JPS60233067A - 2-imino-1,3,4-thiadiazoline derivative, its preparation and agricultural and horticultural fungicide composed of said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 is halogen, lower alkyl, lower alkylmercapto, etc.; R2 is lower alkyl or lower alkenyl; R3 is group of formula II (X is halogen, lower alkyl, lower alkoxy, etc.; n is 0, 1 or 2), etc.]. EXAMPLE:2-[N-(2,6-difluorobenzoyl)imino]-3,5-dimethyl-1,3,4-thiadiazol ine. USE:An agricultural and horticultural fungicide. PREPARATION:The compound of formula I can be prepared by reacting the compound of formula III (A is halogen) with the compound of formula B-R3 (R3 is group of formula II, etc.; B is halogen) in the presence of an acid acceptor (e.g. ammonia, sodium carbonate, etc.) in an inert solvent at room temperature -60 deg.C for 1-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the general formula (1) [wherein - represents a halogen atom, a lower alkyl group, a lower alkyl mercapto group, a lower diloalkyl group or a halogen-substituted phenyl group, Bird represents a lower alkyl group, a lower alkoxy group or a lower haloalkyl group, and n is 0.
Indicates 1 or 2. (G-5O2 (wherein, Y represents a halogen atom, a lower alkyl group, or a nitro group, and n represents o, 1 mercaguto group,
It represents a lower alkylamino group or a phenoxy group, and 2 represents an oxygen or sulfur atom. ]. The present invention relates to 2'-imino-1,3,4-thiadiazolin derivatives represented by the following formula, methods for producing them, and agricultural and horticultural fungicides containing these compounds as active ingredients.

BACKGROUND OF THE INVENTION Many studies have been conducted on 1,5,4-thiadiazole derivatives, and a large number of compounds have been synthesized and a large number of compounds exhibiting physiological activity in the field of agricultural medicine have been discovered. However, not many compounds are known for 2-imino-1,3,,4-thiadiazoline derivatives, and only a few compounds with physiological activity have been reported.

Examples of 2-imino-1,3,4-thiadiazoline derivatives having bactericidal activity include 2-iodoacetylimino-3 described in U.S. Pat. No. 4,264,616;
-Methyl-5-trifluoromethyl-1,6°4-thiadiazoline is known as a fungicide effective against damping-off fungi. However, its activity is limited only against damping-off fungi, and it does not always give satisfactory results when used at low concentrations. Therefore, it cannot be said to be sufficient for use as a fungicide for agriculture and horticulture.

Problems to be Solved by the Invention An object of the present invention is to provide a highly effective medicine, a fungicide for agricultural and horticultural use, and a method for producing the same, which does not cause phytotoxicity to plants, has low toxicity, and can be used safely. .

Means and action for solving the problem In order to solve the problem, the present inventors have developed a 2-imino-
As a result of various studies on 1j, 4-thiomerulin derivatives, it was found that the general formula (1) [wherein is] a halogen atom, a lower alkyl group, a lower alkylmercapto group, a lower alkyl group, or a halogen-substituted phenyl group , ``bird'' represents a lower lower alkyl group, a lower alkoxy group, or a lower ``lower alkyl group'', and ``ru'' represents 0.1 or 2. ], (aromatic "" group 2 represents an oxygen or sulfur atom.) 2-imino-1,3,4-
The present invention has been completed by discovering that thiadiazoline derivatives have superior control effects against many plant pathogens, which was unexpected from known compounds.

The compound of the present invention represented by the general formula (1) is a new compound, specifically, in the formula, - is a halogen atom; methyl, ethyl, leupropyl, isopropyl, n-butyl, isobutyl, tert-butyl, leupentyl, Lower alkyl groups such as impentyl; lower alkylmercapto groups such as methylmercapto, ethylmercapto, n-propylmercapto, and isopropylmercapto; lower haloalkyl groups such as trifluoromethyl, difluoromethyl, trichloromethyl, and 2-fluoroethyl ; or represents a halo, gen-substituted phenyl group, R2 is methyl, ethyl, 7L -
propyl, isopropyl, looptyl, isobutyl, t
Lower alkyl groups such as ert-butyl, n-pentyl, and impentyl, or lower alkyl groups such as vinyl, allyl, 2-methyl-2-propenyl, 2-71-thyl-1-propyl, ethyl, leupropyl, isopropyl, and tert-butyl. Alkyl group; methoxy, ethoxy, n-propyloxy,
It represents a lower alkoxy group such as inpropyloxy or tert-butyloxy, or a lower haloalkyl group such as trifluoromethyl, difluoromethyl, trichloromethyl or 2-fluoroethyl, and n represents 0.1 or 2. ] benzoyl group, group -802-@yY1 [however,
In the formula, Y represents a halogen atom; a lower alkyl group such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, or a nitro group, and n represents 1 or 2. [However, in the formula, R represents an alkyl group (a linear or branched alkyl group having 1 to 1.2 carbon atoms; is a lower alkoxy group such as methoxy, ethoxy, n-propyloxy, isopropyloxy, looptyloxy, inbutyloxy; methylmercapto,
Lower alkyl mercapto groups such as ethyl mercapto, a-propyl mercapto, isopropyl mercapto, n-butyl mercapto, and inbutyl mercapto; lower alkylamino groups such as methylamino, ethylamino, 9-propylamino], and dimethylamino or phenoxy groups; 2 represents an oxygen or sulfur atom. ] represents a phosphate ester group.

It can be produced according to the reaction route described below.

5 (1) (In the formula, R2 and H each have the above-mentioned meanings. A and B) represent a rogen atom. ) That is, thiosemicarbazide and a compound represented by the general formula R1000H (wherein R1 has the above meaning) are reacted in the presence of phosphorus oxychloride to form 2-2-
An amino-1,5,4-thiadiazole derivative is obtained.

In this compound (g), R2 and A in the general fih-AC formula
respectively have the above meanings. ] A compound represented by the general formula (II) obtained by the reaction with a compound represented by the general formula R3-B (wherein R3 and B each have the meanings described above) Compound (I) of the present invention can be obtained by reacting in an active solvent in the presence of an acid binder. As an inert solvent,
Common inert solvents i.e. benzene, toluene, xylene,
Chloroform, carbon tetrachloride, diethyl ether, dioxane, acetone, methylethylchloride, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, etc. can be used. In addition, acid binders include ammonia, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide,
Basic substances such as triethylamine and pyridine are used.

The reaction temperature is 0 to 80°C, preferably room temperature to 6°C, and the reaction time is 1 to 5 hours. After the reaction is completed, insoluble materials are separated from P, and the reaction solution is washed with dilute hydrochloric acid, water, aqueous alkali solution, etc. in sequence, dried, and the solvent is distilled off, or
Alternatively, after separating the insoluble matter from the reaction mixture, the reaction solvent may be distilled off, and the residue may be extracted with a suitable organic solvent such as benzene and washed with acid, water, alkali, etc. in the same manner. The target compound (1) is obtained by distilling off the solvent, but if necessary, it may be further purified by column chromatography or the like.

The compounds of the present invention have excellent bactericidal activity against plant pathogens and can be applied to control plant diseases caused by a wide variety of fungi. Botrytis ci on plants, especially on cucurbits, tomatoes, strawberries and other hosts.
nerea) and apple leaf spot leaf disease (Alternar).
iamali), and the above-mentioned known compound 2-
It has a different activity spectrum from iodoacetylimino-3-methyl-5-trifluoromethyl-1,5,4-thiadiazolin. In addition, they do not practically cause any phytotoxicity to cultivated plants, and among most of the compounds of the present invention, some of the compounds exhibit not only bactericidal properties but also high insecticidal activity.

The compound of the present invention is 1111! Although it can be used as an artistic fungicide, it is actually mixed with a carrier and optionally other adjuvants to formulate it in the formulations normally used for artistic fungicides, such as powders, coarse powders, and fine granules. , granules, aquariums, emulsions, aqueous solutions, aqueous solutions, oil suspensions, etc.
, # has been used.

The term "carrier" used herein refers to a synthetic or natural carrier that is incorporated into agricultural and horticultural fungicides to help the active ingredient reach the area to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound. means any inorganic or organic substance.

Suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic substances such as diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate, and vegetable organic substances such as soybean flour, sawdust, and wheat flour. and urea.

Suitable liquid carriers include aromatic hydrocarbons such as benzene, toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, carbon tetrachloride, chloroform,
Halogenated hydrocarbons such as dichloroethane, acetone,
Examples include ketones such as methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, alcohols such as methanol, zolopanol, and ethylene gelicol, dimethylformamide, dimethyl sulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used individually or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as pyrogenine sulfonate, anionic surfactants such as alkylbenzene sulfonate, alkyl sulfate, holoxyethylene oryl ether, etc. Examples include nonionic surfactants such as calcium stearate, lubricants such as wax, stabilizers such as isopropylhydrodiene phosphate, and others such as methyl cellulose, carboxyl methyl cellulose, casein, and gum arabic.

However, these components are not limited to the above.

Furthermore, when the compound of the present invention is applied as a fungicide,
Other agricultural chemicals used at the same time, such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, attractants, such as organophosphate compounds, carbamate compounds , dithiocarbamate compounds, thiol carbamate compounds, organochlorine compounds, dinitro compounds, antibiotics, urine compounds, triazine compounds, fertilizers, etc., or can be used as a mixture.

The various formulations or spray preparations containing the active ingredients of the present invention can be applied using the application methods normally practiced in the agrochemical manufacturing field, namely spraying (e.g. liquid spraying, misting, atomairing, dusting, granulation, water surface spraying, etc.). It can be carried out by fumigation, soil application (e.g., mixing, fumigation, 1 note), surface application (e.g., coating, dusting, coating), dipping, etc.

EXAMPLES Next, the content of the present invention will be specifically explained with examples, but the present invention is not limited to these examples.

First, the manufacturing method of the present invention will be specifically explained with reference to manufacturing examples.

Production Example 1 (1) Production of 2-amino-5-trifluoromethyl-1,3°4-thiadiazole 409 (0.44 mol) of thiosemicarbazide,
250 ml of dioxane and 509 (0,44 mo
1) Trifluoroacetic acid was charged to 14 reaction flasks. While thoroughly stirring this mixture, 6Z3, j9
(0.44 mol, 41 ml) of phosphorus oxychloride
Added over 0 minutes. When the resulting thick slurry was gradually heated and refluxed, hydrogen chloride gas was violently generated. After approximately 4 hours of total reflux gas evolution ceased and the product separated as a syrup. The dioxane was now decanted and 40011 Lt of water was added to the residue. After cooling this mixture to room temperature, the pH was adjusted with 50% sodium hydroxide.
Adjusted to 9. After cooling this slurry to 5° C., the product was separated with P, washed, and dried. Melting point 219.5-220.
The target product 52II of No. 5 was obtained.

(2) Production of 2-imino-6-methyl-5-trifluoromethyl-1,3,4-thiadiazol-4-yne HI salt xOg (0,177 mo+) of 2-amino-5-trifluoromethyl-1 ,3,4-thiadiazole and 60d
t of dioxane and 17.6 fi (0,!l 7
mol, 23, I II/) of iodomethane to 30
01tl! reaction flask. Add this mixture to 2
It was refluxed for 0 hours.

After cooling to room temperature, the resulting willow was separated from P, thoroughly washed with dioxane and toluene, and then dried.

58. Salt with melting point 190-192°C I got li+.

(3) 2-(N-(2,6-difluorobenzoyl)
Imino'] -Manufacture of -5,5-dimethyl-1,5,4-thiadiazolin (compound number 5) 2-imino-3,5-dimethyl-1,3,4-thiadiazolin HI salt 1.09 (0,004 mol ) and 15
Tmp of 1111 and 1.2 fi (0,0'12
mol, 1.71i1) of triethylamine was added to 50
mA' reaction flask and stir well. Water cooling 0
．． After gradually dropping 72p (0,0041 mol) of 2,6-cyfluoropenzoyl chloride, 4
Allowed time to react.

After the reaction was completed, insoluble materials were separated and the reaction solvent was distilled off. 1 omi of benzene was added to this residue to dissolve the product, which was then washed with water. Furthermore, it was washed with about 1 to 2 N hydrochloric acid and water. Next, it was washed with an aqueous potassium carbonate solution, and after washing with water, it was dried using a dehydrating agent. After distilling off benzene under reduced pressure, 0.9I of the target product was fractionated by silica gel column chromatography (hexane:ethyl acetate=7:3). m p
, 151-154°C.

NMR (ODOA'3) data δ2.56 (51-1
, S), 396 (3H, S), 6.92 (2H, t,
J=8Hz), Z27 (IH, m).

Elemental analysis 0,1H,F2N308 HNFS Theoretical value (chronic 49.07 3.37 15./+0 1
4.1111.91 measurement value (qQ4'9.39 3.2
1 15.49 13.87 11.74 Example 22-
Production of (N-(2-methylbenzoyl)imino]-3-'methyl-5-(6-chlorophenyl)-1,3,4-thiadiazolin (compound number '9) 2-imino-3-methyl-5- (3-I'chlorophenyl-1,3,4-thiadiazoline HI salt 1.5.9 (0
,0042mo1) and 20m1 of benzene and 1.2j
9 (0,012 mol 1.7 ml) of triethylamine was placed in a 50 ml reaction flask and stirred well. 0.6511<0.0.042moj) under water cooling
-40° after gradually dropping methylbenzoyl chloride
The reaction was carried out at C for 6 hours.

After the reaction is complete, insoluble matter is filtered off, and the filtrate is treated with 1 to 2 N hydrochloric acid,
It was washed successively with water and an aqueous potassium carbonate solution, and then dehydrated by adding a desiccant.

After benzene was distilled off under reduced pressure, 1.3 g of the target product was collected by silica gel column chromatography (hexane:ethyl acetate = 4:1). m, p.

148-150℃.

NMR (0DO(Is) data δ2.72 (3H
, s ), 4.09 (3H', s), Z3 (6H, m)
, 7.68 (1H,'m), 788 (IH, m) Elemental analysis 0. , H,,CIN,O801(N On
S theoretical value (arrogant 59.40 4.0B 12.25 10
．． 32.9.52 measurement value ←) 59.17 4.02
12.3110.2<S 9.38 Example 32-(N-
(4-Methyl-3-nitrobenzenesulfonyl)imino]-6-methyl-5-trifluoromethyl-1,3,4
-Production of thiadiazoline (compound number 35): 2-iminoni-6-methyl-5-trifluoromethyl-1,3,
4-Thiadiazoline HI salt 1.5 g (0,0048 m
ol ) and 20 mJ THF and 15 g (0,015
mol 2.0 ml) of triethylamine in 50r
Pour the mixture into a 100ml reaction flask and stir well. Under water cooling 1,
After 2 g (0,005 mcli'') of 6-nitro-4-methylbenzenesulfonyl chloride was gradually added dropwise, the mixture was reacted at room temperature for 4 hours.

After the reaction was completed, insoluble matter was filtered off, and the reaction solvent was distilled off. After adding 1,0 ml of benzene to the residue and dissolving the product, the product was washed successively with 1 to 2 N hydrochloric acid, water, an aqueous potassium carbonate solution, and water, and then dehydrated with a desiccant.

After distilling off benzene under reduced pressure, silica gel column chromatography (hexane: ethyl acetate = 3: 2
) 155 g of the target product was collected from K. m.

p, 179-1795°C NMR (acetone-d, : DM80-d6=1
: 1) 2.62 (3H, s), 5.74 (3H, s
), 7.72 (1H, d, J=2Hz), 8.0
8 (IH, m), 8.36 (IH, d, J = 2H2
) Elemental analysis OH1HgF3N40A820HN F 8 Theoretical value (down 34.55 2.56 14.66 14
．． 92 16.75 measured value (134,682,!+1
14.55 14.79 16.88 Example 42-[:
5.0! i(0
, 028 mol, 3.7 ml) in benzene 20 ml
Add it inside and cool it on ice. In this, n-propyl mercaptan 2
．． 15fi (0,028mol1.2.5ml) and triethylamine4. ．． 5g (0.04mo1-6.'2m
1 ornl of a benzene mixture containing 1) was gradually added dropwise, and the mixture was allowed to react at room temperature for 5 hours. After the reaction was completed, the reaction solvent was distilled off, and further vacuum distillation (bp, 81-83°C/'
2 mmNg) to obtain 0-ethyl-8-n-propyldithiophosphoric acid chloride.

2-Imino-6,5-dimethyl-1,3,4-thiadiazolin HI salt2. j9 (0,0078 mol) and benzea□25ml and triethylamine y1.2,j
il' (0,012mol, 1,6ml) 50ml
1.7 of 0-ethyl-8-71,-propyldithiophosphoric acid chloride was added to a reaction flask and stirred well under ice cooling.
5 jj (0,008 mo+) was gradually added dropwise, and the mixture was allowed to react at room temperature for 4 hours.

After the reaction is complete, insoluble matter is filtered off, and the filtrate is treated with 1 to 2 N hydrochloric acid,
It was washed successively with water and an aqueous potassium carbonate solution, and then dehydrated by adding a desiccant.

After benzene was distilled off under reduced pressure, the target product 1.6I was fractionated by silica gel chromatography (benzene).

? L5081.5871 NMR (anal, ) δ; 0.9B (31-1
,t, J=7.411z), 1.4(](3H,t,
J=7Hz), 1.64 (2H,'m), 244(
! IH,S), 2.8 (2H,,m), 3.6
6 (3H, S), 4.16 (2H, m) Elemental analysis C1111 (18N30PS30HNPS Theoretical value ((6) 34,73 5.79 13.50
997 30.87 measurement value ←) 34,57 6.02
13.25 10.3030.48 Table (1) - (
5) shows representative examples of the compounds of the present invention along with their structural formulas, physical constants, and analytical values.

Next, formulation examples will be explained below using specific examples.

The active ingredient compounds are indicated by compound numbers in Table 1 above. 1
Parts represent parts by weight.

Formulation Example 1 Wettable powder compound (1): 300 parts, diatomaceous earth: 440 parts, clay: 200 parts, sodium ligninsulfonate = 25 parts,
Sodium alkylbenzenesulfonate: '15 parts, and poly-11oxyethylene nonylphenyl ether = 2
0 parts were uniformly ground and mixed to obtain the compound (1 part) as an active ingredient.
) was obtained.

Formulation Example 2 Emulsion Compound (42) 400 parts, cyclohexanone: 10
0 parts, 300 parts of xylene di, and 200 parts of Trupol (a surfactant manufactured by Toho Chemical Co., Ltd.) were uniformly dissolved and mixed to obtain an emulsion containing 40% of compound (42) as an active ingredient.

Formulation Example 6 Powder Compound (3): 20 parts, calcium stearate:
5 parts, powdered silica gel = 5 parts, diatomaceous earth: 200 parts,
50 parts of white clay and 470 parts of talc were uniformly ground and mixed to obtain a powder containing 2 parts of compound (3) as an active ingredient.

Formulation Example: 10 parts of oil compound (23') and 90 parts of ethylseronulp were mixed and dissolved to prepare compound (23') as an active ingredient.
) was obtained.

Effect of the invention The effects of the present invention will be specifically explained using test examples.

Test Example 1 Apple spot leaf drop disease (pot test) Approximately 8 newly developed leaves
Apple seedlings (Star King, 2-year-old seedlings) planted in No. 3 clay pots, which had become leaves, were treated with 250 ppm of active ingredients (each test compound was used as an irrigation agent and diluted with water according to the method of Formulation Example 1 above). Using a spray gun (1&p/i,
A conidial suspension of apple spot leaf fall fungus cultured in -S Gies medium was spray-inoculated and kept at 23-25°C and humidity of 95°C or more for 3 days.

The number of lesions was investigated for each of the eight leaves of each spindle, and the control value was calculated from the number of lesions per leaf using the following formula. The results are shown in Table 2.

As a control drug, we used the commercially available Spudside, which has been shown to have a high control effect on apple leaf spot and is widely used.

It is clear from Table 2 that the compound of the present invention exhibits a high control effect on apple leaf spot leaf disease that is equivalent to or greater than that of Subatsu 1 side.

Test Example 2 Gray mold (bean leaf test) prescribed concentration (5
00,2'50ppm) of the drug (each test compound was
□ Green bean cotyledons (top telop) spread out in a hydrating powder (diluted with water according to the method in Penal Case 1) were immersed for about 2 to 3 minutes, and then air-dried. Gray mold fungus discs (diameter 5), which had been plate-cultured in advance on PEA medium, were inoculated onto leaves, placed in a greenhouse at 18°C in the dark, and incubated for 4 to 5 days.
Days later, the diameter of the lesions was examined, and the control value was calculated using the following formula.

・The results are shown in Table 3.

Table 3 *1 Active ingredient concentration *2 Topgin M (1,2-bis(6-medoxycarbonyl-2-thioureido)benzene) 70% As a control drug, it was found to be effective as a gray turtle glare repellent. The commonly used commercially available Topgin M was used.

It is clear from Table 6 that the compound of the present invention exhibits a higher control effect than Topgin M against Botrytis blight (bean leaf test) K.

Test Example 3 Botrytis blight (Cucumber fruit test) Wash Cucumber fruit (commercially available) well, cut into 4-5 cm pieces, and add 500 p.m.
pm drug (each test compound was diluted with an irrigation agent and water according to Example 1 above) for about 2 to 3 minutes and air-dried. Air-dried cucumber fruits are placed on top of the fungi of gray mold fungus (5 to 7 days), which have been plate-cultured on a PSA medium in advance. Thereafter, the plants were kept in a humid greenhouse at 18° C. for 4 to 5 days, and the growth and growth of fungus on the surface of the cucurbits was examined, and the control value was calculated using the following formula. The results are shown in Table 4.

Table 4 *Tono19F (1,2-bis(3-methoxycarbonyl-2-thiouredo)benzene) 70% The control drug was used as a botrytis blight control agent, and the compound of the present invention was used as a botrytis blight control agent. -Top Gin M, a commercially available product that has been recognized for its effectiveness and is commonly used, was used.

It is clear from the 5g4 table that it has a higher control effect than Topgin M against the 5g-4 test.

As is clear from the results of Test Examples 1 to 3, Himi゛□ Azoline derivatives, which are drugs that are generally difficult to control and exhibit high control effects, are highly effective against completely different plant diseases such as apple spot leaf fall and gray mold. Shows pest control effect. These plant diseases are desired.

Currently, several agricultural and horticultural disinfectants are commercially available to control these diseases, but although they show relatively high control effects against a single disease, they do not have a control effect against other diseases. do not have. Spudside, which was used as a control drug in Test Example 1, shows a ivy control effect on apple spot leaf fall, but does not show a practical effect on gray mold at practical concentrations. Furthermore, Topgin M, which was used as a control drug in Test Example 2.3, also shows a controlling effect on gray mold, but does not show a controlling effect on apple spot leaf fall at practical concentrations.

Therefore, the compound of the present invention, which exhibits high control effects against different plant diseases such as apple leaf spot and gray mold, is considered to be a drug with high utility value.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Scope of Claims] (1) General formula (1) [In the formula, R1 represents a halogen atom, a lower alkyl group, a lower alkylmercapto group, a lower haloalkyl group, or a halogen-substituted phenyl group, and - represents a lower alkyl group or a lower It represents an alkenyl group, which represents a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group, and n is 0.1 or 2.
shows. ],]Group -802-o''Yn, where Y represents a halogen atom, a lumercapto group, a lower alkylamino group, or a phenoxy group, and 2 represents an oxygen or sulfur atomω
shows. ] A 2-imino-1,3,4-thiadiazolin derivative represented by: (2) Mu general formula (iD ・ (wherein, FLI represents a halogen atom, a lower alkyl group, a lower alkylmercapto group, a lower haloalkyl group, or a halogen-substituted phenyl group, and - represents a lower alkyl group or a lower alkenyl group. , A is H and X is] 70 gen atoms,
It represents a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group, R represents 0, Y represents a halogen atom, a lower alkyl group, or a dinito group, and R represents 0.1 or 2. R6 represents a lower alkoxy group, a lower a'
represents an alkylmerkabuto group, a lower alkylamino group or a phenoxy group, and Z represents an oxygen or sulfur atom),
B represents a halogen atom. ]. 2-imii-' represented by the general formula (1) (wherein R1, FL2 and island each have the above-mentioned meanings). i, 7. Method for producing a 4-thiadiazoline derivative. 5.1 (6) General formula (1)... [In the formula, RI is a halogen atom, a lower alkyl group, a lower alkylmercapto group, a lower haloalkyl group, or a halo ,
Indicates a gen-substituted phenyl group, - is a lower lower alkyl group,
It represents a lower alkyl group or a lower haloalkyl group, and R represents 0, 1 or 2. ), (7" group -8O□ (wherein, Y represents a group, a lower alkyl group, or a nitro group, and n represents 0, a cokite group, a lower alkylmercapto group, a lower alkyl group, a mino group, or a phenoxy group. and 2 represents an oxygen or sulfur atom.] 2-imino-1,3,
An agricultural and horticultural fungicide characterized by containing a 4-thiadiazoline derivative as an active ingredient.