CA1045630A - Triazolylphosphorus compounds - Google Patents

Abstract

Abstract of the Disclosure Trinzolylphosphones compounds of the formula wherein R1 represents hydrogen, alkyl, cycloalkyl, phenyl, benzyl or phenethyl, and one of the symbols R2 and R3 represents alkoxy, phenoxy or benzyloxy, and the other represents the radical

Description

The present invention relates to triazolylphosphorus compounds and to processes for their production, and to the use of the said compounds for pest control.
The triazolylphosphorus compounds correspond to the formula Rl - N " / 3 R2 ~ N ~ ~ P \

2 5 wherein Rl represents Cl-C3-alkyl R2 represents methoxy or ethoxy and R3 represents ethyl, ethoxyl or propylthio.
Examples of alkyl radicals are: methyl, ethyl, and propyl.
The compounds of formula I are produced by the reaction of a) a hydroxy-triazole of the formula Rl- N --N

R2- C ~ N~C OH

wherein Rl and R2 have the meanings given under formula I with a phosphoric acid halide of the formula Hal- P ~III), wherein Hal represents chlorine or bromine, and R3 has the meanings given under formula 1, in the presence of an acid-binding agent.
Suitable acid-binding agents are, for example, the following bases:
tertiary amines such as triethylamine, dimethylaniline, pyridine, inorganic bases such as hydroxides and carbonates of alkali and alkaline-earth metals, preferably sodium and potassium carbonate.
The reactions are preferably carried out in solvents or diluents which are inert to the reactants. The following, for example, are suitable:
aromatic hydrocarbons such as benzene, toluene, ligroins, halogenated hydro-carbons, chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated alkanes having 1 to 3 carbon atoms, ethers such as dioxane, tetrahydrofuran; esters such as ethyl acetate; ketones such as methyl ethyl ketone, diethyl ketone, nitriles, e.g. acetonitrile.
The starting materials of formula II are in some cases known, or can be produced by reaction of an imino compound of the formula R'O O
> C = N - C or Cl \ Cl R'O ~ O
~C = N - C or R "O Cl

-3-R'O\ ll ~ = N - C - OR " ' or Cl = N - C //
~ " \OR "

with a hydrazine of the formula , RIV
- RV > N NH2 whereby in the formulae the symbols R', R" and R"' represent alkyl or unsubstituted or substituted phenyl, RIV represents hydrogen or alkyl, and R represents hydrogen, alkyl or phenyl.

Furthermore, products of formula II can be obtained from 5-halogen-3-hydroxy-1,2,4-triazoles by reaction with alcoholates or phenolates.

The compounds of formula I have a broad biocidal action, and can be used for the control of diverse plant and animal pests. The said compounds are suitable, in lS particular, for the control of insects of the families:
Acrididae, Blattidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, B~ ~

~045630 Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae, as well as acarids of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.
The insecticidal and/or acaricidal action can be substantially broadened and adapted to suit the particular circumstances by the addition of other insecticides and/or acaricides.
In addition to possessing the abové mentioned properties, the com-~
pounds of formula I are moreover effective against members of the division Thallophyta. Some of these compounds thus have a bactericidal action. They are, however, particularly effective against fungi, especially against the phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomy-cetes, Ascomycetes, Basidiomycetes, Denteromycetes. The compounds of formula I also 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, fruit, tubers, etc., for protection against fungus infec-tions. The compounds of formula I are suitable too for the control of phyto-pathological 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 prac-tice, such as, e.g. natural and regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application, the compounds of formula I 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 I with the suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances; The active sub-stances 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 solid preparations ~dusts, scattering agents) are produced by the mixing of the active substances with solid carriers. Suitable carriers are, e.g. kaolin, talcum, bole, loess, chalk, limestone, ground limestone, attapulgite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline-earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nut-shells, cellulose powder, residues of plant extractions, active charcoal, etc., alone or in admixture with each other.
Granulates can be very easily prepared by a process in which an active substance of formula I is dissolved in an organic solvent, the thus obtained solution applied to a graunulated mineral, e.g. attapulgite, SiO2, granicalcium, bentonite, etc., and the organic solvent then evaporated off.
It is possible also to produce polymer granulates; in this case the active substances of formula I are mixed with polymerisable compounds ~urea/
formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde, or others);
polymerisation is then carefully carried out in a manner which leaves the active substances unaffected, and granulation performed actually during the gel forming process. It is more favourable, however, to impregnate finished porous polymer granules ~urea/formaldehyde, polyacrylonitrile, polyester and others), having a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, e.g. in the form of their solutions ~in a low-boiling solvent), and to then remove the solvent.

Polymer granulates of this kind can be also sprayed in the form of micro-granulates, having bulk weights of preferably 300 g/litre to 600 g/litre, with the aid of spray apparatus. Spraying can be carried out over extensive areas of useful plant crops by the use of aeoplanes.
Granulates can also be obtained by the compacting of the carrier material with the active substances and additives, and a subsequent reducing operation.
Moreover, it is possible to add to these mixtures additives stabilis-ing the active substance and/or nonionic, anion-active and cation-active sub-stances which improve, e.g. the adhesiveness of the active substances on plants and parts of plants ~adhesives and agglutinants), and/or ensure a better wettability ~wetting agents) as well as dispersibility (dispersing agents).
The following substances are, for example, suitable: olein/lime mixture, cellulose derivatives ~methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, ligninsulphonic acid, the alkali metal and alkaline-earth metal salts thereof, polyethylene glycol ethers ~carbowaxes), fatty alcohol polyglycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation pro-ducts of urea-and formaldehyde, as well as latex products.
Water-dispersible concentrates of active substances, i.e. wettable powders, pastes and emulsion concentrates, are agents which can be diluted with water to obtain any desired concentration. They consist of active sub-stance, carrier, optionally additives which stabilise the active substance, surface-active substances, and anti-foam agents and, optionally, solvents.
The wettable powders and pastes are obtained by the mixing and grinding of the active substances with dispersing agents and pulverulent car-riers, in suitable devices, until homogeneity is obtained. Suitable carriers are, e.g. those previously mentioned in the case of solid preparations. It is lO~S630 advantageous in some cases to use mixtures of different carriers. As dis-persing agents it is possible to use, e.g.: condensation products of sulphon-ated naphthalene and sulphonated napthalene derivatives with formaldehyde, condensation products of napthalene or of naphthalenesulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline-earth metal salts of ligninsulphonic acid, also alkylarylsulphonates, alkali metal salts and alkaline-earth metal salts of dibutyl naphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyl dilauryl ammonium chloride, and fatty acid alkali-metal and alkaline-earth metal salts.
Suitable anti-foam agents are, e.g. silicones.
The active substances are so mixed, ground, sieved and strained with the above mentioned additives that the solid constituent in the case of wettable powders has a particle size not exceeding 0.02 to 0.04 mm, and in the case of pastes not exceeding 0.03 mm. For the preparation of emulsion con-centrates and pastes, dispersing agents are used such as those mentioned in the preceding paragraphs, organic solvents and water. Suitable solvents are, e.g. alcohols, benzene, xylene, toluene, dimethylsulphoxide, and mineral oil fractions boiling in the range of 120 to 350C. The solvents must be prac-tically odourless, non-phytotoxic, and inert to the active substances.
Furthermore, the agents according to the invention can be used in the form of solutions. For this purpose, the active substance, or several active substances, of the general formula I is dissolved in suitable organic solvents, solvent mixtures, or water. As organic solvents it is possible to use aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkyl-naphthalenes, mineral oils on their own or in admixture with each other.
The content of active substance in the above described agents is between 0.1 and 95%; it is to be mentioned in this connection that in the case of application of the agents from an aeroplane, or by means of some other suitable application devices, concentrations of up to 99.5% can be used, or even the pure active substance.

The active substances of formula I can be prepared, e.g. as follows:
Dusts:
The following substances are used for the preparation of a) a 5%
dust, and b) 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.-The following substances are used to produce a 5% granulate:
5 parts of active substance, 0.25 parts of epichlorhydrin, 0.25 parts of cetyl 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 thus obtained solution is sprayed on the kaolin, and the acetone subsequently evaporated in vacuo.
~ettable powder:
The following constituents are used for the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid.
b) 25 parts of active substance,

4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture tl:l), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, _ g _ ~04S630 19.5 parts of Champagne chalk 28.1 part of kaolin.
c) 25 parts of active substance, ; 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 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 ~uspensions ~f any desired concentration.
Emulsiiable concentrates:
The following substances are used to produce a) a 10% and b) a 25%
emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene.
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/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:
parts of active substance, 1 part of epichlorhydrin, 94 parts of ligroin (boiling limits 160 - 190C).
Example 1 Production of the starting material:
1-Isopropyl-3-hydroxy-5-methoxy-1,2,4-triazole An amount of 166 g of 1-isopropyl-3-hydroxy-5-chloro-1,2,4-triazole is added to a solution of 115 g of sodium in 1000 ml of methanol; the mixture is then refluxed for 15 hours. After separation by filtration of the pre-cipitated sodium chloride, and concentration of the filtrate in vacuo, the residue is taken up in dilute acetic acid, and extracted twice with ether.
The ether is evaporated off, and the partially crystalline residue dissolved in a little methanol. On cooling of the solution to -70C, the product crystallises out. There is thus obtained 43.5 g of 1-isopropyl-3-hydroxy-5-methoxy-1,2,4-triazole inthe form of white crystals, M.P. 102-103C.
Production of the new phosphorus compounds a) O,O-diethyl-O-!l-isopropyl-5-methoxy-1,2,4-triazolyl-(3)/-thiophos-phate A mixture of 15.3 g of 1-isopropyl-3-hydroxy-5-methoxy-1,2,4-triazole and 13.8 g of potassium carbonate in 500 ml of methyl ethyl ketone is refluxed for one hour. An addition is then made at 50& of 19.0 g of O,O-diethylthiophosphoric acid chloride, and the mixture refluxed for 1 1/2 hours.
After the precipitated salts have been filtered off through Hyflo, the fil-; trate is concentrated in vacuo to obtain the compound of the formula ~045630 CH
~ - N ~ -N
CH3 CH3 ~ ~ 0 _ ~(OC2H5)2 in the form of pale yellow oil, n20 = 1.4773.
b) 0-Ethyl-S-n-propyl-0-[1-isopropyl-5-methoxy-1,2,4-~riazolyl-(3)]-dithiophosphate A mixture of 15.3 g of 1-isopropyl-3-hydroxy-5-methoxy-1,2,4-triazole, 13.8 g of potassium carbonate and 500 ml of acetonitrile is refluxed for two hours, and then cooled to room temperaturej and addition is subsequently made of 22.0 g of 0-ethyl-S-n-propyl-dithiophosphoric acid chloride, and the whole thereupon refluxed for two hours. m ere is obtained, after processing, the compound of the formula CH

3 ~ N ~ ~ \

as yellow oil, n20 = 1.5120.
The following compound too is produced analogously:
CH3 \

CH - N N

- ~N ~S \OC H nD = 1,4886 C2H50 - C~ nD = 1,4783 C2H50 - C~ ~ C - - P (C2 5)2 nD = 1,4893 Example 3 A) Insecticidal stomach poison action Tobacco and potato plants were sprayed with a 0.05%
aqueous active substance emulsion (obtained from a 10%
emulsifiable concentrate).

After the drying of the coating, Egyptian cotton leaf worms (Spodoptera litoralis) were placed on the tobacco plants, and Colorada beetle larvae (Leptinotarsa decemlineata) on the po~ato plants. The test was carried out at 24C
with 60% relative humidity.
i 10 The compounds according to Example 2 exhibited in the above test stomach poison action against Spodoptera litoralis and Leptinotarsa decemlineata.
.
B) Systemic insecticidal action - In order to determine the systemic action, rooted bean plants (Vicia faba) were placed into a 0.01% aqueous active substance solution (obtained from a 10% emulsifiable concentrate). After a period of 24 hours, bean aphids (Aphis fabae) were placed on to the parts of the plants above the soil. The insects were protected by a special device from the effect of contact and of gas. The test was carried out at 24C with 70% relative humidity.
In the above tests, the compounds according to Example 2 exhibited stomach poison action and systemic insecticidal action, ~ 3 ' ' t '$A~ ' .,_ .., ~ 045630 Example 4 Action a~ainst Chilo suppressalis Rice plants of the type Caloro were planted, 6 plants per pot, in plastic pots have a top diameter of 17 cm, and grown to a height of ca. 60 cm. Infestation w-ith Chilo suppressalis larvae (Ll; 3-4 mm long) was carried out 2 days after application of the active substance in granule form (amount applied 8 kg of active substance per hectare) to the paddy water. The evaluation of the insecticidal action was made 10 days after application of the granules.

The compounds according to Example 2 were effective against Chilo suppressalis in the above test.

Example 5 Sterilised compost soil was homogeneously mixed with a ~ wettable powder containing 25% of active substance, so ; that an applied amount of 8 kg of active substance per hectare resulted.

Young zucchetti plants (Cucumis pepo) were potted`with the treated soil in plastic pots (three plants per pot of 7 cm diameter). The said pots were infested immediately afterwards with 5 Aulacophora femoralis larvae, 5 Pachmoda larvae and 5 Chortophila larvae, respectively. The assessment of the results was made 4, 8, 16 and 32 days after infestation with the larvae.

In the case of 80-100% destruction on the first assessment, . '`~ .

a repeated infestation was carried out, 5 larvae being placed into the same sample of soil with 3 new zucchetti plants, Where the action was less than 80%, the remaining larvae were left in the test soil until the next control assessment. If a substance with an applied amount of 8 kg per hectare ef~ected a 100% destruction, then subsequent tests were made with 4 and 2 kg of active substance per hectare, respectively.

~ The compounds according to Example 2 were effective in the above test against Aulacophora femoralis larvae, Pachmoda larvae and Chlortophila larvae.

Example 6 Action a~ainst ticks A) Rhipicephalus bursa In each case, 5 adult ticks were placed into one small glass test tube and 50 tick larvae into another; the test tubes were then immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 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 the cotton 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.
The compounds according to Example 2 were effective in the above tese against adults and larvae of Rhipicephalus bursa.

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~04~;30 B) Boophilus microplus (larvae) With a dilution series analogous to that in Test A, tests were carried out with 20 sensitive larvae and OP-resistant larvae, respectively (the resistance is with respect to diazinon compatibility).

The compounds according to Example 2 were effective in these tests against adults and larvae of Rhipicephalus bursa and against sensitive and OP-resistant larvae, respectively, of Boophilus microplus.

Example 7 Acaricidal action Phaseolus vulgaris (bush beans) were infested, 12 hours before the test for acaracidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae.
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 the "holding time" in greenhouse compartments at 25~C.

The compounds according to Example 2 were effective in the above test against adults, larvae and egges of Tetranychus urticae. ~ ' }~
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Example 8 Action a~ainst 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 root-gall-S nematodes (~Ieloidogyne arenaria), and the whole intimatelymixed. 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 the planting and sowing, respectively.

The active substances according to Example 2 exhibited Ln this tes~ a good action against Mel~idogyne arenaria.

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Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula wherein R1 represents C1-C3-alkyl R2 represents methoxy or ethoxy and R3 represents ethyl, ethoxyl or propylthio.

2. The compound according to claim 1 of the formula

3. The compound according to claim 1 of the formula

4. The compound according to claim 1 of the formula

5. The compound according to claim 1 of the formula

6. A process for the production of a compound according to claim 1, the said process comprising the reaction of a hydroxy-triazole of the formula with a phosphoric acid halide of the formula in the presence of an acid binding agent.

7. A method of combating various plant or animal pests at a locus, which method comprises applying to the locus a compound as claimed in claim 1.

8. A method according to claim 7, wherein the pests are of the class Insecta or Nematoda or of the order Acarina.