Combating fungi with substituted 1-azolyl-butan-2-ones and -2-ols

Substituted 1-azolyl-but-2-ones and -2-ols of the formula ##STR1## in which B is --CO-- or --CH(OH)-- PA1 Az represents a 1,2,4-triazol-1-yl or -4-yl or imidazol-1-yl radical, PA1 R.sup.1 represents a hydrogen atom, an alkyl, alkenyl, alkinyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted phenoxyalkyl or optionally substituted aralkyl radical, PA1 n is 0 or 1, PA1 R.sup.2 represents a cyano radical or a grouping of the general formula --X--R.sup.3 or --CO--NR.sup.4 R.sup.5, or, if n does not represent O at the same time as R.sup.1 represents a hydrogen atom and Az represents a 1,2,4-triazolyl radical, PA1 R.sup.2 also additionally represents an optionally substituted aryl or alkoxycarbonyl radical, and wherein PA1 X represents an oxygen or sulphur atom or an SO or SO.sub.2 group, PA1 R.sup.3 represents an alkyl, halogenoalkyl, optionally substituted aryl or optionally substituted aralkyl radical, PA1 R.sup.4 represents a hydrogen atom or an alkyl or optionally substituted aryl radical, and PA1 R.sup.5 represents a hydrogen atom or an alkyl radical, or acid addition salts or metal salt complexes thereof which possess fungicidal activity and plant growth regulatory and which can be reduced to the corresponding alcohols which are also fungicidally active.

The present invention relates to certain new substituted 
1-azolyl-butan-2-ones, and -2-ols 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, 
.omega.-(1,2,4-triazol-1-yl)-2,4-dichloroacetophenone, 
1-(4-chlorophenyl)-4,4-dimethyl-2-(,2,4-triazol-1-yl)-pentan-3-one and 
1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-ol, have generally good 
fungicidal activity (see U.S. Ser. No. 792,756, filed May 2, 1977, now 
pending, and also DE-OS (German Published Specification) Nos. 2,431,407 
and 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 
1-azolyl-butan-2-ones and -2-ols of the general formula 
##STR2## 
in which B represents --CO-- or --CH(OH)--, 
Az represents a 1,2,4-triazol-1-yl or -4-yl or imidazol-1-yl radical, 
R.sup.1 represents a hydrogen atom, an alkyl, alkenyl, alkinyl, optionally 
substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally 
substituted phenoxyalkyl or optionally substituted aralkyl radical, 
n is 0 or 1, 
R.sup.2 represents a cyano radical or a grouping of the general formula 
--X--R.sup.3 or --CO--NR.sup.4 R.sup.5, or, if n does not represent 0 at 
the same time as B represents --CO--, R.sup.1 represents a hydrogen atom 
and Az represents the 1,2,4-triazolyl radical, 
R.sup.2 also additionally represents an optionally substituted aryl or 
alkoxycarbonyl radical, 
and wherein 
X represents an oxygen or sulphur atom or an SO or SO.sub.2 group, 
R.sup.3 represents an alkyl, halogenoalkyl, optionally substituted aryl or 
optionally substituted aralkyl radical, 
R.sup.4 represents a hydrogen atom or an alkyl or optionally substituted 
aryl radical, and 
R.sup.5 represents a hydrogen atom or an alkyl radical, or acid addition 
salts or metal salt complexes thereof. 
According to the present invention there is further provided a process for 
the production of a compound of the present invention, characterized in 
that 
(a) a halogenoketone of the general formula 
##STR3## 
in which Hal represents a halogen atom, in particular a chlorine or 
bromine atom, and R.sup.2 and n have the abovementioned meanings, but in 
the grouping --X--R.sup.3 the substituent X only represents oxygen or 
sulphur, is reacted with an azole of the general formula 
EQU H--Az (III) 
in which Az has the abovementioned meaning, 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 R.sup.1 is other than 
a hydrogen atom, the compound produced by reaction variant (a) of the 
general formula 
##STR4## 
in which Az, n and R.sup.2 have the abovementioned meanings, is reacted 
with an alkylating agent of the formula 
EQU R.sup.1 --Z (IV) 
in which R.sup.1 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; 
(c) if a compound of formula (I) is required in which X represents SO or 
SO.sub.2, a compound obtained by reaction variant (a) or (b), of the 
general formula 
##STR5## 
in which AZ, R.sup.1, n and R.sup.3 have the abovementioned meanings, is 
oxidized, and 
(d) if a compound of formula (I) is required in which B is --CH(OH)--, the 
corresponding compound wherein B is --CO-- is reduced; 
and, if desired, an acid or a metal salt is then added on to the resulting 
compound of formula (I) obtained by reaction variant (a), (b), (c) or (d). 
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 1-azolyl-butan-2-ones and -2-ols of the present 
invention have powerful fungicidal properties. Surprisingly, the compounds 
according to the invention exhibit a better fungicidal action than the 
triazolyl-keto derivatives 
3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one, .omega.-(1,2,4-triazol-1- 
71)-2,4-dichloroacetophenone, 
1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-one and 
1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-ol, which are known 
from the state of art and are similar compounds chemically and from the 
point of view of their action. 
The new substituted 1-azolyl-butan-2-ones of the formula (I) are also 
interesting intermediate products for the preparation of other active 
compounds for plant protection. Thus, functional derivatives of the keto 
group, such as oximes and oxime ethers, hydrazones and ketals, can be 
obtained by appropriate reactions. Furthermore, compounds of the general 
formula (I) wherein B is --CH(OH)-- can be converted into the 
corresponding ethers at the hydroxyl group in the customary manner (for 
example by the "Williamson ether synthesis"). Furthermore, acyl or 
carbamoyl derivatives of such compounds of the general formula (I) can be 
obtained by reaction with, for 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 1-azolyl-butan-2-ones according to the present 
invention are those in which 
R.sup.1 represents a hydrogen atom or a straight-chain or branched alkyl 
radical with 1 to 12 carbon atoms, a straight-chain or branched alkenyl or 
alkinyl radical with in each case 2 to 12 carbon atoms, an optionally 
C.sub.1 to C.sub.4 alkyl-substituted cycloalkyl radical which has 3 to 7 
carbon atoms, a cycloalkylalkyl radical which has 3 to 7 carbon atoms in 
the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, or, 
preferably, represents an optionally substituted phenoxyalkyl radical with 
1 to 4 carbon atoms in the alkyl part or an optionally substituted aralkyl 
radical with 6 to 10 carbon atoms in the aryl part (such as, especially, 
phenyl) and 1 to 4 carbon atoms in the alkyl part (preferred substituents 
on aryl which may be mentioned in each case being selected from halogen; 
alkyl, alkoxy and alkylthio with in each case 1 to 6 carbon atoms, 
cyclohexyl, dialkylamino with in each case 1 to 4 carbon atoms in each 
alkyl part, halogenoalkyl, halogenoalkoxy and halogenoalkylthio with in 
each case 1 to 4 carbon atoms and 1 to 5 identical or different halogen 
atoms, nitro, cyano, alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl 
part, and phenyl and phenoxy which are optionally substituted by halogen 
and the grouping --CO--NR.sup.7 R.sup.8), 
R.sup.2 represents a cyano radical or a grouping of the general formula 
--X--R.sup.3 or --CO--NR.sup.4 R.sup.5, or, if n does not represents the 
number 0 at the same time as B represents --CO--, R.sup.1 represents a 
hydrogen atom and Az represents a 1,2,4-triazolyl radical, also 
additionally represents an optionally substituted aryl radical with 6 to 
10 carbon atoms (possible substituents being the substituents on aryl 
which have already been mentioned as preferred for R.sup.1), or R.sup.2 
represents an alkoxycarbonyl radical with 1 to 4 carbon atoms in the alkyl 
part, 
R.sup.3 represents a straight-chain or branched alkyl radical with 1 to 6 
carbon atoms, a halogenoalkyl radical with 1 to 4 carbon atoms and 1 to 5 
identical or different halogen atoms, or an optionally substituted aryl 
radical with 6 to 10 carbon atoms or aralkyl optionally substituted 
radical with 6 to 10 carbon atoms in the aryl part and 1 to 2 carbon atoms 
in the alkyl part (possible substituents being the substituents on aryl 
which have already been mentioned as preferred in the case of R.sup.1), 
R.sup.4 represents a hydrogen atom, an alkyl radical with 1 to 4 carbon 
atoms or an optionally substituted aryl radical with 6 to 10 carbon atoms 
(possible substituents being the substituents on aryl which have been 
mentioned as preferred in the case of R.sup.1), 
R.sup.5 represents a hydrogen atom or an alkyl radical with 1 to 4 carbon 
atoms, 
R.sup.7 and R.sup.8 represent hydrogen, alkyl with 1 to 4 carbon atoms, 
optionally halogen- and/or C.sub.1 to C.sub.4 alkyl-substituted phenyl, or 
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, and 
B, Az, X and n have the meanings given in the definition of the invention. 
Particularly preferred compounds of the present invention are those in 
which 
R.sup.1 represents a straight-chain or branched alkyl radical with 1 to 6 
carbon atoms, an alkenyl or alkinyl radical with in each case 2 to 6 
carbon atoms, a cyclohexyl or cyclohexylmethyl radical which is optionally 
substituted by methyl, or an optionally substituted phenoxyalkyl or 
optionally substituted phenylalkyl radical with in each case 1 to 2 carbon 
atoms in the alkyl part (substituents on the phenyl which may be mentioned 
being selected from fluorine, chlorine, methyl, ethyl, isopropyl, 
tert.-butyl, dimethylamino, methoxy, methylthio, cyclohexyl, 
trifluormethyl, trifluormethoxy, trifluormethylthio, nitro and cyano, and 
phenyl and phenoxy which are optionally substituted by fluorine and 
chlorine and the morpholinocarbonyl-, phenylaminocarbonyl-, 
chlorophenylaminocarbonyl- or dibutylaminocarbonyl-group, 
R.sup.2 represents a cyano radical, a grouping of the general formula 
--X--R.sup.3 or --CO--NR.sup.4 R.sup.5, or if n does not represent the 
number 0 at the same time as B represents --CO--, R.sup.1 represents a 
hydrogen atom and Az represents a 1,2,4-triazolyl radical, also represents 
an optionally substituted phenyl radical (possible substituents being the 
substituents on phenyl which have already been mentioned in the case of 
R.sup.1) or R.sup.2 represents a methoxycarbonyl, ethoxycarbonyl or 
isopropoxycarbonyl radical, 
R.sup.3 represents a straight-chain or branched alkyl radical with 1 to 4 
carbon atoms or an optionally substituted phenyl or benzyl radical 
(possible substituents on the particular phenyl radicals being the 
substituents on phenyl which have already been mentioned in the case of 
R.sup.1), 
R.sup.4 represents a hydrogen atom, or a methyl, ethyl or isopropyl radical 
or an optionally substituted phenyl radical (possible substituents being 
halogen and alkyl with 1 to 4 carbon atoms), 
R.sup.5 represents a hydrogen atom or a methyl, ethyl or isopropyl radical, 
and 
B, Az, X and n have the meanings given in the definition of the invention. 
The following compounds of the general formula (I) (in which Az represents 
a 1,2,4-triazol-1-yl or imidazol-1-yl radical) and B is --CO-- or 
--CH(OH)-- may be mentioned specifically, in addition to the compounds 
mentioned in the preparative examples hereinbelow: 
TABLE 1 
______________________________________ 
##STR6## (I) 
R.sup.1 n R.sup.2 
______________________________________ 
H 1 
##STR7## 
C.sub.2 H.sub.5 
1 
##STR8## 
C.sub.4 H.sub.9 
1 
##STR9## 
##STR10## 1 
##STR11## 
##STR12## 1 
##STR13## 
H 1 
##STR14## 
C.sub.2 H.sub.5 
1 
##STR15## 
C.sub.4 H.sub.9 
1 
##STR16## 
##STR17## 1 
##STR18## 
##STR19## 1 
##STR20## 
H 1 
##STR21## 
C.sub.2 H.sub.5 
1 
##STR22## 
C.sub.4 H.sub.9 
1 
##STR23## 
##STR24## 1 
##STR25## 
##STR26## 1 
##STR27## 
H 1 
##STR28## 
C.sub.2 H.sub.5 
1 
##STR29## 
C.sub.4 H.sub.9 
1 
##STR30## 
##STR31## 1 
##STR32## 
##STR33## 1 
##STR34## 
H 1 
##STR35## 
C.sub.2 H.sub.5 
1 
##STR36## 
C.sub.4 H.sub.9 
1 
##STR37## 
##STR38## 1 
##STR39## 
##STR40## 1 
##STR41## 
H 1 
##STR42## 
C.sub.2 H.sub.5 
1 
##STR43## 
C.sub.4 H.sub.9 
1 
##STR44## 
##STR45## 1 
##STR46## 
##STR47## 1 
##STR48## 
H 1 
##STR49## 
C.sub.2 H.sub.5 
1 
##STR50## 
C.sub.4 H.sub.9 
1 
##STR51## 
##STR52## 1 
##STR53## 
##STR54## 1 
##STR55## 
H 1 
##STR56## 
C.sub.2 H.sub.5 
1 
##STR57## 
C.sub.4 H.sub.9 
1 
##STR58## 
##STR59## 1 
##STR60## 
##STR61## 1 
##STR62## 
H 1 
##STR63## 
C.sub.2 H.sub.5 
1 
##STR64## 
C.sub.4 H.sub.9 
1 
##STR65## 
##STR66## 1 
##STR67## 
##STR68## 1 
##STR69## 
H 1 
##STR70## 
C.sub.2 H.sub.5 
1 
##STR71## 
C.sub.4 H.sub.9 
1 
##STR72## 
##STR73## 1 
##STR74## 
##STR75## 1 
##STR76## 
H 1 
##STR77## 
C.sub.2 H.sub.5 
1 
##STR78## 
C.sub.4 H.sub.9 
1 
##STR79## 
##STR80## 1 
##STR81## 
##STR82## 1 
##STR83## 
H 1 
##STR84## 
C.sub.2 H.sub.5 
1 
##STR85## 
C.sub.4 H.sub.9 
1 
##STR86## 
##STR87## 1 
##STR88## 
##STR89## 1 
##STR90## 
H 1 
##STR91## 
C.sub.2 H.sub.5 
1 
##STR92## 
C.sub.4 H.sub.9 
1 
##STR93## 
##STR94## 1 
##STR95## 
##STR96## 1 
##STR97## 
H 1 
##STR98## 
C.sub.2 H.sub.5 
1 
##STR99## 
C.sub.4 H.sub.9 
1 
##STR100## 
##STR101## 1 
##STR102## 
##STR103## 1 
##STR104## 
H 1 
##STR105## 
C.sub.2 H.sub.5 
1 
##STR106## 
C.sub.4 H.sub.9 
1 
##STR107## 
##STR108## 1 
##STR109## 
##STR110## 1 
##STR111## 
H 1 
##STR112## 
C.sub.2 H.sub.5 
1 
##STR113## 
C.sub.4 H.sub.9 
1 
##STR114## 
##STR115## 1 
##STR116## 
##STR117## 1 
##STR118## 
H 1 
##STR119## 
C.sub.2 H.sub.5 
1 
##STR120## 
C.sub.4 H.sub.9 
1 
##STR121## 
##STR122## 1 
##STR123## 
##STR124## 1 
##STR125## 
H 1 
##STR126## 
C.sub.2 H.sub.5 
1 
##STR127## 
C.sub.4 H.sub.9 
1 
##STR128## 
##STR129## 1 
##STR130## 
##STR131## 1 
##STR132## 
H 1 
##STR133## 
C.sub.2 H.sub.5 
1 
##STR134## 
C.sub.4 H.sub.9 
1 
##STR135## 
##STR136## 1 
##STR137## 
##STR138## 1 
##STR139## 
H 1 
##STR140## 
C.sub.2 H.sub.5 
1 
##STR141## 
C.sub.4 H.sub.9 
1 
##STR142## 
##STR143## 1 
##STR144## 
##STR145## 1 
##STR146## 
H 1 
##STR147## 
C.sub.2 H.sub.5 
1 
##STR148## 
C.sub.4 H.sub.9 
1 
##STR149## 
##STR150## 1 
##STR151## 
##STR152## 1 
##STR153## 
H 1 
##STR154## 
C.sub.2 H.sub.5 
1 
##STR155## 
C.sub.4 H.sub.9 
1 
##STR156## 
##STR157## 1 
##STR158## 
##STR159## 1 
##STR160## 
H 1 
##STR161## 
C.sub.2 H.sub.5 
1 
##STR162## 
C.sub.4 H.sub.9 
1 
##STR163## 
##STR164## 1 
##STR165## 
##STR166## 1 
##STR167## 
H 1 
##STR168## 
C.sub.2 H.sub.5 
1 
##STR169## 
C.sub.4 H.sub.9 
1 
##STR170## 
##STR171## 1 
##STR172## 
##STR173## 1 
##STR174## 
H 1 
##STR175## 
C.sub.2 H.sub.5 
1 
##STR176## 
C.sub.4 H.sub.9 
1 
##STR177## 
##STR178## 1 
##STR179## 
##STR180## 1 
##STR181## 
H 1 
##STR182## 
C.sub.2 H.sub.5 
1 
##STR183## 
C.sub.4 H.sub.9 
1 
##STR184## 
##STR185## 1 
##STR186## 
##STR187## 1 
##STR188## 
H 1 
##STR189## 
C.sub.2 H.sub.5 
1 
##STR190## 
C.sub.4 H.sub.9 
1 
##STR191## 
##STR192## 1 
##STR193## 
##STR194## 1 
##STR195## 
H 1 
##STR196## 
C.sub.2 H.sub.5 
1 
##STR197## 
C.sub.4 H.sub.9 
1 
##STR198## 
##STR199## 1 
##STR200## 
##STR201## 1 
##STR202## 
H 1 
##STR203## 
C.sub.2 H.sub.5 
1 
##STR204## 
C.sub.4 H.sub.9 
1 
##STR205## 
##STR206## 1 
##STR207## 
##STR208## 1 
##STR209## 
H 1 
##STR210## 
C.sub.2 H.sub.5 
1 
##STR211## 
C.sub.4 H.sub.9 
1 
##STR212## 
##STR213## 1 
##STR214## 
##STR215## 1 
##STR216## 
H 1 
##STR217## 
C.sub.2 H.sub.5 
1 
##STR218## 
C.sub.4 H.sub.9 
1 
##STR219## 
##STR220## 1 
##STR221## 
##STR222## 1 
##STR223## 
H 1 
##STR224## 
C.sub.2 H.sub.5 
1 
##STR225## 
C.sub.4 H.sub.9 
1 
##STR226## 
##STR227## 1 
##STR228## 
##STR229## 1 
##STR230## 
H 1 
##STR231## 
C.sub.2 H.sub.5 
1 
##STR232## 
C.sub.4 H.sub.9 
1 
##STR233## 
##STR234## 1 
##STR235## 
##STR236## 1 
##STR237## 
H 1 
##STR238## 
C.sub.2 H.sub.5 
1 
##STR239## 
C.sub.4 H.sub.9 
1 
##STR240## 
##STR241## 1 
##STR242## 
##STR243## 1 
##STR244## 
H 1 
##STR245## 
C.sub.2 H.sub.5 
1 
##STR246## 
C.sub.4 H.sub.9 
1 
##STR247## 
##STR248## 1 
##STR249## 
##STR250## 1 
##STR251## 
H 1 
##STR252## 
C.sub.2 H.sub.5 
1 
##STR253## 
C.sub.4 H.sub.9 
1 
##STR254## 
##STR255## 1 
##STR256## 
##STR257## 1 
##STR258## 
H 1 
##STR259## 
C.sub.2 H.sub.5 
1 
##STR260## 
C.sub.4 H.sub.9 
1 
##STR261## 
##STR262## 1 
##STR263## 
##STR264## 1 
##STR265## 
H 1 
##STR266## 
C.sub.2 H.sub.5 
1 
##STR267## 
C.sub.4 H.sub.9 
1 
##STR268## 
##STR269## 1 
##STR270## 
##STR271## 1 
##STR272## 
H 0 
##STR273## 
C.sub.2 H.sub.5 
0 
##STR274## 
C.sub.4 H.sub.9 
0 
##STR275## 
##STR276## 0 
##STR277## 
##STR278## 0 
##STR279## 
H 0 
##STR280## 
C.sub.2 H.sub.5 
0 
##STR281## 
C.sub.4 H.sub.9 
0 
##STR282## 
##STR283## 0 
##STR284## 
##STR285## 0 
##STR286## 
H 0 
##STR287## 
C.sub.2 H.sub.5 
0 
##STR288## 
C.sub.4 H.sub.9 
0 
##STR289## 
##STR290## 0 
##STR291## 
##STR292## 0 
##STR293## 
H 0 
##STR294## 
C.sub.2 H.sub.5 
0 
##STR295## 
C.sub.4 H.sub.9 
0 
##STR296## 
##STR297## 0 
##STR298## 
##STR299## 0 
##STR300## 
H 0 
##STR301## 
C.sub.2 H.sub.5 
0 
##STR302## 
C.sub.4 H.sub.9 
0 
##STR303## 
##STR304## 0 
##STR305## 
##STR306## 0 
##STR307## 
H 0 
##STR308## 
C.sub.2 H.sub.5 
0 
##STR309## 
C.sub.4 H.sub.9 
0 
##STR310## 
##STR311## 0 
##STR312## 
##STR313## 0 
##STR314## 
H 0 
##STR315## 
C.sub.2 H.sub.5 
0 
##STR316## 
C.sub.4 H.sub.9 
0 
##STR317## 
##STR318## 0 
##STR319## 
##STR320## 0 
##STR321## 
H 0 
##STR322## 
C.sub.2 H.sub.5 
0 
##STR323## 
C.sub.4 H.sub.9 
0 
##STR324## 
##STR325## 0 
##STR326## 
##STR327## 0 
##STR328## 
H 0 
##STR329## 
C.sub.2 H.sub.5 
0 
##STR330## 
C.sub.4 H.sub.9 
0 
##STR331## 
##STR332## 0 
##STR333## 
##STR334## 0 
##STR335## 
H 0 
##STR336## 
C.sub.2 H.sub.5 
0 
##STR337## 
C.sub.4 H.sub.9 
0 
##STR338## 
##STR339## 0 
##STR340## 
##STR341## 0 
##STR342## 
H 0 
##STR343## 
C.sub.2 H.sub.5 
0 
##STR344## 
C.sub.4 H.sub.9 
0 
##STR345## 
##STR346## 0 
##STR347## 
##STR348## 0 
##STR349## 
H 0 
##STR350## 
C.sub.2 H.sub.5 
0 
##STR351## 
C.sub.4 H.sub.9 
0 
##STR352## 
##STR353## 0 
##STR354## 
##STR355## 0 
##STR356## 
H 0 
##STR357## 
C.sub.2 H.sub.5 
0 
##STR358## 
C.sub.4 H.sub.9 
0 
##STR359## 
##STR360## 0 
##STR361## 
##STR362## 0 
##STR363## 
H 0 
##STR364## 
C.sub.2 H.sub.5 
0 
##STR365## 
C.sub.4 H.sub.9 
0 
##STR366## 
##STR367## 0 
##STR368## 
##STR369## 0 
##STR370## 
H 0 
##STR371## 
C.sub.2 H.sub.5 
0 
##STR372## 
C.sub.4 H.sub.9 
0 
##STR373## 
##STR374## 0 
##STR375## 
##STR376## 0 
##STR377## 
H 0 
##STR378## 
C.sub.2 H.sub.5 
0 
##STR379## 
C.sub.4 H.sub.9 
0 
##STR380## 
##STR381## 0 
##STR382## 
##STR383## 0 
##STR384## 
H 0 
##STR385## 
C.sub.2 H.sub.5 
0 
##STR386## 
C.sub.4 H.sub.9 
0 
##STR387## 
##STR388## 0 
##STR389## 
##STR390## 0 
##STR391## 
H 0 
##STR392## 
C.sub.2 H.sub.5 
0 
##STR393## 
C.sub.4 H.sub.9 
0 
##STR394## 
##STR395## 0 
##STR396## 
##STR397## 0 
##STR398## 
H 0 
##STR399## 
C.sub.2 H.sub.5 
0 
##STR400## 
C.sub.4 H.sub.9 
0 
##STR401## 
##STR402## 0 
##STR403## 
##STR404## 0 
##STR405## 
H 0 
##STR406## 
C.sub.2 H.sub.5 
0 
##STR407## 
C.sub.4 H.sub.9 
0 
##STR408## 
##STR409## 0 
##STR410## 
##STR411## 0 
##STR412## 
H 0 
##STR413## 
C.sub.2 H.sub.5 
0 
##STR414## 
C.sub.4 H.sub.9 
0 
##STR415## 
##STR416## 0 
##STR417## 
##STR418## 0 
##STR419## 
H 0 
##STR420## 
C.sub.2 H.sub.5 
0 
##STR421## 
C.sub.4 H.sub.9 
0 
##STR422## 
##STR423## 0 
##STR424## 
##STR425## 0 
##STR426## 
H 0 
##STR427## 
C.sub.2 H.sub.5 
0 
##STR428## 
C.sub.4 H.sub.9 
0 
##STR429## 
##STR430## 0 
##STR431## 
##STR432## 0 
##STR433## 
H 0 
##STR434## 
C.sub.2 H.sub.5 
0 
##STR435## 
C.sub.4 H.sub.9 
0 
##STR436## 
##STR437## 0 
##STR438## 
##STR439## 0 
##STR440## 
H 0 
##STR441## 
C.sub.2 H.sub.5 
0 
##STR442## 
C.sub.4 H.sub.9 
0 
##STR443## 
##STR444## 0 
##STR445## 
##STR446## 0 
##STR447## 
H 0 
##STR448## 
C.sub.2 H.sub.5 
0 
##STR449## 
C.sub.4 H.sub.9 
0 
##STR450## 
##STR451## 0 
##STR452## 
##STR453## 0 
##STR454## 
H 0 
##STR455## 
C.sub.2 H.sub.5 
0 
##STR456## 
C.sub.4 H.sub.9 
0 
##STR457## 
##STR458## 0 
##STR459## 
##STR460## 0 
##STR461## 
H 0 
##STR462## 
C.sub.2 H.sub.5 
0 
##STR463## 
C.sub.4 H.sub.9 
0 
##STR464## 
##STR465## 0 
##STR466## 
##STR467## 0 
##STR468## 
H 0 
##STR469## 
C.sub.2 H.sub.5 
0 
##STR470## 
C.sub.4 H.sub. 9 
0 
##STR471## 
##STR472## 0 
##STR473## 
##STR474## 0 
##STR475## 
H 0 
##STR476## 
C.sub.2 H.sub.5 
0 
##STR477## 
C.sub.4 H.sub.9 
0 
##STR478## 
##STR479## 0 
##STR480## 
##STR481## 0 
##STR482## 
H 0 
##STR483## 
C.sub.2 H.sub.5 
0 
##STR484## 
C.sub.4 H.sub.9 
0 
##STR485## 
##STR486## 0 
##STR487## 
##STR488## 0 
##STR489## 
H 0 
##STR490## 
C.sub.2 H.sub.5 
0 
##STR491## 
C.sub.4 H.sub.9 
0 
##STR492## 
##STR493## 0 
##STR494## 
##STR495## 0 
##STR496## 
H 0 
##STR497## 
C.sub.2 H.sub.5 
0 
##STR498## 
C.sub.4 H.sub.9 
0 
##STR499## 
##STR500## 0 
##STR501## 
##STR502## 0 
##STR503## 
H 0 
##STR504## 
C.sub.2 H.sub.5 
0 
##STR505## 
C.sub.4 H.sub.9 
0 
##STR506## 
##STR507## 0 
##STR508## 
##STR509## 0 
##STR510## 
H 0 
##STR511## 
C.sub.2 H.sub.5 
0 
##STR512## 
C.sub.4 H.sub.9 
0 
##STR513## 
##STR514## 0 
##STR515## 
##STR516## 0 
##STR517## 
H 0 
##STR518## 
C.sub.2 H.sub.5 
0 
##STR519## 
C.sub.4 H.sub.9 
0 
##STR520## 
##STR521## 0 
##STR522## 
##STR523## 0 
##STR524## 
H 0 
##STR525## 
C.sub.2 H.sub.5 
0 
##STR526## 
C.sub.4 H.sub.9 
0 
##STR527## 
##STR528## 0 
##STR529## 
##STR530## 0 
##STR531## 
H 0 
##STR532## 
C.sub.2 H.sub.5 
0 
##STR533## 
C.sub.4 H.sub.9 
0 
##STR534## 
##STR535## 0 
##STR536## 
##STR537## 0 
##STR538## 
H 1 OC.sub.4 H.sub.9 
##STR539## 1 OC.sub.4 H.sub.9 
C.sub.2 H.sub.5 
1 OC.sub.4 H.sub.9 
C.sub.4 H.sub.9 
1 OC.sub.4 H.sub.9 
##STR540## 1 OC.sub.4 H.sub.9 
##STR541## 0 COOC.sub.2 H.sub.5 
##STR542## 0 COOC.sub.3 H.sub.7i 
##STR543## 0 CON(CH.sub.3).sub.2 
##STR544## 0 
##STR545## 
##STR546## 0 COOCH.sub. 3 
##STR547## 0 CN 
H 0 CN 
##STR548## 0 
##STR549## 
##STR550## 0 
##STR551## 
##STR552## 0 
##STR553## 
##STR554## 0 
##STR555## 
##STR556## 0 
##STR557## 
##STR558## 0 
##STR559## 
##STR560## 0 
##STR561## 
##STR562## 0 
##STR563## 
H 1 
##STR564## 
C.sub.4 H.sub.9n 
1 
##STR565## 
##STR566## 1 
##STR567## 
##STR568## 1 
##STR569## 
##STR570## 1 
##STR571## 
H 1 
##STR572## 
C.sub.4 H.sub.9n 
1 
##STR573## 
##STR574## 1 
##STR575## 
##STR576## 1 
##STR577## 
##STR578## 1 
##STR579## 
H 1 
##STR580## 
C.sub.4 H.sub.9n 
1 
##STR581## 
##STR582## 1 
##STR583## 
##STR584## 1 
##STR585## 
##STR586## 1 
##STR587## 
H 1 
##STR588## 
C.sub.4 H.sub.9n 
1 
##STR589## 
##STR590## 1 
##STR591## 
##STR592## 1 
##STR593## 
##STR594## 1 
##STR595## 
H 1 
##STR596## 
C.sub.4 H.sub.9n 
1 
##STR597## 
##STR598## 1 
##STR599## 
##STR600## 1 
##STR601## 
##STR602## 1 
##STR603## 
H 1 
##STR604## 
C.sub.4 H.sub.9n 
1 
##STR605## 
##STR606## 1 
##STR607## 
##STR608## 1 
##STR609## 
##STR610## 1 
##STR611## 
H 1 
##STR612## 
C.sub.4 H.sub.9n 
1 
##STR613## 
##STR614## 1 
##STR615## 
##STR616## 1 
##STR617## 
##STR618## 1 
##STR619## 
H 1 
##STR620## 
C.sub.4 H.sub.9n 
1 
##STR621## 
##STR622## 1 
##STR623## 
##STR624## 1 
##STR625## 
##STR626## 1 
##STR627## 
H 1 
##STR628## 
C.sub.4 H.sub.9n 
1 
##STR629## 
##STR630## 1 
##STR631## 
##STR632## 1 
##STR633## 
##STR634## 1 
##STR635## 
H 1 
##STR636## 
C.sub.4 H.sub.9n 
1 
##STR637## 
##STR638## 1 
##STR639## 
##STR640## 1 
##STR641## 
##STR642## 1 
##STR643## 
H 1 
##STR644## 
C.sub.4 H.sub.9n 
1 
##STR645## 
##STR646## 1 
##STR647## 
##STR648## 1 
##STR649## 
##STR650## 1 
##STR651## 
H 1 SC.sub.4 H.sub.9n 
C.sub.4 H.sub.9n 
1 SC.sub.4 H.sub.9n 
##STR652## 1 SC.sub.4 H.sub.9n 
##STR653## 1 SC.sub.4 H.sub.9n 
##STR654## 1 SC.sub.4 H.sub.9n 
H 1 SCH.sub.3 
C.sub.4 H.sub.9n 
1 SCH.sub.3 
##STR655## 1 SCH.sub.3 
##STR656## 1 SCH.sub.3 
##STR657## 1 SCH.sub.3 
H 1 
##STR658## 
C.sub.4 H.sub.9n 
1 
##STR659## 
##STR660## 1 
##STR661## 
##STR662## 1 
##STR663## 
##STR664## 1 
##STR665## 
H 1 
##STR666## 
C.sub.4 H.sub.9n 
1 
##STR667## 
##STR668## 1 
##STR669## 
##STR670## 1 
##STR671## 
##STR672## 1 
##STR673## 
H 1 
##STR674## 
C.sub.4 H.sub.9n 
1 
##STR675## 
##STR676## 1 
##STR677## 
##STR678## 1 
##STR679## 
##STR680## 1 
##STR681## 
H 1 
##STR682## 
C.sub.4 H.sub.9n 
1 
##STR683## 
##STR684## 1 
##STR685## 
##STR686## 1 
##STR687## 
##STR688## 1 
##STR689## 
H 1 
##STR690## 
C.sub.4 H.sub.9n 
1 
##STR691## 
##STR692## 1 
##STR693## 
##STR694## 1 
##STR695## 
##STR696## 1 
##STR697## 
H 1 
##STR698## 
C.sub.4 H.sub.9n 
1 
##STR699## 
##STR700## 1 
##STR701## 
##STR702## 1 
##STR703## 
##STR704## 1 
##STR705## 
H 1 
##STR706## 
C.sub.4 H.sub.9n 
1 
##STR707## 
##STR708## 1 
##STR709## 
##STR710## 1 
##STR711## 
##STR712## 1 
##STR713## 
H 1 
##STR714## 
C.sub.4 H.sub.9n 
1 
##STR715## 
##STR716## 1 
##STR717## 
##STR718## 1 
##STR719## 
##STR720## 1 
##STR721## 
H 1 
##STR722## 
C.sub.4 H.sub.9n 
1 
##STR723## 
##STR724## 1 
##STR725## 
##STR726## 1 
##STR727## 
##STR728## 1 
##STR729## 
H 1 
##STR730## 
C.sub.4 H.sub.9n 
1 
##STR731## 
##STR732## 1 
##STR733## 
##STR734## 1 
##STR735## 
##STR736## 1 
##STR737## 
H 1 
##STR738## 
C.sub. 4 H.sub.9n 
1 
##STR739## 
##STR740## 1 
##STR741## 
##STR742## 1 
##STR743## 
##STR744## 1 
##STR745## 
H 1 
##STR746## 
C.sub.4 H.sub.9n 
1 
##STR747## 
##STR748## 1 
##STR749## 
##STR750## 1 
##STR751## 
##STR752## 1 
##STR753## 
H 1 
##STR754## 
C.sub.4 H.sub.9n 
1 
##STR755## 
##STR756## 1 
##STR757## 
##STR758## 1 
##STR759## 
##STR760## 1 
##STR761## 
H 1 
##STR762## 
C.sub.4 H.sub.9n 
1 
##STR763## 
##STR764## 1 
##STR765## 
##STR766## 1 
##STR767## 
##STR768## 1 
##STR769## 
H 1 
##STR770## 
C.sub.4 H.sub.9n 
1 
##STR771## 
##STR772## 1 
##STR773## 
##STR774## 1 
##STR775## 
##STR776## 1 
##STR777## 
H 1 
##STR778## 
C.sub.4 H.sub.9n 
1 
##STR779## 
##STR780## 1 
##STR781## 
##STR782## 1 
##STR783## 
##STR784## 1 
##STR785## 
H 1 
##STR786## 
C.sub.4 H.sub.9n 
1 
##STR787## 
##STR788## 1 
##STR789## 
##STR790## 1 
##STR791## 
##STR792## 1 
##STR793## 
H 1 
##STR794## 
C.sub.4 H.sub.9n 
1 
##STR795## 
##STR796## 1 
##STR797## 
##STR798## 1 
##STR799## 
##STR800## 1 
##STR801## 
______________________________________ 
If, for example, 1-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: 
##STR802## 
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: 
##STR803## 
If, for example, 
4-(4-chlorophenylthio)-3,3-dimethyl-1-(imidazol-1-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 invention is illustrated by the following equation: 
##STR804## 
In carrying out the oxidation, about 1 to 5 mols of oxidizing agent are 
employed per mol of the compounds of the formula (II b). If 1 mole of 
oxidizing agent (such as m-chloroperbenzoic acid in methylene chloride or 
hydrogen peroxide in acetic anhydride at a temperature between -30.degree. 
and +30.degree. C.) is used, those compounds of the formula (II) in which 
X represents SO are preferentially formed. If an excess of oxidizing 
agents and higher temperatures (10.degree. to 80.degree. C.) are used, 
those compounds of the formula (II in which X represents SO.sub.2 are 
preferentially formed. The oxidation products are isolated in the 
customary manner. 
If, for example, 
5-(4-chlorophenyl)-2-(2,4-dichlorophenoxy)-2-methyl-4-(1,2,4-triazol-1-yl) 
-pentan-3-one and sodium borohydride are used as starting substances, the 
course of the reaction variant (d) according to the present invention is 
illustrated by the following equation: 
##STR805## 
Preferred halogenoketones of formula (II) required as starting substances 
for carrying out reaction variant (a) according to the invention are those 
in which R.sup.2 and n have the meanings given for the preferred and 
particularly preferred compounds of the invention. 
The halogenoketones of the formula (II) are known in some cases (see 
application Ser. No. 819,533, filed July 27, 1977, now U.S. Pat. No. 
4,331,674), some of them are the subject of application Ser. No. 265,050, 
filed May 19, 1981, now U.S. Pat. No. 4,406,909, and some are completely 
new. They are obtained by a process in which a ketone of the general 
formula 
##STR806## 
R.sup.2 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.degree. 
to 60.degree. C. 
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. Pat. No. 3,937,738 and C.A. 82, 30 898 j 
(1975)); some of them are the subject of application Ser. No. 265,269, 
filed Aug. 25, 1981, now U.S. Pat. No. 4,371,708, 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 
##STR807## 
in which n has the abovementioned meaning and 
Y represents a chlorine or bromine atom or a grouping of the general 
formula --O--SO.sub.2 --R.sup.6, 
wherein 
R.sup.6 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 
EQU Me--R.sup.2 (VII) 
in which 
R.sup.2 has the abovementioned meaning and 
Me represents an alkali metal, such as, preferably, 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.degree. and 
150.degree. C. 
The keto derivatives of the formula (VI) are known (see, for example U.S. 
Pat. No. 4,255,434, issued Mar. 10, 1981) 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-1-yl radical. 
The azoles of the formula (III) are generally known compounds of organic 
chemistry. 
The formula (Ia) provides a general definition of 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 
reaction variant (b) according to the invention are those in which R.sup.1 
represents those radicals which have already been mentioned for this 
substituent in connection with the description of the preferred and 
particularly preferred substances of the formula (I) according to the 
invention and Z represents an electron-withdrawing leaving group, such as 
halogen, p-methylphenylsulphonyloxy, the grouping --O--SO.sub.2 --OR or 
--NR.sub.3. 
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 variant (c) according to 
the invention. 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) according 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 hydrocarbons. 
Reaction variant (a) according to the invention is carried out in the 
presence of an acid-binding agent. Any of the inorganic or organic 
acid-binding agents which can customarily be used may be added, such as 
alkali metal carbonates (for example sodium carbonate, potassium carbonate 
and sodium bicarbonate), lower tertiary alkylamines, cycloalkylamines or 
aralkylamines (for example triethylamine, N,N-dimethylcyclohexylamine, 
dicyclohexylamine and N,N-dimethylbenzylamine) and furthermore pyridine 
and diazabicyclooctane. Preferably, an appropriate excess of azole is 
used. 
The reaction temperatures can be varied within a substantial range in 
reaction variant (a) according to the invention. In general, the reaction 
is carried out at a temperature between 20.degree. and 150.degree. C., 
preferably at a temperature between 60.degree. and 120.degree. C. If a 
solvent is present, it is expedient to carry out the reaction at the 
boiling point of the particular solvent. 
In carrying out reaction variant (a) according to the invention, 2 to 4 
mols of azole and 1 to 4 mols of acid-binding agent are preferably 
employed per mol of the compounds 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) according to the invention are 
inert organic solvents. These include, preferably, aromatic hydrocarbons 
(such as benzene, toluene or xylene), halogenated hydrocarbons (such as 
methylene 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 in the 
presence of a base. Any of the customary 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 reaction is carried out at a temperature between 0.degree. and 
100.degree. C., preferably between 20.degree. and 100.degree. C. 
In carrying out reaction variant (b) according to the invention, 1 to 1.2 
mols of the agent of formula (IV) are preferably 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 solution 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.degree. and 
100.degree. C., preferably between -30.degree. and 80.degree. C. 
In carrying out the oxidation, according to the invention, in reaction 
variant (c), about 1 to 5 mols of oxidizing agent are employed per mol of 
the compounds of the formula (Ib) according to the invention. If 1 mol of 
oxidizing agent is used, such as m-chloroperbenzoic acid in methylene 
chloride or hydrogen peroxide in acetic anhydride at temperatures between 
-30.degree. and +30.degree. C., the compounds of the formula (I) according 
to the invention in which X=SO are preferentially formed. In the case of 
an excess of oxidizing agent and higher temperatures (10.degree. to 
80.degree. C.), the compounds of the formula (I) according to the 
invention in which X=SO.sub.2 are preferentially formed. The oxidation 
products are isolated in the customary manner. 
The reduction (d) according to the invention is 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 aluminum 
isopropylate in the presence of a diluent. 
If complex hydrides are used, possible diluents for the reaction according 
to the invention are polar organic solvents. These include, preferably, 
alcohols (such as methanol, ethanol, butanol or isopropanol) and ethers 
(such as diethyl ether or tetrahydrofuran). 
The reaction using complex hydrides is in general carried out at a 
temperature between 0.degree. and 30.degree. C., preferably between 
0.degree. and 20.degree. C. 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 aluminum isopropylate is used, preferred possible diluents 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.degree. and 120.degree. C., preferably 
between 50.degree. and 100.degree. C. For carrying out the reaction, about 
1 to 2 mols of aluminum isopropylate are employed per mol of the ketone of 
the formula (II). To isolate the reduced compounds of the formula (I), the 
excess solvent is removed by distillation in vacuo and the resulting 
aluminum compound is decomposed with dilute sulphuric acid or sodium 
hydroxide solution. Further working up is effected in the customary 
manner. 
The compounds of the formula (I) which can be prepared according to the 
invention can 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 acids (such as hydrobromic acid and, 
preferably, hydrochloric acid), phosphoric acid, nitric acid, sulphuric 
acid, monofunctional and bifunctional carboxylic acids and 
hydroxycarboxylic acids (such as acetic acid, maleic acid, succinic acid, 
fumaric 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 compound of the formula (I) in a suitable inert 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 subgroups 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 complexes can 
be purified in a known manner, for example by filtration, isolation and, 
if appropriate by recrystallization. 
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 for use as 
plant protection agents. 
Fungicidal agents in plant protection are employed for combating 
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, 
Ascomycetes, Basidiomycetes and Deuteromycetes. 
The good toleration, by plants, of the active compounds, at the 
concentrations required for combating plant diseases, 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 emphasized. Thus, it is 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. 
When used in appropriate concentrations, the substances according to the 
invention also exhibit growth-regulating properties: 
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 compound applied to the plants or 
their environment and the way in which the compounds are applied. In every 
case, growth regulators are intended to influence the crop plants in the 
particular manner desired. 
Plant growth regulating compounds can be employed, for example, to inhibit 
vegetative growth of the plants. Such inhibition of growth is inter alia 
of economic interest in the case of grasses, since it is thereby possible 
to reduce the frequency of cutting the grass is ornamental gardens, parks 
and athletic fields, at borders, at airports or in fruit orchards. The 
inhibition of growth of herbaceous and woody plants at borders and in the 
vicinity of pipelines or overland lines or, quite generally, in areas in 
which heavy additional growth of plants is undesired, is also of 
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 regulators for shortening and strengthening the stem enables 
higher amounts of fertilizer 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 planting possible, so that greater yields per area of ground can be 
achieved. An advantage of the smaller plants thus produced is also that 
the crop can be worked and harvested more easily. 
Inhibition of the vegetative growth of plants can also 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 utility if it is the vegetative parts of the 
plants which are harvested. Promoting the vegetative growth can, however, 
also simultaneously lead to a promotion of generative growth, since more 
assimilates are formed, so that more fruit, or larger fruit, is obtained. 
Increases in yield can in some cases be achieved by affecting the plant 
metabolism, without noticeable changes in vegetative growth. A change in 
the composition 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 content of 
sugar in sugar beet, sugar cane, pineapples and citrus fruit 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, 
before or after harvesting. It is also possible favorably to influence the 
production or the efflux of secondary plant constituents. The stimulation 
of latex flux in rubber trees may be mentioned as an example. 
Parthenocarpous fruit can be formed under the influence of growth 
regulators. Furthermore, the gender of the flowers can be influenced. 
Sterility of the pollen can also be produced, which is of great importance 
in the breeding and preparation of hybrid seed. 
Branching of plants can be controlled by using growth 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 
cultivation of ornamental plants, also in connection with growth 
inhibition. On the other hand, however, it is also possible to inhibit the 
growth of side shoots. There is great interest in this action, for 
example, in the cultivation of tobacco or in the planting of tomatoes. 
The amount of leaf on plants can be controlled, under the influence of 
growth regulators, so that defoliation of the plants at a desired point in 
time is achieved. Such defoliation is of great importance in the 
mechanical harvesting of cotton, but is also of interest for facilitating 
harvesting in other crops, such as, for example, in viticulture. 
Defoliation of the plants can also be carried out to lower the 
transpiration of plants before they are transplanted. 
The shedding of fruit can also be controlled with growth regulators. On the 
one hand, it is possible to prevent premature shedding of fruit. However, 
on the other hand, shedding of fruit, or even the fall of blossom, can be 
promoted up to a certain degree (thinning out) in order to interrupt the 
alternance. By alternance there is understood the peculiarity of some 
varieties of fruit to produce very different yields from year to year, for 
endogenic reasons. Finally, using growth regulators it is possible to 
reduce the force required to detach the fruit at harvest time so as to 
permit mechanical harvesting or facilitate manual harvesting. 
Using growth regulators, it is furthermore possible to achieve an 
acceleration or retardation of ripening of the harvest product, before or 
after harvesting. This is of particular advantage, since it is thereby 
possible to achieve optimum adaptation to market requirements. 
Furthermore, growth regulators can at times improve the coloration of 
fruit. In addition, concentrating the ripening within a certain period of 
time is also achievable with the aid of growth regulators. This provides 
the preconditions for being able to carry out complete mechanical or 
manual harvesting in only a single pass, for example in the case of 
tobacco, tomatoes or coffee. 
Using growth regulators, it is furthermore possible to influence the latent 
period of seeds or buds of plants, so that the plants, such as, for 
example, pineapple or ornamental plants in nurseries, germinate, shoot or 
blossom at a time at which they normally show no readiness to do so. 
Retarding the shooting of buds or the germination of seeds with the aid of 
growth regulators can be desirable in regions where frost is a hazard, in 
order to avoid damage by late frosts. 
Finally, the resistance of plants to frost, drought 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 of application of the growth regulators depends on the 
climatic and vegetative circumstances. 
The foregoing 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 circumstances must be 
determined empirically. 
The active compounds can be converted to the customary formulations, such 
as solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, natural and synthetic materials impregnated with active 
compound, 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 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 hydrocarbons, 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 paraffins, for example 
mineral oil fractions, alcohols, such as butanol or glycol as well as 
their ethers and esters, ketones, such as acetone, methyl ethyl 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 which 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, alumina 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 sawdust, coconut shells, corn cobs and tobacco stalks. 
As emulsifying and/or foam-forming agents there may be used non-ionic and 
anionic emulsifiers, such as polyoxyethylene-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 methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic 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 percent by weight of 
active compound, preferably from 0.5 to 90 percent 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 repellents, growth factors, 
plant nutrients and agents for improving soil structure. 
The active compounds can be used as such or in the form of their 
formulations or the use forms prepared therefrom by further dilution, such 
as ready-to-use solutions, emulsions, suspensions, powders, pastes and 
granules. They are used in the customary manner, for example by watering, 
immersion, spraying, atomizing, misting, vaporizing, injecting, forming a 
slurry, brushing on, dusting, 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 1 and 0.0001% by weight, preferably between 
0.5 and 0.001%. 
In the treatment of seed, amounts of active compound 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 concentrations of 0.00001 to 
0.1% by weight, preferably 0.0001 to 0.2%, are required at the place of 
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, preferably 0.05 to 10 kg, of active compound are used per 
hectare of soil surface. 
When applied in appropriate higher amounts, the compounds according to the 
invention also exhibit a herbicidal action. 
The present invention also provides a fungicidal or plant growth 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 
plants which comprises applying 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 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 alone 
or in admixture with a diluent or carrier. 
It will be seen that the usual methods of providing a harvested crop may be 
improved by the present invention. 
The following examples illustrate the synthesis of compounds of the formula 
I wherein B is --CO--: