Claims
- 1. A substituted 4-amino-2-oxaindan having the formula: ##STR50## wherein R.sub.1 stands for a methyl or ethyl group.
Priority Claims (7)
| Number |
Date |
Country |
Kind |
| 62-281563 |
Nov 1987 |
JPX |
|
| 62-281564 |
Nov 1987 |
JPX |
|
| 62-281565 |
Nov 1987 |
JPX |
|
| 63-177751 |
Jul 1988 |
JPX |
|
| 63-191919 |
Jul 1988 |
JPX |
|
| 63-191920 |
Jul 1988 |
JPX |
|
| 63-193598 |
Aug 1988 |
JPX |
|
[Method (A)]
This is a divisional of copending application(s) Ser. No. 07/259,283 filed on Oct. 18, 1988 now U.S. Pat. No. 4,877,441.
The present invention relates to substituted carboxylic acid derivatives, processes for preparing the same and agricultural or horticultural fungicides containing the same as an active ingredient.
Fungicidal activity of some carboxylic acid derivatives is reported in e.g., Japanese patent Kokai Nos. 52-87168, 58-96069 and 60-34949, U.S. Pat. No. 4134987, G. A. Whites: "Pesticide Biochemistry and Physiology 14, 26 (1980), J. L. Huppatz: Aust. J. Chem. 36, 135 (1983), B. Janks: Pestic. Sci., 2, 43, 1971, DEOS 2611601, Chem. Abst. 70, 87799j (S. African 67 06, 681 Uniroyal Inc.), G. A. White et al.: "Pesticide Biochemistry and Physiology 5, 380-395, 1975 and M. Shell et al.: Phytopathology 60, 1164-1169, 1970. However, chemicals have been demanded which have higher fungicidal activity, since those known compounds are not satisfactory in activity.
After extensive research on compounds having high fungicidal activity has been made, the present inventors find substituted carboxylic acid derivatives (hereinafter referred to as the present compound) having the formula: ##STR3## wherein R.sub.1 stands for a methyl or ethyl group; A stands for ##STR4## R.sub.2 stands for a methyl, ethyl or trifluoromethyl group; R.sub.3 stands for a methyl group or a halogen or hydrogen atom; R.sub.4 stands for a fluorine or hydrogen atom; R.sub.5 stands for a methyl, nitro, or trifluoromethyl group or a halogen atom; Z stands for a .dbd.CH--group or an N atom; R.sub.6 stands for a methyl, ethyl or trifluoromethyl group; and R.sub.7 stands for an amino, methyl group or a chlorine atom.
According to the present invention, processes for preparing the present compound and agricultural or horticultural fungicides containing the present compound as an active ingredient are provided, too.
The present compound has preventive, curative and systemic controlling effects on various plant microbes, especially on plant diseases caused by microbes belonging to Basidiomycetes and gives almost no adverse influence to environment.
The following are plant diseases on which the present compound has an excellent controlling effect; Rhizoctonia solani and Rhizoctonia oryzae, R. solani III B on rice plant; Puccinia striiformis, P. graminis, P. recondita, P. hordei, Typhula incarnata, T. ishikariensis, Ustilago tritici and U. nuda on wheat and barley; Rhizoctonia solani and Corticium rolfsii on various crops; Rhizoctonia solani on potato and beet; Gymnosporangium haraeanum on pear; Venturia inaequalis on apple; Rhizoctonia solani, Corticium rolfsii, Uromyces trifolii and Typhula incarnata, T. ishikariensis on pasture and lawn.
Preferred compound among the present ones from a view point of fungicidal activity is a substituted carboxylic acid derivative having the formula: ##STR5## wherein R.sub.1, R.sub.2 and R.sub.3 are the same as those defined above, more preferred is one having the formula: ##STR6## wherein R.sub.8 stands for a methyl or trifluoromethyl group and R.sub.9 stands for a halogen atom, and the most preferred ones are ##STR7##
The present compound includes optically active isomers thereof which owe to an asymmetric carbon atom existed therein. One of the isomers is a substituted carboxylic acid derivative having the formula: ##STR8## wherein R.sub.1, R.sub.2 and R.sub.3 have the same meanings as those defined above.
Method for preparing the present compound will be explained in detail below.
Among the present compounds, a substituted carboxylic acid derivative having the formula: ##STR9## wherein A and R.sub.1 have the same meanings as those defined above, is prepared by allowing a substituted carboxylic acid having the formula:
The reaction is usually conducted in the presence of solvent which is not always necessary. The solvents are, for example, hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene, methylene chloride, chloroform and carbon tetrachloride, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile, dimethylsulfoxide, dimethylformamide, water, etc., preferably tetrahydrofuran.
Amounts of the reagents used in said reaction are 0.4-1.5 equivalents, preferably 0.5-1.1 equivalents of the substituted carboxylic acid represented by the formula (III) or reactive derivative thereof per equivalent of the substituted 4-amino-2-oxaindan represented by the formula (IV).
The reaction is carried out at optional temperature from the freezing point to the boiling point of the solvent, preferably from 0.degree. C. to the boiling point of the solvent.
The substituted carboxylic acid represented by the formula (III) or reactive derivative thereof includes the corresponding carboxylic acids, acid anhydrides, acid chlorides, acid bromides, carboxylic esters, etc.
The reaction may be conducted in the presence of a reaction assistant depending on the substituted carboxylic acids represented by the formula (III) or reactive derivatives thereof. The reaction assistant is, for example, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimidemethiodide and dicyclohexylcarbodiimide when carboxylic acid is used, sodium hydride, sodium methylate, sodium ethylate, etc. when carboxylic ester is used, and sodium hydroxide, potassium hydroxide, triethylamine, N-methylmorpholine, pyridine etc., when acid halide or acid anhydride is used. The reaction assistant is usually used in an amount of from a catalytic amount to 2 equivalents, preferably 0.95-1.1 equivalents.
After the reaction is over, the reaction assistant or reaction products thereof are removed by filtration or washing with water. The solvent was removed by distillation to give the desired substituted carboxylic acid derivatives of the formula (I). If necessary, the product is further subjected to chromatography, recrystallization, etc. in order to purify the same.
Among the present compounds, a substituted carboxylic acid derivative having the formula (II) is produced by allowing a substituted carboxylic acid having the formula: ##STR11## wherein R.sub.2 and R.sub.3 are the same as those defined above, or a reactive derivative thereof to react with a substituted 4-amino-2-oxaindan having the formula: ##STR12## wherein R.sub.1 is the same as that defined above.
The reaction is usually conducted in the presence of solvent, which is not always necessary Examples of the solvent are hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene, methylene chloride, chloroform and carbon tetrachloride, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile, dimethylsulfoxide, dimethylformamide and water, preferably tetrahydrofuran.
Amounts of the reagents are 0.4-1.5 equivalents, preferably 0.5-1.1 equivalents of the substituted carboxylic acid represented by the formula (V) or reactive derivatives thereof per equivalent of the substituted 4-amino-2-oxaindan represented by the formula (VI).
The reaction is conducted at a temperature of from the freezing point to the boiling point of the solvent, preferably from 0.degree. C. to the boiling point of the solvent.
The substituted carboxylic acid having the formula (V) or reactive derivatives thereof are the corresponding carboxylic acids, acid anhydrides, acid chlorides, acid bromides and carboxylic esters.
The reaction may be conducted in the presence of a reaction assistant depending on the substituted carboxylic acids having the formula (V) or reactive derivatives. Reaction assistants are, for example, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimidemethiodide and dicyclohexylcarbodiimide when carboxylic acid is used; sodium hydride, sodium methylate and sodium ethylate when carboxylic ester is used; and sodium hydroxide, potassium hydroxide, triethylamine, N-methylmorpholine and pyridine when acid halide or acid anhydride is used. The reaction assistant is usually used in an amount of from a catalytic amount to 2 equivalents, preferably 0.95-1.1 equivalents.
After the reaction is over, the reaction assistant or reaction products thereof are removed by filtration or washing with water. The solvent was removed by distillation to give the desired substituted carboxylic acid derivatives of the formula (II). If necessary, the product is further subjected to chromatography, recrystallization, etc. in order to purify the same.
Among the present compounds, a substituted carboxylic acid derivative having the formula: ##STR13## wherein R.sub.1 and R.sub.6 are the same as those defined above and R.sub.10 stands for an amino or methyl group is prepared by allowing a substituted 4-amino-2-oxaindan derivative having the formula: ##STR14## wherein R.sub.1 and R.sub.6 are the same as those defined above, to react with a thioamide derivative having the formula: ##STR15## wherein R.sub.10 is the same as that defined above.
The reaction is usually conducted in the presence of a solvent which is not always necessary. Examples of the solvent are hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, esters such as ethyl acetate, alcohols such as methanol and ethanol, dimethylsulfoxide, dimethylformamide and water.
Amounts of the reagents are not critical but usually 0.5-10 equivalents, preferably 1-3 equivalents of the thioamide derivative having the formula (IX) per equivalent of the substituted 4-amino-2-oxaindan derivative having the formula (VIII).
The reaction is conducted at a temperature of from the freezing point of the solvent to the boiling point thereof, preferably from 0.degree. C. to the boiling point of the solvent.
The reaction may be conducted in the presence of a base as a reaction assistant. The base is, for example, ammonia water, amines such as triethylamine and N-methylmorpholine, and inorganic bases such as potassium carbonate and sodium carbonate.
After the reaction is over, the reaction assistant or reaction products thereof are removed by filtration or washing with water, and then the filtrate is subjected to distillation to remove the solvent until the desired substituted carboxylic acid derivative having the formula (VII) is obtained. If necessary, the product may be purified by, for example, chromatography.
Among the present compounds, a substituted carboxylic acid derivative having the formula (II) is also prepared by subjecting a substituted carboxylic acid derivative having the formula (I') to an optically active column, for example, "Sumipack OA".RTM.4100 (Sumika Chemical Analysis Service Ltd.) until a separation is made.
Substituted 4-amino-2-oxaindan having the formula (IV), one of the starting materials for preparing the present compound, is prepared, for example, from 4-acetaminophthalide mentioned in Jean Vene and Jean Tirouflet Compt rend 231, 911-12 (1950): ##STR16## wherein R.sub.1 is the same as that defined above.
That is, 4-acetaminophthalide is allowed to react with a methyl Grignard reagent such as methylmagnesium iodide (4-12 equivalents) in an ether solvent such as diethyl ether and tetrahydrofuran at a temperature from -10.degree. C. to room temperature, until diol (a) is obtained. The diol (a) is allowed to react with activated manganese dioxide (5-20 equivalents) in an ether solvent such as dioxane and tetrahydrofuran or a halogenated hydrocarbon solvent such as chloroform and dichloroethane under refluxing to obtain lactone (b). Then, the lactone (b) is allowed to react with methyllithium or ethyllithium (2-4 equivalents) in an ether solvent such as diethyl ether and tetrahydrofuran at a temperature from -30.degree. C. to room temperature until acetal (c) is obtained. The acetal (c) is allowed to react with hydrogen in an alcohol solvent such as methanol and ethanol at room temperature in the presence of catalytic amounts of palladium carbon and conc. hydrochloric acid until anilide (d) is obtained. The anilide (d) is then allowed to react with alkali metal hydroxide such as sodium hydroxide and potassium hydroxide (5-20 equivalents) in an ethylene glycol and water solvent under refluxing, until substituted 4-amino-2-oxaindan (IV) is obtained.
Substituted 4-amino-2-oxaindan having the formula (VI) may be obtained by, for example, optical resolution of substituted 4-amino-2-oxaindan (IV) with (1) optically active carboxylic acid or (2) an optically active column.
When the present compound is used as an active ingredient of fungicides, it may be used without adding any other components, but usually, it is formulated into emulsifiable concentrates, wettable powders, suspension formulations, granules, dusts, liquids and the like by mixing with a solid or liquid carrier, a surface active agent and other auxiliaries for formulation.
The content of the present compound as an active ingredient in these formulations is 0.1 to 99.9%, preferably 0.2 to 80% by weight.
The solid carriers include, for example, fine powders or granules of kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn starch powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide and the like. The liquid carrier includes for example aromatic hydrocarbons such as xylene, methylnaphthalene and the like, alcohols such as isopropanol, ethylene glycol, cellosolve and the like, ketones such as acetone, cyclohexanone, isophorone and the like, vegetable oils such as soybean oil, cotton seed oil and the like, dimethyl sulfoxide, acetonitrile, water and the like.
The surface active agents used for emulsification, dispersion, wetting, etc. include, for example, anionic surface active agents such as salts of alkyl sulfate, alkyl (aryl) sulfonates, dialkyl-sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, naphthalenesulfonic acid/formalin condensates, etc. and nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. The auxiliaries for formulation include , for example, lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (acid isopropyl phosphate), etc.
These formulations as such or diluted with, for example, water are applied to soil or directly to plants. In more detail, they are used in various forms, e.g., spraying or dusting on plants or spraying, dusting or granule-sprinkling onto soil surface or if necessary, subsequent further soil incorporation. Furthermore, when they are used as seed treating agents, seeds are covered therewith or dipped therein. These formulations may also be used in admixture with other fungicides, insecticides, acaricides, nematocides, herbicides, plant growth regulating agent, fertilizers, soil improvers and the like.
The present compounds are used as an active ingredient of fungicides to be used for paddy field, plowland, orchard, pasture, turf and the like.
When the present compound is used as an active ingredient of fungicide, its dosage is usually 0.5 to 100 g, preferably 1 to 50 g per are, although it depends on weather conditions, form of formulations, time, method and place of application, diseases to be controlled, crops to be treated, etc. When the emulsifiable concentrate, wettable powder, suspension formulation, liquid formulation, etc. are diluted with water for use, the concentration is 0.0001 % to 1 %, preferably 0.0005 % to 0.5 %. Granule and dust are used as they are without any dilution.
The present compound is able to be used as an active ingredient of fungicides for various kinds of applications, since the present compound is remarkably active against various plant diseases, particularly those by microorganisms belonging to Basidiomycetes.
The present invention will be explained in more detail by the following synthesis examples, reference examples, formulation examples and test examples.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
| 4816592 |
Maggioni et al. |
Mar 1989 |
|
Divisions (1)
|
Number |
Date |
Country |
| Parent |
259283 |
Oct 1988 |
|
Patent Grant
5004816
