Note: Descriptions are shown in the official language in which they were submitted.
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)
CH3
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
1 3
Az - CH2 - C0 - C - (CH2)n - R (Ia)
CH3
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:
CH3
Rl CH - CO - C - (CH2)n (I)
Az CH3
Rl n R
CH3
H 1 -O- ~ CH3
CH~
C2H5 1 -0--~G~CH3
Cy~
C4Hg 1 ~ ~ -CH3
CH\3
Cl ~ CH2- -O ~ CH3
CH3
CH2- 1 ~ ~ CH3
-5-
~:`
~; ~
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-@~
CF3
C2 Hs 1 _o_<~
CF3
C4Hg 1 -0-@~
c~3
Cl-<g~) -CH2 ~ 1 ~~~ CF3
CH2 - 1 -0-~
CF3
CH~,CH3
H 1 -0-~,)
CH~ ,CH3
C2 H5 1 -O- ~
CH3 CH3 .,
C~, ~Ig 1 -0-0
CH3 CH3
Cl-~-CH~- 1 ~~~S
CH~ /CH3
(~ -C~2 - 1 . -O -~
Le A 20 763
~- g ~_
~ ";,Jj? C~
R' n R2
H 1 -O-~ -CH3
CH3
C2 H~ O- (~ -CH3
CH3
C~, Hg1 -O-~ -CH3
~ CH3
Cl-~-CH2-1 -O~)-CH3
CH3
CH2 - 1 -0-~> - CH3
CH3
CH3 ~
H 1 -O-~>
CH3
C~I3
Cz H5 1 -O-~
C4Hg 1 -O-~
CH3
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-~
CH3
C2 H5 Cl
CH3
C4 Hg Cl
CH3
Cl-~ -CH2 - . -O- <~
/ CH3
(~>-CH2- 1 -0-~
Cl~
Le A 20 763
R' n R2
CH3
H 1 Cl
GH3
Cz H~ 0~
CH3
C4 Hg 1 -0~>
Cl
CH3
Cl-~-CH2- 1 Cl
CH~
@ CH2- 1 cl~
,CH3
H 1 -0-~3-Cl
CH3
C2 H5 1 -0-~-Cl
CH3
C4 Hg 1 -0-~5-Cl
CH3
Cl-~>-CH2- 1 -0-~-Cl
CH3
~- CH2- 1 -0-(~-Cl
CH3
H 1 -0- ~-Cl
CH3
C2 H5 1 -0-~-Cl
CH3
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-~<
CH3
C2 H5 1 -0
CH3
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
/ CH3
C2 H5 1 -0- ~Cl
CH3
CH3
C4 Hg 1 -0-~ Cl
CH3
Cl-~>-CH~ - 1 -0-~ Cl
CH3
Le A 20 763
~ ~17~3~8'~
Rl n R2
~ CH3
(~CH2 - 1 -0-~ Cl
CH3
-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-,~
C2 5
Cl
C2 Hs 1 -0-~
C2H5
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
C4 H9 1 -0
CN
Cl-~-CH2 - 1 -0
C..l
O-CH2- 1 -0-~>
H 1 -0-CH2 -O -Cl
. Le A 20 763
h7
1 1
,~
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
CH3
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~
CH3
<~ -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
37
-- 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~
CF3
C2 Hs 0 _o_@
~CF3 . .
C4Hg -0-@~
CF3
Cl-~3-CH2- o _0_~
CF3
~-CHz- --@~
CF3
CH~ CH3
H ~~ O
CH~CH3
C2 H~ O ~
CH~,CH3
C4 Hg . O _o_~
CH3 CH3
cl-~?-CH2- ' ' --~S
CH3 ,CH3
~-CH2- 0 ' -0-~
.
Le A 20 763
37
'' '`Cl
Rl n R2
.
H . 3 -O~-CH3
CH3
-O-~-CH3
CH3
. C~Hg O -O-~-CH3
C~3
~;~ 5 Cl-<~-CH~- -~-C~3
CH
CH2- 0 -O~>-CH3
. CH3
. CH
: H ~~~
CH3
CH3
C2 H~ O ` o ~)
CH3
X3
C4EIs -0-~
,r~3
CH3
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 -
CH3
C2 Hs 0 -0-~>
Cl
CH3
C4 Hg 0 -0
Cl -
CH3
Cl~ CH2- 0 -0-~)
Cl
CH~
~- CH2- 0 Cl~
,CX3
H 0 -0-~-Cl
CH3
C2 H5 0 --(~S-
CH3
Cs Hg -0-<~-Cl
CH3
Cl-~~CH2- 0 O-~-C
,cx3
(~)- CH2- 0 -0-~-Cl
CH3
H 0 -0-~>-Cl
CH3
C2 H5 0 -0-~> -Cl
- CH3
C4 Hg 0 -0-~ -Cl
CH3
Cl~-CH2- 0 -0~-Cl
Le A 20 763
c?~
R' n R2
CH3
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-~
CX3
Cl
C2 H5 -0
.. . CH3
Cl
C4 Hg ~~~
CH
Le A 20 763
_ ,~ .
Rl n R2
C1
Cl~-C~2- . ` ~
CH3
CH2- 0 -~
CH3
H 0 -0~
C 1 CL~3
C2 H~ 0 -0~
C1 CH3
C~ H9 0 --OE~
cr ~'r.3
Cl~ C~2- 0 -0~
C1 CH3
~> -Ch-2- O -~
C1 CH3
C~3
~I - 0 ~0-~-C1
CH3
C~3
C2~IS 0 -0-~C1
CH3
C~ H9 0 0-~. C1
CH3
C1-~>-CH2- 0 ~0-~ CH
A 20 763
~ ~ ~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-,~
C 5
C2 ]~s O -0-,~
C2 H5
C~ g o o ~
C2 H5
Cl-~>-CH2- 0 -0-
c~5
CH2- O . O ~<,
C2 H5
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
H 0 -0
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
CH3
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
CH3
- C4 Hg -n 1 -S-~0 -Cl
CH3
- CHz -~) -Cl 1 -S~ -Cl
CH3
15- CH2 -~ 0 CF3 1 -S -,~ - Cl
CH3
-CH2-~-CF3 1 -S-,~-Cl
CH3
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
$~3'7
C3 s~3
Rt n R2
H l S CH2 ~ Cl
-C4 Hg -n 1 -S-CH2 ~ -Cl
`Cl
-CH2 - ~-Cl 1 -S-CH2 ~) -Cl
`Cl
-cH2-<~-ocF3 1 . -S-C~2-~>-C
- -CH2-~-CF, iS CH2 <~ -Cl
H l ~ CF
-C" Hg -n 1 -S~
CF,
-CH2-<~>-Cl 1 -S~
C~,
~ -CH2-~>-OCF3 1 -S~>
. ~ CF3
~ -CH2-<~)-CF3 1 -S-~
:~. ` CF3
H 1 -S~>-CF3
.
-C4 Hg -:~ 1 -S~ -CF3
-CH2-<~-Cl 1 -S~>-CF3
-CH2-~)-OCF3 1 -S-<~>-CF3
-CH2-~-CF3 1 -S~>-cF3
.
Le A 20 763
-
.3 ' ~
,~
R' n R2
1 -S-CH
-C4 Hg -n 1 -S-CH
-CH2~ Cl 1 C13
-CH2~ OCF3 1 -S-CH
-CH2 -<~ -CF3 1 -S-CH2 ~
-S-<~ - ~-Cl
-C4 Hg -n 1 -S~ -~> -Cl
-CH2~ Cl 1 ~S~>-<~-Cl
~ -C~2~ OC~ 1 -S-(~ -Cl
-CH2-~-CF3 1 -S~>~ Cl
H 1 -S~) -O-~-Cl
-C4 Hg -n 1 -S~> -0-<~ -Cl
-~2-<~-Cl 1 -S~-O-~-C
-CH2-~)-OCF3 1 -S~$-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
CH3
H2C - CO - C - CH - SO ~ Cl
N CH3
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
CH3 ~ CO - C ~ (CH2)n (V)
CH3
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
CH3
C~ - CO - C - (CH ) - ~ (VI)
CH3
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
OH CH3
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
CH3 -- C0 - C - 0 ~ Cl
CH3
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
CIH3
CH3 - C0 - C - Br
CH3
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
117
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.
I 3 3
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.
1 3
CH - C0 - C - CH20H
- CH3
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
H3
(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 )
CH3
~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.
7 3
. CH3 - C0 - C - CH2 - S ~ Cl
CH3
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.
ICH3
CH3 - C0 - C - CH2Cl
CH3
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
1 3
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
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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
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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 acetone0 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).
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~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. - ' -
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