JP3014473B2 - Phenylcarbamate derivative, method for producing the same, and agricultural / horticultural fungicide containing the derivative as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenyl carbamate derivative, a method for producing the same, and a fungicide for agricultural and horticultural use containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Many fungicides have been developed and put to practical use for controlling disease on agricultural and horticultural crops. In particular, ergosterol biosynthetic inhibitors, which have recently attracted attention as EBI agents (ergosterol biosynthetic inhibitors), such as bitertanol, triadimefon, and fenarimol, have been used as fruit trees for scab (Venturia inaequalis) and scab (Cymnospora).
ngium yamadae), powdery mildew (Podosphaera leucotrich)
a), gray rot (Moniliniafructigena), powdery mildew on vegetables (Sphaerotheca fuliginea), powdery mildew on cereals (Erysiphe graminis), rust (Piccinia striiformi)
s, P.graminis, P.recondita), etc., have been found to have excellent control effects at low doses and are widely used today. However, the emergence of bacteria resistant to powdery mildew and the like in these series of EBI agents has led to problems that are difficult to control. In addition, these EBI agents can be used for diseases caused by so-called oomycetes (Phytophthpra melonis-cucumber disease, P. capsici-solanaceae disease, P. infestans-potato,
Tomato late blight, P. nicotiana-tobacco late blight, downy mildew (Pseudoperonospora cubensis-cucumber downy mildew, Plas)
mopara viticola-downy mildew, Pseudoperonospora
It is pointed out that it is ineffective for important diseases such as humuli-hop downy mildew. Currently, acylalanine compounds such as metalaxyl and oxadixyl have been developed and put to practical use against downy mildew and plague. The deadlock is getting worse.

Hitherto, dithiocarbamate fungicides such as mancozeb and manneb, TPN and captan have been widely used as agents for controlling these plagues and downy mildews, all of which require a high concentration of about 1500 ppm. . In addition, it is necessary to control disease in advance, and it is difficult to control the disease therapeutically after occurrence. In reality, disease control of agricultural and horticultural crops is performed more or less after symptoms appear, so that these fungicides also have a drawback that their effects cannot be sufficiently exerted. In addition, it has been pointed out that these bactericides have almost no control effect on the powdery mildew which occurs simultaneously.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned drawbacks of the prior art and exerts both preventive and therapeutic effects at lower doses, and is effective for downy mildew, plague, and powdery mildew. A novel compound having an excellent control effect on main diseases such as rust, and a fungicide for agricultural and horticultural use containing the compound as an active ingredient.

The present invention also provides a method for producing the compound in a high yield.

[0006]

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on various unsubstituted or substituted phenyl carbamate derivatives, and as a result, have found that substituted unsubstituted aminopyrimidines and ethylene bonds are bonded via ethylene bonds. The bound phenyl carbamate derivative shows a totally unexpected high bactericidal activity, especially the powdery mildew, downy mildew, plague,
The present inventors have found that the present invention is effective at a low dose for important rust diseases, and that the derivative has extremely low toxicity to warm-blooded animals, thereby completing the present invention. As described above, it is impossible to control the above-mentioned diseases widely using conventional fungicides, and other than the expectation of a certain control effect by mixing two or three agents, it is necessary to take measures. Therefore, it can be said that the contribution of the present invention is extremely large.

The phenyl carbamate derivative of the present invention is broadly defined as an alkylaminopyrimidine derivative disclosed in JP-A-2-85263, but is substituted or substituted with a substituted aminopyrimidine such as the compound of the present invention. Derivatives in which unsubstituted phenyl carbamates are bonded particularly via an ethylene bond are not disclosed in the publication. That is, the gazette specifically discloses only a compound in which a substituted aminopyrimidine and a substituted phenyl carbamate form a linear alkylene bond having 6 carbon atoms. (Compound No. 94)

[0008]

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Furthermore, the compound No. 94 has not been tested for insecticidal, acaricidal or bactericidal activity in terms of physiological activity. As a result, the inventors of the present invention performed a test for bactericidal activity after synthesizing a compound including compound No. 94 in the course of comparative study of a series of phenyl carbamate derivatives as described above. It has been found that this is not recognized, as shown in the comparative test examples of the examples of the present invention.

The bactericidal activity shown as an example in JP-A-2-85263 is an assay only for rice blast, and JP-A-2-85263 discloses that the phenyl carbamate derivative of the present invention should be the most characteristic. It is clear that no studies have been attempted on disease, plague, rust and powdery mildew. The present inventors have conducted intensive studies as described above, and found that the carbon number of the bonded alkylene in the substituted aminopyrimidine and the substituted or unsubstituted phenyl carbamate moiety plays a very important role in bactericidal properties. Preferably, it has been found that a bond of an alkylene having 3 or more carbon atoms, as disclosed in JP-A-2-85263, significantly inhibits bactericidal activity, and the present invention has been achieved.

The phenyl carbamate derivative of the present invention comprises
General formula (I)

[0012]

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(Wherein R ₁ is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group,
The same or different substituents selected from the group consisting of a lower haloalkyl group, a lower haloalkoxy group, a nitro group, a cyano group and an allyl group, and n represents an integer of 1 to 5.
X represents oxygen or sulfur, R _2, R ₃ represents a lower alkyl group optionally hydrogen atoms or identical or said, R ₄
Represents a halogen atom. ) And further includes an acid addition salt of the phenyl carbamate derivative. These added acids include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as alkylsulfonic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid, phenylphosphoric acid and alkylsulfuric acid. As the halogen atom for R _{1 in} the compound of the present invention, chlorine, bromine, fluorine, iodine, and the lower alkyl group include, for example, methyl group, ethyl group, n-
Examples of lower alkoxy groups such as propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group include methoxy group, ethoxy group, n-propoxy group,
-Propoxy group, n-butoxy group, i-butoxy group, se
Examples of lower alkylthio groups such as c-butoxy group and tert-butoxy group include methylthio group, ethylthio group, n
-Propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, etc .; lower haloalkyl groups include trifluoromethyl groups; and lower haloalkoxy groups include trifluoromethoxy groups.
Examples of the lower alkyl group of R ₂ and R ₃ which may be the same or different include a methyl group and an ethyl group. Examples of the halogen atom for R ₄ include chlorine, bromine, fluorine and iodine.

In the compounds of the present invention, when any one of the carbon atoms is an asymmetric carbon, there are various optical isomers and racemic compounds, and these are all included in the present invention. Table 1 shows typical examples of the phenyl carbamate derivative of the present invention represented by the above general formula (I) and acid addition salts thereof (hereinafter, referred to as the present compound), and physical properties thereof.

Table 1 No. R ₁ R ₂ R ₃ R ₄ X Acid Melting Point (° C.) Refractive Index 14 4-Cl HH Cl S 129 2 4-Cl HH Br O 136 3 3-Me HH Br O 95 4 2, 6-Me HH Br O 150 5 HHH Cl O 115 6 4-Br HH Cl O 124 7 2-Cl HH Cl O 95 8 3-Cl HH Cl O 92 9 4-Cl HH Cl O 131 10 4-Cl HH Cl O 1 (E) 115 11 4-Cl HH Cl O 1 (S) 160 12 4-Cl HH Cl O 1/2 (R) 80 13 4-Cl HH Cl O 1 (R) 163 14 4-Cl HH Cl O 1 (β) 1.529 15 4-Cl HH Cl O 1 (HD) 62 16 4-Cl HH Cl O 1 (OD) 163 17 4-Cl HH Cl O 1 (DB) 1.545 18 4-Cl HH Cl O 2 (DB) 1.509 19 4-Cl HH Cl O 3 (DB) 1.524 20 2,3-Cl Cl HH Cl O 103 21 2,4-Cl Cl HH Cl O 95 22 2,5-Cl Cl HH Cl O 104 23 2,5-DiCl HH Cl O 1 (DB) 1.549 24 2,6-DiCl HH Cl O 136 25 2,6-DiCl HH Cl O 1 (DB) 153 26 3,4-DiCl HH Cl O 145 27 3,5-ClCl HH Cl O 130 28 2,4,6-Tri Cl HH Cl O 141 29 2,4,6-Tri Cl HH Cl O 1 (DB) 35 30 2,3,4, 5-tetraCl HH Cl O 132 31 2-FHH Cl O 84 32 2-FHH Cl O 1 (DB) 92 33 3-FHH Cl O 84 34 4-FHH Cl O 113 35 2,4-4-FHH Cl O 89 36 2,4- ゛ FHH Cl O 1 (DB) 34 37 3,4- ゛ F HH Cl O 115 38 3,4- ゛ FHH Cl O 1 (DB) 35 39 4-IHH Cl O 105 40 3-NO ₂ HH Cl O 121 41 4-NO ₂ HH Cl O 187 42 4-NO ₂ HH Cl O 1 (DB) 158 43 4-CF ₃ HH Cl O 124 44 3-CN HH Cl O 119 45 3-Me HH Cl O 77 46 4-Me HH Cl O 117 47 2,3-diMeHH Cl O 127 48 2,4-diMe HH Cl O 118 49 2,4-diMe HH Cl O 1 (DB) 58 50 2,6-diMe HH Cl O 140 51 2,6-diMe HH Cl O 1 (DB ) 1.541 52 3,5-DiMe HH Cl O 109 53 3,5-DiMe HH Cl O 1 (DB) 57 54 2,4,5-Tri Me HH Cl O 136 55 2,4,5-Tri Me HH Cl O 1 (DB) 38 56 2,4,6-triMe HH Cl O 130 57 2-MeO HH Cl O 1.581 58 3-MeO HH Cl O 116 59 4-MeO HH Cl O 123 60 2,5-゛ MeS HH Cl O 79 61 2-MeS HH Cl O 89 62 3-MeS HH Cl O 87 63 3-Et HH Cl O 47 64 4-Et HH Cl O 104 65 2,6- ゛ Et HH Cl O 103 66 2,6-CiEt HH Cl O 1 (DB) 35 67 4-EtO HH Cl O 118 68 2,6-CiPr HH Cl O 139 69 2,6-CiPr HH Cl O 1 (DB) 45 70 4 -Phenyl HH Cl O 141 71 4-Phenyl HH Cl O 1 (DB) 48 72 2-Cl, 4-NO ₂ HH Cl O 132 73 2-Cl, 5-NO ₂ HH Cl O 115 74 2-Cl, 5 -NO ₂ HH Cl O 1 (DB) 34 75 2-C l, 5-CF ₃ HH Cl O 97 76 2-Cl, 5-CF ₃ HH Cl O 1 (DB) 33 77 2-Cl, 6-Me HH Cl O 112 78 2-Cl, 6-Me HH Cl O 1 (DB) 110 79 2-F, 4-Cl HH Cl O 95 80 2-F, 4-Cl HH Cl O 1 (DB) 35 81 3-F, 4-Me HH Cl O 103 82 2-NO ₂ , 4-Cl HH Cl O 102 83 2-NO ₂ , 4-Cl HH Cl O 1 (DB) 71 84 3-NO ₂ , 4-Cl HH Cl O 140 85 2-NO ₂ , 4-Me HH Cl O 63 86 2-NO ₂ , 4-Me HH Cl O 1 (DB) 34 87 3-NO ₂ , 4-Me HH Cl O 120 88 3-NO ₂ , 4-Me HH Cl O 1 (DB) 59 89 2 -CF ₃ , 4-Cl HH Cl O 120 90 2-Me, 4-Cl HH Cl O 116 91 2-Me, 3-NO ₂ HH Cl O 143 92 2-Me, 4-NO ₂ HH Cl O 143 93 2-Me, 4-NO ₂ HH Cl O 1 (DB) 117 94 2-Me, 5-NO ₂ HH Cl O 111 95 2-Me, 5-NO ₂ HH Cl O 1 (DB) 35 96 2-Me , 6-Et HH Cl O 118 97 2-Me, 6-Et HH Cl O 1 (DB) 35 98 2-Me, 6-iPr HH Cl O 141 99 2-Me, 6-iPr HH Cl O 1 (DB ) 35 100 2-Me, 6-tBu HH Cl O 143 101 2,6-diMe, 4-Br HH Cl O 137 102 2,6-diMe, 4-Br HH Cl O 1 (DB) 60 103 2 -Me, 6-tBu HH Cl O 1 (DB) 51 104 2-MeO, 5-Cl HH Cl O 112 105 2-MeO, 5-Cl HH Cl O 1 (DB) 142 106 2-MeO, 5-Me HH Cl O 80 107 2-Et, 6-iPr HH Cl O 89 108 2-Et, 6-iPr HH Cl O 1 (DB) 35 109 HH Me Cl O 135 110 3-Cl H Me Cl O 126 111 4-Cl H Me Cl O 153 112 4-Cl H Me Cl O 1 (E) 127 113 4 -Cl H Me Cl O 1 (S ) 165 114 4-Cl H Me Cl O 1/2 (R) 115 115 4-Cl H Me Cl O 1 (R) 1.522 116 4-Cl H Me Cl O 1 (MP ) 85 117 4-Cl H Me Cl O 1 (β) 1.590 118 4-Cl H Me Cl O 1 (HD) 42 119 4-Cl H Me Cl O 1 (OD) 180 120 4-Cl H Me Cl O 1 (DB) 45 121 2,3-DiCl H Me Cl O 1.588 122 2,4-DiCl H Me Cl O 89 123 3-FH Me Cl O 90 124 2,5-DiFH Me Cl O 97 125 2, 5- ゛ FH Me Cl O 112 126 2,5- ゛ FH Me Cl O 1 (DB) 1.540 127 2-CF ₃ H Me Cl O 83 128 2-CF ₃ H Me Cl O 1 (DB) 33 129 3- CF ₃ H Me Cl O 120 130 3,5-C CF ₃ H Me Cl O 152 131 3,5-C CF ₃ H Me Cl O 1 (DB) 43 132 4-CN H Me Cl O 143 133 2-Me H Me Cl O 1 (DB) 104 134 2-Me H Me Cl O 35 135 3-Me H Me Cl O 109 136 2,3- ゛ Me H Me Cl O 103 137 2,5- ゛ Me H Me Cl O 113 138 2,5-DiMe H Me Cl O 1 (DB) 1.536 139 3,4-DiMe H Me Cl O 128 140 3,4-DiMe H Me Cl O 1 (DB) 43 141 2-MeO H Me Cl O 62 142 2,5- ゛ MeO H Me Cl O 83 143 2,5-diMeO H Me Cl O 1 (DB) 1.521 144 3,5-diMeO H Me Cl O 155 145 2-Et H Me Cl O 91 146 3-Et H Me Cl O 93 147 2-iPr H Me Cl O 122 148 4-iPr H Me Cl O 157 149 2,6-diPr H Me Cl O 127 150 4-nBu H Me Cl O 112 151 4-nBu H Me Cl O 1 (DB) 45 152 4 -tBuO H Me Cl O 100 153 3-Cl, 4-FH Me Cl O 142 154 3-Cl, 4-FH Me Cl O 1 (DB) 38 155 3-F, 4-Me H Me Cl O 154 156 3 -F, 4-Me H Me Cl O 1 (DB) 39 157 3-CF ₃ , 4-Cl H Me Cl O 118 158 2-Me, 3-Cl H Me Cl O 115 159 2-Me, 3-Cl H Me Cl O 1 (DB) 110 160 2-Me, 5-Cl H Me Cl O 98 161 2-Me, 5-Cl H Me Cl O 1 (DB) 48 162 2-Me, 5-FH Me Cl O 117 163 2-Me, 5-FH Me Cl O 1 (DB) 34 164 2-Me, 4-Br H Me Cl O 110 165 2-Me, 4-MeO H Me Cl O 108 166 2-Me, 4- MeO H Me Cl O 1 (DB) 68 167 2-MeO, 3-Cl H Me Cl O 1.572 168 2-MeO, 5-Me H Me Cl O 119 169 2-MeO, 5-Me H Me Cl O 1 ( DB) 1.545 170 3-Cl H Et Cl O 117 171 3-Cl H Et Cl O 1 (DB) 34 172 4-Cl H Et Cl O 158 173 4-Cl H Et Cl O 1 (DB) 57 174 3- Me H Et Cl O 112 175 3-Me H Et Cl O 1 (DB) 106 176 H Me H Cl O 100 177 4-Br Me H Cl O 119 178 2-Cl Me HC l O 1.576 179 3-Cl Me H Cl O 1.578 180 4-Cl Me H Cl O 101 181 2,4-DiCl Me H Cl O 104 182 2,5-DiCl Me H Cl O 75 183 3-F Me H Cl O 92 184 4-F Me H Cl O 96 185 4-CF ₃ O Me H Cl O 99 186 4-Me Me H Cl O 83 187 2,6-diMe Me H Cl O 108 188 2-MeO Me H Cl O 1.574 189 3-MeO Me H Cl O 1.558 190 2,5-diMeO Me H Cl O 1.570 191 3-MeS Me H Cl O 77 192 4-Et Me H Cl O 109 193 4-EtO Me H Cl O 100 194 2-Me, 4-Cl Me H Cl O 135 195 H Et H Cl O 90 196 2-Cl Et H Cl O 1.568 197 3-Cl Et H Cl O 1.572 198 4-Cl Et H Cl O 125 199 3-F Et H Cl O 82 200 4-F Et H Cl O 76 201 4-NO ₂ Et H Cl O 61 202 4-CF ₃ Et H Cl O 95 203 4-CF ₃ O Et H Cl O 75 204 4 -Me Et H Cl O 27 205 2,5-diMe Et H Cl O 1.567 206 2,5-diMe Et H Cl O 121 207 4-Et Et H Cl O 1.564 208 4-EtO Et H Cl O 72 ( Notes) (1) Symbols other than the element symbols in Table 1 have the following meanings.

-Me: -CH ₃ (E): hydrochloric acid -MeO: -CH ₃ O (R): sulfuric acid -MeS: -CH ₃ S (S): nitric acid -Et: -C ₂ H ₅ (β): β- naphthalenesulfonic acid _{-EtO: -C 2 H 5 O (} HD): hexadecyl sulfate _{-iPr: -iC 3 H 7 (DB} ): dodecylbenzenesulfonate _{-tBu: -tC 4 H 9 (MP} ): monophenyl -tBuO _{phosphate: -tC 4 H 9 O (OD} ): numbers in the column of acid octadecyl sulfonate (2) table of 1 means the number of moles of added acid.

Next, a method for producing the compound of the present invention will be described. Production Method (I) A production method of the compound of the present invention represented by the general formula (I) is shown in a reaction scheme (1) and will be described in detail below. Reaction scheme (1)

[0018]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , n and X
Is the same as above. The above reaction is carried out in the presence of a catalyst in the absence of a solvent or in a solvent at 0 to 150 ° C., preferably 20 to 1
It is performed at a temperature of 00 ° C. The general formula (II) and the general formula (II
The molar ratio of the compound represented by I) is from 0.2 to 5.0, preferably from 0.9 to 1.1.

The catalyst includes a base catalyst and an acid catalyst. Examples of the base catalyst include organic bases such as pyridine, triethylamine, N-methylpiperidine, N, N-diethylaniline, sodium methoxide, potassium ethoxide, sodium acetate, and potassium acetate. And inorganic bases such as sodium carbonate; and acid catalysts include mineral acids such as hydrochloric acid and carbonic acid; and Lewis acids such as aluminum chloride, tin chloride and zinc chloride.

The solvent is not particularly limited as long as it does not participate in the reaction. For example, chlorinated solvents such as benzene, toluene, xylene, ethylbenzene, petroleum ether, hexane, heptane, chlorobenzene, methylene chloride, cyclohexane and the like are used. Aromatic or not,
Examples thereof include aliphatic and alicyclic hydrocarbons, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, and anisole.

The reaction product is usually isolated and purified by, for example, extraction, recrystallization, column chromatography and the like. Production method (II) A method for producing an acid addition salt of the compound represented by the general formula (I) is shown in a reaction scheme (2) and will be described in detail below.

Reaction scheme (2)

[0024]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , n and X are the same as described above, and A is a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like or an alkylsulfonic acid, an alkylbenzenesulfonic acid,
Shows organic acids such as naphthalenesulfonic acid. The above reaction is carried out by dissolving or suspending the compound represented by the general formula (I) in a solvent, adding an acid while stirring at a temperature of 0 to 120 ° C, preferably 20 to 80 ° C, for 0.1 to 2 hours. By doing so, an acid addition salt is obtained. At this time, the molar ratio of the compound represented by the formula (I) to the acid is 1: 1 to 3, preferably about 1: 1.

The solvent is not particularly limited as long as it does not participate in the reaction, but preferably dissolves the acid addition salt to be formed. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, chlorinated such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, methylene chloride, chloroform, or Aromatic and aliphatic hydrocarbons, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, and dioxane.

When the compound of the present invention is used as a fungicide for agricultural and horticultural use, it has a very low dose and a very high protective and curative effect on downy mildew, plague, powdery mildew and rust. Shows bactericidal effect. 65-260pp as chemical concentration
m is sufficient, and the dosage is lower than each fungicide conventionally applied to these diseases. In addition to the compound of the present invention alone, it can be used in combination with other fungicides, pesticides such as insecticides, herbicides, plant growth regulators, etc., soil conditioners or fertilizers.

The compound of the present invention is prepared using an auxiliary agent such as a solvent, a carrier, a surfactant and the like usually used as a pesticide in a pharmaceutical preparation, and put into practical use. That is, emulsions, wettable powders, powders, granules,
Each can be formulated into a dosage form such as a flowable agent. The carrier referred to here is divided into a solid carrier and a liquid carrier. As the solid carrier, an inorganic substance such as talc, kaolin, bentonite, calcium carbonate, zeolite,
Diatomaceous earth, silica gel, alumina, sulfur powder, ammonium sulfate and the like, and animal and plant organic substances include starch, soybean powder, wood flour, wheat flour, milk powder and the like. Examples of the liquid carrier include water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as dioxane and tetrahydronaphthalene, halogenated hydrocarbons such as dimethylchlorobenzene, and dimethylformamide. Examples include amines, ethyl acetate, esters such as glycerin esters of fatty acids, nitriles such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide.

When the compound of the present invention is used in actual applications, it is adjusted to dosage forms such as wettable powders, emulsions, powders, flowables, granules and the like, and the following auxiliary agents may be used. I can do it. Anionic surfactants such as lignin sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene alkyl phosphate, polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether, poly Examples include oxyalkylenealkylamines, polyoxyalkylene fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, calcium stearate, wax, casein, carboxymethylcellulose, polyvinyl alcohols, and the like, but are not limited thereto. The content of the compound of the present invention as an active ingredient in the composition is usually 20 to 75% by weight for wettable powders, 5 to 25% by weight for emulsions, 0.5 to 10% by weight for powders, and 0.1 for granules. 10 to 70% by weight, 10 to 70% by weight for a sloatable agent, 0.5 to 10% for a water solvent.
% By weight. However, there may be cases where these ratios are deviated. Among these preparations, when diluted with water and sprayed such as wettable powders, emulsions, flowables and aqueous solvents, the active ingredient concentration of the compound of the present invention which is usually applied is 65%.
Effective disease control can be achieved at about 260 ppm.

[0030]

The production method of the compound of the present invention will be described in more detail with reference to synthesis examples. Synthesis Example 1 4- (2- (2-chlorophenylcarbamoyl) -2-
Production of methylethylamino) -5-chloro-6-ethylpyrimidine (synthesis of compound No. 178) 4- (2-hydroxy-2-methylethylamino) -5
1.33 g (6.1 mmol) of -chloro-6-ethylpyrimidine
And 0.92 g of 2-chlorophenyl isocyanate (6.
0 mmol) is dissolved in 8 ml of benzene and
1 g was added and the mixture was stirred at 50 ° C. for 1 hour. After completion of the reaction, water was added and the mixture was extracted with benzene. After the benzene solution was dried over anhydrous sodium sulfate, benzene was distilled off under reduced pressure, and 2.18 g of the obtained crude product was purified by column chromatography (silica gel, developing solvent benzene-ethanol (20: 1)). 1.83 g of the product were obtained. n _D (25 ° C.) 1.576 ¹ H-NMR (CDCl ₃ ) δ (ppm) 1.23 (t, 3H), 1.36 (d, 2H),
2.76 (q, 2H), 3.70 (m, 2H), 5.16
(M, 1H), 6.96 (t, 1H), 7.25 (m, 3
H), 8.40 (s, 1H) Synthesis Example 2 Production of 4- (2- (4-chlorophenylcarbamoyl) ethylamino) -5-chloro-6-ethylpyrimidine (Synthesis of Compound No. 9) 4- ( 2-hydroxyethylamino) -5-chloro-6
1.25 g (6.2 mmol) of -ethylpyrimidine and 0.9 g (5.9 mmol) of 4-chlorophenylisocyanate were dissolved in 7 ml of benzene, and 0.1 g of pyridine was added, followed by stirring at room temperature for 2 hours. After completion of the reaction, water was added and the mixture was extracted with benzene. The benzene solution was dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure. The obtained crude product (2.1 g) was purified by column chromatography (silica gel, developing solvent benzene-ethanol (20: 1)) to obtain the desired product. 1.78g
I got 131 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm) 1.23 (t, 3H), 1.30 (d, 3H),
2.77 (q, 2H), 4.26 (m, 2H), 4.55
(M, 1H), 7.27 (m, 4H), 8.37 (s, 1
H) Synthesis Example 3 4- (2- (4-chlorophenylcarbamoyl) -1-
Production of methylethylamino) -5-chloro-6-ethylpyrimidine (synthesis of compound No. 111) 4- (2-hydroxy-1-methylethylamino) -5
1.33 g (6.1 mmol) of -chloro-6-ethylpyrimidine
And 0.9 g of 4-chlorophenyl isocyanate (5.9
mmol) in 8 ml of benzene and then 0.1 ml of pyridine
g was added and stirred at 50 ° C. for 1 hour. After completion of the reaction, water was added and the mixture was extracted with benzene. After the benzene solution was dried over anhydrous sodium sulfate, benzene was distilled off under reduced pressure, and 2.17 g of the obtained crude product was subjected to column chromatography (silica gel,
Purification with a developing solvent of benzene-ethanol (20: 1)) yielded 1.81 g of the desired product. Melting point 153 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm) 1.23 (t, 3H), 1.30 (d, 3H),
2.77 (q, 2H), 4.26 (m, 2H), 4.55
(M, 1H), 7.27 (n, 4H), 8.37 (s, 1
H) Synthesis Example 4 Production of 4- (2- (4-chlorophenylcarbamoyl) ethylamino) -5-chloro-6-ethylpyrimidine hydrochloride (Synthesis of Compound No. 10) 4- (2- (4-chlorophenylcarbamoyl) ) Ethylamino) -5-chloro-6-ethylpyrimidine 1.07 g
(3.0 mmol) in 15 ml of ethanol and then 3
0.33 g (3.3 mmol) of 6% hydrochloric acid aqueous solution was added, and the mixture was added at room temperature for 30 minutes.
For a minute. After completion of the reaction, ethanol and water were distilled off under reduced pressure to obtain 1.18 g of the desired product. 115 ° C. ¹ H-NMR (CD ₃ SOCD ₃ ) δ (ppm) 1.33 (t, 3H), 2.98 (q, 2H),
3.97 (q, 2H), 4.42 (t, 2H), 7.39
(D, 2H), 7.57 (d, 2H), 8.80 (s, 1
H) Synthesis Example 5 4- (2- (4-chlorophenylcarbamoyl) -1-
Production of methylethylamino) -5-chloro-6-ethylpyrimidine dodecylbenzenesulfonate (Compound No.
120) 4- (2- (4-chlorophenylcarbamoyl) -1-
1.1 g (3.0 mmol) of methylethylamino) -5-chloro-6-ethylpyrimidine are dissolved in 15 ml of ethanol and then 1.05 g of dodecylbenzenesulfonic acid (3.2 g).
mmol) and stirred at room temperature for 3 hours. After completion of the reaction, ethanol was distilled off under reduced pressure to obtain 2.15 g of the desired product. 45 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm) 0.87 (m, 6H), 1.23 (m, 15H),
1.40 (d, 3H), 1.56 (m, 3H), 2.40-2.
60 (m, 1H), 2.81 (q, 2H), 4.26 (m, 1H)
2H), 4.68 (m, 1H), 7.16 (m, 4H), 7.
40 (d, 2H), 7.80 (d, 2H), 8.52 (s,
1H) Synthesis Example 6 Compounds 1 to 8, 20 to 22, 24, 26 to 28, 30, 3 in Table 1 were treated in the same manner as in Production Examples 1 to 3.
1,33-35,37,39-41,43-48,5
0, 52, 54, 56 to 65, 67, 68, 70, 7
2,73,75,77,79,81,82,84,8
5,87,89-92,94,96,98,100,1
01, 104, 106, 107, 109, 110, 12
1-125, 127, 129, 130, 132, 13
3,135-137,139,141,142,144
~ 150,152,153,155,157,158,
160, 162, 164, 165, 167, 168, 1
70, 172, 174, 176, 177, 179-20
The compound shown as 8 was obtained. By treating in the same manner as in Production Examples 4 and 5, compound numbers 11 to 19 and 2
3,25,29,32,36,38,42,49,5
1,53,55,66,69,71,74,76,7
8,80,83,86,88,93,95,97,9
9, 102, 103, 105, 108, 112-11
9, 126, 128, 131, 134, 138, 14
0,143,151,154,156,159,16
1,163,166,169,171,173,175
Was obtained.

The following are specific formulation examples, but the carriers, surfactants and the like to be added are not limited to those listed in these examples. In the following, “parts” means “parts by weight”. Formulation Example 1-wettable powder 20 parts of compound No. 2, 56 parts of acid clay, 15 parts of white carbon, calcium ligninsulfonate 4
And 5 parts of polyoxyethylene alkylphenyl ether were uniformly mixed and pulverized to obtain 100 parts of a wettable powder. Formulation Example 2 Emulsion To 10 parts of the compound of Compound No. 70, 32.8 parts of xylene, 55 parts of dimethylformamide, and 2.2 parts of Newcargen ST-20 (manufactured by Takemoto Yushi) as an emulsifier were added and mixed and dissolved to obtain emulsion 100. Got a part. Formulation Example 3-Flowable Agent 30 parts of compound No. 3, 0.2 part of xanthan gum,
Sodium naphthalene sulfonate formaldehyde condensate 5 parts, polyoxyethylene nonyl phenyl ether 3
Part, 3 parts of propylene glycol and 61.8 parts of water were wet-pulverized with a sand grinder to obtain 100 parts of a flowable agent. Formulation Example 4-Granule 5 parts of compound No. 6, 3 parts of calcium ligninsulfonate, sodium dodecylbenzenesulfonate 1
Parts, 30 parts of bentonite, and 61 parts of clay are thoroughly crushed and mixed, water is added and kneaded well, and the mixture is granulated by an ordinary method using an extruder and dried.
00 parts were obtained. Formulation Example 5-Dust 10 parts of compound No. 8 (3 parts), 3 parts of white carbon, 30 parts of clay, and 64 parts of talc are uniformly mixed and pulverized.
0 parts were obtained.

Next, the bactericidal effect of the compound of the present invention will be specifically shown by test examples. The following compounds were used as comparative compounds for comparison. Comparative compound (a): Compound described in JP-A-2-85263 (Compound No. 94)

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Comparative compound (b): Compound described in JP-A-2-85263 (compound No. 50)

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Comparative compound (c): Compound described in JP-A-2-85263 (compound No. 53)

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Comparative compound (d): TPN (chlorothalonil) (a commercial fungicide)

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Comparative compound (e): Manzeb (commercial fungicide)

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Comparative compound (f): Triadimefon (commercially available fungicide)

[0043]

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Comparative compound (g): quinomethionate (commercial fungicide)

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Test Example 1 Test for Preventive Effect of Cucumber Downy Mildew A cucumber seedling of the 1.5 leaf stage (cultivar Sagami Hanshiro) cultivated in a plastic pot having a diameter of 6 cm was formulated into a wettable powder according to Formulation Example 1. A water dilution of the compound was evenly sprayed using a spray gun. One day after spraying, a zoospore spore solution of cucumber downy mildew (Pseudoperonospora cubensis) was spray-inoculated, left in a room with a high humidity of 25 ° C. for 24 hours, and maintained in a greenhouse until the investigation. Six days after the inoculation, the degree of onset was investigated according to the following criteria, and the control value (effect of suppressing onset) was calculated. The results are shown in Table 2. The meanings of the control values in Tables 2 and 3 are as follows.

Disease severity = B / A A: Number of leaves examined B: 100 × a + 50 × b + 25 × c + 12.5 × d + 6.
25 × ea a: the number of leaves in which a lesion is found in 50% or more of the leaves b: the number of leaves in which a lesion is found in 25 to 50% of the leaves c: the number of leaves in which a lesion is found in 12.5 to 25% of the leaves d : The number of leaves where the lesion is 6.25 to 12.5% of the leaves e: The number of leaves where the disease is observed and the lesion is 6.25% or less of the leaves Control value = [1-D / C] × 100 C: Degree of onset in untreated plot D: Degree of onset in treated plot Table 2 Test result of cucumber downy mildew prevention effect Compound No. Active ingredient concentration (ppm) Control value 1 256 100 64 100 2 256 100 64 100 9 256 100 64 100 10 256 100 64 100 15 256 100 64 100 22 256 100 64 100 33 256 100 64 100 43 256 100 64 100 45 256 100 64 100 50 256 100 64 100 57 256 100 4 100 62 256 100 64 100 81 256 100 64 100 90 90 256 100 64 100 111 256 100 64 100 122 256 100 64 100 173 256 100 64 100 177 256 100 64 100 179 256 100 64 100 180 256 100 64 100 64 100 Comparative compound (a) 256 48 64 0 Comparative compound (b) 256 33 64 0 Comparative compound (c) 256 45 640 Comparative compound (d) 512 83 128 45 Test example 2. Pepper disease prevention effect test 6 cm in diameter A four-leaf green pepper seedling (variety Ace) cultivated in a plastic pot was uniformly sprayed with a water dilution of the compound of the present invention formulated into an emulsion according to Formulation Example 2 using a spray gun. One day after spraying, the pepper fungus (Ph
Ytophthora capsici) was sprayed and inoculated, and allowed to stand in a room with a high humidity of 25 ° C. for 24 hours. Two days after the inoculation, the degree of onset was investigated according to the criteria of Test Example 1, and the control value was calculated. The results are shown in Table 3.

Table 3 Results of Test for Preventive Effect of Pepper Blight Compound No. Active ingredient concentration (ppm) Control value 5 256 99 38 256 100 47 256 100 57 256 99 67 256 96 78 256 100 112 256 100 113 256 100 115 256 100 117 256 100 118 256 97 121 256 100 143 256 97 156 256 100 169 256 98 180 256 97 182 256 100 189 256 99 197 256 100 Comparative compound (a) 256 24 Comparative compound (b) 256 13 Comparative compound (c) 256 20 Comparative Compound (e) 256 88 Test Example 3. Barley powdery mildew prevention effect test A 1.5-leaf stage barley seedling (variety Akagi Nijo) cultivated in a plastic pot having a diameter of 6 cm was milked according to Formulation Example 2. The aqueous dilution of the compound of the present invention prepared in the formulation was uniformly sprayed using a spray gun. One day after spraying, the contaminated spores of barley powdery mildew (Erysiphe graminis) were placed in close proximity to diseased seedlings producing a large number of conidia, so that the disease was naturally caused.
Six days after the application of the drug, the degree of onset was investigated according to the following criteria, and the control value was calculated. Table 4 shows the results. Table 4,
The meaning in Table 5 is as follows.

Disease severity = B / A A: Number of leaves examined B: 100 × a + 50 × b + 25 × c + 12.5 × d + 6.
25 x ea: number of leaves with 30 or more lesions b: number of leaves with 15 to 29 lesions c: number of leaves with 8 to 14 lesions d: 4 to 7 lesions Number of observed leaves e: Number of leaves having 1 to 3 lesions Control value = [1-D / C] x 100 C: Disease severity in untreated plot D: Disease magnitude in treated plot Table 4 Barley powdery mildew Preventive effect test result Compound number Active ingredient concentration (ppm) Control value 4 256 100 10 256 100 13 256 97 15 256 100 16 256 100 17 256 100 18 256 256 19 19 256 96 55 256 96 79 256 98 80 256 100 91 256 100 101 256 100 120 256 98 132 256 98 159 256 99 166 256 100 172 256 100 174 256 100 185 56 100 Comparative compound (a) 256 28 Comparative compound (b) 256 0 Comparative compound (c) 256 0 Comparative compound (f) 256 87 Test Example 4. Wheat rust prevention effect test Cultivated in a plastic pot with a diameter of 6 cm 1. A five-leaf barley seedling (variety Norin 61) was evenly sprayed with a water dilution of the compound of the present invention prepared in a flowable according to Formulation Example 3 using a spray gun. One day after spraying, a uredospore extract of wheat leaf rust (Puccinia recondita) was sprayed and inoculated, left in a room with a high humidity of 25 ° C for 24 hours, and maintained in a greenhouse until the investigation. Ten days after the inoculation, the degree of onset was investigated according to the criteria of Test Example 3, and the control value was calculated.
Table 5 shows the results.

Table 5 Results of Wheat Rust Prevention Effect Test Compound No. Effective ingredient concentration (ppm) Control value 3 256 100 6 256 100 28 256 100 34 256 100 35 256 100 41 256 100 46 256 100 51 256 100 64 256 100 69 256 95 71 256 97 86 256 100 128 256 100 134 256 100 141 256 100 178 256 99 183 256 100 184 256 100 191 256 96 193 256 100 201 256 100 203 256 100 204 256 100 205 205 256 100 Compound (256) 38 Comparative compound (b) 256 24 Comparative compound (c) 256 32 Comparative compound (f) 256 85 Test Example 5. Therapeutic effect of cucumber powdery mildew Cucumber seedlings cotyledon stage were cultivated in plastic pots of a test diameter 6 cm (cultivar Sagamihanpaku), conidia Ken Nuo liquid of cucumber powdery mildew (Sphaerotheca fuliginea) were inoculated by spraying. Five days after inoculation, a water-diluted solution of the compound of the present invention formulated in a wettable powder according to Formulation Example 1 was evenly sprayed on cucumber seedlings at an early stage of disease onset using a spray gun. Seven days after spraying, the therapeutic effect on the cotyledons of the cucumber seedlings was investigated according to the following criteria. Table 6 shows the results. The numbers in the effect column mean the following.

5: No recurrent lesion is observed. 4: Disease incidence is low. 3: Moderate onset. 2: There are many cases. 1: Significant onset, comparable to untreated plot.

[0052] Table 6 Cucumber Powdery Mildew Test of Curative Effect on results Compound No. active ingredient concentration (ppm) Effect 5 256 5 9 256 5 34 256 5 45 256 5 90 256 5 111 256 5 Comparative Compound (a) 256 1 comparative compound (b ) 256 1 Comparative compound (c) 256 1 Comparative compound (g) 256 3

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Industrial Applicability The phenylcarbamate derivative of the present invention represented by the general formula (I) and the acid addition salt thereof are excellent as fungicides for agricultural and horticultural use in controlling various crop diseases. In particular, it has an excellent control effect at a very low concentration on diseases such as downy mildew, plague, powdery mildew, and rust, which could not be controlled by a conventional fungicide alone. Extremely useful.

Continuation of the front page (72) Inventor Toshio Oshida 6992 Goi, Ichihara-shi, Chiba Maruzen Petrochemical Iwasaki Ryo (56) References JP-A-2-300176 (JP, A) JP-A-57-206651 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 239/42 A01N 47/20 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) (Wherein R ₁ is the same or different from the group consisting of a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a lower haloalkyl group, a lower haloalkoxy group, a nitro group, a cyano group and an allyl group) A substituent, n represents an integer of 1 to 5. X represents oxygen or sulfur, R ₂ and R ₃ represent a hydrogen atom or a lower alkyl group which may be the same or different, and R ₄ represents a halogen atom. The phenyl carbamate derivative represented by the formula: or an acid addition salt thereof. 2. A compound of the general formula (II) (Wherein R ₂ , R ₃ , and R ₄ have the same meanings as in claim 1) by converting the compound represented by the general formula (III) into (Wherein R ₁ , n, and X have the same meanings as in claim 1). The production of a phenyl carbamate derivative or an acid addition salt thereof according to claim 1, characterized by reacting with a compound represented by the formula: Law. 3. A downy mildew, a powdery mildew, a rust, comprising at least one compound according to claim 1 as an active ingredient.
An agricultural and horticultural fungicide for plague.