CA1311491C - Substituted oxirane intermediates - Google Patents

Abstract

Abstract of the Disclosure The present invention relates to novel intermediates use-ful in the preparation of fungicides and to a process for preparing the intermediates. The intermediates are represented by formula II which defines an oxirane of the formula II

(II) in which R represents alkyl or cycloalkyl in each case optionally mono-, di- or tri-substituted by identical or different substitu-ents from the group consisting of methyl, ethyl, isopropyl, meth-oxy and ethoxy, or phenyl which is optionally mono-, di- or tri-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl, tri-fluoromethyl, phenyl and chlorophenyl, X represents the grouping -OCH2-, -SCH2-, -(CH2)p- or -CH=CH-, Y represents the grouping -CO-Y1, -C(OR4)2-Y1 or , or the grouping -C(Y1)=N-OY2, Y1 represents hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by C1-4 alkyl or C1-2 alkoxy, or phenyl or benzyl each of which phenyl or benzyl is optionally mono- or di-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl and trifluoro-methyl, Y2 represents hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by halogen, C1-4 alkyl or C1-2 alkoxy or benzyl optionally substituted by halogen, alkyl with 1 to 4 carbon atoms; alkoxy and alkylthio with in each case 1 or 2 carbon atoms;

Le A 21 965-CA DIV I

halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cyclohexyl, dialkylamino with 1 to 4 carbon atoms in each alkyl part, nitro, cyano, alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part and optionally halogen-substituted phenyl, Z
represents halogen, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkylthio and the indices m and p re-present 0, 1 or 2.

Description

1 31 ~ ~ ~1 23189-5606D

This application relates to novel intermediates of ~ormula II (as defined below) useful in the preparation o~ fungi-cides of formula I, and to a process for preparing the inter-mediates. This application is di~ided out of the parent application Serial No. 438,569 filed October 6, 1983.
The invention of the parent application relates to new substituted l-hydroxyethyl-triazolyl derivatives, several pro-cesses for their preparation and their use as fungicides.
It has already been disclosed that 3,3-dimethyl-1-phenoxy-2-(1,2,4-triazol-1-yl-methyl)-2-butanols have good fungicidal properties (compare DE-OS (German Published Specifica-tion), 3,018,866 [Le A 20 330]). However, the action of these compounds is not always completely satisfactory, especially when low amounts and concentrations are applied~
According to one aspect of the parent application there is provided a substituted l-hydroxyethyl-triazolyl derivative of the formula OH
~ X - C - R
m IH2 N -in which R represents alkyl or cycloalkyl in each case optionally mono-, di- or tri-substituted by identical or different substitu-ents from the group consisting o~ methyl, ethyl, isopropyl, methoxy and ethoxy, or phenyl which is optionaIly mono-, di- or Le A 21 965-CA DIV I
,,. ~ :.

'..

~ 3 ~

tri-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl, tri-fluoromethyl, phenyl and chlorophenyl, X represents the grouping -OCH2-, -SCH2~, -(CH2) - or -CH=CH-, Y represents the grouping -co-Yl, -C(OR )2_yl or yl O / (CH2)q , or the grouping -C(Y )-N-OY , yl represents hydrogen, alkyl, alkenyl, alkinyl, cyclo-alkyl optionally substituted by Cl 4 alkyl or Cl 2 alkoxy, or phenyl or benzyl each of which phenyl or benzyl is optionally mono- or di-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl and trifluoromethyl, ~.
Y represents hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by halogen, Cl 4 alkyl or Cl 2 alkoxy or benzyl optionally substituted by halogen, alkyl with 1 to 4 carbon atoms; alkoxy and alkylthio with in each case 1 or 2 carbon atoms; halogenoalkyl, halogenoalkoxy and halogenoalkyl-thio with in each case 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, cyclohexyl, dialkylamino with 1 to 4 carbon atoms in each alkyl part, nitro, cyano, alkoxycarbonyl :
with 1 to 4 carbon atoms in the alkyl part and optionally halogen-substituted phenyl, Z represents halogen, alkyl, alkoxy, alkylthio, halo-genoalkyl, haloyenoalkoxy or halogenoalkylthio and the indices m and p represent 0, 1 or 2, or a non-phytotoxic addition product . , .

, .. . .. ., - .

~ ~L31~

thereoE with an acid selected from the group consisting of hydro-gen halide acids, phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids, hydroxycarboxylic acids, and sulphonic acids or with a halide, phosphate, nitrate or sulphate of a metal of main groups II to IV and of sub-groups I and II and IV to VIII of the Periodic Table.
The compounds of the formula (I) possess an asymetric carbon atom and can therefore be obtained in the two optical isomer forms. The compounds of the formula (I) may also occur in the form of various geometric isomers, depending on the meaning of the substituents X and Y.
It has furthermore been found that the substituted 1-hydroxyethyl-triazolyl derivatives of the formula (I) are obtained by a process ln which a) oxiranes of the formula z _' ~ } O / \CH (II) .in which R, X, Y, Z and m have the abovementioned meaning, are reacted with 1,2,4-triazole of the formula ,N=I
M - N ¦ (III) in which M represents hydrogen or an alkali metal in the presence of a diluent and if appropriate in the presence of a base, or b) triazolylmethyl-oxiranes of the formula - 2a -~ . , .
. . ', , ' .
.
.

' ' .

3.~

/ o CH2 (IV) 1'/ \ :

N
ln whlch R has the abovementioned meanlng, are reacted wlth (thlo)phenols of the formula 10~ _xl _ H (V) in which Zm Y, Z and m have the abovementioned meaning and: ;
xl represents oxygen or sulphur, ln the presence o~ a diluent and lf appropriate ln the presence of a base, or c) the compounds according to the inventlon which are obtalnable by processes (a~ :
and (b) and have the formula ~ :

.~, I
- X - C - R

~ IH2 / N
~ fl N ~
~ N
in whlch R, X, Z and m have the abovementloned m~anlng and Y3 repre~
sents the grouplng -CO-Yl~ or an acetal or ketal derlvatlve thereof, are reacted wlth hydroxylamine derlvatives of the ~ormula : ~ ~: H2N - o - z i:VI) - . - : . : : , -, ~ .: ~ `-, ;. :
~ . . - .

- \ ~ 3 ~

in which y2 has the abovementioned meaning, in the presence of a diluent, or d) the compounds according to the invention which are obtainable by processes (a), (b) and (c) and have the formula yl HO-N=C OH

~ X - C - R (Ib) m IH2 N~N
~ .
in which R, X, yl~ z and m have the abovementioned meaning, are reacted with halides of the formula Y - Hal (VII) in which Hal represents chlorine, bromine or iodine and Y4 has the meanings of Y2r with the exception of hydro-gen, in the presence of a diluent and if appropriate in the pre-sence of a base.
If desired, an acid or a rnetal salt can then be added onto the compounds of the formula (I) thus obtained. ~:
It has also been found that the new substituted l-hydroxy-ethyl-triazolyl derivatives of the formula (I) have powerful fungi-cidal properties, Surprisingly, the substituted l-hydroxyethyl-triazolyl derivatives of the formula (I) display better fungicidal actio.ns , .

:

- 1 3 ~ 9 ~

23189-5606(D) than the above-mentioned 3,3-dimethyl-1-phenoxy-2-(1,2,-triazol-1-yl-methyl)-2-butanols which are known from the prior art and are closely related compounds structurally and from the point of vie~ of their action. The active compounds according ~o the invention of the parent application thus represent an enrichment of the art.
According to one aspect of the present invention there is provided an oxirane of the formula II

Zm 0 - CH~

in which R represents tert.-butyl or isopropyl, or represents cyclopropyl, cyclopentyl or cyclohexyl, in each case optionally mono-, di- or tri-substituted by identical or different substituents from the group consisting of methyl, ~ :
ethyl, isopropyl, methoxy and ethoxy, or represents phenyl which is optionally mono-, di- or tri-substituted by identical or different substituents selected from the group consisting of 1uorine, chlorine, methyl, trifluoromethyl, phenyl and ~ :
chlorophenyl, or represents thç grouping : CH2Rl : H3 -C _ CH3 or -C(CH2)n-R3 r~
: CH2R C 3 ~herein : R1 represents hydrog~n, fluorine or chlorine: :

, ~ 11 3 ~
23189~606~D) R represents fluorine or chlorine;
R represents ~e~h~ ethyl, propyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, vinyl, methoxycarbonyl, ethoxycarbonyl or cyano, or represents phenyl, phenoxy, phenylthio, phenylmethoxy or phenylmethylthio, the last five radicals mentioned may be substituted by fluorine, chlorine, methyl, ethyl, methoxy, methylthio~ trifluoromethyl, trifluoromethoxy, trifluoromethylthio, dimethylamino, methoxy-carbonyl and ethoxycarbonyl; and n represents the number 0, l or 2;
X represents the grouping -OCE~2-, -SCH2-, ~(CH2)p or -CH=CH-;

Y represents the groupin~ -co-Yl, -C(oR4)2-Yl or yl/ O\

\ / (CH2)q , or the grouping -C(Yl)=N-OY2;

O

yl represents hydrogen, methyl, ethyl or isopropyl, or represents phenyl, which is optionally mono- or dl-substituted by-identical or different substituents selected from the group consisting of fluorine, chlorine, methyl and trifluoromethyl;

Y represents hydrogen, methyl, ethyl~ n-pxopyl, n- ~

butyl, allyl or propargyl, or represents ben~yl which is optlon-ally mono- or di-substituted by identical or different substitu-ents selected from the group consisting of fluorine, chlorine, ~

.

methyl, trifluoromethyl and trifluoromethoxy;
R4 represents methyl~ ethyl or propyl;
q represents the number 2 or 3;

~ .
:
5a . . .

~31~g~
23189-5606(D) Z represents fluorine, chlorine, bromine, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, m represents the number 0l 1 or 2; and p represents the number 0, 1 or 2.
Formula (I) provides a general definition of the substituted 1-hydroxyethyl-triazolyl derivatives according to the invention. Preferably, in thi~ formular R represents straight-chain or branched alkyl with 1 to 4 carbon atoms, or represents cycloalkyl which has 3 to 7 carbon atoms and is optionally mono- or poly-substituted by identical or different substituents, substituents which may be mentioned beiny: methylj ethyl, isopropyl, methoxy and ethoxy or represents phenyl which is optionally mono- or poly-substituted by identical or different substituents, possible substituents being fluorine, chlorine, methyl, trifluoromethyl, phenyl or chlorophenyl, or represents the grouping :

: - 6 - . : . - . : . ~. , - ' , '- ~ ~' ~ ` ' '' :L 3 ~

CH R CH ::

-C - CH3 or ~1~(CH2)n~R

Rl represents hydrogen, or R represents halogen;
R3 represents alkyl, alkoxy or alkylthio with in each case 1 to 4 carbon atoms, or represents halogenoalko~y or halogeno-alkylthio wi:th in each case 1 or 2 carbon atoms and 1 to 5 iden-tical or different halogen atoms, such as fluorine and chlorine atoms, or represents alkenyl with 2 to 6 carbon atoms, or represents alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part, or re-presents cyano or in each case optionally mono- or poly-substituted phenyl, phenoxy, phenylthi.o, phenylalkoxy with 1 to 4 carbon atoms in the alkyl part or phenylalkylthio with 1 to 4 carbon atoms in the alkyl part, preferred substituents on the phenyl which may be mentioned in each case being: halogen, alkyl with 1 to 4 carbon atoms; alkoxy and alkylthio with in each case 1 or 2 carbon atoms;
halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as, i.n particular, fluorine and chlorine atoms, cyclo-hexyl, dialkylamino with 1 to 4 carbon atoms in each alkyl part, nitro, cyano, alkoxycarbonyl with l~to 4 carbon atoms in the alkyl part and optionally halogen-substituted phenyl, n represents the number 0, 1 or 2;
Y represents the grouping -co-Yl~ -C(OR )2-Y or -C ~ ~ CH2)q or the grouping -C(Y )=N-OY ;
O

- 6a -~ .

~ 3 ~

Y represents hydro~en, or represents alkyl with 1 to 4 carbon atoms, or represents alkenyl or alkinyl with in each case 2 to 4 carbon atoms, or represents cycloalkyl which has 3 to 7 carbon atoms and is optionally mono- or poly-substituted by identical or different substituents, substituents which may be mentioned being: halogen, alkyl with 1 to 4 carbon atoms and alkoxy with 1 or 2 carbon atoms, or represents phenyl or benzyl, each of which is optionally mono- or poly-substituted by identical or different substituents, possible substituents being the sub-stituents on phenyl mentioned ~or ~3;
Y represents hydrogen, or represents straight-chain or branched alky~ with 1 to 4 carbon atoms, - 6b -3~9~

or represents alkenyl or alkinyl with ;n each case 2 to 6 carbon atorns, or represents cyclo-alkyl which has 3 to 7 carbon atoms and is option-alLy mono- or poly-substituted by ider,tical or different substituents, substituents which may be mentioned being: halogen, alkyl with 1 to 4 carbon atoms and alkoxy with 1 or 2 carbon atoms, or represents benzyl, which is optionally mono- or poly-substituted by identical or different sub-stituents, possible substituents being the sub-stituents on phenyl mentioned for R3, R4 represents alkyl with 1 to 4 carbon atoms;
q represents the number 2 or 3;
Z represents halogen, or represents alkyl, alkoxy or alkylthio w;th in each case 1 to 4 carbon atoms~
or represents halogenoalkyl, halogenoalkoxy or halogenoalkylthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms;
Z0 m represents the number 0, 1 or 2; and p represents the number 0, 1 or 2.
Particularly preferred compounds of the formula (I) are those in which ZS R represents tert.-~utyl ~r ;sopropyl, or repre-sents cyclopropyl, cyclopentyl or cyclohexyl, each~ of which is optionally mono-, di- or tri-subst;tuted by identical or different substituents, substituents which~may be mentioned being: methyl, ethyl, isopropyl, methoxy and ethoxy~ or repre-sents phenyl wh;ch is optionally mono-~ di-~or tri-substituted by identical or different su~b~
stituents, sub~st~ituents whic~h may~ be mentioned ~ 1 being: fluorine,~chlorine~, methyl, trifluorom~thyl~
phenyl and~chlorophenyl, or represe~nts the group~
ing I
Le A 21 965~

~ , , : :

:

:
:

3 ~

8 2318~-5606D

CH2Rl or CH3 -C-CH3 -C-tCH2)n-R3 CH2R2 ~H3 whereln Rl represents hydrogen, fluorlne or chlorine;
R2 represents fluorine or chlorine;
R3 represents methyi, ethyl, propyl, methoxy, ethoxy, methyl-thlo, ethylthlo, trlfluoromethoxy, trlfluoromethylthio, vlnyl, methoxycarbonyl, ethoxycarbonyl or cyano, or represents phenyl, phenoxy, phenylthlo, phenylmethoxy or phenylme~hylthlo, each o~
whlch ls optlonally mono- or di-substituted by ldentlcal or dlfferent ~ub~tltuents, substltuents on the phenyl Whlch may be mentloned in each case belng: fluorlne, chlorlne, methyl, ethyl, methoxy, methylthlo, trlfluoromethyl, trifluoromethoxy, trlfluoro-methylthio, dimethylamino, methoxycarbonyl and ethoxycarbonyl; and : n represents the number 0, 1 or 2; X represents the grouping -CH2-~ -ScH2-l (C~2)p or -CH=CH-;
Y represents the grouplng -co-Yl, ~C~oR4)2-Yl, yl o \ /
or -C J CH2)q~ or th~ grouplng -C~Yl)=N_oy2 O : ' whereln yl represents~hydrogen, methyl, ethyl or lsopropyl, or~
represents phenyl, whlch ls optlonally mono- or di-substituted : identlcal or dlfferent substltuents ~rom the group comprlsln~
: fluorlne, chlorine, methyl and trifluoromethyl; y2 represents , ~ hydrogen, methyl, ethyl, n-propyl, n-butyl, allyl or propargyl, or :: , ~ represents benzyl whlch ls optlonally mono- or di-substltuted by ~

identical or different substituents from the gr~up comprising fluorine, chlorine, methyl, trifluoromethyl and trifluoromethoxy;
R4 represents methyl, ethyl or propyl, and q represents the number 2 or 3;
Z represents fluorine, chlorine, bromine, methyl, meth-oxy, methylthio, trifluoromethyl, trifluoromethoxy or -trifluoro-methylthio, m represents the number 0, 1 or ~; and p represents the number 0, 1 or 2.
Preferred compounds according to the invention of the parent application also include addition products of àcids and those substituted l-hydroxyethyl-triazolyl derivatives of the for-mula (I) in which the substituents R, X, Y and Zm have the mean-ings which have already been given as preferred for these sub-stituents.
Acids which can be added on are hydrogen ha'ide acids, such as, for example, hydrochloric acid and hydrobromic acid, especially hydrochloric acid, and furthermore phosphoric acid, nitric acid, mono- functional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p-toluenesulphonic acid and 1,5-naphthalene-disulphonic acid.
Other compounds according to the invention o~ the parent application are addition products of salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII and those ~:
: ' g _ ~

~: ~

~ 3 ~

substituted l-hydroxyethyl-triazolyl derivatives of the formula (I) in which the substituents X, ~ and Zm have the meanings which have already been mentioned as preferred for these substituents.
Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred here. Possible anions of these salts are those which are derived from acids which lead to physiologically acceptable addition products. In this connection, particularly preferred acids of this type are the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid, nitric acid and sulphuric acid.
If, for example, 2-{2-[4-(1,3-dioxolan-2-yl)-phenyl]-ethenyl} 2-tert.-butyl-oxirane and sodium 1,2,4-triazole are used as starting substances, the course of process (a) can be represent-ed by the following equation:

> ~- ~ -CH=CH - C - C(CH3)3 -~ Na - ~ _ C ~ ~ -cH=cH-c-c(cH3)3 ~ N ~N
~1~

If, for example, 2-tert.-butyl-2-(1,2,4-triazol-1-yl-methyl)-oxirane and p-hydroxyacetophenone are used as starting substances, the course of process (b) can be represented by the following equation:

,-.

.

CH2-l-c(cH3)3 CH3CO- ~ OH

~N ~N CH3CO ~ O-CH2-l-C(CH3)3 If, for example, 2-(4-acetophenoxymethyl)-3,3-dimethyl-1-(1,2,4-triazol-l-yl)-2-butanol and hydroxylamine hydrochloride are used as starting substances, the course of process (c) can be represented by the following equation:
OH
3 ~ _ o-CH2-1C-C(CH3)3 CIH2 + NH20Hx HCl -~ `N OH
N~ HON=C- ~ O-CH2-C-C(cH3)3 CH3 f 2 ~N~N

If, for example, 3,3-dimethyl-1-[4-(1-hydrox-iminoethyl)-phenoxy~-1-(1,2,4-triazol-l-yl)-2-butanol and 2,4-dichlorobenzyl chloride are used as starting substances, the course of process (d) can be represented by the following equation:

:

;

- :, :-.
. : :

OH

HO~=C ~ O-CH2-l-C(CH3)3 Cl CH3 CIH2 + Cl ~ O~ - OEI2-Cl >

N~N
ll ~ Cl N ~ OH
Cl ~ H20N=C ~ O-CH2-C-C(CH3)3 Formula (II~ provides a general definition of the oxi-ranes to be used as starting substances in carrying out process (a). In this formula, R, X, Y and Z and the index m preferably have the meanings which have already been mentioned as preferred for these substituents and for the index m in connection with the description of the substances of the formula (I).
The oxiranes of the formula (II) are not yet known. They are`interesting intermediates, and can be obtained in a generally known manner, by the following process, which is another aspect of the present invention~ in which ketones of the formula ~ -X - CO-R (VIII) m in which R, X, Y, Z and m have the abovementioned meaning, ~:
either ~) are reacted with trimethyloxosulphonium methylide of the for-mula 11 3 ~

~+ ~--( 3)2 2 (IX) in the presence of a diluent, or ~) are reacted with trimethylsulphonium methyl-sulphate of the formula _ _ (+) (-) . ( 3)3 (CH3504) (X) in the presence of an inert organic solvent and in the presence of a base.
The ketones of the formula (VIII) re~uired as starting substances in the preparation of the oxiranes of the formula (II) can be prepared by processes which are known in principle (compare, for example, the preparation examples).
The dimethyloxosulphonium methylide of the - 12a -. ,, , , ~ .

.
.:
- ~ . .

formula (VII~ required in process variant t~) is known (compare J. Amer. Chem. Soc~ 87, 1363-1364 (1965)). In the above reaction, it is processed in the freshly prepared state, by be;ng produced in situ by reaction of trimethyl~
oxosulphonium iodide with sodium hydr;de, sod;um amide or potassium tert.-butylate in the presence of a diluent.
The trimethylsulphonium methylsulphate of the formula (VIII) requ;red in process varian~ t~) is l;ke-~ k~rsc~cl~5 w;se known (compare Hei~ff~r~ 8, 397 (1977~)~ In the `~
above react;on, it ;s likew;se employed in the freshly prepared state, by being produced in situ by reaction of d;methylsulph;de w;th dimethylsulphate~
D;methylsulphoxide is the preferred possible dil uent in variat (~) of the process for the preparation of the oxiranes of the formula (II).
The reaction temperatures can be varied wi~hin a substantial range in process variant (~) described above.
In general, the react;on is carried out at temperatures between 20C and 80C
2û The process for the preparat;on of the ox;ranes of the formula (II) by variant (~) and the working up of the reaction mixture obtained in this synthesis are carried out by customary methods (compare J. Amer. Chem. Soc~ ~7, 1363-1364 (1965)).
Z5 Acetonitrile is the preferred possible inert organic solvent in variant (~) for the preparation of the oxiranes of the formula (II).
Strong inorganic or organic bases can be used as the base in process variant (~). Sodium methylate is pre-ferably used.
The reaction temperatures can be varied within a certain range in process variant (~) described above. In general, the reaction is carried out at temperatures between 0C and 60C, preferably at room temperature.
The process for the preparation of ~the oxiranes of the fornula (II) by variant t~ and the work;ng up o~
Le A Z1 965 :

.

the reaction product obtained in this synthesis are carried out by customary methods (compare Heterocycles 8, 397, (1977)).
If appropriate, the oxiranes o~ ~he formula ~II) can be further reacted directly in the process without being isolated.
Formula (III) provides a general definition of the 1,2,4-triazoles also to be used as starting substances for process (a) In this formula, M preferably represents hydrogen, sodium or potas-sium.
The 1,2,4-triazoles of the formula (III) are generally known compounds of organic chemistry.
Formula (IV) provides a general definition of the tri-azolylmethyloxiranes to be used as starting substances in carrying out process (b). In this formula, R preferably has the meanings which have already been mentioned as preferred for this substitu-ent in connection with the description of the substances of the formula (I).
The triazolylmethyloxiranes of the formula ~IV) are known (compare DE-OS (German Published Specification) 3,111,238 [Le A 20 886] and EP 0.044,605), or they are the subject of German publication DE-OS 32 02 601 published on August 4, 1983, or they can be obtained in a ge~erally known manner, by a process in which triazolylketones of the formula ~' L N ~ CH2 ~ CO -R (XI) in which R has the abovementioned meaning, are epo~idised in accordance with process variants (~) and (~) described above.

.
' ' . ' ~, ~ 3~

The triazolyl-ketones of the formula (XI) are known tcompare DE-OS (German Published Specification) 2,a31,407 [Le A 15 735], DE-OS (German Published Specification) 2,638,470, DE-OS (German Published Specification) 2,820,361 ~Le A 18 843] and DE-OS (German Published Specification) 3,048,266 [Le A 2n 763]), or they can be prepared by processes which are known in principle.
Formul~ (V) provides a general definition of the ~thio)-phenols also to be used as starting substances for process (b). In this formula, Y, Z and the index m preferably have the meanings which have already been mentioned as preferred for these substitu-ents and for the index m in connection with the description of the substances of the formula (I). Xl preferably represents oxygen or sulphur.
The (thio)phenols of the formula (V) are known, or they are the subject of German Publication DE-OS 31 32 335 published on March 3, 1983, or they can be obtained in a generally customary manner.
The compounds of the formula (Ia) to be used as star~ing substances in carrying out process (c) are substances according to thelinvention of the parent application.
Formula (VI) provides a general definition of the hydroxy-lamine derivatives also to be used as star-ting substances for pro-cess (c). In this formula, y2 preferably has the meanings which have already been mentioned as preferred for this substituent in connection with the description of the substances of the formula tI)-The hydroxylamines of the formula (VI) are generally known compounds of organic ~hemistry.

.... - - ~ :

.

~ 3 ~

The compounds of the formula (Ib) to be used as starting substances in carrying out process (d) are substances according to the invention of the parent application.
Formula (VII) provides a general definition of the hal-ides also to be used as starting substances for process (d). In this formula, Y4 preferably has the meanings which have already been mentioned as preferred for y2 in connection with the descrip-tion of the substances of the formula (I) with the exception of hydrogen.
The halides of the formula (VII) are generally known com-pounds of organic chemistry.
Possible diluents for processes (a) and ~b) are organic solvents which are inert under the reaction conditions. These solvents include, preferably, alcohols, such as, for example, ethanol, methoxyethanol or propanol; ketones, such as, for example, 2-butanol; nitriles, such as, for example, acetonitrile; esters, such as, for example, ethyl acetate; ethers, such as, for example, dioxane; aromatic hydrocarbons, such as, for example, benzene and toluene; and amides, such as, for example, dimethylformamide.

Possible bases for the reactions are all the inorganic and organic bases which can usually be employed. These include, preferably, alkali metal carbonatesr such as, for example, sodium and potassium carbonate; alkali metal hydroxides, such as, for example, sodium hydroxide; alkali metal alcoholates, such as, for example, sodium and potassium methylate and ethylate; alkali metal hydrides, such as, for example, sodium hydride; and lower tertiary alkylamines, cycloalkylamines and aralkylamines, such as, in par-~ 3 ~

ticular, triethylamine.
The reaction temperatures can be varied within a substan-tial range in carrying out processes (a) and (b~. In general, the reactions are carried out at temperatures between 0 and 200C, preferably between 60 and 150C.
In carrying out process (a), 1 to 2 mols of azole and, if appropriate, catalytic to 2-molar amounts of base are preferably employed per mol of oxirane of the formula (II); in carrying out process (b), 1 to 2 mols of (thio)phenol of the formula (V) and, if appropriate, catalytic to 2-molar amounts of base are prefer-ably employed per mol of triazolylmethyl-oxirane of the formula (IV). The end products are in each case isolated in the generally customary manner.
Preferred possible diluents for process (c) are alcohols and water, or mixtures of the two.
The reaction temperatures can be varied within a substan-tial range in process (c). In general, the reaction is carried out between 20 and 120C, preferably between 50 and 100C.
In carrying out process (c), 1 to 1.5 mols of hydroxyl-amine derivative of the formula (VI) are preferably employed per mol of the compound of the formula (Ia). The compounds of the formula (I) are isolated by customary methods.
In a preferred embodiment of process (c), the hydroxyl-amine derivatives of the formula (VI) are employed in the form of their salts, in part~cular as hydrochlorides, if appropriate in the presence of an acid-binding agent, such as, for example, sodium acetate (~ompare also the preparation examples).

w ~: :

Possible diluents for the reaction in process (d) are inert organic solvents. These include, preferably, ethers, such as tetrahydrofuran and dioxane; aromatic hydrocarbons, such as toluene and benzene; in~individual cases also chlorinated hydro-carbons, such as chloroform, methylene chloride or carbon tetra-chloride; and hexamethylphosphoric acid triamide, acid amides, such as dimethylEormamide, and sulphoxides, such as dimethylsul-phoxide.
If appropriate, the reaction in process (d) is carried out in the presence of a strong base. Preferred strong bases in-clude alkali metal amides, hydrides, hydroxides and carbonates, such as, for example, sodium amide, carbonate, hydroxide or hydride and potassium amide, carbonate, hydroxide or hydride, and ~uater-nary ammonium hydroxides and phosphonium hydroxides, such as, for example, tetramethylammonium hydroxide, benzyl-trimethyl-ammonium hydroxide or dibenzyl-dimethyl-ammonium hydroxide, and tetraphenyl-phosphonium hydroxide or methyl-triphenyl-phosphonium hydroxide.
The reaction temperatures can be varied within a substan-tial range in process (d). In general, the reaction is carried out between 20 and 150C, preferably at room temperature. In individual cases, it is advantageous to carry out the reaction at the boiling point of the solvent, for example between 60 and 100C.
In carrying out process (d), 1 to 3 mols of halide of the formula (VII) are preferably employed per mol of the compounds of the formula (Ib). To isolate the end products, the reaction mixture is freed from the solvent, and water and an organic solvent are added to the residue. The organic phase is separated off, and .. . . .
, 3 ~

worked up and purified in the customary manner.
In a preferred embodiment of process (d), the reaction is carried out in a two-phase systeml such as, for example, aqueous sodium hydroxide or potassium hydroxide solution/toluene or methylene chloride, with addition of 0.01 - 1 mol of a phase transfer catalyst, such as, for example, ammonium or phosphonium compounds, the alcoholates being formed in the organic phase or at the phase boundary and reacting with the halides in the organic phase.
The compounds of the formula (I) obtainable by the above process can be converted into acid addition salts or metal salt complexes.
The following acids are used for the preparation of non-phytotoxic acid addition salts of the compounds of the formula (I):
the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and further-more phosphoric acid, nitric aeid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumarie acid, tartaric acid, citrie acid, salicylic acid, sorbic aeid and lactic acid, and sulphonic acids, such as, for example, p-toluene sulphonie acid and 1,5-naphthalenedisulphonic aeid.
The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the aeid, for example hydrogen chloride, and they ean be isolated in a known manner, for '`f~

. . ~, . , .,. :
; ~ , :, '' , : ' ~ .
.

~ 3 ~

example by filtration, and if appropriate purified by washing with an inert organic solvent.
Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII are used for the preparation of metal salt complexes of the compounds of the formula (I), examples of metals which may be mentioned being copper, zinc, manganese, mag-nesium, tin, iron and nickel. Possible anions of the salts are preferably those which are derived from the following acids:
hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid, nitric acid and sulphuric acid.
The metal salt complexes of compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of -~he formula (I).
The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystal-lisation.
The active compounds according to the invention of the parent application exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms.
The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant pro,tection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, . . ., ~ .

, : , ' , ':
: ' " i ' ' ~ "
' ~ 3 ~

permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents~ the active compounds can be ?
used with particularly good success for combating cereal diseases, such as against powdery mildew of barley (Erysiphe graminis) and stripe disease of barley (Drechslera graminea), and against Cochliobolus sativus, and furthermore for combating species of Podosphaera, such as, for example, against the powdery mildew of apple causative organism (Podosphaera Leucotricha), species of Botrytis, such as, for example, against the grey mould causative organism (Botrytis cinerea), and also for combating rice diseases, such as Pyricularia oryzae and Pellicularia sasakii. The compounds also have a good action against Puccinia and Pyrenophora teres on cereal.
It should be emphasised that the substances according to the invention of the parent appIication not only have a protective action, but in some cases also have a systemic action. It is thus possible to protect plants from fungal attack if the active com-pound is fed to the above-ground parts of the plants via the soil and the root or via the seed.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble pow-ders, granules, aerosols, suspension-emulsion concentrates, seed treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances ana in coating compositions for seed, and formulations used with burning .
.

~ 3.~

equipment, such as fumigating cartridges, fumi.gating cans, fumi-gating coils and the like, as well as ULV cold mist and warm mist formulations.
These formuations are produced in known manner, for ex-ample by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid car-riers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary sol~ents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketonej methyl iso-butyl ketone or cyclohexanone, strongly polar solvents, such as di-methylformamide and dimethylsulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for ex-ample aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid . . .

., .
.. ' ' ~

~ 3 ~
carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepio-lite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as e~ulsifying and/
or foam-forming agents there are suitable: for example non ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pig-ments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestu:Efs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as ~:.
salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%, The active compounds - 22a -- , ~ .

L 3 ~
~ Z3 -can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared there-from by further dilution, such as ready-to-use solutions, emulsions, suspensions~ powders, pastes and granules.
They are used in the customary manner, for exampLe by watering, immersion, spraying, atomising, misting, vapor-ising, injecting, forming a slurry, brushing on~ dusting, scatter;ng, dry dress;ng, moist dressing, wet dressing, slurry dress;ng or encrusting.
In the treatment of parts of plants, the active compound concentrations ;n the use forms can be var;ed w;th;n a substantial range. They are, in ~ener3l, between 1 and O.OD01% by we;ght, preferably between 0.5 and 0.001~.
In the treatment of seed, amounts of act;ve com-pound of 0~001 to 50 9 per kilogram of seed, preferabLyO.û1 to 10 9 are generally requ;red.
For the treatment of soil, active compound concen-trat;ons of 0.00001 to 0.1% by we;ght, preferably O.OûO1 to 0.02% by we;ght are required at the place of action.
25 Preparat;on examples: ;
Example 1 OH
CH3CO~O-CH2-~-C:tCH3)3 C H ;~

~:
~Process b) ;
A solution of 2~9~ 9 (0.16 mol) of 2-tert.-butyl-Le A 21 965 _ : :
- :

:~ :

:

~ ~ 3 ~ 9 ~

2-(1,2,4-tr;azol-1~yl-methyl)-oxirane in 50 ml of n-pro-panol is added dropwise to a soLution of 24.5 9 (0.1~ mol) of p-hydroxyacetophenone and ~.46 9 (0.02 mol) of sodium ;n 150 ml of n-propanol at room temperature, with stirring.
The reaction mixture is then heated under reflux for 4 days. It is then concentrated, the residue is taken up in ethyl acetate and the mixture is ~lashed twice with 1~
sodium hydroxide so~ution, twice with water and once wi~h saturated sodium chloride solut;on. The ethyl acetate phase is dried over sodium sulphate and concentrated. The residue is chromatographed over a silica gel column (methylene chloride/ethyl acetate = 4 : 1). The resulting product crystallises after addition of ether~ 26.9 g (53%
of theory) of 2-(4-acetoohenoxymethyl)-3,3-dimethyl-1- ;
(1,2,4-triazol-1-yl)-2-butanol of melt;ng ?oint of 93-99C are obtained.
Example 2 . OH
HON=C ~O-CH2-C-C( CH3) 3 CH3 CHz ~ N ~N
N
: ; .
(Process c) 43~5 9 (0.137 mol) of 2-(4-acetophenoxymethyl)-3~3-d;methyl~ 2~4-triazol-1-yl)-z-butanol (Example 1), 14.28 9 (0~2055 mol) of hydroxylamine hydrochloride and 16.~5 9 (n.2055 mol) of sodium acetate are dissolved in a mixture of 150 ml of water and 250 ml of ethanol and the solution is heated under reflux overnight. The react;on m;xture is then concentrated, the residue is taken up in watertethyl acetate and the mixture ;s rendered basic~
with 1N sodium hydroxide solution. The organ;c phase is separated off and~the aqueous phase is extracted twice with ethyl acetate. The combined organic ohase~s are Le A 21 965 ._ : , ' , ~ : -:

:: :
;

~ 3 ~

washed once wlth dilute and twice wlth saturated sodlum chlorl,d,e solutlon, dried over sodlum sulphate and concentrated. Recrystal-llsation of the residue from acetonltrile gives 34.8 g (76.5 % of theory) of 3,3-dimethyl-2-[4-(1-hydroximlnoethyl)-phenoxymethyl,-l-(l,Z,4-trlazol-1-yl)-2-butanol of melting point 129-132C.
Example 3 Cl OH
Cl ~ CH2ON=C ~ O-CH2-C-c(cH3)3 / N \
ll N
N
(Process d~
1.44 g (0.06 mol) of sodlum hydride (80~ strength in paraffin oil) are added to a solution of 14.94 g ~0.0~45 mol) of 3,3-dlmethyl-Z-[4-(1-hydroxlminoethyl)-phenoxymethyl]-1-(1,2,4-triazol-l-yl)-2-butanol (Example 2) in 120 ml of absolute dl-methylsulphoxide. The reaction mlxture ls stirred at room temperature for about l hour, until a clear solution has formed.
a.33 ml (0.06 mol) of 2,4-dichlorobenzyl chloride are then ad,~ed and the reaction mixture is subsequently stirred at room tempera-ture for 1.5 hours. Thereafter, water and glacial acetic acid are carefully added and the mixture is concentrated. The residue i8 taken up in ethyl acetate and the mixture is washed several tlmes with dilute sodium chloride solutlon, drled over so~ium sulphate and concentrated. The residue is chromatographed over a silica gel column (methylene chloride/ethyl acetate ~= 4 , 1) and the product ls recrystalllsed from, acetonitrlle. 16.2 g (73% of .

~ 3.~
....

25a 23189-5606D
theory) of 2-{4-[l-(2,4-dlchlorobenzyllmlno)-ethyl]-phenoxymethyl}-3,3-dimethyl-1-(1,2,4-trlazol-1-yl)-2-butanol of ~elting point 101C are obtained.

, :
: . : : . .

~: , :

-~ ~3~9~

Example 4 OH
r ~ CH=CH-C-C(CH3)3 ~ C,H2 /N~N
N ll tProcess a) 25.6 g (0.093 mol) of 2-~2-C4-(1,3~d;oxolan-2-yl)-5 phenyl]-ethenyl}-2-tert.-butyl-ox;rane ;n 47 ml of absol-ute dimethylformamide are added dropw;se, at rooln tempera-twre, to a solution of sodium triazolide, prepared by slowLy introducing 12.9 9 (0.1~7 mol) of 1,2,4-triazole into a suspension of 5.6 g (0.187 mol) of sodium hydride 10 (80X strength in paraffin oil) in 137 ml of absolute di-methylformamide. The react;on m;xture is stirred at 80C
for 4 hours and left to stand overnight at room temperature Thereafter, the~reaction mixture ;s poured onto ;ce water and extracted several times with ethyl ace;tate. The com-15 bined ethyl acetate phases are washed tw;ce with waterand once with saturated sodium chloride solution, dried over sod;um sulphate and concentrated. The residue is chromatographed oyer a siliGa gel column (methylene chlor-ide/ethyl acetate = 2 : 1) and the product is recrystal-20 l;sed from n-hexane/ethyl acetate. 7.75 9 t24 ~ of theory~
of 3,3-dimethyl-2-~2-~4-(1,3-d;oxolan-2-yl)-phenyl~-ethenyl3-1-t1,2,4-triazol-1-yl)-2-butanol of melt;ng point 109.5 - 110C are obtained.
Preparati_n of -the start;ng substance ;
: ::
z 5 ~ ;3 C H ~ C H - , C ~ _ r t C H 3 ) 3 O--C H 2 ~ ~ :
:`

;~ ~ Le A 21 965 . . . _ ':

8.1 ~ (0.13 mol) of iodomethane are slowly added dro?wise to a solution of 9~9 ml (0.135 mol) of dimethyl sulphide in 75 ml of absolute dimethylsulphoxide and 35 ml of absolute tetrahydrofuran, during which the internal temperature must not rise above 35C. This suspension is subsequently stirred at room temperature overnight, and 15.7 9 (0.14 mol) of potassium tert.-butylate are then added in portions. The mixture is subsequently stirred at room temperature for 30 minutes and cooled to 0C, and 26 9 (n.1 mol) of 4,4-dimethyl-1-C4-(1,3-dioxolan-2-yl)-phenyl]-1-penten-3-one are added in portions. The re-action mixture is subsequently stirred at room temperature overn1ght, water ;s then added and the mixture is extracted three times with toluene. The combined toluene phases are washed with water and saturated sod;um chloride solu-tion, dried over sodium sulpnate and concentrated. 25.6 9 of crude 2-~2-C4-(1,3-dioxolan-2-yl)-phenyl~ethenyl~-2-tert~-butyl-oxirane are obtained as an oil, which is further reacted directly.

[ ~ -~ ~ CH=cH-co-c(cH3)3 100 9 (0.5612 mol) of 4-(1,3-dioxolan-2-yl)-benz-aLdehyde and 56.1 9 (0.56 mol) of pinacoline are dis-solved in a mixture of 2~0 ml of ethanol and 56 ml of water~ and 17 ml of 10 % strength sodium hydroxide solut;on are added at room temperature. The mixture is subsequently stirred for 1 hour, 0.56 9 of solid sodium hydroxide are added and the mixture is subsequently stirred ~or 2 days.
Thereafter, the precipitate is filtered off with suction, washed with 200 ml of ethanol/water (1:1) and then with water, dried and recrystalLised twice from ethanol~
5S.5 9 (39 ~ of theory) of 4,4-dimethyl-1-C4-(1,3-dioxo-lan~2-yl~-phenyl]-1-penten-3 one of melting ooint 79-31C
Le A 21 965 .. ,~.,., .., .

'' ' ~ 3 ~

are obtained.

Example 5 OH
CH3ON=CH ~ CH=CH-C-C(CH3)3 N
(Process c) 1 g (0.0029 mol) of 3,3-dimethyl-2-{2-[4-(1,3-dioxolan-2-yl)-phenyl]-ethenyl}-1-(1,2,4-triazol-1-yl)-2-butanol (Example 4), 0.42 g (0.005 mol) of O-methylhydroxylamine hydrochloride and 0.41 g (0.005 mol) of sodium acetate are di.ssolved in 20 ml of ethanol and 15 ml of water and the solution is heated under reflux for 2 hours. The reaction mixture is concentrated, the residue is taken up in ethyl acetate and the mixture is washed twice with water and once with saturated sodium chloride solution, dried over sodium sul~hate and concentrated. The crystalline residue is wash-ed with a little ether and recrystallised from n-hexane/ethyl acetate. 0.67 g (70 % of theory) of 3,3-dimethyl-2-[2-(4-methox-iminomethylphenyl)-ethenyl]-1-(1,2,4~triazol-1-yl)-2-butanol of meIting point 140-142C are obtained.
The following compounds of the general formula OH
- X - C - R (I) ~N~N: : :
N ~
are obtained in an analogous mannQr corresponding to processes (a) to (d):

:: - 28 -,,,~.

1 3 ~

Example I~ o - _ R ¦ ( C ) o r n ~ L

6 4-CH30N=CH- -- -OCH2~ --C ( CH3) 3 92-93 7 4-CH301N=C~CH3)- - -0CH2- ~C( CH3) 3 9z-94 8 4-CH2=CH-CH2GN=C(CH3)^ _ -0CH2- -C(CH3)3 1.5445 9 4-CH3CO- - -OCH2- -c(cH3)2cH2F 111 4-OH~C- - -OCHZ- -C'~H3)3 1 5451 1 1 4-CH3CO- . ~ -OCH 7- -CtCH3)~ 80-81 1, ~1 ~ ~ C L, ~
12 4-OHC- - -OCH2- -ctCH3)2 1.54S7 13 4-CH30N=C(CH3)- - -OCHz- -C(CH3)2CH2 94.5-35 14 4^CH30N=CH - -CH2CH2- -C(CH3)3 77_79 4-CH~ON-CH- - -OCHZ- -C(CH3j2 1.-430 '6 4-C~30N=C(CH3)- --OC~CH3)2 62-5_ : ~ . C~.20C.~3 17 4~2=CH~H2-ON=cH- OCH2~(C~3)3 ~ 1~5560 18 4~ 12--C(CH3)3 1 .;692 19 3 - [~ 2-~ (t~H3) 3 73_75 ~
4--L7- ~Cl 135-36,S
1 3{~30W~- ~ ~ ~2-~ ~ ~(t~H3)3 ~ 76-78 Z2 2~3~ ~ ~2- ~(CH3) 3 ~105,~
23 2~I30N=C(t~3)~ ~ 2 -C(CH3)3 ; ~ ~ Le A 21 965 :: :

31~9~

Use examPles The substances shown below are used as comparlson compounds in the use examples whlch follow:
OH
(A) ~ -o-cH2-p-c(cH3)3 f~2 / N

N
OH
~ I
(B) CH3 ~ 0-CH2-C-C~cH3)3 /N~
r N
N - 1 ¦
.

OH
~ I
(C) Cl ~ O-CH2-1C-c(cH3)3 ~N~
ll N
N -~
OH
I .
(D) F ~ O-CH2-C-C(CH3) ' .
/ N

N
-:

, . . - - - ~ ~,: . . . . . .

- ` ~ 3 ~

Example A
Cochl;obolus sativus test (barley) / protect;ve Solvent: 100 parts by we;ght of d;methylformam;de Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of act;ve compound ;s mixed with the stated amounts of solvent and emulsifier~ and the concentrate is diluted with water to the desired con-centration.
To test for protective activity, young plants aresprayed with the preparat;on of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a con;dia suspension of Cochliobolus sativus. The plants rema;n ;n an ;ncuba-tion cabinet for 48 hours at 20C and 10û~ relative atmospheric humidity.
The plants are placed in a greenhouse at a temperature of about Z0C and a relative atmospheric humidity of about 30~.
Evaluation is carried out 7 days after the inoculation.
In this test~ a clearly superior activity com-pared with the prior art is shown, for example, by the compounds accord;ng to the following preparation examples:
o and 7.

Le A 21 965 -:

.

.
: '' ~: ;

:~3~9~ .
, . , Example B
Erysiphe test (barley) / seed treatment The active compounds are used as dry dress;ngs.
These are prepared by extending the particular active compound with a ground m;neral to give a finely pulveru-lent mixture, which ensures uniform distribution on ~he seed surface.
To apply the dress;ng, the seed is shaken with the dressing in a closed glass flask for 3 minutes.
3 batches of 12 ~rains of the barley are sown 2 cm deep in standard soil. 7 days after sowing, when the young plants have unfolded their first leaf, they are dusted with spores of Erysiphe graminis f. sp. hordei.
The plants are placed in a greenhouse at a tempera-ture of about 20C and a relative atmospheric humidity of about 30% in order to promote the develooment of powdery m;ldew pustules.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to ~e f~llowing preparation examples: 7.

:

:- ..

Le A 21 965 ~ :
' :
,,:
"'' :

.

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Example C
Drechslera graminea test (barley)/seed treatment (syn. Helminthosporium gramineum) The act;ve compounds are used as dry dressings.
These are prepared by extending the particular active compound with a ground mineral to give a finely pulver-ulent mixture, which ensures uniform distribution on the seed surface.
To apply the dressing, the infected seed is shaken with the dressing in a closed glass flask for 3 minutes.
The seed is embedded in sieved, mo;st standard soil and ;s exposed to a temperature of 4C in closed Petri dishes in a refrigerator for 10 days. Germination of the barley, and possibly also of the ~ungus spores, is thereby initiated. 2 batches of Sû grains of the preger-minated barley are subsequently sown 3 cm deep in stand-ard soil and are cultivated ;n a greenhouse at a tempera-ture of about 18C, in seedboxes which are exposed to light for 15 hours daily.
About 3 weeks after sowing, the plants are eva-luated for symptoms of stripe disease.
In this test, a clearly superior activity com~;
pared with the prior art is shown, for example, by the compounds according to the following preparation examples:
6 and 7.

: -~ Le A 21 965~

"`J

:: :

~:

~ 3 ~
,, -- S~t --Example D
Podosphaera test (apple) / protective Solvent: 4.7 parts by weight of ace~one Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound ;s mixed w;th the stated amounts of solvent and emulsifier, and the con-centrate is diluted with water to the desired concentration~
To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated by dusting w;th conidia of the powdery mildew of apple causative organism ~Podosphaera leucotricha).
15 The plants are then placed in a ~reenhouse at 23C and a relative atmospheric humidity of about 70%.
Evaluation is carried out ~ days after the inoculation.
In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 7 an~d 6.

~: :

-Le A 21 ~65 " ~ , :

' ~L 3 ~
~5 -Example E
Botrytis test (bean)/protertive Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by we;ght of act;ve compound ;s m;xed w;th the stated amounts of solvent and emuls;fier~ and the concentrate is diluted w;th water to the desired concen-tration.
To test for protective activity, young plants are sprayed with the preparation of ac~ive compound until dripping wet. After the spray coating has dried on, 2 small p;eces of agar covered with aotrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened humid;ty chamber at 2ûC. 3 days after the inoculat;on, the s;ze of the ;nfected spots on the leaves is evaluatedn In this test a clearly super;or act;v;ty compared with the pr;or art ;s shown, for example, by the compounds 2~ according to the following preparat;on examples: 6.

' :
:
: :
~:

Le A 21 963~

:-:
., . ~..... . : :

: .

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.i ~

Example F
Pyricularia test (rice)/protective Solvent: 12.5 parts by weight of acetone Emulsifier: û.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, 10 to the desired concentration.
To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension 15 of Pyricularia oryzae. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and 25C.
Evaluat;on of the disease infestation is carried out 4 days after the ;noculation.
In this test, a good activity is shown, for example Z0 by the compounds according to the following prepar3tion examples: 6.

Le A 21 965 '' ~ ' ` ' ~, ~ 3 ~

Example G
Pyricularia test (rice)/systemic Solvent: 1Z.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly~lycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentrat;on.
To test for systemic properties, standard soil in which young rice plants have been grown ;s watered w;th 40 ml of the preparation of active compound. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. There-after, the plants remain in a greenhouse at a temperature of 25C and a relat;ve atmospheric humidity of 100%
unt;l they are evaluated.
Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, a clearly superior activity compared~
with the prior art is shown, for example~ by the compounds according to the following preparation examples: 7.

Le A 21 965 .

3 ~

Example H
Pellicularia test (rice) Solvent: 12.5 parts by weight of acetone Emulsifier- 0.3 part by weight of alkylaryl polyglycol ether rO produce a suitable preparation of active com-pound, 1 part by weight of active compound is ~ixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount oF emulsifier, to the desired concentration.
To test for activ;ty~ young rice plants in the 3 to 4 leaf stage are sprayed until dripping wet. The plants remain in a greenhouse until they have dried off.
The plants are then inoculated with Pellicularia sasakii and are placed at 25C and 100~ relative atmospheric humidity.
The evaluation of the disease infestation is carried out 5 to 8 days after the inoculation.
In this test, a good activity is shown, for example, by the compounds according to the following preparalion examples: 6.

.

Le A 21 965 ~:

:

Claims

23189-5606(D) THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An oxirane of the formula II

(II) in which R represents tert.-butyl or isopropyl, or represents cyclopropyl, cyclopentyl or cyclohexyl, in each case optionally mono-, di- or tri-substituted by identical or different substituents from the group consisting of methyl, ethyl, isopropyl, methoxy and ethoxy, or represents phenyl which is optionally mono-, di- or tri-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl, trifuoromethyl, phenyl and chlorophenyl, or represents the grouping or ;

wherein R1 represents hydrogen, fluorine or chlorine;

23189-5606(D) R2 represents fluorine or chlorine;
R3 represents ethyl, propyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, vinyl, methoxycarbonyl, ethoxycarbonyl or cyano, or represents phenyl, phenoxy, phenylthio, phenylmethoxy or phenylmethylthio, the last five radicals mentioned may be substituted by fluorine, chlorine, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, dimethylamino, methoxy-carbonyl and ethoxycarbonyl; and n represents the number 0, 1 or 2;
X represents the grouping -OCH2-, -SCH2-, -(CH2)p or -CH=CH-;
Y represents the grouping -CO-Y1, -C(OR4)2-Y1 or , or the grouping -C(Y1)=N-OY2;

Y1 represents hydrogen, methyl, ethyl or isopropyl, or represents phenyl, which is optionally mono- or di-substituted by identical or different substituents selected from the group consisting of fluorine, chlorine, methyl and trifluoromethyl;
Y2 represents hydrogen, methyl, ethyl, n-propyl, n-butyl, allyl or propargyl, or represents benzyl which is option-ally mono- or di-substituted by identical or different substitu-ents selected from the group consisting of fluorine, chlorine, methyl, trifluoromethyl and trifluoromethoxy;
R4 represents methyl, ethyl or propyl;
q represents the number 2 or 3;

23189-5606(D) z represents fluorine, chlorine, bromine, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, m represents the number 0, 1 or 2; and p represents the number 0, 1 or 2.

2. A compound according to claim 1 wherein R represents the grouping or wherein R1, R2, R3 and n are as defined in claim 1.

3. A compound according to claim 1 wherein R is tert.-butyl.

4. A compound of the formula 5. A compound of the formula 6. A compound of the formula 23189-5606(D) 7. A compound of the formula 8. A process for preparing an oxirane of formula II as defined in claim 1 which comprises reacting a ketone of formula VIII

(VIII) wherein R, X, Y, Z and m are as defined in claim 1 , with either .alpha.) a trimethyloxosulphonium methylide of formula IX

(CH3)2SO CH2 (IX) in contact with a diluent, or .beta.) a trimethylsulphonium mehtyl-sulphate of formula X

(CH3SO4) (-) (X) in contact with an inert organic solvent and a base.