ZA200203200B

ZA200203200B - Oxime o-ether compounds and fungicides for agricultural and horticultural use.

Info

Publication number: ZA200203200B
Application number: ZA200203200A
Authority: ZA
Inventors: Hiroshi Sano; Tadashi Sugiura; Yuuki Nakagawa; Hiroshi Hamamura; Akira Mitani; Takahiro Ando
Original assignee: Nippon Soda Co
Priority date: 1999-11-05
Filing date: 2002-04-23
Publication date: 2002-10-24

Description

A

- SPECIFICATION " Oxime O-ether Compounds and Fungicides for Agricultural and

Horticultural Use

Field of Invention

The present invention relates to novel oxime O-ether compounds and fungicides containing said compound as an active principle for agricultural and horticultural use.

Background Art

For agricultural and horticultural crop culture, various agricultural plant protection chemicals have been used for controlling plant diseases. However, due to deterioration of plant protection chemicals in their activity and the appearance of resistant stains of plant pathogenic microorganisms to those chemicals, the use of fungicides plant protection use has been restricted. In addition, many fungicides cause phytotoxicity to plants or are toxic to humans and animals. Consequently, although there are many fungicides for plant protection use have been " developed and used, most of them are not satisfactory in view of said disadvantages. As a result, there is a need yet to provide fungicides for plant protection use, which do not have the above-described disadvantages and can be used safely.

For example, oxime O-ether compounds similar to the compounds as defined in the present invention are disclosed in EP4754, EP24888,

W093/21157 as compounds having insecticidal and acaricidal activity.

Furthermore, it is disclosed in Jpn. Pat. Appln. Publication (KOKAI) No. 9-3047 that oxime O-ether compounds represent by the following chemical formula are useful as a fungicide. —N CH, H,

H.C o}

CH,

Disclosure of the Invention

It is an object of the present invention to provide novel oxime

O-ether compounds, those which can be an excellent fungicide for agricultural and horticultural use, advantageous for the production in an industrial scale, having firm biological effectiveness, and causing less phytotoxicity.

The inventors of the present invention found that the fungicidal activity of said oxime O-ether compounds represented by the following general formula [I] can be enhanced and - phytotoxicity caused thereby can be reduced by introducing an oxygen functional group into the 2nd position of the benzene ring of said oxime O-ether compound and a substituent into an arbitrary position, particularly the 6th position of the benzene ring.

Therefore, the present invention is directed to oxime O-ether compounds represented by a general formula [I]: (RY, A R® (RO),

Rae ona (1) :

N Rr? R* 0)

RS wherein Rl represents Ci1-¢ alkyl, C3.g cycloalkyl, Cji_g alkoxy, Cj-g alkylthio, amino, mono- or di-(Cj-g alkyl)amino, Cj_g acyloxy, Ci-g alkoxy Cy_g alkyl, C{_g haloalkyl, hydroxy or Halogen atom; m represents an integer of 1 to 4, and when m is 2 or more integer, each of R1 may be same or different from one to another;

RZ represents hydrogen atom, Cj_g alkyl or C3_g cycloalkyl;

R3 and R% are same or different from one to another and each independently represents hydrogen atom or Ci-g alkyl;

RO represents hydrogen atom, Cj_g alkyl, C3_g cycloalkyl,

C1-6 haloalkyl, Ci_g alkoxy Ci_g alkyl, Cq_g alkoxy Cj_g alkoxy

Ci-¢ alkyl, Cy_710 aralkyl, Cy_70 aralkyloxy Cj-g alkyl, Cji-g alkylcarbonyl, Ci_g alkylsulfonyl or Cj_g haloalkylsulfonyl;

R® represents C1_g alkyl, C3-g cycloalkyl, Cy_g alkenyl, Co_g alkynyl, Ci-g alkoxy, Ci-g alkoxy Ci_g alkoxy, Ci1-6 alkylcarbonyloxy, Cj.g alkoxy Cj_g alkyl, Cj-g haloalkyl, cyano, nitro, amino, mono- or di-(Cj-¢ alkyl) amino, Ci-6 alkylcarbonylamino, Cj_g alkylthio, hydroxy or Halogeno atom atom atom; and - n represents an integer of 1 to 4, and when n is 2 or more integer, each of R6 may be same or different from one to another, © and fungicides for agricultural and horticultural use containing the oxime O-ether compound or a salt thereof as the active ingredient.

More specifically, in the general formula [I], rl represents Cj_g alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers, an optionally-substituted C3_g cycloalkyl, such as cyclopropyl, cyclopentyl, l1-methylcyclopentyl, cyclohexyl, and l-methylcyclohexyl,

C1-6 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, and t-butoxy,

C1-g alkylthio, such asmethylthio, ethylthio, isopropylthio, and butylthio, amino, mono- or di-(Cqi_g alkyl)amino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and ethylisopropylamino,

C1-¢ acyloxy, such as acetoxy, and propionyloxy, pivaloyloxy,

Ci1-6 alkoxy C1_g alkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, and butoxymethyl;

Ci1-¢ haloalkyl, such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl; hydroxy, or

Halogeno atom atom atom, such as fluorine, chlorine bromine and iodine; m represents an integer of 1 to 4, and when m is 2 or more integer, each of RI may be same or different from one another;

RZ represents hydrogen atom,

Ci1-6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers, or an optionally-substituted C3_.g cycloalkyl, such as cyclopropyl, cyclopentyl, l-methylcyclopentyl, cyclohexy, and l-methylcyclohexyl; BN ~~ RY and RY may be same or different from one to another and each independently represents hydrogen atom, or

Ci-6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers;

RO represents hydrogen atom,

C1-¢ alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers, an optionally-substituted C3.g cycloalkyl, such as cyclopropyl, cyclopentyl, l-methylcyclopentyl, cyclohexyl, and l-methylcyclohexyl,

C1-¢ haloalkyl, such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl,

C1-g alkoxy C1-g alkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, and butoxymethyl,

Ci-6 alkoxy Ci1-6 alkoxy Ci-6 alkyl, such as methoxyethoxymethyl and ethoxyethoxymethyl,

C7-10 aralkyl, such as benzyl and phenetyl,

C7-10 aralkyloxy Cl-6 alkyl, such as benzyloxymethyl and benzyloxyethyl,

Ci1-6 alkylcarbonyl, such as acetyl, propionyl, and pivaloyl,

Ci-6 alkylsulfonyl, such as methanesulfonyl and ethanesulfonyl, or

Ci1-¢ haloalkylsulfonyl, such as chloromethylsulfonyl and trifluoromethylsulfonyl;

R® represents Cqj_g, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers,

an optionally-substituted C3.g cycloalkyl, such as cyclopropyl, cyclopentyl, l-methylcyclopentyl, cyclohexyl, and 1-methylcyclohexyl,

Co-g alkenyl, such as vinyl, propenyl, and isopropenyl, ~~ Cp.g alkynyl, such as ethynyl, and propalgyl,

Ci1-6 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, CL butoxy, sec-butoxy, isobutoxy and t-butoxy,

Ci-¢ alkoxy Cj_g alkoxy, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, propoxymethoxy, and butoxymethoxy,

C1-g alkylcarbonyl, such as acetoxy, propionyloxy, and pivaloyloxy,

C1-6 alkoxy Cq_g alkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, and butoxymethyl, .C1-6 haloalkyl, such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroehtyl, cyano, nitro, amino, mono- or di-(Ci_g alkyl)amino, such as methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and ethylisopropylamino,

Ci-6 alyklcarbonylamino, such as acetylamino, and pivaloylamino,

Ci-¢ alkylthio, such as methylthio, ethylthio, and isopropylthio, hydroxy, or

Halogeno atom atom atom, such as fluorine, chlorine, bromine and iodine; and n represents an integer of 1 to 4, and when n is 2 or more integer, each of R® may be same or different from one another.

Of the compounds defined in the present invention, compounds represented by a general formula [I']:

(Ry, Ra. oF ®), oT 7; (r) =N. Rr? RY 0) — — R° _ ~~ whereinRl, RZ, R3, RY, RS, RG, mand n are as defined above, of which benzene ring is substituted by one of the groups exampled above for R® at the 6th position, have excellent activity as a fungicide for agricultural and horticultural use. (Fungicide for Agricultural and Horticultural Use)

Each of the compounds defined in the present invention has excellent fungicidal activity against wide range of fungi belonging to, for example, Oomycetes, Ascomycetes, Deuteromycetes and

Basidiomycetes. In particular, the compounds of the present invention have remarkable fungicidal activity against a fungus of gray mold disease, Botrytis cinerae, compared to the known compounds described above.

The composition containing the compound of the present invention as the active ingredient can be used for controlling various plant diseases infesting on agricultural and horticultural crops including ornamental flowers, lawns and forage crops by means of seed treatment, foliage application soil application, water surface application, etc. -

Example of plant diseases those which can be controlled by the application of a composition containing the compound of the present invention include the following.

Sugar beet: Cercospora leaf spot (Cercospora beticola)

Groundnut: Leaf spot (Mycosphaerella arachidis)

Late leaf spot (Mycosphaerella berkeleyi)

Cucumbers: Powdery mildew (Sphaerotheca fuligineg)

Gummy stem blight (Mycosphaerella melonis)

Sclerotinia rot (Sclerotinia sclerotiorum)

Gray mold (Botrytis cinerea)

Scab (Cladosporium cucumerinum)

Tomatoes: Gray mold (Botrytis cinerea)

Leaf mold (Cladosporium fulvum)

Eggplants: Gray mold (Botrytis cinerea)

Black rot (Corynespora melongenea)

Powdery mildew (Erysiphe cichoracearum)

Strawberries: Gray mold (Botrytis cinerea)

Powdery mildew (Sphaerotheca aphanis)

Onion: Gray-mold neck rot (Botrytis allii) Gray-mold (Botrytis cinerea)

Kidney bean: Sclerotinia rot (Sclerotinia sclerotiorum)

Gray mold (Botrytis cinerea) .

Apples: Powdery mildew (Podosphaera leucotricha)

Scab (Venturia inaequalis)

Blossom blight (Monilinia mali)

Oriental persimon: Powdery mildew (Phyllactinia kakicola)

Anthracnose (Gloeosporium kaki)

Angular leaf spot (Cercospora kaki)

Peach & Cherries: Brown rot (Monilinia fructicola)

Grapes: Gray mold (Botrytis cinerea)

Powdery mildew (Uncinula necator)

Ripe rot (Glomerella cingulata)

Pears: Scab (Venturia nashicola)

Rust (Gvmnosporangium asiaticum)

Black spot (Alternaria kikuchiang)

Tea plant: Gray blight (Pestalotia theae)

Anthracnose (Colletotrichum theae-sinensis)

Citrus: Scab (Elsinoce fawcetti)

Blue mold (Penicillium italicum)

Common green mold (Penicillium digitatum)

Gray mold (Botrytis cinerea)

Barley: Powdery mildew (Erysiphe graminis f.sp. hordei)

Loose smut (Ustilago nuda)

Scab (Gibberella zeae)

Leaf rust (Puccinia recondita)

Spot blotch (Cochliobolus sativus)

Eye spot (Pseudocercosporella herpotrichoides)

Glume bltch (Leptosohaeria nodorum)

Powdery mildew (Erysiphe graminis f.sp, tritici)

Snow mould (Micronectriella nivalis)

Paddy rice: Blast (Pyricularia oryzae)

Sheath blight (Rhizoctonia solani)

Bakanae disease (Gibberella fujikuroi)

Helminthosporium leaf spot (Cochliobolus mivabeanus) i Tobacco: Sclerotinia rot (Sclerotinia sclerotiorum)

Bent grass: Sclerotinia snow blight (Sclerotinia borealis)

Orchard grass: Powdery mildew (Erysiphe graminis)

Soybean: Purple speck (Cercospora kikuchii)

Potatoes & Tomatoes: Downy mildew (Phytophthora infestans)

Cucumbers: Downy mildew (Pseudoperonospora cubensis)

Grape: Downy mildew (Plasmopara viticola)

Besides, in recent years, it should be noted that various plant pathogenic fungi have developed resistance to plant protection chemicals, such as benzimidazole fungicides and carbodiimide fungicides. It follows that there is a problem in the control of such a problematic plant disease, because no fungicide can control those plant diseases sufficiently. Therefore, an effective fungicide, which can control such fungi being resistant against those problematic plant diseases is badly desired. The compounds of the present invention are effective to those resistant strains of fungi to aforementioned fungicides as well as susceptible ones.

The compounds of the present invention are effective to not only the susceptible fungi but also the resistant strains of fungi including gray mold fungus (Botrytis cinerea), sugar beet leaf spot fungus (Cercospora beticola), apple scab fungus (Venturia inaequalis), and pear scab fungus (Venturia nashicola) to, for examples, thiophanate methyl, benomyl and carbendazim.

In addition, the compounds defined in the present invention are also effective against gray mold diseases caused by Botrytis cinerea which are resistant to dicarboxyimide fungicides, such as vinclozolin, procymidone and iprodione. The fungicidal activity against the resistant strains of gray mold fungus of the compounds of the present invention is as effective as that against the susceptible strains.

Specifically, examples of plant diseases to those which a fungicidal composition (fungicide for agricultural and horticultural use) containing the compound of the present invention ) is used more preferably are Cercospora leaf spot of sugar beet, powdery mildew of wheat, blast of paddy rice, scab of apples, gra mold of Kidney bean, leaf spot of groundnut and so on.

Furthermore, the compounds of the present invention can also be used as an antifouling agent for preventing structures in water, such as the bottoms of ships and fishing nets, from fouling of aqueous life.

Embodiments

The compounds according to the present invention are produced according to a process represent by the following reaction equation; 1) 3 3 (RY, \ R (Rp, A R

Yeon + AL — ES enotoar =N Rr? rR =N Rr? R* (11 (111) } (1) wherein RI, RZ, R3, R% and m are as defined above, Ar represents a substituted phenyl group represented by a formula; 0)

RS wherein RO, R® and n are as defined above, and L represents Halogeno atom atom atom, such as chlorine, bromine and iodine, or an eliminating group, such as methanesulfonyloxy and p- toluenesulfonyloxy.

Specifically, in the reaction equation (1) given above, the compounds represented by the general formula [I] can be produced by allowing a compound of the formula [II] and a compound of the formula [III] to react with each other without solvent or preferably in a solvent while stirring for 10 min. to 24 hours at a reaction temperature of 0 to 150°C and in the presence of a deacidifying agent.

Examples of the solvent to be used in the above reaction (1) include a ketone, such as acetone and 2-butanone, an ether, such as diethyl ether and tetrahydrofuran, an aromatic hydrocarbon, such as benzene and toluene, an alcohol, such as methanol and ethanol, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide and water.

One or more solvents recited above can be used in combination for the reaction.

Examples of the base to be used in the above reaction (1) include an inorganic base, such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium hydride, an alkali metal alcolate, such as sodium methylate and sodium ethylate, and an organic base, such as pyridine, triethylamine and DBU.

The stating material represented by the formula [II] for producing the compounds according to the present invention can be produced according to the process disclosed in Jap. Pat. Appln.

KOKAI Publication No. 9-3047. 2) (RY, \ R® (Rn 7 R®

Yo + Ar—f- OH, —_— TE en-ofoa =N Rr? R* =N Rr? R* (1v] v] (1) wherein rl, RZ, R3, RE, Ar and m are as defined above.

Specifically, in the reaction equation (2) given above, the compound represented by the general formula [I] is produced by allowing a compound resented by the formula [IV] and a compound represented by the formula [V] or a salt thereof to react with each other while stirring without solvent or preferably in a solvent for a period of from 10 min. to 24 hours at a reaction temperature in a range of from 0 to 150°C.

Example of the solvent to be used in the above reaction (2) include an alcohol, such as ethanol and methanol, an ether, such as diethyl ether, tetrahydrofuran and dioxane, a cellosolve, such as methyl cellosolve and ethyl cellosolve, an aromatic hydrocarbon, such as benzene and toluene, acetic acid, N,N-dimethylformamide, dimethylsulfoxide, and water. One or more solvents recited above can also be used in combination for the reaction (2). The reaction (2) does not require the presence of a catalyst, however, the reaction may be accelerated by an addition of an acid or a base sometime. Examples of the catalytic acid include an inorganic acid, such as sulfuric acid and hydrochloric acid, and an organic acid, such as p-toluenesulfonic acid. Examples of the catalytic base include acetic acid and the like.

Following to the completion of the reactions (1) and (2), the targeted compounds can be obtained by subjecting the reaction products to common post-reaction processing. Note that the obtained targeted compounds can be further chemically modified to produce various derivatives thereof. More specifically, as said chemical modification, functional group conversion represented by induction of nitro group to amino group by reduction reaction, deblocking of functional groups, such as methoxymethyl group, recognized in the organic chemistry field as a protecting group, induction of functional groups, such as hydroxy group and amino group, generated by the deblocking by means of alkylation and acylation, and induction of functional groups, represented by

Sonogashira reaction, recognized as a deblocking group in the organic chemistry field, such halogen atoms, with use of a nucleophilic reagent are exemplified.

Said salts of the compound of the formula [I] can be produced by performing a reaction of the compound of the formula [I] and either an inorganic acid or an organic acid in an appropriate solvent.

The chemical structures of the compounds according to the present invention are determined by use of NMR, mass spectrum, and so on. [Fungicide]

The fungicide according to the present invention contains one or more of the compounds defined in the present invention as the active ingredient. In the practical application of the compounds

Claims

. CLAIMS :

1. Oxime O-ether compounds represented by a general formula [I]; 3 (RY), EH) R (F8), —=N-0 (I) I Se es 2 o RS wherein Rl represents Ci1-¢ alkyl, C3_g cycloalkyl, Cj-g alkoxy, C1-g alkylthio, amino, mono- or di-(Cj_g alkyl)amino, Cj_g acyloxy, Cj-g alkoxy Cj-g alkyl, C1_g haloalkyl, hydroxy or Halogen atom; m represents an integer of 1 to 4, and when m is 2 or more integer, each of rl may be same or different from one to another; RZ represents hydrogen atom, Cj_g alkyl or C3z_g cycloalkyl; R3 and R? are same or different from one to another, and each independently represents hydrogen atom or C1-¢ alkyl; R° represents hydrogen atom, Cj_g alkyl, C3_-¢ cycloalkyl, Ci1-¢ haloalkyl, Cj-g alkoxy Ci-g alkyl, Cj.g alkoxy Ci-g alkoxy Ci-¢ alkyl, Cy-30 aralkyl, Cy-30 aralkyloxy Ci_g alkyl, Ci-g alkylcarbonyl, Cj_g alkylsulfonyl or Cj_g haloalkylsulfonyl; R® represents C1.g alkyl, C3_g cycloalkyl, Co_g alkenyl, Co_g alkynyl, Ci1-6 alkoxy, Ci1-6 alkoxy Cqi_g alkoxy, Ci-6 alkylcarbonyloxy, Cj-.g alkoxy Ci_g alkyl, Ci_g haloalkyl, cyano, nitro, amino, mono- or di-(Cq1-¢ alkyl) amino, Ci1-6 alkylcarbonylamino, Cq-g alkylthio, hydroxy or Halogeno atom atom atom; and n represents an integer of 1 to 4, and when n is 2 or more integer, each of RO may be same or different from one to another.

2. Oxime ether compounds according to claim 1 represented by a general formula [I'];

rT XE Hpneo (r) =N Rg? R* 0) R® — wherein RL, RZ2,—R3; RE, RY; R6andmare—asdefined—above,

3. A fungicide for agricultural and horticultural use characterized by comprising one or more of the oxime ether compounds represented by the general formula [I]; 3 (RY, \ R (RE), = eno (1) =N R® rR? oO R® wherein RI, RZ, R3, RE, RO, RS, n and m are as defined above, or the salts thereof as the active ingredient.

4. A fungicide according to claim 3, characterized in that the active ingredient is a compound represented by the general formula [I']; Re 6 (Ry, \ R (R),., Eno ) =N Rg? R* 0) R® wherein rl, RZ, R3, rR%, RO, RO, m and n are as defined above.