Pesticidal 1,3,5-triazapenta-1,4-dienes
United States Patent 1191 Pissiotas Apr. 1, 1975 [1 PESTICIDAL I 1,3,5-TRIAZAPENTA-1,4-DIENES [75] Inventor:  
 [73] Assignee: Ciba-Geigy Corporation, Ardsley, N.Y.  
 Georg Pissiotas, Lorrach, Germany [22] Filed: June 12, 1974 [21] Appl. No.: 478,679  
 [30] Foreign Application Priority Data June 25, i973 Switzerland 9243/73 Apr. 26, 1974 Switzerland 5755/74 [52] U.S. CL... 260/564 RF, 260/465 D, 260/465 E, 260/470, 260/47] R, 424/304, 424/309, 424/326 [51] Int. Cl. C07c 123/00 [58] Field of Search 260/564 RF, 565 D, 470, 260/471 R [56] References Cited UNITED STATES PATENTS 12/1973 Harrison ct al. 260/564 RF Primary E.\&#39;aminerLeon Zitver Assistant Examiner-Gerald A. Schwartz Attorney, Agent, or FirmHarry Falber; Frederick H. Rabin [57 ABSTRACT 1,3,5-Tria2apental ,4-diehes having the formula R represents hydrogen or, according to n, one or more identical or different radicals such as halogen, alkyl, alkoxy, alkylthio, alkenyloxy, cyano, nitro dialkylamino or carbalkoxy,  
 n stands for the numbers 1 to 5,  
 R represents hydrogen or alkyl, and  
 R and R, each represent alkyl,  
 processes for their preparation, and their use in pest control.  
 7 Claims, No Drawings wherein R, represents hydrogen or, according to 11, one or more identical or different radicals such as halogen, alkyl, alkoxy, alkylthio, alkenyloxy, cyano, nitro, dialkylamino or carbalkoxy, n stands for the numbers 1 to 5, R represents hydrogen or alkyl, and R and R each represent alkyl. The alkyl, alkoxy, alkylthio, alkenyloxy and carbalkoxy groups denoted by R, to R, contain in the chain one to l8 carbon atoms, in the case of R,, R and R particularly one to six, and in the case of R one to four, or in the case of the alkenyl chains three to 18, preferably three to five carbon atoms. These chains can be straight-chain or branched-chain, unsubstituted, or preferably substituted by one or more identical or different halogen atoms, cyano, hydroxyl, alkoxy or ethylthio groups. By halogen is meant fluorine, chlorine, bromine and/or iodine. Examples of such groups are, inter alia, methyl, methoxy, methylthio, ethyl, ethoxy,  
 ethylthio, trifluoromethyl, chloroethyl, propyl, isopromore identical or different radicals such as chlorine or methyl, It stands for the numbers 1 to 2, R represents hydrogen, and R and R each represent methyl.  
 The compounds of formula l can be prepared, for example, by the following methods known per se:  
  =t -R NCOC H HlICHl 3 R R ya 2 4 II III -C H OH IV V POCl  
 oder  
 SOCl  
  In formulae II to V, the symbols R, to R and n have the meanings given for formula I. The reactions are performed under normal pressure, at a temperature of between 0 and 200C, and preferably in solvents and diluents inert to the reactants. Suitable solvents or diluents are, for example, the following: aromatic hydrocarbons such as benzene, toluene or ligroins, halogenated hydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated alkanes having one to three carbon atoms, ethers such as dioxane or tetrahydrofuran; esters such as acetic acid ethyl ester; ketones such as methyl ethyl ketone, diethylketone, nitriles, etc..  
 - The starting materials of formulae II to V are in some cases known compounds, or can be prepared by known methods.  
  The compounds of formula I have a broad biocidal action, and can be used for the control of various animal and plant pests. They are particularly suitable for the control of insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidac, Stomoxydae, Muscidae, Calliphoridae, Trypetidae and Pulicidae, as well as acarids of the families: lxodidae, Argasidae, Tetranychidae and Dermanyssidae.  
  The insecticidal or acaricidal action can be appreciably broadened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are, for example: organic phosphorus compounds; nitrophenols and derivatives thereof; formamidines; carbamates; ureas; pyrethrin-like compounds and chlorinated hydrocarbons.  
  In addition to possessing the above-mentioned properties, the compounds of formula I are effective also against members of the division Thallophyta. Some of these compounds thus have a bactericidal action. In particular, however, they are effective against fungi, especially against phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Denteromycetes. The compounds of formula I moreover have a fungitoxic action in the case of fungi which attack the plants from the soil. Furthermore, the new active substances are suitable for the treatment of seed, fruits, tubers, etc., for protection against fungus infections. The compounds of formula I are suitable also for the control of phytopathogenic nematodes.  
  The compounds of formula I can be used on their own or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid. and correspond to the substances common in formulation practice, such as, e.g. natural and regenerated substances, solvents, dipersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.  
  For application, the compounds of formula 1 can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays, or solutions, the formulation of these preparations being effected in a manner commonly known in practice. Also to be mentioned are cattle dips and spray races, in which aqueous preparations are used.  
  The agents according to the invention are produced in a manner known per se by the intimate mixing and- /or grinding of active substances of formula 1 with the suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following preparation forms:  
 solid preparations: dusts, scattering agents, granulates, coated granulates, impregnated granulates and homogeneous granulates;  
 liquid preparations:  
 a. water dispersible active-substance concentrates:  
  wettable powders, pastes, emulsions; b. solutions.  
  The content of active substance in the described agents is between 0.1 and 95%; it is to be mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable devices, it is possible to use an even higher concentration of active substance.  
  The active substances of formula I can be prepared, for example, as follows:  
 Dusts:  
  The following substances are used in the preparation of (a) a dust, and (h) a 2% dust:  
 a. 5 parts of active substance,  
 95 parts of talcum;  
 b. 2 parts of active substance,  
 1 part of highly dispersed silicic acid,  
 97 parts of talcum.  
  The active substances are mixed and ground with the carriers.  
 Granulate:  
  The following substances are used to produce a 5% granulate:  
 5 parts of active substance,  
 0.25 parts of epichlorhydrin,  
 0.25 parts of cctyl polyglycol ether,  
 3.50 parts of polyethylene glycol,  
 91 parts of kaolin (particle size 0.3 0.8 mm).  
  The active substance is mixed with epichlorhydrin and dissolved with 6 parts of acetone: the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to kaolin, and the acetone subsequently evaporated off in vacuo. Wettable powder:  
  The following constituents are used for the preparation of (a) a 40%, (h) and (c) a 25%, and (d) a 10% wettable powder:  
 a. 40 parts of active substance,  
 5 parts of sodium lignin sulphonate,  
 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, parts of Champagne chalk, 28.1 parts of kaolin.  
 c. 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethyleneethanol 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1  
 8.3 parts of sodium aluminium silicate,  
 16.5 parts of kieselguhr,  
 46 parts of kaolin.  
 d. 10 parts of active substance,  
 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,  
 5 parts of naphthalenesulphonic acid/formaldehyde condensate,  
 82 parts of kaolin.  
  The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration. Emulsifiable concentrates:  
  The following substances are used to produce (a) a 10% and (h) a 25% emulsifiable concentrate:  
 u. 10 parts of active substance,  
 3.4 parts of epoxidised vegetable oil,  
 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt,  
 40 parts of dimethylformamide,  
 43.2 parts of xylene.  
 h. 25 parts of active substance,  
 2.5 parts of epoxidised vegetable oil,  
 10 parts of an a1kylarylsulphonate/fatty alcohol polyglycol ether mixture 5 parts of dimethylformamide,  
 57.5 parts of xylene.  
  From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.  
 Spray:  
  The following constituents are used to prepare a 5% spray:  
 5 parts of active substance,  
 1 part of epichlorhydrin,  
 94 parts of ligroin (boiling limits l60-l90C).  
 EXAMPLE 1 tion of the resulting reaction product, there is obtained.  
 the compound of the formula A. lnsecticidal stomach poison action Cotton and potato plants were sprayed with a 0.05% aqueous active-substance emulsion (obtained from a 1071 emulsifiable concentrate).  
  After the drying of the obtained coating, .S&#39;poduprera liroralis or HeIim/zis virescens larvae L were placed onto the cotton plants, and Colorada beetle larvae (Lcplinomrsa decemll&#39;neata) onto the potato plants. The test was carried out at 24C with 60% relative humidity.  
  The compounds according to Example 1 exhibited in the above test a good insecticidal stomach poison action against Spudoptera limralis, Heliothis and Leplirwrarsa zlec&#39;emlim&#39;ata larvae.  
 B. Systemic insectidical action In order to determine the systemic action, rooted bean plants (Vicia faha) were placed into a 0.01% aqueous active-substance solution (obtained from a 10% emulsifiable concentrate). After a period of 24 liours, bean aphids (Aphis falme) were placed onto the parts of the plants above the soil. The insects were protected by a special device from the effects of contact and of gas. The test was carried out at 24C with 707! relative humidity.  
  In the above test, the compounds according to Example 1 exhibited a systemic action against Ap/iis fabae.  
 EXAMPLE 3 Action against Chilo .s-uppressalis Rice plants of the type Caloro were planted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of ca. 60 em. lnfestation with Chi/0suppress-(111.9 larvae L 3-4 mm long) was carried out 2 days after application of the active substance in granular form (amount applied 8 kg of active substance per hectare) to the paddy water. The evaluation of the insecticidal action was made 10 day after application of the granules.  
  The compounds according to Example I were effective against C/zilo .s&#39;uppressalis in the above test.  
 EXAMPLE 4 Action against ticks A. Rhipicc&#39;phalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a&#39;small glass test tube, and the test tubes then immersed for l to 2 minutes in 2. ml of an aqueous emulsion from a dilution series of 100, l(), l and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active substance emulsion could be absorbed by thecotton wool.  
  An evaluation in the case of the adults was made after 2 weeks, and in the case of the larvae after 2 days. There were two repeats for each test.  
 B. Buoplzilus microplus (larvae) With the dilution series analogous to that in Test A, tests were carried out with 20 sensitive larvae and OP- resistant larvae, respectively (resistance is with respect to diazinon compatibility).  
  Compounds according to Example I were effective in these tests against adults and larvae of Rhipiceplmlus bursa and against sensitive and OP-resistant larvae, re spectively, of Booplzilus micro 2111s.  
 EXAMPLE 5 Acarieidal action P/ItlSLU/ILY vulgarl&#39;s (plants) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tatranyc&#39;hus urtit-ae. The transferred mobile stages were sprayed with the emulsified test preparations from a chromatography-sprayer in a manner ensuring no running off of the spray liquor. An assessment was made after 2 to 7 days, by examination under a binocular, of the living and of the dead larvae, adults and eggs, and the results expressed in percentages. The treated plants were kept during holding time&#34; in greenhouse compartments at 25C.  
  The compounds according to Example I were effective in the above test against adults, larvae and eggs of Tetranyc/zus urticae.  
 EXAMPLE 6 Action against soil nematodes In order to test the action against soil nematodes the active substances were added, in the concentration stated in each case, to soil infested with rootgallnematodes (Meloidogyne arenaria), and the whole intimately mixed. In the one test series, tomato seedlings were planted immediately afterwards in the thus prepared soil, and in the other test series tomatoes were planted after a waiting time of 8 days.  
  For an assessment of the nematicidal action, the galls present on the roots were counted 28 days after planting and sowing, respectively.  
  Active substances according to Example 1 exhibited in this test a good action against Meluidogyne arenaria.  
 What we claim is:  
 1. A l,3,5-triazapenta-l,4-diene of the formula CH=N-R 3 N C N I I R 4 &#39;.l. n 2  
 wherein 2. A compound according to claim 1 wherein R is selected from the group consisting of hydrogen, chlorine, alkyl of from one to four carbon atoms, haloalkyl of from one to four carbon atoms, alkoxy of from one to four carbon atoms, alkylthio offrom one to four carbon atoms, alkenyloxy of from three to five carbon atoms, cyano, nitro, dialkylamino wherein the alkyl chains contains from one to four carbon atoms and carbalkoxy wherein the alkoxy chain contains from one to four carbon atoms,  
 n is an integer of from 1 vto 3,  
 R represents hydrogen, and  
 R and R each represent an alkyl radical of from one to six carbon atoms.  
 3. A compound according to claim 2 wherein R is selected from the group consisting of hydrogen chlorine and methyl,  
 )1 is l or 2,  
 R represents hydrogen, and  
 R and R each represent methyl.  
 4. The compound according to claim 3 of the formula 5. The compound according to claim 3 ot&#39;thc formula 6. The compound according to claim 3 ot&#39;the formula gn cu-lii-cu u-cig 70 7. The compound according to claim 3 of the formula -N=CH-N-CH=N-CH CH 0 CH 3