JPS61129156A - Substituted propargyloxyacetonitrile derivative, preparation thereof, and herbicide and agricultural and horticultural fungicide containing said derivative - Google Patents

Abstract

NEW MATERIAL:A substituted propargyloxyacetonitrile derivative. EXAMPLE:alpha-(3-Bromopropargyloxy)-4-fluorobenzoylaminoacetonitrile. USE:Herbicide and agricultural and horticultural fungicide. It has wide application range as a herbicide for paddy field, and low toxicity to crops and fish. It is useful as a fungicide for the prevention and remedy of various plant diseases such as downey mildew, etc., and exhibits excellent controlling such as downey mildew, etc., and exhibits excellent controlling effect to the sol vermin such as the vermin of damping-off. PREPARATION:The titled compound can be prepared by (1) reacting the acid chloride of formula A-COCl (A is pheynl, 2-fluorophenyl, naphthyl, etc.) with aminoacetonitrile, (2) treating the resultant acylaminoacetonitrile with a halogena tion agent, and (3) reacting with 3-bromopropargyl alcohol, 3-chloropropargyl alcohol, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to α-(3-bromopropargyloki/)-4-
Fluorobenzoylaminoacetonitrile, α-(5-
bromopropargyloxy)-3-promobenzoylaminoacetonitrile, α-(6-bromopropargyloxy)-6-methoxybenzoylaminoacetonitrile, α-(5-bromopropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(5-bromopropargyloxy)-3,5-dimethoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,4-methylenedioxybenzoylaminoacetonitrile, α-(6-bromopropargyloxy/) -5-1-Lifluoromethylbenzoylaminoacetonitrile, α-(6-bromopropargyloxy)-4-trifluoromethylbenzoylaminoa pseudotonitrinope α-(3-bromopropargyloxy)-6
-nitrobenzoylaminoacetonitrile, α-(3-
bromopropargyloxy)-3-7anopenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,4-dimethylbenzoylaminoacetonitrile, α-(5-bromopropargyloxy)-1-
Naphthoylaminoacetonitrile, α-(S-bromopropargyloxy)-,2-naphthoylaminoacetonitrile, α-(3-chloropropargyloxy)-5
-chlorobenoylaminoacetonitrile, α-(3-
Chloropropargyloxy7)-3,5-dichlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)
Benzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-
4-Chlorobenzoylaminoacetonitrile, α-(1
-methylfuropargyloxy)-2-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α-(1-methylfuropargyloxy7)-4-fluorobenzoylamino Acetonitrile, α-(1-methylfuropargyloxy)-5--y” lomobenzoylaminoacetonitrile, α-(1-methylfuropargyloxy)-6-methylbenzoylaminoacetonitrile, α-(1-methylfuropargyloxy)-6-methylbenzoylaminoacetonitrile, (pargyloxy)-4-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-6-methylbenzoylaminoacetonitrile α -(1-methylpropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(1-methylfuropargyloxy) -3,5-dimethoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy) -3,4 ~Methylenenoquine benzoylaminoacetonitrile IJ /L/, α-(1-methylglobargyloxy7)-3-trifluoromethylbenzoylaminoacetonitrile, α-(1-methylfuropargyloxy)-3-nitrobenzoyl Aminoacetonitrile, α-(1-methylfuropargyloki7) -3--
Cyanopenzoylaminoacetonitrinope α-(1-
methylpropargyloxy)-3,4-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-naphthoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α- (1-ethylpropargyloxy/)-3-chlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)
-3,5-dichlorobenzoylaminoacetonitrile α-(1-ethylpropargyloxy) -3-)
IJ Fluoromethylbenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-methoxybenzoylaminoacetonitrile and α-(1-
The present invention relates to a substituted propargyloxyacetonitrile derivative selected from (ethylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, a method for producing the same, and a herbicide for paddy fields or a fungicide for agriculture and horticulture containing the same.

[Prior art]

A great deal of research has been carried out on amide derivatives useful in agriculture and horticulture, and many compounds exhibiting characteristic physiological activities have been discovered and put into practical use.

For example, substituted benzamide derivatives include ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate (benzoylprop-ethyl) as a herbicide, and 2-methyl-N-(3-aminoprop-ethyl) as a fungicide. -isopropoxyphenyl)benzamide (mepronil) and the like are known.

In addition, as -aryloxyacetonitrile derivatives, JP-A-57-167978, 57-176958 and 5
B-69866 discloses herbicides and fungicides.

Among them, JP-A-57-176938 discloses allyloxyacetonitrile derivatives, but there is no description of substituted propargyloxyacetonitrile derivatives.

Further, in JP-A-57-176938, the use of allyloxyacetonitrile derivatives as fungicides and herbicides is mentioned.

Herbicides have been tested for their herbicidal activity before and after germination, as well as their phytotoxicity against sugar beets, rapeseed, cotton, soybeans, corn, wheat, and rice.

Selective crops include cotton, sugar beet, rapeseed, lettuce, and peas, and it is specified that these derivatives are useful compounds for crops of the Asteraceae and Fabaceae families. No selectivity has been found for rice, and rice is considered to be a crop to which these compounds cannot be applied. Although many herbicides such as amide compounds, thiol carbamate compounds, and diphenyl ether compounds have been developed and put into practical use as herbicides for paddy fields, their performance is still not sufficient. The amide compound butachlor is used before and after rice planting, but chemical damage to rice caused by temperature conditions has always been a problem. The use of the thiol carbamate compound molinate is regulated due to fish toxicity. Furthermore, Benthiocarb poses a problem of phytotoxicity to paddy rice under reducing soil conditions. Diphenyl ether compounds, like butachlor, are used immediately after rice planting, but their activity drops significantly if the treatment is delayed.

All of these herbicides have excellent performance in some respects, and are therefore widely used in reality. There is a strong demand for herbicides for paddy fields that have excellent performance.

On the other hand, the compound described in JP-A No. 57-176958 is said to be effective as a fungicide against podobe rot and tomato late blight. Captafor, TPN, cabtan, or dithiocarbamate drugs are widely used to treat late blight and downy mildew of various crops, and have contributed to increased crop production. However, all of these compounds mainly have a preventive effect against late blight and downy mildew, and cannot be expected to have any therapeutic effect. Therefore, it has a major drawback in that sufficient effects cannot be expected even when the occurrence of disease is recognized. In reality, when considering the spraying of chemicals to control crop diseases, they are more or less sprayed after the disease has appeared, and it is difficult to completely control the disease with these compounds. In order to improve these points, research into new pest control agents has continued, and now N-phenylalanine ester derivatives, such as metalaxis (N-(
2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alanine methyl ester] and the like have been developed and are being put into practical use worldwide. However, the resistance of these N-phenylalanine ester derivatives to bacteria has already become a problem.

In addition, a method conventionally proposed as a method for producing substituted aminoacetonitrile derivatives (Japanese Patent Application Laid-Open No. 57-176958
No. 5B-69866), in the halogenation step, a hydrolysis reaction of the nitrile group occurs to form a carbamoyl derivative, so the desired acetonitrile derivative is obtained by, for example, alkoxylating the halogen and then dehydrating the carbamoyl group. This required a long process, and the yield was low.

[Problem to be solved by the invention]

The present invention overcomes the drawbacks of the prior art described above, and provides a compound having extremely excellent properties as a herbicide for paddy fields and a fungicide for agriculture and horticulture, a method for producing the compound, and a noxious weed control agent containing the compound as an active ingredient. The objective is to provide a microbial control agent.

In other words, as a herbicide, it is suitable for use in paddy fields during a wide range of seasons, has little phytotoxicity to paddy rice, and has low toxicity to fish, and as a fungicide, it has preventive and therapeutic effects against late blight and downy mildew of various plants. A compound with a wide range of applications that has both of these properties and also has an excellent control effect on soil diseases such as seedling damping-off of various plants, a simple and high-yielding method for producing them, and An object of the present invention is to provide an agrochemical composition containing them.

[Means and effects for solving the problem] As a result of intensive research on amide-substituted acetonitrile derivatives to solve the above-mentioned problem, it was found that substituted propargyloxyacetonitrile derivatives have physiological activities that could not be predicted from the patent exemplified compounds. As a herbicide for paddy fields, it is suitable for a wide range of seasons, has little phytotoxicity to paddy rice, and has low toxicity to fish, while as a fungicide it is effective as a preventive and therapeutic agent against late blight and downy mildew of various plants. We have completed the present invention by discovering that it has both of these effects and also exhibits an excellent control effect against soil diseases such as seedling damping-off of various plants.

α-(3-bromopropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(3--
Bromopropargyloxy)-3-bromobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-6-methoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(3 -bromopropargyloxy) -3,5-dimethoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy) -3,4-methylenedioxybenzoylaminoacetonitrile, α-(5-bromopropargyloxy)-5-4+7fluoro a-Methylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)
-4-Trifluoromethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-5-ditropenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-6-dianobenzoylaminoacetonitrile, α-(5 -bromopropargyloxy) -3,4-dimethylbenzoylaminoacetonitrile, α-(6-bromopropargyloxy)-1-naphthoylaminoacetonitrile, α-(3-bromopropargyloxy)-2-naphthoylaminoacetonitrile, α -(3-chloropropargyloxy)-5-chlorobenzoylaminoacetonitrile, α-(5-chloropropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy7)-3,5- Dimethylbenzylaminoacetonitrile, α-(1-methylpropargyloxy)penzoylaminoacetonitrinope α-(1-methylpropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)penzoylaminoacetonitrile oxy)-4-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-fluorobenzoylaminoacetonitrile,
α-(1-Methylpropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-bromobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-
3-Methylbenzoylaminoacetonitrile, α-(1
-Methylpropargyloxy)-4-methylbensyla epsilon acetonitrile, α-(1-methylpropargyloxy) = 5.5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-
3-Methoxybenzoylaminoacetonitrile, α-(
1-methylpropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,5-dimethoxybengylaminoacetonitrile, α-(1-methylpropargyloxy)-3,4-methylenedi Oxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3
-) Lifluoromethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-6-nidropenzoylaminoacetonitrile, α-(1-methylpropargyloxy/)-6-dianobenzoylaminoacetonitrile, α-(1 -methylpropargyloxy)
-3,4-dimethylbenzoylaminoacetonitrile α-(1-methylpropargyloxy)-2-naphthoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α-(1-ethyl propargyloxy)-6-
Chlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)=3-trifluoromethylbenzoylaminoacetonitrile, α-(1-ethylpropargyl) oxy)-3-methoxybenzoylaminoacetonitrile α-(1-ethylpropargyloxy)-3,5-
This is a new compound selected from dimethylbenzoylaminoacetonitrile.

In addition, as a result of intensive studies to overcome the shortcomings of the prior art, we have found that the method for producing the novel substituted propargyloxyacetonitrile derivatives according to the present invention is capable of producing the desired product in substantially shorter steps and in high yield. I found a method and completed it.

That is, general formula (1) % formula % (1: (wherein A is a phenyl group, 2-fluorophenyl group, 3
-Fluorophenyl group, 4-fluorophenyl L3-'
70 Lophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 3-bromophenyl group, 5-methylphenyl group, a-methylphenyl group, 3,4-dimethylphenyl group, 3.5-dimethylphenyl group, 6-trifluoromethylphenyl group, 4-1-lifluoromethylphenyl group, 6-methoxyphenyl group, 4-methoxyphenyl group, 5.5-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 3- Nitrophenyl group, 3-
7 Anophenyl group or naphthyl group) is reacted with aminoacetonitrile to form an acyl compound represented by the general formula (II) A-CONHCH2CN(II) (wherein A represents the above meaning). Aminoacetonitrile is obtained and treated with a halogenating agent to give the general formula value) A - C! 0NHfJζ (10 (in the formula, A represents the above meaning, and
Substituted propargyl alcohol, characterized in that it is reacted with lolopropargyl alcohol, '1-methylpropargyl alcohol or Ul-ethylpropargyl alcohol.
This is a method for producing acetonitrile derivatives. The production method according to the present invention is shown in a reaction scheme and explained below.

Acid chloride and aminoacetonitrile represented by the reaction scheme % formula % (wherein A and X represent the above meanings and R1 is water general formula (1) p, -coal (wherein A represents the above meanings) to form acylaminoacetonitrile (I
I) is obtained. When this is treated with a halogenating agent in a suitable solvent, a halogenated intermediate (l[) is obtained. These solvents include aliphatic halides such as dichloromethane, chloroform, carbon tetrachloride, and 1,4-dichloroethane, aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, and ethyl acetate improvinopropionate, and carbon disulfide. However, good results can be obtained by using aliphatic carboxylic acid esters, especially ester solvents such as ethyl acetate. Bromine, chlorine, phosphorus oxychloride, sulfuryl chloride, phosphorus tribromide, etc. can be used as the halogenating agent. The reaction temperature is in the range of 0 to 120°C, preferably room temperature.

Note that this reaction may be performed in an inert gas atmosphere. Since the halogenated intermediate (Iff) is unstable, it is used immediately after its preparation. This halogenated compound (ID) is reacted with a substituted propargyl alcohol surface.

This reaction can be carried out in the presence of an acid acceptor. Examples of acid acceptors include, for example, triethylamine, dimethylaniline,
Examples include, but are not limited to, organic bases such as pyridine, and inorganic bases such as ammonia, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, and ammonium carbonate. This reaction is preferably carried out in a solvent or diluent. Pyridine can be used both as a solvent and as an acid acceptor. Since this reaction does not have good thermal stability of the intermediate, it is not desirable to react at too high a temperature, and since it is an exothermic reaction, it is desirable to carry out the reaction under cooling. At low temperatures, reaction intermediates tend to precipitate, slowing down the reaction rate and making it impractical, so it is desirable to carry out the reaction at -60 to 50°C, preferably -20 to 20°C. The desired substituted propargyloxyacetonitrile derivative thus obtained can be easily isolated and purified by conventional methods such as recrystallization and column chromatography.

Furthermore, the present invention provides α-(3-bromopropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-
Bromobenzoylaminoacetonitrile, α-(5-bromopropargyloxy)-3-methoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy) -3,5
-dimethoxybenzoylaminoacetonitrile, α-(
6-bromopropargyloxy)-3,4-methylenedioxybenzoylaminoacetonitrile, α-(6-bromopropargyloxy)-5-trifluoromethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-4-tri Fluoromethylbenzoylaminoacetonitrile, α-(6-bromopropargyloxy)-3-nitrobenzoylaminoacetonitrile, α-(5-bromopropargyloxy)-6-diatubenzoylaminoacetonitrinohe α-(3-bromopropargyl) (oxy) -3,4-dimethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-1-naphthoylaminoacetonitrile, α
-(6-bromopropargyloxy)-2-7toylaminoacetonitrile, α-(3-chloropropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy) -3,5-
Dichlorobenzoylaminoacetonitrile, α-(3-
chloropropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)benzoylaminoacetonitrile, α-(
1-Methylpropargyloxy)-5-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-fluorobenzoylaminoacetonitrile, α- (1-methylpropargyloxy)-5-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-fluorobenzoylaminoacetonitrile,
α-(1-Methylpropargyloxy)-6-bromobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4
-Methylbenzoylaminoacetonitrile, α-(1-
methylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-methylbenzoylaminoacetonitrile α-(1-methylpropargyloxy)-4-
Methoxybenzoylaminoacetonitrile, α-(1-
methylpropargyloxy)-3,5-)methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,4-methylenedioxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-1-)ly Fluoromethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-nitrobenzoylaminoacetonitrile, α
-(1-ethylpropargyloxy)-3-cyanobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy) -3,4-dimethylbenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-2-naphtho Ylaminoacetonitrinohe α-
(1-Ethylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-5-chlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3
,5-dichloro to/soylaminoacetonitrile, α-
(1-ethylpropargyloxy) -5= trifluoromethylpencyylaminoacetonitrile, α-(1
-ethylpropargyloxy)-3-methoxybensylaminoacetonitrile and α-(1-ethylpropargyloxy)-S,S-dimethyl/soylaminoacetonitrile. The present invention provides a herbicide for paddy fields and a fungicide for agriculture and horticulture.

When using the compound of the present invention as a herbicide for paddy fields, the application amount varies depending on the growth stage of the weed, the type of weed, the dosage form of the preparation, the application method, various environmental conditions, etc., but is usually 0.1 per area. ~100? is suitable, preferably 0.5 to 251. Its herbicidal activity is characteristically strong against grass weeds, but it also shows a strong suppressive effect on other weeds even when they are not killed.

These characteristics are considered to be extremely advantageous when considering application by mixtures or tank mixes in some cases. In particular, the same tendency is observed for weeds of the Cyperaceae family, such as Cyperaceae and firefly, and also for other weeds, although the strength varies depending on the type of weed.

Furthermore, the timing of application of the compound of the present invention is wide ranging from before the emergence of weeds to the growing season. Compared to the known amide compound butachlor and the thiol carbamate compound benchocarb, the compound of the present invention has a much wider usable period and has superior characteristics not found in the past. It can be easily used as a herbicide. Although the practical dosage of herbicidal activity against Japanese millet naturally depends on the treatment period, penthiocarb and butachlor are insufficiently effective at practical dosages against Japanese millet at the 3rd and 5th leaf stage, whereas the compounds of the present invention They exhibit sufficient activity for practical use at doses lower than their practical doses.

The compound of the present invention has extremely low phytotoxicity to transplanted paddy rice no matter when it is used at any time of treatment.

When the compound of the present invention is used as an agricultural and horticultural fungicide, it is not only effective against late blight and downy mildew of various crops caused by algal fungi, but also effective against diseases caused by various other plant pathogenic fungi. It is also effective against

The main diseases to be controlled are potato late blight, tomato late blight, tobacco late blight, strawberry late blight, adzuki bean stem blight, grape blight, kiuribe blight, Honopupe blight, Shi-Ngikube blight, Aquanomyces sp., Pythium sp. Examples include various crop seedling damping-off diseases caused by fungi.

Methods for applying the compound of the present invention include seed disinfection, foliage spraying,
Examples include soil treatment, but any application method commonly used by those skilled in the art will exhibit sufficient efficacy. The application amount and concentration will depend on the target crop, target disease, degree of disease occurrence,
It varies depending on the dosage form of the compound, application method, various environmental conditions, etc., but when spraying, the amount is 5 to 200 per area.
is suitable, preferably 910~10o? It is.

A suitable spray concentration is 20 to 1.000 ppm, preferably 50 to 500 ppm.

The herbicide and agricultural and horticultural fungicide of the present invention may contain other biologically active compounds, such as other fungicides, insecticides, herbicides,
Not only can it be used in combination with agricultural chemicals such as plant growth regulators, soil conditioners, or fertilizing substances, but also mixed formulations with these are also possible.

Although the compounds of the invention may be applied neat, they are preferably applied in the form of a composition mixed with a carrier including a solid or liquid diluent. The term "carrier" as used herein refers to a synthetic or natural inorganic or organic material that is incorporated to help the active ingredient reach the area to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound. do.

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, vegetable organic substances such as soybean flour, sawdust, and wheat flour; Examples include urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and Kume 7, paraffinic hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, and ketones such as acetone and methyl ethyl ketone. , ethers such as dioxane and tetrahydrofuran, alcohols such as methanol, propanol, and ethylene glycol, dimethylformamide, dimethylsulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used alone 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 genin sulfonate, nonionic surfactants such as alkylbenzene sulfonate, alkyl sulfate, calcium stearate, wax, etc. lubricants, stabilizers such as isopropylhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic. However, these components are not limited to the above.

The amount of active ingredient in the composition of the compound of the present invention is usually 0 when used as a powder.
．． 5-20% by weight, I/I 10-90% by weight for irrigation agents,
0.1-20% by weight for granules, 5-50% by weight for emulsions
and 10 to 90% by weight for flowable agents.

〔Example〕

The physical property values of the compounds according to the present invention are shown in Table 1, and the methods for producing them will be specifically explained by giving synthesis examples.

Synthesis example-1 α-(3-bromopropargyloxy)-4-fur-aurobenzoylaminoacetonitrile (compound number-1
) Synthesis of 4-fluorobenzoylaminoacetonitrile 5.61
Bromine 462 was added all at once to a 100 ml solution of ethyl acetate at room temperature. After stirring until the color of bromine in the reaction solution disappeared, the reaction solution was cooled to 0 to 5°C. 3-bromopropargyl alcohol 4.91 and triethylamine 3
, 11 was dissolved in 1 ovte of ethyl acetate, and this solution was added dropwise to the previously prepared ethyl acetate solution of the bromide under water cooling. After the dropwise addition was completed, the reaction was continued for an additional 30 minutes at room temperature. After the reaction was completed, triethylamine bromate was separated from the reaction mixture, and the r solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography.

Elution was performed using a hexane-ethyl acetate system, and the solvent was distilled off from the eluate to obtain 5.8L of α-(5-bromopropargylox/)-4-fluorobenzoylaminoacetonitrile as a white solid. Obtained. Yield 627%, m, ri, 85-87
°C, CDC13 NMR (CDC13N, δ), δ (ppm):
4.40 (2H, s).

MS 3,56 (I H, d), 3,9-8.1 (5H
, m) Synthesis Example-2 α-(3-chloropropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile (compound number-
15) Synthesis of 3.5-dichlorobenzoylaminoacetonitrile 46
1 ethyl acetate 100mA! 3.2 bromine in solution at room temperature
2 were added at once. After stirring until the color of bromine in the reaction solution disappeared, the reaction solution was cooled to 0 to 5°C. 6-chloropropargyl alcohol 2n1, triethylamine 4
．． A mixture of No. 11 and 501 L of tetrahydrofuran was cooled to 0 to 5° C. in a water bath, and the previously prepared ethyl acetate solution of the bromide was added dropwise while stirring. After the dropwise addition was completed, the reaction was continued for 30 minutes under water cooling, and then water was added at 100 W.
lI! was added to dissolve the precipitated triethylamine bromate. The oil layer was separated, washed with water, and dried, and then the solvent was distilled off under reduced pressure. The residue was recrystallized from ethyl ether to give α-(3
-Chloropropargyloki7)-3,5-dichlorobenzoylaminoacetonitrile as a white solid 4.81
Obtained. Yield 75.3cm m,'p, 125~1
25°C NMR (100MHz, δ): δCIXJ3-DMSO
-d6 (ppm): 438 (2a.

MS s), 3,28 (IH, d), 7.8-8.1
(5H, ml, 10.23 (IH, d) 6-bromopropargyl alcohol and 3-chloropropargyl alcohol used as raw materials were “Bul I, Chem.
Soc, Jpn, 45.2'611 (1972)".

Synthesis example = 5 α-(1-methylpropargyloxy)-5-dimethylbenzoylaminoacetonitrile (compound number-2
6) Synthesis of 3.5-dimethylbenzoylaminoacetonitrile 3,
Add bromine 52 to a 100 WL6 solution of 82 in ethyl acetate at room temperature.
1 was added at once. After stirring until the color of bromine in the reaction solution disappeared, the reaction solution was cooled to 0 to 5°C.

1-butyn-3-ol 17? and triethylamine 41? was dissolved in ethyl acetate iomJ, and added dropwise to the previously prepared ethyl acetate solution of bromide under water cooling and stirring. After the dropwise addition was completed, the reaction was continued for an additional 30 minutes at room temperature. After the reaction was completed, the reaction mixture was divided into portions of citriethylamine bromate, and the P solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography.

Elute from hexane-ethyl acetate system, distill off the solvent from the eluate, and α-(1-methylpropargyloxy)-3,
361 of 5-dimethylbenzoylaminoacetonitrile was obtained as a white solid. Yield 696 cm, p, 83-8
5°C NMR (100MHz, δ): δ 3 (pI)m)
:1.54 (3H, dd).

MS 2.28 (6H, S), 2.62 (IH, t), 4
．． 54 (IH, m), 3,50 (IH.

dd), 7.1-7.7 (4H, m) The acylaminoacetonitrile used as a starting material can be easily produced by reacting an acyl halide with aminoacetonitrile in a conventional manner. can.

For example, a 10% sodium hydroxide aqueous solution is cooled in ice water, and aminoacetonitrile sulfate is added and dissolved while stirring. A toluene solution of an acidolide is added dropwise to this solution while cooling with water, and after the addition is complete, the mixture is further stirred at the same temperature. The precipitated crystals were collected through a suction port, and the resulting crystals were washed with toluene and water, and then dried, and used.

Next, the formulation method of the herbicide for paddy fields or the fungicide for agriculture and horticulture of the present invention will be explained using formulation examples.

The active ingredient compounds are shown by compound numbers in Table 1 above. "Part" represents "part by weight."

Formulation Example-1 Powder Compound (1): 3 parts, diatomaceous earth: 20 parts, white clay: 30
1 part and 47 parts of talc were uniformly ground and mixed to make powder 1.
Obtained 000 copies.

Formulation Example-2 Wettable powder compound (2): 30 parts, diatomaceous earth: 44 parts, clay = 20 parts, sodium ligninsulfonate = 1 part, and sodium alkylbenzene sulfonate: 2 parts were uniformly ground and mixed to make an irrigation agent. Got 100 copies.

Formulation Example-3 Emulsion Compound (3): 40 parts, chlorhexanone: 10 parts, xylene: 30 parts, and Norpol (surfactant manufactured by Toho Chemical Co., Ltd.) 20 parts were uniformly dissolved and mixed to obtain 100 parts of an emulsion. .

Formulation example - 4 granules Compound (4): 1 part, bentonite 278 parts, talc:
After mixing 2 o parts and 1 part of sodium ligninsulfonate, adding an appropriate amount of water and kneading, the mixture was granulated using an extrusion granulator in a conventional manner, and after drying, 100 g of granules were prepared.
I got the department.

Formulation Example-5 Granule Compound (10) Nia part, polyethylene glycol nonylphenyl ether: 1 part, polyvinyl alcohol = 3 parts, and 289 parts of clay were uniformly mixed, and after hydrogranulation, it was dried to obtain 100 parts of granule. .

Formulation Example-6 Powder Compound ((S): 2 parts, Cal/Rum Carbonate: 40 parts, and Clay=58 parts were uniformly ground and mixed to obtain 100 parts of a powder).

Formulation Example-7 Irrigation compound (s): 50 parts, Merck: 40 parts, sodium lauryl phosphate = 5 parts, and sodium alkylnaphthalene sulfonate: 5 parts were mixed to obtain 100 parts of an irrigation agent.

Formulation Example-8 Irrigation compound (s): 50 parts, lignin sulfonate: 10 parts, alkylnaphthalene sulfonate sodium = 5 parts, white carbon: 10 parts, diatomaceous earth: 25 parts were mixed and ground to form an irrigation agent of 100 parts. I got the department.

Formulation example-9 Flowable agent compound (7): 40 parts, carboxymethyl cellulose:
6 parts, sodium ligninsulfonate = 2 parts, dioctyl sulfosacunnate sodium salt = 1 part and water 54
A portion was wet-ground using a sand grinder to obtain 100 parts of a flowable agent.

Next, the efficacy of the compounds of the present invention as herbicides will be explained using test examples.

Test Example 1 Weeding test before the emergence of rice fields A''/'5ooo Filled with soil in a Wagner pot, weeded millet, broad-leaved weeds (Kikashigusa, azalea, Japanese azalea, etc.),
Seeds of firefly, Heraomodaka and Tamagayatsuri were sown, and the area was flooded. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. One day after transplanting paddy rice and before weeds appeared, a predetermined amount of the test compound was submerged in water using granules prepared according to the method described in Formulation Example 5 above. Processing 30
A day later, weed growth and chemical damage to water sweepers were investigated. The results are shown in Table-2.

In the table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by comparing the emergence or growth of crops or weeds with that of the untreated air-dried type according to the evaluation criteria below. The test compounds were indicated by compound numbers in Table 1 above (the same applies hereinafter).

Evaluation standard 0: Survival rate shown by air dry weight ratio vs. untreated area 91-100
%1: 71~9
o Person in charge 2: 41~
70 Section 3: 11
~40% 4: 6
~10%5: o
~ Section 5 Control compound A: α-allyloxy-6-chlorobenzoylaminoacetonitrile B: α-allyloxy-3,5-dichlorobenzylaminoacetonitrile C: Furiclor (2-chloro-2(6'-diethyl-
N-(butoxymethyl)acetanilide) D: Benthiocarb (diethylthiocarb ε-doic acid s
-p-chlorobenzyl) Table 2 Weeding test before rice field emergence Test example 2 Rice field growing season weeding test Earl / 5.000 Pack soil into a Wagner pot, and fill it with soil and weeds such as Japanese millet, broadleaf weeds (Kikashigusa, azalea, Japanese azalea, etc.)
Seeds of , firefly, yellowtail, and cyperus were sown and flooded. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. During the weed growth period 12 days after transplanting paddy rice, a predetermined amount of the test compound was submerged in water using granules prepared according to the method described in Formulation Example 4 above. Thirty days after the treatment, weed growth conditions and chemical damage to paddy rice were investigated, and the results are shown in Table 3. In this table, the degree of chemical damage to crops and the growth status of weeds were expressed according to the method shown in Test Example 1.

The results shown in Tables 2 and 3 show that the compounds of the present invention are effective against various noxious weeds that are a problem in rice fields, both in pre-emergence treatments and in growing season treatments, where it has been difficult to achieve herbicidal effects. It is clear that it is an excellent compound that exhibits broad herbicidal activity and has almost no phytotoxicity to paddy rice.

In addition, the compound group disclosed in JP-A-57-176938, namely α-allyloxy-3-chlorobenzoylaminoacetonitrile, α-71J Roxy 3.5
- Dichlorobenzoylaminoacetonitrile etc. showed phytotoxicity to paddy rice in a pre-emergence herbicide test and was not selective as a herbicide for paddy fields, whereas the compounds of the present invention showed no phytotoxicity to paddy rice and were excellent. It is clear that the compound exhibits selectivity and has excellent properties that could not be expected from the compound disclosed in JP-A-57-176938.

Next, the efficacy of the agricultural and horticultural fungicide of the present invention as a fungicide will be explained using test examples. In this section, a comparative test with an amide-substituted allyloxyacetonitrile derivative, which is a compound considered to have a relatively similar structure to the compound according to the present invention, was shown.

Test Example 3 Potato Phytophthora control test (preventive effect) A prescribed concentration of the drug (test compound) was added to potatoes grown in pots in a greenhouse (variety: Otokoshaku, plant height approximately 25 crIL) in water according to the method of Formulation Example 2. Prepare a phase agent and dilute it with water to a predetermined concentration) using a spray gun (1, Okg/
d) was used to spray 5Qml per 3 pots and air dry. A zoospore suspension was prepared from late blight potatoes that had been previously cultured on potato sections for 7 days. This suspension was sprayed and inoculated onto the potato plants sprayed with the drug, and the test plants were
After being maintained at ~19° C. and 95% or higher humidity for 6 days, the degree of lesion formation was investigated.

The disease severity index was determined by observing and evaluating the lesion area ratio for each leaf, and the disease severity was determined for each plot using the following formula.

1:N The evaluation criteria are as follows.

Disease severity index 0: Lesion area ratio 0%1:
〃 1-5% 2: 〃 6-25% 3: 〃 26-50% 4: ``51% or more no: Number of leaves with disease severity index O n,: tt l n (12: // 2 // (13 :// 3 // n4:〃4/l The results are shown in Table-4.

Control compound A: α-allyloxy-3-chlorobenzoylaminoacetonitrile B: α-allyloxy-3,5-dichloropenzoylaminoacetonitrile E: Compound of zinc ethylene bis(dithiocarbamate), E and F are used for late blight of potato, cucumber and A drug commercially available as a disease control agent.

(Common to the following test examples).

Test Example-4 Potato late blight control test (therapeutic effect) A suspension of potato Phytophthora zoospores prepared in the same manner as Test Example-3 was sprayed on potatoes grown in pots in a greenhouse (variety: Otokoshaku, plant height approximately 25 cIrL). Inoculated. After maintaining the temperature at 17-19°C and 95% humidity for 20 hours, a drug of a predetermined concentration (a wettable powder was prepared from the test compound according to the method of Formulation Example 2 and diluted to a predetermined concentration) was added. Spraying was performed using a spray gun (1° Ok!?/, ffl). After air-drying, the specimens were kept at 17-19° C. and humidity of 95% or higher for 5 days, and then the extent of lesion formation was examined.

The evaluation criteria and disease severity display method were as shown in Test Example-3.

The results are shown in Table-5.

Test Example-5 Cucumber and disease control test (preventive effect) Cucumbers grown in pots in a greenhouse (variety: Sumo Hanshiro, 2 true leaves developed) were treated with a prescribed concentration of drug (test compound according to the method of Formulation Example 2). Prepare a hydrating powder according to the same method, dilute it with water to a specified concentration) and spray it with a spray gun y' (-1.0 kg/c++
! ) was used to spray 3 c) rnl per 3 pots and air-dried. Downy mildew bacteria were collected from lesions on cucumber leaves infected with downy mildew, a spore suspension was prepared with demineralized water, and the suspension was sprayed for inoculation. Immediately keep the inoculated pots at 18-20°C and 95% humidity for 24 hours, then place them in a greenhouse (at room temperature 1.
After 7 days, the degree of lesion formation was examined.

The evaluation criteria and disease severity display method are as shown in Test Example-3.

The results are shown in Table-6.

Test Example 6 Cucumber and disease control test (therapeutic effect) A suspension of cucumber and disease fungus spores was prepared and inoculated by spraying onto cucumbers similar to those used in Test Example 5.

After maintaining the temperature at 18 to 20°C for 24 hours and at a humidity of 95% or higher, a drug at a predetermined concentration (the test compound was made into a wettable powder by the method of Test Example 2 and diluted with water to a predetermined concentration) was applied. 3 per 3 pots using a spray gun (1,0 kg/i >
Qrnl was sprayed. The plants were transferred to a greenhouse (temperature: 18-27°C), and after 6 days, the degree of lesion formation was examined.

The evaluation criteria and disease severity display method were as shown in Test Example-3.

The results are shown in Table-7.

Table 4 Potato late blight control test (preventive effect) Table 5 Potato late blight test (therapeutic effect) Table 6 Cucumber and disease control test (preventive effect) Table 7 Cucumber and disease control test (therapeutic effect) Table 4.5. From the results shown in 6 and 7, the compounds of the present invention are currently commercially available and widely used against potato late blight and cucumber rot It shows a preventive effect at an extremely low dose compared to
Moreover, the compound group disclosed in the above two drugs, namely α-allylox-7-3-chlorobenzoylaminoacetonitrile, α-allyloxy-3,5-dichlorobenzoylaminoacetoni) has superiority that could not be expected from IJru et al. It is clear that the substituted propargyloxyacetonitrile derivative according to the present invention has a pesticidal effect of -0 °C. It has a wide range of excellent herbicidal effects during the appropriate period, which could not be expected with conventional herbicides, and as an agricultural and horticultural fungicide, it is effective against various diseases caused by algae and fungi in various crops, including soil diseases, and conventional commercially available agents are not effective. It has excellent control properties that show preventive effects at low dosages and concentrations and also have therapeutic effects. The agricultural chemicals containing the substituted propargyloxyacetonitrile derivatives according to the present invention can be used as herbicides and agricultural and horticultural agents. It has excellent properties and is useful as a disinfectant.

In addition, in the method for producing substituted propargyloxyacetonitrile derivatives according to the present invention, since the nitrile group does not undergo hydrolysis in the halogenation step, the process is substantially shortened by adding the reaction raw material to the obtained halogenated intermediate as it is. The desired product can be obtained easily and in a high yield, and it is superior to the methods conventionally proposed for producing substituted aminoacetonitrile derivatives.

Claims (3)

[Claims] (1) α-(3-bromopropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-bromobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-methoxy benzoylaminoacetonitrile,
α-(3-bromopropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,5-dimethoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,4- Methylenedioxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)
-3-Trifluoromethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-4-trifluoromethylbenzoylaminoacetonitrile, α
-(3-bromopropargyloxy)-3-nitrobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-cyanobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,
4-Dimethylbenzoylaminoacetonitrile, α-(
3-bromopropargyloxy)-1-naphthoylaminoacetonitrile, α-(3-bromopropargyloxy)-2-naphthoylaminoacetonitrile, α-(3-bromopropargyloxy)-2-naphthoylaminoacetonitrile,
-chloropropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3,
5-dimethylbenzoylaminoacetonitrile, α-(
1-Methylpropargyloxy)benzoylaminoacetonitrile, α-(1-methylpropargyloxy)-
3-chlorobenzoylaminoacetonitrile, α-(1
-methylpropargyloxy)-4-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α-( 1-Methylpropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-bromobenzoylaminoacetonitrile, α
-(1-methylpropargyloxy)-3-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,
5-dimethylbenzoylaminoacetonitrile, α-(
1-methylpropargyloxy)-3-methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,
5-dimethoxybenzoylaminoacetonitrile, α-
(1-methylpropargyloxy)-3,4-methylenedioxybenzoylaminoacetonitrile, α-(1-
methylpropargyloxy)-3-trifluoromethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-nitrobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-
3-cyanobenzoylaminoacetonitrile, α-(1
-Methylpropargyloxy)-3,4-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-naphthoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α -(1-ethylpropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)
-3,5-dichlorobenzoylaminoacetonitrile,
α-(1-ethylpropargyloxy)-3-trifluoromethylbenzoylaminoacetonitrile, α-(1
A substituted propargyloxyacetonitrile derivative selected from -ethylpropargyloxy)-3-methoxybenzoylaminoacetonitrile and α-(1-ethylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile. (2) General formula (I) A-COCl (I) (wherein A is a phenyl group, 2-fluorophenyl group, 3
-Fluorophenyl group, 4-fluorophenyl group, 3-
Chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 3-bromophenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3 -Trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 3-nitrophenyl group , 3-cyanophenyl group, naphthyl group) and aminoacetonitrile are reacted to form a compound of the general formula (II) A-CONHCH_2CN(II) (wherein A represents the above meaning). Obtain the acylaminoacetonitrile represented by the formula and treat it with a halogenating agent to form the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, A represents the above meaning, and X (representing a halogen atom), and then reacting this with 3-bromopropargyl alcohol, 3-chloropropargyl alcohol, 1-methylpropargyl alcohol or 1-ethylpropargyl alcohol. -(3-bromopropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-bromobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-methoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)
-4-Methoxybenzoylaminoacetonitrile, α-
(3-bromopropargyloxy)-3,5-dimethoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,4-methylenedioxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3- Trifluoromethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-4-trifluoromethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-
3-Nitrobenzoylaminoacetonitrile, α-(3
-bromopropargyloxy)-3-cyanobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,4-dimethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-1-
Naphthoylaminoacetonitrile, α-(3-bromopropargyloxy)-2-naphthoylaminoacetonitrile, α-(3-chloropropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3 , 5-dichlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)benzoylaminoacetonitrile, α-(1-methylpropargyloxy)- 3-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy) -3-fluorobenzoylaminoacetonitrile,
α-(1-Methylpropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-bromobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-
3-Methylbenzoylaminoacetonitrile, α-(1
-Methylpropargyloxy)-4-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-
Methoxybenzoylaminoacetonitrile, α-(1-
methylpropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,5-dimethoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3
, 4-methylenedioxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-trifluoromethylbenzoylaminoacetonitrile, α-
(1-Methylpropargyloxy)-3-nitrobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-cyanobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3,4
-dimethylbenzoylaminoacetonitrile, α-(1
-Methylpropargyloxy)-2-naphthoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α
-(1-ethylpropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)
-3-trifluoromethylbenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-methoxybenzoylaminoacetonitrile or α-(1
-Ethylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile manufacturing method. (3) α-(3-bromopropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-bromobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-methoxy benzoylaminoacetonitrile,
α-(3-bromopropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,5-dimethoxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3,4- Methylenedioxybenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-trifluoromethylbenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-4-
trifluoromethylbenzoylaminoacetonitrile,
α-(3-bromopropargyloxy)-3-nitrobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3-cyanobenzoylaminoacetonitrile, α-(3-bromopropargyloxy)-3
, 4-dimethylbenzoylaminoacetonitrile, α-
(3-bromopropargyloxy)-1-naphthoylaminoacetonitrile, α-(3-bromopropargyloxy)-2-naphthoylaminoacetonitrile, α-(
3-chloropropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile, α-(3-chloropropargyloxy)-3
, 5-dimethylbenzoylaminoacetonitrile, α-
(1-methylpropargyloxy)benzoylaminoacetonitrile, α-(1-methylpropargyloxy)
-3-chlorobenzoylaminoacetonitrile, α-(
1-Methylpropargyloxy)-4-chlorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α- (1-methylpropargyloxy)-4-fluorobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-bromobenzoylaminoacetonitrile,
α-(1-Methylpropargyloxy)-3-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-methylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3
, 5-dimethylbenzoylaminoacetonitrile, α-
(1-Methylpropargyloxy)-3-methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-4-methoxybenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3
,5-dimethoxybenzoylaminoacetonitrile, α
-(1-methylpropargyloxy)-3,4-methylenedioxybenzoylaminoacetonitrile, α-(1
-methylpropargyloxy)-3-trifluoromethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-3-nitrobenzoylaminoacetonitrile, α-(1-methylpropargyloxy)
-3-cyanobenzoylaminoacetonitrile, α-(
1-methylpropargyloxy)-3,4-dimethylbenzoylaminoacetonitrile, α-(1-methylpropargyloxy)-2-naphthoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-fluorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-chlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3,5-dichlorobenzoylaminoacetonitrile, α-(1-ethylpropargyloxy)-3-trifluoro Methylbenzoylaminoacetonitrile, α-(
A rice field characterized by containing a substituted propargyloxyacetonitrile derivative selected from 1-ethylpropargyloxy)-3-methoxybenzoylaminoacetonitrile and α-(1-ethylpropargyloxy)-3,5-dimethylbenzoylaminoacetonitrile. herbicide or fungicide for agriculture and horticulture.