CA2291441A1 - Fluoroalkene carboxylic acid derivatives, method for producing said derivatives, and insecticidal agents containing the same - Google Patents
Fluoroalkene carboxylic acid derivatives, method for producing said derivatives, and insecticidal agents containing the same Download PDFInfo
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- CA2291441A1 CA2291441A1 CA002291441A CA2291441A CA2291441A1 CA 2291441 A1 CA2291441 A1 CA 2291441A1 CA 002291441 A CA002291441 A CA 002291441A CA 2291441 A CA2291441 A CA 2291441A CA 2291441 A1 CA2291441 A1 CA 2291441A1
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- C07—ORGANIC CHEMISTRY
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
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- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
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- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/195—Radicals derived from nitrogen analogues of carboxylic acids
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
The invention relates to fluoroalkene carboxylic acid derivatives of general formula (I), in which R1 and R2 are hydrogen (independently of each other), or alkyl, a group of formula (II), cycloalkyl, alkenyl or alkynyl, which are optionally substituted; R3 is hydrogen, fluorine, or methyl; m is 0, 1, 2, 3, 4 or 5; n is 0 or 1; X is oxygen or NR4 and R4 is hydrogen or C1-C6-alkyl or benzyl, which are optionally substituted. The invention also relates to a method for their production, to insecticides containing the new fluoroalkene carboxylic derivatives as active agent, and their use against harmful insects and acarians.
Description
-,~ 30022/A
FILE, 'HIS AMf~l~
T-~''I~R~~i~LA,TIA~
FLUOROALKENECARBOXYLIC ACID DERIVATIVES, PROCESSES FOR THEIR
PREPARATION AND INSECTICIDAL COMPOSITIONS COMPRISING THEM
The present invention relates to novel fluoroalkenecarboxylic acid derivatives, to processes for their preparation, to insecticidal compositions comprising the novel fluoroalkenecarboxylic acid derivatives as active compounds, and to use of the novel fluoroalkenecarboxylic acid derivatives for controlling harmful insects and acarides.
The present invention provides compounds of the formula o ~, F~C/c~c~ c~,cH c o,c"2;c x~N,c~~ ( l ) l~
m ~ n in which R, and R2 independently of one another are hydrogen; or alkyl, a group N~ , aryl, cycloalkyl, alkenyl or alkynyl, which are substituted or unsubstituted;
R3 is hydrogen, fluorine or methyl;
m is0,1,2,3,4or5;
n is0orl;
X is oxygen or NR4, and R4 is hydrogen or C,-Cs-alkyl or benryl, which are substituted or unsubstituted, and, if appropriate, its possible E/Z isomers, EJZ isomer mixtures and/or tautomers, in each case in free form or in salt form, with the proviso that a) R3 is not hydrogen or fluorine and m and n are not both 0 if X is oxygen and R, and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or heteroaryl; b) R3 is not hydrogen or fluorine and m and n are not both 0 if R4 is hydrogen and R, and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, aryl or heteroaryl; c) m is not 0, 1 or 2 and R4 is hydrogen, alkyl or haloalkyl if one of the radicals R, or R2 is 4-alkylsulphonyloxyphenyl, 4-haloalkylsulphonyloxyphenyl or 4-haloalkoxysulphonyloxyphenyl which may or may not carry further substituents, and the other radical is substituted or unsubstituted phenyl; and d) m is not 0, 1 or 2 and R4 is not hydrogen, alkyl or haloalkyl and n is not 0 if one of the radicals R, and R2 is 4-perhaloalkoxyphenyl which may or may not carry further substituents and the other is substituted or unsubstituted phenyl, a process for the preparation and the use of these compounds, IJZ isomers and tautomers;
pesticides whose active compound is selected from these compounds; FJZ isomers and tautomers; and a process for the preparation and the use of these compositions;
intermediates, and, if appropriate, their possible IJZ isomers, E2 isomer mixtures and/or tautomers, in freeform or in salt form, for preparing these compounds, if appropriate .
tautomers, in free form or in salt form, these intermediates; and a process for the preparation and the use of these intermediates and their tautomers.
Preferred groups of compounds of the formula (I) are - taking into account the provisos listed above - those in which R, and R2 independently of one another are hydrogen or alkyl, cycloalkyl, alkenyl or alkynyl, which are substituted or unsubstituted, R3 is hydrogen, fluorine or methyl, m is0,1,2,3,4or5;nis0orl, X is oxygen or NR4 , and R4 is hydrogen or unsubstituted or substituted C,-Cs-alkyl or benzyl;
in which R~ is hydrogen or unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl, R2 is hydrogen or unsubstituted or substituted aryl or heteroaryl, R3 is hydrogen, fluorine or methyl, m is0,1,2,3,4or5;nis0orl, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C~-CB-alkyl or benzyl;
and in which R, and R2 independently of one another are H or aryl, which are substituted or unsubstituted, R3 is hydrogen, fluorine or methyl, m is0,1,2,3,4or5;nis0orl, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C,-Cs-alkyl or benzyl.
The general terms used in the above definitions of the substituents of R,, R2, R3 and R4 are defined below as follows:
Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine and in particular chlorine.
Alkyl is a straight-chain or branched alkyl radical having 1 to 20 carbon atoms, which may be unsubstituted or mono- or polysubstituted. R, and R2 as alkyl groups are preferably straight-chain or branched alkyl radicals having 1 to 8 carbon atoms and particularly preferably alkyl radicals having 1 to 4 carbon atoms. Suitable substituents of R, and R2 as alkyl groups are hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, aryl, aryloxy, arylthio, arylsulphonyl, arylsulphonyloxy, arylcarbonyl or heteroaryl, where aryl or heteroaryl groups for their part may be mono- or polysubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio. The alkyl radicals which are present as alkyl groups in the substituents of R, and R2 preferably have 1 to 4 carbon atoms. These alkyl radicals are particularly preferably methyl or ethyl radicals. Examples of R, and R2 as alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2,2-dimethylpropyl, isopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 1,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl. Preferred substituents of R, and R2 as alkyl groups are hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, allrylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, where phenyl, phenoxy, phenylthio;
FILE, 'HIS AMf~l~
T-~''I~R~~i~LA,TIA~
FLUOROALKENECARBOXYLIC ACID DERIVATIVES, PROCESSES FOR THEIR
PREPARATION AND INSECTICIDAL COMPOSITIONS COMPRISING THEM
The present invention relates to novel fluoroalkenecarboxylic acid derivatives, to processes for their preparation, to insecticidal compositions comprising the novel fluoroalkenecarboxylic acid derivatives as active compounds, and to use of the novel fluoroalkenecarboxylic acid derivatives for controlling harmful insects and acarides.
The present invention provides compounds of the formula o ~, F~C/c~c~ c~,cH c o,c"2;c x~N,c~~ ( l ) l~
m ~ n in which R, and R2 independently of one another are hydrogen; or alkyl, a group N~ , aryl, cycloalkyl, alkenyl or alkynyl, which are substituted or unsubstituted;
R3 is hydrogen, fluorine or methyl;
m is0,1,2,3,4or5;
n is0orl;
X is oxygen or NR4, and R4 is hydrogen or C,-Cs-alkyl or benryl, which are substituted or unsubstituted, and, if appropriate, its possible E/Z isomers, EJZ isomer mixtures and/or tautomers, in each case in free form or in salt form, with the proviso that a) R3 is not hydrogen or fluorine and m and n are not both 0 if X is oxygen and R, and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or heteroaryl; b) R3 is not hydrogen or fluorine and m and n are not both 0 if R4 is hydrogen and R, and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, aryl or heteroaryl; c) m is not 0, 1 or 2 and R4 is hydrogen, alkyl or haloalkyl if one of the radicals R, or R2 is 4-alkylsulphonyloxyphenyl, 4-haloalkylsulphonyloxyphenyl or 4-haloalkoxysulphonyloxyphenyl which may or may not carry further substituents, and the other radical is substituted or unsubstituted phenyl; and d) m is not 0, 1 or 2 and R4 is not hydrogen, alkyl or haloalkyl and n is not 0 if one of the radicals R, and R2 is 4-perhaloalkoxyphenyl which may or may not carry further substituents and the other is substituted or unsubstituted phenyl, a process for the preparation and the use of these compounds, IJZ isomers and tautomers;
pesticides whose active compound is selected from these compounds; FJZ isomers and tautomers; and a process for the preparation and the use of these compositions;
intermediates, and, if appropriate, their possible IJZ isomers, E2 isomer mixtures and/or tautomers, in freeform or in salt form, for preparing these compounds, if appropriate .
tautomers, in free form or in salt form, these intermediates; and a process for the preparation and the use of these intermediates and their tautomers.
Preferred groups of compounds of the formula (I) are - taking into account the provisos listed above - those in which R, and R2 independently of one another are hydrogen or alkyl, cycloalkyl, alkenyl or alkynyl, which are substituted or unsubstituted, R3 is hydrogen, fluorine or methyl, m is0,1,2,3,4or5;nis0orl, X is oxygen or NR4 , and R4 is hydrogen or unsubstituted or substituted C,-Cs-alkyl or benzyl;
in which R~ is hydrogen or unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl, R2 is hydrogen or unsubstituted or substituted aryl or heteroaryl, R3 is hydrogen, fluorine or methyl, m is0,1,2,3,4or5;nis0orl, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C~-CB-alkyl or benzyl;
and in which R, and R2 independently of one another are H or aryl, which are substituted or unsubstituted, R3 is hydrogen, fluorine or methyl, m is0,1,2,3,4or5;nis0orl, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C,-Cs-alkyl or benzyl.
The general terms used in the above definitions of the substituents of R,, R2, R3 and R4 are defined below as follows:
Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine and in particular chlorine.
Alkyl is a straight-chain or branched alkyl radical having 1 to 20 carbon atoms, which may be unsubstituted or mono- or polysubstituted. R, and R2 as alkyl groups are preferably straight-chain or branched alkyl radicals having 1 to 8 carbon atoms and particularly preferably alkyl radicals having 1 to 4 carbon atoms. Suitable substituents of R, and R2 as alkyl groups are hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, aryl, aryloxy, arylthio, arylsulphonyl, arylsulphonyloxy, arylcarbonyl or heteroaryl, where aryl or heteroaryl groups for their part may be mono- or polysubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio. The alkyl radicals which are present as alkyl groups in the substituents of R, and R2 preferably have 1 to 4 carbon atoms. These alkyl radicals are particularly preferably methyl or ethyl radicals. Examples of R, and R2 as alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2,2-dimethylpropyl, isopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 1,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl. Preferred substituents of R, and R2 as alkyl groups are hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, allrylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, where phenyl, phenoxy, phenylthio;
phenylsulphonyl, phenylsulphonyloxy, benzoyl and pyridyl may be substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro or cyano.
Mono- or polysubstitution of a radical R, or R2 is in particular mono- to tetrasubstitution, .
preferably mono- to disubstitution and particularly preferably monosubstitution, where R, and R2 in particular as lower alkyl radicals, such as methyl or ethyl, may be perhalogenated, in particular perfluorinated, in the case of a substitution by halogen. In the case of polysubstitution, the respective substituents may be identical or different.
Aryl is phenyl or naphthyl, preferably phenyl.
Heteroaryl means aromatic radicals having 5 or 6 ring members and 1 or 2 heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur. Examples of heteroaryl radicals are pyrrolyl, furyl, thienyl, imidazolyl, pyrrazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, where the radicals R~ and R2 as heteroaryl radicals are in each case attached by a carbon atom and, if appropriate, a benzene ring may be fused to the radicals. Preferred heteroaryl radicals are pyridyl, pyrimidinyl, quinolyl, furyl and thienyl.
Aryl radicals and heteroaryl radicals may be unsubstituted or mono- or polysubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphonyloxy, haloalkylsulphonyloxy, haloalkoxysulphonyloxy, vitro, cyano, benzoyl, phenyl, phenoxy, phenylthio, trialkylsilyl, benzyloxy, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, anilino; cycloalkylalkoxy or halocycloalkylalkoxy, heteroaryl or heteroaryloxy, where benzoyl, phenyl, phenoxy, phenylthio, benzyloxy, anilino, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or polysubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, halophenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy. The alkyl groups which are present as or in the substituents of R, and R2 as aryl or heteroaryl groups preferably have 1 to 4 carbon atoms. These alkyl groups are particularly preferably methyl or ethyl groups.
Alkenyl means straight-chain or branched alkenyl radicals having 3 to 20, preferably 3 to 8, carbon atoms and particularly preferably alkenyl radicals having 3 to 5 carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen. Alkenyl preferably refers to those alkenyl radicals which are attached via a saturated carbon atom, i.e.
alkenyl radicals having an intermittent or terminal double bond. Examples of alkenyl radicals are allyl, methallyl, but-2-en-1-yl, but-3-en -1-yl, pent-2-en-1-yl, pent-3-en-1-yl, pent-4-en-1-yl, 2-methylbut-2-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1 yl, hept-2-en-1-yl, oct-2-en-1-yl and dec-2-en-1-yl. Particularly preferred alkenyl radicals are allyl and methallyl.
Alkynyl means straight-chain or branched alkynyl radicals having 3 to 20, preferably 3 to 8 carbon atoms and particularly preferably alkynyl radicals having 3 to 5 carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen. Alkynyl preferably refers to those alkynyl radicals which are attached via a saturated carbon atom, i.e.
alkynyl radicals having an intermittent or terminal triple bond. Examples of alkynyl radicals are propargyl, but-2-yn-1-yl, but-3-yn-1-yl, pent-2-,- 3- or -4-yn-1-yl, hex-2-, -3-,- 4- or 5-yn-1-yl, hept-2-, -3-, -4--5- or -6-yn-1-yl and oct-2-,-3-,-4-,-5-,-6- or -7-yn-1-yl. A particularly preferred alkynyl radical is the propargyl radical.
Cycloalkyl means cycloalkyl radicals having 3 to 7 carbon atoms which may be unsubstituted or mono- or polysubstituted by halogen, alkyl or haloalkyl, where the alkyl and haloalkyl radicals preferably contain 1 to 4 carbon atoms and particularly preferably 1 to 2 carbon atoms. Examples of cycloalkyl radicals are cyclopropyl, 2-melthylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3,4-dimethylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 4-methylcyclohexyl, 3,4-dimethylcyclohexyl, 2,4-dimethylcyclohexyl and cycloheptyl.
The meaning illustrated above of the general terms used in the definition applies, unless expressly stated otherwise, to the entire present description.
The present invention relates in particular to compounds of the formula (I) in which, taking into account the provisos listed above, R, and R2 independently of one another are hydrogen; C,-C~-alkyl, which may be straight-chain or branched and and may be mono- to tetrasubstituted by hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulphonyl, naphthylsulphonyl, phenylsulphonyloxy, naphthylsulphonyloxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where the aryl or heteroaryl groups mentioned for their part may be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio;
C3-C~-alkenyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
-s-C3-Coo-alkynyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
C3-C,-cycloalkyl, which may be mono- or tetra-substituted by halogen, alkyl or haloalkyl;
Phenyl or naphthyl, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylsulphonyloxy, haloalkylsulphonyloxy, haloalkoxysulphonyloxy, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenyfthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxyradicals as substituents may for their part be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy;
heteroaryl having 5 bis 6 ring members and 1 to 2 heteroatoms N, O or S, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, vitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl;
benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono-or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy, halocycloalkylalkoxy;
R3 is hydrogen, fluorine or methyl;
m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1; and X is oxygen or NR4, where R4 is hydrogen, C,-C4-alkyl which may be mono- or polysubstituted by halogen, C,-C4-alkoxy or di-C,-C4-alkylamino, or is benzyl which may be mono- or polysubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-C4-alkoxy; vitro or cyano.
Preference is given to compounds of the formula (I) in which, taking into account the provisos listed above, R, and R2 independently of one another are hydrogen, C,-CB-alkyl, which may be straight-chain or branched and may be mono-or disubstituted by hydroxyl, halogen, C,-C4-alkoxy, halo-C,-C4-alkoxy, C,-C4-alkoxyalkoxy, C,-Ca-alkythio, halo-C,-C4-alkylthio, C~-C4-alkylsulphinyl, C,-C4-alkylsulphonyl, C,-C4-alkylsulfonyloxy, C,-C4-alkylcarbonyl, di-C,-Ca-alkylamino, pyrrolidino, piperidino, morpholino, C,-C4-alkoxycarbonyl, C,-C4-alkylcarbonyloxy, C3-Cs-cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulphonyl, naphthylsulphonyl, phenyl-sulphonyloxy, naphthylsulphonyloxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy having to 6 ring members and 1 to 2 hetero atoms N, O or S, where the aryl or heteroaryl groups mentioned for their part may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-Ca-alkoxy; halo-C,-C4-alkoxy, C,-C4-alkylthio, vitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio;
C3-C$-alkenyl which may be straight-chain or branched and may be mono- or disubstituted by halogen;
C3-C8-alkynyl which may be straight-chain or branched and may be mono- or disubstituted by halogen;
C3-C,-cycloalkyl which may be mono- or disubstituted by halogen, C,-C4-alkyl or halo-Ci-C4-alkyl;
phenyl or naphthyl which may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-Ca-alkoxy, halo-C,-C4-alkoxy, C3-Cs-cycloalkyl-C,-C4-alkoxy, halo-C,-C4-cycloalkyl-C~-Ca-alkoxy, C,-C4-alkylthio, halo-C,-C4-alkylthio, C,-C4-alkylsulphonyloxy, halo-C,-C4-alkylsulphonyloxy, halo-C,-C4-alkoxysulphonyloxy, C,-C4-alkylamino, di-C,-C4-alkylamino, pyrrolidino, piperidino, morpholino, vitro, cyano, tri-C,-CQ-alkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino; naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-C4-alkoxy, halo-C~-C4-alkoxy, C,-C4-alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, C3-Cs-cycloalkyl-C,-C4-alkoxy or halo-C3-Ce-cycloalkyl-C,-C4-alkoxy, heteroaryl having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S which may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, Ci-C4-alkoxy, halo-C,-C4-alkoxy, C3-Cs-cycloalkyl-C,-Ca-alkoxy, halo-C3-Cg-cycloalkyl-C,-C4-alkoxy, C,-Ca-alkylthio, halo-C,-Ca-alkylthio, C,-C4-alkylamino, di-C,-C4-alkylamino, pyrrolidino, piperidino, -8.
morpholino, nitro, cyano, tri-C~-C<-alkylsilyl, phenyl, phenoxy, phenylthio;
benzoyl, benzyloxy, anilino, naphthyl; heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino; naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C~-C4-alkyl, C,-Ca-alkoxy, halo-C,-C4-alkoxy, C,-CQ-alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, C3-Cg-cycloalkyl-C,-C4-alkoxy or halo-C3-CB-cycloalkyl-C,-Ca-alkoxy, R3 is hydrogen, fluorine or methyl, m is 0, 1, 2, 3 or 4, n is 0 or 1 and X is oxygen or NR4, where R4 is hydrogen, C,-CQ-alkyl which may be mono- to disubstituted by halogen C,-alkoxy or di-C,-Ca-alkylamino, or is benzyl which may be mono- to disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-C4-alkoxy, vitro or cyano.
The preferred meanings defined above of the radicals R,, R2, R3 and R4 apply analogously to the subgroups of compounds of the formula (I) defined above.
Among the compounds of the formula (I), preference is furthermore given to those in which .
a) R3 is hydrogen;
b) m is 0, 1, 2, 3 or 4, particularly preferably 1 or 4;
c) n is 0;
d) R4 is hydrogen;
e) R, and R2 are as defined above, R3 is hydrogen, m is 0,1, 2, 3 or 4, n is 0 or 1, and X is oxygen or NH;
f) R, and R2 are as defined above, R3 is hydrogen, m is 1 or 4, n is 0, and X
is oxygen or NH;
Mono- or polysubstitution of a radical R, or R2 is in particular mono- to tetrasubstitution, .
preferably mono- to disubstitution and particularly preferably monosubstitution, where R, and R2 in particular as lower alkyl radicals, such as methyl or ethyl, may be perhalogenated, in particular perfluorinated, in the case of a substitution by halogen. In the case of polysubstitution, the respective substituents may be identical or different.
Aryl is phenyl or naphthyl, preferably phenyl.
Heteroaryl means aromatic radicals having 5 or 6 ring members and 1 or 2 heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur. Examples of heteroaryl radicals are pyrrolyl, furyl, thienyl, imidazolyl, pyrrazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, where the radicals R~ and R2 as heteroaryl radicals are in each case attached by a carbon atom and, if appropriate, a benzene ring may be fused to the radicals. Preferred heteroaryl radicals are pyridyl, pyrimidinyl, quinolyl, furyl and thienyl.
Aryl radicals and heteroaryl radicals may be unsubstituted or mono- or polysubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphonyloxy, haloalkylsulphonyloxy, haloalkoxysulphonyloxy, vitro, cyano, benzoyl, phenyl, phenoxy, phenylthio, trialkylsilyl, benzyloxy, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, anilino; cycloalkylalkoxy or halocycloalkylalkoxy, heteroaryl or heteroaryloxy, where benzoyl, phenyl, phenoxy, phenylthio, benzyloxy, anilino, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or polysubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, halophenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy. The alkyl groups which are present as or in the substituents of R, and R2 as aryl or heteroaryl groups preferably have 1 to 4 carbon atoms. These alkyl groups are particularly preferably methyl or ethyl groups.
Alkenyl means straight-chain or branched alkenyl radicals having 3 to 20, preferably 3 to 8, carbon atoms and particularly preferably alkenyl radicals having 3 to 5 carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen. Alkenyl preferably refers to those alkenyl radicals which are attached via a saturated carbon atom, i.e.
alkenyl radicals having an intermittent or terminal double bond. Examples of alkenyl radicals are allyl, methallyl, but-2-en-1-yl, but-3-en -1-yl, pent-2-en-1-yl, pent-3-en-1-yl, pent-4-en-1-yl, 2-methylbut-2-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1 yl, hept-2-en-1-yl, oct-2-en-1-yl and dec-2-en-1-yl. Particularly preferred alkenyl radicals are allyl and methallyl.
Alkynyl means straight-chain or branched alkynyl radicals having 3 to 20, preferably 3 to 8 carbon atoms and particularly preferably alkynyl radicals having 3 to 5 carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen. Alkynyl preferably refers to those alkynyl radicals which are attached via a saturated carbon atom, i.e.
alkynyl radicals having an intermittent or terminal triple bond. Examples of alkynyl radicals are propargyl, but-2-yn-1-yl, but-3-yn-1-yl, pent-2-,- 3- or -4-yn-1-yl, hex-2-, -3-,- 4- or 5-yn-1-yl, hept-2-, -3-, -4--5- or -6-yn-1-yl and oct-2-,-3-,-4-,-5-,-6- or -7-yn-1-yl. A particularly preferred alkynyl radical is the propargyl radical.
Cycloalkyl means cycloalkyl radicals having 3 to 7 carbon atoms which may be unsubstituted or mono- or polysubstituted by halogen, alkyl or haloalkyl, where the alkyl and haloalkyl radicals preferably contain 1 to 4 carbon atoms and particularly preferably 1 to 2 carbon atoms. Examples of cycloalkyl radicals are cyclopropyl, 2-melthylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3,4-dimethylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 4-methylcyclohexyl, 3,4-dimethylcyclohexyl, 2,4-dimethylcyclohexyl and cycloheptyl.
The meaning illustrated above of the general terms used in the definition applies, unless expressly stated otherwise, to the entire present description.
The present invention relates in particular to compounds of the formula (I) in which, taking into account the provisos listed above, R, and R2 independently of one another are hydrogen; C,-C~-alkyl, which may be straight-chain or branched and and may be mono- to tetrasubstituted by hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulphonyl, naphthylsulphonyl, phenylsulphonyloxy, naphthylsulphonyloxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where the aryl or heteroaryl groups mentioned for their part may be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio;
C3-C~-alkenyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
-s-C3-Coo-alkynyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
C3-C,-cycloalkyl, which may be mono- or tetra-substituted by halogen, alkyl or haloalkyl;
Phenyl or naphthyl, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylsulphonyloxy, haloalkylsulphonyloxy, haloalkoxysulphonyloxy, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenyfthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxyradicals as substituents may for their part be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy;
heteroaryl having 5 bis 6 ring members and 1 to 2 heteroatoms N, O or S, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, vitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl;
benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono-or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy, halocycloalkylalkoxy;
R3 is hydrogen, fluorine or methyl;
m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1; and X is oxygen or NR4, where R4 is hydrogen, C,-C4-alkyl which may be mono- or polysubstituted by halogen, C,-C4-alkoxy or di-C,-C4-alkylamino, or is benzyl which may be mono- or polysubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-C4-alkoxy; vitro or cyano.
Preference is given to compounds of the formula (I) in which, taking into account the provisos listed above, R, and R2 independently of one another are hydrogen, C,-CB-alkyl, which may be straight-chain or branched and may be mono-or disubstituted by hydroxyl, halogen, C,-C4-alkoxy, halo-C,-C4-alkoxy, C,-C4-alkoxyalkoxy, C,-Ca-alkythio, halo-C,-C4-alkylthio, C~-C4-alkylsulphinyl, C,-C4-alkylsulphonyl, C,-C4-alkylsulfonyloxy, C,-C4-alkylcarbonyl, di-C,-Ca-alkylamino, pyrrolidino, piperidino, morpholino, C,-C4-alkoxycarbonyl, C,-C4-alkylcarbonyloxy, C3-Cs-cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulphonyl, naphthylsulphonyl, phenyl-sulphonyloxy, naphthylsulphonyloxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy having to 6 ring members and 1 to 2 hetero atoms N, O or S, where the aryl or heteroaryl groups mentioned for their part may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-Ca-alkoxy; halo-C,-C4-alkoxy, C,-C4-alkylthio, vitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio;
C3-C$-alkenyl which may be straight-chain or branched and may be mono- or disubstituted by halogen;
C3-C8-alkynyl which may be straight-chain or branched and may be mono- or disubstituted by halogen;
C3-C,-cycloalkyl which may be mono- or disubstituted by halogen, C,-C4-alkyl or halo-Ci-C4-alkyl;
phenyl or naphthyl which may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-Ca-alkoxy, halo-C,-C4-alkoxy, C3-Cs-cycloalkyl-C,-C4-alkoxy, halo-C,-C4-cycloalkyl-C~-Ca-alkoxy, C,-C4-alkylthio, halo-C,-C4-alkylthio, C,-C4-alkylsulphonyloxy, halo-C,-C4-alkylsulphonyloxy, halo-C,-C4-alkoxysulphonyloxy, C,-C4-alkylamino, di-C,-C4-alkylamino, pyrrolidino, piperidino, morpholino, vitro, cyano, tri-C,-CQ-alkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino; naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-C4-alkoxy, halo-C~-C4-alkoxy, C,-C4-alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, C3-Cs-cycloalkyl-C,-C4-alkoxy or halo-C3-Ce-cycloalkyl-C,-C4-alkoxy, heteroaryl having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S which may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, Ci-C4-alkoxy, halo-C,-C4-alkoxy, C3-Cs-cycloalkyl-C,-Ca-alkoxy, halo-C3-Cg-cycloalkyl-C,-C4-alkoxy, C,-Ca-alkylthio, halo-C,-Ca-alkylthio, C,-C4-alkylamino, di-C,-C4-alkylamino, pyrrolidino, piperidino, -8.
morpholino, nitro, cyano, tri-C~-C<-alkylsilyl, phenyl, phenoxy, phenylthio;
benzoyl, benzyloxy, anilino, naphthyl; heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino; naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or disubstituted by halogen, C,-C4-alkyl, halo-C~-C4-alkyl, C,-Ca-alkoxy, halo-C,-C4-alkoxy, C,-CQ-alkylthio, vitro, cyano, phenoxy, phenylthio, halophenylthio, C3-Cg-cycloalkyl-C,-C4-alkoxy or halo-C3-CB-cycloalkyl-C,-Ca-alkoxy, R3 is hydrogen, fluorine or methyl, m is 0, 1, 2, 3 or 4, n is 0 or 1 and X is oxygen or NR4, where R4 is hydrogen, C,-CQ-alkyl which may be mono- to disubstituted by halogen C,-alkoxy or di-C,-Ca-alkylamino, or is benzyl which may be mono- to disubstituted by halogen, C,-C4-alkyl, halo-C,-C4-alkyl, C,-C4-alkoxy, vitro or cyano.
The preferred meanings defined above of the radicals R,, R2, R3 and R4 apply analogously to the subgroups of compounds of the formula (I) defined above.
Among the compounds of the formula (I), preference is furthermore given to those in which .
a) R3 is hydrogen;
b) m is 0, 1, 2, 3 or 4, particularly preferably 1 or 4;
c) n is 0;
d) R4 is hydrogen;
e) R, and R2 are as defined above, R3 is hydrogen, m is 0,1, 2, 3 or 4, n is 0 or 1, and X is oxygen or NH;
f) R, and R2 are as defined above, R3 is hydrogen, m is 1 or 4, n is 0, and X
is oxygen or NH;
p1o-O
g) R, is as defined above, R3 is hydrogen and R2 is a group N- in which alk is methyl or ethyl and the phenyl ring is substituted or unsubstituted.
Particularly preferred individual compounds are compounds of the formula (I) in which R3 is hydrogen and a) R, is hydrogen, R2 is hydrogen, X is oxygen, m is 1 and n is 0;
b) R, is methyl, R2 is methyl, X is oxygen, m is 1 and n is 0; ' c) R, is methyl, R2 is phenyl, X is oxygen, m is 1 and n is 0;
d) R, is methyl, R2 is 4-trifluoromethylphenyl, X is oxygen, m is 1 and n is 0;
e) R, is methyl, R2 is 4-nitrophenyl, X is oxygen, m is 1 and n is 0;
f) R1 is methyl, R2 is 4-tert-butylphenyl, X is oxygen, m is 1 and n is 0;
g) R, is phenyl, R2 is phenyl, X is oxygen, m is 1 and n is 0; .
h) R, is hydrogen, R2 is phenyl, X is oxygen, m is 1 and n is 0;
i) R, is phenyl, R2 is benryl, X is oxygen, m is 1 and n is 0;
j) R, is ethyl, R2 is 4-chlorophenyl, X is oxygen, m is 1 and n is 0;
k) R, is hydrogen, R2 is methyl, X is NH, m is 1 and n is 0;
I) R, is methyl, R2 is methyl, X is NH, m is 1 and n is 0;
m) R, is methyl, R2 is phenyl, X is NH, m is 1 and n is 0;
n) R, is methyl, R2 is 3-trifluoromethylphenyl, X is NH, m is 1 and n is 0;
o) R, is methyl, R2 is 4-tert-butylphenyl, X is NH, m is 1 and n is 0;
p) R, is phenyl, R2 is phenyl, X is NH, m is 1 and n is 0;
q) R, is hydrogen, R2 is phenyl, X is oxygen, m is 1 and n is 0;
r) R, is phenyl, R2 is benryl, X is NH, m is 1 and n is 0;
s) R, is ethyl, R2 is 4-chlorophenyl, X is NH, m is 1 and n is 0;
t) R, is hydrogen, R2 is hydrogen, X is NH, m is 1 and n is 1;
g) R, is as defined above, R3 is hydrogen and R2 is a group N- in which alk is methyl or ethyl and the phenyl ring is substituted or unsubstituted.
Particularly preferred individual compounds are compounds of the formula (I) in which R3 is hydrogen and a) R, is hydrogen, R2 is hydrogen, X is oxygen, m is 1 and n is 0;
b) R, is methyl, R2 is methyl, X is oxygen, m is 1 and n is 0; ' c) R, is methyl, R2 is phenyl, X is oxygen, m is 1 and n is 0;
d) R, is methyl, R2 is 4-trifluoromethylphenyl, X is oxygen, m is 1 and n is 0;
e) R, is methyl, R2 is 4-nitrophenyl, X is oxygen, m is 1 and n is 0;
f) R1 is methyl, R2 is 4-tert-butylphenyl, X is oxygen, m is 1 and n is 0;
g) R, is phenyl, R2 is phenyl, X is oxygen, m is 1 and n is 0; .
h) R, is hydrogen, R2 is phenyl, X is oxygen, m is 1 and n is 0;
i) R, is phenyl, R2 is benryl, X is oxygen, m is 1 and n is 0;
j) R, is ethyl, R2 is 4-chlorophenyl, X is oxygen, m is 1 and n is 0;
k) R, is hydrogen, R2 is methyl, X is NH, m is 1 and n is 0;
I) R, is methyl, R2 is methyl, X is NH, m is 1 and n is 0;
m) R, is methyl, R2 is phenyl, X is NH, m is 1 and n is 0;
n) R, is methyl, R2 is 3-trifluoromethylphenyl, X is NH, m is 1 and n is 0;
o) R, is methyl, R2 is 4-tert-butylphenyl, X is NH, m is 1 and n is 0;
p) R, is phenyl, R2 is phenyl, X is NH, m is 1 and n is 0;
q) R, is hydrogen, R2 is phenyl, X is oxygen, m is 1 and n is 0;
r) R, is phenyl, R2 is benryl, X is NH, m is 1 and n is 0;
s) R, is ethyl, R2 is 4-chlorophenyl, X is NH, m is 1 and n is 0;
t) R, is hydrogen, R2 is hydrogen, X is NH, m is 1 and n is 1;
u) R, is methyl, R2 is methyl, X is NH, m is 1 and n is 1;
v) R, is methyl, RZ is phenyl, X is NH, m is 1 and n is 1;
w) R, is methyl, R2 is 3-trifluoromethylphenyl, X is NH; m is 1 and n is 1;
x) R, is methyl, R2 is 4-tert-butylphenyl, X is NH, m is 1 and n is 1;
y) R, is phenyl, R2 is phenyl, X is NH, m is 1 and n is 1;
z) R, is hydrogen, R2 is phenyl, X is oxygen, m is 1 and n is 1;
aa) R, is phenyl, R2 is benzyl, X is NH, m is 1 and n is 1; or bb) R, is ethyl, R2 is 4-chlorophenyl, X is NH, m is 1 and n is 1.
The present invention furthermore provides a process for preparing a compound of the formula (I) which comprises a) preparing a compound of the fofmula (I) in which n is 0 and R,, R2, R3, X
arid m are as defined above under formula (I) by reacting a compound of the formula F~C~C\CHz CH ~CHz C\Yz ( II ) m F
in which R3 and m are as defined under formula (I) and Y2 is CI, Br or OS02-alkyl with a compound of the formula R~
Hx-N= (111) \
Rz in which R,, R2 and X are as defined under formula (I);
b) preparing compounds of formula (I) in which n is 0 and X is NR4 and R,, R2, R3 and m are as defined under formula (I) by reacting a compound of the formula F ~ C CHz C NHz 'C~ 'CHz ~CHz \N/ ( IV ) m in which R3, R4 and m are as defined under formula (I) with a compound of the formula _11 R~
O- ~ (V) RZ
in which R~ and R2 are as defined under formula (I); and c) preparing compounds of the formula (I) in which n is 1 and R,, R2, R3, R4, X and m are as defined under formula (I) by reacting a compound of the formula F C CHZ C
\C ~ \CHZ ~CHZ 'OH ( VI ) m F
in which R3 and m are as defined above under formula (I) with a compound of the formula R~
Y~CHz'C~X~N~C~R (VII) in which Y, is CI, Br or OS02-alkyl and X, R, and R2 are as defined above under formula (I).
The starting materials of the formulae (II) and (VI) are known or can be prepared analogously to known processes.
The starting materials of the formula (III) can be prepared in a manner known per se by reacting a ketone of the above formula (V) with hydrazine, with a hydrazine which is monosubstituted by R4 according to the above definition or with hydroxylamine, where the ketones of the formula (V) for their part are obtainable by customarry processes known for preparing ketones.
The starting materials of the formula (II) can be obtained by reacting an acyl halide of the formula F~ ~C~ CHZ C~
CH2 ~CHZ Hal m F
in which Hal is chlorine or bromine with a hydrazine which is monosubstituted by R4 according to the definition given above.
The starting materials of the formula (VII) can be obtained by reacting a chloroacetyl halide, for example chloroacetyl chloride, with a compound of the formula (III) according to the above definition.
The reaction of the process a) is preferably carried out in an inert solvent which is free of hydroxyl groups, in the presence of an organic base, for example pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline, or a bicyclic non-nucleophilic base, such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1;5-diazabicyclo[4.3.0] non-5-ene (DBN) or 1,8-diazabicyclo[5.4.OJundec-7-ene (1,5-5) (DBU).
The reaction is generally carried out at temperatures from -30°C to +70°C, preferably from -10°C to +50°C. It is advantageously carried out in the presence of a solvent or solvent mixture which is inert to the reaction. Suitable for this purpose are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane;
halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether-like compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitrites, such as acetonitrile, propionitrile;
esters, such as ethyl acetate, propyl acetate or butyl acetate; ketones, such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with one another. However, the reaction can also be carried out in an excess of one of the abovementioned bases, or, instead of the base, it is also possible to employ a second equivalent or else an even greater excess of the compound of the formula I. The reaction is carried out under atmospheric pressure;
however, it is also possible to carry out the reaction under elevated or reduced pressure.
The reaction of process b) is advantageously carried out in an inert solvent at a temperature of from 20°C to 150°C, preferably from 40°C to 120°C, if appropriate in the presence of a catalytic amount of an acid, such as acetic acid or p-toluenesulphonic acid.
Preferred inert solvents are lower alkanols, in particular methanol and ethanol.
The reaction of the process c) is advantageously carried out in an inert solvent in the presence of a base and, if appropriate, in the presence of a catalyst, for example Nal or CsF, preferred inert solvents being polar aprotic solvents, such as N,N-dimethylformamide, dimethyl sulphoxide, dioxane and tetrahydrofuran. Suitable bases are, in particular, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline, or a bicyclic non-nucleophilic base, such as 1 ,4-diazabicyclo[2.2.2]octane (DABCO); 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (1,5-5) (DBU).
The reactions described above and below are carried out in a manner known per se; for example in the absence or, if appropriate, presence of a suitable solvent or diluent or a mixture thereof, as required with cooling, at room temperature or with heating, for example in a temperature range of approximately -80°C to the boiling point of the reaction mixture, preferably from approximately -20°C to approximately +150°C and, if required, in a closed vessel, under superatmospheric pressure, in an atmosphere of inert gas and/or under anhydrous conditions. Particularly advantageous reaction conditions are shown in the examples.
The compounds of the formula (I) according to the invention are tolerated favourably by homoiotherms, fish and plants, and they are useful active compounds in the field of pest control. The active compounds according to the invention are active, in particular, against insects and arachnids, as encountered on useful and ornamental plants in agriculture and horticulture, in particular in rice, cotton, vegetable and fruit plantings, and in forests. The compounds of the formula (I) are particularly suitable for controlling insects in crops of rice, fruit and vegetables, in particular plant-damaging insects, such as Aphis craccivora, Nila-parvata lugens and Nephotettix cincticeps. Other areas of use of the active compounds according to the invention are the protection of stored products and materials and the hygiene sector, in particular the protection of pets and useful animals. The compounds of the formula (1) are active against all or individual developmental stages of normally-sensitive, but also resistant, pest species. Their effect may become apparent for example in the destruction of pests, either immediately or only after some time has elapsed, for example during ecdysis, or as a reduced oviposition and/or hatching rate.
The animal pests mentioned include, for example, those mentioned in the European Patent Application EP-A-736'252. EP-A-736'252 is therefore included by reference in the present subject-matter of the invention.
The compounds of the formula (I) are suitable, in particular, for use as active compounds for controlling pests from the order Homoptera and from the order Akarina.
The compounds of the formula (I) are particularly suitable for controlling pests in crops of cotton, vegetable, fruit and rice, such as spider mites, aphids, caterpillars of butterflies and moths, and rice leaf hoppers. Control is directed mainly against spider mites, such as Panonychus ulmi, aphids, such as Aphis craccivora, caterpillars of moths and butterflies, such as those of Heliothis virescens, and rice leafhoppers, such as Nilaparvata lugens or Nephotettix cincticeps.
The good pesticidal action of the compounds of the formula (I) according to the invention corresponds to a destruction rate (mortality) of at least 50-60% of the pests mentioned.
The activity of the compounds of the formula (1) according to the invention and of the compositions comprising them can be substantially widened and adapted to specific circumstances by addition of other insecticides and/or acaricides. Suitable additives are, for example, representatives of the following classes of active compounds: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroides, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
The compounds of the formula (I) are employed as such or, preferably, together with auxiliaries which are customary in the art of formulation, and accordingly, they can be processed, for example, to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or encapsulations in polymeric substances, in a known manner. The application methods, such as spraying, atomizing, dusting, broadcasting or watering, are, like the compositions, chosen according to the intended aims and the prevailing conditions.
The formulation, i.e. the agents, preparations or compositions comprising an active compound (I), or combinations of these active compounds with other insecticides or acaricides, and, if appropriate, a solid or liquid additive are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with extenders, for example solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).
Suitable auxiliaries, such as solvents, solid carriers, surtace-active compounds, nonionic surfactants, cationic surfactants, anionic surtactants and other auxiliaries in the compositions used according to the invention are, for example, the same as those described in EP-A-736'252.
The pesticidal preparations generally comprise from 0:1 to 99%, in particular from 0.1 to 95%, of active compound I or of the combination of this active compound with other insecticides and/or acaricides and from 1 to 99.9%, in particular from 5 to 99.9%, of a solid or liquid auxiliary, where generally from 0 to 25%, in particular from 0.1 to 20%, of the preparations may be surfactants (per cent means in each case per cent by weight). Whereas concentrated compositions are usuaNy preferred as commercial products; the end user generally employs dilute preparations which have a substantially lower concentration of active compound. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally from 1 to 1000 g of active compound per hectare, preferably from 25 to 500 g/ha.
Preferred formulations have, in particular, the following composition (% = per cent by weight):
Emulsifiable concentrates:
Active compound: from 1 to 90%, preferably from 5 to 20%
Surfactant: from 1 to 30%, preferably from 10 to 20%
Liquid carrier: from 5 to 94%, preferably from 70 to 85%
Dusts:
Active compound: from 0:1 to 10%, preferably from 0.1 to Solid carrier: from 99.9 to 90%, preferably from 99.9 to 99%
Suspension concentrates:
Active compound: from 5 to 75%, preferably from 10 to 50%
Water: from 94 to 24%, preferably from 88 to 30%
Surfactant: from 1 to 40%, preferably from 2 to 30%
Wettable aowders:
Active compound: from 0.5 to 90%, preferably from 1 to 80%
Surfactant: from 0.5 to 20%, preferably from 1 to 15%
Solid carrier: from 5 to 95%; preferably from 15 to 90%
Granules:
Active compound: from 0.5 to 30%, preferably from 3 to 15%
Solid carrier: from 99.5 to 70%, preferably from 97 to 85%
The preparations may also comprise other auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil; preservatives, viscosity regulators; binders and/or tackifiers, and also fertilizers or other active compounds for obtaining special effects.
The examples below serve to illustrate the invention. They do not limit the invention.
Temperatures are stated in degrees Celsius.
Example H1:
l~ ~ H3 FZC=CH-ECH~C-O-N= ;
0.73 g (10 mmol) of acetone oxime and 1.01 g (10 mmol) of triethylamine are dissolved in 30 ml of anhydrous benzene. At 5-10°C, the solution is admixed over a period of 30 minutes and with vigorous stirring with 1.68 g (10 mmol) of 6,6-difluorohex-5-enoic acid chloride (DAHSCI), and the mixture is stirred at room temperature for another 10 hours and then filtered through a glass suction filter, and the filtrate is concentrated using a rotary evaporator. The resulting crude product is separated by silica gel column chromatography (ethyl acetate:isohexane = 20:80). This gives the title compound of no~° = 1.6893.
Example H2:
/ sHs FZC=CH-ECH~-C-NH-N= \
CsHs 1.5 g (7.6 mmol) of benzophenone hydrazone and 0.77 g (7.6 mmol) of triethylamine are dissolved in 30 ml of anhydrous benzene, and at 5-10°C the solution is admixed with 1.29 g (7.6 mmol) of 6,6-difluoro-hex-5-enoic acid chloride (DAHSCI) over a period of 30 minutes.
The mixture is then stirred at room temperature for another l0 hours and filtered through a glass suction filter, and the filtrate is concentrated using a rotary evaporator. The resulting crude product is separated by silica gel column chromatography (ethyl acetate:isohexane =
20:80). This gives the title compound of m.p. 70-71 °C.
Example H3:
~ H3 FZC=CH-ECH~--C-NH-N=C\
H
0.5 g (10 mmol) of hydrazine hydrate is added to 1.64 g (10 mmol) of methyl 6,6-difluorohex-5-enoate in 10 ml of methanol. The solution is heated under reflux on a water bath for 10 minutes and then concentrated using a rotary evaporator. The residue is suspended in 20 ml of methylene chloride and, at 0°C, admixed with 0.445 g (10 mmol) of acetaldehyde, and the mixture is then stirred at room temperature for another 10 hours. The methylene chloride is evaporated and the crude product is separated by silica gei column chromatography (methyl acetate:isohexane = 20:80). This gives the title compound of m.p. 78-79°C.
Examine H4:
II II i gHs FZC=CH-ECH2~--C-O-CHZ-C-NH-N=C
3 \
Cr6H5 3.6 g (18.4 mmol) of benzophenone hydrazone and 1.85 g (18.3 mmol) of triethylamine are dissolved in 50 ml of benzene, and the mixture is cooled to 5°C. With efficient stirring, 2.06 g (18.2 mmol) of chloroacetyl chloride are slowly added dropwise such that the temperature can be kept at from 5 to 10°C at all times. After the addition of the chloroacetyl chloride, stirring is continued at room temperature for 14 hours. The mixture is filtered and the filtrate is concentrated. The residue is washed with a small amount of isohexane:acetic acid =
80:20, filtered and dried. This gives the title compound of m.p. 92-93°C.
A mixture of 1.7 g (6.2 mmol) of chloroacetylbenzophenone hydrazide, 0.93 g (6.2 mmol) of 6,6-difluorohex-5-enoic acid, 0.63 g (6:2 mmol) of triethylamine and 0.2 g of Naf in 10 ml of dimethylformamide is stirred at room temperature for 14 hours. The reaction mixture is poured onto ice, the mixture is extracted with chloroform and the extract is dried over Na2S04. The solvent is distilled off and the crude product is separated on silica gel (isohexane:ethyl acetate = 80:20). This gives the title compound no~° =
1.5678.
Example H5:
II II /cH3 F2C=CH-ECH~-C-O-CH2-C-NH-N=C
3 \
0.5 g (10 mmol) of hydrazine hydrate is added to a solution of 0.9 g (10 mmol) of methyl glycolate in 10 ml of methanol. For 10 minutes, the solution is heated under reflux on a water bath, and it is then concentrated using a rotary evaporator. The residue is suspended in ml of methanol and admixed with 0:58 g (10 mmol) of acetone, and the mixture is then stirred at room temperature for 10 hours. The methanol is evaporated and the residue is then suspended in 20 ml of dichloromethane/tetrahydrofuran. 1.5 g (10 mmol) of 6,6-difluorohex-5-enoic acid, 406 g (10 mmol) of DCC and 0.1 g of 4-dimethylaminopyridine are added to this mixture, which is then stirred for 14 hours and filtered through a glass suction filter, and the filtrate is concentrated using a rotary evaporator. The resulting crude product is purified by silica gel column chromatography (ethyl acetate:isohexane =
20:80). This gives the title compound of no~° =1.6768.
In a manner similar to that described in Examples H1 to H5, it is possible to prepare the compounds of the formula (I) listed in Tables 1 to 20.
Table 1: Compounds of the formula H O
F~C~C~CH C~O~N~C~Rz F R~
Comp. No. R, R2 phys. Data 1:01 H H
1.02 H CH3 1.03 H C2H5 1.04 H C3H~-n 1.05 H C3H,-i 1.06 H Calls-n 1.07 H C4Hs-t 1.08 H CsH,3-n 1.09 H C,oH2,-n 1.10 H CH2C(CH3)a 1.11 CH3 H
1.12 CH3 CH3 1.13 CH3 C2H5 1.14 CH3 C3H~-n 1.15 CH3 C3Hri 1.16 CH3 C4Hs-n 1.17 CH3 C4Hs-t .. CA 02291441 1999-11-23 Comp. No. R, R2 phys. Data 1.18 CH3 CgH,3-n 1.19 CH3 C,pH2,-n 1.20 CH3 CHZC(CH3)s 1:21 CH3 CsHs 1.22 CH3 CBH4-2-CI
1.23 CH3 CsH4-3-CI
1.24 CH3 CsH4-4-CI
1.25 CH3 C6H4-2-CF3 1.26 CH3 CsH4-3-CF3 1.27 CH3 CsH4-4-CF3 1.28 CH3 CsH4-2-CN
1.29 CH3 CsH4-3-CN
1.30 CH3 C6H4-4-CN
1.31 CH3 C6Ha-2-N02 1.32 CH3 CsH4-3-N02 1.33 CH3 C6H4-4-N02 1.34 CH3 CsH4-4-C6H5 1.35 CH3 C6H4-4-OCsHS
1.36 CH3 CgH4-4-C(CH3)3 1.37 CH3 CsH4-4-OCF3 1.38 CH3 CsH4-4-COOC2H5 1:39 CH3 CsFS
1.40 CH3 -CsH~-3,4,5-(OCH3)3 Comp. No. R, R2 phys. Data 1.41 CH3 / \
N O
U
1.42 CH3 ~ ~ N
~N
1.43 CH3 \ ~ OH
1.44 CsH5 CF3 1.45 C6H5 C2H5 1.46 CgHS C3H,-n 1.47 C6H5 C3H,-i 1.48 CsHs C4H9-t 1.49 CsH5 C4H9-n 1.50 C6H5 cyclopropyl 1.51 CsHs cyclopentyl 1.52 C6H5 cyclohexyl 1.53 CsHS CsHS
1:54 CsH5 CsH4-4-CI
1.55 C6H5 C6H4-4-CF3 1.56 C6H5 CsH4-4-CN
1.57 CsH5 C6H4-4-N02 1.58 CgH5 CgH4-4-CsH5 1.59 CsHS CsH4-4-OCsHS
Comp. No. R, R2 phys. Data 1.60 CBHS CgH4-4-C(CH3)s 1.61 CsHS CgH4-4-OCF3 1:62 CsH4-4-CI CF3 , 1.63 C6H4-4-CI C2H5 1.64 C6H4-4-CI C3Hr~
1.65 CsHa-4-CI C3Hri 1.66 CgH4-4-CI C4H9-t 1.67 CsH4-4-CI C4H9-n 1.68 CsH4-4-CI CH2CsH5 1.69 C6H4-4-CI CH2CgH4-4-CH3 1.70 CsH4-4-CI CsH4-4-CI
1.71 CsH4-4-CI C6H4-4-OH
1.72 CsH4-4-CI CsH4-2-CH3 1.73 CsH4-4-CI C6H4-2-CI
1.74 C6H4-4-CI C6H4-4-Br 1.75 C6H4-4-CI 4-pyridyl 1:76 CsH4-4-CI CgH4-4-OCH2-CsH4-3-CF3 1.77 CsH4-4-Cl oBH~
F
F
1:78 H CgHS
1.79 C6H5 CH2CsH5 1.80 C2H5 -C6H4-4-CI
Table 2: Compounds of the formula H O
F~C~C~CH C~N~N~Ci~
F H R~
Comp. No. R, RZ phys. Data 2.01 H H
2.02 H CH3 2.03 H CzHs 2.04 H C3H,-n 2.05 H C3Hri 2.06 H C4Hs-n 2.07 H C4Hs-t 2.08 H CsH,3-n 2.09 H C,oH2,-n 2.10 H CH2C(CH3)s 2.11 CH3 H
2.12 CH3 CH3 2.13 CH3 C2H5 2.14 CH3 C3Hr-n 2.15 CH3 C3H,-i 2.16 CH3 C4Hs-n 2.17 CH3 CaHs-t 2.18 CH3 CsH,3-n 2.19 CH3 C,oH~,-n 2.20 CH3 CH2C(CH3)s Comp. No. R, R2 phys. Data 2.21 CH3 CsH5 2.22 CH3 CsH4-2-CI
2.23 CH3 CgH4-3-CI
2.24 CH3 CsH4-4-CI
2.25 CH3 CsH4-2-CF3 2.26 CH3 CgH4-3-CF3 2.27 CH3 CsH4-4-CF3 2.28 CH3 C6H4-2-CN
2.29 CH3 C6H4-3-CN
2.30 CH3 C6H4-4-CN
2.31 CH3 CsH4-2-N02 2.32 CH3 CsH4-3-N02 2.33 CH3 C6H4-4-N02 2.34 CH3 C6H4-4-C6H5 2.35 CH3 CsH4-4-OC6H5 2.36 CH3 CsH4-4-C(CH3)s 2.37 CH3 CsH4-4-OCF3 2.38 CH3 CsH4-4-COOC2H5 2.39 CH3 C6F5 2.40 CH3 CsH2-3,4,5-(OCH3)s 2.41 CH3 / \
N O
V
Comp. No. R, R2 phys. Data 2.42 CH3 / \
N~ N
2.43 CH3 OH
2.44 CsHS CF3 2.45 CsHS CZHS
2.46 CsHS C3H~-n 2.47 C6H5 C3H,-i 2.48 CsHS C4Hs-t 2.49 CsH5 CaHs-n 2.50 C6H5 cyclop~opyl 2.51 C6H5 cyclopentyl 2.52 C6H5 cyclohexyl 2.53 C6Hs C6H5 2.54 CsHS CsH4-4-CI
2.55 CsHs C6H4-4-CF3 2.56 CsHs CsH4-4-CN
2.57 CsHs CsH4-4-NO2 2.58 CsH5 CsH4-4-CsH5 2.59 CsH5 C6H4-4-OCsHs 2.60 CsH5 CsH4-4-C(CH3)s 2.61 CsHS CsH4-4-OCF3 Comp. No. R, R2 phys. Data 2:62 CsH4-4-CI CF3 2.63 CsH4-4-CI C2H5 2.64 CsH4-4-CI C3H,-n 2.65 C6H4-4-CI C3Hri 2.66 CsH4-4-CI C4Hg-t 2.67 . CsH4-4-CI C4H8-n 2.68 CsH4-4-CI CH2C6H5 2.69 CgH4-4-CI CH2CsH4-4-CH3 2.70 CsH4-4-CI CsH4-4-CI
2.71 CsH4-4-CI C6Ha-4-OH
2.72 CsH4-4-CI CsH4-2-CH3 2.73 C6H4-4-CI C6H4-2-CI
2:74 C6H4-4-CI CsH4-4-Br 2.75 C6H4-4-CI 4-pyridyl 2.76 C6H4-4-CI -CsH4-4-OCH2-CsH4-3-CF3 2.77 CsH4-4-C) CsH4-~-CHZ
F
F
2.78 H -CsH5 2.79 CsH5 CH2C6H5 2.80 C2H5 -C6H4-4-CI
Table 3: Compounds of the formula I II I
F~C~C~CH C~O~CHZ'C~N~N~C~R
F O
Comp. No. R, R2 phys. Data 3.01 H H
3.02 H CH3 3.03 H C2H5 3.04 H C3Hrn 3.05 H C3Hri 3:06 H C4H9-n 3.07 H C4H9-t 3.08 H CsH,3-n 3.09 H C,oH2,-n 3.10 H CHZC(CH3)s 3.11 CH3 H
3.12 CH3 CH3 3.13 CH3 C2H5 3.14 CH3 C3Hrn 3.15 CH3 C3Hri 3:16 CH3 C4H9-n 3.17 CH3 C4H9-t 3.18 CH3 C6H,3-n 3.19 CH3 C,oH2,-n 3.20 CH3 CH2C(CH3)a Comp. No. R~ R2 phys. Data 3.21 CH3 CsHs 3:22 CH3 CsH4-2-CI
3.23 CH3 C6H4-3-CI
3.24 CH3 C6H4-4-CI
3.25 CH3 CgH4-2-CF3 3.26 CH3 C6H4-3-CF3 ' 3.27 CH3 C6H4-4-CF3 3.28 CH3 C6Ho-2-CN
3.29 CH3 CsH4-3-CN
3.30 CH3 CsH4-4-CN
3.31 CHs CsH4-2-N02 .
3.32 CH3 C6H4-3-N02 3.33 CH3 CsH4-4-N02 3.34 CH3 C6H4-4-CsHs 3.35 CH3 C6H4-4-OC6H5 3.36 CH3 C6H4-4-C(CH3)s 3.37 CH3 C6H4-4-OCF3 3.38 CH3 CsH4-4-COOC2H5 3.39 CH3 CsFS
3.40 CH3 CsH2-3,4,5-(OCH3)s n 3.41 CH3 .28_ Comp. No. R, R2 phys. Data 3.42 CH3 / \ N
~N
3.43 CH3 -\ / OH
3.44 CsHs 3.45 CsH5 ~H5 3.46 CsH5 C3Hrn 3.47 C6H5 CsH~-i 3.48 CsHs C4H9-t 3.49 C6H5 C4H9-n 3.50 CsHS cyciopropyl 3.51 CsH5 cyclopentyl 3.52 CsHS cyclohexyl 3.53 CgH5 CsH5 3.54 CeHS C6H4-4-CI
3.55 CsHs CsH4-4-CF3 3.56 C6H5 CsH4-4-CN
3.57 CgHs C6H4-4-N02 3.58 CgHS CsH4-4-CsHs 3.59 CsHS C6H4-4-OC6H5 3.60 CsHS CsH4-4-C(CH3)a 3.61 CsHS CgH4-4-OCF3 _ CA 02291441 1999-11-23 Comp. No. R, R2 phys. Data 3.62 CgH4-4-CI CF3 3.63 CsH4-4-CI C2H5 3:64 CsH4-4-CI C3Hrn 3.65 CsH4-4-CI C3Hri 3.66 CsH4-4-CI C4H9-t 3.67 CsH4-4-CI CaH9-n 3.68 CsH4-4-CI CH2CsH5 3.69 C6H4-4-CI CH2CsH4-4-CH3 3.70 CgH4-4-CI CsH4-4-CI
3:71 CsH4-4-CI CsH4-4-OH
3.72 C6H4-4-CI C6H4-2-CH3 3.73 CsH4-4-CI C6H4-2-CI
3.74 CsH4-4-CI C6H4-4-Br 3:75 CsH4-4-CI 4-pyridyl 3.76 C6H4-4-CI CsH4-4-OCH2-CsH4-3-CF3 3.77 C6H4-4-CI CBH,-O-CHZ
F
F
3.78 H CgH5 3.79 C6H5 CH2C6H5 3.80 C2H5 -CsH4-4-CI
Table 4:
Compounds of the formula H O
F~C~C\CHZ
CHZ'C~
C~O/N~C~R~
Rz Comp. R2 No. phys.
R~ Data 4.1 H
H
4.2 CH3 H no~
=1.6869 4.3 C2H5 H
4.4 C3Hrn H
4.5 C3H~-i H
4.6 C4H9-n H
4.7 CaH9-t H
4.8 CsH~3-n H
4.9 C~oH2wn H
4.10 CH2C(CH3)a H
4.11 H
4.12 CH3 CH3 np2 =1.6893 4.13 C2H5 4.14 C3H,-n 4.15 C3H~-i 4.16 C4H9-n 4.17 C4H9-t 4.18 CsH,3-n 4.19 C~oH~-n Comp. R~ R2 phys. Data No.
4.20 CH3 CH2C(CH3)s 4.21 CH3 C6H5 np~ =1.50731 4.22 CH3 CsH4-2-CI Oil 4.23 CH3 CgH4-3-CI no~ =1.6883 4.24 CH3 CgH4-4-CI Oil 4.25 CH3 C6H4-2-CF3 np2 =1.4667 4.26 CH3 CsH4-3-CF3 np~ =1.6765 4.27 CH3 C6H4-4-CF3 4.28 CH3 C6H4-2-CN
4.29 CH3 CsH4-3-CN amorphous 4.30 CH3 CsH4-4-CN m.p.:
4.31 CH3 CsH4-2-N02 n~2 =1.6888 4.32 CH3 CsH4-3-N02 np2 =1.6897 4.33 CH3 C6H4-4-N02 np2 = 1.6853 4.34 CH3 C6H4-4-Cells m.p.: 51-52C
4.35 CH3 CsH4-4-OCsHs Oil 4.36 CH3 C6H4-4-C(CH3)3 no~ =1.6754 4.37 CH3 C6H4-4-OCF3 npz = 1.6843 4.38 CH3 CsH4-4-COOC2H5 amorphous 4.39 CH3 CsF5 Oil 4.40 CH3 C6H2-3,4,5-(OCH3)3 n~2 =1.5207 4.41 CH3 ~ ~ N o amorphous U
Comp. No. R, R2 phys. Data 4.42 CH3 ~ ~ N
~N
4.43 CH3 - m.p.: 79-81 °C
~ OH
4.44 CsHs CF3 4.45 CsHS C2H5 4.46 C6H5 C3Hrn 4.47 C6H5 C3Hri Oil 4.48 CsHS C4H9-t noz _ 1.4850 4.49 CsHS CaH9-n 4.50 C6H5 cyclopropyl np2 = 1.5132 4.51 CsHS cyclopentyl 4.52 CsHS cyclohexyl 4.53 CsH5 CsH5 np2 =1.5503 4.54 CsHs CsH4-4-CI Oil 4.55 CBH5 C6H4-4-CF3 np~ =1.5130 4.56 CsH5 CsH4-4-CN
4.57 C6H5 C6H4-4-N02 amorphous 4.58 C6H5 CsH4-4-CsHs 4.59 CsH5 CsH4-4-OC6H5 4.60 CsHS CsH4-4-C(CH3)a 4.61 CsHS CgH4-4-OCF3 -Comp. R, R2 phys. Data No.
4:62 CgH4-4-CI CF3 noz =1.4709 4.63 C6H4-4-CI C2H5 4.64 C6H4-4-CI CsH,-n 4.65 CsH4-4-CI C3H~-i 4.66 CsH4-4-CI C4H9-t 4.67 CgH4-4-CI C4H9-n ' 4.68 CsH4-4-CI CH2C6H5 4.69 C6H4-4-CI CH2CsH4-4-CH3 4.70 C6H4-4-CI CsH4-4-CI m.p.:66-67C
4.71 C6H4-4-CI C6H4-4-OH
4.72 CsH4-4-CI CsH4-2-CH3 .
4.73 CsHa-4-CI CsH4-2-CI
4.74 C6H4-4-CI CsH4-4-Br 4.75 CgH4-4-CI 4-pyridyl np2 = 1.5575 4.76 CsH4-4-CI C6H4-4-OCH2-C6H4-3-CF3 4.77 C6H4_4_CI CsHa-~-CHZ
F
F
4.78 H C6H5 np2 =1.5131 4.79 CsHS CH2CsH5 np2 =1.6744 4.80 C2H5 -CsH4-4-CI no2 =1.6768 4.81 CH3 C6H3-3,5-(CF3)2 np~ =1.4509 4.82 cyclopropyl -C6H3-4-CI np2 =1.6820 Comp. No. R, R2 phys. Data ,o-Et 4.83 CH3 j m.p.:
/ I 138-140°C
o ~ cF, ,o-Me 4.84 CH3 ~ np~ =1.5350 Iw / O/ / I G
,O-Et 4.85 CH3 ~ B~ np~° =1.5568 I / o w I
,o-Me 4.86 CH3 I np~ =1.4770 cI /~
'\ v _O-CF -CHF
z z ,QEt 4.87 C2H5 j ~~ no = 1.4768 I I
/ o ,O-Me 4.88 C2H5 I np~ = 1.5113 /
I/ \I
4.89 CH3 np~ =1.5510 4.90 CH3 np~ =1.5282 Comp. No. R~ R2 phys.
Data ,o-Me ~
4.91 CH3 ~ np = 1.5110 i / O \ CF
O-Me . 3 m.p .: 36-37 C
i CHFZ
~
~ ~
4.93 CH3 ~ np~ = i .5175 v N-4.94 -C6H5 C6H4-2-F nom = 1.5390 4.95 -CsHS CsH3-2,4-F2 nom =1.5267 4.96 -CsHs CsH4-4-F np25 = 1.5343 4.97 -CsH4-4-F CsH4-4-F m.p. :55-57C
4.98 -CsH5 CsH4-3-CF3 np~ = 1.5143 4.99 -CsH4-3-CF3CsH4-3-CF3 no = 1.4831 4.100 -CsHs C6H4-2-CI nom = 1.5523 4.101 m.p.: 52-54°C
' ~ I ~
/ /
4.102 o2N ' ' No2 m.p.:
/ ~ / 136-138C
4.103 -C6H5 -CgH3-4-CI-3-N02 m.p.:72-75C
4.104 -CsHS -CsH4-3-N02 nom = 1.5615 4.105 -CgHS -CgH~-2,4-CI2 np~ =1.5490 Comp. No. R, RZ phys. Data 4.106 -CsHs -CsH4-4-S-CsH4-4-CI np~ = 1.5757 4.107 -CsH5 nom = 1.5058 4.108 -CsH4-4- -CgH4-4-O-CH3 np2 =1:5578 n-C H
~ "
4.109 -CsMs ~ / o m.p.: 44-46C
F
O i F
o 4.110 -C6H5 ~ / np23 = 1.5045 F
O ~
F
4.111 -CsH4-4-F np~ =1.5000 F
4.112 ~ \ np2a =1.6060 v ~ w Table 5: Compounds of the formula H O
F\C~C'CH CHZ~CH C~N~N\C~Ri F H RZ
Comp. No. R, R2 phys. data 5.1 H H
5.2 H CH3 m.p.: 78-79C
5.3 H C2H5 5.4 H C3Hrn 5.5 H C3Hri 5.6 H C4H9-n 5.7 H C4H9-t 5.8 H C6H,3-n 5.9 H C,oH2,-n 5.10 H CH2C(CH3)s 5.11 CH3 H
5.12 CH3 CH3 np~ =1.7589 5.13 CH3 C2H5 5.14 CH3 C3H~-n 5.15 CH3 C3H,-i 5.16 CH3 C4H9-n 5.17 CH3 C4H9-t 5.18 CH3 CeH,3-n Comp. No. R, R2 phys. data 5.19 CH3 C,oH~,-n 5.20 CH3 CH2C(CH3)s 5.21 CH3 CsHs m.p.: 64-66C
5.22 CH3 CsH4-2-CI m.p.: 79-82C
5.23 CH3 C6H4-3-CI m.p.: 75-78C
5.24 CH3 CsH4-4-CI m.p:: 104-106C
5.25 CH3 C6H4-2-CF3 np~ _ 1.4941 5.26 CH3 CgH4-3-CF3 m.p.: 82-83C
5.27 CH3 CsH4-4-CF3 m.p.: 68-69C
5.28 CH3 CsH4-2-CN
5.29 CH3 C6H4-3-CN m.p.: 123-124C
5.30 CH3 CsH4-4-CN
5.31 CH3 CsH4-2-N02 m.p.: 80-84C
5.32 CH3 C6H4-3-N02 m.p.: 129-130C
5.33 CH3 CsH4-4-N02 m.p.: 159-161 C
5.34 CH3 C6H4-4-CgHS m.p.: 193-195C
5.35 CH3 C6H4-4-OCsHS m.p.: 108-109C
5.36 CH3 CsH4-4-C(CH3)3 m.p.: 106-108C
5.37 CH3 C6H4-4-OCF3 m.p.: 93-94C
5.38 CH3 C6H4-4-COOC2H5 m.p.: 98-101 C
5.39 CH3 CsFS m.p.: 119-124C
5.40 CH3 CsH~-3,4,5-(OCH3)3 m.p.:106-108C
5.41 CH3 / \ o m.p.:145-146°C
U
Comp. No. R, R2 phys. data 5.42 CH3 ~ \ N~ m.p.:138-140°C
~N
5.43 CH3 m.p.: 132-133°C
OH
5.44 -CsH5 CF3 5.45 -CsHs C2Hs 5.46 -CsH5 C3Hrn 5.47 -CsHS C3H,-i 5.48 -C6H5 CQH9-t m.p.:38-39°C
5.49 -C6H5 C4H9-n 5.50 -CsH5 cyclopropyl no~° =1.5962 5.51 -CsH5 cyclopentyl 5.52 -CsHS cyclohexyl 5.53 -CsHS CsH5 m.p.: 70-71 °C
5.54 -CsHS C6H4-4-CI m.p.: 129-131 °C
5.55 -CsHs CsH4-4-CF3 m.p.:119-120°C
5.56 -CsHS CsH4-4-CN
5.57 -CsHs C6H4-4-N02 m.p.:88-90°C
5.58 -C6H5 CsH4-4-CsHS m.p.:130-132°C
5.59 -C6H5 C6H4-4-OCsHS
5.60 -CsHS C6H4-4-C(CH3)a 5.61 -CsHS C6H4-4-OCF3 Comp. No. R, R2 phys. data 5.62 -CsH4-4-CI CF3 5.63 -CsH4-4-CI C2H5 5.64 -C6H4-4-CI C3Hrn 5.65 -CsH4-4-CI C3Hri 5.66 -CsH4-4-CI C4H9-t 5.67 -CsH4-4-CI C4H9-n 5.68 -CsH4-4-CI CH2CsH5 5.69 -CsH4-4-CI CH2CsH4-4-CH3 5.70 -C6H4-4-CI -C6H4-4-CI m.p.:114-116C
5.71 -CsH4-4-CI -C6H4-4-OH
5.72 _CsH4_4_CI _CsH4-2_CH3 5.73 -CsH4-4-CI -CsH4-2-CI
5.74 -C6H4-4-CI -C6H4-4-Br 5.75 -C6H4-4-CI 4-pyridyl m.p.:144-148C
5.76 -CsH4-4-CI -C6H4-4-OCH2-CsH4-3-CF3Resin 5.77 -CsH4-4-CI CsHo-O-CH2 F Resin F
5.78 H -CsHs m.p.: 60-63C
5.79 -CsH5 -CH2CsH5 m.p.: 95-96C
5.80 -C2H5 -CsH4-4-CI m.p.: 106-107C
5.81 -CsH4-4-CI -CsH4-4-OS02N(CH3)2 m.p.:105-115C
5.82 m.p.: 151-155°C
ci ~ ~ ci - Comp. No. R, R2 phys. data 5.83 -CsHs cyclopropyl m.p.:80-82C
5.84 -CH3 -CsH3-3,5-(CF3)2 m.p.:103-105C
5.85 -C6H5 -CsH4-4-F m.p.:77-78C
5.86 -C6H5 -CsH3-2,4-F2 m.p.:109-110C
5.87 -CsH5 -CsH4-4-F m.p.: 99-101 C
5.88 -CBH4-4-F -C6H4-4-F m.p.:76-77C
5.89 m.p.: 130-132°C
i i 5.90 -C6H5 -CsH4-3-N02 m.p.:102-106°C
5.91 -CsHS -CsH~-3-CF3 m. p.: 49-50°C
O-Et 5.92 -C6H5 ~ m.p.:81-82°C
i 5.93 -CgH4-3-CF3 -C6H4-3-CF3 m.p.:62-63°C
5.94 -CsH4-4-OCH3 -C6H4-4-OCH3 m.p.:82-83°C
5.95 -C6H4-4-OCH3 -CH2-C6H4-4-OCH3 m.p.:123-124°C
5.96 -CgHs -CsH4-2-CI m.p.:69-70°C
5.97 -CgHS -C6H3-2,4-Ci2 m.p.:117-118°C
5.98 -CsH4-4-N(CH3)2 -C6H4-4-N(CH3)2 m.p.:93-94°C
5.99 -CgH5 -C6H4-4-S-CsH4-4-CH3 m.p.:112-113°C
o-~
5.100 -CsH5 \ np~° =1.5510 I /
Comp. No. R, R2 phys. data ~Isobutyl 5.101 -CsHs no2° = 1.5355 W
Table 6: Compounds of the formula F~ yC~ ~CH2' ~C~ /CHZ\ /N~ /C~
I CHZ CHZ O (I N R2 O
Comp. No. R, R2 phys. data 6.1 H H
6.2 H CH3 no~ = 1,6815 6.3 H C2H5 6.4 H C3H,-n 6.5 H C3H~-i 6.6 H C4H9-n 6.7 H C4H9-t 6.8 H CsH,3-n 6.9 H C,oH2,-n 6.10 H CH2C(CH3)s 6.11 CH3 H
6.12 CH3 CH3 amorphous 6.13 CH3 C2H5 6.14 CH3 C3H~-n Comp. No. R, R2 phys.
data 6.15 CH3 C3H,-i 6.16 CH3 C4Hg-n 6.17 CH3 C4H9-t 6.18 CH3 CsH,3-n 6.19 CH3 C,oH2,-n 6.20 CH3 CHZC(CH3)3 6.21 CH3 CgHS m.p .: 92-94C
6.22 CH3 CgH4-2-Ct ~ m.p .:58-60C
6.23 CH3 CsH4-3-CI m.p .: 126-127C
6.24 CH3 C6H4-4-CI m.p .: 125-127C
6:25 CH3 CsH4-2-CF3 m.p .: 62-64C
6.26 CH3 CgH4-3-CF3 m.p .: 148-149C
6.27 CH3 CeH4-4-CF3 m.p .: 103-104C
6.28 CH3 CeH4-2-CN
6.29 CH3 C6H4-3-CN m.p .: 130-131 C
6.30 CH3 CsH4-4-CN m.p .: 141-142C
6.31 CH3 CgH4-2-N02 m.p .: 81-84C
6.32 CH3 CsH4-3-N02 m.p .: 150-152C
6.33 CH3 CgH4-4-N02 m.p.:
6.34 CH3 C6H4-4-CBHS m.p.:
6.35 CH3 CsH~-4-OCsH5 m:p.:
6.36 CH3 CsH4-4-C(CH3)3 m.p.:157-158C
6.37 CH3 CsH4-4-OCF3 m.p.:
6.38 CH3 CgH4-4-COOC2H5 m.p.:127-129C
Comp. No. R, R2 phys. data 6.39 CH3 CsF5 m. p.: 73-76C
6.40 CH3 C6H2-3,4,5-(OCH3)3 m.p.: 139-141 C
6.41 CH3 ~ \ m.p.:142-144C
o N
~1 6.42 CH3 ~ \ N~ m.p.:146-148°C
~N
6.43 CH3 m.p.: 168-170°C
\ ~ OH
6.44 CsH5 CF3 6.45 C6H5 C2H5 6.46 CsHS C3H,-n 6.47 CsHs C3H~-i np2 =1.6978 6.48 C6H5 C4H9-t no2 =1.6988 6.49 C6H5 C4H9-n 6.50 CsHS cyclopropyl m.p.:60-62C
6.51 C6H5 cyclopentyl 6.52 CsH5 cyclohexyl 6.53 CgHS CsHs m.p.:.50-53C
6.54 CsHS CsH4-4-CI m.p.:102-102C
6.55 C6H5 C6H4-4-CF3 6.56 CgH5 C6H4-4-CN
6.57 C6H5 C6H4-4-N02 Comp. R~ R2 phys. data No.
6.58 CsH5 CgH4-4-CsH5 6.59 CsHS C6H4-4-OCsH5 6.60 CsH5 C6H4-4-C(CH3)s 6.61 CgHs CsH4-4-OCF3 6.62 CsH4-4-CI CF3 6.63 CsH4-4-CI C2H5 ' 6:64 C6H4-4-CI C3H,-n 6.65 CsH4-4-CI C3H,-i 6.66 CsH4-4-CI CaHs-t 6.67 C6H4-4-CI C4Hs-n 6.68 CsH4-4-CI CH2C6H5 .
6.69 CsH4-4-CI CH2CsH4-4-CH3 6.70 C6H4-4-CI CsH4-4-CI m.p.:73-75C
6.71 CsH4-4-CI CsH4-4-OH
6.72 CsH4-4-CI C6H4-2-CH3 6.73 CgH4-4-CI C6H4-2-CI
6.74 CsH4-4-CI C6H4-4-Br 6.75 CsH4-4-CI 4-pyridyl 6.76 CsH4-4-CI C6H4-4-OCHz-C6H4-3-CFs 6.77 CsH4-4-CI CsH~-~-CHZ
F
F
6.78 H -CsHS m.p.: 72-75°C
6.79 CsHS -CH2CsH5 m.p.:104-106°C
' Comp. No. R, R2 phys. data 6.80 C2H5 -CBH4-4-CI m.p.:79-80C
6.81 CH3 -CgH3-3,5-(CF3)2 m.p.:148-150C
6.82 C2H5 -CsH4-4-CI m.p.:79-80C
Table 7: Compounds of the formula H O
z F'C~C'CHz CH ~CHz C\O/N~'C~R
F RZ
Comp. No. R, R2 phys. data 7.01 H H
7.02 H CH3 7.03 H C2H5 7.04 H C3H,-n 7.05 H C3H,-i 7.06 H C4H9-n 7.07 H C4H9-t 7.08 H CsH,3-n 7.09 H C,oH2,-n 7.10 H CH2C(CH3)a 7.11 CH3 H
7.12 CH3 CH3 7.13 CH3 C2H5 7.14 CH3 C3H,-n Comp. No. R, R2 phys. data 7.15 CH3 C3H,-i 7.16 CH3 C4H9-n 7.17 CH3 C4H9-t 7.18 CH3 CsH,3-n 7.19 CH3 C,oH2,-n 7.20 CH3 CH2C(CH3)3 7.21 ~ CH3 CsH5 7.22 CH3 C6H4-2-CI
7.23 CH3 CsH4-3-CI
7.24 CH3 C6H4-4-CI
7.25 CH3 CsH4-2-CF3 7.26 CH3 CsH4-3-CF3 7.27 CHa CsH4-4-CF3 7.28 CH3 CsH4-2-CN
7.29 CH3 CsH4-3-CN
7.30 CH3 CsH4-4-CN
7.31 CH3 CsH4-2-N02 7.32 CH3 C6H4-3-N02 7.33 CH3 C6H4-4-N02 7.34 CH3 C6H4-4-C6H5 7.35 CH3 C6H4-4-OC6H5 7.36 CH3 C6H4-4-C(CH3)3 7.37 CH3 C6H4-4-OCF3 7.38 CH3 CsH4-4-COOC2H5 Comp. No. R, R2 phys. data 7.39 CH3 CsFS
7.40 CH3 CsH2-3,4,5-(OCH3)s 7.41 CH3 /-\ ~
N O
U
7.42 CH3 / \
N
~ N
7.43 CH3 OH
7.44 CsHs CF3 7.45 CsHs C2H5 7.46 CsH5 C3H,-n 7.47 CsHS C3H~_I
7.48 C6H5 C4H9-t 7.49 CsH5 C4H9-n 7.50 CsHS cyclopropyi 7.51 C6H5 cyclopentyl 7.52 CgHS cyclohexyl 7.53 C6H5 C6H5 7.54 CsH5 CsH4-4-CI
7:55 C6H5 CsH4-4-CF3 7.56 CsHs CsH4-4-CN
7.57 CsHs CgH4-4-N02 w CA 02291441 1999-11-23 Comp. No. R, R2 phys. data 7.58 CsHS CsH4-4-C6H5 7.59 CsH5 CsH4-4-OCsHs 7.60 C6H5 C6H4-4-C(CH3)3 7:61 CsHs CsH4-4-OCF3 7.62 CsH4-4-CI CF3 7.63 C6H4-4-CI C2H5 7.64 C6H4-4-CI C3Hrn 7.65 C6H4-4-CI C3H,-i 7.66 CsH4-4-CI C4H9-t 7.67 CsH4-4-CI CQH9-n 7.68 C6H4-4-CI CH2C6H5 7.69 C6H4-4-CI CH2C6H4-4-CH3 7.70 CsH4-4-CI CsH4-4-CI
7.71 CgH4-4-CI CsH4-4-OH
7.72 CsH4-4-CI CsH4-2-CH3 7.73 C6H4-4-CI CsH4-2-CI
7.74 CsH4-4-CI CsH4-4-Br 7.75 CsH4-4-CI 4-pyridyl 7.76 CsHa-4-CI CsH4-4-OCH2-CsH4-3-7.77 C6H4-4-CI C6H,-O-CHZ
F
F
7.78 H C6H5 7.79 CsHS CHZCgHS
Comp. No. R, R2 phys. data 7.80 C2H5 -CsH4-4-CI
Table 8:
Compounds of the formula H O
CH C~N~N~C~R
~ CH
z F'C~C\CH
Z Z
Comp. R, R2 phys.
No. data 8.01 H H
8.02 H CH3 8.03 H C2H5 8.04 H C3H,-n 8.05 H C3H~-i 8.06 H CaH9-n 8.07 H CaH9-t 8.08 H C6H,3-n 8.09 H C,oH2,-n 8.10 H CH2C(CH3)s 8.i CH3 H
8.12 CH3 CH3 8.13 CH3 CZHS
8.14 CH3 C3H,-n 8.15 CH3 C3H~-i 8.16 CH3 C4H9-n Comp. No. R, R2 phys. data 8.17 CH3 C4H9-t 8.18 CH3 CgH,3_n 8.19 CH3 C,oH2,-n 8.20 CH3 CH2C(CH3)s 8.21 CH3 CeHS
8.22 CH3 C6H4-2-CI ' 8.23 CH3 C6H4-3-CI
8.24 CH3 CsH4-4-CI
8.25 CH3 CsH4-2-CF3 8:26 CH3 CsH4-3-CF3 8.27 CH3 C6H4-4-CF3 8.28 CH3 CsH4-2-CN
8.29 CH3 C6H4-3-CN
8.30 CH3 C6H4-4-CN
8.31 CH3 CsH4-2-N02 8.32 CH3 CsH4-3-N02 8.33 CH3 CsH4-4-N02 8:34 CH3 CsH4-4-CsHs 8.35 CH3 C6H4-4-OCgH5 8.36 CH3 CsH4-4-C(CH3)s 8.37 CH3 CsH4-4-OCF3 8.38 CH3 CsH4-4-COOC2H5 8.39 CH3 CsFs 8.40 CH3 CsH2-3,4,5-(OCH3)s Comp. No: R, R2 phys. data 8.41 CH3 N O
U
8.42 CH3 ~-\ N
~N
8.43 CH3 OH
8.44 CBHs CF3 8.45 CsHs C2Hs 8.46 C6Hs C3H,-n 8.47 C6Hs C3H~-i 8.48 C6Hs C4H9-t 8.49 CgHs C4H9-n 8.50 CsHs cyclopropyl 8.51 C6Hs cyclopentyl 8.52 C6Hs cyclohexyl 8.53 C6Hs CsHs 8.54 CgHs CsH4-4-CI
8.55 CsHs CsH4-4-CF3 8.56 CBHs CsH4-4-CN
8.57 CsHs C6H4-4-NOZ
8.58 CsHs CsH4-4-C6Hs 8.59 CgHs CsH4-4-OCgHs -c~-Comp. No. R, R2 phys. data 8.60 CgHs C6H4-4-C(CH3)s 8.61 CsHS CsH4-4-OCF3 8.62 CsH4-4-CI CF3 8.63 C6H4-4-CI C2H5 8.64 C6H4-4-CI C3Hrn 8.65 CsH4-4-CI CsH~-i 8.66 CgH4-4-CI C4Hg-t 8.67 C6H4-4-CI C4H9-n 8.68 CsH4-4-CI CH2CsH5 8.69 CsH4-4-CI CH2CsH4-4-CH3 8.70 CsH4-4-CI CgH4-4-CI
8.71 C6H4-4-CI CsH4-4-OH
8.72 C6H4-4-CI CsH4-2-CH3 8.73 CsH4-4-CI C6H4-2-CI
8.74 CsH4-4-CI CsH4-4-Br 8.75 C6H4-4-CI 4-pyridyl 8.76 CsH4-4-CI CsH4-4-OCH2-CsH4-3-CF3 8.77 C6H4-4-CI CsH4-~-CHZ
F
F
8.78 H -CsHs 8.79 C6H5 -CH2CsH5 8.80 C2H5 -C6H4-4-CI-Table 9: Compounds of the formula I
F~ CH C~ ~CHZ\ N C
~C~ O C/ \N~ \R
CHz C~
CH
~
F O
Comp. R, R2 phys. data No.
9.01 H H
9.02 H CH3 9.03 H C2H5 9:04 H C3H,-n 9.05 H C3H~-i 9.06 H C4H9-n 9.07 H CQH9-t 9.08 H CsH,3-n 9.09 H C,oH2,-n 9.10 H CH2C(CH3)a 9.11 CH3 H
9.12 CH3 CH3 9.13 CH3 C2H5 9.14 CH3 C3H,-n 9.15 CH3 C3H~-i 9.16 CH3 C4H9-n 9.17 CH3 C4H9-t 9.18 CH3 CsH,3-n 9.19 CH3 C,oH2,-n 9.20 CH3 CH2C(CH3)s Comp. R~ R2 phys: data No.
9.21 CH3 CsH5 9.22 CH3 C6H4-2-CI
9.23 CH3 CsH4-3-CI
9.24 CH3 CsH4-4-CI
9.25 CH3 CgH4-2-CF3 9:26 CH3 CsH4-3-CF3 9.27 CH3 CsH4-4-CF3 9.28 CH3 C6H4-2-CN
9.29 CH3 CsH4-3-CN
9.30 CH3 CBH4-4-CN
9.31 CH3 CsH4-2-NOZ
9.32 CH3 C6H4-3-N02 9.33 CH3 CsH4-4-N02 9.34 CH3 CsH4-4-CsHs 9.35 CH3 CsH4-4-OC6H5 9.36 CH3 C6H4-4-C(CH3)s 9.37 CH3 CsH4-4-OCF3 9:38 CH3 CsH4-4-COOC2H5 9.39 CH3 C6F5 9.40 CH3 CsH2-3,4,5-(OCH3)s 9.41 CH3 /
N O
U
Comp. No. R, R2 phys. data 9.42 CH3 / \ N
~N
9.43 CH3 OH
\ /
9.44 CsHS CF3 9.45 CsH5 C2H5 9.46 CBH5 C3H,-n 9.47 CsHS C3H,-i 9.48 C6H5 C4H9-t 9.49 C6H5 C4H9-n 9.50 CsH5 cyclopropyl 9.51 CsHS cyclopentyl 9.52 CsHs cyclohexyl 9.53 CsH5 CsHs 9.54 CsHS CsH4-4-CI
9.55 C6H5 C6H4-4-CF3 9.56 C6H5 C6H4-4-CN
9.57 CsHS CsH4-4-N02 9.58 CsHs CsH4-4-CsHS
9.59 CsHS CsH4-4-OCgH5 9.60 CsHS CsH4-4-C(CH3)s 9.61 CsH5 CsH4-4-OCF3 Comp. No. R~ R2 phys. data 9.62 CsH4-4-CICF3 9.63 CsH4-4-CIC2H5 9.64 CsH4-4-CIC3Hrn 9.65 C6H4-4-CIC3Hri 9:66 C6H4-4-CIC4H9-t 9.67 CsH4-4-CICQH9-n ' 9.68 CsH4-4-CICH2C6H5 9.69 C6H4-4-CICH2CsH4-4-CH3 9.70 CsH4-4-CICsH4-4-CI
9.71 C6H4-4-CICsH4-4-OH
9.72 C6H4-4-CIC6H4-2-CH3 9.73 C6H4-4-CIC6H4-2-CI
9.74 C6H4-4-CICsH4-4-Br 9.75 CsH4-4-CI4-pyridyl 9.76 CsH4-4-CI-CsH4-4-OCH2-CsH4-3-CsH4_O-CHz 9.n CsH4-4-CI F
F
9.78 H CgHS
9.79 CgHS CH2CsH5 9.80 CZHS -CsH4-4-CI
Table 10: Compounds of the formula H O
z F\C/C~CHz CH ~CHz C~p~N~C~R
F Rz Comp. R, R2 phys. data No.
10.01 H H
10.02 H CH3 10:03 H C2H5 10.04 H C3H~-n 10.05 H C3Hri 10.06 H C4H9-n 10.07 H C4H9-t 10.08 H C6H,3-n 10.09 H C,oH2,-n 10.10 H CH2C(CH3)s 10.11 CH3 H
10.12 CH3 CH3 10.13 CH3 C2H5 10.14 CH3 C3H,-n 10.15 CH3 C3Hri 10.16 CH3 C4H9-n 10.17 CH3 C4H9-t -10.18 CH3 CgH,3-n 10.19 CH3 C,oH2,-n Comp. R, R2 No. phys. data 10.20 CH3 CH2C(CH3)s 10.21 CH3 CsHs 10.22 CH3 CBH4-2-CI
10.23 CH3 CsH4-3-CI
10.24 CH3 CsH4-4-CI
10.25 CH3 CsH4-2-CF3 10.26 CH3 C6H4-3-CF3 10.27 CH3 C6H4-4-CF3 10.28 CH3 C6H4-2-CN
10.29 CH3 CsH4-3-CN
10.30 CH3 C6H4-4-CN
10.31 CH3 C6H4-2-N02 10.32 CH3 CsH4-3-N02 10.33 CH3 CsH4-4-N02 10.34 CH3 CsH4-4-CsHs 10.35 CH3 CsH4-4-OCsHS
10.36 CH3 C6H4-4-C(CH3)s 10.37 CH3 CsH4-4-OCF3 10.38 CH3 C6H4-4-COOC2H5 10.39 CH3 C6F5 10.40 CH3 CsH2-3,4,5-(OCH3)a 10.41 CH3 / \
N O
U
-6p_ Comp. No. R~ R2 phys. cJata 10.42 CH3 /-~ N
~N
10.43 CH3 OH
10.44 CsH5 CF3 10.45 C6H5 C2H5 10.46 CsHS C3H,-n 10.47 CsHS C3H~-i 10.48 CsHs C4H9-t 10.49 C6H5 C4Hg-n 10.50 C6H5 cyclopropyl 10.51 CsHs cyclopentyl 10.52 CsHS cyclohexyl 10.53 CsHS C6H5 i 0.54 CsH5 CsH4-4-CI
10.55 C6H5 C6H4-4-CF3 10.56 CsH5 CsH4-4-CN
10.57 C6H5 C6H4-4-N02 10.58 CgHS CsH4-4-CsH5 10.59 C6H5 CsH4-4-OC6H5 10.60 C6H5 CsH4-4-C(CH3)s 10.61 CBHS C6H4-4-OCF3 Comp. No. R, R2 phys. data 10.62 CsH4-4-CI CF3 10.63 CsH4-4-CI C2H5 10.64 CsH4-4-CI C3Hrn 10.65 CsH4-4-CI C3Hri 10.66 CsH4-4-CI C4H9-t 10.67 C6H4-4-CI C4H9-n 10.68 C6H4-4-CI CH2C6H5 10.69 CsH4-4-CI CHzCsH4-4-CH3 10.70 C6H4-4-CI CsH4-4-CI
10.71 CBHQ-4-CI CgH4-4-OH
10.72 C6H4-4-CI CsH4-2-CH3 10.73 CsH4-4-CI C6H4-2-CI
10.74 CsH4-4-CI CsH4-4-Br 10.75 CsH4-4-CI 4-pyridyl 10.76 C6H4-4-CI CsH4-4-OCH2-CsH4-3-CF3 10.77 CsH4-4-CI C6H,-O-CHZ
F
F
10.78 H CsHS
10.79 CsHs CH2C6H5 10.80 C2H5 -CsH4-4-CI
Table 11: Compounds of the formula H o z F~C~C~CHZ CH ~CHZ C~N~N~C~R
H HZ
Comp. No. R, R2 phys. data 11.01 H H
11.02 H -CH3 11.03 H -C2H5 11.04 H -C3Hrn 11.05 H -C3H~-i 11.06 H -C4H9-n 11.07 H -CaH9-t 11.08 H -CsH,3-n 11.09 H -C,oH2,-n 11.10 H -CH2C(CH3)s 11.11 CH3 H
11.12 CH3 -CH3 11.13 CH3 -CZHS
11.14 CH3 -C3Hrn 11.15 CH3 -C3Hri 11.16 CH3 -C4H9-n 11.17 CH3 -C4H9-t 11.18 CH3 -CgH,3-n 11.19 CH3 -C,oH2,-n -Comp. No. R, R2 phys. data 11.20 CH3 -CH2C(CH3)s 11.21 CH3 -C6H5 11.22 CH3 -CsH4-2-CI
11.23 CH3 -C6H4-3-CI
11.24 CH3 -C6H4-4-CI
11.25 CH3 -CsH4-2-CF3 ' 11.26 CH3 -CsH4-3-CF3 11.27 CH3 -C6H4-4-CF3 11.28 CH3 -CsH4-2-CN
11.29 CH3 -CsH4-3-CN
11.30 CH3 -CsH4-4-CN
11.31 CH3 -C6H4-2-NOZ
11.32 CH3 -CsH4-3-N02 11.33 CH3 -C6H4-4-N02 11.34 CH3 -CsH4-4-C6H5 11.35 CH3 -CsH4-4-OCsH5 11.36 CH3 -CsH4-4-C(CH3)s 11.37 CH3 -CeH4-4-OCF3 11.38 CH3 -C6H4-4-COOC2H5 11.39 CH3 CsFs 11.40 CH3 -CsH2-3,4,5-(OCH3)a 11.41 CH3 / \
N O
U
-Comp. No. R, R2 phys. data 11:42 CH3 / ~ N
~N
11.43 CH3 OH
11.44 CsHs -CF3 11.45 CsHs -C2Hs 11.46 CsHs -C3H~-n 11.47 CsHs -C3H~-i 11.48 C6Hs -C4H9-t 11.49 C6Hs -C4H9-n 11.50 C6Hs cyclopropyl 11.51 CsHs cyclopentyl 11.52 CsHs cyclohexyl 11.53 C6Hs -C6Hs 11.54 C6Hs -CsH4-4-CI
11.55 C6Hs -CBH4-4-CF3 11.56 CsHs -C6H4-4-CN
11.57 CsHs -CsH4-4-N02 11.58 C6Hs -C6H4-4-C6Hs 11.59 C6Hs -CsH4-4-OCsHs 11.60 CsHs -C6H4-4-C(CH3)3 11.61 CsHs -CsH4-4-OCF3 Comp. No. R, R2 phys. data 11.62 CsH4-4-CI-CF3 11.63 C6H4-4-CI-C2H5 11.64 C6H4-4-CI-C3H,-n 11.65 CsH4-4-CI-C3H~-i 11.66 C6H4-4-CI-C4H9-t 11.67 CsH4-4-CI-C4H9-n 11.68 C6H4-4-CI-CHZCsHS
11.69 C6H4-4-CI-CH2CsH4-4-CH3 11.70 CsH4-4-CI-C6H4-4-CI
11.71 CsH4-4-CI-C6H4-4-OH
11.72 CsH4-4-CI-CsH4-2-CH3 11.73 C6H4-4-CI-CsH4-2-CI
11.74 CsH4-4-CI-C6H4-4-Br 11.75 CsH4-4-CI4-pyridyl 11.76 CsH4-4-CI-CsH4-4-OCH2-CsH4-3-11.77 CsH4-4-CI CBH4-O-CHZ
F
F
11.78 H -CsHS
11.79 C6H5 -CHZCsHS
11.80 C2H5 -CsH4-4-CI
Table 12: Compounds of the formula I
F C CHZ C CHZ N C
'C~ \CHz ~CHZ \O/ ~C/ \N~ \RZ
F O
Comp. No. R, R2 phys. data 12.01 H H
12.02 H CH3 12.03 H C2H5 12.04 H C3Hrn 12:05 H C3Hri 12.06 H C4H9-n 12.07 H CQH9-t 12.08 H C6H,3-n 12.09 H C,oH2,-n 12.10 H CH2C(CH3)s 12.11 CH3 H
12.12 CH3 CH3 12.13 CH3 C2H5 12.14 CH3 C3H,=n 12.15 CH3 C3Hri 12.16 CH3 CaH9-n 12.17 CH3 C4H9-t 12.18 CH3 CsH,3-n 12.19 CH3 C,oH2,-n 12.20 CH3 CH2C(CH3)a Comp. No. R~ R2 phys. data 12.21 CH3 CsHs 12.22 CH3 CsH4-2-CI
12.23 CH3 CsH4-3-CI
12.24 CH3 CsH4-4-CI
12.25 CH3 CsH4-2-CF3 12.26 CH3 CsH4-3-CF3 12.27 CH3 C6H4-4-CF3 12.28 CH3 CgH4-2-CN
12.29 CH3 CsH4-3-CN
12.30 CH3 C6H4-4-CN
12.31 CH3 CsH4-2-N02 12.32 CH3 CsH4-3-NOZ
12.33 CH3 CsH4-4-N02 12.34 CH3 CsH4-4-C6Hs 12.35 CH3 CsH4-4-OC6Hs 12.36 CH3 C6H4-4-C(CH3)3 12.37 CH3 CsH4-4-OCF3 12.38 CH3 CsH4-4-COOC2Hs 12.39 CH3 C6Fs 12.40 CH3 C6H2-3,4,5-(OCH3)a 12.41 CH3 / \
N O
U
Comp. No. R, R2 phys. data 12.42 CH3 /-~ N
~N
12.43 CH3 OH
12.44 CsHs CF3 12.45 CgHS C2H5 12.46 C6H5 C3H,-n 12.47 C6H5 C3Hri 12.48 CsHS C4H9-t 12.49 C6H5 C4H9-n 12.50 CsH5 cyclopropyl 12.51 C6H5 cyclopentyl 12.52 C6H5 cyclohexyl 12.53 C6H5 CsHS
12.54 CsH5 CsH4-4-CI
12.55 C6H5 C6H4-4-CF3 12.56 C6H5 CsH4-4-CN
12.57 C6H5 CsH4-4-N02 12.58 C6H5 CsH4-4-CsHS
12.59 CsH5 CsH4-4-OCsHS
12.60 C6H5 C6H4-4-C(CH3)s 12.61 CgH5 CsH4-4-OCF3 Comp. No. R, R2 phys. data 12.62 CsH4-4-CICF3 12.63 C6H4-4-CIC2H5 12.64 C6H4-4-CIC3H~-n 12.65 CgH4-4-CIC3Hri 12.66 CsH4-4-CIC4H9-t 12.67 CsH4-4-CIC4H9-n ' 12.68 CsH4-4-CICH2CsH5 12.69 CsH4-4-CICH2CsH4-4-CH3 12.70 CsH4-4-CICsH4-4-CI
12.71 C6H4-4-CICsH4-4-OH
12.72 CsH4-4-CICsH4-2-CH3 12.73 CsH4-4-CICsH4-2-CI .
12.74 C6H4-4-CIC6H4-4-Br 12.75 C6H4-4-CI4-pyridyl 12.76 CsH4-4-CICsH4-4-OCH2-CsH4-3-12.77 CsH4-4-CI CeH,-O-CH2 F
F
12.78 H CsH5 12.79 C6H5 CH2C6H5 12.80 C2H5 -C6H4-4-CI
Table 13: Compounds of the fomnula H o F\C/C CH ~ CH
'CH
Rz Comp. R, R2 No. phys.
data 13.01 H H
13.02 H CH3 13.03 H C2H5 13.04 H C3H,-n 13.05 H C3H,-i 13.06 H C4H9-n 13.07 H C4H9-t 13.08 H C6H,3-n 13.09 H C,oH2,-n 13.10 H CH2C(CH3)s 13.11 CH3 H
13.12 CH3 CH3 13.13 CH3 CZHS
13.14 CH3 C3Hrn 13.15 CH3 C3H~-i 13.16 CH3 C4H9-n 13.17 CH3 C4H9-t 13.18 CH3 CsH,3-n 13.19 CH3 C,oH2,-n Comp. No. R~ R2 phys. data 13.20 CH3 CH2C(CH3)s 13.21 CH3 CsHs 13.22 CH3 CsH4-2-CI
13.23 CH3 C6H4-3-CI
13.24 CH3 C6H4-4-CI
13.25 CH3 CsH4-2-CF3 13.26 CH3 C6H4-3-CF3 13.27 CH3 CsH4-4-CF3 13.28 CH3 C6H4-2-CN
13.29 CH3 C6H4-3-CN
13.30 CH3 CsH4-4-CN
13.31 CH3 C6H4-2-N02 13.32 CH3 C6H4-3-N02 13.33 CH3 CsH4-4-N02 13.34 CH3 CsH4-4-CsHs 13.35 CH3 C6H4-4-OCsHS
13.36 CH3 C6H4-4-C(CH3)s 13.37 CH3 CsH4-4-OCF3 13.38 CH3 CsH4-4-COOC2H5 13.39 CH3 CsFs 13.40 CH3 CsH2-3,4,5-(OCH3)s 13.41 CH3 ~ ~ NCO
V
Comp. No. R, R2 phys. data 13.42 CH3 ~ ~ N
~N
13.43 CH3 ~ ~ OH
13:44 C6H5 CF3 13.45 C6H5 C2H5 13.46 CgHS C3H,-n 13.47 CsHs C3H,-i 13.48 CsHS C4H9-t 13.49 CsHS C4H9-n 13.50 C6H5 cyclopropyl 13.51 C6H5 cyclopentyl 13.52 CsH5 cyclohexyl 13.53 CsHs CsHs 13.54 CsHs CsH4-4-CI
13:55 CsHs CsH4-4-CF3 13.56 CsH5 CsH4-4-CN
13.57 CsHS C6H4-4-N02 13.58 CsHS CsH4-4-C6H5 13.59 C6H5 CsH4-4-OC6H5 13.60 CsHs C6H4-4-C(CH3)s 13.61 CsHS CsH4-4-OCF3 Comp. No. R, R2 phys. data 13.62 CsH4-4-CI CF3 13.63 CsH4-4-CI C2H5 13.64 CsH4-4-CI C3Hrn 13.65 CsH4-4-CI C3H~-i 13.66 CsH4-4-CI C4H9-t 13.67 CsH4-4-CI C4H9-n 13.68 CsH4-4-CI CH2CsH5 13.69 CeH4-4-CI CH2C6H4-4-CH3 13.70 CsH4-4-CI C6H4-4-CI
13.71 C6H4-4-CI CsH4-4-OH
13.72 CsH4-4-CI CsH4-2-CH3 13.73 CgH4-4-CI C6H4-2-CI
13.74 C6H4-4-CI CsH4-4-Br 13.75 C6H4-4-CI 4-pyridyl 13.76 CsH4-4-CI CsH4-4-OCH2-C6H4-3-13.77 CsH4_4_CI CsHa-~-CHZ
F
F
13.78 H CgHg 13.79 CsH5 CH2C6H5 13.80 C2H5 -CsH4-4-CI
. CA 02291441 1999-11-23 - Table 14: Compounds of the formula H O
z F\C/C\CHz CH ~CHz C~N/N~C/R
F H Rz Comp. No. R, R2 phys. data 14.01 H H
14.02 H CH3 14.03 H CaHS
14.04 H C3H,-n 14.05 H C3H,-i 14.06 H C4H9-n 14.07 H C4H9-t 14.08 H CsH,3-n 14.09 H C,oH2,-n 14.10 H CH2C(CH3)s 14.11 CH3 H
14.12 CH3 CH3 14.13 CH3 C2Hs 14.14 CH3 C3Hrn 14.15 CH3 C3Hri 14.16 CH3 C4H9-n 14.17 CH3 CaH9-t 14.18 CH3 CsH,3-n 14.19 CH3 C,oH2,-n Comp. No. R, R2 phys. data 14.20 CH3 CH2C(CH3)3 14.21 CH3 CgHS
14.22 CH3 CsH4-2-CI
14.23 CH3 CsH4-3-CI
14.24 CH3 CsH4-4-CI
14.25 CH3 C6H4-2-CF3 14.26 CH3 CsH4-3-CF3 14.27 CH3 CgH4-4-CF3 14.28 CH3 CsH4-2-CN
14.29 CH3 CsH4-3-CN
14.30 CH3 C6H4-4-CN .
14.31 CH3 CsH4-2-N02 14.32 CH3 CsH4-3-N02 14.33 CH3 CgH4-4-N02 14.34 CH3 C6H4-4-C6H5 14.35 CH3 CsH4-4-OC6H5 14.36 CH3 CeH4-4-C(CH3)3 14.37 CH3 CgH4-4-OCF3 14.38 CH3 CsH4-4-COOC2H5 14.39 CH3 CsFs 14.40 CH3 C6H2-3,4,5-(OCH3)s 14.41 CH3 ~ ~ N ~O
Comp. No. R, R2 phys. data 14.42 CH3 ~ ~ N
~N
14.43 CH3 ~ ~ OH
14.44 C6H5 CF3 14.45 CgH5 C2H5 14.46 C6H5 C3Hrn 14.47 CgHs C3Hri 14.48 C6H5 C4Hg-t 14.49 C6H5 C4H9-n 14.50 C6H5 cyclopropyl 14.51 C6H5 cyclopentyl 14.52 C6H5 cyclohexyl 14.53 CsHS CsH5 14.54 C6H5 CsH4-4-CI
14.55 CsHs CsH4-4-CF3 14.56 C6H5 CsH4-4-CN
14.57 CBHS C6H4-4-N02 14.58 C6H5 C6H4-4-CsHs 14.59 CsHS CsH4-4-OCsHS
14.60 CsHS CBH4-4-C(CH3)3 14.61 C6H5 CgH4-4-OCF3 -n-Comp. No. R, R2 phys. data 14.62 CeH4-4-CICF3 14.63 C6H4-4-CIC2H5 14.64 C6H4-4-CIC3Hrn 14.65 C6H4-4-CIC3Hri 14.66 C6H4-4-CIC4H9-t 14.67 CsH4-4-CIC4H9-n 14.68 CsH4-4-CICH2CsH5 14.69 CeH4-4-CICH2CsH4-4-CH3 14.70 CsH4-4-CICsH4-4-CI
14.71 CsH4-4-CICsH4-4-OH
14.72 C6H4-4-CICsH4-2-CH3 14.73 CsH4-4-CIC6H4-2-CI
14.74 CsH4-4-CICsH4-4-Br 14.75 CsH4-4-CI4-pyridyl 14.76 CsH4-4-CICsH4-4-OCH2-C6H4-3-14.77 CsH4-4-CI CBH4-~-CHZ
F
F
14.78 H C6H5 14.79 C6H5 CH2CsH5 14.80 C2H5 -CgH4-4-CI
Table 15: Compounds of the formula I II i I
F~ ~C~ CHZ C~ ~CHz' N C
C~ CH2 ~CHZ O C/ \N~ \RZ
F O
Comp. R, R2 phys. data No.
v) R, is methyl, RZ is phenyl, X is NH, m is 1 and n is 1;
w) R, is methyl, R2 is 3-trifluoromethylphenyl, X is NH; m is 1 and n is 1;
x) R, is methyl, R2 is 4-tert-butylphenyl, X is NH, m is 1 and n is 1;
y) R, is phenyl, R2 is phenyl, X is NH, m is 1 and n is 1;
z) R, is hydrogen, R2 is phenyl, X is oxygen, m is 1 and n is 1;
aa) R, is phenyl, R2 is benzyl, X is NH, m is 1 and n is 1; or bb) R, is ethyl, R2 is 4-chlorophenyl, X is NH, m is 1 and n is 1.
The present invention furthermore provides a process for preparing a compound of the formula (I) which comprises a) preparing a compound of the fofmula (I) in which n is 0 and R,, R2, R3, X
arid m are as defined above under formula (I) by reacting a compound of the formula F~C~C\CHz CH ~CHz C\Yz ( II ) m F
in which R3 and m are as defined under formula (I) and Y2 is CI, Br or OS02-alkyl with a compound of the formula R~
Hx-N= (111) \
Rz in which R,, R2 and X are as defined under formula (I);
b) preparing compounds of formula (I) in which n is 0 and X is NR4 and R,, R2, R3 and m are as defined under formula (I) by reacting a compound of the formula F ~ C CHz C NHz 'C~ 'CHz ~CHz \N/ ( IV ) m in which R3, R4 and m are as defined under formula (I) with a compound of the formula _11 R~
O- ~ (V) RZ
in which R~ and R2 are as defined under formula (I); and c) preparing compounds of the formula (I) in which n is 1 and R,, R2, R3, R4, X and m are as defined under formula (I) by reacting a compound of the formula F C CHZ C
\C ~ \CHZ ~CHZ 'OH ( VI ) m F
in which R3 and m are as defined above under formula (I) with a compound of the formula R~
Y~CHz'C~X~N~C~R (VII) in which Y, is CI, Br or OS02-alkyl and X, R, and R2 are as defined above under formula (I).
The starting materials of the formulae (II) and (VI) are known or can be prepared analogously to known processes.
The starting materials of the formula (III) can be prepared in a manner known per se by reacting a ketone of the above formula (V) with hydrazine, with a hydrazine which is monosubstituted by R4 according to the above definition or with hydroxylamine, where the ketones of the formula (V) for their part are obtainable by customarry processes known for preparing ketones.
The starting materials of the formula (II) can be obtained by reacting an acyl halide of the formula F~ ~C~ CHZ C~
CH2 ~CHZ Hal m F
in which Hal is chlorine or bromine with a hydrazine which is monosubstituted by R4 according to the definition given above.
The starting materials of the formula (VII) can be obtained by reacting a chloroacetyl halide, for example chloroacetyl chloride, with a compound of the formula (III) according to the above definition.
The reaction of the process a) is preferably carried out in an inert solvent which is free of hydroxyl groups, in the presence of an organic base, for example pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline, or a bicyclic non-nucleophilic base, such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1;5-diazabicyclo[4.3.0] non-5-ene (DBN) or 1,8-diazabicyclo[5.4.OJundec-7-ene (1,5-5) (DBU).
The reaction is generally carried out at temperatures from -30°C to +70°C, preferably from -10°C to +50°C. It is advantageously carried out in the presence of a solvent or solvent mixture which is inert to the reaction. Suitable for this purpose are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane;
halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether-like compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitrites, such as acetonitrile, propionitrile;
esters, such as ethyl acetate, propyl acetate or butyl acetate; ketones, such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with one another. However, the reaction can also be carried out in an excess of one of the abovementioned bases, or, instead of the base, it is also possible to employ a second equivalent or else an even greater excess of the compound of the formula I. The reaction is carried out under atmospheric pressure;
however, it is also possible to carry out the reaction under elevated or reduced pressure.
The reaction of process b) is advantageously carried out in an inert solvent at a temperature of from 20°C to 150°C, preferably from 40°C to 120°C, if appropriate in the presence of a catalytic amount of an acid, such as acetic acid or p-toluenesulphonic acid.
Preferred inert solvents are lower alkanols, in particular methanol and ethanol.
The reaction of the process c) is advantageously carried out in an inert solvent in the presence of a base and, if appropriate, in the presence of a catalyst, for example Nal or CsF, preferred inert solvents being polar aprotic solvents, such as N,N-dimethylformamide, dimethyl sulphoxide, dioxane and tetrahydrofuran. Suitable bases are, in particular, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline, or a bicyclic non-nucleophilic base, such as 1 ,4-diazabicyclo[2.2.2]octane (DABCO); 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (1,5-5) (DBU).
The reactions described above and below are carried out in a manner known per se; for example in the absence or, if appropriate, presence of a suitable solvent or diluent or a mixture thereof, as required with cooling, at room temperature or with heating, for example in a temperature range of approximately -80°C to the boiling point of the reaction mixture, preferably from approximately -20°C to approximately +150°C and, if required, in a closed vessel, under superatmospheric pressure, in an atmosphere of inert gas and/or under anhydrous conditions. Particularly advantageous reaction conditions are shown in the examples.
The compounds of the formula (I) according to the invention are tolerated favourably by homoiotherms, fish and plants, and they are useful active compounds in the field of pest control. The active compounds according to the invention are active, in particular, against insects and arachnids, as encountered on useful and ornamental plants in agriculture and horticulture, in particular in rice, cotton, vegetable and fruit plantings, and in forests. The compounds of the formula (I) are particularly suitable for controlling insects in crops of rice, fruit and vegetables, in particular plant-damaging insects, such as Aphis craccivora, Nila-parvata lugens and Nephotettix cincticeps. Other areas of use of the active compounds according to the invention are the protection of stored products and materials and the hygiene sector, in particular the protection of pets and useful animals. The compounds of the formula (1) are active against all or individual developmental stages of normally-sensitive, but also resistant, pest species. Their effect may become apparent for example in the destruction of pests, either immediately or only after some time has elapsed, for example during ecdysis, or as a reduced oviposition and/or hatching rate.
The animal pests mentioned include, for example, those mentioned in the European Patent Application EP-A-736'252. EP-A-736'252 is therefore included by reference in the present subject-matter of the invention.
The compounds of the formula (I) are suitable, in particular, for use as active compounds for controlling pests from the order Homoptera and from the order Akarina.
The compounds of the formula (I) are particularly suitable for controlling pests in crops of cotton, vegetable, fruit and rice, such as spider mites, aphids, caterpillars of butterflies and moths, and rice leaf hoppers. Control is directed mainly against spider mites, such as Panonychus ulmi, aphids, such as Aphis craccivora, caterpillars of moths and butterflies, such as those of Heliothis virescens, and rice leafhoppers, such as Nilaparvata lugens or Nephotettix cincticeps.
The good pesticidal action of the compounds of the formula (I) according to the invention corresponds to a destruction rate (mortality) of at least 50-60% of the pests mentioned.
The activity of the compounds of the formula (1) according to the invention and of the compositions comprising them can be substantially widened and adapted to specific circumstances by addition of other insecticides and/or acaricides. Suitable additives are, for example, representatives of the following classes of active compounds: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroides, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
The compounds of the formula (I) are employed as such or, preferably, together with auxiliaries which are customary in the art of formulation, and accordingly, they can be processed, for example, to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or encapsulations in polymeric substances, in a known manner. The application methods, such as spraying, atomizing, dusting, broadcasting or watering, are, like the compositions, chosen according to the intended aims and the prevailing conditions.
The formulation, i.e. the agents, preparations or compositions comprising an active compound (I), or combinations of these active compounds with other insecticides or acaricides, and, if appropriate, a solid or liquid additive are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with extenders, for example solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).
Suitable auxiliaries, such as solvents, solid carriers, surtace-active compounds, nonionic surfactants, cationic surfactants, anionic surtactants and other auxiliaries in the compositions used according to the invention are, for example, the same as those described in EP-A-736'252.
The pesticidal preparations generally comprise from 0:1 to 99%, in particular from 0.1 to 95%, of active compound I or of the combination of this active compound with other insecticides and/or acaricides and from 1 to 99.9%, in particular from 5 to 99.9%, of a solid or liquid auxiliary, where generally from 0 to 25%, in particular from 0.1 to 20%, of the preparations may be surfactants (per cent means in each case per cent by weight). Whereas concentrated compositions are usuaNy preferred as commercial products; the end user generally employs dilute preparations which have a substantially lower concentration of active compound. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally from 1 to 1000 g of active compound per hectare, preferably from 25 to 500 g/ha.
Preferred formulations have, in particular, the following composition (% = per cent by weight):
Emulsifiable concentrates:
Active compound: from 1 to 90%, preferably from 5 to 20%
Surfactant: from 1 to 30%, preferably from 10 to 20%
Liquid carrier: from 5 to 94%, preferably from 70 to 85%
Dusts:
Active compound: from 0:1 to 10%, preferably from 0.1 to Solid carrier: from 99.9 to 90%, preferably from 99.9 to 99%
Suspension concentrates:
Active compound: from 5 to 75%, preferably from 10 to 50%
Water: from 94 to 24%, preferably from 88 to 30%
Surfactant: from 1 to 40%, preferably from 2 to 30%
Wettable aowders:
Active compound: from 0.5 to 90%, preferably from 1 to 80%
Surfactant: from 0.5 to 20%, preferably from 1 to 15%
Solid carrier: from 5 to 95%; preferably from 15 to 90%
Granules:
Active compound: from 0.5 to 30%, preferably from 3 to 15%
Solid carrier: from 99.5 to 70%, preferably from 97 to 85%
The preparations may also comprise other auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil; preservatives, viscosity regulators; binders and/or tackifiers, and also fertilizers or other active compounds for obtaining special effects.
The examples below serve to illustrate the invention. They do not limit the invention.
Temperatures are stated in degrees Celsius.
Example H1:
l~ ~ H3 FZC=CH-ECH~C-O-N= ;
0.73 g (10 mmol) of acetone oxime and 1.01 g (10 mmol) of triethylamine are dissolved in 30 ml of anhydrous benzene. At 5-10°C, the solution is admixed over a period of 30 minutes and with vigorous stirring with 1.68 g (10 mmol) of 6,6-difluorohex-5-enoic acid chloride (DAHSCI), and the mixture is stirred at room temperature for another 10 hours and then filtered through a glass suction filter, and the filtrate is concentrated using a rotary evaporator. The resulting crude product is separated by silica gel column chromatography (ethyl acetate:isohexane = 20:80). This gives the title compound of no~° = 1.6893.
Example H2:
/ sHs FZC=CH-ECH~-C-NH-N= \
CsHs 1.5 g (7.6 mmol) of benzophenone hydrazone and 0.77 g (7.6 mmol) of triethylamine are dissolved in 30 ml of anhydrous benzene, and at 5-10°C the solution is admixed with 1.29 g (7.6 mmol) of 6,6-difluoro-hex-5-enoic acid chloride (DAHSCI) over a period of 30 minutes.
The mixture is then stirred at room temperature for another l0 hours and filtered through a glass suction filter, and the filtrate is concentrated using a rotary evaporator. The resulting crude product is separated by silica gel column chromatography (ethyl acetate:isohexane =
20:80). This gives the title compound of m.p. 70-71 °C.
Example H3:
~ H3 FZC=CH-ECH~--C-NH-N=C\
H
0.5 g (10 mmol) of hydrazine hydrate is added to 1.64 g (10 mmol) of methyl 6,6-difluorohex-5-enoate in 10 ml of methanol. The solution is heated under reflux on a water bath for 10 minutes and then concentrated using a rotary evaporator. The residue is suspended in 20 ml of methylene chloride and, at 0°C, admixed with 0.445 g (10 mmol) of acetaldehyde, and the mixture is then stirred at room temperature for another 10 hours. The methylene chloride is evaporated and the crude product is separated by silica gei column chromatography (methyl acetate:isohexane = 20:80). This gives the title compound of m.p. 78-79°C.
Examine H4:
II II i gHs FZC=CH-ECH2~--C-O-CHZ-C-NH-N=C
3 \
Cr6H5 3.6 g (18.4 mmol) of benzophenone hydrazone and 1.85 g (18.3 mmol) of triethylamine are dissolved in 50 ml of benzene, and the mixture is cooled to 5°C. With efficient stirring, 2.06 g (18.2 mmol) of chloroacetyl chloride are slowly added dropwise such that the temperature can be kept at from 5 to 10°C at all times. After the addition of the chloroacetyl chloride, stirring is continued at room temperature for 14 hours. The mixture is filtered and the filtrate is concentrated. The residue is washed with a small amount of isohexane:acetic acid =
80:20, filtered and dried. This gives the title compound of m.p. 92-93°C.
A mixture of 1.7 g (6.2 mmol) of chloroacetylbenzophenone hydrazide, 0.93 g (6.2 mmol) of 6,6-difluorohex-5-enoic acid, 0.63 g (6:2 mmol) of triethylamine and 0.2 g of Naf in 10 ml of dimethylformamide is stirred at room temperature for 14 hours. The reaction mixture is poured onto ice, the mixture is extracted with chloroform and the extract is dried over Na2S04. The solvent is distilled off and the crude product is separated on silica gel (isohexane:ethyl acetate = 80:20). This gives the title compound no~° =
1.5678.
Example H5:
II II /cH3 F2C=CH-ECH~-C-O-CH2-C-NH-N=C
3 \
0.5 g (10 mmol) of hydrazine hydrate is added to a solution of 0.9 g (10 mmol) of methyl glycolate in 10 ml of methanol. For 10 minutes, the solution is heated under reflux on a water bath, and it is then concentrated using a rotary evaporator. The residue is suspended in ml of methanol and admixed with 0:58 g (10 mmol) of acetone, and the mixture is then stirred at room temperature for 10 hours. The methanol is evaporated and the residue is then suspended in 20 ml of dichloromethane/tetrahydrofuran. 1.5 g (10 mmol) of 6,6-difluorohex-5-enoic acid, 406 g (10 mmol) of DCC and 0.1 g of 4-dimethylaminopyridine are added to this mixture, which is then stirred for 14 hours and filtered through a glass suction filter, and the filtrate is concentrated using a rotary evaporator. The resulting crude product is purified by silica gel column chromatography (ethyl acetate:isohexane =
20:80). This gives the title compound of no~° =1.6768.
In a manner similar to that described in Examples H1 to H5, it is possible to prepare the compounds of the formula (I) listed in Tables 1 to 20.
Table 1: Compounds of the formula H O
F~C~C~CH C~O~N~C~Rz F R~
Comp. No. R, R2 phys. Data 1:01 H H
1.02 H CH3 1.03 H C2H5 1.04 H C3H~-n 1.05 H C3H,-i 1.06 H Calls-n 1.07 H C4Hs-t 1.08 H CsH,3-n 1.09 H C,oH2,-n 1.10 H CH2C(CH3)a 1.11 CH3 H
1.12 CH3 CH3 1.13 CH3 C2H5 1.14 CH3 C3H~-n 1.15 CH3 C3Hri 1.16 CH3 C4Hs-n 1.17 CH3 C4Hs-t .. CA 02291441 1999-11-23 Comp. No. R, R2 phys. Data 1.18 CH3 CgH,3-n 1.19 CH3 C,pH2,-n 1.20 CH3 CHZC(CH3)s 1:21 CH3 CsHs 1.22 CH3 CBH4-2-CI
1.23 CH3 CsH4-3-CI
1.24 CH3 CsH4-4-CI
1.25 CH3 C6H4-2-CF3 1.26 CH3 CsH4-3-CF3 1.27 CH3 CsH4-4-CF3 1.28 CH3 CsH4-2-CN
1.29 CH3 CsH4-3-CN
1.30 CH3 C6H4-4-CN
1.31 CH3 C6Ha-2-N02 1.32 CH3 CsH4-3-N02 1.33 CH3 C6H4-4-N02 1.34 CH3 CsH4-4-C6H5 1.35 CH3 C6H4-4-OCsHS
1.36 CH3 CgH4-4-C(CH3)3 1.37 CH3 CsH4-4-OCF3 1.38 CH3 CsH4-4-COOC2H5 1:39 CH3 CsFS
1.40 CH3 -CsH~-3,4,5-(OCH3)3 Comp. No. R, R2 phys. Data 1.41 CH3 / \
N O
U
1.42 CH3 ~ ~ N
~N
1.43 CH3 \ ~ OH
1.44 CsH5 CF3 1.45 C6H5 C2H5 1.46 CgHS C3H,-n 1.47 C6H5 C3H,-i 1.48 CsHs C4H9-t 1.49 CsH5 C4H9-n 1.50 C6H5 cyclopropyl 1.51 CsHs cyclopentyl 1.52 C6H5 cyclohexyl 1.53 CsHS CsHS
1:54 CsH5 CsH4-4-CI
1.55 C6H5 C6H4-4-CF3 1.56 C6H5 CsH4-4-CN
1.57 CsH5 C6H4-4-N02 1.58 CgH5 CgH4-4-CsH5 1.59 CsHS CsH4-4-OCsHS
Comp. No. R, R2 phys. Data 1.60 CBHS CgH4-4-C(CH3)s 1.61 CsHS CgH4-4-OCF3 1:62 CsH4-4-CI CF3 , 1.63 C6H4-4-CI C2H5 1.64 C6H4-4-CI C3Hr~
1.65 CsHa-4-CI C3Hri 1.66 CgH4-4-CI C4H9-t 1.67 CsH4-4-CI C4H9-n 1.68 CsH4-4-CI CH2CsH5 1.69 C6H4-4-CI CH2CgH4-4-CH3 1.70 CsH4-4-CI CsH4-4-CI
1.71 CsH4-4-CI C6H4-4-OH
1.72 CsH4-4-CI CsH4-2-CH3 1.73 CsH4-4-CI C6H4-2-CI
1.74 C6H4-4-CI C6H4-4-Br 1.75 C6H4-4-CI 4-pyridyl 1:76 CsH4-4-CI CgH4-4-OCH2-CsH4-3-CF3 1.77 CsH4-4-Cl oBH~
F
F
1:78 H CgHS
1.79 C6H5 CH2CsH5 1.80 C2H5 -C6H4-4-CI
Table 2: Compounds of the formula H O
F~C~C~CH C~N~N~Ci~
F H R~
Comp. No. R, RZ phys. Data 2.01 H H
2.02 H CH3 2.03 H CzHs 2.04 H C3H,-n 2.05 H C3Hri 2.06 H C4Hs-n 2.07 H C4Hs-t 2.08 H CsH,3-n 2.09 H C,oH2,-n 2.10 H CH2C(CH3)s 2.11 CH3 H
2.12 CH3 CH3 2.13 CH3 C2H5 2.14 CH3 C3Hr-n 2.15 CH3 C3H,-i 2.16 CH3 C4Hs-n 2.17 CH3 CaHs-t 2.18 CH3 CsH,3-n 2.19 CH3 C,oH~,-n 2.20 CH3 CH2C(CH3)s Comp. No. R, R2 phys. Data 2.21 CH3 CsH5 2.22 CH3 CsH4-2-CI
2.23 CH3 CgH4-3-CI
2.24 CH3 CsH4-4-CI
2.25 CH3 CsH4-2-CF3 2.26 CH3 CgH4-3-CF3 2.27 CH3 CsH4-4-CF3 2.28 CH3 C6H4-2-CN
2.29 CH3 C6H4-3-CN
2.30 CH3 C6H4-4-CN
2.31 CH3 CsH4-2-N02 2.32 CH3 CsH4-3-N02 2.33 CH3 C6H4-4-N02 2.34 CH3 C6H4-4-C6H5 2.35 CH3 CsH4-4-OC6H5 2.36 CH3 CsH4-4-C(CH3)s 2.37 CH3 CsH4-4-OCF3 2.38 CH3 CsH4-4-COOC2H5 2.39 CH3 C6F5 2.40 CH3 CsH2-3,4,5-(OCH3)s 2.41 CH3 / \
N O
V
Comp. No. R, R2 phys. Data 2.42 CH3 / \
N~ N
2.43 CH3 OH
2.44 CsHS CF3 2.45 CsHS CZHS
2.46 CsHS C3H~-n 2.47 C6H5 C3H,-i 2.48 CsHS C4Hs-t 2.49 CsH5 CaHs-n 2.50 C6H5 cyclop~opyl 2.51 C6H5 cyclopentyl 2.52 C6H5 cyclohexyl 2.53 C6Hs C6H5 2.54 CsHS CsH4-4-CI
2.55 CsHs C6H4-4-CF3 2.56 CsHs CsH4-4-CN
2.57 CsHs CsH4-4-NO2 2.58 CsH5 CsH4-4-CsH5 2.59 CsH5 C6H4-4-OCsHs 2.60 CsH5 CsH4-4-C(CH3)s 2.61 CsHS CsH4-4-OCF3 Comp. No. R, R2 phys. Data 2:62 CsH4-4-CI CF3 2.63 CsH4-4-CI C2H5 2.64 CsH4-4-CI C3H,-n 2.65 C6H4-4-CI C3Hri 2.66 CsH4-4-CI C4Hg-t 2.67 . CsH4-4-CI C4H8-n 2.68 CsH4-4-CI CH2C6H5 2.69 CgH4-4-CI CH2CsH4-4-CH3 2.70 CsH4-4-CI CsH4-4-CI
2.71 CsH4-4-CI C6Ha-4-OH
2.72 CsH4-4-CI CsH4-2-CH3 2.73 C6H4-4-CI C6H4-2-CI
2:74 C6H4-4-CI CsH4-4-Br 2.75 C6H4-4-CI 4-pyridyl 2.76 C6H4-4-CI -CsH4-4-OCH2-CsH4-3-CF3 2.77 CsH4-4-C) CsH4-~-CHZ
F
F
2.78 H -CsH5 2.79 CsH5 CH2C6H5 2.80 C2H5 -C6H4-4-CI
Table 3: Compounds of the formula I II I
F~C~C~CH C~O~CHZ'C~N~N~C~R
F O
Comp. No. R, R2 phys. Data 3.01 H H
3.02 H CH3 3.03 H C2H5 3.04 H C3Hrn 3.05 H C3Hri 3:06 H C4H9-n 3.07 H C4H9-t 3.08 H CsH,3-n 3.09 H C,oH2,-n 3.10 H CHZC(CH3)s 3.11 CH3 H
3.12 CH3 CH3 3.13 CH3 C2H5 3.14 CH3 C3Hrn 3.15 CH3 C3Hri 3:16 CH3 C4H9-n 3.17 CH3 C4H9-t 3.18 CH3 C6H,3-n 3.19 CH3 C,oH2,-n 3.20 CH3 CH2C(CH3)a Comp. No. R~ R2 phys. Data 3.21 CH3 CsHs 3:22 CH3 CsH4-2-CI
3.23 CH3 C6H4-3-CI
3.24 CH3 C6H4-4-CI
3.25 CH3 CgH4-2-CF3 3.26 CH3 C6H4-3-CF3 ' 3.27 CH3 C6H4-4-CF3 3.28 CH3 C6Ho-2-CN
3.29 CH3 CsH4-3-CN
3.30 CH3 CsH4-4-CN
3.31 CHs CsH4-2-N02 .
3.32 CH3 C6H4-3-N02 3.33 CH3 CsH4-4-N02 3.34 CH3 C6H4-4-CsHs 3.35 CH3 C6H4-4-OC6H5 3.36 CH3 C6H4-4-C(CH3)s 3.37 CH3 C6H4-4-OCF3 3.38 CH3 CsH4-4-COOC2H5 3.39 CH3 CsFS
3.40 CH3 CsH2-3,4,5-(OCH3)s n 3.41 CH3 .28_ Comp. No. R, R2 phys. Data 3.42 CH3 / \ N
~N
3.43 CH3 -\ / OH
3.44 CsHs 3.45 CsH5 ~H5 3.46 CsH5 C3Hrn 3.47 C6H5 CsH~-i 3.48 CsHs C4H9-t 3.49 C6H5 C4H9-n 3.50 CsHS cyciopropyl 3.51 CsH5 cyclopentyl 3.52 CsHS cyclohexyl 3.53 CgH5 CsH5 3.54 CeHS C6H4-4-CI
3.55 CsHs CsH4-4-CF3 3.56 C6H5 CsH4-4-CN
3.57 CgHs C6H4-4-N02 3.58 CgHS CsH4-4-CsHs 3.59 CsHS C6H4-4-OC6H5 3.60 CsHS CsH4-4-C(CH3)a 3.61 CsHS CgH4-4-OCF3 _ CA 02291441 1999-11-23 Comp. No. R, R2 phys. Data 3.62 CgH4-4-CI CF3 3.63 CsH4-4-CI C2H5 3:64 CsH4-4-CI C3Hrn 3.65 CsH4-4-CI C3Hri 3.66 CsH4-4-CI C4H9-t 3.67 CsH4-4-CI CaH9-n 3.68 CsH4-4-CI CH2CsH5 3.69 C6H4-4-CI CH2CsH4-4-CH3 3.70 CgH4-4-CI CsH4-4-CI
3:71 CsH4-4-CI CsH4-4-OH
3.72 C6H4-4-CI C6H4-2-CH3 3.73 CsH4-4-CI C6H4-2-CI
3.74 CsH4-4-CI C6H4-4-Br 3:75 CsH4-4-CI 4-pyridyl 3.76 C6H4-4-CI CsH4-4-OCH2-CsH4-3-CF3 3.77 C6H4-4-CI CBH,-O-CHZ
F
F
3.78 H CgH5 3.79 C6H5 CH2C6H5 3.80 C2H5 -CsH4-4-CI
Table 4:
Compounds of the formula H O
F~C~C\CHZ
CHZ'C~
C~O/N~C~R~
Rz Comp. R2 No. phys.
R~ Data 4.1 H
H
4.2 CH3 H no~
=1.6869 4.3 C2H5 H
4.4 C3Hrn H
4.5 C3H~-i H
4.6 C4H9-n H
4.7 CaH9-t H
4.8 CsH~3-n H
4.9 C~oH2wn H
4.10 CH2C(CH3)a H
4.11 H
4.12 CH3 CH3 np2 =1.6893 4.13 C2H5 4.14 C3H,-n 4.15 C3H~-i 4.16 C4H9-n 4.17 C4H9-t 4.18 CsH,3-n 4.19 C~oH~-n Comp. R~ R2 phys. Data No.
4.20 CH3 CH2C(CH3)s 4.21 CH3 C6H5 np~ =1.50731 4.22 CH3 CsH4-2-CI Oil 4.23 CH3 CgH4-3-CI no~ =1.6883 4.24 CH3 CgH4-4-CI Oil 4.25 CH3 C6H4-2-CF3 np2 =1.4667 4.26 CH3 CsH4-3-CF3 np~ =1.6765 4.27 CH3 C6H4-4-CF3 4.28 CH3 C6H4-2-CN
4.29 CH3 CsH4-3-CN amorphous 4.30 CH3 CsH4-4-CN m.p.:
4.31 CH3 CsH4-2-N02 n~2 =1.6888 4.32 CH3 CsH4-3-N02 np2 =1.6897 4.33 CH3 C6H4-4-N02 np2 = 1.6853 4.34 CH3 C6H4-4-Cells m.p.: 51-52C
4.35 CH3 CsH4-4-OCsHs Oil 4.36 CH3 C6H4-4-C(CH3)3 no~ =1.6754 4.37 CH3 C6H4-4-OCF3 npz = 1.6843 4.38 CH3 CsH4-4-COOC2H5 amorphous 4.39 CH3 CsF5 Oil 4.40 CH3 C6H2-3,4,5-(OCH3)3 n~2 =1.5207 4.41 CH3 ~ ~ N o amorphous U
Comp. No. R, R2 phys. Data 4.42 CH3 ~ ~ N
~N
4.43 CH3 - m.p.: 79-81 °C
~ OH
4.44 CsHs CF3 4.45 CsHS C2H5 4.46 C6H5 C3Hrn 4.47 C6H5 C3Hri Oil 4.48 CsHS C4H9-t noz _ 1.4850 4.49 CsHS CaH9-n 4.50 C6H5 cyclopropyl np2 = 1.5132 4.51 CsHS cyclopentyl 4.52 CsHS cyclohexyl 4.53 CsH5 CsH5 np2 =1.5503 4.54 CsHs CsH4-4-CI Oil 4.55 CBH5 C6H4-4-CF3 np~ =1.5130 4.56 CsH5 CsH4-4-CN
4.57 C6H5 C6H4-4-N02 amorphous 4.58 C6H5 CsH4-4-CsHs 4.59 CsH5 CsH4-4-OC6H5 4.60 CsHS CsH4-4-C(CH3)a 4.61 CsHS CgH4-4-OCF3 -Comp. R, R2 phys. Data No.
4:62 CgH4-4-CI CF3 noz =1.4709 4.63 C6H4-4-CI C2H5 4.64 C6H4-4-CI CsH,-n 4.65 CsH4-4-CI C3H~-i 4.66 CsH4-4-CI C4H9-t 4.67 CgH4-4-CI C4H9-n ' 4.68 CsH4-4-CI CH2C6H5 4.69 C6H4-4-CI CH2CsH4-4-CH3 4.70 C6H4-4-CI CsH4-4-CI m.p.:66-67C
4.71 C6H4-4-CI C6H4-4-OH
4.72 CsH4-4-CI CsH4-2-CH3 .
4.73 CsHa-4-CI CsH4-2-CI
4.74 C6H4-4-CI CsH4-4-Br 4.75 CgH4-4-CI 4-pyridyl np2 = 1.5575 4.76 CsH4-4-CI C6H4-4-OCH2-C6H4-3-CF3 4.77 C6H4_4_CI CsHa-~-CHZ
F
F
4.78 H C6H5 np2 =1.5131 4.79 CsHS CH2CsH5 np2 =1.6744 4.80 C2H5 -CsH4-4-CI no2 =1.6768 4.81 CH3 C6H3-3,5-(CF3)2 np~ =1.4509 4.82 cyclopropyl -C6H3-4-CI np2 =1.6820 Comp. No. R, R2 phys. Data ,o-Et 4.83 CH3 j m.p.:
/ I 138-140°C
o ~ cF, ,o-Me 4.84 CH3 ~ np~ =1.5350 Iw / O/ / I G
,O-Et 4.85 CH3 ~ B~ np~° =1.5568 I / o w I
,o-Me 4.86 CH3 I np~ =1.4770 cI /~
'\ v _O-CF -CHF
z z ,QEt 4.87 C2H5 j ~~ no = 1.4768 I I
/ o ,O-Me 4.88 C2H5 I np~ = 1.5113 /
I/ \I
4.89 CH3 np~ =1.5510 4.90 CH3 np~ =1.5282 Comp. No. R~ R2 phys.
Data ,o-Me ~
4.91 CH3 ~ np = 1.5110 i / O \ CF
O-Me . 3 m.p .: 36-37 C
i CHFZ
~
~ ~
4.93 CH3 ~ np~ = i .5175 v N-4.94 -C6H5 C6H4-2-F nom = 1.5390 4.95 -CsHS CsH3-2,4-F2 nom =1.5267 4.96 -CsHs CsH4-4-F np25 = 1.5343 4.97 -CsH4-4-F CsH4-4-F m.p. :55-57C
4.98 -CsH5 CsH4-3-CF3 np~ = 1.5143 4.99 -CsH4-3-CF3CsH4-3-CF3 no = 1.4831 4.100 -CsHs C6H4-2-CI nom = 1.5523 4.101 m.p.: 52-54°C
' ~ I ~
/ /
4.102 o2N ' ' No2 m.p.:
/ ~ / 136-138C
4.103 -C6H5 -CgH3-4-CI-3-N02 m.p.:72-75C
4.104 -CsHS -CsH4-3-N02 nom = 1.5615 4.105 -CgHS -CgH~-2,4-CI2 np~ =1.5490 Comp. No. R, RZ phys. Data 4.106 -CsHs -CsH4-4-S-CsH4-4-CI np~ = 1.5757 4.107 -CsH5 nom = 1.5058 4.108 -CsH4-4- -CgH4-4-O-CH3 np2 =1:5578 n-C H
~ "
4.109 -CsMs ~ / o m.p.: 44-46C
F
O i F
o 4.110 -C6H5 ~ / np23 = 1.5045 F
O ~
F
4.111 -CsH4-4-F np~ =1.5000 F
4.112 ~ \ np2a =1.6060 v ~ w Table 5: Compounds of the formula H O
F\C~C'CH CHZ~CH C~N~N\C~Ri F H RZ
Comp. No. R, R2 phys. data 5.1 H H
5.2 H CH3 m.p.: 78-79C
5.3 H C2H5 5.4 H C3Hrn 5.5 H C3Hri 5.6 H C4H9-n 5.7 H C4H9-t 5.8 H C6H,3-n 5.9 H C,oH2,-n 5.10 H CH2C(CH3)s 5.11 CH3 H
5.12 CH3 CH3 np~ =1.7589 5.13 CH3 C2H5 5.14 CH3 C3H~-n 5.15 CH3 C3H,-i 5.16 CH3 C4H9-n 5.17 CH3 C4H9-t 5.18 CH3 CeH,3-n Comp. No. R, R2 phys. data 5.19 CH3 C,oH~,-n 5.20 CH3 CH2C(CH3)s 5.21 CH3 CsHs m.p.: 64-66C
5.22 CH3 CsH4-2-CI m.p.: 79-82C
5.23 CH3 C6H4-3-CI m.p.: 75-78C
5.24 CH3 CsH4-4-CI m.p:: 104-106C
5.25 CH3 C6H4-2-CF3 np~ _ 1.4941 5.26 CH3 CgH4-3-CF3 m.p.: 82-83C
5.27 CH3 CsH4-4-CF3 m.p.: 68-69C
5.28 CH3 CsH4-2-CN
5.29 CH3 C6H4-3-CN m.p.: 123-124C
5.30 CH3 CsH4-4-CN
5.31 CH3 CsH4-2-N02 m.p.: 80-84C
5.32 CH3 C6H4-3-N02 m.p.: 129-130C
5.33 CH3 CsH4-4-N02 m.p.: 159-161 C
5.34 CH3 C6H4-4-CgHS m.p.: 193-195C
5.35 CH3 C6H4-4-OCsHS m.p.: 108-109C
5.36 CH3 CsH4-4-C(CH3)3 m.p.: 106-108C
5.37 CH3 C6H4-4-OCF3 m.p.: 93-94C
5.38 CH3 C6H4-4-COOC2H5 m.p.: 98-101 C
5.39 CH3 CsFS m.p.: 119-124C
5.40 CH3 CsH~-3,4,5-(OCH3)3 m.p.:106-108C
5.41 CH3 / \ o m.p.:145-146°C
U
Comp. No. R, R2 phys. data 5.42 CH3 ~ \ N~ m.p.:138-140°C
~N
5.43 CH3 m.p.: 132-133°C
OH
5.44 -CsH5 CF3 5.45 -CsHs C2Hs 5.46 -CsH5 C3Hrn 5.47 -CsHS C3H,-i 5.48 -C6H5 CQH9-t m.p.:38-39°C
5.49 -C6H5 C4H9-n 5.50 -CsH5 cyclopropyl no~° =1.5962 5.51 -CsH5 cyclopentyl 5.52 -CsHS cyclohexyl 5.53 -CsHS CsH5 m.p.: 70-71 °C
5.54 -CsHS C6H4-4-CI m.p.: 129-131 °C
5.55 -CsHs CsH4-4-CF3 m.p.:119-120°C
5.56 -CsHS CsH4-4-CN
5.57 -CsHs C6H4-4-N02 m.p.:88-90°C
5.58 -C6H5 CsH4-4-CsHS m.p.:130-132°C
5.59 -C6H5 C6H4-4-OCsHS
5.60 -CsHS C6H4-4-C(CH3)a 5.61 -CsHS C6H4-4-OCF3 Comp. No. R, R2 phys. data 5.62 -CsH4-4-CI CF3 5.63 -CsH4-4-CI C2H5 5.64 -C6H4-4-CI C3Hrn 5.65 -CsH4-4-CI C3Hri 5.66 -CsH4-4-CI C4H9-t 5.67 -CsH4-4-CI C4H9-n 5.68 -CsH4-4-CI CH2CsH5 5.69 -CsH4-4-CI CH2CsH4-4-CH3 5.70 -C6H4-4-CI -C6H4-4-CI m.p.:114-116C
5.71 -CsH4-4-CI -C6H4-4-OH
5.72 _CsH4_4_CI _CsH4-2_CH3 5.73 -CsH4-4-CI -CsH4-2-CI
5.74 -C6H4-4-CI -C6H4-4-Br 5.75 -C6H4-4-CI 4-pyridyl m.p.:144-148C
5.76 -CsH4-4-CI -C6H4-4-OCH2-CsH4-3-CF3Resin 5.77 -CsH4-4-CI CsHo-O-CH2 F Resin F
5.78 H -CsHs m.p.: 60-63C
5.79 -CsH5 -CH2CsH5 m.p.: 95-96C
5.80 -C2H5 -CsH4-4-CI m.p.: 106-107C
5.81 -CsH4-4-CI -CsH4-4-OS02N(CH3)2 m.p.:105-115C
5.82 m.p.: 151-155°C
ci ~ ~ ci - Comp. No. R, R2 phys. data 5.83 -CsHs cyclopropyl m.p.:80-82C
5.84 -CH3 -CsH3-3,5-(CF3)2 m.p.:103-105C
5.85 -C6H5 -CsH4-4-F m.p.:77-78C
5.86 -C6H5 -CsH3-2,4-F2 m.p.:109-110C
5.87 -CsH5 -CsH4-4-F m.p.: 99-101 C
5.88 -CBH4-4-F -C6H4-4-F m.p.:76-77C
5.89 m.p.: 130-132°C
i i 5.90 -C6H5 -CsH4-3-N02 m.p.:102-106°C
5.91 -CsHS -CsH~-3-CF3 m. p.: 49-50°C
O-Et 5.92 -C6H5 ~ m.p.:81-82°C
i 5.93 -CgH4-3-CF3 -C6H4-3-CF3 m.p.:62-63°C
5.94 -CsH4-4-OCH3 -C6H4-4-OCH3 m.p.:82-83°C
5.95 -C6H4-4-OCH3 -CH2-C6H4-4-OCH3 m.p.:123-124°C
5.96 -CgHs -CsH4-2-CI m.p.:69-70°C
5.97 -CgHS -C6H3-2,4-Ci2 m.p.:117-118°C
5.98 -CsH4-4-N(CH3)2 -C6H4-4-N(CH3)2 m.p.:93-94°C
5.99 -CgH5 -C6H4-4-S-CsH4-4-CH3 m.p.:112-113°C
o-~
5.100 -CsH5 \ np~° =1.5510 I /
Comp. No. R, R2 phys. data ~Isobutyl 5.101 -CsHs no2° = 1.5355 W
Table 6: Compounds of the formula F~ yC~ ~CH2' ~C~ /CHZ\ /N~ /C~
I CHZ CHZ O (I N R2 O
Comp. No. R, R2 phys. data 6.1 H H
6.2 H CH3 no~ = 1,6815 6.3 H C2H5 6.4 H C3H,-n 6.5 H C3H~-i 6.6 H C4H9-n 6.7 H C4H9-t 6.8 H CsH,3-n 6.9 H C,oH2,-n 6.10 H CH2C(CH3)s 6.11 CH3 H
6.12 CH3 CH3 amorphous 6.13 CH3 C2H5 6.14 CH3 C3H~-n Comp. No. R, R2 phys.
data 6.15 CH3 C3H,-i 6.16 CH3 C4Hg-n 6.17 CH3 C4H9-t 6.18 CH3 CsH,3-n 6.19 CH3 C,oH2,-n 6.20 CH3 CHZC(CH3)3 6.21 CH3 CgHS m.p .: 92-94C
6.22 CH3 CgH4-2-Ct ~ m.p .:58-60C
6.23 CH3 CsH4-3-CI m.p .: 126-127C
6.24 CH3 C6H4-4-CI m.p .: 125-127C
6:25 CH3 CsH4-2-CF3 m.p .: 62-64C
6.26 CH3 CgH4-3-CF3 m.p .: 148-149C
6.27 CH3 CeH4-4-CF3 m.p .: 103-104C
6.28 CH3 CeH4-2-CN
6.29 CH3 C6H4-3-CN m.p .: 130-131 C
6.30 CH3 CsH4-4-CN m.p .: 141-142C
6.31 CH3 CgH4-2-N02 m.p .: 81-84C
6.32 CH3 CsH4-3-N02 m.p .: 150-152C
6.33 CH3 CgH4-4-N02 m.p.:
6.34 CH3 C6H4-4-CBHS m.p.:
6.35 CH3 CsH~-4-OCsH5 m:p.:
6.36 CH3 CsH4-4-C(CH3)3 m.p.:157-158C
6.37 CH3 CsH4-4-OCF3 m.p.:
6.38 CH3 CgH4-4-COOC2H5 m.p.:127-129C
Comp. No. R, R2 phys. data 6.39 CH3 CsF5 m. p.: 73-76C
6.40 CH3 C6H2-3,4,5-(OCH3)3 m.p.: 139-141 C
6.41 CH3 ~ \ m.p.:142-144C
o N
~1 6.42 CH3 ~ \ N~ m.p.:146-148°C
~N
6.43 CH3 m.p.: 168-170°C
\ ~ OH
6.44 CsH5 CF3 6.45 C6H5 C2H5 6.46 CsHS C3H,-n 6.47 CsHs C3H~-i np2 =1.6978 6.48 C6H5 C4H9-t no2 =1.6988 6.49 C6H5 C4H9-n 6.50 CsHS cyclopropyl m.p.:60-62C
6.51 C6H5 cyclopentyl 6.52 CsH5 cyclohexyl 6.53 CgHS CsHs m.p.:.50-53C
6.54 CsHS CsH4-4-CI m.p.:102-102C
6.55 C6H5 C6H4-4-CF3 6.56 CgH5 C6H4-4-CN
6.57 C6H5 C6H4-4-N02 Comp. R~ R2 phys. data No.
6.58 CsH5 CgH4-4-CsH5 6.59 CsHS C6H4-4-OCsH5 6.60 CsH5 C6H4-4-C(CH3)s 6.61 CgHs CsH4-4-OCF3 6.62 CsH4-4-CI CF3 6.63 CsH4-4-CI C2H5 ' 6:64 C6H4-4-CI C3H,-n 6.65 CsH4-4-CI C3H,-i 6.66 CsH4-4-CI CaHs-t 6.67 C6H4-4-CI C4Hs-n 6.68 CsH4-4-CI CH2C6H5 .
6.69 CsH4-4-CI CH2CsH4-4-CH3 6.70 C6H4-4-CI CsH4-4-CI m.p.:73-75C
6.71 CsH4-4-CI CsH4-4-OH
6.72 CsH4-4-CI C6H4-2-CH3 6.73 CgH4-4-CI C6H4-2-CI
6.74 CsH4-4-CI C6H4-4-Br 6.75 CsH4-4-CI 4-pyridyl 6.76 CsH4-4-CI C6H4-4-OCHz-C6H4-3-CFs 6.77 CsH4-4-CI CsH~-~-CHZ
F
F
6.78 H -CsHS m.p.: 72-75°C
6.79 CsHS -CH2CsH5 m.p.:104-106°C
' Comp. No. R, R2 phys. data 6.80 C2H5 -CBH4-4-CI m.p.:79-80C
6.81 CH3 -CgH3-3,5-(CF3)2 m.p.:148-150C
6.82 C2H5 -CsH4-4-CI m.p.:79-80C
Table 7: Compounds of the formula H O
z F'C~C'CHz CH ~CHz C\O/N~'C~R
F RZ
Comp. No. R, R2 phys. data 7.01 H H
7.02 H CH3 7.03 H C2H5 7.04 H C3H,-n 7.05 H C3H,-i 7.06 H C4H9-n 7.07 H C4H9-t 7.08 H CsH,3-n 7.09 H C,oH2,-n 7.10 H CH2C(CH3)a 7.11 CH3 H
7.12 CH3 CH3 7.13 CH3 C2H5 7.14 CH3 C3H,-n Comp. No. R, R2 phys. data 7.15 CH3 C3H,-i 7.16 CH3 C4H9-n 7.17 CH3 C4H9-t 7.18 CH3 CsH,3-n 7.19 CH3 C,oH2,-n 7.20 CH3 CH2C(CH3)3 7.21 ~ CH3 CsH5 7.22 CH3 C6H4-2-CI
7.23 CH3 CsH4-3-CI
7.24 CH3 C6H4-4-CI
7.25 CH3 CsH4-2-CF3 7.26 CH3 CsH4-3-CF3 7.27 CHa CsH4-4-CF3 7.28 CH3 CsH4-2-CN
7.29 CH3 CsH4-3-CN
7.30 CH3 CsH4-4-CN
7.31 CH3 CsH4-2-N02 7.32 CH3 C6H4-3-N02 7.33 CH3 C6H4-4-N02 7.34 CH3 C6H4-4-C6H5 7.35 CH3 C6H4-4-OC6H5 7.36 CH3 C6H4-4-C(CH3)3 7.37 CH3 C6H4-4-OCF3 7.38 CH3 CsH4-4-COOC2H5 Comp. No. R, R2 phys. data 7.39 CH3 CsFS
7.40 CH3 CsH2-3,4,5-(OCH3)s 7.41 CH3 /-\ ~
N O
U
7.42 CH3 / \
N
~ N
7.43 CH3 OH
7.44 CsHs CF3 7.45 CsHs C2H5 7.46 CsH5 C3H,-n 7.47 CsHS C3H~_I
7.48 C6H5 C4H9-t 7.49 CsH5 C4H9-n 7.50 CsHS cyclopropyi 7.51 C6H5 cyclopentyl 7.52 CgHS cyclohexyl 7.53 C6H5 C6H5 7.54 CsH5 CsH4-4-CI
7:55 C6H5 CsH4-4-CF3 7.56 CsHs CsH4-4-CN
7.57 CsHs CgH4-4-N02 w CA 02291441 1999-11-23 Comp. No. R, R2 phys. data 7.58 CsHS CsH4-4-C6H5 7.59 CsH5 CsH4-4-OCsHs 7.60 C6H5 C6H4-4-C(CH3)3 7:61 CsHs CsH4-4-OCF3 7.62 CsH4-4-CI CF3 7.63 C6H4-4-CI C2H5 7.64 C6H4-4-CI C3Hrn 7.65 C6H4-4-CI C3H,-i 7.66 CsH4-4-CI C4H9-t 7.67 CsH4-4-CI CQH9-n 7.68 C6H4-4-CI CH2C6H5 7.69 C6H4-4-CI CH2C6H4-4-CH3 7.70 CsH4-4-CI CsH4-4-CI
7.71 CgH4-4-CI CsH4-4-OH
7.72 CsH4-4-CI CsH4-2-CH3 7.73 C6H4-4-CI CsH4-2-CI
7.74 CsH4-4-CI CsH4-4-Br 7.75 CsH4-4-CI 4-pyridyl 7.76 CsHa-4-CI CsH4-4-OCH2-CsH4-3-7.77 C6H4-4-CI C6H,-O-CHZ
F
F
7.78 H C6H5 7.79 CsHS CHZCgHS
Comp. No. R, R2 phys. data 7.80 C2H5 -CsH4-4-CI
Table 8:
Compounds of the formula H O
CH C~N~N~C~R
~ CH
z F'C~C\CH
Z Z
Comp. R, R2 phys.
No. data 8.01 H H
8.02 H CH3 8.03 H C2H5 8.04 H C3H,-n 8.05 H C3H~-i 8.06 H CaH9-n 8.07 H CaH9-t 8.08 H C6H,3-n 8.09 H C,oH2,-n 8.10 H CH2C(CH3)s 8.i CH3 H
8.12 CH3 CH3 8.13 CH3 CZHS
8.14 CH3 C3H,-n 8.15 CH3 C3H~-i 8.16 CH3 C4H9-n Comp. No. R, R2 phys. data 8.17 CH3 C4H9-t 8.18 CH3 CgH,3_n 8.19 CH3 C,oH2,-n 8.20 CH3 CH2C(CH3)s 8.21 CH3 CeHS
8.22 CH3 C6H4-2-CI ' 8.23 CH3 C6H4-3-CI
8.24 CH3 CsH4-4-CI
8.25 CH3 CsH4-2-CF3 8:26 CH3 CsH4-3-CF3 8.27 CH3 C6H4-4-CF3 8.28 CH3 CsH4-2-CN
8.29 CH3 C6H4-3-CN
8.30 CH3 C6H4-4-CN
8.31 CH3 CsH4-2-N02 8.32 CH3 CsH4-3-N02 8.33 CH3 CsH4-4-N02 8:34 CH3 CsH4-4-CsHs 8.35 CH3 C6H4-4-OCgH5 8.36 CH3 CsH4-4-C(CH3)s 8.37 CH3 CsH4-4-OCF3 8.38 CH3 CsH4-4-COOC2H5 8.39 CH3 CsFs 8.40 CH3 CsH2-3,4,5-(OCH3)s Comp. No: R, R2 phys. data 8.41 CH3 N O
U
8.42 CH3 ~-\ N
~N
8.43 CH3 OH
8.44 CBHs CF3 8.45 CsHs C2Hs 8.46 C6Hs C3H,-n 8.47 C6Hs C3H~-i 8.48 C6Hs C4H9-t 8.49 CgHs C4H9-n 8.50 CsHs cyclopropyl 8.51 C6Hs cyclopentyl 8.52 C6Hs cyclohexyl 8.53 C6Hs CsHs 8.54 CgHs CsH4-4-CI
8.55 CsHs CsH4-4-CF3 8.56 CBHs CsH4-4-CN
8.57 CsHs C6H4-4-NOZ
8.58 CsHs CsH4-4-C6Hs 8.59 CgHs CsH4-4-OCgHs -c~-Comp. No. R, R2 phys. data 8.60 CgHs C6H4-4-C(CH3)s 8.61 CsHS CsH4-4-OCF3 8.62 CsH4-4-CI CF3 8.63 C6H4-4-CI C2H5 8.64 C6H4-4-CI C3Hrn 8.65 CsH4-4-CI CsH~-i 8.66 CgH4-4-CI C4Hg-t 8.67 C6H4-4-CI C4H9-n 8.68 CsH4-4-CI CH2CsH5 8.69 CsH4-4-CI CH2CsH4-4-CH3 8.70 CsH4-4-CI CgH4-4-CI
8.71 C6H4-4-CI CsH4-4-OH
8.72 C6H4-4-CI CsH4-2-CH3 8.73 CsH4-4-CI C6H4-2-CI
8.74 CsH4-4-CI CsH4-4-Br 8.75 C6H4-4-CI 4-pyridyl 8.76 CsH4-4-CI CsH4-4-OCH2-CsH4-3-CF3 8.77 C6H4-4-CI CsH4-~-CHZ
F
F
8.78 H -CsHs 8.79 C6H5 -CH2CsH5 8.80 C2H5 -C6H4-4-CI-Table 9: Compounds of the formula I
F~ CH C~ ~CHZ\ N C
~C~ O C/ \N~ \R
CHz C~
CH
~
F O
Comp. R, R2 phys. data No.
9.01 H H
9.02 H CH3 9.03 H C2H5 9:04 H C3H,-n 9.05 H C3H~-i 9.06 H C4H9-n 9.07 H CQH9-t 9.08 H CsH,3-n 9.09 H C,oH2,-n 9.10 H CH2C(CH3)a 9.11 CH3 H
9.12 CH3 CH3 9.13 CH3 C2H5 9.14 CH3 C3H,-n 9.15 CH3 C3H~-i 9.16 CH3 C4H9-n 9.17 CH3 C4H9-t 9.18 CH3 CsH,3-n 9.19 CH3 C,oH2,-n 9.20 CH3 CH2C(CH3)s Comp. R~ R2 phys: data No.
9.21 CH3 CsH5 9.22 CH3 C6H4-2-CI
9.23 CH3 CsH4-3-CI
9.24 CH3 CsH4-4-CI
9.25 CH3 CgH4-2-CF3 9:26 CH3 CsH4-3-CF3 9.27 CH3 CsH4-4-CF3 9.28 CH3 C6H4-2-CN
9.29 CH3 CsH4-3-CN
9.30 CH3 CBH4-4-CN
9.31 CH3 CsH4-2-NOZ
9.32 CH3 C6H4-3-N02 9.33 CH3 CsH4-4-N02 9.34 CH3 CsH4-4-CsHs 9.35 CH3 CsH4-4-OC6H5 9.36 CH3 C6H4-4-C(CH3)s 9.37 CH3 CsH4-4-OCF3 9:38 CH3 CsH4-4-COOC2H5 9.39 CH3 C6F5 9.40 CH3 CsH2-3,4,5-(OCH3)s 9.41 CH3 /
N O
U
Comp. No. R, R2 phys. data 9.42 CH3 / \ N
~N
9.43 CH3 OH
\ /
9.44 CsHS CF3 9.45 CsH5 C2H5 9.46 CBH5 C3H,-n 9.47 CsHS C3H,-i 9.48 C6H5 C4H9-t 9.49 C6H5 C4H9-n 9.50 CsH5 cyclopropyl 9.51 CsHS cyclopentyl 9.52 CsHs cyclohexyl 9.53 CsH5 CsHs 9.54 CsHS CsH4-4-CI
9.55 C6H5 C6H4-4-CF3 9.56 C6H5 C6H4-4-CN
9.57 CsHS CsH4-4-N02 9.58 CsHs CsH4-4-CsHS
9.59 CsHS CsH4-4-OCgH5 9.60 CsHS CsH4-4-C(CH3)s 9.61 CsH5 CsH4-4-OCF3 Comp. No. R~ R2 phys. data 9.62 CsH4-4-CICF3 9.63 CsH4-4-CIC2H5 9.64 CsH4-4-CIC3Hrn 9.65 C6H4-4-CIC3Hri 9:66 C6H4-4-CIC4H9-t 9.67 CsH4-4-CICQH9-n ' 9.68 CsH4-4-CICH2C6H5 9.69 C6H4-4-CICH2CsH4-4-CH3 9.70 CsH4-4-CICsH4-4-CI
9.71 C6H4-4-CICsH4-4-OH
9.72 C6H4-4-CIC6H4-2-CH3 9.73 C6H4-4-CIC6H4-2-CI
9.74 C6H4-4-CICsH4-4-Br 9.75 CsH4-4-CI4-pyridyl 9.76 CsH4-4-CI-CsH4-4-OCH2-CsH4-3-CsH4_O-CHz 9.n CsH4-4-CI F
F
9.78 H CgHS
9.79 CgHS CH2CsH5 9.80 CZHS -CsH4-4-CI
Table 10: Compounds of the formula H O
z F\C/C~CHz CH ~CHz C~p~N~C~R
F Rz Comp. R, R2 phys. data No.
10.01 H H
10.02 H CH3 10:03 H C2H5 10.04 H C3H~-n 10.05 H C3Hri 10.06 H C4H9-n 10.07 H C4H9-t 10.08 H C6H,3-n 10.09 H C,oH2,-n 10.10 H CH2C(CH3)s 10.11 CH3 H
10.12 CH3 CH3 10.13 CH3 C2H5 10.14 CH3 C3H,-n 10.15 CH3 C3Hri 10.16 CH3 C4H9-n 10.17 CH3 C4H9-t -10.18 CH3 CgH,3-n 10.19 CH3 C,oH2,-n Comp. R, R2 No. phys. data 10.20 CH3 CH2C(CH3)s 10.21 CH3 CsHs 10.22 CH3 CBH4-2-CI
10.23 CH3 CsH4-3-CI
10.24 CH3 CsH4-4-CI
10.25 CH3 CsH4-2-CF3 10.26 CH3 C6H4-3-CF3 10.27 CH3 C6H4-4-CF3 10.28 CH3 C6H4-2-CN
10.29 CH3 CsH4-3-CN
10.30 CH3 C6H4-4-CN
10.31 CH3 C6H4-2-N02 10.32 CH3 CsH4-3-N02 10.33 CH3 CsH4-4-N02 10.34 CH3 CsH4-4-CsHs 10.35 CH3 CsH4-4-OCsHS
10.36 CH3 C6H4-4-C(CH3)s 10.37 CH3 CsH4-4-OCF3 10.38 CH3 C6H4-4-COOC2H5 10.39 CH3 C6F5 10.40 CH3 CsH2-3,4,5-(OCH3)a 10.41 CH3 / \
N O
U
-6p_ Comp. No. R~ R2 phys. cJata 10.42 CH3 /-~ N
~N
10.43 CH3 OH
10.44 CsH5 CF3 10.45 C6H5 C2H5 10.46 CsHS C3H,-n 10.47 CsHS C3H~-i 10.48 CsHs C4H9-t 10.49 C6H5 C4Hg-n 10.50 C6H5 cyclopropyl 10.51 CsHs cyclopentyl 10.52 CsHS cyclohexyl 10.53 CsHS C6H5 i 0.54 CsH5 CsH4-4-CI
10.55 C6H5 C6H4-4-CF3 10.56 CsH5 CsH4-4-CN
10.57 C6H5 C6H4-4-N02 10.58 CgHS CsH4-4-CsH5 10.59 C6H5 CsH4-4-OC6H5 10.60 C6H5 CsH4-4-C(CH3)s 10.61 CBHS C6H4-4-OCF3 Comp. No. R, R2 phys. data 10.62 CsH4-4-CI CF3 10.63 CsH4-4-CI C2H5 10.64 CsH4-4-CI C3Hrn 10.65 CsH4-4-CI C3Hri 10.66 CsH4-4-CI C4H9-t 10.67 C6H4-4-CI C4H9-n 10.68 C6H4-4-CI CH2C6H5 10.69 CsH4-4-CI CHzCsH4-4-CH3 10.70 C6H4-4-CI CsH4-4-CI
10.71 CBHQ-4-CI CgH4-4-OH
10.72 C6H4-4-CI CsH4-2-CH3 10.73 CsH4-4-CI C6H4-2-CI
10.74 CsH4-4-CI CsH4-4-Br 10.75 CsH4-4-CI 4-pyridyl 10.76 C6H4-4-CI CsH4-4-OCH2-CsH4-3-CF3 10.77 CsH4-4-CI C6H,-O-CHZ
F
F
10.78 H CsHS
10.79 CsHs CH2C6H5 10.80 C2H5 -CsH4-4-CI
Table 11: Compounds of the formula H o z F~C~C~CHZ CH ~CHZ C~N~N~C~R
H HZ
Comp. No. R, R2 phys. data 11.01 H H
11.02 H -CH3 11.03 H -C2H5 11.04 H -C3Hrn 11.05 H -C3H~-i 11.06 H -C4H9-n 11.07 H -CaH9-t 11.08 H -CsH,3-n 11.09 H -C,oH2,-n 11.10 H -CH2C(CH3)s 11.11 CH3 H
11.12 CH3 -CH3 11.13 CH3 -CZHS
11.14 CH3 -C3Hrn 11.15 CH3 -C3Hri 11.16 CH3 -C4H9-n 11.17 CH3 -C4H9-t 11.18 CH3 -CgH,3-n 11.19 CH3 -C,oH2,-n -Comp. No. R, R2 phys. data 11.20 CH3 -CH2C(CH3)s 11.21 CH3 -C6H5 11.22 CH3 -CsH4-2-CI
11.23 CH3 -C6H4-3-CI
11.24 CH3 -C6H4-4-CI
11.25 CH3 -CsH4-2-CF3 ' 11.26 CH3 -CsH4-3-CF3 11.27 CH3 -C6H4-4-CF3 11.28 CH3 -CsH4-2-CN
11.29 CH3 -CsH4-3-CN
11.30 CH3 -CsH4-4-CN
11.31 CH3 -C6H4-2-NOZ
11.32 CH3 -CsH4-3-N02 11.33 CH3 -C6H4-4-N02 11.34 CH3 -CsH4-4-C6H5 11.35 CH3 -CsH4-4-OCsH5 11.36 CH3 -CsH4-4-C(CH3)s 11.37 CH3 -CeH4-4-OCF3 11.38 CH3 -C6H4-4-COOC2H5 11.39 CH3 CsFs 11.40 CH3 -CsH2-3,4,5-(OCH3)a 11.41 CH3 / \
N O
U
-Comp. No. R, R2 phys. data 11:42 CH3 / ~ N
~N
11.43 CH3 OH
11.44 CsHs -CF3 11.45 CsHs -C2Hs 11.46 CsHs -C3H~-n 11.47 CsHs -C3H~-i 11.48 C6Hs -C4H9-t 11.49 C6Hs -C4H9-n 11.50 C6Hs cyclopropyl 11.51 CsHs cyclopentyl 11.52 CsHs cyclohexyl 11.53 C6Hs -C6Hs 11.54 C6Hs -CsH4-4-CI
11.55 C6Hs -CBH4-4-CF3 11.56 CsHs -C6H4-4-CN
11.57 CsHs -CsH4-4-N02 11.58 C6Hs -C6H4-4-C6Hs 11.59 C6Hs -CsH4-4-OCsHs 11.60 CsHs -C6H4-4-C(CH3)3 11.61 CsHs -CsH4-4-OCF3 Comp. No. R, R2 phys. data 11.62 CsH4-4-CI-CF3 11.63 C6H4-4-CI-C2H5 11.64 C6H4-4-CI-C3H,-n 11.65 CsH4-4-CI-C3H~-i 11.66 C6H4-4-CI-C4H9-t 11.67 CsH4-4-CI-C4H9-n 11.68 C6H4-4-CI-CHZCsHS
11.69 C6H4-4-CI-CH2CsH4-4-CH3 11.70 CsH4-4-CI-C6H4-4-CI
11.71 CsH4-4-CI-C6H4-4-OH
11.72 CsH4-4-CI-CsH4-2-CH3 11.73 C6H4-4-CI-CsH4-2-CI
11.74 CsH4-4-CI-C6H4-4-Br 11.75 CsH4-4-CI4-pyridyl 11.76 CsH4-4-CI-CsH4-4-OCH2-CsH4-3-11.77 CsH4-4-CI CBH4-O-CHZ
F
F
11.78 H -CsHS
11.79 C6H5 -CHZCsHS
11.80 C2H5 -CsH4-4-CI
Table 12: Compounds of the formula I
F C CHZ C CHZ N C
'C~ \CHz ~CHZ \O/ ~C/ \N~ \RZ
F O
Comp. No. R, R2 phys. data 12.01 H H
12.02 H CH3 12.03 H C2H5 12.04 H C3Hrn 12:05 H C3Hri 12.06 H C4H9-n 12.07 H CQH9-t 12.08 H C6H,3-n 12.09 H C,oH2,-n 12.10 H CH2C(CH3)s 12.11 CH3 H
12.12 CH3 CH3 12.13 CH3 C2H5 12.14 CH3 C3H,=n 12.15 CH3 C3Hri 12.16 CH3 CaH9-n 12.17 CH3 C4H9-t 12.18 CH3 CsH,3-n 12.19 CH3 C,oH2,-n 12.20 CH3 CH2C(CH3)a Comp. No. R~ R2 phys. data 12.21 CH3 CsHs 12.22 CH3 CsH4-2-CI
12.23 CH3 CsH4-3-CI
12.24 CH3 CsH4-4-CI
12.25 CH3 CsH4-2-CF3 12.26 CH3 CsH4-3-CF3 12.27 CH3 C6H4-4-CF3 12.28 CH3 CgH4-2-CN
12.29 CH3 CsH4-3-CN
12.30 CH3 C6H4-4-CN
12.31 CH3 CsH4-2-N02 12.32 CH3 CsH4-3-NOZ
12.33 CH3 CsH4-4-N02 12.34 CH3 CsH4-4-C6Hs 12.35 CH3 CsH4-4-OC6Hs 12.36 CH3 C6H4-4-C(CH3)3 12.37 CH3 CsH4-4-OCF3 12.38 CH3 CsH4-4-COOC2Hs 12.39 CH3 C6Fs 12.40 CH3 C6H2-3,4,5-(OCH3)a 12.41 CH3 / \
N O
U
Comp. No. R, R2 phys. data 12.42 CH3 /-~ N
~N
12.43 CH3 OH
12.44 CsHs CF3 12.45 CgHS C2H5 12.46 C6H5 C3H,-n 12.47 C6H5 C3Hri 12.48 CsHS C4H9-t 12.49 C6H5 C4H9-n 12.50 CsH5 cyclopropyl 12.51 C6H5 cyclopentyl 12.52 C6H5 cyclohexyl 12.53 C6H5 CsHS
12.54 CsH5 CsH4-4-CI
12.55 C6H5 C6H4-4-CF3 12.56 C6H5 CsH4-4-CN
12.57 C6H5 CsH4-4-N02 12.58 C6H5 CsH4-4-CsHS
12.59 CsH5 CsH4-4-OCsHS
12.60 C6H5 C6H4-4-C(CH3)s 12.61 CgH5 CsH4-4-OCF3 Comp. No. R, R2 phys. data 12.62 CsH4-4-CICF3 12.63 C6H4-4-CIC2H5 12.64 C6H4-4-CIC3H~-n 12.65 CgH4-4-CIC3Hri 12.66 CsH4-4-CIC4H9-t 12.67 CsH4-4-CIC4H9-n ' 12.68 CsH4-4-CICH2CsH5 12.69 CsH4-4-CICH2CsH4-4-CH3 12.70 CsH4-4-CICsH4-4-CI
12.71 C6H4-4-CICsH4-4-OH
12.72 CsH4-4-CICsH4-2-CH3 12.73 CsH4-4-CICsH4-2-CI .
12.74 C6H4-4-CIC6H4-4-Br 12.75 C6H4-4-CI4-pyridyl 12.76 CsH4-4-CICsH4-4-OCH2-CsH4-3-12.77 CsH4-4-CI CeH,-O-CH2 F
F
12.78 H CsH5 12.79 C6H5 CH2C6H5 12.80 C2H5 -C6H4-4-CI
Table 13: Compounds of the fomnula H o F\C/C CH ~ CH
'CH
Rz Comp. R, R2 No. phys.
data 13.01 H H
13.02 H CH3 13.03 H C2H5 13.04 H C3H,-n 13.05 H C3H,-i 13.06 H C4H9-n 13.07 H C4H9-t 13.08 H C6H,3-n 13.09 H C,oH2,-n 13.10 H CH2C(CH3)s 13.11 CH3 H
13.12 CH3 CH3 13.13 CH3 CZHS
13.14 CH3 C3Hrn 13.15 CH3 C3H~-i 13.16 CH3 C4H9-n 13.17 CH3 C4H9-t 13.18 CH3 CsH,3-n 13.19 CH3 C,oH2,-n Comp. No. R~ R2 phys. data 13.20 CH3 CH2C(CH3)s 13.21 CH3 CsHs 13.22 CH3 CsH4-2-CI
13.23 CH3 C6H4-3-CI
13.24 CH3 C6H4-4-CI
13.25 CH3 CsH4-2-CF3 13.26 CH3 C6H4-3-CF3 13.27 CH3 CsH4-4-CF3 13.28 CH3 C6H4-2-CN
13.29 CH3 C6H4-3-CN
13.30 CH3 CsH4-4-CN
13.31 CH3 C6H4-2-N02 13.32 CH3 C6H4-3-N02 13.33 CH3 CsH4-4-N02 13.34 CH3 CsH4-4-CsHs 13.35 CH3 C6H4-4-OCsHS
13.36 CH3 C6H4-4-C(CH3)s 13.37 CH3 CsH4-4-OCF3 13.38 CH3 CsH4-4-COOC2H5 13.39 CH3 CsFs 13.40 CH3 CsH2-3,4,5-(OCH3)s 13.41 CH3 ~ ~ NCO
V
Comp. No. R, R2 phys. data 13.42 CH3 ~ ~ N
~N
13.43 CH3 ~ ~ OH
13:44 C6H5 CF3 13.45 C6H5 C2H5 13.46 CgHS C3H,-n 13.47 CsHs C3H,-i 13.48 CsHS C4H9-t 13.49 CsHS C4H9-n 13.50 C6H5 cyclopropyl 13.51 C6H5 cyclopentyl 13.52 CsH5 cyclohexyl 13.53 CsHs CsHs 13.54 CsHs CsH4-4-CI
13:55 CsHs CsH4-4-CF3 13.56 CsH5 CsH4-4-CN
13.57 CsHS C6H4-4-N02 13.58 CsHS CsH4-4-C6H5 13.59 C6H5 CsH4-4-OC6H5 13.60 CsHs C6H4-4-C(CH3)s 13.61 CsHS CsH4-4-OCF3 Comp. No. R, R2 phys. data 13.62 CsH4-4-CI CF3 13.63 CsH4-4-CI C2H5 13.64 CsH4-4-CI C3Hrn 13.65 CsH4-4-CI C3H~-i 13.66 CsH4-4-CI C4H9-t 13.67 CsH4-4-CI C4H9-n 13.68 CsH4-4-CI CH2CsH5 13.69 CeH4-4-CI CH2C6H4-4-CH3 13.70 CsH4-4-CI C6H4-4-CI
13.71 C6H4-4-CI CsH4-4-OH
13.72 CsH4-4-CI CsH4-2-CH3 13.73 CgH4-4-CI C6H4-2-CI
13.74 C6H4-4-CI CsH4-4-Br 13.75 C6H4-4-CI 4-pyridyl 13.76 CsH4-4-CI CsH4-4-OCH2-C6H4-3-13.77 CsH4_4_CI CsHa-~-CHZ
F
F
13.78 H CgHg 13.79 CsH5 CH2C6H5 13.80 C2H5 -CsH4-4-CI
. CA 02291441 1999-11-23 - Table 14: Compounds of the formula H O
z F\C/C\CHz CH ~CHz C~N/N~C/R
F H Rz Comp. No. R, R2 phys. data 14.01 H H
14.02 H CH3 14.03 H CaHS
14.04 H C3H,-n 14.05 H C3H,-i 14.06 H C4H9-n 14.07 H C4H9-t 14.08 H CsH,3-n 14.09 H C,oH2,-n 14.10 H CH2C(CH3)s 14.11 CH3 H
14.12 CH3 CH3 14.13 CH3 C2Hs 14.14 CH3 C3Hrn 14.15 CH3 C3Hri 14.16 CH3 C4H9-n 14.17 CH3 CaH9-t 14.18 CH3 CsH,3-n 14.19 CH3 C,oH2,-n Comp. No. R, R2 phys. data 14.20 CH3 CH2C(CH3)3 14.21 CH3 CgHS
14.22 CH3 CsH4-2-CI
14.23 CH3 CsH4-3-CI
14.24 CH3 CsH4-4-CI
14.25 CH3 C6H4-2-CF3 14.26 CH3 CsH4-3-CF3 14.27 CH3 CgH4-4-CF3 14.28 CH3 CsH4-2-CN
14.29 CH3 CsH4-3-CN
14.30 CH3 C6H4-4-CN .
14.31 CH3 CsH4-2-N02 14.32 CH3 CsH4-3-N02 14.33 CH3 CgH4-4-N02 14.34 CH3 C6H4-4-C6H5 14.35 CH3 CsH4-4-OC6H5 14.36 CH3 CeH4-4-C(CH3)3 14.37 CH3 CgH4-4-OCF3 14.38 CH3 CsH4-4-COOC2H5 14.39 CH3 CsFs 14.40 CH3 C6H2-3,4,5-(OCH3)s 14.41 CH3 ~ ~ N ~O
Comp. No. R, R2 phys. data 14.42 CH3 ~ ~ N
~N
14.43 CH3 ~ ~ OH
14.44 C6H5 CF3 14.45 CgH5 C2H5 14.46 C6H5 C3Hrn 14.47 CgHs C3Hri 14.48 C6H5 C4Hg-t 14.49 C6H5 C4H9-n 14.50 C6H5 cyclopropyl 14.51 C6H5 cyclopentyl 14.52 C6H5 cyclohexyl 14.53 CsHS CsH5 14.54 C6H5 CsH4-4-CI
14.55 CsHs CsH4-4-CF3 14.56 C6H5 CsH4-4-CN
14.57 CBHS C6H4-4-N02 14.58 C6H5 C6H4-4-CsHs 14.59 CsHS CsH4-4-OCsHS
14.60 CsHS CBH4-4-C(CH3)3 14.61 C6H5 CgH4-4-OCF3 -n-Comp. No. R, R2 phys. data 14.62 CeH4-4-CICF3 14.63 C6H4-4-CIC2H5 14.64 C6H4-4-CIC3Hrn 14.65 C6H4-4-CIC3Hri 14.66 C6H4-4-CIC4H9-t 14.67 CsH4-4-CIC4H9-n 14.68 CsH4-4-CICH2CsH5 14.69 CeH4-4-CICH2CsH4-4-CH3 14.70 CsH4-4-CICsH4-4-CI
14.71 CsH4-4-CICsH4-4-OH
14.72 C6H4-4-CICsH4-2-CH3 14.73 CsH4-4-CIC6H4-2-CI
14.74 CsH4-4-CICsH4-4-Br 14.75 CsH4-4-CI4-pyridyl 14.76 CsH4-4-CICsH4-4-OCH2-C6H4-3-14.77 CsH4-4-CI CBH4-~-CHZ
F
F
14.78 H C6H5 14.79 C6H5 CH2CsH5 14.80 C2H5 -CgH4-4-CI
Table 15: Compounds of the formula I II i I
F~ ~C~ CHZ C~ ~CHz' N C
C~ CH2 ~CHZ O C/ \N~ \RZ
F O
Comp. R, R2 phys. data No.
15.01 H H
15.02 H CH3 15.03 H C2H5 15.04 H C3H~-n 15.05 H C3Hri 15.06 H C4H9-n 15.07 H C4H9-t 15.08 H CsH, 3-n 15.09 H C,oH2,-n 15.10 H CH2C(CH3)s 15.11 CH3 H
15.12 CH3 CH3 15.13 CH3 C2H5 15.14 CH3 C3H,-n 15.15 CH3 C3H~-i 15.16 CH3 C4H9-n 15.17 CH3 C4H9-t 15.18 CH3 CsH,3-n 15.19 CH3 C,oH2,-n 15.20 CH3 CH2C(CH3)3 _79-' Comp. No. R, R2 phys. data 15.21 CH3 CsHs 15.22 CH3 CsH4-2-CI
15.23 CH3 C6H4-3-CI
15.24 CH3 C6H4-4-CI
15.25 CH3 CsH4-2-CF3 15.26 CH3 CsH4-3-CF3 15.27 CH3 C6H4-4-CF3 15.28 CH3 CsH4-2-CN
15.29 CH3 CsH4-3-CN
15.30 CH3 C6H4-4-CN
15.31 CH3 CsH4-2-N02 15.32 CH3 CsH4-3-N02 15.33 CH3 C6H4-4-NOZ
15.34 CH3 CsH4-4-CsH5 15.35 CH3 CsH4-4-OCsHs 15.36 CH3 CsH4-4-C(CH3)s 15.37 CH3 CsH4-4-OCF3 15.38 CH3 C6H4-4-COOC2H5 15.39 CH3 CsFs 15.40 CH3 CsH2-3,4,5-(OCH3)3 15.41 CH3 ~ ~ N
Comp. No. R, R2 phys. data 15.42 CH3 ~ ~ N
~N
15.43 CH3 ~ ~ OH
15.44 CsHS CF3 15.45 CsHs C2H5 15.46 CsHS C3H~-n 15.47 CsHS C3H~-i 15.48 CsHs C4H9-t 15.49 C6H5 C4H9-n 15.50 C6H5 cyclopropyl 15.51 CsHS cyclopentyl 15.52 CsHS cyclohexyl 15.53 CsH5 CsHs 15.54 CsHs CsH4-4-CI
15.55 C6H5 CsH4-4-CF3 15.56 C6H5 CsH4-4-CN
15.57 CgHS CsH4-4-N02 15.58 C6H5 CBH4-4-C6H5 15.59 CsHs CsH4-4-OCsHS
15.60 CsHS CsH4-4-C(CH3)s 15.61 CsHs C6H4-4-OCF3 ' Comp. No. R, R2 phys. data 15.62 CBH4-4-CI CF3 15.63 CsH4-4-CI C2H5 15.64 C6H4-4-CI C3Hrn 15.65 CsH4-4-CI C3H,-i 15.66 CsH4-4-CI C4H9-t 15.67 CsH4-4-CI C4H9-n 15.68 CsH4-4-CI CH2C6H5 15.69 C6H4-4-CI CH2C6H4-4-CH3 15.70 C6H4-4-CI C6H4-4-CI
15.71 CsH4-4-CI CsH4-4-OH
15.72 CsH4-4-CI CsH4-2-CH3 .
15.73 C6H4-4-CI CsH4-2-CI
15.74 CsH4-4-CI C6H4-4-Br 15.75 C6H4-4-CI 4-pyridyl 15.76 C6H4-4-CI CsH4-4-OCH2-C6H4-3-15.77 C6H4-4-CI Csli,-o-CH2 F
F
15.78 H -CsHS
15.79 CsHS CHZCsHs 15.80 C2H5 -C6H44-CI
_8Q_ Table 16: Compounds of the formula H O
F\C~C\CH CH2~Ch12 C\O/N'C/R~
2 ~
F RZ
Comp. No. R, RZ phys. data 16.01 H H
16.02 H CH3 16.03 H C2H5 16.04 H C3Hrn 16.05 H C3H,-i 16.06 H C4H9-n 16.07 H C4H9-t 16.08 H C6H,3-n 16.09 H C,oH2,-n 16.10 H CH2C(CH3)3 16.11 CH3 H
16.12 CH3 CH3 16.13 CH3 C2H5 16.14 CH3 C3H,-n 16.15 CH3 C3Hri 16.16 CH3 C4H9-n 16.17 CH3 C4H9-t 16.18 CH3 CsH,3-n 16.19 CH3 C,oH~-n - Comp. No. R1 R2 phys. data 16.20 CH3 CH2C(CH3)s 16.21 CH3 CsH5 16.22 CH3 C6H4-2-CI
16.23 CH3 CeH4-3-CI
16.24 CH3 CgH4-4-CI
16.25 CH3 CsH4-2-CF3 16.26 CH3 C6H4-3-CF3 16.27 CH3 G6H4-4-CF3 16.28 CH3 CsH4-2-CN
16.29 CH3 C6H4-3-CN
16.30 CH3 CsH4-4-CN
16.31 CH3 C6H4-2-N02 16.32 CH3 C6H4-3-N02 16.33 CH3 CsH4-4-N02 16.34 CH3 CsH4-4-CsHs 16.35 CH3 C6H4-4-OC6H5 16.36 CH3 C6H4-4-C(CH3)s 16.37 CH3 CsH4-4-OCF3 16.38 CH3 CeH4-4-COOC2H5 16.39 CH3 CsFs 16.40 CH3 C6H2-3;4,5-(OCH3)s 16.41 CH3 ~ ~ N O
U
-Comp. No. R, R2 phys. data 16.42 CH3 ~ ~ N
16.43 CH3 ~ ~ OH
16.44 CsH5 CF3 16.45 C6H5 C2H5 16.46 CsHS C3H,-n 16.47 CsHS C3H,-i 16.48 CsH5 C4H9-t 16:49 CsHs C4H9-n 16.50 CsHS cyclopropyl 16:51 C6H5 cyclopentyl 16.52 CBHS cyclohexyl 16.53 CgHs CsH5 16.54 CsHS CsH4-4-CI
16.55 C6H5 CgH4-4-CF3 16.56 CgHs CgH4-4-CN
16.57 CsH5 CsH4-4-N02 16.58 CgHs CsH4-4-C6H5 16.59 CsHS CsH4-4-OCsHS
16.60 CsHs CsH4-4-C(CH3)s 16.61 CsHs CsH4-4-OCF3 -g5_ Comp. No. R, R2 phys. data 16.62 CsH4-4-CICF3 16.63 CsH4-4-CIC2H5 16.64 CsH4-4-CIC3Hy-n 16.65 C6H4-4-CIC3H,-i 16.66 C6H4-4-CIC4H9-t 16.67 CgH4-4-CIC4Hg-n 16.68 CsH4-4-CICH2C6H5 16.69 CsH4-4-CICH2C6H4-4-CH3 16.70 C6H4-4-CICBH4-4-CI
16.T1 C6H4-4-CICsH4-4-OH
16.72 CsH4-4-CICsH4-2-CH3 16.73 CsH4-4-CIC6H4-2-CI
16.74 C6H4-4-CICsH4-4-Br 16.75 C6H4-4-CI4-pyridyl 16.76 C6H4-4-CICsH4-4-OCH2-CsH4-3-16.77 CsH4_4_CI CsHs-~-CHZ
F
F
16.78 H CsH5 16.79 C6H5 CH2C6H5 16.80 C2H5 -CsH4-4-CI
Table 17: Compounds of the formula H O
F C ~CH2 C N ~ R~
\C~ \CHZL ~CHZ \N/ ~C/
F H RZ
Comp. No. R, R2 phys. data 17.01 H H
17.02 H CH3 17.03 H C2H5 17.04 H C3H;-n 17.05 H C3H~-i 17.06 H CQH9-n 17.07 H C4H9-t 17.08 H CsH,3-n 17.09 H C,oH2,-n 17.10 H CH2C(CH3)s 17.11 CH3 H
17.12 CH3 CH3 17.13 CH3 C2H5 17.14 CH3 C3Hrn 17.15 CH3 C3Hri 17.16 CH3 C4H9-n 17.17 CH3 C4H9-t 17.18 CH3 CsH,3-n 17.19 CH3 C,oH2,-n Comp. No. R, R2 phys. data 17.20 CH3 CH2C(CH3)s 17.21 CH3 CsHS
17.22 CH3 C6H4-2-CI
17.23 CH3 CsH4-3-CI
17.24 CH3 C6H4-4-CI
17.25 CH3 CsH4-2-CF3 ' 17.26 CH3 C6H4-3-CF3 17.27 CH3 C6H4_4_CF3 17.28 CH3 CsH4-2-CN
17.29 CH3 CsH4-3-CN
17.30 CH3 CsH4-4-CN
17.31 CH3 C6H4-2-N02 17.32 CH3 CsH4-3-N02 17.33 CH3 CsH4-4-N02 17.34 CH3 CsH4-4-CsHs 17.35 CH3 CsH4-4-OC6H5 17.36 CH3 CsH4-4-C(CH3)s 17.37 CH3 C6H4-4-OCF3 17.38 CH3 CsH4-4-COOC2H5 17.39 CH3 CsFs 17.40 CH3 -C6H2-3,4,5-(OCH3)s 17.41 CH3 ~ ~ N
$$ -Comp. No. R, R2 phys. data 17.42 CH3 ~ ~ N
~N
17.43 CH3 ~ ~ OH
17.44 C6H5 CF3 17.45 C6H5 C2H5 17.46 CsHs C3H,-n 17.47 CsH5 C3H~-i 17.48 C6Hs CQH9-t 17.49 CsHS CaH9-n 17.50 CsHs cyclopropyl 17.51 C6H5 cyclopentyl 17.52 C6Hs cyclohexyl 17.53 C6H5 CsHS
17.54 CBH5 C6H4-4-CI
17.55 CBHS CgH4-4-CF3 17.56 CsH5 C6H4-4-CN
17.57 C6H5 CsH4-4-N02 17.58 C6H5 C6H4-4-CsHs 17.59 CsHs CsH4-4-OCsHS
17.60 CsHS CsH4-4-C(CH3)s 17.61 CsHS CsH4-4-OCF3 _89-Comp. No. R, RZ phys. data 17.62 C6H4-4-CI CF3 17.63 CsH4-4-CI C2H5 17.64 C6H4-4-CI C3H~-n 17.65 C6H4-4-CI C3H,-i 17.66 C6H4-4-CI C4H9-t 17.67 CsH4-4-CI CoH9-n 17.68 C6H4-4-CI CH2CsH5 17.69 CsH4-4-CI CH2CsH4-4-CH3 17.70 CsH4-4-CI CsH4-4-CI
17.71 CsH4-4-CI C6H4-4-OH
17.72 C6H4-4-CI C6H4-2-CH3 17.73 CsH4-4-CI C6H4-2-CI
17.74 C6H4-4-CI CsH4-4-Br 17.75 C6H4-4-CI 4-pyridyl 17.76 C6H4-4-CI C6H4-4-OCH2-CsH4-3-CF3 17.77 C6H4_4_CI CsHs-~' CH2 F
F
17.78 H CsHS
17.79 C6H5 CH2C6H5 17.80 C2H5 -C6H4-4-CI
Table 18: Compounds of the formula I
F~ ~C~ CHZ C~ ~CHz\ N ~C
C~ CHZ ~CHZ O C/ 'N~ \RZ
F O
Comp. No. R, R2 phys. data 18.01 H H
18.02 H CH3 18.03 H C2H5 18.04 H C3H,-n 18.05 H C3H~-i 18.06 H C4H9-n 18.07 H CaH9-t 18.08 H CeH,3-n 18.09 H C,oH2,-n 18.10 H CH2C(CH3)s 18.11 CH3 H
18.12 CH3 CH3 18.13 CH3 C2H5 18.14 CH3 C3H,-n 18.15 CH3 C3H,-i 18.16 CH3 C4H9-n 18.17 CH3 C4H9-t 18.18 CH3 CsH,3-n 18.19 CH3 C,oH2,-n _91 _ ' Comp. No. R~ R2 phys. data 18.20 CH3 CH2C(CH3)s 18.21 CH3 CsHs 18.22 CH3 C6H4-2-CI
18.23 CH3 C6H4-3-CI
18.24 CH3 CsH4-4-C) 18.25 CH3 CgH4-2-CF3 18.26 CH3 CsH4-3-CF3 18.27 CH3 CsH4-4-CF3 18.28 CH3 CsH4-2-CN
18.29 CH3 CsH4-3-CN
18.30 CH3 CsH4-4-CN
18.31 CH3 CsH4-2-NO2 18.32 CH3 C6H4-3-N02 18.33 CH3 CsH4-4-N02 18.34 CH3 C6H4-4-CsHs 18.35 CH3 C6H4-4-OCsHs 18.36 CH3 CsH4-4-C(CH3)3 18.37 CH3 C6H4-4-OCF3 18.38 CH3 CsH4-4-COOC2Hs 18.39 CH3 C6Fs 18.40 CH3 CsH2-3,4,5-(OCH3)s ~ ~
18.41 CH3 NV
Comp. No. R, R2 phys. data 18.42 CH3 ~ ~ N
18.43 CH3 ~ ~ OH
18.44 C6H5 CF3 18.45 CsHs C2Hs 18.46 C6H5 C3Hrn 18.47 CsHS C3Hri 18.48 CsHs Calls-t 18.49 C6H5 C4H9-n 18.50 CsHS cyclopropyl 18.51 CsHS cyclopentyl 18.52 CsHs cyclohexyl 18.53 C6H5 CsHs 18.54 C6H5 C6H4-4-CI
18.55 C6H5 CsH4-4-CF3 18.56 CsHS C6H4-4-CN
18.57 C6H5 C6H4-4-N02 18.58 CsH5 C6H4-4-CsHS
18.59 CsHs C6H4-4-OC6H5 18.60 CgH5 CgH4-4-C(CH3)s Comp. No. Ri R2 phys. data 18.61 CsH5 C6H4-4-OCF3 18.62 CsH4-4-CI CF3 18.63 CsH4-4-CI CZHS
18.64 C6H4-4-CI C3H~-n 18.65 CsH4-4-CI C3H,-i 18.66 C6H4-4-CI C4H9-t 18.67 CgH4-4-CI C4H9-n 18.68 C6H4-4-CI CH2CsH5 18.69 CsH4-4-CI CH2CsH4-4-CH3 18.70 CsH4-4-CI C6H4-4-CI
18.71 CsH4-4-CI CsH4-4-OH
18.72 CsH4-4-CI C6Ha-2-CH3 18.73 C6H4-4-CI CsH4-2-CI
18.74 C6H4-4-CI CsH4-4-Br 18.75 CsH4-4-CI 4-pyridyl 18.76 CsH4-4-CI CsH4-4-OCH2-C6H4-3-CFs 18.77 CsH4-4-CI C6H~-O-CH2 F
F
18.78 H C6H5 18.79 CsHS CH2CsH5 18.80 C2H5 -CsH4-4-CI
. Table 19: Compounds of the formula F O
z F ~ C ~ ~N R1 ~C C X
Comp. No. R, R2 X n phys. data 19.1 -CsH5 -C6H5 NH 0 19.2 -CsHS -C6H5 NH 1 m.p.:92-93C
19.3 -CeHS -CsH5 NH 2 19.4 -C6H5 -CsH5 NH 3 19.5 -C6H5 -CsHs NH 4 19.6 -CgHs -C6H5 NH 5 19.7 -CsHs -CBHS O 0 19.8 -CsHs -C6H5 O 1 amorphous 19.9 -CsHS -C6H5 O 2 19.10 -C6H5 -CsH5 O 3 19.11 -CsHs -CsH5 O 4 19.12 -CsHS -CsH4-4-CI O 5 19.13 CH3 -CsH4-4-CI NH 0 19.14 CH3 -CsH4-4-CI NH 1 19.15 CH3 -C6H4-4-CI NH 2 19.16 CH3 -C6H4-4-CI NH 3 19.17 CH3 -CsH4-4-CI NH 4 19.18 CH3 -CsH4-4-CI NH 5 19.19 CH3 -CsH4-4-CI O 0 Comp. No. R, RZ X n phys. data 19.20 CH3 -CgH4-4-CI O 1 19.21 CH3 -CsH4-4-CI O 2 19.22 CH3 -CsH4-4-CI O 3 19.23 CH3 -CsH4-4-CI O 4 19.24 CH3 -C6H4-4-CI O 5 19.25 -CsH4-4-CI-CsH4-4-CI NH 1 19.26 -CsH4-4-CI-CsH4-4-CI O 1 Table 20: Compounds of the formula F ~ C ~ ~N R1 \C C X
Comp. No. R, R2 X n phys. data 20.1 -C6H5 -C6H5 NH 0 20.2 -CsH5 -CgHs NH 1 m.p.:89-100C
20.3 -CsHS -CsH5 NH 2 20.4 -C6H5 -C6H5 NH 3 20.5 -CsHs -CsHS NH 4 20.6 -CsHs -C6H5 NH 5 20.7 -CsHs -CsH5 O 0 20.8 -CsHS -CsHS O 1 np2 =1.5530 20.9 -CeHS -C6H5 O 2 20.10 -CeHS -CsHS O 3 ' Comp. No. R, R2 X n phys. data 20.11 -CsHS -CsHS O 4 20.12 -C6H5 -CsH4-4-CI O 5 20.13 CH3 -CsH4-4-CI NH 0 20.14 CH3 -CsH4-4-CI NH 1 20.15 CH3 -C6H4-4-CI NH 2 20.16 CH3 -CsH4-4-CI NH 3 20.17 CH3 -CsH4-4-CI NH 4 20.18 CH3 -CsH4-4-CI NH 5 20.19 CH3 -CsH4-4-CI O 0 20.20 CH3 -CsH4-4-CI O 1 20.21 CH3 -CsH4-4-CI O 2 20.22 CH3 -CgH4-4-CI O 3 20.23 CH3 -C6H4-4-CI O 4 20.24 CH3 -CsH4-4-CI O 5 20.25 -CsH4-4-CI-CsH4-4-CI NH 1 20.26 -CsH4-4-CI-C6H4-4-CI O 1 Biological Examples Examale B1: Ovicidal action on Heliothis virescens Heliothis virescens eggs which have been deposited on filter paper are briefly immersed into an acetonic/aqueous test solution comprising 400 ppm of the active compound to be tested.
After the test solution has dried on, the eggs are incubated in Petri dishes.
After 6 days, the percentage hatching rate of the eggs is evaluated in comparison with untreated control batches (% reduction in hatching).
_97_ In this test, compounds according to tables 1 - 20 are very effective against Heliothis virescens. Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5:53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78; 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example 82: Action a4ainst Nilaparvata luaens Rice plants are treated with an aqueous emulsion spray liquor comprising 400 ppm of the active compound. After the spray coating has dried on, the rice plants are populated with 2nd and 3rd instar larvae of Nilaparvata lugens. 21 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Nilaparvata lugens.
The compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B3: Activity against Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the maize seedlings are populated with 10 second instar larvae of Diabrotica balteata and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Diabrotica balteata.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 6.53, 6.21, 6.78, 6.79, 6.12, 6.02, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B4: Activity against Tetranychus urticae Young bean plants are populated with a mixed population of Tetranychus urticae and, 1 day later, sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. The plants are subsequently incubated for 6 days at 25°C and then evaluated.
The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Tetranychus urticae.
Compounds 4.80, 4.53; 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B5: Activity a4ainst Spodoptera littoralis catemillars Young soya plants are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the soya plants are populated with 10 third instar caterpillars of Spodoptera littoralis and introduced into a plastic container. Three days later, the test is evaluated. The percentage reduction in population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage, respectively, on the treated plants with those on the untreated plants.
In this test, the compounds of Tables 1- 20 are very effective against Spodoptera littoralis.
Compounds 4.80, 4.53, 4.12, 4.21, 4.36, 5.77, 5.53, 5.21, 5.78, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B6: Activity against Plutella xylostella catemillars .
Young cabbage plants are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the cabbage plants are populated with 10 third instar caterpillars of Plutella xylostella and introduced into a plastic container. 3 days later, the test is evaluated. The percentage reduction in population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage, respectively, on the treated plants with those on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Plutella xylostella.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.77, 5.53, 5.78, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80, in particular, exhibit an activity of over 80%.
Example B7: Activity against Aphis craccivora Pea seedlings are infected with Aphis craccivora and subsequently sprayed with a spray liquor which comprises 400 ppm of the active ingredient and incubated at 20°C. 3 and 6 days later, respectively, the test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of dead leaf spars on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Aphis craccivora.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.36, 4.26, 5.77, 5.53, 5.21, 5.78, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80, in particular, exhibit an activity of over 80%.
Example B8: Activity a4ainst Mvzus persicae Pea seedlings are infected with Myzus persicae and subsequently sprayed with a spray liquor which comprises 400 ppm of the active compound and incubated at 20°C. 3 and 6 days later, respectively, the test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of dead aphids on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Myzus persicae.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.36, 4.26, 5.21, 5.78, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80, in particular, exhibit an activity of over 80%.
Example B9: Systemic action against Myzus aersicae Pea seedlings are infected with Myzus persicae, the roots are then placed in a spray liquor which comprises 400 ppm of the active compound, and the seedlings are incubated at 20°C.
3 and 6 days later, respectively, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Myzus persicae.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 5.21, 5.78, 5.02, 5.12, 6.21, 6.78, 6.79 and 6.80, in particular, exhibit an activity of over 80%.
Example B10: Ovo/larvicidal action on Heliothis virescens Heliothis virescens eggs which have been deposited on cotton are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars is evaluated in comparison with untreated control batches (% reduction in population).
In this test, compounds of Tables 1 - 20 are very effective against Heliothis virescens.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6:53, 6.21, 6.78, 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B11: Ovicidal activity a4ainst Tetranvchus urticae Young bean plants are populated with female Tetranychus urticae which are removed again after 24 hours. The plants which are populated with eggs are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. The plants are subsequently incubated at 25°C for 6 days and then evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Tetranychus urticae.
Compounds 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5:78, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B12: Activity against Panonychus ulmi (OP and Carb. resistent) Apple seedlings are populated with adult females of Panonychus ulmi. After seven days, the infected plants are sprayed to run off point with an aqueous emulsion spray liquor comprising 400 ppm of the compound to be tested, and cultivated in a greenhouse. After 14 days, the test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of dead spider mites on the treated plants with that on the untreated plants.
In the above test, the compounds of Tables 1 - 20 are very effective.
Compounds 4.53, 4.78, 4.12, 4.21, 4,79, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
15.02 H CH3 15.03 H C2H5 15.04 H C3H~-n 15.05 H C3Hri 15.06 H C4H9-n 15.07 H C4H9-t 15.08 H CsH, 3-n 15.09 H C,oH2,-n 15.10 H CH2C(CH3)s 15.11 CH3 H
15.12 CH3 CH3 15.13 CH3 C2H5 15.14 CH3 C3H,-n 15.15 CH3 C3H~-i 15.16 CH3 C4H9-n 15.17 CH3 C4H9-t 15.18 CH3 CsH,3-n 15.19 CH3 C,oH2,-n 15.20 CH3 CH2C(CH3)3 _79-' Comp. No. R, R2 phys. data 15.21 CH3 CsHs 15.22 CH3 CsH4-2-CI
15.23 CH3 C6H4-3-CI
15.24 CH3 C6H4-4-CI
15.25 CH3 CsH4-2-CF3 15.26 CH3 CsH4-3-CF3 15.27 CH3 C6H4-4-CF3 15.28 CH3 CsH4-2-CN
15.29 CH3 CsH4-3-CN
15.30 CH3 C6H4-4-CN
15.31 CH3 CsH4-2-N02 15.32 CH3 CsH4-3-N02 15.33 CH3 C6H4-4-NOZ
15.34 CH3 CsH4-4-CsH5 15.35 CH3 CsH4-4-OCsHs 15.36 CH3 CsH4-4-C(CH3)s 15.37 CH3 CsH4-4-OCF3 15.38 CH3 C6H4-4-COOC2H5 15.39 CH3 CsFs 15.40 CH3 CsH2-3,4,5-(OCH3)3 15.41 CH3 ~ ~ N
Comp. No. R, R2 phys. data 15.42 CH3 ~ ~ N
~N
15.43 CH3 ~ ~ OH
15.44 CsHS CF3 15.45 CsHs C2H5 15.46 CsHS C3H~-n 15.47 CsHS C3H~-i 15.48 CsHs C4H9-t 15.49 C6H5 C4H9-n 15.50 C6H5 cyclopropyl 15.51 CsHS cyclopentyl 15.52 CsHS cyclohexyl 15.53 CsH5 CsHs 15.54 CsHs CsH4-4-CI
15.55 C6H5 CsH4-4-CF3 15.56 C6H5 CsH4-4-CN
15.57 CgHS CsH4-4-N02 15.58 C6H5 CBH4-4-C6H5 15.59 CsHs CsH4-4-OCsHS
15.60 CsHS CsH4-4-C(CH3)s 15.61 CsHs C6H4-4-OCF3 ' Comp. No. R, R2 phys. data 15.62 CBH4-4-CI CF3 15.63 CsH4-4-CI C2H5 15.64 C6H4-4-CI C3Hrn 15.65 CsH4-4-CI C3H,-i 15.66 CsH4-4-CI C4H9-t 15.67 CsH4-4-CI C4H9-n 15.68 CsH4-4-CI CH2C6H5 15.69 C6H4-4-CI CH2C6H4-4-CH3 15.70 C6H4-4-CI C6H4-4-CI
15.71 CsH4-4-CI CsH4-4-OH
15.72 CsH4-4-CI CsH4-2-CH3 .
15.73 C6H4-4-CI CsH4-2-CI
15.74 CsH4-4-CI C6H4-4-Br 15.75 C6H4-4-CI 4-pyridyl 15.76 C6H4-4-CI CsH4-4-OCH2-C6H4-3-15.77 C6H4-4-CI Csli,-o-CH2 F
F
15.78 H -CsHS
15.79 CsHS CHZCsHs 15.80 C2H5 -C6H44-CI
_8Q_ Table 16: Compounds of the formula H O
F\C~C\CH CH2~Ch12 C\O/N'C/R~
2 ~
F RZ
Comp. No. R, RZ phys. data 16.01 H H
16.02 H CH3 16.03 H C2H5 16.04 H C3Hrn 16.05 H C3H,-i 16.06 H C4H9-n 16.07 H C4H9-t 16.08 H C6H,3-n 16.09 H C,oH2,-n 16.10 H CH2C(CH3)3 16.11 CH3 H
16.12 CH3 CH3 16.13 CH3 C2H5 16.14 CH3 C3H,-n 16.15 CH3 C3Hri 16.16 CH3 C4H9-n 16.17 CH3 C4H9-t 16.18 CH3 CsH,3-n 16.19 CH3 C,oH~-n - Comp. No. R1 R2 phys. data 16.20 CH3 CH2C(CH3)s 16.21 CH3 CsH5 16.22 CH3 C6H4-2-CI
16.23 CH3 CeH4-3-CI
16.24 CH3 CgH4-4-CI
16.25 CH3 CsH4-2-CF3 16.26 CH3 C6H4-3-CF3 16.27 CH3 G6H4-4-CF3 16.28 CH3 CsH4-2-CN
16.29 CH3 C6H4-3-CN
16.30 CH3 CsH4-4-CN
16.31 CH3 C6H4-2-N02 16.32 CH3 C6H4-3-N02 16.33 CH3 CsH4-4-N02 16.34 CH3 CsH4-4-CsHs 16.35 CH3 C6H4-4-OC6H5 16.36 CH3 C6H4-4-C(CH3)s 16.37 CH3 CsH4-4-OCF3 16.38 CH3 CeH4-4-COOC2H5 16.39 CH3 CsFs 16.40 CH3 C6H2-3;4,5-(OCH3)s 16.41 CH3 ~ ~ N O
U
-Comp. No. R, R2 phys. data 16.42 CH3 ~ ~ N
16.43 CH3 ~ ~ OH
16.44 CsH5 CF3 16.45 C6H5 C2H5 16.46 CsHS C3H,-n 16.47 CsHS C3H,-i 16.48 CsH5 C4H9-t 16:49 CsHs C4H9-n 16.50 CsHS cyclopropyl 16:51 C6H5 cyclopentyl 16.52 CBHS cyclohexyl 16.53 CgHs CsH5 16.54 CsHS CsH4-4-CI
16.55 C6H5 CgH4-4-CF3 16.56 CgHs CgH4-4-CN
16.57 CsH5 CsH4-4-N02 16.58 CgHs CsH4-4-C6H5 16.59 CsHS CsH4-4-OCsHS
16.60 CsHs CsH4-4-C(CH3)s 16.61 CsHs CsH4-4-OCF3 -g5_ Comp. No. R, R2 phys. data 16.62 CsH4-4-CICF3 16.63 CsH4-4-CIC2H5 16.64 CsH4-4-CIC3Hy-n 16.65 C6H4-4-CIC3H,-i 16.66 C6H4-4-CIC4H9-t 16.67 CgH4-4-CIC4Hg-n 16.68 CsH4-4-CICH2C6H5 16.69 CsH4-4-CICH2C6H4-4-CH3 16.70 C6H4-4-CICBH4-4-CI
16.T1 C6H4-4-CICsH4-4-OH
16.72 CsH4-4-CICsH4-2-CH3 16.73 CsH4-4-CIC6H4-2-CI
16.74 C6H4-4-CICsH4-4-Br 16.75 C6H4-4-CI4-pyridyl 16.76 C6H4-4-CICsH4-4-OCH2-CsH4-3-16.77 CsH4_4_CI CsHs-~-CHZ
F
F
16.78 H CsH5 16.79 C6H5 CH2C6H5 16.80 C2H5 -CsH4-4-CI
Table 17: Compounds of the formula H O
F C ~CH2 C N ~ R~
\C~ \CHZL ~CHZ \N/ ~C/
F H RZ
Comp. No. R, R2 phys. data 17.01 H H
17.02 H CH3 17.03 H C2H5 17.04 H C3H;-n 17.05 H C3H~-i 17.06 H CQH9-n 17.07 H C4H9-t 17.08 H CsH,3-n 17.09 H C,oH2,-n 17.10 H CH2C(CH3)s 17.11 CH3 H
17.12 CH3 CH3 17.13 CH3 C2H5 17.14 CH3 C3Hrn 17.15 CH3 C3Hri 17.16 CH3 C4H9-n 17.17 CH3 C4H9-t 17.18 CH3 CsH,3-n 17.19 CH3 C,oH2,-n Comp. No. R, R2 phys. data 17.20 CH3 CH2C(CH3)s 17.21 CH3 CsHS
17.22 CH3 C6H4-2-CI
17.23 CH3 CsH4-3-CI
17.24 CH3 C6H4-4-CI
17.25 CH3 CsH4-2-CF3 ' 17.26 CH3 C6H4-3-CF3 17.27 CH3 C6H4_4_CF3 17.28 CH3 CsH4-2-CN
17.29 CH3 CsH4-3-CN
17.30 CH3 CsH4-4-CN
17.31 CH3 C6H4-2-N02 17.32 CH3 CsH4-3-N02 17.33 CH3 CsH4-4-N02 17.34 CH3 CsH4-4-CsHs 17.35 CH3 CsH4-4-OC6H5 17.36 CH3 CsH4-4-C(CH3)s 17.37 CH3 C6H4-4-OCF3 17.38 CH3 CsH4-4-COOC2H5 17.39 CH3 CsFs 17.40 CH3 -C6H2-3,4,5-(OCH3)s 17.41 CH3 ~ ~ N
$$ -Comp. No. R, R2 phys. data 17.42 CH3 ~ ~ N
~N
17.43 CH3 ~ ~ OH
17.44 C6H5 CF3 17.45 C6H5 C2H5 17.46 CsHs C3H,-n 17.47 CsH5 C3H~-i 17.48 C6Hs CQH9-t 17.49 CsHS CaH9-n 17.50 CsHs cyclopropyl 17.51 C6H5 cyclopentyl 17.52 C6Hs cyclohexyl 17.53 C6H5 CsHS
17.54 CBH5 C6H4-4-CI
17.55 CBHS CgH4-4-CF3 17.56 CsH5 C6H4-4-CN
17.57 C6H5 CsH4-4-N02 17.58 C6H5 C6H4-4-CsHs 17.59 CsHs CsH4-4-OCsHS
17.60 CsHS CsH4-4-C(CH3)s 17.61 CsHS CsH4-4-OCF3 _89-Comp. No. R, RZ phys. data 17.62 C6H4-4-CI CF3 17.63 CsH4-4-CI C2H5 17.64 C6H4-4-CI C3H~-n 17.65 C6H4-4-CI C3H,-i 17.66 C6H4-4-CI C4H9-t 17.67 CsH4-4-CI CoH9-n 17.68 C6H4-4-CI CH2CsH5 17.69 CsH4-4-CI CH2CsH4-4-CH3 17.70 CsH4-4-CI CsH4-4-CI
17.71 CsH4-4-CI C6H4-4-OH
17.72 C6H4-4-CI C6H4-2-CH3 17.73 CsH4-4-CI C6H4-2-CI
17.74 C6H4-4-CI CsH4-4-Br 17.75 C6H4-4-CI 4-pyridyl 17.76 C6H4-4-CI C6H4-4-OCH2-CsH4-3-CF3 17.77 C6H4_4_CI CsHs-~' CH2 F
F
17.78 H CsHS
17.79 C6H5 CH2C6H5 17.80 C2H5 -C6H4-4-CI
Table 18: Compounds of the formula I
F~ ~C~ CHZ C~ ~CHz\ N ~C
C~ CHZ ~CHZ O C/ 'N~ \RZ
F O
Comp. No. R, R2 phys. data 18.01 H H
18.02 H CH3 18.03 H C2H5 18.04 H C3H,-n 18.05 H C3H~-i 18.06 H C4H9-n 18.07 H CaH9-t 18.08 H CeH,3-n 18.09 H C,oH2,-n 18.10 H CH2C(CH3)s 18.11 CH3 H
18.12 CH3 CH3 18.13 CH3 C2H5 18.14 CH3 C3H,-n 18.15 CH3 C3H,-i 18.16 CH3 C4H9-n 18.17 CH3 C4H9-t 18.18 CH3 CsH,3-n 18.19 CH3 C,oH2,-n _91 _ ' Comp. No. R~ R2 phys. data 18.20 CH3 CH2C(CH3)s 18.21 CH3 CsHs 18.22 CH3 C6H4-2-CI
18.23 CH3 C6H4-3-CI
18.24 CH3 CsH4-4-C) 18.25 CH3 CgH4-2-CF3 18.26 CH3 CsH4-3-CF3 18.27 CH3 CsH4-4-CF3 18.28 CH3 CsH4-2-CN
18.29 CH3 CsH4-3-CN
18.30 CH3 CsH4-4-CN
18.31 CH3 CsH4-2-NO2 18.32 CH3 C6H4-3-N02 18.33 CH3 CsH4-4-N02 18.34 CH3 C6H4-4-CsHs 18.35 CH3 C6H4-4-OCsHs 18.36 CH3 CsH4-4-C(CH3)3 18.37 CH3 C6H4-4-OCF3 18.38 CH3 CsH4-4-COOC2Hs 18.39 CH3 C6Fs 18.40 CH3 CsH2-3,4,5-(OCH3)s ~ ~
18.41 CH3 NV
Comp. No. R, R2 phys. data 18.42 CH3 ~ ~ N
18.43 CH3 ~ ~ OH
18.44 C6H5 CF3 18.45 CsHs C2Hs 18.46 C6H5 C3Hrn 18.47 CsHS C3Hri 18.48 CsHs Calls-t 18.49 C6H5 C4H9-n 18.50 CsHS cyclopropyl 18.51 CsHS cyclopentyl 18.52 CsHs cyclohexyl 18.53 C6H5 CsHs 18.54 C6H5 C6H4-4-CI
18.55 C6H5 CsH4-4-CF3 18.56 CsHS C6H4-4-CN
18.57 C6H5 C6H4-4-N02 18.58 CsH5 C6H4-4-CsHS
18.59 CsHs C6H4-4-OC6H5 18.60 CgH5 CgH4-4-C(CH3)s Comp. No. Ri R2 phys. data 18.61 CsH5 C6H4-4-OCF3 18.62 CsH4-4-CI CF3 18.63 CsH4-4-CI CZHS
18.64 C6H4-4-CI C3H~-n 18.65 CsH4-4-CI C3H,-i 18.66 C6H4-4-CI C4H9-t 18.67 CgH4-4-CI C4H9-n 18.68 C6H4-4-CI CH2CsH5 18.69 CsH4-4-CI CH2CsH4-4-CH3 18.70 CsH4-4-CI C6H4-4-CI
18.71 CsH4-4-CI CsH4-4-OH
18.72 CsH4-4-CI C6Ha-2-CH3 18.73 C6H4-4-CI CsH4-2-CI
18.74 C6H4-4-CI CsH4-4-Br 18.75 CsH4-4-CI 4-pyridyl 18.76 CsH4-4-CI CsH4-4-OCH2-C6H4-3-CFs 18.77 CsH4-4-CI C6H~-O-CH2 F
F
18.78 H C6H5 18.79 CsHS CH2CsH5 18.80 C2H5 -CsH4-4-CI
. Table 19: Compounds of the formula F O
z F ~ C ~ ~N R1 ~C C X
Comp. No. R, R2 X n phys. data 19.1 -CsH5 -C6H5 NH 0 19.2 -CsHS -C6H5 NH 1 m.p.:92-93C
19.3 -CeHS -CsH5 NH 2 19.4 -C6H5 -CsH5 NH 3 19.5 -C6H5 -CsHs NH 4 19.6 -CgHs -C6H5 NH 5 19.7 -CsHs -CBHS O 0 19.8 -CsHs -C6H5 O 1 amorphous 19.9 -CsHS -C6H5 O 2 19.10 -C6H5 -CsH5 O 3 19.11 -CsHs -CsH5 O 4 19.12 -CsHS -CsH4-4-CI O 5 19.13 CH3 -CsH4-4-CI NH 0 19.14 CH3 -CsH4-4-CI NH 1 19.15 CH3 -C6H4-4-CI NH 2 19.16 CH3 -C6H4-4-CI NH 3 19.17 CH3 -CsH4-4-CI NH 4 19.18 CH3 -CsH4-4-CI NH 5 19.19 CH3 -CsH4-4-CI O 0 Comp. No. R, RZ X n phys. data 19.20 CH3 -CgH4-4-CI O 1 19.21 CH3 -CsH4-4-CI O 2 19.22 CH3 -CsH4-4-CI O 3 19.23 CH3 -CsH4-4-CI O 4 19.24 CH3 -C6H4-4-CI O 5 19.25 -CsH4-4-CI-CsH4-4-CI NH 1 19.26 -CsH4-4-CI-CsH4-4-CI O 1 Table 20: Compounds of the formula F ~ C ~ ~N R1 \C C X
Comp. No. R, R2 X n phys. data 20.1 -C6H5 -C6H5 NH 0 20.2 -CsH5 -CgHs NH 1 m.p.:89-100C
20.3 -CsHS -CsH5 NH 2 20.4 -C6H5 -C6H5 NH 3 20.5 -CsHs -CsHS NH 4 20.6 -CsHs -C6H5 NH 5 20.7 -CsHs -CsH5 O 0 20.8 -CsHS -CsHS O 1 np2 =1.5530 20.9 -CeHS -C6H5 O 2 20.10 -CeHS -CsHS O 3 ' Comp. No. R, R2 X n phys. data 20.11 -CsHS -CsHS O 4 20.12 -C6H5 -CsH4-4-CI O 5 20.13 CH3 -CsH4-4-CI NH 0 20.14 CH3 -CsH4-4-CI NH 1 20.15 CH3 -C6H4-4-CI NH 2 20.16 CH3 -CsH4-4-CI NH 3 20.17 CH3 -CsH4-4-CI NH 4 20.18 CH3 -CsH4-4-CI NH 5 20.19 CH3 -CsH4-4-CI O 0 20.20 CH3 -CsH4-4-CI O 1 20.21 CH3 -CsH4-4-CI O 2 20.22 CH3 -CgH4-4-CI O 3 20.23 CH3 -C6H4-4-CI O 4 20.24 CH3 -CsH4-4-CI O 5 20.25 -CsH4-4-CI-CsH4-4-CI NH 1 20.26 -CsH4-4-CI-C6H4-4-CI O 1 Biological Examples Examale B1: Ovicidal action on Heliothis virescens Heliothis virescens eggs which have been deposited on filter paper are briefly immersed into an acetonic/aqueous test solution comprising 400 ppm of the active compound to be tested.
After the test solution has dried on, the eggs are incubated in Petri dishes.
After 6 days, the percentage hatching rate of the eggs is evaluated in comparison with untreated control batches (% reduction in hatching).
_97_ In this test, compounds according to tables 1 - 20 are very effective against Heliothis virescens. Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5:53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78; 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example 82: Action a4ainst Nilaparvata luaens Rice plants are treated with an aqueous emulsion spray liquor comprising 400 ppm of the active compound. After the spray coating has dried on, the rice plants are populated with 2nd and 3rd instar larvae of Nilaparvata lugens. 21 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of surviving leaf hoppers on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Nilaparvata lugens.
The compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B3: Activity against Diabrotica balteata larvae Maize seedlings are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the maize seedlings are populated with 10 second instar larvae of Diabrotica balteata and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Diabrotica balteata.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 6.53, 6.21, 6.78, 6.79, 6.12, 6.02, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B4: Activity against Tetranychus urticae Young bean plants are populated with a mixed population of Tetranychus urticae and, 1 day later, sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. The plants are subsequently incubated for 6 days at 25°C and then evaluated.
The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Tetranychus urticae.
Compounds 4.80, 4.53; 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B5: Activity a4ainst Spodoptera littoralis catemillars Young soya plants are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the soya plants are populated with 10 third instar caterpillars of Spodoptera littoralis and introduced into a plastic container. Three days later, the test is evaluated. The percentage reduction in population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage, respectively, on the treated plants with those on the untreated plants.
In this test, the compounds of Tables 1- 20 are very effective against Spodoptera littoralis.
Compounds 4.80, 4.53, 4.12, 4.21, 4.36, 5.77, 5.53, 5.21, 5.78, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B6: Activity against Plutella xylostella catemillars .
Young cabbage plants are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the cabbage plants are populated with 10 third instar caterpillars of Plutella xylostella and introduced into a plastic container. 3 days later, the test is evaluated. The percentage reduction in population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage, respectively, on the treated plants with those on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Plutella xylostella.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.77, 5.53, 5.78, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80, in particular, exhibit an activity of over 80%.
Example B7: Activity against Aphis craccivora Pea seedlings are infected with Aphis craccivora and subsequently sprayed with a spray liquor which comprises 400 ppm of the active ingredient and incubated at 20°C. 3 and 6 days later, respectively, the test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of dead leaf spars on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Aphis craccivora.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.36, 4.26, 5.77, 5.53, 5.21, 5.78, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80, in particular, exhibit an activity of over 80%.
Example B8: Activity a4ainst Mvzus persicae Pea seedlings are infected with Myzus persicae and subsequently sprayed with a spray liquor which comprises 400 ppm of the active compound and incubated at 20°C. 3 and 6 days later, respectively, the test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of dead aphids on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Myzus persicae.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.36, 4.26, 5.21, 5.78, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80, in particular, exhibit an activity of over 80%.
Example B9: Systemic action against Myzus aersicae Pea seedlings are infected with Myzus persicae, the roots are then placed in a spray liquor which comprises 400 ppm of the active compound, and the seedlings are incubated at 20°C.
3 and 6 days later, respectively, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Myzus persicae.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 5.21, 5.78, 5.02, 5.12, 6.21, 6.78, 6.79 and 6.80, in particular, exhibit an activity of over 80%.
Example B10: Ovo/larvicidal action on Heliothis virescens Heliothis virescens eggs which have been deposited on cotton are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars is evaluated in comparison with untreated control batches (% reduction in population).
In this test, compounds of Tables 1 - 20 are very effective against Heliothis virescens.
Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6:53, 6.21, 6.78, 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B11: Ovicidal activity a4ainst Tetranvchus urticae Young bean plants are populated with female Tetranychus urticae which are removed again after 24 hours. The plants which are populated with eggs are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. The plants are subsequently incubated at 25°C for 6 days and then evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants.
In this test, the compounds of Tables 1 - 20 are very effective against Tetranychus urticae.
Compounds 4.53, 4.78, 4.12, 4.21, 4,79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5:78, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Example B12: Activity against Panonychus ulmi (OP and Carb. resistent) Apple seedlings are populated with adult females of Panonychus ulmi. After seven days, the infected plants are sprayed to run off point with an aqueous emulsion spray liquor comprising 400 ppm of the compound to be tested, and cultivated in a greenhouse. After 14 days, the test is evaluated. The percentage reduction in population (%
activity) is determined by comparing the number of dead spider mites on the treated plants with that on the untreated plants.
In the above test, the compounds of Tables 1 - 20 are very effective.
Compounds 4.53, 4.78, 4.12, 4.21, 4,79, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36, 6.26 and 6.80, in particular, exhibit an activity of over 80%.
Claims (19)
1. A compound of the formula in which R1 and R2 independently of one another are hydrogen; or alkyl, a group , aryl, cycloalkyl, alkenyl or alkynyl, which are substituted or unsubstituted;
R3 is hydrogen, fluorine or methyl;
m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1;
X is oxygen or NR4; and R4 is hydrogen or C1-C6-alkyl or benzyl, which are substituted or unsubstituted, and, if appropriate, its possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in free form or in salt form, with the proviso that a) R3 is not hydrogen or fluorine and m and n are not both 0 if X is oxygen and R1 and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or heteroaryl; b) R3 is not hydrogen or fluorine and m and n are not both 0 if R4 is hydrogen and R1 and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, aryl or heteroaryl; c) m is not 0, 1 or 2 and R4 is hydrogen, alkyl or haloalkyl if one of the radicals R1 or R2 is 4-alkylsulphonyloxyphenyl, 4-haloalkylsulphonyloxyphenyl or 4-haloalkoxysulphonyloxyphenyl which may or may not carry further substituents, and the other radical is substituted or unsubstituted phenyl; and d) m is not 0, 1 or 2 and R4 is not hydrogen, alkyl or haloalkyl and n is not 0 if one of the radicals R1 and R2 is 4-perhaloalkoxyphenyl which may or may not carry further substituents and the other is substituted or unsubstituted phenyl.
R3 is hydrogen, fluorine or methyl;
m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1;
X is oxygen or NR4; and R4 is hydrogen or C1-C6-alkyl or benzyl, which are substituted or unsubstituted, and, if appropriate, its possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in free form or in salt form, with the proviso that a) R3 is not hydrogen or fluorine and m and n are not both 0 if X is oxygen and R1 and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or heteroaryl; b) R3 is not hydrogen or fluorine and m and n are not both 0 if R4 is hydrogen and R1 and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, aryl or heteroaryl; c) m is not 0, 1 or 2 and R4 is hydrogen, alkyl or haloalkyl if one of the radicals R1 or R2 is 4-alkylsulphonyloxyphenyl, 4-haloalkylsulphonyloxyphenyl or 4-haloalkoxysulphonyloxyphenyl which may or may not carry further substituents, and the other radical is substituted or unsubstituted phenyl; and d) m is not 0, 1 or 2 and R4 is not hydrogen, alkyl or haloalkyl and n is not 0 if one of the radicals R1 and R2 is 4-perhaloalkoxyphenyl which may or may not carry further substituents and the other is substituted or unsubstituted phenyl.
2. A compound of the formula (I) according to Claim 1 in free form.
3. A compound of the formula (I) according to Claim 1 in which R1 and R2 independently of one another are hydrogen; C1-C20-alkyl, which may be straight-chain or branched and and may be mono- to tetrasubstituted by hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylsulphonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morpholino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulphonyl, naphthylsulphonyl, phenylsulphonyloxy, naphthylsulphonyloxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 hetero atoms N, O or S, where the aryl or heteroaryl groups mentioned for their part may be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio;
C3-C20-alkenyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
C3-C20-alkynyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
C3-C7-cycloalkyl, which may be mono- or tetra-substituted by halogen, alkyl or haloalkyl;
Phenyl or naphthyl, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylsulphonyloxy, haloalkylsulphonyloxy, haloalkoxysulphonyloxy, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxyradicals as substituents may for their part be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy;
heteroaryl having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy, halocycloalkylalkoxy;
R3 is hydrogen, fluorine or methyl;
m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1; and X is oxygen or NR4, where R4 is hydrogen, C1-C4-alkyl which may be mono- or polysubstituted by halogen, C1-C4-alkoxy or di-C1-C4-alkylamino, or is benzyl which may be mono- or polysubstituted by halogen, C1-C4-alkyl, halo-C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano.
C3-C20-alkenyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
C3-C20-alkynyl, which may be straight-chain or branched and may be mono- to tetrasubstituted by halogen;
C3-C7-cycloalkyl, which may be mono- or tetra-substituted by halogen, alkyl or haloalkyl;
Phenyl or naphthyl, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylsulphonyloxy, haloalkylsulphonyloxy, haloalkoxysulphonyloxy, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxyradicals as substituents may for their part be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy;
heteroaryl having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, which may be mono- to tetra-substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, pyrrolidino, piperidino, morpholino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy having 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, where phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents for their part may be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy, halocycloalkylalkoxy;
R3 is hydrogen, fluorine or methyl;
m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1; and X is oxygen or NR4, where R4 is hydrogen, C1-C4-alkyl which may be mono- or polysubstituted by halogen, C1-C4-alkoxy or di-C1-C4-alkylamino, or is benzyl which may be mono- or polysubstituted by halogen, C1-C4-alkyl, halo-C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano.
4. A compound of the formula (I) according to any one of Claims 1 or 2 in which R1 and R2 independently of one another are hydrogen or unsubstituted or substituted alkyl, cycloalkyl, alkenyl or alkynyl, R3 is hydrogen, fluorine or methyl, m is 0, 1, 2, 3, 4 or 5;
n is 0 or 1, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C1-C6-alkyl or benzyl.
n is 0 or 1, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C1-C6-alkyl or benzyl.
5. A compound of the formula (I), according to Claim 1 or 2 in which R1 is hydrogen or unsubstituted or substituted alkyl, alkenyl, alkynyl or cycloalkyl, R2 is hydrogen or unsubstituted or substituted aryl or heteroaryl, R3 is hydrogen, fluorine or methyl, m is 0, 1, 2, 3, 4 or 5 and n is 0 or 1, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C1-C6-alkyl or benzyl.
6. A compound of the formula (I) according to Claim 1 or 2 in which R1 and R2 independently of one another are hydrogen or unsubstituted or substituted aryl, R3 is hydrogen, fluorine or methyl, m is 0, 1, 2, 3, 4 or 5 and n is 0 or 1, X is oxygen or NR4, and R4 is hydrogen or unsubstituted or substituted C1-C6-alkyl or benzyl.
7. A compound of the formula (I) according to any one of Claims 1-5 in which R3 is hydrogen and R1, R2, R4, m, n and X are as defined.
8. A compound of the formula (I) according to any one of Claims 1-5 in which m is 0, 1, 2, 3 or 4 and R1, R2, R3, R4, n and X are as defined.
9. A compound of the formula (I) according to any one of Claims 1-5 in which m is 1 or 4 and R1, R2, R3, R4, n and X are as defined.
10. A compound of the formula (I) according to any one of Claims 1-5 in which n is 0 and R1, R2, R3, R4, m and X are as defined.
11. A compound of the formula (I) according to any one of Claims 1-5 in which n is 0 and m is 1 or 4 and R1, R2, R3, R4 and X are as defined.
12. A compound of the formula (I) according to any one of Claims 1-5 in which R3 is hydrogen, n is 0 and m is 1 or 4, X is NH or oxygen and R1 and R2 are as defined.
13. A process for preparing a compound as defined in Claim 1, formula (I), which comprises a) preparing compounds of the formula (I) in which n is 0 and R1, R2, R3, X
and m are as defined above under formula (I) by reacting a compound of the formula in which R3 and m are as defined under formula (I) and Y2 is Cl, Br or OSO2-alkyl with a compound of the formula in which R1, R2 and X are as defined under formula (I);
b) preparing compounds of formula (I) in which n is 0 and X is NR4 and R1, R2, R3 and m are as defined under formula (I) by reacting a compound of the formula in which R3, R4 and m are as defined under formula (I) with a compound of the formula in which R1 and R2 are as defined under formula (I); and c) preparing compounds of the formula (I) in which n is 1 and R1, R2, R3, R4, X and m are as defined under formula (I) by reacting a compound of the formula in which R3 and m are as defined above under formula (I) with a compound of the formula in which Y1 is C1, Br or OSO2-alkyl and X, R1 and R2 are as defined above under formula (I).
and m are as defined above under formula (I) by reacting a compound of the formula in which R3 and m are as defined under formula (I) and Y2 is Cl, Br or OSO2-alkyl with a compound of the formula in which R1, R2 and X are as defined under formula (I);
b) preparing compounds of formula (I) in which n is 0 and X is NR4 and R1, R2, R3 and m are as defined under formula (I) by reacting a compound of the formula in which R3, R4 and m are as defined under formula (I) with a compound of the formula in which R1 and R2 are as defined under formula (I); and c) preparing compounds of the formula (I) in which n is 1 and R1, R2, R3, R4, X and m are as defined under formula (I) by reacting a compound of the formula in which R3 and m are as defined above under formula (I) with a compound of the formula in which Y1 is C1, Br or OSO2-alkyl and X, R1 and R2 are as defined above under formula (I).
14. A pesticide which contains, in addition to inert auxiliaries and carriers, at least one compound of the formula (I) according to Claim 1 as active substance.
15. A process for preparing a pesticide according to Claim 14 which comprises mixing a compound of the formula (I) according to Claim 1 with inert auxiliaries and carriers.
16. A method for controlling pests, which comprises applying a compound of the formula (I) as described in Claim 1 or a composition as described in Claim 14 to the pests or their habitat.
17. The use of a compound of formula (I) as described in Claim 1 or, if appropriate, an E/Z
isomer or tautomer thereof, in free form or in agrochemically useable salt form for preparing a composition as described in Claim 14.
isomer or tautomer thereof, in free form or in agrochemically useable salt form for preparing a composition as described in Claim 14.
18. A method according to Claim 16 for protecting plant propagation stock, which comprises treating the propagation stock or the location where the propagation stock is planted.
19. The use of a compound of the formula (I) as described in Claim 1 or of a composition as described in Claim 14 for controlling pests.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1327/97 | 1997-06-03 | ||
| CH132797 | 1997-06-03 | ||
| PCT/EP1998/003214 WO1998055448A2 (en) | 1997-06-03 | 1998-05-29 | Fluoroalkene carboxylic acid derivatives, method for producing said derivatives, and insecticidal agents containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2291441A1 true CA2291441A1 (en) | 1998-12-10 |
Family
ID=4207875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002291441A Abandoned CA2291441A1 (en) | 1997-06-03 | 1998-05-29 | Fluoroalkene carboxylic acid derivatives, method for producing said derivatives, and insecticidal agents containing the same |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0986534A2 (en) |
| JP (1) | JP2002502405A (en) |
| CN (1) | CN1259118A (en) |
| AU (1) | AU734489B2 (en) |
| BR (1) | BR9809912A (en) |
| CA (1) | CA2291441A1 (en) |
| WO (1) | WO1998055448A2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7842727B2 (en) | 2001-03-27 | 2010-11-30 | Errant Gene Therapeutics, Llc | Histone deacetylase inhibitors |
| WO2003099789A1 (en) | 2002-05-22 | 2003-12-04 | Errant Gene Therapeutics, Llc. | Histone deacetylase inhibitors based on alphachalcogenmethylcarbonyl compounds |
| CA2486303C (en) | 2002-05-22 | 2013-04-30 | Errant Gene Therapeutics, Llc | Histone deacetylase inhibitors based on alpha-ketoepoxide compounds |
| MXPA05008118A (en) * | 2003-02-19 | 2005-09-30 | Ciba Sc Holding Ag | Halogenated oxime derivatives and the use thereof as latent acids. |
| WO2009079797A1 (en) | 2007-12-26 | 2009-07-02 | Critical Outcome Technologies, Inc. | Compounds and method for treatment of cancer |
| CA2730890C (en) | 2008-07-17 | 2018-05-15 | Critical Outcome Technologies Inc. | Thiosemicarbazone inhibitor compounds and cancer treatment methods |
| CA2999435A1 (en) | 2010-04-01 | 2011-10-06 | Critical Outcome Technologies Inc. | Compounds and method for treatment of hiv |
| US11234970B2 (en) | 2017-04-10 | 2022-02-01 | Mitsui Chemicals Agro, Inc. | Parasitic pest control agents comprising pyridone compounds as active ingredients and methods for using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG43002A1 (en) * | 1994-01-05 | 1997-10-17 | Ciba Geigy | Hydrazone derivatives |
| DE19524436A1 (en) * | 1995-07-05 | 1997-01-09 | Bayer Ag | Fluorobutenic acid oxime ester |
| CN1226230A (en) * | 1996-07-24 | 1999-08-18 | 诺瓦蒂斯公司 | Pesticidal composition |
| AU4297197A (en) * | 1996-08-08 | 1998-03-06 | Novartis Ag | Substituted 4-nitroimino-perhydro-1,3,5-oxadiazine derivatives, their use as pesticides and intermediates for their preparation |
-
1998
- 1998-05-29 CA CA002291441A patent/CA2291441A1/en not_active Abandoned
- 1998-05-29 BR BR9809912-4A patent/BR9809912A/en not_active IP Right Cessation
- 1998-05-29 AU AU82116/98A patent/AU734489B2/en not_active Ceased
- 1998-05-29 EP EP98932100A patent/EP0986534A2/en not_active Withdrawn
- 1998-05-29 CN CN98805795A patent/CN1259118A/en active Pending
- 1998-05-29 WO PCT/EP1998/003214 patent/WO1998055448A2/en active Search and Examination
- 1998-05-29 JP JP50145099A patent/JP2002502405A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998055448A3 (en) | 1999-05-06 |
| AU8211698A (en) | 1998-12-21 |
| BR9809912A (en) | 2000-10-03 |
| WO1998055448A2 (en) | 1998-12-10 |
| EP0986534A2 (en) | 2000-03-22 |
| CN1259118A (en) | 2000-07-05 |
| JP2002502405A (en) | 2002-01-22 |
| AU734489B2 (en) | 2001-06-14 |
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