CA1196648A - 4-BENZYLOXY-.alpha.-TRICHLOROMETHYL-BENZYLAMINES, A PROCESS FOR THEIR PREPARATION, PEST-COMBATING AGENTS CONTAINING THEM, AND THE PREPARATION AND USE OF THESE AGENTS - Google Patents
4-BENZYLOXY-.alpha.-TRICHLOROMETHYL-BENZYLAMINES, A PROCESS FOR THEIR PREPARATION, PEST-COMBATING AGENTS CONTAINING THEM, AND THE PREPARATION AND USE OF THESE AGENTSInfo
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- CA1196648A CA1196648A CA000389045A CA389045A CA1196648A CA 1196648 A CA1196648 A CA 1196648A CA 000389045 A CA000389045 A CA 000389045A CA 389045 A CA389045 A CA 389045A CA 1196648 A CA1196648 A CA 1196648A
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- benzyloxy
- trichloromethyl
- benzyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- A—HUMAN NECESSITIES
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
- A01N33/10—Amines; Quaternary ammonium compounds containing oxygen or sulfur having at least one oxygen or sulfur atom directly attached to an aromatic ring system
-
- A—HUMAN NECESSITIES
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Epoxy Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A 4-benzyloxy-?- trichloromethyl-benzylamine of the formula in which R is an optionally substituted phenyl radical, R1 and R2 each independently is a hydrogen or halogen atom or an optionally substituted alkyl or alkoxy radical, and R3 is an optionally substituted alkyl, cycloalkyl, alkenyl or alkinyl radical, or a salt, thereof which possesses pesticidal activity, e.g.
against Arthropods.
* * * * * * * * * * * * * * * * * * *
A 4-benzyloxy-?- trichloromethyl-benzylamine of the formula in which R is an optionally substituted phenyl radical, R1 and R2 each independently is a hydrogen or halogen atom or an optionally substituted alkyl or alkoxy radical, and R3 is an optionally substituted alkyl, cycloalkyl, alkenyl or alkinyl radical, or a salt, thereof which possesses pesticidal activity, e.g.
against Arthropods.
* * * * * * * * * * * * * * * * * * *
Description
~36~
- 1 Type Ia The present invention relates to certain new 4-benzyloxy-~-trichloromethyl-benzylamines, a process for their production, to their use as pest-combating agents, preferably against Arthropoda.
Certain 4-formyl- or 4-dialkylamino-a-t-richloro~
methylbenzylamlnes have been disclosed as intermediate products and as substances which have an action, which has not been described in more detail, against viruses, tumours, fungi and insects (see Tetrahedron 1967~ 23, pages 1713-1721 and British Patent S.pecification 1,173,677).
In pràctice, however, their action is inadequate, especially when low amounts are applied.
It has furthermore been disclosed that~certain 4,4'-disubstituted a-trichloromethylbenzyl-anilines can be used as insecticides (see German Offenlegungsschrift tGerman Published Specification) 2,301,397). Howeverg the insecticidal action of these substances is also unsatisfactory, especially when low amounts are applied.
It has also been disclosed thak certain diphenyl ether derivatives can be used for combating harmful insects. Nevertheless, the action of khese cornpounds is not completely satisfactory for some types of use, especially when low concent:rations are applied (see German Offenlegungsschrift (German Published Speclfication)
- 1 Type Ia The present invention relates to certain new 4-benzyloxy-~-trichloromethyl-benzylamines, a process for their production, to their use as pest-combating agents, preferably against Arthropoda.
Certain 4-formyl- or 4-dialkylamino-a-t-richloro~
methylbenzylamlnes have been disclosed as intermediate products and as substances which have an action, which has not been described in more detail, against viruses, tumours, fungi and insects (see Tetrahedron 1967~ 23, pages 1713-1721 and British Patent S.pecification 1,173,677).
In pràctice, however, their action is inadequate, especially when low amounts are applied.
It has furthermore been disclosed that~certain 4,4'-disubstituted a-trichloromethylbenzyl-anilines can be used as insecticides (see German Offenlegungsschrift tGerman Published Specification) 2,301,397). Howeverg the insecticidal action of these substances is also unsatisfactory, especially when low amounts are applied.
It has also been disclosed thak certain diphenyl ether derivatives can be used for combating harmful insects. Nevertheless, the action of khese cornpounds is not completely satisfactory for some types of use, especially when low concent:rations are applied (see German Offenlegungsschrift (German Published Speclfication)
2~4l8~343).
The present invention now provides, as new com-pounds, the 4 benzyloxy-cl-trichloromethyl-benzylamines of the general formula ~2 (I) C 2 ~-C~-NXR
Le A 20 670 in which R is a phenyl radical of the Eormula R4 ~ ~
~<' /
Rl and R2 each independently is a hydrogen or halogen atom, or an alkyl or alkoxy radical optionally substituted by 1 or more halogen atoms;
R3 is an alkyl, cycloalkyl, alkylcycloalkyl, alkenyl or alkinyl radical optionally substituted by 1 or more halogen atoms, alkyl, alkoxy, alkylthio radical or hetero cyclo alkyl radical 1~ containing 1 to 3 different hetero atoms substituted by an alkyl radical or halogen atom, or a salt thereof;
R4 and R5 each independently is a hydrogen or halogen atom, or a nitro or cyano radical, or an alkyl, alkoxy or alkyl-thio radical optionally substituted by 1 or more halogen atoms.
According to the present invention there .is further provided a process for the production of a compound of the present invention, characterised i.n that a compound o:E the general formula R-CH2-0~ CH=NR ( II ) in which R, R, R and R have the abovementioned meani.ng, is Le A 20 670 -2-i6 ~
reacted with trichloroacetic acid, if appropriate in -the presence of a solvent, and, if desired, a salt thereof is prepared by further reaction of the product with an acid.
The optionally subs~ituted phenyl radical of R can contain one or more identical or different substituentsO
One of the radicals R4 and R5 is preferably in the 3-or 4-position, in particular in the 4-position. Preferably, R
represents a hydrogen atom. Particularly preferably, R4 repre-sents a hydrogen atom and ~5 represents a substituent in the 4-position. Alkyl, alkoxy and alkylthio radicals of R4 and R are straight-chain or branched and preferably con~ain 1 to 8, in particular 1 to 4 and very particularly preferably 1 or 2, carbon atoms. These alkyl, alkoxy and alkylthio radicals can contain one or more, prefexably 1 to 5 and in particular 1 to 3, identical or different substituents, preferred substi-tuents being halogen, such as fluorine, chlorine, brom:ine and iodine, preferably fluorine and chlorine. Examples of alkyl, alkoxy and alkylthio and of halogenoalkyl, halogenoalkoxy and halogenoalkyl-thio radicals which may be mentioned are: methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, chloromethyl, chlorodifluoro-methyl, trifluoromethyl, l,l-difluoro-2,2-dichloroethyl, trifluo-romethoxy, l,l-difluoro-2,2-dichloroethoxy, chloromethylthio, trifluoromethylthio and l,l~difluoro-2,2-dichloroethylthio.
R4 and R5, when halogen, denote fluorine, chlorine, bromine or iodine atoms, preferably fluorine, chlorine or bromine atoms, and in particular fluorine or chlorine atoms.
Le A 20 670 -3-~6~
Particularly preferred substituted phenyl radicals of R
which may be mentioned are: 4-methylphenyl, 4-trifluoromethyl-phenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-trifluoro-methylthiophenyl and 4-chloro and 4 fluoro-phenyl (iOe. those in which R4 represents a hydrogen atom and R5 represents 4-methyl, 4-trifluoro-Le A 20 670 -3a-methyl3 4-methoxy, 4~trifluoromethoxy, 4-tri~luoromethylthio, 4-chloro or 4-fluoro radical).
The substituents Rl and R2 can occupy the various free positions in the phenyl ring o~ the benzylamine part.
Preferably, one of the radicals Rl and R2 is in the 3-position. Preferably, one of the radicals Rl and R2 represents a hydrogen atom, and particularly preferably both the radicals Rl and R2 are hydrogen atoms.
Optionally substituted alkyl and alkoxy radicals of Rl and R2 are straight-chain or branched and preferably contain 1 to 5, in particular 1 to 3 and very particularly preferably 1 or 2, carbon atoms. A possible substituent of these radicals is, above all, halogen, such as fluorine, chlorine, bromine and iodine, in particular fluorine and chlorine. Examples which may be mentioned are: methyl, ethyl, n- and i-propyl, methoxy, ethoxy and trifluoro-methoxy. Rl and R2, when halogen~ denotes fluorine, chlorine, bromine or iodine atoms, preferably fluorine, chlorine or bromine atoms.
Particularly preferred compounds of the present invention are those in which one of the radicals Rl and R2 represents a halogen atom or an al~oxy radical, or both th~ radicals Rl and R2 represent halogen atoms. Com-pounds of the present in~ention in which Rl and R2 both represent hydrogen are very partlcularly preferred~
The optionally substitu~ed alkyl ra~ica~. of R~ is straight-chain or branched and preferably contains 1 to 18, in particular 1 to 6 and particularly preferably 1 to 4 carbon atoms. Examples which may be mentioned are methyl, ethyl~ n- and i-propyl and n-~ s- and t-butyl.
~ he optionally substituted cycloalkyl radical of R3 preferably contains 3 to 7, in particular 3, 5 or 6g ring carbon atoms. In addition to being substituted by the substituents mentioned below, it can also be substit-uted by alkyl with pre~erably 1 to 4 carbon atoms 3 prefer-Le A 2~ 670 5ably by methyl. Examples which ~lay be mentioned are cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl.
The optionally substituted alkenyl or alkinyl radical of R3 is straight-chain or branched and preferably contains 3 to 8g in particular 3 to 6, carbon atoms9 these radicals preferably con~aining 1 double or triple bond.
Examples which may be mentioned are allyl, propargyl and l,l-diethyl-propargyl.
The optional.ly substituted alkyl~ alkenyl and alkinyl radicals of R3 can carry one or more, preferably 1 to 3 and in particular 1, substituents. Preferred substituents which may be mentioned in this context are halogen (such as fluorine, chlorine, bromine and iodine), hydroxyl3 cyano, alkoxy, alkylthio or a hetercyclic ring.
Alkoxy and alkylthio here preferably contain 1 to 5, in particular 1 or 2, carbon atoms. Examples which may be mentioned are methoxy, ethoxy, methylthio and ethylthio.
~ he heterocyclic ring as a substituent of the above radicals R3, preferably of R3 when an alkyl radical, in particular when a methyl radical, preferably contains 5 to 7, in particular 5 or 6, ring members and 1 to 3, preferably l or 2, identical or different hetero-atoms, such as nitrogen, sulphur and oxygen. It can be saturated or contain l to 3 double bonds and have an aromatic character. The heterocyclic ring can also be substituted, for example by alkyl, (such as methyl) or halogen (such as chlorine). Examples which may be mentioned are pyrldyl~ imidazolyl, thiazolyl and, prefer~
ably~ thienyl and furyl.
Substituent R3 in compounds of the present in~ention particularly preferably represents an alkyl radical which has 1 to 18 carbon atoms and is optionally substituted by alkoxy with 1 or 2 carbon atoms, alkyl which has 1 to 4 carbon atoms (preferably methyl) and is subs.t.i.t.uted by 2.-.furyl or. 2~thienyl,. or c.yc.lo.he~yl, Le A 20 670 methylcyclohexyl or alkenyl or alki-nyl with 3 to 6 carbon atoms.
Preferred compounds according tc the present invention are those in which R represents a radical of the general formula R ~ (Ia) in which R5 R4 and R5 are identical or di~ferent and rep-resent a hydrogen or halogen atom or a nitro or cyano radical or an optionally substituted alkyl~
alkoxy or alkylthio radical, and Rl represents a hydrogen or halogen atomg R2 represents a hydrogen or halogen atom or an alkoxy radical and R3 represents an alkyl radical, which is optionally substituted by alkoxy, furyl or thienyl~ or cyclo-alkyl, alkylcycloalkyl, alkenyl or alkinyl.
Particularly pre~erred compounds according to the present invention are those in which R represents a radical of the general formula (Ia), as shown above, in which R4 and R5 are identical or different and represent a hydrogen or halogen atom or a nitro or cyano radical or an optionally substituted alkyl, alkoxy or alkylthio radical with in each case l to 4 car-bon atoms in the alkyl part, and Rl represents a hydrogen or halogen atom, R represents a hydrogen or halogen atom or an alkoxy radical with 1 to 5 carbon atoms and R3 represents an alkyl radical with l to 18 carbon atoms, an alkyl radical which has l to 4 carbon atoms and is substituted by alkoxy with l to 5 . carbon.atoms, furyl or..thienyl, or a c.yc.loalkyl or Le A 20 670 methylcycloalkyl radical or an alkenyl or alkinyl radical with 3 to 8 carbon atoms.
By salts o~ the compounds of the formula (I) there are to be understood the cu~tomary salts which are formed with inorganic acids (~or example hydrogen halide acids~
such as HCl, HBr or HI, or nitric acid), or with organic acids (for example oxalic acid or CX3COOH, in ~hich X = ~, Cl or Br)~ and which are tolerated by plants.
By the compounds of the present invention there are understood both the racemates and the optically active stereoisomers, which are obtainable by the generally customary metho~s of resolution.
The following compounds according to the invention may be mentioned specifically: (4-benzyloxy-~-trichloromethyl-benzyl)-methylamine, (4-benzyloxy-a-trichloromethyl-benzyl)~ethylamine, (4-benzyloxy-a-tri-chloromethyl benzyl)~n-propylamine, (4-benzyloxy-a-tri-chloromethyl-benzyl)-i-propylamine, (4-benzyloxy-a-tri-chloromethyl benzyl)-n-butylamineg (4-benzyloxy--tri-chloro~ethyl-benzyl)-i-butylamine~ (4-benzyloxy-a-tri-chloromethyl-benzyl)-furfurylamine~ (4-benzyloxy-a-tri-chloromethyl-benzyl)-thienylmethylamine, l-(4-benzyloxy-a-trichloromethyl-benzyl)-3-ethoxy-propylaminel C4-(4'-chloro-benzyloxy)-~-tr~chloromethyl-benzyl~-ethylamine, [4~(4'-chloro-benzyloxy)-a-trichloromethyl-benæyl]~n-propylamine, ~4-(4'-chloro-benzyloxy) -trichloromethyl-benzyl~ propylamine, [4-(4'-chloro-benzyloxy)-a-tri-chloromethyl-benzyll-n-butylamineg [4-(4'-chloro-benzyl-oxy)-a-trichloromethyl-benzyl~-i-butylamine, [4-(4'-
The present invention now provides, as new com-pounds, the 4 benzyloxy-cl-trichloromethyl-benzylamines of the general formula ~2 (I) C 2 ~-C~-NXR
Le A 20 670 in which R is a phenyl radical of the Eormula R4 ~ ~
~<' /
Rl and R2 each independently is a hydrogen or halogen atom, or an alkyl or alkoxy radical optionally substituted by 1 or more halogen atoms;
R3 is an alkyl, cycloalkyl, alkylcycloalkyl, alkenyl or alkinyl radical optionally substituted by 1 or more halogen atoms, alkyl, alkoxy, alkylthio radical or hetero cyclo alkyl radical 1~ containing 1 to 3 different hetero atoms substituted by an alkyl radical or halogen atom, or a salt thereof;
R4 and R5 each independently is a hydrogen or halogen atom, or a nitro or cyano radical, or an alkyl, alkoxy or alkyl-thio radical optionally substituted by 1 or more halogen atoms.
According to the present invention there .is further provided a process for the production of a compound of the present invention, characterised i.n that a compound o:E the general formula R-CH2-0~ CH=NR ( II ) in which R, R, R and R have the abovementioned meani.ng, is Le A 20 670 -2-i6 ~
reacted with trichloroacetic acid, if appropriate in -the presence of a solvent, and, if desired, a salt thereof is prepared by further reaction of the product with an acid.
The optionally subs~ituted phenyl radical of R can contain one or more identical or different substituentsO
One of the radicals R4 and R5 is preferably in the 3-or 4-position, in particular in the 4-position. Preferably, R
represents a hydrogen atom. Particularly preferably, R4 repre-sents a hydrogen atom and ~5 represents a substituent in the 4-position. Alkyl, alkoxy and alkylthio radicals of R4 and R are straight-chain or branched and preferably con~ain 1 to 8, in particular 1 to 4 and very particularly preferably 1 or 2, carbon atoms. These alkyl, alkoxy and alkylthio radicals can contain one or more, prefexably 1 to 5 and in particular 1 to 3, identical or different substituents, preferred substi-tuents being halogen, such as fluorine, chlorine, brom:ine and iodine, preferably fluorine and chlorine. Examples of alkyl, alkoxy and alkylthio and of halogenoalkyl, halogenoalkoxy and halogenoalkyl-thio radicals which may be mentioned are: methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, chloromethyl, chlorodifluoro-methyl, trifluoromethyl, l,l-difluoro-2,2-dichloroethyl, trifluo-romethoxy, l,l-difluoro-2,2-dichloroethoxy, chloromethylthio, trifluoromethylthio and l,l~difluoro-2,2-dichloroethylthio.
R4 and R5, when halogen, denote fluorine, chlorine, bromine or iodine atoms, preferably fluorine, chlorine or bromine atoms, and in particular fluorine or chlorine atoms.
Le A 20 670 -3-~6~
Particularly preferred substituted phenyl radicals of R
which may be mentioned are: 4-methylphenyl, 4-trifluoromethyl-phenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-trifluoro-methylthiophenyl and 4-chloro and 4 fluoro-phenyl (iOe. those in which R4 represents a hydrogen atom and R5 represents 4-methyl, 4-trifluoro-Le A 20 670 -3a-methyl3 4-methoxy, 4~trifluoromethoxy, 4-tri~luoromethylthio, 4-chloro or 4-fluoro radical).
The substituents Rl and R2 can occupy the various free positions in the phenyl ring o~ the benzylamine part.
Preferably, one of the radicals Rl and R2 is in the 3-position. Preferably, one of the radicals Rl and R2 represents a hydrogen atom, and particularly preferably both the radicals Rl and R2 are hydrogen atoms.
Optionally substituted alkyl and alkoxy radicals of Rl and R2 are straight-chain or branched and preferably contain 1 to 5, in particular 1 to 3 and very particularly preferably 1 or 2, carbon atoms. A possible substituent of these radicals is, above all, halogen, such as fluorine, chlorine, bromine and iodine, in particular fluorine and chlorine. Examples which may be mentioned are: methyl, ethyl, n- and i-propyl, methoxy, ethoxy and trifluoro-methoxy. Rl and R2, when halogen~ denotes fluorine, chlorine, bromine or iodine atoms, preferably fluorine, chlorine or bromine atoms.
Particularly preferred compounds of the present invention are those in which one of the radicals Rl and R2 represents a halogen atom or an al~oxy radical, or both th~ radicals Rl and R2 represent halogen atoms. Com-pounds of the present in~ention in which Rl and R2 both represent hydrogen are very partlcularly preferred~
The optionally substitu~ed alkyl ra~ica~. of R~ is straight-chain or branched and preferably contains 1 to 18, in particular 1 to 6 and particularly preferably 1 to 4 carbon atoms. Examples which may be mentioned are methyl, ethyl~ n- and i-propyl and n-~ s- and t-butyl.
~ he optionally substituted cycloalkyl radical of R3 preferably contains 3 to 7, in particular 3, 5 or 6g ring carbon atoms. In addition to being substituted by the substituents mentioned below, it can also be substit-uted by alkyl with pre~erably 1 to 4 carbon atoms 3 prefer-Le A 2~ 670 5ably by methyl. Examples which ~lay be mentioned are cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl.
The optionally substituted alkenyl or alkinyl radical of R3 is straight-chain or branched and preferably contains 3 to 8g in particular 3 to 6, carbon atoms9 these radicals preferably con~aining 1 double or triple bond.
Examples which may be mentioned are allyl, propargyl and l,l-diethyl-propargyl.
The optional.ly substituted alkyl~ alkenyl and alkinyl radicals of R3 can carry one or more, preferably 1 to 3 and in particular 1, substituents. Preferred substituents which may be mentioned in this context are halogen (such as fluorine, chlorine, bromine and iodine), hydroxyl3 cyano, alkoxy, alkylthio or a hetercyclic ring.
Alkoxy and alkylthio here preferably contain 1 to 5, in particular 1 or 2, carbon atoms. Examples which may be mentioned are methoxy, ethoxy, methylthio and ethylthio.
~ he heterocyclic ring as a substituent of the above radicals R3, preferably of R3 when an alkyl radical, in particular when a methyl radical, preferably contains 5 to 7, in particular 5 or 6, ring members and 1 to 3, preferably l or 2, identical or different hetero-atoms, such as nitrogen, sulphur and oxygen. It can be saturated or contain l to 3 double bonds and have an aromatic character. The heterocyclic ring can also be substituted, for example by alkyl, (such as methyl) or halogen (such as chlorine). Examples which may be mentioned are pyrldyl~ imidazolyl, thiazolyl and, prefer~
ably~ thienyl and furyl.
Substituent R3 in compounds of the present in~ention particularly preferably represents an alkyl radical which has 1 to 18 carbon atoms and is optionally substituted by alkoxy with 1 or 2 carbon atoms, alkyl which has 1 to 4 carbon atoms (preferably methyl) and is subs.t.i.t.uted by 2.-.furyl or. 2~thienyl,. or c.yc.lo.he~yl, Le A 20 670 methylcyclohexyl or alkenyl or alki-nyl with 3 to 6 carbon atoms.
Preferred compounds according tc the present invention are those in which R represents a radical of the general formula R ~ (Ia) in which R5 R4 and R5 are identical or di~ferent and rep-resent a hydrogen or halogen atom or a nitro or cyano radical or an optionally substituted alkyl~
alkoxy or alkylthio radical, and Rl represents a hydrogen or halogen atomg R2 represents a hydrogen or halogen atom or an alkoxy radical and R3 represents an alkyl radical, which is optionally substituted by alkoxy, furyl or thienyl~ or cyclo-alkyl, alkylcycloalkyl, alkenyl or alkinyl.
Particularly pre~erred compounds according to the present invention are those in which R represents a radical of the general formula (Ia), as shown above, in which R4 and R5 are identical or different and represent a hydrogen or halogen atom or a nitro or cyano radical or an optionally substituted alkyl, alkoxy or alkylthio radical with in each case l to 4 car-bon atoms in the alkyl part, and Rl represents a hydrogen or halogen atom, R represents a hydrogen or halogen atom or an alkoxy radical with 1 to 5 carbon atoms and R3 represents an alkyl radical with l to 18 carbon atoms, an alkyl radical which has l to 4 carbon atoms and is substituted by alkoxy with l to 5 . carbon.atoms, furyl or..thienyl, or a c.yc.loalkyl or Le A 20 670 methylcycloalkyl radical or an alkenyl or alkinyl radical with 3 to 8 carbon atoms.
By salts o~ the compounds of the formula (I) there are to be understood the cu~tomary salts which are formed with inorganic acids (~or example hydrogen halide acids~
such as HCl, HBr or HI, or nitric acid), or with organic acids (for example oxalic acid or CX3COOH, in ~hich X = ~, Cl or Br)~ and which are tolerated by plants.
By the compounds of the present invention there are understood both the racemates and the optically active stereoisomers, which are obtainable by the generally customary metho~s of resolution.
The following compounds according to the invention may be mentioned specifically: (4-benzyloxy-~-trichloromethyl-benzyl)-methylamine, (4-benzyloxy-a-trichloromethyl-benzyl)~ethylamine, (4-benzyloxy-a-tri-chloromethyl benzyl)~n-propylamine, (4-benzyloxy-a-tri-chloromethyl-benzyl)-i-propylamine, (4-benzyloxy-a-tri-chloromethyl benzyl)-n-butylamineg (4-benzyloxy--tri-chloro~ethyl-benzyl)-i-butylamine~ (4-benzyloxy-a-tri-chloromethyl-benzyl)-furfurylamine~ (4-benzyloxy-a-tri-chloromethyl-benzyl)-thienylmethylamine, l-(4-benzyloxy-a-trichloromethyl-benzyl)-3-ethoxy-propylaminel C4-(4'-chloro-benzyloxy)-~-tr~chloromethyl-benzyl~-ethylamine, [4~(4'-chloro-benzyloxy)-a-trichloromethyl-benæyl]~n-propylamine, ~4-(4'-chloro-benzyloxy) -trichloromethyl-benzyl~ propylamine, [4-(4'-chloro-benzyloxy)-a-tri-chloromethyl-benzyll-n-butylamineg [4-(4'-chloro-benzyl-oxy)-a-trichloromethyl-benzyl~-i-butylamine, [4-(4'-
3 chloro-benzyloxy)-a-t~ichloromethyl-benzyl~-n~hexylamine~
~4-(4'-chloro-benzyloxy)-a-trichloromethyl-benzyl]-fur-~urylamine9 ~4-(4~-chloro-benzyloxy)-a-trichloromethyl-benzyl~-thienyl~methylamine, ~4-(4'-methylbenzyloxy)-a-trichloromethyl-benzyl]-methylamine, [4-(4'-methyl-Le A 2G 670 benzyloxy)-a-trichloromethyl-benz~Jl~-ethylamine, ~4-(4'-methyl-benzyloxy)-a-trichloromethyl-benzyl~ -n-propylamine, ~4-(4' methyl-benzyloxy)--trlchloromethyl-benzyl~
propylamine, ~4~ methyl-benzyloxy)-a-trichloromethyl-benzyl]-allylamine, [4-(4'-methyl-benzyloxy)-~-trichloro-methyl-benzyl~-propargylamine, [4-(4'-methyl-benzyloxy)-a-trichloromethyl-benzyl~-n-butylamine~ ~4-(4'-methyl-benzyloxy)--trichloromethyl-benzyl~-i-butylamine, [4-(4'-methyl-lDenzyloxy)-~-trichloromethyl-benzyl¦-sec.-butyl-10 amine, l4-(4'-methyl7benzyloxy)-a-trichloromethyl-benzyl~-tert.-butylamine, r4-(4l-methyl-benzyloxy)~a-trichloro-methyl-benzyl~-n-hexylamine~ ~4-(4'-methyl-benzyloxy)-~-trichloromethyl-benzyl~-2-ethyl-hexylamine, L4_(4 t -methyl-benzyloxy)-~-trichloromethyl-benzyl~-n-dodecylamine, ~4-(4'~methyl-benzyloxy)-~-trichloromethyl-benzyl]-cyclohexyl-amine, [4-(4t-methyl-benzyloxy)-a-trichloromethyl-benzyl~-fur~urylamine, ~4-(4~-methyl-benzyloxy)-a-trichloro-methyl-benzyl~-thienylmethylamine, l-L4-(4 t -methyl-benzyloxy)-~-~richloromethyl-benzyl]-3-ethoxy-propyl-2 0 amine, ~4-(4i-methoxy-benzyloxy)~a-trichloromethYl~
benzyl~-methylamine, [4-(4'-methoxy-benzyloxy)--tri-chloromethyl-benzyl~-ethylamine, ~4-(4'-methoxy-benzyl-oxy)-~-trichloromethyl-benzyl~-i-propylamine, [4-(4'-methoxy-benzyloxy)-~-trichloromethyl-benzyl~-n-butyl-amine, [4-(4'-methoxy-benzyloxy)-~-trichloromethyl-benzyl~ butylamine, ~ 4- ( 4'-methoxy-benzyloxy)-a-tri-chloromethyl-benzyl~-sec.-butylamine, L4-( L~ I -methoxy-benzyloxy)-~-trichloromethyl-benzyl~-n-hexylamine, [Li_ ( 4 I -methoxy-benzyloxy)-~-trichloromethyl-benzyl]-~ur-~urylamine, [4-(4'-methoxy-benzyloxy)-~-trichloromethyl-benzyl]-thienylmethylamine, 1-[4-(4'-methoxy-benæyloxy)-a-trichloromethyl-benzyl~-3-ethoxy-propylamine, L4-(4'~
methyl-benzyloxy)-3-methoxy-a-trichloromethyl-benzyl~
n-butylamine, ~4-(4'-methyl-benzyloxy)-3-methoxy-a-tri-chloromethyl-benzy.l~-i-butylamine, ~4-(4'-methyl-benzyl-Le A 20 670 6~
g oxy)-3-~ethoxy a-trichloromethyl-benzyl]-furfurylamine~
~4-( 4 ~ -methyl-benzyloxy)-3-methoxy-a-trichloromethyl-benzyl~-thi~nylmethylamine~ L4- ( 4 -methoxy-benzyloxy)-3-methoxy-a-trichloromethyl-benzyl~-n-butylamine, ~4-(4'-methoxy-benzyloxy)-3-methoxy-~trichloromethyl-benzyl] -furfurylamine, [4-(4 t -me~hoxy-benzyloxy)-3-methoxy ~-trichloromethyl~benzyl~-thienylmethylamine~ L4 ( 4 fluoro-benzyloxy)-a-trichloromethyl~benzyl~-n-butyl-amine, ~-(4'-fluoro-benzyloxy)-~-trichloromethyl-benzyl~-furfurylamine~ ~4- ( 4 -trifluoromethyl-benzyl-oxy)-a-trichloromethyl-benzyl~ utylami.ne, [4-(4~-tri-fluoromethyl-benzyloxy)-a~trichloromethyl-benzyl¦-n-hexylamine, [4-(4'-trifluoromethyl-benzyloxy)--tri-chloromethyl-benzyl~-furfurylamine~ L4- (3'-trifluoro-methy1-4~-chloro-benzyloxy)-a-trichloromethyl-benzyl~-i-butylamine, [4- ~ 4~-tri~luoromethoxy-benzyloxy)-a-tri chloromethyl-benzyl]-i-propylamine, 14-~4 t -trifluoro-methoxy-benzyloxy)-~-trichloromethyl-benzyl]-n-butyl-amine, ~4-(4'-trifluoromethoxy-benzyloxy)-a-trichloro-methyl-benzyl~-i-butylarnine, [4-(4'-trifluoromethoxy-benzyloxy)-a-trichloromethyl-benzyl]-n-hexylamine~ [4-(4'-trifluoromethoxy-benzyloxy)-a-trichloromethyl-benzyl]-fu.rfurylamine, [4-(4'-trifluoromethoxy~benzyl-oxy)-~-trichloromethyl-benzyll-thienylmethylamine~ r4-25 ( L~ r~luorothiome~hyl -benzyloxy)-a-trichlo.roMeth~l-benzyl~ n-butylamine and [4-(4'-trifluorothiomethyl benzyloxy)-a-trichloromethyl-benzyl]-furfurylamine and chlorides and trichloroacetates thereof.
If l-~4-(4'-methyl-benzyloxy-)-benzylidene~-3-3 ethoxy-propylamine and trichloroacetic acid are used as starting substances~ the course of the reaction for the preparation of the new active compounds according to the invention can be illustrated by the ~ollowing equation:
Le A`20 670 CH3 ~ CH2 ~ CH=N-(cH2)3oc2Hs ~ CC13C2 3 ~ 2 ~ -cH~NH-(cH2)3 C2~5 2 CCl Most of the Schiff's bases of the gener21 formula (II) required for the preparation of the ~-trichloromethyl-amines of the general formula (I) are known (see German Offenlegungsschrifk (C;erman Published Specification) 2,631,948), or they can be prepared by known processes (see Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry)3 Volume VII/l year 19549 pages 454 to 458 and ~olume XI/2 year 1958, pages 74 to 85, Thieme Verlag, Stuttgart)-Possible solvents for the process according tothe învention are any of the inert organic solvents, for example optionally halogenated aliphatic or aromatic hydrocarbons (such as cyclohexane, benzene, toluene, xylene~ chlorobenzene and carbon tetrachloride). The process according to the invention can also be carried out without a solvent, but the yields in this case are usually poorer. Toluene or xylene is preferably used as the solvent.
It is expedient to bring the starting substances together at a temperature from 80 to 130C, preferably a~
90 to 110C, and also to carry out the reaction at these temperatures.
The reaction is in general carried out under normal pressure.
In carrying out the process according to the invention, 1 to 3 moles~ in particular 1 to 2 moles~ of trichloroacetic acid are preferabl~ empl~oyed per mole of Le A 20 670 6~
Schiff's base of formula (II).
~he course of the process according to the inven~ion can be followed in a simple manner by means of the evolution of C02.
The reaction mixture is wor~ed up by generally known methods. It is expedient to distil off the solvent and, if desired~ to recrystallise the resu].ting product, ~or example from petroleum ether.
The salts can be obtained by the generally cus-tomary salt formation methods from the compounds of the formula (I) and corresponding inorganic acids, such as hydrogen halide acids (HC1, HBr or HI) or nitric acid or corresponding organic acids, such as oxalic acid and tri-halogenoacetic acids (CX3COO~; in which X - F, C1 or Br).
The new compounds of the present invention have a low toxicity to warm-blooded animals and, surprisingly, have a very good action against Arthropoda, in par~icular insects, and also have a good action as egg sterilisers.
In the followlng text, by "active compounds" according to the invention there are understood in each case the compounds of the formula I and thelr salts.
The active compounds are well tolerated by plants, have a favourable level of toxiciky ~o warm-blooded animals, and are suitable for combating arthropod pests, especially insects and arachnida, and nematodes, whlch are encountered in agriculture, in forestry, in the protection o~ stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of 3 development. The abovementioned pests include:
from the class of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber;
from the class of the Diplopoda, for example Blaniulus guttulatus;
from the class of the Chilopoda, for example Geophilus Le A 20 670 carpophagus and Scutigera spec.;
from the class of ~he Symphyla, for example Scuti-gerella immaculata;
from the order of the Thysanura, for example Lepisma saccharina;
from the order of the Collembola, for example Onychiurus armatus;
from the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllo-talpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria;
from the order o~ the Dermaptera, for example ~or~icula auricularia;
~rom the order of the Isoptera, for example Reticulitermes spp.;
~rom the order of the Anoplura, for example Phylloxera vastatrix9 Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Lino~nathus spp.;
from the order of the Mallophaga, ~or example Trichodectes spp. and Damalinea spp.;
from the order of the Thysanoptera, for example Hercinothrips ~emoralis and Thrips tabaci;
~rom the order of the Heteroptera~ for example Eurygaster~spp., Dysdercus intermedius, Piesma quadrata,Cimex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera~ ~or example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brasslcae, Cryptomyzus ribis~ Doralis fabae, Doralis pomi, Eriosoma lani~erum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humu~i, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, ~aodelphax striatellus, Nilaparvata lugens,. Aonidiella aurantii~..Aspidiotus heder.ae~
Le A 20 670 6~8 Pseudococcus spp. and Psylla spp.;
from the order o~ the Lepidoptera, for example Pectinophora gossypiellag Bupalus piniarius, Cheimatobia brumata~ Lithocalletis blancardella, Hyponomeuta padella~
Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua~
Mamestra brassicae, Panolis flammea, Prodenia liturag Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambi~uella, Homona magn~n; m~ and Tortrix viridana;
from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrllpes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp~, Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus~ Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Atta~enus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, A~riotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica;
from the order of the Hymenopte.ra, ~or example 3~ Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.;
from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogasterS
Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., C'uter.ebra spp.~ Gast.rophilus Le A 20 6700 ~ 14 -spp., Hyppobosca spp.~ Stomoxys spp., Oestrus spp., Hypoder~a spp., Tabanus spp., Tannia spp., Bibio hortulanusg ~scinella fri~, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa;
from the order of the Siphonaptera3 for example Xenopsylla cheopis and Ceratophyllus spp., from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans, from the order of the Acarina, for example Acarus siro, Argas spp., ~rnithodoros spp., Dermanyssus gallinae, ~riophyes ribis, Phyllocoptruta oleivorag Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and ~etranychus spp..
T~e active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams~ pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations u ed with burning equipment, such as fumigating cartridges~
fumigating cans, fumigating coils and the like, as well as ULV cold mist ax-ld warm mist formulations.
These formulations may be produced in know~ manner, for example by mi~ing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use o.~ surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers~ especially solven~s, there are suitable in the main, aromatic hydrocarbons, such as. xy.len.e,..'olue.n.e. or alkyl naphthale.nes,. chlorinat.ed .
Le A 20 670 aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone~
methyl isobutyl ketone or cyclohe~anone, or strongly polar solven~s, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatureand under normal pressure, for example aerosol propellants~
such as halogenated hydrocarbons as well as butane~
propane, nitrogen and carbon dioxide.
15 As s.olid carriers there may be used ground natural minerals, such as kaolins, clays3 talc, chalk, quartz, aktapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicatesO As solid carriers for granules there may be used crushed and`fractionated natural roc~s such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells~ maize cobs and tobacco stalks.
As emul.sifying and/or foam-forming agents there may be used non ionic and anionic emulsil~iers, such as polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol 3 ethers, alkyl sulphonatesg alkyl sulphates, aryl sulphon-ates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthet.i.c polymers in.the form of powd.ers, ~ . . . .
granules or latices, such as gum arabic, polyvinyl alcohol Le A 20 670 i6~
and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide~ titanium oxide and Prussian Blue, and organic dyestuf~s, such as alizarin dyes~uffs, azo dyestuffs or metal phthalocyanine dyestuffs~
and trace nutrients, such as salts of iron~ manganese, boron, copper~ cobalt, molybdenum and zinc.
~ he formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weightO
The active compounds according to the invention can be present in their commercially available formula-tions and in the use forms~ prepared from these formula-tions, as a mixture with other active compoundsg such as insecticides, baits, sterilising agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicidesO The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons~ phenylureas and ~ substances produced by micro-organisms.
The active compounds according to the lnvention can f~rthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents.
Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can 3 vary within wide limits. The active compound concen-tration of the use forms can be from 0.0000001 to 100% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate far the use forms.
Le A 20 67~
When used against pests harmful to health ancl pests of stored products~ the active compounds are distinguished by an e~cellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
The present invention also provides a pesticidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
~ he present invention also provides a method of combating pests (in particular arthropodsg especially insects or acarids~ or nematodes) which comprises applying to the pests, or to a habitat thereo~, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of freeing or protecting domesticated animals from parasites which comprises applying to said animals a compound according to the present invention, in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by pests by being ~rown in a~eas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The present invention f~rther provides domestic-ated animals whenever freed or protected from parasites by the application to said animals of a compound according to the present invention~ in admi~ture T~ith a diluent or carrier.
i:
Le A 20 670 The activity of the compounds of this invention is illustrated by the followin~ biotest Examples~
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example.
Example A
Aedes test Solvent: 3 parts ~y weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent and the stated amount o~ emulsifier, and the concentrate was diluted with water to the desired concentrationS-. The aqueous preparations of active compound werefilled into glass vessels and about 20 mosquito larvae (Aedes aeg~pti) were then placed in each glass vessel.
After the desired period of time, the destruction in % was determined. 100% meant that all the animals had been ~illed; 0% meant that none of the animals had been killed.
In this test, in an experiment carried out for example with an active compound concentration of 0.0001 the following compounds, for example, exhibited a degree of destruction of 100% after 14 days: compounds (18), (28), (30), (34), (35), (36), (40), (42), (57), (58) and (72).
E~ample B
Plutella test 3 Solvent: 3 parts by weight of ace~one ~mulsifi~r: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound was mixed with the st.a.ted amount jof solven.t and the stat.e-d. amount. o~
, . . . . . . . . . .
Le A 20 670 1196~ ~8 emulsifier, and the conc~ntrate was diluted. with water to the desired concentration~
Cabbage plants (Br2ssica oleracea) were treated by being sprayed with the preparation of active compound of the desired concentration, After the spray coating had dried on, a leaf was removed from the treated plant and was placed in a plastic container and infested with caterpillars of the diamond-back moth (Plutella maculipennis). After 2 and 4 days, in each case one further leaf from the same plant was used as subsequent feed.
After the desired period o~ time, the destruction in ~ was determined. 100% meant that all the animals had been killed; 0% meant that none of the animals had been killed.
. In this test, in an experiment carried out for example with an active compound concentration of 0.01%, the following compounds, for example, exhibited a degree of destruction of lO0~ a~ter 14 days: ccmpounds (l), (2), (3), (4), (17)~ (18)~ (27)~ (2~), (30), (33), (34), (35), (36), (39), (40), (42), (51), (56), (57), (58), (70) and (72).
The preparation of the compounds according to the invention is illustrated with the aid of the following preparative E~amples (all the ~ data relate to percent-ages by weight and all the temperature data are in C).
Example l N- ~4-(4'-Methyl-benzyloxy)-~trichloromekhyl-benzyl~
furfurylamine CH3~ ~ 2 ~ -CH-NH-C~2~0 3 a) Trichloroacetic acid was distilled into a weighed , flask using an oil.pump and in.the abse.nce.,of,~ois.ture, .... . . .
Le A 20- 670 and dry toluene was then added. in an amount such that 1 g of solution contained o.6 g of trichloroacetic acid.
b) 114 g (0.42 mole) of the trichloroacetic acid solution prepared under a) were added dropwise to 91.5 g (0.3 mole) of ~4-(4'~methyl-benzyloxy)-benzylidene~-fur-furylamine in 300 ml of dry toluene at 100C in a manner such that the evolution of C02 did not become too vigorous. The mixture was then stirred for a further 2 hours at 100C, cooledg washed with water~ dried and evaporated and the crude product was recrystallised from petroleum ether.
Yield: 86 ~ = 68% of theory Melting point: 80C
Example 2 ~4~(4'-Methyl-benzyloxy)-~-trichloromethyl-benzyl~-n-butylamine _E3- ~ C~l2 ~ CC 3 a) [4-(4'-Methyl-benzyloxy)-benzylidene]-n-butylamine 3 ~ C 2 ~ -CH=N-C~Hg-n 2 moles of 4-methyl-benzyloxy-benzaldehyde and 2.6 moles of n-butylamine in 1 litre of toluene were heated under reflux with 0.5 g of p-toluenesulphonic acid, using a water separator, until no further water was separated off. The toluene was then evaporated off in vacuo and the crude product was distilled in vacuo.
Boiling point o 1 H 215-220C; melting point: 43C
Yield. 505 g ~ 90% o$ theory b) 1 mole. of the .Sch1ff's base obtained under a)g Le A 20 670 6'~
immediately above, was reacted with 2 moles of trichloro-acetic acid in dry toluene in a manner analogous to that in Example lb). 366 g of [4-(4'-methyl-benzyloxy)-~trichloromethyl-benzylJ-n-butylamine = 91% of theory were obtained as a yellow oil of nD 1.5619 Example 3 ~4-(4'-Methyl-benzyloxy)-~-trichloromethyl-benzyl~-ethylamine 3 ~ 2 ~ -CE- H-C2H5 a) [4-(4'-Methyl-benæyloxy)-benzylidene~-ethylamine CH3 ~ CX2 ~ -C~=N-C2H~
70 g of anhydrous Na2S04 were added to 120 ml of a 50% strength solution of ethylamine in water and 600 ml of toluene, the mixture was stirred for 30 minutes and filtered, the solution was added to a mixture of 113 g (0.5 mole) of 4-methyl-benzyloxy-benzaldehyde and 60 g of anhydrous Na2S0~, the mixture was stirred for 10 hours at room temperature and filtered, the filtrate was evaporated and the residue was distilled in vacuo g P 0.15 mm Hg: 195 G; melting point: 67C
Yield: 105 g - 90% of theory b) 145 g of trichloroacetic acid in 250 ml of dry toluene were rapidly added dropwise to 93.6 g (0.4 mole) of the Schiff's base from a), immediately above, in 400 ml of dry toluene at 100C, the mixture was stirred at 100C
for 4 hours, cooled, washed with water, dried and evapor-ated and the residue was recrystallised from petroleum ether.
Melting point: 103 to 104C
30 . Yie.ld:- 128 g = .8~. of..t.heory of ~4-.(4-'.-methyl-ben.zyloxy)~
Le A 2G 670 6 ~1~
a-trichloromethyl-benzyl]-ethylamine Example 4 Salt of trichloroacetic acid and [4-(4'-mlethyl-benzyloxy--trichloromethyl-benzy ~ -ethylamine A solution of l mole of trichloroacetic acid in toluene was added to a solution of 1 mole of [4-(4'-methyl-benzyloxy)-a-trichloromethyl benzyl~-ethylamine in toluene and the toluene was evaporated off in vacuo.
Yield: 525 g = 98% of theory Melting point: 126C
~ he following compounds of Table 1 could be pre-pared in an analogous manner:
Le- A 20 670 o ,_ .
c~
o _, a, S~ 4~r ~ o o ~0 ~
C) ~rl ~d' ,~ q~ o ~ r~ L~
~ 4 ~ , ~
Lt~
~
U V ~ -- O V
o ,i ' ~) L~ ' ' X ~ X X ~ X
!
o ~_ X O
,~
Le- A 20 670 Table l ~continuation) - - Melting point ( C ) Example R4 R5 . . . Rl R2 R3 refractive index ~) ~ .
o 13 H 4-Cl E~ H C3H7i 14 ~ 4 -Cl H H -C4 Hgn 16 H 4-Cl H H -C6EI13n 1 o5641 17 H 4-Cl H H -CH2~ --C2H5 1 "5543 C4Hgn , 18 H 4-Cl H H -CH21~ 135958 19 E~ 4-Cl E~ H -CH
30 3-C1 4-Cl H H -C4Hgn 21 3-Cl 4-Cl H H C12 25 1 ~5480 22 3-Cl 4-C1 H H C14 29 1 ~5408 23 3 C1 4-C1 H H {~3 165717 -~ Table l (continuation~ . Melting point (C) O Example R4 R5 -- ~l . R2 R3 - refractive index ~,20 24 3~~1 4-C1 3-Br 5-Br C4Hgs 1~587 25 H 4-C~3 H H CH3 26 H 4-CH3 H ~. -C3H7n 27 H 4-CH3 H H -C`H i 106 28 H 4-CH3 H H -CH2-CH=CH2 51 29 H 4-CH3 H H -CH -C=CH
3G H 4-CH3 H H -C~Hgi 65-66 31 H 4-CH3 H H c4 9 33 H 4-CH3 H H -C6H13n 1,5541 Tab le 1 ( c ont inuat i on ) Melting point ( C ) Example 4 R5 Rl ~2 ........ R3 refractive index (n20) 35 H 4-CH3 H H-CH2-CH-C2H5 1 ~5528 C4 Hgn 36 H 4-C~3 H H-C12H~5n 38 37 ~ ~-CH3 ~ HC14~29 52 38 H 4-CH3 H H-C16~33n 56 r~ C~
40 H 4-CH3 H H ~ 68 - 70 41 H 4-C~3 H H ~ 41 - 44 42 H 4 - CH3 H H-CH2~ 3OC2H5 1 ~5561 43 H 4 -CH3 H H-CH2~
~ab le 1 ~ Cont inuat i on ) Melting point (C) ~ Examp le , or O . No..... .... R4 ..... R5. Rl R2 R3 refractive index ~20) 44 H 3-CH3 H H-C4Hgs 1~o5583
~4-(4'-chloro-benzyloxy)-a-trichloromethyl-benzyl]-fur-~urylamine9 ~4-(4~-chloro-benzyloxy)-a-trichloromethyl-benzyl~-thienyl~methylamine, ~4-(4'-methylbenzyloxy)-a-trichloromethyl-benzyl]-methylamine, [4-(4'-methyl-Le A 2G 670 benzyloxy)-a-trichloromethyl-benz~Jl~-ethylamine, ~4-(4'-methyl-benzyloxy)-a-trichloromethyl-benzyl~ -n-propylamine, ~4-(4' methyl-benzyloxy)--trlchloromethyl-benzyl~
propylamine, ~4~ methyl-benzyloxy)-a-trichloromethyl-benzyl]-allylamine, [4-(4'-methyl-benzyloxy)-~-trichloro-methyl-benzyl~-propargylamine, [4-(4'-methyl-benzyloxy)-a-trichloromethyl-benzyl~-n-butylamine~ ~4-(4'-methyl-benzyloxy)--trichloromethyl-benzyl~-i-butylamine, [4-(4'-methyl-lDenzyloxy)-~-trichloromethyl-benzyl¦-sec.-butyl-10 amine, l4-(4'-methyl7benzyloxy)-a-trichloromethyl-benzyl~-tert.-butylamine, r4-(4l-methyl-benzyloxy)~a-trichloro-methyl-benzyl~-n-hexylamine~ ~4-(4'-methyl-benzyloxy)-~-trichloromethyl-benzyl~-2-ethyl-hexylamine, L4_(4 t -methyl-benzyloxy)-~-trichloromethyl-benzyl~-n-dodecylamine, ~4-(4'~methyl-benzyloxy)-~-trichloromethyl-benzyl]-cyclohexyl-amine, [4-(4t-methyl-benzyloxy)-a-trichloromethyl-benzyl~-fur~urylamine, ~4-(4~-methyl-benzyloxy)-a-trichloro-methyl-benzyl~-thienylmethylamine, l-L4-(4 t -methyl-benzyloxy)-~-~richloromethyl-benzyl]-3-ethoxy-propyl-2 0 amine, ~4-(4i-methoxy-benzyloxy)~a-trichloromethYl~
benzyl~-methylamine, [4-(4'-methoxy-benzyloxy)--tri-chloromethyl-benzyl~-ethylamine, ~4-(4'-methoxy-benzyl-oxy)-~-trichloromethyl-benzyl~-i-propylamine, [4-(4'-methoxy-benzyloxy)-~-trichloromethyl-benzyl~-n-butyl-amine, [4-(4'-methoxy-benzyloxy)-~-trichloromethyl-benzyl~ butylamine, ~ 4- ( 4'-methoxy-benzyloxy)-a-tri-chloromethyl-benzyl~-sec.-butylamine, L4-( L~ I -methoxy-benzyloxy)-~-trichloromethyl-benzyl~-n-hexylamine, [Li_ ( 4 I -methoxy-benzyloxy)-~-trichloromethyl-benzyl]-~ur-~urylamine, [4-(4'-methoxy-benzyloxy)-~-trichloromethyl-benzyl]-thienylmethylamine, 1-[4-(4'-methoxy-benæyloxy)-a-trichloromethyl-benzyl~-3-ethoxy-propylamine, L4-(4'~
methyl-benzyloxy)-3-methoxy-a-trichloromethyl-benzyl~
n-butylamine, ~4-(4'-methyl-benzyloxy)-3-methoxy-a-tri-chloromethyl-benzy.l~-i-butylamine, ~4-(4'-methyl-benzyl-Le A 20 670 6~
g oxy)-3-~ethoxy a-trichloromethyl-benzyl]-furfurylamine~
~4-( 4 ~ -methyl-benzyloxy)-3-methoxy-a-trichloromethyl-benzyl~-thi~nylmethylamine~ L4- ( 4 -methoxy-benzyloxy)-3-methoxy-a-trichloromethyl-benzyl~-n-butylamine, ~4-(4'-methoxy-benzyloxy)-3-methoxy-~trichloromethyl-benzyl] -furfurylamine, [4-(4 t -me~hoxy-benzyloxy)-3-methoxy ~-trichloromethyl~benzyl~-thienylmethylamine~ L4 ( 4 fluoro-benzyloxy)-a-trichloromethyl~benzyl~-n-butyl-amine, ~-(4'-fluoro-benzyloxy)-~-trichloromethyl-benzyl~-furfurylamine~ ~4- ( 4 -trifluoromethyl-benzyl-oxy)-a-trichloromethyl-benzyl~ utylami.ne, [4-(4~-tri-fluoromethyl-benzyloxy)-a~trichloromethyl-benzyl¦-n-hexylamine, [4-(4'-trifluoromethyl-benzyloxy)--tri-chloromethyl-benzyl~-furfurylamine~ L4- (3'-trifluoro-methy1-4~-chloro-benzyloxy)-a-trichloromethyl-benzyl~-i-butylamine, [4- ~ 4~-tri~luoromethoxy-benzyloxy)-a-tri chloromethyl-benzyl]-i-propylamine, 14-~4 t -trifluoro-methoxy-benzyloxy)-~-trichloromethyl-benzyl]-n-butyl-amine, ~4-(4'-trifluoromethoxy-benzyloxy)-a-trichloro-methyl-benzyl~-i-butylarnine, [4-(4'-trifluoromethoxy-benzyloxy)-a-trichloromethyl-benzyl]-n-hexylamine~ [4-(4'-trifluoromethoxy-benzyloxy)-a-trichloromethyl-benzyl]-fu.rfurylamine, [4-(4'-trifluoromethoxy~benzyl-oxy)-~-trichloromethyl-benzyll-thienylmethylamine~ r4-25 ( L~ r~luorothiome~hyl -benzyloxy)-a-trichlo.roMeth~l-benzyl~ n-butylamine and [4-(4'-trifluorothiomethyl benzyloxy)-a-trichloromethyl-benzyl]-furfurylamine and chlorides and trichloroacetates thereof.
If l-~4-(4'-methyl-benzyloxy-)-benzylidene~-3-3 ethoxy-propylamine and trichloroacetic acid are used as starting substances~ the course of the reaction for the preparation of the new active compounds according to the invention can be illustrated by the ~ollowing equation:
Le A`20 670 CH3 ~ CH2 ~ CH=N-(cH2)3oc2Hs ~ CC13C2 3 ~ 2 ~ -cH~NH-(cH2)3 C2~5 2 CCl Most of the Schiff's bases of the gener21 formula (II) required for the preparation of the ~-trichloromethyl-amines of the general formula (I) are known (see German Offenlegungsschrifk (C;erman Published Specification) 2,631,948), or they can be prepared by known processes (see Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry)3 Volume VII/l year 19549 pages 454 to 458 and ~olume XI/2 year 1958, pages 74 to 85, Thieme Verlag, Stuttgart)-Possible solvents for the process according tothe învention are any of the inert organic solvents, for example optionally halogenated aliphatic or aromatic hydrocarbons (such as cyclohexane, benzene, toluene, xylene~ chlorobenzene and carbon tetrachloride). The process according to the invention can also be carried out without a solvent, but the yields in this case are usually poorer. Toluene or xylene is preferably used as the solvent.
It is expedient to bring the starting substances together at a temperature from 80 to 130C, preferably a~
90 to 110C, and also to carry out the reaction at these temperatures.
The reaction is in general carried out under normal pressure.
In carrying out the process according to the invention, 1 to 3 moles~ in particular 1 to 2 moles~ of trichloroacetic acid are preferabl~ empl~oyed per mole of Le A 20 670 6~
Schiff's base of formula (II).
~he course of the process according to the inven~ion can be followed in a simple manner by means of the evolution of C02.
The reaction mixture is wor~ed up by generally known methods. It is expedient to distil off the solvent and, if desired~ to recrystallise the resu].ting product, ~or example from petroleum ether.
The salts can be obtained by the generally cus-tomary salt formation methods from the compounds of the formula (I) and corresponding inorganic acids, such as hydrogen halide acids (HC1, HBr or HI) or nitric acid or corresponding organic acids, such as oxalic acid and tri-halogenoacetic acids (CX3COO~; in which X - F, C1 or Br).
The new compounds of the present invention have a low toxicity to warm-blooded animals and, surprisingly, have a very good action against Arthropoda, in par~icular insects, and also have a good action as egg sterilisers.
In the followlng text, by "active compounds" according to the invention there are understood in each case the compounds of the formula I and thelr salts.
The active compounds are well tolerated by plants, have a favourable level of toxiciky ~o warm-blooded animals, and are suitable for combating arthropod pests, especially insects and arachnida, and nematodes, whlch are encountered in agriculture, in forestry, in the protection o~ stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of 3 development. The abovementioned pests include:
from the class of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber;
from the class of the Diplopoda, for example Blaniulus guttulatus;
from the class of the Chilopoda, for example Geophilus Le A 20 670 carpophagus and Scutigera spec.;
from the class of ~he Symphyla, for example Scuti-gerella immaculata;
from the order of the Thysanura, for example Lepisma saccharina;
from the order of the Collembola, for example Onychiurus armatus;
from the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllo-talpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria;
from the order o~ the Dermaptera, for example ~or~icula auricularia;
~rom the order of the Isoptera, for example Reticulitermes spp.;
~rom the order of the Anoplura, for example Phylloxera vastatrix9 Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Lino~nathus spp.;
from the order of the Mallophaga, ~or example Trichodectes spp. and Damalinea spp.;
from the order of the Thysanoptera, for example Hercinothrips ~emoralis and Thrips tabaci;
~rom the order of the Heteroptera~ for example Eurygaster~spp., Dysdercus intermedius, Piesma quadrata,Cimex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera~ ~or example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brasslcae, Cryptomyzus ribis~ Doralis fabae, Doralis pomi, Eriosoma lani~erum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humu~i, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, ~aodelphax striatellus, Nilaparvata lugens,. Aonidiella aurantii~..Aspidiotus heder.ae~
Le A 20 670 6~8 Pseudococcus spp. and Psylla spp.;
from the order o~ the Lepidoptera, for example Pectinophora gossypiellag Bupalus piniarius, Cheimatobia brumata~ Lithocalletis blancardella, Hyponomeuta padella~
Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua~
Mamestra brassicae, Panolis flammea, Prodenia liturag Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambi~uella, Homona magn~n; m~ and Tortrix viridana;
from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrllpes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp~, Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus~ Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Atta~enus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, A~riotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica;
from the order of the Hymenopte.ra, ~or example 3~ Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.;
from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogasterS
Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., C'uter.ebra spp.~ Gast.rophilus Le A 20 6700 ~ 14 -spp., Hyppobosca spp.~ Stomoxys spp., Oestrus spp., Hypoder~a spp., Tabanus spp., Tannia spp., Bibio hortulanusg ~scinella fri~, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa;
from the order of the Siphonaptera3 for example Xenopsylla cheopis and Ceratophyllus spp., from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans, from the order of the Acarina, for example Acarus siro, Argas spp., ~rnithodoros spp., Dermanyssus gallinae, ~riophyes ribis, Phyllocoptruta oleivorag Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and ~etranychus spp..
T~e active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams~ pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations u ed with burning equipment, such as fumigating cartridges~
fumigating cans, fumigating coils and the like, as well as ULV cold mist ax-ld warm mist formulations.
These formulations may be produced in know~ manner, for example by mi~ing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use o.~ surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers~ especially solven~s, there are suitable in the main, aromatic hydrocarbons, such as. xy.len.e,..'olue.n.e. or alkyl naphthale.nes,. chlorinat.ed .
Le A 20 670 aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone~
methyl isobutyl ketone or cyclohe~anone, or strongly polar solven~s, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatureand under normal pressure, for example aerosol propellants~
such as halogenated hydrocarbons as well as butane~
propane, nitrogen and carbon dioxide.
15 As s.olid carriers there may be used ground natural minerals, such as kaolins, clays3 talc, chalk, quartz, aktapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicatesO As solid carriers for granules there may be used crushed and`fractionated natural roc~s such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells~ maize cobs and tobacco stalks.
As emul.sifying and/or foam-forming agents there may be used non ionic and anionic emulsil~iers, such as polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol 3 ethers, alkyl sulphonatesg alkyl sulphates, aryl sulphon-ates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthet.i.c polymers in.the form of powd.ers, ~ . . . .
granules or latices, such as gum arabic, polyvinyl alcohol Le A 20 670 i6~
and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide~ titanium oxide and Prussian Blue, and organic dyestuf~s, such as alizarin dyes~uffs, azo dyestuffs or metal phthalocyanine dyestuffs~
and trace nutrients, such as salts of iron~ manganese, boron, copper~ cobalt, molybdenum and zinc.
~ he formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weightO
The active compounds according to the invention can be present in their commercially available formula-tions and in the use forms~ prepared from these formula-tions, as a mixture with other active compoundsg such as insecticides, baits, sterilising agents, acaricides, nematicides, fungicides, growth-regulating substances or herbicidesO The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons~ phenylureas and ~ substances produced by micro-organisms.
The active compounds according to the lnvention can f~rthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents.
Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can 3 vary within wide limits. The active compound concen-tration of the use forms can be from 0.0000001 to 100% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate far the use forms.
Le A 20 67~
When used against pests harmful to health ancl pests of stored products~ the active compounds are distinguished by an e~cellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
The present invention also provides a pesticidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
~ he present invention also provides a method of combating pests (in particular arthropodsg especially insects or acarids~ or nematodes) which comprises applying to the pests, or to a habitat thereo~, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of freeing or protecting domesticated animals from parasites which comprises applying to said animals a compound according to the present invention, in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by pests by being ~rown in a~eas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The present invention f~rther provides domestic-ated animals whenever freed or protected from parasites by the application to said animals of a compound according to the present invention~ in admi~ture T~ith a diluent or carrier.
i:
Le A 20 670 The activity of the compounds of this invention is illustrated by the followin~ biotest Examples~
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example.
Example A
Aedes test Solvent: 3 parts ~y weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent and the stated amount o~ emulsifier, and the concentrate was diluted with water to the desired concentrationS-. The aqueous preparations of active compound werefilled into glass vessels and about 20 mosquito larvae (Aedes aeg~pti) were then placed in each glass vessel.
After the desired period of time, the destruction in % was determined. 100% meant that all the animals had been ~illed; 0% meant that none of the animals had been killed.
In this test, in an experiment carried out for example with an active compound concentration of 0.0001 the following compounds, for example, exhibited a degree of destruction of 100% after 14 days: compounds (18), (28), (30), (34), (35), (36), (40), (42), (57), (58) and (72).
E~ample B
Plutella test 3 Solvent: 3 parts by weight of ace~one ~mulsifi~r: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound was mixed with the st.a.ted amount jof solven.t and the stat.e-d. amount. o~
, . . . . . . . . . .
Le A 20 670 1196~ ~8 emulsifier, and the conc~ntrate was diluted. with water to the desired concentration~
Cabbage plants (Br2ssica oleracea) were treated by being sprayed with the preparation of active compound of the desired concentration, After the spray coating had dried on, a leaf was removed from the treated plant and was placed in a plastic container and infested with caterpillars of the diamond-back moth (Plutella maculipennis). After 2 and 4 days, in each case one further leaf from the same plant was used as subsequent feed.
After the desired period o~ time, the destruction in ~ was determined. 100% meant that all the animals had been killed; 0% meant that none of the animals had been killed.
. In this test, in an experiment carried out for example with an active compound concentration of 0.01%, the following compounds, for example, exhibited a degree of destruction of lO0~ a~ter 14 days: ccmpounds (l), (2), (3), (4), (17)~ (18)~ (27)~ (2~), (30), (33), (34), (35), (36), (39), (40), (42), (51), (56), (57), (58), (70) and (72).
The preparation of the compounds according to the invention is illustrated with the aid of the following preparative E~amples (all the ~ data relate to percent-ages by weight and all the temperature data are in C).
Example l N- ~4-(4'-Methyl-benzyloxy)-~trichloromekhyl-benzyl~
furfurylamine CH3~ ~ 2 ~ -CH-NH-C~2~0 3 a) Trichloroacetic acid was distilled into a weighed , flask using an oil.pump and in.the abse.nce.,of,~ois.ture, .... . . .
Le A 20- 670 and dry toluene was then added. in an amount such that 1 g of solution contained o.6 g of trichloroacetic acid.
b) 114 g (0.42 mole) of the trichloroacetic acid solution prepared under a) were added dropwise to 91.5 g (0.3 mole) of ~4-(4'~methyl-benzyloxy)-benzylidene~-fur-furylamine in 300 ml of dry toluene at 100C in a manner such that the evolution of C02 did not become too vigorous. The mixture was then stirred for a further 2 hours at 100C, cooledg washed with water~ dried and evaporated and the crude product was recrystallised from petroleum ether.
Yield: 86 ~ = 68% of theory Melting point: 80C
Example 2 ~4~(4'-Methyl-benzyloxy)-~-trichloromethyl-benzyl~-n-butylamine _E3- ~ C~l2 ~ CC 3 a) [4-(4'-Methyl-benzyloxy)-benzylidene]-n-butylamine 3 ~ C 2 ~ -CH=N-C~Hg-n 2 moles of 4-methyl-benzyloxy-benzaldehyde and 2.6 moles of n-butylamine in 1 litre of toluene were heated under reflux with 0.5 g of p-toluenesulphonic acid, using a water separator, until no further water was separated off. The toluene was then evaporated off in vacuo and the crude product was distilled in vacuo.
Boiling point o 1 H 215-220C; melting point: 43C
Yield. 505 g ~ 90% o$ theory b) 1 mole. of the .Sch1ff's base obtained under a)g Le A 20 670 6'~
immediately above, was reacted with 2 moles of trichloro-acetic acid in dry toluene in a manner analogous to that in Example lb). 366 g of [4-(4'-methyl-benzyloxy)-~trichloromethyl-benzylJ-n-butylamine = 91% of theory were obtained as a yellow oil of nD 1.5619 Example 3 ~4-(4'-Methyl-benzyloxy)-~-trichloromethyl-benzyl~-ethylamine 3 ~ 2 ~ -CE- H-C2H5 a) [4-(4'-Methyl-benæyloxy)-benzylidene~-ethylamine CH3 ~ CX2 ~ -C~=N-C2H~
70 g of anhydrous Na2S04 were added to 120 ml of a 50% strength solution of ethylamine in water and 600 ml of toluene, the mixture was stirred for 30 minutes and filtered, the solution was added to a mixture of 113 g (0.5 mole) of 4-methyl-benzyloxy-benzaldehyde and 60 g of anhydrous Na2S0~, the mixture was stirred for 10 hours at room temperature and filtered, the filtrate was evaporated and the residue was distilled in vacuo g P 0.15 mm Hg: 195 G; melting point: 67C
Yield: 105 g - 90% of theory b) 145 g of trichloroacetic acid in 250 ml of dry toluene were rapidly added dropwise to 93.6 g (0.4 mole) of the Schiff's base from a), immediately above, in 400 ml of dry toluene at 100C, the mixture was stirred at 100C
for 4 hours, cooled, washed with water, dried and evapor-ated and the residue was recrystallised from petroleum ether.
Melting point: 103 to 104C
30 . Yie.ld:- 128 g = .8~. of..t.heory of ~4-.(4-'.-methyl-ben.zyloxy)~
Le A 2G 670 6 ~1~
a-trichloromethyl-benzyl]-ethylamine Example 4 Salt of trichloroacetic acid and [4-(4'-mlethyl-benzyloxy--trichloromethyl-benzy ~ -ethylamine A solution of l mole of trichloroacetic acid in toluene was added to a solution of 1 mole of [4-(4'-methyl-benzyloxy)-a-trichloromethyl benzyl~-ethylamine in toluene and the toluene was evaporated off in vacuo.
Yield: 525 g = 98% of theory Melting point: 126C
~ he following compounds of Table 1 could be pre-pared in an analogous manner:
Le- A 20 670 o ,_ .
c~
o _, a, S~ 4~r ~ o o ~0 ~
C) ~rl ~d' ,~ q~ o ~ r~ L~
~ 4 ~ , ~
Lt~
~
U V ~ -- O V
o ,i ' ~) L~ ' ' X ~ X X ~ X
!
o ~_ X O
,~
Le- A 20 670 Table l ~continuation) - - Melting point ( C ) Example R4 R5 . . . Rl R2 R3 refractive index ~) ~ .
o 13 H 4-Cl E~ H C3H7i 14 ~ 4 -Cl H H -C4 Hgn 16 H 4-Cl H H -C6EI13n 1 o5641 17 H 4-Cl H H -CH2~ --C2H5 1 "5543 C4Hgn , 18 H 4-Cl H H -CH21~ 135958 19 E~ 4-Cl E~ H -CH
30 3-C1 4-Cl H H -C4Hgn 21 3-Cl 4-Cl H H C12 25 1 ~5480 22 3-Cl 4-C1 H H C14 29 1 ~5408 23 3 C1 4-C1 H H {~3 165717 -~ Table l (continuation~ . Melting point (C) O Example R4 R5 -- ~l . R2 R3 - refractive index ~,20 24 3~~1 4-C1 3-Br 5-Br C4Hgs 1~587 25 H 4-C~3 H H CH3 26 H 4-CH3 H ~. -C3H7n 27 H 4-CH3 H H -C`H i 106 28 H 4-CH3 H H -CH2-CH=CH2 51 29 H 4-CH3 H H -CH -C=CH
3G H 4-CH3 H H -C~Hgi 65-66 31 H 4-CH3 H H c4 9 33 H 4-CH3 H H -C6H13n 1,5541 Tab le 1 ( c ont inuat i on ) Melting point ( C ) Example 4 R5 Rl ~2 ........ R3 refractive index (n20) 35 H 4-CH3 H H-CH2-CH-C2H5 1 ~5528 C4 Hgn 36 H 4-C~3 H H-C12H~5n 38 37 ~ ~-CH3 ~ HC14~29 52 38 H 4-CH3 H H-C16~33n 56 r~ C~
40 H 4-CH3 H H ~ 68 - 70 41 H 4-C~3 H H ~ 41 - 44 42 H 4 - CH3 H H-CH2~ 3OC2H5 1 ~5561 43 H 4 -CH3 H H-CH2~
~ab le 1 ~ Cont inuat i on ) Melting point (C) ~ Examp le , or O . No..... .... R4 ..... R5. Rl R2 R3 refractive index ~20) 44 H 3-CH3 H H-C4Hgs 1~o5583
4 5 E~ 3 -CH H H4 9 46 H 3-CH3 H H-C6H13n 125516 47 H 3-CH3 H H~ ~CH2) 30C2H5 1 ,~5461 4 8 H 4 -CH3 H 3 -OCH3 3 " ~
4 9 H 4 -CH3 H 3 -OCH3 C2H5 ~ ~) 5Q H 4-C~3 __ 3 -C4Hgs 54-57 0 51 H 4{~3 H 3~3 -CH;~ 5842 52 H 4~3 H H ~H3 1, 53 H 4 ~CH3 H H ~2H5 54 H 4~)CH3 H H c3H7n H 4~CH3 H H -C4Hgi (D Table 1 ~Continuation) :D
o o~
O Melting point (C ) Example . 2 or 20 No. . R4:R5. - . R~ . R .... . R3.......... r.e~r.ac.tive index ~nD ) 56 ~4 OCH3 EI H ~6H1 3n 1 ,5559 57 H4~CH3 H H (CH2) 3 2 5 1,5582 ! ~9 sa H4~3 H H H2¢ 3 78-84 59 H4 OCH3 H H ~H2 s H4{)CH3 3{)CH3 {~4H9i 61 H 3 H 3 CCH3 ~H2~ 1, 53 62 ~ 4 GC4 9 H H ~4Hgi 1"5505 Q
63 H 4 CF3 H H ~4Hgn Table 1 ~Continuation) . Melting point ~C) O Example ~ R5 Rl ~2 R3 or 20 65 H 4-SCF3 H H -C4Hgi N
C~3 67 H 4-F ~ H -C4Hgn 68 H 4~X~3 H H ~C4H9n 69 H 4-O~F3 H H ~C4Hgi 70 H 4-OCF3 H H -C4H~s 1,5242 ~ Table l ( Continuation .o Melting point ~C) o ExamPle ~ 5 Rl R2 R3 refractive index ~nD ) H H 6 13 1 s 5203 72 H 4 OCF3 ~2~3 1,, 5432 73 ~ 4~F3 H H -CH2--S
74 H 4-No2 H H ~4Hgn 75 H 4-No2 H E~ ~6H13 76 H 4-~2 H H - (CH2 ) 3O~2H5 62 78 H ~1--CH HH HH -CH2CH2 CF3 6 6 - 6 8
4 9 H 4 -CH3 H 3 -OCH3 C2H5 ~ ~) 5Q H 4-C~3 __ 3 -C4Hgs 54-57 0 51 H 4{~3 H 3~3 -CH;~ 5842 52 H 4~3 H H ~H3 1, 53 H 4 ~CH3 H H ~2H5 54 H 4~)CH3 H H c3H7n H 4~CH3 H H -C4Hgi (D Table 1 ~Continuation) :D
o o~
O Melting point (C ) Example . 2 or 20 No. . R4:R5. - . R~ . R .... . R3.......... r.e~r.ac.tive index ~nD ) 56 ~4 OCH3 EI H ~6H1 3n 1 ,5559 57 H4~CH3 H H (CH2) 3 2 5 1,5582 ! ~9 sa H4~3 H H H2¢ 3 78-84 59 H4 OCH3 H H ~H2 s H4{)CH3 3{)CH3 {~4H9i 61 H 3 H 3 CCH3 ~H2~ 1, 53 62 ~ 4 GC4 9 H H ~4Hgi 1"5505 Q
63 H 4 CF3 H H ~4Hgn Table 1 ~Continuation) . Melting point ~C) O Example ~ R5 Rl ~2 R3 or 20 65 H 4-SCF3 H H -C4Hgi N
C~3 67 H 4-F ~ H -C4Hgn 68 H 4~X~3 H H ~C4H9n 69 H 4-O~F3 H H ~C4Hgi 70 H 4-OCF3 H H -C4H~s 1,5242 ~ Table l ( Continuation .o Melting point ~C) o ExamPle ~ 5 Rl R2 R3 refractive index ~nD ) H H 6 13 1 s 5203 72 H 4 OCF3 ~2~3 1,, 5432 73 ~ 4~F3 H H -CH2--S
74 H 4-No2 H H ~4Hgn 75 H 4-No2 H E~ ~6H13 76 H 4-~2 H H - (CH2 ) 3O~2H5 62 78 H ~1--CH HH HH -CH2CH2 CF3 6 6 - 6 8
Claims (12)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
A 4-benzyloxy-,?-trichloromethyl-benzylamine of the formula in which R is a phenyl radical of the formula R1 and R2 each independently is a hydrogen or halogen atom, or an alkyl or alkoxy radical optionally substituted by 1 or more halogen atoms;
R3 is an alkyl, cycloalkyl, alkylcycloalkyl, alkenyl or alkinyl radical optionally substituted by 1 or more halogen atoms, alkyl, alkoxy, alkylthio radical or hetero cyclo alkyl radical containing 1 to 3 different hetero atoms substituted by an alkyl radical or halogen atom, or a salt thereof;
R4 and R5 each independently is a hydrogen or halogen atom, or a nitro or cyano radical, or an alkyl, alkoxy or alkylthio radical optionally substituted by 1 or more halogen atoms. - 2. A compound as claimed in claim 1 wherein R4 and R5 are independently alkyl, alkoxy or alkylthio radicals containing 1 to 8 carbon atoms optionally substituted by 1 to 5 identical or different fluorine, chlorine, bromine or iodine atoms R1 and R2 are hydrogen atoms;
R3 is a cycloalkyl radical with 3 to 7 carbon atoms optionally substituted by alkyl with 1 to 4 carbon atoms, or an alkyl, alkenyl or alkinyl radical optionally substituted by 1 to 3 fluorine, chlorine, bromine or iodine atoms or hydroxyl, cyano, alkoxy, alkylthio radicals or a heterocyclic ring;
or a salt thereof. - 3. A compound as claimed in claim 1 wherein R4 and R5 are fluorine or chlorine atoms or alkyl, alkoxy or alkylthio radicals with 1 to 4 carbons in the alkyl part option-ally substituted by 1 to 3 fluorine or chlorine atoms;
R2 is a C1-5 alkoxy radical;
R3 is an alkyl radical with 1 to 18 carbon atoms, or an alkyl radical with 1 to 4 carbon atoms optionally substituted by alkoxy with 1 to 5 carbon atoms, furyl or thienyl, or cycloalkyl or methylcycloalkyl radical or an alkenyl or alkinyl radical with 3 to 8 carbon atoms; and R1 and R have the same meaning as in claim 1;
or a salt thereof. - 4. [4-(4'-Methyl-benzyloxy)- ? -trichloromethyl-benzyl]-n-butylamine of the formula or a salt thereof.
- 5. [4-(4' Methyl-benzyloxy)- ?-trichloromethyl-benzyl]-ethylamine of the formula or a salt thereof.
- 6. [4-(4'-Methyl-benzyloxy)-? -trichloromethyl-benzyl]-isopropylamine of the formula or a salt thereof.
- 7. [4-(4'-Methyl-benzyloxy)-? -trichloromethyl-benzyl]-isobutylamine of the formula or a salt thereof.
- 8. [4-(4'-Methyl-benzyloxy)- ?-trichloromethyl-benzyl]-cyclohexylamine of the formula or a salt thereof.
- 9. [4-(4'-Methyl-benzyloxy)-?-trichloromethyl-benzyl]-(3-ethoxy-n-propylamine) of the formula or a salt thereof.
- 10. A method of combating pests which comprises applying to the pests, or to a habitat thereof, a pesticidally effective amount of a compound or salt according to claim 1.
- 11. A method according to claim 10 wherein the compound is applied in the form of a composition containing said compound as active ingredient, in admixture with a suitable diluent or carrier.
- 12. A method according to claim 10 or 11, wherein said compound is [4-(4'-methyl-benzyloxy)-?-trichloromethyl-benzyl]-n-butylamine, [4-(4'-methyl-benzyloxy)-?-trichloromethyl-benzyl]-ethylamine, [4-(4'-methyl-benzyloxy)-?-trichloromethyl-benzyl]-isopropylamine, [4-(4'-methyl-benzyloxy)-?-trichloromethyl-benzy] -isobutylamine, [4-(4'-methyl-benzyloxy)-?-trichloromethyl-benzyl]-cyclohexylamine, or [4'(4'-methyl-benzyloxy)-?-trichloromethyl-benzyl]-(3-ethoxy-n-propylamine), or a salt thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3040912.2 | 1980-10-30 | ||
| DE19803040912 DE3040912A1 (en) | 1980-10-30 | 1980-10-30 | 4-BENZYLOXY- (ALPHA) -TRICHLORMETHYL-BENZYLAMINE, A METHOD FOR THE PRODUCTION THEREOF, PEST CONTROLLERS CONTAINING IT, THEIR PRODUCTION AND USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196648A true CA1196648A (en) | 1985-11-12 |
Family
ID=6115569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000389045A Expired CA1196648A (en) | 1980-10-30 | 1981-10-29 | 4-BENZYLOXY-.alpha.-TRICHLOROMETHYL-BENZYLAMINES, A PROCESS FOR THEIR PREPARATION, PEST-COMBATING AGENTS CONTAINING THEM, AND THE PREPARATION AND USE OF THESE AGENTS |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0051196B1 (en) |
| JP (1) | JPS5799561A (en) |
| AT (1) | ATE5252T1 (en) |
| CA (1) | CA1196648A (en) |
| DE (2) | DE3040912A1 (en) |
| HU (1) | HU188151B (en) |
| IL (1) | IL64125A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ227042A (en) * | 1987-11-27 | 1991-05-28 | Banyu Pharma Co Ltd | Substituted alkylamine derivatives and pharmaceutical compositions |
| US5234946A (en) * | 1987-11-27 | 1993-08-10 | Banyu Pharmaceutical Co., Ltd. | Substituted alkylamine derivatives |
| EP3036222A2 (en) * | 2013-08-23 | 2016-06-29 | Virginia Commonwealth University | Ester nitrates derivatives of aromatic aldehydes with multiple pharmalogic properties to treat sickle cell disease |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941842A (en) * | 1972-12-26 | 1976-03-02 | The University Of Illinois Foundation | P,P'-Disubstituted α-trichloromethylbenzylanilines |
| DE2631948A1 (en) * | 1976-07-15 | 1978-01-19 | Bayer Ag | PEST CONTROL |
-
1980
- 1980-10-30 DE DE19803040912 patent/DE3040912A1/en not_active Withdrawn
-
1981
- 1981-10-19 EP EP81108487A patent/EP0051196B1/en not_active Expired
- 1981-10-19 AT AT81108487T patent/ATE5252T1/en not_active IP Right Cessation
- 1981-10-19 DE DE8181108487T patent/DE3161379D1/en not_active Expired
- 1981-10-26 JP JP56170243A patent/JPS5799561A/en active Pending
- 1981-10-27 IL IL64125A patent/IL64125A/en unknown
- 1981-10-29 CA CA000389045A patent/CA1196648A/en not_active Expired
- 1981-10-30 HU HU813193A patent/HU188151B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL64125A (en) | 1985-05-31 |
| JPS5799561A (en) | 1982-06-21 |
| EP0051196A1 (en) | 1982-05-12 |
| HU188151B (en) | 1986-03-28 |
| IL64125A0 (en) | 1982-01-31 |
| EP0051196B1 (en) | 1983-11-09 |
| DE3040912A1 (en) | 1982-06-09 |
| ATE5252T1 (en) | 1983-11-15 |
| DE3161379D1 (en) | 1983-12-15 |
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