JPS623836B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to imidazolines, their preparation, intermediates thereof, insecticidal compositions containing the imidazolines, and their use as insecticides. The inventors have discovered that compounds of formula () and their acid addition salts have activity against arthropods, such as those of the order Acarina. The compound of formula () has the following formula [wherein X is O or NH; and Y is
Br, F, ^I , _-NO2 , -OR, _-CO2R , ^-CONR1R2
or -SO ₂ NR ¹ R ² and when X is NH, Y may also be selected from Cl, CN or alkyl of 1 to 4 carbon atoms and R is of 1 to 18 carbon atoms, preferably an alkyl group of 1 to 4 carbon atoms or 12 to 18 carbon atoms; and R ¹ and R ² which may be equal or different
each of R 1 and R 2 is hydrogen or an alkyl group of 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms or 12 to 18 carbon atoms, and preferably only one of R ¹ and R ² is an alkyl group of 1 to 18 carbon atoms. [is something]
belongs to. Preferred compounds of formula () can be represented by formula (a). [wherein X is as defined above, and
Y ¹ is F, Br, -NO ₂ , CH ₃ O-, or -
CO ₂ C ₂ H ₅ or X is NH and
Y ¹ is Cl]. Certain compounds of formula () may exist in their solvated forms. Preferred compounds of formula () are: 1-[N-(4-methoxyphenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline; 1-[N-(4-chlorophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-
2-imidazoline; 1-[N-(4-bromophenyl)carbonyl]
-2-(2,3-dimethylphenoxymethyl)-2
-Imidazoline; 1-[N-(4-nitrophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline; 1-[N-(4-fluorophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline; and 1-[N-(4-bromophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-
2-Imidazoline. Compounds of formula () and their acid addition salts are:
Active against arthropods. Compounds of formula () can be used, for example, in animals such as Rhipicephalus appendeculatus.
appendiculatus), Boophilus decolaratus, Boophilus microplus, Rhipicephalus evertsi, Amblyomma
hebraeum), Soroptes obis (Psoroptes
ovis) and Hyaloma species (Hyaloma
It can be used to control pests such as Tetranychus species) and Tetranychus species in plants. The compounds of formula () have improved stability in aqueous media compared to known imidazolines. Compounds of formula () may be prepared by known methods for the preparation of compounds of similar structure. In particular, a compound of formula () is a compound of formula () 2- of [In the formula, X is as limited above]
From substituted imidazolines or their acid addition salts,
By direct addition reaction of isocyanate (giving N-substituted carbamoyl compound) or by formula () [wherein Y is as defined above, and
X ¹ can be prepared either by substitution reaction with a compound, for example a group to be removed such as halo, acyl, alkoxy (eg carbamate) or sulfonyloxy. The reaction is optionally carried out in water or an organic solvent such as chloroform or methylene chloride, preferably a base such as an alkali metal hydroxide, an alkali metal carbonate, or a tertiary organic base such as triethylamine, pyridine or substituted pyridines or piperidines such as pentamethylpiperidine or in the presence of tetramethylpiperidine; and generally from -70°C to 120°C, preferably -10°C.
It can be carried out at temperatures between 0°C and 40°C. Especially based on

Compounds of formula () in which [formula] does not have strong electron removal properties are those of formula () [wherein Y is as defined above] is combined with a suitable 2,3-dimethylphenoxyalkyl or 2,3-dimethylanilinoalkylcarboxylic acid or a reactive derivative thereof such as imidate, thioimidate, They can be prepared by reaction with imidohalides, esters, amidines, thioamides, nitriles or carboxyalkylthioamides. These reactants have the formula () [wherein X is as defined above and Q is a compound of formula () when reacted with a compound of formula ()
is a carboxyl group leading to an imidazoline ring structure or a reactive derivative thereof]. Suitable derivatives include:

【formula】

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【formula】

[expression] and

##STR1## where 'Alk' is an alkyl group having 1 to 6 carbon atoms, and one of A and B is S and the other is S or O. The conditions under which this reaction may be carried out will of course depend on the nature of the starting materials used and a liquid medium may be present or absent; high and low temperatures can be used and various pressures can be used. When the carboxylic acid derivative is an imidate, it is preferably in the form of an acid addition salt, such as a hydrogen halide salt, and is prepared from a nitrile and a suitable anhydrous alkanol such as ethanol or methanol, dry diethyl ether or chloroform, and the presence of hydrogen chloride. can be produced at low temperatures. The reaction may be carried out at temperatures ranging from -20°C to room temperature. The reaction with ethylenediamine of formula () may be carried out in an inert anhydrous medium such as chloroform, methylene chloride or ether. The reactants are preferably heated to reflux until the reaction is complete. Thioimidate intermediates in the form of acid addition salts may be prepared from the corresponding nitriles by reaction with alkyl mercaptans and hydrogen halide gas in the presence of dry diethyl ether at low temperatures of about 0°C. The thioimidate can then be reacted with ethylenediamine of formula (), the reaction being carried out at the reflux temperature of the reaction mixture. The ester intermediates may be suitably prepared by known methods from the corresponding acids, and the acids themselves may be prepared from the corresponding nitriles. They may then be reacted with ethylenediamine of formula (), preferably in the presence of a liquid medium which may be polar or non-polar. The reaction is preferably carried out at elevated temperatures. Compounds of formula () may be prepared from imidohalide intermediates by reaction with ethylenediamine of formula () under anhydrous conditions, in the presence or absence of an acid acceptor, and optionally at elevated temperature. The reaction mixture may include a polar or non-polar liquid medium such as a lower alkanol or an ether. Amidine intermediates in the form of bases or acid addition salts thereof can be prepared by heating to reflux with ethylenediamine of formula () in the presence of a polar or non-polar liquid medium such as a lower alkanol until evolution of ammonia ceases. It is suitably converted into a compound. The amidine intermediate itself may be prepared by any known method, but preferably from the corresponding imidate by reaction with ammonia. The thioamide and amide intermediates may be prepared from the corresponding nitriles or by any other suitable method, and with ethylenediamine of formula ()
It may be converted to a compound of formula () by heating at reflux or higher temperature in the presence or absence of a polar or non-polar solvent. Preferably, the reaction is carried out under partial vacuum to induce the removal of ammonia and/or hydrogen sulfide from the reaction mixture. The nitrile intermediate may be reacted with ethylenediamine of formula () or a salt thereof in the presence or absence of a liquid medium; the reaction may be carried out in the presence of hydrogen sulfide. A liquid medium such as a lower alkanol can be included in the reaction mixture which can be heated to reflux temperature or to a higher temperature in a sealed vessel, optionally in the presence of an inert gas such as nitrogen. If the intermediate is a carboxylic acid, ester or thioamide, the formula () The acylethylenediamines of the formula (wherein X and Y are as defined above and W is oxygen or sulfur) can be isolated as intermediates, and the compounds can be further treated with a dehydrating agent such as calcium oxide. It is of course understood that the compound of formula () may be converted at that site either by or by continuing the reaction to completion under the original conditions giving rise to the compound of formula (). Probably. A compound of formula () is a compound of formula () A phenol or amine, or an o- or N-metal compound thereof, of the formula (wherein X is as defined for the formula ()) is expressed by the formula () It can be prepared by reacting with a compound of the formula: wherein Y is as defined for formula () and V is a group to be removed derived from a suitable inorganic or organic acid. Suitable derivatives are halo such as chloro, iodo or bromo, alkylsulfonyloxy or arylsulfonyloxy such as p-toluenesulfonyloxy. Compounds of formula () may be in the form of their bases or their acid addition salts. The reaction is preferably carried out in a polar solvent such as acetonitrile or isopropanol, or an inert liquid which can be dimethyl sulfoxide, sulfolane, methyl ethyl ketone, dimethyl formamide, acetone, dimethyl acetamide, N-methyl-2-pyrrolidone, or mixtures thereof. It can be carried out in a medium. When V is chloro in the compound of formula (), a small catalytic amount of an iodide salt, such as sodium iodide, or a phase transfer catalyst, such as a quaternary ammonium salt such as benzyltrimethylammonium chloride, is added to the reaction mixture. may be advantageously included. The reactants may be heated together under an inert atmosphere, such as nitrogen, at the reflux temperature of the reaction mixture. Compounds of formula () are also compounds of formula () ^A compound of the formula () It can be prepared by reacting with a suitable activated amine in which Y is as defined for formula (). Compounds of formula () can be isolated as the free base or in the form of acid addition salts. Bases may be converted into their acid addition salts by known techniques with the aid of suitable acids, and the salts of the compounds may also be converted into the free base or other acid addition salts. For use as a neutralizer, compounds of formula () may be provided in the form of their acid addition salts or, more preferably, as their free bases. Suitable salts of compounds of formula () include their hydrohalides, sulfates, nitrates, phosphates,
thiocyanate, acetate, propionate,
stearate, naphthenate, perchlorate,
Benzoates include methanesulfonate, ethanesulfonate, tosylate and benzenesulfonate. Compounds of formula () interact with other arthropods, including insects, large ticks, small mites, and free-living arthropods as well as ectoparasites of plants, mammals, and birds. as an insecticide and can be used alone or as a wetting agent, diluent, stabilizer, thickener, emulsifier,
It may be used in combination with additives which may take the form of one or more carriers used in formulation technology such as dispersants or surfactants or other standard carrier ingredients. The formulation may be an aqueous solution of an acid addition salt of a compound of formula (), or a suspension of a compound of formula () in water, and may be used alone or in combination with a suitable surfactant. The formulation itself may be used alone or diluted with water for use against pests, or by spraying or dipping into their immediate environment. The formulation comprises a compound of formula () in its free base form, or a miscible compound comprising an emulsifier and an equimolar amount of a suitable organic acid such as oleic acid or naphthenic acid to provide the salt soluble in an organic solvent. It can be in the form of a miscible oil and can be used as an emulsion by spraying or dipping. The formulation may be a non-aqueous solution or suspension of a compound of formula () in a suitable organic solvent for direct use by the "pour-on" method. The formulation may also be in the form of a wettable powder for dilution with water and use by dipping or spraying. Other solid formulations may also be used directly without dilution, such as dusts, powders and granules. Still other formulations are pastes, greases containing a compound of formula () and a suitable carrier.
or a gel, and can be used by applying the formulation to the infected area. Acid addition salts or bases of compounds of formula () preferably contain from 5 to 80%, calculated by weight of base.
and particularly preferred formulations are present in the insecticidal formulation in an amount of about 20%, calculated by weight of the base.
contains. The concentration of compounds of formula () used in pests or their immediate environment may be in the range 0.001%-20%, calculated by weight of base. From the foregoing description, it can be appreciated that what we claim encompasses primarily, but not exclusively, any novel features described herein, such as: (a) Novel 2,3-dimethylphenoxyalkyl or 2,3-dimethylanilinoalkyl imidazoline compounds of formula () and their acid addition salts; (b) Novel compounds of formula () and them (c) a method for controlling arthropod pests, particularly those of the order Acari, by using a compound of formula () in the pest or the pest's environment; (d) a compound of formula () and a carrier thereof; (e) a method for producing a formulation consisting of mixing a carrier and a compound of formula (); and (f) a novel intermediate formed in the production of imidazolines. Examples are presented below for the purpose of illustrating the invention, but they should not be considered as limiting the invention. Example 1 1-[N-(4-chlorophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)
-2-imidazoline 2-(2,3-dimethylanilinomethyl)-2-
Imidazoline (4.20 g: 0.024 mol) was stirred in methylene chloride (90 ml), cooled to 0°C,
Then 4-chlorophenyl isocyanate (3.66 g; 0.024 mol) in methylene chloride (10 ml) was added dropwise. A white precipitate formed rapidly. Stirring was continued for 2 to 3 hours at 0°C after the addition, then the reaction mixture was allowed to reach room temperature and stirring was continued for 1 hour.
It continued through the night. The reaction mixture was then evaporated to dryness under reduced pressure and the solid residue thus obtained was recrystallized from propan-2-ol to give 1-[N-(4-chlorophenyl)-carbamoyl]-2-(2・3-
White crystals of dimethylanilinomethyl)-2-imidazoline (melting point 153-155°C) were formed. Following the method of Example 1, but without the recrystallization step, 1-[N-(4-dimethylsulfonamidophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-2-imidazoline, Melting point 151−
Produced 153℃. Examples 2 to 6 The compounds of Examples 2 to 6 below were also prepared by a method similar to that described in Example 1 above. Example 2 1-[N-(4-bromophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline, monohydrate, melting point 150
−151℃ (white powder). Example 3 1-[N-(4-methoxyphenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline, melting point 126-127°C (white powder). Example 4 1-[N-(4-nitrophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline, monohydrate, melting point 182
-185℃ (light yellow powder). Example 5 1-[N-(4-carbethoxyphenyl)carbamoyl-2-(2,3-dimethylphenoxymethyl)-2-imidazoline, melting point 153°C (white powder). Example 6 1-[N-(4-fluorophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)
-2-imidazoline, melting point (approximately 5% impurities) 172
−173℃. Example 7 Preparation of 1-[N-(4-bromophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)-2-imidazoline A in methylene chloride (300 ml).
A solution of 3-dimethylphenoxymethyl)-2-imidazoline (20.4 g; 1.0 mol) was cooled to -65°C and diluted with methylene chloride (300 ml).
4-bromophenyl isocyanate (19.8
g; 1.0 mol) was added dropwise over 30 minutes. The reaction mixture was then warmed to room temperature and left for 2 hours when a precipitate formed. The reaction mixture was evaporated under reduced pressure and the residue was recrystallized from acetone to give 1-[N-(4-bromophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)-2-imidazoline, A monohydrate (melting point 150-151°C) was obtained. B 2-(2,3-dimethylphenoxymethyl)-
Via N-chlorocarbamoyl adduct of 2-imidazoline 3.2% solution of phosgene in toluene (containing 0.5521 g
g; _0.00549 mol of CoCl2) was dissolved in 2-(2,3-dimethylphenoxymethyl)-2-imidazoline (2.40 g; 0.0115 mol) in dry chloroform (20 ml).
mol) was added slowly at 0° C. with stirring. When the addition was complete, the reaction mixture was left at room temperature for 2 hours, diluted with an equal volume of diethyl ether, and filtered rapidly. 2-(2・3
The solution containing the N-chlorocarbamoyl adduct of -dimethylphenoxymethyl)-2-imidazoline was treated with freshly distilled dry 4-bromoaniline (1.22 g, 0.00714 mol) and the mixture was heated overnight at room temperature. Upon standing, tlc showed the main compound to be the desired product. The mixture was evaporated to dryness in vacuo and the residue was taken up in a mixture of aqueous sodium carbonate and dichloromethane. The organic layer was washed with water, dried over magnesium sulfate and evaporated to dryness to give a residue which was purified as described in (A) above to give the same 1-[N -(4-bromophenyl)
Carbamoyl-2-(2,3-dimethylphenoxymethyl)-2-imidazoline was obtained. Examples 8 to 10 The following compounds were prepared in a similar manner to that described in Example 1: 1-[N-(4-methylphenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-
2-imidazoline (melting point 154-15°C); 1-[N-(4-cyanophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-
2-imidazoline; and 1-[N-(4-bromophenyl)carbamoyl]
-2-(2,3-dimethylanilinomethyl)-2-
Imidazoline (melting point 161.6-162.2°C). Example 11 Boophillus micropulus
Engorged female large mites of the Biarra Strain (microplus) are immersed in a wash solution containing a range of test compounds in groups of 20 ticks per concentration.The wash solution is applied immediately before testing. , prepared by dilution (with water) of the test compound. The ingredients may be in the form of miscible oils or wettable formulations. The desired range of concentrations for testing is obtained by further dilution of the stock solution or wash solution. The mites are removed from the wash after 10 years, dried, and attached dorsally to double-sided adhesive tape. They are held in this position for 14 days and the number with viable eggs is counted. From this data, regression Plot the aregression line (concentration versus % inhibition of egg production) and IR99 (996% inhibition of egg production).
(concentration at which inhibition occurs). The results obtained are shown in Table 1 below.

TABLE The following formulations are provided to illustrate how the insecticidal compounds of the present invention may be applied to pests or environments susceptible to pest attack. Formulation 1 Removed powder active compound 1.0 20.0 parts by weight Talc 99.0 80.0 parts by weight 100.0 100.0 Formulation 2 Wettable powder active compound 25.0 parts by weight Sodium dioctyl sulfosuccinate 1.0 〃 Dispersol ACA 2.0 〃 Kaolin 72.0 〃 100.0 Formulation 3 Aqueous dispersion Active compound 20.0 parts by weight Keltrol 0.4 〃 Sodium dioctyl sulfosuccinate 0.5 〃 Water 79.1 〃 100.0 Formulation 4 Pour-on Active compound 0.5 parts by weight Dimethylformamide 85.0 〃 Castor oil 10.0 〃 100.0 Formulation 5 Grease activity Compound 6.0 parts by weight Yellow petrolatum 94.0 〃 100.0 Formulation 6 Miscible oil Compound of Example 3 10.0 parts by weight Aromasol H 70.0 〃 Nonylphenol ethoxylate 20.0 〃 100.0 Stability The compound of Example 1 lasted for 6 months in an aqueous medium at pH 7 while that of 2-(2,3-dimethylphenoxy)-2-imidazoline was about 2 weeks.

Claims (1)

[Claims] 1 Formula () [Wherein, X is O or NH; Y is Br, F,
I, -NO ₂ , -OR, -CO ₂ R, -CONR ¹ R ² or -
SO ₂ NR ¹ R ² or when X is NH, Y may also be selected from Cl, CN or alkyl of 1 to 4 carbon atoms, R is an alkyl group of 1 to 18 carbon atoms, and each of R ¹ and R ² , which may be equal or different, is hydrogen or an alkyl group having 1 to 18 carbon atoms; or an acid addition salt thereof. 2. Compounds according to claim 1, wherein Y is -OR or _-CO2R , and R is an alkyl group of 1 to 4 carbon atoms or 12 to 18 carbon atoms. 3 Y is -CONR ¹ R ² or SO ₂ NR ¹ R ² ,
R ¹ and R ² which may be equal or different
Each of hydrogen or 1 to 4 carbon atoms or 12
~18 alkyl groups, claim 1
Compounds according to Section. 4 At most one of R ¹ and R ² is a carbon atom 12-18
A compound according to claim 3 which is an alkyl group of 5 Formula (a) [wherein X is O or NH and Y ¹ is F, Br, -NO ₂ , CH ₃ O- or -CO ₂ C ₂ H ₅ or X is NH and Y ¹ is Cl Compounds according to claim 1 or acid addition salts thereof. 6 1-[N-(4-methoxyphenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)-2-imidazoline, 1-[N-(4-chlorophenyl)carbamoyl]-2-( 2,3-dimethylanilinomethyl)-2-imidazoline, 1-[N
-(4-bromophenyl)carbamoyl]-2-
(2,3-dimethylphenoxymethyl)-2-imidazoline, 1-[N-(4-nitrophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)-2-imidazoline, 1-[ N-(4-fluorophenyl)carbamoyl]-2-(2,3-dimethylphenoxymethyl)-2-imidazoline and 1-[N-(4-bromophenyl)carbamoyl]-2-(2,3- dimethylanilinomethyl)-
A compound according to claim 1 selected from 2-imidazolidine, or an acid addition salt thereof. 7 1-[N-(4-chlorophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-
A compound according to claim 1 which is a 2-imidazoline or an acid addition salt thereof. 8 1-[N-(4-chlorophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)-
A compound according to claim 1 which is a 2-imidazoline. 9 formula () [Wherein, X is O or NH; Y is Br, F,
I, -NO ₂ , -OR, -CO ₂ R, -CONR ¹ R ² or -
SO ₂ NR ¹ R ² or when X is NH, Y may also be selected from Cl, CN or alkyl of 1 to 4 carbon atoms, R is an alkyl group of 1 to 18 carbon atoms, and each of R ¹ and R ² which may be equal or different is hydrogen or an alkyl group having 1 to 18 carbon atoms], or an acid addition salt thereof; () A compound of the formula (wherein X is as defined above) or an acid addition salt thereof as an isocyanate or a compound of the formula () [In the formula, Y is as defined above, and
X ¹ is the group to be removed]; (b) formula () A compound of [wherein Y is as defined above] or a salt thereof with the formula () (c) with a compound of formula (wherein X is as defined above and Q is a carboxyl group or a reactive derivative thereof); (d) ring-closing a compound of formula (wherein X and Y are as defined above and W is oxygen or sulfur); A phenol or amine, or an o- or N-metal compound thereof, of the formula (wherein X is as defined above), wherein Y is as defined above and V is a group to be removed derived from an inorganic or organic acid, or an acid addition salt thereof; or (e) () A compound of the formula (wherein X is as defined above and P is the group to be removed) and then, if desired, converting the compound of formula () into an acid addition salt, or acid addition of a compound of formula (). A process consisting of converting a salt into the free base or another acid addition salt. 10 formula () [Wherein, X is O or NH; Y is Br, F,
I, -NO ₂ , -OR, -CO ₂ R, -CONR ¹ R ² or -
SO ₂ NR ¹ R ² or when X is NH, Y may also be selected from Cl, CN or alkyl of 1 to 4 carbon atoms, R is an alkyl group of 1 to 18 carbon atoms, and each of R ¹ and R ² , which may be equal or different, is hydrogen or an alkyl group of 1 to 18 carbon atoms], or an acid addition salt thereof, and a carrier thereof. −
Hazardous product composition. 11. A composition according to claim 10, wherein the carrier is a surfactant. 12 Claim 10, wherein the carrier is a liquid
Composition according to Section. 13. A composition according to claim 12, wherein the carrier is a suspending agent. 14. In the form of an aqueous solution or suspension, a miscible oil, a non-aqueous solution or suspension, a paste, a grease, a gel, a wettable powder, a fine powder, a powder or a granule. A composition according to any one of clause 13. 15. A composition according to any one of claims 10 to 14, containing from 5 to 80% of the compound defined in claim 10, calculated by weight of free base. 16 1-[N-(4-chlorophenyl)carbamoyl]-2-(2,3-dimethylanilinomethyl)
A composition according to any one of claims 10 to 15, comprising a -2-imidazoline. 17. Composition according to claim 16 in the form of a wettable powder. 18. A composition according to claim 16 in the form of a miscible oil.