TREA

Benzhydryl derivatives

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Information

  • Patent Grant
  • 6767923
  • Patent Number
    6,767,923
  • Date Filed
    Tuesday, October 29, 2002
    22 years ago
  • Date Issued
    Tuesday, July 27, 2004
    20 years ago
Information
Abstract
Benzhydryl derivatives of the formula I, where the index and the variables are as defined below:X is oxygen or sulfur;R1, R3 are halogen, cyano, nitro, hydroxyl, mercapto, amino, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylcarbonyloxy, formyloxy, alkylthio, alkenylthio, alkynylthio, alkylamino, dialkylamino, alkylcarbonyl or formyl, where the carbon atoms in the radicals mentioned may be partially or fully halogenated;R2 is halogen, cyano, nitro, hydroxyl, mercapto, amino, alkyl, alkoxy, haloalkyl or haloalkoxy, where the groups R2 may be different if n=2;R4 is alkyl, alkenyl or alkynyl, where the carbon atoms in these radicals may be unsubstituted or partially or fully halogenated;R5, R6 are hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, alkenyloxy, haloalkoxy, haloalkenyloxy, cycloalkyl, cycloalkylalkyl, cycloalkoxy or cycloalkylalkoxy;n is 0, 1 or 2;processes for preparing the compounds I, compositions comprising them and their use for controlling phytopathogenic harmful fungi are described.
Description




DESCRIPTION




The invention relates to benzhydryl derivatives of the formula I,











where the index and the variables are as defined below:




X is oxygen or sulfur;




R


1


, R


3


are halogen, cyano, nitro, hydroxyl, mercapto, amino,




C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyloxy, C


2


-C


6


-alkynyloxy, C


1


-C


6


-alkylcarbonyloxy, formyloxy, C


1


-C


6


-alkylthio, C


2


-C


6


-alkenylthio, C


2


-C


6


-alkynylthio, C


1


-C


6


-alkylamino, di-C


1


-C


6


-alkylamino, C


1


-C


6


-alkylcarbonyl or formyl, where the carbon atoms in the radicals mentioned may be partially or fully halogenated;




R


2


is halogen, cyano, nitro, hydroxyl, mercapto, amino, C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-haloalkyl or C


1


-C


6


-haloalkoxy, where the groups R


2


may be different if n=2;




R


4


is C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl or C


2


-C


6


-alkynyl, where the carbon atoms in these radicals may be unsubstituted or partially or fully halogenated;




R


5


, R


6


are hydroxyl, C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


1


-C


6


-haloalkyl, C


2


-C


6


-haloalkenyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyloxy, C


1


-C


6


-haloalkoxy, C


2


-C


6


-haloalkenyloxy, C


3


-C


8


-cycloalkyl, C


3


-C


8


-cycloalkyl-C


1


-C


3


-alkyl, C


3


-C


8


-cycloalkoxy or C


3


-C


8


-cycloalkyl-C


1


-C


3


-alkoxy;




n is 0, 1 or 2.




Additionally, the invention relates to processes for preparing the compounds I, to compositions comprising them and to the use of the compounds I for controlling phytopathogenic fungi.




In JP 08225474 various benzhydryl alcohols have been described as starting materials for pharmaceutics.




EP-A 461 079 discloses various benzhydryl alcohols having herbicidal action.




Benzhydryl alcohols having fungicidal action are already known, for example




(RS)-2,4′-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)benzhydryl alcohol (flutriafol; EP-A 015 756) or




(R,S)-2,4′-dichloro-alpha-(pyrimidin-5-yl)benzhydryl alcohol (fenarimol; GB 1 218 623). However, their action is not entirely satisfactory.




Benzophenones having fungicidal action are known from EP-A 727 141.




It is an object of the present invention to provide benzhydryl derivatives having a higher efficacy in the control of harmful fungi.




We have found that this object is achieved by the benzhydryl derivatives of the formula I. Furthermore, we have found processes for preparing the compounds I and compositions comprising them for controlling harmful fungi.




The compounds of the formula I differ from the benzhydryl alcohols disclosed in JP 08225474 by the substitution pattern on the phenyl rings.




The compounds of the formula I differ from the herbicidally active benzhydryl alcohols disclosed in EP-A 461 079 by the substituents of the phenyl rings, which substituents are fixed in positions 2, 2, 2′, 2′, 3′, 4 and 4′.




The compounds of the formula I are secondary alcohols or thiols, whereas the compounds disclosed in EP-A 015 756 and GB 1 218 623 are tertiary alcohols which furthermore differ from compounds of the formula I in the substitution pattern on the phenyl rings.




The compounds of the formula I differ from the fungicidally active benzophenones disclosed in EP-A 727 141 in that the keto group is replaced by an alcohol or thiol function, and by the substitution patterns on the phenyl rings.




In the definitions of the symbols given in the formulae above, collective terms were used which, in general, represent the following substituents:




Halogen: fluorine, chlorine, bromine or iodine, preferably chlorine or bromine;




Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 or 1 to 6 carbon atoms, for example C


1


-C


6


-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;




Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C


1


-C


2


-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;




Alkoxy: straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above), which are attached to the phenyl ring via an oxygen atom (—O—);




Haloalkoxy: straight-chain or branched haloalkyl groups having 1 to 6 carbon atoms (as mentioned above) which are attached to the phenyl ring via an oxygen atom (—O—);




Alkylthio: straight-chain or branched alkyl groups having 1 to 6 or 1 to 4 carbon atoms (as mentioned above) which are attached to the phenyl ring via a sulfur atom (—S—);




Alkylamino: a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached to the phenyl ring via an amino group (—NH—);




Dialkylamino: two independent straight-chain or branched alkyl groups having in each case 1 to 6 carbon atoms (as mentioned above) which are attached to the phenyl ring via a nitrogen atom;




Alkylcarbonyloxy: a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached to the phenyl ring via a carbonyloxy group (—CO


2


—);




Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position, for example C


2


-C


6


-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;




Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;




Alkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the phenyl ring via an oxygen atom (—O—);




Haloalkenyloxy: unsaturated, straight-chain or branched alkenyloxy groups having 3 to 6 carbon atoms (as mentioned above), it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;




Alkenylthio: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the phenyl ring via a sulfur atom (—S—);




Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 6 carbon atoms and a triple bond in any position, for example C


2


-C


6


-alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;




Alkynyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 6 carbon atoms and a triple bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the skeleton via an oxygen atom (—O—);




Alkynylthio: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 6 carbon atoms and a triple bond in any position which is not adjacent to the heteroatom (as mentioned above), which are attached to the skeleton via a sulfur atom (—S—).




With respect to the intended use of the benzhydryl compounds of the formula I, the following meanings of the substituents are particularly preferred, in each case on their own or in combination:




Benzhydryl derivatives of the formula I as claimed in claim 1 where the variables are as defined below:




X is oxygen or sulfur;




R


1


, R


3


independently of one another are halogen, hydroxyl, mercapto, amino,




C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, C


1


-C


6


-haloalkyl, C


2


-C


6


-haloalkenyl, C


2


-C


6


-haloalkynyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyloxy, C


2


-C


6


-alkynyloxy, C


1


-C


6


-haloalkoxy, C


2


-C


6


-haloalkenyloxy, C


2


-C


6


-haloalkynyloxy, C


1


-C


6


-alkylcarbonyloxy, C


1


-C


6


-haloalkylcarbonyloxy, formyloxy, C


1


-C


6


-alkylthio, C


2


-C


6


-alkenylthio, C


2


-C


6


-alkynylthio, C


1


-C


6


-haloalkylthio, C


2


-C


6


-haloalkenylthio, C


2


-C


6


-haloalkynylthio, C


1


-C


6


-alkylamino, di-C


1


-C


6


-alkylamino, C


1


-C


6


-haloalkylamino, di-C


1


-C


6


-haloalkylamino, C


1


-C


6


-alkylcarbonyl, C


1


-C


6


-haloalkylcarbonyl or formyl;




R


2


is halogen, hydroxyl, C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-haloalkyl or C


1


-C


6


-haloalkoxy, where the radicals R


2


may be different if n=2;




R


4


is C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, C


1


-C


6


-haloalkyl, C


2


-C


6


-haloalkenyl or C


2


-C


6


-haloalkynyl;




R


5


, R


6


independently of one another are hydroxyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyloxy, C


1


-C


6


-haloalkoxy or C


2


-C


6


-haloalkenyloxy;




n is 0, 1 or 2.




Particular preference is given to compounds I in which X is oxygen or sulfur;




R


1


and R


3


independently of one another are halogen, hydroxyl, mercapto, amino, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-haloalkoxy or C


1


-C


6


-alkylcarbonyl;




R


2


is halogen, hydroxyl, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy or C


1


-C


6


-haloalkoxy, where the radicals R


2


may be different if n=2;




R


4


is methyl;




R


5


, R


6


independently of one another are hydroxyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyloxy, C


1


-C


6


-haloalkoxy or C


2


-C


6


-haloalkenyloxy and




n is 0 or 1.




Especially preferred are compounds I in which X is oxygen.




Preference is furthermore given to compounds I in which R


1


and R


3


independently of one another are halogen, hydroxyl, amino, mercapto, nitro, cyano, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy, C


1


-C


6


-haloalkoxy, C


1


-C


6


-alkylcarbonyloxy, C


1


-C


6


-haloalkylcarbonyloxy, C


1


-C


6


-alkylthio, C


1


-C


6


-haloalkylthio, C


1


-C


6


-alkylcarbonyl or C


1


-C


6


-haloalkylcarbonyl. Here, particular mention may be made of: fluorine, chlorine, bromine or iodine, hydroxyl, mercapto, amino, methyl, ethyl, methoxy, ethoxy, methylcarbonyloxy, ethylcarbonyloxy, methylthio, ethylthio, trifluoromethyl, difluoromethoxy or chlorofluoromethoxy.




In addition, preference is given to compounds I in which R


1


and R


3


independently of one another are halogen, hydroxyl, mercapto, amino, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy or C


1


-C


6


-haloalkoxy. Here, particular mention may be made of: fluorine, chlorine, bromine or iodine, hydroxyl, mercapto, amino, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or chlorofluoromethoxy.




Particular preference is furthermore given to compounds I in which R


1


and R


3


independently of one another are halogen, such as fluorine, chlorine, bromine or iodine, hydroxyl, C


1


-C


6


-alkyl, such as methyl or ethyl, C


1


-C


6


-alkoxy, such as methoxy or ethoxy, or C


1


-C


6


-alkylcarbonyloxy, such as methylcarbonyloxy or ethylcarbonyloxy.




In addition, particular preference is given to compounds I in which R


1


and R


3


independently of one another are halogen, such as fluorine, chlorine, bromine or iodine, hydroxyl, C


1


-C


6


-alkyl, such as methyl or ethyl, or C


1


-C


6


-alkoxy, such as methoxy or ethoxy.




Very particular preference is given to compounds I in which R


1


and R


3


independently of one another are halogen, such as chlorine or bromine, or C


1


-C


6


-alkyl, such as methyl or ethyl.




Likewise, very particular preference is given to compounds I in which R


1


and R


3


independently of one another are hydroxyl, C


1


-C


6


-alkoxy, such as methoxy or ethoxy, or C


1


-C


6


-alkylcarbonyloxy, such as methylcarbonyloxy or ethylcarbonyloxy.




In addition, very particular preference is given to compounds I in which R


1


and R


3


independently of one another are hydroxyl or C


1


-C


6


-alkoxy, such as methoxy or ethoxy.




Moreover, preference is also given to compounds I in which R


2


is halogen, hydroxyl, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy or C


1


-C


6


-haloalkoxy, where the groups R


2


may be different if n=2. Here, particular mention may be made of: fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethoxy, chlorofluoromethoxy.




Especially preferred are also compounds I in which R


2


is halogen, hydroxyl or C


1


-C


6


-alkoxy, such as methoxy or ethoxy.




Very particular preference is given to compounds I in which R


2


is halogen, in particular bromine or chlorine.




Moreover, particular preference is given to compounds I in which R


4


is C


1


-C


6


-alkyl or C


1


-C


6


-haloalkyl. Here, particular mention may be made of: methyl, ethyl and trifluoromethyl.




Especially preferred are compounds I in which R


4


is methyl.




Moreover, particular preference is given to compounds I in which R


5


and R


6


independently of one another are hydroxyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyloxy, C


1


-C


6


-haloalkoxy or C


2


-C


6


-haloalkenyloxy. Here, particular mention may be made of: hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentoxy, hexoxy, propenyloxy, trifluoromethoxy, difluoromethoxy and chlorofluoromethoxy.




Particular preference is furthermore given to compounds I in which R


5


and R


6


independently of one another are hydroxyl or C


1


-C


6


-alkoxy, such as methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy.




Very particular preference is given to compounds I in which R


5


and R


6


are methoxy.




In addition, particular preference is given to compounds I in which n is 0 or 1, very particularly preferably 1.




Very particular preference is given to compounds I in which R


1


and R


3


independently of one another are fluorine, chlorine, bromine, iodine, hydroxyl, mercapto, methylthio, amino, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, fluorochloromethoxy, trifluoromethoxy, methylcarbonyloxy or ethylcarbonyloxy, R


2


is fluorine, chlorine, bromine, iodine, hydroxyl, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or chlorofluoromethoxy, R


4


is methyl, ethyl or trifluoromethyl, R


5


and R


6


independently of one another are hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy and n is 0 or 1.




With respect to their use, particular preference is given to the compounds I-A compiled in the tables below. The groups mentioned in the tables for a substituent are furthermore in their own right, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.




Table 1




Compounds of formula I-A in which n is 0, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound corresponds in each case to one row of Table A




Table 2




Compounds of the formula I-A in which n is 1, R


2


is 3-methyl, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 3




Compounds of the formula I-A in which n is 1, R


2


is 5-methyl, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 4




Compounds of the formula I-A in which n is 1, R


2


is 3-trifluoromethyl, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 5




Compounds of the formula I-A in which n is 1, R


2


is 5-trifluoromethyl, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 6




Compounds of the formula I-A in which n is 1, R


2


is 3-hydroxyl, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 7




Compounds of the formula I-A in which n is 1, R


2


is 5-hydroxyl, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 8




Compounds of the formula I-A in which n is 1, R


2


is 3-methoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 9




Compounds of the formula I-A in which n is 1, R


2


is 5-methoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 10




Compounds of the formula I-A in which n is 1, R


2


is 3-ethoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 11




Compounds of the formula I-A in which n is 1, R


2


is 5-ethoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 12




Compounds of the formula I-A in which n is 1, R


2


is 3-difluoromethoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 13




Compounds of the formula I-A in which n is 1, R


2


is 5-difluoromethoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 14




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorofluoromethoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 15




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorofluoromethoxy, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 16




Compounds of the formula I-A in which n is 1, R


2


is 3-fluorine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 17




Compounds of the formula I-A in which n is 1, R


2


is 5-fluorine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 18




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 19




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 20




Compounds of the formula I-A in which n is 1, R


2


is 3-bromine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 21




Compounds of the formula I-A in which n is 1, R


2


is 5-bromine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 22




Compounds of the formula I-A in which n is 1, R


2


is 3-iodine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 23




Compounds of the formula I-A in which n is 1, R


2


is 5-iodine, R


4


is methyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 24




Compounds of the formula I-A in which n is 0, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 25




Compounds of the formula I-A in which n is 1, R


2


is 3-methyl, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 26




Compounds of the formula I-A in which n is 1, R


2


is 5-methyl, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 27




Compounds of the formula I-A in which n is 1, R


2


is 3-trifluoromethyl, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 28




Compounds of the formula I-A in which n is 1, R


2


is 5-trifluoromethyl, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 29




Compounds of the formula I-A in which n is 1, R


2


is 3-hydroxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 30




Compounds of the formula I-A in which n is 1, R


2


is 5-hydroxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 31




Compounds of the formula I-A in which n is 1, R


2


is 3-methoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 32




Compounds of the formula I-A in which n is 1, R


2


is 5-methoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 33




Compounds of the formula I-A in which n is 1, R


2


is 3-ethoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 34




Compounds of the formula I-A in which n is 1, R


2


is 5-ethoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 35




Compounds of the formula I-A in which n is 1, R


2


is 3-difluoromethoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 36




Compounds of the formula I-A in which n is 1, R


2


is 5-difluoromethoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 37




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorofluoromethoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 38




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorofluoromethoxy, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 39




Compounds of the formula I-A in which n is 1, R


2


is 3-fluorine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 40




Compounds of the formula I-A in which n is 1, R


2


is 5-fluorine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 41




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 42




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 43




Compounds of the formula I-A in which n is 1, R


2


is 3-bromine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 44




Compounds of the formula I-A in which n is 1, R


2


is 5-bromine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 45




Compounds of the formula I-A in which n is 1, R


2


is 3-iodine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 46




Compounds of the formula I-A in which n is 1, R


2


is 5-iodine, R


4


is ethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 47




Compounds of the formula I-A in which n is 0, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 48




Compounds of the formula I-A in which n is 1, R


2


is 3-methyl, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 49




Compounds of the formula I-A in which n is 1, R


2


is 5-methyl, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 50




Compounds of the formula I-A in which n is 1, R


2


is 3-trifluoromethyl, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 51




Compounds of the formula I-A in which n is 1, R


2


is 5-trifluoromethyl, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 52




Compounds of the formula I-A in which n is 1, R


2


is 3-hydroxyl, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 53




Compounds of the formula I-A in which n is 1, R


2


is 5-hydroxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 54




Compounds of the formula I-A in which n is 1, R


2


is 3-methoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 55




Compounds of the formula I-A in which n is 1, R


2


is 5-methoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 56




Compounds of the formula I-A in which n is 1, R


2


is 3-ethoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 57




Compounds of the formula I-A in which n is 1, R


2


is 5-ethoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 58




Compounds of the formula I-A in which n is 1, R


2


is 3-difluoromethoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 59




Compounds of the formula I-A in which n is 1, R


2


is 5-difluoromethoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 60




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorofluoromethoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 61




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorofluoromethoxy, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 62




Compounds of the formula I-A in which n is 1, R


2


is 3-fluorine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 63




Compounds of the formula I-A in which n is 1, R


2


is 5-fluorine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 64




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 65




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 66




Compounds of the formula I-A in which n is 1, R


2


is 3-bromine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 67




Compounds of the formula I-A in which n is 1, R


2


is 5-bromine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 68




Compounds of the formula I-A in which n is 1, R


2


is 3-iodine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 69




Compounds of the formula I-A in which n is 1, R


2


is 5-iodine, R


4


is trifluoromethyl and R


6


is methoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 70




Compounds of the formula I-A in which n is 0, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 71




Compounds of the formula I-A in which n is 1, R


2


is 3-methyl, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 72




Compounds of the formula I-A in which n is 1, R


2


is 5-methyl, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 73




Compounds of the formula I-A in which n is 1, R


2


is 3-trifluoromethyl, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 74




Compounds of the formula I-A in which n is 1, R


2


is 5-trifluoromethyl, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 75




Compounds of the formula I-A in which n is 1, R


2


is 3-hydroxyl, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 76




Compounds of the formula I-A in which n is 1, R


2


is 5-hydroxyl, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 77




Compounds of the formula I-A in which n is 1, R


2


is 3-methoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 78




Compounds of the formula I-A in which n is 1, R


2


is 5-methoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 79




Compounds of the formula I-A in which n is 1, R


2


is 3-ethoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 80




Compounds of the formula I-A in which n is 1, R


2


is 5-ethoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 81




Compounds of the formula I-A in which n is 1, R


2


is 3-difluoromethoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 82




Compounds of the formula I-A in which n is 1, R


2


is 5-difluoromethoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 83




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorofluoromethoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 84




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorofluoromethoxy, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 85




Compounds of the formula I-A in which n is 1, R


2


is 3-fluorine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 86




Compounds of the formula I-A in which n is 1, R


2


is 5-fluorine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 87




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 88




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 89




Compounds of the formula I-A in which n is 1, R


2


is 3-bromine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 90




Compounds of the formula I-A in which n is 1, R


2


is 5-bromine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 91




Compounds of the formula I-A in which n is 1, R


2


is 3-iodine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 92




Compounds of the formula I-A in which n is 1, R


2


is 5-iodine, R


4


is methyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 93




Compounds of the formula I-A in which n is 0, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 94




Compounds of the formula I-A in which n is 1, R


2


is 3-methyl, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 95




Compounds of the formula I-A in which n is 1, R


2


is 5-methyl, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 96




Compounds of the formula I-A in which n is 1, R


2


is 3-trifluoromethyl, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 97




Compounds of the formula I-A in which n is 1, R


2


is 5-trifluoromethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 98




Compounds of the formula I-A in which n is 1, R


2


is 3-hydroxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 99




Compounds of the formula I-A in which n is 1, R


2


is 5-hydroxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 100




Compounds of the formula I-A in which n is 1, R


2


is 3-methoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 101




Compounds of the formula I-A in which n is 1, R


2


is 5-methoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 102




Compounds of the formula I-A in which n is 1, R


2


is 3-ethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 103




Compounds of the formula I-A in which n is 1, R


2


is 5-ethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 104




Compounds of the formula I-A in which n is 1, R


2


is 3-difluoromethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 105




Compounds of the formula I-A in which n is 1, R


2


is 5-difluoromethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 106




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorofluoromethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 107




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorofluoromethoxy, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 108




Compounds of the formula I-A in which n is 1, R


2


is 3-fluorine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 109




Compounds of the formula I-A in which n is 1, R


2


is 5-fluorine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of 35 Table A, where R


1


is different from R


3






Table 110




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 111




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 112




Compounds of the formula I-A in which n is 1, R


2


is 3-bromine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 113




Compounds of the formula I-A in which n is 1, R


2


is 5-bromine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 114




Compounds of the formula I-A in which n is 1, R


2


is 3-iodine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 115




Compounds of the formula I-A in which n is 1, R


2


is 5-iodine, R


4


is ethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 116




Compounds of the formula I-A in which n is 0, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 117




Compounds of the formula I-A in which n is 1, R


2


is 3-methyl, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 118




Compounds of the formula I-A in which n is 1, R


2


is 5-methyl, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 119




Compounds of the formula I-A in which n is 1, R


2


is 3-trifluoromethyl, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 120




Compounds of the formula I-A in which n is 1, R


2


is 5-trifluoromethyl, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 121




Compounds of the formula I-A in which n is 1, R


2


is 3-hydroxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 122




Compounds of the formula I-A in which n is 1, R


2


is 5-hydroxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 123




Compounds of the formula I-A in which n is 1, R


2


is 3-methoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 124




Compounds of the formula I-A in which n is 1, R


2


is 5-methoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 125




Compounds of the formula I-A in which n is 1, R


2


is 3-ethoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 126




Compounds of the formula I-A in which n is 1, R


2


is 5-ethoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 127




Compounds of the formula I-A in which n is 1, R


2


is 3-difluoromethoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 128




Compounds of the formula I-A in which n is 1, R


2


is 5-difluoromethoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 129




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorofluoromethoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 130




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorofluoromethoxy, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 131




Compounds of the formula I-A in which n is 1, R


2


is 3-fluorine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 132




Compounds of the formula I-A in which n is 1, R


2


is 5-fluorine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 133




Compounds of the formula I-A in which n is 1, R


2


is 3-chlorine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 134




Compounds of the formula I-A in which n is 1, R


2


is 5-chlorine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 135




Compounds of the formula I-A in which n is 1, R


2


is 3-bromine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 136




Compounds of the formula I-A in which n is 1, R


2


is 5-bromine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3






Table 137




Compounds of the formula I-A in which n is 1, R


2


is 3-iodine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A




Table 138




Compounds of the formula I-A in which n is 1, R


2


is 5-iodine, R


4


is trifluoromethyl and R


6


is ethoxy and the combination of the radicals R


1


, R


3


and R


5


for a compound in each case corresponds to one row of Table A, where R


1


is different from R


3















TABLE A























I-A





















No.




R


1






R


3






R


5











A-1




CH


3






CH


3






OH






A-2




CH


2


CH


3






CH


3






OH






A-3




CF


3






CH


3






OH






A-4




F




CH


3






OH






A-5




Cl




CH


3






OH






A-6




Br




CH


3






OH






A-7




I




CH


3






OH






A-8




OH




CH


3






OH






A-9




SH




CH


3






OH






A-10




SCH


3






CH


3






OH






A-11




NH


2






CH


3






OH






A-12




OCH


3






CH


3






OH






A-13




OCHF


2






CH


3






OH






A-14




OCHFCl




CH


3






OH






A-15




OCF


3






CH


3






OH






A-16




OC(═O)CH


3






CH


3






OH






A-17




OC(═O)CH


2


CH


3






CH


3






OH






A-18




CH


2


CH


3






CH


2


CH


3






OH






A-19




CF


3






CH


2


CH


3






OH






A-20




F




CH


2


CH


3






OH






A-21




Cl




CH


2


CH


3






OH






A-22




Br




CH


2


CH


3






OH






A-23




I




CH


2


CH


3






OH






A-24




OH




CH


2


CH


3






OH






A-25




SH




CH


2


CH


3






OH






A-26




SCH


3






CH


2


CH


3






OH






A-27




NH


2






CH


2


CH


3






OH






A-28




OCH


3






CH


2


CH


3






OH






A-29




OCHF


2






CH


2


CH


3






OH






A-30




OCHFCl




CH


2


CH


3






OH






A-31




OCF


3






CH


2


CH


3






OH






A-32




OC(═O)CH


3






CH


2


CH


3






OH






A-33




OC(═O)CH


2


CH


3






CH


2


CH


3






OH






A-34




CF


3






CF


3






OH






A-35




F




CF


3






OH






A-36




Cl




CF


3






OH






A-37




Br




CF


3






OH






A-38




I




CF


3






OH






A-39




OH




CF


3






OH






A-40




SH




CF


3






OH






A-41




SCH


3






CF


3






OH






A-42




NH


2






CF


3






OH






A-43




OCH


3






CF


3






OH






A-44




OCHF


2






CF


3






OH






A-45




OCHFCl




CF


3






OH






A-46




OCF


3






CF


3






OH






A-47




OC(═O)CH


3






CF


3






OH






A-48




OC(═O)CH


2


CH


3






CF


3






OH






A-49




F




F




OH






A-50




Cl




F




OH






A-51




Br




F




OH






A-52




I




F




OH






A-53




OH




F




OH






A-54




SH




F




OH






A-55




SCH


3






F




OH






A-56




NH


2






F




OH






A-57




OCH


3






F




OH






A-58




OCHF


2






F




OH






A-59




OCHFCl




F




OH






A-60




OCF


3






F




OH






A-61




OC(═O)CH


3






F




OH






A-62




OC(═O)CH


2


CH


3






F




OH






A-63




Cl




Cl




OH






A-64




Br




Cl




OH






A-65




I




Cl




OH






A-66




OH




Cl




OH






A-67




SH




Cl




OH






A-68




SCH


3






Cl




OH






A-69




NH


2






Cl




OH






A-70




OCH


3






Cl




OH






A-71




OCHF


2






Cl




OH






A-72




OCHFCl




Cl




OH






A-73




OCF


3






Cl




OH






A-74




OC(═O)CH


3






Cl




OH






A-75




OC(═O)CH


2


CH


3






Cl




OH






A-76




Br




Br




OH






A-77




I




Br




OH






A-78




OH




Br




OH






A-79




SH




Br




OH






A-80




SCH


3






Br




OH






A-81




NH


2






Br




OH






A-82




OCH


3






Br




OH






A-83




OCHF


2






Br




OH






A-84




OCHFCl




Br




OH






A-85




OCF


3






Br




OH






A-86




OC(═O)CH


3






Br




OH






A-87




OC(═O)CH


2


CH


3






Br




OH






A-88




I




I




OH






A-89




OH




I




OH






A-90




SH




I




OH






A-91




SCH


3






I




OH






A-92




NH


2






I




OH






A-93




OCH


3






I




OH






A-94




OCHF


2






I




OH






A-95




OCHFCl




I




OH






A-96




OCF


3






I




OH






A-97




OC(═O)CH


3






I




OH






A-98




OC(═O)CH


2


CH


3






I




OH






A-99




OH




OH




OH






A-100




SH




OH




OH






A-101




SCH


3






OH




OH






A-102




NH


2






OH




OH






A-103




OCH


3






OH




OH






A-104




OCHF


2






OH




OH






A-105




OCHFCl




OH




OH






A-106




OCF


3






OH




OH






A-107




OC(═O)CH


3






OH




OH






A-108




OC(═O)CH


2


CH


3






OH




OH






A-109




SH




SH




OH






A-110




SCH


3






SH




OH






A-111




NH


2






SH




OH






A-112




OCH


3






SH




OH






A-113




OCHF


2






SH




OH






A-114




OCHFCl




SH




OH






A-115




OCF


3






SH




OH






A-116




OC(═O)CH


3






SH




OH






A-117




OC(═O)CH


2


CH


3






SH




OH






A-118




SCH


3






SCH


3






OH






A-119




NH


2






SCH


3






OH






A-120




OCH


3






SCH


3






OH






A-121




OCHF


2






SCH


3






OH






A-122




OCHFCl




SCH


3






OH






A-123




OCF


3






SCH


3






OH






A-124




OC(═O)CH


3






SCH


3






OH






A-125




OC(═O)CH


2


CH


3






SCH


3






OH






A-126




NH


2






NH


2






OH






A-127




OCH


3






NH


2






OH






A-128




OCHF


2






NH


2






OH






A-129




OCHFCl




NH


2






OH






A-130




OCF


3






NH


2






OH






A-131




OC(═O)CH


3






NH


2






OH






A-132




OC(═O)CH


2


CH


3






NH


2






OH






A-133




OCH


3






OCH


3






OH






A-134




OCHF


2






OCH


3






OH






A-135




OCHFCl




OCH


3






OH






A-136




OCF


3






OCH


3






OH






A-137




OC(═O)CH


3






OCH


3






OH






A-138




OC(═O)CH


2


CH


3






OCH


3






OH






A-139




OCHF


2






OCHF


2






OH






A-140




OCHFCl




OCHF


2






OH






A-141




OCF


3






OCHF


2






OH






A-142




OC(═O)CH


3






OCHF


2






OH






A-143




OC(═O)CH


2


CH


3






OCHF


2






OH






A-144




OCHFCl




OCHFCl




OH






A-145




OCF


3






OCHFCl




OH






A-146




OC(═O)CH


3






OCHFCl




OH






A-147




OC(═O)CH


2


CH


3






OCHFCl




OH






A-148




OCF


3






OCF


3






OH






A-149




OC(═O)CH


3






OCF


3






OH






A-150




OC(═O)CH


2


CH


3






OCF


3






OH






A-151




OC(═O)CH


3






OC(═O)CH


3






OH






A-152




OC(═O)CH


2


CH


3






OC(═O)CH


3






OH






A-153




OC(═O)CH


2


CH


3






OC(═O)CH


2


CH


3






OH






A-154




CH


3






CH


3






OCH


3








A-155




CH


2


CH


3






CH


3






OCH


3








A-156




CF


3






CH


3






OCH


3








A-157




F




CH


3






OCH


3








A-158




Cl




CH


3






OCH


3








A-159




Br




CH


3






OCH


3








A-160




I




CH


3






OCH


3








A-161




OH




CH


3






OCH


3








A-162




SH




CH


3






OCH


3








A-163




SCH


3






CH


3






OCH


3








A-164




NH


2






CH


3






OCH


3








A-165




OCH


3






CH


3






OCH


3








A-166




OCHF


2






CH


3






OCH


3








A-167




OCHFCl




CH


3






OCH


3








A-168




OCF


3






CH


3






OCH


3








A-169




OC(═O)CH


3






CH


3






OCH


3








A-170




OC(═O)CH


2


CH


3






CH


3






OCH


3








A-171




CH


2


CH


3






CH


2


CH


3






OCH


3








A-172




CF


3






CH


2


CH


3






OCH


3








A-173




F




CH


2


CH


3






OCH


3








A-174




Cl




CH


2


CH


3






OCH


3








A-175




Br




CH


2


CH


3






OCH


3








A-176




I




CH


2


CH


3






OCH


3








A-177




OH




CH


2


CH


3






OCH


3








A-178




SH




CH


2


CH


3






OCH


3








A-179




SCH


3






CH


2


CH


3






OCH


3








A-180




NH


2






CH


2


CH


3






OCH


3








A-181




OCH


3






CH


2


CH


3






OCH


3








A-182




OCHF


2






CH


2


CH


3






OCH


3








A-183




OCHFCl




CH


2


CH


3






OCH


3








A-184




OCF


3






CH


2


CH


3






OCH


3








A-185




OC(═O)CH


3






CH


2


CH


3






OCH


3








A-186




OC(═O)CH


2


CH


3






CH


2


CH


3






OCH


3








A-187




CF


3






CF


3






OCH


3








A-188




F




CF


3






OCH


3








A-189




Cl




CF


3






OCH


3








A-190




Br




CF


3






OCH


3








A-191




I




CF


3






OCH


3








A-192




OH




CF


3






OCH


3








A-193




SH




CF


3






OCH


3








A-194




SCH


3






CF


3






OCH


3








A-195




NH


2






CF


3






OCH


3








A-196




OCH


3






CF


3






OCH


3








A-197




OCHF


2






CF


3






OCH


3








A-198




OCHFCl




CF


3






OCH


3








A-199




OCF


3






CF


3






OCH


3








A-200




OC(═O)CH


3






CF


3






OCH


3








A-201




OC(═O)CH


2


CH


3






CF


3






OCH


3








A-202




F




F




OCH


3








A-203




Cl




F




OCH


3








A-204




Br




F




OCH


3








A-205




I




F




OCH


3








A-206




OH




F




OCH


3








A-207




SH




F




OCH


3








A-208




SCH


3






F




OCH


3








A-209




NH


2






F




OCH


3








A-210




OCH


3






F




OCH


3








A-211




OCHF


2






F




OCH


3








A-212




OCHFCl




F




OCH


3








A-213




OCF


3






F




OCH


3








A-214




OC(═O)CH


3






F




OCH


3








A-215




OC(═O)CH


2


CH


3






F




OCH


3








A-216




Cl




Cl




OCH


3








A-217




Br




Cl




OCH


3








A-218




I




Cl




OCH


3








A-219




OH




Cl




OCH


3








A-220




SH




Cl




OCH


3








A-221




SCH


3






Cl




OCH


3








A-222




NH


2






Cl




OCH


3








A-223




OCH


3






Cl




OCH


3








A-224




OCHF


2






Cl




OCH


3








A-225




OCHFCl




Cl




OCH


3








A-226




OCF


3






Cl




OCH


3








A-227




OC(═O)CH


3






Cl




OCH


3








A-228




OC(═O)CH


2


CH


3






Cl




OCH


3








A-229




Br




Br




OCH


3








A-230




I




Br




OCH


3








A-231




OH




Br




OCH


3








A-232




SH




Br




OCH


3








A-233




SCH


3






Br




OCH


3








A-234




NH


2






Br




OCH


3








A-235




OCH


3






Br




OCH


3








A-236




OCHF


2






Br




OCH


3








A-237




OCHFCl




Br




OCH


3








A-238




OCF


3






Br




OCH


3








A-239




OC(═O)CH


3






Br




OCH


3








A-240




OC(═O)CH


2


CH


3






Br




OCH


3








A-241




I




I




OCH


3








A-242




OH




I




OCH


3








A-243




SH




I




OCH


3








A-244




SCH


3






I




OCH


3








A-245




NH


2






I




OCH


3








A-246




OCH


3






I




OCH


3








A-247




OCHF


2






I




OCH


3








A-248




OCHFCl




I




OCH


3








A-249




OCF


3






I




OCH


3








A-250




OC(═O)CH


3






I




OCH


3








A-251




OC(═O)CH


2


CH


3






I




OCH


3








A-252




OH




OH




OCH


3








A-253




SH




OH




OCH


3








A-254




SCH


3






OH




OCH


3








A-255




NH


2






OH




OCH


3








A-256




OCH


3






OH




OCH


3








A-257




OCHF


2






OH




OCH


3








A-258




OCHFCl




OH




OCH


3








A-259




OCF


3






OH




OCH


3








A-260




OC(═O)CH


3






OH




OCH


3








A-261




OC(═O)CH


2


CH


3






OH




OCH


3








A-262




SH




SH




OCH


3








A-263




SCH


3






SH




OCH


3








A-264




NH


2






SH




OCH


3








A-265




OCH


3






SH




OCH


3








A-266




OCHF


2






SH




OCH


3








A-267




OCHFCl




SH




OCH


3








A-268




OCF


3






SH




OCH


3








A-269




OC(═O)CH


3






SH




OCH


3








A-270




OC(═O)CH


2


CH


3






SH




OCH


3








A-271




SCH


3






SCH


3






OCH


3








A-272




NH


2






SCH


3






OCH


3








A-273




OCH


3






SCH


3






OCH


3








A-274




OCHF


2






SCH


3






OCH


3








A-275




OCHFCl




SCH


3






OCH


3








A-276




OCF


3






SCH


3






OCH


3








A-277




OC(═O)CH


3






SCH


3






OCH


3








A-278




OC(═O)CH


2


CH


3






SCH


3






OCH


3








A-279




NH


2






NH


2






OCH


3








A-280




OCH


3






NH


2






OCH


3








A-281




OCHF


2






NH


2






OCH


3








A-282




OCHFCl




NH


2






OCH


3








A-283




OCF


3






NH


2






OCH


3








A-284




OC(═O)CH


3






NH


2






OCH


3








A-285




OC(═O)CH


2


CH


3






NH


2






OCH


3








A-286




OCH


3






OCH


3






OCH


3








A-287




OCHF


2






OCH


3






OCH


3








A-288




OCHFCl




OCH


3






OCH


3








A-289




OCF


3






OCH


3






OCH


3








A-290




OC(═O)CH


3






OCH


3






OCH


3








A-291




OC(═O)CH


2


CH


3






OCH


3






OCH


3








A-292




OCHF


2






OCHF


2






OCH


3








A-293




OCHFCl




OCHF


2






OCH


3








A-294




OCF


3






OCHF


2






OCH


3








A-295




OC(═O)CH


3






OCHF


2






OCH


3








A-296




OC(═O)CH


2


CH


3






OCHF


2






OCH


3








A-297




OCHFCl




OCHFCl




OCH


3








A-298




OCF


3






OCHFCl




OCH


3








A-299




OC(═O)CH


3






OCHFCl




OCH


3








A-300




OC(═O)CH


2


CH


3






OCHFCl




OCH


3








A-301




OCF


3






OCF


3






OCH


3








A-302




OC(═O)CH


3






OCF


3






OCH


3








A-303




OC(═O)CH


2


CH


3






OCF


3






OCH


3








A-304




OC(═O)CH


3






OC(═O)CH


3






OCH


3








A-305




OC(═O)CH


2


CH


3






OC(═O)CH


3






OCH


3








A-306




OC(═O)CH


2


CH


3






OC(═O)CH


2


CH


3






OCH


3








A-307




CH


3






CH


3






OCH


2


CH


3








A-308




CH


2


CH


3






CH


3






OCH


2


CH


3








A-309




CF


3






CH


3






OCH


2


CH


3








A-310




F




CH


3






OCH


2


CH


3








A-311




Cl




CH


3






OCH


2


CH


3








A-312




Br




CH


3






OCH


2


CH


3








A-313




I




CH


3






OCH


2


CH


3








A-314




OH




CH


3






OCH


2


CH


3








A-315




SH




CH


3






OCH


2


CH


3








A-316




SCH


3






CH


3






OCH


2


CH


3








A-317




NH


2






CH


3






OCH


2


CH


3








A-318




OCH


3






CH


3






OCH


2


CH


3








A-319




OCHF


2






CH


3






OCH


2


CH


3








A-320




OCHFCl




CH


3






OCH


2


CH


3








A-321




OCF


3






CH


3






OCH


2


CH


3








A-322




OC(═O)CH


3






CH


3






OCH


2


CH


3








A-323




OC(═O)CH


2


CH


3






CH


3






OCH


2


CH


3








A-324




CH


2


CH


3






CH


2


CH


3






OCH


2


CH


3








A-325




CF


3






CH


2


CH


3






OCH


2


CH


3








A-326




F




CH


2


CH


3






OCH


2


CH


3








A-327




Cl




CH


2


CH


3






OCH


2


CH


3








A-328




Br




CH


2


CH


3






OCH


2


CH


3








A-329




I




CH


2


CH


3






OCH


2


CH


3








A-330




OH




CH


2


CH


3






OCH


2


CH


3








A-331




SH




CH


2


CH


3






OCH


2


CH


3








A-332




SCH


3






CH


2


CH


3






OCH


2


CH


3








A-333




NH


2






CH


2


CH


3






OCH


2


CH


3








A-334




OCH


3






CH


2


CH


3






OCH


2


CH


3








A-335




OCHF


2






CH


2


CH


3






OCH


2


CH


3








A-336




OCHFCl




CH


2


CH


3






OCH


2


CH


3








A-337




OCF


3






CH


2


CH


3






OCH


2


CH


3








A-338




OC(═O)CH


3






CH


2


CH


3






OCH


2


CH


3








A-339




OC(═O)CH


2


CH


3






CH


2


CH


3






OCH


2


CH


3








A-340




CF


3






CF


3






OCH


2


CH


3








A-341




F




CF


3






OCH


2


CH


3








A-342




Cl




CF


3






OCH


2


CH


3








A-343




Br




CF


3






OCH


2


CH


3








A-344




I




CF


3






OCH


2


CH


3








A-345




OH




CF


3






OCH


2


CH


3








A-346




SH




CF


3






OCH


2


CH


3








A-347




SCH


3






CF


3






OCH


2


CH


3








A-348




NH


2






CF


3






OCH


2


CH


3








A-349




OCH


3






CF


3






OCH


2


CH


3








A-350




OCHF


2






CF


3






OCH


2


CH


3








A-351




OCHFCl




CF


3






OCH


2


CH


3








A-352




OCF


3






CF


3






OCH


2


CH


3








A-353




OC(═O)CH


3






CF


3






OCH


2


CH


3








A-354




OC(═O)CH


2


CH


3






CF


3






OCH


2


CH


3








A-355




F




F




OCH


2


CH


3








A-356




Cl




F




OCH


2


CH


3








A-357




Br




F




OCH


2


CH


3








A-358




I




F




OCH


2


CH


3








A-359




OH




F




OCH


2


CH


3








A-360




SH




F




OCH


2


CH


3








A-361




SCH


3






F




OCH


2


CH


3








A-362




NH


2






F




OCH


2


CH


3








A-363




OCH


3






F




OCH


2


CH


3








A-364




OCHF


2






F




OCH


2


CH


3








A-365




OCHFCl




F




OCH


2


CH


3








A-366




OCF


3






F




OCH


2


CH


3








A-367




OC(═O)CH


3






F




OCH


2


CH


3








A-368




OC(═O)CH


2


CH


3






F




OCH


2


CH


3








A-369




Cl




Cl




OCH


2


CH


3








A-370




Br




Cl




OCH


2


CH


3








A-37l




I




Cl




OCH


2


CH


3








A-372




OH




Cl




OCH


2


CH


3








A-373




SH




Cl




OCH


2


CH


3








A-374




SCH


3






Cl




OCH


2


CH


3








A-375




NH


2






Cl




OCH


2


CH


3








A-376




OCH


3






Cl




OCH


2


CH


3








A-377




OCHF


2






Cl




OCH


2


CH


3








A-378




OCHFCl




Cl




OCH


2


CH


3








A-379




OCF


3






Cl




OCH


2


CH


3








A-380




OC(═O)CH


3






Cl




OCH


2


CH


3








A-381




OC(═O)CH


2


CH


3






Cl




OCH


2


CH


3








A-382




Br




Br




OCH


2


CH


3








A-383




I




Br




OCH


2


CH


3








A-384




OH




Br




OCH


2


CH


3








A-385




SH




Br




OCH


2


CH


3








A-386




SCH


3






Br




OCH


2


CH


3








A-387




NH


2






Br




OCH


2


CH


3








A-388




OCH


3






Br




OCH


2


CH


3








A-389




OCHF


2






Br




OCH


2


CH


3








A-390




OCHFCl




Br




OCH


2


CH


3








A-391




OCF


3






Br




OCH


2


CH


3








A-392




OC(═O)CH


3






Br




OCH


2


CH


3








A-393




OC(═O)CH


2


CH


3






Br




OCH


2


CH


3








A-394




I




I




OCH


2


CH


3








A-395




OH




I




OCH


2


CH


3








A-396




SH




I




OCH


2


CH


3








A-397




SCH


3






I




OCH


2


CH


3








A-398




NH


2






I




OCH


2


CH


3








A-399




OCH


3






I




OCH


2


CH


3








A-400




OCHF


2






I




0CH


2


CH


3








A-401




OCHFCl




I




OCH


2


CH


3








A-402




OCF


3






I




OCH


2


CH


3








A-403




OC(═O)CH


3






I




OCH


2


CH


3








A-404




OC(═O)CH


2


CH


3






I




OCH


2


CH


3








A-405




OH




OH




OCH


2


CH


3








A-406




SH




OH




OCH


2


CH


3








A-407




SCH


3






OH




OCH


2


CH


3








A-408




NH


2






OH




OCH


2


CH


3








A-409




OCH


3






OH




OCH


2


CH


3








A-410




OCHF


2






OH




OCH


2


CH


3








A-411




OCHFCl




OH




OCH


2


CH


3








A-412




OCF


3






OH




OCH


2


CH


3








A-413




OC(═O)CH


3






OH




OCH


2


CH


3








A-414




OC(═O)CH


2


CH


3






OH




OCH


2


CH


3








A-415




SH




SH




OCH


2


CH


3








A-416




SCH


3






SH




OCH


2


CH


3








A-417




NH


2






SH




OCH


2


CH


3








A-418




OCH


3






SH




OCH


2


CH


3








A-419




OCHF


2






SH




OCH


2


CH


3








A-420




OCHFCl




SH




OCH


2


CH


3








A-421




OCF


3






SH




OCH


2


CH


3








A-422




OC(═O)CH


3






SH




OCH


2


CH


3








A-423




OC(═O)CH


2


CH


3






SH




OCH


2


CH


3








A-424




SCH


3






SCH


3






OCH


2


CH


3








A-425




NH


2






SCH


3






OCH


2


CH


3








A-426




OCH


3






SCH


3






OCH


2


CH


3








A-427




OCHF


2






SCH


3






OCH


2


CH


3








A-428




OCHFCl




SCH


3






OCH


2


CH


3








A-429




OCF


3






SCH


3






OCH


2


CH


3








A-430




OC(═O)CH


3






SCH


3






OCH


2


CH


3








A-431




OC(═O)CH


2


CH


3






SCH


3






OCH


2


CH


3








A-432




NH


2






NH


2






OCH


2


CH


3








A-433




OCH


3






NH


2






OCH


2


CH


3








A-434




OCHF


2






NH


2






OCH


2


CH


3








A-435




OCHFCl




NH


2






OCH


2


CH


3








A-436




OCF


3






NH


2






OCH


2


CH


3








A-437




OC(═O)CH


3






NH


2






OCH


2


CH


3








A-438




OC(═O)CH


2


CH


3






NH


2






OCH


2


CH


3








A-439




OCH


3






OCH


3






OCH


2


CH


3








A-440




OCHF


2






OCH


3






OCH


2


CH


3








A-441




OCHFCl




OCH


3






OCH


2


CH


3








A-442




OCF


3






OCH


3






OCH


2


CH


3








A-443




OC(═O)CH


3






OCH


3






OCH


2


CH


3








A-444




OC(═O)CH


2


CH


3






OCH


3






OCH


2


CH


3








A-445




OCHF


2






OCHF


2






OCH


2


CH


3








A-446




OCHFCl




OCHF


2






OCH


2


CH


3








A-447




OCF


3






OCHF


2






OCH


2


CH


3








A-448




OC(═O)CH


3






OCHF


2






OCH


2


CH


3








A-449




OC(═O)CH


2


CH


3






OCHF


2






OCH


2


CH


3








A-450




OCHFCl




OCHFCl




OCH


2


CH


3








A-451




OCF


3






OCHFCl




OCH


2


CH


3








A-452




OC(═O)CH


3






OCHFCl




OCH


2


CH


3








A-453




OC(═O)CH


2


CH


3






OCHFCl




OCH


2


CH


3








A-454




OCF


3






OCF


3






OCH


2


CH


3








A-455




OC(═O)CH


3






OCF


3






OCH


2


CH


3








A-456




OC(═O)CH


2


CH


3






OCF


3






OCH


2


CH


3








A-457




OC(═O)CH


3






OC(═O)CH


3






OCH


2


CH


3








A-458




OC(═O) CH


2


CH


3






OC(═O)CH


3






OCH


2


CH


3








A-459




OC(═O)CH


2


CH


3






OC(═O)CH


2


CH


3






OCH


2


CH


3








A-460




CH


3






CH


3






OCH


2


CH


2


CH


3








A-461




CH


2


CH


3






CH


3






OCH


2


CH


2


CH


3








A-462




CF


3






CH


3






OCH


2


CH


2


CH


3








A-463




F




CH


3






OCH


2


CH


2


CH


3








A-464




Cl




CH


3






OCH


2


CH


2


CH


3








A-465




Br




CH


3






OCH


2


CH


2


CH


3








A-466




I




CH


3






OCH


2


CH


2


CH


3








A-467




OH




CH


3






OCH


2


CH


2


CH


3








A-468




SH




CH


3






OCH


2


CH


2


CH


3








A-469




SCH


3






CH


3






OCH


2


CH


2


CH


3








A-470




NH


2






CH


3






OCH


2


CH


2


CH


3








A-471




OCH


3






CH


3






OCH


2


CH


2


CH


3








A-472




OCHF


2






CH


3






OCH


2


CH


2


CH


3








A-473




OCHFCl




CH


3






OCH


2


CH


2


CH


3








A-474




OCF


3






CH


3






OCH


2


CH


2


CH


3








A-475




OC(═O)CH


3






CH


3






OCH


2


CH


2


CH


3








A-476




OC(═O)CH


2


CH


3






CH


3






OCH


2


CH


2


CH


3








A-477




CH


2


CH


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-478




CF


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-479




F




CH


2


CH


3






OCH


2


CH


2


CH


3








A-480




Cl




CH


2


CH


3






OCH


2


CH


2


CH


3








A-481




Br




CH


2


CH


3






OCH


2


CH


2


CH


3








A-482




I




CH


2


CH


3






OCH


2


CH


2


CH


3








A-483




OH




CH


2


CH


3






OCH


2


CH


2


CH


3








A-484




SH




CH


2


CH


3






OCH


2


CH


2


CH


3








A-485




SCH


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-486




NH


2






CH


2


CH


3






OCH


2


CH


2


CH


3








A-487




OCH


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-488




OCHF


2






CH


2


CH


3






OCH


2


CH


2


CH


3








A-489




OCHFCl




CH


2


CH


3






OCH


2


CH


2


CH


3








A-490




OCF


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-491




OC(═O)CH


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-492




OC(═O)CH


2


CH


3






CH


2


CH


3






OCH


2


CH


2


CH


3








A-493




CF


3






CF


3






OCH


2


CH


2


CH


3








A-494




F




CF


3






OCH


2


CH


2


CH


3








A-495




Cl




CF


3






OCH


2


CH


2


CH


3








A-496




Br




CF


3






OCH


2


CH


2


CH


3








A-497




I




CF


3






OCH


2


CH


2


CH


3








A-498




OH




CF


3






OCH


2


CH


2


CH


3








A-499




SH




CF


3






OCH


2


CH


2


CH


3








A-500




SCH


3






CF


3






OCH


2


CH


2


CH


3








A-501




NH


2






CF


3






OCH


2


CH


2


CH


3








A-502




OCH


3






CF


3






OCH


2


CH


2


CH


3








A-503




OCHF


2






CF


3






OCH


2


CH


2


CH


3








A-504




OCHFCl




CF


3






OCH


2


CH


2


CH


3








A-505




OCF


3






CF


3






OCH


2


CH


2


CH


3








A-506




OC(═O)CH


3






CF


3






OCH


2


CH


2


CH


3








A-507




OC(═O)CH


2


CH


3






CF


3






OCH


2


CH


2


CH


3








A-508




F




F




OCH


2


CH


2


CH


3








A-509




Cl




F




OCH


2


CH


2


CH


3








A-510




Br




F




OCH


2


CH


2


CH


3








A-511




I




F




OCH


2


CH


2


CH


3








A-512




OH




F




OCH


2


CH


2


CH


3








A-513




SH




F




OCH


2


CH


2


CH


3








A-514




SCH


3






F




OCH


2


CH


2


CH


3








A-515




NH


2






F




OCH


2


CH


2


CH


3








A-516




OCH


3






F




OCH


2


CH


2


CH


3








A-517




OCHF


2






F




OCH


2


CH


2


CH


3








A-518




OCHFCl




F




OCH


2


CH


2


CH


3








A-519




OCF


3






F




OCH


2


CH


2


CH


3








A-520




OC(═O)CH


3






F




OCH


2


CH


2


CH


3








A-521




OC(═O)CH


2


CH


3






F




OCH


2


CH


2


CH


3








A-522




Cl




Cl




OCH


2


CH


2


CH


3








A-523




Br




Cl




OCH


2


CH


2


CH


3








A-524




I




Cl




OCH


2


CH


2


CH


3








A-525




OH




Cl




OCH


2


CH


2


CH


3








A-526




SH




Cl




OCH


2


CH


2


CH


3








A-527




SCH


3






Cl




OCH


2


CH


2


CH


3








A-528




NH


2






Cl




OCH


2


CH


2


CH


3








A-529




OCH


3






Cl




OCH


2


CH


2


CH


3








A-530




OCHF


2






Cl




OCH


2


CH


2


CH


3








A-531




OCHFCl




Cl




OCH


2


CH


2


CH


3








A-532




OCF


3






Cl




OCH


2


CH


2


CH


3








A-533




OC(═O)CH


3






Cl




OCH


2


CH


2


CH


3








A-534




OC(═O)CH


2


CH


3






Cl




OCH


2


CH


2


CH


3








A-535




Br




Br




OCH


2


CH


2


CH


3








A-536




I




Br




OCH


2


CH


2


CH


3








A-537




OH




Br




OCH


2


CH


2


CH


3








A-538




SH




Br




OCH


2


CH


2


CH


3








A-539




SCH


3






Br




OCH


2


CH


2


CH


3








A-540




NH


2






Br




OCH


2


CH


2


CH


3








A-541




OCH


3






Br




OCH


2


CH


2


CH


3








A-542




OCHF


2






Br




OCH


2


CH


2


CH


3








A-543




OCHFCl




Br




OCH


2


CH


2


CH


3








A-544




OCF


3






Br




OCH


2


CH


2


CH


3








A-545




OC(═O)CH


3






Br




OCH


2


CH


2


CH


3








A-546




OC(═O)CH


2


CH


3






Br




OCH


2


CH


2


CH


3








A-547




I




I




OCH


2


CH


2


CH


3








A-548




OH




I




OCH


2


CH


2


CH


3








A-549




SH




I




OCH


2


CH


2


CH


3








A-550




SCH


3






I




OCH


2


CH


2


CH


3








A-551




NH


2






I




OCH


2


CH


2


CH


3








A-552




OCH


3






I




OCH


2


CH


2


CH


3








A-553




OCHF


2






I




OCH


2


CH


2


CH


3








A-554




OCHFCl




I




OCH


2


CH


2


CH


3








A-555




OCF


3






I




OCH


2


CH


2


CH


3








A-556




OC(═O)CH


3






I




OCH


2


CH


2


CH


3








A-557




OC(═O)CH


2


CH


3






I




OCH


2


CH


2


CH


3








A-558




OH




OH




OCH


2


CH


2


CH


2








A-559




SH




OH




OCH


2


CH


2


CH


3








A-560




SCH


3






OH




OCH


2


CH


2


CH


3








A-561




NH


2






OH




OCH


2


CH


2


CH


3








A-562




OCH


3






OH




OCH


2


CH


2


CH


3








A-563




OCHF


2






OH




OCH


2


CH


2


CH


3








A-564




OCHFCl




OH




OCH


2


CH


2


CH


3








A-565




OCF


3






OH




OCH


2


CH


2


CH


3








A-566




OC(═O)CH


3






OH




OCH


2


CH


2


CH


3








A-567




OC(═O)CH


2


CH


3






OH




OCH


2


CH


2


CH


3








A-568




SH




SH




OCH


2


CH


2


CH


3








A-569




SCH


3






SH




OCH


2


CH


2


CH


3








A-570




NH


2






SH




OCH


2


CH


2


CH


3








A-571




OCH


3






SH




OCH


2


CH


2


CH


3








A-572




OCHF


2






SH




OCH


2


CH


2


CH


3








A-573




OCHFCl




SH




OCH


2


CH


2


CH


3








A-574




OCF


3






SH




OCH


2


CH


2


CH


3








A-575




OC(═O)CH


3






SH




OCH


2


CH


2


CH


3








A-576




OC(═O)CH


2


CH


3






SH




OCH


2


CH


2


CH


3








A-577




SCH


3






SCH


3






OCH


2


CH


2


CH


3








A-578




NH


2






SCH


3






OCH


2


CH


2


CH


3








A-579




OCH


3






SCH


3






OCH


2


CH


2


CH


3








A-580




OCHF


2






SCH


3






OCH


2


CH


2


CH


3








A-581




OCHFCl




SCH


3






OCH


2


CH


2


CH


3








A-582




OCF


3






SCH


3






OCH


2


CH


2


CH


3








A-583




OC(═O)CH


3






SCH


3






OCH


2


CH


2


CH


3








A-584




OC(═O)CH


2


CH


3






SCH


3






OCH


2


CH


2


CH


3








A-585




NH


2






NH


2






OCH


2


CH


2


CH


3








A-586




OCH


3






NH


2






OCH


2


CH


2


CH


3








A-587




OCHF


2






NH


2






OCH


2


CH


2


CH


3








A-588




OCHFCl




NH


2






OCH


2


CH


2


CH


3








A-589




OCF


3






NH


2






OCH


2


CH


2


CH


3








A-590




OC(═O)CH


3






NH


2






OCH


2


CH


2


CH


3








A-591




OC(═O)CH


2


CH


3






NH


2






OCH


2


CH


2


CH


3








A-592




OCH


3






OCH


3






OCH


2


CH


2


CH


3








A-593




OCHF


2






OCH


3






OCH


2


CH


2


CH


3








A-594




OCHFCl




OCH


3






OCH


2


CH


2


CH


3








A-595




OCF


3






OCH


3






OCH


2


CH


2


CH


3








A-596




OC(═O)CH


3






OCH


3






OCH


2


CH


2


CH


3








A-597




OC(═O)CH


2


CH


3






OCH


3






OCH


2


CH


2


CH


3








A-598




OCHF


2






OCHF


2






OCH


2


CH


2


CH


3








A-599




OCHFCl




OCHF


2






OCH


2


CH


2


CH


3








A-600




OCF


3






OCHF


2






OCH


2


CH


2


CH


3








A-601




OC(═O)CH


3






OCHF


2






OCH


2


CH


2


CH


3








A-602




OC(═O)CH


2


CH


3






OCHF


2






OCH


2


CH


2


CH


3








A-603




OCHFCl




OCHFCl




OCH


2


CH


2


CH


3








A-604




OCF


3






OCHFCl




OCH


2


CH


2


CH


3








A-605




OC(═O)CH


3






OCHFCl




OCH


2


CH


2


CH


3








A-606




OC(═O)CH


2


CH


3






OCHFCl




OCH


2


CH


2


CH


3








A-607




OCF


3






OCF


3






OCH


2


CH


2


CH


3








A-608




OC(═O)CH


3






OCF


3






OCH


2


CH


2


CH


3








A-609




OC(═O)CH


2


CH


3






OCF


3






OCH


2


CH


2


CH


3








A-610




OC(═O)CH


3






OC(═O)CH


3






OCH


2


CH


2


CH


3








A-611




OC(═O)CH


2


CH


3






OC(═O)CH


3






OCH


2


CH


2


CH


3








A-612




OC(═O)CH


2


CH


3






OC(═O)CH


2


CH


3






OCH


2


CH


2


CH


3








A-613




CH


3






CH


3






OCH(CH


3


)


2








A-614




CH


2


CH


3






CH


3






OCH(CH


3


)


2








A-615




CF


3






CH


3






OCH(CH


3


)


2








A-616




F




CH


3






OCH(CH


3


)


2








A-617




Cl




CH


3






OCH(CH


3


)


2








A-618




Br




CH


3






OCH(CH


3


)


2








A-619




I




CH


3






OCH(CH


3


)


2








A-620




OH




CH


3






OCH(CH


3


)


2








A-621




SH




CH


3






OCH(CH


3


)


2








A-622




SCH


3






CH


3






OCH(CH


3


)


2








A-623




NH


2






CH


3






OCH(CH


3


)


2








A-624




OCH


3






CH


3






OCH(CH


3


)


2








A-625




OCHF


2






CH


3






OCH(CH


3


)


2








A-626




OCHFCl




CH


3






OCH(CH


3


)


2








A-627




OCF


3






CH


3






OCH(CH


3


)


2








A-628




OC(═O)CH


3






CH


3






OCH(CH


3


)


2








A-629




OC(═O)CH


2


CH


3






CH


3






OCH(CH


3


)


2








A-630




CH


2


CH


3






CH


2


CH


3






OCH(CH


3)




2








A-631




CF


3






CH


2


CH


3






OCH(CH


3


)


2








A-632




F




CH


2


CH


3






OCH(CH


3


)


2








A-633




Cl




CH


2


CH


3






OCH(CH


3


)


2








A-634




Br




CH


2


CH


3






OCH(CH


3


)


2








A-635




I




CH


2


CH


3






OCH(CH


3


)


2








A-636




OH




CH


2


CH


3






OCH(CH


3


)


2








A-637




SH




CH


2


CH


3






OCH(CH


3


)


2








A-638




SCH


3






CH


2


CH


3






OCH(CH


3


)


2








A-639




NH


2






CH


2


CH


3






OCH(CH


3


)


2








A-640




OCH


3






CH


2


CH


3






OCH(CH


3


)


2








A-641




OCHF


2






CH


2


CH


3






OCH(CH


3


)


2








A-642




OCHFCl




CH


2


CH


3






OCH(CH


3


)


2








A-643




OCF


3






CH


2


CH


3






OCH(CH


3


)


2








A-644




OC(═O)CH


3






CH


2


CH


3






OCH(CH


3


)


2








A-645




OC(═O)CH


2


CH


3






CH


2


CH


3






OCH(CH


3


)


2








A-646




CF


3






CF


3






OCH(CH


3


)


2








A-647




F




CF


3






OCH(CH


3


)


2








A-648




Cl




CF


3






OCH(CH


3


)


2








A-649




Br




CF


3






OCH(CH


3


)


2








A-650




I




CF


3






OCH(CH


3


)


2








A-651




OH




CF


3






OCH(CH


3


)


2








A-652




SH




CF


3






OCH(CH


3


)


2








A-653




SCH


3






CF


3






OCH(CH


3


)


2








A-654




NH


2






CF


3






OCH(CH


3


)


2








A-655




OCH


3






CF


3






OCH(CH


3


)


2








A-656




OCHF


2






CF


3






OCH(CH


3


)


2








A-657




OCHFCl




CF


3






OCH(CH


3


)


2








A-658




OCF


3






CF


3






OCH(CH


3


)


2








A-659




OC(═O)CH


3






CF


3






OCH(CH


3


)


2








A-660




OC(═O)CH


2


CH


3






CF


3






OCH(CH


3


)


2








A-661




F




F




OCH(CH


3


)


2








A-662




Cl




F




OCH(CH


3


)


2








A-663




Br




F




OCH(CH


3


)


2








A-664




I




F




OCH(CH


3


)


2








A-665




OH




F




OCH(CH


3


)


2








A-666




SH




F




OCH(CH


3


)


2








A-667




SCH


3






F




OCH(CH


3


)


2








A-668




NH


2






F




OCH(CH


3


)


2








A-659




OCH


3






F




OCH(CH


3


)


2








A-670




OCHF


2






F




OCH(CH


3


)


2








A-671




OCHFCl




F




OCH(CH


3


)


2








A-672




OCF


3






F




OCH(CH


3


)


2








A-673




OC(═O)CH


3






F




OCH(CH


3


)


2








A-674




OC(═O)CH


2


CH


3






F




OCH(CH


3


)


2








A-675




Cl




Cl




OCH(CH


3


)


2








A-676




Br




Cl




OCH(CH


3


)


2








A-677




I




Cl




OCH(CH


3


)


2








A-678




OH




Cl




OCH(CH


3


)


2








A-679




SH




Cl




OCH(CH


3


)


2








A-680




SCH


3






Cl




OCH(CH


3


)


2








A-681




NH


2






Cl




OCH(CH


3


)


2








A-682




OCH


3






Cl




OCH(CH


3


)


2








A-683




OCHF


2






Cl




OCH(CH


3


)


2








A-684




OCHFCl




Cl




OCH(CH


3


)


2








A-685




OCF


3






Cl




OCH(CH


3


)


2








A-686




OC(═O)CH


3






Cl




OCH(CH


3


)


2








A-687




OC(═O)CH


2


CH


3






Cl




OCH(CH


3


)


2








A-688




Br




Br




OCH(CH


3


)


2








A-689




I




Br




OCH(CH


3


)


2








A-690




OH




Br




OCH(CH


3


)


2








A-69l




SH




Br




OCH(CH


3


)


2








A-692




SCH


3






Br




OCH(CH


3


)


2








A-693




NH


2






Br




OCH(CH


3


)


2








A-694




OCH


3






Br




OCH(CH


3


)


2








A-695




OCHF


2






Br




OCH(CH


3


)


2








A-696




OCHFCl




Br




OCH(CH


3


)


2








A-697




OCF


3






Br




OCH(CH


3


)


2








A-698




OC(═O)CH


3






Br




OCH(CH


3


)


2








A-699




OC(═O)CH


2


CH


3






Br




OCH(CH


3


)


2








A-700




I




I




OCH(CH


3


)


2








A-701




OH




I




OCH(CH


3


)


2








A-702




SH




I




OCH(CH


3


)


2








A-703




SCH


3






I




OCH(CH


3


)


2








A-704




NH


2






I




OCH(CH


3


)


2








A-705




OCH


3






I




OCH(CH


3


)


2








A-706




OCHF


2






I




OCH(CH


3


)


2








A-707




OCHFCl




I




OCH(CH


3


)


2








A-708




OCF


3






I




OCH(CH


3


)


2








A-709




OC(═O)CH


3






I




OCH(CH


3


)


2








A-710




OC(═O)CH


2


CH


3






I




OCH(CH


3


)


2








A-711




OH




OH




OCH(CH


3


)


2








A-712




SH




OH




OCH(CH


3


)


2








A-713




SCH


3






OH




OCH(CH


3


)


2








A-714




NH


2






OH




OCH(CH


3


)


2








A-715




OCH


3






OH




OCH(CH


3


)


2








A-716




OCHF


2






OH




OCH(CH


3


)


2








A-717




OCHFCl




OH




OCH(CH


3


)


2








A-718




OCF


3






OH




OCH(CH


3


)


2








A-719




OC(═O)CH


3






OH




OCH(CH


3


)


2








A-720




OC(═O)CH


2


CH


3






OH




OCH(CH


3


)


2








A-721




SH




SH




OCH(CH


3


)


2








A-722




SCH


3






SH




OCH(CH


3


)


2








A-723




NH


2






SH




OCH(CH


3


)


2








A-724




OCH


3






SH




OCH(CH


3


)


2








A-725




OCHF


2






SH




OCH(CH


3


)


2








A-726




OCHFCl




SH




OCH(CH


3


)


2








A-727




OCF


3






SH




OCH(CH


3


)


2








A-728




OC(═O)CH


3






SH




OCH(CH


3


)


2








A-729




OC(═O)CH


2


CH


3






SH




OCH(CH


3


)


2








A-730




SCH


3






SCH


3






OCH(CH


3


)


2








A-731




NH


2






SCH


3






OCH(CH


3


)


2








A-732




OCH


3






SCH


3






OCH(CH


3


)


2








A-733




OCHF


2






SCH


3






OCH(CH


3


)


2








A-734




OCHFCl




SCH


3






OCH(CH


3


)


2








A-735




OCF


3






SCH


3






OCH(CH


3


)


2








A-736




OC(═O)CH


3






SCH


3






OCH(CH


3


)


2








A-737




OC(═O)CH


2


CH


3






SCH


3






OCH(CH


3


)


2








A-738




NH


2






NH


2






OCH(CH


3


)


2








A-739




OCH


3






NH


2






OCH(CH


3


)


2








A-740




OCHF


2






NH


2






OCH(CH


3


)


2








A-741




OCHFCl




NH


2






OCH(CH


3


)


2








A-742




OCF


3






NH


2






OCH(CH


3


)


2








A-743




OC(═O)CH


3






NH


2






OCH(CH


3


)


2








A-744




OC(═O)CH


2


CH


3






NH


2






OCH(CH


3


)


2








A-745




OCH


3






OCH


3






OCH(CH


3


)


2








A-746




OCHF


2






OCH


3






OCH(CH


3


)


2








A-747




OCHFCl




OCH


3






OCH(CH


3


)


2








A-748




OCF


3






OCH


3






OCH(CH


3


)


2








A-749




OC(═O)CH


3






OCH


3






OCH(CH


3


)


2








A-750




OC(═O)CH


2


CH


3






OCH


3






OCH(CH


3


)


2








A-751




OCHF


2






OCHF


2






OCH(CH


3


)


2








A-752




OCHFCl




OCHF


2






OCH(CH


3


)


2








A-753




OCF


3






OCHF


2






OCH(CH


3


)


2








A-754




OC(═O)CH


3






OCHF


2






OCH(CH


3


)


2








A-755




OC(═O)CH


2


CH


3






OCHF


2






OCH(CH


3


)


2








A-756




OCHFCl




OCHFCl




OCH(CH


3


)


2








A-757




OCF


3






OCHFCl




OCH(CH


3


)


2








A-758




OC(═O)CH


3






OCHFCl




OCH(CH


3


)


2








A-759




OC(═O)CH


2


CH


3






OCHFCl




OCH(CH


3


)


2








A-760




OCF


3






OCF


3






OCH(CH


3


)


2








A-761




OC(═O)CH


3






OCF


3






OCH(CH


3


)


2








A-762




OC(═O)CH


2


CH


3






OCF


3






OCH(CH


3


)


2








A-763




OC(═O)CH


3






OC(═O)CH


3






OCH(CH


3


)


2








A-764




OC(═O)CH


2


CH


3






OC(═O)CH


3






OCH(CH


3


)


2








A-765




OC(═O)CH


2


CH


3






OC(═O)CH


2


CH


3






OCH(CH


3


)


2








A-766




CH


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-767




CH


2


CH


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-768




CF


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-769




F




CH


3






OCH


2


CH


2


CH


2


CH


3








A-770




Cl




CH


3






OCH


2


CH


2


CH


2


CH


3








A-771




Br




CH


3






OCH


2


CH


2


CH


2


CH


3








A-772




I




CH


3






OCH


2


CH


2


CH


2


CH


3








A-773




OH




CH


3






OCH


2


CH


2


CH


2


CH


3








A-774




SH




CH


3






OCH


2


CH


2


CH


2


CH


3








A-775




SCH


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-776




NH


2






CH


3






OCH


2


CH


2


CH


2


CH


3








A-777




OCH


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-778




OCHF


2






CH


3






OCH


2


CH


2


CH


2


CH


3








A-779




OCHFCl




CH


3






OCH


2


CH


2


CH


2


CH


3








A-780




OCF


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-781




OC(═O)CH


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-782




OC(═O)CH


2


CH


3






CH


3






OCH


2


CH


2


CH


2


CH


3








A-783




CH


2


CH


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-784




CF


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-785




F




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-786




Cl




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-787




Br




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-788




I




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-789




OH




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-790




SH




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-791




8CH


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-792




NH


2






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-793




OCH


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-794




OCHF


2






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-795




OCHFCl




CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-796




OCF


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-797




OC(═O)CH


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-798




OC(═O)CH


2


CH


3






CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3








A-799




CF


3






CF


3






OCH


2


CH


2


CH


2


CH


3








A-800




F




CF


3






OCH


2


CH


2


CH


2


CH


3








A-801




Cl




CF


3






OCH


2


CH


2


CH


2


CH


3








A-802




Br




CF


3






OCH


2


CH


2


CH


2


CH


3








A-803




I




CF


3






OCH


2


CH


2


CH


2


CH


3








A-804




OH




CF


3






OCH


2


CH


2


CH


2


CH


3








A-805




SH




CF


3






OCH


2


CH


2


CH


2


CH


3








A-806




SCH


3






CF


3






OCH


2


CH


2


CH


2


CH


3








A-807




NH


2






CF


3






OCH


2


CH


2


CH


2


CH


3








A-808




OCH


3






CF


3






OCH


2


CH


2


CH


2


CH


3








A-809




OCHF


2






CF


3






OCH


2


CH


2


CH


2


CH


3








A-810




OCHFCl




CF


3






OCH


2


CH


2


CH


2


CH


3








A-811




OCF


3






CF


3






OCH


2


CH


2


CH


2


CH


3








A-812




OC(═O)CH


3






CF


3






OCH


2


CH


2


CH


2


CH


3








A-813




OC(═O)CH


2


CH


3






CF


3






OCH


2


CH


2


CH


2


CH


3








A-814




F




F




OCH


2


CH


2


CH


2


CH


3








A-815




Cl




F




OCH


2


CH


2


CH


2


CH


3








A-816




Br




F




OCH


2


CH


2


CH


2


CH


3








A-817




I




F




OCH


2


CH


2


CH


2


CH


3








A-818




OH




F




OCH


2


CH


2


CH


2


CH


3








A-819




SH




F




OCH


2


CH


2


CH


2


CH


3








A-820




SCH


3






F




OCH


2


CH


2


CH


2


CH


3








A-821




NH


2






F




OCH


2


CH


2


CH


2


CH


3








A-822




OCH


3






F




OCH


2


CH


2


CH


2


CH


3








A-823




OCHF


2






F




OCH


2


CH


2


CH


2


CH


3








A-824




OCHFCl




F




OCH


2


CH


2


CH


2


CH


3








A-825




OCF


3






F




OCH


2


CH


2


CH


2


CH


3








A-826




OC(═O)CH


3






F




OCH


2


CH


2


CH


2


CH


3








A-827




OC(═O)CH


2


CH


3






F




OCH


2


CH


2


CH


2


CH


3








A-828




Cl




Cl




OCH


2


CH


2


CH


2


CH


3








A-829




Br




Cl




OCH


2


CH


2


CH


2


CH


3








A-830




I




Cl




OCH


2


CH


2


CH


2


CH


3








A-831




OH




Cl




OCH


2


CH


2


CH


2


CH


3








A-832




SH




Cl




OCH


2


CH


2


CH


2


CH


3








A-833




SCH


3






Cl




OCH


2


CH


2


CH


2


CH


3








A-834




NH


2






Cl




OCH


2


CH


2


CH


2


CH


3








A-835




OCH


3






Cl




OCH


2


CH


2


CH


2


CH


3








A-836




OCHF


2






Cl




OCH


2


CH


2


CH


2


CH


3








A-837




OCHFCl




Cl




OCH


2


CH


2


CH


2


CH


3








A-838




OCF


3






Cl




OCH


2


CH


2


CH


2


CH


3








A-839




OC(═O)CH


3






Cl




OCH


2


CH


2


CH


2


CH


3








A-840




OC(═O)CH


2


CH


3






Cl




OCH


2


CH


2


CH


2


CH


3








A-841




Br




Br




OCH


2


CH


2


CH


2


CH


3








A-842




I




Br




OCH


2


CH


2


CH


2


CH


3








A-843




OH




Br




OCH


2


CH


2


CH


2


CH


3








A-844




SH




Br




OCH


2


CH


2


CH


2


CH


3








A-845




SCH


3






Br




OCH


2


CH


2


CH


2


CH


3








A-846




NH


2






Br




OCH


2


CH


2


CH


2


CH


3








A-847




OCH


3






Br




OCH


2


CH


2


CH


2


CH


3








A-848




OCHF


2






Br




OCH


2


CH


2


CH


2


CH


3








A-849




OCHFCl




Br




OCH


2


CH


2


CH


2


CH


3








A-850




OCF


3






Br




OCH


2


CH


2


CH


2


CH


3








A-851




OC(═O)CH


3






Br




OCH


2


CH


2


CH


2


CH


3








A-852




OC(═O)CH


2


CH


3






Br




OCH


2


CH


2


CH


2


CH


3








A-853




I




I




OCH


2


CH


2


CH


2


CH


3








A-854




OH




I




OCH


2


CH


2


CH


2


CH


3








A-855




SH




I




OCH


2


CH


2


CH


2


CH


3








A-856




SCH


3






I




OCH


2


CH


2


CH


2


CH


3








A-857




NH


2






I




OCH


2


CH


2


CH


2


CH


3








A-858




OCH


3






I




OCH


2


CH


2


CH


2


CH


3








A-859




OCHF


2






I




OCH


2


CH


2


CH


2


CH


3








A-860




OCHFCl




I




OCH


2


CH


2


CH


2


CH


3








A-861




OCF


3






I




OCH


2


CH


2


CH


2


CH


3








A-862




OC(═O)CH


3






I




OCH


2


CH


2


CH


2


CH


3








A-863




OC(═O)CH


2


CH


3






I




OCH


2


CH


2


CH


2


CH


3








A-864




OH




OH




OCH


2


CH


2


CH


2


CH


3








A-865




SH




OH




OCH


2


CH


2


CH


2


CH


3








A-866




SCH


3






OH




OCH


2


CH


2


CH


2


CH


3








A-867




NH


2






OH




OCH


2


CH


2


CH


2


CH


3








A-868




OCH


3






OH




OCH


2


CH


2


CH


2


CH


3








A-869




OCHF


2






OH




OCH


2


CH


2


CH


2


CH


3








A-870




OCHFCl




OH




OCH


2


CH


2


CH


2


CH


3








A-871




OCF


3






OH




OCH


2


CH


2


CH


2


CH


3








A-872




OC(═O)CH


3






OH




OCH


2


CH


2


CH


2


CH


3








A-873




OC(═O)CH


2


CH


3






OH




OCH


2


CH


2


CH


2


CH


3








A-874




SH




SH




OCH


2


CH


2


CH


2


CH


3








A-875




SCH


3






SH




OCH


2


CH


2


CH


2


CH


3








A-876




NH


2






SH




OCH


2


CH


2


CH


2


CH


3








A-877




OCH


3






SH




OCH


2


CH


2


CH


2


CH


3








A-878




OCHF


2






SH




OCH


2


CH


2


CH


2


CH


3








A-879




OCHFCl




SH




OCH


2


CH


2


CH


2


CH


3








A-880




OCF


3






SH




OCH


2


CH


2


CH


2


CH


3








A-881




OC(═O)CH


3






SH




OCH


2


CH


2


CH


2


CH


3








A-882




OC(═O)CH


2


CH


3






SH




OCH


2


CH


2


CH


2


CH


3








A-883




SCH


3






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-884




NH


2






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-885




OCH


3






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-886




OCHF


2






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-887




OCHFCl




SCH


3






OCH


2


CH


2


CH


2


CH


3








A-888




OCF


3






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-889




OC(═O)CH


3






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-890




OC(═O)CH


2


CH


3






SCH


3






OCH


2


CH


2


CH


2


CH


3








A-891




NH


2






NH


2






OCH


2


CH


2


CH


2


CH


3








A-892




OCH


3






NH


2






OCH


2


CH


2


CH


2


CH


3








A-893




OCHF


2






NH


2






OCH


2


CH


2


CH


2


CH


3








A-894




OCHFCl




NH


2






OCH


2


CH


2


CH


2


CH


3








A-895




OCF


3






NH


2






OCH


2


CH


2


CH


2


CH


3








A-896




OC(═O)CH


3






NH


2






OCH


2


CH


2


CH


2


CH


3








A-897




OC(═O)CH


2


CH


3






NH


2






OCH


2


CH


2


CH


2


CH


3








A-898




OCH


3






OCH


3






OCH


2


CH


2


CH


2


CH


3








A-899




OCHF


2






OCH


3






OCH


2


CH


2


CH


2


CH


3








A-900




OCHFCl




OCH


3






OCH


2


CH


2


CH


2


CH


3








A-901




OCF


3






OCH


3






OCH


2


CH


2


CH


2


CH


3








A-902




OC(═O)CH


3






OCH


3






OCH


2


CH


2


CH


2


CH


3








A-903




OC(═O)CH


2


CH


3






OCH


3






OCH


2


CH


2


CH


2


CH


3








A-904




OCHF


2






OCHF


2






OCH


2


CH


2


CH


2


CH


3








A-905




OCHFCl




OCHF


2






OCH


2


CH


2


CH


2


CH


3








A-906




OCF


3






OCHF


2






OCH


2


CH


2


CH


2


CH


3








A-907




OC(═O)CH


3






OCHF


2






OCH


2


CH


2


CH


2


CH


3








A-908




OC(═O)CH


2


CH


3






OCHF


2






OCH


2


CH


2


CH


2


CH


3








A-909




OCHFCl




OCHFCl




OCH


2


CH


2


CH


2


CH


3








A-910




OCF


3






OCHFCl




OCH


2


CH


2


CH


2


CH


3








A-911




OC(═O)CH


3






OCHFCl




OCH


2


CH


2


CH


2


CH


3








A-912




OC(═O)CH


2


CH


3






OCHFCl




OCH


2


CH


2


CH


2


CH


3








A-913




OCF


3






OCF


3






OCH


2


CH


2


CH


2


CH


3








A-914




OC(═O)CH


3






OCF


3






OCH


2


CH


2


CH


2


CH


3








A-915




OC(═O)CH


2


CH


3






OCF


3






OCH


2


CH


2


CH


2


CH


3








A-916




OC(═O)CH


3






OC(═O)CH


3






OCH


2


CH


2


CH


2


CH


3








A-917




OC(═O)CH


2


CH


3






OC(═O)CH


3






OCH


2


CH


2


CH


2


CH


3








A-918




OC(═O)CH


2


CH


3






OC(═O)CH


2


CH


3






OCH


2


CH


2


CH


2


CH


3
















The compounds of the formula I can be obtained by different routes. Compounds of the formula I in which X is oxygen are obtained, for example, by reacting aldehydes of the formula II,











where the variables R


1


, R


2


, R


3


and n are as defined for formula I and may be protected by a protective group Q which is removed after the reaction, with halobenzene derivatives of the formula III,











where the variables R


4


, R


5


and R


6


are as defined for formula I and A is halogen, and A is converted, in an intermediate step, into a group B, where B is a suitable metal or a suitable halometal group.




Suitable groups A are fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.




Suitable groups B are, for example, Li, Na, MgY (Y=halogen, in particular Br), Sn(R′)


2


(R′═CH


3


, CH


2


CH


3


), ZnR′, Cu(CN)ZnI [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 920-929 and the literature cited therein].




Preferred groups B are Na and MgY.




The reaction is carried out by converting the halogen group A into the group B in a manner known per se, followed by in situ reaction of the resulting benzene derivatives with aldehydes of the formula II [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 920-929 and the literature cited therein].




If B is Li, Na or MgY, the reaction is carried out, for example, at temperatures of from −20° C. to 150° C., preferably from 20° C. to 100° C., in an inert organic solvent, using at least equimolar amounts of Li, Na or Mg, based on the halobenzene III, and, if B is Li or Na, if appropriate under reaction-accelerating conditions, such as the addition of dibromoethane or iodine, or the use of ultrasound [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 920-929 and the literature cited therein].




The protective group Q is introduced into the aldehydes of the formula II by methods known from the literature [cf. T. W. Greene, Protective Groups in Organic Chemistry, J. Wiley & Sons, 1991, pp. 10-142].




Suitable protective groups for R


1


, R


2


, R


3


=hydroxyl, mercapto or amino are, for example, groups that can be removed under Lewis-acidic conditions, such as alkyl, in particular methyl.




In a preferred embodiment of the reaction, the variables R


1


, R


2


and R


3


are inert under the reaction conditions.




For preparing compounds I in which R


1


and R


3


contain carbonyl functionalities, the process described below, which uses the corresponding benzophenones IV as starting materials, is preferred.




Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitrites, such as acetonitrile and propionitrile, preferably ethers, very particularly preferably diethyl ether and tetrahydrofuran.




It is also possible to use mixtures of the solvents mentioned.




The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of compounds of the formula III, based on compounds of the formula II.




The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.




The starting materials of the formula II required for preparing the compounds I can be prepared, for example, by reducing the corresponding benzoic acids or benzoic esters with diisobutylaluminum hydride, described, for example, in EP-A 727 141, or they can be prepared in the manner known per se [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 501-521, pp 641-758, pp. 982-1161.].




The starting materials of the formula III required for preparing the compounds I can be prepared by methods known from the literature from gallic acid or its derivatives, or in a manner known per se [cf. J. March, Advanced Organic Chemistry, J. Wiley & Sons, New York, 1992, pp. 501-521, pp. 641-758, pp. 982-1161.].




Compounds of the formula I in which X is oxygen can also be prepared by reduction of the analogous benzophenone derivatives of the formula IV,











where the variables are as defined for formula I or denote a group which, after the reaction, can be converted into these radicals, using hydrides or by catalytic reduction with H


2


.




Suitable hydrides are, preferably, borohydrides and aluminum hydrides, such as NaBH


4


or LiAlH


4


[cf. M. Hudlicky, Reductions in Organic Chemistry, ACS Monograph 188, American Chemical Society, Washington D.C., 1996, p. 152 ff.; Tetrahedron Lett. 28 (4), pp. 4725-4728 (1987)], or elemental aluminum in ammonia [cf. Chem. Soc. Jpn. 63(1), pp. 290-292 (1990)].




The reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −78° C. to 0° C., in an inert organic solvent.




Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, preferably ethers, articularly preferably tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.




The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of reducing agent, based on compounds of the formula IV.




The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.




The reduction can also be carried out in the manner known per se using H


2


and catalysts based on transition metals. Suitable transition metals are palladium, platinum, rhodium and ruthenium.




This reaction is usually carried out at temperatures of from 0° C. to 150° C., preferably from 0° C. to 50° C., in an inert organic solvent [cf. Organotransition Metal Chemistry, Academic Press, New York, 1974, pp. 65-70 and the literature cited therein; JP-A 10273455].




Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, particularly preferably methanol, ethanol or isopropanol. It is also possible to use mixtures of the solvents mentioned.




In a preferred embodiment of the reduction with H


2


, chiral catalysts are employed, so that it is possible to obtain the (R) or (S) isomer of the benzhydryl alcohol I in a selective manner [cf. Org. Lett. 2(5), pp. 659-662, (2000)].




If the variables R


1


, R


2


or R


3


are groups which can be reduced under the reaction conditions, such as nitro or formyl, it may be necessary to re-establish these groups after the reaction by selective oxidation. It may also be advantageous to introduce such reducible groups only after the reduction of the benzophenones IV has taken place, by oxidizing appropriate groups (for example introducing a nitro group by oxidation of an amino group or introducing a formyl group by oxidation of a hydroxyl group).




Compounds I in which R


1


is formyl can be obtained, for example, by selective oxidation of corresponding compounds in which R


1


is hydroxymethyl, which may be formed in the reduction according to the invention from a formyl group [cf. M. Hudlicky, Oxidations in Organic Chemistry, ACS Monograph 186, American Chemical Society, Washington D.C., 1990, pp. 114-127].




It may also be advantageous to obtain compounds of the formula I in which R


1


is hydroxyl by reducing compounds of the formula IV in which R


1


is alkylcarbonyloxy. Here, R


1


and the keto group that bridges the phenyl groups are reduced simultaneously.




For compounds I in which the variables R


1


, R


2


, R


3


or R


4


are alkenyl or alkynyl, the process described above, which uses halobenzene derivatives III and aldehydes II as starting materials, is preferred.




The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.




The starting materials of the formula IV required for preparing the compounds I are known from the literature (for example from EP-A 727 141), or they can be prepared in accordance with the literature cited.




If individual compounds I are not accessible by the routes described above, they can be prepared by derivatization of other compounds I.











The benzhydryl thiols Ib can be obtained from the corresponding alcohols Ia under conditions known from the literature. The reaction is usually carried out at temperatures of from 0° C. to 180° C., preferably from 20° C. to 140° C., in an inert organic solvent [cf. Liebigs Ann. Chem., p. 177 (1989)].




Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, and dimethylene glycol, particularly preferably toluene and dimethylene glycol.




It is also possible to use mixtures of the solvents mentioned.




Suitable sulfurizing agents are, for example, phosphorus pentasulfide or Lawesson's reagent.




The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of sulfurizing agent, based on Ia.




Benzhydryl thiols Ib can also be obtained by reducing the corresponding thioketones V, which can be prepared from the benzophenones IV.











The reduction to give the benzhydryl thiols Ib can be carried out using, for example, borohydrides or aluminum hydrides [cf. Synth. Commun. 23 (9), pp. 1267-1271 (1993); Tetrahedron: Asymmetry 7(12), pp. 3553-3558 (1996); Can. J. Chem. 48, p. 3593, (1970)], or using elemental ytterbium in tetrahydrofuran [cf. Chem. Lett. 3, p. 611 (1994)].




The conversion of the benzophenones IV into the thioketones V is carried out analogously to the reaction of the benzhydryl alcohols Ia described above.




The compounds I are suitable as fungicides. They have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically and can be employed in crop protection as foliar- and soil-acting fungicides.




They are especially important for controlling a large number of fungi in a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grape vines, fruit species, ornamentals and vegetable species such as cucumbers, beans, tomatoes, potatoes and cucurbits, and also in the seeds of these plants.




Specifically, they are suitable for controlling the following plant diseases:




Alternaria species in vegetables and fruit,




Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentals and grape vines,




Cercospora arachidicola in groundnuts,




Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,




Erysiphe graminis (powdery mildew) in cereals,




Fusarium and Verticillium species in a variety of plants,




Helminthosporium species in cereals,




Mycosphaerella species in bananas and groundnuts,




Phytophthora infestans in potatoes and tomatoes,




Plasmopara viticola in grape vines,




Podosphaera leucotricha in apples,




Pseudocercosporella herpotrichoides in wheat and barley,




Pseudoperonospora species in hops and cucumbers,




Puccinia species in cereals,




Pyricularia oryzae in rice,




Rhizoctonia species in cotton, rice and lawns,




Septoria nodorum in wheat,




Uncinula necator in grape vines,




Ustilago species in cereals and sugar cane, and




Venturia species (scab) in apples and pears.




The compounds I are also suitable for controlling harmful fungi such as


Paecilomyces variotii


in the protection of materials (for example wood, paper, paint dispersions, fibers or tissues) and in the protection of stored products.




The compounds I are employed by treating the fungi or the plants, seeds, materials to be protected against fungal attack or the soil with a fungicidally effective amount of the active compounds. The application may be carried out before or after the infection of the materials, plants or seeds by the fungi.




The fungicidal compositions generally comprise from 0.1 to 95, preferably from 0.5 to 90, % by weight of active compound.




For use in crop protection, the application rates are, depending on the kind of effect desired, from 0.01 to 2.0 kg of active compound per ha.




The treatment of seeds generally requires active compound quantities of from 0.001 to 0.1 g, preferably from 0.01 to 0.05 g, per kilogram of seed.




For use in the protection of materials or stored products, the active compound application rate depends on the kind of application area and effect desired. Customary application rates in the protection of materials are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active compound per cubic meter of treated material.




The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the specific intended use; in any case, it should ensure fine and uniform distribution of the compound according to the invention.




The formulations are prepared in a known manner, e.g. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Suitable auxiliaries for this purpose are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. finely divided silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and dispersants such as lignosulfite waste liquors and methylcellulose.




Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and alkali metal salts and alkaline earth metal salts thereof, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.




Suitable for preparing directly sprayable solutions, emulsions, pastes or oil dispersions are petroleum fractions having medium to high boiling points, such as kerosene or diesel oil, furthermore coal-tar oils and oils of plant or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.




Powders, compositions for broadcasting and dusts can be prepared by mixing or jointly grinding the active substances with a solid carrier.




Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gel, silicas, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.




The formulations generally comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound. The active compounds are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to the NMR spectrum).




Examples of Formulations are:




I. 5 parts by weight of a compound according to the invention are thoroughly mixed with 95 parts by weight of finely divided kaolin. This affords a dusting composition comprising 5% by weight of the active compound.




II. 30 parts by weight of a compound according to the invention are thoroughly mixed with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This affords an active compound preparation having good adhesive properties (active compound content 23% by weight).




III. 10 parts by weight of a compound according to the invention are dissolved in a mixture comprising 90 parts by weight of xylene, 6 parts by weight of the addition product of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil (active compound content 9% by weight).




IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture comprising 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the addition product of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 5 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil (active compound content 16% by weight).




V. 80 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and ground in a hammer mill (active compound content 80% by weight).




VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone, affording a solution which is suitable for use in the form of very small drops (active compound content 90% by weight).




VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture comprising 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil. The solution is poured into 100 000 parts by weight of water and finely dispersed therein, affording an aqueous dispersion comprising 0.02% by weight of active compound.




VIII. 20 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and ground in a hammer mill. The mixture is finely dispersed in 20 000 parts by weight of water, affording a spray liquor comprising 0.1% by weight of active compound.




The active compounds can be applied as such, in the form of their formulations or in the application forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusting compositions, compositions for broadcasting, or granules, by spraying, atomizing, dusting, broadcasting or watering. The application forms depend entirely on the intended uses; in any case, they should ensure the finest dispersion possible of the active compounds according to the invention.




Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances can be homogenized in water as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers. However, concentrates comprising active compound, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil which are suitable for dilution with water can also be prepared.




The active compound concentrations in the ready-to-use preparations can be varied over a relatively wide range. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.




It is also possible to use the active compounds with good success in the ultra-low-volume method (ULV), it being possible to apply formulations comprising more than 95% by weight of active compound or even the active compound without additives.




Oils of various types, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if desired even immediately prior to application (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10:1.




The compositions according to the invention in the use form as fungicides may also be present in combination with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. In many cases, a mixture of the compounds I, or of the compositions comprising them, in the use form as fungicides with other fungicides results in a broader fungicidal spectrum of activity.




The following list of fungicides in combination with which the compounds according to the invention can be used is intended to illustrate the possible combinations, but not to impose any limitation:




a sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithio-carbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine-bisdithiocarbamate, tetramethylthiuram disulfides, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc (N,N′-propylenebisdithiocarbamate), N,N′-polypropylenebis-(thiocarbamoyl)disulfide;




nitro derivatives, such as dinitro-(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitroisophthalate;




heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo-[4,5-b]quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazole-carbamate, 2-methoxycarbonylaminobenzimidazole, 2-(furyl-(2))-benzimidazole, 2-(thiazolyl-(4))-benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloro-methylthiophthalimide,




N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfuric diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine 2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethyl-furan-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl-2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine 2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)-formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-tri-chloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethyl-morpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol, (2RS, 3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole, α-(2-chlorophenyl) -α-(4-chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,




strobilurins, such as methyl E-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate, methyl E-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl E-methoxyimino-[α-(2-phenoxyphenyl)]acetamide, methyl E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide, methyl E-2-{2-[(2-trifluoromethylpyrid-6-yl)oxymethyl]phenyl}-3-methoxyacrylate, methyl (E,E)-methoximino-{2-[1-(3-trifluoro-methylphenyl)ethylideneaminooxymethyl]phenyl}acetate, methyl N-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}phenyl)-N-methoxycarbamate,




anilinopyrimidines, such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N-[4-methyl-6-(l-propynyl)pyrimidin-2-yl]aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,




phenylpyrroles, such as 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,




cinnamamides, such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine,




and a variety of fungicides, such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl ester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenyl-acetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichloro-phenyl)-2,4-dioxo-1,3-oxazolidine, 3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropyl carbamoylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-meth-oximino]acetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)-benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis-(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.











SYNTHESIS EXAMPLES




The procedures given in the synthesis examples below were used to obtain further compounds I by appropriate modification of the starting materials. The compounds obtained in this manner are listed in the tables which follow, together with physical data.




Example 1




Preparation of 5-bromo-6,6′-dimethyl-2,2′, 3′, 4′-tetramethoxybenz-hydryl alcohol











2.36 g of 2,3,4-trimethoxy-6-methylbromobenzene and 0.32 g of agnesium turnings were initially charged in 5 ml of anhydrous tetrahydrofuran, 0.57 ml of 1,2-dibromoethane was added and the reaction mixture was heated at reflux temperature for about 40 min. After cooling to 30° C., 1.40 g of 5-bromo-2-methoxy-6-methylbenzaldehyde were added dropwise, and the solution was stirred for about two hours. Water/2N hydrochloric acid (1/1) was added, the aqueous phase was extracted with ethyl acetate, the organic phases were washed with water and dried and the solvent was distilled off, and the residue was then purified by column chromatography (mobile phase petroleum ether/ethyl acetate 85/5). 1.5 g of the title compound were isolated as a violet viscous oil.




Example 2




Preparation of 2,5-dichloro-6,6′-dimethyl-2′, 3′, 4′-trimethoxy-benzhydryl alcohol











Under protective gas conditions, at about −78° C., 1 ml of a 1-molar solution of LiAlH


4


in tetrahydrofuran was added dropwise to a solution of 0.37 g of 2,5-dichloro-6,6′-dimethyl-2′, 3′, 4′-trimethoxybenzophenone in 20 ml of anhydrous tetrahydrofuran, and the mixture was stirred for about 1 hour. At 20-25° C., sat. NaHCO


3


solution was added to the reaction solution, the solution was extracted with ethyl acetate and the organic phase was washed with water and sat. NaCl solution and dried, and the solvent was then distilled off. The residue gave, after purification by column chromatography (mobile phase: ethyl acetate/cyclohexane 1:9), 150 mg of the title compound as a yellow viscous oil.




Example 3




Preparation of 5-chloro-2-hydroxy-6,6′-dimethyl-2′, 3′, 4′-trimethoxybenzhydryl alcohol











At −20° C., under an atmosphere of protective gas, 3 mmol of a 1-molar solution of LiAlH


4


in tetrahydrofuran (THF) were added dropwise to a solution of 0.86 g of 5-chloro-2-hydroxy-6,6′-dimethyl-2′, 3′, 4′-trimethoxybenzophenone in 10 ml of anhydrous THF. The reaction mixture was warmed to room temperature and then admixed with ice water, acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined organic phases were washed with sat. NaCl solution, dried and purified by column chromatography (mobile phase: ethyl acetate/cyclohexane 3:7). This gave 0.46 mg of the title compound as a white solid of m.p. 140-142° C.












TABLE I



















































phys. data






No.




R


1






(R


2


)


n






R


3






R


4






R


5






R


6






(m.p.[° C.])









I-1




OCH


3






5-Br




CH


3






CH


3






OCH


3






OCH


3






oil






I-2




Cl




5-Cl




CH


3






CH


3






OCH


3






OCH


3






oil






I-3




OH




5-Cl




CH


3






CH


3






OCH


3






OCH


3






140-142














Examples of the Activity Against Harmful Fungi




The fungicidal activity of the compounds of the formula I was demonstrated by the following experiments:




The active compounds were formulated, separately or together, as a 10% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) and diluted with water to the desired concentration.




After conclusion of the tests, in each case the lowest concentration at which the compounds still caused 80-100% inhibition in comparison to untreated controls (activity threshold or minimum concentration) was determined.




Use Example 1




Activity Against Mildew of Wheat




Leaves of potted wheat seedlings cv. “Kanzler” were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution made of 10% of active compound, 63% of cyclohexanone and 27% of emulsifier. 24 hours after the spray coating had dried on, the leaves were dusted with spores of mildew of wheat (Erysiphe graminis forma specialis tritici). The test plants were then placed in a greenhouse at 20-24° C. and 60-90% rel. atmospheric humidity. After 7 days, the extent of the mildew development was determined visually as % infection of the total leaf area.




In this test, the plants which had been treated with 4 or 16 ppm of the active compounds I-1, I-2 and 1-3 showed an infection of in each case at most 30%, whereas the untreated plants were infected to 90%.



Claims
  • 1. A fungicidally active benzhydryl derivative of the formula I, where the index and the variables are as defined below:X is oxygen or sulfur; R1,R3 are halogen, cyano, nitro, hydroxyl, mercapto, amino, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkylcarbonyloxy, formyloxy, C1-C6-alkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, C1-C6-alkylamino, C1-C6-alkylcarbonyl or formyl, where the carbon atoms in the radicals mentioned may be partially or fully halogenated; R2 is halogen, cyano, nitro, hydroxyl, mercapto, amino, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-haloalkyl or C1-C6-haloalkoxy, where the groups R2 may be different if n=2; R4 is C1-C6-alkyl or C1-C6-haloalkyl; R5,R6 are hydroxyl, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C1-C6-haloalkoxy, or C2-C6-haloalkenyloxy, n is 0, 1, or 2.
  • 2. A compound of the formula I as claimed in claim 1 where X is oxygen.
  • 3. A compound of the formula I as claimed in claim 1 where the variables are as defined below:R1,R3 independently of one another are halogen, hydroxyl, amino, mercapto, nitro, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylcarbonyloxy, C1-C6-haloalkylcarbonyloxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylcarbonyl or C1-C6-haloalkylcarbonyl.
  • 4. A compound of the formula I as claimed in claim 1 whereR2 is halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy.
  • 5. A compound of the formula I as claimed in claim 1, where the variables are as defined below:R1,R3 are halogen, hydroxyl, amino, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy or C1-C6-alkylcarbonyl; R2 is halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy; R4 is methyl; R5,R6 are C1-C6-alkoxy; n is 0 or 1.
  • 6. A process for preparing compounds of the formula I as claimed in claim 1 in which X is oxygen, by reacting aldehydes of the formula II, where the variables R1 R2, R3 and n are as defined for formula I and may be protected by a protective group Q which is removed after the reaction, with halobenzene derivatives of the formula III, where the variables R4, R5 and R6 are as defined for formula I and A is halogen, and A is converted, in an intermediate step, into a group B, where B is a suitable metal or a suitable halometal group.
  • 7. A process for preparing compounds of the formula I as claimed in claim 1 in which X is oxygen, by reduction of benzophenone derivatives of the formula IV, where the variables are as defined for formula I or denote a group which, after the reaction, can be converted into these radicals using hydrides or by catalytic reduction with H2.
  • 8. A composition suitable for controlling phytopathogenic harmful fungi, which comprises a solid or liquid carrier and a compound of the formula I as claimed in claim 1.
  • 9. A method for controlling phytopathogenic fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack with an effective amount of a compound of the formula I as claimed in claim 1.
Priority Claims (1)
Number Date Country Kind
101 53 300 Oct 2001 DE
US Referenced Citations (2)
Number Name Date Kind
3340294 Richter et al. Sep 1967 A
3510517 Mayer et al. May 1970 A
Foreign Referenced Citations (6)
Number Date Country
0 015 756 Sep 1980 EP
0 461 079 Dec 1991 EP
0 727 141 Aug 1996 EP
0 801 048 Oct 1997 EP
1 218 623 Jan 1971 GB
09-235255 Sep 1997 JP