AU584530B2

Azole derivatives

Abstract

This record has no abstract on file.

AU584530B2, drawing sheet 1 — Sheet 1 of 347

Term

Term ended

Expired 10 November 2007, 18.9 years ago.

5 claims: 3 independent, 2 dependent

1
CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:1. An azole derivative represented by the formula(I) : 1 2 wherein R and R respectively represent a (C^ - C^) alkyl group or a hydrogen atom;X represents a halogen atom, a (C^ - C_) alkyl group or a phenyl group;n represents an integer of from 0 to 2 and A represents a nitrogen atom or a 1 2 CH, provided that R is not a hydrogen atom when R is a hydrogen atom.
4
A process for producing an azole derivative re- presented by the formula(I):1 2 wherein R and R respectively represent a (.C^ - C^) alkyl group ora hydrogen atom;X represents a halogen atom, a (C^ - C,-) alkyl group or a phenyl group;n represents an integer of from 0 to 2 and A represents a nitrogen atom or a 1 2 CH, provided that R is not a hydrogen atom when R is a hydrogen atom, which process comprises the steps of a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid with a substituted benzyl halide and reacting the thus obtained alkyl ester of 1-[substituted benzyl).-2-oxocyclopentanecarboxylic acid with a (C^ - Cg) alkyl halide, Cii) reacting an alkyl ester of 3-[C^ - C^ alkyl).-2-oxocyclopentanecarboxylic acid with a substituted benzyl halide or (iii) reacting 1-(substituted benzyl).-3-[C^ o - C 5 alkyl)-2oxocyclopentanecarboxylic acid with a (C^ - Cgl alkyl halide, thereby obtaining an ester derivative of cyclopentanecarboxylic acid represented by the formula(V): I ο e ο « 9 ο βοβο e β α β Ο fc 5 α ρ · ρ ο a ο ο « ο ο ο ο ο · * ♦ Ο Ο e © ο 1 2 wherein R and R respectively represent a (C n - C^) alkyl group or a hydrogen atom;R represents a (C^ - C^) alkyl group;X represents a halogen atom, a (.0^ - C^) alkyl group or a phenyl group and n represents an integer of from 0 to 2, 1 2 provided that R is not a hydrogen atom when R is a hydrogen atom, b) subjecting the thus obtained ester derivative of cyclo pentanecarboxylic acid to hydrolytic decarboxylation, thereby obtaining a cyclopentanone derivative represented by the formula(IV): (IV) wherein R^, R , X and n respectively represent the same defined as above, c) subjecting the thus obtained cyclopentanone derivative to an oxirane reaction while using sulfonium ylide or oxosulfonium . i X 116 ylide, or subjecting a methylenecyclopentane derivative obtained from the thus obtained cyclopentanone derivative by Wittig reaction and represented by the formula (III) : r τ » i r t t 1 2 wherein R , R , X and n respectively represent the same defined as above, to epoxidation, thereby converting the cyclopentanone derivative into an oxirane derivative represented by the formula (II): 1 2 wherein R , R , X and n respectively represent the same defined as above, and then d) reacting the thus obtained oxirane derivative with an 1,2,4-triazole or an imidazole represented by the formula (VI) : (VI) 117 wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a CH. t t ’· : ’ t 4 I t group or a 1 wherein R represented by the yi ely represent a (C^ - C^) alkyl presents a halogen atom, a en atom;X of group and n represents an 0 to 2, provided th^t R^ is not a hydrogen (c x - C c ) integ group or a phen 6. represented by the formula A methylenecyclopentane derivat^v azole derivative represented by t for producing an \w.hich is wherein R group or a hydrogen atom,;1 - Cj.) alkyl represents a (C^ - C^) alkyl group;X represent^a halogen atom, a (C^ - C^) alkyl group or a phenyl a Sup and n represents an integer of from 0 to 2, 1 2 provi that R is not a hydrogen atom when R is a hydrogen respectively An agricultural and horticultural composition having a fungicidal activity and a plant growth regulating activity, which comprises, as an active ingredient, an azole derivative represented by the formula(I) : 1 2 wherein R and R respectively represent a (.(^ - C 5 ) alkyl group or a hydrogen atom;X represents a halogen atom, a (Ci - C_) alkyl group or a phenyl group;n represents an 1 5 IH - integer of from 0 to 2 and A represents a nitrogen atom or a 1 . 2 CH, provided that R is not a hydrogen atom when R is a hydrogen atom. o ft 4 « 4k 6 O © o © © © ©to * to © ·3 Γ $ O©to 0to ♦« « 0a © «to ” o © 0 0 0 0Oto (s’ λθ·. An agricultural and horticultural composition
5
5 1 according to claim^^, wherein R is a hydrogen atom or a (Ci - C 4 ) alkyl, R is a hydrogen atom or a (C.^ - C 3 ) alkyl;X is a halogen atom substituting the 4-position of the benzene ring;n is 1 and A is represented by a nitrogen atom . 1 2 or a CH, provided that R is not a hydrogen atom when R is a «to 0 o © rt «to to 0 ft © ο a © o ©to © to to to 9 O 0 to o to · ♦ « a a « t a « « i r i ff I I I € S I * hydrogen atom. 7· An agricultural and horticultural composition . 1 2 according to claim^lO', wherein R and R respectively represent a hydrogen atom or a (C^ - C^) alkyl group;X is a halogen atom substituting the 4-position of the benzene ring;n is 1 and A is represented by a nitrogen atom, provided 1 2 that R is not a hydrogen atom when R is a hydrogen atom. % .£2. Compounds of the formula (I) methods for their manufacture or agricultural or horticultural compositions containing them, substantially as hereinbefore described with reference to the Examples and/or the drawings. -τ · /ao - zt·• ?p., compos-Uinn π......a-nd—fiempnarvdg· referred to or indicated in the specificatsga of this application, individriad?ly or collectively, and any and all combin^t^d^s^^oZany^ two or more of said steps or ·£ area

Independent claims3

1,660 paragraphs in 80 sections, as filed

COMPLETE SPECIFICATION (ORIGINAL)

FOR OFFICE USE

CLASS

INT. CLASS

Application Number: Lodged:

Complete Specification Lodged: Accepted: Published:

Priority:

Related Art:

g ' : ί

This document contains the i amendments made under ) Section 49 and is correct for printing- ..... J

NAME OF APPLICANT: KUREHA KAGAKU KOGYO KABUSHIKI KAISHA

ADDRESS OF APPLICANT: 9-11 Horidome-cho 1-chome, Nihonbashi, Chuo-ku, Tokyo,

Japan.

NAME(S) OF INVENTOR(S) Satoru KUMAZAWA

Susumu SHIMIZU

Hiroyuki ENARI Atsushi ITO

ADDRESS FOR SERVICE:

Susumu IKEDA

Nobuo SATO

Toshihide SAISHOJI

DAVIES & COLLISON, Patent Attorneys

Little Collins Street, Melbourne, 3000.

COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED:

NOVEL AZOLE DERIVATIVE, PROCESS FOR PRODUCING THEREOF AND AGRICULTURAL AND HORTICULTURAL CHEMICAL COMPOSITION CONTAINING THE SAME

The following statement is a full description of this invention, including the best method of performing it known to us :-1-

>1’ i <

- 1A TITLE OF THE INVENTION:

NOVEL AZOLE DERIVATIVE, PROCESS FOR PRODUCING

THEREOF AND AGRICULTURAL AND HORTICULTURAL

CHEMICAL COMPOSITION CONTAINING THE SAME

BACKGROUND OF THE INVENTION:

The present invention relates to an azole derivative having a plant diseases controlling activity and plant growth regulating activity, a process for producing the azole derivative and an agricultural and horticultural composition containing the azole derivative as an active ingredient. More in detail, the present invention relates to

1) an azole derivative represented by the formula (I):

i !ί

- 2 1 2 wherein R and R respectively represent a (C^-C^) alkyl group or a hydrogen atom; X represents a halogen atom, a (C^- C^)alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or

2 a CH, provided that R is not a hydrogen atom when R is a hydrogen atom,

2) a process for producing the azole derivative represented by the formula (I), which process comprises the steps of

a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid with a substituted benzyl halide and reacting the thus obtained alkyl ester of 1-(substituted benzyl )-2-oxocyclopentanecarboxylic acid with a(C^- C^)alkyl halide, (ii) reacting an alkyl ester of 3-(C^ - C5 alkyl)-2-oxocyclopentanecarboxylic acid with a substituted benzyl halide, or (iii) reacting 1-(substituted benzyl)-3-(C^ - alkyl)-

2-oxocyclopentanecarboxylic acid with a (C^ - C^)alkyl halide, thereby obtaining an ester derivative of cyclopentanecarboxylic acid represented by the formula (V):

2 wherein R and R respectively represent a (C^ - ) alkyl group or a hydrogen atom; R represents a (C^ - Cg)alkyl halogen atom, a(C^ - C^)alkyl group n represents an integer of from

R is not a hydrogen atom when R is group; X represents a or a phenyl group and to 2, provided that a hydrogen atom,

b) subjecting the thus obtained ester derivative of cyclopentanecarboxylic acid to hydrolytic decarboxylation, thereby obtaining a cyclopentanone derivative represented by the formula (IV):

o O

Q ft

0 ft

9 0

Ο O 9

O 0 *

(IV) e •0090» ft 0

0 0 9 0 0 o a

Θ · ©

O 0 ft · « 0

Q 6 6 ft V 0

2 wherein R , R , X and n respectively represent the same defined as above,

c) subjecting the thus obtained cyclopentanone derivative to an oxirane reaction while using sulfonium ylide or oxosulfonium ylide or subjecting a methylenecyclopentane derivative obtained from the thus obtained cyclopentanone derivative by Wittig reaction and represented by the formula (III):

(III) wherein R , R , X and n respectively represent the same defined as above, into epoxidation, thereby converting the cyclopentanone derivative into an oxirane derivative represented by the formula (II):

. 1 2 .

wherein R , R , X and n respectively represent the same defined as above, and then

d) reacting the thus obtained oxirane derivative with an

1,2,4-triazole or an imidazole represented by the formula (VI):

(VI)

I wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a

-CH=, thereby obtaining the azole derivative represented by the formula (I):

f t I t f f ’ c « t I : r t Γ

Ϊ f « <

< r » r t t t r r t trit r t c r e a r « ft r t t t wherein R

(I) respectively represent a(C^ - C^)alkyl group or a hydrogen atom; X represents a halogen atom, t » • t t re * r* t £ t '· n represents an c

t f « t i t £ t t

r i r t U t t a(C^ - C^)alkyl group or a phenyl group;

integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that RP is not a hydrogen atom when

R is a hydrogen atom, and

3) an agricultural and horticultural composition having a fungicidal activity and a plant growth regulating activity, which comprises an effective amount of the azole derivative represented by the formula (I).

The damage of the crops due to various plant diseases is enormous, and also, a problem due to the environmental pollution by the chemicals for controlling these plant diseases has arisen.

Accordingly, an offer of an agricultural and horticultural chemical which has a controlling effect against the plant diseases, is low in toxicity to men, beasts, birds and fishes and is low in phytotoxicity to useful plants, that is, an agricultural and horticultural chemical which is high in safety on handling, small in influence to the environment and has an excellent controlling effect against plant diseases in a broad range has been demanded.

In order to fulfill such a demand, the following agricultural and horticultural fungicides have hitherto been proposed.

(1) Compounds of triazoles or imidazoles represented by the following formula:

Z

wherein R1 represents a -CH=CH-X, a -C = C-X or a -CH2-CH2~X (wherein X is a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkaxyalkyl group, a cycloalkyl group, a substituted aryl group which may be substituted, an aralkyl i : group which may be substituted, an aryloxyalkyl group which may be substituted or a heterocyclic group which may be substituted); R represents an alkyl group, a cycloalkyl group or an aryl group which may be substituted; Z represents a chlorine atom, a cyano group or a -OR (where3 in R is a hydrogen atom, an acetyl group, an alkyl group,

an alkenyl group or an aralkyl group) and Y represents a nitrogen atom or a CH, an acid addition salt thereof and a metal complex thereof [refer to Japanese Patent Application LaidOpen(KOKAI) No. 57-114577 (1982) corresponding to U.S.

Patent No. 4507140 and European Patent No. 52424.].

(2) Compounds of triazoles or imidazoles represented by the following formula:

wherein R represents a cross-linking group: -(CH?) -(wherein n is 0, 1 or 2), a cross-linking group: a -CH=CH-, an -0-, an -S-, an -NH- or a -C(=0)-; X represents a nitrogen atom or a CH;

Y and Z may be the same or different from each other and respectively represents 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, an acid thereof, a metal complex thereof and functional derivatives thereof [refer to Japanese Patent Application Laid Open No. 57126479 (1982) corresponding to European Patent No. 52425] .

(3) Derivatives of 1-hydroxyethylazole, represented by the following formula:

wherein R represents an alkyl group, a cycloalkyl group which may be substituted or a phenyl group which may be substituted, X represents a nitrogen atom or a CH; Y represents a --OCH2~, a -CH2-CH2~ or a -CH--CH-; Z represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, a halogenoalkyl group, a halogenoalkoxy group, a halogenoalkylthio group, phenyl group which may be substituted, a phenoxy group which may be substituted or phenylalkyl group which may be substituted or a phenylalkoxy group which may be substituted and m represents 0, 1, 2 or 3, an acid addition salt thereof and

Λ j

a metal complex thereof [refer to Japanese Patent Application

Laid-Open (KOKAI) No. 57-16868 (1982) corresponding to (4) Cycloaliphatic alcoholic compounds represented by the following formula:

A '

OH

R6 wherein R^ represents an unsubstituted phenyl group or a phenyl group substituted by from 1 to 5 groups selected from the group consisting of halogen atom(s), amino group(s), nitro group(s), cyano group(s), phenyl group (s), halogenophenyl group (s), (C.^ -C1Q) alkyl group (s), halogeno ) alkyl (C-l-C 0) alkoxy group (s), halogeno (C1-C1Q) alkoxy (C.J--C1Q) alkylthio group (s), (C^-C^q ) alkylenedioxy (C^-C^o) alkylamino group(s) and di(C^-C^g) alkylamino represents a nitrogen atom or a methine group; a group(s) group(s) group(s) groups; X ring A is a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, an indane ring, a tetrahydronaphthalene ring or a benzocyclopeptane ring, each of the respective rings not having been substituted or having been substituted

H..4.

i in the benzene ring thereof by from one to four of the above-mentioned substituents [refer to Japanese Patent Application Laid-Open (KOKAI) No. 58-189171 (1983) corresponding to U.S. Patent No. 4503062 and European Patent No. 94146].

(5) Triazole compounds or imidazole compounds represented by the following formula:

W--N —

wherein W is a CH or a nitrogen atom; Q is a substituted or unsubstituted aryl group, particularly a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl, or a substituted or unsubstituted alkyl group; r1, R2, R3, R4 , R5, R®, R7and R8 may be the same or different from each other and respectively represent a hydrogen atom, a hydroxy group, an alkyl group, a cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, or any of the pairs of R1 and R2, R3 and R4 , R5 and R6 or R7 and R8 represents a carbonyl group (C=O) together with the

10 adjacent ring-carbon atom; R and R 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 n is 0 or 1, a stereoisomer thereof, an acid addition salt thereof and a metal complex thereof [refer to Japanese Patent Application Laid-Open (KOKAI) No. 60-215674 (1985) corresponding to European Patent No. 153797].

(A .,1

«9 « ♦ 9 « ·» 4

0 « 0 ©

0 4 © 4 «

As a result of the studies of some of the present inventors for providing an agricultural and horticultural fungicide which is high in safety on handling, is small in influence to the environment and shows an excellent controlling effect against the plant diseases of a broad range, they have found an azole derivative represented by the following formula:

“***« wherein X represent respectively a halogen atom, an alkyl group, a haloalkyl group, a phenyl group, a cyano group or a nitro group; n represents an integer of from 0 to 5 and A represents a nitrogen atom or a CH, provided that X may be the same or different from each other when n is 1 to 5

[refer to Japanese Patent Application Laid-Open (KOKAI) No. 62-149667 (1987) corresponding to

UK Patent No. 2180236A1.

t I 9 tit ♦t r< * r r · tttt *« · « f ·* * t e < t « t ( < « f I I t « <· ' ί « e τ i

The present inventors have further studied a synthesis of many azole derivatives and an examination on the utility thereof in order to obtain an agricultural and horticultural fungicide which is low in toxicity to men and beasts, is high in safety on handling and shows an excellent controlling effect against plant diseases of a broad range, and as a result it has been found that an azole derivative represented by the formula (I):

2 ’ wherein R and R respectively represent a (C^ - 'V) alkyl group or a hydrogen atom; X represents a halogen atom, a(C^ - Cg)alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or

2 a CH, provided that R is not a hydrogen atom when R is a hydrogen atom, 'not only has the afore-mentioned specific properties but also can be effectively applied as a plant growth regulating agent, and on the basis of their finding, the present invention have been attained.

Namely, the object of the present invention is to provide with an azole derivative having the utility as the active ingredient of the agricultural and horticultural composition having a plant diseases controlling activity and a plant growth regulating activity, a process for producing the azole derivative, and an agricultural and horticultural composition which contains, as an active ingredient, the azole derivative which shows an excellent controlling effect on the plant diseases in a broad range and at the same time, shows a plant growth regulating effect, is low in toxicity and is excellent in safety on handling.

SUMMARY OF THE INVENTION:

In a first aspect of the present invention, there is provided an azole derivative represented by the formula (I):

2 wherein R and R respectively represent a (C^ - C^)alkyl group or a hydrogen atom; X represents a halogen atom, a (C-^ - C^) alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or

2 a CH, provided that R is not a hydrogen atom when R is a hydrogen atom.

In a second aspect of there is provided a process for represented by the formula (I):

the present invention, producing an azole derivative

(I)

2 wherein R and R respectively represent a (C^ - C^)alkyl group or a hydrogen atom; X represents a halogen atom, a (C^ - C5)alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or

2 .

a CH, provided that R is not a hydrogen atom when R is a hydrogen atom, which process comprises the steps of

(

A' (ii) reacting an alkyl ester of 3-(C^ - alkyl)-2oxocyclopentanecarboxylic acid with a substituted benzyl alkyl)-2-oxocyclopentanecarboxylie halide or (iii) reacting 1-(substituted benzyl)-3-(C^ acid with a (C^ - C^)alkyl derivative of cyclohalide, thereby obtaining an ester

·* Γ

C t < ·

C ’ ' pentanecarboxylic acid represented

by the formula (V):

(V)

2 wherein R and R respectively represent a (C.^ - C5) alkyl group or a hydrogen atom; R represents a (C^ - C^)alkyl group; X represents a halogen atom, a (C^ - C5)alkyl group or a phenyl group and n represents an integer of from 0 to

2 .

2, provided that R is not a hydrogen atom when R is a hydrogen atom,

b) subjecting the thus obtained ester derivative of cyclopentanecarboxylic acid to hydrolytic decarboxylation, thereby obtaining a cyclopentanone derivative represented by the formula (IV):

2 wherein R , R , X and n respectively represent the same defined as above,

c) subjecting the thus obtained cyclopentanone derivative to an oxirane reaction while using sulfonium ylide or oxosulfonium ylide, or subjecting a methylenecyclopentans derivative obtained from the thus obtained cyclopentanone derivative by Wittig reaction and represented by the formula (III) :

- a i-

2 wherein R , R , X and n respectively represent the same defined as above, to epoxidation, thereby converting the cyclopentanone derivative into an oxirane derivative represented by the formula (II):

2 wherein R , R , X and n respectively represent the same defined as above, and then

d) reacting the thus obtained oxirane derivative with a

1,2,4-triazole or an imidazole represented by the formula (VI) :

(VI)

wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a CH.

In a third aspect of the present invention, there is provided an agricultural and horticultural composition having a fungicidal activity and a plant growth regulating activity, which comprises, as an active ingredient, an azole derivative represented by the formula (I):

2 wherein R and R respectively represent a (C^ - C^)alkyl group or a hydrogen atom; X represents a halogen atom, a - C5)alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that R^ is not a hydrogen atom when

R is a hydrogen atom.

In a fourth aspect of the present invention, there is provided an oxirane derivative for producing an azole derivative represented by the formula (I), which is represented by the formula (II):

2 wherein R and R respectively represent a (C^ - C^)alkyl

- -e .· r« e « *t : tr t

c r tt ' it « · r « group or a hydrogen atom; X represents a halogen atom, a (C^ - C^)alkyl group or a phenyl group and n represents an integer of from 0 to 2, provided that is not a hydrogen 2 atom when R is a hydrogen atom.

In a fifth aspect of the present invention, there ·’ t- c c C is provided a methylenecyclopentane derivative for producing an azole derivative represented by.the formula (I), which is represented .by the formula (III):

2 ' wherein R and R respectively represent group or a hydrogen atom; X represents a a (C^ - Cg)alkyl halogen atom, a (C^.- C5)alkyl group or a phenyl group and n represents i t If

an integer of from 0 to 2, provided that is not a hydrogen atom when R is a hydrogen atom.

In a sixth aspect of the present invention, there is provided a cyclopentanone derivative for producing an azole derivative represented by the formula (I), which is represented by the formula (IV):

• t « r t t ♦ t « M t

I t I i r t t t t ft » r t.

t r t t f1· t r « * € t t *· ♦ ♦· ·

(IV)

2 wherein R and R respectively represent a (C^ - C^)alkyl group or a hydrogen atom; X represents a halogen atom, a (C^ - C^)alkyl group or a phenyl group and n represents an integer of from 0 to

2, provided that R is not a hydrogen atom when R is a hydrogen atom.

In a seventh aspect of the present invention, there

C t(crut is provided an ester derivative of a cyclopentanecarboxylic acid for producing an azole derivative represented by the tee t i t formula (I), which is represented by the formula (V):

«•tree

(V)

I

Ιϊ ' lr

I s .:

• 1

I

- 21 1 2 wherein R and R respectively represent a (C^ - C^)alkyl group or a hydrogen atom; R represents a (C^ - C^)alkyl group; X represents a halogen atom, a (C^ - C^)alkyl group or a phenyl group and n represents an integer of from 0 to

2, provided that R is not a hydrogen atom when R is a hydrogen atom.

BRIEF EXPLANATION OF DRAWINGS :

Of the attached drawings, Figs. 1 to 76 show the infrared absorption spectra of the azole derivatives according to tha present invention shown in Table 1.

Namely, Fig. 1 shows the infrared absorption spectrum of the compound No. 1 in Table 1, Fig. 2 shows the infrared absorption spectrum of the compound No. 2 in Table 1, Fig. 3 shows the infrared absorption spectrum of the compound No. 3 in Table 1, and Figs. 4 to 76 show the respective infrared absorption spectra of the respective compounds Nos. 4 to 76 in Table 1.

The heart of the present invention lies in a novel azole derivative represented by the formula (I):

2 or a CH, provided that R is not a hydrogen atom when R is a hydrogen atom, a. process for producing the azole derivative represented by the formula (I), each of the compounds used as the intermediates, namely an oxirane derivative represented by the formula (II), a methylenecyclopentane derivative represented by the formula (III), a cyclopentanone derivative represented by the formula (IV) and an ester derivative of cyclopentanecarboxylic acid.

represented by the formula (V), and an agricultural and horticultural composition containing the azole derivative represented by the formula (I) as an active ingredient and having fungicidal activity and plant growth regulating activity.

- 23 The physical and chemical properties of the azole derivative represented by the formula (I) and each of the intermediates for producing the above-mentioned azole derivative are shown in Tables 1 to 5.

Besides, every one of these intermediates is a novel compound .

Table 1 Azole derivatives

<td rowspan="2"> Compound No.</td><td colspan="4"> Indication in Formula (I)</td><td rowspan="2"> Indication of Stereoisomer</td><td rowspan="2"> Melting point UC)</td><td rowspan="2"> N M R Spectral Data</td><td rowspan="2"> (CDCJ . δ ppm)</td>

Table 1 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="4"> Indication in Formula (I)</td><td rowspan="2"> Indication of Stereoisomer</td><td rowspan="2"> Melting point (*C)</td><td rowspan="2"> N M R Spectral Data (CDCI , Sppill)</td>

r t

V J f ’ li-i

»· *r « * w *»·«

Table 1 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="4"> Indication in Formula' (I)</td><td rowspan="2"> Indication of Stereoisaner</td><td rowspan="2"> Melting point (Ό)</td><td rowspan="2"> N M R Spectral Data</td><td rowspan="2"> (CDCI . <5ppm) V</td>

<td> 20</td><td> ch3</td><td> H ·</td><td> 4-C I</td><td> Ν’</td><td> B -type</td><td> Oily material</td><td colspan="2"> 0.88((1,3H.>6.6). 1.05-2.45(11,7H). 2.62-2.92(11,1H). 3.85-4.25(b, 1H,OH).4.31 (s,2H). 6.98((1,2H.J-8.8), 7.22((1,2H,>8.8), 7.95(S.1H). 8.26(S,1H)</td>

<td> 21</td><td> ch3</td><td> ch3</td><td> H</td><td> N</td><td> A -type</td><td> Oily material</td><td> 0.63(S,3H), 1.03(s.3H). 1.13-2.83(11,7H), 3.57(s.1H), 8.00(S, 1H). 8.17(S, 1H)</td><td> 4.23(5,2H). 7.23(S,5H),</td>

I

M Οϊ

I

Table 1 (Continued)

<td rowspan="2"> Compound - No.</td><td colspan="4"> Indication in Formula (I)</td><td rowspan="2"> Indication of Stereoisaner</td><td rowspan="2"> Melting point (Ό)</td><td rowspan="2"> N M R Spectral Data (CDCI^ , δ ppm)</td>

<td> 35</td><td> c2 h5</td><td> c2 h5</td><td> 4-C 1</td><td> CH</td><td> A -type</td><td> Oiiy material</td><td> O.87(t,66,.1=6). 1.07—2.50(1», 116) . 3.33(s,16), 3.90(0,16, J=14) 4.18(0,16,J=14) , 6.70-7.23(1», 66). 7.67(s, 16)</td>

Table 1 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="4"> Indication in Formula (I)</td><td rowspan="2"> Indication of Stereoiscmer'</td><td rowspan="2"> Melting point CO)</td><td rowspan="2"> N M R Spectral Data (CDCI , Spplfl) * u</td>

I

Table 1 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in Formula</td><td> I)</td><td rowspan="2"> Indicatior of Stereoisomer ,</td><td rowspan="2"> Melting point CC)</td><td rowspan="2"> N M R Spectral Data (COCI , δρρίΐ) o</td>

<td> 48</td><td> C2 H5</td><td> H</td><td> 4-t- c4 h9</td><td> N</td><td> A -type</td><td> Oily material</td><td> O.85(t,3H,J=7), 1.29(S,-9H). 0.90—1.90(m,8H). 2.41 (dll. 1H. J=14.10) , 2.49((1(1.1H,J=14,5). 4.23(S.2H). 7.07(d,2H,J=8.3), 7.28((1,2H,J=8.3), 7.96(s,1H). 8.01(s,1H)</td>

<td> 51</td><td> n- c5 Hn</td><td> H</td><td> 4-C 1</td><td> N</td><td> A -type</td><td> Oily material</td><td> 0.8G(t,3H, J=G. 8). 0.90—1.98(11,14H) . 2.38(dd,1H, J=13.4,9.3). 2.46((1(1,1H,.1=13.4,5.4). 2.57(s. 1H). 4.23(S,2H), 7.06(d,2H,J=8.3). 7.22((),2H,J=8.3), 7.97(S, 1H). 8.08(S,1H)</td>

<td> 54</td><td> H</td><td> n- C5 «11</td><td> 4-C1</td><td> N</td><td> A</td><td> Oily material</td><td> 0.88(t,3H,J=6.8), 1.00—1.94(11,14H) , 2.31(11,2.11), 3.70(l>S, 1H) , 4.05((1,1H, .)=13.7) . 4.26((1,1H, .)=13.7) . 6.89((1,2H,J=8.3), 7.17(d, 2H, .)=8.3), 7.99(8,1H), 8.15(S,1H)</td>

Table 1 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="2"> Indication in</td><td> Formula</td><td> (I)</td><td> Indicatior of</td><td> Melting point</td><td rowspan="2"> N M R Spectral Data (CDCI , (5[)|)fn) u</td>

<td> R1</td><td> R 2</td><td>Xn</td><td> A</td><td> Stereoisctner</td><td> CO)</td>

<td> 59</td><td> c3 h7</td><td> H</td><td> 4-C I</td><td> CH</td><td> A -type</td><td> Oily material</td><td> 0.97((1,3H..1=7). 1.00((1,3H,J=7). 1.23—2.53(m. 10H) . 3.90(0,1H,J=14) . 4.17((1,1H.J=14) . 6.90—7.43(1»,6H). 7.53(bS,1H)</td>

• · • · ·· © » * · « ♦ · Ο • · 4 4

9 Ο a 9 9 « β 4 9 9 « 94 «44449 «

2«» 4 9 * 4 4 β Ο β β 4 4 6 · β 4 ·9 · »·4 • · β 4 C C ο 4 ' δ

β * a a·*

)·:

J •ί

Table 1 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="4"> Incidation in-Formula (I)</td><td rowspan="2"> Indicatior of Stereoisomer</td><td rowspan="2"> Melting point CO)</td><td rowspan="2"> N M R Spectral Data (CDCI , Sppin) O</td>

<td> 62</td><td> H</td><td> c3h7</td><td> 4-0 I</td><td> N</td><td> B -type</td><td> Oily material</td><td> 0.60—3.17(111,15H) . 3.43(bs.1H) . 4.20(s,2H), 6.92((1,2H,J=8). 7.15((1,29,.)=8). 7.87(S,1H), 8.07(s,1H)</td>

<td> 66</td><td> nc4h9</td><td> H</td><td> 4-CI</td><td> CH</td><td> A -type</td><td> Oily material</td><td> 0.57-2.67(1», 179) , 3.05(s,19). 3.95(S,2H), 6.68-7.25(1»,6H). 7.38(bs,1H)</td>

<td> 68</td><td> K</td><td> n- C4H9</td><td> 4-CI</td><td> N</td><td> B -type</td><td> Oily material</td><td> 0.60-2.33(1», 16H) , 2.90-3.20(1»,1H). 3.30(s,1H). 4.22(s,2H). 6.88((1,2H,J=8), 7.12((1,2H,J=8). 7.83(s,1H), 8.02(s,1H)</td>

<td> 69</td><td> 0 4H 9</td><td> H</td><td> 4-CI</td><td> N</td><td> A -type</td><td> Oily material</td><td> 0.78((1,3H,J=6). 0.88((1,39, J=6). 1.07-2.27(i»,9H). 2.33-2.67(1»,3H), 4.22(S,2H). 7.00((1,29,.)=9), 7.2((1,29,J=9) . 7.93(s,19). 8.05(s, 19)</td>

<td> 70</td><td> c4h9</td><td> H</td><td> 4-CI</td><td> CH</td><td> A -type</td><td> Oily material</td><td> 0.81((1,39, J-G). 0.88((1,39, J=6). 1.03-2.10(1», 99). 2.26-2.70(1», 29), 3.88(s, 1H), 4.00(s,2H). 6.70-7.30 (In. 69). 7.46(s,19)</td>

<td> 71</td><td> n- C 4H g</td><td> H</td><td> 4-CI</td><td> N</td><td> A -type</td><td> oily materia]</td><td> 0.60-2.63(1», 179) . 2.80(s, 19). 4.23(S,29). 7.07((1,29, J=8). 7.27((1,29, J=8). 8.00(s, 19). 8.13(s, 19)</td>

I

I

S$&·;

«I

Table 1 (Continued)

<td colspan="2" rowspan="2"> Compound No.</td><td colspan="3"> Indication in fbrmula(I)</td><td rowspan="2"> A</td><td rowspan="2"> Indication of Stereoisomer</td><td rowspan="2"> Melting point CO)</td><td rowspan="2"> N M R Spectral Data (CDCl , SpDffl)</td>

<td rowspan="2"> 72</td><td> Isomer a</td><td> gh3</td><td> c2 h5</td><td> 4-GI</td><td> N</td><td> A -type</td><td> Mixture of 72-a & 72-b</td><td rowspan="2"> 0.57—1.02 (in. GH). 1.12—2.55 (m. 9H). 3.55. 3.67(2s. 1H) . 4.20(bs,2H) . 6.95((I,2H, J=9), 7.18((1,2H, .)=9) 7.92(s, 1H). 8.12(S,1H)</td>

<td> Iscmer b</td><td> c2 h5</td><td> ch3</td><td> 4-C I</td><td> N</td><td> A -type</td><td> 98—101</td>

<td rowspan="2"> 73</td><td> Iscmer a</td><td> CHj</td><td> c2 h5</td><td> 4-C 1</td><td> N</td><td> B -type</td><td> Mixture of 73-a & 73-b</td><td rowspan="2"> 0.67—1.05(m, GH). 1.05—3.12 (in, 9H), 3.77, 3.92(28,1H) , 4.35(s,2H). 6.95((1,2H,J=8). 7.18((1,2H,.)=8). 7.90(8,1H). 8.15, 8.15(2s,1H)</td>

<td> Isomer b</td><td> c2 h5</td><td> ch3</td><td> 4-C 1</td><td> N</td><td> B -type</td><td> 117—119</td>

<td rowspan="2"> 74</td><td> Iscmer a</td><td> ch3</td><td> c2 h5</td><td> 4-C 1</td><td> CH</td><td> B -type</td><td> Mixture of 74-a & 74-b</td><td rowspan="2"> 0.63—1.08(UI, 6H), 1.08—3.07()11,9H). 3.33(s,1H). 4.12(bs,2H) , 6.80—7.30(m,6H), 7.70(bs,1H)</td>

<td> Iscmer b</td><td> c2 h5</td><td> ch3</td><td> 4-C 1</td><td> CH</td><td> B -type</td><td> 122— 127</td>

<td colspan="2"> 75</td><td> ch3</td><td> ch3</td><td> 4-t- C4 H9</td><td> N</td><td> B -type</td><td> Oily material</td><td> 0.77(s,3H). 1.O1(S,3H), 1.28(S,9H), 1.39—2.11 (b,5H). 2.12-2.54(ni,2H). 3.78(bs, 1H) . 4.34(s,2H). 6.95((1,2H,J=8.4). 7.20((1,2H,J=8.4), 7.88(S, 1H). 8.14(s,1H)</td>

Table 2 Oxirane Derivative

(H-A) (JI-B)

<td> Compound</td><td colspan="3"> Indication in formula (II)</td><td> Indication of</td><td> Physical</td><td rowspan="2"> N M R Spectral data (CDCIj , δΡΡΠ1)</td>

<td> No.</td><td> R1</td><td> R 2</td><td> *n</td><td> Stereoisomer</td><td> property</td>

<td> 77</td><td> ch3</td><td> ch3</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> O.83(S,3H). 0.95(s,3H). 1.33-1.73(18,4H). 2.33—2.53(ffl.3H). 2.52((1,1H,.1=4). 2.67((1,1H, .)=4). 7.03((1,2H, .)=8), 7.23((1,2H.J=8)</td>

<td> 78</td><td> ch3</td><td> ch3</td><td> 4-CI</td><td> B -type</td><td> Oily material</td><td> 0.87(s, 3H), 0.93(s,3H). 1.45-1.73(111.4H). 2.13-2.70(18,3H), 2.60((1,1H,J=4). 2.83((1,1H, .)=4), 7.02((1,2H.J=8), 7.23((1,2H,J=8)</td>

<td> 79</td><td> ch3</td><td> ch3</td><td> 4-Br</td><td> A -type</td><td> Oily material</td><td> 0.83(s,3H), 0.93(s,3H), 1.17-1.73(18,4H). 2.17-2.67(18,3H). 2.50((1,1H,J=4). 2.60(S,1H, J=4). 6.80-7.33(18,4H)</td>

<td> 80</td><td> ch3</td><td> ch3</td><td> 4-Br</td><td> B -type</td><td> Oily material</td><td> 0.87(s,3H). 0.93(s,3H). 1.20-2.73(18,7H). 2.60(0,1H,J=4). 2.80((1,1H,J=4), 6.80-7.47(18,4H)</td>

<td> 81</td><td> ch3</td><td> ch3</td><td> 4-F</td><td> A -type</td><td> Oily material</td><td> 0.80(S,3H). 0.90(s,3H). 1.00-2.00(18,4H). 2.00-2.67(1»,5H). 6.70-7.23(m,4H)</td>

<td> 82</td><td> ch3</td><td> ch3</td><td> 4-F</td><td> B -type</td><td> Oily material</td><td> 0.88(s,3H), 0.93(s,3H), 1.03-2.00(m,4H). 2.00-2.93(m,5H), 6.70—7.27(m,4H)</td>

<td> 83</td><td> ch3</td><td> ch3</td><td> 2.4-C I 2</td><td> A -type</td><td> Oily material</td><td> 0.85(s,3H), 0.92(s,3H), 1.27-1.82(m,4H). 2.28-2.78(18,5H), 6.92-7.28(18,30)</td>

<td> 84</td><td> ch3</td><td> ch3</td><td> 2.4-C I 2</td><td> B -type</td><td> Oily material</td><td> 0.87(s,3H). 0.97(s,3H). 1.48-1.72(18,4H). 2.33-2.77(18,3H). 2.62(0,1H,J=4), 2.85((1,1H,J=4). 7.05-7.37(18,3H)</td>

<td> 85</td><td> ch3</td><td> H</td><td> 4-CI</td><td> A -type</td><td> Oily material</td><td> 0.80((1,3H,J=6). 1.14-2.51(18,6H). 2.31-2.51 (b,2H). 2.63(s,2H), 7.00((1,2H,.1=9), 7.19((1,2H,.)=9)</td>

Table 2 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in formula (II)</td><td rowspan="2"> Indiestior of Stereoisaner</td><td rowspan="2"> Physical property</td><td rowspan="2"> N M R Spectral Data (CDCI^ , SppUl)</td>

<td> 86</td><td> H</td><td> ch3</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.89(d,3H, J=6). 0.85—2.68(n,6H), 2.32-2.42(b, 2H). 2.47(d. 111. J=4.6). 2.78((1,1H, J=4.6), 6.75-7.28(1», 4H)</td>

<td> 87</td><td> H</td><td> ch3</td><td> 4-C I</td><td> B -type</td><td> Oily material</td><td> 0.81(d,3H,J=6), 3.93—3.00(01,8H), 2.54(d,1H, J=4.6). 2.79((1,1H,J=4.6), 6.80-7.33(01,4H)</td>

<td> 88</td><td> ch3</td><td> H</td><td> 4-C 1</td><td> B -type</td><td> Oily material</td><td> 1.09((1,3H,J=G), 0.83—3.26(l», 10H) , 6.95(d,2H, J=9). 7.14(d,2H,J=9)</td>

<td> 89</td><td> ch3</td><td> ch3</td><td> H</td><td> A -type</td><td> Oily material</td><td> 0.73~2.07(n,5H). 0.87(s,3H), 0.97(s,3H). 2.27-2.77(1»,2H). 2.55(d,1H,J=4), 2.67(d, 111, J=4). 7.23(s,5H)</td>

<td> 90</td><td> ch3</td><td> ch3</td><td> 4-CH3</td><td> A -type</td><td> Oily material</td><td> 0.83(s,3H), 0.97(S,3H). 1.17-1.97 (n,5H). 2.17-2.77(01,2H), 2.27(s,3H). 2.55((1,1H,J=4), 2.65(d,1H,J=4), 7.00(s,4H)</td>

<td> 91</td><td> ch3</td><td> ch3</td><td> 4-CH3</td><td> B -type</td><td> Oily material</td><td> 0.87(s,3H). 0.93(S,3H), 1.47-1.77(m,5H), 2.17-2.97(01,2H), 2.30(S,3H), 2.65(d,1H,J=4), 2.87(d,1H,J=4), 7.07(s,4H)</td>

<td> 92</td><td> ch3</td><td> ch3</td><td> 2-F-4--C 1</td><td> A -type</td><td> Oily material</td><td> O.83(s,3H), 0.93(s,3H), 1.09-2.79(m,9H). 6.83-7.15(οι,3H)</td>

<td> 93</td><td> c2 |-l5</td><td> H</td><td> 4-C 1</td><td> A -type</td><td> Oily material</td><td> 0.60-2.83(1», 11H) , 2.43(hs,2H) . 2.65(s,2H), 6.92-7.33(m,4H)</td>

<td> 94</td><td> H</td><td> c2 h5</td><td> 4-C 1</td><td> A -type</td><td> Oily material</td><td> 0.67—2.77(n,11H) , 2.37(bs,2H) , 2.53(d,1H, J=4). 2.85(d,1H,J=4), 6.87-7.33(1»,411)</td>

<td> 95</td><td> H</td><td> c2 h5</td><td> 4-C 1</td><td> B -type</td><td> Oily material</td><td> 0.60-2.92(1», 13H) . 2.57(d, 1H, J=4). 2.82(d,1H,J=4). 6.87-7.30(m, 4H)</td>

TE^^-~--^=ggsn3;ssva.;

Table 2 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in·formula (II)</td><td rowspan="2"> Indicatior of Sterecisaner</td><td rowspan="2"> Physical Property</td><td rowspan="2"> N M R Spectral Data (CDCI , Sppm) o</td>

<td> 96</td><td> c2 h5</td><td> H</td><td> 4-C I</td><td> B -type</td><td> Oily material</td><td> 0.67~2.85(a,13H) . 2.75(s,26), 6.88-7.33(·, 4H)</td>

<td> 97</td><td> c2 h5</td><td> c2 h5</td><td> 4-C !</td><td> A -type</td><td> Oily material</td><td> 0.57-1.03(8,66). 1.03—2.05(8,96), 2.38(bs,26) . 2.57(d,16.J=4). 2.67(d, 16,J=4), 6.90-7.30(8,46)</td>

<td> 98</td><td> c2h5</td><td> c2 h5</td><td> 4-C I</td><td> B -type</td><td> Oily material</td><td> 0.63-1.03(8,66). 1.03-1.90(8.96). 2.07-2.50(8,26). 2.62((1,16,J=4). 2.75((1,16, J=4). 6.83-7.23(8.46)</td>

<td> 99</td><td> n-C3 H7</td><td> H</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.59-1.02(8,36), 1.02—2.29(8,10H) , 2.29-2.52(8,26), 2.68(S,26), 7.05((1,26. J=9). 7.25(d,2H, J=9)</td>

<td> 100</td><td> H</td><td> n-C3 H7</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.62-1.03(8.36). 1.03-2.32(8,106) . 2.32-2.48(b,26). 2.53(d,16, J=4.4), 2.86((1.16, >4.4). 7.03((1,26, J=9), 7.22((1,26, J-9)</td>

<td> 101</td><td> c2 h5</td><td> H</td><td> 2,4-C I 2</td><td> A -type</td><td> Oily material</td><td> 0.67-3.10(8.136) , 2.70(s,26). 7.10(8,26). 7.28(1,16)</td>

<td> 102</td><td> c2h5</td><td> H</td><td> 4-F</td><td> A -type</td><td> Oily material</td><td> 0.65-2.50(8.136) . 2.62(s,26), 6.60-7.24(«.4H)</td>

<td> 103</td><td> c2 h5</td><td> H</td><td> 4-Br</td><td> A .^type</td><td> Oily material</td><td> 0.67-2.13(8.116) . 2.42(8,26). 2.65(s.2H). 6.98(d,26.J=8). 7.35(d,26,>8)</td>

<td> 104</td><td> c2 h5</td><td> H</td><td> 4-C 6H 5</td><td> A.-type</td><td> SOlid np:69—71Ό</td><td> 0.63-2.58(8,136) , 2.66(s,2H). 7.04-7.68(8,96)</td>

<td> 105</td><td> c2 h5</td><td> H</td><td> 4-t-C 4H 9</td><td> A -type</td><td> Oily material</td><td> 0.69-2.55(8.136) . 1.27(S.9H). 2.65(s,26). 6.93-7.42(8,46)</td>

Table 2 (Continued)

<td> Compound</td><td colspan="3"> Indication in formula (II)</td><td rowspan="2"> Indication of Stereoiscmer</td><td> Physical</td><td rowspan="2"> N M R Spectral- Data (CDCI , δ ppm)</td>

<td> No.</td><td> R1</td><td> R 2</td><td> X n</td><td> property</td>

<td> 106</td><td> i-C 3h 7</td><td> H</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.85(d.6H.J=7). 1.00—2.83(·,9Η), 2.63(s,2H). 6.90-7.33(d), 4H)</td>

<td> 107</td><td> n-C 5Hn</td><td> H</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.87(t.3H.J=6.8). 1.00—2.56(D),1GH) . 2.67((1,1H,>4.4). 2.71 (d, 1H,>4.4), 7.08((1,2H.>8.3). 7.22((1,2H, >8.3)</td>

<td> 108</td><td> H</td><td> n-C 5Ηη</td><td> 4-C 1</td><td> A -type</td><td> Oily material</td><td> 0.87(t,3H,>6.«). 1.00—2.54(0.16H) . 2.56((1,1H,>4.4). 2.88((1,1H.>4.4). 7.09((1,211, >8.3). 7.23((1,2H,>8.3)</td>

<td> 109</td><td> ch3</td><td> ch3</td><td> 4-t-C 4H 9</td><td> A -type</td><td> Oily material</td><td> 0.80(s,3H). 0.94(s,3H), 1.28(S,9H). 1.41—1.96(m,4H). 2.18~2.48(1>,3H), 2.55((1,1H,>4.4). 2.64(d, 1H,>4.4), 7.02(d,2H,>8), 7.18((1,2H,>8)</td>

<td> 110</td><td> ch3</td><td> ch3</td><td> 4-t-C 4H θ</td><td> B -type</td><td> ‘ Oily material</td><td> 0.87(s,3H), 0.94(s,3H). 1.28(S,9H), 1.40-1.93(m.4H). 2.20-2.76(m,3H). 2.60((1,1H,>4.4), 2.84((1,1H,>4.4). 7.02(d,2H,>8). 7.27(d,2H, J=8)</td>

<td> 111</td><td> ch3</td><td> ch3</td><td> <-C6 H5</td><td> A -type</td><td> Oily material</td><td> 0.83(s,3H), 0.92(s,3H), 1.10—2.18(0,4H). 2.47(bS,3H) . 2.50(d, 1H,>4). 2.63((1,1H. >4). 6.97—7.63(m,9H)</td>

<td> 112</td><td> ch3</td><td> ch3</td><td>4-°6 H5</td><td> B -type</td><td> Oily material</td><td> 0.85(s,3H). 0.93(S,3H), 1.20—1.97(0,4H). 1.97—2.90(m,3H). 2.57((1,1H,>4), 2.82((1,111,>4). 6.97-7.58(m.9H)</td>

cs-.

Table 2 (Continued)

<td colspan="2" rowspan="2"> Compound No.</td><td colspan="3"> Indication in formula (II)</td><td rowspan="2"> Indication of Stereor iscmer</td><td rowspan="2"> Physical property</td><td rowspan="2"> N M R Spectral Data (CDCI^ , δρρίλ)</td>

<td></td><td> 113</td><td> H</td><td> •·θ 3H 7</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.82((1.3H,.1=6). 0.85(0,30,.1=6). 0.97-2.73(s, 90), 2.60((1.1H.J=4). 2.88(0,10,.1=4). 6.93-7.37(1», 40)</td>

<td colspan="2"> 114</td><td> H</td><td> i-C 3H 7</td><td> 4-C I</td><td> B -type</td><td> Oily material</td><td> 0.67—1.03(w,GH), 1.03—2.77(n.9H), 2.50(<l, 1H.J=4). 2.83(0,10, J=4). 6.90—7.33 (m, 40)</td>

<td colspan="2"> 115</td><td> i-C 3h J</td><td> H</td><td> 4-C I</td><td> B -type</td><td> Oily material</td><td> 0.87(0,30,J=6), 0.90((1,3H,.1=6). 1.10-3.20(1», 90). 2.87(s.2H). 6.90-7.40(1». 40)</td>

<td colspan="2"> 116</td><td> 0-C4 Hg</td><td> H</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.63-2.80(1», 17H) . 2.67(s,20), 6.93-7.37(1», 40)</td>

<td colspan="2"> 117</td><td> H</td><td> n-C4Hg</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.50-2.70(ι». 17H) . 2.50(0.10, J=4), 2.83(0,111, J=4). 6.90-7.30(1», 4H)</td>

<td colspan="2"> 118</td><td> H</td><td> n-C4 Hg</td><td> 4-C I</td><td> B -type</td><td> Oily material</td><td> 0.63-2.73(1». 17H) , 2.53(0,1H.J=4), 2.77(0,1H,J=4), 6.80-7.23(1», 4H)</td>

<td colspan="2"> 119</td><td> i-C, H9</td><td> H</td><td> 4-C I</td><td> A -type</td><td> Oily material</td><td> 0.78(0,30, .)-7), 0.88(0,30, J=7). 1.00-2.27(1». 90). 2.27-2.50(1».20). 2.63(s,20). 6.87-7.33(01.40)</td>

<td rowspan="2"> 120</td><td> Isaner a</td><td> ch3</td><td> C 2H 5</td><td> 4-C I</td><td> A -type</td><td> Mixture of 120a a 120b</td><td rowspan="2"> 0.68-0.97 (m, 60). 0.97-1.85(1», 60). 2.15-2.75(01,50). 7.00(0,20,.)=8). 7.17(0,20,J=8)</td>

<td> Iscmer b</td><td> c2h5</td><td> ch3</td><td> 4-C 1</td><td> A -type</td><td> Oily material</td>

<td rowspan="2"> 121</td><td> Isaner a</td><td> ch3</td><td> c2h5</td><td> 4-C I</td><td> B -type</td><td> Mixture of 121a & 121b</td><td rowspan="2"> 0.67-1.00(01,60). 1.00-1.90(10,60), 2.13-2.90(01.50), 6.97(0,20, J=8). 7.17(0,20, >8)</td>

<td> Isaner b</td><td> c2h5</td><td> ch3</td><td> 4-C I</td><td> B -type</td><td> Oily material</td>

T·*1-

· V 0 < < € *4 99 *4 ·· *9 »

S > 9 e » · « * 0 0 * * < » » · r · 0 *40

0*0 0 ··· e·» * * • · 0 · a &

e » « ·*. ♦ # < 0» e ««!»·» J • 04» 0 0 » V 9 • · β> ί * * * »

S » 0« «· 0*0

Table 3

(Π) (Methylenecyclopentane Derivatives)

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in Formula (III)</td><td rowspan="2"> Physical property</td><td rowspan="2"> N M R Spectral Data (CDCI . δρρ·) o</td>

<td> 122</td><td> CH 3</td><td> CH 3</td><td> 4-C I</td><td> Oily material</td><td> 1.03(s,3H), 1.08(s,3H), 1.28—1.85(1.48). 2.35—3.12(9.3H). 4.75—4.95(m.2H). 7.07(d.2H. J-8). 7.27((1,2H.J=8)</td>

<td> 123</td><td> CH 3</td><td> CH 3</td><td> 4-Br</td><td> Oily material</td><td> 1.00(s.3H). 1.03(s,3H). 1.13—1.77(·.5H). 2.30—3.10(«,2H). 4.63—4.80(0,2H). 6.83-7.40(1.48)</td>

<td> 124</td><td> CH 3</td><td> CH 3</td><td> 4-F</td><td> Oily material</td><td> 1.00(s,3H). 1.07(s.3H). 1.13-2.00(·,4Η). 2.00-3.13(«, 3H). 4.72-4.90(n,2H). 6.70—7.28(1,48)</td>

<td> 125</td><td> CH 3</td><td> CH 3</td><td> 2,4-C 12</td><td> Oily material</td><td> 1.O7(S, 3HX2). 1.27—1.80(l.4H). 2.43—3.18(m, 3H). 4.72-4.88(ffl,2H). 7.05-7.37(1,38)</td>

I

GJ

I

Table 3 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in formula (III)</td><td rowspan="2"> Physical property</td><td rowspan="2"> N M R ..Spectral Data (CDCI . δρρ8) V</td>

<td> 126</td><td> CH J</td><td> CH 3</td><td> 4-CH3</td><td> Oily material</td><td> 1.03(s,3H). 1.O7(S.3H). 0.66-1.90(8.56). 2.17-3.13(8,26). 4.83(bs,2H) . 7.07(s,46)</td>

<td> 127</td><td> CH 3</td><td> CH 3</td><td>4-l-C4 Hg</td><td> Oily material</td><td> 1.03(s,36). 1.08(s.3H). 1.30(S,9H), 1.36-1.86(8,46), 2.20-3.13(8,36). 4.76—4.93(bs,26) . 7.07((1,26. M). 7.27((1,26, J=8)</td>

<td> 128</td><td> CH 3</td><td> CH J</td><td> 4-CG H5</td><td> Oily material</td><td> 1.O3(S,3H). 1.10(s,36). 1.10-1.92(8,46). 2.17-3.17(8,36). 4.83(bs,26) . 7.08—7.70(8,9H)</td>

<td> 129</td><td> c2 h5</td><td> H</td><td> 4-C I</td><td> Oily material</td><td> 0.93(t,36,J=7). 1.08-3.08(8.106) . 4.76-4.93(8,2H). 6.97-7.37(8,46)</td>

<td> 130</td><td> i-C3 h7</td><td> H</td><td> 4-C I</td><td> Oily material</td><td> 0.60((1,36. J=8). 0.70((1,36. J=8). 0.87-2.97(8,96). 4.57-4.83(8,26). 6.77-7.20(8,46)</td>

<td> 131</td><td> c2 h5</td><td> c2 h5</td><td> 4-C I</td><td> Oily material</td><td> 0.63-1.05(8.66). 1.05-1.93(8,86). 2.13-3.13(8,36). 4.00(dd. 26. J=12,2). 6.95-7.33(8,46)</td>

<td> 132</td><td> CH 3</td><td> c2 h5</td><td> 4-C I</td><td> • Oily material</td><td> 0.63-1.10(8,66), 1.10—1.80(8,66), 2.23-3.13(8,3H). 4.67-4.87(8,2H). 7.03((1,26. J=9). 7.23((1,26, J=9)</td>

·&

'X;,

I

Table 4

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in Formula (IV)</td><td rowspan="2"> Physical property</td><td rowspan="2"> N M R Spectral Data (CDCI , δ ppm) V .</td>

<td> 133</td><td> CH 3</td><td> CH 3</td><td> 4-C 1</td><td> Oily material BP 124Ό draiHy)</td><td> 0.83(s,3H), 1.05(0,311), 1.52~1.83(lH,4H), 2.25-3.17(01,3H). 6.97((1,2H,J=8), 7.17((1,211, J=8) '</td>

<td> 134</td><td> CH 3</td><td> CH 3</td><td> 4-Br</td><td> Oily material BP 131- 2Ό (0.7ffliHy)</td><td> 0.87(S,3H), 1.O7(S,3H). 1.17—3.27(m, 7H), 6.83-7.53()0,4H)</td>

<td> 135</td><td> CH 3</td><td> CH 3</td><td> 4-F</td><td> Oily material BP 95- 8Ό (0.7«Hy)</td><td> 0.85(s,3ll), 1.07(s,3ll), 1.20-3.23()0, 7H). 6.73-7.27(01, 4H)</td>

<td> 136</td><td> CH 3</td><td> CH 3</td><td> 2,4-C l2</td><td> Oily material BP 142- 6Ό (1.5«Hy)</td><td> 0.90(s,3H). 1.05(s,3H), 1.3—2.07(m,4H), 2.23~3.40(m,3H), 7.C—7.32(111,311) J</td>

<td> 137</td><td> CH 3</td><td> H</td><td> 4-C 1</td><td> Oily material BP 120- 145Ό (3mrfly)</td><td> 0.97, 1.08(2(1,311,.)=7,J=G) , 1.20-3.27(01,8H). 7.03((1,2H,J=7). . 7.19((1,2H, J=7)</td>

<td> 13»</td><td> CH 3</td><td> CH 3</td><td> H</td><td> Oily material BP 93-94Ό (0.3mHg)</td><td> 0.87(s,3H), 1.03(5,3H), 0.83-3.23(0),7H). 7.07(s,5H)</td>

Table 4 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="3"> Indication in Formula (IV)</td><td rowspan="2"> Physical Property</td><td rowspan="2"> N M R Spectral Data (CDCI , δ ppm) 0</td>

<td> 139</td><td> CH 3</td><td> CH 3</td><td> 4-CH3</td><td> Oily material</td><td> O.87(S,3H). 1.O7(S,3H). 1.20—3.20(m,7H). 2.37(6,3H). 7.70(s,4H)</td>

<td> 140</td><td> CH 3</td><td> CH 3</td><td> 2-F -4-C I</td><td> Oily material BP 102— 104’C (0.</td><td> 0.89(s,3H), 1.05(S,3H), 1.32—3.49(m,7H), 6.83—7.21 (m,3H)</td>

<td> 141</td><td> CH 3</td><td> CH 3</td><td> 4t-Cj| Hg</td><td> Oily material BP 132— 140°C (1.0»H(J)</td><td> 0.8G(s,3ll), 1.04(s,3H), 1.26(s-,9H), 1.37—3.21 (m, 7H). 6.95((1,211,.)=8.4), 7.18((1,2H, .1=8.4)</td>

<td> 142</td><td> CH 3</td><td> CH 3</td><td> *-c6 H5</td><td> Solid IIP 63-661}</td><td> O.87(S,3H). 1.03(5,311), 1.17-3.40(m,7H). 7.00-7.67(m,9H)</td>

<td> 143</td><td> C2 H 5</td><td> H ·</td><td> 4-C I</td><td> Oily material BP 135— 145’C ( 0.65jrf(j)</td><td> 0.89(t,3H,J=7). 1.10—3.28(m,10H) . 7.05(d,2H, J=9), 7.27((1,2H,J=9)</td>

<td> 144</td><td> C2 H 5</td><td> H</td><td> 4-F</td><td> Oily material BP 102— 108’C (0.2/mH(J)</td><td> 0.70—1.10(m,3H). 1.20—3.28(m, 10H) , 6.70-7.25 (in, 4H)</td>

<td> 145</td><td> C2 H 5</td><td> H</td><td> 4-Br</td><td> Oily material BP 126— 128Ό (0.</td><td> 0.87(t,3H,.)=7), 1.10-3.40(m,10H) , 6.97(d,2H,.)=8), 7.32(d,2H, .)=8)</td>

<td> 146</td><td> C2 H 5</td><td> H</td><td> 2.4-C I 2</td><td> Oily material BP 178— 179Ό (4/nmHg)</td><td> 0.90(t,3H, .)=7), 1.10-3.G0(lli,10H) , 7.13-7.30(m, 3H)</td>

Table 4 (Continued)

<td> Compound</td><td colspan="3"> Indication in formula (IV)</td><td> Physical</td><td rowspan="2"> N M R Spectral Data (CDCI , δ ppm) o</td>

<td> No.</td><td> R1</td><td> R 2</td><td>Xn</td><td> property</td>

<td> 147</td><td> θ2 H 5</td><td> H</td><td> 4-t-C 4H θ</td><td> Oily material BP 132 °C (O.OwiHg)</td><td> 0.87(t,3H,.)=7), 1.00-3.30(m,10H) , 6.87-7.43(111,4H)</td>

<td> 148</td><td> c2h5</td><td> H</td><td> *-c6 h5</td><td> Solid IIP 72-75Ό</td><td> 0.70-1.07(81,3H), 1.13-3.30(81,10H) , 6.98-7.65(81,9«)</td>

<td> 149</td><td> n-C3 H 7</td><td> H</td><td> 4-C I</td><td> Oily material BP150-WOO (3mmHg)</td><td> O.GG- 1.08(m,3H), 1.08-3.26(01,12«) . 7.04((1,2H,J=9), 7.24((1,2H.J=9)</td>

<td> 150</td><td> i-C3 H 7</td><td> H</td><td> 4-C I</td><td> Oily material BP 143- 149Ό (1.2/iiiiiHg)</td><td> 0.60-1.07(111,6H). 1.07-3.27(18,9H). 6.83-7.27(81,4H)</td>

<td> 151</td><td>n'C4H 9</td><td> H</td><td> 4-C 1</td><td> material BP 140- 149'C (0. )</td><td> 0.87 (t, 3H, .1=7.0), 1.03-3.28 (m. 14H). 7.02((1,2H,J=9.0), 7.25((1,2H,J=9.0)</td>

<td> 153</td><td> C2 H 5</td><td>C2 H 5</td><td> 4-C 1</td><td> Oily material</td><td> 0.57-1.07(18,6«). 1.07—3.27(81,11H) . 6.95-7.37(18,4H)</td>

<td> 154</td><td> i-C4 H 9</td><td> H</td><td> 4-C 1</td><td> Oily material BP 130— 136Ό (0.3/mHg)</td><td> 0.85((1,3«, .1=6), 0.90(d,3H,J=6), 1.10-3.33(81,11H) . 7.00(d,2H, J=9), 7.21(d,2H,J=9)</td>

<td> 155 _</td><td> CH 3</td><td> c2h5</td><td> 4-CI</td><td> Oily rfeT-ilire (0.2miHg)</td><td> 0.57—1.07(81,6H). 1.17-3.23(81,9H), 7.00(d,2H, J=9). 7.20(d,2H, J=9)</td>

Table 5

(V) (Ester Derivatives of Cyclopentanecarboxylic acid)

<td> Compound No.</td><td colspan="3"> Indication in Formula (V)</td><td></td><td> Physical property</td><td rowspan="2"> N M R Spectral Data (CDCI^ , Spplil)</td>

<td> 156</td><td> CH 3</td><td> CH 3</td><td> 4-C I</td><td> CH .3</td><td> Oily material BP 142— 143°C (0.7irfg)</td><td> O.72(S,3H). 1.05(s,3H), 1.37-2.40(1»,4H), 3.13(S,2H). 3.70(s,3H), 7.07(d,2H,J=9), 7.27((1.2H. J=9)</td>

<td> 157</td><td> CH 3</td><td> CH 3</td><td> 4-Br</td><td> CH 3</td><td> Oily material</td><td> 0.70(S,3H). 1.03(s,3H). 1,25-2.43(«l,4H). 3.07(s,2H). 3.63(s,3H), 6.80—7.53(m. 4II) .</td>

<td> 158</td><td> CH 3</td><td> CH 3</td><td> 4-F</td><td> CH 3</td><td> Oily material</td><td> 0.70(s,3H). 1.08(s,3H), 1.20-2.57(»,4H), 3.13(s,2H). 3.67(s,3H). 6.73-7.37(m,4H)</td>

<td> 159</td><td> CH 3</td><td> CH 3</td><td> 2.4-C I 2</td><td> CH 3</td><td> Oily material BP 130d33°C ( 0.60/rfg)</td><td> 0.70(S,3H). 1.05(S,3H), 1.20-2.45(10,4«). 3.10(s,2H), 3.65(S,3H). 7.05-7.30(1,3H)</td>

<td> 1G0</td><td> CH 3</td><td> H</td><td> 4-C I</td><td> CH 3</td><td> Oily material BP 142— 145Ό (0.1/mHg)</td><td> 0.83- 1.12(m,3H). 1.40-2.63(m,5H), 3.12, 3.15(2s,2H) . 3.70(s,3H). 7.07(d,2H,J=8). 7.27(0,2H,J=8)</td>

<td> 161</td><td> CH 3</td><td> CH 3</td><td> H</td><td> CH 3</td><td> Oily material</td><td> 0.67(S,3H), 1.03(S,3H), 0.77-3.23(01,4H). 3.10(s,2H), 3.63(s,3H), 7.07(S,!tH)</td>

<td> 162</td><td> CH 3</td><td> CH 3</td><td> 4-CH3</td><td> CH 3</td><td> Oily material</td><td> 0.70(s,3H), 1.03(s,3H), 1.13-2.40(MH). 2.27(s,3H). 3.07(s,2H), 3.67(s,3H), 6.97(S.4H)</td>

<td> 163</td><td> CH 3</td><td> CH 3</td><td> 2-F -4-C I</td><td> CH 3</td><td> Oily material</td><td> O.79(S,3H), 1.09(s,3H), 1.18-2.61(10,4H). 3.00(0,1H,J=14) . 3.33((1,1H,J=14) , 3.70(s,3H). 6.89-7.32(01,3H)</td>

Table 5 (Continued)

<td> Compound</td><td colspan="3"> Indication in Formula (V)</td><td></td><td rowspan="2"> Physical property</td><td rowspan="2"> Μ M R: Spectral bata (CDCI , Sppin) o</td>

<td> 164</td><td> CH 3</td><td>CH 3</td><td> 4-t-C 4H g</td><td> CH 3</td><td> Oily material</td><td> 0.68(s,3H), 1.05(S,3H), 1.26(s,9H), 1.32-2.62(18,4H). 3.10(bS,2H) , 3.68(s,3H), 7.01((l,2H, J=8.6), 7.26((1,2H, J=8.6)</td>

<td> 165</td><td> CH 3</td><td> CH 3</td><td> 4-C GH 5</td><td> CH 3</td><td> Solid nip. 95—981'</td><td> 0.75(s,3H). 1.05(S,3H), 1.13-2.88(m,4H). 3.13(S,2H), 3.62(s,3H), 6.95-7.62(m,9H)</td>

<td> 166</td><td> c2h5</td><td> H</td><td> 4-C 1</td><td> C2 H s</td><td> Oily material BP 152— 160*C ( 0.45/wnHy)</td><td> 0.67—1.03(ni,3H), 1.20(t,3H, J=7), 1.45-2.53(1»,9H), 3.03, 3.08(2s,2H) ; 4.10(q,2H,J=7), 6.98((1,2H, J=9). 7.20((1,211,.)=7)</td>

<td> 167</td><td> c 2H 5</td><td> H</td><td> 4-F</td><td> CH 3</td><td> Oily material BP 144— 154Ό (3.0raiH(|)</td><td> 0.63—1.10(m,3H), 1.21-2.68(11,711), 3.07, 3.11(2s,2H, 3.66(S,3H), 6.70-7.22 (in, 4H)</td>

<td> 168</td><td> c 2h 5</td><td> H</td><td> 4-Br</td><td> CH 3</td><td> Oily material Bl> 149— 151Ό (0.5mH(j)</td><td> 0.60—2.90(ni, 10H) . 3.07,3.12(2s,2H), 3.67(s,3H), 7.06(d,2H,.)=8.0), 7.42(d,2H,J=8.0)</td>

<td> 169</td><td> C 2H 5</td><td> H</td><td> 2,4-C 1 2</td><td> CH 3</td><td> Oily material BP 143Ό (0.5ffwiH(J)</td><td> 0.67-2.82(111.10H) , 3.10((1.0.4H. J=14) , 3.15(d,0.6H,J=16) , 3.45((1,0.4H,.)=14) , 3.50(d,0.6H,J=14) , 3.68(S,3H), 7.08(l»,2H). 7.30(18,1H)</td>

<td> 170</td><td> c 2h 5</td><td> H</td><td> 4-t-C 4H g</td><td> CH 3</td><td> Oily material BP 152— 156Ό (0.2/wnHy)</td><td> 0.72-2.52(1», 10H) , 1.27(s,9H), 3.09(bs,2H) . 3.65(s,3H), 6.79-7.39(m,4H)</td>

<td> 171</td><td> C 2H 5</td><td> H</td><td> 4-C fiH s</td><td> CH 3</td><td> Solid nip. 52-54Ό</td><td> 0.61-1.10(1»,3H). 1.45-2.50(in.7H). 3.11, 3.16(2s,2H) , 3.66(S,3H). G.96—7.61(18,9H)</td>

Table 5 (Continued)

<td rowspan="2"> Compound No.</td><td colspan="4"> Indication in formula (V)</td><td rowspan="2"> Physical property</td><td rowspan="2"> NMR Spectral Data (CDCI^ , Spplll)</td>

<td> 172</td><td> Π-c 3H 7</td><td> H</td><td> 4-C I</td><td> c2h5</td><td> Oily material</td><td> 0.54—1.08(1»,3H). 1.22(ΐ,3Η, .)=7,4), 1.08—2.61 (m, 9H). 3.08,3.13(2s,2H), 4.15((|,2H, J=7.4), 7.06((1,2H,J=9.8), 7.27((1,2H, J=9.8)</td>

<td> 173</td><td>n'C 4.H g</td><td> H</td><td> 4-C I</td><td> CH 3</td><td> Oily material BP 16Ο-υ172Ό (0. 3mH(J)</td><td> 0.85(t,3H). 0.97-2.12(ni. 11H) . 3.03. 3,03, 3.08(2s,2H) , 3.62(S,3H). 6.92((1,2H,J=8), 7.13((1,2H,J=8)</td>

<td> 174</td><td> n-C 5Ηή</td><td> H</td><td> 4-C 1</td><td> CH 3</td><td> Oily material BP 185— 186Ό ( 0.25mmH(j)</td><td> 0.86(t,3H). 0.98—2.32(m, 13H) . 3.05-3.16(m,2H), 3.69, 3.71(2S,3H) , 7.04((1,2H,J=8.3), 7.22((1,2H,J=8.3)</td>

<td> 175</td><td> c2h5</td><td> c2h5</td><td> 4-C 1</td><td> CH 3</td><td> Oily material</td><td> 0.50—2.63(1», 14H) . 2.90((1,1H,J=14) . 3.27((1,1H,J=14) . 3.67(s.3H), 6.93-7.37(m,4H)</td>

<td> 176</td><td> i-C 3H 7</td><td> H</td><td> 4-C 1</td><td> CH 3</td><td> Oily material</td><td> 0.58—1.10(m,6H). 1.10—3.01(n,6H). 3.08,3.12(2s,2H), 3.71(S,3H). 6.84-7.30(m,4H)</td>

<td> 177</td><td> i-C 4H g</td><td> H</td><td> 4-C 1</td><td> CH 3</td><td> Oily material</td><td> 0.82((1,3H,J=6). 0.89((1,3H,.1=6). 1.04-3.00(m.8H). 3.07. 3.11(2s,2H) . 3.69(s.3H). 6.77-7.24(in,4H)</td>

<td> 178</td><td> CH 3</td><td> C 2H 5</td><td> 4-C 1</td><td> CH 3</td><td> Oily material BP 145— 155Ό (O.G/mHg)</td><td> 0.58-1.17(m,6H), 1.17—2.87(m,6H), 3.05. 3.12(2s,2H) , 3.70(s,3H) , 7.03((1,2H,J=9), 7.25(d,2H, J=9)</td>

The NMR by using TMS spectra of compounds in the Table 1 to 5 are measured as internal standard. The notations are as follows.

<td> s---</td><td> --- singlet.</td><td> d---</td><td> --- doublet.</td><td> t---</td><td> --- triplet,</td>

<td> q---</td><td> --- quartet.</td><td> m---</td><td> — multiplet.</td><td> b---</td><td> ---broad line,</td>

<td> j---</td><td> --- coupling</td><td> constant</td><td> (unit, Hz).</td><td></td><td></td>

C tc cue t

u u c c < <

The infrared absorption spectrum of each of the · azole derivatives exemplified in Table 1 is shown in each of the attached figures 1 to 76.

In the azole derivative represented by the formula (I), according to the view points of the plant diseases controlling activity and the plant growth regulating activity, an azole derivative wherein is a .

hydrogen atom or a (C1 - C4)alkyl; R is a hydrogen atom or

2 a (C^ - C^) alkyl (both R and R do not represent hydrogen atoms at the same time); X is a halogen atom substituting the 4-position of the benzene ring; n is 1 and A is represented by a nitrogen atom or a CH is preferable, and

2 furthermore, ..an azole derivative wherein R and R respectively represent a hydrogen atom or a (C^ - C^)alkyl

2 group (both R and R do not represent hydrogen atoms at the same .time); X represents a halogen atom substituting the 4-position of the benzene ring; n is represented by 1 and A is represented by a nitrogen atom is particularly preferable.

Of the compounds exemplified in Table 1, those azole derivatives of Compound Nos. 1 - 3, 5, 9 - 11, 16, 18, 29 - 32, 37, 38,.42 - 45, 50, 59, 62, 63, 65 and 69 are preferable.

I iv i·

''Ύ

The azole derivative according to the present invention is produced by the following process.

The objective azole derivative represented by the formula (I) can be obtained by reacting the oxirane derivative represented by the formula (II) with a 1,2,4-triazole or

imidazole represented by the following formula (VI) in the presence of a diluent:

MN \=N (VI) wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a CH.

The oxirane derivative represented by the formula

TH), which is used as the starting substance can be obtained by the following process.

Namely, by reacting the cyclopentanone represented by the formula (IV) with sulfonium ylide or oxosulfonium · ylide, for instance, dimethyloxosulfonium methylide or dimethylsulfonium methylide in the presence of a diluent while following the methods described in Org. Syn. 4 9, (1968) and in J. Amer, Chem. Soc., (1965) 1353, the oxirane derivative represented by the formula (II) is

Ί . Λ ύ

• <

• . .

obtained (this method is referred to as A-method).

Still more, as a different method (referred to as

B-method), there is a method by which a methylenecyclopentane represented by the formula (III) is obtained from a cyclopentanone represented by the formula (IV) through the Wittig reaction [refer to Org. Syn. 40 , 66 (1966) and

J. Org. Chem. 28 , 1128 (1963)], and then the oxirane derivative represented by the formula (II) can be obtained from the thus prepared compound by the epoxidation [refer to Org. Syn. Coll, vol., 4, 552 (1963), 49, 62 (1969)].

The reaction formulae according to the abovementioned A-method and B-method are shown below.

Methods for producing the oxirane derivative represented by the formula (II):

(IV)

Dimethyloxosulfonium methylide or

X Dimethylsulfonium n methylide

Wittig reaction

Epoxidation (III)

Still more, the cyclopentanone derivative represented by the formula (IV) can be obtained by the

following method: .

1' 2 Namely, m the case where both R and R of the formula (IV) are the same (C^ - C^)alkyl groups, a cyclopentanone compound represented by the formula (VII) is subjected to dialkylation, thereby converting into the ester derivative of cyclopentanecarboxylic acid represented by the formula (V) and the ester derivative represented by the formula (V) is subjected to hydrolysis and decarboxyh

2 lation, and in the case where any one of R and R is a (C^ - C^)alkyl group and the other one is a hydrogen atom, a desired benzyl group is introduced into the alkylcyclopentane carboxylate derivative represented by the formula (VIII) to obtain the ester derivative of cyclopentanecarboxylic acid represented by the formula (V) and then the thus obtained ester derivative is subjected to hydrolysis and decarboxylation. By doing so, the cyclopentanone derivative represented by the formula (IV) can be obtained.

Further, in the case where R and R -of the formula (IV) are the mutually different (C^ - C^)alkyl groups, after introducing a different (C^ - C^)alkyl group into an ester derivative of cyclopentanecarboxylic acid

2 represented by formula (V) in which either of R or R is a (C^ - Cj)alkyl group and the other (remainder) is a

hydrogen atom, the obtained ester derivative is subjected to hydrolysis and decarboxylation, thereby obtaining the desired derivative represented by the formula (IV).

The reaction form of the above-mentioned cyclopentanone is shown below.

Synthetic route of cyclopentanone of the formula (IV)

C i-

(VIII)

Alkylation

Hydrolysis and

Decarboxylation tut V € * I t ί ί ί » t • 0 t

(IV) i5

.Τ-

By the way, the compounds shown in the formulae (VII) and (VIII) are known and can be obtained from an alkyl ester of 2-oxocyclopentanecarboxylic acid by the method described in Org. Syn. _4_5, 7 (1965) and J. Org. Chem. 29, 2781 (1964).

As the diluent used in reactions in the process of producing the azole derivative represented by the formula (I) according to the present invention, hydrocarbons such as benzene, toluene, xylene, etc.; halogenohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; alcohols such as methanol, ethanol, etc.; ethers such as diethyl ether, diisopropyl ether, tetrahydrofurane, dioxane, etc. and as the others, acetonitrile, acetone, dimethylformamide, dimethylsulfoxide, etc. may be exemplified.

Still more, in the process for producing the azole derivative according to the present invention, the reaction is carried out in the coexistence of a base or an acid in addition to the above-mentioned diluent. As the base used herein, alkali metal carbonates such, as sodium carbonate, potassium carbonate, etc.; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc.; alkali metal alcoholates such as sodium methylate, sodium ethylate, potassium tertiarybutylate, etc.; alkali metal hydrides such as sodium hydride, potassium hydride, etc,; alkyl compounds of an alkali metal such as n-butyl lithium, etc. and as the others, triethylamine, pyridine may be exemplified.

As the acid, inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, etc.

and organic acids such as formic acid, acetic acid, butyric acid, p-toluenesulfonic acid, etc. may be exemplified.

In order to enforce the process for production of the azole derivative according to the present invention, for instance, in the case of obtaining the ester derivative of cyclopentanecarboxylic acid represented by the formula r * <

' / .·/ r ;:· Z t t

c *

I 1 «ί • C Sf t t· i » € tt (V), it is preferable to react substituted benzyl halide with a halogenated alkyl or a the compound represented by the formula (VII) or the formula (VIII) which has been dissolved in the diluent, in the presence of the base as occasion demands.

The reaction temperature may be selected optionally in the range of from the solidifying temperature of the diluent as the solvent to the boiling point thereof, preferably from 0 to 100°C.

The derivative represented by the formula (IV) can be obtained by subjecting the ester derivative of cyclopentanecarboxylic acid represented by the formula (V) to decarboxylation at a temperature of from 80 to 150°C with the inorganic acid or organic acid for from 2 to 24 hours, preferably under agitation.

In order to produce the oxirane derivative represented by the formula (II), in the case of applying the

A-method, it is preferable to add a solution prepared by . f· J

J

dissolving a ketone represented by the formula (IV) in the diluent (particularly, dimethylsulfoxide is preferable) to dimethyloxosulfonium methylide or dimethylsulfonium methylide prepared by equivalently mixing the base (for instance, sodium hydride) and trimethyloxosulfonium iodide or trimethylsulfonium iodide, and to react the two compounds.

In this case, the reaction amount of dimethyloxosulfonium methylide or dimethylsulfonium methylide is preferably from 1.0 to 2.0 equivalent amount of the cyclopentanone derivative represented by the formula (IV). The reaction is preferably carried out at a temperature in the range of from 25 to 100°C for from 1 to 40 hours.

On the other hand, in the case where the production is carried out by the B-method, the cyclopentanone derivative represented by the formula (IV) is added to triphenylphosphine methylide (Wittig reagent) prepared by equivalently mixing the base (for instance, sodium hydride), and methyltriphenylphosphonium halide in the diluent (particularly, dimethylsulfoxide is preferable), and to react the two compounds for from 2 to 10 hours at a temperature of from 0 to 100°C.

The thus formed methylenecyclopentanone derivative represented by the formula (III) is isolated, dissolved in the diluent and reacted at a temperature of from -10 °C to the boiling point of the diluent, preferably from -10 to 8 0°.C after adding hydrogen peroxide or an organic per- acid such as

peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, etc .

The oxirane compound (II) obtained from the cyclopentanone derivative represented by the formula (IV) by the A-method or B-method takes the following stereoijomeric structures concerning the conformation of the oxirane group at the 3-position and the substituted benzyl group at the 7-position in the 1-oxaspiro [2,4]heptane of the oxirane compound represented by the formula (II):

(II-A type) (II-B type)

The separation of these stereoisomers represented by the formulae (II-A) and (II-B) can be carried out by, for instance, chromatography (thin-layer chromatography, column chromatography, high performance liquid chromatography, etc.). The characteristics of the structure of these stereoisomers can be found by, for instance, NMR spectrum.

ί.

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 the base as occasion demands, to a solution prepared by dissolving the azole compound represented by the formula (VI) into the diluent, or conversely, an alkali metal salt of the azole compound is added to a solution prepared by dissolving the oxirane compound in the diluent, to react the two compounds. The reaction temperature may be selected optionally in the range of from the solidifying point to the boiling point of the diluent, however, practically, it is preferable to carry out the reaction at a temperature of from 0 to 120°C, more preferably from 60 to 120°C for from one to 10 hours under agitation.

After finishing the reaction, the thus obtained reaction mixture is cooled and extracted by an organic solvent such as ethyl acetate, chloroform, methylene chloride, benzene, etc. in a iced water. After separating the organic layer, washing it with water and drying the washed layer, the solvent is distilled off under a reduced pressure from the organic layer. By subjecting the thus obtained residue to purification treatment, the objective compound can be obtained. The purification treatment can be carried out by subjecting the residue to recrystallization, silica gel-chromatography, etc.

- 56 Because of the existence of the two isomers represented by the formulae (II-A) and (II-B) in the oxirane compound which is the starting compound of the azole, derivative represented by the formula (I), there are the following stereoisomers in the objective azole derivative represented by the formula (I) which is obtained by the reaction of the oxirane compound represented by the formula (II) and 1,2,4-triazole or imidazole represented by the formula (VI):

(I-A type) (I-B type)

- 57 ------- = in the back of the depicted plane, __ = on the depicted plane, —i = in front of the depicted plane.

Of course, the separation of the isomers represented by the formulae (I-A) and (I-B) can be carried out by, for instance, chromatography.

The utility of the azole derivative (azolylcyclopentanol derivative) represented by the formula (I) according to the present invention as an active ingredient of the agricultural and horticultural composition will be explained.

(1) Fungicidal action to plant disease fungi:

The azole derivative according to the present invention shows the controlling effect against the following plant diseases in a broad range.

Pyricularia oryzae on rice plant,

Cochliobolus miyabeanus on rice plant,

Xanthomonas oryzae on iice plant,

Rhizoctonia solani /n xice plant,

Helminthosporium sigiuoideum on rice plant,

Gibberella fujikuroi on rice plant,

Podosphaera leucotricha on apple,

Venturia inaequalis on apple,

Sclerotinia mali on apple,

Alternaria mali on apple,

Valsa mali on apple, ·

Alternaria kikuchiana on pear,

Phyllactinia pyri on pear,

Gymnosporangium haraeonum on pear,

Venturia nashicola on pear,

Unccinula necator on grape,

Phakospora ampelopsidis on grape,

Glomerella cingulata on grape,

Erysiphe graminis f, sp.. hordei on barley,

Rhynchosporium secalis on barley, .

Puccinia graminis on barley,

Puccinia triformis on barley,

Puccinia recondita on wheat,

Septoria tritici on wheat,

Puccinia triformis on wheat,

Erysiphe graminis f. sp. tritici on wheat, .

Sphaerotheca fuliginea on melons,

Colletotrichum lagenarium on melons,,

Fusarium oxysporum on watermelon,

Fusarium oxysporum f. cucumerinum on cucumber,

Fusarium oxysporum f. raphani on Japanese radish

Erysiphe cichoracearum on tomato,

Alternaria solani on tomato,

Erysiphe cichoracearum on egg plant,

Sephaerotheca humuli on strawberry,

Erysiphe cichoracearum on tobacco,

Alternaria longipes on tobacco,

Cercospora beticola on sugar beet,

Alternaria solani on potato,

Septoria glycines on soybean,

Cercospora kikuchii on soybean,

Sclerotinia cinerea on stone fruit trees,

Botrytis cinerea on various crops,

Sclerotinia sclerotiorum, etc.

Furthermore, the azole derivative according to the present invention takes not only the prophylactic controlling effect but also the therapeutic effect on a few diseases among the plant diseases.

(2) Plant growth regulating action:

Accompanying with the elucidation of the mechanism of the plant growth regulation by plant hormones, the chemicals which are called as the plant growth regulating agent have come to be used in the production field of agriculture and horticulture in recent years.

For instance, production of seedless grapes by gibberellin, promotion of rooting of cuttings by anaphthaleneacetic acid and utilization of 2-chloroethyltrimethylammonium chloride (trade name of CCC) as a growth retardant for wheat have been known.

-I

I

Besides, the application of the’regulating technique of the plant life circle by using the plant growth regulating agent has been enlarged not only to crop plants such as cereals, vegetables, fruit trees, etc.

but also to horticultural plants such as flowers, etc.

and further to trees as the plants in a broad range, and the function of the plant growth regulating agent has s .!

0 A A A A A

O * e a o 0 0 9 fl O

A Ο O 0 »0 • O o

Ο Ο O «

A

O 0 o

A © O GA tt

O O . o o •o •· « o » GO •» O < « · possibility of cover the promotion of rooting, control of blooming, fruit bearing, enlargement of fruits,growth promotion, growth control and control of metabolism.

Accordingly, both the kinds and the use of the plant growth regulating agent have increasing tendency in recent years, however, amount of shown the it is the actual state that the practical use of the plant growth regulating agent has not been promoted so much as is expected.

The azole derivative (azolylcyclopentanol derivative) according to the present invention has a specific property of showing the diverse plant growth regulating activity on plants in a broad range, which will be exemplified as follows.

i) the ii)

Inhibition of vegetative grow of plants, particularly growth inhibition of the height of plants,

Increasing activity of the content of the useful component of plants, and • i

Λ r

e to to · '· · to 0 to * w * * 0 0 iii) Controlling activity of the ripe timing and the flowering timing of’plants .

As the example of utilizing the growth inhibiting activity of i), the growth inhibition of weeds (herbicidal function) and turf; the prevention of falling-down of the easily falling plants such as rice plant, barley, wheat, etc.; the application of the mechanical-yield method of soybean and cotton flower by inhibiting the height thereof; the inhibition of the germination of auxiliary buds for the 'growth promotion of the leaves of tobabco; the alleviation of the pruning operation by the growth inhibition of hedges; the improvement of the commercial value of the appreciation plants by growth retardation thereof, etc. may be mentioned.

As the example of utilizing the increasing activity of the content of the useful component of plants of ii), the improvement of the quality of sugar beet, sugar cane and citrus fruits by the increase of sugar; the improvement of the quality of cereals and soybean by the increase of protein, etc. may be mentiond, and further, as the example of utilizing the controlling activity concerning the ripe timing of the fruits and flowering timing of iii), the appropriation of the shipment of the fresh fruits and live flowers while complying with the demanding season, etc. may be mentioned.

J

C'

J

In order to apply the azole derivative represented by the formula (I) as the fungicide and plant growth regulating agent, the derivative itself or a mixture of the derivative and a carrier (diluent) is processed into powders, wettable powders, granules, emulsifiable concentrate, . liquid preparations, etc. and the thus prepared preparations can be advantageously used.

Still more, it is also possible, of course, to make sure of the effect by adding ad juvants,-such as spreaders, emulsifiers, wetting agents, sticking agents other than the carrier as occasion demands.

By the way, 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 as the form of an acid addition salt with an inorganic acid or organic, acid, or as the form of a metal complex.

Still more, since in the azole derivative represented by the formula (I) according to the present invention, an azolylmethyl group, a (C^ - C^)alkyl group and a substituted benzyl group are respectively contained at the 1-position, the 2-position and the 5-position of the cyclopentane ring, the stereoisomers such as geometrical isomers of cis and trans and optical isomers can exist, and the present invention includes each of the isomers and the mixtures of each isomer m an optional ratio. » is

Accordingly, it is to be recognized that the agricultural and horticultural composition according to the present invention includes those containing the single isomer or the mixture of the isomers as the active ingredient. ·

The azole derivative represented by the formula (I) according to the present invention is excellent the plant : diseases controlling activity and the plant growth regulating ’ activity, and is a useful compound as the active ingredient t of theagricultural and horticultural composition.

’ ’ The effectiveness of the present invention will t · be explained while showing the concrete examples of the agricultural and horticultural composition utilizing the azole derivative according to the present invention as the active ingredient, however, the present invention is not limited to the following examples so far as not coming over the essential features thereof.

[I] The examples of production of the azole derivative represented by the formula (I) and of each of the intermediates for producing the azole derivative represented by the formula (I).

EXAMPLE 1:

Production of methyl 1-(4-chlorobenzyl)-3,3-dimethyl-

2-oxocyclopentanecarboxylate (the intermediate compound No. 156 shown in Table 5).

Into 150 ml of anhydrous benzene, 5.0 g of sodium hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene) were added while stirring under a helium atmosphere, and 50 g of methyl 1-(4-chlorobenzyl)-2-oxocylopentanecarboxylate were added to the mixture, and the whole mixture was stirred for 40 min at 8 0°C. After cooling the reaction mixture to room temperature, 29.4 g of methyl iodide were dropped into the reaction mixture and the thus formed mixture was stirred for 2 hours at 8 0°C. After cooling the reaction mixture to room temperature, 5.0 g of sodium hydride (one equivalent) were added to the reaction mixture and the -reaction mixture was stirred for 30 min at 80 °C. After cooling the reaction mixture again to room temperature, 29.4 g of methyl iodide (one equivalent) were added to the reaction mixture and the reaction mixture was stirred for 8 hours at 80°C.

After leaving the thus obtained reaction mixture to cooling, the reaction mixture was poured into a mixture of acetic acid and iced water, and the whole mixture was extracted by ethyl acetate to obtain an organic layer. After washing the thus obtained organic layer with an aqueous solution of sodium hydrogen carbonate and then with a saline solution, the thus washed organic layer was dried on anhydrous sodium sulfate and the solvent in the organic layer was distilled off under a reduced pressure.

By subjecting the thus obtained residue to distillation under a reduced pressure and to purification, 44.8 g of the objective compound [boiling point: 142 - 143 °C (0.7 mmHg)) were obtained.

EXAMPLE 2:

. Production of 5-(4-chlorobenzyl)-2,2-dimethyl-1. cyclopentanone(the intermediate compound No. 133 shown in Table 4. · ' ’ Into 120 ml of 47 % hydrobromic acid, 44.8 g of methyl 1-(4-chlorobenzyl)-3,3-dimethyl-2-oxocyclopentanecarboxylate (the compound No. 156 shown in Table 5) were added, and the thus formed mixture was vigorously stirred for 12 hours at 100 °C.

' After leaving the thus obtained reaction mixture to cooling, the reaction mixture was poured into iced 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 hydrogen carbonate and then with an aqueous saline solution, the organic layer was dried on anhydrous sodium sulfate. By distilling the solvent off from the organic layer under a reduced pressure, a residue was obtained. By subjecting the thus obtained residue to distillation under a

reduced pressure and to purification, 31 g of the objective compound [boiling point: 124°C (1 mmHg)] were obtained.

EXAMPLE 3:

Production of 5-(4-chlorobenzyl)-2,2-dimethyl-lmethylenecyclopentane- (the intermediate compound No. 122 shown in Table 3.

Into 50 ml of anhydrous dimethylsulfoxide, 3.6 g of sodium hydride (prepared by washing 60 % oily sodium hydride with “anhydrous benzene) were added under a helium atmosphere, and the thus formed mixture was stirred for 30 min at 70°C. After cooling the reaction mixture with iced water, 53.6 g of methyltriphenyl phosphonium bromide were added to the reaction mixture, and the thus formed mixture was stirred for 30 min under cooling with iced water and then, the thus cooled mixture was stirred for 10 min at room temperature. Then, 23.6 g of 5- (,4-chlorobenzyl)-2,2-dimethyl-l-cyclopentanone (the compound No. 133 shown in Table 4). were added to the mixture, and the whole mixture was stirred for one hour at room temperature and then for 30 min at 70°C to complete the reaction. .

After leaving the reaction mixture to cooling, the reaction mixture was poured into iced water and was extracted with ethyl acetate to obtain an organic layer. After washing the thus obtained organic layer with an aqueous saline solution, the thus washed organic layer was dried on anhydrous

If sodium sulfate, and the solvent was distilled off from the thus dried organic layer under a reduced pressure.

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

EXAMPLE 4;

Production of 7-(4-chlorobenzyl)-4,4-dimethyl-loxaspiro [2 · 4 ]heptane (the intermediate compounds No. 77 and No. 78 shown in Table 2 by the A-method).

Into ‘70 ml of anhydrous dimethylsulfoxide, 3 g of sodium hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene) were added while stirring dimethylsulfoxide under a helium atmosphere, and then 27.5 g of trimethyloxosulfonium iodide were added to the thus formed mixture. After stirring the whole mixture for 30 min at room temperature, a solution of 23.6 g of 5-C4-chlorobenzyl).-2,2-dimethyl-l-cyclopentanone (the compound No. 133 shown in Table 4) in 20 ml of anhydrous dimethylsulfoxide was added within 30 min to the mixture, and the whole mixture was stirred for 2 hours at 90°C.

After leaving the thus obtained reaction mixture to cooling, it was poured into iced water and the thus obtained mixture was extracted with ethyl acetate to obtain an organic layer. After washing the organic layer with an aqueous saline solution, the layer was dried on anhydrous sodium sulfate and the solvent was distilled off from the thus dried organic layer under a reduced pressure. The thus obtained residue was subjected to silica gel column chromatography to obtain 13.95 g the objective compound No. 77 and 1.05 g of the objective compound No. 78.

t * λ t r « , / EXAMPLE 5:

< t t ---------------------------< ? * 1 *Z< Production of 7- (4-fluorobenzy1)-4,4-dimethyl-l·«« * -'t oxaspiro[2·4]heptane Cthe intermediate compounds » ί r “ »’»“« No. 81 and No. 82 shown in Table 2 according to t « , , . .., , ,. , , , ., . ' ——— — —.. —— the B-method).

*’ Into 170 ml of chloroform, 17 g of 5- (4-fluorobent 4 ί zyl)-2,2-dimethyl-l-methylenecyclopentane Cthe compound No.

V ‘V’*·'. 124 shown in Table 3) were dissolved, and then, 27.1 g of mt X i i ί ' = chloroperbenzoic acid were added to the mixture within 10 t1' min, and the thus obtained mixture was stirred for 2 hours at room temperature. In the next place, 25.4 g of calcium . hydroxide were added to the mixture within 10 min, and the mixture was stirred for 30 min at room temperature., .

After filtering the separated solid material, the chloroform layer of the filtrate was condensed to obtain a colourless oily material. The thus remained oily material was subjected to silica gel column chromatography to be purified, thereby obtaining 4.5 g of the objective compound

No. 81 and 8.6 g of the objective compound No. 82.

Q β R t « I

O Q

O0 o © e « »

O 04 »0 · e a « ot • a 11 o e

0 « o « «

EXAMPLE 6: · ' Production of C-5-(2,4-dichlorobenzyl)-2,2-dimethyl1-(lH-imidazol-l-ylmethyl)-r-l-cyclopentanol(the compound No. 15 shown in Table 1).

Into 18 ml of anhydrous dimethylformamide, 996 mg of sodium hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene) were added in a helium atmosphere while stirring. In the next place, 2.83 g of 1Himidazole were added to the thus formed mixture and the whole mixture was stirred at room temperature until the bubbling stopped. To the thus obtained solution, a solution prepared by dissolving 5.93 g of 7-(.2,4-dichlorobenzyl)-4,4-dimethyl1-oxaspiro[2·4]heptane (the compound No. 83 shown in Table 2) into 10 ml of anhydrous dimethylformamide was dropped, and the thus obtained mixture was stirred for 2 hours at 80°C.

After leaving the thus obtained reaction mixture to cooling, it was poured into iced water, and the thus obtained 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 fran the organic layer under a reduced pressure.

The thus obtained residue was subjected to purification by silica gel column chromatography, and further to

recrystallization with a mixture of n-hexane and ethyl, acetate. As a result, 2.7 g of the objective compound were obtained.

EXAMPLE 7:

Production of t-5~(4-chlorobenzyl)-2,2-dimethyl1-(1H-1,2,4-triazol-l-ylmethyl)-r-l-cyclopentanol (the compound No. 2 of Table 1) .

Into 30 ml of anhydrous dimethylformamide, 5.0 g of

7- (,4-chlorobenzy 1)-4,4-dimethyl-l-oxaspiro [2· 4]heptane (the compound No. 78 of Table 2) were added and dissolved while stirring under a helium atmosphere, and 2.2 g of sodium salt of 1H-1,2,4-triazole (purity: 90 % , commerciallized, made by Aldrich Co.) were slowly added to the thus formed solution. Then the mixture was stirred for 2 hours at 70°C.

After leaving the thus obtained reaction mixture to cooling, it was poured into iced 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 a reduced pressure. - The thus obtained residue was purified by subjecting the residue to silica gel column chromatography to obtain 3.1 g of the objective compound.

- 71 EXAMPLE 8:

Production of 2-(4-chlorobenzy1)-5-methy1-1-cyclopentanone (the intermediate compound No. 137 of Table 4). Into 126 ml of anhydrous benzene, 3.04 g of sodium

' c hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene) were added, and then 18 g of methyl 3methyl-2-oxocyclopentanecarboxylate were added to the thus formed mixture. After stirring the whole mixture for one hour at room temperature, 21.5 g of 4-chlorobenzyl chloride were added to the mixture and the thus obtained mixture was refluxed for 6 hours in an oil bath at 90°C.

After’ leaving the reaction mixture to cooling, it was extracted with benzene and the benzene layer was washed with an aqueous saline solution. After drying the benzene layer on anhydrous sodium sulfate, the solvent was distilled off from the dried benzene layer under a reduced pressure to obtained 33.6 g of a yellowish brown oily material of methyl 1-(4-chlorobenzyl)-3-methyl-2-oxocyclopentanecarboxylate (the intermediate compound No. 160 of Table 51.

Without purifying the thus obtained ester, 100 ml of 47 % hydrobromic acid were added to the ester, and the thus formed mixture was vigorously stirred for 18 hours at 110°C.

After leaving the reaction mixture to cooling, it was extracted with methylene chloride and the organic layer was washed with an aqueous solution of sodium carbonate and then with an }

i-’

I r;

aqueous saline solution. The thus washed organic layer was dried on anhydrous sodium sulfate, and the solvent was distilled off from- the organic layer under a reduced pressure.

< * < ft T « r r

The thus obtained residue was purified by distillation under a reduced pressure to obtain 17.4 g of the objective compound.

EXAMPLE 9:

Production of methyl 1-(4-chlorobenzyl)-3-ethyl_ 3-methyl-2-oxocyclopentanecarboxylate (the intermediate compound No. 178 shown in Table 5).

Into 80 ml of anhydrous tetrahydrofurane, 1.7 g of sodium hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene) were added while stirring under a helium atmosphere, and then, 18.2 g of methyl 1-(.4-chlorobenzyl)-3-methyl-2-oxocyclopentanecarboxylate (.the intermediate compound No. 160 shown in Table 5). were added to the thus formed mixture and the whole mixture was stirred for 2 hours at a room temperature.

In the next place, 11.1 g of ethyl iodide were dropped into the mixture while maintaining the mixture at a temperature of from 20 to 30°C, and then the whole mixture was stirred for one hour at a temperature of from 20 to 30°C and successively for one hour at a temperature of 60°C.

After leaving the reaction mixture to cooling, it was poured into a mixture of acetic acid and iced water and

i .

the whole mixture was extracted with ethyl acetate to obtain an organic ..layer. After washing the organic layer with an aqueous solution of sodium hydrogen carbonate then, with an aqueous saline solution, the thus washed organic layer was

dried on anhydrous sodium sulfate and the solvent was distilled off from the dried organic layer under a reduced pressure.

The thus obtained residue was purified by distillation under a reduced pressure to obtain 15 g of the objective compound.

EXAMPLE 10:

Production of 4-C4-chlorobenzyl)-7-methyl-loxaspiro [2 · 4] heptane (.the intermediate compound No. 85 in Table 2).

Into 37 ml of anhydrous dimethylsulfoxide, 1.44 g of sodium hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene) were added while stirring under a helium atmosphere, and then 13.2 g of trimethyloxosulfonium iodide were added to the thus formed mixture and the whole mixture was stirred for 30 min at room temperature. In the next place, a solution of 12.2 g of 2-(.4-chlorobenzyl).5-methyl-l-cyclopentanone (.the compound No. 137 of Table 4) in 12 ml of anhydrous dimethylsulfoxide was added to the mixture within 10 min, and the whole mixture was stirred for hours at room temperature.

The thus obtained reaction liquid was poured into

iced water, and the thus formed mixture was extracted with methylene chloride to obtain an organic layer. After washing the organic layer with an aqueous saline solution, the organic solvent layer was dried on anhydrous sodium sulfate, and the was distilled off from the organic layer under a reduced pressure.

The thus obtained residue was purified by subjecting the residue to silica gel column chromatography to obtain t

? T

f. f ' t • t t t t <

f t t

- ct : tt s « t tt

6.67 g of the objective compound.

Still more, other than the objective compound, three kinds of isomers of the objective compound were isolated.

Namely, 0.15 g of the intermediate compound

No. 8 6;

O'. 16 g of the intermediate compound No. 87 and 0.16 g of the i

c fit intermediate compound No. 88 of Table 2 were obtained.

EXAMPLE 11:

Production of 4-(,4-chlorobenzyl)-7-ethyl-l oxaspiro [2 · 4] heptane (.the intermediate compounds

Nos. 93, 94, 95 and 96 in Table 2) .

zyl)-5-ethyl-l-methylenecyclopentane (.the compound No. 129 shown in Table 3) were dissolved, and then 11.6 g of m chloroperbenzoic acid were added to the thus formed mixture within 5 min, and the whole mixture was stirred for hours at room temperature. In the next place, 11 g of calcium hydroxide were added to the mixture under cooling with v

iced water, and the whole mixture was stirred for 30 min at room temperature. .

The thus separated solid material was filtered off, and the chloroform layer of the filtrate was condensed to obtain a colourless oily material. The oily material was purified by subjecting it to silica gel column chromatography to obtain 0.7 g of the compound No. 93; 2.4 g of the compound No. 94; 2.2 g of the compound No. 95 and 2.6 g of the com-

pound No. 96 of the entitled compound.

EXAMPLE 12:

Production of C-2-(4-chlorobenzyl)-5-methyl-l(1H-1,2,4-triazol-l-ylmethyl)-r-l-cyclopentanol

(.the compound No. 16 of Table 1) .

Into 10 ml of anhydrous dimethylformamide, 630 mg of sodium hydride (prepared by washing 60 % oily sodium hydride with anhydrous benzene), were added and then, 1.8 g of 1H-1,2,4-triazole were added to the mixture and the whole mixture was stirred at room temperature until the bubbling was settled.

Into the thus obtained reaction mixture, a solution of 3.1 g of 4- (,4-chlorobenzyl)-7-methyl-l-oxaspiro [ 2 · 4] heptane (the compound No. 85 in Table 2) in 6.2 ml of anhydrous dimethylformamide was added, and the thus formed mixture was stirred for one hour at 80°C.

After leaving the thus obtained reaction liquid to

- 76 cooling, it was poured into iced water, and the thus obtained mixture was extracted with methylene chloride to obtain an organic layer.

After washing the organic layer with an aqueous saline solution, the organic layer was dried on anhydrous sodium sulfate and the solvent was distilled off from the organic layer under a reduced pressure.

The thus obtained residue was purified by subjecting the residue to silica gel column chromatography, and was

further. recrystallized from a mixture of n-hexane and ethyl acetate to obtain 2.83 g of the objective compound.

EXAMPLE 13: .

Production of C-2 (.4-chlorobenzyl)-5-methyl-l-(1Himidazol-l-ylmethyl)-r-l-cyclopentanol (the compound No. 17 of Table 1).

Into 10 ml of anhydrous dimethylformamide, 670 mg of sodium hydride (prepared by washing 60 % oily sodium hydride) were added and then, 1.9 g of ΙΗ-imidazole were added to the thus formed mixture and the whole mixture was stirred at room temperature until the bubbling was settled.

In the next place, a solution of 3.3 g of 4-(4chlorobenzyl)-7-methyl-l-oxaspiro [2 · 4] heptane (.the compound

No. 85 of Table 2) in 6.6 ml of anhydrous dimethylformamide was added to the mixture, and the whole mixture was stirred for one hour at 80°C.

After leaving the thus obtained reaction liquid to cooling, it was poured into iced.water and the thus formed mixture was extracted with methylene chloride to obtain an organic layer.

After washing the organic layer with an aqueous saline solution, the organic layer was dried on anhydrous f

sodium sulfate and the solvent was distilled off from the organic layer under a reduced pressure.

The thus obtained residue was purified by subjecting the. residue to silica gel column chromatography and was further recrystallized from a mixture of n-hexane and ethyl acetate to obtain ^3.16 g of the objective compound.

[II] The examples of preparing the agricultural and horticultural fungicide compositions.

EXAMPLE 14: Dust (powder)

Three parts by weight of the azole derivative according to the present invention (the compound No. 3), 40 parts by weight of clay and 57 parts by weight of talc were mixture and pulverized to prepare an agricultural and horticultural fungicide composition of dust form.

The thus prepared composition is used by scattering.

EXAMPLE 15; Wettable powder

Fifty parts by weight of the azole derivative 4 according to the present invention Cth.e compound No. 1)., 5 ί parts by weight of a salt of ligninsulfonic acid, 3 parts by weight of a salt of alkylsulfonic acid and 42 parts by weight of diatomaceous earth were mixed and pulverized to prepare a wettable powder.

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

EXAMPLE 16: Granule

Five parts by weight of the azole derivative according to the present invention (.the compound No. 16) , 43 parts by weight of bentonite, 45 parts by weight of clay and 7 parts by weight of a salt of ligninsulfonic acid were uniformly mixed, and after adding water to the mixture, the whole materials were kneaded together, processed into granular form by an extruding granulator and dried to obtain the composition of granular form.

EXAMPLE 17: Emulsifiable concentrate .

Twenty parts by weight of the azole derivative according to the present invention (.the compound No. 13), 10 parts by weight of a polyoxyethylene alkyl aryl ether, 3 parts by weight of a polyoxyethylene sorbitan monolaurate and parts by weight of xylene were uniformly mixed together to prepare the composition of emulsifiable concentrate form.

Ί9 [III] The examples of application of the agricultural and horticultural fungicide composition according to the present invention to plant diseases.

EXAMPLE 18:

Test for controlling effect against Erysiphe graminis f. sp. tritici on wheat

Onto the young seedlings of wheat of the secondleaf stage (variety: NORIN No. 64, 16 seedlings per pot and pots being used in the treated plot), which had been . cultured while using unglazed pots of 10 cm in diameter, 5 ml δ : £ ' t ♦ .

per pot of a diluted emulsifiable concentrate such as that of

,. Example 15 (diluted with water to a predetermined concentration) were applied. After air drying the applied dilution, a suspension of the summer spores of Erysiphe graminis f. sp. tritici, which had been collected from the attacked leaf of wheat was sprayed onto the seedlings in the pots, the pots ',.. were maintained at from 20 to 24°C for 24 hours under a highly humid condition and then the pots were left in a glass room.

On the day after 9 to .11 days of the inoculation, the extent . of -the disease on the seedlings was investigated according to the following investigation standards and the control value of the fungicide composition was calculated according to the following formula.

'ί

ΤΊ

- 80 (Investigation standards)

Degree of disease

Extent of disease

<td> 0</td><td> not attacked</td>

<td> 0.5</td><td> The rate of area of the disease spots is below 10 %</td>

<td> 1</td><td> The rate of area of the disease spots is not less than 10 % and below 20 %</td>

<td> 2</td><td> The rate of area of the disease spots is not less than 20 % and below 40 %</td>

<td> 3</td><td> The rate of area of the disease spots is not less than 40 % and below 60 %</td>

<td> 4</td><td> The rate of area of the disease spots is not less than 60 % and below 80 %</td>

<td> 5</td><td> The rate of area of the disease spots is not less than 80 %.</td>

Control value = (1 Degree of disease on treated plot)

Degree of disease on control plot

The results of the test are shown in Table 6.

x 100(.%)

Table 6

<td> Compound tested (No. in Table 1)</td><td> Concentrabionof spray (ppm)</td><td> .Control value (%)</td>

Table 6 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

* / i'·

Table 6 (continued) t i tl '

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

Ml h

Table 6 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

Table 6 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

<td> Commerciallized material</td><td> 125</td><td> 100</td>

<td> *) Triadimephon</td><td></td><td></td>

<td> Control (not treated)</td><td></td><td> 0</td>

(Note) *)·: Triadimephon of the conunerciallized material las the compound represented by the following formula as the active ingredient.

EXAMPLE 19;

Test for controlling effect against Sphaerotheca fuliginea on cucumber.

Onto the cucumber plants of the second-leaf stage (variety: SAGAMI HAMPAKU, one plant per pot and 3 pots being used in the treated plot), which had been cultured while using unglazed pots of 10 cm in diameter, 5 ml per pot of a diluted emulsifiable concentrate such as that of Example 15 (diluted with water to a predetermined concentration) were applied. After air-drying the applied leaves, the spores of Sphaerotheca fuliginea were sprinkled with a brush from the diseased leaf of cucumber to inoculate the cucumber plants and the disease was caused on the plants in a glass room.

On the day after from 9 to 11 days of the inoculation, the degree of disease on the cucumber plants was investigated according to the following investigation standards and the control value of the fungicide composition was calculated according to the following formula:

(Investigation standards).

Degree of disease Extent of disease

<td> 0</td><td> not attacked</td>

<td> 0.5</td><td> The rate of area of the disease spots is below 10 %</td>

<td> 1</td><td> The rate of area of the disease spots is not less than 10 % and below 20 %</td>

<td> 2</td><td> The rate of area of the disease</td>

spots is not less than 20 % and below 40 %

Degree of disease

Extent of disease < ί < I

The rate spots is below 60

The rate spots is below 80

The rate spots is of area of the disease not less than 40 % and g„

Ό of area of the disease not less than 60 % and % of area of the disease not less than 80 % „ . , Ί , Ί Degree of disease on treated plot, ΊΓ,η ,o.

Control value = (,1--3------------------------------------)x 100 (.%)

Degree of disease on control plot

The results are shown in Table 7.

i« . I

V

Table 7

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value(%)</td>

<td> Commerciallized material Triadimephon *)</td><td> 125</td><td> 100</td>

<td> Control (not treated)</td><td></td><td> 0</td>

ft·

V •4.1

I

EXAMPLE 20:

Test for controlling effect against Puccinia recondita on wheat.

Onto the young seedlings of wheat of the secondleaf stage (variety: NORIN No. 64, 16 seedlings per pot and 3 pots being used in the treated plot), which had been cultured while using unglazed pots of 10 cm in diameter, 5 ml per pot of a diluted emulsifiable concentrate such as that of Example 15 (diluted with water to a predetermined concentration) were applied by spraying.

After air-drying the applied dilution, a suspension of the summer spores of Puccinia recondita, which had been collected from the contracted leaf of wheat, was sprayed onto the seedlings in the pots, the pots were maintained at from 20 to 23°C for 24 hours under a highly humid condition and then the pots were left in a glass .room. On the day after 7 to 10 days of the inoculation, the extent of the disease on ten seedlings was investigated according to the following investigation standards and the control value of the fungicide composition was calculated according to the following formula from the mean degree of disease per leaf.

(Investigation standards)

Degree of disease

Extent of disease

0.5 not attacked

The rate of area of the disease spots is.below 10 %

K ϊΐ

- 90 Degree of disease Extent of disease

The rate of area of the disease spots is not less than 10 % and below 20 %

The rate of area of the disease spots is not less than 20 % and below 40 %

The rate of area of the disease spots is not less than 40 % and below 60 %

The rate of area of the disease spots is not less than 60 % and below 80 %

The rate of area of the disease spots is not less than 80 %.

Control value = Cl - ^-ree· °f dis-^-5e °n-^eated plot) χ 10Q (%) Degree of disease on control plot

The results are shown in Table 8.

. i

I

Table 8

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

*5 ?v

A '1 ft

Table 8 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm) .</td><td> Control value (%)</td>

Table 8 (continued)

<td> Compound tested</td><td> Concentration</td><td> Control</td>

<td></td><td> of spray</td><td> value</td>

<td> (No. in Table 1)</td><td> (ppm)</td><td> (%)</td>

i .

Table 8 (continued) r

♦ ε i t r t t

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray T p p m)</td><td> Control i value I (%)</td>

<td> Commerciallized material</td><td rowspan="2"> 125</td><td rowspan="2"> 95</td>

<td> Triadimephon *)</td>

<td> Control (not treated)</td><td></td><td> 0 ’</td>

/ft '^V~ li

EXAMPLE 21:

Test for controlling effect against Botrytis cinerea on kidney bean.

Onto the leaves of kidney bean plants at the first true-leaf stage (variety: HONKINTOKI), which had been cultured while using unglazed pots of 10 cm in diameter, 5 ml per pot of a diluted emulsifiable concentrate such as that of € < ' f ... ς t t *t tI t I <« « <t t e f r r.c

Example 15 (diluted with water to a predetermined concentration) were applied by spraying.

After air-drying the thus applied leaves, a circular cutting of agar of a diameter of 4 mm containing the fungi of Botrytis cinerea, which had been preliminarily cultured for 3 days at 20°C while using a sugar-added agar medium containing potato soup, was directly adhered to the center part of the leaf of kidney bean plants, and the plants were maintained at a temperature of from.20 to 22°C under a highly humid condition. On the 3rd day of the inoculation, the area of disease spot of the thus treated plot was compared with that of the control (untreated) plot to investigate the degree of disease according to the following investigation standards and the control value of the fungicide composition was calculated according to the following formula.

(Investigation standards)

Degree of disease

Extent of attack not attacked

I

V

Degree of disease

Extent of attack

t ' t t t

€ t t

If f t ’ c r <' t <: Γ t <:

• Ct· e tt re « c c

0.5

Only attacked the part just below the inoculated fungi-containing agar and the peripheral parts thereof .

The rate of area of the disease spots is below 20 %

The rate of area of the disease spots is not less than 20 % and below 40 %

The rate of area of the disease spots is not less than 40 % and below 60 %

The rate of area of the disease spots is not less than 60 % and below 80 %

The rate of area of the disease spots is not less than 80 %.

Control value = (1 - De.gree o£ disease On treated pjot^ χ 1Q0 (%) Degree of disease on control plot

The results are shown in Table 9.

Table 9 t L · € ( t tec.

t < * 1 C € t

I c

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

Table 9 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

-'-i

J

Table 9 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value (%)</td>

100

Table 9 (continued)

<td> Compound tested (No. in Table 1)</td><td> Concentration of spray (ppm)</td><td> Control value . (%)</td>

<td> Commerciallized material Rovral *)</td><td> 500</td><td> 100</td>

(Note) *): The commerciallized material (Rovral) contains the compound represented by the following formula as an active ingredient.

/CH

N—CONHCH. ° ch3

J

- 101 EXAMPLE 22:

Test for controlling effect against Cochliobolus miyabeanus on rice plant.

In each of unglazed pots of 10 cm in diameter, 16 seeds of rice plate (variety: SASANISHIKI) were sown, and at

r ? « e e i * ♦ t *

I 4 t < f « i ff t t 4. <

Γ i 11 ·.

* c i c ί t t

* · 4' ♦· 4 t • * i

the time when the rice seedlings became the 4-5 leaf-stage, a diluted emulsifiable concentrate such as that of Example 15 (diluted to a predetermined concentration with water) was sprinkled onto the seedlings.

After air-drying the thus treated leaves, 5 ml per pot of a suspension of the spores of Cochliobolus miyabeanus, which had been preliminarily cultured, were applied by spraying to the thus treated seedlings. Under the microscope of 150 magnifications, 15 spores of the fungus in the suspension were found in the field.

Just after finishing the inoculation, the thus treated pots were introduced into an inoculation room at 25°C and at a saturated humidity and after keeping the pots therein for 2 days, the pots were introduced into a glass house to be attacked. On the 5th day of the inoculation, the number of disease spots on 10 leaves per pot was counted, and the control value of the fungicidal composition was calculated according to the following formula:

Number of disease spots on the

Control value = (.1 - —treated plot----------------_ χ 100(%)

Number of disease spots on the control (untreated) plot

The results are shown in Table 10.

- 102 Table 10

<td> Compound tested (No. in Table 1)</td><td> Concentration of sprav (ppm)</td><td> Control value . (%)</td>

<td> Commerciallized material : Rovral</td><td> 125</td><td> 85</td>

<td> Control (not treated)</td><td></td><td> 0</td>

·· v

r al a a i

EXAMPLE 23:

Antifungal test against several pathogenic fungi.

The present example shows the results of the antifungal property of the azole derivative according to the present invention against various plant-pathogenic fungi.

Test method:

The compound according to the present invention is ft o · <· a μ a ft fa Oft ft ft ft A ft ft a a a • ft ft «ο a o ft a a

A ft 9 0 ft

9 0 • ft 9 ft ft ft dissolved into dimethyl sulfoxide so as to of the predetermined prepared solution is medium of about 60°C give a solution concentration and 0.6 well mixed with 60 ml in a conical flask of ml of the thus of the PAS culture

100 ml in capacity.

The thus formed mixture is poured into a glass dish and is solidified to be a flat culture medium containing the ft ft ft e ft o ft ft ft compound.

On the other hand, the test fungus, which has been « a a ft β ft a fa ft a

• · a a a · preliminarily cultured in a flat culture medium, is striked by a cork borer of 4 mm in diameter and the thus striked ft 9 ft a * ft piece of the culture medium containing the test fungus is

JI inoculated on the flat culture medium containing the compound.

After inoculation, the thus prepared culture medium containing the compound and the fungus is cultured for from 1 .to 3 days at an appropeiate temperature for growing each of the fungi, and the growth of the fungus is measured by the diameter of the fungal colony. By comparing the growth of the fungus in the thus prepared culture medium with that in the untreated

104 plot (the culture medium not containing the compound), the rate of inhibiting the mycelial growth of the fungus is obtained according to the following formula:

R = (de - dt) 100/dc wherein R is the rate of inhibiting the mycelial growth;

de is the diameter of fungal colony on the flat medium not containing the compound and dt is the diameter of fungal colony on the flat medium containing the compound.

The results are evaluated into 5 stages according to the following standards and shown in Table 11.

Rate of inhibiting the mycelial growth:

<td> 5:</td><td> The rate of inhibiting the smaller than 90. - 100 %</td><td> growth</td><td> is</td><td> not</td>

<td> 4:</td><td colspan="2"> The rate of inhibiting the growth smaller than 70 % and below 90 %</td><td> is</td><td> not</td>

<td> 3:</td><td colspan="2"> The rate of inhibiting the growth smaller than 40 % and below 70 %</td><td> is</td><td> not</td>

<td> 2:</td><td colspan="2"> The rate of inhibiting the growth smaller than 20 % and below 40 %</td><td> is</td><td> not</td>

<td> 1:</td><td> The rate of inhibiting the</td><td> growth</td><td> is</td><td> below 20 %</td>

I

Table 11

<td rowspan="2"> No. of canpound tested (No. in Tahle Ϊ1</td><td rowspan="2"> Concentration of Canpound</td><td colspan="16"> Fungus Tested</td><td></td>

105

«* ♦ < * · « D C 9 9 a 6 4 σ * ο 4 9 ♦ _ a

Table11 (Continued)

<td rowspan="2"> No. of canpound tested (No. in Table 1)</td><td rowspan="2"> Concentration of □aqpound (ucr/ml)</td><td colspan="17"> Fungus Tested</td>

106

Table 11 (Continued)

<td rowspan="2"> No. of canpound tested (No. in Table 1)</td><td rowspan="2"> Ooicentraticnof Compound</td><td colspan="16"> Fungus tested</td><td rowspan="2"> G.c.</td>

107

Table 11 (Continued)

<td> No. of ccmpcxind tested</td><td rowspan="2"> Concentration of □onpound (pg/ml)</td><td colspan="8"> Fungus t</td><td colspan="9"> nested</td>

<td> (No. in Table 1)</td><td> P.O.</td><td> C.n.</td><td> G.f.</td><td> H.s.</td><td> R.s.</td><td> Bo.c.</td><td> S.s.</td><td> F.n.</td><td> F.c.</td><td> F. Γ.</td><td> C.l.</td><td> C.b.</td><td> S.C.</td><td> V.m.</td><td> A.k.</td><td> A.·.</td><td> G.C.</td>

108

y109

The abbreviation in Table 11 shows each of the

<td colspan="3"> following fungi :</td>

<td></td><td> P.O. :</td><td> Pyricularia oryzae on rice plant</td>

<td></td><td> C .m. :</td><td> Cochliobolus miyabeanus on rice plant</td>

<td></td><td> G.f. :</td><td> Gibberella fujikuroi on rice plant</td>

<td>r » 0 0</td><td> H.s. :</td><td> Helminthosporium sigmoideum on rice plant</td>

<td> o · « 0 O 9 ft ft ft Q</td><td> R.s · :</td><td> Rhizoctonia solani on rice plant</td>

<td> O 0 0 0 0 9 9 CO</td><td> S . s · :</td><td> Sclerotinia sclerotirum '</td>

<td> α · e 0 0«</td><td> F .n . :</td><td> Fusarium oxysporum f. niveum on water melon</td>

<td> 9 ·</td><td> F .c . :</td><td> Fusarium oxysporum f. cucumerinum on cucumber'</td>

<td> • 9 0 0 · 0 0 9 0</td><td> F.r. :</td><td> Fusarium oxysporum f. raphani on J.apanese radish</td>

<td> 0 » 9</td><td> C.l. :</td><td> Colletotrichum lagenarium on melons</td>

<td> • « <</td><td> C.b. :</td><td> Cercospola beticola on sugar beet</td>

<td> < 1 t t t t t t t</td><td> S .c . :</td><td> Sclerotinia cinerea on peach</td>

<td> ' ‘'r</td><td> V.m. :</td><td> Valsa mali on apple</td>

<td> ,,.:. j</td><td> A .m. :</td><td> Alternaria mali on apple</td>

<td></td><td> A .k . :</td><td> Alternaria alternata (kikuchianal on pear</td>

<td></td><td> G .c . :</td><td> Glomerella cingulata on grape</td>

[IV] The examples of the agricultural and horticultural plant growth regulating agent containing the azole derivative according to the present invention as an active ingredient.

110

EXAMPLE 24:

Form of wettable powder

Fifty parts by weight of the azole derivative according to the present' invention (the compound No. 3 in Table 1), 5 parts by weight of a salt of ligninsulfonic acid, 3 parts by weight of a salt of alkylsulfonic acid and 42 parts by weight of diatomaceous earth were mixed and pulverized to obtain a composition of the form of wettable powder. The composition is used after diluting with water.

EXAMPLE 25:

Form of emulsifiable concentrate .Twenty five parts by weight of the azole derivative according to the present invention (the compound No. 20 in Table 1), 65 parts by weight of xylene and 10 parts by weight of polyoxyethylene alkyl aryl ether were uniformly mixed together to obtain a composition of the form of emulsifiable concentrate. The composition is used after diluting with water.

EXAMPLE 26:

Form of dust(powder)

Eight parts by weight of the azole derivative according to the present invention (.the compound No. 11 in Table 1), 40 parts by weight of bentonite, 45 parts by weight of clay and 7 parts by weight of a salt of ligninsulfonic .5 ii;

•I

- Ill

acid were mixed uniformly, and after adding water to the thus formed mixture, the whole mixture was kneaded together and processed into granular form by an extruding granulator and the granular material was dried to be the composition of the form of dust.

EXAMPLE 27:

Plant height-restraining effect on rice plant

Into each of the glass dishes of 8.5 cm in diameter, 10 ml of a solution containing each of the compounds according to the present invention at a concentration of 10 ppm were introduced, and 10 seed of rice plant (.variety: SASANISHIKI) were sown in the glass dish. The dishes were kept in a room at 27°C for 7 days to germinate the seeds, and then the height of the seedlings were measured to obtain the data shown in Table 12.

As are seen in Table 12, every one of the tested azole derivatives according to the present invention showed the growth-restraining effect without giving any phytotoxicity.

- 112 Table 12

<td> No . of compound (No. in Table 1)</td><td> Rate of restraining the height ( % )</td><td> Phytotoxicity</td>

r* 'S’

-» *

- 113 THE-

Contents80

347 sheets

Sheet 1
Sheet 2
Sheet 3
Sheet 4
Sheet 5
Sheet 6
Sheet 7
Sheet 8
Sheet 9
Sheet 10
Sheet 11
Sheet 12
Sheet 13
Sheet 14
Sheet 15
Sheet 16
Sheet 17
Sheet 18
Sheet 19
Sheet 20
Sheet 21
Sheet 22
Sheet 23
Sheet 24
Sheet 25
Sheet 26
Sheet 27
Sheet 28
Sheet 29
Sheet 30
Sheet 31
Sheet 32
Sheet 33
Sheet 34
Sheet 35
Sheet 36
Sheet 37
Sheet 38
Sheet 39
Sheet 40
Sheet 41
Sheet 42
Sheet 43
Sheet 44
Sheet 45
Sheet 46
Sheet 47
Sheet 48
Sheet 49
Sheet 50
Sheet 51
Sheet 52
Sheet 53
Sheet 54
Sheet 55
Sheet 56
Sheet 57
Sheet 58
Sheet 59
Sheet 60
Sheet 61
Sheet 62
Sheet 63
Sheet 64
Sheet 65
Sheet 66
Sheet 67
Sheet 68
Sheet 69
Sheet 70
Sheet 71
Sheet 72
Sheet 73
Sheet 74
Sheet 75
Sheet 76
Sheet 77
Sheet 78
Sheet 79
Sheet 80
Sheet 81
Sheet 82
Sheet 83
Sheet 84
Sheet 85
Sheet 86
Sheet 87
Sheet 88
Sheet 89
Sheet 90
Sheet 91
Sheet 92
Sheet 93
Sheet 94
Sheet 95
Sheet 96
Sheet 97
Sheet 98
Sheet 99
Sheet 100
Sheet 101
Sheet 102
Sheet 103
Sheet 104
Sheet 105
Sheet 106
Sheet 107
Sheet 108
Sheet 109
Sheet 110
Sheet 111
Sheet 112
Sheet 113
Sheet 114
Sheet 115
Sheet 116
Sheet 117
Sheet 118
Sheet 119
Sheet 120
Sheet 121
Sheet 122
Sheet 123
Sheet 124
Sheet 125
Sheet 126
Sheet 127
Sheet 128
Sheet 129
Sheet 130
Sheet 131
Sheet 132
Sheet 133
Sheet 134
Sheet 135
Sheet 136
Sheet 137
Sheet 138
Sheet 139
Sheet 140
Sheet 141
Sheet 142
Sheet 143
Sheet 144
Sheet 145
Sheet 146
Sheet 147
Sheet 148
Sheet 149
Sheet 150
Sheet 151
Sheet 152
Sheet 153
Sheet 154
Sheet 155
Sheet 156
Sheet 157
Sheet 158
Sheet 159
Sheet 160
Sheet 161
Sheet 162
Sheet 163
Sheet 164
Sheet 165
Sheet 166
Sheet 167
Sheet 168
Sheet 169
Sheet 170
Sheet 171
Sheet 172
Sheet 173
Sheet 174
Sheet 175
Sheet 176
Sheet 177
Sheet 178
Sheet 179
Sheet 180
Sheet 181
Sheet 182
Sheet 183
Sheet 184
Sheet 185
Sheet 186
Sheet 187
Sheet 188
Sheet 189
Sheet 190
Sheet 191
Sheet 192
Sheet 193
Sheet 194
Sheet 195
Sheet 196
Sheet 197
Sheet 198
Sheet 199
Sheet 200
Sheet 201
Sheet 202
Sheet 203
Sheet 204
Sheet 205
Sheet 206
Sheet 207
Sheet 208
Sheet 209
Sheet 210
Sheet 211
Sheet 212
Sheet 213
Sheet 214
Sheet 215
Sheet 216
Sheet 217
Sheet 218
Sheet 219
Sheet 220
Sheet 221
Sheet 222
Sheet 223
Sheet 224
Sheet 225
Sheet 226
Sheet 227
Sheet 228
Sheet 229
Sheet 230
Sheet 231
Sheet 232
Sheet 233
Sheet 234
Sheet 235
Sheet 236
Sheet 237
Sheet 238
Sheet 239
Sheet 240
Sheet 241
Sheet 242
Sheet 243
Sheet 244
Sheet 245
Sheet 246
Sheet 247
Sheet 248
Sheet 249
Sheet 250
Sheet 251
Sheet 252
Sheet 253
Sheet 254
Sheet 255
Sheet 256
Sheet 257
Sheet 258
Sheet 259
Sheet 260
Sheet 261
Sheet 262
Sheet 263
Sheet 264
Sheet 265
Sheet 266
Sheet 267
Sheet 268
Sheet 269
Sheet 270
Sheet 271
Sheet 272
Sheet 273
Sheet 274
Sheet 275
Sheet 276
Sheet 277
Sheet 278
Sheet 279
Sheet 280
Sheet 281
Sheet 282
Sheet 283
Sheet 284
Sheet 285
Sheet 286
Sheet 287
Sheet 288
Sheet 289
Sheet 290
Sheet 291
Sheet 292
Sheet 293
Sheet 294
Sheet 295
Sheet 296
Sheet 297
Sheet 298
Sheet 299
Sheet 300
Sheet 301
Sheet 302
Sheet 303
Sheet 304
Sheet 305
Sheet 306
Sheet 307
Sheet 308
Sheet 309
Sheet 310
Sheet 311
Sheet 312
Sheet 313
Sheet 314
Sheet 315
Sheet 316
Sheet 317
Sheet 318
Sheet 319
Sheet 320
Sheet 321
Sheet 322
Sheet 323
Sheet 324
Sheet 325
Sheet 326
Sheet 327
Sheet 328
Sheet 329
Sheet 330
Sheet 331
Sheet 332
Sheet 333
Sheet 334
Sheet 335
Sheet 336
Sheet 337
Sheet 338
Sheet 339
Sheet 340
Sheet 341
Sheet 342
Sheet 343
Sheet 344
Sheet 345
Sheet 346
Sheet 347

64 members in 28 offices

This recordMember, by publication datePriority claim18 more offices are in the list below

Priority claims3

Priority claims
Document	Office	Kind	Date
26555986	Japan	A	1986-11-10
16112687	Japan	A	1987-06-30
27127787	Japan	A	1987-10-27

Members64

Family members, oldest first
Document	Office	Kind
DK588687D0	Denmark	D0	1987-11-10
DK588687A	Denmark	A	1988-05-11
EP0267778A2	European Patent Office (EPO)	A2	1988-05-18
AU8096187A	Australia	A	1988-05-19
BR8706104A	Brazil	A	1988-06-14
IL85428A0	Israel	A0	1988-07-31
IL85428D0	Israel	D0	1988-07-31
MA21204A1	Morocco	A1	1988-10-01
IE880375L	Ireland	L	1988-12-30
CN1030232A	China	A	1989-01-11
HUT47254A	Hungary	A	1989-02-28
JPH0193574A	Japan	A	1989-04-12
EP0267778A3	European Patent Office (EPO)	A3	1989-04-19
AU584530B2This record	Australia	B2	1989-05-25
KR890012981A	Republic of Korea	A	1989-09-20
ZA878260B	South Africa	B	1989-09-27
KR900003269B1	Republic of Korea	B1	1990-05-12
NZ223444A	New Zealand	A	1990-06-26
US4938792A	United States of America	A	1990-07-03
CS103388A2	Czechoslovakia (until 1993)	A2	1990-12-13
DD289523A5	German Democratic Republic (until 1990)	A5	1991-05-02
US5028254A	United States of America	A	1991-07-02
CS274740B2	Czechoslovakia (until 1993)	B2	1991-10-15
CN1059825A	China	A	1992-04-01
HU206023B	Hungary	B	1992-08-28
US5159118A	United States of America	A	1992-10-27
IL85428A	Israel	A	1992-12-01
JPH0565243A	Japan	A	1993-03-19
EP0267778B1	European Patent Office (EPO)	B1	1993-03-24
AT87309T	Austria	T	1993-04-15
ATE87309T1	Austria	T1	1993-04-15
DE3784999D1	Germany	D1	1993-04-29
CN1020606C	China	C	1993-05-12
DE3784999T2	Germany	T2	1993-07-01
US5239089A	United States of America	A	1993-08-24
RU1837767C	Russian Federation	C	1993-08-30
AR245703A1	Argentina	A1	1994-02-28
JPH0625140B2	Japan	B2	1994-04-06
CA1331006C	Canada	C	1994-07-26
ES2053564T3	Spain	T3	1994-08-01
TR26948A	Türkiye	A	1994-09-12
JPH06263693A	Japan	A	1994-09-20
JPH06279424A	Japan	A	1994-10-04
MD74B1	Republic of Moldova	B1	1994-11-30
JPH06104643B2	Japan	B2	1994-12-21
LV10436A	Latvia	A	1995-02-20
MD74C2	Republic of Moldova	C2	1995-03-31
US5414105A	United States of America	A	1995-05-09
JPH0747565B2	Japan	B2	1995-05-24
LV10744A	Latvia	A	1995-08-20
LTIP1864A	Lithuania	A	1995-08-25
RU2047605C1	Russian Federation	C1	1995-11-10
JPH07108905B2	Japan	B2	1995-11-22
LV10744B	Latvia	B	1995-12-20
LV10436B	Latvia	B	1996-08-20
LT4014B	Lithuania	B	1996-08-26
DK171542B1	Denmark	B1	1996-12-30
MD422C2	Republic of Moldova	C2	1997-04-30
IE74147B1	Ireland	B1	1997-07-02
UA18635A	Ukraine	A	1997-12-25
GEP19981269B	Georgia	B	1998-07-07
GEP19981389B	Georgia	B	1998-11-10
CN1044659C	China	C	1999-08-18
UA27101A1	Ukraine	A1	2000-02-28