DE2756639A1 - IMIDAZOLINES, THE PROCESS FOR THEIR MANUFACTURING, INTERMEDIATE PRODUCTS AND THEIR USE AS PESTICIDES - Google Patents

Description

I) R. BIiRC I) IfI .ING SlAPI I) II ¹ I.-IN (J SCHWAIUi ') RI) R. SANDMAIR

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19th December 1977

The Wellcome Foundation Limited London / England

"] it] ιίίΊΓ-oJ j no, process for their production, intermediate products and their use as pesticides "

]) i <; j; e KrJ'indunc, relates to imidazolines, processes and intermediates to their manufacture]] unß, pesticide Formu] ierunpen that the ID number and their use as a pest control

It was established that the compounds of the general formula (J) and their acid addition salts are effective against arthropods,

• It Ü III

HI KIiSMI ¹ I ΓΑΙΙ III IV

t ^! 4-m HI Ki- <l

HHnU'inlin IU (Ki Bank MUnihrn *

im / Ίΐι; ιΐΊ 11 s »iii ι.« ir inroiii mm ll.u «\ nnnsliiinl Munihni 4MIOi (HI / 7 (II3II77II | I'.islvhixl Mim.hon I.M41 WW (HI /

in particular against members of the order Acarina.

The compounds of the invention are those of the general Formula (I)

N.

wherein Ar is an unsubstituted or mono-, di- or trisubstituted phenyl radical in which the substituents are the same or different and alkyl, alkoxy, halogen, hydroxy, cyano, amino, trifluoromethyl and / or nitro groups are and at to which two adjacent carbon atoms ^ on the phenyl ring can optionally be connected by a carbon chain with 3 or 4 carbon atoms,

X ^{1 is} O or NH,

1 2
the best R and R, identical or different, and hydrogen

or are alkyl and _2

Z is a group SO _n R or a group -C, in which X

Is 0, S or NR ^{4 , R}

R ^ alkyl, aryl, alkyloxy, aryloxy or NR ^ R ⁶ , R * alkyl, aryl, alkyloxy, aryloxy, alkylthio, arylthio or

NR ^{5 is} R ⁶ ,

the radicals R ^ U _n ^ r6, identical or different, and hydrogen,

Are alkyl, aryl, COR ⁷ or SO ₂ R ⁷ , R ⁷ alkyl, aryl, alkyloxy or aryloxy,

ft η ⁱ i <* 2 ^r 3 ^; m 3

η = s 1 or 2,

R ^{ö is} alkyl, aryl or NR ^C) R ^1Ü and

the radicals R 'and R, identical or different, and hydrogen, Are alkyl or aryl,

with the proviso that when Ar is an unsubstituted phenyl radical is, R and R ^ are H, X is NH, Z is C * g5, X = O and R ^ is not a methyl group.

In the general formula (I) halogen includes chlorine, bromine and fluorine atoms, and the alkyl and alkoxy groups and their parts each have 1 to 4 carbon atoms. Certain Compounds of the general formula (I) can be solvated in their Forms are available. The group Ar in the general formula (I) is preferably unsubstituted or has substituents Alkyl (preferably methyl) and / or halogen (preferably chlorine) groups.

Under the term "aryl" as used herein, phenyl or naphthyl groups are either unsubstituted or unsubstituted to be understood as substituted by one or more substituents, the substituent or substituents being the same or are different and preferably alkyl, alkoxy, halogen, nitro, cyano and / or amino groups.

Preferred compounds of the general formula (I) include those in which

(1) Ar phenyl or 2. ^ -dimethylphenyl and / or

^ X ²

(2) Z ~ ^G. where X ^ is O or S and R ^ NR ^ R ^.

R ^

η π ί · ι> ^f »'η ο

27b6639 AS

Particularly preferred compounds of the general formula (1)

1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, i-U-fo-naphthyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline,

-1_lj _ (/ l-Gl) l orphenyl) -carbamoyl-2- (2,3-diraethylphenoxymet; hyl) -2-imidazoline and

1_n_ (4-cyanophenyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline.

The compounds of the general formula (1) and their acid addition salts indicate effectiveness on Re ^ en arthropods, in particular the order Acarina. The connections of the general Formula (1) can be used to combat pests such as Khipicephalus appendi culatuB., DoophiluQ decoloratus, Boophilus microplus, Khipicephalus evertsi, Amblyomrna hebraeum, l'Goroptei; ovis, nowie the hyal oma-Sjxji'.iuij on animals and Tetranychua species can be applied to plants.

Di <: compounds of the alli ^ a formula (!) Can be according to any known processes for the production of compounds of an analogous structure.

In particular, the compounds of the al ■ pe ί> ·, mn Frrnr. ι (. 1.: tierces- ¹ ei 1 ·; will; :: aua 2-subnti.tuierten imidazole in the general formula (11) or a üäureedditionssalζ these compounds

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Ar-X ¹ -C <f I (II),

Ί Ί?

wherein Ar, X, R and R have the meaning defined above either by direct addition reaction with an isocyanate or isothiocyanate (to form a compound of the general formula (I), in which Z is an N-substituted carbamoyl or thiocarbamoyl group), with a Ketene (to form a compound of general formula (I) in which Z is an acyl group) or with a carbodiimide (to form a compound of the general formula (I) in which Z is an amidino group) or by a substitution reaction with a compound of the general formula (III)

ZX ¹ (III),

wherein Z has the meaning defined above and X ^{1 is} a leaving group such as a halogen (for example in acid chlorides or haloformate esters), acyl (for example in acid anhydrides), alkoxy or alkylthio (for example carbamates, imidates, thiocarbamates or thioimidates ) or sulfonyloxy group (for example in mixed anhydrides).

In a particular application of the substitution reaction described above, the compounds of the general formula (1), in which Z is a thiocarbamoyl group, can be prepared in such a way that a compound of the general formula (]]) is mixed with a compound of the general formula (III) ,

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where Z is a thiocarbamoyl group and X ^{1 is} NHg (ie ZX ^{1 is} a thiourea).

The reaction can optionally be carried out in water or an organic solvent such as chloroform or methylene chloride, preferably in the presence of 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, for example penbamethylpiperidine or tetramethylpiperidine and in general at Temperatures of -70 to 120 ° C, preferably at temperatures of -10 to 40 ⁰ C are carried out.

Compounds of general formula (I), in particular those in which Z is a strong electron withdrawing group, can be prepared by using an ethylenediamine of the general Formula (IV) or a salt thereof

H ₂ N. ₂ 0Η ₂ 0Η ₂ 1Ι. Ζ (IV),

wherein Z has the meaning defined above, with a suitable phenoxyalkyl or aniline alkyl carboxylic acid or a reactive one Derivative thereof such as an imidate, thioimidate, imidohalide, ester, amidine, thioamide, nitrile or carboxyalkylthioamide implements. These reactants can conveniently be represented by the general formula (V)

R ¹
Ar-X ¹ -CQ (V),

R ^

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275C639

11 2

wherein the radicals Ar, X, R and R have the meaning defined above and Q is a carboxyl group or a reactive one Is a derivative of the same, whereby the [rnidazole ring structure of form general formula (I) when they are reacted with a compound of general formula (IV).

Suitable derivatives include:

NH

'OAIk

(Imidate),

OAIk

-C-OAIk (Orthoester),

OAIk

NH

-C (thioimidate),

SAIk

NH

-C (imidohalide),

'Shark

-C (ester),

¹ OAIk

NH

(Amidine),

(Thioamide),

-CSN (nitrile) and

NHCO ₂ AIk

(Carbox.yalk.yl thioamide),

wherein "Alk" is an alkyl group having 1 to 6 carbon atoms.

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275C639

-X-

Ai

The conditions under which this reaction will be carried out can, of course, depend on the nature of the starting materials used from and whether or not a liquid medium is present, with high and low temperatures and various Pressures can be used.

If the carboxylic acid derivative is an imidate, this is preferably in the form of an acid addition salt such as a hydrogen halide salt, it being possible to prepare it from the nitride and a suitable anhydrous alkanol such as ethanol or methanol in the presence of dry diethyl ether or chloroform and hydrogen chloride at low temperatures. The reaction may be carried out at a temperature of -20 ⁰ C to room temperature. The reaction with an ethylenediamine of the general formula (IV) is carried out in an inert anhydrous medium such as chloroform, methylene chloride or ether. The reactants are preferably refluxed until the reaction has occurred.

The thioimidate intermediates in the form of the acid addition salts can be prepared from the corresponding nitrile, for which an alkyl mercaptan and a hydrogen halide gas are reacted at low temperatures of about ⁰ ° C. in the presence of dry diethyl ether. The thioimidate can then be reacted with an ethylenediamine of the general formula (IV), it being possible for the reaction to be effected at the reflux temperature of the reaction mixture.

The ester intermediates can expediently from the ent-

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ok

speaking acids by known methods and the acids as such can be prepared from the corresponding nitriles will. You can then use an ethylenediamine of general Formula (IV), preferably in the presence of a liquid medium, which can be both polar and non-polar, implemented will. The reaction is preferably carried out at an elevated temperature.

The compounds of general formula (I) can be prepared from the imidohalide intermediates, including one an ethylenediamine of the general formula (IV) under anhydrous conditions in the presence or without an acid acceptor and optionally reacts at an elevated temperature · The reaction mixture can be a polar or non-polar liquid Include medium such as a lower alkanol or an ether.

The amidine intermediate in the form of the base or its acid addition salts is preferably converted to a compound of the general formula (I), for which purpose it is refluxed with an ethylenediamine of the general formula (IV) in the presence of a polar or non-polar liquid medium, for example of a lower alkanol heated until the ammonia formation ceases. The amidine intermediates as such can be by means of any known method, but convenient from the corresponding imidates by reaction with ammonia.

The thioamide and amide intermediates can be prepared from the corresponding Nitriles or by means of another expedient

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Process prepared and converted into the compounds of general formula (I), for which purpose they are treated with an ethylenediamine of the general formula (IV) at reflux or at higher temperatures in the presence or without a polar or not polar solvent heated. The reactions are expediently carried out in part under reduced pressure in order to the removal of ammonia and / or hydrogen sulfide from to cause the reaction mixture.

The nitrile intermediates are in the presence or without a liquid medium with an ethylenediamine of the general formula (IV) or a salt thereof reacted, the reaction being carried out in the presence of hydrogen sulfide can. A liquid medium, such as a lower alkanol, can be added to the reaction mixture which is at reflux temperature or to a higher temperature in a closed vessel, optionally in the presence of an inert gas such as nitrogen can be heated.

It is of course clear that, provided that the intermediate is the Carboxylic acid, the ester or the thioamide, these can be isolated as an intermediate product of the acylethylenediamines general formula (VI)

Ar-X-C-C (VI),

N-CH ₂ CH ₂ NH ₂

Ί 2 1 wherein Ar, X , R, R ¹ and Z have the meaning defined above

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2ä

ben and W is oxygen or sulfur and as such these compounds can be converted to a compound in situ of general formula (I), either by separate treatment with a dehydrating agent such as calcium oxide or by continuing the reaction to completion under the initial conditions, thereby obtaining a compound of the general formula (I) receives.

The compounds of the general formula (I) can be prepared by using a phenol or amine of the general formula Formula (VII) or an O- or N-metal compound thereof

Ar-X ¹ -H (VII),

wherein Ar and X are those defined in the general formula (I) Have meaning, reacts with a compound of the general formula (VIII)

V-C - <Q J (VIII),

1 2

wherein R, R and Z have the meaning defined in the general formula (I) and V is a leaving group which is derived from a suitable inorganic or organic acid. Suitable derivatives include halogen such as chlorine, iodine or bromine, alkylsulfonyloxy or arylsulfonyloxy such as p-

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Toluenesulfonyloxy.

The compounds of the general formula (VIII) can be present in the form of their bases or as their acid addition salts. Man carries out the reaction in an inert liquid medium, which is preferably a polar liquid such as acetonitrile or Isopropanol, or dimethyl sulfoxide, suIfolan, methyl ethyl ketone, Dimethylformamide, acetone, dimethylacetamide, N-methyl-2-pyrrolidone or mixtures thereof. In the event that V is chlorine in a compound of the general formula (VIII), a small catalytic amount of an iodide salt, e.g. sodium iodide, or a phase transfer catalyst, such as a quaternary ammonium salt such as benzyltrimethylammonium chloride advantageously be added to the reaction mixture. The reactants can work together under one inert atmosphere, such as nitrogen, are heated at the reflux temperature of the reaction mixture.

The compounds of the general formula (I), in which Z and R ^ is alkoxy, aryloxy or NR ^ R, can furthermore thereby be found that a compound of the general formula (IX)

where Ar, X ¹ , X ² , R ¹ and ^ ² _g <äy.jg ^ ej ^ have a defined meaning

~ at "

ben and Y is a leaving group (such as halo, acyl, alkoxy, alkylthio, S ~, SH, sulphonyloxy or carbalkoxy) is reacted with a suitable active hydrogen-containing compound of general formula (X)

R ¹¹ -H (X),

11 S 6 5

wherein R is alkoxy, aryloxy or NR- ^ R and the radicals R and R have the meaning defined above.

In a particular embodiment, this process can be used to prepare compounds of the general formula (I) in which Z is a carbamoyl group, for which purpose a compound (IX) in which Y is -SR "and X is NR in which R is as defined above and R "is an alkyl group , treated with a suitably effective hydrogen-containing compound of the general formula (X) as defined above. The intermediates of the general formula (IX), wherein Y SR "and

2 4-
X is NR can be prepared from compounds of general formula (XI)

Ar-X ¹ -C- <I (XI),

NHR "

wherein Ar, X ¹ , R ¹ , R ² and R "have the meaning defined above.

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The compounds of the general formula (I), wherein Z C ^^^^ ^,

, 2 4 ^R

R ^ has the meaning defined above and X is NR, wherein R ^ has the meaning defined in the general formula (I), can also be prepared by reacting a compound of the general formula (II) as defined above with an imidoyl dihalide of the general formula (XII)

R ⁴ -NC (Hal) ₂ (XII),

wherein R ^ has the meaning defined in the general formula (I) and Hai is chlorine, bromine or iodine, whereby an intermediate of the general formula (IX), as defined above, where X ^ R-N and Y is Hai, which is then in a compound of the general formula (I) can be converted by the method described above.

The compounds of the general formula (I) can be isolated from the reaction mixture as the free base or in the form of an acid addition salt. The bases can be converted into their acid addition salts by known methods with the aid of the appropriate acid, and the salts of the compound can likewise be converted into the free bases or into other acid addition salts .

For use as a pesticide, the compounds of the general formula (I) can be presented in the form of their free bases or as their acid addition salts. Suitable salts of the general formula (I) include hydrohalide, sulfate, nitrate, phosphate, thiocyanate, acetate, propionate, stearate, naphthenate, perchlorate, benzoate, methanesulfonate , ethanesulfonate

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phonate, tosylate and benzenesulfonate acid addition salts.

The compounds of the general formula (I) can be used to control insects, ticks, mites and others Arthropods, including the wild and those ectoparasites of plants, mammals and birds and they can be used alone or together with an additive that takes the form of one or more carriers can have, as they are customary in formulations, such as wetting agents, diluents or extenders, stabilizers, Thickeners, emulsifiers, dispersants or surfactants, or other standard carrier ingredients.

A formulation can be an aqueous solution of an acid addition salt a compound aar general formula (I) or it can be a suspension of a compound of the general formula (I) in water and it can be used alone or together be applied with suitable surfactants. The formulation as such can be used alone or diluted in water can be used to apply them to the pests or their immediate environment by spraying or dipping.

A formulation can be in the form of a miscible oil which contains a compound of the general formula (I) in the form of it free base or with an equimolar amount of a suitable organic acid such as oleic or naphthenic acid, whereby a salt is obtained that is in organic solvents

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is soluble and when using emulsifiers can be applied as an emulsion by spraying or dipping.

A formulation can be a non-aqueous solution or suspension of a compound of general formula (I) in a suitable Organic solvents for immediate use by means of the "pour-on" method. A formulation can also be in the form of a wettable powder for dilution with water and applied by dipping or spraying will. Other solid formulations can also be used immediately without dilution as a dusting agent, powder and granules can be used.

Another formulation may be in the form of a paste, a fat or a gel, which is a compound of the general Formula (I) and a suitable carrier and it can be infected by spreading the formulation Area to be applied.

An acid addition salt or the base of a compound of the general formula (I) is preferably in a pest control formulation in an amount between 5 and 80 #, calculated on the weight of the base, present and particularly preferred Formulations contain about 20Ji, calculated according to the Weight of the base. The concentration of a compound of the general formula (I), which is in the pests or their immediate Environment applied can be in the range of 0.001 to 20 # calculated from the weight of the base.

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-vr-

From the above, it can be seen that the present invention mainly and not exclusively includes the following items, namely, for example

(a) a novel substituted phenoxyalkyl or aniline alkyl imidazoline compound of the general formula (I) and its acid addition salts,

(b) a process for the preparation of this compound of the general Formula (I) and its acid addition salts,

(c) a method for controlling arthropod pests, in particular members of the order Acarina, for which purpose one is given to the pest or in the vicinity of the pest Compound of general formula (I) applies,

(d) a pest control formulation that includes a compound of the general formula (I) and a carrier suitable therefor and

(e) a process for the preparation of a formulation comprising a mixture of a carrier and a compound of the general Formula (I) includes.

The following examples serve exclusively to illustrate the invention without restricting the scope of the invention.

example 1

Production of 2- (2,3-dimethylphenoxymethyl) -1-acetyl-2-imidazoline

A solution of acetic anhydride (3.0 ml, 0.032 mol) in diethyl ether (10 ml) are added dropwise over 10 minutes

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- ie -

with stirring to a suspension of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (6.12 g, 0.030 mol) (prepared from 0-ethyl-2,3-dimethylphenoxyacetimidate and ethylenediarain) in diethyl ether (100 ml), whereby the Mixture cools to keep its temperature below 20 ° C. After stirring for 2 hours fil "trated to the reaction mixture and recrystallize the precipitate from acetone to give white crystals of 2- (2,3-dimethylphenoxymethyl) -1-acetyl-2-imidazoline, mp receives up to 130 ⁰ C.

Analysis: Calculated: % 68.27 C, 7.37 H, 11.37 N Found: # 68.13 C, 7.44-H, 11.13 N.

Example 2

2- (2,3-Dimethylphenoxymethyl) -1-N.N-dimeth.ylthiocarbamoyl-2-imidazoline

A solution of dimethylthiocarbamoyl chloride (2.47 g, 0.020 mol) in chloroform (10 ml) is added dropwise over 10 minutes with stirring to a solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (4.08 g, 0.020 mol ), prepared as in Example 1, and triethylamine (2.0 g, 0.20 mol) in chloroform (50 ml) , with cooling to keep the reaction below 5 ° C. The reaction temperature is then allowed to rise to room temperature and the reaction mixture is finally refluxed for 5 hours. After cooling, the reaction mixture is washed with water, dried and evaporated. The residue is crystallized from Ieopropanol to and white crystals of 2- (2,3-Di methylphenoxymethyl) -1- (N, N-dimethylthiocarbamoyl) -2-imidaz olin, Melting point: 124-127 ⁰ C.

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Analysis: Calculated % C 61.84, H 7.27, N 14.42 Found % -. C 62.15, H 7.64, N 14.35

Example 3 2- (2,3-Dimethylphenoxymethyl) -1- (N-methylthiocarbamoyl) -2- imidazoline

A solution of methyl isothiocyanate (1.46 g, 0.20 mol) in chloroform (10 ml) is added dropwise over 10 minutes with stirring to a solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (4.08 g, 0.020 mol), prepared as in Example 1, in chloroform (50 ml), with cooling to keep the reaction below 5 ° C. The reaction mixture is then allowed to warm to room temperature and is finally refluxed for 5 hours. The chloroform is then evaporated off under vacuum, the residue is recrystallized from isopropanol and white crystals of 2- (2,3-dimethylphenoxymethyl) -1-N-methylthiocarbamoyl-2-imidazoline, melting point approx. 100 ^° C., with disintegration are obtained.

Ij ₁ -KMR (deuterochloroform - tetramethylsilane internal standard):

8.1-8.3 Å 1H wide singlets
6.8-7.2 i 3H multiplets

5.0 £ 2H Singlet The KMR spectrum corresponds

the proposed structure 3.6-4.5 6 4H multiplet

3.1 ί 3Η doublet

2.2 $ 6H doublet

Example 4

1-N-phen. yicarbamoyl-2- (2.3-dimethylaniline methyl) -2-imidazoline 2- (2.3-dimethylaniline methyl) -2-imidazoline (4.20 g, 0.024 mol)

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The mixture is stirred in methylene chloride (90 ml), cooled to ⁰ ° C. and a solution of phenyl isocyanate (2.84 g, 0.024 mol) in methylene chloride (10 ml) is then added dropwise. A white precipitate forms quickly. ^{Stirring is continued at 0 0} G for 2 to hours after the addition and then allowed to react. Ions to reach room temperature while stirring is continued overnight. The reaction mixture is then evaporated to dryness under reduced pressure, thus obtaining a solid residue which is recrystallized from propan-2-ol to give white crystals of 1-N-phenylcarbamoyl-2- (2,3-dimethylanilinemethyl) -2- imidazoline (0.735H2O) »melting point 137 ° C.

example 5

1-H- (2,3-Dimethylphenoxycarbonyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline

2- (2,3-Dimethylphenoxymethyl) -2-imidazoline (3.0 g, 0.0147 mol) is dissolved in dry chloroform (*> 40 ml) and cooled to ⁰ ° C. Tetramethylpiperidine (2.07 g » 0.0147 mol) in dry chloroform (w 7 nil) to the cooled stirred solution. Then 2,3-dimethylphenyl chloroformate (2.71 g, 0.0147 mol as a 30% w / v solution in benzene) is slowly added. A white precipitate forms and stirring is continued at ⁰ ° C. for 2 hours. The temperature of the reaction mixture is then allowed to rise to room temperature. Tetramethylpiperidin.Hydrochlorid is precipitated by adding dry acetone and removed by filtration. The piltrate is evaporated under reduced pressure

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and the white residue is recrystallized from propan-2-ol to give 1-N- (2,3-dimethylphenoxycarbonyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, m.p. 126-127 ⁰ C.

Examples 6 to 27

By procedures analogous to those described in Examples 1 to 5 above the following compounds of Examples 6 to 27 can also be prepared.

Example 6

1-N-methyloxycarbonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, Melting point 120 ° C.

Example 7

1-N-methylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, Melting point 147-15O ° C (decomposition).

Example 8

1-N-phenylthiocarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp .102-104 ⁰ C.

Example 9

1-N-4-toluenesulfonylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 120 ^° C.

Example 10
1-N- (ot-naphthyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-

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imidazoline, m.p. 156-158 ° C.

Example 11

1_N- (4-chlorophenyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, Melting point 132 ° C.

Example 12

1-N- (4-cyanophenyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) ■ 2-imidazoline, m.p. 172-174-oc.

Example 13

1-N-Phenylcarbamoyl-2-phenoxymethyl-2-imidazoline, melting point 170 ° C.

example

1-N.N-Diphenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, Melting point

Example 15

1-N-p-tolylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, Melting point 137 ° C

Example 16

iN-phenylcarbamoyl-2- (ei-phenyloxyäthyl) -2-imidaz olin, mp 159 ⁰ C.

Example 17

1-N - («- Naphthyl) -carbamoyl-2-phenoxymethyl-2-imidazoline,

Melting point 160-163 ° C.

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Example 18

1_ii_C _i yclohexylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 63 ⁰ C

Example 19

1-N-phenylcarbamoyl-2- (2-chloroaniline methyl) -2-imidaz olin, mp 169 ⁰ C.

Example 20

1- (N-phenyl-N-methyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 112 ⁰ C.

Example 21

1-N-phenylcarbamoyl-2- ( "" - dimethylphenoxymethyl) -2-imidazoline, mp 81-85 ⁰ C.

Example 22

1-N-hexadecylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 76-77 ⁰ C.

Example 23

1-N- (o (-naphthyl) carbamoyl-2- (3-methylaniline methyl) -2-imidazoline, mp 146 ⁰ C.

Example 24

1-N-phenylcarbamoyl-2- (2-chloroaniline methyl) -2-imidazoline, m.p. 168-169 ⁰ C.

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Example 25

1_Ν- (2.6-dimethylphenyl) -carbamoyl-2- (2.3-dimethylphenoxymethyl) -2-imidazoline perchlorate salt, Melting point 221-222 ° C.

Example 26

1_N_ (2.3-dichlorophenyl) -carbamoyl-2- (2.3-dimethylphenoxymethyl) -2-imidazoline, melting point 175-18O ⁰ C.

Example 27

1-N-phenylcarbamoyl-2- (3-methoxyphenoxymethyl) -2-imidazoline, Melting point

Example 28

Preparation of 1-methanesulfonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline

2- (2,3-Dimethylphenoxymethyl) -2-imidazoline (8.0 g, 0.0392 mol) in dry ether (75 ml) and sufficient dry chloroform (50 ml) and cool the solution in ice (whereby sufficient chloroform is used to avoid precipitation of the imidazoline on cooling). Methanesulfonyl chloride is added (4.50 g, 0.0393 mol) dropwise to the cold, stirred solution. When the addition is complete, give Pentamethylpiperidine (6.08 g, 0.0392 mol) was added and the reaction mixture was refluxed until thin layer chromatography (tlc) shows that the reaction has ended (about 3 hours). The reaction mixture is then concentrated under reduced pressure Pressure and extract the residue with a water / chloroform mixture (1: 1, about 100 ml). One washes the chloro-

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Form layer with water, dry over magnesium sulfate and evaporate under reduced pressure. This gives you one Residue which is recrystallized from isopropanol to form 1-methanesulfonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, Melting point

Example 29

Following a procedure obtained by analogy using the procedure of Example 28, 1-benzenesulfonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, m.p. 108-110 ⁰ C.

Example 30 Production of 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxy-

methyl) -2-imidazoline

(A) The mixture is cooled, a solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (20.4 g, 1.0 mole) in methylene chloride (300 ml) at -65 ⁰ C and a solution of phenyl isocyanate (11, 9 6 »1.0 mol) in methylene chloride (300 ml) was added dropwise over 30 minutes. The reaction mixture is then allowed to warm to room temperature and is allowed to stand for 2 hours until a precipitate has formed. The reaction mixture is evaporated under reduced pressure and the residue crystallized from acetone to and receives 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, m.p. 150-152 ⁰ C.

(B) Method via the N-chlorocarbamoyl adduct of 2- (2.3-di-

yi J - ^ - i midazolin

A 17 # solution of phosgene in toluene (3.2 g, er-

809825/0991

- Φ-

holds 0.5521 g, 0.00549 mol GOCl ₂ ) in dry chloroform (15 ml) slowly with stirring at ⁰ ° C to a solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (2.40 g, 0, 0115 mol) in dry chloroform (20 ml). After the addition has ended, the reaction mixture is left to stand for 2 hours at room temperature, diluted with an equal volume of dry diethyl ether and quickly filtered. The filtrate, which contains the N. chlorocarbamoyl adduct of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline, treated mannitol of freshly distilled dry aniline (0.664 g, 0.00714 mol) and allowed the reaction mixture to stand at room temperature overnight, followed by thin layer chromatography shows that the main compound is the desired product. The mixture is evaporated to dryness under vacuum and the residue is taken up in a mixture of aqueous sodium carbonate and dichloromethane. The organic layer is washed with water, dried over magnesium sulfate and evaporated to dryness to give a residue which is purified as described under (A), whereby 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2- imidazoline, which corresponds to that contained in (A).

Example 31

Filled female ticks of the Biarra strain of Boophilus microplus are dipped in groups of 20 ticks per concentration to a range of various dilutions of the compound under test. The laundry is provided immediately before the experiment in such a way that the compound under experiment is diluted (with water). the

809825/0991

Ingredients can be in the form of miscible oil or wettable powder formulations. The desired ones are obtained Concentration ranges for investigation through further dilution of the batch solution or batch washing.

The ticks are removed from the laundry after 10 minutes, dried and attached dorsally by means of double-sided adhesive tape. They remain in this position for 14 days and then the number of animals that lay viable eggs is determined. A biological regression line is determined from these values (by plotting the concentration versus the % inhibition of egg production) and the IR90 and IR99 (ie the concentrations at which egg production is inhibited by 90 # and 99 $, respectively) are determined.

The results obtained are shown in Table I below specified.

Table I.

Connection m * ^f IR90 IR99

1-N-phenylcarbamoyl-2- (2.3-

dimethylphenoxymethyl) ~ 2- 30 <0.016 #

imidazoline

1-N- (oc-naphthyl) -carbamoyl-2-

(2,3-dimethylphenoxymethyl) - 10 $ 0.0032 2-imidazoline

i-N-Phenylcarbamoyl-2-phenoxymethyl-2-imidazoline 13 <0.2 #

809825/0991

33

Example 32

Test compounds are formulated in polyethylene glycol and uses it to inject ticks at a point immediately anterior to the trunk part. After 14 days, the percentage is determined Egg production inhibition (IR). The results are given in Table II below.

Table II

link

example
No.

IR

1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline

i-N-Phenylcarbamoyl-2-phenoxymethyl-2-imidazoline

1-N-Phenyicarbamoyl-2- (2,3-dimethylani1inmethy1) -2-imidaz oil

1-N - («- Naphthyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoeline

1-N.N-Diphenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline

1-N- (4-chlorophenyl) -carbamoyl-2-

(2.3-d imethylphenoxymethyl) -2-imide az oil in

1-N- (4-toluenesulfonyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline

1-N- (4-tolyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2- imidazoline

1-N-methylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline

1-N- (c (-N aphthyl) -carbamoyl-2-phenoxymethyl-2-imidazoline

11

17th

at 0.1mg / ml 30 70516 at 1.0mg / ml 13 IOO515 at 10mg / ml

at 0.1mg / ml

10 405t at 0.1mg / ml

at 1.0mg / ml

at 0.1mg / ml

lOOjli at 1.0mg / ml

? at 0.1mg / ml 15 9OS6 at 1.0mg / ml

80 # at 1.0mg / ml

at 1.0mg / ml

The following formulations serve to explain in

809825/0991

how the pesticidal compounds of the invention are used in pests or their environments that affect the pest sets can be applied.

Formulation 1 dust powder, active ingredient talc

1.0 20.0 parts by weight

99.0 80.0 "100.0 100.0

Formulation 2 wettable powder

Active ingredient 25.0 parts by weight Sodium dioctyl sulfosuccinate 1.0 Dispersol ACA 2.0 » kaolin 72.0 " 100.0 Formulation J Aqueous dispersion Active ingredient 20.0 parts by weight Keltrol 0.4 " Sodium dioctyl sulfosuccinate 0.5 water 79.1 100.0

Formulation 4 pour-on
Active ingredient

5.0 parts by weight

809825/0991

Dimethylformamide castor oil

85.0 parts by weight

10.0 ^M 100.0

Formulation; fat

Active ingredient Petrol Jelly 6.0 parts by weight

94.0 "100.0

Formulation Miscible oil Compound of example Aroma oil H Nonylphenol ethoxylate 10.0 parts by weight 70.0 "

20.0 " 100.0

-Pat compliant-

809825/0991

Claims (22)

? a t e η ·; a r. s ρ r 'C h f \ 'l / compound of general formula (I) ,1 Ar-X ¹ -C - <r I (D, wherein Ar is unsubstituted or mono-, di- or trisubstituted Phenyl radical in which the substituents are identical or different and are alkyl, alkoxy, halogen, hydroxy, cyano, Are amino, trifluoromethyl or nitro groups and in which two adjacent carbon atoms on the phenyl ring are optional by a carbon chain with 3 or 4 carbon atoms can be connected X ^{1 is} 0 or NH, 1 2
the radicals R and R, identical or different, and hydrogen or alkyl and _o Q ^ p Λ. ρ Z is a group SO R or a group -C ■ , wherein X Is 0, S or NR ^, R ⁵ alkyl, aryl, alkyloxy, aryloxy or NR ⁵ R ⁶ , R alkyl, aryl, alkyloxy, aryloxy, alkylthio, arylthio or NR ^{5 is} R ⁶ , the radicals R ⁵ and R ^6, identical or different, and hydrogen, Alkyl, aryl, COR? or SO ₂ R? are, W alkyl, aryl, alkyloxy or aryloxy, η * 1 or 2, R ^{8 is} alkyl, aryl, or NR ⁹ R ¹⁰ and 809823/0991 -ί- the radicals R ° and R, identical or different, and hydrogen, Are alkyl or aryl, with the proviso that when Ar is an unsubstituted phenyl radical is, the radicals R ¹ and R ^{2 are} hydrogen, X NH, Z - ( and X 0 and R ^{3 is} not methyl,
or their acid addition salts. 2. A compound according to claim 1, characterized in that Ar is an unsubstituted or phenyl substituted phenyl radical with one or more substituents which are identical or different and alkyl or halogen are. 3. A compound according to any one of claims 1 or 2, characterized in that Ar is a substituted one Phenyl radical with one or more substituents, which are identical or different and are alkyl or halogen. 4. A compound according to any one of claims 1 to 3 »characterized in that Ar is a substituted one Is phenyl in which the substituents are methyl and / or chlorine. 5 · compound according to any of the preceding claims, characterized in that Ar is a Disub stituted phenyl. U098 2b / 0991 _ , _e.g. 27 ^ 6639 6. A compound according to any one of the preceding claims, characterized in that Ar 2,3-dimethylphenyl is. 7. A compound according to any one of the preceding claims, characterized in that Z is a group -C -χ where Jr and R ^p are as defined in claim 1 have meaning. 8. A compound according to any one of claims 1 to 7 »characterized in that Z is a group -C c- c, wherein the radicals R ^y and R are those in claim 1 ^ V ⁵ have a defined meaning. 9. A compound according to any one of claims 1 to 7 »d a, characterized in that Z -C is, in which the radicals R- ⁷ and R have the meaning defined in claim Λ. 10. A compound according to claim 8 or 9 »characterized in that Br is hydrogen and R is aryl. 11. A compound according to claim 10, characterized in that R
Is cyanophenyl or «-naphthyl. indicates that R is phenyl, 4-chlorophenyl, 4- 12. 1-N-Phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2- 809825/0931 imidazoline or its acid addition salt. 13. 1 -N- (οί-naphthyl) -car bamoyl-2- (2,3-dimethylphenoxymethyl) 2-iraidazoline or its acid addition salt. 14. 1-N- (4-chlorophenyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl ) -2-imidaz ol in or its acid addition salt. 15. 1-N- (4-Cyanophenyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-iraidazoline or its acid addition salt. 16. A process for the preparation of a compound of the general formula (I) according to Claim 1 or its addition salt, characterized in that one (a) a compound of the general formula (II) ί · " : -X ² -i .-O Ar-X ^c -Ö- ^ I (II), 11 2 wherein Ar, X, R and R. have the meaning defined in claim 1 with an isocyanate, isothiocyanate, ketene, carbodiimide or a compound ZX ¹ , in which Z has the meaning defined in claim 1 and X ^{1 is} a leaving group , (b) a compound of the general formula (V) 80982B / 0991 R ¹ Ar-X'-C-Q (V), I ² wherein Ar, X, R and R have the meaning defined in claim Λ and Q is a carboxyl group or a reactive derivative thereof, with an ethylenediamine of the general formula (IV) H ₀ N.CH ₀ CH ₀ .NHZ (IV), wherein Z has the meaning defined in claim 1, converts (c) a compound of the general formula (VI) Ar-X'-C-C '(VI), _R 2 ^ NCH ₂ CH ₂ NH ₂ Z Λ Λ Ο wherein Ar, X, R, R and Z have the meaning defined in claim 1 and W is oxygen or sulfur, cyclizes, (d) a compound of the general formula (VII) or an N- or O-metal salt thereof Ar-X ¹ -H (VII), wherein Ar and X have the meaning defined in claim 1, with a compound of the general formula (VIII) 80d825 / O9S1 (VIII), Ί 2 wherein R, R and Z have the meaning defined in claim 1 and V is a leaving group derived from a suitable inorganic or organic acid or (c) when Z in formula (I) -G 3, and R ^ alkoxy, aryloxy or ^^ R
NR ^ R is a compound of the general formula (IX) (IX), 12 1 2
wherein Ar, X, X, R ¹ and R have the meaning defined in the formula (I) and Y is a leaving group, with a compound of the general formula (X) R "-H (X), wherein R "is alkoxy, aryloxy or NR ^ R ⁶ , in which R ^ and R ^{6 have} the meaning defined in claim 1. 17. The method according to claim 16 (a), characterized in that the reaction in Vasser or 809825/0991 carried out in an organic solvent 18. The method according to any one of claims I6 (a) or 17, characterized in that the reaction effected in the presence of a base, namely an alkali metal hydroxide, an alkali metal carbonate and / or a tertiary organic base. 19. The method according to claim I6 (b), characterized that a compound is used in which Q in the general formula (V) is an imidate, ortho-ester, Thioimidate, imidohalide, ester, amidine, thioamide, nitrile, carboxyalkylthioamide and / or a carboxyl group. 20. The method according to claim 16 (c), characterized that one uses a compound of the general formula (VI) which is obtained from a compound of the general formula (V) as defined in claim 16 (b). 21. The method according to claim 16 (d), characterized in that a compound of the general Formula (VIII) is used, in which V is chlorine, iodine, bromine, alkylsulfonyloxy and / or arylsulfonyloxy. 22. The method according to claim 16 (e), characterized that a compound of the general formula (IX) is used in which Y is halogen, acyl, alkoxy, 809825/0991 27B6577 amine, sec-dutylamine, n-amylamine, isoamylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, undecylamine, Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, Ilethylisopropylamine, methylhexylamine, methylnonylamine, Methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyl octylamine, hexylheptylamine, hexyloctylamine, Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, Di-n-amylamine, diisoamylamine, dihexylamine, Di-heptylamine, dioctylamine, trimethylamine, triethylamine, Tri-n-propylamine, triisoj) ropylamine, tri-n-butylamine, triisobutylamine, Tri-sec.-butylamine, tri-n-amylamine, ethanolamine, n-propanolamine, isopropanolamine, diethanolamine, N, N-diethy] ethanolamine, N-ethylpropanolamine, N-dutylethanolamine, Allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-Diniethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, and propylenediamine, primary arylamines such as aniline, methoxyaniline, ethoxyaniline, o, m, p-toluidine, plienylenediamine, 2,4,6-tribromaniline, benzidine, naphthylamine, o, m, p-chloroaniline, and the like; heterocyclic amines such as pyridine, morpholine, piperidine, pyrrolidine, indoline, azepine and the like. In the aqueous reaction system described above, the submitted reactants initially form the honor and disalts of N-phosphonomethyliminodiacetic acid (dependent of the stoichiometry), and these salts are then, as - / 6 80982B / 0981 -S- 2 / 5S577 they arise, oxidized to N-phosphonomethylglycine salts, as indicated below for the disodium salt or the monoethylamine salt. Disodium salt of N-Phosphonomethy! Glyci n CH ₂ COOH CH ₂ OOOH O ₂ CH ₂ OOONa 0 I /> ° catalyst! I / water I ff water A N-CH ₂ P-OH + 2 NaOH >> N-CH ₃ P-OH> NH + CH ₂ O + CO. OH X3Na CH ₂ COOH CH ₂ COONa Monoethylamine salt of N-phosphonomethylgylein CH ^ OOOH CH ₂ OOOH O ₂ £> catalyst water water N-CH ₂ P-OH + CH ₃ CH ₂ NH ₂ > N-CH ₂ P-OH> e
CH., CH ₂ COOH CH ₂ COOH CH ₂ COOH NH + CH-O + CO ₀ I / CH ₀ P-OH Ό CH ₃ CH ₂ NH ₃ - / 7 809825/0981 / - 275G677 As used herein, "molecular oxygen-containing gas" means any gas containing molecular oxygen, with or without a diluent, which does not react with the oxygen or the reactant or product under the reaction conditions. Such gases are, for example, air, oxygen, oxygen diluted with helium, argon, nitrogen or another inert gas, oxygen-hydrocarbon mixtures and the like. Preferably gases with 20 and more% by weight of molecular oxygen, even better gases with 90 and more% by weight of molecular oxygen, are used. Of course, if gases containing molecular oxygen and other inert gases are used, the pressure must be increased so that an adequate partial pressure of oxygen and hence a sufficient rate of reaction are maintained in the system. The amount of molecular oxygen-containing gas used can vary widely. However, it is obvious that the best yield of N-phosphonomethylglycine salts is obtained when at least stoichiometric amounts of oxygen be used. For a good reaction and the best yields, this should normally be the case in most cases an amount of oxygen of at least 1/2 mole of oxygen used per 1 mol of N-phosphonomethyliminodiacetic acid salt will. In practice, however, the amount of oxygen used is 1/2 to 1 or more moles per each mole 809825/0981 " ^{/ 8} - * - 2 7 bü b V N-Phosphonomethyliminodiacetic acid salt, since the efficiency the oxygen usage is usually less than 100%. The aqueous solution of the iminodiacetic acid salt can be mixed with the molecular oxygen-containing gas and the activated carbon can be brought into contact in very different ways. So the solution can e.g. in a closed container, which contains molecular oxygen in a space left free, given and shaken vigorously or ge be stirred, or the molecular oxygen-containing gas can either through the solution containing the activated carbon be blown through a straight pipe or a pipe provided with a distribution frit. Contact can also take place in a tubular, continuous reaction vessel which is filled with activated carbon. In the invention Process must therefore above all the gas containing the molecular oxygen actively with the aqueous solution of the N-phosphonomethyliminodiacetic acid salt, which is the activated carbon catalyst contains, be brought into contact. If only an aqueous solution of the iminodiacetic acid salt is left, contains the activated carbon, standing in the air under suitable conditions, then one obtains, as for the It is readily apparent to those skilled in the art that a certain, but very small, amount of the desired product is present. - / 9 809826/0981