Note: Descriptions are shown in the official language in which they were submitted.
3'7~
The present invention relates to certain new substituted
l-azolyl-butan-2-ols, to a process for kheir production and to
their use as plant protection agents and as intermediate products
for the synthesis o~ further plant protection agents.
It has already been disclosed that certain triazolyl-
keto and -carbinol derivatives, such as 3 r 3-dimethyl-1-(1,2,4-
triazol-l-yl)~butan-2-one and 1-(4~chlorophenyl)-2-(1,2,4-triazol-
l-yl)-propan-l-ol, have a generally good fungicidal activity (see
our DE-OS ~German Published Specification~ 2,~31,407~. 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 application now provides, as new compounds,
the substituted l-azolyl-butan-2-ols of the general formula
OH CH3
R -CH-c~l-c-(c~2)n-R (I)
Az CH3
in which
Az is a 1,2,4-triazol-1-yl or -4-yl or imidazol-l-yl radical,
Rl is a hydrogen atom or an alkyl radical with 1 to 6 carbon
atoms, an alkenyl or alkinyl radical with 2 to 6 carbon atoms, an
optionally methyl-substituted cyclohexyl or cyclohexylmethyl
radical, or an optionally substituted phenoxyalkyl or phenylalkyl
radical with 1 to 2 carbon atoms in the alkyl part and optionally
substituted as defined above for Rl,
n is 0 or 1,
R2 is an optionally substituted phenyl radical or a cyano,
methoxycarbonyl, ethoxycarbonyl or isopropoxycarbonyl radical or
~, .
~ .~ --1--
7q.~
a group of the formula -X-R3 or -Co-NR~R5,
X is an oxygen or sulphur atom or an So or So2 group,
R3 is an alkyl or halogenoalkyl radical wi-th 1 to ~ carbon
atoms, or an optionally substituted phenyl or optionally substituted
benzyl radical,
R4 is a hydrogen atom, a Cl to C4-alkyl radical or an
optionally halogen- or Cl to C4-alkyl-substituted phenyl radical,
and
R5 is a hydrogen atom or an alkyl radical of 1 to 4 carbon
atoms, in which the optional substituents on the phenoxyalkyl or
phenylalkyl radical of Rl, on the phenyl radical of R2 and on the
phenyl or benzyl radical of R are selected from the group
consisting of fluorine, chlorine, bromine, methyl, ethyl, isopropyl,
tert.-butyl, dimethylamino, methoxy, methylthio, cyclohexyl,
trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro,
cyano, phenyl, phenoxy, chlorophenyl, fluorophenyl, chlorophenoxy,
fluoropheno~y, and -co-NR7R8~ in which R7 and R8 each independently
is hydrogen, alkyl with 1 to 4 carbo~ atoms, optionally halo~en~
and/or Cl to C4 alkyl-substituted phenyl, or both together with
the adjacent nltrogen atom form a saturated 5- or ~membered riny
system which may possess one additional nitrogen or oxygen atom
as hetero atoms,
or acid addition salts or metal salt complexes thereof which are
tolerated by plants.
In some cases, the compounds of the formula II) of
the present invention have two asymmetric carbon atoms; they can
then exist in the form of the two geometric isomers Ithreo-form
and erythro-form~, which can be obtained in various proportionsO
~ -2-
'7~j
In both ca~es, they are in the ~orm of optional lsomers. A11 the
isomers are claimed according to the invention.
According to the present invention we further provide
a process for the production of a compound of the present
invention, characterised in that a substituted l-azolyl-butan-2-
one of the general formula
CH3
R -CH-CO-C-(cH2)n-R
Az C~I3 (II)
in which
Az, Rl, R2 and n have the abovementioned meaning/ is reduced
and, if desired, an acid or a metal salt is then added on.
The new substituted l-azolyl-butan-2-ols of the formula
~I~ have good fungicidal and plant growth-regulating properties
and can therefore be used as plant protection agents.
Surprisingly, the substituted 1-azolyl-butan-2-ols
according to the present invention exhibit a better fungicidal
activity than the triazole derivatives 3,3-dimethyl-1-(1,2,4-
triaæol-l-yl)-butan-2-one and 1-(4-chlorophenyl)-2-(1,2,4-triazol-
l-yl)-propan-l-ol~ which are known from the state of the art and
are closely related compounds chemically and from the point of
view of their action.
In addition, the new substituted l-azolyl-butan-2 ols
are interesting intermediate products for the preparation of
further active compounds for plant protection. Thus, for example,
the compounds of the general formula ~I) can be converted into
-the corresponding ethers at the hydroxyl group in the cus-tomary
7¢ ~7~
manner (for example by the "Williamson ether synthesis").
Furthermore, acyl or carbamoyl derivatives of the compounds of
the general formula (I) can be obtained by reaction with, ~or
example, acyl halides or carbamoyl chlorides in a manner which
is known in principle.
The substances according to the invention thus represent
a valuable enrichment of the art.
Preferred substituted l-azolyl-butan 2-ols of the ormula
~ I ) according to the present invention are those in which R5
represents a hydrogen atom or a methyl or isopropyl radical,
and also those in which the optional substituents on the phenyl-
alkyl or phenyl radical of Rl, on the phenyl radical of R2 and on
the phenyl or benzyl radicals of R3 are selected from the group
consisting of fluorine, chlorine, bromine, methyl, methoxy,
trifluoromethoxy, ethoxycarbonyl, phenyl, and -Co-NR7R8 in which
R7 and R8 each independently is hydrogen, alkyl with 1 to 4 carbon
atoms, phenyl or chlorophenyl, or R7 and R8 together with the
nitrogen atom represent a morpholino group.
Particularly preferred compounds of the formula (I)
are:
4-(1,2,4-triazol-1-yl)-2-methyl-2-p-chlorophenoxymethyl~
butan-3-ol;
4 (1,2,4-triazol-1-yl)-2-methyl-2-p-chlorophenoxymethyl-
octan-3-ol;
5-(p-chlorophenyl)-4-~1,2,4-triazol-1-yl)-2-methyl-2-
carboethoxy-pentan-3-ol;
5-cyclohexyl-4-(imidazol-1-yl)-2-methyl-2-p-chlorophenoxy-
methyl-pentan-3-ol of the formula;
~ '7~7~
4-(1,2,4-triazol-l~yl) 2-methyl-2-p-bromophenoxymethyl-
octan-3-ol.
The following compounds of the general formula ~I)
(in which Az represents 1,2,4-triazol-1-yl or imidazol-l-yl)
~ -5-
~7'7
-- 6 --
may be mentioned speci~ically, in addition to the
compounds mentioned in the Preparative Examples:
OH CH~
R1 ~ CH ~ CH ~ C ~ (CH2)~ - R (I)
lz ~H~
R2
CH3
C~
~2 Hs 1 -0- ~ -CH~
CH
C4Hg 1 -O- ~ ~CH~
` CH
Cl- ~ -C~2- 1 -0 ~ -CH3
CH~
~ CH~ O- ~ -CH3
H 1 0- ~ -CH3
CzH~ 1 -O- ~ CH3
C~Hg 1 . -0- ~ -CH3
Cl~ ~ -~2 - 1 -O- ~ - CH3
~ -CH~- 1 ~0~ ~ ~CH3
H 1 -O- ~ -C(CH3),
C2~ 1 -o~ c(~
C6H~ ~ 1 O_ ~ -C~C~ 33
Cl ~~C~a ~ -Q ~-C~CH3?Y
Le ~ 2~ 762
'7
-- 7 ~
R1 22 R2
@~-C~2~
H 1_O- ~-C2 ~5
C2 H~ 1-O~ -C2 H~
C.~Hg 1 O-~-C2H~s
Cl~ CH2 ~ 2 ~
~ `C~2 ~ 1~0~> -C2 ~g
H 1 -O~
C2 H~ 1 -O~
Cl, H9 1 ~~~> ~
~-CH2~ o_(~
~-C~2_ 1 ~~~
H , 1 -O~ OCF3
C2 Ho~ 1 ~~ OCF3
C" H9 1 -O~ OCF3
Cl- OE~ -CH2 - 1-0~) -OCE 3
Hæ~ OCF3
F1~
7~
-- 8 ~
R n R2
C2~y 1 ~ ~C
F3
C~ Hg 1 ~ 0- @~
Cl-~CH2~ F
<~ -CH - ~ CF
H 1 0
C2Hy ~
C4 Hg 1 --~S
c
@) -~2 - GH~
H 1 ~O~
~c~3
C2 Hg 1 -O-~-CH3
C4 ~9 1 -0~
CH
Cl ~-CH2- 1 -O~-CH3
~ 7t~
_ g _
R1 n R2
H . 1 -0-~>
CH~
CH3
C2H~ 1 -0-~>
~E~3
CH3
~ H~, 1 -0-~>
CH3
CH3
c~ C~I2- 1 -0~)
CH3
CH3
~- CH2- 1 -0
CH3'
H 1 -O - ~OCH,
Ca H, 1 0- 0 'O~I3
Cl, ~9 1 ~0-~ -OC:~
Cl-~- CH2 ~ 1 ~O~OCE~
~ H2~ 1 -O~ OC~
H 1 ~O~ N~
CH3
c2~ 1 -~) N~ C~I3
'7~
~ 10 -
~9 2~ ~a
Ct, H~ 0(~
CH3
Cl-~ C H2- 1 ~ OE~ N,~
CH~s
(~CH2 _ 1 ~> ~ CH
,CH,
}~
Cl
CH3
C2 H., 1 -0-~
Cl
C4 Hg ~. C~
Cl~ 2- C:L~
~ c~3
C~a~ 0-~
~1
H 1 _o ~)
~H3
C2 ~g ~ . -0-~>
Cl
CH~s
G~H,~ 1 0
~1
q~'7
11 ~
~,t ~, R8
_____
~!1
H2- 1 -0-,~
Cl
CH
~GH2 1 -0
C~
~o~3
H 1~ -O ~-Gl
c~3
C2 ~3 1 -~ C~.
::H3
C" Hg 1 O-~-Cl
CH~
C~I2 :L ;0-~ Cl
CH3
~2 - 1 -O-~-Cl
CH~
O~
CH3
C2 H,~ 1 - 0->~ -Cl
CH~
C" H9 1 -0~ Cl
CHs
Cl~-C}~2- 1 -O~-Cl
~H~
@~H2- 1 -
CH~
H 1 -0
~3 t l
~2 H~ 1 _o~>
C~3 Cl
C~, H~ 0~
I:~Q~
~}7~
R2
~1 ~1
,Cl~ 2- 1 -0~
CH3~ Cl
@~-CH2- 1 -0~
0~ -
C2 H~ 1 -0
Ct~g 1 0-~
Cl- ~ -CH2 - 1 -0
<~>-CH2- 1 -~
Cl
H 1 -0
CH3
C2 H~ 1 -~S
C:H3
C~, H9 1 ~-~S
CHI"
- 1 0~>~
C~
~I3
-0~
~7'~'7
-- 13 --
Rl n R2
C2 Hs 1 --,
Cl CH~
~ 4~9 1 _0_~
Ci H3
Cl-~-CHz- 1 -0~
Cl CH3
~CH2- 1 -0-~
Cl CH
C~I3
H 1 -O-~-Cl
CH3
~CH3
C2H5 1 -O-~Cl
CH~,
c~3
C"H9 1 ~O~Cl
CH3
CH~
CH2- 1 -O ~ Cl
CH3
~CH~ ` -- CH
H 1 -o~ CH3
Cl
~2 ~ t)~CH3
7~7
14 -
Rl n R2
I9 1 -O ` ~
Cl
Cl~ CH;!- 1 0~ CH3
~, ' ' 1
C~I3
~ 1 ~0-~
C2'H~
Cl
~2 ~ ~S
~2 H5
Cl
C,~ Hs~ 1 -O- ~/
C~I
2 g
CH2 - 1 -0
C2 Hs
Cl
~CH2- 1 -0-~
C2 H3
Cl
H 1 -o~>
C ( CH )3
Cl
0-~
C(CH3 ~3
Cl
0~
CH3~
-- 15 --
Rl n R2
H2~ 1 -0
C CH3 )~
Cl
~H2~ 1 -0~)
C(CH3
t ~ ;C(~H3 ):~
C2 H, 1 -O-~c-C ( CH3 )3
C,~, H9 1 -O- ~-C (CH3 )~,
Cl~ 2 - 1 -O-~;C(CH3
~2 1 -O-~C ( CH3 )3
1
3I 1 -O~ CN
~2 H, 1 -O-~-CN
C~, H~, 1 ; 0-~ -CN
Cl~ -C:H2 1 -0~ ~ CN
H2 - 1 ~ 0~ -CN
t::N
H 1 -0-~
-- 16 --
R1 2~, RZ
CN
C2 H5 1 _0~
CN
C, H9 1 -0~
CN
Cl~-C~2~
~CN
OE~- C~2- 1 -0~
CN
H 1. -0~>
CN
C~2 H5 1 _0~>
CN
C" H9 1 -0~
CN
Cl~-C~2- 1 -0
CN
~ C~2- 1 ~3
CH2 ~) C1
C~ ~ 1 O-C~k ~@~ -C1
C~ HD 1 -O_CH2 ~ G1
H2~ 1 , -~H2 OE~
~ O C~
-~ 2-,~
~:1
~ 17 -
R~ Fla
C~ Hg 1 ~C~2
C,~ Hi~ 1 -0-
C
Cl- ~-CH2 1 -O~CH
<~ 2~ CH2-~
H 1 -0-CH2-~
C2 Hg 1 O-CH2 ~>
C4H~ 1 ~0-CH2~>
CH2~
0 0 -~H2 - 1-0-~H2 ~\
H 1-O-C:H2 - ~-Cl
Cl
C2E~ 1~0 CH ~
C4 ~3 1 ~
. ~
37~:3
- 18 -
R2
C
H 1 0-CH2-~-CF~
C2 H, 1 -O-CH2 - ~-CF~
~ 4 H9 1 -0-CH2 -~) -CF~
Cl~ Ha 1 -9-CH2 ~-CF!s
~-CH2 1 -0-CH2 - ~-CF3
H 1 -0-CH2-~
Cl
C2~ 0CH
C~Hg 1 -O~CH2 ~)
Cl
H2 - 1 -O-CH2 ~)
Cl
@~ ~CH2 - 1 -- C~2 ~
H ' 1 -C~2 ~) -N2
c2~ 1 ~0-CH2 ~-N0
~ 4 ~ 1 --~2 ~ `N2
- 19 -
Rq n R2
t l' ~- ~ H2 ~ 02
@~ t H2 - 1 ~O-CH2 ~ NO2
H 1-O-CH2-~-CH3
C2 H~ 1-O-CHz ~ -C~3
C4 Hg 1 -C~-CH
C7 -~-CH2 ` 1O-CH2~ CH~
<~> CH2 _ 1-0-~H2 -~ -CH3
H 1`O~ SCP~
e2 H, 1O- ~>-SCF~
C" H9 1~O~ SCF~
Cl~CH2 1 -O-O-SCF3
-CH2W 1-O- ~ -SC~
Cl CH3
Ca H, 1 _o~
~1 C~
C4 ~9 . 1 -0~
Cl O-CH2 - 1o ~ CH~;
~ CH3
~7~7~
-- 20 --
R1 x~ FLa
H C~
C2 ~
C~
H" ~ . -0~
C ~ X2 ~ 0 _o~ -CHz
a
0
C2 ~ O -0~
C~ Hs j 0-~> -CH3
C1~ CH2- 0 o~ cH3
~ 2- ~ o
H 0 -0~ (CH3 ~
c~Z~3 . o, ~ 3
C4 H~ O-~ -C ( CH
ClU~-CH2_ 0 O-~C(CH )~
O -O~
2 ~5
~2}~3 0 . 0~>-C2
~ Hg O ~ O~ C2 ~
-- 21 --
aa
~2 - -~ C2 H~
~CH2 - O -0~> -C2 H~
~ ~ O -O ~ ~>
C2 ~ O~
C" H9 O -O~
Cl~ CH20 ~~
~>-CH2 - O -O-~ - ~>
H O -O~ OCF~
C2 ~ O . -O~ -OCF,
H~, O -O-~)-OC~
~iz- O .' -O~-OCE~
(~- CH2- o -~ OCF3
H -~C
Fy
~ ~ O O-~
H5, o _o_
~:!~Q~2
-- 22 --
R Il R~
CF3
C~2 ~ ~o_~
CF
H3
}~ O -0- ~>
C~3 CH~3
C2~I3 ~~S
C4 H9 . O ,~ _o_~)
C~ CH
Cl-~-CH2- --~S
CH~
2- 0 _o_~
; 0
CH3
C2 ~ -O~ H~
,-~'1 !
9 0 -o~
~ ~H3
CHz ~- I O -0~ -CH ~
H3
~-~2 - O -0~> -~H3
~ CH ,
CH3
~3
7>~
~ 23 -
P~ n , Ra
CH3
C2~, 0 -0
CHs
CH~,
C4,X~9 --~>
Hs
CH3
Cl~>-CH2- -O~)
CH3
CH3
~- CH2- O -O~
CH~
H O -O (~-OCX3
C2 H, O -O~ OCH~
C~ Hg O -O~ OCH
Cl-~-CH~ O -O~)-OCH~
0 O~CH2~ 0 -O-~-OCH~
~ . O -O~ N~
C2 H3 ~) 0~) N~ 3
~ CH3
C,~ ) ~ N~
CH
CH2 ~ O - ~~) -N~ 3
CH3
~C~z= O _o~ N~CH~
I:~Q~ ~ CH3
_ 24 ~
3~ n ~,2
O ~0
C e Hg O -
CH.
C.~I3, ' t) -0~
CH
~ 2- 0 -0
Cl
@~ CH ~ ~ O -0
~1
O 0~
t 2 H O ~-0-~)
O -0
Cl
Cl~ ' O -0-~>
~ C}~2- CH~
H O ~S,CH,
~ a H~ O ~ ~S-~ :
.
t7~j
-- 25
R' !~ R~
CH3
C~, ~I9 o -
CH3
2- 0 -O ~-Cl
: ~ H3
2~ o -O-~-Cl
CHy
E~ O ~ Cl
C~
C2 Hg O -0-~ -Cl
CH,
Eg ~ -0~-Cl
CH~
Cl~>o~,- O -O~)-Cl
2- 0 -O-a~>-Cl
CH3 &1
~ O _o~
CH3 1~1
Cz ~ ~ . -0~
CHI Cl
C4~9 ~) _o~
CH3 Cl
Cl~ -0~
C}l Cl
z O
~I o
C2~ ~ o-~.
0 -0-~
- 26 -
;~,1 a R~
C~ a~ t)
~>-CH2~ O ~0
H O ~$~
C~3
C~5 0 -0
CH~s
~1
C~.H9 ~~S
GH..~
2-, O
C~I, .
el
2- o _o~
CH,
H O -0
Cl ~H~
C2 H~ !' , O ,~
Cl Hg
C4 H9 0 ~-~?
Cl ~H3
H2- O 0~
Cl ~3
o ~ Q
C: H~5
...
~ 27 -
R1 ~, ~,z
~ CH3
O -0-~) Cl
~3
C~
C2 H C~ ~0
CE~
C~I3
C~ H9 o -0-~ Cl
CH3
~ H2~ 0
CH~
~2 ~ -0-~--Cl
~ _o @~ .
Cl
C2 HS o -O-'~;CH3
. , 1
G" E19 , O O~ 3
~ H2'~ o _o~
Cl
2~ O 0~ 3
CH3
," ,~- .
`~2 ~
1:~
2~ -
R~
__
C2~ 0 -0~
. .,. ~ C2 ~I5
,Cl
4 }~5~ 0 _o_ (~
C2''H,,
C~
Cl-~-CH2- 0 Q~
Cz~lH5
~1
@>--CH2- 0 _0_<~
C2 E~
Cl
H O -0
C(CH3 )~
C2~ O C~ .
H~l ~3
Cl
C~ H9 o _o_}~
C~C~
Cl~ -C~2 - - ~>
C(CH3 )3
Cl
0 <~> -CH2- 0 0-~
C''( C~ 3
H o . -O~ C(CH~ )3
Cl
~2}I~ O _o-<~C(~ )3
I:~Q~
'7~7~
-- 29 ~-
~' n F2
o _0-~ C(C~ ~3
Cl
~2 - 0 oO_ ~C(CHs ~3
~2 - -O-<~;C ( CH~
}~ O -O~ CN
C2 H, O -O-~-CN
C,~ ~I9 0 , -0~ CN
Cl~-CH2- O -O-~-CN
2- -O~-CN
CN
~
~CN
C2 H, O -0~
CN
C4 H9 -~
CN
~Cl~)-~R2-~ ~
CN
<~-CH2 0 -0~
CN
H . O ~>
C~
C2~3 0 ~ 0~
CN
0
7~ .`b
-- 30 --
Rl ~ ~,2
_ _ .
Cl~ 0;;~
H2D O -~
~ 2 ~ ' ~ 2 ~ Cl
C4Hs~ O -O-CH2~ Cl
O ~0 ~H2
H7-~)
H O `O-
Cl
0 C2 H~ --C~2 ~)
C~Hg O ~O~CH
C
'I ~.-~"-CH2 - O ~ H2
Cl
OE)--CH2- 0 -0-CH2-~
Cl
O . ~O-t
C2E~ , O ~0 ~I~
~ 4 EI~ -~2
~,~Q~
i1.3~7~
R9 n F~,2
~CH2 - O ---C~2 ~)
H O ~V~CH2 ~oCl
Cl
C2 H~ O -C:H2 -~-Cl
Cl
C~ H9 0 ~
Cl
Cl~ O-CH2 ~Cl
Cl
~>-CH2- 0 O-CH2-~ell
H O -O CH2 - ~-CF~
C2 H3 ~ ~0 ~CH2 ~-CF~
C~ H9 0 -O-CHz ~ -CFy
Cl~ -C Ha ~ -O-CH2 - ~-CF'3
CH2 - 0 . -0-(~H2 - ~ CF~
, Cl
Cl
~ a~s -O-CH2 ~)
'7~
- ~2 -
Rl ~:~, R2
t 4 ~9 -~ 2 ~)
Cl
Cl- ~-CH2 O -O-CH2 ~ '
Cl
2 - 0 ~ 2 ~)
H -O-CH2 ~ -N2
C2 H, O -Q~ N2
~Hg t:)--C~2 ~ -NO2
2 - 0 -C~2 ~ -N2
@~CH2 - t)o~ 2 - ~) -N2
H O-O-CH2-~) ~3
C2 H, -O-CH2 ~ -CH3
C" H9 0-O ~ CH2 ~
Cl ~ -C~2 - ~ H2 O -CH~s
a~ ~-C~2~
33 -
Rl n R~
~, _
H O ~ S~F3
C2 H.~ o ~o~ SCF3
C4 Hg O -0-~ -SCF3
Cl~CH2 o -o-~-SCF~
2- o -o-~-SCF~
CH3
H Q -0-~
~1 CH3
Cz H., O --0
Cl CH~
C" H9 0 0-~
c~ C:H2- 0 ,OE~
z- O -0-,~
H 1 -OC4 H9
2 ~ 1 -OC,~ Hg
C2 H5 1 0-C4 Hs~
C" Hg 1 -0~ C4 Hg
Cl ~> ( H2 - 1 O C4 Hs
F3 C~ CH2 - O -COOC2 H~
F, C~ H~ ~ O -COOC~ H7 ~1
~5L2~2
7~7
- 34 -
R~ n R2
F3 C-~-CH2 - O CON (C~3 )2
F3 C~ H2 ~ -CC)NH-~ -Cl
F3 CO~ C~ COOCH"~
F3 CO~ CH2 - O -CN
H O -CN
H O ~
O ~-Cl
H O ~-Cl
~ ~-~
H 1 S~ F
~C,~ H9 -n 1 -S- <~ -F
-CH2 - ~)-Cl 1 S~) -F .
-CH2-~-OCF, 1 -S~-F
-CHz~ S~ F
H 1 -S-~>-SCF3
-C~ Ilg ~ 1 -S-~ -SCF3
C~2 ~ ~) -Cl 1 ~S-~-SCF3
-CH5!-~-OC~3 1 ~S-~-SCF~
~a ~) C~3 1 -S~ ;CF3
35 .w
~ ~ R,2
R 1 ~ O~F~
-C,~ Hg -rl 1 S~ -OCF3
-~2~ S~ OC~s
-CH2 - ~ -OCF3 1 -S~ .-O~F3
-CH2 ~ OCF~ 1 -S- ~ ~OCFg
~. -S-~-~
-C4 ~9 -n 1 ~S~ -~
-CH2 - ~-Cl 1 -S~ -~)
-CH2~ OCF~ 1 -S~-~
~CH2-~-CF, 1 ~S~-~
H ~ -S~-CH3
-C4 H~ -n 1 -S-~ -CH3
-CH2 ~-Cl 1 ~ -S <~>-CH~
~CH2~-OCF.~ 1 S~
-CH~2-~ -CF~ S~ CH~s
H 1 -S~ Cl
~H3
~C4 H~, -n 1 -S-,~ -Cl
a~Q~
- 36 -
Rl D. ~
S~> ~Cl
CH3
-GH2-~-OCF 1 -S~ Cl
CH3
~Hz ~>~CF3 1 -S~ Cl
CH~
~ S~ N
9 ~ -S -~ -NO
-~2 ~ ~Cl 1 -S~ -No
-CH2 O OCF~ 1 -5~) -NO
-~2 ~ CF~ S- O_NO2
H 1 -S~-Cl
`Cl
~C4 Hg -n 1 -S-~ ~Cl
Cl
-CH2-~-Cl 1 ~ Cl
-GH2-~-OCF~ 1 -S~3-Cl
-CH2~ CFy 1 -S~ Cl
Cl
H 1 -S-~-Cl
~1
~C4~ S~-Cl
Cl
~CH2-~Cl 1 C~3
OCF~ 1 -S-~Cl
~ ~7 ~
1~ ' R2
-S~
-C4 ~9 -Sl C13
-~2~ 1 Cl~
~CH2-~-OCF~ S~)
-~2~ CF~ 1 Cl~
H 1 ~ Cl
-C4 Hg ~n 1 -S~
0 -'CH2-~ Cl 1 S-~
-CH2-~-OCF~, 1 . -S~
-CH2 ~ ~)-CF.~ 1 -S~
S-C~, H5, -n
~C~ Hg ~n 1-S-C4 H9 ~n
DCH2 ~ -C~ C,~ ~Ig -n
-CH2 -~ -OCF~ S-C4 ~9 n
2 @~ CF3 1-S-C4 Hg n
3t7
- 3~ ~
Rl ra ' R2
H 1 -SCH.~
C4~ n 1 -SCH3
-CH2 ~ SC~I3
-CH2~ OCE~ 1 -SCH3
CHz~-CF~ 1 -SCH.,
S-~H2 ~>
C4Hs-~ 1 -S~CH2 ~
-~H2 ~ C1 1-S CH2 ~>
0 -~2 ~ OCF~ S-CH
C~I2 ~ C~ 1S-CH2 ~
H 1-S~H2 ~ ~Cl
-C4 H9 -n 1-S-CH2 ~) Cl
-~ H2 ~ S~ Cl
-~ H2 ;~) -OCF 1~S~CH2~ Cl
~G~Ha-~>ocF~ ; CH2 ~
-- 39 --
,2
H 1 -S-CH2 - O -Cl
Cl
~C4~s n 1 S-CH2~)-Cl
Cl
-CH2 - ~-Cl 1 -S-CH2~> -Cl
Cl
-CH2~ oCF~ 1 -S-CH2-~-Cl
Cl'
2 '-<~>; CF3 1 -S-CH2 ~ -Cl
Cl
H 1 -S-CH2 ~ -~F3
-C4Hs~ -n 1 -S ~CH2 ~ OCF3
~2 ~ Cl 1 -S CH2 ~ -OCF3
-CH2 ~-OCF~ 1 S-OEI2 ~ -OC~
-CH2 -~ -CF3 1 -S~CH2 ~ -OCF3
H 1 -S-CH2~ SCF3
-C~ Hs~ - n 1 -S~CH2 ~ -SCF~,
CH2 -~-Cl 1 S-CH2 ~ -SCF~s
~ ~2 -~ -OC~3 1 -S-CH2 ~ -~CF3
~CH~ CF~ S~CH2 ~ -SCF3
. .
I:~
t7~j
- ~0
F~ n R2
S-C~2 ~ -Cl
-C4 ~ n 1 -S-CH2 -~ -Cl
-CH2 ~ C1 1 - S-CH2 ~) ~C~
'Cl
5-cH2-~-ocF3 1 -S-CH2-(~-Cl
-CH2~ CF~ 1 -S-'C~2-~j
H 1 -S ~
CE`3
-C,~ H9 -n 1 ~S~
~F3
-~:H2-~> Cl 1 . -S~
CFg
0 -CH2 ~ ; ~ CF3
-C}12 ~~> -C Fg 1 -S-~2
CF!!~
H 1 o5-~CF3
'C4 H9 -n 1 S~> -CF,
-C~2~ Cl 1 S~ C~3
-CH2~ OCF3 1 S~ CF3
-CH2-~-CF~ 1 -S~> `CE`3
_ 41 -
Rl s~ R~
-S~CH
-C~ ~9 n 1 ~S-CH2 ~>
~z ~ ~)-Cl 1 -S-CH2 -~)
-CH2~ ocF3 1 -S-CHCl~)
~CH2-~-CF3 1 -S-CHCl~)
H 1 -S-<~ >-Cl
~ H9 -n 1 -S~) -~ -Cl
-CH2 ~ S~>~ Cl
-C~2~ OcF~ 1 -S-~-~>-Cl
~CH2-O-CF3 1 -S~>-~.-Cl
H 1-S~ -O~ ~> Cl
H9 ~ S~) O-~ Cl
~H2 - ~-Cl 1 ~S~ o~ el
~2~ 0C~ ~ Cl
S F~ S-~ -0-~ Cl
3~3
~ 42-
R2
H 1 -S~ Br
-C~ ~9 -n 1 -S~ Br
-CH2 - ~-Cl 1 -S-~ -Br
5~CH2~ OCF~ 1 -S-~-Br
-CH2-~ CF~ 1 -S-~-Br
H 1 -S-CH2 ~ -~-Cl
-C~ H9 -n 1 ~S-CH2 ~ ) -Cl
2 ~ Cl 1 -S-CH2 ~> -~ -Cl
0-CH2 -~-OCF3 1 -S-CHz ~ -~Cl
-CH2- ~>-CF, 1 -S-CH2 ~ >~ ~ -Cl
H 1 --S-CH2 ~) -O~ Cl
~,H~,-n 1 -S~2 ~ -O~ Cl
2 Q~) -C l 1 -S-C~12 ~ 0-@~ -Cl
~5-CH2 -~> -OCF~ 1 ~S~CH2 ~) -O ~ ~ -Cl
-~2 -~CFI 1 -SCH2 ~3 O~> -Cl
'7'~.3'~
-- 43 --
2a ~a
-SO2 ~ -~1
~C~ n 1-SO2 2~> -Cl
C~2~ SO2-~-Cl
-CH2-~ OCF3 1 ~SO2-~-Cl
CHz -CF~ 1 ~SO2 ~ -Cl
H 1 ~-SO2~3 -F
-C4Hg~n 1 -SO2 ~ -F
-CH2~ Cl 1 -SO~ F
-CHz `OE~OCF3~ 1 -SO2~-F
WCH2-~-C~ SO2-~-F
H 1 -SO2-~OCF
~C" H9 -n 1-SO2 ~ -OCF~
Cl 1 -SO~ OC~
~eH2 OE~ F~ 302-~O~F3
C~2 ~ B 1-~52 ~) . ~t F3
44 -
~1 n ............... R2
H 1 -S02-C~2 ~ -Cl
-C4Hg-n 1 -S2-cH2~-C
-CH2~Cl 1 -S2-cH2~-C
CH2 ~ OCF3 1 -S2-cH2 ~ -Cl
CH2 ~ CF3 1 -S02-CH2- ~ -Cl
If, for exampleg 5-(4~chlorophenyl)-2-~294-
dichlorophenoxy)-2-methyl-4-(1,2,4-triazol-1-yl)-pentan-
3-one and sodium borohydride are used as starting sub-
stances, the course of the reaction according to the pres-
ent invention is illustrated by the ~ollowing equation:
CH3 Cl
Cl- ~ -CH2-CH-CO-C-O- ~ -Cl NaBH4
~N`N CH3
~ .
OH CH3 \
C1- ~ -CH2-CH-CH-~-O- ~ -Cl
~ CH3
Preferred substituted l-azolyl-butan-2~ones of
formula (II) to be used as starting substanc~s for the
process according to the invention are those in which Az,
R 9 R and n have those meanings which have already been
mentioned in the case of the preferred and particularly
preferred compounds of the formula (I) accordin~ to
Le A 20 762
'7~7~:~
the present invention.
The subst.ituted l-azolyl-butan-2-ones of the formula (II)
are not yet known; some of them are the subject of our European
application 0 044 993 published February 3, 1982 (Le A 20 458), or
of our European application 0 054 865 published June 20, 1982
(Le A 20 763), and they are obtained by a process in which
a) a halogenoketone of the general formula
CH3 2
Hal-CH -Co-C-tCH ) -R (III)
CH3
in which
Hal represents a halogen atom, in particular a
chlorine or bromine atom, and
R and _ have the abovementioned meanings, but in the
grouping -X-R3 the substituent X represents only oxygen
or sulphur,
is reacted with an azole of the general formula
H - Az (IV)
in which
Az has the abovementioned meaning,
in the presence of an inert organic solvent (such as acetonitrile)
and in the presence of an acid-binding agent (such as potassium
carbonate) or an excess of azole, at a temperature between 60 and
120C; and, if appropriate,
b) the resulting compound of the general formula
CH3 2
Az-CH -CO C-(CH ) -R (IIa)
CH3
-45-
~77~7~;i
- 46 -
in ~hich
Az, n and R2 have the abovementioned meaning,
is reacted with an alkylating agent of the formula
Rl z (V3
in which
Rl has the abovementioned meaning and
Z represents an electron-withdrawing leaving
group, such as halogen, p-methylphenylsulphonyl-
oxy or sulphate,
in the presence of an inert organic solvent (such as
dimethylsulphoxide) at a temperature between 0 and 100C,
and, if appropriate~
c) the compound obtained by processes (a) and (b)~ of
the formula
C~
Rl-CH-Co-C-(CH2)n-S-R3 (II b)
Az CH3
in which
Az, Rl, n and R3 have the abovementioned meaning9
is oxidised in the customary manner (for example by reaction
with hydrogen peroxide in glacial acetic acid at a tem-
perature between -30 and 80C) In ¢arrying out the
oxidation, about 1 to 5 mol of oxidisi.ng agent are employed
per mol o.~ the compounds of the formula (II b). I~ 1
mol of oxidi.sing agent (such as m-chloroperbenzoic acid in
methylene chloride or hydrogen peroxide in acetic
anhydride at a temperature between -30 and ~30C) is used,
those compounds of the formula (II) in which X represents
S0 are pre~erentially formed. If an excess of oxidising
agents and higher temperatures (lO to 80C) are used~
those compounds of the ~ormula (II) in which X represents
S2 are preferentially ~ormed The oxidation products
are isolated in the customary manner.
Le A-20 762
Some of the halogenoketones o ~he formula (III) are
known (see our DE-OS IGerman Published Specification) 2,635,663,
some of them are the subject of our European application 0 042 980
pub~ished January 6, 1982 (Le A 20 356~, and some of them are
completely new. They are obtained by a process in which a ketone
of the general formula
C,H3 2
CH -CO-C-(CH ) -R ~VI)
CH3
in which
R and n have the abovementioned meanings,
is reacted with chlorine or bromine in the presence of an inert
organic solvent (such as ethers or chlorinated or non-chlorinated
hydrocarbons) at room temperature, or with customary chlorinating
agents (such as sulphuryl chloride) at 20 to 60C.
Some of the ketones of the formula (VI) are known
(see J. Org. Chem. 42, 1709-1717 (1977~; J. Am. Chem. Soc.
98, 7882-84 (1976); J. Org. Chem. 37, 2834-2840 (1972); United
States Patent Specification 3,937,738 and C.A. 82, 30898j (1975)),
some of them are the subject of our European application 0 041 671
published December 16, 1981 ~Le A 20 355); and some of them are
new. They can be obtained by the processes described in the
mentioned patent application, for example by a procedure in which
a keto derivative of the formula
cl~3
3 , 2 n (VII)
CH3
-47-
7'^~ 7
- 48 -
in which
n has the abovementioned meaning and
Y represents a chlorine or bromine atom or a
grouping of the general ~ormula -O~S02-R ,
wherein
R6 represents an alkyl radical with 1 to 4 carbon
atoms or a phenyl radical which i~ optionally
substituted by alkyl with 1 to 4 carbon atoms,
is reacted with a compound of the general formula
Me_R2 (VIII)
in which
R2 has the abovementioned meaning and
Me represents an alkali metal, such as, preferably,
sodium or potassium, or a hydrogen atom,
in the presence of an organic solvent (such as glycol or
dimethylformamide) and if appropriate in the presence of an
acid-binding agent (such as sodium carbonate) at a tem~
perature between 80 and 150C.
The keto derivatives of the formula (VII) are
known (see for example, DE-OS (German Published Specific-
ation) 2,632,603 and J. Org. Chem. 35, 2391 (1970)), or
they can be obtained in the generally known manner.
The compounds of the formula (VIII) are generally
known compounds of organic chemistry and, if appropriate,
they are employed as compounds which are produced i situ~
The azoles o~ the formula (IV) and the alkylating
agents of the formula (V) are like~ise generally known
compounds of organic chemistry.
The reduction according to the in~ention is
3 carried out in the customary manner for example by
reaction with complex hydrides~ if appropriate in the
presence of a diluent or by reaction with aluminîum
isopropylate in the presence of a diluent~
If complex hydrides are used~ possible diluents
Le A`2-~ 762
. . .
q~
- ~9 -
for the reaction according to the invention are polar
organic solvents. These include, preferably, alcohols
~such as methanol, ethanolg butanol or isopropanol) and
ethers (such as diethyl ether or tetrahydro~uran).
The reaction using complex hydrides i8 in general
carried out at a temperature between 0 and 30C, preferably
between 0 and 20C. For this reaction, about 1 mol of
a complex hydride (such as sodium hydride or lithium
alanate) is employed per mol of the ketone of the formula
(II). To isolate the reduced compounds of the formula (I),
the residue is taken up in dilute hydrochloric acid and
the mixture is then rendered alkaline and extracted with
an organic solvent. Further working up is effected in
the customary manner.
If aluminium isopropylate is used) preferred
possible dîluents for the reaction according to the
invention are alcohols (such as isopropanol) or inert
hydrocarbons (such as benzene). The reaction temperatures
can again be caried within a substantial range; in general,
the reaction is carried out at a temperature between 20 and
120C, preferably between 50 and 100C. For carrying out
the reaction, about 1 to 2 mol of aluminium isopropylate
are employed per mol of the keto~e of the fo~mula (II).
To isolate the reduced compounds Or ~he formula (I) 3
the excess solvent is removed by distillation i vacuo
and the resulting aluminium compound is decomposed with
dilute sulphuric acid or sodium hydroxide solution,
Further working up is effected in the customary manner.
The following acids can preferably be used for
the preparation of physiologically ~cceptable acid addition
salts o~ the compounds o~ the formula (I); hydrogen
halide acids (such as hydrobro~ic acid and, preferably,
hydrochloric acid)~ phosphoric acid, nitric acid; sulphuric
acid~ monofunctional and bifunctional carboxylic acids and
~5 hydroxycarboxylic acids (such as acetic acid~ maleic acid9
Le- A 2~ 762
- 50 -
succinic acid, fumaric acid~ tartaric acid~ citric acid,
salicylic acid, sorbic acid and lactic acid) and sulphonic
acids (such as p-toluenesulphonlc acid and 1,5-naphthalene-
disulphonic acid) The acid addition salts of the com-
pounds Or the formula (I) can be obtained in a simple mannerby customary salt formation methods, for example by dis-
solving a compound of the formula (I) in a suitable ine~t
solvent and adding the acid~ for example hydrogen chloride,
and they can be isolated in a known manner, for example by
filtration, and if appropriate purified by washing with an
inert organic solvent.
Salts of metals of main groups II to IV and of
sub-groups I and II and rV to VIII are preferably used
for the preparation of metal salt complexes of the com-
pounds of the formula (I), examples o~ metals which maybe 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;
hydro~en halide acids (such as hydrochloric acid and
hydrobromic acid), 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 c~s-
tomary processes, thus, for example~ by dissolving themetal salt in alcohol (for example ethanol) and adding
the solution to the compound of the formula (I). The
metal salt complexes can be purified in a known manner,
for example by filtration, isolation and, if appropriate~
by recrystallisation.
The active compounds according to the invention
exhibit a powerful microbicidal action and can be
employed in practice for combating undesired micro-
organisms. The active compounds are suitable ~or use
as plant protection agents.
Le A 2~ 762
- 51 -
Fungicidal agents in plant protection are
employed ~or combating Plasmodiophoromycet~s, Oomycetes,
Chytridiomycetes, Zygomycetes, Ascomycetes~ Basidiomy-
cetes an~ Deuteromycetes.
The good toleration, by plants, of the active com-
pounds~ 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 3 the active compounds
according to the invention ~an be employed with particu-
larly good success for combating those fungi which cause
powdery mildew diseases~ thus for combating Erysiphe
species, such as against the powdery mildew of barley or
of cereal causative organism (Erysiphe graminis) or the
powdery mildew of cucumber causative organism (Erysiphe
cichoracearum). It should be emphasised that some of
the substances according to the invention have a systemic
action. It is thus possible to protect plants from
fungal attack if the active compound is fed to the above-
ground parts of the plant via the soil and the root.
The active compounds which can be used according
to the invention engage in the metabolism of the plants
and can therefore be employed as growth regulators.
Experience to date of the mode of action of plant
growth regulators has shown that an active compound can
also exert several different actions on plants. The
actions of the compounds depend essentially on the point in
time at which they are used, relative to the stage of
development of the plant~ and on the amounts of active
Le A 20 7-62
77~
- 52
compound applied to the plants or their envirsnment and
the way in which the compounds are applied. In every
case, growth regulator~ are intended to in nuence the
cnop plants in the particular manner desired.
Plant growth regulating compounds can be
employed, for example, to inhibit vegetative growth o~
the plantsO Such lnhibition of growth is inter alia
o~ economic interest in the case of grasses, since it is
thereby possible t~ reduce the frequency of cutting the
grass in ornamental gardens, parks and sportsgrounds, at
verges, at airports or in fruit orchards The inhibi-
tion of growth of herbaceous and woody plants at verges
and in the vicinity of pipelines or overland lines or,
quite general~y, in areas in ~hich hea~y additional
growth of plants is undesired, is also o~ importance
The use of growth regulators to inhibit the
growth in length of cereals is also important. The
danger of lodging of the plants before harvesting is
thereby reduced or completely eliminated. Furthermore,
growth regulators can strengthen the stem of cereals,
which again counteracts lodging. Use of growth regu-
lators for shortening and strengthening the stem enables
higher amounts of fertiliser -to be applied to increase
the yield, without danger of the cereal lodging.
In the case of many crop plants~ inhibition of
the vegetative growth makes denser plan-ting possible, so
that greater yields per area of ground can be achieved.
An advantage of the smaller plants thus prod~ced is also
that the crop can be worked and harvested more easily.
Inhibition of the vegetative growth of plants can
al~o lead to increases in yield, since the nutrients and
assimilates benefit blossoming and fruit formation to a
greater extent than they benefit the vegetative parts of
plants.
Promotion of vegetative growth can also frequently
be achieved with growth regulators. This is of great
- ~3 -
utillty if it i5 the vegetative parts o~ the pl~nts which
are harve~ted. Promoting the vegetative growth can,
however, also simultaneously lead to a promotion o~
generative growth, ~i~ce more assimilates are ~ormed, so
-that more ~ruit, or larger fruit, is obta~ned,
Increases in yield can ln some cases be achieved
by a~fecting the plant metabolism9 withaut no-ticea~le
changes in vegetative growth. A change in the com
position of plants, which in turn can lead to a better
quality of the harvested products, can furthermore be
achieved with growth regulators. Thus it is possible,
for example, to increase the co~tent of sugar in sugar
beet, sugar cane, pineapples and citrus ~ruit or to
increase the protein content in soya or cereals.
Using growth regulators it is also possible, for example
to inhibit the degradation of desired constituents, such
as, for example, sugar in sugar beet or sugar cane,
be~ore or after harvesting. It is also possible
favourably to influence the production or the e~flux of
secondary plant constituents. The stimulation of
latex ~lux in rubber trees may be mentioned as an
example,
Parthenocarpous fruit can be ~ormed under the
influence of growth regulators, Furthermore, the
gender of the n owers can be in~lu~nced. Ster~lity
o~ the pollen can also be pro~uced~ which is of great
importance in the breed~ng and preparation of hybrid
seed
Branching of plants can be controlled by using
gro~th regulators. On the one hand, by breaking the
apical dominance the development of side shoots can be
promoted~ which can be very desirable, especially in the
culti~ation of ornamental plants9 also in connection
with growth inhibition. On the other hand, however,
35 it is also possible to inhibit the growth o~ side shoots
There is great interest in this action, for exa~ple, in
7~
_ ~4 _
the cultlvation o~ tobacco or in the plantin~ of
tomatoes.
The amount of leaf on plants can be controlled,
under the influence o~ growth regulators, so that
defoliation of the plants at a desired point in time is
aohieved. ~uch de~oliation is o~ great importance in
the mechanical harvesting of cotton~ but i~ also of
interest for ~acilitating harvesting in other crops,
such as7 for example, in viticulture Defoliation o~
the plants can also be carried out to lower the trans-
piration o~ plants be~ore they are transplanted
The shedding of fruit can also be controlled w~th
growth regulators. On the one hand9 it is possible
to prevent premature shedding of fruit. However, o~
the o~her hand, shedding of ~ruit, or even the fall o~
blossom, can be promoted up -to a certain degree (thinn-
ing out) in order to interrupt the alternance. By
~lternance there is understood the peculiarity o~ some
varieties of fruit to produce very different yields ~rom
year to year, for endogenic reasons. Finally, using
growth regulators it is possible to reduce the force
required to detach the fruit at harvest tlme so as to
permit meahanical harvesting or facilitate manual harrest-
ing.
Using growth regulator~, it i ~urthermore
possible to achieve an acceleration or retardation o~
ripening of the harvest product, before or after hQr~est~
ing This is of particular ad~antage, since it is
thereby possible to achieve optimum adaptation to mar~et
requirements Furthermore, growth regulators can at
times improve the coloration of fruit. In addition,
concentrating the ripening wi-thin a certain period of
i time is also achievable with the aid of growth regula-
tors. This provides the precon~itiolls ~or being able
to carry out complete mechanical or manual harvesting in
only a single pass~ for example in the case of tobacco,
3'7
tomatoes or co~ee.
Using ~rowth re~ulators, it is ~urthermore pO8-
sible to in~luence the latent period o~ seeds or buds o~
plants, so that the plants, such as, for example, pine-
apple or ornamental plants in nurseries, germinate, shootor blossom at a time at which they normally show no read-
iness to do so. Retarding the shooting of buds or the
germination o~ seeds with the aid Or growth regulators
can be desirable in regions where frost is a hazard, in
order to avoid damage by late frosts.
~ inally, the resistance of plants to frost,
drou~ht or a high salt content in the soil can be induced
with growth regulators~ Cultivation of plants in
regions which are usually unsuitable for this purpose
thereby becomes possible,
The preferred time o~ application Or the growth reg-
ulators depends on the climatic and vegetative circumstances
The ~oregoing description should not be taken as
implying that each of the compounds can exhibit all of the
described effects on plants. The effects exhibited by
a compound in any particular set of ci~cumstances must be
determined empirically.
The active compounds can be converted to the
customary formulations, such as solutions, emulsions;
suspensions, powders, foams, pastes~ granules J aerosols,
very fine capsules in polymeric substances and in coat-
ing compositions for seed, a~ well as ULV formulations.
These for~ulations may be produced in known manner3
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 disperslng
agents and/or foam-forming agents. In the case of the use
o~ water as an exte~der~ organic solvents can, for example,
also be used as auxiliary solvents.
Le A 2~ 762
3 a~ t~
- 56 -
As liquid diluents or carrier3, especially
solvents~ there are suitable in the main~ aromatic hydro-
carbons, such as xylene, toluene or alkyl naphthalene~,
chlorinated aroma~ic or chlorinated aliphatic hydrocarbons,
such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic or alicyclic hydrocarbons, such a3
cyclohexane or para~ins 3 for example mineral oil fraction~
alcohols, such as b~tanol or glycol a3 well as their eth~r8
and esters, ketones, such as acetone, methyl ethyl ketone,
methyl isobutyl ketone or cyclohexanone~ or strongly polar
solvents, such as dimethyl~ormamide and dimethylsulphoxide,
as well as water.
By liquefied gaseous diluents or carriers are
meant liquids which would be gaseous at normal temperature
and under normal pressureg 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, alumina and silicates. As solid carriers for
granules there may be used crushed and fractionated natuxal
rocks such as calcite, marbleg pumice, sepiolite and
dolomite, as well as synthetic ~ranules of inorganic and
organic meals, and granules of organic material such as
sawdust, coconut shells, maize cobs and tobacco skallcs.
As emulsifying and/or foam-forming agents there may
be used non-ionic and anionic ~mulsifiers~ such as polyoxy-
ethylene-~atty acid esters~ polyoxyethylene-fatty alcohol
ethers, for example alkylaryl polyglycol etners, alkyl
culphonates~ alkyl sulphates, aryl sulphonates as well
as albumin hydrolysis products, Dispersing agents include,
for example, lignin sulphite waste liquors and methyl-
cellulose~
Le A~2~ 762
- 57 -
Adhesive~ such as carboxymethylcellulo~e and
natural and synthetic polymers in the form o~ powder3,
granules or latices, such as gum arabic, pol~vinyl
alcohol and polyvinyl acetate, can be used in the ~ormul-
ations.
It is possible to use colorants such a~ inorganicpigments~ for example iron oxide, titanium oxide and
Prussian Blue~ and organic dyestuffs, such as alizarin
dyestuf~s, azo dyestuffs or metal phthalocyanine dyestu~s 3
and trace nutrients, such as salts o~ iron, manganese,
boron, copper, cobalt 9 molybdenum and zinc.
The formulation~ 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 mixtures 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 ~uch or in
the form of their rormulations or in the use forms pre-
pared ther~rom by further dilution, ~uch as ready-to~
use solutions, emulsion~, suspensions, powders, pa~tes and
granules, They are used in the customary manner, for
example by watering, immersion, spraying; atomi~ing,
mi3ting, vaporising, injecting, forming a slurryp brushing
on3 dusting, scattering~ dry dre~sing~ moist dressing, wet
dressing, ~lurry dressing or encrusting,
Especially in thè treatment o~ parts of plants~ the
concentrations of active compound in the use form can be
varied within a ~ubstant~l range. They are in general
between 1 and 0.0001% by weight, preferahly between 0,5
and 0,001%
-he A ~ 762
__
- 58 -
In the treatment of seed, amounts of active com-
pound o~ 0.001 to 50 g per kilogram of seed, preferably
0.01 to 10 g, are in general required.
In the treatment of soil, concentrations of
active compound of 0.00001 to 0.1% by weight, preferably
of 0.0001 to 0.02%, are required at the place o~ action.
In the case of use as plant growth regulators,
the active compound concentrations can be varied within
a substantial range. In general~ 0~01 to 50 kg~
10 preferably 0.05 to 10 kg, of active compound are used
per hectare of soil surface.
When ~pplied in appropriate higher amounts~ the
compounds according to the invention also exhibit a
herbicidal action.
The present invention also provides a ~ungicidal
or plant ~rowth regulating composition containing as
active ingredient a compound of the present invention in
admixture with a solid or liquefied gaseous diluent or
carrier or in 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 also provides a method of
regulating the growth of plant~ which comprises applyi~g to
the plants, 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 o~ the present
invention in admixture with a diluent or car~ier~
The present invention further proYides crops
protected from damage by fungi by being grown in areas in
which immediately prior to and/or during the time of growing
Le A ~0 762
~'7'~
- 59 -
a compound of the present inventlon was applied alone
or in admixture with a diluent or carrier.
The present invention further provides plants~ the
growth of which has been regulated by their 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 alone or in admixture with a diluent or
car~-ier.
It will be seen that the usual methods of providing
a harvested crop may be improved by the present invention.
~ ~e
Exampl'e 1
Cl
OH CH3 ~
C1 ~ CH2-CH CH-C-O ~ Cl x HCl ~1)
~ CH3
10 g (0.0228 mol) of 5-(4-chlorophenyl)-2-(2,4-
dichlorophenoxy)-2-methyl-4-(1,2,4-triazol-1-yl)-pentan-
3-one were dissolved in lOO ml of methanol, 1 g of sodium
borohydride was added in portions at O to 5C~ the mixture
was subsequently stirred at room temperature for 15 hours,
and 50 ml of 2 N hydrochloric acid were added. After
4 hours~ the mixture was concentraked by the solvent being
distilled off in va'c'uo. The residue was taken up in
200 ml o~ methylene chloride and the organic phase was
stirred with 100 ml o~ saturated sodium bicarbonate solu-
tion, separated off, washed twice with 100 ml of water
each time, dried over sodium sulphate and concentrated
in 'vacuo. The residue was dissolved in 100 ml of
ether9 and ethereal hydrochloric acid was added. 7 8 g
(81% of theory) o~ 5-~4-chlorophenyl)-2-(2,4-dichloro-
phenoxy)-2-methyl-4-~192~4-triazol-l-yl~-pentan-3 ol
3 hydrochloride of melting point 46 to'50C were obtained
Le A 20 762
~ 7~3~t~
- 60 -
' P'r'ep'~r~a~t'i'o'n''of't~'e''s't'~r't'in'g' mat'e'r'i'al
CH3 \
Cl~CH2-CH-CO-C-O-~Cl
~ CH3
First 5.6 g of potassium hydroxide in 12 ml of
water and then 16.1 g (0.1 mol) of 4-chlorobenzyl chlor-
ide in 5 ml of dimethylsulphoxide were added dropwise to31.4 g (0.1 mol) of 3-(2j4-dichlorophenoxy)-3-methyl-1-
(1,2~4-triazol-1-yl)-butan-2-one in 100 ml of dimethyl-
sulphoxide 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 each time and
dried over sodium sulphate and the solvent was distilled
off under a waterpump vacuum. The residue was taken
up in 200 ml Or ether, the mixture was heated under reflux
and the crystals which have precipitated were filtered off~
21.3 g (48% of theory) of 5~(4-chlorophenyl)-2-(2,4-
dichlorophenoxy)-2~methyl-4-(1,2',4-triazol-l~yl)~pentan-
3-one of melting point 10~ to 108C were ob~ined.
20 ' Exa ~
OH CH
CH2 CH-CH-C-CH2-0 ~ C1 (2)
~ H3
10 g (0.034 mol) of 1-(4-chlorophenoxy)-5-cyclo-
hexyl-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-pentan~3-one
were dissolved in 100 ml of methanol,'l,7'g of sodium
borohydride were added in portions at O to 5C 3 the mixture
was subsequently stirred at room temperature for 15 hours~
and 20 ml of 2 N hydrochloric acid were added'dropwise.
Le A 2'~ 762
-
7 ~ 7 ~
- 61 -
A~ter 5 hours, the mixture was concentrated by the solvent
being distilled o~ in ~acuo, the residue was taken up
_ __
in 100 ml of methylene chloridej and the organic phase
wa3 stirred with 100 ml of saturated sodium bicar-
bonate solution, separated off, washed t~ice with 50 mlof water each time, dried over sodium sulphate and con-
centrated in vacuo. The residue was triturated with 50 ml
of diisopropyl ether. 7.2 g (54% of theory) of 1-(4-
chlorophenoxy)-5-cyclohexyl-2,2-dimethyl-4-(1~2,4-triazol-
1-yl)-pentan-3-ol of melting point 105 to 108C were
obtained.
Preparation of th starting material
CH
H2-cH-co-c-cH
N ` CH
First 5.6 g of potassium hydroxide in 12 ml of
water and then 17.7 g (0.1 mol~ Or cyclohexylmethyl
bromide in 5 ml of dimethylsulphoxide were added dropwise
to 29.3 g (0.1 mol) of 1-(4~chlorophenoxy)-232-dimethyl-
4-(1,2,4-triazol-l~yl3-buta~ 3 one in 100 ml o~ dimethyl-
sulphoxide at 20C. The reaction mixture was subsequen~y
stirred at room temperature rOr 15 hours and was poured
onto 200 ml of water and extracted with 200 ml o~ methylene
chloride, The organic phase was washed three times with
100 ml of water each time, dried over sodium sulphate and
concentrated by the solvent being distilled off~ The
residue was taken up in 100 ml of ether, where~pon it
crystallised out. 18.6 g (47~ of theory) of 1-(4-
chlorophenoxy)-5-cyclohexyl-2~2-dimethyl~4-(1,2,4-triazol~
l-yl)~pentan-3 o~e Or melting point 58 to 60C we~e obtained.
Le A 20 76 ?
- 62 -
''EXa~'pl'e' 3
N-CH2-CH-C-CH -S ~ Cl t3)
0.3 g (0.0079 mol) of sodium borohydride in 8 ml
o~ water was added dropwise to 7 g (0.024 mol) of 4-(4-
chlorophenylmercapto)-3J3-dimethyl-1-(imidazol-1-yl)-
butan-2-one at room temperature The reaction mixture
was subsequently stirred at room temperature for 1 hour
and was poured onto water. The crystals which had
precipitated were filtered off, and dried at 50C in vacuo.
6.5 g (91~ of theory) of 4-(4-chlorophenylmercapto)-3,3-
dimethyl-l-(imidazol-l-yl)-butan-2-ol of melting point
109-110C were obtained.
Preparation of the s'tart'in~ ma'terial
~N-cH2-co-c CH2-S~Cl
'CH3
199 g (0.618 mol) o~ 1-bromo-4-(4-chlorophenyl-
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 o~ acetone were stirred under reflux for 5
hours. The mixture was then allowed to cool, the
inorganic salts were filtered o~f and the filtrate was
concentrated. The ~esidue was taken up in methylene
chloride and the mixture was washed three times with
water~ dried over sodium sulphate and concentrated.
After recrystallisation from diisopropyl ether, 156 g
(82% of theory) of 4-(4-chlorophenylmercapto)-313-
dimethyl-l-(imidazol-l-~ butan 2-one of melting point
50C were obtained.
m e following compounds of the general formula
Le A 2~ 762
___
- 63 -
OH CH3
Rl-CH-CH-C~(CH2)n-R2 (I)
Az CH3 .
according to the invention were obtained in a corre~ponding
manner:
Le ~ 20 762
>~
y~ ~ ~
~` x
o~ ~ov $
~ p ~
o ;o ~ O
R ;~ F:
8 - o
m E~ ~ $
(~ ~) ~ 3~ 3r
<~ ~
m 5~
t7/~j
_ 6i~; -
bO
~d~
oO ~ V
. ~1
a ~ ~ D ~ ~ D O~
a) a) o
~ U ~I
L~ 3 L~
O
¢ " ~ ~ ~r'
a~
I i~ O O ~ tu
~ ~;
- 66 _
o ~o
o ~ o
~P P ~ ~o
~ o ~ ~ to
X ~: ~ co ~ ~ ~ ~
c~ V r1
~ ~ ~
~ o o o ~ , ~
~ p~ v ~ ~ ~
a)
~z;' u~ O
~Q~
~77
6 7
~o
tl:
~d~ . - V~ .
.. ~ ~ ~ Q
,_ ~ æ s~
o~ '
_ _, .-~ .~
~ #
~, _,
~ o~ ~ o ~ a~ ~ o
X ~ ~q ~1
I . I I
o o o o o
l l l
" c~ ~~ r~
~ P~ c-) c.) ~ ~
~rl O ~ ~1 1~ `tl~
N ~1 N ~1 N N
~!~ .
t~.7
~n 68
. ~ 'n --~ ~n
~i ~i N ~'J X
O O K X X t`
~m ~o o ~ '~
r~ ~ r~
~ ~ ~ V~
~: o o o o o
æl~
P~
r-l 1~ r1 ~ rl ~--1 ~) r l 1 J~
~o~
!~Z; a) o~ o ~ ~
~I ~`J 1~ i~ P'\
~o
o~
o ~ o
o a~ o
~p ~
0 ~ ~D
æ ~ ~q r J O ~r
~L N ~ 3 V)
~ Z~ ~ Zl!~'~
~, v I I ~ ~r~
a~
~ ~h ~ ~ u~
7
o~
v ~)
o ~o
o a~ o
r~ ` ~ ~o ~ ~o o~
~ p~
~ 1~1 ~ m~ ~3
CC7 ~ Z~ Z ~
o
o
; ~ ;l ;I` ;l -;1` ~ J
9'7~i
- 71 -
~d
d~
,_ ~
o~
o a~ c~
. ~ ~
,
,,
O U ~ U~
r O O
0
a
r~ 3 N ~ U
1:~
'.~,,~'7t71'3'7
- 72 ~
P~
~ ~`
C~ ~ C)
o ~o
o~ ~ ~
b4~ bO ~D
~ ~ ~ U) ~ o
O In u~ Lt- In
C~ O
~P~ ~~
~ o o o o o o
Z-
!~
U N
U U U U O U
,b 7,~o
'7~
~o
...~
~`
C~ V
o ~o
o a~ o
P~P ~
~ ~ U~ o
~ .
~P~
,
o o o ~ o o
,æ ' ' ~ ' ~
I ~
~ ~ U~ ~ U
a
~ O ~ S~J
~ .
~'7'7
- 7~ -
~C
.~
~`
_, _.
O G) O
~P
~ O ~r
h ~1 ~ O u~ ~D o
~1 ~1 ,1 ~ O ~ 0 ~7
U7
:~
~ U
T p o
o o o o o
l l l
U U X ~ ,~
a)
~0
~O~q~
0~ ~0
o a~ o
b~ b4 0
s~ o
~ , ~ O
T ''~ ~o J ~
,~
~C ~ 0 1:
~Q~
7~7~
-- 76 --
:~:
O Q~ O
O N ~ 10 0 0
~ V~ ~
~ , ~
~ IZ~ D p ~ ~' c
* U ~ v g~
~i ~æ r~ 3` ~ ec CD
L~
-- 77
O^~
0~
,
o a) o
~i~ bO -~ ~ .O~ o~
h ~1 0 O m ~ P o c~
~- _ x ~ x ~ x ~ ~
.
I U
CYc p ~ N N ~ Ç9
~ ,~ O
Sr~ , z~
N t) 5~ ~1 N N O
~ rl~ V~
0
. ~ O
I~
- 70 -
O ~ O
~ C ~ C:
~ ~ O ~ W 10 X -- X ~
~~ `
0=~
C~ ~
O O O
O O O O -
~ Z~ Y
' a!:
. d
~ lut ~ ~ 3 U
~ ~ ) N ~ N
~ c~r V
- ~g
~ ~Z;
~s~i7~
_ 79 _
...~
0 ~0
.
~ ~ P.
00~ bO
h~ ~ N
O ~ T . X ~
U ~ ~ D=7 e
,
~ O O
c i~ ll
~ .
N ~V ~ y~
~ 0 Z; a~ ~ ~ 8 o o o
~77~
-- 80 --
Olq
_ ~ ~
O~ ~,OV ~ ~n
a ~
0 ~ ~ ~ o
la ~ ~ o
m v u o ~~ ~
_ ~ _
N~ B , ~ u
o o, o
o o o _ _
, ~ . . ~ ,
t~
~:Z' O O O O O O
, ~Q~
'7~j
-- 81 --
0~
_
oU ~V
_~ ~
o a~ o
bO~ ~0
o~
h ~1
m
~ O~ l
. ~ O ~ O
~ _.
~:~ ~ :
Z~ ~ J D
IU L~
.
. ' ~
~l~ '7~7~3'7~:;
_ _
a
~: Z Z
e:
,_ ,_
2 a~ ~e x
~,: ~ _ ~
o ~
a~ ~7
l ~
o a~ o
_ I~ co ~ o o
O~ ~ ~ OD .
~ t) c
_1~ ~
~ ~ o
~: ~; m
~ x~ ~ '
I Z Z
o o ~
o o o
I u ~ ~ ~ ~ ~
r( ;'1 ~ $ 51 xa~
m I ,~ r
O U ~ O O
g w r~ o ,~
o ~ _ ~ ~ ~ ~ ~ ~ ~ a~
~ ~ , ~ ~, , ~ ~ _
k~
83
X
o
~ a
o" XO
G~
Q O O r` ~D
:~ P.
t~ tJ
~ ~ ~ .
tD
~J O
,_ ~ ,_ ,_
~-
C~ ~
O
O U~ 0
~Z
O
t7~ t;;~
. - 84 - .
Thb fungio,idal and plant~rowth 'regulant
activity o~ the compounds Or this invention i5 illustrate~
by the ~ollowing biotest Examples.
In these Examples, the compounds according to the
~resent invention are each identified by the number (given
in brackets) oT the corre~ponding preparative Example.
The know~ comparison compounds are identi~ied as
follow~:
(A) ~Ch3)3C-CO-CH2-
OH
(B) C1 ~ CH-CH-CH3
~N`N
N
Exa~le A
Erysiphe test (barley)/protective
Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 part by weight of alkylaryl 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 emulsifier3 and the
concentrate was diluted with water to the desired concen-
tration,
To test for protective activity, young plants
were sprayed witn the preparation oT active compound until
dew-moist, A~ter the spray coati~g had dried on, the
plants were dusted with spores of Erysiphe graminis fosp~
hordei,
The plants were placed in a greenhouse at a tem-
perature of about 20C and a relative atmospheric humidity
Le A 2~ 762
~'îJ'7¢.3'~
. - 8s
of about 80%, in order to promote the deveIopment of powd'ery
mildew pustules.
Evaluation was carried out 7 days after the
inoculation.
ln thi~ test, a clearly superior activity com-
pared with the prior art wa~ shown, for example~ by the
compounds (18), (7~, (8~, (9), (5), (14) and (17).
Example B
Powdery mildew of barley test (Erysiphe graminis var,
hordei)/systemic (fun~al disease of cereal shoots)
The active compounds were used as pulverulent seed
treatment a~ents. 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 mixture
0~ the desired concentration of active compound.
For the treatment o.~ seed, barley seed was shaken
with the'extended active co~pound in a closed glass bottle.
The seed was sown at the rate of 3 x 12 grains in flowerpots,
2 cm deep in a mixture of one part by volume of Fruhstorfer
standard soil and one part by volume of quartz s~nd. 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 ~ar. hordei
and grown on at 21 to 22C and 80 to 90% relative atmospheric
humidity and 16 hour~ exposure to light. The typical
mildew pustules formed on the leave~ with 6 days.
The de~ree of infection was expre~sed as a per-
centage of the infection of the untreated control plants,
~hus, 0~ denoted ~o infection and 100% denoted the same
degree of infection as in the case of the untreated control.
The more active was ~he active compo~nd, the lower was the
degree of mildew infection.
In this test, a clearly superior activity compared
with the prior art is shown, for example, by the'compoundæ
Le A'2'~'7'6'2
'7~
-- 86 --
(8)~ (9) and (17).
Erysiphe test (cucumbers)/protective
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether
Water: 95.0 parts by weight
' The amount of the active compound required for the
desired concentration of active compound in the Qpray liquid
was mixed with the ~tated amount of solvent and the concen-
trate was diluted with the stated amount of water which contained the stated additions.
Young cucumber plants with about three foliage
leaves were sprayed with the spray liquid until dripping wet.
The cucumber plants remained in a greenhouse for 24 hours to
dry. They were then, for the purpose of inoculation~
dusted with conidia of tne fungus Erysiphe cichoreacearum,
The plants were subsequently placed in a greenhouse at 23 to
24C and at a relative atmospheric humidity of about 75%.
A~ter 12 days~ the infection of the cucumber plants
was determined The assess~ent data were converted to
per cent infection. 0% denoted no infection and 100%
denoted that the plants were totally in~ected.
In this test, a clearly superior activity com-
pared with the prior art is shown, for example, by thb
compounds (18)~ (7), (9~ and (17).
Inhibition o'f ~rowth o~ so~a beans
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
To produce a suitable preparation o~ active compound,
1 part by weight of acti~e compound was mixed with the stated
amounts of solvent and emulsirier and the mixture was made
up to the desired concentratiOn with water.
Soya bean plants were grown in a greenhouse until
Le;~ 2~ 762
~'7~7t~
- 87 ~
the ~ir~t secondary lea~ Had u~folded completely. In
thi~ stage, the plants were sprayed with the preparations
of active compound until dripping wet. A~ter 3 weeks;
the additional growth was measured on all the plants and
the inhibition of growth in per cent of the additional
growth of the control plants was calculated. 100%
inhibition of growth meant that growth had stopped and
0% denoted a growth corrssponding to that of the control
plants.
In this test, compound (17) exhibited a marked
inhibition of growth in comparison with the control.
Example' E
Influence on ~r wth of s'u~r beet
301vent: 30 parts by weight of dimethylformamide5 Emulsifier: 1 part by weight of polyoxyethylene sorbitane
monolaurate
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 mixture was
made up to the desired concentration with water.
Sugar beet was grown in a greenhouse until formation
of the cotyledons was complete. In this stage, the
plants were sprayed with the preparations of active com~
pound until dripping wet. After 14 days, the additional
~rowth of the plants was measured and the influence on
growth in per cent of the additional growth of the control
plants was calculated. 0% influence on growth denoted a
growth which corresponded to that of the control plants.
Negative values characterised an inhibition of growth in
comparison to the control plants~ whilst posi~ive values
characterised a promotion o~ growth in comparison to the
control plants,
In this test 9 compounds (5) and ~17) showed a
marked in~luence on growth in comparison with the control.
Le A~ 2~ 7~2
