Abstract:
Insects, and particularly the larvae of Lepidoptera and Coleoptera, are controlled by application of 4,6-diamino-1,2-dihydro-dihydro-1,3,5-trazine derivatives, and agriculturally acceptable salts thereof, having the following structure; ##STR1## when they are admixed with a compatible agricultural vehicle; additionally, certain related novel heterocyclyl, phenyl, and naphthyl triazines and their substituted counterparts are also taught.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to certain chemical compounds and compositions containing the same which are useful for controlling insects in agricultural crops. More particularly, this invention relates to certain 1,3,5-triazine compounds and compositions, and their use as insecticides against a variety of insects, especially those of the order Lepidoptera and Coleoptera. 
     DESCRIPTION OF RELATED ART 
     Numerous of the triazine compounds employed in the compositions of this invention and their preparation, have been described in the literature for use in a variety of fields, but not as insecticides. 
     Thus, British Patents 1,053,113 and 1,053,307 disclose diamino-1,3,5-triazines as hypotensives, vasodilators, and CNS agents; British application BE 765,176 discloses like triazine derivatives as antimalarial or antimicrobial agents, as does BE 743,964. 
     Additionally, preparation and use of triazine compounds used in the compositions of this invention are disclosed in U.S. Pat. Nos. 2,976,288 (bactericides); 3,105,074 (bactericide intermediates); 3,660,394 (antiparasites); 3,682,912 (antimalarials); 3,723,429 (antimalarials); and British Patent 1,297,273 (antimalarials). 
     Mamalis et al have also written extensively concerning the antimicrobial and antimalarial properties of these triazines and their derivatives. See, for example, Mamalis et al, &#34;Dihydrotriazines and Related Heterocycles&#34;, J. Chem. Soc. (London), 1962, 3915; &#34;Antimicrobial Activity of Some O-Ethers of 4,6-Diamino-1,2-dihydro-1-hydroxy-2-substituted 1,3,5-Triazines&#34;, J. Med. Chem., 8, 684-91 (1965); (ibid) J. Chem. Soc., 1829-43 (1965); and &#34;The Anti-Malaria Activity of N-Benzyloxy Dihydrctriazines&#34;, Annals of Tropical Medicine and parasitology, 76, No. 1 (1982). 
     See also, &#34;Amino-Oxy Derivatives. Part III. Dihydrotriazines and Related Heterocycles&#34;, Mamalis et al., J. Chem. Soc. (London), 1962, p. 3915, and &#34;Amino-Oxy Derivatives. Part II. Some Derivatives of N-Hydroxydiguanide&#34;, Mamalis et al., J. Chem. Soc. (London), 1962, p. 229, which further disclose methods for making these compounds. 
     None of these patents or literature references suggests the use of these dihydrotriazine derivatives as insecticides, some of which are effective in doses of as little as about 1 ppm. 
     SUMMARY OF THE INVENTION 
     In accordance with the present invention it has been found that 4,6-diamino-1,2-dihydro-1,3,5-triazine derivatives, and agriculturally acceptable salts thereof, which are useful as active ingredients in the compositions and methods of this invention, may be represented by the following structure: ##STR2## wherein R is selected from the group consisting of hydrogen, straight or branched chain alkyl, haloalkyl, (substituted aryl)haloalkyl, arylalkyl, (substituted aryl)alkyl, (α-cycloalkyl)arylalkyl, cycloalkyl, arylcycloalkyl, (substituted aryl)cycloalkyl, alkenyl, cycloalkenyl, arylalkenyl, (substituted aryl)alkenyl, alkynyl, arylalkynyl, (substituted aryl)alkynyl, alkoxy, (substituted aryl)alkoxy, aryl, aryloxy, (substituted aryl)oxy, arylthio, (substituted aryl)thio, heterocyclyl, alkoxycarbonyl, and substituted aryl of the structure ##STR3## wherein 
     V, W, X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, lower alkyl, haloalkyl, cycloalkyl, arylalkyl, alkoxy, haloalkoxy, arylalkoxy, aryl (e.g. biphenyl), substituted aryl (e.g. substituted biphenyl), aryloxy, (substituted aryl)oxy, alkylthio, alkylsulfoxy, alkylsulfonyl, cyano, and nitro; 
     V and W, or W and X, when taken together, comprise the ring-forming group ##STR4## (such as naphthyl or substituted naphthyl), wherein V&#39;, W&#39;, X&#39; and Y&#39; have the same definition as V, W, X, and Y (above); 
     n is 1 to 5; 
     R 1  is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl; 
     R 2  is selected from the group consisting of hydrogen, and lower alkyl, preferably methyl; 
     R 1  and R 2  may be taken together to form a spirocycloalkane ring; 
     R 3  is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl; 
     and agriculturally acceptable salts thereof. It will be understood that where applicable, these compounds also encompass their cis- and trans- forms. 
     Of these compounds, among the more preferred ones for use in the compositions and methods of this invention are those wherein R is cycloalkyl (including adamantyl); aryl (such as naphthyl); substituted phenoxy (preferably alkyl); substituted phenylthio (preferably halo); or substituted phenyl of the structure ##STR5## wherein 
     V, W, X, Y, and Z are independently halogen, or alkoxy, wherein at least one of V to Z is not hydrogen; 
     n is 1 to 4; 
     R 1  is methyl or ethyl; 
     R 2  is methyl; and R 3  is hydrogen, 
     or acid salts thereof. 
     Particularly preferred amongst the above compounds which may be employed in this invention are those which correspond to certain of the numbered compounds in Table 1 below; i.e., those where R is di- or tri-alkylphenoxy, such as Compounds 124, 191, 192 and 196 of Table 1 below; halophenyl such as Compounds 144, 146, 147, 205, and 217; or halophenylthio, such as Compound 127. 
     Also preferred are those where R is cycloalkyl, (e.g. Compound 113 or 201); 1-alkoxyphenyl(alkyl), (e.g. Compound 116); or aryl (e.g. Compound 166). 
     Illustrative of the more preferred of these compounds, corresponding to those of Table 1 below, are the following: 
     
         ______________________________________Cmpd 113  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-     cycloheptylmethoxy-1,3,5-triazine     hydrobromide;Cmpd 116  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(4-     methoxyphenyl)butoxy]-1,3,5-triazine     hydrobromide;Cmpd 124  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-     (2,4,6-trimethylphenoxy)propoxy]-1,3,5-     triazine hydrobromide;Cmpd 127  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(4-     chlorophenylthiomethoxy)-1,3,5-triazine     hydrochloride;Cmpd 144  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-     (2,6-dichlorophenyl)propoxy]-1,3,5-triazine     hydrobromide;Cmpd 146  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-     trichlorophenylmethoxy)-1,3,5-triazine, pamoic     acid salt;Cmpd 147  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(5-     bromo-2,4-dichlorophenylmethoxy)-1,3,5-     triazine, pamoic acid salt;Cmpd 166  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-     (naphth-1-ylmethoxy)-1,3,5-triazine, pentanoic     acid salt;Cmpd 191  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-     (2,4-dimethylphenoxy)propoxy]-1,3,5-triazine     hydrobromide;Cmpd 192  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-     (2,5-dimethylphenoxy)propoxy]-1,3,5-triazine     hydrobromide;Cmpd 196  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-     (2,3,5-trimethylphenoxy)propoxy]-1,3,5-     triazine hydrobromide;Cmpd 201  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-     (adamant-1-yl)ethoxy]-1,3,5-triazine     hydrobromide;Cmpd 205  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(4-     bromophenylmethoxy)-1,3,5-triazine     hydrobromide;Cmpd 217  4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2-     bromo-4,5-dichlorophenyl)propoxy]-1,3,5-     triazine hydrochloride.______________________________________ 
    
     Each of these above compounds is preferred because they were all highly effective at low dosages. 
     For purposes of this invention, as regards the above substituent groups, the following definitions apply. The term alkyl includes straight or branched chain alkyl of from 1 to 13 carbon atoms, preferably 4 to 8 carbon atoms; alkenyl includes 2 to 13 carbon atoms, preferably 4 to 8 carbon atoms; while halogen includes chlorine, bromine, and fluorine atoms. The terms haloalkyl and haloalkoxy include branched or straight chain C 1-13  alkyl groups wherein one or more hydrogen atoms have been replaced with halogen atoms. The cycloalkyl groups, including any cis and trans forms, and which may be saturated or unsaturated, as for example hexyl or hexenyl, desirably contain from 3 to 7 carbon atoms and may be substituted by halogen, alkyl, substituted aryl, cyano, or the like. The terms aryl and substituted aryl include phenyl, naphthyl, and phenanthryl, preferably phenyl or substituted phenyl. The term substituted aryl includes those aryl groups substituted with one or more alkyl, halo, alkoxy, cycloalkyl, aryl, haloalkyl, haloalkoxy, cyano, nitro, dialkylamino, thioalkyl, or like moieties. The terms arylalkyl, arylcycloalkyl, and (α-cycloalkyl)arylalkyl, particularly as applied to the R group, include phenylalkyl, where the alkyl group may be straight or branched; and phenylcycloalkyl. Illustrations of these compounds include Compounds 117, 171, 178, 179 and 180 of Table 1 (below). 
     The term heterocyclic as employed herein includes thienyl, furyl, pyranyl, triazinyl, pyrrolyl, imidazolyl, pyridyl, pyridazinyl, isoxazolyl groups, and the like. Also included in the definition of heterocyclic substituents are those 5- and 6-member rings which are fused with an aryl group, typically phenyl, to form such heterocyclic groups as benzothienyl, isobenzofuranyl, indolyl, quinolyl, and the like. In addition, as shown in the examples below, R may also include such heterocyclic substituents as phthalimido, benzodioxolyl, benzodioxanyl, benzofuranyl, and benzopyranyl triazine derivatives. 
     Spirocycloalkanes include those having from 3 to 9 carbon atoms in their cycloalkane group, for example, spirocyclohexane. 
     As aforestated, the present 1,3,5-triazine compounds, when admixed with suitable carriers and applied to insect-infected crops such as cotton, tobacco, corn, and cole, are highly effective in controlling such insects as the larvae of the order Lepidoptera and Coleoptera, for example the tobacco budworm, beet armyworm, cabbage looper, corn earworm, diamondback moth, Mexican bean beetle, and the like. Uniquely, many of these compositions are highly effective at very low dosages, in contrast to known insecticides for this purpose, such as methomyl, which latter compound must be applied in higher amounts to provide equal effect. 
     In a further embodiment of this invention there are also contemplated certain classes of novel compounds per se which fall within the scope of Formula I (above), and which have insecticidal activity as described above. 
     Amongst them are included substituted triazine compounds of the formula ##STR6## and agriculturally acceptable salts thereof, wherein R is a heterocyclyl moiety selected from the following ##STR7## wherein R 1  is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl; 
     R 2  is selected from the group consisting of hydrogen and methyl, and 
     R 1  and R 2  may be taken together to form a spirocycloalkane ring; 
     R 3  is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl; and 
     R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13  are independently hydrogen, halogen, alkyl, or alkoxy with the proviso that both of R 7  and R 8  may not be hydrogen and with the further proviso that R 9  may not be hydrogen. 
     Typical illustrations of these novel compounds are the heterocyclyl- and substituted heterocyclyl-triazines exemplified by Compounds 35-37, and 130-132 of Table I below. 
     In yet another embodiment there are also contemplated certain other novel derivatives of the 1,3,5-triazines within Formula I (above) which are also useful as insecticides in the manner described below, and as antimalarial and antimicrobial compounds. Illustrative of these are Compounds 114-117, and 171-180 of Table I, below, and which have the formula ##STR8## and agriculturally acceptable salts thereof, wherein R is selected from phenyl or naphthyl, phenylalkyl, phenylmethylalkyl, (α-cycloalkyl)phenylmethyl, or (phenyl-substituted)cycloalkyl wherein each phenyl or naphthyl group may optionally be substituted with lower alkyl, halogen, and lower alkoxy and each alkyl may be straight or branched; 
     n is 1 to 5; 
     R 1  is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl; 
     R 2  is selected from the group consisting of hydrogen and methyl, and 
     R 1  and R 2  may be taken together to form a spirocycloalkane ring; and 
     R 3  is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl, with the proviso that R 3  is not hydrogen or lower alkylcarbonyl when R is (optionally substituted)phenyl, (optionally substituted)naphthyl, or phenylalkyl. 
     Each of the novel compounds of these additional embodiments may be prepared in the same or similar manner as those compounds of Formula I above. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Synthesis of The Compounds 
     The compounds employed as insecticides in accordance with this invention are generally known to those skilled in the art, or may readily be prepared from these compounds by known methods. See, for example, the Mamalis et al. articles above. These and other methods are described in further detail in the examples below. 
     Thus, for example, using modified methods of Mamalis et al. (supra), 1-(alkoxy or arylalkoxy)diguanide may be prepared. Cyclization of this diguanide with an aldehyde or a ketone, e.g., acetone, in the presence of concentrated hydrochloric acid gives the corresponding dihydrotriazine hydrochloride. Examples of this salt prepared in this manner are 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine hydrochloride (Compound 92 below) and 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-phenylmethoxy-1,3,5-triazine hydrochloride (Compound 37 below). This procedure is outlined in detail in Example 1. 
     The compounds of the present invention may conveniently be prepared in the form of the mono-acid addition salts which may be formed from a wide range of acids. When this occurs, the acid is usually an inorganic acid such as a hydrohalic acid, sulfuric acid, nitric acid and the like, preferably hydrochloric or hydrobromic acid. The acid addition salts tend to be greater in stability than the parent free-base, and so may be made with advantage. 
     However, salts may be made by simple reaction of the parent compounds with acid subsequent to their formation and isolation. Inorganic acids (such as those above) or organic acids may be used. Suitable organic acids include picric, acetic, maleic, phthalic, succinic, para-nitrobenzoic, stearic, mandelic, pamoic, citric, tartaric, alkylsulphonic, barbituric, or gluconic acid; (see e.g., Example 8), or sulfamethoxypyridazine salts. 
     The free-base may optionally be reacted with a salt-forming acid, for example, nonanoic acid, yielding the corresponding salt. Examples of such salts prepared in this manner are 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine nonanoic acid salt (Compound 93 below) and the corresponding tetradecanoic acid salt (Compound 94 below). 
     In a method for preparing 4,6-di(substituted amino) derivatives of the hydrochloride salt, the free-base of the salt may be prepared by reaction of the salt with sodium carbonate in an appropriate solvent. The free-base may then in turn be reacted in-situ with two equivalents of an acid halide, for example, 2-furanoyl chloride, in the presence of an acid acceptor, yielding the corresponding 4,6-di(substituted-amino) derivatives of the hydrochloride salt. An example of the 4,6-di(substituted-amino) derivative of the salt is 4,6-di(furan-2-ylcarbonylamino)-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine (Compound 106 below). The preparation of the corresponding 4,6-di(substituted amino) derivatives is presented in detail in Example 7. 
     Where the salt is obtained first, the free-base of the salt may also be obtained by its treatment with a strongly basic gel-type resin in ethanol and water. An example of the free-base is 4,6-diamino-1,2-dihydro-2,2 -dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine (Compound 95 below). This procedure to the free-base is presented in detail in Example 2. 
     Additional dihydrotriazine hydrohalide salts are prepared using a method described in U.S. Pat. No. 3,723,429. Using this method, a 1-(arylalkoxy)triazine hydrochloride, for example, 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-phenylmethoxy-1,3,5-triazine hydrochloride (Compound 37 below) is prepared, as previously described, and hydrogenolyzed in ethanol in the presence of 10% platinium oxide on charcoal, affording the corresponding 1-hydroxytriazine hydrochloride. The 1-hydroxytriazine hydrochloride, for example 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine hydrochloride is then converted to the free-base by methods previously described and in turn may be reacted with an appropriately substituted halide, for example, 2,4,5-trichlorophenylmethyl bromide, in dimethylformamide, yielding the corresponding dihydrotriazine hydrohalide. The halide moiety of the substituted halide chosen to react with the 1-hydroxytriazine governs which hydrohalide salt is obtained. Examples of salts prepared in this manner are 4,6-diamino-1,2-dihydro-1-(2,4,5-trichlorophenylmethoxy)-2,2-dimethyl-1,3,5-triazine hydrobromide (Compound 60 below), and 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-(naphth-1-yl)ethoxy]-1,3,5-triazine hydrobromide (Compound 98 below). The procedure described in U.S. Pat. No. 3,723,429 is presented in detail in Examples 3 and 4. 
     The following examples, which disclose the preparation of representative compounds of this invention (Table 1, Compounds 92, 95, 60, 98, 99, 16, 106, and 146 corresponding to Examples 1-8, respectively), are for the purpose of illustrating known methods for the preparation of the compounds employed in the methods and formulations of this invention. 
    
    
     EXAMPLE 1 
     SYNTHESIS OF 4,6-DIAMINO-1,2-DIHYDRO-2,2-DIMETHYL-1-(NAPHTH-1-YLMETHOXY)-1,3,5-TRIAZINE HYDROCHLORIDE (COMPOUND 92) 
     Step A: Synthesis of 1,1-dimethylethyl N-hydroxycarbamate as an intermediate 
     A mixture of 49.1 grams (0.225 mole) of di(1,1-dimethylethyl) dicarbonate and 15.6 grams (0.225 mole) of hydroxylamine in 150 ml of methanol was stirred, and a solution of 32.9 ml (0.236 mole) of triethylamine in 60 ml of methanol was added dropwise. Upon completion of addition, the reaction mixture was stirred for one hour and then was concentrated under reduced pressure to a residue. The residue was extracted with 300 ml of diethyl ether. The ether extract was washed with 50 ml of aqueous 1N hydrochloric acid and then with two 50 ml portions of water. The organic layer was concentrated under reduced pressure, yielding 22.9 grams of 1,1-dimethylethyl N-hydroxycarbamate. The NMR spectrum was consistent with the proposed structure. 
     Step B: Synthesis of 1,1-dimethylethyl N-(naphth-1-ylmethoxy)carbamate as an intermediate 
     Under a nitrogen atmosphere, a suspension of 1.6 grams (0.041 mole) of 60% sodium hydride (in mineral oil) in dimethylformamide was stirred, and 5.4 grams (0.041 mole) of 1,1-dimethylethyl N-hydroxycarbamate was carefully added portionwise. Upon completion of the evolution of hydrogen, 5.8 grams (0.032 mole) of naphth-1-ylmethyl chloride was added. Upon completion of addition, the reaction mixture was stirred for about 30 minutes. After this time the reaction mixture was poured into 200 ml of water. The mixture was extracted with 200 ml of diethyl ether. The ether extract was washed with three 50 ml portions of water. The organic layer was concentrated under reduced pressure to a residual oil. The oil was purified by column chromatography on silica gel. Elution was accomplished with mixtures of 5% to 20% diethyl ether in petroleum ether. The appropriate fractions were combined and concentrated under reduced pressure, yielding 3.4 grams of 1,1-dimethylethyl N-(naphth-1-ylmethoxy)carbamate. The NMR spectrum was consistent with the proposed structure. 
     Step C: Synthesis of (naphth-1-ylmethoxy)amine hydrochloride as an intermediate 
     A solution of 3.4 grams (0.012 mole) of 1,1-dimethylethyl N-(naphth-1-ylmethoxy)carbamate in 30 ml of ethanol was stirred, and dry hydrogen chloride gas was bubbled into the solution during a 1 minute period. After this time, thin layer chromatographic analysis of the reaction mixture indicated that the reaction had gone to completion. The reaction mixture was concentrated under reduced pressure, yielding 2.5 grams of (naphth-1-ylmethoxy)amine hydrochloride; m.p. 193°-195° C. (Lit. m.p. 198° C.). 
     Step D: Synthesis of 1-(naphth-1-ylmethoxy)diguanide as an intermediate 
     Under a nitrogen atmosphere, a stirred solution of 2.5 grams (0.012 mole) of (naphth-1-ylmethoxy)amine hydrochloride and 1.2 grams (0.014 mole) of cyanoguanidine in 15 ml of ethanol was heated at reflux during a 2 hour period. To promote purification, the dihydrochloride salt of the reaction product was prepared by bubbling hydrogen chloride gas into the reaction mixture during a 30 second period. The reaction mixture was then taken up in an additional 7 ml of ethanol and 75 ml of diethyl ether. The resultant solid was collected by filtration and dried. The solid was dissolved in water and treated with a solution of 2.8 grams (0.020 mole) of potassium carbonate in 10 ml of water. The resultant solid was collected by filtration and dried under vacuum, yielding 1.9 grams of 1-(naphth-1-ylmethoxy)diguanide; m.p. 147°-149° C. (lit. m.p. 145° C.). The NMR spectrum was consistent with the proposed structure. 
     Step E: Synthesis of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine hydrochloride (Compound 92) 
     Under a nitrogen atmosphere, a stirred solution of 1.3 grams (0.005 mole) of 1-(naphth-1-ylmethoxy) diguanide and 0.42 ml (0.005 mole) of concentrated hydrochloride acid in 150 ml of acetone was heated at reflux for six hours. After this time the reaction mixture was concentrated under reduced pressure to a residual oil. Following unsuccessful attempts to crystallize the oil, it was redissolved in 150 ml of acetone, and 0.42 ml of concentrated hydrochloric acid was added. The solution slowly became cloudy and some crystals formed. The mixture was briefly heated to reflux, and then it was allowed to cool to ambient temperature where it was stirred for about 60 hours. The resultant solid was collected by filtration, yielding 1.3 grams of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine hydrochloride; m.p. 217°-218° C. (lit. m.p. 215° C.). The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 2 
     SYNTHESIS OF 4,6-DIAMINO-1,2-DIHYDRO-2,2-DIMETHYL-1-(NAPHTH-1-YLMETHOXY)-1,3,5-TRIAZINE (COMPOUND 95) 
     A solution of 0.8 gram (0.002 mole) of 4,6-diamino-1,2-dihydro-1-(naphth-1-ylmethoxy)-2,2-dimethyl-1,3,5-triazine hydrochloride in about 10 ml of 1:1-water-ethanol was passed slowly though a 2.25 cm diameter column containing 10 ml of a strongly basic gel-type ion-exchange resin (sold under the trademark Amberlite® IRA-400 (OH) ion-exchange resin). An additional 25 ml of 1:1-water-ethanol was passed through the column to remove the maximum amount of product. The combined eluants were cooled in a freezer, and the resultant solid was collected by filtration. The solid was dried, yielding 0.3 gram of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine; m.p. 170°-171° C. (lit. m.p. 168°-170° C.). The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 3 
     SYNTHESIS OF 4,6-DIAMINO-1,2-DIHYDRO-2,2-DIMETHYL-1-(2,4,5-TRICHLOROPHENYLMETHOXY)-2,2-DIMETHYL-1,3,5-TRIAZINE HYDROBROMIDE (COMPOUND 60) 
     Step A Synthesis of 1-phenylmethoxydiguanide as an intermediate 
     This compound was prepared in a manner analogous to that of Example 1, Step D, using 100 grams (0.63 mole) of phenylmethoxyamine hydrochloride (commercially available) and 65 grams (0.77 mole) of cyanoguanidine in 200 ml of ethanol. This procedure differed from Example 1, Step D, in that the dihydrochloride salt was not prepared. Following treatment with potassium carbonate in water, the reaction mixture was extracted with 300 ml of ethyl acetate. The extract was concentrated under reduced pressure, yielding 120.1 grams of 1-phenylmethoxydiguanide; m.p.; 95°-100° C. 
     Step B: Synthesis of 4,6-diamino-1,2-dihydro-1-phenylmethoxy-2,2-dimethyl-1,3,5-triazine hydrochloride (Compound 37) for insecticidal testing and as an intermediate 
     This compound was prepared in a manner analogous to that of Example 1, Step E, using 120.1 grams (0.58 mole) of 1-phenylmethoxydiguanide, 95 ml of concentrated hydrochloric acid, and 400 ml of acetone in 400 ml of ethanol. The reaction mixture was concentrated under reduced pressure to near-dryness. The concentrate was mixed with a hot mixture of 50 ml of ethanol in 400 ml of acetone. The resultant solid was collected by filtration, yielding 96.5 grams of 4,6-diamino-1,2-dihydro-1-phenylmethoxy-2,2-dimethyl-1,3,5-triazine hydrochloride, m.p. 218°-219° C. The NMR spectrum was consistent with the proposed structure. 
     Step C: Synthesis of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine hydrochloride as an intermediate 
     A solution of 10.0 grams (0.035 mole) of 4,6-diamino-1,2-dihydro-1-phenylmethoxy-2,2-dimethyl-1,3,5-triazine hydrochloride and 20 ml of water in 30 ml of ethanol was hydrogenated in the presence of 1.0 gram of 5% palladium on charcoal using a Parr hydrogenator. Upon completion of the uptake of the theoretical amount of hydrogen, the reaction mixture was filtered. The filtrate was concentrated under reduced pressure to a residual solid. The solid was recrystallized from ethanol, yielding 4.7 grams of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine hydrochloride, m.p. 241° C. (dec.). The NMR spectrum was consistent with the proposed structure. The reaction was repeated several times to provide sufficient material for the next step. 
     Step D: Synthesis of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2,-dimethyl-1,3,5-triazine as an intermediate 
     This compound was prepared in a manner analogous to that of Example 2, using 47.9 grams (0.247 mole) of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine hydrochloride in 100 ml of water and a 3.5 cm - diameter column containing 350 ml of a strongly basic gel-type ion-exchange resin. An additional 500 ml of water was passed through the column to remove the maximum amount of product. The combined eluants were concentrated under reduced pressure, yielding 37.9 grams of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine; m.p. 211°-212° C. (dec). The NMR spectrum was consistent with the proposed structure. 
     Step E: Synthesis of 2,4,5-trichlorophenylmethyl bromide as an intermediate 
     Under a nitrogen atmosphere, a stirred solution of 5.0 grams (0.026 mole) of 2,4,5-trichlorotoluene and 5.3 grams (0.030 mole) of N-bromosuccinimide in 30 ml of carbon tetrachloride was heated to reflux and then was irradiated with a sun lamp during a 10 minute period. The reaction mixture was allowed to cool to ambient temperature at which time it was filtered to remove excess succinimide. The filtrate was concentrated under reduced pressure to a residual oil. The oil was distilled under vacuum, yielding four fractions in the boiling point range of 130°-152° C./5 mm Hg. NMR analysis of the fractions indicated that two fractions, boiling point 140°-150° C./5 mm Hg., contained the majority of the reaction product. The two fractions were combined and diluted with 1 ml of petroleum ether. The mixture was filtered to remove unreacted starting material. The filtrate was diluted with 12 ml of petroleum ether, and the solution was cooled in dry-ice. The solvent was removed from the resultant solid by pipette. The solid was dried under reduced pressure, yielding 2.7 grams of 80% pure 2,4,5-trichlorophenylmethyl bromide. The NMR spectrum was consistent with the proposed structure. 
     Step F: Synthesis of 4,6-diamino-1,2-dihydro-1-(2,4,5-trichlorophenylmethoxy)-2,2-dimethyl-1,3,5-triazine hydrobromide (Compound 60) 
     A solution of 0.6 gram (0.004 mole) of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine and 1.6 grams (0.006 mole) of 2,4,5-trichlorophenylmethyl bromide in 5 ml of dimethylformamide was stirred in a closed reaction vessel during about an 18 hour period. After this time the reaction mixture was concentrated under reduced pressure to a residual solid. The solid was washed with 50 ml of acetone. The dried solid was recrystallized from 125 ml of water, yielding 1.1 grams of 4,6-diamino-1,2-dihydro-1-(2,4,5-trichlorophenylmethoxy)-2,2-dimethyl-1,3,5-triazine hydrobromide, m.p. 247°-248° C. The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 4 
     SYNTHESIS OF 4,6-DIAMINO-1,2-DIHYDRO-2,2-DIMETHYL-1-[2-(NAPHTH-1-YL)ETHOXY]-1,3,5-TRIAZINE HYDROBROMIDE (COMPOUND 98) 
     This compound was prepared in a manner analogous to that of Example 3, Step F, using 0.8 gram (0.005 mole) of 4,6-diamino-1,2-dihydro-1-hydroxy-2,2-dimethyl-1,3,5-triazine (prepared in Example 3) and 1.3 grams (0.006 mole) of 2-(naphth-1-yl)ethyl bromide (commercially available) in 15 ml of dimethylformamide. The reaction product was recrystallized from water, yielding 0.4 gram of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-(naphth-1-yl)ethoxy]-1,3,5-triazine hydrobromide. The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 5 
     SYNTHESIS OF 4,6-DIAMINO-2-ETHYL-1,2-DIHYDRO-2-METHYL-1-(NAPHTH-1-YLMETHOXY)-1,3,5-TRIAZINE HYDROCHLORIDE (COMPOUND 99) 
     This compound was prepared in a manner analogous to that of Example 1, Step E, using 1.0 gram (0.004 mole) of 1-(naphth-1-ylmethoxy)diguanide (prepared in Example 1, steps A-D), and 0.8 ml of concentrated hydrochloric acid in 20 ml of ethyl methyl ketone. The yield of 4,6-diamino-2-ethyl-1,2-dihydro-2-methyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine hydrochloride was 0.9 gram; m.p. 206°-208° C. The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 6 
     SYNTHESIS OF 4,6-DIAMINO-1,2-DIHYDRO-2,2-DIMETHYL-1-[2,3-DIBROMO-3-(3,4-DICHLOROPHENYL)PROPOXY]-1,3,5-TRIAZINE HYDROCHLORIDE (COMPOUND 16) 
     A stirred suspension of 0.8 gram (0.002 mole) of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(3,4-dichlorophenyl)prop-2-enoxy]-1,3,5-triazine hydrochloride (Compound 20 - prepared in a manner analogous to that of Example 3) in 10 ml of acetic acid was cooled in an ice-water bath. The reaction vessel was covered with aluminum foil to maintain darkness, and then 0.1 ml (0.002 mole) of bromine in 10 ml of acetic acid was added dropwise. Upon completion of addition, the reaction mixture was stirred about 1 hour until the bromine color had disappeared. The reaction mixture was then concentrated under reduced pressure to a residue. The residue was stirred in 25 ml of boiling water containing 1 ml of aqueous 6N hydrochloric acid. The mixture was cooled, and a solid was collected by filtration. The solid was dried, yielding 0.5 gram of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2,3-dibromo-3-(3,4-dichlorophenyl)propoxy]-1,3,5-triazine hydrochloride. The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 7 
     SYNTHESIS OF 4,6-DI(FURAN-2-YLCARBONYLAMINO)-1,2-DIHYDRO-2,2-DIMETHYL-1-(NAPHTH-1-YLMETHOXY)-1,3,5-TRIAZINE (COMPOUND 106) 
     To a stirred mixture of 0.7 gram (0.002 mole) of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine hydrochloride (prepared in a manner analogous to that of Example 1) and 0.9 gram (0.009 mole) of sodium carbonate in 30 ml of methylene chloride was added 0.6 gram (0.005 mole) of 2-furanoyl chloride, followed by 1 ml of triethylamine. Upon completion of addition, the reaction mixture was stirred for about 18 hours after which time it was concentrated under reduced pressure to a residue. The residue was taken up in 100 ml of ethyl acetate and 100 ml of water. An insoluble material was removed by filtration. The organic layer was washed with 500 ml of an aqueous solution saturated with sodium chloride. The organic layer was then dried with sodium sulfate and filtered through a layer of silica gel. The filtrate was concentrated under reduced pressure to a residue. This residue was stirred with a solution of 20 ml of diethyl ether and 0.5 ml of methylene chloride. The solid was collected by filtration and was washed with ethanol, yielding, when dried, 0.4 gram of 4,6-di(furan-2-ylcarbonylamino)-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine; m.p. 173°-177° C. The NMR spectrum was consistent with the proposed structure. 
     EXAMPLE 8 
     SYNTHESIS OF 4,6-DIAMINO-1,2-DIHYDRO-2,2-DIMETHYL-1-(2,4,5-TRICHLOROPHENYLMETHOXY)-1,3,5-TRIAZINE,PAMOIC ACID SALT (COMPOUND 146) 
     Step A Synthesis of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine as an intermediate 
     A solution of 0.5 gram (0.001 mole) of 4,6-diamino-1,2-dihydro 2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine hydrobromide (Compound 60 - Prepared in Example 3) in 30 ml of water was stirred and 1 ml (0.007 mole) of triethylamine was added. The resultant solid was collected by filtration and dried, yielding 0.4 gram of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine. The NMR spectrum was consistent with the proposed structure. 
     Step B Synthesis of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine, pamoic acid salt (Compound 146) 
     A solution of 0.4 gram (0.001 mole) of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine and 0.2 gram (0.0005 mole) of pamoic acid in 50 ml of tetrahydrofuran was stirred for about 15 minutes. The reaction mixture was concentrated under reduced pressure to a residual solid. The solid was dried under high vacuum, yielding 0.6 gram of 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine, pamoic acid salt, m.p. 180° C., dec. The NMR spectrum was consistent with the proposed structure. 
     Appended TABLE 1 lists 229 species of triazines and salts thereof falling within Formula I (supra) of this invention, the preparation of certain of which species are illustrated in accordance with foregoing Examples 1-8. TABLE 1-a provides the melting point and emperical formula of the majority of these species. 
     
                                           TABLE 1__________________________________________________________________________4,6-DIAMINO-1,2-DIHYDRO-1,3,5-TRIAZINE DERIVATIVES__________________________________________________________________________ ##STR9##wherein R.sup.1, R.sup.2 are CH.sub.3 and R.sup.3 is hydrogen:Compound Number         n     R                   Salt__________________________________________________________________________ 1            1     CH.sub.3            HBr 2            1     C.sub.2 H.sub.5     HCl 3            1     C.sub.3 H.sub.7     HCl 4            1     C.sub.5 H.sub.11    HBr 5            1     C.sub.8 H.sub.17    HBr 6            1     C.sub.8 H.sub.17    -- 7            1     C.sub.9 H.sub.19    HBr 8            1     C.sub.10 H.sub.21   HBr 9            1     C.sub.11 H.sub.23   HBr 10           1     C.sub.12 H.sub.25   HBr 11           1     C.sub.13 H.sub.27   HBr 12           2     CH(CH.sub.3).sub.2  HBr 13           1     CH(C.sub.2 H.sub.5).sub.2                                   HBr 14           1     Cyclopropyl         HBr 15           1     Cyclobutyl          HBr 16           1     1,2-Dibromo-2-      HCl               (3,4-dichlorophenyl)-               ethyl 17           1     CHCH.sub.2          HBr 18           2     CHCH.sub.2          HBr 19           1     2-Phenylethenyl     HBr 20           1     2-(3,4-dichloro-    HCl               phenyl)ethenyl 21           1     CCH                 HBr 22           3     CCCH.sub.3          HCl 23           3     CCC.sub.2 H.sub.5   HCl 24           3     CCC.sub.3 H.sub.7   HCl 25           1     2-(3,4-Dichloro-    HCl               phenyl)ethynyl 26           1     CH.sub.2 F          HBr 27           2     OC.sub.2 H.sub.5    HBr 28           3     Oφ;             HBr               2,4,5-Cl.sub.3 29           3     Oφ;             --               2,4,5-Cl.sub.3 30           1     CO.sub.2 CH.sub.3   HBr 31           2     pyridin-2-yl        -- 32           2                ##STR10##          HBr 33           3                ##STR11##          HBr 34           1                ##STR12##          HBr 35           1                ##STR13##          HBr 36           1                ##STR14##          HBr 37           1                ##STR15##__________________________________________________________________________ ##STR16##wherein R.sup.1, R.sup.2 are CH.sub.3 ; R.sup.3 is hydrogen; and R is, ##STR17##Compound Number      n   V    W        X     Y  Z    Salt__________________________________________________________________________ 38        1   H    H        H     H  H    HCl 39        3   H    H        H     H  H    HBr 40        1   Cl   H        H     H  H    HCl 41        1   H    Cl       H     H  H    HBr 42        1   H    H        Cl    H  H    HCl 43        2   H    H        Cl    H  H    HCl 44        1   F    H        H     H  H    HCl 45        1   H    H        F     H  H    HBr 46        1   Cl   Cl       H     H  H    HBr 47        1   Cl   H        Cl    H  H    HCl 48        1   Cl   H        H     Cl H    HCl 49        1   Cl   H        H     Cl H    HBr 50        1   Cl   H        H     H  Cl   HCl 51        1   H    Cl       Cl    H  H    HCl 52        1   H    Cl       Cl    H  H    -- 53        2   H    Cl       Cl    H  H    HCl 54        3   H    Cl       Cl    H  H    HCl 55        4   H    Cl       Cl    H  H    HCl 56        1   H    Cl       H     Cl H    HCl 57        1   F    H        H     H  F    HBr 58        1   Cl   Cl       H     Cl H    HBr 59        1   H    Cl       Cl    Cl H    HCl 60        1   Cl   H        Cl    Cl H    HBr 61        1   Cl   H        Cl    Cl H    -- 62        1   F    H        F     H  F    HBr 63        1   Cl   H        Cl    Br H    HBr 64        1   F    F        F     F  F    HBr 65        1   F    F        CH.sub.3                              F  F    HBr 66        1   Cl   H        Cl    φ                                 H    HBr 67        1   CH.sub.3               H        H     H  CH.sub.3                                      HBr 68        1   H    cyclohexyl                        H     H  H    Hl 69        2   H    H        OCH.sub.3                              H  H    HBr 70        1   H    OC.sub.7 H.sub.15                        H     H  H    HBr 71        1   H    O(CH.sub.2).sub.3 φ                        H     H  H    HBr 72        1   H    NO.sub.2 H     H  H    HBr 73        1   H    H        NO.sub.2                              H  H    HBr 74        1   H    H        CF.sub.3                              H  H    HBr 75        1   H    OCF.sub.3                        H     H  H    HBr 76        1   H    OCF.sub.2 CHF.sub.2                        H     H  H    HCl 77        1   φ               H        H     H  H    HCl 78        1   H    φ    H     H  H    HBr 79        1   H    H        φ H  H    HBr 80        1   CH.sub.3               φ    H     H  H    HCl 81        1   CH.sub.3               φ    H     H  CH.sub.3                                      HBr 82        1   H    φ;   H     H  H    HBr               4-Cl 83        1   H    φ;   H     H  H    HBr               4-F 84        1   H    φ    H     H  H    HCl 85        1   H    H        φ H  H    HCl 86        1   H    φ    F     H  H    HBr__________________________________________________________________________ ##STR18##wherein R is ##STR19##                             Point of                             AttachmentCompound Number     n R1     R2    R3       on Naphthyl                                     Salt__________________________________________________________________________ 87       1 CH.sub.3              H     H        1       HCl 88       1 C.sub.2 H.sub.5              H     H        1       HCl 89       1 CH.sub.2 CH.sub.2 φ              H     H        1       HCl 90       1 CHCHφ              H     H        1       HCl              a Hydrate 91       1 φ; H     H        1       2HCl       2-OCH.sub.3An isopropanol Complex 92       1 CH.sub. 3              CH.sub.3                    H        1       HCl 93       1 CH.sub.3              CH.sub.3                    H        1       Nonanoic                                     Acid 94       1 CH.sub.3              CH.sub.3                    H        1       Tetradecan-                                     oic Acid 95       1 CH.sub.3              CH.sub.3                    H        1       -- 96       1 CH.sub.3              CH.sub.3                    H        2       HCl 97       1 CH.sub.3              CH.sub.3                    H        2       -- 98       2 CH.sub.3              CH.sub.3                    H        1       HBr 99       1 C.sub.2 H.sub.5              CH.sub.3                    H        1       HCl100       1 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                    H        1       HCl101       1 CH.sub.3              CH.sub.3                    C(O)CH.sub.3                             1       --102       1 CH.sub.3              CH.sub.3                    C(O)C.sub.2 H.sub.5                             1       --103       1 CH.sub.3              CH.sub.3                    C(O)CH(CH.sub.3).sub.2                             1       --104       1 CH.sub.3              CH.sub.3                    Cyclopropyl-                             1       --                    carbonyl105       1 CH.sub.3              CH.sub.3                    C(O)CH.sub.2 OCH.sub.3                             1       --106       1 CH.sub.3              CH.sub.3                    Furan-2- 1       --                    ylcarbonyl__________________________________________________________________________ ##STR20##wherein R.sup.1, R.sup.2 are CH.sub.3 and R.sup.3 is hydrogen.Compound Number         n     R                   Salt__________________________________________________________________________107           1     H                   HBr108           1     C.sub.6 H.sub.13    HBr109           1     C.sub.7 H.sub.15    HBr110           3     CH(CH.sub.3).sub.2  HBr111           1     Cyclohexyl          HBr112           1     Cyclohex-3-ene      HBr113           1     Cycloheptane        HBr114           1     1-(2-Fluorophenyl)- HBr               propan-2-yl115           1     1-(4-Methoxyphenyl)-                                   HBr               propan-2-yl116           2     1-(4-Methoxyphenyl)-                                   HBr               ethyl117           2     (Cyclopropyl)(phenyl)-                                   HBr               methyl118           1     2-(2,4,5-Trichloro- HCl               phenyl)ethenyl119           1     2-(2,5-dichloro-4-  HCl               methylphenyl)ethenyl120           1     2-(2,5-Dibromo-4-   HCl               methylphenyl)ethenyl121           5     CH.sub.2 Cl         HBr               70% Component of               Compound 123122           5     CH.sub.2 Br         HBr               30% Compound of               Compound 123123           A mixture of Compounds 121 and 122                                   HBr124           3     Oφ;             HBr               2,4,6-Trimethyl125           2     Naphth-1-yloxy      HBr126           2     Naphth-2-yloxy      HBr127           1     Sφ;             HCl               4-Cl128           1     5-Chlorothien-      HCl               2-yl129           1                ##STR21##          HBr130           2                ##STR22##          HBr131           3                ##STR23##          HBr132           1                ##STR24##          HCl__________________________________________________________________________wherein R.sup. 1, R.sup.2 are CH.sub.3 ; R.sup.3 is hydrogen; and R is, ##STR25##Compound Number      n   V    W     X    Y     Z   Salt__________________________________________________________________________133        1   H    Br    H    H     H   HBr134        1   H    I     H    H     H   HBr135        1   H    H     I    H     H   HBr136        1   CH.sub.3               H     H    H     H   HBr137        1   H    H     OCH.sub.3                          H     H   HBr138        1   H    H     OC.sub.2 H.sub.5                          H     H   HBr139        1   H    H     OCF.sub.3                          H     H   HBr140        1   SCH.sub.3               H     H    H     H   HBr141        1   F    H     Br   H     H   HBR142        1   Cl   H     H    Br    H   HBR143        1   F    H     H    Br    H   HBr144        3   Cl   H     H    H     Cl  HBr145        1   H    Br    F    H     H   HBr146        1   Cl   H     Cl   Cl    H   Pamoic*                                    acid147        1   Cl   H     Cl   Br    H   Pamoic*                                    acid148        1   Cl   H     CH.sub.3                          Cl    H   HBr149        1   Br   H     CH.sub.3                          Br    H   HBr150        1   Cl   H     Cl   CH.sub.3                                H   HBr151        3   Cl   H     Cl   Cl    H   HCl152        1   Cl   H     Cl   H     Cl  HCl153        3   Cl   H     CH.sub.3                          Cl    H   HCl154        3   Br   H     CH.sub.3                          Br    H   HCl155        1   Cl   H     Cl   OCH.sub.3                                H   HBr156        3   H    φ H    H     H   HBr157        1   H    φ H    H     H   Pamoic*                                    acid158        1   H    φ;                     H    H     H   HBr               3,4-Cl.sub.2159        1   F    φ H    H     H   HBr160        1   H    φ F    H     H   HBr161        1   H    φ F    H     H   HBr               4-F162        1   Cl   H     H    φ H   HBr163        1   F    H     H    φ H   HBr164        1   F    φ F    H     H   HBr__________________________________________________________________________wherein R is ##STR26##                        Point of                        AttachmentCompound Number      n   R1   R2   R3  on Naphthyl                                 Salt__________________________________________________________________________165        1   CH.sub.3               CH.sub.3                    H   1        Butyric                                 acid166        1   CH.sub.3               CH.sub.3                    H   1        Pentanoic                                 acid167        1   CH.sub.3               CH.sub.3                    H   1        Hexanoic                                 acid168        1   CH.sub.3               CH.sub.3                    H   1        D-gluconic*                                 acid169        1   CH.sub.3               CH.sub.3                    H   1        Barbituric*                                 acid__________________________________________________________________________ ##STR27##wherein R.sup.1, R.sup.2 are CH.sub.3 and R.sup.3 is hydrogen.Compound Number         n      R                 Salt__________________________________________________________________________170           2      C(CH.sub.3).sub.3 HBr171           1      3-Phenylcyclohexyl                                  HBr                15% trans-85% cis172           1      3-(2-Methylphenyl)-                                  --                cyclohexyl                5% trans-95% cis173           1      3-(3-Methylphenyl)-                                  HBr                cyclohexyl                100% cis174           1      3-(4-Methylphenyl)-                                  HBr                cyclohexyl                5% trans-95% cis175           1      3-(4-Methylphenyl)                                  HBr                cyclohexyl                70% trans-30% cis176           1      1-Phenylpropan-2-yl                                  HBr177           1      1-(3-Bromophenyl)-                                  HBr                propan-2-yl178           2      1-Phenylethyl     HBr179           2      (Cyclopropyl)(4-fluoro-                                  HBr                phenyl)methyl180           2      (Cyclopropyl)(4-methoxy-                                  HBr                phenyl)methyl181           1      2-(5-Bromo-2,4-   HCl                dichlorophenyl)ethenyl182           1      2-(4-Bromo,2,5-   HCl                dichlorophenyl)ethenyl183           1      2-(2-Bromo-4,5-   HCl                dichlorophenyl)ethenyl184           2      Oφ;           HBr                4-Cl185           2      Oφ;           HCl                4-Br186           3      Oφ            HBr187           3      Oφ;           HBr                2-CH.sub.3188           3      Oφ;           HBr                3-CH.sub.3189           3      Oφ;           HBr                4-CH.sub.3190           3      Oφ;           HBr                2,3-(CH.sub.3).sub.2191           3      Oφ;           HBr                2,4-(CH.sub.3).sub.2192           3      Oφ;           HBr                2,5-(CH.sub.3).sub.2193           3      Oφ;           HBr                2,6-(CH.sub.3).sub.2194           3      Oφ ;          HBr                3,4-(CH.sub.3).sub.2195           3      Oφ;           HBr                3,5-(CH.sub.3).sub.2196           3      Oφ;           HBr                2,3,5-(CH.sub.3).sub.3197           3      Oφ;           HBr                3,4,5-(CH.sub.3).sub.3198           2      Oφ;           HBr                2,3,6-(CH.sub.3).sub.3199           2      Sφ            HCl200           2      Sφ;           --                4-Cl201           2      Adamant-l-yl      HBr202           1      Benzo[b]thien-2-yl                                  HBr203           3      2,2-Dimethyl-     HBr                benzofuran-7-yloxy__________________________________________________________________________wherein R.sup.1, R.sup.2 are CH.sub.3 ; R.sup.3 is hydrogen; and R is: ##STR28##Compound  n   V     W     X     Y     Z   Salt__________________________________________________________________________204    3   H     H     Cl    H     H   HCl205    1   H     H     Br    H     H   HBr206    1   H     F     H     H     H   HBr207    1   H     CF.sub.3                  H     H     H   HBr208    1   H     CN    H     H     H   HBr209    1   H     H     CN    H     H   HBr210    3   H     H     OCF.sub.3                        H     H   HBr211    1   H     F     F     H     H   HBr212    1   Cl    H     H     NO.sub.2                              H   HBr213    1   Cl    H     Cl    Br    H   --214    1   Cl    H     Cl    Br    H   *Sulfameth-                                  oxypyridazine215    3   Cl    H     Cl    Br    H   HCl216    3   Cl    H     Br    Cl    H   HCl217    3   Br    H     Cl    Cl    H   HCl218    1   CH.sub.3            H     CH.sub.3                        CH.sub.3                              H   HBr219    3   H     H     OCH.sub.3                        H     H   HBr220    3   OCH.sub.3            H     OCH.sub.3                        OCH.sub.3                              H   HBr221    1   H     φ;                  H     H     H   HBr            2-Cl222    1   H     φ;                  H     H     H   HBr            3-Cl223    1   H     φ;                  H     H     H   HBr            4-OCF.sub.3224    3   Cl    H     H     φ H   HBr225    1   F     H     H     φ;                              H   HBr                        4-F226    1   F     H     H     φ;                              H   HBr                        2,6-F.sub.2227    1   F     φ ;                  F     H     H   HBr__________________________________________________________________________wherein R.sup.1 and R.sup.2 are CH.sub.3 ; R.sup.3 is hydrogen; and R, inwhich V and W, taken together, form an arylring, is ##STR29##Compound   n   X   Y    Z   V&#39;  W&#39;   X&#39;  Y&#39;  Salt__________________________________________________________________________228     1   Cl  H    H   H   H    H   H   HBr229     1   H   H    H   H   H    Br  H   HBr__________________________________________________________________________ ##STR30## ##STR31## ##STR32## ##STR33##__________________________________________________________________________ 
    
     
                       TABLE 1-a______________________________________        Melting PointCompound Number        (°C.)                    Empirical Formula______________________________________1            197-200     C.sub.7 H.sub.16 BrN.sub.5 O2            206-208     C.sub.8 H.sub.18 C1N.sub.5 O3            204-206     C.sub.9 H.sub.20 ClN.sub.5 O4            204-207     C.sub.11 H.sub.24 BrN.sub.5 O5            196-197     C.sub.14 H.sub.30 BrN.sub.5 O6            148-149     C.sub.14 H.sub.29 N.sub.5 O7            195-196     C.sub.15 H.sub.32 BrN.sub.5 O8            195-197     C.sub.16 H.sub.34 BrN.sub.5 O9            199-200     C.sub.17 H.sub.36 BrN.sub.5 O10           199-200     C.sub.18 H.sub.38 BrN.sub.5 O11           199-200     C.sub.19 H.sub.40 BrN.sub.5 O12           206-209     C.sub.10 H.sub.22 BrN.sub.5 O13           --          C.sub.11 H.sub.24 BrN.sub.5 O14           205-207     C.sub.9 H.sub.18 BrN.sub.5 O15           212-215     C.sub.10 H.sub.20 BrN.sub.5 O16           209-211     C.sub.14 H.sub.18 Br.sub.2 Cl.sub.3 N.sub.5 O17           193-195     C.sub.8 H.sub.16 BrN.sub.5 O18           218-220     C.sub.9 H.sub. 18 BrN.sub.5 O19           216-218     C.sub.14 H.sub.20 BrN.sub.5 O20           231-232     C.sub.14 H.sub.18 Cl.sub.3 N.sub.5 O21           198-200     C.sub.8 H.sub.14 BrN.sub.5 O22           200-202     C.sub.11 H.sub.20 ClN.sub.5 O23           194-198     C.sub.12 H.sub.22 ClN.sub.5 O24           208-212     C.sub.13 H.sub.24 ClN.sub.5 O25           210-211     C.sub.14 H.sub.16 Cl.sub.3 N.sub.5 O26           215-217     C.sub.7 H.sub.15 BrFN.sub.5 O27           202-204     C.sub.9 H.sub.20 BrN.sub.5 O.sub.228           191-193     C.sub.14 H.sub.19 BrCl.sub.3 N.sub.5 O.sub.229           209-211     C.sub.14 H.sub.18 Cl.sub.3 N.sub.5 O.sub.230           145-149     C.sub.8 H.sub.16 BrN.sub.5 O.sub.331           218, dec.   C.sub.12 H.sub.18 N.sub.6 O32           216-219     C.sub.15 H.sub.19 BrN.sub.6 O.sub.333           200-202     C.sub.16 H.sub.21 BrN.sub.6 O.sub.334           210-212     C.sub.13 H.sub.18 BrN.sub.5 O.sub.335           187-190     C.sub.16 H.sub.24 BrN.sub.5 O.sub.236           226-228     C.sub.16 H.sub.20 BrN.sub.5 O.sub. 437           227-230     C.sub.17 H.sub.22 BrN.sub.5 O.sub.538           218-219     C.sub.12 H.sub.18 ClN.sub.5 O39           --          C.sub.14 H.sub.22 BrN.sub.5 O40           213-214     C.sub.12 H.sub.17 Cl.sub.2 N.sub.5 O41           241-242     C.sub.12 H.sub.17 BrClN.sub.5 O42           241-242     C.sub.12 H.sub.17 Cl.sub.2 N.sub.5 O43           230-232     C.sub.13 H.sub.19 Cl.sub.2 N.sub.5 O44           223-225     C.sub.12 H.sub.17 ClFN.sub.5 O45           218-220     C.sub.12 H.sub.17 BrFN.sub.5 O46           209-212     C.sub.12 H.sub.16 BrCl.sub.2 N.sub.5 O47           219-220     C.sub.12 H.sub.16 Cl.sub.3 N.sub.5 O48           236-238     C.sub.12 H.sub.16 Cl.sub.3 N.sub.5 O49           211-213     C.sub.12 H.sub.16 BrCl.sub.2 N.sub.5 O50           232-233     C.sub.12 H.sub.16 Cl.sub.3 N.sub.5 O51           234-235     C.sub.12 H.sub.16 Cl.sub.3 N.sub.5 O52            169-170,   C.sub.12 H.sub.15 Cl.sub.2 N.sub.5 O        remelts at 22453           249-250     C.sub.13 H.sub.18 Cl.sub.3 N.sub.5 O54           231-232     C.sub.14 H.sub.20 Cl.sub.3 N.sub.5 O55           218-219     C.sub.15 H.sub.22 Cl.sub.3 N.sub.5 O56           231-233     C.sub.12 H.sub.16 Cl.sub.3 N.sub.5 O57           226-228     C.sub.12 H.sub.16 BrF.sub.2 N.sub.5 O58           --          C.sub.12 H.sub.15 BrCl.sub.3 N.sub.5 O59           233-234     C.sub.12 H.sub.15 Cl.sub.4 N.sub.5 O60           247-248     C.sub.12 H.sub.15 BrCl.sub.3 N.sub.5 O61           200, dec.,  C.sub.12 H.sub.14 Cl.sub.3 N.sub.5 O        remelts at 24562           214-217     C.sub.12 H.sub.15 BrF.sub.3 N.sub.5 O63           244-245     C.sub.12 H.sub.15 Br.sub.2 Cl.sub.2 N.sub.5 O64           216-218     C.sub.12 H.sub.13 BrF.sub.5 N.sub.5 O65           220-222     C.sub.13 H.sub.16 BrF.sub.4 N.sub.5 O66           160, dec.   C.sub.18 H.sub.20 BrClN.sub.5 O67           214-216     C.sub.14 H.sub.22 BrN.sub.5 O68           207-209     C.sub.18 H.sub.30 IN.sub.5 O69           213-216     C.sub.14 H.sub.22 BrN.sub.5 O.sub.270           165-168     C.sub.19 H.sub.32 BrN.sub.5 O.sub. 271           182-185     C.sub.21 H.sub.28 BrN.sub.5 O.sub.272           236-238     C.sub.12 H.sub.17 BrN.sub.6 O.sub.373           233-235     C.sub.12 H.sub.17 BrN.sub.6 O.sub.374           223-225     C.sub.13 H.sub.17 BrF.sub.3 N.sub.5 O75           202-204     C.sub.13 H.sub.17 BrF.sub.3 N.sub.5 O.sub.276           208-216     C.sub.14 H.sub.18 BrF.sub.4 N.sub.5 O.sub.277           221-222     C.sub.18 H.sub.22 ClN.sub.5 O78           213-215     C.sub.18 H.sub.22 BrN.sub.5 O79           233-236     C.sub.18 H.sub.22 BrN.sub.5 O80           211-213     C.sub.19 H.sub.24 ClN.sub.5 O81           215-217     C.sub.20 H.sub.26 BrN.sub.5 O82           222-225     C.sub.18 H.sub.21 BrClN.sub.5 O83           225-228     C.sub.18 H.sub.21 BrFN.sub.5 O84           200-203     C.sub.18 H.sub.22 ClN.sub.5 O.sub.285           224-226     C.sub.18 H.sub.22 ClN.sub.5 O.sub.286           216-219     C.sub.18 H.sub.21 BrFN.sub.5 O.sub.287           219-224     C.sub.15 H.sub.18 ClN.sub.5 O88           150         C.sub.16 H.sub.20 ClN.sub.5 O89           152         C.sub.22 H.sub.24 ClN.sub.5 O90           232-234     C.sub.22 H.sub.24 ClN.sub.5 O91           201-203     C.sub.24 H.sub.31 Cl.sub.2 N.sub.5 O.sub.392           217-218     C.sub.16 H.sub.20 ClN.sub.5 O93           Paste       C.sub.25 H.sub.37 N.sub.5 O.sub.394           178-186     C.sub.30 H.sub.47 N.sub.5 O.sub.395           170-171     C.sub.16 H.sub.19 N.sub.5 O96           234-235     C.sub.18 H.sub.20 ClN.sub.5 O97            169-170,   C.sub.16 H.sub.19 N.sub.5 O        remelts at 24498           --          C.sub.17 H.sub.22 BrN.sub.5 O99           206-208     C.sub.17 H.sub.22 ClN.sub.5 O100          216-218     C.sub.19 H.sub.24 ClN.sub.5 O101          152-154     C.sub.20 H.sub.23 N.sub.5 O.sub.3102          164-166     C.sub.22 H.sub.27 N.sub.5 O.sub.3103          169-171     C.sub.24 H.sub.31 N.sub.5 O.sub.3104          183-184     C.sub.24 H.sub.27 N.sub.5 O.sub.3105          137-138     C.sub.22 H.sub.27 N.sub.5 O.sub.5106          173-177     C.sub.26 H.sub.23 N.sub.5 O.sub.5107          178-180     C.sub.6 H.sub.14 BrN.sub.5 O108          192- 194    C.sub.12 H.sub.26 BrN.sub.5 O109          196-197     C.sub.13 H.sub.28 BrN.sub.5 O110          217-219     C.sub.11 H.sub.24 BrN.sub.5 O111          229-231     C.sub.12 H.sub.24 BrN.sub.5 O112          232-234     C.sub.12 H.sub.22 BrN.sub.5 O113          220-222     C.sub.13 H.sub.26 BrN.sub.5 O114          188-191     C.sub.15 H.sub.23 BrFN.sub.5 O115          213-216     C.sub.16 H.sub.26 BrN.sub.5 O116          201-203     C.sub.16 H.sub.26 BrN.sub.5 O117          218-221     C.sub.17 H.sub.26 BrN.sub.5 O118          249-250     C.sub.14 H.sub.17 Cl.sub.4 N.sub.5 O119          225-227     C.sub.15 H.sub.20 Cl.sub.3 N.sub.5 O120          222-223     C.sub.15 H.sub.20 Br.sub.2 ClN.sub.5 O121          196-198     C.sub.11 H.sub.23 BrClN.sub.5 O122          196-198     C.sub.11 H.sub.23 Br.sub.2 N.sub.5 O123          196-198     C.sub.22 H.sub.46 Br.sub.3 ClN.sub.10 O.sub.2124          215-217     C.sub.17 H.sub.28 BrN.sub.5 O.sub.2125          190-193     C.sub.17 H.sub.22 BrN.sub.5 O.sub.2126          201-204     C.sub.17 H.sub.22 BrN.sub.5 O.sub.2127          198-200     C.sub.12 H.sub.17 Cl.sub.2 N.sub.5 OS128          224-226     C.sub.10 H.sub.15 Cl.sub.2 N.sub.5 OS129          220-222     C.sub.14 H.sub.17 BrN.sub.6 O.sub.5130          192-195     C.sub.15 H.sub.17 BrCl.sub.2 N.sub.6 O.sub.3131          210-213     C.sub.16 H.sub.19 BrCl.sub.2 N.sub.6 O.sub.3132          231-232     C.sub.13 H.sub.17 Cl.sub.2 N.sub.5 O.sub.3133          227-229     C.sub.12 H.sub.17 Br.sub.2 N.sub.5 O134          232-235     C.sub.12 H.sub.17 BrIN.sub.5135          228-231     C.sub.12 H.sub.17 BrIN.sub.5136          212-214     C.sub.13 H.sub.20 BrN.sub.5 O137          215-217     C.sub.13 H.sub.20 ClN.sub.5 O.sub.2138          215-217     C.sub.14 H.sub.22 BrN.sub.5 O.sub.2139          220-222     C.sub.13 H.sub.17 BrF.sub.3 N.sub.5 O.sub.2140          213-216     C.sub.13 H.sub.20 BrN.sub.5 OS141          218-220     C.sub.12 H.sub.16 Br.sub.2 FN.sub.5 O142          218-220     C.sub.12 H.sub.16 Br.sub.2 ClN.sub.5 O143          237-240     C.sub.12 H.sub.16 Br.sub.2 FN.sub.5 O144          205-207     C.sub.14 H.sub.20 BrCl.sub.2 N.sub.5 O145          218-220     C.sub.12 H.sub.16 Br.sub.2 FN.sub.5 O146          180, dec.   C.sub.47 H.sub.44 Cl.sub.16 N.sub.10 O.sub.8147          Gum         C.sub.47 H.sub.44 Br.sub.2 Cl.sub.14 N.sub.10                    O.sub.8148          238-241     C.sub.13 H.sub.18 BrCl.sub.2 N.sub.5 O149          238-240     C.sub.13 H.sub.18 Br.sub.3 N.sub.5 O150          230-231     C.sub.13 H.sub.18 BrCl.sub.2 N.sub.5 O151          230-231     C.sub.14 H.sub.19 Cl.sub.4 N.sub.5 O152          232-233     C.sub.12 H.sub.15 Cl.sub.4 N.sub.5 O153          222-223     C.sub.15 H.sub.22 Cl.sub.3 N.sub.5 O154          220-221     C.sub.15 H.sub.22 Br.sub.2 ClN.sub.5 O155          215-216     C.sub.13 H.sub.18 BrCl.sub.2 N.sub.5 O.sub.2156          208-210     C.sub.20 H.sub.26 BrN.sub.5 O157          Gum         C.sub.59 H.sub.58 N.sub.10 O.sub.8158          225-227     C.sub.18 H.sub.20 BrCl.sub.2 N.sub.5 O159          225-227     C.sub.18 H.sub.21 BrFN.sub.5 O160          212-214     C.sub.18 H.sub.21 BrFN.sub.5 O161          220-223     C.sub.18 H.sub.20 BrF.sub.2 N.sub.5 O162          221-224     C.sub.18 H.sub.21 BrClN.sub.5 O163          226-228     C.sub.18 H.sub.21 BrFN.sub.5 O164          223-225     C.sub.18 H.sub.20 BrF.sub.2 N.sub.5 O165          167-170     C.sub.20 H.sub.27 N.sub.5 O.sub.3166          Paste       C.sub.21 H.sub.29 N.sub.5 O.sub.3167          Paste       C.sub.22 H.sub.31 N.sub.5 O.sub.3168          Paste       C.sub.22 H.sub.31 N.sub.5 O.sub.3169          202, dec.   C.sub.20 H.sub.23 N.sub.7 O.sub.4170          220-222     C.sub.11 H.sub.24 BrN.sub.5 O171          218-220     C.sub.18 H.sub.28 BrN.sub.5 O        dec.172          100         C.sub.19 H.sub.29 N.sub.5 O173          231-232     C.sub.19 H.sub.30 BrN.sub.5 O174          241-242     C.sub.19 H.sub.30 BrN.sub.5 O        dec.175          228-229     C.sub.19 H.sub.30 BrN.sub.5 O        dec.176          192-197     C.sub.15 H.sub.24 BrN.sub.5 O177          208-211     C.sub.15 H.sub.23 Br.sub.2 N.sub.5 O178          187-188     C.sub.15 H.sub.24 BrN.sub.5 O179          223-224     C.sub.17 H.sub.25 BrFN.sub.5 O180          221-222     C.sub.18 H.sub.28 BrN.sub.5 O181          234-235     C.sub.14 H.sub.17 BrCl.sub.3 N.sub.5 O182          242-243     C.sub.14 H.sub.17 BrCl.sub.3 N.sub.5 O        dec.183          236-237     C.sub.14 H.sub.17 BrCl.sub.3 N.sub.5 O184          205-207     C.sub.13 H.sub.19 BrClN.sub.5 O.sub.2185          202-205     C.sub.13 H.sub.19 BrClN.sub.5 O.sub.2186          205-207     C.sub.14 H.sub.22 BrN.sub.5 O.sub.2187          205         C.sub.15 H.sub.24 BrN.sub.5 O.sub.2188          209         C.sub.15 H.sub.24 BrN.sub.5 O.sub.2189          223         C.sub.15 H.sub.24 BrN.sub.5 O.sub.2190          214-215     C.sub.16 H.sub.26 BrN.sub.5 O.sub.2191          211         C.sub.16 H.sub.26 BrN.sub.5 O.sub.2192          210         C.sub.16 H.sub.26 BrN.sub.5 O.sub.2193          240-242     C.sub.16 H.sub.26 BrN.sub.5 O.sub.2194          214-215     C.sub.16 H.sub.26 BrN.sub.5 O.sub.2195          205         C.sub.16 H.sub.26 BrN.sub.5 O.sub.2196          212         C.sub.17 H.sub.28 BrN.sub.5 O.sub.2197          205         C.sub.17 H.sub.28 BrN.sub.5 O.sub.2198          210-212     C.sub.17 H.sub. 28 BrN.sub.5 O.sub.2199          198-200     C.sub.13 H.sub.20 ClN.sub.5 OS200          197-200     C.sub.13 H.sub.18 ClN.sub.5 OS201          226-227     C.sub.17 H.sub.30 BrN.sub.5 O202          223-225     C.sub.14 H.sub.28 BrN.sub.5 OS203          184-185     C.sub.18 H.sub.28 BrN.sub.5 O.sub.3204          221-223     C.sub.14 H.sub.21 Cl.sub.2 N.sub.5 O205          215-217     C.sub.12 H.sub.17 Br.sub.2 N.sub.5 O206          221-223     C.sub.12 H.sub.17 BrFN.sub.5 O207          212-214     C.sub.13 H.sub.17 BrF.sub.3 N.sub.5 O208          235-237     C.sub.13 H.sub.17 BrN.sub.6 O209          233-236     C.sub.13 H.sub.17 BrN.sub.6 O210          207-209     C.sub.15 H.sub.21 BrF.sub.3 N.sub.5 O.sub.2211          212-216     C.sub.12 H.sub.16 BrF.sub.2 N.sub.5 O212          239-240     C.sub.12 H.sub.16 BrClN.sub.6 O.sub.3213          233-234     C.sub.12 H.sub.14 BrCl.sub.2 N.sub.5 O214          161-168     C.sub.23 H.sub.26 BrCl.sub.2 N.sub.9 O.sub.4 S215          233-234     C.sub.14 H.sub.19 BrCl.sub.3 N.sub.5 O216          229-230     C.sub. 14 H.sub.19 BrCl.sub.3 N.sub.5 O217          219-220     C.sub.14 H.sub.19 BrCl.sub.3 N.sub.5 O218          225-227     C.sub.15 H.sub.24 BrN.sub.5 O219          209-212     C.sub.15 H.sub.24 BrN.sub.5 O.sub.2220          210-211     C.sub.17 H.sub.28 BrN.sub.5 O.sub.4221          216-217     C.sub.18 H.sub.21 BrClN.sub.5 O222          210-213     C.sub.18 H.sub.21 BrClN.sub.5 O223          213-214     C.sub.19 H.sub.21 BrF.sub.3 N.sub.5 O.sub.2224          206-208     C.sub.20 H.sub.25 BrClN.sub.5 O225          237-238     C.sub.18 H.sub.20 BrF.sub.2 N.sub.5 O226          220-222     C.sub.18 H.sub.19 BrF.sub.3 N.sub.5 O227          233-235     C.sub.18 H.sub.19 BrF.sub.3 N.sub.5 O228          --          C.sub.16 H.sub.19 BrClN.sub.5 O229          --          C.sub.16 H.sub.19 Br.sub.2 N.sub.5 O______________________________________ 
    
     Insecticide Formulations 
     In the normal use of the insecticidal triazines of the present invention, the triazines usually will not be employed free from admixture or dilution, but ordinarily will be used in a suitable formulated composition compatible with the method of application and comprising an insecticidally effective amount of the triazine. The triazines of this invention, like most pesticidal agents, may be blended with the agriculturally acceptable surface-active agents and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application of an insecticide may affect the activity of the material. The present triazines may be applied, for example, as sprays, dusts, or granules to the area where pest control is desired, the type of application varying of course with the pest and the environment. Thus, the triazines of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, and the like. It will be understood that the insecticides themselves may be present as essentially pure compounds, or as mixtures of these triazine compounds. 
     Granules may comprise porous or nonporous particles, such as attapulgite clay or sand, for example, which serve as carriers for the triazines. The granule particles are relatively large, a diameter of about 400-2500 microns typically. The particles are either impregnated with the triazine from solution or coated with the triazine, adhesive sometimes being employed. Granules generally contain 0.05-10%, preferably 0.5-5%, active ingredient as the insecticidally effective amount. 
     Dusts are admixtures of the triazines with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which acts carriers for the insecticide. These finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful for controlling insects contains 1 part of triazine, such as 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(3,4-dichlorophenylmethoxy)-1,3,5-triazine (Compound 2), and 99 parts of talc. 
     The triazines of the present invention may be made into liquid concentrates by dissolution or emulsification in suitable liquids and into solid concentrates by admixture with talc, clays, and other known solid carriers used in the pesticide art. The concentrates are compositions containing, as an insecticidally effective amount, about 5-50% triazine, and 95-50% inert material, which includes surface-active dispersing, emulsifying, and wetting agents, but even higher concentrations of active ingredient may be employed experimentally. The concentrates are diluted with water or other liquids for practical application as sprays, or with additional solid carrier for use as dusts. 
     Typical carriers for solid concentrates (also called wettable powders) include fuller&#39;s earth, clays, silicas, and other highly absorbent, readily wetted inorganic diluents. A solid concentrate formulation useful for controlling insects contains 1.5 parts each of sodium lignosulfonate and sodium lauryl sulfate as wetting agents, 25 parts of Compound 52 (above), and 72 parts of attapulgite clay. 
     Manufacturing concentrates are useful for shipping low melting products of this invention. Such concentrates are prepared by melting the low melting solid products together with one percent or more of a solvent to produce a concentrate which does not solidify on cooling to the freezing point of the pure product or below. 
     Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water or other liquid carriers. They may consist entirely of the triazines with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively non-volatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and normally applied as sprays to areas to be treated. 
     Typical surface-active wetting, dispersing, and emulsifying agents used in pesticidal formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfates of higher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises about 1-15% by weight of the insecticidal composition. 
     Other useful formulations include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentrations, such as acetone or other organic solvents. 
     An insecticidally effective amount of triazine in an insecticidal composition diluted for application is normally in the range of about 0.001% to about 8% by weight. Many variations of spraying and dusting compositions known in the art may be used by substituting the triazines of this invention into compositions known or apparent in the art. 
     The insecticidal compositions of this invention may be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc. In using the compositions to control insects, it is only necessary that an insecticidally effective amount of triazine be applied to the locus where control is desired. Such locus may, e.g., be the insects themselves, plants upon which the insects feed, or the insect habitat. When the locus is the soil, e.g., soil in which agricultural crops are or will be planted, the active compound may be applied to and optionally incorporated into the soil. For most applications, an insecticidally effective amount will be about 75 to 4000 g per hectare, preferably 150 g to 3000 g per hectare. 
     In both the solid and liquid formulations described above, it has been found that the addition of an ultra-violet light (u.v.) stabilizer to the formulations is particularly useful and advantageous in prolonging the activity, i.e., the photostability, of the compounds of this invention when they are exposed to light or photosensitizers on the leaves of the sprayed plants. Thus, for example, the addition of 2-hydroxy-4-n-octoxybenzophenone in photostabilizing amounts to the insecticidal formulation of Compound 78 (above) can reduce the photolysis rate of the triazines several-fold when tested in artificial sunlight. In particular, it has been found that the addition of from about 0.02 to 2.0 parts by weight of the above octoxybenzophenone per part by weight of the triazine composition, is effective for this purpose. 
     Biological Data 
     Representative compounds of the present invention were tested in the laboratory as aqueous acetone or aqueous methanol solutions containing a small amount of octylphenoxypolyethoxyethanol surfactant. The insecticidal activity of these compounds against the tobacco budworm is summarized in TABLE 2 (below). 
     Compounds 60 and 78 were also formulated as 10% wettable powder formulations. A typical 10% wettable powder formulation consists of the following: 
     
         ______________________________________Wettable Powder, 10%            Percent by Weight______________________________________Active ingredient (95%)            10.5Dispersing Agent 4.0Wetting Agent    1.0Carrier/Diluent  84.5            100.00______________________________________ 
    
     The dispersing agent was sugar free, sodium based sulfonates of Kraft lignin sold under the trademark &#34;Polyfon F&#34;. (Westvaco Polychemical Corp., Charleston Heights, S.C.) The wetting agent was sodium alkylnaphthalene sulfonate sold under the trademark &#34;Nekal BX-78&#34;. (Rhone Poulenc, Dayton, N.J.) The carrier/diluent was an attapulgite clay. 
     The 4,6-diamino-1,2-dihydro-1,3,5-triazine derivatives of the present invention were tested for insecticidal activity in foliar evaluations against the tobacco budworm (Heliothis virescens [Fabricius]). 
     In these tests against the tobacco budworm, nine-day-old chickpea plants (Cicer arietinum) were sprayed at 20 psi to runoff on both upper and lower leaf surfaces with solutions of test chemical to provide application rates as high as 3000 ppm of active ingredient. The solvent used to prepare the solutions of the test chemical was 10% acetone or methanol (v/v), and 0.1% of the surfactant, octylphenoxypolyethoxyethanol in distilled water. Four replicates, each containing four chickpea plants, for each rate of application of test chemical were sprayed. The treated plants were transferred to a hood where they were kept until the spray had dried. 
     The four chickpea plants in each replicate treated with test chemical as described above were removed from their pots by cutting the stems just above the soil line. The excised leaves and stems from the four plants in each replicate were placed in individual 8-ounce paper cups. Five first-instar (4-5 days old) tobacco budworms were counted into each cup, taking care not to cause injury. An opaque plastic lid was placed on each cup which was then held in a growth chamber for a 96 hour exposure period at 25° C. and 50% relative humidity. At the end of the 96 hour exposure period the cups were opened, and the numbers of dead and live insects were counted. Moribund larvae which were disoriented or unable to crawl normally were counted as dead. Using the insect counts, the efficacy of the test chemical was expressed in percent mortality. The condition of test plant was also observed for phytotoxicity and for reduction of feeding damage as compared to an untreated check. 
     In an alternate test method, 10% wettable powder formulations of Compounds 146, 147, and 157 were tested against tobacco budworm on chickpea plants and cabbage looper on pinto bean (Phaseolus vulgaris) plants. The candidate insecticides were applied as aqueous solutions of the 10% wettable powder formulations at rates o application equivalent to 1.0 pound active ingredient/acre (lb/A) and submultiples thereof, for example 0.5 lb/A, 0.25 lb/A, and so on. In these tests, nine-day-old test plants were sprayed with the test chemical solutions at a delivery rate of 30 gallons/acre at 40 psi with the nozzle of the spray machine adjusted to 10.5 inches above the foliage of the test plants. Four replicates each containing four plants for each rate of application of test chemical, were sprayed. 
     The aqueous test chemical solutions were prepared by dissolving 1.2 grams of the 10% wettable powder formulation in 30 ml of distilled water. For the 1.0 lb/A rate of application, 15 ml of the solution was sprayed onto the test plants as described above. The remaining 15 ml of test solution was diluted with 15 ml of distilled water. A 15 ml aliquot of the resultant solution was removed and sprayed onto test plants to provide a rate of application of 0.5 lb/A. The serial dilution and spraying was continued to provide the appropriate lower rates of application. 
     Upon completion of spraying the remaining portion of the test was conducted as described above with the 4-5 day-old tobacco budworm. 
     These tested compounds (Compounds 146, 147, and 157) were likewise generally very active against the tobacco budworm. The results of these alternate tests are also reported in TABLE 2 below. 
     Selected compounds of the present invention were also tested by the foliar spraying methods of compounds 1 et seq. of TABLE 2 (other than the wettable powder) against other insect species, which included fall armyworm (Spodoctera frugiperda [J. E. Smith]), imported cabbageworm (Pieris rapae [Linnaeus]), Mexican bean beetle (Epilachna varivestis Mulsant), southern armyworm (Spodoptera eridania [Cramer]), soybean looper (Pseudoplusia includens [Walker], beet armyworm (Spodoptera exigua [Hubner]), corn earworm (Heliothis zea [Boddie]), cabbage looper (Trichoplusia ni [Hubner]), diamondback moth (Pluttela xylostella [Linnaeus]), European corn borer (Ostrinia nubilalis [Hubner]), and black cutworm (Agrotis ipsilon [Hufnagel]). The insecticidal activity against these species is summarized in TABLE 3 below. 
     The compounds of the present invention appear to be especially suited for use on cole crops, sweet corn, tobacco, and cotton against foliar-feeding lepidoptera. 
     
                       TABLE 2______________________________________RESULTS OF FOLIAR SPRAY EVALUATIONS* AGAINSTSELECTED SPECIES OF THE ORDER LEPIDOPTERA(TOBACCO BUDWORM - TBW)Cmpd           RateNo.            (PPM)    % KILL______________________________________ 1             30       90          10       19 2             300      33          30        0 3             300      85          30        0 4             30       70          10       11 5             30       72          10       25 6             30       84          10       85 7             30       67          10       13 8             30       81          10        0 9             30       42          10       11 10            30       13          10       12 11            30        6          10        0 12            30       60          10        0 13            10       85           3       11 14            300      44          30        0 15            30       75          10       28 16            300      95          30       47 17            300      17          30        6 18            300      70          30        0 19            300      33          30       10 20            300      44          30       13 21            300       5          30       42 22            300       0 23            300      95          30       38 24            30       63          10        0 25            300       0 26            300       0 27            300       0 28            30       79          10       55 29            30       75          10       60 30            300       0 31            300      89          30       37 32            30       90          10        6 33            30       85          10       40 34            300      90          30       17 35            300       6          30        6 36            300      10          30        0 37            30       42          10       11 38            300      39          100      15 39            300       0 40            300      90          100      70 41            30       31          10       38 42            100      70          30       70 43             3       65           1        0 44            30       44          10       50 45            300      70          30        0 46            300      89          30        5 47            64       60          32       70 48            30       29          10       42 49            300      90          30       18 50            1000     50          300       0 51            100      90          54       82 52            32       93          17       73 53            10       80           3       21 54            30       95          10       85 55            30       50          10        0 56            30       25          10        0 57            3000     84          1000     33 58            30       60          10       13 59            30       75          10       20 60             3       72           1        6 61            30       85          10       25 62            3000     65          1000     31 63             3       70           1       53 64            3000     30          1000      6 65            1000     79          540      65 66            30       95          10       60 67            3000     36          1000      5 68            30       29          10        0 69            10       61          6.4      100 70            300      90          30        5 71            300      85          30        0 72            300      90          100      70 73            300      90          30       11 74            300      45          30        0 75            30        0 76            30        0 77            300      11          30        0 78            30       95          10       65 79            300      85          30        0 80            300      90          30        6 81            3000     78          1000     25 82            30       95          10       24 83            30       89          10       72 84            30       31          10        0 85            1000     75          540      85 86            300      95          30       12 87            300       5          30        5 88            300       0 89            300       0 90            300       0 91            300       5          30        0 92            30       95          10       71 93            30       72          10        6 94            30       20          10        0 95            32       93          17       80 96            30       95          10       75 97            32       93          17       87 98             3       75           1       10 99            300      95          30       50100            300       5          30       11101            30       65          10        5102            30       47          10       10103            30       47          10        0104            300      95          30       30105            30       45          10        0106            30       60          10        0107            300      56          30       18108            30       95          10       67109            30       50          10       12110            30       26          10        0111            30       95          10       53112            30       90          10       75113            10       95           3       21114            30       95          10       85115            300      95          30       80116            30       95          10       90117            30       95          10       75118            640      80          320      65119            300      15          30        0120            300      70          30        0121            No Data122            No Data123            300      95          30       47124             3       44           1        0125            300      95          30       79126            300      90          100      90127            10       90           3       65128            300      90          100      85129            300      68          30       74130            5000      0131            300      80          30       35132            100      95          30       80133            170      80          100      58134            100      72          30       42135            30       85          10       25136            300      85          100      45137            300      95          100      33138            1000     95          300      65139            300      95          100      75140            300      95          100      75141            100      95          30       58142            30       33          10       13143            100      80          30       47144            10       95           3       75145            100      95          30       59146            1**      100147            1**      100148            30       95          10       55149            30       67          10       32150            30       95          10       80151            30       95          10       47152            1000     10          300       0153            10       95           3       35154            30       95          10       90156            30       70          10        6157            1**      100158            30       75          10       16159            30       95          10       55160            30       95          10       85161            30       90          10       45162            30       80          10       50163            30       89          10       17164            30       95          10       65165            300      95          30       65166            30       90          10       75167            30       75          10       53168            30       55          10       22169            No Data170            No Data171            100      94          30       83172            100      95          30       65173            100      95          30       70174            100      90          30       69175            100      65          30       55176            30       95          10       90177            30       95          10       89178            30       95          10       50179            100      95          30       85180            30       80          10       21181            300      16          100       6182            300      33          100       6183            300      53          100       5184            100      80          30       15185            300      95          100      55186            30       95          10       55187            100      95          30       95188            300      95          100      89189            30       83          10       61190            10       95           3       70191             3       75           1       21192            10       94           3       72193            30       84          10       74194            30       95          10       78195            30       95          10       85196            10       95           3       84197            100      95          30       74198            100      95          30       95199            30       83          10       40200            100      89          30       89201            30       95          10       100202            100      95          30       55203            300      90          100      50204            30       95          10       90205            100      90          30       85206            300      85          100      50207            100      75          30       35208            100      95          30       95209            100      63          30       15210            300      94          100      94211            300      90          100      47212            100      85          30       15213            100      87          30       94214            30       94          10       82215            30       95          10       56216            10       80           3       30217            30       95          10       85218            300      95          100      95219            30       95          10       50220            100      95          30       80221            30       95          10       60222            100      95          30       75223            100      95          30       70224            100      95          30       53225            100      90          30       45226            30       90          10       21227            100      95          30       90______________________________________ *Exposure time  96 hrs **Cmpds 146, 147, 157  indicates data for a compound formulated as a 10% wettable powder.  Cmpds 146, 147, 157  indicates rate units are in lbs/acre 
    
     
                                           TABLE 3__________________________________________________________________________RESULTS OF FOLIAR SPRAY EVALUATIONS AGAINST SELECTEDSPECIES OF THE ORDER LEPIDOPTERA AND COLEOPTERA     Percent Kill at 100 ppmCOMPOUND NO.     *FAW         ICW            MBB SAW SBL  BAW CEW CL DBM ECB                                           BCW__________________________________________________________________________6                              5      5013                            50  90  7028            20 100          55  80  10029                                    9030                5                   8542                            45  50  3050                   4051                       .sup. 18.sup.1                         9552        65     45               95  9053        70  95 90  65       60  85  9559        100.sup.2         70  5  20       95  90  9063        .sup. 90.sup.2         30 70           50  85  6566               100          50  40  3069               .sup.  5.sup.3   50  8572                                    5078        55.sup.2         95 100          70  65  9092        95     .sup. 25.sup.3                10    I.sup.4 **                          6  .sup. 13.sup.1                                 .sup. 40.sup.5                                    70  44 095                       .sup. 19.sup.1                         10096        100     5  50       33  .sup. 56.sup.1                                 .sup. 30.sup.5                                    75  44 097                       .sup. 18.sup.1                         10098        .sup. 85.sup.2            .sup. 70.sup.2                35       85  100 65107                   0108       65     10           35  40  65111       60112                           25         70123                           .sup. 65.sup.3127                           40      55128       40                          25134       65                          90135                           70      30139                            5      37144                           15      95146                           100.sup.6                                 100.sup.6147                           100.sup.6                                 100.sup.6150                           35      90152                            0153       70     100 95                  45154       75     100 95       70  90     15155                           .sup. 35.sup.3157                           100.sup.6                                 100.sup.6162                           35177                           .sup. 10.sup.3                                 95186                           11190                           72193                           11194                           32199                           10200                           10204                           15      90205                           25      11210                            6212                           .sup. 25.sup.3214                           30215                            5      95216                            6218                           .sup. 25.sup.3219                           19221                           71222                           80226                           25227                            5__________________________________________________________________________ *FAW  fall armyworm  ICW  imported cabbage worm  MBB  Mexican bean beetle  SAW  southern armyworm  SBL  soybean looper  BAW  beet armyworm  CEW  corn earworm  CL  cabbage looper  DBM  diamondback moth  ECB  European corn borer  BCW  black cutworm **I  Inactive .sup.1 at 32 ppm .sup.2 at 30 ppm .sup.3 at 1000 ppm .sup.4 at 15 ppm .sup.5 at 10 ppm .sup.6 at 0.5 lbs/acre