Insecticidal 4,6-diamino-1,2-dihydro-1,3,5-triazine derivatives

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, "Dihydrotriazines and Related Heterocycles", J. Chem. Soc. (London), 1962, 3915; "Antimicrobial Activity of Some O-Ethers of 4,6-Diamino-1,2-dihydro-1-hydroxy-2-substituted 1,3,5-Triazines", J. Med. Chem., 8, 684-91 (1965); (ibid) J. Chem. Soc., 1829-43 (1965); and "The Anti-Malaria Activity of N-Benzyloxy Dihydrctriazines", Annals of Tropical Medicine and parasitology, 76, No. 1 (1982).
See also, "Amino-Oxy Derivatives. Part III. Dihydrotriazines and Related Heterocycles", Mamalis et al., J. Chem. Soc. (London), 1962, p. 3915, and "Amino-Oxy Derivatives. Part II. Some Derivatives of N-Hydroxydiguanide", 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, (.alpha.-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', W', X' and Y' have the same definition as V, W, X, and Y (above);
n is 1 to 5;
R.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl;
R.sup.2 is selected from the group consisting of hydrogen, and lower alkyl, preferably methyl;
R.sup.1 and R.sup.2 may be taken together to form a spirocycloalkane ring;
R.sup.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.sup.1 is methyl or ethyl;
R.sup.2 is methyl; and R.sup.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.sub.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 (.alpha.-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.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl;
R.sup.2 is selected from the group consisting of hydrogen and methyl, and
R.sup.1 and R.sup.2 may be taken together to form a spirocycloalkane ring;
R.sup.3 is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl; and
R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 are independently hydrogen, halogen, alkyl, or alkoxy with the proviso that both of R.sup.7 and R.sup.8 may not be hydrogen and with the further proviso that R.sup.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, (.alpha.-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.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl;
R.sup.2 is selected from the group consisting of hydrogen and methyl, and
R.sup.1 and R.sup.2 may be taken together to form a spirocycloalkane ring; and
R.sup.3 is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl, with the proviso that R.sup.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.degree.-195.degree. C. (Lit. m.p. 198.degree. 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.degree.-149.degree. C. (lit. m.p. 145.degree. 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.degree.-218.degree. C. (lit. m.p. 215.degree. 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.RTM. 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.degree.-171.degree. C. (lit. m.p. 168.degree.-170.degree. 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.degree.-100.degree. 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.degree.-219.degree. 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.degree. 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.degree.-212.degree. 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.degree.-152.degree. C./5 mm Hg. NMR analysis of the fractions indicated that two fractions, boiling point 140.degree.-150.degree. 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.degree.-248.degree. 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.degree.-208.degree. 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.degree.-177.degree. 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.degree. 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 O.phi.; HBr 2,4,5-Cl.sub.3 29 3 O.phi.; -- 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 .phi. 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 .phi. 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 .phi. H H H H HCl 78 1 H .phi. H H H HBr 79 1 H H .phi. H H HBr 80 1 CH.sub.3 .phi. H H H HCl 81 1 CH.sub.3 .phi. H H CH.sub.3 HBr 82 1 H .phi.; H H H HBr 4-Cl 83 1 H .phi.; H H H HBr 4-F 84 1 H .phi. H H H HCl 85 1 H H .phi. H H HCl 86 1 H .phi. 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 .phi. H H 1 HCl 90 1 CHCH.phi. H H 1 HCl a Hydrate 91 1 .phi.; 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 O.phi.; HBr 2,4,6-Trimethyl125 2 Naphth-1-yloxy HBr126 2 Naphth-2-yloxy HBr127 1 S.phi.; 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 .phi. H H H HBr157 1 H .phi. H H H Pamoic* acid158 1 H .phi.; H H H HBr 3,4-Cl.sub.2159 1 F .phi. H H H HBr160 1 H .phi. F H H HBr161 1 H .phi. F H H HBr 4-F162 1 Cl H H .phi. H HBr163 1 F H H .phi. H HBr164 1 F .phi. 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 O.phi.; HBr 4-Cl185 2 O.phi.; HCl 4-Br186 3 O.phi. HBr187 3 O.phi.; HBr 2-CH.sub.3188 3 O.phi.; HBr 3-CH.sub.3189 3 O.phi.; HBr 4-CH.sub.3190 3 O.phi.; HBr 2,3-(CH.sub.3).sub.2191 3 O.phi.; HBr 2,4-(CH.sub.3).sub.2192 3 O.phi.; HBr 2,5-(CH.sub.3).sub.2193 3 O.phi.; HBr 2,6-(CH.sub.3).sub.2194 3 O.phi. ; HBr 3,4-(CH.sub.3).sub.2195 3 O.phi.; HBr 3,5-(CH.sub.3).sub.2196 3 O.phi.; HBr 2,3,5-(CH.sub.3).sub.3197 3 O.phi.; HBr 3,4,5-(CH.sub.3).sub.3198 2 O.phi.; HBr 2,3,6-(CH.sub.3).sub.3199 2 S.phi. HCl200 2 S.phi.; -- 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 .phi.; H H H HBr 2-Cl222 1 H .phi.; H H H HBr 3-Cl223 1 H .phi.; H H H HBr 4-OCF.sub.3224 3 Cl H H .phi. H HBr225 1 F H H .phi.; H HBr 4-F226 1 F H H .phi.; H HBr 2,6-F.sub.2227 1 F .phi. ; 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' W' X' Y' 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 (.degree.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'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 "Polyfon F". (Westvaco Polychemical Corp., Charleston Heights, S.C.) The wetting agent was sodium alkylnaphthalene sulfonate sold under the trademark "Nekal BX-78". (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.degree. 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

Claims

1. An insecticidal composition comprising an insecticidal amount of the compound ##STR34## wherein R is selected from the group consisting of hydrogen, straight or branched chain alkyl, haloalkyl, (substituted aryl)haloalkyl, arylakyl, (substituted aryl)alkyl, (.alpha.-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, heterocyclclyl, alkoxycarbonyl, and substituted phenyl of the structure ##STR35## 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, substituted aryl, aryloxy, (substituted aryl)oxy, alkylthio, alkylsulfoxy, alkylsulfonyl, cyano, and nitro;
or V and W, or W and X, when taken together, comprise the ring-forming group ##STR36## wherein V', W', X' and Y' have the same definition as V, W, X, and Y;
n is 1 to 5;
R.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl;
or R.sup.2 is selected from the group consisting of hydrogen and lower alkyl,
R.sup.1 and R.sup.2 taken together form a spirocycloalkane ring of 3 to 9 carbon atoms;
R.sup.3 is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl;
and agriculturally acceptable salts thereof, in admixture with a compatible agricultural vehicle, wherein each alkyl, alkenyl, and alkynyl group independently contains up to 13 carbon atoms; the cycloalkyl groups contain 3 to 7 carbon atoms; and each aryl group is independently selected from the group consisting of phenyl, naphthyl, or phenanthryl which optionally substituted by one or more alkyl, halo, alkoxy, cycloalkyl, aryl, haloalkyl, haloalkoxy, cyano, nitro, dialkylamino or thioalkyl groups, and
wherein the heterocyclyl groups are selected from the group consisting of thienyl, furyl, pyranyl, triazinyl, pyrrlyl, imidazolyl, pyridyl, pyridazinyl, isoxazolyl, benzothienyl, isobenzofuranyl, indolyl, quinolyl, phthalimido, benzodioxolyl, benzodioxanyl, benzofuranyl, and benzopyranyl.
2. The composition of claim 1 wherein R is cycloalkyl, aryl, substituted phenoxy, substituted phenylthio, or substituted phenyl of the structure ##STR37## 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.sup.1 is methyl or ethyl;
R.sup.2 is methyl;
R.sup.3 is hydrogen;
or the acid salts thereof.
3. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(cycloheptylmethoxy)-1,3,5-triazine hydrobromide.
4. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(4-methoxyphenyl)butoxy]-1,3,5-triazine hydrobromide.
5. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,4,6-trimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
6. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(4-chlorophenylthiomethoxy)-1,3,5-triazine hydrochloride.
7. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,6-dichlorophenyl)propoxy]-1,3,5-triazine hydrobromide.
8. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine, pamoic acid salt.
9. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(5-bromo-2,4-dichlorophenylmethoxy)-1,3,5-triazine, pamoic acid salt.
10. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine, pentanoic acid salt.
11. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,4-dimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
12. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,5-dimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
13. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,3,5-dimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
14. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-(adamant-1-yl)ethoxy]-1,3,5-triazine hydrobromide.
15. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(4-bromophenylmethoxy)-1,3,5-triazine hydrobromide.
16. The composition of claim 1 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2-bromo-4,5-dichlorophenyl)propoxy]-1,3,5-triazine hydrochloride.
17. A method for controlling insects which comprises applying to the locus where control is desired an insecticidal amount of a compound of the formula ##STR38## where R is selected from the group consisting of hydrogen, straight or branched chain alkyl, haloalkyl, (substituted aryl)haloalkyl, arylakyl, (substituted aryl)alkyl, (.alpha.-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, heterocyclclyl, alkoxycarbonyl, and substituted phenyl of the structure ##STR39## 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, substituted aryl, aryloxy, (substituted aryl)oxy, alkylthio, alkylsulfoxy, alkylsulfonyl, cyano, and nitro;
or V and W, or W and X, when taken together, comprise the ring-forming group ##STR40## wherein V', W', X' and Y' have the same definition as V, W, X, and Y;
n is 1 to 5;
R.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl;
R.sup.2 is selected from the group consisting of hydrogen and lower alkyl;
or R.sup.1 and R.sup.2 taken together form a spirocycloalkane ring of 3 to 9 carbon atoms;
R.sup.3 is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl;
and agriculturally acceptable salts thereof, in admixture with a compatible agricultural vehicle, wherein each alkyl, alkenyl, and alkynyl group independently contains up to 13 carbon atoms; the cycloalkyl groups contain 3 to 7 carbon atoms; and each aryl group is independently selected from the group consisting of phenyl, naphthyl, or phenanthryl which optionally are substituted by one or more alkyl, halo, alkoxy, cycloalkyl, aryl, haloalkyl, haloalkoxy, cyano, nitro, dialkylamino or thioalkyl groups, and
wherein the heterocyclyl groups are selected from the group consisting of thienyl, furyl, pyranyl, triazinyl, pyrrlyl, imidazolyl, pyridyl, pyridazinyl, isoxazolyl, benzothienyl, isobenzofuranyl, indolyl, quinolyl, phthalimido, benzodioxolyl, benzodioxanyl, benzofuranyl, and benzopyranyl.
18. The method of claim 17 wherein R is cycloalkyl, aryl, substituted phenoxy, substituted phenylthio, or substituted phenyl of the structure ##STR41## 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.sup.1 is methyl or ethyl;
R.sup.2 is methyl
R.sup.3 is hydrogen;
or the acid salts thereof.
19. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-cycloheptylmethoxy)-1,3,5-triazine hydrobromide.
20. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(2,4,5-trichlorophenylmethoxy)-1,3,5-triazine, pamoic acid salt.
21. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(5-bromo-2,4-dichlorophenylmethoxy)-1,3,5-triazine, pamoic acid salt.
22. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(naphth-1-ylmethoxy)-1,3,5-triazine, pentanoic acid salt.
23. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,4-dimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
24. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,5-dimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
25. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2,3,5-trimethylphenoxy)propoxy]-1,3,5-triazine hydrobromide.
26. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-(adamant-1-yl)ethoxy]-1,3,5-triazine hydrobromide.
27. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(4-bromophenylmethoxy)-1,3,5-triazine hydrobromide.
28. The method of claim 17 wherein the insecticidal compound is 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(2-bromo-4,5-dichlorophenyl)propoxy]-1,3,5-triazine hydrochloride.
29. Compounds of the formula ##STR42## and agriculturally acceptable salts thereof, wherein R is a heterocyclyl moiety selected from the following ##STR43## wherein R.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl, wherein aryl is phenyl, naphthyl, or phenanthryl;
R.sup.2 is selected from the group consisting of hydrogen and methyl;
or R.sup.1 and R.sup.2 taken together form a spirocycloalkane ring of 3 to 9 carbon atoms;
R.sup.3 is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl; and
R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 are independently hydrogen, halogen, alkyl, or alkoxy with the proviso that R.sup.7 and R.sup.8 are not both hydrogen and with the further proviso that R.sup.9 is not hydrogen, and wherein each alkyl and alkenyl group independently contains up to 13 carbon atoms.
30. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-(4,5-dichloro-1-phthalimido)ethoxy]-1,3,5-triazine.
31. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-(4,5-dichloro-1-phthalimido)propoxy]-1,3,5-triazine.
32. Compounds of the formula ##STR44## and agriculturally acceptable salts thereof, wherein R is selected from phenyl or naphthyl, phenylalkyl, phenylmethylalkyl, (.alpha.-cycloalkyl)phenylmethyl, or (phenyl-substituted)cycloalkyl, wherein each phenyl or naphthyl group optionally is substituted with lower alkyl, halogen, and lower alkoxy and each alkyl is straight or branched, wherein each cycloalkyl group independently contains 3 to 7 carbon atoms;
n is 1 to 5;
R.sup.1 is selected from the group consisting of lower alkyl, arylalkyl, arylalkenyl, and alkoxyaryl, wherein aryl is phenyl, naphthyl, or phenanthryl;
R.sup.2 is selected from the group consisting of hydrogen and methyl;
or R.sup.1 and R.sup.2 taken together form a spirocycloalkane ring of 3 to 9 carbon atoms; and
R.sup.3 is selected from the group consisting of hydrogen, lower alkylcarbonyl, cyclopropylcarbonyl, methoxymethylcarbonyl, and 2-furanylcarbonyl, with the proviso that R.sup.3 is not hydrogen or lower alkylcarbonyl when R is (optionally substituted)phenyl, (optionally substituted)naphthyl, or phenylalkyl, and wherein each alkyl and alkenyl group independently contains up to 13 carbon atoms.
33. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-methyl-3-(2-fluorophenyl)propoxy]-1,3,5-triazine.
34. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[2-methyl-3-(4-methoxyphenyl)propoxy]-1,3,5-triazine.
35. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[3-(4-methoxyphenyl)butoxy]-1,3,5-triazine.
36. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[cis/trans-3-(2-methylphenyl)cyclohexylmethoxy]-1,3,5-triazine.
37. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[cis-3-(3-methylphenyl)cyclohexylmethoxy]-1,3,5-triazine.
38. 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-[cis/trans-3-(4-methylphenyl)cyclohexylmethoxy]-1,3,5-triazine.
39. The compound 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(3-cyclopropyl-3-phenylpropoxy)-1,3,5-triazine hydrobromide.
40. The compound 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(cis/trans-3-phenylcyclohexylmethoxy)-1,3,5-triazine hydrobromide.

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Insecticidal 4,6-diamino-1,2-dihydro-1,3,5-triazine derivatives

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US Referenced Citations (5)

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