CA1178587A - Substituted 1-azolyl-butan-2-ones, processes for their preparation and their use as fungicides and as intermediate products - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Substituted 1-azolyl-butan-2-ones of the formula

Description

The present invention relates to certain new substituted l-azolyl-butan-2-ones, to several processes for their production and to their use as fungicides and as intermediate products for the synthesis of other plant protection agents.
It has already been disclosed that certain triazolyl-keto derivatives, such as 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one, ~-(1,2,4-triazol-1-yl)-2,4-dichloroacetophenone or 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-one, having a generally good fungicidal activity (see our DE-OS
(German Published Specification) 2,431,407 and also DE-OS (German Published Specification) 2,734,426). However, in certain fields of indication, the action of these triazole derivatives is not always completely satisfactory, especially when low amounts and concentrations are applied.
The present invention now provides, as new compounds, the l-azolyl-butan-2-ones of the general formula CH
R CH - CO - C - (CH2)n - R2 (I) Az CH3 in which Az represents a 1,2,4-triazol-1-yl or -4-yl or imidazol-l-yl radical, Rl represents a hydrogen atom, an alkyl radical with 1 to 6 carbon atoms, an alkenyl or alkinyl radical with 2 to 6 carbon atoms, a cyclohexyl or cyclohexylmethyl radical optionally substituted by methyl, a phenoxyalkyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl moiety, the phenyl moiety being optionally substituted by fluorine, chlorine, methyl, ethyl, {~
i ~ --1--~v~

a~ 7 isopropyl, tert.-butyl, dimethylamino, methoxy, methylthio, cyclohexyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, phenyl, phenoxy, fluorophenyl, chlorophenyl, chlorophenoxy, fluorophenoxy or the group -Co-NR7R8, in which R7 and R8 each independently is hydrogen, alkyl with 1 to 4 carbon atoms, optionally halogen- and Cl to C4 alkyl-substituted phenyl, or R7 and R8 both together with the adjacent nitrogen atom form a saturated 5- or 6-membered ring system which may possess nitrogen or oxygen as additional hetero atoms;
n is O or 1, R represents a cyano radical or a grouping of the general formula -X-R3 or -CO-NR R , or, if _ does not represent O at the same time as Rl represents a hydrogen atom and Az represents a 1,2,4-triazolyl radical, R may also represent a phenyl radical which is optionally substituted as defined for phenyl under Rl or an alkoxycarbonyl radical having 1 to 3 carbon atoms in the alkoxy moiety, and wherein X represents an oxygen or sulphur atom or an SO or S02 group, R3 represents an alkyl or halogenoalkyl radical having 1 to 4 carbon atoms, or a phenyl or benzyl radical which is optionally substituted as defined for phenyl under Rl, R represents a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, or a phenyl radical which is optionally substituted as defined for phenyl under Rl, and R5 represents a hydrogen atom or an alky~ radical having 1 to 3 carbon atoms, ~ 3~ ~

or acid addition salts or metal salt complexes thereof.
Accordi.ng to the present invention there is further provided a process for the production of a compound of the present invention, characterised in that a) a halogenoketone of the general formula C,H3 R2 Hal - CH2 - CO - C - (CH2)n (II) in which Hal represents a halogen atom, in particular a chlorine ox bromine atom, and R and n have the abovementioned meanings, but in the grouping -X-R3 the substituent X only represents oxygen or sulphur, is reacted with an azole of the general formula H-Az (III) in which Az has the abovementioned meaning, -2a-in the presence of a diluent and in the presence of an acid-binding agent; and b) if a compound of formula (I) is required in which R1 is other than a hydrogen atom, the compound produced by reaction variant (a) of the general formula Az - CH2 - C0 - C - (CH2)n - R (Ia) in which Az, n and R2 have the abovementioned meanings, is reacted with analkylating agent of the formula Rl-Z (IV) in which R1 has the same meaning as in formula (I), other than a hydrogen atom and Z represents an electron-withdrawing leaving group, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst; and c) if a compound of formula (I) is required in which X
represents S0 or S02~ a compound obtained by reaction variant (a) or (b), of the general formula CH3 (Ib) Rl _ CH - C0 - C - (CH2)n - S - R
I .
Az CH3 in which Az, Rl, n and R3 have the abovementionea mea. ng, i5 oxidised, and~ if desired, an acid or a metal salt is then added on to the resulting compound of the formula (I) obtained by Le A 20 763 reaction variant (a), (b) or (c).
In some cases, it proves to be advantageous to obtain the compounds of the formula (I) in the pure form via their salts.
The new substituted l-azolyl-butan-2-ones of the present invention have powerful fungicidal properties. Surprisingly, the compounds according to the invention exhibit a better fungicidal aetion than the triazolylketo derivatives 3,3-dimethyl-1-(1,2,4-triazol-l-yl)-butan-2-one, ~(1,2,4-triazol-1-yl)-2,4-dichloro-aeeteophenone and 1-(4-ehlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-one, which are known from the state of the art and are similar eompounds chemically and from the point of view of their action.
The new substituted l-azolyl-butan-2-ones of the formula (I) are also interesting intermediate products for the preparation of other active compounds for plant protection. Thus, as will also be described, it is also possible, for example, for the keto group to be reduced to a -CH(OH) group. Furthermore, functional derivatives of the keto group, such as oximes and oxime ethers, hydrazones and ketals, can be obtained by appropriate reactions.
The substances according to the invention thus represent a valuable enrichment of the art.
Partieularly preferred compounds of the present invention are those in which Rl represents hydrogen, a straight-chain or branched alkyl radical with 1 to 6 carbon atoms or benzyl which is optionally substituted in the ring by chlorine, ~ ~ 4 R2 represents a grouping of the formula -X-R3 in which X is oxygen or sulphur, and R3 represents a straight-chain or branched alkyl radical with 1 to 4 carbon atoms or phenyl or benzyl substituted in the ring by chlorine or bromine.
The following compounds of the general formula (1) (in which Az represents a 1,2,4-triazol-1-yl or imidazol-l-yl radical) may be mentioned specifically, in addition to the compounds mentioned in the Preparative Examples:

Rl CH - CO - C - (CH2)n (I) Az CH3 Rl n R

H 1 -O- ~ CH3 CH~
C2H5 1 -0--~G~CH3 Cy~
C4Hg 1 ~ ~ -CH3 CH\3 Cl ~ CH2- -O ~ CH3 CH2- 1 ~ ~ CH3 ~:`

~; ~

Rl. . .. n . . . . R2. . . .

H 1 -0- ~ -CH3 C2H5 1 ~ ~ CH3 C4H9 1 ~ CH3 Cl ~ -CH2 1 ~ CH3 -CHz- 1 -0- ~ -CH3 H 1 -0- ~ -C(CH3~3 C2H5 1 -0- ~ -C(CH3)3 C4Hg 1 -0- ~ -C(CH3)3 Cl- ~ -CH - 1 -0- ~ -C(CH3)3 -CH2- 1 ~ ~ -C(CH3)3 H 1 -0 ~ -C2H5 Le A-20 763 "5~ffS, ~;7 Rl n .. .. R .

C2H5 1-0~-C2H5 C 4Hg 1_ 0~ - C 2H5 C 1~ - CH2- 1- 0~ - C H5 CH2- 1~) 2 5 H 1-0-~-~

' C 2 H5 1- 0~) C4H9 1-0~-~

C1~-CH2- 1-o~

@~-CH2- 1o~~OE~

H 1-0~-OCF3 C2H5 1-O~)-OcF3 C4H9 1~ OCF3 Le A 20 763 3'7 R n R2 Cl-~-CH2- 1 -O-<~>-OCF3 ~ - CH2 - 1 -O- ~ -OCF3 H 1 -0-@~

C2 Hs 1 _o_<~

C4Hg 1 -0-@~
c~3 Cl-<g~) -CH2 ~ 1 ~~~ CF3 CH2 - 1 -0-~

CH~,CH3 H 1 -0-~,) CH~ ,CH3 C2 H5 1 -O- ~
CH3 CH3 ., C~, ~Ig 1 -0-0 Cl-~-CH~- 1 ~~~S
CH~ /CH3 (~ -C~2 - 1 . -O -~

Le A 20 763 ~- g ~_ ~ ";,Jj? C~

R' n R2 H 1 -O-~ -CH3 C2 H~ O- (~ -CH3 C~, Hg1 -O-~ -CH3 ~ CH3 Cl-~-CH2-1 -O~)-CH3 CH2 - 1 -0-~> - CH3 CH3 ~
H 1 -O-~>

C~I3 Cz H5 1 -O-~

C4Hg 1 -O-~

Cl~>-CH2-- CH3 ~- CH2 - CH3 CH3~

H 1 -O- ~-OCH3 C2H5 - 1_o_<~>-OCH3 Le A 20 76~

R1 n R2 C4 Hg 1 -O-~ -OCH3 c~ CH2~ 1 -O~-OCH3 <~- CH2- 1 -O-<~>-OCH3 ~ CH3 H 1 -O-~>-N

~ CH3 C2 H5 1 -~> ~ CH
C4 Hg 1 0 <~ N.~ CH

,CH3 cl-<~-CH2- 1 -O-~>-N

~) -CH2- 1 . O ~) N~CH~
~CH3 H 1 -O-~

C2 H5 Cl C4 Hg Cl Cl-~ -CH2 - . -O- <~

(~>-CH2- 1 -0-~
Cl~
Le A 20 763 R' n R2 H 1 Cl Cz H~ 0~

C4 Hg 1 -0~>
Cl Cl-~-CH2- 1 Cl CH~
@ CH2- 1 cl~
,CH3 H 1 -0-~3-Cl C2 H5 1 -0-~-Cl C4 Hg 1 -0-~5-Cl Cl-~>-CH2- 1 -0-~-Cl ~- CH2- 1 -0-(~-Cl H 1 -0- ~-Cl C2 H5 1 -0-~-Cl C4 Hg 1-0~) -Cl c~3 Cl~>-CH2- 1 -0~-Cl Le A 20 763 :l i r'~5~
~æ

R' n R2 cx3 ~) -CH2- 1 -O-~-Cl CH3 ,Ç~l H 1 -0~
CH3 Cl C2 Hs 1 -0~
CH3 Cl C4 Hs 1 -0~>
CH3 Cl Cl- ~-CH2 - 1 -0~
CH3 Cl CH2 - ' 1 -0~

H 1 -0~ - ~>

' C2H5 1 --~

0 C4 Hg 1 -o- ~ _ Cl- ~ -CX2 -- 1 . -0-<~) -(3) -CH2 - 1 -O- <~-~
Cl H . 1 -0-~<

C4 ~9 CH3' Le A 20 763 Rl n R2 Cl~CH2- 1 -0-~
c~3 <~-CH2- 1 -0~) _, H 1 -0~,~
Cl CH3 C2 Hs 1 -0-~
Cl H3 C4 Hg 1 --OE>
Cl ~3 Cl-@-CH2- 1 -0~
Cl CH3 -CH2- 1 -0-~
Cl H3 H CH

C2 H5 1 -0- ~Cl C4 Hg 1 -0-~ Cl Cl-~>-CH~ - 1 -0-~ Cl Le A 20 763 ~ ~17~3~8'~

Rl n R2 ~ CH3 (~CH2 - 1 -0-~ Cl -0-~ -CH3 .
C2 H~ 1 ._o_~-CH3 Cl C" Hg 1 _o~ CH3 Cl-~>-CH2- 1 -0-<~?~-CH3 Cl ~CH2- 1 ~Cl Cl H 1 -0-,~

Cl C2 Hs 1 -0-~

Cl C4 H9 1 -0- (~
C 'H

Cl-OE~-CH2- 1 --OE~
C2'H5 - Cl - ~ -CHz- 1 -0-<~

Le A 20 763 ..

.3 /S

Rl n R2 Cl H 1 -0~>
C(CH3 )3 C2 H5 1 C~
C ( CH3 ) 3 C4 Hg 1 -0-~
c~C~I3 )3 Cl~>-CH2- 1 -0-~>
C(C~3 )3 <~CH2- 1 _o_~>
C(CH3 )3 H 1 (~Cl C2 H5 1 ._o_@~-C ( C.~3 )3 C4Hg 1 -0-~-C(CH3 )3 Cl 10 Cl-~> -CH2 ~ 1 -0- O-C ( CH3 )3 \Cl OE~-CH2 - 1 -O-~C ( CH3 ), Le A 20 763 `' ~ /G, R' n R2 H 1 -0-&~-CN

C2 H5 1 -0- ,~ -CN

C4 Hg 1 -0-~> -CN

Cl~>-CH2- 1 -0-~-CN

<~-CH2 - 1 -0-(~ -CN
CN
H 1 -0-<~
CN
C2 H5 1 -0~
CN
C4 Hg i 0~
CN
10 . Cl~-C~2- 1 -o~
CN
(~-CH2- 1 -0-~

CN
H ~ -0 CN
C2Hs 1 -0 CN

CN
Cl-~-CH2 - 1 -0 C..l O-CH2- 1 -0-~>

H 1 -0-CH2 -O -Cl . Le A 20 763 h7 ,~
R' n R2 .

C2 ~5 1 -O-CH2 -~) -Cl C4 Hg 1 -O-CH2 -O -Cl C~ -CH2.- 1 -O-CH2-~-Cl ~>-CH2- 1 -O-CH2-<~-Cl H 1 -O-CH2 -~
CI

C2Hs l -O-CH~ ~

C4 Hg 1 -O-CH2 ~>

Cl- (~ -CH2 ~ 1 -O-CH2 -~

~ -CH2- - 1 -O-CH2 (~) H 1 -O-CH2-~
C2Hs l -O-CHz~
C4 Hg 1 -O- CH2 ~>
Cl ~> - CH2 ~ 1 - O - CH
~> -CH2 - 1 -O - CH
~ .

g~ ~
"~``1~ ~

R' n R2 H 1 -0-CT.~2 - ~-Cl Cl C2 H5 1 -O-CH2 ~ Cl Cs EIs ~ Cl Cl-~ -CH2 ~ 0-CHz -@~ -Cl <~-CH7- 1 -O-CH2~-Cl H 1 -0-CH2 ~ &\ -CF3 C2 H5 1 -0-CH2 - (~)-CF3 C4Hg 1 -O-CH2-~>-CF3 Cl-~ -CHa - 1 -0-CH2 - ~-CF3 <~ -CH2 - ~ -0-CH2 - O-CF3 H 1 -o-CH2-~3 Cl C2 H5 1 -0-Cn2 -~
CI

Le A 20 76 ~

s ~y

- 2~ -Rl n R2 Cl C4 Hg 1 -O-CH2 ~) Cl Cl~ CH2 ~ 1 --CH2 ~) Ccl-@>-CH2 ~ o-CH2 i~

H 1 -0-CH2 ~ -M02 C2 Hs 1 -0-CH2 -~ -N02 C4 Hg 1 -0-CH2 -~> -N02 Cl- <~ -CH2 ~ 1 -0-CH2 -~ -N0~

~> -CH2-- 1 -O-CH2-~)-NO2 H 1 -O-CH2-<~-C~3 C2 H5 1 -0-CH2 ~ -CH3 C4 H9 1 -0 CH2 -<~ - CH3 Cl-~ -CH2 - 1 -0-CH2 - ~ -CH3 CH2 - 1 -O-CH2 -~ -CH3 Le A 20 76 ~

7~

.~

R' n . R2 H 1 -0-~-S~F3 .CzH5 1 _O-~-SCF

C~ Hg 1 -O-~>-SCF

Cl~cH2 1 -O-~-SCF

~-CHa- 1 -O-<~-SCF

H 1 -0-~
Cl CH3 C2 H~ 1 -o~
Cl CH3 C~, H5, 1 -O ~

Cl~-CH~ C~3 Cl , CH3 (~ CH2 -- 1 -O-Cl Le A 2Q 763

3 ~ ~

R' ! n R2 C~
H 0 c~ 3 C2 ~.g ! --0--~--C~J-3 CY.~ ..
C~ Hg O -0-~ -Cn3 CH
Cl~ Cr~2- 0 -0~-CH~

<~ -CH2- O _o_~ H3 H 0 -0~ CH~

C2 ~ig O - -O- ~ -C~.i3 C~ Hg , O -0-~> -CH~
Cl- <~>-Cr~2 - ~0 ~~ OE~ -C~3 <~ C~ ", O -O-(~>-CH3 O -O-<~-C(C-rI3 C2 ~ , _o_~ -C ( CH3 ~.s ! .

Le A 20 763 -- 2~--Rl n R2 C4H9 _o_~-C(CH~ ~3 Cl-<~ -CH2 - _o ~ -C (CH3 -)3 ~-CH2- 0 . -os<~-c(cH3 )3 H O -O~ C2 H

C2 H5 o . -o-~> -C2 Hs ,: .
. C4Hg O -O-(~-C2 Hs Cl-~-C-sI2 - -O-~>-C2 Hs <~ -C~z _ O 0~ -C2 ~s ~ : 10 H O o @ <~>
s 0 -0-~

- ~ C,~Hg O . -0-(~

Cl-~-CH2- 0 -0-<~

-CH2 ~ ~~~> ~

H O -O- ~) -OCF~

. C2 Hs O . -0-~) -OCF, C~ H9 O -O- ~-OCF3.
Le A 20 763 ~.. .

- ~ -R n R2 c~ -CH2- -O~>-OCF3 CH2- 0 -O-~-OCF3 H O -0~

C2 Hs 0 _o_@
~CF3 . .

C4Hg -0-@~

Cl-~3-CH2- o _0_~

~-CHz- --@~

CH~ CH3 H ~~ O
CH~CH3 C2 H~ O ~
CH~,CH3 C4 Hg . O _o_~

cl-~?-CH2- ' ' --~S
CH3 ,CH3 ~-CH2- 0 ' -0-~

.

Le A 20 763 '' '`Cl Rl n R2 .
H . 3 -O~-CH3 -O-~-CH3 . C~Hg O -O-~-CH3 C~3 ~;~ 5 Cl-<~-CH~- -~-C~3 CH

CH2- 0 -O~>-CH3 . CH3 . CH
: H ~~~

C2 H~ O ` o ~) C4EIs -0-~
,r~3 Cl~>-CH2- 0~) CH
~>- CH2- 0 _o~>
: CH3 H O ~ -O- ~-OCH~

i - C2 H5 0 -0-~ -OCH3 Le A 20 763 .

~-.

~s - 2~--R' n R2 _ _ .
C ~ Hg o -0~ OCH3 Cl-~-CH2- 0 -O~OCH3 ~>- CHz- O -O~ OCH3 H O O ~> N~ C}' C2 Hs . -0~> -N~

C" Hg O O (~ N~ CH

Cl-<~-CY,2- . O O ~> N~CY3 ~CH2- 0 o ~> N~CH5 H O O ~C
Cl' C~i3 C2 ~S O Cl~

C4 H9 0 ,~
Cl Cl~ >-C~2- 0 Cl/~

<~-C~2- o 0 ~
Cl' Le A 20 763 q~
R' n R2 CH
H 0 -0-~
Cl -C2 Hs 0 -0-~>
Cl C4 Hg 0 -0 Cl -Cl~ CH2- 0 -0-~) Cl CH~

~- CH2- 0 Cl~
,CX3 H 0 -0-~-Cl C2 H5 0 --(~S-Cs Hg -0-<~-Cl Cl-~~CH2- 0 O-~-C
,cx3 (~)- CH2- 0 -0-~-Cl H 0 -0-~>-Cl C2 H5 0 -0-~> -Cl C4 Hg 0 -0-~ -Cl Cl~-CH2- 0 -0~-Cl Le A 20 763 c?~

R' n R2 CH2- 0 -O-~-Cl CX3 . ,~1 H 0 -G~) C~3 Cl Cz Hs ~~>
CH3~ Cl C4 Hs 0 _o~
CH3 Cl Cl~ CH2- O -0~
C~I ,Cl ~-CHz- 0 -0~

H ~~> ~ ~>

C2 H~s O -0-~-~

0 C4 Hg 0 Cl- ~ -C~2 - -0-~ - ,~

~ -C~2 ~ -O- <~

H -0-~

Cl .. . CH3 Cl C4 Hg ~~~
CH

Le A 20 763 _ ,~ .
Rl n R2 Cl~-C~2- . ` ~

CH2- 0 -~

H 0 -0~
C 1 CL~3 C2 H~ 0 -0~

C~ H9 0 --OE~
cr ~'r.3 Cl~ C~2- 0 -0~

~> -Ch-2- O -~

C~3 ~I - 0 ~0-~-C1 C~3 C2~IS 0 -0-~C1 C~ H9 0 0-~. C1 C1-~>-CH2- 0 ~0-~ CH

~ ~ ~q R' n R2 H O -0-(~ C
~ ~ CH3 H O <~C

C2~5 0 <~C~

C,, Hg ! O -O- @~-CH3 Cl Cl-~>-CH2- 0 Cl CH2- 0 '~1 H O -0-,~

C2 ]~s O -0-,~

C~ g o o ~

Cl-~>-CH2- 0 -0-c~5 CH2- O . O ~<, Le A 20 763 -3~

R' n R2 Cl H O -0~>
C(C~-3 )3 Cl C2 ~5 0 -0~
C~ CH3 ) 3 C4 Hg ~ O -0-~
C~C~3 )3 Cl~)-C~I2- 0 -0-~
C~CH3 )3 <~ -CH2- 0 -0-~
C(C~3 )3 H O _o~ -C ( CH3 ~3 Cl C2 H5 0 -o-@~-c ( CH3 )3 ' C4 Hg . O -O- ~-C ( CX3 )3 Çl 10Cl-~-CH2~ 0 _o-~-C(cH3 )3 Cl -CH2 - O -O -~- C ( CH3 ~ 3 ,, Le A 20 763 a~ 7 3i _ ~;
R~ n R2 H o -o-@-cN

C2 H5 0 -0~ CN

C4 Hg 0 .-0-(~> -CN

Cl~>-CX2- 0 -0-<~) CN

~-CH2 - 0 -0-~ -CN
_" CN
H 0 0-<~
CN
C2 H5 0 -0--$~
CN
C4 Hg 0 -0~
CN
. Cl~>-CH2- 0 -0~
~CN
(~ -CH2 - O -0 CN

C~
C2H~ ~ ~>
CN
C~ H~ 0 -0-~>
CN
Cl-~-CH2- 0 -0~) CN
<~_C~2~ 0_~

H 0 -o-CH2~ Cl Le A 20 763 3 i~. 7 '` 3Z~J

~' n R2 C2 H5 0 -0-CH2 -<~> -Cl C4 Hg O -O - CH2 - ~ - Cl Cl-<~ , - O -O-C~I2 -~ - Cl ~>-CHZ- O -O-CH2-<~-Cl H O -O-CH2-,~

C2 H; O -O C~

C4 Hg -O-CH2 ;

C~ -CH2 - O -O-CH

(~ ''CH2 - O -O-CH2 -~

H O -O-CH2 -~

-O-CH2 ~
C4Hg o -0-CH2 ~) Cl~) -CH2 - O ~ -O-CH
(~> -CH2- 0 -O-CH2-~

Le A 20 763 J'~3 ~

R' n R2 .. ... --.-H O -O CH2 - ~-Cl C2~5 0 --C~-2~
Cl C4 Hg O -O-CH2 ~ -Cl Cl-~-c~-2- o . -O-CH2-~-Cl ~3>-CH2~ 0 -O-CH2-@~-Cl Cl H O -o-CH2 - ~ -CF3 C2 H5 0 -O-CH2 - ~-CF3 C4 Hg O -O-CH2 -~ -CF3 Cl-~ -CHa - O -o-cH2 - ~-CF3 <~)-CH2- o . Cl H O -O-CH2-~>

C
C2 H5 . -0-CH

Le A 20 763 .= . ~ . __ . .

Rl n R2 C~Hg 0 -O-CH
. Cl Ci- <~)-CH2 - O -O-CH2 ~) Cl CH2 0 -O-CH2 ~>

- 5 H O -O-CH2 ~-N2 C2 H5 0 --C~2 -~) -NO~
C" Hg O -o-cH2 -~ -N2 Cl-~-C~H2- _o-c-~z-<~)-No2 CrI2 - O -o-CH2 - ~ -;!T2 H O -O-CH2-~-C~3 - C2 H~; -O-CH2 ~ -CH3 C4 Ng _O-CH2 -~ -C~-3 Cl-~)-CH2- -O-CH2-<~-CH3 ~) -CH2 - -0-CH2 ~ -CH3 Le A 20 763 ~.. 4~ 3 ~ ' 7 J~_ --,~L-- --R' ~ n R2 H O -O-~-SCF3 C2 H~; O -~- ~-SCF~

C~ Hg O -0-~ -SCF3 Cl~CH2 0 -O-~>-SCF3 ~-CH~- O -O-<~)-SCF3 H O -0-~
Cl / CH3 C2 H~ -~
Cl CH3 C4 Hg ~ -0 Cl~-C~2- ,<~
Cl , CH3 -CH2 - O -O- (~
Ci Le A 20 763 ,~ _ R~ n R2 H l -O-C4 Hg ~ -CH2 - 1 -0-C4 H~
CzHs l -O-C4Hg C~ Hg l -O-C4 Hg Cl- <~>-CH2 ~ 1 -0-C4 Hg F3 C~ -C~-2 - . -COOC2 H5 F3 c-~>-CH2 ~ -COOC3 H7 -i F3 C- OE) -CH2 ~ -CON ( CH3 )2 F3 C -~ -C~z ~ -CO~
F3 t~O- ~ -CH2 ~ -COOCH3 F3 CO-~-CH2 ~ -CN

H O -CN

F3 C~ CH2 ~ O _~

F3 C-~-CHz - O

Fa C~~~) -CH2 - O - ~) Cl F3 C- ~ -CH2 - O _ ~ -F

Le A 20 763 _ Rl . n R2 _ .. _ ~ _ _ _ . . .. . ... . . . ~
H 1 -S- ~-F
C4 Hg -n 1 -S- ~ -F
-CH2 - ~>-Cl 1 -S~ -F
5-CH2-(~>-OCF3 1 -S-<~-F
-CH2-<~-CF3 1 -S-~-F
H 1 -S - (~> -SCF3 -C4 H9 -n 1 ~ S-~ -SCF3 -C~2 -<~ ~Cl 1 -S- ~> -SCF3 10-CH~-~)-OCF3 1 -S-<~3-ScF3 -CH2 -<~3 -CF3 1 S- ~> -SCF3 H 1 -S- ~ -OCF3 -C4 H9 -n -S~ -OCF3 -CH2-~-Cl 1 -S-~-OCF3 15-CH2-~-OCF3 1 -S~-OCF3 -CHz -~> -OCF3 1 -S- ~>-OCF3 Le A 20 763 ~g~
- ~ -R' n R2 H 1 -S~

-C4 ~9 -n 1 -S~> -(~

-CH~ Cl 1 -S~

-CH2-<~-OCF3 1 -S~

-CH2-~ CF3 1 -S~_<~

H 1 -S~-CH3 -C4 Hg -n 1 -S-~ -CH3 -CH2 -@ -Cl 1 -S- ~ -CH3 .-CH2-<~-OCF3 1 -S-~>-CH3 -CH2-~>-CF3 1 -S-~)-C~3 H 1 -S~)-Cl - C4 Hg -n 1 -S-~0 -Cl - CHz -~) -Cl 1 -S~ -Cl 15- CH2 -~ 0 CF3 1 -S -,~ - Cl -CH2-~-CF3 1 -S-,~-Cl Le A 20 763 ~y Rl n R2 H 1 -s-~3-N32 -C4 Hg -n 1 S ~) NO2 -CHz - ~>-Cl 1 -S ~ J2 CH2-~)-OCF3 1 ~>-NO2 -CX2 ~ CF3 1 -S- ~>-NO2 H 1 `Cl -C" Hg -n 1 ~S-<~3 -Cl `Cl -C~2-~-Cl 1 -S-~3-Cl -CH2-~-OC~3 1 --S~-Cl `Cl -CH2 ~>-CF3 1 Cl H Cl -C4 Hs~ -n 1 -S~> -Cl Cl -CH2-~)-Cl 1 -S~-Cl -CH2-~-OCF3 1 Cl~>

-CHz-~-CF3 1 -S-~-Cl - Cl Le A 20 763 ,.3 Lfd -- .-4~ --R' n R2 C~
H 1 -S~

-C4 Hg -n 1 -S-~
Cl Cl~
-~H2~ Cl 1 -S~>
Cl~
5-CH2-<~3-oCF.~ 1 C~
Cl - -CH2-~ CF3 1 -SCl~>

H 1 ~--Cl -C4 Hg -n 1 -S~

-CH2-~)-Cl 1 -S-~ Ccl ~-CH2-~-OCF3 1 -S~ Cl -CH2-~>-CF3 1 ~'--Cl ~I 1 -S-C4 Hg-n -C4, H9 -n 1 -S-C4 H9 -n -CH2 -~) -Cl 1 -S-C4 Hg -n -CH2 -~ -OCF3 1 -S-C4 Hg -n -CH2-~-CF3 1 -S-C4Hg-n Le A 20 763 .

lt/
Rl n R2 .
H 1 -sc~3 -C4 ~9 -n 1 -S CH3 -CH2 - ~-Cl 1 -SCH3 -CH2-<~-OCF3 1 -SCH3 -CH2-~-CF3 1 -SCH3 H 1 -S-CH2 ~) -C4 Hg -n 1 -S-CH~ ~

-CrI2 ~ Cl 1 -S-CH2 ~>

~-CH2 -<~> -OCF3 1 -S-CH2 ~) -C~2 -O -CF3 1 -S -CH2 ~
E~ 1 -S-~H2 ~> -Cl ~Ce, Hg -n 1 ` -S-CH2 -~) -Cl -CH2 -<~> -Cl 1 -S-CH2 ~> -Cl -CH2-~>-OCF3 1 -S-CH2-~>-Cl -CH2-~-CF3 1 -S-CH2-~>-Cl Le A 20 763 R' n R2 . . _ . . . . .
H 1 -~-CH2 - (~-Cl -C~, Hg -n 1 -S-CH2~ -Cl -CH2 - ~)-Cl 1 -S-CHz~> -Cl -CH2-~-OCF3 1 Cl~
-CH2 -~>-CF3 1 Cl -Cl H 1 -S-CH2~ OCF3 -Cl, Hg -n 1 -SlCH2 @ -OCF,.
-CH~ 3-Cl 1 --S-C~2 ~ -OCF3 ~-CH2-~-OCF3 1 -S-CH~ GCF3 -CH2 -~> -CF3 ` 1 -S-CH2 ~$ -OCF3 H1 -S-CH2-~-SCF3 -C~ Hs~ -n 1 -S-CH2 -<,~> -SCF3 -CH2 -~-Cl 1 -S-CH2 ~ -SCF?
-CH2 -~> -OCF3 1 -S-CH2 ~> -SCF3 -CH2 -~> -CF3 1 -S -CH2 -<~ -SCF3 Le A 20 763 $~3'7 C3 s~3 Rt n R2 H l S CH2 ~ Cl -C4 Hg -n 1 -S-CH2 ~ -Cl `Cl -CH2 - ~-Cl 1 -S-CH2 ~) -Cl `Cl -cH2-<~-ocF3 1 . -S-C~2-~>-C

- -CH2-~-CF, iS CH2 <~ -Cl H l ~ CF

-C" Hg -n 1 -S~
CF, -CH2-<~>-Cl 1 -S~
C~, ~ -CH2-~>-OCF3 1 -S~>
. ~ CF3 ~ -CH2-<~)-CF3 1 -S-~
:~. ` CF3 H 1 -S~>-CF3 .
-C4 Hg -:~ 1 -S~ -CF3 -CH2-<~-Cl 1 -S~>-CF3 -CH2-~)-OCF3 1 -S-<~>-CF3 -CH2-~-CF3 1 -S~>-cF3 .

Le A 20 763 -.3 ' ~

,~
R' n R2 -C4 Hg -n 1 -S-CH

-CH2~ Cl 1 C13 -CH2~ OCF3 1 -S-CH

-CH2 -<~ -CF3 1 -S-CH2 ~

-S-<~ - ~-Cl -C4 Hg -n 1 -S~ -~> -Cl -CH2~ Cl 1 ~S~>-<~-Cl ~ -C~2~ OC~ 1 -S-(~ -Cl -CH2-~-CF3 1 -S~>~ Cl H 1 -S~) -O-~-Cl -C4 Hg -n 1 -S~> -0-<~ -Cl -~2-<~-Cl 1 -S~-O-~-C

-CH2-~)-OCF3 1 -S~$-o~;>-Cl -CH2-~ -CF3 1 -S-~-0-~)-Cl Le A 20 763 R~ n R2 .. . . .
H 1 -S- ~-Br -C4 ~9 -n 1 -S-~ -Br >-Cl 1 -S-~-Br -CH2-<~)-OCF3 1 -S~ Br -CH2-@-CF3 1 -S-<~>-Br H 1 -S-CH2 ~ - ~-Cl -C4 Hg -n 1 -S-CH2 -~ -~ -C' -CH2 -<~ -Cl 1 -S-CH2 ~ -~ -Cl lo ~ CH2 -@-ocF~ 1 s cH2 ~ _@-C~l -CH2-~>-CF3 1 -S-CH2-~ Cl -S-CH2 ~) -O-(~>-Cl -C4 H9 -n 1 -S-CH2 ~ -O- ~ -Cl -CY.z -<~ -Cl 1 -S-CH2 ~ --~) -Cl -CH2 -~) -OCF3 1 -S-CH2 ~) -O-~-Cl -CH2-~>-CF3 1 -S-CH2 &) -O~-Cl Le_A 20 ?63 o':P~ 7 Rl n R2 H 1 -SO2 ~> -Cl -C", Hg -n 1 -52 ~) -Cl -CH2~ Cl 1 -SO2-~>-Cl -CH2 -<~> OCF3 1 -SO ~ -~ -Cl -CH2-~>-CF3 1 ' -SO2-~-Cl . H -SO2 ~) -F

-C4 Hg -n 1 -SO2 ~) -F

-CH2-~>-Cl 1 -So2-@-F

. ~ -CH2 -~ -OCF3 1 -SO2 -<~ ~F

-CH2-~>-CF3 1 -So2-@-F

S2~ 0C~3 -C4 Hg -n 1 -SO2 -~i -OCF3 -CH2-<~-Cl 1 -So2~ cF3 -CH2-~-OCF3 1 -SO2-~>-OCF3 -CH2 -~> -CF3 1 -SO2 ~ -OCF3 Le A 20 763 . .

~,1 . R ~ ~ ~ . . n. - ~2 1_So2_CH2~-Cl -C4Hg-n 1-S02-CH2-~-Cl CH2 ~3 Cl 1-S2-cH2~-Cl CH2 ~ 3 1S2 CH2 ~ -Cl -CH2-~-CF3 1-S02-CH2-~-Cl If, for example, l-bromo-3-(4-chlorophenoxy)-3-methyl-butan-2-one and 1,2,4-triazole are used as the -starting substances, the course of the reaction variant (a) according to the present invention is illustrated by the following equation;

Br-CH2-C0-C-0- ~ -Cl + H-N~ - > ~N-CH2-C0-C-0 CH, H3C

Cl If~ for example, 3-(2,4-dichlorophenoxy)-3-methyl-1-(1,2,4-triazol-1-yl)-butan-2-one and 4-chlorobenzyl chloride are used as starting substances the course of the reaction variant (b) according to the present invention is illustrated by the following equation:
Cl H2C-CO - C-0- ~ Cl + Cl- ~ -CH2-~N~N CH3 Le A 20 763 D ~ 7 3 ~ ~
Cl ~ CH2 - CH - CO - C - O ~ Cl f ~ CH3 N

If, for example, 4-(4-chlorophenylthio)-3,3-dimethyl-1-(imidazol-l-yl)-butan-2-one and hydrogen peroxide in glacial acetic acid are used as the starting substances, the course of the reaction variant (c) according to the present inver.tion is illustrated by the following equation:

CH

H2C - CO - C - CH2 - S ~ Cl ~ H2O2/glacial acetic acid-~

N~N~ CH3 H2C - CO - C - CH - SO ~ Cl N ~

Preferred halogenoketones of formula (II) required as starting substances for carrying out reaction variant (a) according to the invention are those in which R2 and n have the meanings given for the preferred and particulaxly preferred compounds of the inventîon.
The halogenoketones of the formula (II) are known in some cases (see our DE-OS (German Published Specification) 2,635,663), and some of them are the subject of our European application 0 042 980 published January 6, 1982, and some of them are completely new. They are obtained by a process in which a ketone of the general formula CH3 ~ CO - C ~ (CH2)n (V) R2 and n have the abovementioned meanings, is reacted with chlorine or bromine in the presence of an inert organic solvent (such as ether or chlorinated or non-chlorinated hydrocarbons) at room temperature, or with customary chlorinating agents ~such as sulphuryl chloride) at 20 to 60C.
The ketones of the formula (V) are known in some cases (see J. Org. Chem. 42, 1709-1717 (1977); J. Am. Chem. Soc. 98, 7882-84 (1976); J. Org. Chem. 37, 2834-2840 (1972); U.S. Patent Specification 3,937,738; C.A. 82, 30 898 j (1975)); and our European application 0 041 671 published December 16, 1981; and some of them are new. They can be obtained by the processes described in the mentioned references, for example by a procedure in which a keto derivative of the general formula C~ - CO - C - (CH ) - ~ (VI) in which n has the abovementioned meaning and Y represents a chlorine or bromine atom or a grouping of the general formula -O-SO2-R , wherein R6 represents an alkyl radical with 1 to 4 carbon atoms or a phenyl radical which is optionally substituted by alkyl with 1 to 4 carbon atoms, is reacted with a compound of the general formula ~,~

~ Q
.~ ~0 _ ~_ Me_R2 (VII) in which R2 has the abovementioned meaning and Me represents an alkali metal, such as, pre~erably, sodium or potassium, or hydrogen atom, in the presence of an organic solvent (such as xylene, glycol or dimethylformamide) and~ if appropriate, in the presence of an acid-binding agent, ~such as sodium carbonate) at a temperature between 80 and 150C.
10 The keto derivatives of the formula (~I) are known (see, for example DE-OS (German Published Specification) 2,632,603 and J~ Org. Chem. 35, 2391 (1970)), or they can be obtained in a generally known manner, The compounds of the formula (VII) are generally known compounds of organic chemistry and, if appropriate, are employed as compounds which are prepared in situ.
Preferred azoles of formula (III) which are also to be used as starting substances for reaction variant (a) according to the invention are those in which Az preferably represents a 1,2,4-triazol-1-yl or -4-yl or imidazol-l-yl radical.
The azoles of the formula (III) are generally known compounds of organic chemistry.
The formula (Ia) provides a general definition o~
the compounds to be used as starting substances for carrying out reaction variant (b) according to the invention. The compounds of the formula (Ia) are themselves substances according to the invention~
Preferred agents of formula (IV) also to be used as starting substances for re~ction variant (b) according to the invention are those in which Rl represents those rad-icals which have already been mentioned for this sub-stituent in connection with the description of the preferred and particularly preferred substances of the formula (I) Le A 20 763 7~3'i~

according to the invention and Z represents an electron-withdrawing leaving group, such as halogen, p-methylphenyl-sulphonyloxy, the grouping -0-S02-OR or -NR3.
The alkylating agents of the formula (IV) are generally known compounds of organic chemistry.
The formula (Ib) provides a general definition of the compounds to be used as starting substances for carrying out reaction ~ariant (c) according to the invent-ion~ The compounds of the formula (Ib) are themselves substances according to the invention.
The oxidation according to the invention is carried out by reaction with customary inorganic or organic oxidising agents. These include, preferably, organic peracids (such as peracetic acid , p-nitroperbenzoic acid and m-chloroperbenzoic acid~, inorganic peracids (such as periodic acid) and furthermore hydrogen peroxide in glacial acetic acid or methanol, potassium permanganate and chromic acid.
Possible diluents for reaction variant (a) accord-ing to the invention are inert organic solvents. These-include, preferably, ketones (such as diethyl ketone and,in particular, acetone and methyl ethyl ketone), nitriles (such as propionitrile, and in particular acetonitrile), alcohols (such as ethanol or isopropanol), ethers (such as tetrahydrofuran or dioxane), aromatic hydrocarbons (such as toluene, benzene or chlorobenzene), formamides (such as, in particular, dimethylformamide) and halogenated hydro-carbons.
Reaction variant (a) according to the invention is carried out in the presence of an acid-binding agent.
3o Any of the inorganic or organic acid-binding agents which can customarily b~ used may be added, such as alkali metal carbonaGes (for example sodium carbonate, potassium carbon-ate and sodi~m bicarbonate), lower tertiary alkylamines, cycloalkylamines or aralkylamines (for example triethyl-amine, N,N-dimethylcyclohexyIamine, dicyclohexylamine and Le A 20` 763 t .. S~

N,N-dimethylbenzylamine) and furthermore pyridine and diazabicyclooctane Preferably, an appropriate excess of azole is used.
The reaction temperatures can be varied wikhin a substantial range in reaction variant ~a) according to the invention. In general, the reaction is carried out at a temperature between 20 and 150C, preferably at a te,nper-ature between 60 and 120C. If a solvent is present, it is expedient to carry out the reaction at the boiling pPint of the particular solvent.
- In carrying out reaction variant (a) according to the invention, 2 to 4 mol of azole and 1 to ~ mol of acid-binding agent are preferably employed per mol of the com-pounds of the formula (II). To isolate the compounds of the formula (I), the solvent is distilled off and the residue is worked up in the customary manner, Possible diluents for reaction variant (b) accord-ing to the invention are inert organic solvents. These-include, preferably, aromatic hydrocarbons ~such as benzene,-toluene or xylene), halogenated hydrocarbons ~such asmethylene chloride, carbon tetrachloride, chloroform or chlorobenzene), esters (such as ethyl acetate), formamides (such as dimethylformamide) and dimethylsulphoxide, Reaction variant (b) according to the invention is carried out ln the presence of a base. Any of the cus-tomary organic and, in particular, inorganic bases can be employed, such as, preferably, alkali metal hydroxides or alkali metal carbonates, and examples which may be mentioned are sodium hydroxide and potassium hydroxide.
The reaction temperatures can be varied within a substantial range in carrying out reaction variant (b) according to the invention. In general, the re~c~ion is caL~ied ~t at a te~,perature between 0 and 100C, preferab~ between 20 and 100C.
In carrying out reaction variant (b) according to the invention, 1 to 1.2 mol of the agent of formula (IV) Le A 2-0-763 ~ 3 -- , --are preferabIy 'employed per mol of the compound of the formula (Ia). The end products'of the formula (I) are isolated in the generally customary manner.
Reaction variant (b) according to the invention can also be carried out in a two-phase system (for example aqueous sodium hydroxide sol~tion or potassium hydroxide solution/toluene or methylene chloride) if appropriate with the addition of 0.1 to 1 mol of a phase transfer catalyst, (such as ammonium or phosphonium compounds, examples which may be mentioned being benzyldodecyldimethyl-ammonium chloride and triethyl-benzyl-ammonium chloride).
The reaction temperatures can be varied within a substantial range in carrying out the oxidation of reaction variant (c). In general, the reaction is carried out at a temperature between 50 and 100C, preferably between -30 and 80C.
In carrying out the oxidation, according to the invention, in reaction variant (c), about 1 to ~ mol of oxidising agent are employed per mol of the compounds of the formula (Ib) according to the inve~tion. If 1 mol of oxidising agent is used, such as m-chloroperbenzoic acid in methylene chloride or hydrogen peroxide in acetic anhydride at temperatures between -30 and +30C, the compounds of the formula (I) according to the invention in which X = S0 are preferentially formed. In the case of an excess of oxidising agent and-higher temperatures (10 to 80C), the compounds of the formula (I) according to the invention in which X = S02 are preferentially formed.
The oxidation products are isolated in the customary manner.
3 The compounds of the formula (I) which can be pre-pared according to the invention ~an be converted into acid addition salts or metal salt complexes.
The following acids can preferably be used for the preparation of physiologically acceptable acid addition salts of the compounds of the,'formula (I): hydrogen halide Le A 20 763 S~
_ ,,,~ _ acids (such as hydrobrcmic acid and, preferably, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bi-functional carboxylic acids and hydroxycarboxylic acids (such as acetic acid, maleic acid, succinic acid, fum~ric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonic acids (such as p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid).
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 com-pound of the formula (I) in a suitable inert solvent andadding the acid, for example hydrogen chloride~ and they can be isolated in a known manner, for example by filtra-tion, 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 preferably 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, magnesium, tin, iron and nickel.
Possible anions of the salts are, preferably, those which are derived from the following acids: hydrogen halide acids (such as hydrochloric acid and hydrobromic acid) and furthermore phosphoric acid, nitric acid and sulphuric acid.
The metal salt complexes of the 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 the formula (I). The metal salt com-3 plexes can be purified in a known marner, for example by filtration~ isolation and~ if appropriate by recrystallis~
ation.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed Le A 20 763 .~'J'~

S~
.
in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes, Zygomycetes, ~scomycetes, Basidiomycetes and Deuteromycetes.
The good toleration, by plants~ of the active compounds 3 at the concentrations required for combating plant diseases, 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 according to the invention can be used with particularly good success for combating those fungi which cause powdery mildew diseases, thus, for combating Erysiphe species for example against the powdery mildew of barley or cereal causative organism (Erysiphe graminis), or for combating Podosphaera species~ for example against the powdery mildew Of apple causative organism (Podosphaera leucotricha).
The systemic action of some of the substances according to the invention is to be emphasised. Thus, it is possible to protect plants from fungal attack if the actîve compound is fed to the above-ground parts of the plant via the soil and the root.
When used in appropriate concentrations, the sub-stances according to the invention also exhibit growth-regulating properties.
The active compounds can be converted to the cus-tomary formulations, such assolutions, emulsions, suspen-sions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active ~ompound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment~ such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist Le- A 20 763 3~ 7 G

and warm mist formulations These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say 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 solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydro-carbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffi.ns, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids wh~ich would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used 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~ ~lumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as Le A 20 763 L ' 9~ 't~
"~

, sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and~or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, po~yvinyl alcohol and poly-vinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0 1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention 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 3 form of their formulations or the use forms prepared there-from by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pasues and granules.
They are used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vapori-sing, injecting, forming a slurry, brushing on, dusting, Le A 20 763 7 ~ ~? ~ ~1 , scattering, dry dressing, moist dressing, wet dressing,slurry dressing or encrusting.
Especially in the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between l and 0.0001% by weight, preferably between 0.5 and 0.001%.
In the treatment of seed, amounts of active com-pound of 0.001 to 50 g per-kilogram of seed, preferably 0.01 to-10 g, are generally required.
For the treatment of soil, active compound con-centrations of 0.00001 to 0,1% by weight, preferably 0.0001 to 0 2%, are required at the place of action.
The present invention also provides fungicidal composi~ion containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or n admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi-by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied 3 alone or in admixture with a diluent or carrier It wil be seen that the usual methods of providing a harvested crop may be improved by the present inventi~n.
As already mentioned, the new substituted l-azolyl-butan-2-ones of the general formula (I) are also interesting intermediate products. For example, they Le A ? 763 ~ ~ 7~

,~
can éasily be: converted into l-azolyl~butan-2-ols of thé
formula Rl _ CH - CH - C - (CH2)n (VIII) Az CH~ -in which Rl, R2, Az and n have the abovementioned meaning, by a process in which a compound of the formula (I) is reduced, for example by reaction with a complex hydride (such as, preferably, sodium borohydride) if appropriate in the presence of a polar organic solvent ~such as an alcohol) at a temperature between O and 30C.
The compounds of the formula ~VIII) have powerful fungicidal properties and can'therefore be used as plant protection agents.
Preparative EXamples _ _ Exampl _1 N=~ ICH3 L N - CH2 - CO - C - O - ~ - Cl (1) (Reaction variant (a)) 20 g (0.1 mol) of 1-bromo-3-(4-chlorophenoxy)-3-methyl-butan-2-one were added dropwise'to a boiling mixture of 14 g (0.2'mol) of triazole and 14 g (0.1 mol) of potassium carbonate in 200 ml of acetone, and the mixture was allowed to after-react under reflux for 5 hours. The organic residue was then filtered off, the solvent was dis-tilled off from the filtrate under a water pump vacuum, the organic residue was taken up in 200 ml of methylene chloride/200 ml of water, the organic phase was separated off, ~ash~' twi.ce with 100 ml of water each time and dried over sodium sulphate and the solvent was distilled off under a water pump vacuum. The residue was recrystallised from cyclohexane/isopropanol (~ 20:1). 17 g (70% of .
Le A 20 7'63 ~b~ 3 rj~3 t~
~0 ~_ thebry) of 3-~4-chlorophenoxy)~3-methyl~1-(1,2,4-triazol-l-yl)-butan-2-one of melting point 101 to 103C were obtained.
Pre~aration of the startin~ material ___ _________ ____________ _________ Br- CH2 - C0 - C - 0 ~ Cl 110~2 g ~0.5 mol) of 3-(4-chlorophenoxy)-3-methyl-butan-2-one were dissolved in 500 ml of methylene chloride, and 83 g (0.52 mol) of bromine were added dropwise at room temperature in a manner such that continuous decoloration occurred. When the addition had ended, the mixture was subsequently stirred for 30 minutes~ the organic phase was washed in each case twice with 300 ml of water and 300 ml of saturated sodium bicarbonate solution and was dried over sodium sulphate and distilled. 105.9 g (70% of theory) of 1-bromo-3-(4-chlorophenoxy)-3-methyl-butan-2-one of boiling point 115 to 118C/0.1 mm Hg were obtained.

CH3 -- C0 - C - 0 ~ Cl 130 g (o.8 mol) of 3-bromo-3-methyl-butan-2-one, 120 g (0.9 mol) of p-chlorophenol and 139 g-(l.0 mol) of potassium carbonate in 500 ml of acetone were heated under reflux for 6 hours, with stirring. The inorganic pre-cipitate was filtered off, the solvent was distilled off from the filtrate under-a water pump vacuum at 20 to 30C, the residue was taken up in 300 ml of methylene chloride/
300 ml of water, the aqueous ~hase was ~epa ited off, the organic phase was washed twice with 100 ml of 5% strength sodium hydroxide solution each time, rinsed twice with 100 ml of water each time and was dried over sodium Le--A-20-7-6-3 -_~ _ sulphate and distilled. - 110 2 g (65% of theory) of 3-(4-chIorophenoxy)-3-methyl-butan-2-one of boiling point 80-95c/o.1 mm Hg and with a refractive inde~ nDQ f 1.5150 were obtained CH3 - C0 - C - Br 86 g (1 mol) of methyl isopropyl ketone were dis-solved in 500 ml of methylene chloride, and 159 8 g (1 mol) of bromine were added dropwise at room temperature in a manner such that continuous decoloration occurs. When the addition had ended, the mixture was subsequently stirred for 30 minutes. The organic solution was washed in each case twice with 500 ml of water and 500 m] of saturated sodium bicarbonate solution, dried over sodium sulphate and distilled. 130 g (80% of theory) of 3-bromo-3-methyl-butan-2-one of boiling point 39C/12 mm Hg and with a refractive index n20 of 1.4543 were obtained.
Example' 2 ' CH C1 Cl ~ - CH2 - CH - C0 - C - o ~ Cl ,N`N C (2) ~ H3 (Reaction va:riant (b)) First 5 6'g of potassium hydroxide in 12 ml of water and then 16.1 g'(0.1 mol) of 4-chlorobenzyl chloride in 5 ml of dimethylsulphoxide were added dropwise to 31.4 g (0.1 mol)'of 3-~2,4-dichlorophenoxy)-3-methyl-1-(1,2,4-triazol-l-yl)-butan-2-one (prepared as described in Example 1) in lOO'ml of dimetl;ylsulphoxide at 20C, with cooling.
The mixture was allowed to after-react at 20C for 15 hours, the solution was poured into 200 ml of water, the mixture was extracted with 200 ml of methylene chloride, the organic phase was washed three times with 200 ml of water Le A 20 763 l~
.
each'time and dried over sodium sulphate'and the solvent was distilled off under a water pump vacuum. The residue was taken up in 200 ml of ether, the mixture was heated under reflux and the crystals which had precipitated were filtered off.
21.3 g t48% of theory) of 5-(4-chlorophenyl)-2-(2,4-dichlorophenoxy)-2-methyl-4-(1,2,4-triazol-1-yl)-pentan-3-one of melting point 104-108C were obtained.
Exa-mp-le' 3 CH

~ N - CH2 - C0 - C - CH2 - 0 ~ Cl 3 (3) (Reaction variant (a)) 304 g (1 mol) of 4-bromo-1-(4-chlorophenoxy)-2,2-dimethyl-butan-3-one were added dropwise to 200 g (2.9 mol) of triazole and 140 g (1 mol) of potassium carbonate in 1,000 ml of acetone at the boiling point.
The mixture was allowed to after-react under reflux for 15 hours, the inorganic precipitate was filtered off, the solvent was distilled off from the filtrate under a water pump vacuum, the residue was taken ùp in 2 litres of methylene chloride and the organic phase was washed four times with 500 ml of water each time, dried over sodium sulphate and concentrated by distilling off the solvent in ~acuo. The residue was taken up in 500 ml of ether, whereupon the product crystallised out. 201.8 g (69% of ~
theory) of 1-(4-chlorophenoxy)-2,2-dimethyl-4-(1,2,4-triazol -l-yl)-butan-3-one of melting point 90-92C were obtained.
Pre~aration of the star_ing material CH
Br - CH2 - C0 - C - CH2 - 0 ~ Cl bH3 36 g (0.159 mol~ of 1-~4-chlorophenoxy)-2,2-dimethyl~
butan-3-one were dissolved'in'3aO ml of chloroform, and . .
Le A 20 763 .;

- ~~ -25.5 g (0.159 mol) of bromine were added dropwise at 20C in a manner such that continuous decoloration occurred.
When the addition had ended~ the mixture was stirred at room temperature for 30 minutes and was then concentrated by distilling off the solvent in vacuo. 48.5 g (quantitative conversion) of crude 1-bromo-4-(4-chlorophenoxy)-3~3-dimethyl-butan-2-one were obtained as an oil.

CH3 - C0 - C - CH2 - 0 ~ Cl CH~

29.7 g (0.55 mol) of sodium methylate were dis-solved in 500 ml of methanol, and 70.4 g (0.55 mol) of4-chlorophenol were added, with stirring. After stirring the mixture for 10 minutes, the solvent was distilled off under reduced pressure and the residue was taken up in 100 ml of glycol. This solution was added to a solution o~ 135 g (0.5 mol) of 2,2-dimethyl-1-tosyloxy-butan-3 one in 200 ml of glycol. The mixture was stirred at 100 to 120C for 4~ hours and cooled and the reaction mixture was stirred into 2,000 ml of water. The mixture was extracted twice with 250 ml of diethyl ether each time and the combined organic phases were washed three times with 100 ml of water each time, once with 100 ml of 10%
strength sodium hydroxide solution and again with 100 ml of water, dried over sodium sulphate and distilled.
62.9 g (55.7% of theory) of 1-(4~chlorophenoxy)-2,2-dimethyl-butan-3-one of boiling point 135-140C/0.4 mm Hg were obtained.

47,6 g (0 25 mol~ of 4-toluenesulphonyl chloride were dissolved in 100 ml of chloroform~ 35 g (0 3 mol) of .
Le A 20 763 _ `~t~ O ~

2,2-dimethyl-l~hydroxy-hutan-3~oné were added, and 40 ml (0.5 mol) of pyridine were added dropwise at 0 to 50C.
The reaction mixture was subsequently stirred at room tem-perature for 15 hours and poured on to 200 g of ice and 70 ml of concentrated hydrochloric acid and the organic phase was separated off, rinsed three times with 200 ml of water each time, dried over sodium sulphate and concentrated.
The residue was taken up in 100 ml of petroleum ether, whereupon the end product crystallised out. 46 g (71% of theory) of 2,2-dimethyl-1-tosyloxy^butan-3-one were obtained as colourless crystals of melting point 49 to 52C.

66 g (2,2 mol) of paraformaldehyde and 1 g of potassium hydroxide in 10 ml of methanol were added drop-wise to 172 g (2 mol) of methyl isopropyl ketone in 1,000ml of methanol. The mixture was heated under reflux for 15 hours and the methanol was then distilled off over a column at an internal temperature of 82C. The residue was distilled under a water pump vacuum. 152,7 g (68%
of theory) of 2,2-dimethyl-1-hydroxy-butan-3-one of boiling point 80-82C/12 mm Hg were obtained.
Example 4 CH2 - CH - C0 - C - CH2 - 0 ~ Cl ~ ~ 3 (4) N

(Reaction variant (b)) First 5.6 g of potassium hydroxide in 12 ml of water and then 17.7 g-(0.1 mol) of cyclohexylmethyl-bromide in 5 ml of dimethylsulphoxide were added dropwise to 29 3 g (0.1 mol) of 1-(4-chlorophenoxy)-2~2-dimethyl-4-(1,2,4-triazol 1-yl)-butan-3-one (prepared as described in Le A 2~ 763 Gs-Example 3) in 100 ml of dimet~ylsulphoxide at 20C, The reaction mixture was subsequently stirred at room tem-perature for 15 hours, poured into 200 ml of water and extracted with 200 ml of methylene chloride. The organic phase was washed three times with 100 ml of water each time, dried over sodium sulphate and concentrated by distilling off the solvent. The residue was taken up in 100 ml of ether, whereupon the product crystallised out.
18.6 g (47% of thoery) of 1-(4-chlorophenoxy)-5-cyclohexyl-2,2-dimethyl-4-(1,2~4-triazol-1-yl)-pentan-3-one of melting point 58-60C were obtained.
Example 5 CH
N=~ 1 3 L N ~ CH2 ~ C0 - Cl - S CF3 (Reaction variant (a)) 26.5 g (0.1 mol) of 1-bromo-3-methyl-3-trifluoro-methylthio-butan-2-one were-added'dropwise'to a mixture of 8.3 g (0.12 mol) of 1,2,4-triazole and 28 g (0.2 mol) of potassium carbonate in 150 ml of acetone at room tempera-ture. The mixture was subsequently stirred under reflux for 1 hour, the inorganic salts were filtered off and the filtrate was concentrated. The residue was taken up in methylene chloride, washed with water, dried over sodium sulphate and distilled. 15.5 g (62% of theory) of 3-methyl-1-(1,2,4-trlazol-1-yl)-3-tri~luoromethylmercapto-butan-2-one of boiling point 91C/0.5 mm Hg and of melting point ~ 45C were obtained.
' EXamp'le' 6 CH

j~N - CH2 - C O - C - CH2 - S ~--C 1 ( 6 ) ~eaction variant (a)) Le A 2 0 7-6 3 ~ - C. li~78~8~7 , . . . . ... ~ .
199 g (0'.618 mol).'of- 1-b.r'omo~4-(4-chIorophe'nyl-mercapto)-3,3-dimethyl-butan-2-one, 120 g (1.76 mol) of imidazole and 243.5 g (1.76 mol) of potassium carbonate '~
in 3 litreS of acetone were stirred under reflux for 5 hours.
The mixture was then allowed to cool, the inorganic salts were filtered off and the filtrate was concentrated. The residue was taken up in methylene chloride and the mixture was washed three times with water, dried over sodium sul-phate and concentrated. After recrystallisation of the residue from diisopropyl ether, 156 g (82% of theory) of

4-(4.-chlorophenylmercapto)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-one of melting point 50C were obtained Pre~aration of the starting materials ___ ___________ _________ ___ ______ CH3'' '' '' ~' Br - CH2 - C0 - C - CH2 - S ~ - C1 . CH3 64 g (0.4 mol) of bromine were slowly added to :: 97 g (0.4 mol) of 1-(4-chlorophenylmercapto)-2,2-dimethyl-~: butan-3-one at room'temperature. The reaction mixture , . .
was worked up in a manner corresponding to that in Example 1. 127. g (9g~ of theory) of 1-bromo-4-(4-chloro-':~ 20 phenylmercapto)-3,3-dimethyl-butan-2-one were obtained as ~ a viscous oil.

. CH3 - C0 - C - CH2 - S ~ Cl 134 5 g (1 mol) of 4-chloropinacolin were stirred with 216 g (1.5 mol) of 4-chlorothiophenol and 210 g (1.~2 mol) of potassiu~ carbonate in 500 ml of dimethyl-formami.de at 150C and under a pressure of 2 to 4 bars for 15 hours. The mixture was allowed to cool to room temperature and was stirred with 10 litres of water and . extr.ac.t.ed with.ether, The..ether phase was. dri.ed.over Le A 2~ 763 ~ <~ 7~

.
sodium sulphate and concentrated and the residue was distilled _ vacuo. 151 g (62% of theory) of 1-(4-chloro-phenylmercapto)-2,2-dimethyl-butan-3-one of boiling point 146C/0.5 mm Hg were obtained.

CH3 - C0 - C - CH2Cl 11.6 g (0.1 mol) of 2,2-dimethyl-1-hydroxy-butan-3-one (for the preparation, see Example 3) were added dropwise to 20.5 g (0.1 mol) of N,N-diethyl-1,2,2-tri-chlorovinyl-amine at 50 to 60C (cooling with ice).
After the mixture had been stirred at 60C for two hours, it was distilled under a water pump vacuum 8.1 g (60%
of theory) of 4-chloropinacolin of melting point 60-62C/12 mm Hg were obtained.
The following compounds of the general formula Rl - CH - C0 - C - (CH2)n ~ R (I) Az CH3 according to the invention were obtained in a corresponding manner and by the process described;

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-- -- .
The fungicidal ac~ivity of the compounds of this invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding prep-arative Example.
The known comparison compounds are identified as follows: -/~
(A) (CH3)3C - C0 - CH2 - N

(B) Cl ~ -C0-CH2-N

(C) Cl ~ CH2-1CH-C0-C(CH3~3 N
Example A
Erysiphe test; (barley)/protective Solvent: :L00 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkyl-aryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concen-trate w~s d_lute~ with water to the desired concentration.
To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the plants Le A 2~ 763 t ~ r ;~

_ . -- . --were dusted with spores of Erysiphe graminis f.sp. hordei.
The plants were placed in a greenhouse at a tem-perature of about 20C and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.
Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity compared with the state of the art was shown, for example, by the 10 compounds (43), (28~, (29)~ (22), (3), (44), (24), (1) and (38).
Example B
-Powdery mildew of barley test ~Erysiphe graminis var.
hordei)/systemic (fungal disease of cereal shoots) The active compounds were used as pulverulent seed treatment agents. These were produced by extending the active compound with a mixture of equal parts by weight of talc and kieselguhr to give a finely pulverulent mix-ture of the desired concentration of active compound.
For the treatment of seed, barley seed was shaken with the extended active compound in a closed glass bottle.
The seed was sown at the rate of 3 x 12 grains in flower-pots, 2 cm deep in a mixture of-one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand. The germination and emergence took place under favourable conditions in a greenhouse. 7 days after sowing, when the barley plants had unfolded their first leaf, they were dusted with fresh spores of Erysiphe graminis var~ hordei and grown on at 21 to 22C and 80 to 90% relative atmospheric humidity and 16 hours t exposure to light~ The typical mildew pustules formed on the leaves within 6 days.
The degree of infection was expressed as a percent-age of the infection of the untreated control plants.
Thus, 0% denoted no infection and 100% denoted the same - Le A 20 763 degree of infection as in'the' case of the untreatéd control, The more active was the active compound, the lower was the degree of mildew infection, In this test, a clearly superior activity compared with the state of the art is ~hown, for example, by the compound (29), Example C
Podosphaera test (apple)/protective ~Solvent: 4.7 parts by weight of acetone 0 Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether Water: 95,0 parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated additions.
Young apple seedlings in the 4 to 6 leaf stage were sprayed with the spray liquid until dripping wet, The plants remained in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of 70%. They were then inoculated by dusting with conidia of the apple powdery mildew causative organism (Podosphaera leucotricha) and placed in a greenhouse at a temperature of 21 to 23C and at a relative atmospheric humidity of about 70%, 10 days after the inoculation~ the infection of the seedlings was determined. The assessment data were'con-verted to percent infection. C% denoted no infection and 100% denoted that the plantswere totally infected, 3 In this test, a clearly superior activity compared with the state of the crt was shown, for example, by the compounds (43), (28) and (29).

Le A-20~763 ~q The' following bi:otest Example shows, for example, the superior action of 4-(4-chlorophenylmercapto)-3,3-dimethyl-1-(1,2l4-triazol-1-yl)-butan-2-ol (which is a compound of formula (VIII) produced from a compound of formula (I) according to the present invention) in comparison with the known compound (A).
Examp-le D
Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide 0 Emulsifier: 0.25 part by weight of alkyl-aryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concen-tration.
To test for protective activity, young plants were sprayed with the preparation of active compound until dew-moist. After the spray coating had dried on, the plants were dusted with spores o~ Erysiphe graminis f.sp.
hordei.
m e plants were placed in a greenhouse at a tem-perature of about 20C and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules Evaluation was carried out 7 days after the inoculation.
In this test, a clearly superior activity com-pared with the known compound (A) was shown by 4~(4-chlorophenylmercapto)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol. - ' -'Le A 2-0 763 ~ . .

Claims (24)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A substituted 1-azolyl-butan-2-one of the formula (I) in which Az represents a 1,2,4-triazol-1-yl or -4-yl or imidazol-1-yl radical, R1 represents a hydrogen atom, an alkyl radical with 1 to 6 carbon atoms, an alkenyl or alkinyl radical with 2 to 6 carbon atoms, a cyclohexyl or cyclohexylmethyl radical optionally substituted by methyl, a phenoxyalkyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl moiety, the phenyl moiety being optionally substituted by fluorine, chlorine, methyl, ethyl, isopropyl, tert.-butyl, dimethylamino, methoxy, methylthio, cyclohexyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, phenyl, phenoxy, fluoro-phenyl, chlorophenyl, chlorophenoxy, fluorophenoxy or the group -CO-NR7R8, in which R7 and R8 each independently is hydrogen, alkyl with 1 to 4 carbon atoms, optionally halogen and C1 to C4 alkyl-substituted phenyl, or R7 and R8 both together with the adjacent nitrogen atom form a saturated 5- or 6-membered ring system which may possess nitrogen or oxygen as additional hetero atoms;

n is O or 1, R2 represents a cyano radical or a grouping of the general formula -X-R3 or -CO-NR4R5, or, if n does not represent O at the same time as R1 represents a hydrogen atom and Az represents a 1,2,4-triazolyl radical, R2 may also represent a phenyl radical which is optionally substituted as defined for phenyl under R1 or an alkoxycarbonyl radical having 1 to 3 carbon atoms in the alkoxy moiety, and wherein X represents an oxygen or sulphur atom or an SO or SO2 group, R3 represents an alkyl or halogenoalkyl radical having 1 to 4 carbon atoms, or a phenyl or benzyl radical which is optionally substituted as defined for phenyl under R1, R4 represents a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, or a phenyl radical which is optionally substituted as defined for phenyl under R1, and R5 represents a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, or an acid addition salt or metal salt complex thereof.

2. A compound according to claim 1, in which R1 represents hydrogen, alkyl with 1 to 6 carbon atoms or benzyl which is optionally substituted in the ring by chlorine, R2 represents a grouping of the general formula -X-R3 in which X is oxygen or sulphur and R3 is alkyl of 1 to 4 carbon atoms or phenyl or benzyl substituted in the ring by chlorine or bromine,

3. A compound according to claim 2, wherein Az is 1,2,4-triazol-1-yl.

4. A compound according to claim 2, in which Az is imidazol-1-yl.

5. A compound according to claim 1 in the form of the free base or in the form of a non-phytotoxic acid-addition salt or metal salt complex thereof.

6. 1-(4-Chlorophenoxy)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one of the formula

7. 2-(4-Chlorophenoxy)-2-methyl-4-(1,2,4-triazol-1-yl)-octan-3-one of the formula

8. 2-(2,4-Dichlorobenzyloxy)-2-methyl-4-(1,2,4-triazol-1-yl)-butan-3-one of the formula

9. 1-(4-Bromophenoxy)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one of the formula

10. 1-Methoxy-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-5-(2,4-dichloro-phenyl)-pentan-3-one of the formula

11. A process for the production of a compound of formula (I) according to claim 1, characterized in that a) a halogenoketone of the general formula (II) in which Hal represents a halogen atom, and R2 and n have the same meanings as in claim 1, but in the grouping -X-R3 the substituent X only represents oxygen or sulphur, is reacted with an azole of the general formula H-Az (III) in which Az has the same meaning as in claim 1, in the presence of a diluent and in the presence of an acid-binding agent, and, b) if a compound of formula (I) is required in which R1 is other than a hydrogen, the compound produced by reaction variant(a) of the general formula (Ia) in which Az and n have the same meanings as in claim 1 and R has the same meaning as in reaction variant (a) is reacted with an agent of the formula R1 - z (IV) in which R1 has the same meaning as in claim 1, other than a hydrogen atom, and Z represents an electron-withdrawing leaving group, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, and c) if a compound of formula (I) is required in which X represents SO or SO2) a compound obtained by reaction variant (a) or (b), of the general formula (Ib) in which Az, R1, n and R3 have the same meanings as in claim 1, is oxidised, and, where required, a resulting compound of the formula (I) is converted into an acid-addition salt or metal salt complex thereof.

12. A method of combating fungi comprising applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound according to claim 5.

13. A method according to claim 11 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.

14. A method according to claim 13, characterised in that a composition is used containing from 1 to 0.0001% of said compound, by weight.

15. A method according to claim 14, characterized in that a composition is used containing from 0.5 to 0.001% of said compound, by weight.

16. A method according to claim 12, 13 or 15, characterized in that said compound is applied to soil in an amount of 0.00001 to 0.1 per cent by weight.

17. A method according to claim 12, 13 or 15, characterized in that said compound is applied to soil in an amount of 0.0001 to 0.2 per cent by weight.

18. A method according to claim 12, 13 or 15, characterized in that said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

19. A method according to claim 12, 13 or 15, characterized in that said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

20. The method according to claim 12, 13 or 15, wherein the compound is 1-(4-chlorophenoxy)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-2-3-one.

21. The method according to claim 12, 13 or 15, wherein the compound is 2-(4-chlorophenoxy)-2-methyl-4-(1,2,4-triazol-1-yl)-octan-3-one.

22. The method according to claim 12, 13 or 15, wherein the compound is 2-(2,4-dichlorobenzyloxy)-2-methyl-4-(1,2,4-triazol-1-yl)-butan-3-one.

23. The method according to claim 12, 13 or 15, wherein the compound is 1-(4-bromophenoxy)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one.

24. The method according to claim 12, 13 or 15 wherein the compound is 1-methoxy-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-5-(2,4-dichlorophenyl)-pentan-3-one.