CA1056385A - 1,3-diphenyl-2-trichloromethylimidazolidines - Google Patents
1,3-diphenyl-2-trichloromethylimidazolidinesInfo
- Publication number
- CA1056385A CA1056385A CA246,767A CA246767A CA1056385A CA 1056385 A CA1056385 A CA 1056385A CA 246767 A CA246767 A CA 246767A CA 1056385 A CA1056385 A CA 1056385A
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- Canada
- Prior art keywords
- formula
- compound
- acid addition
- compounds
- insects
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to novel substituted 1,3-diphenyl-2-trichloromethyl-imidazolidines and acid addition salts thereof as well as to processes for their production.
The compounds according to the invention show good insecticidal and acaricidal activity. Processes for the production of the novel compounds are described and examples of certain of the novel compounds are given.
Pesticidal compositions according to the present invention are described and exemplified.
The invention relates to novel substituted 1,3-diphenyl-2-trichloromethyl-imidazolidines and acid addition salts thereof as well as to processes for their production.
The compounds according to the invention show good insecticidal and acaricidal activity. Processes for the production of the novel compounds are described and examples of certain of the novel compounds are given.
Pesticidal compositions according to the present invention are described and exemplified.
Description
- ~OS638S
The present invention relates to substituted l~3-diphenyl-
The present invention relates to substituted l~3-diphenyl-
2-trichloromethyl-imidazolidines, in which the two phenyl moieties present are different, as well as to pesticidal compositions containing such compounds as act;ve ingredient. The compounds of the present invention show inter-esting insecticidal and acaricidal activity.
According to one feature of the present invention there are provided compounds of the formula:-Rz ~ CC13 R4R3[(wherein Rl, R2~ R3 and R4, which may be the same or different, each represents a hydrogen or halogen atom or a nitro or lower alkyl or alkoxy group, the said Rl,R2, R3 and R4 being in the
According to one feature of the present invention there are provided compounds of the formula:-Rz ~ CC13 R4R3[(wherein Rl, R2~ R3 and R4, which may be the same or different, each represents a hydrogen or halogen atom or a nitro or lower alkyl or alkoxy group, the said Rl,R2, R3 and R4 being in the
3-, 4- or 5- position) with the proviso that ring A and ring B
are different] and acid addition salts thereof.
It will be appreciated that ring A and ring ~ may differ by having different substituents in either the same or different substitutional positionsin each ring or by having the same substituents in each ring but in different substitional positions.
The compounds of formula I and the acid addition salts thereof show good activity against various pests. Thus, for ~-example, houseflies (Musca domestica) cockroaches (e.g. Phyllo~
droma germanica), spider mites ~e.g. Tetranychus urticae), aphids , :
:''' (e.g. Aphis fabae), caterpillars (e.g. of Plutella maculipennis) and bugs (e.g. Epilachna varivestis) may be exterminated by the use of even small doses of active ingredient.
Examples of compounds of the present invention include the following:
1-(4-chlorophenyl)-3~phenyl-2-trichloromethyl-imidazoiidine and 1-(3-chlorophenyl)-3-(4-methylphenyl)-2-trichloromethyl- ~ -imidazolidine, and the acid addition salts thereof.
The compounds of formula I may, for example, be produced by reacting a corresponding diaryl-substituted ethylene diamine of formula II with chloral according to known processes (e.g. H.~. Wanzlick and E. Schikora, Chem.
Ber 94, 2839 (1961)).
Thus according to a further feature of the present invention there is provided a process for the preparation of compounds of formula I as hereinbefore defined or an acid addition salt thereof which comprise9 reacting a compound of the formula--2 NH - CH2 - CH2 - NH ~ II
(wherein Rl, R2, R3 and R4 are as hereinbefore defined) with a compound of the formula:-' OHC - CCl III
whereby a compound of formula I is obtained and, if desired, subsequently converting the compound of formula I thus obtained into an acid addition salt thereof. The reaction is preferably effected in the presence of glacial acetic acidi or a mixture of glacial acetic acid and hydrochloric acid as solvent and advantageously at ambient tempeLature or at an elevated temperature e.g. a slightly elevated temperature. It is often advantageous to effect the reaction between the compound of formula II and the compound of formula III with simultaneous removal of water formed in the reaction from a solvent immiscible with water e.g. by azeotropic distillation. The substantially water immiscible solvents include, for example, benzene, toluene or xylene. The reaction ~ ;
may also, if desired~ be effected in the presence of a catalyst e.g. a reaction accelerator e.g. an acidic catalyst, such as ~-toluenesulfonic acid. This modified process results in a higher purity and in better yields, of the compounds of formula I even when a diamine, in which one of the phenyl moieties is unsubstituted or ~-substituted~ is used as the compound of formula II.
The starting compound of formula III may, for example, be obtained by reacting a compound of the formula:-~ - 4 ':
. , ' ': "
'~: . - ' Rl ~ ~H_cH~_cH2_x ~IV) (wherein Rl and R2 are as hereinbefore defined and X represents .an atom or group removable as an anion e.g. a chlorine or bromine atom) with an aniline of the formula:-2 ~ ~V~
(wherein R3 and R4 are as herein~e~ore defined) with theremoval of HX. The compounds of formula IV may, for example, be prepared according to various methods, for example by reactîng an anil~ine f the fonmula:-1 ~ . ', 2 (VI) , ~wherein Rl and R2 are as hereinbefore defined), with ethyleneoxide ~Houben-Weyl, Methoden der organischen Chemie, vol. XI/l, page 313 (1957)~ or with ethylene chlorohydrin or ethylene bromohydrin, whereby a compound of the formula : 1 ~ NH-cH2cH2-oH (VIII) 2 ~- :
: : . ~ 5 ~ ~:
.
-. , . , .. : .
~056385 (w~erein Rl and R2 are as hereinbefore defined) is obtained,after which the hydroxy group is replaced by group X according to conventional pr~cesses, preferably by chlorine or bromine. ~ -Moreover certain compounds of formula IV may, for example, be obtained from compounds of formula:
Rl ~ NH-CO-CH2-X (VII) (wherein Rl and R2 are as hereinbefore defined) by reduction with NaAlH2 (OCH2CH2-OCH3)2 (Tetrahedron Letters 1968, page 3303).
According to a still further feature of the present invention there are provided insecticidal and acaricidal compositions comprising as active ingredient at least one compound of formula I as hereinbefore defined or an acid addition salt thereof in association with an inert carrier or diluent~
For the control of insects the active ingredients are preferably used in the conventional manner together with diluentsJand carriers e.g. emulsifiable concentrates wettable powders, solutions, aerosols, dusting powders, granulates or colloidal dispersions.
, ,; . ' ' The preferred concentration of active ingredient for use in insecticidal and acaricidal composit~ ns according to the invention is from 0.02 to 5% by weight.
If required, the concentrates may be mixed with water, so that a spray preferably having a concentration of approximately 0.02 to 5% by weight of active ingredient is obtained.
The active ingredient content in concentrates of the present invention may, if desired, amount to 80% by weight.
Carriers and additives which may conveniently be used according to the present invention include for example solvents, diluents, stabilizers, dispersion agents, wetting agents and emulsifying agents. Moreover the insect-icidal and acaricidal compositions according to the present lnvention may, if desired, also contain urther known insecticidal or acaricidal agents.
T~e compositions of the present invention are, in general, specific in their activity against insects and acarids and as a result they may be used for specific plant protection. The compositions of the present invention , are substantially non-toxic to w~rm-blooded animals.
Moreover the active ingredients of the compositions of the present invention decompose with r;lease of chloroform . . .
- ; ..
and degrade rapidly to give non-toxic compounds which do not harm the environment.
According to a further feature of the present invention there is provided a method of preventing o_ inhibi~ing the growth or proliferation of insects and/or acarids which comprises applying to a site infested with or susceptible to infestation by insects and/or acarids an effective amount of a compound of formula I as hereinbefore described or . an acid addition salt thereof. -. The following non-limiting Examples illustrate the invention:-. ' , .
.
- 8 - :.
~ :
: .
- ....
l~S6~5 Formulatio_ Examples Example A
Wettable Powder 50 parts by weight of 1-(4-chlorophenyl)-3-phenyl-2-trichloromethyl-imidazolidine 8 " " " of sodium lignine sulfonate 2 " " " of sodium naphthalene sulfonate " " " of kaolin " " " of silicious chalk The components are mixed and milled in a stud mill.
The particle size of the product is approximately 2 to 6 ~.
The active ingredient content may be increased by decreasing the carriers and may amount to approximately 80 parts by weight.
For use, a spray of the desired concentration of active ingredient is made by mixing the above-identified composition with water; the concentration amounts, in general, to from approximately 0.02 to 5%.
Example B
, usting Powder 1.5 parts by weight of 1-(3-chlorophenyl)-3-(4-methylphenyl)_ ;. .. .
2-trichloromethyl-imidazolidine 98.0 parts by weight of talcum 0.5 " " " of aluminium stearate The active ingredient is milled in a stud mill and mixed ~ ~
~: -.
~':
` ;1~5638S
with the remaining components.
Example C
Colloid Formulation 20.0 parts by weight of 1~ chlorophenyl)-3-(4-methyl-phenyl)-2-trichloromethyl-imidazolidine 2.5 " " " of ethoxylated isotridecanol polyglycol ether (wetting agent, emulsifier) 2.5 ~ ethoxylated coconut fat alcohol polyglycol ether (wetting agent, emulsifier) 1.5 " " " of alkylphcnol polyglycol ether 73.5 " " " of liquid n-paraffins The ingredients are pre-dispersed and the dispersion is then milled in a glass bead mill until a particle size under 2 ~ (20% of the particles having a size under 1.1 ~) is obtained.
Example D
Aerosol 0.5 parts by weigh't of 1-(4-chlorophenyl)-3-phenyl-2-tri-chloromethyl-imidazolidine 35.0 parts by weight of talcum 0.5 " " " of zinc stearate 0.5 " " " of hexadecyl alcohol 63.5 " " " of propellant (Frigene) Propane/butane, nitrogen, carbon dioxide or air may also be used as the propellant instead of Frigene.
' .. ... ~ . . . .. . . ~ .. . . .
~OS638S
Exa~
1-(3-Chlorophenyl)-3-(4-methylphenyl)-2-trichloromethyl-imidazolidine .. ..
12.2 g of N-(3-chlorophenyl)-N'-(4-methylphenyl)-ethylene diamine, 9 g of chloral and 100 ml of toluene are mixed with 1.2 g of p-toluenesulfonic acid and heated to the boiling temperature of the reaction mixture in a water-separator.
After 45 minutes the reaction mixture is filtered when still hot and the filtrate is evaporated in vacuo.
After coolîng, the oily product is triturated with a little glacial acetic acid, whereby crystals of the title compound are formed. The crystals are filtered off with !
suctîon, washed with a little cold methanol and recrystallised from ethanol; yield: 6.5 g, m.p. 84 to 86C.
m e compounds listed in the following table are obtained in a similar maDner:
'' ,` ~
~ . .
: :;
.~ .
~ ' ' .
:
~056385 , Ex~mple Rl R2 3 _ 4 _ _ ~: 2 H H 3-CH3 5-CH3130 : ~ 3 H H 4-CH3 H 80 . ~.
. H H 4-OCH3 H 120-122 6 ~ 3-Cl H 4-Cl H 4 144 ; 7 4-CH3 H 4-OCH3 H 111-113 -8 ~ 4-CH3 H 4-Cl H 124-125 9 . 4-CH3 H 4-C2H5 H 98-100 . 10 3-CH3 H 3-Cl H oil ~: 11 3-Cl 5~-Cl 3-CH3 5-CH3 163 12 : 3-CH3 5-CH3 4-Cl H 112 ; 13 ¦ 4-CH3 ¦ H 3-C1 ¦ 5-C1 117 ;
.. .. . ..
J
~ ~ . ' : : ' ' The starting materials used for the production of the novel compounds may be obtained as follows:- -N-(3-chlorophenyl)-N'-(4-methylphenyl~-ethylenediamine a) N-(2-hydroxyethyl)-3-chloroaniline ______ ____ ___ __________________ 50.8 g of 3-chloroaniline, 36 g of ethylene chlorohydrin ~ and 50 g of anhydrous sodium carbonate are refluxed for
are different] and acid addition salts thereof.
It will be appreciated that ring A and ring ~ may differ by having different substituents in either the same or different substitutional positionsin each ring or by having the same substituents in each ring but in different substitional positions.
The compounds of formula I and the acid addition salts thereof show good activity against various pests. Thus, for ~-example, houseflies (Musca domestica) cockroaches (e.g. Phyllo~
droma germanica), spider mites ~e.g. Tetranychus urticae), aphids , :
:''' (e.g. Aphis fabae), caterpillars (e.g. of Plutella maculipennis) and bugs (e.g. Epilachna varivestis) may be exterminated by the use of even small doses of active ingredient.
Examples of compounds of the present invention include the following:
1-(4-chlorophenyl)-3~phenyl-2-trichloromethyl-imidazoiidine and 1-(3-chlorophenyl)-3-(4-methylphenyl)-2-trichloromethyl- ~ -imidazolidine, and the acid addition salts thereof.
The compounds of formula I may, for example, be produced by reacting a corresponding diaryl-substituted ethylene diamine of formula II with chloral according to known processes (e.g. H.~. Wanzlick and E. Schikora, Chem.
Ber 94, 2839 (1961)).
Thus according to a further feature of the present invention there is provided a process for the preparation of compounds of formula I as hereinbefore defined or an acid addition salt thereof which comprise9 reacting a compound of the formula--2 NH - CH2 - CH2 - NH ~ II
(wherein Rl, R2, R3 and R4 are as hereinbefore defined) with a compound of the formula:-' OHC - CCl III
whereby a compound of formula I is obtained and, if desired, subsequently converting the compound of formula I thus obtained into an acid addition salt thereof. The reaction is preferably effected in the presence of glacial acetic acidi or a mixture of glacial acetic acid and hydrochloric acid as solvent and advantageously at ambient tempeLature or at an elevated temperature e.g. a slightly elevated temperature. It is often advantageous to effect the reaction between the compound of formula II and the compound of formula III with simultaneous removal of water formed in the reaction from a solvent immiscible with water e.g. by azeotropic distillation. The substantially water immiscible solvents include, for example, benzene, toluene or xylene. The reaction ~ ;
may also, if desired~ be effected in the presence of a catalyst e.g. a reaction accelerator e.g. an acidic catalyst, such as ~-toluenesulfonic acid. This modified process results in a higher purity and in better yields, of the compounds of formula I even when a diamine, in which one of the phenyl moieties is unsubstituted or ~-substituted~ is used as the compound of formula II.
The starting compound of formula III may, for example, be obtained by reacting a compound of the formula:-~ - 4 ':
. , ' ': "
'~: . - ' Rl ~ ~H_cH~_cH2_x ~IV) (wherein Rl and R2 are as hereinbefore defined and X represents .an atom or group removable as an anion e.g. a chlorine or bromine atom) with an aniline of the formula:-2 ~ ~V~
(wherein R3 and R4 are as herein~e~ore defined) with theremoval of HX. The compounds of formula IV may, for example, be prepared according to various methods, for example by reactîng an anil~ine f the fonmula:-1 ~ . ', 2 (VI) , ~wherein Rl and R2 are as hereinbefore defined), with ethyleneoxide ~Houben-Weyl, Methoden der organischen Chemie, vol. XI/l, page 313 (1957)~ or with ethylene chlorohydrin or ethylene bromohydrin, whereby a compound of the formula : 1 ~ NH-cH2cH2-oH (VIII) 2 ~- :
: : . ~ 5 ~ ~:
.
-. , . , .. : .
~056385 (w~erein Rl and R2 are as hereinbefore defined) is obtained,after which the hydroxy group is replaced by group X according to conventional pr~cesses, preferably by chlorine or bromine. ~ -Moreover certain compounds of formula IV may, for example, be obtained from compounds of formula:
Rl ~ NH-CO-CH2-X (VII) (wherein Rl and R2 are as hereinbefore defined) by reduction with NaAlH2 (OCH2CH2-OCH3)2 (Tetrahedron Letters 1968, page 3303).
According to a still further feature of the present invention there are provided insecticidal and acaricidal compositions comprising as active ingredient at least one compound of formula I as hereinbefore defined or an acid addition salt thereof in association with an inert carrier or diluent~
For the control of insects the active ingredients are preferably used in the conventional manner together with diluentsJand carriers e.g. emulsifiable concentrates wettable powders, solutions, aerosols, dusting powders, granulates or colloidal dispersions.
, ,; . ' ' The preferred concentration of active ingredient for use in insecticidal and acaricidal composit~ ns according to the invention is from 0.02 to 5% by weight.
If required, the concentrates may be mixed with water, so that a spray preferably having a concentration of approximately 0.02 to 5% by weight of active ingredient is obtained.
The active ingredient content in concentrates of the present invention may, if desired, amount to 80% by weight.
Carriers and additives which may conveniently be used according to the present invention include for example solvents, diluents, stabilizers, dispersion agents, wetting agents and emulsifying agents. Moreover the insect-icidal and acaricidal compositions according to the present lnvention may, if desired, also contain urther known insecticidal or acaricidal agents.
T~e compositions of the present invention are, in general, specific in their activity against insects and acarids and as a result they may be used for specific plant protection. The compositions of the present invention , are substantially non-toxic to w~rm-blooded animals.
Moreover the active ingredients of the compositions of the present invention decompose with r;lease of chloroform . . .
- ; ..
and degrade rapidly to give non-toxic compounds which do not harm the environment.
According to a further feature of the present invention there is provided a method of preventing o_ inhibi~ing the growth or proliferation of insects and/or acarids which comprises applying to a site infested with or susceptible to infestation by insects and/or acarids an effective amount of a compound of formula I as hereinbefore described or . an acid addition salt thereof. -. The following non-limiting Examples illustrate the invention:-. ' , .
.
- 8 - :.
~ :
: .
- ....
l~S6~5 Formulatio_ Examples Example A
Wettable Powder 50 parts by weight of 1-(4-chlorophenyl)-3-phenyl-2-trichloromethyl-imidazolidine 8 " " " of sodium lignine sulfonate 2 " " " of sodium naphthalene sulfonate " " " of kaolin " " " of silicious chalk The components are mixed and milled in a stud mill.
The particle size of the product is approximately 2 to 6 ~.
The active ingredient content may be increased by decreasing the carriers and may amount to approximately 80 parts by weight.
For use, a spray of the desired concentration of active ingredient is made by mixing the above-identified composition with water; the concentration amounts, in general, to from approximately 0.02 to 5%.
Example B
, usting Powder 1.5 parts by weight of 1-(3-chlorophenyl)-3-(4-methylphenyl)_ ;. .. .
2-trichloromethyl-imidazolidine 98.0 parts by weight of talcum 0.5 " " " of aluminium stearate The active ingredient is milled in a stud mill and mixed ~ ~
~: -.
~':
` ;1~5638S
with the remaining components.
Example C
Colloid Formulation 20.0 parts by weight of 1~ chlorophenyl)-3-(4-methyl-phenyl)-2-trichloromethyl-imidazolidine 2.5 " " " of ethoxylated isotridecanol polyglycol ether (wetting agent, emulsifier) 2.5 ~ ethoxylated coconut fat alcohol polyglycol ether (wetting agent, emulsifier) 1.5 " " " of alkylphcnol polyglycol ether 73.5 " " " of liquid n-paraffins The ingredients are pre-dispersed and the dispersion is then milled in a glass bead mill until a particle size under 2 ~ (20% of the particles having a size under 1.1 ~) is obtained.
Example D
Aerosol 0.5 parts by weigh't of 1-(4-chlorophenyl)-3-phenyl-2-tri-chloromethyl-imidazolidine 35.0 parts by weight of talcum 0.5 " " " of zinc stearate 0.5 " " " of hexadecyl alcohol 63.5 " " " of propellant (Frigene) Propane/butane, nitrogen, carbon dioxide or air may also be used as the propellant instead of Frigene.
' .. ... ~ . . . .. . . ~ .. . . .
~OS638S
Exa~
1-(3-Chlorophenyl)-3-(4-methylphenyl)-2-trichloromethyl-imidazolidine .. ..
12.2 g of N-(3-chlorophenyl)-N'-(4-methylphenyl)-ethylene diamine, 9 g of chloral and 100 ml of toluene are mixed with 1.2 g of p-toluenesulfonic acid and heated to the boiling temperature of the reaction mixture in a water-separator.
After 45 minutes the reaction mixture is filtered when still hot and the filtrate is evaporated in vacuo.
After coolîng, the oily product is triturated with a little glacial acetic acid, whereby crystals of the title compound are formed. The crystals are filtered off with !
suctîon, washed with a little cold methanol and recrystallised from ethanol; yield: 6.5 g, m.p. 84 to 86C.
m e compounds listed in the following table are obtained in a similar maDner:
'' ,` ~
~ . .
: :;
.~ .
~ ' ' .
:
~056385 , Ex~mple Rl R2 3 _ 4 _ _ ~: 2 H H 3-CH3 5-CH3130 : ~ 3 H H 4-CH3 H 80 . ~.
. H H 4-OCH3 H 120-122 6 ~ 3-Cl H 4-Cl H 4 144 ; 7 4-CH3 H 4-OCH3 H 111-113 -8 ~ 4-CH3 H 4-Cl H 124-125 9 . 4-CH3 H 4-C2H5 H 98-100 . 10 3-CH3 H 3-Cl H oil ~: 11 3-Cl 5~-Cl 3-CH3 5-CH3 163 12 : 3-CH3 5-CH3 4-Cl H 112 ; 13 ¦ 4-CH3 ¦ H 3-C1 ¦ 5-C1 117 ;
.. .. . ..
J
~ ~ . ' : : ' ' The starting materials used for the production of the novel compounds may be obtained as follows:- -N-(3-chlorophenyl)-N'-(4-methylphenyl~-ethylenediamine a) N-(2-hydroxyethyl)-3-chloroaniline ______ ____ ___ __________________ 50.8 g of 3-chloroaniline, 36 g of ethylene chlorohydrin ~ and 50 g of anhydrous sodium carbonate are refluxed for
4 hours with stirring. The reaction mixture is then filtered hot with suction over a suction filter and the filter residue is washed with ethyl acetate. &bsequently, the filtrate is distilled under decreased pressure, the desired product being distilled off at 14 Torr and 182C.
b) N-(2-bromoethyl)-3-chloroaniline-hydrobromide ----------------------__ ____________________ __________ 50 g~of 50% hydrobromic acid are slowly added dropwise, with stirring,to 19 g of the product obtained according to (a3. The apparatus is equipped with a Vigreux column until a temperature of approximately 124C is reached. After 3 hours ~bout 35 ml of liquid ~re distilled off. The residue solidifies on cooling and is purified by washing with cold acetone.
Yield: 22 g, m.p. 148C.
N-(3-chloro~henyl)-N'-(4-methyl~henyl)-ethylenediamine 15.8 g of N-(2-bromoethyl)-3-chloroaniline hydrobromide and 10.7 g of 4-methylaniline in 50 ml of toluene are :~ .
mixed together and refluxed for 8 hours while stirring.
- 1.3 - .
~. .
The reaction mixture is filtered and the residue washed with ethyl acetate. The filtrate is evaporated by strong heating in vacuo~ 10 g of an oil remain, which may be used unpurified for further reaction.
N-Phenyl-N'-(3,5-dimethylphenyl)-ethylenediamine a) [N-(395-dimethyl~henyl)-~lycine~-anilide ____ ________ _ ___ ___ _ _____________ After addition of 25 g of sodium carbonate to 17 g of chloroacetanilide and 20 g of 3,5-dimethylaniline the mixture is maintained at a temperature of 185C for 6 hours on an oil~ bath. The reaction rnixture is then mixed with water and the organic phase is taken up in ethyl acetate.
.
The mixture thus obtained is dried with sodium sulfate and evaporated in vacuo, to yield a light-brown oil. The oil gradually solidifles; yield: 20 g.
b) N-~henyl-N~-~3L5-dimethyl~henyl2-eth~lenediamine ~ ----------__________ A solution of the product obtained according to (a) in 35 ml of benzene is added dropwise to a solution of 25 g of sodium-bis-(2-methoxyethoxy)-dihydroaluminate in lO0 ml of benzene. The temperature of the reaction mixture rises and hydrogen is given off. The reaction mixture , is refluxed for a further 2 hours and after cooling is mixed dropwise with 200 ml of 20% sulfuric acid. The benzene is distilled off by means of steam. The ., . ~ .
aqueous residue is made alkaline with concentrated ammonium :
....... ~.. , ~, .
~ OS6385 hydroxide and made up with water to a volume of 2 litres.
The title product is extracted from the mixture with ethyl acetate, the solution thus obtained is dried with ::odium sulfate and after evaporation in vacuo the title compound is obtained as an oil, which may be reacted to produce the compounds of the invention without puri-fication.
The remaining starting materials of formula III may be obtained according to the processes detailed in the preceding two :~ Examples.
., - .
. ~ . .
': ' : .
:
',~ ' , :
,:
:, ` ' ' , . ' . ~ ~ ' , , ' .
, -," ... . . .. ..
b) N-(2-bromoethyl)-3-chloroaniline-hydrobromide ----------------------__ ____________________ __________ 50 g~of 50% hydrobromic acid are slowly added dropwise, with stirring,to 19 g of the product obtained according to (a3. The apparatus is equipped with a Vigreux column until a temperature of approximately 124C is reached. After 3 hours ~bout 35 ml of liquid ~re distilled off. The residue solidifies on cooling and is purified by washing with cold acetone.
Yield: 22 g, m.p. 148C.
N-(3-chloro~henyl)-N'-(4-methyl~henyl)-ethylenediamine 15.8 g of N-(2-bromoethyl)-3-chloroaniline hydrobromide and 10.7 g of 4-methylaniline in 50 ml of toluene are :~ .
mixed together and refluxed for 8 hours while stirring.
- 1.3 - .
~. .
The reaction mixture is filtered and the residue washed with ethyl acetate. The filtrate is evaporated by strong heating in vacuo~ 10 g of an oil remain, which may be used unpurified for further reaction.
N-Phenyl-N'-(3,5-dimethylphenyl)-ethylenediamine a) [N-(395-dimethyl~henyl)-~lycine~-anilide ____ ________ _ ___ ___ _ _____________ After addition of 25 g of sodium carbonate to 17 g of chloroacetanilide and 20 g of 3,5-dimethylaniline the mixture is maintained at a temperature of 185C for 6 hours on an oil~ bath. The reaction rnixture is then mixed with water and the organic phase is taken up in ethyl acetate.
.
The mixture thus obtained is dried with sodium sulfate and evaporated in vacuo, to yield a light-brown oil. The oil gradually solidifles; yield: 20 g.
b) N-~henyl-N~-~3L5-dimethyl~henyl2-eth~lenediamine ~ ----------__________ A solution of the product obtained according to (a) in 35 ml of benzene is added dropwise to a solution of 25 g of sodium-bis-(2-methoxyethoxy)-dihydroaluminate in lO0 ml of benzene. The temperature of the reaction mixture rises and hydrogen is given off. The reaction mixture , is refluxed for a further 2 hours and after cooling is mixed dropwise with 200 ml of 20% sulfuric acid. The benzene is distilled off by means of steam. The ., . ~ .
aqueous residue is made alkaline with concentrated ammonium :
....... ~.. , ~, .
~ OS6385 hydroxide and made up with water to a volume of 2 litres.
The title product is extracted from the mixture with ethyl acetate, the solution thus obtained is dried with ::odium sulfate and after evaporation in vacuo the title compound is obtained as an oil, which may be reacted to produce the compounds of the invention without puri-fication.
The remaining starting materials of formula III may be obtained according to the processes detailed in the preceding two :~ Examples.
., - .
. ~ . .
': ' : .
:
',~ ' , :
,:
:, ` ' ' , . ' . ~ ~ ' , , ' .
, -," ... . . .. ..
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Compounds of the formula:- I
[(wherein R1, R2, R3 and R4, which may be the same or different, each represents a hydrogen or halogen atom or a nitro or lower alkyl or alkoxy group, the said R1, R2, R3 and R4 being in the 3-, 4- or 5-position) with the proviso that ring A and ring B are different] and acid addition salts thereof.
[(wherein R1, R2, R3 and R4, which may be the same or different, each represents a hydrogen or halogen atom or a nitro or lower alkyl or alkoxy group, the said R1, R2, R3 and R4 being in the 3-, 4- or 5-position) with the proviso that ring A and ring B are different] and acid addition salts thereof.
2. 1-(4-Chorophenyl)-3-phenyl-2-trichloromethyl-imidazolidine and acid addition salts thereof.
3. 1-(3-Chlorophenyl)-3-(4-methylphenyl)-2-trichloromethyl-imidazoli-dine and acid addition salts thereof.
4. A process for the preparation of compounds of formula I as defined in claim 1 or an acid addition salt thereof which comprises reacting a com-pound of the formula II
(wherein R1, R2, R3 and R4 are as defined in claim 1) with a compound of the formula:-OHC-CCl3 III
whereby a compound of formula I is obtained and, if desired, subsequently converting the compound of formlua I thus obtained into an acid addition salt thereof.
(wherein R1, R2, R3 and R4 are as defined in claim 1) with a compound of the formula:-OHC-CCl3 III
whereby a compound of formula I is obtained and, if desired, subsequently converting the compound of formlua I thus obtained into an acid addition salt thereof.
5. A process as claimed in claim 4 wherein water formed in the reaction is removed by azeotropic distillation with a substantially water immiscible solvent.
6. A process as claimed in claim 5 wherein the substantially water im-miscible solvent comprises benzene, toluene or xylene.
7. A process as claimed in claim 6 wherein the reaction is affected in the presence of an acidic catalyst.
8. A process as claimed in claim 7 wherein the acidic catalyst comprises p-toluene sulfonic acid.
9. A process as claimed in claim 4 wherein the compound of formula II
is first prepared by reacting a compound of the formula:- IV
(wherein R1 and R2 are as defined in claim 4 and X represents an atom or group removable as an anion) with a compound of the formula:- V
(wherein R3 and R4 are as defined in claim 4).
is first prepared by reacting a compound of the formula:- IV
(wherein R1 and R2 are as defined in claim 4 and X represents an atom or group removable as an anion) with a compound of the formula:- V
(wherein R3 and R4 are as defined in claim 4).
10. A process as claimed in claim 9 wherein a compound of formula IV
is used in which X represents a chlorine or bromine atom.
is used in which X represents a chlorine or bromine atom.
11. A process as claimed in claim 9 or claim 10 wherein the compound of formula IV is first prepared by reacting a compound of the formula:- VI
(wherein R1 and R2 are as defined in claim 1) with ethylene oxide, ethylene chlorohydrin or ethylene bromohydrin whereby a compound of the formula:- VII
(wherein R1 and R2 are as defined in claim 1) is obtained and subsequently converting the compound of formula VII into the compound of formula IV.
(wherein R1 and R2 are as defined in claim 1) with ethylene oxide, ethylene chlorohydrin or ethylene bromohydrin whereby a compound of the formula:- VII
(wherein R1 and R2 are as defined in claim 1) is obtained and subsequently converting the compound of formula VII into the compound of formula IV.
12. A method of preventing or inhibiting the growth or proliferation of insects and/or acarids which comprises applying to a site infested with or susceptible to infestation by insects and/or acarids an effective amount of a compound of formula I as defined in claim 1 or an acid addition salt thereof.
13. A method as claimed in claim 12 wherein an effective amount of the compound of formula I as defined in claim 2 or claim 3 is applied to a site infested with or susceptible to infestation by insects and/or acarids.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752508715 DE2508715A1 (en) | 1975-02-28 | 1975-02-28 | INSECTICIDAL AND ACARICIDAL ACTIVE SUBSTANCES AND THEIR USES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1056385A true CA1056385A (en) | 1979-06-12 |
Family
ID=5940068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA246,767A Expired CA1056385A (en) | 1975-02-28 | 1976-02-27 | 1,3-diphenyl-2-trichloromethylimidazolidines |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS51110567A (en) |
| BE (1) | BE839055R (en) |
| CA (1) | CA1056385A (en) |
| CH (1) | CH607632A5 (en) |
| DE (1) | DE2508715A1 (en) |
| ES (1) | ES445620A2 (en) |
| FR (1) | FR2302300A2 (en) |
| GB (1) | GB1511072A (en) |
| HU (1) | HU176496B (en) |
| IT (1) | IT1057252B (en) |
| NL (1) | NL7602022A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2263239C3 (en) * | 1972-12-23 | 1982-02-25 | Celamerck Gmbh & Co Kg, 6507 Ingelheim | New derivatives of 2-trichloromethylimidazolidine, their preparation and insecticidal and acaricidal agents containing them |
-
1975
- 1975-02-28 DE DE19752508715 patent/DE2508715A1/en not_active Ceased
-
1976
- 1976-02-26 IT IT4830476A patent/IT1057252B/en active
- 1976-02-26 HU HUCE001076 patent/HU176496B/en unknown
- 1976-02-26 CH CH238576A patent/CH607632A5/en not_active IP Right Cessation
- 1976-02-27 CA CA246,767A patent/CA1056385A/en not_active Expired
- 1976-02-27 JP JP2101576A patent/JPS51110567A/en active Pending
- 1976-02-27 FR FR7605664A patent/FR2302300A2/en active Granted
- 1976-02-27 GB GB786176A patent/GB1511072A/en not_active Expired
- 1976-02-27 NL NL7602022A patent/NL7602022A/en not_active Application Discontinuation
- 1976-02-27 BE BE164748A patent/BE839055R/en active
- 1976-02-27 ES ES445620A patent/ES445620A2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2508715A1 (en) | 1976-09-09 |
| FR2302300A2 (en) | 1976-09-24 |
| CH607632A5 (en) | 1978-09-29 |
| ES445620A2 (en) | 1977-11-16 |
| BE839055R (en) | 1976-08-27 |
| HU176496B (en) | 1981-03-28 |
| IT1057252B (en) | 1982-03-10 |
| FR2302300B2 (en) | 1979-08-31 |
| JPS51110567A (en) | 1976-09-30 |
| NL7602022A (en) | 1976-08-31 |
| GB1511072A (en) | 1978-05-17 |
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