiophene.

4. The insecticidal composition according to claim 3, wherein the substituted thiophene is 2,3,5-triphenylthiophene.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is hydrogen, chlorine, bromine, CF_3, C_1-C
_3 alkyl, phenyl, methoxy or methylthio, a is 1 or 2, Y is hydrogen, phenylthio, phenylsulfono, nitrophenylthio, nitro or chlorophenylthio, Z is hydrogen or phenyl)
1. A method for controlling ticks or insect pests, which comprises applying an acaricidal or insecticidal amount of a substituted thiophene having the following properties to areas susceptible to attack by ticks or insects.