New 2 (nitromethylene) - 1,3-diazacycloalcanes, insecticidal compositions the container and their use to fight against undesirable insects.

The present invention relates to novel 2 - (nitromethylene), 1.3 and diazacycloalkanes, insecticidal compositions containing them and their use for combating unwanted insects.

The invention provides compounds of the formula

(HAS)

wherein n is 2, 3 or 4j R is an alkyl group, halogénoslcoyle, alkoxyalkyl, époxyalcoyle, alcoylthioalcoyle, alcanoyloxyalcoyle, alkenyl, haloalkenyl, alkynyl, hydroxyl, alkoxy, alkylamino, dialkylamino or single - or halogen,

R is hydrogen, halogen or nitro group

%

or alkyl, R is an alkyl group and m is 0 or 1.

It should be noted that the compounds represented by (has) also include the various hybrid resonance, geometric and tautomlres as well as mixtures thereof. For example, a of®, possible shapes comprises the resonance hybrid represented by the formula (d)

The form (has) may be referred to as a 2 - (nitromethylene) - 1.3 and trees, ' the form (β) may be called a hydroxide inner salt 2 - (ICR-nitromethyl) - 1.3 and diazacycloalcanolium and shape (C.) may be referred to as a 2 - (nitromethyl)

- 1.3-diaza 2 a-cycloalkene.

The hybrid resonance may exist in the form of two geometrical isomers, depending on the spatial relationship portions about the bond between the carbon atom of the portion Nitromethylene and the carbon atom of the ring to which it is connected.

To simplify, the compounds of the present invention will be generally termed 2 - (nitromethylene) - 1.3 and diazaccloalcane. This expression is to be understood as including all structures participating in the hybrid resonance, geometric and tautomers, as well as mixtures thereof.

The tautomeric derivatives (C.) in which hydrogen of the alpha position is replaced, for example, by a halogen or an alkyl group are also included in the framework of the present invention.

In any case, each alkyl group, alkenyl, alkynyl or alkylene contains not more than eight carbon atoms, or preferably not more than six, each can be configured to be straight chain or branched chain, unless otherwise specified.

Is particularly interesting, the subclass of such compound wherein n=2.3 or 4, where R " is an alkyl group * ^ - ^ c, alkenyl, haloalkenyl or alkynyl, is hydrogen or halogen (preferably Cl or brr)

and m=0. And among these, the highest activity is the visual level -

-|

an overarching 3 or those in which n=2, R is. a methyl group,

w 2-propenyl, 3-chloro 2-propenyl or 2-propynyl and R is hydrogen..

The compounds of the invention may be prepared by the following methods:

METHOD - HAS - Processing a substituted dimethyl nitrocexene mercaptole (NKDM) with a diamine, there - from correspondingly substituted diamines (according to the definition of R and R * ' (R Gompper and H. Schaefer-, Berichte, 100, 591 (1967)).

METHOD - 3 - Substitution of a fragment on the fonctionm=NH - 2 - (nitromethylene) a - 1.3-a diazacycloalkane (NîiDCA); a process for preparing the latter type of compound is described in the article of Gompper and Schaefer-, hereinafter of -

PRCCBDE - - C. Reaction of trichloronitroethylene (TCNE) (gg.b, Bachmann and other, J 92. Mal, 25, 1312 (i960); Patent no. 3.054.828 E.U.A.) with a diamine, including correspondingly substituted diamines,

METHOD - - D. Direct halogenation of compounds prepared by any of the above methods.

In the process - has -, the reaction is carried out by mixing the body reaction in a suitable solvent at moderately elevated temperatures under anhydrous conditions. Suitably, the reaction may be carried out between about 50 °c to about 100 °c. Often, it can be convenient to conduct the reaction at reflux temperature. Solvents that can be used are lower alkanols, in particular ethanol or isopropyl alcohol. In some cases, it will be advantageous to use an excess low (5 - 10%) to moderate (50 - 75%) in reaction of the diamine. The diamines unsubstituted and appropriately are generally materials known.

In the process - and b -, n-substitution is suitably conducted by introducing the trees (MDCA), prepared by the process quipeut - - has, in an anhydrous mixture, cold of a dispersion of sodium hydride in oil and at dimethylformamide as solvent in an inert atmosphere and then treating the resulting mixture (containing the derivative-sodium of the NMDCA) with a halide of the fragment to substitute, the reaction is general for the alkylating agent. Conveniently, the addition of 1' halide is conducted at a temperature less than about 10 °c, particularly at the temperature of an ice bath. It will be advantageous in many cases, to use a slight excess (5 a-25c/O-) sodium hydride and an excess low (5 a-10c/O-) to moderate (50 - 75/0 of 1' halide.

In the process c, TCNE is introduced into a stirred mixture of the diamine and sodium carbonate in a suitable solvent, at a temperature less than about 15 °c, then the mixture is stirred without cooling it. Usable solvents are lower alkanols, in particular methanol.

Conveniently, used equivalent amounts of TCLS and sodium carbonate, these being excess low (5 - 10^to moderate (20 a-30c/O-) relative to the diamine. The diamines unsubstituted and so are adapted générâlement materials known.

The d-d - ^ - in the method, a solution of the heterocyclic compound, optionally containing a acceptear acid, in a suitable solvent, e.g. water, is processed by the halogen to replace the atom or two hydrogen atoms in the alpha position on the portion Nitromethylene (or nitrométhyle). The reaction may be conducted at room temperature or at a temperature somewhat higher (e.g. 15 and 45°)" the number of halogen atoms which are introduced depends on the AC -

2/⁰

the R racterede (r=h only if two halogen atoms may êxre introduced easily) and in part on the amount of halogen and/or acid acceptor used, relatively more used halogen, more substitution is strong. In some cases, the product is sufficiently non-basicue character does not form a salt with the halide acid formed as a by-product. In these cases, the desired product can be collected by subjecting the reaction mixture to extraction using an appropriate solvent insoluble in water and evaporating the solvent. Solvents usable are of alkanes, as methyl chloride nene.quand the product forms the salt, the product can be collected by treating the reaction mixture with a base, such as sodium bicarbonate, to release the product, and the thereafter obtaining by solvent extraction of the aqueous mixture with an alkane halogen.

The techniques for collecting and purifying the compositions from the mixture, the final crude reaction are conventional and are illustrated in the examples hereinafter.

The above methods of preparing the compounds of the invention are illustrated in the exeirr next the preparation of particular species of the compounds of the present invention. In all cases, the identity of the product was confirmed by elemental analyses and by analyses of the infrared spectrum of the nuclear magnetic resonance spectrum.

SUCH AS I - Method has 1 - methyl 2 - (nitromethylene) - the IRR idazolidine.nor

A mixture of 16, 52g NKDM, 8, 14g of m-methyl -

5■

ethylènediamine and 200 cm of absolute ethanol is heated at reflux for 1.5 hour. The mixture is then cooled and the reddish-brown crystalline product formed is separated by filtration. 6, 3G a portion of the product is recrystallized from ethanol (charcoal) to give 4, 8g of 1 _, in the form of white needles, melting point 142.5 - 143.5 °c.

SUCH AS II - Method has, hexahydro 1-methyl 2-nitrate methylene) (2) pyrimidine derivatives •

A mixture of 8, 2g of NKDK, ' of 7₅ 3g of xUrméthyl L_F. 3 a-propanediamine and of 100 cm. ^ of absolute ethanol is heated at reflux for 1 hour -. Then the mixture is cooled, 2 of 4, 9g precipitating in the form of crystals of tan color, melting point 114 and 115 degrees Celsius.

SUCH AS III - Process b, 2 - (nitromethylene) - L-- (2 a-propynyl) - - Inductor

dazolidine.

Z

A mixture frozen anhy - 50 cm of dimethylformamide

as DRE and a dispersion 1, 77g 57% by weight of sodium hydride in mineral oil -, maintained under nitrogen atmosphere, is treated with 5, 16g of 2 - imidazolin - (nitromethylene). After shaking for 1 hour, 7, 97g added propargyl bromide. The mixture is stirred 10 °c for one hour additional, y Fe2 allowed heated to ambient temperature. and then you're ODBC 400 cm. ^ of saturated aqueous solution of sodium sulfate. The goods are processed by extraction with three portions of 300 cm of methylene chloride. The combined extract is dried with magnesium sulfate and the solvent is evaporated. The addition of ether to the residual oil gives a solid material that is récris tallized~from chloroform (charcoal) to give 3, 1g of 3, in the form of crystals of tan color, melting point 146 and 147 degrees Celsius.

ZXZhPLS VI - Process b, 2 - - 1 - (nitromethvlene) (2 a-propenyl) - imidazolidine derivatives (4)

With 1.77 g of a dispersion to 57% by weight of hydride

3

sodium in oil in 50 cm of anhydrous dimethylformamide, is added 5, 16g of 2 - (nitromethylene) imidazoline derivatives. The mixture is cooled with an ice bath, and stirred and the scus maintains an atmosphere of nitrogen. After 1.5 hour, 5, 08g added allyl bromide. The mixture is stirred for about an additional neure 10 °c, then allowed to warm up to room temperature and poured into 400 cm. ^ of saturated aqueous solution of sodium sulfate. 4,_I resulting mixture is treated

3

by extracting twice with 300 cm portions of methylene chloride. The combined extract is dried (magnesium sulfate) and the solvent evaporated. The addition of ether to give a solid residue oil, which by recrystallization from chloroform (charcoal) gives 2_} 1g of 4 in the form of crystals of tan color, melting point 97 and 98 degrees Celsius.

ZXShPLS therein - E, hexahydro 1-methyl 2 a-nitrome~hylene) - 1h-a 1, 3-diazepine (5)

By the procedure of the process, the reaction of NKDr '. with the 1.4-to-diaminobutane gave 1 'hexahydro-a 2 - (nitromé -

thylene) - 1h-to-1.3-diazepine, melting point 152 and 154°. 3, 14g of this

3

compound in 25 cm of anhydrous dimethylformamide are treated with 0, 884g dispersion to 57% in ' weight of sodium hydride in oil and then with 2, 98g methyl iodide. L_{in ES} experimental conditions and processing operations are similar to those of examples III and IV. The recrystallization of the crude product from inéthanol gives 0, 8g of 5 in the form of a solid color of tan, melting point 88 and 89 °, ZX27.? VI - Process c, 2 - (chloronitromethylene) - (6) 1-methylimidazolidine

Has a cooled mix (10 and 15 degrees Celsius) and stirred 3, 6g of X-méthyléthylénediamine 8, 3g and potassium carbonate in 50 cm of methanol, is added slowly 9, 1g of TCME.

After urur.e hour, mixture is filtered. The solid obtained by evaporating the filtrate is recrystallized from ethanol to give 1, 5g of 6 melting point 145 and 146 °C with decomposition.

The other species the following compounds of the present invention were prepared by the method indicated.

ZXZ.-TO-.FLE VII. - 1 a-ethyl 2 - (nitromethylene) imidazolidlne (7)

Method has, by reacting NKDL with n-e-to-the Thyl-ethylenediamine. Melting point of 110 and 111° imposition.

ZXEXFLS VIII. - 2 - (rr.itrom ethylene) - 1 a-prooylimidazolidine (8)

Method has, by reacting NKDM with n-propyléthylènediamine, melting point 147 and 148 degrees Celsius.

THE EXE? CLP IX. - 1.4-dimethyl 2 - (nitromethylene) - and 1.5-dimethyl 2 -(nitromethylene) imidazoltdine, iso 4/1 mixturemother (9 _)

Process b, by reacting 4 a-méthvl-a 2 - (nitromethylene) - imidazoline derivatives with methyl iodide, melting point 100 and 102 degrees Celsius.

X-ZXEXPLE - Kexahydro-a 2 - (nitromethylene) - -1 (2 a-prooényl) (10) - pyrimldine

Process b, by reacting 1 'hexahydro-a 2 - (toto nitroir. ethylene) pyrimidin (HNMP), prepared by the method has by reacting NKDM with 1.3 to-propanediainine, with allyl bromide. Melting point 125 and 126°.

EXAMPLE XII - Hexahydro 2 - - 1 - (nitrométhylèns) (2 a-propynyl) - pyrimidine derivatives (11)

Process b, by reacting with HNKP of propargyl bromide. Melting point 157 and 15s °C.

EXAMPLE XII. - 1 - (3 chloro-2 a-propenyl) - 2 - (nitromethylene) - imidazolidine derivatives (12)

Process b, by reacting 2 - (nitromethylene)

- imidazolidine derivatives with 1.3-dichloro 1-propene. Melting point 134 and 135 degrees Celsius.

EXAMPLE XIII. - Method b - 1 - (2 chloro-2 a-propenyl) - 2 - (nitromethylene) imidazolidine derivatives(13)

Prepared the sodium salt of 2 - (nitromethylene) imidazolidine derivatives by treating a mixture of 1, 33g dispersion to 57% by weight of sodium hydride in oil - and 35 cm of dimethylformamide with 3,s7g of 2 - (nitromethylene) imidazolidine derivatives.

The resulting mixture is cooled to about 20 °c and stirred while adding dropwise 3, 47g of 2.3-dichloro 1-propene.

After 2 hours, the mixture is subjected to stripping under reduced pressure. The residue is slurried in methylene chloride and filtered. The solvent is evaporated from the IF ', Trat and the resultant crude solid product is recrystallized from ethanol to give 1 _ 3, in the form of crystals of tan color, melting point 146 and 147 degrees Celsius.

EXAMPLE-XIV - Process b - hexahydro 2 - (nitromethylene) - 1 - (2 a-propynyl) - 1h-to-1.3-to-diazéoine(14)

Is treated 'hexahydro 1 and 2 - (nitromethylene) - 1h-a 1, 3-diazepine with sodium hydride and the resulting salt is treated with of propargyl bromide according to the procedure in example XIII., the crude product is purified by dry column chromatography on silica gel, using a mixture of ethyl acetate, hexane and tetrahydrofuran (2:1: 2 by volume) as eluent, to obtain 1 _ 4, in the form of brown crystals, melting point 134 and 135 °,

EXAMPLE XV FRAMES - Method d 2 - (bromonitromethylene) - 1 a-méthvlimidazolidine (15)

An agitated solution of 3, 57g of 1-methyl 2 - (nitromethylene) imidazolidine derivatives (compound .1.) in 25 cm '* water is treated dropwise with 3, 99g bromine at room temperature. After 30 min, the reaction mixture is treated by extracting to methylene chloride. The extract is dried (MgSO ^) and solvent evaporated to give crude product 3, 0g, melting point 100 °c (with decomposition violent),

EXAMPLE XIV - Process d, 2 - (dibromonitrométhyl) - 1-methyl 1, 4, 5, 6 a-téxrahydropyrimidine(16)

7, 99G is added dropwise bromine to a ' - OS

3

lution agitated 7, 85g of compound 2' in 50 CNRs water.

Acre 30 min, the mixture is treated with 4, 2g sodium bicarbonate ' in 20 cm of water. The mixture is then processed by ' methylene chloride extraction. The extract is dried (KgSO ^) and solvent evaporated to give 1, 5g of J_ 6, melting point 1c6-to-107 °c.

EXAMPLE XVII PROPERTIES - Process d, 2 - (dibromonitrométhyl) - L-methyl-2 imidazoline (17)

In an agitated solution 7, 15g of _ 1 and 5, 3g sodium carbonate in 50 cm of water is treated at room temperature with 16 grams bromine. The temperature of the mixture rises to about 45 °c. After half an hour, the product is isolated by filtration. The recrystallization from methanol/water and drying under reduced pressure at room temperature gives 17, melting point 89 and 92°.

Other species of these compounds and methods by which they may be prepared are as follows:

1 - (2 a-chloroëtnyl) - - 2 - - (nitroraethylene)

imidazolinide, process b

- 1 - (methoxymethyl) - 2 - (nitromethylene) - '

imidazolidine derivatives, process b

1 - (methylthiomethyl) - 2 - (nitromethylene) - -

the imidazolidine, preceded b.

1 - (2 methoxyethyl) - 2 - (nitromethylene) - -

imidazolidine derivatives, method has

- 1 - (2 - (methylthio) ethyl) - 2 - (nitromexhylene) imidazolidine derivatives, method has

- 1 - (2.3 to-epoxypropyl) - 2 - (nitromé thylene) -

imidazolidine derivatives, process b

- 1 - (2 acrylamidomethylacetylacetone} - 2 - (nitromethylene) -

iicidazolidine, process b

- Hexahydro 2 - (nitromethylene) - -1 (2 a-propenyl) -

- 1H-to-1.3-diazepine derivatives, process b

- 1-chloro 2 - (nitromethylene ^ imidazolidine derivatives,

d

1-amino 2 - (nitromethylene) - imidazolidine derivatives

method has

1 - (dimethylamino) - 2 - (nitromethylene) - -

imidazolidine derivatives, method has

1 - (dimethylamino) - hexahydro 2 - (nitromethylene) pyrimidin, method has

- 1 methyl 2 - (1 a-nitroethylidene) imidazolidine derivatives,

method has

- Hexahydro 1-methyl 2 - (1 a-nitroethylidene) -

pyrimidine derivatives, method has

- 1 methyl 2 - (fluoronitromethylene) imidazolidine derivatives,

method has

2 - (chloronitroœethylene) - hexahydro 1-methyl -

pyrimidine derivatives, process d

The compounds of the invention exhibit insecticidal useful, being particularly useful for combating forms "crawler" or "worm" insect genus Heliothi, as The Zea H (track ears of corn, cotton bollworm, armyworm tomatoes) and H virescens (tobacco bud worm the AES), the genus AnAgrotis, as Has, Cutworm (worm black), the genus Trichoplusia, as T nor (track - cabbage looper moth) and genus Willwill soodootera, as The S. littoralis (track of film - ' the cotton). They are attractive also provides control aphids and whitefly greenhouses. Some are advantageous to domestic flies. In tests that have been conducted, they showed that little or nothing of toxicity to other insects, as rice weevil, red spider and mosquito larvae. Some acting very quickly, "boring" quickly insects in some cases, even if the compound is not very toxic to insects.

z-:: 5. - :? the XIII

The activity of compounds according to the invention in YES relates insects was determined by setting the dose the LC ^ Q-(in milligrams of compound tested by 100 cm of solvent in the solution or suspension of the compound tested used spray) for killing 50% experimental insects. The liquid vehicle is composed of 2 parts by weight of acetone, of 8 parts by volume of water and 0.05 part by weight of atlox 1045a, a wetting agent based polyoxyethylated sorbitol laurate. Insects experiment were the housefly, corncobs and the track, the track

5 cabbage looper moth, the worm black, the mosquito, the pea aphid rice weevil and spider red.

All compounds 1 to 9 _, dd ., there> 15 and Jo are inactive or slightly active on rice weevil, mites and mosquito larvae. With regard to the track corn cobs, the doses the LC ^ Q of all compounds j at 9, dd ., 12, Jj3 and j6 are less than 0.04. In the pea aphid, doses ^ j to the LC compounds j2, 15 and 16 are less than 0.01. The Sn for the housefly, doses CRA ^ Q of compounds j to j4 j6 and are less than 0.5. Has been⁷ enhances as the compounds j and 2 against the worm black and cabbage loopers, the doses the LC ^ respective Q being in any case lower ' has 0.04, we found also that the compounds 1 and 2 are very toxic to the crawler cotton sheets. In tests on cotton plants, the compound J has been effectively^W.ficace against the larvae of the worm-of the capsule and against the tobacco bud worm. It was also effective against whitefly greenhouses.

As indicated above, the present invention comprises in its general framework insecticidal compositions comprising an adjuvant, it is to say a vehicle, optionally a surfactant and, as active ingredient, at least one insecticide from ' the present invention. Similarly, the invention also includes a method of combating insect pests at a locus which comprises applying to the locus an effective amount of at least one insecticide.

The term "vehicle" as used herein denotes

a solid or fluid, which may be inorganic or organic and of synthetic or natural origin, with which the MOC -22 laid active is mixed or reacted composition for facilitating its application to the plant, to seeds, ground, or to another object to TR ' has' tert, or its storage, transportation or handling.

L-·.' tènsio-active agent in an emulsifying agent may be ouou.un dispersant or wetting agent, it can be non-ionic or ionic.

Any materials as well as surface-active agents typically used in the preparation of pesticides can be used in the compositions according to the invention, and described examples of suitable, by exemexem.le, in British Patent no. 1.232.930.

The compositions of the invention can be prepared in the form of wettable powders, of pouss: eras, granules, solutions, emulsifiable concentrates, emulsions of suspension concentrates or aerosols. encapsulées and compositions are controlled release compositions' are also contemplated, as well as compositions comprising a bait, wettable powders are usually composed in such a manner that it contieinent 25, 50 or 75% by weight of toxic and they usually contain, in addition to a solid 3 to 10% by weight of a dispersing agent and, when necessary, 0 to 10% by weight of one or more stabilizers and/or other additives such as penetration agents or adhesives. The dusts are typically made in the form of a concentrate in dust having a composition similar to that of unq ' wettable powder, but without a dispersant, and are diluted to the site of use with additional vehicle to yield a composition containing 0.5 to 10% usually by weight of toxic. The granules are usually prepared so that they will have a size of between 0,152 and 1,676 mm and may be produced by methods of agglomeration or impregnation. Generally, the granules will contain 0.5 to 25 * o by weight of 0 to 10% and toxic by weight of additives, such as stabilizers, modifiers for slow release and binders. The emulsifiable concentrates usually contain, in addition to the solvent, and, when necessary, of the cosolvent, 10 to 50% by weight of/volume and 2 to 20% of toxic weight/volume of 0 to 20% emulsifiers and weight/volume of suitable additives, such as stabilizers.

penetration agents and corrosion inhibitors. The suspension concentrates feels compounds so as also to ob ΐ: β ΐη℮ a fluid product, a stable non-depositing, and they usually contain 10 to 75% by weight of toxic, 0.5 to 15% by weight of dispersing agents, 0.1 to 10% by weight of suspending agents of such as protective colloids and thoxitropes agents, 0 to 10% by weight of suitable additives such as defoamers, corrosion inhibitors, stabilizers, penetration agents and co11 s and, as carrier, water or an organic liquid in which the toxic is substantially insoluble; certain organic additives or inorganic salts may be dissolved in the vehicle to assist in preventing sedimentation or as antifreeze for the water.

Aqueous emulsions and dispersions, for example compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, also lie within the general framework of the present invention.

This O emulsions may be water-in-oil or oil-in-water type and they may have a thick consistency of "the mayonnaise".

The compositions of the invention may also contain other ingredients, for example other compounds with pesticidal properties, especially insecticidal, acaricidal, herbicides or fungicides, or bisexual attractants, such as "pheromone", andc attractive food ingredients, for use in lures and compositions for traps.

When the compositions are used in amounts sufficient to provide the effective dose of toxic at the place * to be protected.

This dose depends on many factors, including the vehicle used, the technique and the conditions d.' applet, the fact that the composition is present at that point considered in the form of an aerosol, of a film or discrete particles, the thickness or film the particle size, the insect species against which control, it is to the_: the man nettle the art hold duly consider its factors to determine the dose of active material needed in a place, in-general, however, the dose affective disorder of the poisons of the present invention at the locus to be protected, it is to say the dose FWD: - c-which the insect comes in contact, is in the range of 0.5% to 0,001% relative to the total weight of the composition, although in some cases the effective concentration can be as low as of 0.0001% or as strong as of 2% or that one may even use a greater quantity of the compound with good results insecticidally. Concentrates useful for dilution at the site of use and/or for applications•ARs spray in very small volume may 25 - 50% by weight toto cntenir up to or even more than 1' insecticidal.

When used to control insects, the compound according to the invention can be used as the only ingredient toxic insecticide composition or it may be used in conjunction with other materials having an activated insecticidal.

As insects representative of this class, there can be mentioned insecticides that are found in nature, as the pyréthre, rotenone or sabadille, including the various synthetic insecticides comprising benzene hexachloride, the thiodiphenylamine, cyanides, tetraethyl pyrophosphate, the thiophosphate and P-nitrophenyl diethyl, dimethyl and 2.2 to-dichlorcvinyle, phosphate 1.2-dibromo 2.2-to-dichloroethyl and dimethyl, azobenzene and the various compounds of arsenic, lead and/or fluorine.