RU2047605C1 - Azole derivatives and intermediate compounds for their synthesis - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: derivatives of azole (I). Intermediate products for synthesis of azole (I) derivatives of oxirane (II); derivatives of methylenecyclopentane (III); derivatives of cyclopentanone (IV); derivatives of cyclopentanecarboxylic acid ester (IV). Compounds (I) (IV) (III) (II) (I) were synthesized. Synthesized compounds were used for struggle against plant disease and their growth. EFFECT: improved method of synthesis. 8 cl, 35 tbl

Description

(1) в которой R¹ и R² представляют собой соответственно С₁-С₅-алкильную группу или атом водорода; Х атом галогена или алкильную группу с 1-5 атомами углерода или фенильную группу; n целое число 0-2; А атом азота или СН при условии, что R¹ не является Н, если R² является атомом водорода;
2) способа получения производного азола, представленного формулой (1), включающего следующие операции:
а) (i) взаимодействие сложного алкильного эфира 2-оксициклопентанкарбоновой кислоты с подходящим замещенным галоидным бензилом и взаимодействие полученного таким образом сложного алкильного эфира 1-(замещенный бензил)-2-оксоциклопентанкарбоновой кислоты с С₁-С₅-алкилгалогенидом; (ii) взаимодействие сложного алкильного эфира 3-(С₁-С₅-алкил)-2-оксоциклопентанкарбоновой кислоты с замещенным галоидным бензином или (iii) взаимодействие 1-(замещенный бензил)-3-(С₁-С₅-алкил)-2-оксоциклопентан- карбо- новой кислоты с галоидным С₁-С₅-алкилом, с получением при этом производного сложного эфира циклопентанкарбоновой кислоты, представленной формулой

(V) в которой R¹ и R² соответственно представляют собой С₁-С₅-алкильную группу или атом водорода: R C₁-C₅-алкильную группу; Х атом галогена; С₁-С₅ алкильную группу или фенильную группу и n означает целое число 0-2, при условии, что R¹ не является атомом водорода, если R² является атомом водорода;
в) гидролитическое декарбоксилирование полученного таким образом производного сложного эфира циклопентан- карбоновой кислоты с получением при этом производного циклопентанона, представленного формулой

(IV) в которой R¹, R² X и n соответственно имеют те же значения, определенные для них выше;
с) полученное таким образом производное циклопентанона подвергают оксирановой реакции, используя илиды сульфония или оксосульфония, или подвергают метиленциклопентановое производное, полученное таким образом из производного циклопентанона реакций Виттига и представленное формулой

(III) в которой R¹, R², X и n соответственно имеют значения, определенные ранее, эпоксидированию, обращая при этом производное циклопентанона в этиленоксидное производное, представленное формулой

_, (II) в которой R1, R², X и n соответственно представляют собой те же значения, которые были определены для них ранее, и затем
d) взаимодействие полученного этиленоксидного производного с 1,2,4-триазолом или амидазолом, представленным формулой
HN

(VI) где М представляет собой атом водорода или атом щелочного металла и А атом азота или -СН= с получением при этом азольного производного, представленного формулой

(I) в которой R¹ и R² соответственно представляют собой алкильную группу с 1-5 углеродными атомами или атом водорода; Х является атомом галогена, алкильной группой с 1-5 атомами углерода или фенильной группой; n целое число 0-2 и А атом водорода или СН при условии, если R¹ не является атомом водорода, а R² является атомом водорода, и композиции для использования в полеводстве и садоводстве, обладающей фунгицидной активностью и регулирующей рост растений активностью, которая включает эффективное количество производного азола, представленного формулой (1).The invention relates to an azole derivative having activity in combating plant diseases and the growth of regulatory activity, methods for producing the azole derivative and intermediates to obtain an azole derivative. In particular, the invention relates to
1) an azole derivative represented by the formula (1)

(1) in which R ¹ and R ² are respectively a C ₁ -C ₅ alkyl group or a hydrogen atom; X is a halogen atom or an alkyl group with 1-5 carbon atoms or a phenyl group; n is an integer of 0-2; A nitrogen atom or CH, provided that R ^{1 is} not H, if R ² is a hydrogen atom;
2) a method for producing an azole derivative represented by the formula (1), comprising the following operations:
a) (i) reacting an alkyl ester of 2-hydroxycyclopentanecarboxylic acid with a suitable substituted benzyl halide and reacting the thus obtained alkyl ester of 1- (substituted benzyl) -2-oxocyclopentanecarboxylic acid with a C ₁ -C ₅ alkyl halide; (ii) interaction of 3- (C ₁ -C ₅ -alkyl) -2-oxo-cyclopentanecarboxylic acid alkyl ester with substituted halide gasoline; or (iii) interaction of 1- (substituted benzyl) -3- (C ₁ -C ₅ -alkyl) -2-oxo-cyclopentane-carboxylic acid with a C ₁ -C ₅ halide alkyl, to thereby produce a cyclopentanecarboxylic acid ester derivative represented by the formula

(V) in which R ¹ and R ² respectively represent a C ₁ -C ₅ alkyl group or a hydrogen atom: RC ₁ -C ₅ alkyl group; X is a halogen atom; A C ₁ -C ₅ alkyl group or phenyl group and n is an integer of 0-2, provided that R ^{1 is} not a hydrogen atom if R ² is a hydrogen atom;
c) hydrolytic decarboxylation of the cyclopentane carboxylic acid ester derivative thus obtained, thereby obtaining a cyclopentanone derivative represented by the formula

(IV) in which R ¹ , R ² X and n respectively have the same meanings as defined above;
c) the cyclopentanone derivative thus obtained is subjected to an oxirane reaction using sulfonium or oxosulfonium ylides, or the methylene cyclopentane derivative obtained in this way from the Wittig reaction cyclopentanone derivative and represented by the formula

(III) in which R ¹ , R ² , X and n respectively have the meanings previously defined epoxidation, while turning the cyclopentanone derivative into an ethylene oxide derivative represented by the formula

_, (II) in which R1, R ² , X, and n respectively represent the same values that were previously determined for them, and then
d) the interaction of the obtained ethylene oxide derivative with 1,2,4-triazole or amidazole represented by the formula
Hn

(VI) where M represents a hydrogen atom or an alkali metal atom and A a nitrogen atom or —CH = to obtain the azole derivative represented by the formula

(I) in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; X is a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group; n is an integer of 0-2 and A is a hydrogen or CH atom, provided that R ^{1 is} not a hydrogen atom and R ² is a hydrogen atom, and compositions for use in field cultivation and gardening having fungicidal activity and regulating plant growth activity, which includes an effective amount of an azole derivative represented by the formula (1).

 The damage caused to plant crops by plant diseases is enormous, and there is also the problem of environmental pollution caused by chemicals used in the fight against plant diseases.

 Therefore, the proposal of a chemical for field cultivation and gardening that would be effective in combating plant diseases had low toxicity to humans, animals, birds and fish and low phytotoxicity to useful plants, i.e. An agricultural chemical that has excellent action against plant diseases in a wide range, is highly safe to handle and has little environmental impact, is an urgent need.

 To satisfy this need, the following fungicides have been proposed for use in field cultivation and horticulture.

в которой R¹ представляет собой -СН=СН-Х, -С=С-Х или -СН₂-СН₂-Х (где Х означает атом водорода, алкильную группу, оксиалкильную группу, алкоксиалкильную группу, циклоалкильную группу, замещенную ариальную группу, которая может быть замещена, аралкильную группу, которая может быть замещена, арилоксиалкильную группу, которая может быть заменена, или гетероциклическую группу, которая может быть замещена); R²представляет собой алкильную группу, циклоалкильную группу или арильную группу, которая может быть замещена; Z представляет собой атом хлора, цианогруппу или -OR³ (где R³ является атомом водорода, ацетильной группой, алкильной группой, алкенильной группой или аралкильной группой) и Y представляет собой атом азота или СН, и их кислые аддитивные соли и их металлические комплексы.1) Compounds of triazoles or imidazoles represented by the following formula:

in which R ¹ represents —CH = CH — X, —C = C — X or —CH ₂ —CH ₂ —X (where X is a hydrogen atom, an alkyl group, an oxyalkyl group, an alkoxyalkyl group, a cycloalkyl group, a substituted aryl group which may be substituted, an aralkyl group which may be substituted, an aryloxyalkyl group which may be substituted, or a heterocyclic group which may be substituted); R ² represents an alkyl group, a cycloalkyl group or an aryl group which may be substituted; Z represents a chlorine atom, a cyano group or —OR ³ (where R ³ is a hydrogen atom, an acetyl group, an alkyl group, an alkenyl group or an aralkyl group) and Y represents a nitrogen or CH atom, and their acid addition salts and their metal complexes.

в которой R представляет собой группу с мостиковой связью: -СН=СН-, -О-, -S-, -NH- или -С(=О)-; Х представляет собой атом азота или СН; Y и Z могут быть одинаковыми или отличными друг от друга и соответственно представляют собой атом галогена, алкильную группу, алкоксигруппу, галоидоалкоксигруппу, галоидалкильную группу, нитрогруппу, фенильную группу или феноксигруппу, а m и P соответственно означают 0, 1, 2 или 3, и их кислоту, металлический комплекс и их функциональные производные.2) Compounds of triazoles or imidazoles represented by the following formula:
(Y)

in which R represents a group with a bridging bond: —CH═CH—, —O—, —S—, —NH— or —C (= O) -; X represents a nitrogen atom or CH; Y and Z may be the same or different from each other and respectively represent a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, a haloalkyl group, a nitro group, a phenyl group or a phenoxy group, and m and P respectively represent 0, 1, 2 or 3, and their acid, metal complex and their functional derivatives.

Y

R

в которой R представляет собой алкильную группу, циклоалкильную группу, которая может быть замещена, или фенильную группу, которая может быть замещена; Х атом азота или СН; Y представляет собой -ОСН₂-, -СН₂-СН₂- или -СН=СН-; Z атом галогена, алкильную группу, циклоалкильную группу, алкоксигруппу, алкилтиогруппу, галогеноалкильную группу, галоидалкоксигруппу, галоидалкилтиогруппу, фенильную группу, которая может быть замещена, феноксигруппу, которая может быть замещена, или фенилалкильную группу, которая может быть замещена, или фенилалкоксигруппу, которая может быть защищена, а m означает 0, 1, 2 или 3; их кислые аддитивные соли и металлические комплексы.3) Derivatives of 1-hydroxyethylazole represented by the following formula:

Y

R

in which R represents an alkyl group, a cycloalkyl group which may be substituted, or a phenyl group which may be substituted; X is a nitrogen atom or CH; Y represents —OCH ₂ -, —CH ₂ —CH ₂ -, or —CH = CH—; Z is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a haloalkylthio group, a phenyl group which may be substituted, a phenoxy group which may be substituted, or a phenylalkyl group which may be substituted, or phenylalkyl, or be protected, and m means 0, 1, 2 or 3; their acid addition salts and metal complexes.

_, в которой R⁶ представляет собой незамещенную фенильную группу или замещенную фенильную группу 1-5 группами, выбранными среди групп, включающих атом (ы) галогена, аминогруппу (ы), нитрогруппу (ы), цианогруппу (ы), фенильную группу (ы), галоидофенильную группу (ы), С₁-С₁₀-алкильную группу (ы), галоидо-С₁-С₁₀-алкильную группу (ы), С₁-С₁₀-алкоксигруппу (ы), галоидо-С₁-С₁₀-алкоксигруппу (ы), С₁-С₁₀-алкилтиогруппу (ы), С₁-С₁₀-алкилендитиоксигруппу (ы), С₁-С₁₀-алкиламиногруппу (ы), и ди-С₁-С₁₀-алкиламиногруппы; Х представляет собой атом азота или метиновую группу; кольцо А является циклопентановым кольцом, циклогексановым, циклогептановым, индановым, тетрагидронафтали- новым или бензоциклопентановым кольцом, каждое из перечисленных колец незамещено или замещено в бензольном кольце 1-4 заместителями из числа упомянутых выше (ссылка на выложенную заявку (Кокай) на патент Японии N 58-189171 (1983), соответствующую патенту США N 4503062 и Европейскому патенту N 94146).4) Compounds of cycloaliphatic alcohols represented by the following formula:

_Wherein R ⁶ represents an unsubstituted phenyl group or substituted phenyl group, 1-5 groups selected from the group consisting of atom (s) halogen, an amino group (s), nitro group (s), cyano group (s), phenyl group (s) , halo-phenyl group (s), C ₁ -C ₁₀ -alkyl group (s), halo-C ₁ -C ₁₀ -alkyl group (s), C ₁ -C ₁₀ -alkoxy-group (s), halo-C ₁ -C _10- alkoxy group (s), C ₁ -C ₁₀ -alkylthio group (s), C ₁ -C ₁₀ -alkylene dioxy group (s), C ₁ -C ₁₀ -alkylamino group (s), and di-C ₁ -C ₁₀ -alkylamino group ; X represents a nitrogen atom or a methine group; ring A is a cyclopentane ring, cyclohexane, cycloheptane, indane, tetrahydronaphthalene or benzocycl pentane ring, each of these rings is unsubstituted or substituted in the benzene ring with 1-4 substituents from the above mentioned (reference to Japanese Patent Application Laid-Open (Kokai) No. 58 -189171 (1983), corresponding to US patent N 4503062 and European patent N 94146).

в которой W является СН или атом азота; 0 замещенной или незамещенной арильной группой, в частности замещенной или незамещенной аралкильной группой, или замещенной или незамещенной алкильной группой; R¹, R², R³, R⁴, R⁵, R⁶, R⁷ и R⁸ могут быть одинаковыми или отличными друг от друга и соответственно представляют собой атом водорода, оксигруппу, алкильную группу, циклоалкильную группу, замещенную или незамещенную аралкильную группу, замещенную или незамещенную фенильную группу или любая из пар радикалов R¹ и R², R³ и R⁴, R⁵ и R⁶ или R⁷ и R⁸ представляет собой карбонильную группу (С=0) вместе с соседним углеродным атомом кольца; R⁹и R¹⁰ могут быть одинаковыми или отличными друг от друга и представляют собой соответственно атом водорода, алкильную группу, циклоалкильную группу, замещенную или незамещенную аралкильную группу или замещенную или незамещенную фенильную группу и означает 0 или 1; их стероизомеры, их кислые аддитивные соли и их металлические комплексы (ссылка на выложенную заявку (Кокай) на патент Японии N 60-215674 (1985), соответствующую Европейскому патенту N 153797).5) Triazole or imidazole compounds represented by the following formula:

in which W is CH or a nitrogen atom; 0 a substituted or unsubstituted aryl group, in particular a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkyl group; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different from each other and respectively represent a hydrogen atom, an oxy group, an alkyl group, a cycloalkyl group, a substituted or unsubstituted aralkyl a group, a substituted or unsubstituted phenyl group, or any of the radical pairs R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ or R ⁷ and R ⁸ represents a carbonyl group (C = 0) together with the adjacent carbon atom of the ring ; R ⁹ and R ¹⁰ may be the same or different from each other and represent respectively a hydrogen atom, an alkyl group, a cycloalkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted phenyl group and is 0 or 1; their steroisomers, their acid addition salts and their metal complexes (reference to Japanese Patent Application Laid-Open (Kokai) to Japanese Patent No. 60-215674 (1985) corresponding to European Patent No. 153797).

в которой Х представляет собой соответственно атом галогена, алкильную группу, фенильную группу, цианогруппу или нитрогруппу; n целое число 0-5 и А представляет собой атом азота или СН при условии, что Х может быть одинаковым или разным, если n равно 1-5, полезное для подавления болезней растений.French patent N 2587028, published March 13, 1987 (corresponding to patent HC N 2180236, published March 15, 1987), discloses the closest analogue of the proposed compounds derived azole of the following formula:

in which X represents respectively a halogen atom, an alkyl group, a phenyl group, a cyano group or a nitro group; n is an integer of 0-5 and A represents a nitrogen atom or CH, provided that X can be the same or different if n is 1-5, useful for suppressing plant diseases.

 Further, the invention provides for the synthesis of many azole derivatives and their testing for usefulness as a fungicide for plant growing and horticulture, which would be toxic to humans and animals, would be safe to use and would be highly effective in controlling a wide range of plant diseases, and as a result Studies have found that the azole derivative represented by the formula (1).

(1) в которой R¹ и R² соответственно представляет собой С₁-С₅-алкильную группу или атом водорода; Х атом галогена, С₁-С₅-алкильную группу или фенильную группу; n означает целое число 0-2 и А атом азота или СН при условии, что R¹ не является атомом водорода, если R² является атомом водорода, не только обладает упомянутыми выше свойствами, но еще и может быть эффективно применено в качестве средства, регулирующего рост растений. На основе установления этих феноменов было создано изобретение.

(1) in which R ¹ and R ² respectively represents a C ₁ -C ₅ alkyl group or a hydrogen atom; X is a halogen atom, a C ₁ -C ₅ alkyl group or a phenyl group; n is an integer of 0-2 and A is a nitrogen or CH atom, provided that R ^{1 is} not a hydrogen atom, if R ² is a hydrogen atom, not only has the properties mentioned above, but can also be effectively used as a means of regulating plant growth. Based on the establishment of these phenomena, an invention was created.

 The purpose of the invention is a derivative of azole, useful as an active ingredient in a composition used in field cultivation and gardening, having activity against plant diseases and exhibiting activity in regulating plant growth, a method for producing an azole derivative and composition for use in field cultivation and gardening, containing as an active ingredient, the azole derivative, which has a high effect in the fight against various plant diseases and at the same time is an effective growth regulator and plants, low-toxic and safe to handle.

(1) в которой R¹ и R² соответственно представляют собой С₁-С₅-алкильную группу или атом водорода; Х атом галогена, С₁-С₅-алкильную группу или фенильную группу; n означает целое число 0-2 и А представляет собой атом азота или СН при условии, что R¹ не является атомом водорода, если R²является атомом водорода.In a first aspect of the invention, an azole derivative represented by the formula (1) is provided

(1) in which R ¹ and R ² respectively represent a C ₁ -C ₅ alkyl group or a hydrogen atom; X is a halogen atom, a C ₁ -C ₅ alkyl group or a phenyl group; n is an integer of 0-2 and A represents a nitrogen atom or CH, provided that R ^{1 is} not a hydrogen atom if R ² is a hydrogen atom.

(1) в которой R¹ и R² соответственно представляют собой С₁-С₅-алкильную группу или атом водорода; Х представляет собой атом галогена или алкильную группу с 1-5 углеродными атомами или фенильную группу; n целое число 0-2 и А представляет собой атом азота или СН при условии, что R¹ не является атомом водорода, если R² является атомом водорода, который (способ) включает следующие операции:
a) (i) взаимодействие сложного алкильного эфира 2-оксоциклопентакарбоновой кислоты с замещенным галоидным бензилом и взаимодействие полученного таким образом сложного алкильного эфира 1-(замещенный бензил)-2-оксоциклопентанкарбоновой кислоты с С₁-С₅-галоидоалкилом; (ii) взаимодействие сложного алкильного эфира 3-(С₁-С₅-алкил)-2-оксоциклопентанкарбоновой кислоты с замещенным галоидным бензилом или (iii) взаимодействие 1-(замещенный бензил)-3-(С₁-С₅-алкил)-2-оксоциклопентанкарбоновой кислоты с С₁-С₅-алкилгалогенидом, получая при этом производное сложного эфира циклопентанкарбоновой кислоты, представленной формулой (V)

(V) в которой R¹ и R² соответственно представляют собой алкильную группу с 1-5 углеродными атомами или атом водорода; R алкильной группой с 1-5 углеродными атомами; Х представляет собой атом галогена, алкильную группу с 1-5 углеродными атомами или фенильную группу и n целое число 0-2 при условии, что R¹ не является атомом водорода, если R² является атомом водорода,
в) гидролитическое декарбоксилирование полученного таким образом производного сложного эфира циклопентан- карбоновой кислоты с получением при этом производного циклопентанона формулы (IV)

(IV) в которой R¹, R², X и n соответственно имеют значения, определенные для них ранее:
с) проведение оксирановой реакции полученного таким образом производного циклопентанона с использованием илидов сульфония или оксосульфония, или эпоксидирование метиленциклопентанового производного, полученного из упомянутого выше производного циклопентанона реакция Виттига и представленного формулой (III):

(III) в которой R¹, R², X и n соответственно имеют значения, определенные выше, превращая при этом производное циклопентанона в оксирановое производное, представленной формулой (II)

(II) где R¹, R², X и n имеют значения, определенные для них ранее, и
d) взаимодействие полученного таким образом оксиранового производного с 1,2,4-триазолом или имидазолом, представленным формулой (VI):
MN

(VI) в которой М представляет собой атом водорода или атом щелочного металла и А представляет собой атом азота или СН.A second aspect of the invention provides a method for producing an azole derivative represented by the formula (1)

(1) in which R ¹ and R ² respectively represent a C ₁ -C ₅ alkyl group or a hydrogen atom; X represents a halogen atom or an alkyl group with 1-5 carbon atoms or a phenyl group; n is an integer of 0-2 and A represents a nitrogen atom or CH, provided that R ^{1 is} not a hydrogen atom, if R ² is a hydrogen atom, which (method) includes the following operations:
a) (i) reacting a 2-oxocyclopentacarboxylic acid alkyl ester with substituted benzyl halide and reacting a 1- (substituted benzyl) -2-oxocyclopentanecarboxylic acid alkyl ester thus obtained with C ₁ -C ₅ haloalkyl; (ii) reacting 3- (C ₁ -C ₅ -alkyl) -2-oxo-cyclopentanecarboxylic acid alkyl ester with substituted halide benzyl; or (iii) reacting 1- (substituted benzyl) -3- (C ₁ -C ₅ -alkyl) -2-oxo-cyclopentanecarboxylic acid with a C ₁ -C ₅ -alkyl halide, thereby preparing a cyclopentanecarboxylic acid ester derivative represented by the formula (V)

(V) in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; R is an alkyl group with 1-5 carbon atoms; X represents a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group and n is an integer of 0-2, provided that R ^{1 is} not a hydrogen atom, if R ² is a hydrogen atom,
c) hydrolytic decarboxylation of the cyclopentanecarboxylic acid ester derivative thus obtained, thereby obtaining a cyclopentanone derivative of the formula (IV)

(IV) in which R ¹ , R ² , X and n, respectively, have the meanings defined for them earlier:
c) carrying out the oxirane reaction of the cyclopentanone derivative thus obtained using sulfonium or oxosulfonium ylides, or epoxidizing the methylene cyclopentane derivative obtained from the aforementioned cyclopentanone derivative of the Wittig reaction and represented by the formula (III):

(III) in which R ¹ , R ² , X and n respectively have the meanings defined above, while converting the cyclopentanone derivative to the oxirane derivative represented by the formula (II)

(II) where R ¹ , R ² , X and n have the meanings previously defined for them, and
d) the interaction of the thus obtained oxirane derivative with 1,2,4-triazole or imidazole represented by formula (VI):
Mn

(VI) in which M represents a hydrogen atom or an alkali metal atom, and A represents a nitrogen atom or CH.

(1) в которой R¹ и R² соответственно представляют собой алкильную группу с 1-5 углеродными атомами или атом водорода; Х атом галогена, алкильную группу с 1-5 атомами углерода или фенильную группу; n целое число 0-2 и А представляет собой атом азота или СН при условии, что R¹ не является атомом водорода, если R² является атомом водорода.A third aspect of the invention provides a composition for use in field cultivation and horticulture, having fungicidal activity and regulating plant growth activity, which contains as an active ingredient the azole derivative represented by the formula (1):

(1) in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; X is a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group; n is an integer of 0-2 and A represents a nitrogen atom or CH, provided that R ^{1 is} not a hydrogen atom if R ² is a hydrogen atom.

(II) в которой R¹ и R² соответственно представляют алкильную группу с 1-5 углеродными атомами или атом водорода; Х атом галогена, алкильную группу с 1-5 углеродными атомами или фенильную группу и n означает целое число 0-2 при условии, что R¹ не является атомом водорода, если R²является атомом водорода.A fourth aspect of the invention provides an ethylene oxide derivative for the preparation of an azole derivative represented by the formula (1), which is represented by the formula (II),

(II) in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; X is a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group and n is an integer of 0-2, provided that R ^{1 is} not a hydrogen atom if R ² is a hydrogen atom.

A fifth aspect of the invention provides a methylene cyclopentane derivative for the preparation of an azole derivative represented by the formula (1), which is represented by the formula (III)
_,
(III)
in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; X is a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group and n is an integer of 0-2, provided that R ^{1 is} not a hydrogen atom if R ² is a hydrogen atom.

_, (IV) где R¹ и R² соответственно представляют С₁-С₅ алкильную группу или атом водорода; Х атом галогена, С₁-С₅ алкильную группу или фенильную группу и n-целое число 0-2, при условии что R¹ не является атомом водорода, когда R²-водород.In a sixth aspect, the invention provides a cyclopentanone derivative for the preparation of an azole derivative represented by formula 1 represented by formula (IV)

_, (IV) where R ¹ and R ² respectively represent a C ₁ -C ₅ alkyl group or a hydrogen atom; X is a halogen atom, a C ₁ -C ₅ alkyl group or phenyl group and an n-integer 0-2, provided that R ^{1 is} not a hydrogen atom when R ^{2 is} hydrogen.

^, (V) в которой R¹ и R² соответственно представляют собой алкильную группу с 1-5 атомами углерода или атом водорода; R алкильную группу с 1-5 углеродными атомами; Х атом галогена, алкильную группу с 1-5 углеродными атомами или фенильную группу и n целое число 0-2 при условии, что R¹ не является атомом водорода, если R² является атомом водорода.A seventh aspect of the invention provides a cyclopentanecarboxylic acid ester derivative to produce an azole derivative represented by formula (I), which is represented by formula (V):

^, (V) in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; R is an alkyl group with 1-5 carbon atoms; X is a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group and n is an integer of 0-2, provided that R ^{1 is} not a hydrogen atom if R ² is a hydrogen atom.

_, (I) в которой R¹ и R² соответственно представляют собой алкильную группу с 1-5 углеродными атомами или атом водорода; Х атом галогена, алкильную группу с 1-5 углеродными атомами или фенильную группу; n целое число 0-2 и А атом азота или СН при условии, что R¹ не является атомом водорода, если R² атом водорода; способе получения азольного производного, представленного формулой (1), каждое из соединений, используемых в качестве промежуточных, а именно оксирановом производном, представленном формулой (II), метиленциклопентановом, представленном фоpмулой (III), циклопентановом, представленном формулой (IV), и производном сложного эфира циклопентакарбоновой кислоты, представ- ленном формулой (V), и в композиции для использования в полеводстве и садоводстве, содержащей азольное производное формулы (I) в качестве активного ингредиента и обладающей фунгицидной активностью и активностью регулятора роста растений.The inventive new azole derivative represented by the formula (I):

_, (I) in which R ¹ and R ² respectively represent an alkyl group with 1-5 carbon atoms or a hydrogen atom; X is a halogen atom, an alkyl group with 1-5 carbon atoms or a phenyl group; n is an integer of 0-2 and A is a nitrogen or CH atom, provided that R ^{1 is} not a hydrogen atom if R ^{2 is} a hydrogen atom; the method for producing the azole derivative represented by the formula (1), each of the compounds used as intermediates, namely the oxirane derivative represented by the formula (II), methylene cyclopentane represented by the formula (III), cyclopentane represented by the formula (IV), and the complex derivative cyclopentacarboxylic acid ester represented by the formula (V) and in a composition for use in field cultivation and horticulture containing the azole derivative of the formula (I) as an active ingredient and having fungicide one activity and activity of a plant growth regulator.

 The physical and chemical properties of the azole derivative represented by the formula (1) and each of the intermediates for the preparation of the azole derivative are shown in Table. 1-5.

 In addition, each of these intermediates is a new compound.

Note to table 1-5. The NMR spectra in Tables 1-5 were measured using tetramethylsilane as the internal standard. The designations are as follows:
S singlet; d doublet; t triplet; q quartet; m multiplet; b wide line; j interaction constant (Hz).

In the azole derivative represented by the formula (1), from the point of view of activity against plant diseases and activity in regulating plant growth, an azole derivative in which R ¹ is a hydrogen atom or an alkyl group with 1-4 carbon atoms; R ² is a hydrogen atom or alkyl with 1-3 carbon atoms (both R ¹ and R ² cannot be hydrogen atoms at the same time); X is a halogen atom replacing the 4th position of the benzene ring; n is equal to unity and A represents a nitrogen atom or CH, preferably, moreover, an azole derivative in which R ¹ and R ² respectively represent a hydrogen atom or an alkyl group with 1-3 carbon atoms (both R ¹ and R ² are not hydrogen atoms at the same time); X represents a halogen atom replacing the 4th position of the benzene ring; means unity and A represents a nitrogen atom, most preferred.

 Of the compounds shown in table. 1, preferred compounds are compounds 1-3, 5, 9-11, 16, 18, 29-32, 37, 38, 42-45, 50, 59, 62, 63, 65, and 69.

 The azole derivative according to the invention is prepared as follows.

(VI) в которой М представляет собой атом водорода или атом щелочного металла и А представляет собой атом азота или СН.The target azole derivative represented by formula (1) can be prepared by reacting an ethylene oxide derivative represented by formula (II) with 1,2,4-triazole or imidazole represented by formula (VI) in the presence of a diluent:
Mn

(VI) in which M represents a hydrogen atom or an alkali metal atom, and A represents a nitrogen atom or CH.

 The ethylene oxide derivative represented by formula (II), which is used as a starting material, can be prepared by the following method, namely, by reacting cyclopentanone represented by formula (IV) with a sulfonium or oxysulfonium ylide, for example dimethyloxosulfonium methylide or dimethyl sulfonyl methylide in the presence of a the method described in Org. Synt. 49 78 (1968) and in I. Amer. chem. Soc. (1965) 1353; to obtain the ethylene oxide compound represented by formula (II) (this method is named as the A-method). And another, different from the first method (called the B-method), according to which methylene cyclopentane represented by formula (II) is obtained from cyclopentanone represented by formula (IV) by the Wittig reaction (Org. Syn. 40, 66 (1966) and I Org. Chem. 28, (1963), 1128) and then the ethylene oxide derivative represented by formula (II) can be obtained by epoxidation from the compound thus obtained (Org. Syn. Coll. Vol. 4, 552 (1963), 49, 62 (1969).

 The reaction scheme according to the A-method and B-method is presented below.

Кроме того, производное циклопентанона, представленное формулой (IV), может быть получено следующим способом. А именно, в случае, если R¹ и R² в формуле (IV) являются одинаковыми, т.е. алкильными группами с 1-5 углеродными атомами, то циклопентаноновое соединение, представленное формулой (VII), подвергают диалкилированию, превращая его при этом в производное сложного эфира циклопентанкарбоновой кислоты, представленной формулой (V), и производное сложного эфира, представленное формулой (I), подвергают гидролизу и декарбоксилированию, а в том случае, когда только один из R¹ и R² является алкильной группой с 1-5 углеродными атомами, а другой является атомом водорода, то желаемую бензильную группу вводят в производное алкилциклопентанкарбоксилата, представленное формулой (VIII), чтобы получить производное сложного эфира циклопентанкарбоновой кислоты, представленное формулой (V), и затем полученное таким образом производное сложного эфира подвергают гидролизу и декарбоксилированию. Проделав это, можно получить циклопентаноновое производное, представленное формулой (IV).Methods for producing an oxirane derivative represented by the formula (II):

In addition, the cyclopentanone derivative represented by formula (IV) can be obtained by the following method. Namely, in the case where R ¹ and R ² in the formula (IV) are the same, i.e. alkyl groups with 1-5 carbon atoms, the cyclopentanone compound represented by formula (VII) is subjected to dialkylation, turning it into a derivative of the cyclopentanecarboxylic acid ester represented by formula (V) and an ester derivative represented by formula (I), is hydrolyzed and decarboxylated, and, in the case where only one of R ¹ and R ² is an alkyl group with 1-5 carbon atoms and the other is hydrogen atom, the desired benzyl derivative group is introduced into alkiltsiklo entankarboksilata represented by formula (VIII), to obtain the ester derivative of cyclopentanecarboxylic acid represented by formula (V), and then the thus obtained ester derivative is subjected to hydrolysis and decarboxylation. Having done this, it is possible to obtain a cyclopentanone derivative represented by the formula (IV).

Further, in the event that R ¹ and R ² in the formula (IV) are mutually different alkyl groups with 1-5 carbon atoms, then after the introduction of a different alkyl group with 1-5 carbon atoms in the derivative of the ester, cyclopentanecarboxylic acid, represented by the formula ( V), in which either R ¹ or R ² is an alkyl group with 1-5 carbon atoms and the other (remaining) is a hydrogen atom, the resulting ester derivative is subjected to hydrolysis and decarboxylation to obtain the desired derivative represented by formula (IV) . The reaction scheme for the preparation of said cyclopentanone is presented below.

Соединения, представленные формулами (VII) и (VIII), являются известными соединениями и могут быть получены из сложного алкилового эфира 2-оксоциклопентанкарбоновой кислоты методами, описанными в Org. Syn. 45, 7 (1965) и I. Org. Chem. 29, 2781, 1964.Scheme for the synthesis of cyclopentanone of formula (IV)

The compounds represented by formulas (VII) and (VIII) are known compounds and can be prepared from 2-oxocyclopentanecarboxylic acid alkyl ester by the methods described in Org. Syn. 45, 7 (1965) and I. Org. Chem. 29, 2781, 1964.

 As the diluent used in the reactions involved in the process for producing the azole derivative represented by the formula (I), for example, hydrocarbons such as benzene, toluene, xylene and the like can be used. halocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc. alcohols, such as methanol, ethanol, etc. ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and the like. and others, including acetonitrile, acetone, dimethylformamide, dimethyl sulfoxide and the like.

 In addition, in the proposed method, the reaction is carried out in the presence of a base or acid in addition to the aforementioned diluent. As the base used in the method, for example, alkali metal carbonates such as sodium carbonate, potassium carbonate and the like; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like; alkali metal alcoholates such as sodium methylate, sodium ethylate, potassium tetrabutylate and the like; alkali metal hydrides such as sodium hydride, potassium hydride and the like; alkali metal alkyl compounds such as n-butyllithium, etc. and others, such as triethylamine, pyridine, etc.

 As the acid, for example, inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid and the like can be used. and organic acids such as formic acid, acetic acid, butyric acid, p-toluenesulfonic acid, etc.

In order to accelerate the process of obtaining the azole derivative, for example, in the case of the preparation of the cyclopentanecarboxylic acid ester derivative represented by the formula (V), it is preferable to react alkyl halide or substituted benzoyl halide with a compound represented by the formula (VII) or the formula (VIII) dissolved in thinner, in the presence of a base as circumstances require. The reaction temperature may be optionally selected in the range of solidification temperature of the diluent as the solvent to its boiling temperature and preferably in the range of 0-100 ° ^C.

Derivative represented by formula (IV), can be obtained by decarboxylation of the ester derivative of cyclopentanecarboxylic acid represented by formula (V) at 80-150 ^{° C} with an inorganic or organic acid for 2-24 hours, preferably under stirring.

 In order to obtain the oxirane derivative represented by formula (II) in the case of method A, it is preferable to add a solution prepared by dissolving the ketone represented by formula (IV) in a diluent (dimethyl sulfoxide is particularly preferred) to dimethyloxesulfonium methylide or to dimethyl sulfonyl methylide obtained by mixing an equivalent amount of base (e.g. sodium hydride) and trimethyloxosulfonium iodide or trimethylsulfonium iodide, and allow the two compounds to react.

In this case, the amount of dimethyloxosulfonium methylide or dimethylsulfonium methylide involved in the reaction is preferably 1.0-2.0 equivalent amounts of the cyclopentanone derivative represented by the formula (IV). The reaction is preferably carried out in the temperature range 25-100 ^about With and for 1-40 hours

In the case of the preparation of the oxirane derivative by Method B, the cyclopentanone derivative represented by the formula (IV) is added to triphenylphosphine methylide (Wittig reagent) prepared by mixing an equivalent amount of a base (e.g. sodium hydride) and methyltriphenylphosphonium halide in a diluent (dimethyl sulfoxide is especially preferred) and the reaction compounds in the temperature range 0-100 ^{° C} and for a time of 2-10 hours. The resulting metilentsiklopentanona derivative represented by formula (III), is isolated, a solution of yayut in diluent and reacted at (-10) ^° C to ^the boiling point of the diluent, preferably (-10) - (80) ^C after addition of hydrogen peroxide or an organic per-acid such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid and the like.

(II A тип)

(II В тип) разделение этих изомеров, представленных формулами (II-A) и (II-B), может быть проведено, например, хроматографическими методами (тонкослойная хроматография, колоночная хроматография, высоко эффективная жидкостная хроматография и так далее). Характеристики структуры этих стереоизомеров могут быть найдены, например, спектром ядерного магнитного резонанса.The oxirane derivative (compound II) obtained from the cyclopentanone derivative represented by formula (IV), by Method A or Method B gives the following stereoisomeric structures with respect to the conformation of the oxirane group at the 3-position and the substituted benzyl group at the 7-position of 1-oxaspiro (2, 4) -heptane of an oxirane compound represented by the formula (II)

(II A type)

(II B type) the separation of these isomers represented by formulas (II-A) and (II-B) can be carried out, for example, by chromatographic methods (thin layer chromatography, column chromatography, high performance liquid chromatography and so on). The structural characteristics of these stereoisomers can be found, for example, by a nuclear magnetic resonance spectrum.

In order to obtain the azole derivative represented by the formula (I), the oxirane compound represented by the formula (II) is added in the presence of a base, as required by circumstances, to a solution prepared by dissolving the azole compound represented by the formula (VI) in a diluent or, alternatively, an alkali metal salt The azole compound is added to the solution prepared by dissolving the oxirane compound in the diluent and the two compounds are allowed to react. The reaction temperature may be optionally selected in the range of solidification point to the boiling point of the diluent, but the reaction is preferably carried out in practice at 0-120 ^{° C} and more preferably 60-120 ^{° C} for 1-10 hours with stirring.

 After completion of the reaction, the reaction mixture thus obtained was cooled and extracted with an organic solvent such as ethyl acetate, chloroform, methylene chloride, benzene, etc. in ice water. After separating the organic layer, washing it with water and drying the washed layer, the solvent was distilled off under reduced pressure from the organic layer. The residue thus obtained was purified and thus the desired compound was obtained. Purification was carried out by subjecting the residue to recrystallization, chromatography on silica gel and the like.

(I-A тип)

(I-B тип)
за воображаемой плоскостью;
______________ на воображаемой плоскости;

перед воображаемой плоскос-тью.Since there are two isomers represented by the formulas (II-A) and (II-B) in the oxirane compound, which is the starting compound for the azole derivative represented by the formula (I), the following stereoisomers in the target azole derivative represented by the formula (I ), which is obtained by the reaction of an oxirane compound represented by the formula (II) and 1,2,4-triazole or imidazole represented by the formula (VI):

(IA type)

(IB type)
beyond an imaginary plane;
______________ on an imaginary plane;

in front of an imaginary plane.

 Of course, that the separation of the isomers represented by the formulas (I-A) and (I-B) can be performed, for example, by chromatographic methods.

 The usefulness of the azole derivative (azolylcyclopentanol derivative) represented by formula (I) as the active ingredient of the composition for field cultivation and horticulture is explained below.

(I) Fungicidal effect on fungal diseases of plants
The azole derivative according to the invention shows efficacy in controlling the following plant diseases in a wide range
Pyricularia oryzae On rice plants
Cochliobolus miyabeanus Same
Xanthomonas oryzae - "-
Rhizoctonia solani - "-
Helminthosporhum sigmo-
deum - "-
Gibberella fujiluroi - "-
Podosphaera leucotricha On Apple Trees
Ventura inaequalis Same
Sclerotinia mali - "-
Alternaria mali - "-
Valsa mali - "-
Alternaria kikuchiana On the pear
trees
Phyllactinia pyri Same
Gymnosporangium Haraeonum - "-
Ventura nashicola - "-
Unccinula necator On the grape
Phakospora ampelopsidis Same
Glomerella cingulata - "-
Erysiphe graminis f. sp. hordei barley
Phynchosporium secalis Same
Puccinia graminis - "-
Puccinia triformis - "-
Puccinia recondia Wheat
Septoria tritici Same
Puccinia triformis - "-
Erysiphe graminis f. sp. tritici - "-
Sphaerotheca fuliginea Watermelon
(melons)
Colletotrichum lagenarium Same
Fusarium oxysporum - "-
Fusarium oxysporum f. On cucumbers
cucumerium
Fusarium oxysporum f. raphani fucking japanese
Erysiphe cichoracearum On tomato
Alternaria solani On tomato
Erysiphe cichoracearum mulberry
tree
Sephaerotheca humuli On Strawberry
Erysiphe cichoracearim Tobacco
Alternaria longipes Tobacco
Cercospora beticola Sugar
beetroot
Alternaria solani Potato
Septoria glicines soya bean
Cercospora kikuchil Soi Kul
tour
Sclerotinia cinerea stone fruit
fruit races
tenias
Botrytis cinerea At various
cultures
Sclerotinia sclerotiorum etc.

 In addition, the azole derivative has not only a preventive effect, but also a therapeutic effect on some plant diseases.

(2) Activity in regulating plant growth
As the mechanism for regulating plant growth by plant hormones has been clarified, the practice of field cultivation and gardening in recent years has included chemicals called plant growth regulators.

 For example, obtaining seedless grapes using gibberellin, stimulating the rooting of cuttings by naphthalene-acetic acid, and using 2-chloroethyltrimethylammonium chloride (trade name CCC) as a growth inhibitor of wheat is known. In addition, the application of plant life cycle management methods using plant growth regulators has spread not only to cultivated plants, such as cereals, vegetable plants, fruit trees, etc. but also to garden plants, such as flowers and others, and further to trees as plants in a broad sense, and the function of plant growth regulators has spread to stimulate rooting, regulate flowering, fruiting, increase fruit size, promote growth, regulate growth and regulate metabolism.

 Consequently, the use of types and amounts of agents for regulating plant growth has a growth trend in recent years, however, the demand for agents for regulating plant growth is ahead of offers that are not stimulated to such an extent as expected.

The azole derivative (azolylcyclopentanol derivative) according to the invention has the specific property of exhibiting various activity for regulating plant growth over a wide range, which is illustrated in the following examples:
i) inhibition of vegetative plant growth, in particular inhibition of plant growth in height;
ii) an increase in the activity and content of the beneficial component of plants; and iii) an activity that regulates the flowering and ripening times of plants.

 An example of the use of growth inhibitory activity according to i) is the inhibition of weed growth (herbicidal function) and turf; preventing lodging of lodging plants such as rice plants, barley, wheat, etc. the use of a mechanical method for regulating the flowering of soybean and cotton by inhibition of growth in height; inhibition of the origin of axillary kidneys to stimulate the growth of tobacco leaves; facilitating trimming operations by inhibiting hedge growth; increasing the commercial value of plants by delaying their growth, etc. which can be used to confirm inhibitory activity.

 An example of the use of activity that increases the content of the beneficial component of plants according to paragraph ii) is to improve the quality of sugar beets, sugar cane and citrus fruits with increased sugar content; improving the quality of crops and soybeans by increasing protein content, etc. and an example of the use of regulatory activity related to the ripening dates of fruits and flowering dates under paragraph iii) is the timing of the transportation of fresh fruits and fresh flowers to the requirements of the season, etc.

 To use the azole derivative represented by formula (I) as a fungicidal agent and plant growth regulator, the derivative itself or a mixture of the derivative and carrier (diluent) is processed into powders, wettable powders, granules, emulsifiable concentrates, liquid preparations, etc. and such formulations can be advantageously applied.

 In addition, it is possible to add auxiliary agents to achieve the effect, such as wetting agents, emulsifiers, binders, in addition to the carrier. Since the azole derivative represented by the formula (I) contains a 1,2,4-triazole ring or an imidazole ring, the azole derivative can be used in the form of an acid addition salt or in the form of a metal complex. In addition, since the azole derivative represented by the formula (I) has an azolylmethyl group, an alkyl group with 1-5 carbon atoms and a substituted benzyl group, respectively, are in the 1st position, in the 2nd and 5th positions of the cyclopentane ring, then stereoisomers such as geometric cis and trans isomers and optical isomers can exist, and the invention includes within its scope each of the isomers and mixtures of each isomer to the extent possible.

 Thus, the proposed composition for use in field cultivation and horticulture includes compositions containing a single isomer or a mixture of isomers as an active ingredient.

 The azole derivative represented by the formula (I) has a high activity against plant diseases and an activity of a plant growth regulator and is a useful compound as an active ingredient in a composition for field cultivation and gardening.

 The effectiveness of the invention can be explained with specific examples of a composition for dusting and horticulture using the azole derivative as an active ingredient, but the invention is not limited to these examples.

 Examples of the preparation of the azole derivative represented by the formula (I) and each of the intermediates for the preparation of the azole derivative.

 PRI me R 1. Obtaining methyl ester of 1- (4-chlorobenzyl) -3,3-dimethyl-2-oxocyclopentanecarboxylic acid, intermediate compound 156, are presented in table. 5.

In 150 ml of anhydrous benzene, 5.0 g of sodium hydride (obtained by washing with 60% oil hydride of sodium hydride with anhydrous benzene) was added with stirring in a helium atmosphere, and 50 g of 1- (4-chlorobenzyl) -2-oxo cyclopentanecarboxylic acid methyl ester and a mixture were added to the mixture. stirred for 40 min at 80 ^C. After cooling the mixture to room temperature, the reaction mixture was added 5.0 g of sodium hydride (one equivalent) and the reaction mixture was stirred for 30 min at 80 ^C. After cooling the reaction mixture to room temperature, the reaction mixture aDDED Yali metal iodide, 29.4 g (one equivalent) and the reaction mixture was stirred for 8 hours at 80 ° ^C.

 After cooling the reaction mixture, it was poured into a mixture of acetic acid and ice water, and the reaction mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer thus obtained with an aqueous solution of sodium hydrogencarbonate and then with brine, the washed organic layer was dried on anhydrous sodium sulfate and the solvent was distilled off from the organic layer under reduced pressure.

The residue thus obtained was distilled under reduced pressure and purified to give 44.8 g of the title compound (m. Bales. 142-143 ^{° C} (0.7 mm Hg).

 PRI me R 2. Obtaining 5- (4-chlorobenzyl) -2,2-dimethyl-1-cyclopentanone (intermediate compound 133 are shown in table. 4).

To 120 ml of 47% hydrobromic acid, 44.8 g of 1- (4-chlorobenzyl) -3,3-dimethyl-2-oxocyclo-pentanecarboxylic acid methyl ester (compound 155 is shown in Table 5) was added and the resulting mixture was vigorously stirred 12 hours at 100 ^about C.

After cooling the reaction mixture, it was poured into ice water and the mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with an aqueous solution of sodium hydrogencarbonate and then with an aqueous brine, the organic layer was dried on anhydrous sodium sulfate. Removal of the solvent from the organic layer under reduced pressure gave a residue. After distillation of the obtained residue under reduced pressure and purification, 31 g of the target compound were obtained (mp. 124 ^° C (1 mm Hg).

 PRI me R 3. Obtaining 5- (4-chlorobenzyl) -2,2-dimethyl-1-methylene cyclopentane (intermediate compound 122, table. 3).

To 50 ml of anhydrous dimethyl sulfoxide was added 3.6 g of sodium hydride (prepared by washing 60% oily sodium hydride with anhydrous benzene) in a helium atmosphere, and the resulting mixture was stirred for 30 min at 70 ^C. After cooling the reaction mixture, iced water was added 53.6 g of methyltriphenylphosphonium bromide and the resulting mixture was stirred for 30 minutes while cooling with ice water and then the cooled mixture was stirred at room temperature for 10 minutes. To the mixture was added 23.6 g of 5- (4-chlorobenzyl) -2,2-dimethyl-1-cyclopentanone (Compound N 133, Tab. 4) and the resulting mixture was stirred for 1 hour at room temperature and 30 min at 70 ° ^C to complete the reaction.

 After cooling the reaction mixture, it was poured into ice water and extracted with ethyl acetate to obtain an organic layer. After washing the obtained organic layer with aqueous saline, the washed organic layer was dried on anhydrous sodium sulfate and the solvent was distilled off from the dried organic layer under reduced pressure.

 From the resulting mixture of an oily substance and a solid, the oily substance was extracted with n-hexane and the obtained n-hexane extract was purified by silica gel column chromatography to obtain 22.1 g of the target compound.

PRI me R 4. Obtaining 7- (4-chlorobenzyl) -4,4-dimethyl-1-oxaspiro (2,4) heptane (intermediate compound 77 and 78, shown in table. 2 and obtained by method A)
To 70 ml of anhydrous dimethyl sulfoxide, 3 g of sodium hydride (obtained by washing with 60% sodium butyric anhydride with anhydrous benzene) was added with stirring of dimethyl sulfoxide in a helium atmosphere, and then 27.5 g of trimethylsulfonium iodide was added to the resulting mixture. After the mixture was stirred at room temperature for 30 minutes, a solution of 23.6 g of 5- (4-cyclobenzyl) -2,2-dimethyl-1-cyclopentanone (compound 133, table 4) in 20 ml of anhydrous dimethyl sulfoxide was added to the mixture for 30 minutes and the whole mixture was stirred 2 hours at 90 ^about C.

 After cooling the reaction mixture, it was poured into ice water and the mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with aqueous saline, the organic layer was dried on anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The obtained residue was subjected to silica gel chromatography, and 13.95 g of the target compound 77 and 1.05 g of the target compound 78 were obtained.

PRI me R 5. Obtaining 7- (4-fluorobenzyl) -4,4-dimethyl-1-oxaspiro (2,4) heptane (intermediate compound N 81 and N 82 shown in table 2, obtained method B)
17 and 5- (4-fluorobenzyl) -2,2 dimethyl-1-methylenecyclopentane (compound N 124, table 3) were dissolved in 170 ml of chloroform, and 27.1 g of m-chloroperbenzoic acid obtained over 10 minutes was added to it the mixture was stirred for 2 hours at room temperature. Next, 25.4 g of calcium hydroxide was added to the mixture over 10 minutes, and the mixture was stirred at room temperature for 30 minutes.

 After filtration to separate the solid, the chloroform layer of the filtrate was condensed to give a colorless oily material. The remaining oily product was subjected to silica gel column chromatography to give 4.5 g of purified target compound 81 and 8.6 g of target compound 82.

 PRI me R 6. Obtaining C-5- (2,4-dichlorobenzyl) -2,2-dimethyl-1- (IH-imidazol-1-yl-methyl) -g-l-cyclopenta nola (compound 15 shown in table 1).

In 18 ml of anhydrous dimethylformamide, 996 mg of sodium hydride (obtained by washing with 60% oily sodium hydride with anhydrous benzene) was added in a helium atmosphere with stirring. Then, 2.83 g of IH-imidazole was added to the resulting mixture, and the mixture was stirred at room temperature until the evolution of gas bubbles turned. A solution obtained by dissolving 5.93 g of 7- (0,2-dichlorobenzyl) -4,4-dimethyl-1-oxaspiro (2,4) heptane (compound 83, table 2) in 10 ml was added dropwise to the resulting solution. anhydrous dimethylformamide, and the resulting mixture was stirred for 2 hours at 80 ^C. After cooling, the reaction mixture was poured into ice water and the resulting mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with water, the organic layer was dried with anhydrous sodium sulfate, and the solvent was distilled off from the organic layer under reduced pressure.

 The resulting residue was purified by silica gel column chromatography and then recrystallized from n-hexane-ethyl acetate. The result was 2.7 g of the target compound.

PRI me R 7. Obtaining t-5- (4-chlorobenzyl) -2,2-dimethyl-1- (1H-1,2,4-triazol-1-yl-methyl) -g-l-cyclopentanol (compound 2, table. 1)
To 30 ml of anhydrous dimethylformamide, 5.0 g of (4-chlorobenzyl) -4,4-dimethyl-1-oxaspiro (2.2) heptane was added and dissolved under stirring in a helium atmosphere (compound 78, table 2) and to the resulting solution 2.2 g of 1H-1,2,4-triazole sodium salt was slowly added (90% purity commercially available from Aldrich Co.). Then the mixture was stirred for 2 hours at 70 ^about C.

 After cooling the resulting reaction mixture, it was poured into ice water and the whole mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with water, the organic layer was dried on anhydrous sodium sulfate, and the solvent was distilled off from the dried organic layer under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 3.1 g of the target compound.

PRI me R 8. Obtaining 2- (4-chlorobenzyl) -5-methyl-1-cyclopentanone intermediate compound 137, table. 4)
To 0.04 ml of anhydrous benzene was added 3.04 g of sodium hydride (obtained by washing with 60% oily sodium hydride with anhydrous benzene) and then 18 g of 3-methyl-2-oxo-cyclopentanecarboxylic acid methyl ester was added. After stirring the mixture for 1 h at room temperature, to the mixture was added 21.5 g of 4-chlorobenzyl chloride, and the resulting mixture was refluxed for 6 hours in an oil bath at 90 ° ^C.

 After cooling the reaction mixture, it was extracted with benzene and the benzene layer was washed with aqueous saline. After the benzene layer was dried on anhydrous sodium sulfate, the solvent was distilled off from the dried benzene layer under reduced pressure to obtain 33.6 g of a tan oily product of 1- (4-chlorobenzyl) -3-methyl-2-oxocylpentanecarboxylic acid methyl ester (intermediate 160 table 5).

Without purification, the resulting ester was added 100 ml of 47% hydrobromic acid and the resulting mixture was vigorously stirred for 18 hours at 110 ^C. After cooling the reaction mixture, it was extracted with methylene chloride and the organic layer was washed with aqueous sodium carbonate solution and then with aqueous brine. The washed organic layer was dried on anhydrous sodium sulfate, and the solvent was distilled off from the organic layer under reduced pressure. The resulting residue was purified by distillation under reduced pressure to obtain 17.4 g of the target compound.

 PRI me R 9. Obtaining methyl ester of 1- (4-chlorobenzyl) -3-ethyl-3-methyl-2-oxocyclopentanecarboxylic acid (intermediate compound 178, table. 5).

To 80 ml of anhydrous tetrahydrofuran, 1.7 g of sodium hydride (obtained by washing with 60% oily sodium hydride) was added with stirring in a helium atmosphere, and then 18.2 g of 1- (4-chlorobenzyl) -3-methyl- methyl ester was added to the resulting mixture. 2-oxocyclopentanecarboxylic acid (Intermediate 160, Table 5), the whole mixture was stirred for 2 hours at room temperature. Thereafter, to the mixture was added dropwise 11.1 g of ethyl iodide while maintaining the mixture temperature between 20-30 ^{° C,} and then the whole mixture was stirred for 1 hour at a temperature of 20-30 ^{° C} and subsequently for 1 hour at 60 ° ^C.

 After cooling, the reaction mixture was poured into a mixture of acetic acid and ice water, and the mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with an aqueous solution of sodium hydrogencarbonate and then with aqueous saline, the washed organic layer was dried on anhydrous sodium sulfate and the solvent was distilled off from the dried organic layer under reduced pressure.

 The resulting residue was purified by distillation under reduced pressure to obtain 15 g of the target compound.

 PRI me R 10. Obtaining 4- (4-chlorobenzyl) -7-methyl-1-oxaspiro (2,4) -heptane (intermediate 85, table. 2). 1.44 g of sodium hydride (obtained by washing with 60% sodium butyric anhydride with anhydrous benzene) was added to 37 ml of anhydrous dimethyl sulfoxide with stirring in a helium atmosphere, and 13.2 g of trimethyloxesulfonium iodide was added to the resulting mixture, and the whole mixture was stirred for 30 min at room temperature. Then, a solution of 12.2 g of 2- (4-chlorobenzyl) -5-methyl-1-cyclopentanone (compound 137, table 4) in 12 ml of anhydrous dimethyl sulfoxide was added to the mixture over 10 min, and the resulting mixture was stirred for 4 h at room temperature.

 The resulting reaction liquid was poured into ice water and the mixture was extracted with methylene chloride to obtain an organic layer. After washing with an aqueous brine, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off from the organic dried layer under reduced pressure.

 The resulting residue was purified by silica gel column chromatography to obtain 6.67 g of the target compound.

 In addition, apart from the target compound, three more types of isomers of the target compound were isolated, namely 0.15 g of intermediate 86, 0.16 g of intermediate 87 and 0.16 g of intermediate 88 (Table 2).

 PRI me R 11. Obtaining 4- (4-chlorobenzyl) -7-ethyl-1-oxaspiro (2,4) -heptane (intermediates 93-96, table 2). 8.0 g of 2- (4-chlorobenzyl) -5-ethyl-1-methylenecyclopentane (compound 129, table 3) was dissolved in 100 ml of chloroform, and 11.6 g of m-chloroperbenzoic was added to the resulting solution over 5 minutes acid and the whole mixture was stirred for 2 hours at room temperature. Under ice-cooling, 11 g of calcium hydroxy was added to the mixture, and the mixture was stirred at room temperature for 30 minutes.

 The solid that separated was isolated by filtration, and the chloroform layer of the filtrate was concentrated to obtain a colorless oily product. The oily substance was purified by silica gel column chromatography to obtain 0.7 g of compound 93; 2.4 g of compound 94; 2.2 g of compound 95 and 2.6 g of compound 96 indicated in the title of example.

 PRI me R 12. Obtaining C-2- (4-chlorobenzyl) -5-methyl-1- (IH-1,2,4-triazol-1-ylmethyl) -g-l-cyclopentanol (compound 16, table 1). 630 mg of sodium hydride (obtained by washing with 60% oily sodium hydride with anhydrous benzene) was added to 10 ml of anhydrous dimethylformamide, and then 1.8 g of 1H-1,2,4-triazole was added to the mixture, and the whole mixture was stirred at room temperature until the bubbling ceased gas.

To the resulting reaction mixture was added a solution of 3.1 g of 4- (4-chlorobenzyl) -7-methyl-1-oxaspiro (2,4) heptane (compound 85, table 2) in 6.2 ml of anhydrous dimethylformamide and the resulting mixture was stirred 1 h at 80 ^C. After cooling, the obtained reaction liquid was poured into ice-water and the resulting mixture was extracted with methylene chloride to obtain an organic layer. After washing the organic layer with an aqueous saline, it was dried on anhydrous sodium sulfate and the solvent was distilled off from the organic layer under reduced pressure. The resulting residue was purified by silica gel column chromatography and then recrystallized from n-gensane-ethyl acetate, and 2.83 g of the target compound was obtained.

Example 13 Preparation of C-2 (4-chlorobenzyl) -5-methyl-1- (1H-imidazol-1-ylmethyl-g-l-cyclopentanol (compound 17, table 1). To 10 ml anhydrous dimethylformamide was added 670 mg of sodium hydride (obtained by washing with 60% oily sodium hydride and then 1.9 g of In-imidazole was added and the mixture was stirred at room temperature until the reaction mixture became clear. Next, a solution of 3.3 g was added to the mixture 4- (4-chlorobenzyl) -7-methyl-1-oxaspiro (2,4) heptane (compound 85, Table. 2) in 6.6 ml of anhydrous dimethylformamide and the mixture was stirred for 1 h at 80 ^C. After cooling, the reaction mixture was poured into ice water and the resulting mixture was extracted with methylene chloride to obtain an organic layer. After washing the organic layer with an aqueous saline, the organic layer was dried on anhydrous sodium sulfate and the solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel chromatography and then recrystallization from n-hexane-ethyl acetate gave 3.16 g of the target compound.

 Examples of obtaining fungicidal compositions for use in field cultivation and gardening.

 PRI me R 14. Dust (powder).

 Three parts by weight of the azole derivative (compound 3), 40 parts by weight clay and 57 parts by weight talcum powder was mixed and pulverized to prepare a fungicidal composition used in field cultivation and horticulture in the form of dust.

 The prepared composition was applied by spraying.

 PRI me R 15. Wetting powder.

 Fifty parts by weight of the azole derivative (compound 1), 5 parts by weight salt of ligninsulfonic acid, 3 parts by weight alkyl sulfonic acid and 42 parts by weight diatomaceous earth was mixed and pulverized to obtain a wettable powder.

 The prepared composition was used as a wettable powder after dilution with water.

 PRI me R 16. Granules.

 Five parts by weight azole derivative (compound 16), 43 parts by weight bentonite, 45 weight. including clay and 7 parts by weight the ligninsulfonic acid salts were homogeneously mixed and, after adding water, mixed, shaped into granules on an extrusion granulator, and dried to obtain a composition in the form of granules.

 PRI me R 17. Emulsifying concentrate. Twenty parts by weight azole derivative (compound 13), 10 parts by weight polyoxyethylene alkylaryl ether, 3 wt. including polyoxyethylene sorbitan monolaurate and 67 parts by weight xylene was homogeneously mixed and the composition was prepared in the form of an emulsifiable concentrate.

 Examples of the use of a fungicidal composition for field cultivation and gardening in the fight against plant diseases.

 PRI me R 18. Tests for effectiveness in the fight against Erysiphe graminis f. sp. tritici on wheat.

ф

ивность

1

Данные приведены в табл. 6.For young seedlings of wheat in the second leaf stage (type: Norin N 64, 16 plants per pot and 3 pots in the experimental plot), which were grown using unglazed pots with a diameter of 10 cm, 5 ml were applied per pot according to Example 15 (diluted with water to a predetermined concentration). After air drying of the applied diluted concentrate, the shoots in pots were sprayed with a suspension of summer spores of Erysiphe graminis f. sp. tritici, which was collected on wheat infected leaves, and the pots maintained at 20-24 ^{° C} for 24 hours in a high humidity and then allowed to pots in the greenhouse for 10 th and 12 th day after the infection spread of the disease was evaluated on wheat seedlings in accordance with the following standards and the effectiveness of the fungicidal composition was calculated according to the following formula (experimental standards):
Degree of Disease Common
disease:
0 Plants do not damage
deny fungus
0.5 Spotting composition
less than 10%
tops
1 Spotting over
10% not less than 20%
surface
2 spotting more
20% but below 40%
surface
3 Spotting more
40% but below 60%
surface
4 spotting more
60% but below 80%
surface
5 Spotting underestimated
More than 80%
tops

f

will

1

The data are given in table. 6.

 PRI me R 19. Test the effectiveness in the fight against Sp. Macrotheca fuliginea on cucumbers.

 On cucumber plants in the second leaf stage (variety: Sagami Hampaku, one potted plant and 3 pots per test plot), which were grown in unglazed pots with a diameter of 10 cm, 5 ml were applied per pot of an aqueous suspension of wettable powder obtained in Example 15 (diluted with water to a predetermined concentration). After the leaves were dried in air, they were applied with a brush to spores of Sphacrotheca fuliginea from the diseased leaves of cucumbers to infect experimental cucumber plants, and the disease was caused on plants contained in the greenhouse.

ф

ивность

1

Результаты испытаний приведены в табл. 7.After 9 and 11 days after infection, the degree of disease of the cucumber plants was studied, guided by the following experimental standards, the effectiveness of the fungicidal composition was calculated by the following formula (experimental standards): Degree of prevalence of the disease:
0 Plants do not damage
deny fungus
0.5 spotting takes
no more than 10%
1 Spotting takes
more than 10% but not pre-
goes 20% over
nosti
2 Spotting takes
more than 20% but not pre-
goes 40% on top
nosti
3 Spotting composition -
It is more than 40% but
no more than 60% on top
nosti
4 Spotting takes
more than 60% but not
less than 80% of the surface
5 Spotting takes
more than 80% on top
nosti

f

will

1

The test results are given in table. 7.

 PRI me R 20. Test for effectiveness against puccinia recondita on wheat.

 On young seedlings of wheat, you are at the second leaf stage (cultivar Norin 64, 16 plants per pot, three pots per test plot), which were grown in unglazed pots with a diameter of 10 cm, applied by spraying 5 ml per pot of an aqueous suspension of wettable powder prepared according to example 15 (diluted with water to a predetermined concentration).

ф

ивность

1

Результаты испытаний представлены в табл. 8.After drying the applied composition to air for seedlings in the pots were applied by spraying spore suspension summer puccinia recondita, collected with shriveled leaves of wheat, and the pots maintained at 20-23 ^{° C} for 24 hours in a high humidity and then allowed to pots in the greenhouse. 7 and 11 days after infection, the prevalence of the disease on wheat plants was investigated, guided by the following experimental standards, and the effectiveness of the fungicidal composition was calculated according to the following formula, based on the average degree of disease per leaf (experimental data): Degree: prevalence of the disease:
0 Fungus affection
not detected
0.5 spotting takes
less than 10% over
nosti
1 Spotting over
10% but less than 20%
surface
2 spotting more
20% but less than 40%
surface
3 Spotting more
40% but above 60%
surface
4 spotting more
60% but not higher than 80%
surface
5 Spotting not less than
80% of the surface
leaves

f

will

1

The test results are presented in table. 8.

 PRI me R 21. Tests for effectiveness against Botrytis cinerea on common beans.

 5 ml diluted emulsifiable concentrate of the composition described in Example 15 (diluted with water to a predetermined concentration) by spraying was applied 5 ml per pot onto the leaves of ordinary beans in the first true leaf stage (cultivar Honkintoki) grown in unglazed pots with a diameter of 10 cm.

ф

ивность

1

Результаты испытаний представлены в табл. 9.After the applied composition has dried on air, a round section of agar with a diameter of 4 mm, containing Botrytis cinerea fungi, which were previously grown for three days at 20 ° C using agar medium with added sugar containing potato broth and the plants were kept at 20-22 ^{° C} under high humidity conditions. On the third day after infection, the area due to the disease spotting of the plants treated in this way was compared with the state of the control plants (untreated) to study the degree of the disease, guided by the following experimental standards, and the effectiveness of the fungicidal composition was calculated by the following formula (experimental standards): Degree of prevalence of the disease:
0 Plants are not
wife's disease
0.5 only affected
part of the sheet, just
under inoculated
fungal
agar and on its peri-
serial part
1 Spotting takes
less than 20% over
nosti
2 Spotting takes
more than 20% but less
40%
3 Spotty no less
40% but not more than 60%
4 Spotting not less
60% but not more than 80%
5 Spotting takes
not less than 80% over
nosti

f

will

1

The test results are presented in table. nine.

 PRI me R 22. Testing the effectiveness of the fungicidal composition against Cochliobolus miyabeanus on rice plants.

 16 rice seeds (Sasanishiki cultivar) were sown in each unglazed pot with a diameter of 10 cm, and when the rice seedlings reached the stage of 4-5 leaves, applying 5 ml of 1 pot of the aqueous suspension of wettable powder described in Example 15 (diluted with water to a predetermined concentration) .

 After air-drying the leaves thus treated, they were sprayed with a suspension of Cochliololus miyabeanus spores previously grown for this purpose at the rate of 5 ml per pot. Under a microscope with a 150-fold increase in the field of the microscope, 15 spores of fungi were found in suspension.

ф

ивность=

1

Результаты испытаний представлены в табл. 10.Immediately after infection thus treated pots were left in the chamber inoculate for two days under high humidity at ²⁵ ° C, after which they were transferred to the greenhouse for further experiment. On the fifth day after infection, the number of disease spots on 10 leaves on each pot was calculated and the effectiveness of the fungicidal composition was calculated by the following formula:

f

will =

1

The test results are presented in table. 10.

 PRI me R 23. Fungicidal tests against some pathogenic fungi.

 This example shows the results of tests of the fungicidal properties of the azole derivative against various plant-pathogenic fungi.

 Test method.

The compound was dissolved in dimethyl sulfoxide so as to give a solution having a predetermined concentration, and 0.6 ml of the resulting solution was thoroughly mixed with 60 ml PAS culture medium at 60 ° ^C in a conical flask of 100 ml. The resulting mixture was poured into glass culture dishes and cured as a homogeneous culture medium containing the compound.

On the other hand, test fungi that were previously grown in a homogeneous culture medium were grabbed with a 4 mm diameter cork drill and the thus taken piece of culture medium containing the test fungus was inoculated in a homogeneous culture medium containing the test compound. After inoculation, the resulting culture medium containing the test compound and the fungus was grown for 1-3 days at a suitable temperature for the growth of each fungus and the growth of the fungi was measured by the diameter of the fungal colony. When comparing the growth of fungi in the culture medium prepared in this way with the growth of fungi in a culture medium that does not contain the test compound, the degree of inhibition of fungal mycelium growth was determined by the following formula:
R (dc dt) 100 / dc, where R is the degree of inhibition of mycelial growth; dc is the diameter of the colony of the fungus in a compound free medium; dt is the diameter of the fungal colony in the medium containing the test compound.

The results were evaluated on a five-point system according to the following standards (see table. 11). The degree of inhibition of mycelial growth:
5 degree of inhibition of mycelial growth of at least 90-100%
4 degree of inhibition of not less than 70% and not more than 90%
3 degree of inhibition of not less than 40% and not more than 70%
2 degree of growth inhibition not less than 20% and not more than 40%
1 degree of inhibition of mycelial growth does not exceed 20%
PO Pyricularia orizae On Rice Plants
CM Cochliobolus miyabeanus Same
GF Gibberella fujkuroi - "-
HS Helmitnthosporium sigmodeum - "-
RS Rhizoctonia solani - "-
Bo.c. Botrytis cinerea On various crops
SS Sclerotinia sclerotirum - "-
FN Fusarium oxysporum f. niveum watermelon
FC Fusarium oxysporum f. cucumerinum cucumber
Fr Fusarium oxyspoyum f. raphani fucking japanese
CL Colletotrichum lagenarium Melon
Cb Cercospola beticola Sugar Beet
SC Scherotinia cinerea On peach
Vm Valsa mali On Apple Trees
Am Alternaria mali On Apple Trees
AL Alternaria alternate On Pear Trees
Gc Glameralla cingulata On the grape
Examples of compositions for use in field cultivation and horticulture that regulate plant growth, containing the azole derivative as an active ingredient.

 PRI me R 24. The form of wettable powder.

 50 parts by weight azole derivative (compound 3, table. 1), 5 parts by weight salt of ligninsulfonic acid, 3 parts by weight salts of alkyl sulfonic acids and 42 parts by weight diatomaceous earth was mixed and pulverized to obtain a composition in the form of a wettable powder. Composition of use after dilution with water.

 PRI me R 25. The form of emulsifiable concentrate.

 25 weight from. azole derivative (compound 20, table. 1), 65 parts by weight xylene and 10 parts by weight polyoxyethylene alkylaryl ether was homogeneously mixed to obtain an emulsifiable concentrate composition. The composition should be used after dilution with water.

 PRI me R 26. The form of dust (powder).

 8 weight including azole compounds (11, table. 1), 40 parts by weight bentonite, 45 parts by weight clay and 7 parts by weight salts of liginsulfonic acids were homogeneously mixed and shaped into granules using an extrusion granulator, and the granular material was dried to obtain a composition in the form of dust (here the mixing of technology for producing dust and granules takes place).

 PRI me R 27. Effects of limiting the growth of rice plants in height.

10 ml of a solution containing each of the compounds at a concentration of 10 mil was introduced into each glass cup with a diameter of 8.5 cm. 10 rice seeds (Sasanishiki variety) were sown and sown in a glass cup. Cup was kept in a room at 27 ^{° C} for 7 days to obtain seedlings of rice, and then measured the height of the seedlings to get the data presented in the Table. 12.

 As can be seen from the data table. 12, each of the azole derivatives involved in these tests showed the effect of limiting growth in height without any phytotoxicity.

PRI me R 28. Emulsifying concentrate, parts by weight The compound of formula I 10
Tenziofiks Gs (trademark of the company Genzia Co.) 3.5 Tenziofiks Ns (- "-) 6.5 Cyclohexanone 15 Xylene 65
The ingredients were combined and mixed, forming an emulsifying concentrate.

 PRI me R 29. Test the effect of suppression of Erysiphe graminis f. sp. tritici on wheat was carried out using the procedure of example 18 except for applying 5 ml per pot of diluted emulsifying concentrate obtained according to example 17 instead of applying 5 ml per pot of an aqueous suspension of wettable powder. The results are shown in table. 13 (compound numbers shown in the following tables are numbers given in table 1).

 PRI me R 30. Test for the effect of suppressing Puccinia recondita on wheat.

 The procedure of Example 20 was used except for applying 5 ml per pot of the diluted emulsifying concentrate obtained according to Example 17, instead of using 5 ml per pot of an aqueous suspension of wettable powder.

 The results are shown in table. 14.

 PRI me R 31. Test for the effect of suppression of Erysiphe gramimis f. sp. tritici on wheat.

 The procedure of Example 18 was used except for the use of 5 ml per pot of the diluted emulsifying concentrate obtained according to Example 28, instead of 5 ml per pot of an aqueous suspension of wettable powder. The results are shown in table. fifteen.

 PRI me R 32. Tests for the effect of suppressing Puccinia recondita on wheat.

 The procedure of Example 20 was used with the exception of applying 5 ml per pot of the diluted emulsifying concentrate obtained according to Example 28 instead of 5 ml of an aqueous suspension of wettable powder. The results are shown in table. sixteen.

 PRI me R 33. The effect of restraining the height of plants on rice plants.

 The procedure of Example 27 was used except that aqueous suspensions of the wettable powder obtained according to Example 24 were added at a concentration of 10 ppm. instead of a solution containing each of the compounds according to the invention with a concentration of 10 ppm

 The results are shown in table. 17. All tested compounds did not show any signs of toxicity to rice plants.

 PRI me R 34. The test for the effect of suppressing Puccinia recondita on wheat was carried out using the procedure of example 20, except for the use of 3 kg / ha of dust, prepared according to example 14, instead of applying 5 ml per pot of aqueous suspension of wettable powder. The results are shown in table. eighteen.

 PRI me R 35. Test for the effect of suppression of Erysiphe graminis f. sp. tritici on wheat was carried out using the procedure of example 18, except for applying 3 kg per 1 ha of dust made according to example 14, instead of applying 5 ml per pot of an aqueous suspension of wettable powder. The results are shown in table. nineteen.

 PRI me R 36. The test granules for the effect of suppressing Puccinia recondita on wheat was carried out using the procedure of example 20, except for the use of 3 kg / ha of granules obtained according to example 16, on young seedlings of wheat at the first leaf stage, instead of applying 5 ml per pot of an aqueous suspension of wettable powder on young wheat seedlings in the second leaf stage. The results are shown in table. 20.

 PRI me R 37. Tests of granules on the suppression effect of Eryciphe graminis f. sp. tritici on wheat was carried out using the procedure of example 18 except for applying 3 kg per 1 ha of granules prepared according to example 16 on frozen wheat seedlings in the first leaf stage, instead of applying 5 ml per pot of an aqueous suspension of wettable powder on young wheat seedlings in the second stage sheet. The results are shown in table. 21.

 PRI me R 38. The effect of granules to inhibit the growth of plants in height on rice plants.

 Seeds of rice plants (a variety of SASANISIKI) were germinated in a seedling box (300x600x30 mm) and grown until the initial stage of the appearance of green mass. 25 g were uniformly scattered on the seedlings on a box of granules obtained according to Example 16. The treated seedlings were stored in the greenhouse for 14 days and the indicators of plant height containment were calculated in accordance with the following equation.

1

100
Результаты представлены в табл. 22.Plant containment rate

1

one hundred
The results are presented in table. 22.

 PRI me R 39. The effect of emulsifying concentrate to inhibit the growth in height in rice plants. The procedure of example 38 was repeated, but 500 ml was used per box of diluted emulsifying concentrate prepared in accordance with example 25. The results are shown in table. 23.

 PRI me R 40. The effect of dust on restraining the height of plants on rice plants.

 Seeds of rice plants (a variety of SASANISIKI) were pollinated in an amount of 0.5 wt. calculated on the dry weight of the dust with the dust prepared according to Example 26. The treated seeds were germinated in a 300x600x30 ml seedling box and then in the greenhouse for 14 days. Indicators of plant height control were calculated in the same manner as in example 38. The results are shown in table. 24.

 PRI me R 41. Test for the effect of suppressing Puccinia recondita on wheat. These tests were carried out using the procedure of example 20, except that 5 ml was used per pot of an aqueous suspension of a wettable powder of the compound shown in table. 25 and 26, instead of the wettable powder of Example 15.

 PRI me R 42. Tests for the effect of suppressing Botrytis cinerea on common beans were carried out using example 21 except for the use of 5 ml per pot of an aqueous suspension of a wettable powder of the compound shown in table. 26, instead of the wettable powder of Example 15.

 PRI me R 43.

Wettable powder wt.h. The compounds of formula 1 80
Synthetic amorphous silicon dioxide 3 Kaolinite 13
Sodium Alkyl Naphthalenesulfonate 2 Sodium Ligninsulfonate 2
The ingredients were mixed to form a wettable powder.

 PRI me R 44.

Dust parts by weight The compound of formula 1 1 Kaolinite 99
The ingredients were mixed and pulverized to form dust.

 PRI me R 45.

Emulsifiable concentrate wt.h. The compound of formula 1 40 Cyclohexanone 15 Xylene 25
Sodium dodecylbenzenesulfonate 8
Butylphenol-polyethylene-
glycol ether (36 mol ethylene oxide) 12
The ingredients were combined and mixed to form an emulsifiable concentrate.

 PRI me R 46. Tests for the effect of suppressing Puccinia recondita on wheat was carried out using the procedure of example 20 except for the use of wettable powder of example 43 instead of wettable powder obtained in example 15. The results are shown in table. 27.

 Suppression Test Erysiphe graminis f. sp. tritici on wheat.

 These tests were carried out using the procedure of example 18, except for the use of a wettable powder obtained in example 43, instead of a wettable powder obtained in example 15.

 The results are shown in table. 28.

 The effect of restraining the height of plants on rice plants.

 Rice plant seeds (variety: SASANISIKI) were germinated in seedling boxes 300x600x300 mm in size until the initial stage of greenery emergence. The diluted wettable powder obtained in Example 43, diluted with water to a predetermined concentration in the amount of 500 ml per box, was uniformly sprayed on the seedlings.

 Treated seedlings were stored in the greenhouse for 14 days and plant height containment ratios were calculated according to the following equation.

1

0
Результаты показаны в табл. 29.Plant containment rate

1

0
The results are shown in table. 29.

 PRI me R 47. Tests for the effect of suppressing Puccinia recondita on wheat was carried out using the procedure of example 20, except that the powder prepared in example 44 was used instead of the wettable powder obtained in example 15. The results are shown in table. thirty.

 Suppression Testing Erysiphe graminis f. sp. tririci on wheat was carried out using the procedure of example 18, except for the use of the powder prepared in example 44, instead of the wettable powder obtained in example 15. The results are shown in table. 31.

 The effect of restraining the height of plants on rice plants when using dust.

 Seeds of rice plants (variety: SASANISIKI) were pollinated with the powder obtained in example 44, in an amount of 0.5 wt. calculated on the dry weight of the seeds. The treated seeds were germinated in a 300x600x30 mm seedling box and grown in a greenhouse for 14 days.

 Indicators of plant height control were calculated in the same manner as in example 46. The results are shown in table. 32.

 PRI me R 48. Tests for the effect of suppressing Puccinia recondita on wheat was carried out using the procedure of example 20, except for the use of emulsifiable concentrate prepared in example 45, instead of the wettable powder obtained in example 15. The results are shown in table. 33.

 Suppression Testing Erysiphe graminis f. sp. tritici on wheat was carried out using the procedure of example 18, except for the use of the emulsifiable concentrate obtained in example 45, instead of the wettable powder obtained in example 15. The results are shown in table. 34.

 The effect of inhibiting plant growth on rice plants.

 Rice plant seeds (variety: SASANISIKI) were germinated in seedling boxes 300x600x300 mm in size until the initial stage of greenery emergence. The diluted emulsifiable concentrate obtained in Example 45 (diluted with water to a predetermined concentration) in an amount of 500 ml per box was uniformly sprayed onto seedlings. The treated seedlings were stored in the greenhouse for 14 days, and the indicators of plant height containment were calculated in the same manner as in example 46. The results are presented in table. 35.

Claims (7)

1. Azole derivatives of the general formula I

where R ¹ and R ² hydrogen or C ₁ C ₅ -alkyl, provided that both cannot simultaneously be hydrogen;
X is halogen, C ₁ C ₅ alkyl or phenyl;
n 0 2;
A nitrogen or a group CH -. 2. Azole derivatives of general formula I according to claim 1, characterized in that R ¹ and R _{2 are} hydrogen or C ₁ C ₃ -alkyl, provided that both cannot be hydrogen at the same time, X is halogen in the 4-position of the benzene ring , n 1, A is nitrogen or a group CH -. 3. The azole derivatives of general formula I according to claim 1, characterized in that R ¹ and R ^{2 are} hydrogen or C ₁ C ₃ -alkyl, provided that both cannot be hydrogen at the same time, X is halogen in the 4th position of the benzene ring, n = 1, A is nitrogen. 4. Derivatives of oxirane of general formula II

where R ¹ and R ² hydrogen or C ₁ C ₅ -alkyl provided that both cannot simultaneously be hydrogen;
X is halogen, C ₁ C ₅ alkyl or phenyl;
n 0 2,
as intermediates for the preparation of azole derivatives of the general formula I. 5. Derivatives of methylene cyclopentane of General formula III

where R ¹ and R ² hydrogen or C ₁ C ₅ -alkyl provided that both cannot simultaneously be hydrogen;
X is halogen, C ₁ C ₅ alkyl or phenyl;
n 0 2,
as intermediates for the preparation of azole derivatives of the general formula I. 6. Derivatives of cyclopentanone of General formula IV

where R ¹ and R ² hydrogen or C ₁ C ₅ -alkyl provided that both cannot simultaneously be hydrogen;
X is halogen, C ₁ C ₅ alkyl or phenyl;
n 0-2,
as intermediates for the preparation of azole derivatives of the general formula I. 7. Derivatives of the ester of cyclopentanecarboxylic acid of General formula V

where RC _{1 is} C ₅ alkyl;
R ¹ and R ^{2 are} hydrogen or C ₁ C ₅ -alkyl provided that both cannot be hydrogen at the same time;
X is halogen, C ₁ C ₅ alkyl or phenyl;
n 0-2,
as intermediates for the preparation of azole derivatives of the general formula I.

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