DD289523A5 - PROCESS FOR THE PREPARATION OF AZOL DERIVATIVES - Google Patents

Abstract

The invention relates to a process for the preparation of azole derivatives of the formula I, which comprises the reaction of an oxirane derivative of the formula II with an * or an imidazole of the formula VI. The compounds of the present invention are used to prepare agricultural and horticultural compositions. Method; manufacture; agricultural composition; horticultural composition}

Description

For this 76 pages drawings

Field of application of the invention

The compounds according to the invention are used for controlling various plant diseases and for plant growth regulation.

Characteristic of the known state of the art

To achieve the stated objectives, the following are agriculturally and horticulturally used fungicides

been proposed;

(1) Compounds of triazoles or imidazoles according to the following formula

¹ 1

Y is N-CH ₂ --C R ^x

R ²

in which the radicals have the following meanings:

- R'-CH = CG-X, -C = C-X or -CH ₂ -CH ₂ -X (with X hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted aryloxyalkyl or optionally substituted heterocyclic Group);

R ^{2 is} alkyl, cycloalkyl or optionally substituted aryl;

Z is chlorine, cyano or -OR ³ (with R ^{3 being} hydrogen, acetyl, alkyl, alkenyl or aralkyl); and

- Y is nitrogen or CH.

Also taught are the acid addition salts of said compounds and the metal complexes thereof (see JP Published Patent Application No. 57-114577 [1982] corresponding to U.S. Patent No. 4507140 and European Patent, United States Patent No. 0052424).

 (2) Compounds of triazoles or imidazoles according to the following formula:

HO

J * -.χ

in which the radicals have the following meanings:

R is a crosslinking group: - (CH ₂ ) _n -, withn 0, 1 or 2, -CH = CH -, - 0 -, - S -, - NH or-C (= O) -; X is nitrogen or CH;

Y and Z are the same or different and each represents halogen, alkyl, alkoxy, haloalkoxy, haloalkyl, nitro, phenyl

or phenoxy; m andp are each and independently of one another 0,1,2 or 3;

as well as acids and metal complexes but also functionally derivatives thereof (see JP published patent application No. 57-126479 [1982] with corresponding European patent, Ver. No. 0052425). (3) Derivatives of 1-hydroxyethylazole according to the following formula:

C - R

S-Ii

in which the radicals have the following meanings: R is alkyl, optionally substituted cycloalkyl or optionally substituted phenyl; X is nitrogen or CH;

Y is -OCH ₂ -, - CH _{2 is} -CH ₂ - or -CH = CH-;

Z is halogen, alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylalkyl or optionally

substituted phenylalkoxy; m is an integer of0.1, 2 or 3;

and acid addition salts and metal complexes thereof (see JP, Published Patent Application No. 57-16868 [1982], corresponding to US Pat. No. 4,532,341 and European Patent, Publ. No. 0040345). (4) Cycloaliphatic alcohols according to the following formula:

JL r *

Ή ОН

in which the radicals have the following meanings:

R ^{6 is} unsubstituted phenyl, substituted phenyl, which may be substituted by one to five of the following groups: (halogen, amino, nitro, cyano, phenyl, НаІодепрпепуЫ ^ -Стоі-АІкуІ, halo (Ci-Ci ₀ ) alkyl , (C ₁ -C ₁₀ I -alkoxy, halo-C ^ ICR balkoxy, _(Cr-C10) alkylthio, (d-Cmi alkylenedioxy, (C ₁ -CiO) -AI alkylamino and di-fd-C l ^ alkylamino;

X is nitrogen or methine;

Ring A cyclopentane, cyclohexane, cycloheptane, indane, tetrahydronaphthalene, benzocyclopeptane, wherein said ring structures are optionally substituted in the benzene ring contained therein by one to four of the above-mentioned substituents (see JP, published patent application No. 58-189171 [1983] , according to the US patent

No. 4,509,062 and the European patent, Ver. No. 0094146).

(5) triazole or imidazole compounds according to the following formula:

in which the radicals have the following meanings:

W is CH or nitrogen;

Q is optionally substituted aryl, especially optionally substituted phenyl, optionally substituted aralkyl or

optionally substituted alkyl; R ¹ to R ⁸ , identical or different, are hydrogen, hydroxy, alkyl, cycloalkyl, optionally substituted aralkyl, optionally substituted phenyl or, in pairs, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ , together carbonyl

together with the adjacent ring C atom; R ⁹ and R ¹⁰ , the same or different, are hydrogen, alkyl, cycloalkyl, optionally substituted aralkyl or optionally

substituted phenyl; η is 0 or 1;

a stereomer thereof, acid addition salts and metal complexes thereof (see, JP Published Patent Application No. 60-215674 [1985], corresponding to European Patent, Publ. No. 0153797).

Object of the invention

The invention provides agriculturally and hortically cultured chemical compounds which exhibit the following properties:

- effects against plant diseases,

low toxicity to humans, livestock, birds and fish and

- low phytotoxicity to crops.

Accordingly, such a composition has a high degree of handling safety, has a small influence on landscape pollutants and an excellent mode of action against plant diseases in a wide range.

Explanation of the essence of the invention

The invention has for its object to provide compounds that can be used to control various plant diseases and plant growth regulation. Specifically, this invention relates to 1) azole derivatives of the formula (I)

in which R ¹ and R ^{2 are} each (C 1 -C 4 -alkyl or hydrogen, X is halogen, a C 1 -C -alkyl or phenyl, A is nitrogen or CH and in which η is an integer from 0 to 2 with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen, 2) a process for preparing the azole derivatives of formula (I), which process comprises the following steps

a) (i) Reaction of an alkyl ester of 2-oxocyclopentanecarboxylic acid with a substituted benzyl halide and reaction of the thus obtained alkyl ester of 1 - (benzyl-substituted-1-oxocyclopentanecarboxylic acid with a (C ₁ -C ₅ ) -

alkyl halide;

(ii) reacting an alkyl ester of a 3- (C ₁ -C ₅ alkyl) -2-oxocyclopentanecarboxylic acid with a substituted one

Benzyl halide or

(iii) Reaction of a 1- (benzyl-substituted) -3- (C ₁ -C ₆ alkyl) -2-oxocyclopentanecarboxylic acid with a (C ₁ -C ₅ ) -alkyl halide to give ester derivatives of the cyclopentanecarboxylic acid of the following formula (V):

in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; R is a (C ₁ -C ₅ ) alkyl group; X is halogen, a (C ₁ -C ₅ ) -alkyl or phenyl and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen,

b) subjecting the thus-obtained ester derivative of cylopentanecarboxylic acid to hydrolytic decarboxylation to give a cyclopentanone derivative of the formula (IV):

(IV),

in which R ¹ , R ² , X and η are each defined identically as above, and

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

CH,

- CH

(III)

in which R ¹ , R ² , X and η are the same as defined above, for epoxidation, whereby said cyclopentanone derivative is converted into an oxirane derivative of the following formula (II):

(II)

in which R ¹ , R ² , X and η are the same as defined above, and then d) reacting the oxirane derivative thus obtained with a 1,2,4-triazole or imidazole of the following formula (IV):

(IV),

lM

in which M is hydrogen or alkali metal and A is nitrogen or -CH =, to give azole derivatives of the formula (I):

in which R ¹ and R ² jefür (C, -C ₅₎ alkyl or hydrogen; X represents halogen, a (С, -С ₆₎ -АІкуІ or phenyl; A is nitrogen or CH and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen; and

3) Agricultural and horticultural compositions containing the above-mentioned azole derivatives as active substances and exhibiting fungicidal and plant growth regulating effects.

The damage to crops due to various plant diseases is enormous. But the problem of landscape pollution due to the chemicals used to combat the above-mentioned plant diseases is also growing.

As a result of studies by some of the inventors of this application, the azole derivatives specified below were found and investigated. Important were the agricultural and horticulturally useful fungicidal properties of the compounds, the safe handling thereof, the low impact on the environment and an excellent effect on plant diseases in a wide range

 The formula of the studied azole derivatives was:

in which the radicals indicated have the following meanings:

X is halogen, alkyl, haloalkyl, phenyl, cyano or nitro;

A is nitrogen or CH;

η is an integer from 0 to 5, with the proviso that X can be the same or different when η is 1 to 5 (see JP

Published Patent Application No. 62-149,667 [1987], corresponding to UK Patent No. 2180 236 A). The inventors of the present invention further studied the synthesis of many azole derivatives and studied the compounds obtained for their usefulness for obtaining an agriculturally and horticulturally applicable fungicide having low toxicity to humans and animals, safe handling and excellent effects against plant diseases of various kinds. As a result, azole derivatives of the following formula (I) were found:

(D,

in which R ¹ and R ² each represents (Ci-C _s) -alkyl or hydrogen; X is halogen, a (Ci-C ₅ ) -alkyl or phenyl; A is nitrogen or CH and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen. It has been found that the compounds of the formula (I) not only have the above-mentioned specific properties, but that these compounds can also be used as effective growth regulators. Based on these findings, the present invention has been accomplished.

The purpose of the present invention is to provide azole derivatives which are useful as active substances in agriculturally and horticulturally to be used compositions, which compositions have effects against plant diseases and also serve as plant growth regulators. Another object of this invention is to provide a process for the preparation of said azole derivatives. Finally, the agricultural and horticultural compositions containing the said compounds as active substances are also an object of this invention. In the first aspect, the present invention relates to azole derivatives of the formula (I)

OH

-CH ₂ - N

CH.

in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; X is halogen, a (C ₁ -Cs) alkyl or phenyl; A is nitrogen or CH and in which π is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen

In a second aspect, the present invention relates to a process for the preparation of the azole derivatives of the following formula (I):

(D,

in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; X is halogen, a (C ₁ -C ₅ alkyl or phenyl; A is nitrogen or CH and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ² hydrogen

which method comprises the following steps

a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid with a substituted benzyl halide and reacting the thus obtained alkyl ester of 1- (benzyl-substituted) -2-oxocyclopentanecarboxylic acid with a (C ₁ -C ₅ ) -alkyl halide;

(ii) reacting an alkyl ester of a 3- (C ₁ -C ₅ alkyl-1-oxocyclopentanecarboxylic acid with a substituted benzyl halide or (iii) reacting a HBenzylsubstituiertenl-Sl ^ -Cs alkyl) -2-oxocyclopentancarboxylsäure with a (C ₁ -C _s ) Alkyl halide, whereby ester derivatives of the cyclopentanecarboxylic acid of the following formula (V) are obtained:

in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; R is a (C ₁ -Cs) -AlkYl; X is halogen, a (C ₁ -Cs) alkyl or phenyl and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen;

b) subjecting the resulting ester derivative of cyclopentanecarboxylic acid to hydrolytic decarboxylation to give a cyclopentanone derivative of formula (IV):

CH

(IV),

in which R ¹ , R ² , X and η are each defined identically as above, and

Subjecting the thus obtained cyclopentanone derivative to an oxirane reaction using sulfonium ylide or oxosulfonium ylide, or subjecting a methylenecyclopentane derivative obtained from the above-obtained cyclopentanone derivative by the Wittig reaction, and represented by the following formula (III):

(III)

in which R ¹ , R ² , X and η are the same as defined above, for epoxidation, whereby said cyclopentanone derivative is converted into an oxirane derivative of the following formula (II):

(II)

in which R ¹ , R ² , X and η are the same as defined above, and then d) reacting the oxirane derivative thus obtained with a 1,2,4-triazole or imidazole of the following formula (VI):

(Vl),

in which Μ is hydrogen or alkali metal and A is nitrogen or -CH =.

In the third aspect, the present invention relates to agricultural and horticultural compositions exhibiting fungicidal activity and plant growth regulating activity which contain, as active substance, an azole derivative of the formula (I):

(D,

in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; X is halogen, a (C ₁ -C ₅ alkyl group or phenyl, A is nitrogen or CH and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ² hydrogen

In a fourth aspect, the present invention relates to an oxirane derivative for the preparation of azole derivatives of the formula (I), which oxirane derivative is represented by the formula (II):

(ID,

in which R ¹ and R ^{2 are} each (C ·) -C ₅ ) -alkyl or hydrogen and X is halogen, ei η (C ₁ -Cs) -AlkYl or phenyl and in which η is an integer from 0 to 2 with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen. In the fifth aspect, the present invention relates to a methylenecyclopentane derivative for the preparation of the azole derivatives of the formula (I), which methylenecyclopentane derivative is represented by the formula (III):

(Ill),

in which R ¹ and R ^{2 are} each (C ₁ -C ₅ ) -alkyl or hydrogen and X is halogen, a (C ₁ -Cs) -alkyl or phenyl and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen In the sixth aspect, the present invention provides a cyclopentanone derivative for the preparation of the azole derivatives of the formula el (I), which cyclopentanone derivative is represented by Formula (IV):

(IV),

in which R ¹ and R ^{2 are} each (C ₁ -C ₆ -alkyl or hydrogen and X is halogen, a (C ₁ -C ₅ -alkyl) or phenyl and in which η is an integer from 0 to 2 with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen In the seventh aspect, the present invention relates to an ester derivative of cyclopentanecarboxylic acid for the preparation of azole derivatives of formula (I), which ester derivative is represented by the formula (V):

in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; R is (C, -C _s ) -alkyl and X is halogen, a (C ₁ -Cs) -alkyl or phenyl and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen is when R ^{2 is} hydrogen

The accompanying drawings, Figs. 1 to 76, show the infrared absorption spectra of the azole derivatives of the present invention shown in Table 1. In other words, Fig. 1 shows the IR absorption spectrum of Compound No. 1 in Table 1; Figure 2 shows the IR absorption spectrum of Compound No. 2 in Table 1; Fig. 3 shows the IR absorption spectrum of Compound No. 3 in Table 1, and Figs. 4 to 76 show the corresponding IR absorption spectra of the corresponding Compound Nos. 4 to 76 in Table 1.

The essence of the present invention are the novel azole derivatives of the following formula (I):

1 OH

-CH ₂ - N

(D,

in which R ¹ and R ^{2 are} each (C ₁ -C ₆ ) -alkyl or hydrogen; X is halogen, a (C, -C ₅ ) -alkyl or phenyl; A is nitrogen or CH and in which η is an integer from 0 to 2, with the proviso that R 'is not hydrogen when R ^{2 is} hydrogen. However, the invention also includes the process for the preparation of the azole derivatives of the formula (I), and also the intermediates for the preparation of said azole derivatives, in other words the oxirane derivative of the formula (II), the methylenecyclopentane derivative of the formula (III), the cyclopentanone derivative of the formula (IV) and the ester derivative of the cyclopentanecarboxylic acid of the formula (V). The invention further includes the agricultural and horticultural compositions which contain the azole derivatives of the formula (I) as an active substance and which exhibit fungicidal activity and plant growth regulating activity.

The physical and chemical properties of the azole derivatives of the formula (I) and those of the intermediates for the preparation thereof are shown in Tables 1 to 5 below.

It should be noted that all of the intermediates mentioned are also new compounds.

Table 1 Azole derivatives

κίϊ .OH / A =]

• cn, -k I

(I -A)

(I-B)

Ver R ¹ Radicals in formula (I) X _n A Stereo- enamel NMRS spectrum (CDCI ₃ · 5ppm) binding no. CH ₃ R ² 4-CI N isomer point ( ⁰ C) 0.60 (s, 3H), 1.00 (s, 3H), 1.07-1.90 (m, 5H), 2.33 (bs, 2H), 3.53 (s, 1H) , 4.13 (s, 2H), 6.80-7.23 (m, 4H), 7.83 (s, 1H), 8.02 (s, 1H) 1 CH ₃ CH ₃ 4-CI N A-type 113-114 0.82 (s, 3H), 1.00 (s, 3H), 1.23-1.93 (m, 4H), 2.07-2.48 (m, 2H), 2.85-3, 07 (m, 1H), 3.90 (s, 1H), 4.37 (s, 2H), 7.03 (d, 2H, J = 8), 7.25 (d, 2H , J = 8), 7.97 (s, 1H), 8.27 (s, 1H) 2 CH ₃ CH ₃ 4-CI CH B-type 113-114 0.80 (s, 3H), 1.03 (s, 3H), 1.13-2.93 (m, 8H), 3.97 (s, 2H), 7.02 (s, 2H), 6.80-7.33 (m, 4H), 7.60 (s, 1H) 3 CH ₃ CH ₃ 4-CI CH A-type 133-134 0.83 (s, 3H), 1.03 (s, 3H), 1.13-3.13 (m, 8H), 4.03 (s, 2H), 6.70-7.23 (m, 6H), 7.63 (s, 1H) 4 CH ₃ CH ₃ 4-Br N B-type 133-134 0.63 (s, 3H), 1.00 (s, 3H), 1.13-1.93 (m, 5H), 2.33 (bs, 2H), 3.60 (s, 1H), 4 , 20 (s, 2H), 6.93-7.50 (m, 4H), 7.97 (s, 1H), 8.17 (s, 1H) 5 CH ₃ CH ₃ 4-Br N A-type 129-130 0.77 (s, 3H), 0.97 (s, 3H), 1.20-3.03 (m, 7H), 3.80 (s, 1H), 4.33 (s, 2H) , 6.87-7.47 (m, 4H), 7.93 (s, 1H), 8.20 (s, 1H) 6 CH ₃ B-type 134-135

Table 1 (continued)

Ver R ¹ Restein formula (I) Xn A Stereo- enamel NMR spectrum (CDCl ₃ · öppm) binding no. CH ₃ R ² 4-Br CH isomer point ( ⁰ C) 0.80 (s, 3H), 1.03 (s, 3H), 1.13-2.53 (m, 8H), 4.00 (s, 2H), 6.80-7.50 ( m, 6H), 7.63 (s, 1H) 7 CH ₃ CH ₃ 4-Br CH A-type 149-150 0.83 (s, 3H), 1.03 (s, 3H), 1.17-2.97 (m, 8H), 4.03 (s, 2H), 6.70-7.40 (m , 6H), 7.57 (s, 1H) 8th CH ₃ CH ₃ 4-F N B-type 134-135 0.67 (s, 3H), 1.03 (s, 3H), 1.17-2.42 (m, 4H), 2.50 (bs, 3H), 3.63 (s, 1H) , 4.23 (s, 2H), 6.73-7.33 (m, 4H), 7.93 (s, 1H), 8.13 (s, 1H) 9 CH ₃ CH ₃ 4-F N Ä type 135-136 0.80 (s, 3H), 1.02 (s, 3H), 1.27-3.10 (m, 7H), 3.90 (m, 1H), 4.37 (s, 2H), 6.73-7.27 (m, 4H), 7.97 (s, 1H), 8.27 (s, 1H) 10 CH ₃ CH ₃ 4-F CH B-type 134-135 0.83 (s, 3H), 1.07 (s, 3H), 0.90-2.00 (m, 5H), 2.25 (bs, 2H), 2.57 (bs, 1H), 4.03 (s, 2H), 6.73-7.27 (m, 6H), 7.67 (s, 1H) 11 CH ₃ CH ₃ 4-F CH A-type 131-133 0.87 (s, 3H), 1.03 (s, 3H), 1.17-3.03 (m, 8H), 4.10 (s, 2H), 6.70-7.27 (m , 6H), 7.73 (bs, 1H) 12 CH ₃ CH ₃ 2,4-Cl ₂ N B-type 104-106 0.56 (s, 3H), 1.01 (s, 3H), 0.79-2.79 (m, 5H), 2.66 (bs, 2H), 3.97 (s, 1H) , 4.27 (s, 2H), 7.2 (bs, 2H), 7.28 (bs, 1H), 7.92 (s, 1H), 8.12 (s, 1H) 13 CH ₃ CH ₃ 2,4-Cl ₂ N A-type 126-127 0.80 (s, 3H), 1.02 (s, 3H), 1.25-1.88 (m, 4H), 2.33-3.03 (m, 2H), 3.75 (s , 1H), 4.37 (s, 2H), 7.08-7.37 (m, 3H), 7.93 (s, 1H), 8.23 (s, 1H) 14 CH ₃ CH ₃ 2,4-Cl ₂ CH B-type 108-110 0.70 (s, 3H), 1.03 (s, 3H), 1.16-2.65Im, 5H), 2.53 (bs, 2H), 2.72 (s, 1H), 4 , 01 (s, 2H), 6.99 (s, 1H), 7.03 (bs, 1H), 7.24 (s, 1H), 7.58 (s, 1H) 15 CH ₃ A-type 131-132

CH ₃ H 4 -Cl N A type

100-102 0.74 (d, 3H, J = 6), 1.00-2.27 (m, 6H), 2.49 (d, 2H, J = 6.4), 3.07 (s, 1 H), 4.20 (s, 2H), 7.03 (d, 2H, J = 8.4), 7.22 (d, 2H, J = 8.4), 7.95 (s, 1H), 8.08 (s, 1H)

CH ₃ H 4-CI CH A type

118-119 0.85 (d, 3H, J = 5.8), 1.07-2.23 (m, 6H), 2.51 (bd, 2H, J = 6.4), 3.34 ( bs, 1H), 3.95 (s, 2H), 6.95 (s, 1H), 6.98 (d, 2H, J = 8), 7.01 (s, 1H), 7.18 (d, 2H, J = 8), 7.48 (s, 1H)

H CH ₃ 4-Cl A-type N

75-76 0.99 (d, 3H, J = 6.4), 1.28-2.24 (m, 6H),

2.28-2.58 (m, 2H), 3.60 (s, 1H), 3.99 (d, 1H, J = 14), 4.39 (d, 1H, J = 14) , 6.97 (d, 2H, J = 9), 8.00 (s, 1H), 8.18 (s, 1H), 7.24 (d, 2H, J = 9)

H CH ₃ 4-Cl N B type

79-81 0.80 {d, 3H, J = 6.4), 0.99-2.56 (m, 7H),

2.73-3.39 (m, 1H), 3.90 (bs, IH), 4.11 (d, 1H, J = 14), 4.38 (d, 1H, J = 14), 7 , 04 (d, 2H, J = 9.4), 7.26 (d, 2H, J = 9.4), 7.92 (s, 1H), 8.22 (s, 1H)

CH ₃ H 4 -Cl N B type

oily 0.88 (d, 3H, J = 6.6), 1.05-2.45 (m, 7H), 2.62-2.92

Substance (m, 1H), 3.85-4.25 (b, 1H, OH), 4.31 (s, 2H), 6.98 (d, 2H, J = 8.8), 7 , 22 (d, 2H, J = 8.8), 7.95 (s, 1H), 8.26 (s, 1H)

21 CH ₃ CH ₃ H N A-type oily substance 0.63 (s, 3H), 1.03 (s, 3H), 1.13-2.83 (m, 7H), 3.57 (s, 1H), 4.23 (s, 2H) , 7.23 (s, 5H), 8.00 (s, 1H), 8.17 (s, IH) 22 CH ₃ CH ₃ H CH A-type 128-130 0.77 (s, 3H), 1.03 (s, 3H), 1.10-2.17 (m, 5H), 1.97 (s, 1H), 2.17-2.50 (m , 2H), 3.97 (s, 2H), 6.87-7.33 (m, 7H), 7.57 (s, 1H) 23 CH ₃ CH ₃ 4-CH ₃ N A-type 123-124 0.57 (s, 3H), 1.02 (s, 3H), 1.10-2.57 (m, 8H), 2.27 (s, 3H), 4.20 (s, 2H), 7 , 02 (s, 4H), 7.95 (s, 1H), 8.13 (s, 1H) 24 CH ₃ CH ₃ 4-CH ₃ N B-type 114-115 0.73 (s, 3H), 0.98 (s, 3H), 1.07-3.00 (m, 7H), 2.25 (s, 3H), 3.72 (s, 1H), 4.28 (s, 2H), 6.93 (s, 4H), 7.83 (s, 1H), 8.10 (s, 1H) 25 CH ₃ CH ₃ 4-CH ₃ CH A-type 132-133 0.75 (s, 3H), 1.02 (s, 3H), 1.02-2.42 (rrt, 8H), 2.27 (s, 3H), 3.93 (s, 2H), 6.98 (s, 4H), 7.02 (s, 2H), 7.58 (s, 1H)

Table 1 (Continuation) Radicals in formula (I) Xn A Stereo- enamel N Μ R spectrum (CDCI ₃ 5ppm) Ver R ² 4-CH ₃ CH isomer point ( ⁰ C) 0.83 (s, 3H), 1.07 (s, 3H), 1.17-3.07 (m, 8H), 2.27 (s, 3H), 4.07 (s, 2H), 6 , 77-7.20 (m, 2H), 6.95 (s, 4H), 7.62 (s, 1H) binding no. R ¹ CH ₃ 2-F, 4-CI N B-type 130-131 0.62 (s, 3H), 1.02 (s, 3H), 1.13-2.67 (m, 7H), 3.82 (s, 1H), 4.21 (s, 2H), 6.23-7.23 (m, 3H), 7.89 (s, 1H), 8.1 Ks, 1H) 26 CH ₃ CH ₃ 2-F, 4-CI CH A-type 129-130 0.78 (s, 3H), 1.02 (s, 3H), 1.10-2.80 (m, 8H), 3.98 (s, 2H), 6.68-7, 20 (m, 5H), 7.57 (s, 1H) 27 CH ₃ CH ₃ 4-CI N A-type 152-154 0.67-2.23 (m, 11H), 2.43 (d, 2H, J = 7), 2.93 (s, 1H), 4.20 (s, 2H), 6, 93-7.33 (m, 4H), 7.93 (s, 1H), 8.07 (s, 1H) 28 CH ₃ H 4-CI N A-type 82-84 0.70-2.13 (m, 11H), 2.13-2.47 (m, 2H), 3.83 (s, 1H), 4.00 (d, 1H, J = 14) , 4.30 (d, 1H, J = 14), 6.88 (d, 2H, J = 8), 7.18 (d, 2H, J = 8), 7.93 (s, 1H), 8.17 (s, 1H) 29 C ₂ H ₅ C ₂ H ₅ 4-CI N A-type 93-95 0.67-3.33 (m, 13H), 3.07 (d, 1H, J = 10), 4.13 (d, 1H, J = 14), 4.40 (d, 1H, J = 14), 7.03 (d, 2H, J = 8), 7.23 (d, 2H, J = 8), 7.97 (s, 1H), 8.18 (s, 1H) 30 H C ₂ H ₅ 4-CI N B-type 76-78 0.67-2.20 (m, 12H), 2.73 (d, 1H, J = 10), 4.15 (s, 1H), 4.30 (s, 2H), 6.95 ( d, 2H, J = 8), 7.20 (d, 2H, J = 8), 7.97 (s, 1H), 8.25 (s, 1H) 31 H H 4-CI N B-type 110-112 0.67-1.07 (m, 6H), 1.07-2.40 (m, 11H), 3.52 (s, 1H), 4.30 (s, 2H), 6.87 ( d, 2H, J = 9), 7.18 (d, 2H, J = 9), 7.93 (s, 1H), 8.18 (s, 1H) 32 C ₂ H ₅ C ₂ H ₅ A-type 124-126 33 C ₂ H ₅

C ₂ H ₅ C ₂ H ₅ 4-CI N

B type 143-145 0.87 (t, 6H, J = 6), 1.10-1.97 (m, 8H), 1.97-2.54

(m, 2H), 2.73 (d, 1H, J = 9), 3.33-3.70 (b, 1H), 4.43 (s, 2H), 6.92 (d, 2H, J = 9), 7.20 (d, 2H, J = 9), 7.97 (s, 1H), 8.27 (s, 1H)

35 C ₂ H ₅ C ₂ H ₅ 4-CI CH A-type oily substance 0.87 (t, 6H, J = 6), 1.07-2.50 (m, 11H), 3.33 (s, 1H), 3.90 (d, 1H, J = 14), 4 , 18 (d, 1H, J = 14), 6.70-7.23 (m, 6H), 7.67 (s, 1H) 36 C ₂ H ₅ C ₂ H ₅ 4-CI CH B-type 143-145 0.87 (t, 6H, J = 6), 1.10-2.33 (m, 10H), 2.53-2.88 (m, 2H), 4.13 (s, 2H), 6.75-7.35 (m, 6H), 7.70 (s, 1H) 37 n- C ₃ H ₇ H 4-CI N A-type 83-85 0.61-2.26 (m, 13H), 2.26-2.57 (m, 2H), 2.51-2.81 (b, 1H), 4.21 (s, 2H) , 7.03 (d, 2H, J = 9), 7.23 (d, 2H, J = 9), 7.96 (s, 1H), 8.07 (s, 1H)

Hn-4-CI N A type

C ₃ H ₇

75-77 0.65-1.04 (m, 3H), 1.04-2.18 (m, 10H), 2.18-2.48

(m, 2H), 3.70 (bs, 1H), 3.98 (d, 1H, J = 14), 4.29 (d, 1H, J = 14), 6.86 (d, 2H, J = 8.4), 7.16 (d, 2H, J = 8.4). 7.94 (s, 1H), 8.12 (s, IH)

39 n- C ₃ H ₇ H 4-CI CH A-type 115-117 0.57-1.04 (m, 3H), 1.04-2.24 (m, 10H), 2.43 (bs, 2H), 2.55 (bs, 1H), 3, 96 (s, 2H), 6.99 (d, 2H, J = 8.4), 7.02 (bs, 2H), 7.20 (d, 2H, J = 8.4), 7.45 (bs, 1H) 40 C ₂ H ₅ H 2,4-Cl ₂ N A-type 124-127 0.63-2.40 (m, 11H), 2.68 (d, 2H, J = 6), 3.10 (s, 1H), 4.23 (s, 2H), 7.13 (bs, 2H), 7.30 (bs, 1H), 7.93 (s, 1H), 8.10 (s, 1H) 41 C ₂ H ₅ H 2,4-Cl ₂ CH A-type 111-113 0.67-2.27 (m, 11H), 2.50 (d, 2H, J = 7), 2.63 (bs, 1H), 3.98 (s, 2H), 6.90 (bs, 2H), 6.97 (bs, 2H), 7.37 (bs, 1H), 7.50 (bs, 1H) 42 C ₂ H ₅ H 4-F N A-type 73-74 0.62-2.19 (m, 11H), 2.30-2.51 (m, 2H), 2.62 (s, 1H), 4.15 (s, 2H), 6, 64-7.23 (m, 4H), 7.88 (s, 1H), 7.99 (s, 1H) 43 C ₂ H ₅ H 4-F CH A-type 111-113 0.66-2.07 (m, 11H), 2.19 (s, 1H), 2.35-2.60 (m, 2H), 3.93 (s, 2H), 6, 63-7.20 (m, 6H), 7.41 (bs, 1H) 44 C ₂ H ₅ H 4-Br N A-type 80-82 0.68-2.25 (m, 11H), 2.43 (d, 2H, J = 7), 2.85 (s, 1H), 4.22 (s, 2H), 7.02 (d, 2H, J = 8), 7.37 (d, 2H, J = 7), 7.93 (s, 1H), 8.08 (s, IH)

Table 1 (continued)

Ver R ¹ Radicals in formula (I) Xn A Stereo- enamel NMRS spectrum (CDCI ₃ · 5ppm) binding no. C ₂ H ₆ R ² 4-Br CH isomer point ("C) 0.60-2.50 (m, 11H), 2.33-3.02 (m, 2H), 3.18 (bs, 1H), 4.00 (s, 2H), 6.88 -7.02 (m, 2H), 7.03-7.35 (m, 3H), 7.48 (bs, 1H) 45 C ₂ H ₅ H 4- C ₆ H ₆ N A-type 117-119 0.56-2.34 (m, 11H), 2.40-2.60 (m, 2H), 2.65 (s, 1H), 4.20 (s, 2H), 7.05 -7.70 (m, 9H), 7.95 (s, 1H), 8.05 (s, 1H) 46 C ₂ H ₅ H 4- C ₆ H ₆ CH A-type 107-109 0.66-2.28 (m, 11H), 2.01 (s, 1H), 2.45-2.72 (m, 2H), 3.96 (s, 2H), 6, 85-7.63 (m, 12H) 47 H A-type 169-170

C ₂ H ₅ H

4-tC ₄ H ₉

A type oily 0.85 (t, 3H, J = 7), 1.29 (s, 9H), 0.90-1.90 (m, 8H),

Substance 2.41 (dd, IH, J = 14.10), 2.49 (dd, 1H, J = 14.5), 4.23 (s, 2H), 7.07 (d, 2H , J = 8.3), 7.28 (d, 2H, J = 8.3), 7.96 (s, 1H), 8.01 (s, 1H)

49 C ₂ H ₅ H 4 -t CH A type 132-133 0.67-2.83 (m, 14H), 1.32 (s, 9H), 4.08 (s, 2H),

C ₄ H ₉ 6.97-7.53 (m, 6H), 7.58 (s, 1H)

50 i-H 4-Cl N A-type 91-92 0.95 (d, 3H, J = 7), 0.97 (d, 3H, J = 7), 1.17-2.93 C ₃ H ₇ (m, 10H), 4,12 (d, 1H, J = 14), 4,41 (d, 1H, J = 14),

6.87-7.40, (m, 4H), 7.97 (s, 1H), 8.13 (s, 1H)

51 n-H 4-Cl N A-type oily 0.86 (t, 3 H, J = 6.8), 0.90-1.98 (m, 14 H), 2.38 (dd, 1H, C ₅ H ₁₁ substance J = 13.4, 9.3), 2.46 (dd, 1 H, J = 13.4, 5, 4), 2.57 (s, 1 H),

4.23 (s, 2H), 7.06 (d, 2H, J = 8.3), 7.22 (d, 2H, J = 8.3), 7.97 (s, 1H) , 8.08 (s, 1H)

52 n-H 4-CI CH A type 92-95 0.87 (t, 3H, J = 6.8), 1.05-1.95 (m, 14H), 2.43 (dd, 1H, C ₅ H ₁₁ J = 13.7, 10.3), 2.56 (dd, 1 H, J = 13.7, 4,4), 3.47

(s, 1H), 3.99 (s, 2H), 6.94 (s, 1H), 7.05 (d, 2H, J = 8.3), 7.06 (s, 1 H), 7.22 (d, 2H, J = 8.3), 7.48 (s, 1H)

C ₂ H ₅ H 4-CI CH

B type 138-140 0.57-0.98 (m, 3H), 0.98-2.17 (m, 9H), 2.73 (d, 1H,

J = 10), 3.43 (bs, 1H), 4.03 (s, 2H), 6.83-7.03 (m, 6H), 7.68 (bs, 1H)

Hn-4-CI N A-type oily

C ₆ H ₁₁ substance

0.88 (t, 3H, J = 6.8), 1.00-1.94 (m, 14H), 2.31 (m, 2H), 3.70 (bs, 1H), 4.05 ( d, 1H, J = 13.7), 4.26 (d, 1H, J = 13.7), 6.89 (d, 2H, J = 8.3), 7.17 (d, 2H , J = 8.3), 7.99 (s, 1H), 8.15 (s, 1H)

CH ₃

CH ₃

4-C ₆ H ₆

A type 122-124 0.63 (s, 3H), 1.02 (s, 3H), 1.10-2.13 (m, 4H), 2.47

(bs, 3H), 3.62 (s, 1H), 4.23 (s, 2H), 7.10-7.73 (m, 9H), 7.97 (s, 1H), 8.17 ( s, 1H)

CH ₃

CH ₃

4-C ₆ H ₅

B type 116-118 0.77 (s, 3H), 0.98 (s, 3H), 1.10-2.80 (m, 5H), 2.33

(d, 1H, J = 9), 2.98 (d, 1H, J = 9), 3.88 (s, 1H), 4.33 (s, 2H), 7.07-7.73 ( m, 9H), 7.97 (s, 1H), 8.25 (s, 1H)

57 CH ₃ CH ₃ 4- C ₆ H ₅ CH A-type 162-163 0.80 (s, 3H), 1.03 (s, 3H), 1.12-2.08 (m, 4H), 2.37 (bs, 3H), 2.43 (s, 1H ), 4.00 (s, 2H), 6.88-7.78 (m, 12H) 58 CH ₃ CH ₃ 4- C ₆ H ₅ CH B-type 165-167 0.85 (s, 3H), 1.03 (s, 3H), 1.13-2.77 (m, 5H), 2.30 (d, 1H, J = 9), 2.95 ( d, 1H, J = 9), 3.60 (s, 1H), 4.13 (s, 2H), 6.90-7.87 (m, 12H) 59 i- C ₃ H ₇ H 4-CI CH A-type oily substance 0.97 (d, 3H, J = 7), 1.00 (d, 3H, J = 7), 1.23-2.53 (m, 10H), 3.90 (d, 1H, J = 14) ), 4.17 (d, 1H, J = 14), 6.90-7.43 (m, 6H), 7.53 (bs, 1H)

60 CH ₃ CH ₃ 4-t-N A-type 107-108 0.62 (s, 3H), 1.01 (s, 3H), 1.27 (s, 9H), 1.17-2.00

C ₄ H ₉ (m, 5H), 2.17-2.67 (m, 2H), 3.50 (s, 1H), 4.22 (s, 2H),

7.00 (d, 2H, J = 8.4), 7.25 (d, 2H, J = 8.4), 7.92 (s, 1H), 8.12 (s, 1H)

61 CH ₃ CH ₃ 4-t CH A type 167-168 0.78 (s, 1H), 1.02 (s, 3H), 1.29 (s, 9H), 1.14-2, 10

C ₄ H ₉ (m, 5H), 2.14 to 2.57 (m, 2 H), 2.40 (s, 1 H), 3.97 (s, 2H)

6.96 (d, 2H, J = 8.4), 7.03 (bs, 2H), 7.23 (d, 2H, J = 8.4), 7.59 (bs, 1H)

Hi- 4-CI N

C ₃ H ₇

B type oily 0.60-3.17 (m, 15H), 3.43 (bs, 1H), 4.20 (s, 2H), 6.92

(d, 2H, J = 8), 7.15 (d, 2H, J = 8), 7.87 (s, 1H), substance 8.07 (s, 1H)

Table 1 (continued)

Ver R ¹ Radicals in formula (i) Xn A Stereo- enamel NMR spectrum (CDCl ₃ × 5 ppm) binding no. H R ² 4-CI N isomer point ( ⁰ C) 0.70-2.33 (m, 15H), 3.47 (bs, 1H), 3.97 (d, 1H, J = I4), 4.38 (d, 1H, J = 14) , 6.73 (d, 2H, J = 8), 7.10 (d, 2H, J = 8), 7.93 (s, 1H), 8.10 (s, 1H) 63 H i- C ₃ H ₇ 4-CI CH A-type 102-103 0.83-2.43 (m, 16H), 3.73 (d, 1H, J = 14), 4.22 (d, 1H, J = 14), 6.60-7.27 (m , 6H), (7.53 s, 1H) 64 C ₃ H ₇ C ₃ H ₇ 4-CI N A-type ρ 146-147 0.70-2.63 (m, 15H), 3.70 (bs, 1H), 4.33 (s, 2H), 7.00 (d, 2H, J = 8), 7.27 (i.e. , 2H, J = 8), 8.07 (s, 1H), 8.40 (s, 1H) 65 n- C ₄ H ₉ H 4-CI CH B-type 120-121 0.57-2.67 (m, 17H), 3.05 (s, 1H), 3.95 (s, 2H), 6.68-7.25 (m, 6H), 7, 38 (bs, 1H) 66 H H 4-CI N A-type oily substance 0.63-2.43 (m, 17H), 3.67 (s, 1H), 3.95 (d, 1H, J = 14), 4.25 (d, 1H, J = 14) , 6.77 (d, 2H, J = 8), 7.07 (d, 2H, J = 8), 7.83 (s, 1H), 8.02 (s, 1H) 67 H n- C ₄ Hg 4-CI N A-type 94-95 0.60-2.33 (m, 16H), 2.90-3.20 (m, 1H), 3.30 (s, 1H), 4.22 (s, 2H), 6.88 (d, 2H, J = 8), 7.12 (d, 2H, J = 8), 7.83 (s, 1H), 8.02 (s, 1H) 68 i- C ₄ Hg n- C ₄ Hg 4-C! N B-type oily substance 0.78 (d, 3H, J = 6), 0.88 (d, 3H, J = 6), 1.07-2.27 (m, 9H), 2.33-2.67 (m, 3H ), 4.22 (s, 2H), 7.00 (d, 2H, J = 9), 7.2 (d, 2H, J = 9), 7.93 (s, 1H), 8, 05 (s, 1H) 69 І- C ₄ Hg H 4-CI CH A-type oily substance 0.81 (d, 3H, J = 6), 0.88 (d, 3H, J = 6), 1.03-2.10 (m, 9H) 2.26-2.70 (m, 2 H), 3.88 (s, 1H), 4.00 (s, 2H), 6.70-7.30 (m, 6H), 7.46 (s, 1H) 70 n- C ₄ Hg H 4-CI N A-type oily substance 0.60-2.63 (m, 17H), 2.80 (s, 1H), 4.23 (s, 2H), 7.07 (d, 2H, J = 8), 7.27 (d, 2H, J = 8), 8.00 (s, 1H), 8.13 (s, 1H) 71 H A-type oily substance

Isomer CH ₃ a

Isomer C ₂ H ₅ b

C ₂ H ₅ 4-CI N

CH ₃

4-CI N

A-type mixture 0.57-1.02 (m, 6H), 1.12-2.55 (m, 9H),

of 72-a 3,55,3,67 (2s, 1H), 4,20 (bs, 2H),

& 72-b 6.95 (d, 2H, J = 9), 7.18 (d, 2H, J = 9),

A type 98-101 7.92 (s, 1H), 8.12 (s, 1H)

Isomer CH ₃

Isomer C ₂ H ₅ b

C ₂ H ₅ 4-CI N B type

CH ₃ 4-CI N B type

Mixture 0.67-1.05 (m, 6H), 1.05-3.12 (m, 9H),

from 73-a 3,77,3,92 (2 s, 1 H), 4,35 (s, 2 H),

& 73-b 6.95 (d, 2H, J = 8), 7.18 (d, 2H, J = 8),

117-119 7.90 (s, 1H), 8,15,8,15 (2 s, 1H)

Isomer CH ₃ a

Isomer C ₂ H ₅ b

C ₂ H ₅ 4-CI CH B type

CH ₃ 4-CI CH B type

Mixture 0.63-1.08 (m, 6H), 1.08-3.07 (m, 9H),

from 74-a 3.33 (s, 1H), 4.12 (bs, 2H),

& 74-b 6.80-7.30 (m, 6H), 7.70 (bs, 1H)

122-127

CH ₃ CH ₃ 4-t-N B type

C ₄ Hg

oily 0.77 (s, 3H), 1.01 (s, 3H), 1.28 (s, 9H), 1.39-2.11

Substance (m, 5H),

2.12-2.54 (m, 2H), 3.78 (bs, 1H), 4.34 (s, 2H),

6.95 (d, 2H, J = 8.4),

7.20 (d, 2H, J = 8.4), 7.88 (s, 1H), 8.14 (s, 1H)

CH ₃ CH ₃ 4-t-CH B type

C ₄ Hg

132-133 0.84 (s, 3H), 1.06 (s, 3H), 1.30 (s, 9H), 1.43-3.10 (m, 8H),

4.13 (s, 2H), 6.87 (bs, 1H), 7.01 (d, 2H, J = 8.4), 7.19 (bs, 1H), 7.29 ( d, 2H, J = 8.4), 7.73 (bs, 1H)

Table 2 (oxirane derivatives), 2

Rl- \

RL.

(HA)

CH

(H-B)

encryption

binding

No. R ¹

Restein formula (II)

Stereo- physi isomer cal own shaft

NMR spectrum

(CDCI _3- head)

77 CH ₃ CH ₃ 4-CI A-type oily substance 0.83 (s, 3H), 0.95 (s, 3H), 1.33-1.73 (m, 4H), 2.33-2.53 (m, 3H), 2.52 (d, 1H, J = 4), 2.67 (d, 1H, J = 4), 7.03 (d, 2H, J = 8), 7.23 (d, 2H, J = 8) 78 CH ₃ CH ₃ 4-CI B-type oily substance 0.87 (s, 3H), 0.93 (s, 3H), 1.45-1.73 (m, 4H), 2.13-2.70 (m, 3H), 2, 60 (d, 1H, J = 4), 2.83 (d, 1H, J = 4), 7.02 (d, 2H, J = 8), 7.23 (d, 2H, J = 8 ) 79 CH ₃ CH ₃ 4-Br A-type oily substance 0.83 (s, 3H), 0.93 (s, 3H), 1.17-1.73 (m, 4H), 2.17-2.67 (m, 3H), 2, 50 (d, 1H, J = 4), 2.60 (s, 1H, J = 4), 6.80-7.33 (m, 4H) 80 CH ₃ CH ₃ 4-Br B-type oily substance 0.87 (s, 3H), 0.93 (s, 3H), 1.20-2.73 (m, 7H), 2.60 (d, 1H, J = 4), 2, 80 (d, 1H, J = 4), 6.80-7.47 (m, 4H) 81 CH ₃ CH ₃ 4-F A-type oily substance 0.80 (s, 3H), 0.90 (s, 3H), 1.00-2.00 (m, 4H), 2.00-2.67 (m, 5H), 6, 70-7.23 (m, 4H) 82 CH ₃ CH ₃ 4-F B-type oily substance 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) 83 CH ₃ CH ₃ 2,4-Cl ₂ A-type oily substance 0.85 (s, 3H), 0.92 (s, 3H), 1.27-1.82 (m, 4H), 2.28-2.78 (m, 5H), 6, 92-7.28 (m, 3H) 84 CH ₃ CH ₃ 2,4-Cl ₂ B-type oily substance 0.87 (s, 3H), 0.97 (s, 3H), 1.48-1.72 (m, 4H), 2.33-2.77 (m, 3H), 2, 62 (d, 1H, J = 4), 2.85 (d, 1H, J = 4), 7.05-7.37 (m, 3H) 85 CH ₃ H 4-CI A-type oily substance 0.80 (d, 3H, J = 6), 1.14-2.51 (m, 6H), 2.31-2.51 (b, 2H), 2.63 (s, 2H) , 7.00 (d, 2H, J = 9), 7.19 (d, 2H, J = 9) 86 H CH ₃ 4-CI A-type oily substance 0.89 (d, 3H, J = 6), 0.85-2.68 (m, 6H), 2.32-2.42 (b, 2H), 2.47 (d, 1H , J = 4.6), 2.78 (d, 1H, J = 4.6), 6.75-7.28 (m, 4H) 87 H CH ₃ 4-CI B-type oily substance 0.81 (d, 3H, J = 6), 0.93-3.00 (m, 8H), 2.54 (d, 1H, J = 4.6), 2.79 (d, 1H, J = 4.6), 6.80-7.33 (m, 4H) 88 CH ₃ H 4-CI B-type oily substance 0.92 (d, 3H, J = 6), 1.13-2.90 (m, 8H), 2.76 (s, 2H), 7.01 (d, 2H, J = 9) ), 7.26 (d, 2 H, J = 9) 89 CH ₃ CH ₃ H A-type oily substance 0.73-2.07 (m, 5H), 0.87 (s, 3H), 0.97 (s, 3H), 2.27-2.77 (m, 2H), 2, 55 (d, 1H, J = 4), 2.67 (d, 1H, J = 4), 7.23 (s, 5H) 90 CH ₃ CH ₃ 4-CH ₃ A-type oily substance 0.83 (s, 3H), 0.97 (s, 3H), 1.17-1.97 (m, 5H), 2.17-2.77 (m, 2H), 2, 27 (s, 3H), 2.55 (d, 1H, J = 4), 2.65 (d, 1H, J = 4), 7.00 (s, 4H) 91 CH ₃ CH ₃ 4-CH ₃ B-type oily substance 0.87 (s, 3H), 0.93 (s, 3H), 1.47-1.77 (m, 5H), 2.17-2.97 (m, 2H), 2, 30 (s, 3H), 2.65 (d, 1H, J = 4), 2.87 (d, 1H, J = 4), 7.07 (s, 4H) 92 CH ₃ CH ₃ 2-F 4-CI A-type oily substance 0.83 (s, 3H), 0.93 (s, 3H), 1.09-2.79 (m, 9H), 6.83-7.15 (m, 3H) 93 C ₂ H ₅ H 4-CI A-type oily substance 0.60-2.83 (m, 11H), 2.43 (bs, 2H), 2.65 (s, 2H), 6.92-7.33 (m, 4H) 94 H C ₂ H ₅ 4-CI A-type oily substance 0.67-2.77 (m, 11H), 2.37 (bs, 2H), 2.53 (d, 1H, J = 4), 2.85 (d, 1H, J = 4 ), 6.87-7.33 (m, 4H) 95 H C ₂ H ₅ 4-CI B-type oily substance 0.60-2.92 (m, 13H), 2.57 (d, 1H, J = 4), 2.82 (d, 1H, J = 4), 6.87-7.30 ( m, 4H) 96 C ₂ H ₅ H 4-CI B-type oily substance 0.67-2.85 (m, 13H), 2.75 (s, 2H), 6.88-7.33 (m, 4H)

Table 2 (continued)

Ver Radicals in formula (I) R ¹ R ² Xn Stereo- physi NMR spectrum (CDCl ₃ -5ppm) binding no. C ₂ H ₅ C ₂ H ₅ 4-CI isomer own property 0.57-1.03 (m, 6H), 1.03-2.05 (m, 9H), 2.38 (bs, 2H), 2.57 (d, 1H, J = 4 ), 2.67 (d, 1H, J = 4), 6.90-7.30 (m, 4H) 97 C ₂ H ₅ C ₂ H ₅ 4-CI A-type oily substance 0.63-1.03 (m, 6H), 1.03-1.90 (m, 9H), 2.07-2.50 m, 2H) 2.62 (d, 1H, J = 4), 2.75 (d, 1H, J = 4), 6.83-7.23 (m, 4H) 98 η- C ₃ H ₇ H 4-CI B-type oily substance 0.59-1.02 (m, 3H), 1.02-2.29 (m, 10H), 2.29-2.52 (m, 2H), 2.68 (s, 2H ), 7.05 (d, 2H, J = 9), 7.25 (d, 2H, J = 9) 99 H n- C ₃ H ₇ 4-CI A-type oily substance 0.62-1.03 (m, 3H), 1.03-2.32 (m, 10H), 2.32-2.48 (b, 2H), 2.53 (d, 1H , J = 4.4), 2.86 (d, 1H, J = 4.4), 7.03 (d, 2H, J = 9), 7.22 (d, 2H, J = 9 ) 100 C ₂ H ₆ H 2,4-Cl ₂ A-type oily substance 0.67-3.10 (m, 13H), 2.70 (s, 2H), 7.10 (m, 2H), 7.28 (m, 1H) 101 C ₂ H ₆ H 4-F A-type oily substance 0.65-2.50 (m, 13H), 2.62 (s, 2H), 6.60-7.24 (m, 4H) 102 C ₂ H ₅ H 4-Br A-type oily substance 0.67-2.13 (m, 11H), 2.42 (m, 2H), 2.65 (s, 2H), 6.98 (d, 2H, J = 8), 7, 35 (d, 2H, J = 8) 103 C ₂ H ₆ H 4-C ₆ H ₅ A-type oily substance 0.63-2.58 (m, 13H), 2.66 (s, 2H), 7.04-7.68 (m, 9H) 104 C ₂ H ₅ H 4-t C ₄ Hg A-type Solid mp: 69-71 ⁰ C 0.69-2.55 (m, 13H), 1.27 (s, 9H), 2.65 (s, 2H), 6.93-7.42 (m, 4H) 105 i- C ₃ H ₇ H 4-CI A-type oily substance 0.85 (d, 6H, J = 7), 1.00-2.83 (m, 9H), 2.63 (s, 2H), 6.90-7.33 (m, 4H ) 106 n- C ₅ H ₁₁ H 4-CI A-type oily substance 0.87 (t, 3H, J = 6.8), 1.00-2.56 (m, 16H), 2.67 (d, 1H, J = 4.4), 2.71 ( d, 1H, J = 4.4), 7.08 (d, 2H, J = 8.3), 7.22 (d, 2H, J = 8.3) 107 H n- 4-CI A-type oily substance 0.87 (t, 3H, J = 6.8), 1.00-2.54 (m, 16H), 2.56 (d, 1H, J = 4.4), 2.88 ( d, 1H, J = 4.4), 7.09 (d, 2H, J = 8.3), 7.23 (d, 2H, J = 8.3) 108 A-type oily substance

109 CH ₃ CH ₃ 4-t-A-type oily 0.80 (s, 3H), 0.94 (s, 3H), 1.28 (s, 9H),

C ₄ H ₉ Substance 1.41-1.96 (m, 4H), 2.18-2.48 (b, 3H), 2.55

(d, 1H, J = 4.4), 2.64 (d, 1H, J = 4.4), 7.02 (d, 2H, J = 8), 7.18 (d, 2 H, J = 8)

110 CH ₃ CH ₃ 4-t-C4H9 B-type oily substance 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 (d, 1H, J = 4.4), 2.84 (d, 1H, J = 4.4), 7.02 (d, 2H, J = 8), 7.27 (d, 2H, J = 8) 111 CH ₃ CH ₃ 4- C ₆ H ₅ A-type oily substance 0.83 (s, 3H), 0.92 (s, 3H), 1.10-2.18 (m, 4H), 2.47 (bs, 3H), 2.50 (d, 1H, J = 4), 2.63 (d, 1H, J = 4), 6.97-7.63 (m, 9H) 112 CH ₃ CH ₃ 4- C ₆ H ₅ B-type oily substance 0.85 (s, 3H), 0.93 (s, 3H), 1.20-1.97 (m, 4H), 1.97-2.90 (m, 3H), 2, 57 (d, 1H, J = 4), 2.82 (d, 1H, J = 4), 6.97-7.58 (m, 9H) 113 H i- C ₃ H ₇ 4-CI A-type oily substance 0.82 (d, 3H, J = 6), 0.85 (d, 3H, J = 6), 0.97-2.73 (m, 9H) 2.60 (d, 1H, J = 4), 2.88 (d, 1H, J = 4), 6.93-7.37 (m, 4H) 114 H i- C ₃ H ₇ 4-CI B-type oily substance 0.67-1.03 (m, 6H), 1.03-2.77 (m, 9H), 2.50 (d, 1H, J = 4), 2.83 (d, 1H , J = 4), 6.90-7.33 (m 4 H) 115 C ₃ H ₇ H 4-CI B-type oily substance 0.87 (d, 3H, J = 6), 0.90 (d, 3H, J = 6), 1.10-3.20 (m, 9H), 2.87 (s, 2H ), 6.90-7.40 (m, 4H) 116 n- C4H9 H 4-CI A-type oily substance 0.63-2.80 (m, 17H), 2.67 (s, 2H), 6.93-7.37 (m, 4H) 117 H n- C ₄ Hg 4-CI A-type oily substance 0.50-2.70 (m, 17H), 2.50 (d, 1H, J = 4), 2.83 (d, 1H, J = 4), 6.90-7.30 ( m, 4H) 118 H n- C ₄ Hg 4-CI B-type oily substance 0.63-2.73 (m, 17H), 2.53 (d, 1H, J = 4), 2.77 (d, 1H, J = 4), 6.80-7.23 ( m, 4H)

Table 2 (continued)

Ver Restein formula ( II) Xn Stereo- physi 0.78 (d, (m, 9H) (m, 4H) NMR spectrum (CDCI ₃ -opprn) binding no. R ¹ R ² 4-CI isomer own property 3H, J = 7), 0.88 (d, 3H, J = 7), 1.00-2.27, 2.27-2.50 (m, 2H), 2.63 (s, 2H), 6.87-7.33 119 i- HC ₄ H ₉ A-type oily substance

120 isomer CH ₃ C ₂ H ₅ 4-CI

Isomer C ₂ H ₅ CH ₃ 4-CI

A-type mixture 0.68-0.97 (m, 6H), 0.97-1.85 (m, 6H), from 120 a 2.15-2.75 (m, 5H), & 120b 7.00 (d, 2H, J = 8), A-type oily 7.17 (d, 2H, J = 8) substance B-type mixture 0.67-1.00 (m, 6H), 1.00-1.90 (m, 6H), from 121 a 2.13-2.90 (m, 5H), 6.97 (d, 2H, J = 8), & 121b 7.17 (d, 2H, J = 8) B-type oily substance

121 isomer CH ₃ C ₂ H ₅ 4-CI

Isomer C ₂ H ₅ CH ₃ 4-CI

Table 3

R '

C И2

- CH

(Ш) (methylenecyclopentane derivatives)

Connection no.

Radicals in formula (III)

Physical property

NMR spectrum

(CDCI ₃ -5ppm)

122 CH ₃ CH ₃ 4-CI oily substance 1.03 (s, 3H), 1.08 (s, 3H), 1.28-1.85 (m, 4H), 2.35-3.12 (m, 3H), 4.75-4, 95 (m, 2H), 7.07 (d, 2H, J = 8), 7.27 (d, 2H, J = 8) 123 CH ₃ CH ₃ 4-Br oily substance 1.00 (s, 3H), 1.03 (s, 3H), 1.13-1.77 (m, 5H), 2.30-3.10 (m, 2H), 4.63 -4.80 (m, 2H), 6.83-7.40 (m, 4H) 124 CH ₃ CH ₃ 4-F oily substance 1.00 (s, 3H), 1.07 (s, 3H), 1.13-2.00 (m, 4H), 2.00-3.13 (m, 3H), 4.72 ^ 1, 90 (m, 2H), 6.70-7.28 (m, 4H) 125 CH ₃ CH ₃ 2,4-Cl ₂ oily substance 1.07 (s, 3H x 2), 1.27-1.80 (m, 4H), 2.43-3.18 (m, 3H), 4.72-4.88 (m, 2H), 7.05-7.37 (m, 3H) 126 CH ₃ CH ₃ 4-CH ₃ oily substance 1.03 (s, 3H), 1.07 (s, 3H), 0.66-1.90 (m, 5H), 2.17-3.13 (m, 2H), 4.83 (bs , 2H), (7.07 s, 4H) 127 CH ₃ CH ₃ 4-tC ₄ H ₉ oily substance 1.03 (s, 3H), 1.08 (s, 3H), 1.30 (s, 9H), 1.36-1.86 (m, 4H), 2.20-3.13 (m, 3H), 4.76-4.93 (bs, 2H), 7.07 (d, 2H, J = 8), 7.27 (d, 2H, J = 8) 128 CH ₃ CH ₃ 4-C ₆ H ₅ oily substance 1.03 (s, 3H), 1.10 (s, 3H), 1.10-1.92 (m, 4H), 2.17-3.17 (m, 3H), 4.83 (bs, 2H), 7.08-7.70 (m, 9H) 129 C ₂ H ₅ H 4-CI oily substance 0.93 (t, 3H, J = 7), 1.08-3.08 (m, 10H), 4.76 - ^, 93 (m, 2H), 6.97-7.37 (m , 4H) 130 1-C ₃ H ₇ H 4-CI oily substance 0.60 (d, 3H, J = 8), 0.70 (d, 3H, J = 8), 0.87-2.97 (m, 9H), 4.57-4.83 (m, 2 H), 6.77-7.20 (m, 4H) 131 C ₂ H ₅ C ₂ H ₅ 4-CI oily substance 0.63-1.05 (m, 6H), 1.05-1.93 (m, 8H), 2.13-3.13 (m, 3H), 4.80 (dd, 2H, J = 12.2) 6.95-7.33 (m, 4H) 132 CH ₃ C ₂ H ₅ 4-CI oily substance 0.63-1.10 (m, 6H), 1.10-1.80 (m, 6H), 2.23-3.13 (m, 3H), 4.67-4.87 (m, 2H ), 7.03 (d, 2H, J = 9), 7.23 (d, 2H, J = 9)

table

-X

_Qj_j- ά -p Л ({у) (cyclopentanone derivatives)

Residues in formula (IV)

binding

No. R ¹ R ² X _n

Physical property

NMR spectrum (CDCI ₃ -opprn)

CH,

CH ₃ 4-CI

oily substance BP 124 ⁰ C (1 mm Hg)

0.83 (s, 3H), 1.05 (s, 3H), 1.52-1.83 (m, 4H), 2.25-3.17 (m, 3H), 6.97 ( d, 2H, J = 8), 7,17 (d, 2H, J = 8)

CH ₃

CH ₃ 4-Br

oily substance BP131-132 ° C (0.7 mm Hg)

0.87 (s, 3H), 1.07 (s, 3H), 1.17-3.27 (m, 7H), 6.83-7.53 (m, 4H)

CH ₃

CH, 4-F

oily substance BP 95-98 ⁰ C (0.7 mm Hg)

0.85 (s, 3H), 1.07 (s, 3H), 1.20-3.23 (m, 7H), 6.73-7.27 (m, 4H)

CH ₃

CH ₃ 2,4-Cl ₂

oily substance BP 142-146 ⁰ C (1,5mm Hg)

0.90 (s, 3H), 1.05 (s, 3H), 1.3-2.07 (m, 4H), 2.23-3.40 (m, 3H), 7.0-7, 32 (m, 3H)

CH ₃

4-CI Oily substance BP 120-145 ⁰ C (3 mm Hg)

0.97, 0.08 (2d, 3H, J = 7, J = 6), 1.20-3.27 (m, 8H), 7.03 <d, 2H, J = 7), 7, 19 (d, 2H, J = 7)

CH ₃

CH ₃ oily substance BP93-94 ⁰ C (0.3 mm Hg)

0.87 (s, 3H), 1.03 (s, 3H), 0.83-3.23 (m, 7H), 7.07 (s, 5H)

CH ₃ CH ₃ 4-CH ₃ oily 0.87 (s, 3H), 1.07 (s, 3H), 1.20-3.20 (m, 7H), 2.27 (s, 3H),

Substance 7.70 (s, 4H)

CH ₃

CH ₃

2-F-4-CI oily substance BP102-104 ⁰ C (0.3 mm Hg)

0.89 (s, 3H), 1.05 (s, 3H), 1.32-3.49 (m, 7H), 6.83-7.21 (m, 3H)

CH ₃

CH ₃ 44-C ₄ H ₉

oily substance BP132-140 ⁰ C (1,0mmHg)

0.80 (s, 3H), 1.04 (s, 3H), 1.26 (s, 9H), 1.37-3.21 (m, 7H), 6.95 (d, 2H, J = 8.4), 7.18 (d, 2H, J = 8.4)

CH ₃

CH ₃ 4-C ₆ H ₅

Solids 0.87 (s, 3H), 1.03 (s, 3H), 1.17-3.40 (m, 7H), 7.00-7.67

HP63-66 ° C (m, 9H)

C ₂ H ₆ H

4-CI oily substance BP 135-145 ⁰ C (0.65 mm Hg)

0.89 (t, 3H, J = 7), 1.10-3.28 (m, 10H), 7.05 (d, 2H, J = 9), 7.27 (d, 2H, J = 9)

C ₇ H = H

4-F oily substance BP102-108 ° C (0.2 mm Hg)

0.70-1.10 (m, 3H), 1.20-3.28 (m, 10H), 6.70-7.25 (m, 4H)

C ₂ H ₅ H

4-Br Oily substance BP126-128 ° C (0.5 mm Hg)

0.87 (t, 3H, J = 7), 1.10-3.40 (m, 10H), 6.97 (d, 2H, J = 8), 7.32 (d, 2H, J = 8th)

C ₂ H ₅ H

2,4-Cl ₂ oily substance BP178-179 ⁰ C (4 mm Hg)

0.90 (t, 3H, J = 7), 1.10-3.60 (m, 10H), 7.13-7.30 (m, 3H)

Table 4 (continued)

Residues in formula (IV)

binding

No. R ¹ R ² X _n

Physical property

NMRS spectrum (CDCI ₃ -5ppm)

C ₅ H

4-tC ₄ H ₉

oily substance BP132X (0.5 mm Hg)

0.87 (t, 3H, J = 7), 1.00-3.30 (m, 10H), 6.87-7.43 (m, 4H)

C ₂ H ₅ H

4-C ₆ H ₅

Solid HP 72-75 ° C

0.70-1.07 (m, 3H), 1.13-3.30 (m, 10H), 6.98-7.65 (m, 9H)

nC ₃ H ₇ H

4-CI

oily substance BP150-160 ⁰ C (3 mm Hg)

0.66-1.08 (m, 3H), 1.08-3.26 (m, 12H), 7.04 (d, 2H, J = 9), 7.24 (d, 2H , J = 9)

iC ₃ H ₇ H

4-CI

oily substance BP 143-149 ° C (1,2mm Hg)

0.60-1.07 (m, 6H), 1.07-3.27 (m, 9H), 6.83-7.27 (m, 4H)

nC ₄ H ₉ H

4-CI

oily substance BP 146-149 "C (0.6 mm Hg)

0.87 (t, 3H, J = 7.0), 1.03-3.28 (m, 14H), 7.02 (d, 2H ₁ J = 9.0), 7.25 (i.e. , 2H, J = 9.0)

Fi-C ₅ H ₁₁ H

4-CI

oily substance BP135-137 ⁰ C (0.06 mm Hg)

0.87 (t, 3H, J = 7.0), 1.10-2.50 (m, 14H), 2.53-3.10 (m, 2H), 7.08 (d, 2H , J = 8.3), 7.24 (d, 2H, J = 8.3)

C ₂ H ₅ C ₂ H ₅ 4-CI

oily substance

0.57-1.07 (m, 6H), 1.07-3.27 (m, 11H), 6.95-7.37 (m, 4H)

JC ₄ H ₉ H

4-CI

oily substance BP130-136 ⁰ C (0.3 mm Hg)

0.85 (d, 3H, J = 6), 0.90 (d, 3H, J = 6), 1.10-3.33 (m, 11H), 7.00 (d, 2H , J = 9), 7.21 (d, 2 H, J = 9)

CH ₃

C ₂ H ₅ 4-CI

oily substance BP 123-130 ⁰ C (0.2 mm Hg)

0.57-1.07 (m, 6H), 1.17-3.23 (m, 9H), 7.00 (d, 2H, J = 9), 7.20 (d, 2H, J = 9)

table

Leftovers in ^H 2 \ J CO ₂ R (V) Physika (Esters of cyclopentanecarboxylic acid) R ² Formula (V) lische property CH ₃ X _n R oily substance BP 142-143 ⁰ C (0.7 mm Hg) 4-CI CH ₃ NMRS spectrum (CDCI ₃ 5ppm) encryption 0.72 (s, 3H), 1.05 (s, 3H), 1.37-2.40 (m, 4H), 3.13 (s, 2H), 3.70 (s, 3H), 7 , 07 (d, 2H, J = 9), 7,27 (d, 2 H, J = 9) Contact No. R ¹ 156 CH ₃

157 CH ₃ CH ₃ 4-Br CH ₃ oily substance 0.70 (s, 3H), 1.03 (s, 3H), 1.25-2.43 (m, 4H), 3.07 (s, 2H), 3.63 (s, 3H), 6.80-7.53 (m, 4H) 158 CH ₃ CH ₃ 4-F CH ₃ oily substance 0.70 (s, 3H), 1.08 (s, 3H), 1.20-2.57 (m, 4H), 3.13 (s, 2H), 3.67 (s, 3H), 6 , 73-7.37 (m, 4H)

CH ₃ CH ₃ 2,4-Cl ₂ CH ₃

oily substance BP130-133 "C (0.60 mm Hg)

0.70 (s, 3H), 1.05 (s, 3H), 1.20-2.45 (m, 4H), 3.10 (s, 2H), 3.65 (s, 3H), 7 , 05-7.30 (m, 3 H)

Table 5 (continued)

encryption

Bond No. R ¹

Restein formula (V)

Physical property

N M R spectrum

160 CH ₃

4-CI

oily substance BP142-145 ⁰ C (0.1 mm Hg)

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 (d, 2H, J = 8)

161 CH ₃ CH ₃ H CH ₃ oily substance 0.67 (s, 3H), 1.03 (s, 3H), 0.77-3.23 (m, 4H), 3.10 (s, 2H), 3.63 (s, 3H), 7 , 07 (s, 5H) 162 CH ₃ CH ₃ 4-CH ₃ CH ₃ oily substance 0.70 (s, 3H), 1.03 (s, 3H), 1.13-2.40 (m, 4H), 2.27 (s, 3H), 3.07 (s, 2H), 3.67 (s, 3H), 6.97 (s, 4H) 163 CH ₃ CH ₃ 2-F-4-CI CH ₃ oily substance 0.79 (s, 3H), 1.09 (s, 3H), 1.18-2.61 (m, 4H), 3.00 (d, 1H, J = 14), 3.33 (d, 1H, J = 14), 3.70 (s, 3H), 6.89-7.32 (m, 3H) 164 CH ₃ CH ₃ 4-TC ₄ H ₉ CH ₃ oily substance 0.68 (s, 3H), 1.05 (s, 3H), 1.26 (s, 9H), 1.32-2.62 (m, 4H), 3.10 (bs, 2H) , 3.68 (s, 3H), 7.01 (d, 2H, J = 8.6), 7.26 (d, 2H, J = 8.6) 165 CH ₃ CH ₃ 4-C ₆ H ₆ CH ₃ Solid mp. 95-98 ⁰ C 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)

C ₂ H ₅ H 4 -Cl C ₂ H

oily substance BP152-160 ⁰ C (0.45 mm Hg)

0.67-1.03 (m, 3H), 1.20 (τ, 3H, J = 7), 1.45-2.53 (m, 9H), 3.03.3.08 (2 s, 2H), 4.10 (q, 2H, J = 7), 6.98 (d, 2H, J = 9), 7.20 (d, 2H, J = 7)

C, H. H

4-F

oily substance BP144-154 ⁰ C (3.0 mm Hg)

0.63-1.10 (m, 3H), 1.21-2.68 (m, 7H), 3.07.3.11 (2s, 2H), 3.66 (s, 3H), 6 , 70-7.22 (m, 4H)

C ₂ H ₅ H 4-Br CH ₃

oily substance BP149-151 ⁰ C (0.5 mm Hg)

0.60-2.90 (m, 10H), 3.07.3.12 (2s, 2H), 3.67 (s, 3H), 7.06 (d, 2H, J = 8, 0), 7.42 (d, 2H, J = 8.0)

169 C ₂ H ₅ H 2,4-Cl ₂ CH ₃

oily substance BP143X (0.5mm Hg)

0.67-2.82 (m, 10H), 3.10 (d, 0.4H, J = 14), 3.15 (d, 0.6H, J = 16), 3.45 (d, 0 , 4H, J = 14), 3.50 (d, 0.6H, J = 14), 3.68 (s, 3H), 7.08 (m, 2H), 7.30 (m, 1 H)

170 C ₂ H ₆ H 4-TC ₄ H ₉ CH

oily substance BP152-156 ⁰ C (0.2 mm Hg)

0.72-2.52 (m, 10H), 1.27 (s, 9H), 3.09 (bs, 2H), 3.65 (s, 3H), 6.79-7.39 (m, 4H)

171 C ₂ H ₅ H 4-C ₆ H ₅ CH ₃ Solid mp. 52-54 ⁰ C 0.61-1.10 (m, 3H), 1.45-2.50 (m, 7H), 3.11.3.16 (2s, 2H), 3.66 (s, 3H), 6 , 96-7.61 (m, 9H) 172 nC ₃ H ₇ H 4-CI C ₂ H ₅ oily substance 0.54-1.08 (m, 3H), 1.22 (τ, 3H, J = 7.4), 1.08-2.61 (m, 9H), 3.08.3.13 (2s, 2H), 4.15 (q, 2H, J = 7.4), 7.06 (d, 2H, J = 9.8), 7.27 (d, 2H, J = 9.8 )

173 nC ₄ H ₉ H 4-CI CH ₃

oily substance BP160-172 ⁰ C (0.3 mm Hg)

0.85 (τ, 3H), 0.97-2.12 (m, 11H), 3.03.3.03.03.08 (2 s, 2H), 3.62 (s, 3H) , 6.92 (d, 2H, J = 8), 7.13 (d, 2H, J = 8)

174 nC ₅ H "H 4-CI CH ₃

oily substance BP185-186 ° C (0.25 mm Hg)

0.86 (τ, 3H), 0.98-2.32 (m, 13H), 3.05-3.16 (m, 2H), 3.69, 3.71 (2s, 3H) , 7.04 (d, 2H, J = 8.3), 7.22 (d, 2H, J = 8.3)

175 C ₂ H ₅ C ₂ H ₅ 4-CI CH ₃ oily substance 0.50-2.63 (m, 14H), 2.90 (d, 1H, J = 14), 3.27 (d, 1H, J = 14), 3.67 (s, 3H), 6.93-7.37 (m, 4H) 176 iC ₃ H ₇ H 4-CI CH ₃ oily substance 0.58-1.10 (m, 6H), 1.10-3.01 (m, 6H), 3.08.3.12 (2s, 2H), 3.71 (s, 3H), 6, 84-7.30 (m, 4H) 177 iC ₄ H ₉ H 4-CI CH ₃ oily substance 0.82 (d, 3H, J = 6), 0.89 (d, 3H, J = 6), 1.04-3.00 (m, 8H), 3.07.3.11 ( 2s, 2H), 3.69 (s, 3H), 6.77-7.24 (m, 4H)

CH ₃

C ₂ H ₅

4-CI

oily substance BP145-155 ⁰ C (0.6 mm Hg)

0.58-1.17 (m, 6H), 1.17-2.87 (m, 6H), 3.05.3.12 (2s, 2H), 3.70 (s, 3H), 7 , 03 (d, 2H, J = 9), 7.25 (d, 2H, J = 9)

The NMR spectra of the compounds in Tables 1 to 5 were measured using TMS as an internal standard. The abbreviations used in the specifications of the spectra mean:

s single «, d doublet.t triplet, q quartet, m multiplier, b broadband and j coupling constant (Hz).

The infrared absorption spectra of each of the azole derivatives of the present invention exemplified in Table 1 are shown in the attached Figures 1 to 76.

With regard to the plant disease-effect effects and the plant growth activities, of the compounds of the formula (I) according to the invention, those with the following radicals are especially preferred:

R ^{1 is} hydrogen or (C ₁ -C ₄ -alkyl);

R ^{2 is} hydrogen or (C ₁ -C ₃₎ alkyl wherein R ¹ and R ^{2 are} not simultaneously hydrogen; X is halogen, substituting the benzene ring in the 4-position;

A is nitrogen or CH; and

R ¹ and R ^{2 are} each hydrogen or (С, -Сз) -АІкуІ (but not R ¹ and R ^{2 are} both hydrogen) X is halogen, substituting the benzene ring in the 4-position;

A nitrogen, and

Of the compounds of Table 1, the following are preferred: Nos. 1-3, 5, 9-11, 16, 18, 29-32, 37, 38, 42-45, 50, 59, 62, 63, 65, and 69 ,

The azole derivatives according to the invention are obtained according to the method described below:

The sought Azo I-Deri vat of formula (I) can be obtained by reacting the oxirane derivative of the formula (II) with a 1,2,4-triazole or imidazole of the following formula (IV) in the presence of a diluent:

MN

(IV),

in which formula M is hydrogen or an alkali metal and A is nitrogen or CH.

The oxirane derivative of the formula (II) used as the starting material can be obtained by a method in which the cyclopentanone of the formula (IV) is reacted with sulfonium ylide or oxosulfonium ylide, for example, dimethyl oxosulfonium methylide or dimethylsulfonium methylide in the presence of a diluent. The method required for this purpose is described in Org. Syn. 49, 78 (1968) and in J. Amer. Chem. Soc., (1965) 1353; while the oxirane derivative of the formula (II) is obtained. (This method is hereinafter referred to as method A). Another synthesis for the preparation of the desired oxirane derivative (hereinafter referred to as method B) is the reaction of a cyclopentanone of the formula (IV) by means of the Wittig reaction, wherein a Methylencyclopentan the Formula (III) is obtained. The said reaction is z. As described in Org. Syn. 40, 66 (1966) and J. Org. Chem. 28, 1280 (1963). From the compound thus obtained, the oxirane derivative of the formula (II) can then be obtained by an epoxidation reaction (see Org. Syn. Coll. Vol., 4, 552 (1963), 49, 62 (1969).

The reaction schemes of the above methods A and B will now be described in detail. Process for the preparation of the oxirane derivative of the formula (II):

, 1 О

Di methyl oxiramide methyl id or

Dimethylsulfonium methyl id

Wittig reaction

CH.

epoxidation

2У

r-CH

(III)

Further, the cyclopentane derivative of the formula (IV) can be obtained according to the following method:

When R ¹ and R ² in the compound of the formula (IV) are the same (C 1 -C ₅ ) -alkyl, a cyclopentanone of the formula (VII) is dialkylated and thus converted into an ester derivative of the cyclopentanecarboxylic acid of the formula (V) , This ester derivative is now subjected to hydrolysis and decarboxylation. At the same time, in the case where R ¹ or R ^{2 is} a (C ₁ -Cs) alkyl and the other radical is hydrogen, the desired benzyl is introduced into the alkylcyclopentane-carboxylic acid derivative of formula (VIII) so as to To obtain ester derivative of the cyclopentanecarboxylic acid of the formula (V); then the resulting ester derivative is subjected to hydrolysis and decarboxylation. Thereby, the cyclopentanone derivative of the formula (IV) is obtained.

If in the compound of the formula (IV) for R ¹ and R ² each two different (C ₁ -Cs) -AIkYl should be present, after introduction of the various (C, -C ₅ ) -alkyl in an ester derivative of the Cyclopentanecarboxylic acid of the formula (V) in which either R ¹ or R ^{2 is} a (C ¹ -C ₅ ) -alkyl and the other radical is hydrogen, the resulting ester derivative is hydrolyzed and decarboxylated. Even so, finally, the desired derivative of the formula (IV) is obtained.

The reactions described above are summarized in the following scheme.

Synthesis of the cyclopentanone derivatives of the formula (IV):

alkylation

(VII)

benzylation

(V)

hydrolysis

and

decarboxylation

(VIII)

(IV)

It should be noted that the compounds of formulas (VII) and (VIII) mentioned above are known per se and from alkyl esters of 2-oxocyclopentanecarboxylic acid by the method described in Org. Syn. 45, 7 (1965) and J. Org Chem. 29, 2781

(1964) can be obtained.

Suitable diluents to be used in the preparation process for obtaining the azole derivatives of the formula (I) are, in particular, the following substances: hydrocarbons such as benzene, toluene, xylene, etc .; Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc .; Alcohols such as methanol, ethanol, etc .; Ethers such as diethyl ether, diis propylene, tetrahydrofuran, dioxane, etc .; but also others such as acetonitrile, acetone, dimethylformamide, dimethylsulfoxide

Further, the process for producing the azole derivatives of the present invention is carried out so that the reaction is carried out in the presence of a base or an acid in addition to the above-mentioned diluent. As the base can be used: alkali metal carbonates such as sodium carbonate, potassium carbonate, etc .; Alkali metal hydroxides such as sodium hydroxides, potassium hydroxide, etc .; Alkyl metal alcoholates such as sodium methylate, sodium ethylate, tertiary potassium butylate, etc .; Alkyl metal hydrides such as sodium hydride, potassium hydride, etc .; Alkyl compounds of alkali metals such as n-butyl-lithium, etc. As further possible bases are to be indicated: triethylamine and pyridine.

Acids which can be used in the process of the invention include the following groups or compounds: inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, etc., but also organic acids such as formic acid, acetic acid, butyric acid, p-toluenesulfonic acid, etc.

In order to improve the preparation of the azole derivatives according to the invention with respect to the equilibrium, it is appropriate, in the case of the preparation of the ester derivative of the cyclopentanecarboxylic acid of the formula (V) halogenated ^ alkyls or a substituted benzyl halide with the compound of formula (VII) or ( VIII), the latter being dissolved in a diluent / solvent and the reaction carried out if necessary in the presence of a base. The reaction temperature may be selected within the range of the diluent / solvent solid points to the boiling point of said material, but preferably between 0 and 100 ^° C.

The derivatives of the formula (IV) can be obtained by subjecting the ester derivative of the cyclopentanecarboxylic acid of the formula (V) to decarboxylation at temperatures between 80 and 150 ^° C., in the presence of inorganic or organic acids. The treatment takes between 2 to 24 hours and is advantageously carried out with stirring.

In order to obtain the oxirane derivative of the formula (II) by the method A, it is advantageous to give a solution of a ketone of the formula (IV) in the diluent (especially dimethylsulfoxide) to dimethyloxosulfonium methylide or dimethylsulfonium methylide, which are prepared by the equivalent mixing of the base

{For example, sodium hydride) and Trimethyloxosulfoniumiodid or Trimethylsulfoniumiodid, and the two compounds react with each other.

In this case, the amount of dimethyloxosulfonium methylide or dimethylsulfonium methylide is about 1.0 to 2.0 equivalents of the cyclopentanone derivative of the formula (IV). The reaction is advantageously carried out at a temperature between 25 and 100 ⁰ C and during reaction times of 1 to 40 hours.

On the other hand, if the preparation is carried out by the method B, the cyclopentanone derivative of the formula (IV) is added to triphenylphosphine methylide (Wittig reagent). The latter is prepared by mixing equivalent amounts of the base (e.g., sodium hydride) and methyltriphenylphosphonium halide in a diluent / solvent (especially dimethylsulfoxide). The two compounds are then reacted together for 2 to 10 hours, at temperatures between 0 and 100 ^° C. The methylenecyclopentanone derivative of formula (III) thus formed is isolated, dissolved in the diluent / solvent and stored at temperatures of -10 ⁰ C to the boiling point of the diluent / solvent, preferably at temperatures of -10 to 8O ⁰ C, after the addition of hydrogen peroxide or an organic peracid such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, etc. reacted.

The oxirane compound of the formula (II) obtained from the cyclopentanone derivative of the formula (IV) by either Method A or Method B takes the stereoisomeric structures described below with respect to the formation of the oxirane group in FIG Position and the substituted benzyl group in the 7-position of the 1-oxaspiro (2 x 4) heptane of the compound, to:

2 «-0 1

H-A type)

2 r-O 1

--CH.

(M-B type)

The separation of these two stereoisomers of the formulas (H-A) and (M-B) can be carried out, for example, by means of chromatography (especially thin-layer chromatography, column chromatography, HPL chromatography, etc.). The characteristics of the structures of the two isomers can then be determined, for example, from the NMR spectrum. In order to obtain the azole derivative of formula (I), the oxirane compound of formula (II), optionally in the presence of a base, is added to a solution of the azole compound of formula (VI) in a diluent / solvent, or on the other hand, an alkali metal salt of the azole compound is added to a solution of the oxirane compound in a diluent / solvent so as to react the two compounds. The reaction temperature can be selected in the range from the fixed point to the boiling point of the diluent / solvent, but preferably a temperature between 0 and 120 ° C, more preferably temperatures between 60 and 120 ° C. The reaction time is chosen between 1 to 10 hours, with stirring of the mixture.

After completion of the reaction, the obtained reaction mixture is cooled and extracted by means of an organic solvent such as ethyl acetate, chloroform, methylene chloride, benzene and the like in an ice water bath. After separating the organic phase, washing it with water and drying, the solvent is distilled off from the organic phase under reduced pressure. After various purification treatments, the residue is obtained as the compound sought. Re-crystallization methods, gel chromatography on diatomaceous earth, etc. are suitable methods for purification.

Since the compound of the formula (M) is in the form of two isomers (HA) and (MB), and since said compound is the starting compound for the preparation of the azole derivatives of the formula (I), the azole derivative of the formula is also present (I) in the two stereoisomeric forms described below. The compound of the formula (I) is known to be obtained by the reaction of the oxirane compound of the formula (II) with 1,2,4-triazole or imidazole of the formula (VI):

(L-ATyp)

(І-ВТур)

In the representations, the different lines mean the following:

------- = behind the presentation level,

= on the presentation level and

! мм «» - - = in front of the presentation plane.

Of course, the separation of isomers according to formulas (I-A) and (I-B) e.g. be carried out by chromatography.

The effect effects of the azole derivatives (azolylcyclopentanol derivative) of the formula (I) according to the invention as active substance in agricultural and horticultural compositions will now be explained below.

(1) Fungicidal effects against fungal attack of plants:

The azole derivatives according to the invention show controlling effect effects against the following fungal attacks on plants in a broad range.

Pyricularia oryzae on rice, Cochliobolus miyabeanus on rice, Xanthomonas oryzae on rice, Rhizoctonia solani on rice, Helminthosporium sigmoideum on rice, Gibberella fujikuroi on rice, Podosphaera leucotricha on apple, Venturia inaequalis on apple, Sclerotinia mali on apple, Alternaria mali on apple, Valsa mali to apple, Alternaria kikuchiana to pear, Phyllactinia pyri to pear, Gymnosporangium haraeonum to pear, Ventura nashicola to pear, Unccinula necator to grape, Phakospora ampelopsidis to grape, Glomerella cingulata to grape, Erysiphegraminisf.sp.hordei to barley, Rynchosporium 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 melon, Colletotrichum lagenarium on melon, 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 eggplant, Sephaerotheca humuli on strawberries, 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 drupes, Botrytis cinerea on various cereals, Sclerotinia sclerotiorum, etc.

Furthermore, the azole derivatives according to the invention not only show prophylactic modes of action, but also, in various cases of plant diseases, therapeutic effects.

(2) Plant growth regulating activity:

Due to the now known mechanism of plant growth regulation by plant hormones, certain chemical compounds termed plant growth regulator agents have been introduced in the agricultural and horticultural production areas in recent years.

Examples include the production of seedless grapes by gibberellin, the enhancement of rooting of cut seedlings by α-naphthalene acetic acid, and the use of 2-chloroethyltrimethylammonium chloride (tradename CCC) as a growth inhibitor for wheat.

Further, such growth control methods have been extended not only to additional crops such as cereals, vegetables, fruit trees, but also to horticultural crops such as flowers and the like. The use of such plant growth regulators provides the opportunity to also influence the following functions: improvement of rooting, control of flowering and fruiting, increase of fruit, increase of growth and control of growth and metabolism.

Therefore, both the fields of application and the number of substances suitable for the above purposes have become greater in recent years. On the other hand, the present state shows that the practical use of these plant growth regulators has not been as widespread as might have been expected. The azole derivatives of the present invention (azolylcyclopentanol derivatives) show a specificity of various plant regulating activities in a wide range; this is exemplified in the following: i) inhibition of the vegetative growth of the plants, especially inhibition of the height-growth of the plants; ii) increasing the contents of the beneficial components of the plants; and iii) controlling the maturity and flowering time of the plants.

As examples of the growth inhibiting activity according to i), the following applications may be mentioned: inhibition of growth of weeds (herbicidal function) and turf; Preventing the fall of plants, such as rice plants, barley, wheat, etc .; enabling the mechanical harvesting of soybeans and cotton flowers by inhibiting the growth of these plants; the inhibition of additional bud formations to promote growth of the leaves of tobacco plants; the facilitation of pruning hedge plants by inhibiting their growth; the improvement of the market value of ornamental plants by plant growth prevention of the same, etc.

As examples of the application of activity ii) of the compounds of the invention, i. their ability to increase the proportion of beneficial constituents of plants may be mentioned as follows: increasing the quality of sugar beet, sugarcane and citrus fruits by increasing the sugar contained therein; Improving the quality of crops and soybeans by increasing the protein content, etc.

Finally, as examples of the application of the controlling activity iii) regarding the ripening time of fruits and the flowering period, the adjustment of the time of shipment of fresh fruits and flowering flowers to the times when the fruits and flowers are sought can be indicated.

To use the azole derivatives of formula (I) in the form of fungicidal compositions or plant growth regulators, the derivative itself or mixtures thereof and a vehicle or diluent are processed into powders, wettable powders, granulators, emulsifiable concentrates, liquid preparations, etc. These preparations can then be used advantageously.

To the mixtures mentioned can, if necessary and sought after side effects, be given auxiliaries such as distribution aids, emulsifiers, wetting agents, adhesives or others.

It should also be noted that, since the azole derivatives of the formula (I) contain a 1,2,4-triazole ring or an imidazole ring, these azole derivatives also in the form of acid addition salts with inorganic or organic acids or in the form of metal complexes can be used.

Further, it should be noted that since the azole derivatives of the formula (I) according to this invention contain an azolylmethyl, a (C 1 -C 5) -alkyl and a substituted benzyl at the 1-position, the 2-position and the 5-position of the cyclopentane ring, stereoisomers such as geometric isomers of the cis and trans form, and also optical isomers of said compounds, and that the present invention also encompasses these isomers and also all mixtures thereof.

Accordingly, the agricultural and horticultural compositions according to the invention contain such mixtures with individual isomers or mixtures of the isomers as active substance (s).

The azole derivatives of the formula (I) according to the invention have excellent effects on the control of plant diseases, especially due to fungal attack, but also with regard to plant growth regulation; they are also useful as active ingredients in agricultural and horticultural compositions.

The effectiveness of the present invention will now be outlined below by concrete examples of the agricultural and horticultural compositions containing the azole derivatives of the present invention as the active ingredient. However, the present invention is by no means limited to the following examples insofar as the essentials thereof are not exceeded.

embodiments

The examples of preparation of the azole derivatives of the formula (I) and all intermediates for the preparation of the mentioned

Derivatives.

example 1 Preparation of methyl 1- (4-chlorobenzyl) -3,3-dimethyl-2-oxocyclopentanecarboxylate (= Intermediate No. 156 in U.S.P. Table 5)

In 150 ml of anhydrous benzene was added 5.0 g of sodium hydride (obtained by washing 60% oily sodium hydride with anhydrous benzene) under stirring and under helium atmosphere. Further 50g methyl-1 were included in this mixture was added (4-chlorbenzyD-2-oxocyclopentanecarboxylate and the whole mixture was stirred at 80 ⁰ C for 40 minutes. After cooling the reaction mixture to room temperature, the same dropwise with 29,4g of methyl iodide and the thus obtained

Mixture for 2 hours at 80 ⁰ C stirred. After cooling the reaction mixture to room temperature, 5.0 g of sodium hydride (one equivalent) was added and the reaction mixture stirred for 30 minutes at 80 ⁰ C. After cooling to room temperature, it was finally treated with 29.4 g of methyl iodide (one equivalent) and the resulting

Reaction mixture for 8 hours at 80 ⁰ C stirred.

After cooling the reaction mixture thus obtained, it was added to a mixture of acetic acid and ice-water.

The whole mixture was then extracted by means of ethyl acetate to obtain an organic phase. After washing the obtained organic phase with an aqueous solution of sodium hydrogencarbonate and then with a saline solution, the thus washed organic phase was dried over anhydrous sodium sulfate and the solvent was taken out therefrom

distilled off reduced pressure.

After distilling the residue under reduced pressure and purifying it, 44.8 g of the title compound were obtained

with a boiling point of 142-143T at 0, 7mmHg.

Example 2 Preparation of S - ^ - ChlorobenzyO ^^ - dimethyM-cyclopentanone (= Intermediate No. 133 in Table 4)

In 120 ml of a 47% hydrobromic acid, 44.8 g of methyl 1- (4-chlorobenzyl) -3,3-dimethyl-2-

oxocyclopentanecarboxylate (Compound No. 156 in Table 5) and the resulting mixture stirred vigorously at 100 ° C for 12 hours.

After cooling the reaction mixture thus obtained, it was poured into ice-water and extracted with ethyl acetate to obtain an organic phase. After washing this phase with an aqueous solution of sodium hydrogencarbonate and then with an aqueous saline solution, the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent from the phase under reduced pressure, a residue was obtained. Distillation of this residue under reduced pressure and purification thereof gave 31 g of the title compound, which had a boiling point of 124 ° C. at 1 mmHg.

Example 3

Preparation of 5- (4-chlorobenzyl) -2,2-dimethyl-1-methylenecyclopentane (= Intermediate No. 122 in Table 3) In 50 ml of anhydrous dimethylsulfoxide was added 3.6 g of sodium hydride (prepared by washing 60% oily sodium hydride with anhydrous Benzene); the addition was done under helium atmosphere. The mixture thus formed

was then stirred for 30 minutes at 70 ⁰ C. After cooling with ice-water, it was washed with 53.6 g

Methyltriphenylphosphoniumbromid added and the resulting mixture for 30 minutes while cooling with ice water and then the cooled mixture stirred for another 10 minutes at room temperature. Then, to the mixture was added 23.6 g of 5- (4-chlorobenzyl) -2,2-dimethyl-1-cyclopentanone (Compound No. 133 in Table 4), and the whole mixture was allowed to stand for 1 hour

stirred at room temperature and then for 30 minutes at 70 ⁰ C to complete the reaction.

After cooling the reaction mixture, it was poured into ice-water and then extracted with ethyl acetate to obtain an organic phase. After washing this phase with an aqueous saline solution, the thus-washed organic phase was dried over anhydrous sodium sulfate, and the solvent was removed therefrom under reduced pressure

distilled off.

As a residue, an oily and a solid material were obtained. The oily material was extracted with η-hexane and the resulting n-hexane extract was purified by chromatography on a silica gel column. Finally, 22.1 g were obtained

Title compound.

Example 4 Preparation of 7- (4-chlorobenzyl) -4,4-dimethyl-1-oxaspiro (2 4) heptane (Intermediate Nos. 77 and 78 in Table 2;

Method A)

Into 70 ml of anhydrous dimethylsulfoxide, 3 g of sodium hydride (prepared by washing 60% oily sodium hydride with anhydrous benzene) was added thereto with stirring under helium atmosphere. Then, the solution was added with 27.5 g of trimethyloxosulfonium and stirred for 30 minutes at room temperature. To the reaction solution was finally added a solution of 23.6 g of 5- (4-chlorobenzyl) -2,2-dimethyl-1-cyclopentanone (Compound No. 133 in Table 4) in 20 ml of anhydrous dimethylsulfoxide. The addition was slow over a period of 30 minutes. Subsequently, the reaction mixture was stirred at 90 ^° C. for 2 hours.

After allowing the reaction mixture to cool, it was poured into ice-water. The mixture thus obtained was then extracted with ethyl acetate to obtain an organic phase. After washing the organic phase with an aqueous salt solution, the phase was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue thus obtained was purified by chromatography on a silica gel column; 13.95 g of the title compound No.77 and 1.05 g of the title compound of No.78 were thus obtained.

Example 5 Preparation of 7- (4-fluorobenzyl) -4,4-dimethyl-1-oxaspiro (2x4) heptane (Intermediate Nos. 81 and 82 in Table 2;

Method B)

In 170 ml of chloroform was dissolved 17 g of 5- (4-fluorobenzyl) -2,2-dimethyl-1-methylenecyclopentane (Compound No. 124 in Table 3). Into the solution was then added, during the course of 10 minutes, 27.1 g of m-chloroperbenzoic acid and then the mixture was stirred for 2 hours at room temperature. It was then treated with 25.4 g of calcium hydroxide which again took about 10 minutes. Then, the reaction mixture was stirred for 30 minutes at room temperature.

After filtering off the precipitated solids, the chloroform phase of the filtrate was condensed; This gave a colorless oily mass. This oily mass was purified by chromatography on a silica gel column; There were thus obtained 4.5 g of the title compound No. 81 and 8.6 g of the title compound No. 82.

Example 6 Preparation of C 5- (2,4-dichlorobenzyl) -2,2-dimethyl-1- (1 H -imidazol-1-ylmethy-O-r-i-cyclopentanol (Compound No. 15 in Table 1}

In 18 g of anhydrous dimethylformamide was added 996 mg of sodium hydride (obtained by washing 60% sodium hydride in oil with anhydrous benzene) under a helium atmosphere and with stirring. Subsequently, 2.83 g of 1H-imidazole were added to the mixture thus obtained, and the whole was stirred at room temperature until the gas formation was completed. To the resulting solution was added another solution, which second solution was obtained by dissolving 5.93 g of added dropwise 7- (2,4-dichlorobenzyl) -4,4-dimethyl-1-oxaspiro (2'4) heptane (Compound No.83 in Table 2) in 10 ml of anhydrous dimethylformamide. The reaction mixture thus obtained was stirred at 80 ^° C. for 2 hours. After allowing the resulting reaction mixture to cool, it was poured into ice-water and the resulting mixture was extracted with ethyl acetate to obtain an organic phase.

After washing the organic phase with water, the phase was dried over anhydrous sodium sulfate and the solvent was distilled off therefrom under reduced pressure.

The residue thus obtained was purified by chromatography over a silica gel column and additionally recrystallized from a mixture of η-hexane and ethyl acetate. Thus, 2.7 g of the title compound were obtained.

Example 7

Preparation of t-5- (4-chlorobenzyl) -2,2-dimethyl-1- (1Hi ^^) triazoM-ylmethyl-ri-cyclopentanol (Compound No. 2 in Table 1) In 30 ml of anhydrous dimethylformamide was added 5.0 g of 7 - (4-chlorobenzyl) -4,4-dimethyl-1-oxaspiro (2'4) heptane (Compound No.78 in Table 2) and dissolved therein with stirring and under helium atmosphere Sodium salt of 1 H-1,2,4-triazole (Reinhiet 90%, manufacturer Aldrich Co.) was added, whereupon this mixture for 2 hours

was stirred at 70 ⁰ C.

After allowing the reaction mixture to cool, it was poured into ice-water, and the whole mixture was extracted with ethyl acetate to obtain an organic phase. After washing the organic phase with water, it became over

dried anhydrous sodium sulfate and the solvent distilled off therefrom under reduced pressure.

The residue was purified by chromatography on a silica gel column; This gave 3.1 g of the

Title compound.

Example 8 Preparation of 2- (4-chlorobenzyl) -5-methyl-1-cyclopentanone (Intermediate No. 137 in Table 4)

Into 126 ml of anhydrous benzene was added 3.04 g of sodium hydride (recovered by washing 60% sodium hydride in oil with anhydrous benzene), and then the resulting mixture was added with 18 g of methyl S-methyl-oxocyclopentanecarboxylate. After stirring the entire mixture at room temperature for 1 hour, 21.5 g of 4-chlorobenzyl chloride were added thereto, and the resulting mixture was stirred on the oil bath for 6 hours

Reflux temperature of 90 ⁰ C held.

After allowing the reaction mixture to cool, it was extracted with benzene and the benzene phase was then washed with aqueous brine. After drying the benzene phase over anhydrous sodium sulfate, the solvent was distilled off therein under reduced pressure. This gave 33.6 g of a tan, oily material containing methyl 1- (4-

chlorobenzyl) -3-methyl-2-oxocyclopentanecarboxylate (Intermediate No. 160 in Table 5).

Without purifying the ester thus obtained, it was treated with 100 ml of a 47% hydrobromic acid, and the resulting mixture was stirred vigorously at 110 ⁰ C for 18 hours. After allowing the reaction mixture to cool, it was extracted with methylene chloride and the organic phase was washed with an aqueous solution of sodium carbonate and then with brine. The thus washed organic phase was dried over anhydrous sodium sulfate

and distilling off the solvent therefrom under reduced pressure.

The residue thus obtained was purified by vacuum distillation; 17.4 g of the title compound were obtained.

Example 9

Preparation of methyl 1- (4-chlorobenzyl) -3-ethyl-3-methyl-2-oxocyclopentanecarboxylate {interm. No. 178 in

Table 5)

Into 80 ml of anhydrous tetrahydrofuran was added 1.7 g of sodium hydride (obtained by washing 60% sodium hydride in oil with anhydrous benzene); the addition was done with stirring and under helium atmosphere. To the resulting mixture was then added 18.2 g of methyl 1- (4-chlorobenzyl) -3-methyl-2-oxocyclopentanecarboxylate (Intermediate No. 160 in Table 5), and the resulting mixture was stirred for 2 hours at room temperature. Subsequently, the mixture was treated dropwise with 11.1 g of ethyl iodide, wherein the temperature of the mixture was maintained at temperatures between 20 ⁰ C and 30 ⁰ C. The mixture was then stirred again for 1 hour at temperatures between 20 ⁰ C and 30 ⁰ C, followed by stirring for another hour, but this time at 60 ⁰ C After allowing the reaction mixture to cool, it was added to a mixture of acetic acid and ice water and then this whole mixture is extracted with ethyl acetate to obtain an organic phase. After washing this organic phase with an aqueous solution of sodium hydrogencarbonate and then with aqueous saline, the thus washed organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off therefrom under reduced pressure

 The residue thus obtained was purified by means of vacuum distillation; This gave 15 g of the title compound.

Example 10

Preparation of 4- (4-chlorobenzyl) -7-methyl-1-oxaspiro (2'4) heptane (Intermediate No. 85 in Table 2)

Into 37 ml of anhydrous dimethyl sulfoxide was added 1.44 g of sodium hydride (obtained by washing 60% oily sodium hydride with anhydrous benzene); the addition was done with stirring and under helium atmosphere. To the resulting mixture was then added 13.2 g of trimethyloxosulfonium iodide and the resulting mixture was stirred for 30 minutes at room temperature. Then, a solution was prepared from 12.2 g of 2- (4-chlorobenzyl) -5-methyl-1-cyclopentanone (Compound No. 137 in Table 4) in 12 ml of anhydrous dimethylsulfoxide; this second solution was added slowly to the first solution over a period of 10 minutes and the whole was stirred for 4 hours at room temperature.

The reaction solution thus obtained was poured into ice-water, and this new mixture was extracted by means of methylene chloride to obtain

to obtain an organic phase. After washing the organic phase with an aqueous saline solution, it became over

dried anhydrous sodium sulfate and the solvent distilled off therefrom under reduced pressure.

The residue thus obtained was purified by means of chromatographic separation over silica gel column; you got like that

6.67g of the title compound.

In addition, 3 more isomers of the title compound were isolated, 0.15 g of Intermediate Compound No.86,0,16g of Intermediate Compound No.87, and 0,16 g of Intermediate Compound No.88, all in Table 2.

Example 11 Preparation of 4- (4-chlorobenzyl) -7-ethyl-1-oxaspiro (2'4) heptane (Intermediate Nos. 93,34,95 and 96 in Table 2)

In 100 ml of chloroform was dissolved 8.0 g of 2- (4-chlorobenzyl) -5-ethyl-1-methylenecyclopentane (Compound No. 129 in Table 3). The solution was then treated with 11.6 g of m-chloroperbenzoic acid and the whole mixture was stirred for 2 hours at room temperature. Then, while cooling the mixture with ice-water, 11 g of calcium hydroxide were added. The new mixture was again stirred for 30 minutes at room temperature.

The precipitated solid was filtered off and the chloroform phase of the filtrate condensed; This gave a colorless oily mass. The oily mass was purified by chromatographic separation on silica gel column; There were thus obtained 0.7 g of Compound No. 93, 2.4 g of Compound No. 94, 2.2 g of Compound No. 95 and 2.6 g of Compound No. 96; all title links.

Example 12

Preparation of C-2- (4-chlorobenzyl) -5-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) -r-1-cyclopentanol (Compound No. 16 in Table 1) In 10 ml Anhydrous dimethylformamide was added 630 mg of sodium hydride (obtained by washing 60% sodium hydride in oil with anhydrous benzene) and then 1.8 g of 1 H-1,2,4-triazole in the resulting solution. The whole mix

was then stirred at room temperature until gas evolution ceased.

To the resulting reaction mixture was added the following solution: 3.1 g of 4- (4-chlorobenzyl) -7-methyl-1-

oxaspiro (2'4) heptane (Compound No. 85 in Table 2) in 6.2 ml of anhydrous dimethylformamide. The mixture thus obtained

was then stirred at 8O ⁰ C for 1 hour.

After allowing the reaction mixture to cool, it was poured into ice-water. The resulting mixture was then on with

Extracted methylene chloride, so as to obtain an organic layer.

After washing the organic layer with an aqueous saline solution, the former became anhydrous

Sodium sulfate dried and the solvent! distilled off therefrom under reduced pressure.

The residue thus obtained was purified by means of chromatographic separation over silica gel column and further from

a mixture of η-hexane and ethyl acetate recrystallized. Received 2.83 g of the title compound.

Example 13

Preparation of C-2- (4-chlorobenzyl) -5-methyl-1 H -imidazoM-1-methyl-1-cyclopentanol (Compound No. 17 in Table 1) In 10 ml of anhydrous dimethylformamide was added 670 mg of sodium hydride (obtained by washing 60% sodium hydride in oil) and then added 1.9 g of 1 H-imidazole. The resulting mixture was stirred at room temperature until

the gas evolution ceased.

Subsequently, into the mixture was added the following solution: 3.3 g of 4- (4-chlorobenzyl) -7-methyl-1-oxaspiro (2'4) heptane (Compound No. 85 in Table 2) in 6.6 ml of anhydrous dimethylformamide. The entire mixture was then for 1 hour

stirred at 80 ° C.

After allowing the reaction mixture to cool, it was poured into ice-water and the resulting mixture was washed with water

Extracted methylene chloride to obtain an organic phase.

After washing the organic phase with an aqueous saline solution, the former became anhydrous sodium sulfate

dried and the solvent distilled off therefrom under reduced pressure.

The residue thus obtained was purified by means of chromatographic separation on silica gel column and further recrystallized from a mixture of η-hexane and ethyl acetate. Finally, 3.16 g of the title compound were obtained.

Examples of the preparation of agrikultureilen and horticultural compositions with fungicidal effects

Example 14

Powder, dust

3 parts by weight of the azole derivative of the present invention (Compound No. 3), 40 parts by weight of clay and 57 parts by weight of talc were mixed and pulverized so as to produce an agriculturally and horticulturally fungicidal composition

To obtain powder form.

The composition thus obtained is applied by sputtering.

Example 15

Wettable powder

50 parts by weight of the azole derivative according to the present invention (Compound No. 1), 5 parts by weight of a salt of lignin sulfonic acid, 3 parts by weight of a salt of an alkylsulfonic acid and 42 parts by weight of silica were mixed and

powdered to obtain a wettable powder.

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

Example 16

granules

5 parts by weight of the azole derivative according to the invention (compound No. 16), 43 parts by weight of bentonite, 45 parts by weight of clay and 7 parts by weight of a salt of lignosulfonic acid were homogeneously mixed and, after water had been added to the mixture, the mass was kneaded and extruded in granulated form. After drying the granules, the composition was in the form mentioned.

Example 17

Emulsifiable concentrate

20 parts by weight of the azole derivative according to this invention (Compound No. 13), 10 parts by weight of a polyoxyethylene alkylaryl ether, 3 parts by weight of a polyoxyethylene sorbitan monolaurate, and 67 parts by weight of xylene were homogeneously mixed so as to obtain the compositions in an emulsifiable, concentrated form.

(III)

Examples of applications of the agricultural and horticultural fungicidal compositions according to this invention

to combat plant diseases.

Example 18

Investigation of the effect against Erysiphe graminis f. sp. tritici of wheat.

On young seedling seedlings (variety: NORIN NR.64, 16 seedlings per pot, 3 pots per assay), which seedlings were grown in unglazed pots of 10 cm diameter were diluted with a dilute wettable powder such as that of Example 15 (Figs with water to a predetermined concentration), treated; in each case 5 ml of concentrate per pot were injected. After the applied suspension had dried, the plants were washed with a suspension of the summer spores of Erysiphe graminis f. sp. tritici treated. These had been obtained from appropriately diseased wheat leaves. DieTöpfewurdendann24 hours maintained at temperatures of 20 ⁰ C to 24 ⁰ C under high humidity and then stored in a greenhouse. On the day after 9 to 11 days of inoculation, the degree of infestation on the seedlings was examined. This test was carried out according to the criteria of examination given below, and the control value of the fungicidal composition was calculated according to the following formula;

investigation criteria

Degree of infestation incidence of the disease

0 not attacked

0.5 less than 10% of the area attacked

1 10% to 20% of the area attacked

2 20% to 40% of the area attacked

3 40% to 60% of the area attacked

4 60% to 80% of the area attacked

5 over 80% of the area attacked

., и χ /. Degree of infestation during treatment \ ", ,,

Control value = I 1 ---- zr - ^ - r-rr; lx 100 (%)

Degree of infestation in comparison I The results of the tests are summarized in Table 6 below. Table 6

Investigated compound (No. according to Table 1) Concentration (ppm) Control value (%) 1 125 100 2 125 100 3 125 95 4 125 100 5 125 100 6 125 100 7 125 95 8th 125 95 9 125 100 10 125 100 11 125 100 12 125 90 13 125 100 14 125 100 15 125 95 16 125 100 17 125 95 18 125 100 19 125 100 20 125 50 21 125 100

Investigated link (No. according to Table D Concentration (ppm) Control value (%) 22 125 100 23 125 100 24 125 100 25 125 100 26 125 100 27 125 100 28 125 100 29 125 100 30 125 100 31 125 100 32 125 100 33 125 100 34 125 100 35 125 100 36 125 100 37 125 100 38 125 100 39 125 100 40 125 100 41 125 100 42 125 100 43 125 95 44 125 100 45 125 100 46 125 95 47 125 100 48 125 100 49 125 100 50 125 100 51 125 100 52 125 100 53 125 75 54 125 100 55 125 100 56 125 100 57 125 100 58 125 100 59 125 100 60 125 100 61 125 100 62 125 100 63 125 100 64 125 100 65 125 100 66 125 100 67 125 100 68 125 100 69 125 100 70 125 100

Investigated compound (number according to Ta at Ie 1) Concentration (ppm) Control value (%) 71 125 100 72 125 100 73 125 100 74 125 100 75 125 100 76 125 100 Commercially available agent Triadimephone * ¹ 125 100 Comparison (not treated) 0

* 'The commercially available product Triadimephon contains, as an active substance, the compound according to the following formula:

Example 19

Investigation of the effect against Sphaerotheca fuliginae on cucumbers.

On cucumber plants in the second leaf stage (variety: SAGAMI HAMPAKU, one plant per pot, 3 pots per examination),

which plants were grown in 10 cm diameter unglazed pots, 5 ml each of a diluted, wettable powder such as that of Example 15 diluted with water to a given concentration was injected. After the suspension had dried in air, the plants were contacted with Sphaerotheca fuliginea spores.

These spores were brushed on infested cucumber leaves. The inoculated plants were then in the greenhouse

given.

On the day after 9 to 11 days of inoculation, the degree of infestation on the cucumber plants was examined according to the criteria of examination defined below. At the same time, the control value for the fungicidal composition according to the

calculated below following formula:

Examination criteria:

Degree of infestation incidence of the disease

0 not attacked

0.5 less than 10% of the area attacked

1 10% to 20% of the area attacked

2 20% to 40% of the area attacked

3 40% to 60% of the area attacked

4 60% to 80% of the area attacked

5 attacked over 80% of the area

Control value = (i - degree of infestation during treatment \

V degree of infestation in comparison / ^{Іищ / о} '

The results of the investigations are summarized in the following Table 7.

Table 7

Investigated link (No. according to Table D Concentration (ppm) Control value (%) 1 125 100 2 125 100 3 125 100 4 125 100 5 125 100 6 125 100 7 125 100 8th 125 100 9 125 100 10 125 100 11 125 100 12 125 100 13 125 100 14 125 100 15 125 100 16 125 100 17 125 100 Commercially available agent Triadimephone * ' 125 100 Comparison (not treated) 0

Example 20

Investigation of the effect against Puccinia recondita on wheat.

On young wheat seedlings in the second leaf stage (variety: NORIN No.64, 16 seedlings per pot, 3 pots per examination),

which seedlings were grown in unglazed pots of 10cm in diameter were each 5ml per pot one

diluted, wettable powder such as that of Example 15 (diluted with water to a predetermined concentration)

applied by spraying.

After the suspension had dried in air, a suspension of Puccinia recondita summer spores was sprayed on the seedlings in the pots. The spores had been obtained from appropriately infested wheat leaves. The pots were then kept for 24 hours at 20 to 23 ° C and high humidity and then transferred to the greenhouse.

On the day after 7 to 10 days of inoculation, the degree of infestation on the seedlings was examined according to the test criteria given below. At the same time, the control value of the fungicidal composition according to the

also calculated below formulas.

Examination criteria:

Degree of infestation incidence of the disease

0 not attacked

0.5 less than 10% of the area attacked

1 10% to 20% of the area attacked

2 20% to 40% of the area attacked

3 40% to 60% of the area attacked

4 60% to 80% of the area attacked

5 attacked over 80% of the area

"" ,, / "degree of infestation in treatment \ _нлл ,,.

Control value = (1 -) χ 100%

\ Degree of infestation in comparison /

The results of the investigations are summarized in Table 8 below. Table 8

Investigated compound (No. according to Table 1) Concentration (ppm) Control value (%) 1 125 100 2 125 95 3 125 100 4 125 95 5 125 100 6 125 100 7 125 100 8th 125 95 9 125 100 10 125 100 11 125 100 12 125 95 13 125 100 14 125 100 15 125 100 16 125 100 17 125 95 18 125 100 19 125 100 21 125 100 22 125 100 23 125 100 24 125 70 25 125 100 26 125 95 27 125 100 28 125 100 29 125 100 30 125 100 31 125 100 32 125 100 33 125 100 34 125 100 35 125 100 36 125 100 37 125 100 38 125 100 39 125 100 40 125 100 41 125 100 42 125 100 43 125 100 44 125 100 45 125 100 46 125 100 47 125 100 48 125 100

Investigated compound (No. according to Table 1) Concentration (ppm) Control value (%) 49 125 90 50 125 100 51 125 100 52 125 100 53 125 95 54 125 100 55 125 100 56 125 100 57 125 100 58 125 90 59 125 100 60 125 90 61 125 90 62 125 100 63 125 100 64 125 100 65 125 100 66 125 100 67 125 100 68 125 100 69 125 100 70 125 100 71 125 100 72 125 100 73 125 100 74 125 100 75 125 90 76 125 90 Commercially available agent Triadimephone * ¹ 125 95 Comparison (not treated) 0

Example 21

Investigation of the effect against botrytis cinerea on beans (kidney bean).

On the bean plant bed (kidney bean) at the first true leaf stage (variety: HON Kl NTO Kl), which plants were grown in unglazed 10 cm diameter pots, 5 ml per pot of a dilute, wetted powder was like that Example 15, diluted with water to a predetermined concentration, applied by spraying. After the spray liquid had dried, the leaves treated with it were covered with round cutouts of agar with a diameter of 4 mm, which agar contained the fungi Botrytis cinerea. The mentioned Agarnährböden were previously cultured for 3 days at 20 ⁰ C, using a sugar-containing agar medium with potato starch solution was used. These agar slices were applied directly to the middle part of the bean leaves, and the plant was then kept at temperatures of 20 to 22 ° C and under a high humidity. On the third day of inoculation, the area of the disease spot on the treated plants was compared with that of non-pretreated plants. Thus, the degree of infestation could be determined; this was done specifically according to the examination criteria below. The control value of the fungicidal composition was calculated according to the formula below as well

 Examination criteria:

Degree of infestation incidence of the disease

0.5 attack only just under the fungus-containing

Agar and on the peripheral part all around

1 less than 20% of the area attacked

2 20% to 40% of the area attacked

3 40% to 60% of the area attacked

4 60% to 80% of the area attacked

5 over 80% of the area attacked

Control value = (i - degree of infestation in treatment V _χ \ degree of infestation in comparison /

The results of the investigations are summarized in the following Table 9. Table 9

Investigated connection (No. according toTableU Concentration (ppm) Control value (%) 1 500 100 2 500 100 3 500 90 4 500 80 5 500 100 6 500 100 7 500 70 8th 500 70 9 500 100 10 500 100 11 500 85 12 500 80 13 500 100 14 500 100 15 500 90 16 500 100 17 500 80 18 500 100 19 500 100 21 500 100 22 500 65 23 500 100 24 500 90 25 500 85 27 500 100 28 500 90 29 500 100 30 500 100 31 500 60 32 500 100 33 500 85 37 500 100 38 500 100 39 500 75 41 500 100 42 500 100 44 500 100 45 500 100 46 500 70 47 500 60 48 500 100 49 500 100 50 500 100 54 500 100 55 500 100 56 500 95 57 500 70

Investigated link (No. according to Table D Concentration (ppm) Control value (%) 58 500 70 59 500 80 60 500 80 61 500 85 62 500 100 63 500 100 64 500 80 65 500 100 66 500 60 67 500 100 68 500 60 69 500 100 70 500 65 71 500 100 72 500 100 73 500 80 74 500 60 75 500 85 76 500 60 Commercially available agent Rovral * ' 500 100

The commercially available agent Rovral contains, as an active substance, the compound according to the following formula: O.

Ν Μ-CONHCH.

Y ^сн з

Example 22

Investigation of the effect against Cochliobolus miyabeanus on rice plants.

In unglazed pots of 10 cm diameter, 16 rice seeds (variety: SASANISHIKI) were sown. At present, as the seedlings showed 4 to 5 leaves, they were splashed with a diluted, wettable powder like that of Example 15, which had been diluted with water to a predetermined concentration.

After the agent had dried on the leaves, 5 ml of a suspension of the spores of Cochliobolus miyabeanus per pot were sprayed onto the pretreated seedlings. The mentioned spores had been cultivated in advance. In the sprayed suspension 15 spores of the fungus were found under the microscope at 150x magnification per field.

Immediately after inoculation, the pots thus treated were placed in an inoculation room at 25 ° C and with moisture saturated air. In it they were left for 2 days and then transferred to the greenhouse. On the 5th day of the inoculation, the number of disease spots was determined on 10 leaves per pot and from this the so-called control value for the fungicidal composition was calculated according to the following formula:

Number of disease spots in pretreated plants

",. /. pretreated plants

Control value = (1 - - -) χ 100%

\ Number of disease spots at non- /

treated plants (control)

The results of the investigations are summarized in Table 10 below. Table 10

Investigated compound (No. according to Table 1) Concentration (ppm) Control value (%) 1 125 100 2 125 100 3 125 100 4 125 100 5 125 100 6 125 100 7 125 100 8th 125 100 9 125 100 10 125 100 11 125 100 12 125 100 13 125 100 14 125 95 15 125 90 16 125 100 17 125 100 Commercially available. Medium: Rovral 125 85 Comparison (not treated) 0

Example 23

Investigation of the effect against various pathogenic fungi

In this example, the results of the fungicidal activity studies with the invention

Azole derivatives against various phytopathogenic fungi indicated.

The examination method was in each case the following:

The compound of the invention is dissolved in dimethyl sulfoxide, up to a predetermined concentration. 0.6 ml of this solution are dissolved in 60 ml of PAS KuIturen. The medium is heated to 60 ^° C. in 100 ml flasks. The mixture thus formed is now placed on shallow glass dishes, where they at room temperature to flat cultivated soils, each one

Contain compound of the invention, solidify.

In addition, various Pflanzenfungi are cultivated, in similar cultures, but without the compounds mentioned.

From each rondelles of 4 mm diameter are cut and placed in the middle of the culture media described above with the compounds of the invention. The preparation is stored after inoculation for one to three days under suitable conditions, after which the actual determination of the effect of the compounds of the invention

he follows. For this purpose average diameters of forming mushroom cultures, once on culture media with

compounds of the invention and once on an analogous medium without compound, measured. Then, according to the following formula, the degree of inhibition for the various compounds is calculated against the fungi tested:

R = (dd) χ 100 / dc.

In the formula, mean: R degree of inhibition,

the diameter of the fungal colony on the nutrient medium

without compound according to the invention, the diameter of the mushroom colonies on the nutrient medium, which

contains one of the compounds of the invention.

The results are divided into 5 categories according to the criteria scale given below:

5: R 90-100% 4: R 70-90% 3: R40- 70% 2: R 20-40% 1: R 20%

The above results are summarized in the following Table 11:

Table 11

Unters.Verb (No. according to Table 1) Konzen tratio Investigated Funqus P.O. Cm. Cf. H.S. R.S. Во. с. S.S. F. п. F. с. F. г. Cl. Cb. S. с. V.u. А. к. At the. G. с. 1 2 100 5 ! ι 5 5 5 5 5 5 5 5 5 S 5 5 5 Γι 5 3 H) O 5 5 5 Г) 5 5 !. 5 5 Г) Г. 5 5 !) Ь Г) Ь !. 100 Ü Ь 5 5 5 5 5 5 5 5  5 5 5 5 5 5 Π 100 100 .Ί Ь 5 5 5 5 5 5 5 5 Г) 5 5 S η Ь Ь 7 100 Γι 5 5 5 5 5 S 5 5 5 S 5 5 Г) 5 5 a 100 Г. 5 5 Г) 5 5 5 5 5 5 5 5 5 ь 5 5 5 <) H) O Γι Г. 5 5 5 5 S S 5 5 5 5 5 5 5 5 5 10 11 100 Γι 5 5 5 5 Ь 5 5 5. 5 5 5 S !) 5 ь 5 12 100 Γι Г) 5 S 4 5 5 5 5 5 5 5 5 ii 5 4 5 13 100 5 5 S 5 5 5 5 5 5 5 5 5 £ !, 5 5 5 5 11 100 5 Γι 5 5 4 5 5 5 5 5 5 5 5 Г) S 5 5 1! I 100 100 Г) 5 5 5 / I 5 5 5 5 5  5 5 5 5 4 5 5 IG 100 г. 5 5 5 5 5 5 5 5 5 5 5 5 5 4 4 5 17 ICO Γι 5 5 5 5 5 5 S 5 5 5 5 5 5 S 4 5 100 5 5 5 Ü 5 5 5 5 5 5 5 5 5 5 5 5 5 Ь 5 5 5 4 5 5 5 5 5 5 S 5 5 5 5 5 S 5 5 5 S Г " 5 5 S 5 5 5 5 S 5 5

N) OO (С

NЛ NJ

Table 11 (continued)

K-onzen tratiori (Uq / ml) Investigated Funqus P.O. Cm. Cf. H.S. R.S. ßü.C. S.S. F. η. F.C. F. г. Cl. Cb. S.C. Ѵ.Ш. А. к. On. G. с. 100 100 5 Г. 5 5 5 D Г. 5 5 5 5 5 Γ " 5 5 5 4 5 4 5 5 100 ü S 5 4 4 Г) 4 5 5 !. 5 5 5 Γ. 5 5 5 100 100 100 ! i 5 Γι 5 4 Г. 5 5 Ь 5 5 5 5 5 5 S Γ. 100 100 5 Γι Ь Г) Г, 5 ί> 5 5 5 5 5 5 S 5 5 5 Unters. Vtrb (number according to Table 1) 100 ii Г. Г) 5 5 ü 5 5 5 5 5 5 5 5 Γ. S Γ. 1fl 19 100 100 Ь S 5 Π Γι Г. 5 Γι 5 5 Γι Γι 5 5 5 5 5 Γ. 20 100 S 5 5 5 4 !) 5 5 5 5 S 5 5 5 5 5 S 21 22 100 ! j 5 5 5 .5 5 5 5 Γι 5 Γ) 5 4 5 5 Γι 5 5 23 100 5 Ь 5 Г) 4 5 5 Γι S 5 5 5 5 5 5th 5 5 5 S 5 24 100 5 5 Ь Г. 5 5 5 5 Γι 5 5 Γι 5 H 5 5 5 5 Γι S 5 5 2!) 100 5 Г) Ь 5 5 5 Ь Γι 5 5 5 ii 5 5 5 Ь Ь 20 100 5 5 5 г, 5 5 5 5 5 5 5 5 5 5 4 4 5 27 28 100 5 5 Г " 5 5 5 5 5 Γ) 5 5 Ь 5 5 5 S 5 29 30 5 5 5 fj 4 Γι S 5 Γι 5 5 5 5 5 5 5 5 31 5 5 5 Г) 5 5 H 5 5 Γ. 5 5 5 5 5 5 5 32 S 5 5 5 S 5 5 5 5 5 5 5 5 5 33 5 Г. 5 5 5 S 5 5 S 5 S 5 34 5 5 5 5 3 5 5 35

N3 OO CD

Table 11 (continued)

(.treatment 100 KX) P.O. Ст. Cf. H.S. Examined fungus R. s. Bü.c. S.S. F. η. F. с. F. г. C.I. Cb. S.C. V. M. А. к. FROM. G.C. 100 100 5 S 5 5 5 5 5 Γι 5 Γι 5 3 5 S Γι S 5 IOD. 100 π 5 5 Ь Γι ü ! ι 5 Ü 5 5 S 5 !. 5 Ь ! ι 100 100 Γι ii Г. !> Ό S 5 ! ι S Γι 5 5 Γ. ! ι !) Γ. Unters. Verb (.Konzen { 100 .Ί 5 5 5 Γι 5 S 4 5 5 5 5 5 5 5 Γι 5 Γι (No. according to table ι) 100 S 5 4 Г. 5 5 S 4 4 4 Γι 3 5 Γ. 4 5 5 5 30 37 100 г, 5 Γι 5 5 5 5 5 5 5 Γι 3 5 !. Γι 5 5 3Γ. 100 Г) Ь 5 5 3 b ! ι Ь 5 5 Γ) 5 5 5 Ь 5 5 3 '.! 100 5 5 5 4 ь 5 Б 5 5 5 5 Γι Γι 5 5 S 40 100 5 Г) Г) Г) 5 5 5 5 5 Γι 5 5 5 !. Γι 5 5 11 M 43 100 ! ι Г) Γι Г. 5 5 5 5 Г. 5 4 Γι 5 Γ. Γι Γ. 5 4 5 44 100 4 5 Ь 3 5 5 4 5 4 5 5 5 Γι 4 4 5 1! I 100 5 5 5 5 5 5 4 5 4 5 5 5 5 5 5 S 5 4G 100 S S 4 5 5 4 5 4 5 4 5 5 5 S 4 5 5 47 100 5 S 5 5 5 5 S 5 5 5 5 5 5 5 Γι 5 5 4П S 5 5 5 Ь 5 S 5 H 5 5 5 5 5 5 4 5 49 г, 4 5 5 4 5 5 4 5 4 5 4 5 5 4 5 5 50 Г> 5 5 5 5 5 5 S 5 5 5 5 5 5 5 5 1) 1 5 S 5 5 5 Γι 5 5 5 5 5 5 5 5 5 4 5 52 5 5 5 4 5 5 5 Ь 4 5 S A 53 54

N3 OO CO

UI Ca)

Table 11 (continued)

Unters. Verb (number according to Table 1) Concentrate / ml) 100 K) O 100 K) O K) O 100 100 K) O P.O. Examined fungus Cm. Cf. H.S. R.S. Во. с. S.S. F. η. F. с. F. г. Cl. Cb. S. с. V. га. А. к. А. га. 6. с. JiG Ь7! »8 Ml GO K) O 100 KKi K) O Γι Γι Γι Γι 4 5 !. Γι 5 Γ. Ь 5 Γι 5 4 5 5 5 4 3 4 3 \ 5 5 ь S - Γι GI 100 Γι 4 Γι 5 4 Γ. 5 Γ » 4 4 4 5 3 Ь Ь 4 3 5 02 100 ϋ Γ) ή 4 ϋ Ь 5 5 5 4 !. Γι S 5 Γι Γι 4 5 Г. 3 Ь 4 5 G3 100 ! ι 5 Γ. ! ι Γ. Γ. ϋ Ь 5 5 ϋ 3 S ! ι г. 4 Ь M 100 !, S 5 5 ! ι Ь Γ. !, !. S 5 5 5 S 5 5 Г) G. ^r . GG 100 Γι ϋ Γι 5 5 Γι Ji 5 5 5 ii 4 5 5 5 • 5 5 G7 100 Γ) 5 5 5 Γι 5 5 5 5 5 5 4 5 Ь ii !. 5 Ь ca 100 5 ίι 5 5 5 S Γ) 5 Γι S 5 5 5 5 ij S Γι 5 G!) 5 5 Γι 5 5 5 5 ! ι 5 5 5 5 5 5 Ь S S S 70 5 5 5 5 ϋ 5 5 !. 5 5 Г) 5 5 .5 ь 4 5 71 5 Γ. Γι 5 5 5 5 5 Ь 5 5 Г. 5 Ь 5 5 5 7II 5 Γ. 5 5 3 5 5 5 S 5 5 5 5 5 4 Ь 5 7G 5 Γι 5 Γι 4 5 5 5 5 5 Γι 5 5 5 H 5 5 5 5 5 3 5 5 4 4 4 5 Ь 5 S 5 4 5 Γι 5 Ь ь 5 5 5 5 5 5   5 Ь Ь 5 4 S 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 S 4 5 5 5 5 5 5 S 5 4

NJ OO

OI N) СО

The abbreviations in Table 11 stand for the following fungi:

P.O .: Pyriculariaoryzaean rice

Cm .: Colchliobolus miyabeanus on rice

G.f .: gibberellafujikuroian rice

H. s .: Helminthosporium sigmoideum on rice

R. s .: Rhizoctoniasolanian rice

Во. с: botrytiscinerea

S.S .: Sclerotinia sclerotirum

F. п .: Fusarium oxysporum. niveum of watermelon

F. с F.r. Cl.

Fusarium oxysporumf. cucumerinum on cucumber Fusarium oxysporum f. raphani anjapanischer radish Colletotrichum lagenarium to melon

C. b .: Cercospola beticola on sugar beet

S. с: Sclerotinia cinerea on peach

V. m .: Valsamali to apple

A.m .: Alternarta mali to apple

A. k .: Alternaria alternate (kikuchiana) on pear

G.c: Glomerellacingulata on grape

Examples of agricultural and horticultural agents for regulating plant growth; these agents contain the azole derivatives according to the invention as active substances

Example 24

Wettable powder

50 parts by weight of an azole derivative of the present invention (specifically, compound 3 in Table 1), 5 parts by weight of a salt of lignin sulfonic acid, 3 parts by weight of a salt of alkylsulfonic acid and 42 parts by weight of diatomaceous earth were mixed and pulverized. There was obtained a composition which is wettable with water. The composition is used after dilution with water.

Example 25

Emulsifiable concentrate

25 parts by weight of an azole derivative of the present invention (specifically, Compound 20 in Table 1), 65 parts by weight of xylene, and 10 parts by weight of polyoxyethylene alkylaryl ether were homogeneously mixed to obtain an emulatable composition in the form of a concentrate. The composition is used after dilution with water.

Example 26

powder

8 parts by weight of an azole derivative according to the invention (especially compound 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 lignosulfonic acid were homogeneously mixed. To this was added water and the mixture extruded after kneading in a granulator. The granular material was dried; This gave a composition in the form of a powder.

Example 27

Examination of the effect effect with regard to the growth regulation of the compounds according to the invention

rice plants

In glass bowls of 8.5 cm diameter were 10ml each of a solution of the compounds of the invention in one

Given concentration of 10 ppm. 10 rice seeds were given to the same glass dishes (variety: SASANISHIKI). Now, the glass dishes were kept at 27 ⁰ C for 7 days to germinate the seeds. After a certain time, the mean heights of the plants were measured and with corresponding plants without addition of compounds according to the invention

compared. The results obtained are summarized in Table 12 below.

As can be seen from Table 12, all azole derivatives of the present invention show a pronounced

Impairment of the growth of plants without showing any phytotoxicity.

Table 12

Investigated compound (No. according toTable 1) Growth prevention phototoxicity 1 84.2 none 2 63.8 none 3 71.8 none 4 70.0 none 5 70.0 none 6 74.6 none 7 85.9 none 8th 72.3 none 9 75.7 none 10 79.7 none 11 76.8 none 12 67.2 none 13 87.0 none 14 76.8 none 15 77.4 none 16 84.2 none 17 76.8 none

Claims (2)

claims: in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; X is a halogen, for one or for phenyl; A is nitrogen or CH; and in which R represents an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen, characterized in that it is the reaction of an oxirane derivative of the formula (II): .CH, (II) in which R ¹ , R ² , X and η are each identically defined as described above, with a 1,2,4-triazole or an imidazole of the formula (VI): (Vi), N =. N in which M is hydrogen or an alkali metal and A is nitrogen or CH. A process according to claim 1, characterized in that said oxirane derivative is prepared by a process comprising 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 (ii) reaction of an alkyl ester of a 3- (C ₁ -C ₅ alkyl) -2-oxocyclopentanecarboxylic acid with a substituted benzyl halide or (iii) reaction of the alkyl ester of a 1- (substituted benzyl) -2-oxocyclopentanecarboxylic acid with a (C ₁ -C ₅ alkyl halide; (Substitutedbenzyl) -3- (Ci-C ₅ alkyl) -2-oxocyclopentancarboxylic acid with a (C ^ CsJ-alkyl halide, whereby each ester derivatives of cyclopentanecarboxylic acid of formula (V) are obtained: 0 CH, in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; R is (C ₁ -C ₅ ) -alkyl, X is halogen, (C ₁ -Cs) -alkyl or phenyl and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen is when R ^{2 is} hydrogen, b) hydrolytic decarboxylation of the derivative of cyclopentanecarboxylic acid thus obtained, whereby a cyclopentanone derivative of the formula (IV) is obtained: (IV), in which formula R ¹ , R ² , X and η are each defined identically as above, and c) subjecting the thus obtained cyclopentanone derivative to an oxirane reaction using a sulfonium ylide or oxosulfonium ylide, or subjecting a methylenecyclopentane derivative obtained from the obtained one Cyclopentanone derivative by the Wittig reaction, which intermediates are represented by the formula (III): (III) in which R ¹ , R ² , X and η are each as defined above, for epoxidation, whereby the cyclopentanone derivative is converted into an oxirane derivative of the formula (II): (II) in which R ¹ , R ² , X and η are each as defined above. Method according to claim 4, characterized in that said process is the following steps include: 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 (Ci-C ₅ ) alkyl halide; (ii) reacting an alkyl ester of a 3- (C ₁ -C ₅ alkyl) -2-oxocyclopentanecarboxylic acid with a substituted benzyl halide or (iii) reacting an alkyl ester of an iso-substituted benzylKS-C ₁ -C 12 alkyl) -2-oxocyclopentanecarboxylic acid with a (Ci -Csbalkyl halide, whereby an ester derivative of cyclopentanecarboxylic acid of formula (V) is obtained; in which R and R ^{2 are} each (C ₁ -C 8) -alkyl or hydrogen; R for a (С, -С ₅ ) -A1ку1; X is a halogen, a (Ci-C ₅ ) -alkyl or phenyl and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen, when R ^{2 is} hydrogen, b) subjecting the resulting ester derivative of cyclopentanecarboxylic acid to hydrolytic decarboxylation to give a cyclopentanone derivative of formula (IV): in which R ¹ , R ² , X and η are as defined above, c) subjecting the thus obtained cyclopentanone derivative to oxirane reaction using sulfonium ylide or oxosulfonium ylide, or subjecting the methylenecyclopentane derivative obtained from the above-obtained cyclopentanone derivative by Wittig reaction, the compounds obtained represented by the formula (III): (III) in which R ¹ , R ² , X and η are each defined identically as above, for epoxidation, whereby the said cyclopentanone derivative is converted into an oxirane derivative, which oxirane derivative is represented by the formula (II). (II) in which R ¹ , R ² , X and η are each as defined above, and subsequently d) reaction of the oxirane derivative thus obtained with a 1,2,4-triazole or an imidazole of the formula (VI): (Vl), in which M is hydrogen or an alkali metal and A is nitrogen or CH. 4. Agricultural and horticultural composition with fungicidal activity and plant growth regulating activity, characterized in that it contains as active substance an azole derivative of the formula (I) (D, in which R ¹ and R ^{2 are} each (C ₁ -C 5) -alkyl or hydrogen; X is halogen, a (C ₁ -Cs) -AlkVl or phenyl and A is nitrogen or CH and in which η is an integer from 0 to 2, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen is, in addition to a carrier contains. 5. Agricultural and horticultural composition according to claim 4, characterized in that in the active substance R ^{1 is} hydrogen or (C ₁ -CJ-AIkYl, R ^{2 is} hydrogen or (C ₁ -C ₃ ) -alkyl; X is halogen, the benzene ring in 4 Position, and A is nitrogen or CH, and in which η is 1, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen. 6. Agricultural and horticultural composition according to claim 5, characterized in that in the active substance R ¹ and R ^{2 are} each hydrogen or (CiC ₃ ) alkyl; X is halogen, substituted in the 4-position by the benzene ring, and A is nitrogen, and in which η is 1, with the proviso that R ^{1 is} not hydrogen when R ^{2 is} hydrogen.