KR940009934B1 - KETENE DITHIO ACETAL Ñß-ANILIDE DERIVATIVES - Google Patents

Abstract

New sterilized compound having a wide sterilizing effect and power is prepd. by: (A) synthesis of β-keto anilide of formula (II) from aniline; (B) synthesis of ketene dithio acetal α-anilide of formula (I) by reacting (II) and alkyl halide, dialkyl sulfate, alkyl alkyl or allyl sulfonate of formula (III) in the presence of CS2. In the formulas, R1, R2, R3, R4 are same or different, respectively hydrogen, aryl and aryl oxy and alkyl, alkenyl, alkoxy, thio alkyl, haloalkyl, nitro, cyano, aryl sulfonyl group; R5 is alkyl, hydrogen or halogen substituted aryl, group; R6 is alkyl or alkyl haloalkyl group.

Description

Ketene dithio acetal α-anilide derivatives

The present invention relates to a derivative of novel ketene dithio acetalα-anilide represented by the following structural formula (I) having a wide range of bactericidal power.

Wherein R ₁ , R ₂ , R _2, and R ₄ are the same or different, and each hydrogen atom, aryl group, aryloxy group, alkyl group, alkenyl group, alkoxy group, thioalkyl group, aroal group, haloalkyl group, halogen atom , A nitro group, a cyano group, an arylsulfonyl group or a heterocycle group, wherein an aryl group is phenyl or a substituted phenyl group, an aryloxy group is a phenoxy or substituted phenoxy group, and an alkyl group is C ₁ -C ₆ A straight or branched alkyl group of which is an alkenyl group is a C ₁ -C ₅ straight or branched alkenyl group, an alkoxy group is a C ₁ -C ₅ straight or branched alkoxy group which is substituted with hydrogen or a halogen, A thioalkyl group is a C ₁ -C ₄ thioalkyl group substituted with hydrogen or a halogen, an aroyl group is a benzoyl or substituted benzoyl group, and a haloalkyl group is a C ₁ -C ₄ straight or branched haloalkyl group, aryl Sulfonyl group is phenyl Or a substituted phenylsulfonyl group, a heterocycle group is preferable when referring to a heterocycle group containing nitrogen such as imidazole, etc., R ₅ is alkyl or a hydrogen atom or an aryl group substituted with halogen, wherein an alkyl group is C A straight chain or branched alkyl group of ₁ -C ₃ , an aryl group is preferred when referring to a hydrogen atom or a substituted phenyl group, R ₆ represents an alkyl group or a benzyl group substituted or unsubstituted by alkyl, haloalkyl and halogen. Wherein the alkyl group is a C ₁ -C ₆ straight or branched alkyl group, and the benzyl group is a C ₁ -C ₅ straight or branched alkyl group or a C ₁ -C ₃ straight or branched haloalkyl group or a halogen group. It is preferred when the benzene nucleus optionally represents a substituted benzyl group.

Conventionally, many researches on organic synthetic compounds useful for agricultural horticulture have been conducted, and many biologically active compounds have been found and put to practical use.

Among them, many active compounds having a skeleton of ketene dithio acetals have been found. For example, in German Patent No. 2,316,921, diisopropyl 1,3-dithiolane-2-ylidenemalonate of formula (A) It is known to be useful for controlling febrile disease.

In addition, fungicides that have been developed and used so far, such as captapol, chlorothalonil and mithio carbamate, have been developed and used in practice, but some of these fungicides cause serious problems such as resistance accumulation and environmental pollution. It is limited.

Accordingly, the present inventors have conducted extensive research on new bactericidal control agents to solve these problems in the compounds useful as conventional bactericides, and thus have produced new compounds useful as bactericides.

Accordingly, an object of the present invention is to provide a ketene dithio acetal α-anilide derivative having a novel structure as an excellent bactericidal compound having a wide range of bactericidal effects and a strong bactericidal effect.

Hereinafter, the present invention will be described in detail.

The present invention relates to a ketene dithio acetal α-anilide derivative represented by the above formula (I).

Preferred substituents in the above formula (I) include R ₁ , R ₂ , and R ₃ R ₄ , all of which are hydrogen or phenyl or substituted phenyl, phenoxy or substituted phenoxy, C ₁ -C ₆ linear or branched chain. Alkyl group, C ₁ -C ₅ straight or branched alkenyl group, hydrogen or halogen substituted C ₁ -C ₅ straight or branched alkoxy group, hydrogen or halogen substituted C ₁ -C ₄ thioalkyl group, benzoyl Or when a heterocyclic group containing nitrogen such as a substituted benzoyl group, a straight or branched haloalkyl group of C ₁ -C ₄ , a phenyl or substituted phenylsulfonyl group, and imidazole, etc., R ₅ is a straight chain of C ₁ -C ₃ Or a branched alkyl, or a hydrogen atom or a halogen-substituted phenyl group, R ₆ is a C ₁ -C ₆ straight or branched alkyl group, or a C ₁ -C ₅ straight or branched alkyl group, C ₁ -C ₃ Linear or branched haloalkyl group or halogen is optionally The case is the benzyl group.

Referring to the present invention in more detail as follows.

According to the present invention, when a compound of the following formula (II) is reacted with an alkyl halide, dialkyl sulfate, alkylalkyl or arylsulfonate represented by the following formula (III) in carbon disulfide (CS ₂ ), the ketene of formula (I) Dithio acetal α-anilides can be prepared.

This is represented by the following scheme.

Wherein R ₁ , R ₂ , R ₃ R ₄ , R ₅ and R ₆ are each as described above, X is a halogen atom, in particular chlorine, bromine, iodine, alkylsulfate, alkyl or aryl Sulfonate.

Looking in more detail the manufacturing process for the novel compounds of the present invention as described above β-keto anilide and carbon disulfide of the formula (II) and alkyl halide, dialkyl sulfate or alkylalkyl or arylsulfonate of the formula (II) Is reacted in the presence or absence of a solvent in the base.

At this time, for example, water; Ketones such as acetone methyl ethyl ketone; Amides such as dimethyl formamide, dimethylacetamide and the like; Alcohols such as methyl alcohol and ethyl alcohol; Aromatic hydrocarbons such as benzene, toluene, xylene and the like; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and the like and acetonitrile, dimethyl sulfoxide or mixtures thereof can be used.

As the base, inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide, potassium alkoxide, sodium hydride, potassium hydride, calcium hydride and the like can be used.

On the other hand, according to the present invention, the reaction for preparing the structural formula (I) is carried out at -80 to 100 ° C, preferably 5 to 25 ° C, and the reaction time is 6 minutes to 48 hours, preferably 30 minutes to 24 hours. Run for hours. In this case, carbon disulfide is used in the amount of 1 to 1.5 equivalents, alkyl halide, dialkyl sulfate or alkylalkyl or arylsulfonate of formula (III) is used in the amount of 1 to 1.5 equivalents, and the amount of base used is 1 to 5 equivalents. Preferably, 1-3 equivalents can be used.

Β-keto anilide of the formula (II), which is a starting material used in the present invention, may be prepared from aniline by the following known methods.

As described above, when R ₅ is CH ₃ , that is, the structural formula (IIa) may be easily prepared by aniline and diketene, and when R ₅ is not CH ₃ , the reaction of β-keto ester with aniline By the β-keto anilide of the formula (II) it can be easily produced.

Compounds of the formula (II), which is a starting material of the present invention prepared as above, are mostly known compounds, but some of them are novel compounds, all of which can be prepared by known methods.

On the other hand, the ketene dithio acetal α-anilide of the formula (I) obtained by the above reaction is discharged in a large amount of water after completion of the reaction, in which case the precipitate is solid and then filtered and dried. In this way, crude crystals of the target can be obtained in a yield of 90% or more.

In the case where the precipitate is an oil phase, a crude product is obtained by extracting in an inert solvent such as ethyl acetate, benzene, toluene, washing with water, dehydrating and depressurizing the solvent under reduced pressure. Since the preparation itself has a relatively high purity, it can be used immediately as a disinfectant without further purification.

However, if necessary, a refined product can be obtained by recrystallization from commonly used solvents such as isopropyl ether, chloroform, carbon tetrachloride, ethyl acetate, ethanol and methanol, or by column chromatography.

Specific examples of the compound of formula (I) according to the present invention are as follows.

N- (2-methoxyphenyl) -α- (bismethylthio iridene) aceto acetamide

N- (4-chloro-2-trifluoromethyl phenyl) -α- (bismethylthio iridene) aceto acetamide

N- (1,4-benzodioxan-6-yl) -α- (bismethylthio yilidene) aceto acetamide

N- (4-t-butylphenyl) -α- (bismethylthio iridene) aceto acetamide

N- (2-phenylsulfonyl phenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (2-Fluoro-5-nitrophenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (2,3,4,5-tetrachloro phenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (4-trifluoromethyl phenyl) -α- (bismethylthio iridene) aceto acetamide

N- (2-trifluoromethyl phenyl) -α- (bismethylthio iridene) aceto acetamide

N- (2-hydroxyphenyl) -α- (bismethylthio iridene) aceto acetamide

N- (2-isopropenyl phenyl) -α- (bismethylthio iridene) aceto acetamide

N- [2- (2-chloro1,1,2-trifluoroethylthio) phenyl] -α- (bismethylthio iridene) aceto acetamide

N- (4-bromo-3-trifluoromethylphenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (4-hexyl phenyl) -α- (bismethylthio iridene) aceto acetamide

N- (4-pentyloxy phenyl) -α- (bismethylthio iridene) aceto acetamide

N- (4-Fluoro-2-nitrophenyl) -α- (bismethylthio iridene) aceto acetamide

N- (4,5-difluoro-2-nitrophenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (4-Fluoro-2-trifluoromethyl phenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (4-Chloro-3-trifluoromethyl phenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (3-trifluoromethylphenyl) -α- (bismethylthio iridene) aceto acetamide

N- (4-Chloro-2-nitrophenyl) -α- (bismethylthio iridene) aceto acetamide

N- (2-nitro-4-trifluoromethyl phenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (2,5-di-t-butylphenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (3-Fluoro-2-trifluoromethyl phenyl) -α- (bismethylthio yilidene) aceto acetamide

N- (4-Chloro-2-trifluoromethyl phenyl) -α- (bismethylthio yilidene) aceto acetamide

The compound of formula (I) has excellent bactericidal and growth-regulating actions against plant germs, and is used for the control and eradication of diseases caused by various plant germs. In particular, the compound of formula (I) has a prominent effect on rice, severe fungal causes such as Rhizoctonia solani and Pyricularia oryzae caused by fungi, and the following crop diseases, namely, Corticium centrifugum), rice blight blight (Xanthomonas oryzae), Chinese cabbage blight (Erwinia aroideae), ulcer disease (Xanthomonas citri), rice hobbitum (Cochliobolus miyabeanus), banana spots (Mycosphaerella musicola), cucumber and strawberry (Greytis fungus of Botrytis) cinerea, Plasmopara viticola, Glomella cingulata of grapes, apples and pears, Sclerotinia sclerotiorum of vegetables, Collettotrichum lagenarium, Diaperthe citri, Apple powder bottle (Podosphaera leucotricha), cucumber powder (Sphaerotheca fuliginea), apple spots (Ahernaria mali) and potato plaques (Alternaria solani) and black spots such as Alternaria kikuchiana, and apples It is also effective for black diseases, such as Venturia inaequalis and emphysema.

In addition, diseases caused by plant germs, which must use a fungicide containing only heavy metals, such as arsenic or mercury, which are toxic to humans and livestock, since the active compounds of the formula (I) according to the present invention have superior sterilization effects as described above. Can also be used effectively.

Such active compounds according to the present invention are solutions, emulsions, wetting agents, suspensions, powders, foaming agents, pasta preparations, powders, granules, aerosols, emulsions, powders for seed treatment, natural and synthetic substances saturated with active compounds, and polymerized. Very fine capsules in materials, seed coating compositions, and fumigation cartridges, fumigation cans, fumigation coils and ULV cold and warm preparations can be converted into formulations for use in heating devices.

Such formulations may be prepared by known methods for mixing the active compound with a weighting agent such as liquid or liquefied gas or solid diluents or carriers, optionally with surfactants such as emulsifiers and dispersants or foaming agents. In addition, when water is used as a weighting agent, an organic solvent may be used as an auxiliary solvent.

Examples of the compounds of formula (I) according to the present invention as described above are shown in Table 1 below.

TABLE 1

Hereinafter, the present invention will be described in detail with reference to Examples, in which the percentages are based on weight.

Example 1

Synthesis of N- (2-methoxyphenyl) -α- (bismethylthioylidene) acetoacetamide (I)

To a solution of aceto acet anilide (20.7 g, 0.1 mol), potassium carbonate (42 g, 0.3 mol) and 50 ml of dimethyl formamide is added carbon disulfide (9 ml, 0.15 mol). After about 15 minutes, iodine methane (36.9 g, 0.26 mol) was slowly added dropwise for 30 minutes. After the dropwise addition, the reaction was completed from the pesticide chromatography after stirring for 12 hours. After the reaction was completed, 500 ml of water was added to the resulting yellow solid, and the filtrate was extracted with 100 ml of ethylaceteart, followed by distillation under reduced pressure.

The yellow solid and the residue from ethyl acetate are dissolved in 100 ml of ethyl alcohol and recrystallized to give 22.7 g (74%) of the product.

Yield: 73%

¹ H NMR (CDC1 ₃ ): δ8.54 (s, 1H), 8.45∼6.90 (m, 4H), 3.89 (s, 3H), 2.46 (s, 9H)

Example 2

Synthesis of N- (chloro-2-trifluoromethyl phenyl) -α- (bismethylthioylidene) acetoacetamide (2)

N- (4-chloro-2-trifluoromethyl phenyl) aceto acetamide (28.0 g, 0.1 mol). To a solution of potassium carbonate (42 g, 0.3 mol) and 50 ml of dimethyl formamide is added carbon disulfide (9 ml, 0.15 mol). After about 15 minutes, iodine methane (36.9 g, 0.26 mol) is slowly added dropwise for 30 minutes. After completion of the dropping, after 12 hours of stirring, the reaction was confirmed that the reaction was completed from the bacterium chromatography. After the reaction was completed, 500 ml of water was added to the resulting yellow solid, and the filtrate was extracted with 100 ml of ethylaceteart, followed by distillation under reduced pressure.

The yellow solid and the residue from ethyl acetate are dissolved in 100 ml of ethyl alcohol and recrystallized to give 19.9 g (52%) of product.

Yield: 52%

¹ H NMR (CDC1 ₃ ): δ2.5 (s, 9H), 8.5-7.3 (m, 3H), 8.7 (s, 1H)

Example 3

Synthesis of N- (1,4-benzodioxan-6-yl) -α- (bismethylthioylidene) acetoacetamide (4)

N- (1,4-benzodioxan-6-yl) aceto acetamide (23.5 g, 0.1 mol). To a solution of potassium carbonate (42 g, 0.3 mol) and 50 ml of dimethyl formamide is added carbon disulfide (9 ml, 0.15 mol). After about 15 minutes, iodine methane (36.9 g, 0.26 mol) is slowly added dropwise for 30 minutes. After the reaction, the reaction mixture is treated as in Example 1 above.

Yield: 72%

¹ H NMR (CDC1 ₃ ): δ2.33 (s, 3H), 2.45 (s, 6H), 4.23 (s, 4H), 7.5 ~ 6.5 (m, 3H), 10.03 (s, 1H)

Example 4

Synthesis of N- (4-t-butylphenyl) -α- (bismethylthioylidene) acetoacetamide (5)

N- (4-t-butyl phenyl) aceto acetamide (23.3 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above to obtain the desired product. Got.

Yield: 70%

¹ H NMR (CDC1 ₃ ): δ1.3 (s, 9H), 2.43 (s, 9H), 7.2 to 7.6 (m, 4H), 8.43 (s, 1H)

Example 5

Synthesis of N- (2-phenylsulfonyl phenyl) -α- (bismethylthioylidene) aceto acetamide (6)

N- (2-phenylsulfonyl phenyl) aceto acetamide (31.7 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above to obtain the desired product. Got.

Yield: 79%

¹ H NMR (CDC1 ₃ ): δ 2.27 (s, 3H), 2.46 (s, 6H), 7.06 ~ 8.56 (m, 9H), 9.9 (s, 1H)

Example 6

Synthesis of N- (2-Fluoro-5-nitrophenyl) -α- (bismethylthioylidene) acetoacetamide (7)

N- (2-fluoro-5-nitrophenyl) aceto acetamide (24.0 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above. The desired product was obtained.

Yield: 73.8%

¹ H NMR (CDC1 ₃ ): δ 2.46 (s, 3H), 2.53 (s, 6H), 7.06 to 7.46 (t, 1H), 7.93 to 8.23 (m, 1H), 9.26 to 9.5 (m, 2H)

Example 7

Synthesis of N- (2, 3, 4, 5-tetrachloro phenyl) -α- (bismethylthioylidene) acetoacetamide (8)

N- (2, 3, 4, 5-tetrachloro phenyl) aceto acetamide (31.4 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) The reaction was carried out together to obtain the desired product.

Yield: 26%

¹ H NMR (CDC1 ₃ ): δ2.56 (s, 3H), 2.63 (s, 6H), 7.33 (s, 1H), 8.7 (s, 1H)

Example 8

Synthesis of N- (4-trifluoromethyl phenyl) -α- (bismethyl thiylidene) aceto acetamide (9)

N- (4-trifluoromethyl phenyl) aceto acetamide (24.5 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above to obtain the desired product. Got.

Yield: 89%

¹ H NMR (CDC1 ₃ ): δ2.5 (s, 9H), 7.53 ~ 7.93 (m, 4H), 8.07 (s, 1H)

Example 9

Synthesis of N- (2-trifluoromethylphenyl) -α- (bismethyl thioylidene) aceto acetamide (10)

N- (2-trifluoromethyl phenyl) aceto acetamide (24.5 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above to obtain the desired product. Got.

Yield: 73%

¹ H NMR (CDC1 ₃ ): δ 2.46 (s, 9H), 7.1 to 7.76 (m, 3H), 8.23 to 8.53 (t, 2H)

Example 10

Synthesis of N- (2-hydroxyphenyl) -α- (bismethylthioylidene) acetoacetamide (11)

N- (2-hydroxy phenyl) aceto acetamide (19.3 g, 0.1 mole), carbon disulfide (9 ml, 0.15 mole) and iodine methane (36.9 g, 0.26 mole) were reacted as in Example 1 to obtain the desired product. Got it.

Yield: 75%

¹ H NMR (CDC1 ₃ ): δ9.73 (brs, 1H), 8.07∼6.57 (brs, 1H), 2.48 (s, 6H), 2.33 (s, 3H)

Example 11

Synthesis of N- (2-isopropenylphenyl) -α- (bismethylthioylidene) acetoacetamide (13)

N- (2-isopropenyl phenyl) aceto acetamide (21.7 g, 0.1 mole), carbon disulfide (9 ml, 0.15 mole) and iodine methane (36.9 g, 0.26 mole) were reacted as in Example 1 above to obtain the desired product. Got.

Yield: 78%

¹ H NMR (CDC1 ₃ ): δ2.1 (s, 3H), 2.43 (s, 9H), 5.0 to 5.33 (m, 2H), 6.97 to 7.4 (m, 4H), 8.5 (s, 1H)

Example 12

Synthesis of N- [2- (2-chloro-1,1,2-trifluoroethyl thio) phenyl] -α- (bismethylthio lylidene) aceto acetamide (15)

N- [2- (2-chloro-1,1,2-trifluoroethyl thio) phenyl] acetoacetamide (32.6 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mole) was reacted as in Example 1 to obtain the desired product.

Yield: 81%

¹ H NMR (CDC1 ₃ ): δ 9.22 (brs, 1H), 8.8 to 8.5 (m, 1H), 7.9 to 6.6 (m, 3H), 2.5 (s, 9H)

Example 13

Synthesis of N- (4-bromo-3-trifluoromethyl phenyl) -α- (bismethylthioylidene) acetoacetamide (16)

N- (4-bromo-3-trifluoromethyl phenyl) aceto acetamide (32.4 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) The reaction was carried out together to obtain the desired product.

Yield: 76%

¹ H NMR (CDC1 ₃ ): δ 2.4 (s, 3H), 2.47 (s, 6H), 7.67 ~ 8.03 (m, 3H), 9.08 (s, 1H)

Example 14

Synthesis of N- (4-hexylphenyl) -α- (bismethylthioylidene) acetoacetamide (17)

N- (4-hexyl phenyl) aceto acetamide (26.1 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 to obtain the desired product. .

Yield: 68%

¹ H NMR (CDC1 ₃ ): δ 0.8 to 0.97 (m, 1H), 1.1 to 1.83 (m, 10H), 2.47 (s, 9H), 7.08 to 7.63 (m, 4H), 8.5 (s, 1H)

Example 15

Synthesis of N- (4-pentyloxy phenyl) -α- (bismethylthioylidene) aceto acetamide (18)

N- (4-pentyloxy phenyl) aceto acetamide (26.3 g, 0.1 mole), carbon disulfide (9 ml, 0.15 mole) and iodine methane (36.9 g, 0.26 mole) were reacted as in Example 1 to obtain the desired product. Got it.

Yield: 74%

¹ H NMR (CDC1 ₃ ): δ 0.92 (m, 1H), 1.23 to 1.87 (m, 6H), 2.43 (s, 3H), 2.47 (s, 6H), 3.85 to 4.07 (t, J = 6.2 Hz , 2H), 6.8 to 7.63 (m, 4H), 8.55 (s, 1H)

Example 16

Synthesis of N- (4-fluoro-2-nitrophenyl) -α- (bismethylthioylidene) aceto acetamide (19)

N- (4-fluoro-2-nitrophenyl) aceto acetamide (24.0 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above. The desired product was obtained.

Yield: 63%

¹ H NMR (CDC1 ₃ ): δ2.7 (s, 9H), 7.23 ~ 8.93 (m, 3H), 10.98 (s, 1H)

Example 17

Synthesis of N- (4,5-difluoro-2-nitrophenyl) -α- (bismethylthioylidene) acetoacetamide (21)

N- (4,5-difluoro-2-nitrophenyl) aceto acetamide (25.8 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) The reaction was carried out together to obtain the desired product.

Yield: 68%

¹ H NMR (CDC1 ₃ ): δ2.53 (s, 9H), 8.03 to 9.1 (m, 2H), 11.03 (s, 1H)

Example 18

Synthesis of N- (4-Fluoro-2-trifluoromethyl phenyl) -α- (bismethylthioylidene) acetoacetamide (22)

N- (4-fluoro-2-trifluoromethyl phenyl) aceto acetamide (26.3 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were prepared as in Example 1 above. Reaction gave the desired product.

Yield: 73%

¹ H NMR (CDC1 ₃ ): δ2.5 (s, 9H), 7.0 to 7.45 (m, 2H), 8.13 to 8.57 (m, 2H)

Example 19

Synthesis of N- (4-chloro-3-trifluoromethyl phenyl) -α- (bismethylthioylidene) aceto acetamide (23)

N- (4-chloro-3-trifluoromethyl phenyl) aceto acetamide (28.0 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were prepared as in Example 1 above. Reaction gave the desired product.

Yield: 69%

¹ H NMR (CDC1 ₃ ): δ 2.47 (s, 3H), 2.5 (s, 6H), 7.43-8.2 (m, 3H), 9.17 (s, 1H)

Example 20

Synthesis of N- (3-trifluoromethyl phenyl) -α- (bismethylthioylidene) acetoacetamide (24)

N- (3-trifluoromethyl phenyl) aceto acetamide (24.5 g, 0.1 mole), carbon disulfide (9 ml, 0.15 mole) and iodine methane (36.9 g, 0.26 mole) were reacted as in Example 1 above to obtain the desired product. Got.

Yield: 78%

¹ H NMR (CDC1 ₃ ): δ2.5 (s, 9H), 7.4-8.07 (m, 4H), 8.93 (s, 1H)

Example 21

Synthesis of N- (4-chloro-2-nitrophenyl) -α- (bismethylthioylidene) aceto acetamide (25)

N- (4-chloro-2-nitrophenyl) aceto acetamide (25.7 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were reacted as in Example 1 above. The desired product was obtained.

Yield: 71%

¹ H NMR (CDC1 ₃ ): δ2.52 (s, 9H), 7.57∼8.93 (m, 3H), 10.8 (s, H)

Example 22

Synthesis of N- (2-nitro-4-trifluoromethyl phenyl) -α- (bismethylthioylidene) acetoacetamide (26)

N- (2-nitro-4-trifluoromethyl phenyl) aceto acetamide (29.0 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were prepared as in Example 1 above. Reaction gave the desired product.

Yield: 67%

¹ H NMR (CDC1 ₃ ): δ2.57 (s, 9H), 7.87-9.23 (m, 3H), 11.03 (s, 1H)

Example 23

Synthesis of N- (2,5-di-t-butylphenyl) -α- (bismethylthioylidene) acetoacetamide (27)

N- (2,5-di-t-butylphenyl) acetoacetamide (28.9 g, 0.1 mol), carbon disulfide (9 ml, 0.15 mol) and iodine methane (36.9 g, 0.26 mol) were prepared as in Example 1 above. Reaction gave the desired product.

Yield: 83%

¹ H NMR (CDC1 ₃ ): δ1.3 (s, 9H), 1.37 (s, 9H), 2.4 (s, 6H), 2.45 (s, 3H), 7.13-7.67 (m, 3H), 8.06 (s , 1H)

Example 24

Synthesis of N- (3-Fluoro-2-trifluoromethylphenyl) -α- (bismethylthioylidene) acetoacetamide (28)

N- (3-Fluoro-2-trifluoromethyl phenyl) aceto acetamide (36.9 g, 0.1 mole), carbon disulfide (9 ml, 0.15 mole) and iodine methane (36.9 g, 0.26 mole) were prepared as in Example 1 above. Reaction gave the desired product.

Yield: 74%

¹ H NMR (CDC1 ₃ ): δ 2.47 (s, 3H), 2.5 (s, 6H), 7.03 to 7.37 (m, 1H), 7.77 to 8.03 (m, 2H), 9.05 (s, 1H)

Example 25

Synthesis of N- (4-chloro-2-trifluoromethylphenyl) -α- [bis- (2.4-dichloro benzyl tier) -ylidene] aceto acetamide (29)

Carbon disulfide (9 ml, 0.15 mol) in a solution of N- (4-chloro-2-trifluoro methyl phenyl) aceto acet anilide (28.0 g, 0.1 mol), potassium carbonate (42 g, 0.3 mol) and 50 ml of dimethyl formamide Add. After about 15 minutes, 2, 4-dichlorobenzyl chloride (40.1 g, 0.205 mol) was slowly added dropwise for 30 minutes. After the reaction was completed, the reaction mixture was treated as in Example 1 above.

Yield: 27%

¹ H NMR (CDC1 ₃ ): δ9.97 (s, 1H), 7.87 ~ 7.07 (m, 9H), 4.33 (s, 4H), 2.25 (s, 3H)

Next, the bactericidal activity of the ketene dithio acetal α-analide derivative of the present invention prepared as in Example was measured by the following test method. At this time, 25mg of ketene dithio acetal α-anilide derivatives were dissolved in 100ml of acetone, and 90ml of Tween 20 250ppm aqueous solution was added to the concentration to 250ppm to investigate the protective dffect of the new compound. After adjustment, 50ml foliar spray was applied to the host plants of a certain size.

The plants sprayed with the medicament were left at room temperature for 24 hours to volatilize the solvent and water, and then inoculated with the pathogens prepared as follows. All experiments were conducted in duplicate.

Test Example 1 bactericidal effect on rice fever

Strains of pathogens (Pyricularia oryzae) were inoculated in rice bran agar medium (Rice Polish 20g, Dextrose 10g, Agar 15g, D.W.1ℓ) and incubated for 2 weeks in a 26 ℃ incubator. The medium on which the pathogen was grown was scraped off the surface of the medium with a rubber gallbladder to remove airborne hyphae, and spores were formed for 48 hours on a fluorescent lamp-turned shelf (25 to 28 ° C.).

Germ inoculation was suspended and the conidia were sprayed sufficiently to make a certain concentration of spore suspension (10 ⁶ spores / ml) using sterilized distilled water. The inoculated rice was placed in a dark state for 24 hours in a wet room, followed by 5 days in a constant temperature and humidity room with a relative humidity of 80% or more and a temperature of 26 ± 2 ° C. In the disease survey, the diseased area formed on the fully developed leaf just below the top leaf of the 3-4 leaf rice was examined based on the standard disease area.

Test Example 2 Bactericidal Effect on Rice Leaf House Blight

A proper amount of wheat flour was placed in a 1 L culture bottle, sterilized, inoculated with agar pieces of pathogen (Rhizoctonia solani) grown on potato agar medium for 3 days, and then incubated in a 27 ± 1 ° C. incubator for 7 days.

The bottle inoculation was crushed into moderately finely cultivated mycelial chunks, and evenly inoculated in the pot (5cm) where Nakdong rice of 2 ~ 3 leaf stages were grown, and then incubated in a humidified room (28 ± 1 ℃) and placed in a constant temperature and humidity room with relative humidity of 80% The pathogenesis was investigated later.

The incidence was investigated by comparing the area ratio of diseased lesions in the leaflets of 2 ~ 3 leaf seedlings based on the ratio of lesion area to leaflet area according to the comparison table.

Test Example 3 bactericidal effect on cucumber gray mold

Strains of pathogens isolated from tomatoes (Botrytis cinerea) were inoculated in potato agar medium (PDA) and plated in a 25 ° C. incubator and incubated for 15 days under light dark conditions to form spores. Spores formed on the medium were put into 10ml of distilled water of the plate, scraped with a brush, and then spores were filtered with gauze to harvest spores, and the spore concentration was 10 ⁶ / ml, followed by spraying one leaf cucumber. After treatment for 3 days at 20 ℃ in the wet room, the leaf area ratio of one leaf of the main leaf was examined.

For the test results of Test Examples 1 to 3, the control value was calculated according to the following equation, which is shown in Table 2 below.

Table 2 Measurement of bactericidal activity of ketene dithio acetal α-anilide derivative (I)

Claims (6)

Ketene dithio acetal α-analide derivative represented by the following structural formula (I).

Wherein R _1, R _2, R _3, and R ₄ are the same or different _, and are each hydrogen atom, aryl group, aryloxy group, alkyl group, alkenyl group, alkoxy group, thioalkyl group, aroyl group, haloalkyl group, halogen An atom, a nitro group, a cyano group, an arylsulfonyl group or a heterocycle group, R ₅ represents alkyl or a hydrogen atom or an aryl group substituted with halogen, and R ₆ represents an alkyl group or benzyl substituted or unsubstituted with halogen or alkyl halo Group. The method according to claim 1, wherein R _1, R _2, R _3, and R ₄ are all hydrogen atoms, phenyl or substituted phenyl group, phenoxy or substituted phenoxy group, C ₁ -C ₆ linear or branched alkyl group, C ₁ -C ₅ straight or branched alkenyl group, hydrogen or halogen substituted C ₁ -C ₅ straight or branched alkoxy group, hydrogen or halogen substituted C ₁ -C ₄ thioalkyl group, benzoyl or substituted A benzoyl group, a C ₁ -C ₄ straight or branched haloalkyl group, a halogen atom, a nitro group, a cyano group, a phenyl or a substituted phenylsulfonyl group or a heterocyclic group containing nitrogen such as imidazole, etc. Dithio α-anilide derivatives. The ketene dithio a-anilide derivative according to claim 1, wherein R ₅ is C ₁ -C ₃ linear or branched alkyl or a phenyl group substituted with a hydrogen atom or a halogen. According to claim 1, wherein R ₆ is C ₁ -C ₆ linear or branched alkyl group or C ₁ -C ₅ linear or branched alkyl group or C ₁ -C ₃ linear or branched haloalkyl or halogen is optional Ketene dithio α-anilide derivatives, characterized in that the benzyl group substituted in the benzene nucleus. Β-ketoanilide represented by the following structural formula (II) and carbon disulfide and alkyl halide, dialkyl sulfate or alkylalkyl or arylsulfonate represented by the following structural formula (III) are reacted in the presence of a base and represented by the following structural formula (I) A process for preparing ketene dithio acetal α-anilide derivatives.

R ₆ X (III) Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each as defined, X is a halogen atom selected from chlorine, bromine, iodine, or an alkylsulfate, alkyl or arylsulfonate Indicates. A horticultural fungicide characterized by containing the ketene dithio acetal α-anilide represented by the following general formula (I) as an active ingredient.

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each as defined above.