GB1595809A - Amidino phorsporic acid thiol esters and their use for combating pests - Google Patents

Amidino phorsporic acid thiol esters and their use for combating pests Download PDF

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GB1595809A
GB1595809A GB54180/77A GB5418077A GB1595809A GB 1595809 A GB1595809 A GB 1595809A GB 54180/77 A GB54180/77 A GB 54180/77A GB 5418077 A GB5418077 A GB 5418077A GB 1595809 A GB1595809 A GB 1595809A
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines

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  • Engineering & Computer Science (AREA)
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  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Description

(54) AMIDINO-PHOSPHORIC ACID THIOL ESTERS AND THEIR USE FOR COMBATING PESTS (71) We, CIBA-GEIGY AG, a Swiss body corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to amidino-phosphoric acid thiol esters, to a process for producing them, to pesticidal compositions containing these compounds as active ingredients, and to the use of the novel compounds for combating pests including insects, Acarina and particularly nematodes.
The novel amidino-phosphoric acid thiol esters constitute a closely limited group of highly effective compounds and they correspond to the formula I
wherein Rl represents hydrogen, Cl-C4-alkyl or cyclopropyl, R2 represents C3-C5-alkyl, R3 represents methyl or ethyl, and Z represents oxygen or sulphur. Preferred compounds are those wherein R1 represents hydrogen or methyl, R2 represents n-propyl, and R3 represents ethyl.
An important subgroup of compounds are those of the formula I wherein Z represents oxygen. Another important subgroup of compounds of the formula I is formed by those in which Z represents sulphur and R3 represents ethyl.
By the alkyl groups given are meant, dependent on the definition given for R, and R, methyl. ethyl, propyl, isopropyl as well as the isomeric butyl and amyl groups.
Phosphorylated formamidines have already become known from the German Offenlegungsschriften Nos. 2,312,738 and 2,451,911. Their nematocidal action is however very unsatifactory. Furthermore, they do not have the high level of soil stability which is essential for combating soil pests.
It has now been shown that the compounds of the formula I of the present invention satisfy to a high degree both of the requirements mentioned above. This is particularly surprising because compounds which are directly homologous have these properties in only a slightly pronounced form, so that for practical purposes they are unsuitable.
The compounds of the formula I may be produced according to the invention by one of the following processes 1 and 2:
SR2 I Itasej 1) R, - C - NWHCl + Cl - P - OR3 1) Rl C NH2 HCI + z Ii NH z (wherein Z, R1. R, andR3 have the meanings given for the formula I). The HC1 salt of the amidine is representative of possible other salts of other acids (e.g. hydrohalic acids, sulphuric acid, nitric acid, phosphoric acid,); its presence is however not essential with regard to the course of the reaction and the free base may be used,.
If Z represents oxygen, compounds of the formula I can be produced also according to the reaction scheme:
S MeYiP 2) Rl - C - NH - P - OR3 l t | [hydrolysis] NH OR3 SMe R2X R1 - C - NH - P = O NH OR3 thiol salt wherein X represents halogen, preferably chlorine, bromine or iodine, or alternatively a sulphate radical, Me represents alkali metal, alkaline-earth metal or NH4, and Y represents oxygen or sulphur.
In process 1) involving amidation of a thiophosphoric acid ester chloride, reaction temperatures of O" to 10U C, preferably 10-45"C. are applied.
The reaction 1) is generally performed in solvents or diluents which are inert to the reactants. The following are for example suitable: aliphatic or aromatic hydrocarbons such as benzene. toluene, xylenes or petroleum ether: halogenated hydrocarbons such as chlorobenzene, methylene chloride. ethylene chloride or chloroform: ethers and ethereal compounds such as dialkyl ethers, dioxane or tetrahydrofuran; nitriles such as acetonitrile: N,N-dialkylated amides such as dimethylformamide; water; or ketones such as methyl ethyl ketone, dimethylsulphoxide, and mixtures of such solvents with each other. Two-phase reaction mediums, e.g. methylene chloride/water, are particularly preferred. The reaction proceeds in the presence of an acid-binding agent or condensation agent. The following are suitable: tertiary amines such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases, such as the oxides and hydroxides, hydrogen carbonates and carbonates of alkali metals and alkaline-earth metals as well as sodium acetate (see German Offenlegungsschrift No. 2.451,911).
Process 2) involving transesterification of an amidino-phosphoric acid thiono ester is performed in the temperature range of 20 - 1()0 C. The hydrolysis step is performed in the presence of the above defined hvdroxide or hydrogen sulphide MeYH. Also suitable however as the reaction medium are mixtures of water and an immiscible solvent, such as a hydrocarbon (e.g. benzene) or chlorinated hydrocarbon (e.g. chloroform). in the sense of a phase-transfer method. In this case, the simultaneous use of quaternary ammonium salts.
such as tetrabutylammonium bromide, is advantageous.
In the second reaction stage, entailing alkylation of the formed thiol salt. non-aqueous polar solvents. e.g. acetonitrile or dimethylformamide, are used (see U. S. Patent Specification 3,896,193).
The two aforementioned reaction courses 1) and 2) are, for the R2S-/RO-"ilkyl- unsymmetrically substituted compounds of the formula 1. practicable ways of obtaining pure end products.
Compounds of the formula I are stable under neutral conditions. and have in the soil a prolonged action against nematodes. This is very surprising since compounds of the formula II are ineffective against nematodes:
(R1 herein has the meaning given under the formula I, and R3 represents methyl or ethyl).
The following Examples illustrate the production of the active substances according to the invention. The temperature value are given in degrees Centigrade.
EXAMPLE 1 20 g (0.21 mole) of acetamidine hydrochloride is dissolved in 100 ml of water. A solution of 40 g (0.2 mole) of O-ethyl-S-n-propylthiophosphoric acid chloride in 400 ml of methylene chloride is added portionwise with vigorous stirring. To the reaction mixture is then added dropwise an 0.4 molar NaOH solution, which corresponds to 16 g of solid NaOH. The temperature meanwhile rises to about 30 . After completion of the reaction, stirring is maintained for about 4 hours at room temperature; the methylene chloride layer is separated, dried over sodium sulphate and concentrated by evaporation to yield 38 g of N-(O-ethyl-S-n-propylthiophosphoryl)-acetamidine as a viscous oil, which solidifies after a short time into the form of colourless crystals, m.p. 48-50 [Compound No. 2]. According to this method or to any of the abovementioned methods the following compounds may be prepared:
SC3H7(n) 1) H - C - NH - P - OC2Hs nD2 = 1.5210 II NH O SC3H7(n) 2) CH3 - C - NH - P - OC2Hs m.p. 55-57 II NH O SC3H7(n) 3) isoQH - G - NH - P - OQH5 n5 = 1,4986 II II NH O SC4H9(n) 4) CH3 - C - NH - P - OC2H5 nD2 = 1,5120 NH O CH3 S - CH - CH3 5) CH3 - C - NH - P - OC2H5 m.p. 83 o II II NH O
S - C5H11(n) 6) H - C - NH - P - OC2H5 nD = 1.5071 II II NH O CH3 S - CH - CH2 - CH3 7) H - C - NH - P - OC2H5 nD 1.5104 II II NH O CH3 S - CHo - CH - CR3 8) CH3 - C - NH - P - OC,H5 m.p. 75-78 II II NH O CH3 CH2 S - CHo - CH - CH3 9) isoC3H7 - C - NH - P - OC2H5 nDt' = 1.4625 NH 0 S - CXH,(n) 10) nC4H) C - NH - P - OC2H5 nD') = 1.4951 II I! NH O ii) S-C3H7(n) nD" = 1.5()73 < C-NH-P-OC2H5 = 1.5073 II II NH O S - C3H7(n) 12) H - C - NH - P - OCR3 viscous NH O
S - C3H7(n) 13) CR3 - C - NH - P - OCR3 viscous II II NH O CR S - CR - CH, - CH3 14) H - C - NH - P - OCR3 viscous oil II II NH O S - C4H9(n) 15) CR3 - C - NH - P - OCR3 resin II II NH O S - C4Hg(sec. ) 16) CR3 - C - NH - P - OC2H5 m.p. 78-81" II II NH o S - C4R9(sec.) 17) CH3 - CH - C - NH - P - OC2H5 nD" = 1.4952 II It CH3 NH O CH7 SUCH. - CR CR3 I CR3 18) H - C - NH - P - OC2H5 nD" 1.5091 II II NH O SC3H7 19) C2H5 - C - NH - P - OC2H, nDi) 1.5069 I! II NH O
rv:r 3 S - CH, - CHt CRCR3 20 20) C2R5 - C - NH - P - OC2H5 n0 1.4978 II II NH O SC3H7 I 21) n - C3R7 - C - NH - P - OC2H5 n20 1.5035 II II NH O EXAMPLE 2 a) Production of the intermediate 20 g (0.21 mole) of acetamidine hydrochloride is dissolved in 100 ml of water. This solution is underlayed with 300 ml of methylene chloride, and 38 g (0.2 mole) of O,O-diethylthiophosphoric acid chloride is added. To the stirred reaction mixture is added dropwise a solution of 16 g (0.4 mole) of NaOH in about 200 ml of water. The phases are separated after four hours' stirring at room temperature. The dried methylene chloride phase yields, after concentration in vacua 40 g of N-(O,O-diethyl-thiophosphoryl)acetamidine as viscous oil, which slowly solidifies to form colourless crystals. m.p. 34-35 .
b) Partial hydrolysis and S-alkvlation 21 g (0.1 mole) of the intermediate obtained under a) with 6 g (0.12 mole) of NaHs in 200 ml of methyl Cellosolve (Cellosolve is a Registered Trade Mark) is heated at 100" for 5 hours; 15 g of n-propyl bromide is added to the cloudly solution, and stirring is maintained at 80" for 2 hours. The reaction mixture is concentrated in vacuo to dryness. The oily/crystalline residue is shaken with water and methylene chloride, and the organic phase is concentrated to dryness to yield 18 g of a crystalline mass, which is recrystallised from ether/petroleum ether. The resulting pure N-(O-ethyl-S-n-propyl-thiophosphoryl)- acetamidine melts at 55-57 [Compound No. 2].
EXAMPLE 3 20 g (0.21 mole) of acetamidine hydrochloride is dissolved in 100 ml of water. A solution of 44 g (0.2 mole) of O-ethyl-S-n-propyl-thionothiol-phosphoric acid chloride in 400 ml of methylene chloride is added portionwise with vigorous stirring. To the reaction mixture is then added dropwise an 0.4 molar NaOH solution, which corresponds to 16 g of solid NaOH. The temperature rises meanwhile to about 30". After completion of the reaction, stirring is maintained for about 4 hours at room temperature; the methylene chloride layer is separated, dried over sodium sulphate and concentrated by evaporation to yield 40 g of N-(O-ethyl-S-n-propyl-thiono-thiolphosphoryl)-acetamidine in the form of colourless crystals, m.p. 76-78 [Compound No. 23].
Also the following compounds are obtained after the manner of Example 3:
SC.7H7(n) 22) H - C - NH - P - OC2H5 m.p. 53-57 II II NH S
SC3H7(n) 23) CH3 - C - NH - P - OC2H5 m.p. 76-78 II II NH S SC3H(n) 24) C2R5 - C - NH - P - OC2Hs ni = 1.5529 II II NH S SC3H,(n) 2() 25) (n)C3H7 - C - NH - P - OC2Hs n2(' = 1.5445 II II NH S SC3H7(n) '(I 26) (n)C4H3 - C - NH - P - OC2Hs n = 1.5369 II II NH S SC3H,(n) CR3 27) CR - CR - C - NH - P - OC2H, oil II - II II NH S 28) SC3H7(n) n' = 1.56;55) < C - N H- P-OC2H5 II II NH S SC3H7(n) 29) isoC3R7 - C - NH - P - OC2Hs n,2," = 1.5406 II II NH S
CH3 S - CH - CR2 - CH3 30) CH3 - C - NH - P - OC2Hs viscous oil II II NH S CR3 S - CH2 - CH - CH3 31) CR3 - C - NH - P - OC2H5 viscous oil II II NH S CH3 S - CR - CH2CH3 32) isoC3Hv - C - NH - P - OC2Hs viscous II It NH S CH3 S - CH2 - CH - CH3 33) isoC3Hv - C - NH - P - OC2Hs viscous II II NH S According to the present invention there is provided a method of combating pests at a locus which comprises applying to the locus a compound of the formula I.
Compounds of the formula I are effective in particular against nematodes of the phytopathogenic type; among these are to be mentioned the following genera: Meloidogyne, Radopholus. Pratylenchus. Ditylenchus, Heterodera, Paratylenchus, Belonolaismus, Trichodorus and Longidorus. The special advantage of these compounds is their systemic action, which enables the pests to be combated not only by means of soil treatment but also by means of leaf application through the plant to be protected (basipetal transport).
Advantageous compositions of application are those which enable a uniform distribution of the active substance throughout a layer of soil extending to a depth of 10 to 20 cm to be ensured. The manner and form of application are dependent in particular on the type of plant, on the climate and on the conditions of the soil. Since the novel active substances are as a rule not phytotoxic and do not impair the capability of germanating. they can be applied usually, without observance of a "waiting period", immediatelv before or after the sowing of the plants. It is likewise possible to treat already existing crops of plants with the novel compositions. In addition, for the purpose of effecting an increase. specific parts of plants, such as seeds, sections of stalk (sugar-cane) or bulbs, as well as roots or seedlings.
can be dressed with dispersions or solutions of the active substances.
Besides having an excellent nematocidal action, the compounds of the formula I have a distinct insecticidal, acaricidal, ectoparasitic and, in some cases, also fungicidal and bactericidal action.
The compounds of the formula I can be used on their own or in the form of pesticidal compositions together with suitable carriers and/or a surface active additive. Suitable carriers and additives can be solid or liquid and they correspond to the substances common in formulation practice, such as natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers. Solid compositions according to the invention contain the active ingredient together with a solid extender and, optionally, a surface active agent. Liquid compositions according to the invention contain the active ingredient together with a liquid diluent and a surface active agent. For widening their sphere of action, the compounds of the formula I can be combined with known insecticides, acaricides or nematocides, as well as with fungicides, herbicides, molluscicides or rodenticides.
The content of active substance in commercial compositions is generally between 0.1 and 90%.
For application, the compounds of the formula I can be in the following forms (the weight-percentage figures in brackets signify advantageous amounts of active substance): solid preparations dusts and scattering agents (up to 10%), granulates [coated granules, impregnated granules and homogeneous granules] (1 to 80%); liquid preparations a) water-dispersible concentrates of active substance: wettable powders and pastes (25 to 90% in the commercial packing, 0.01 to 15% in ready-for-use solutions emulsion concentrates and solution concentrates 10 to 50%, 0.01 to 15% in ready-for-use solutions); b) solutions (0.1 to 20%).
The active substances of the formula I of the present invention can be formulated for example as follows: Dust The following substances are used to produces a) a 5% dust and b) a 2% dust: a) 5 parts of active substance, and 95 parts of talcum; b) 2 parts of active substance, 1 part of highly dispersed silicic acid, and 97 parts of talcum.
The active substances are mixed and ground with the carriers, and in this form they can be applied by dusting.
Granulate The following substance are used to produce a 5% granulate: 5 parts of active substance.
0.25 part of epichlorohydrin.
0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, and 91 parts of kaolin (particle size 0.3 - 0.8 mm).
The active substance is mixed with the epichlorohydrin and dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo. A microgranulate of this kind is advantageously used for combating soil pests.
Wettable powder The following constituents are used to produce a) a 70% wettable powder, b) a 40% wettable powder, c) and d) a 25% wettable powder, and e) a 10% wettable powder: a) 70 parts of active substance, 5 parts of sodium dibutylnaphthylsulphonate, 3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehyde condensate 3:2:1, 10 parts of kaolin, and 12 parts of Champagne chalk; b) 40 parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutylnaphthalenesulphonate, and 54 parts of silicic acid; c) 25 parts of active substance, 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1), 1.5 parts of sodium dibutylnaphthalenesulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, and 28.1 parts of kaolin; d) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, and 46 parts of kaolin; and e) l0 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, and 82 parts of kaolin.
The active substances are intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers. There are obtained wettable powders which have excellent wetting and suspension properties and which can be diluted with water to give suspensions of the desired concentration. These can be used in particular for soil and leaf application.
Emulsifiable concentrate The following substances are used to produce a 25% emulsifiable concentrate: 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, and 57.5 parts of xylene.
Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.
EXAMPLE 4 Test to determine the nematocidal action In order to test its action against soil nematodes, the active substance is added, at concentration of 10 and 2.5 ppm, to soil and sand, respectively, infested with root-gall nematodes (Meloidogyne incognita), and thoroughly mixed in. In the soils prepared in this manner, there are planted immediately afterwards on the one hand tomato seedlings and on the other hand tobacco seedlings. An assessment of the nematocidal action is made, 28 days after planting, by counting the galls present on the roots.
Compounds of the formula I showed in the above test a good action against Meloidogyne incognita, as can be seen from the mean values of three parallel tests. The assessment was based on the following scale of ratings: 0 = 0 - 5 % infestation 1 5 - 25 % infestation 2 = 25 - 80 % infestation 3 = above 80% infestation (ineffective).
The compounds of the formula I exhibited at an active-substance concentration of 10 ppm without exception a complete action (rating 0); at 2.5 ppm they exhibited an almost complete action with a reduction of infestation to 0 to 25% (rating 0 or 1). The compounds Nos. 1. 2, 3, 4, 8, 9, 10, 11, 16, 17, 20, 21, 23, 25, 26. 28, 29, 30 and 31 proved also at this concentration to be fully effective (rating 0).
Compounds which structurally are directly homologous, such as
SCHIZ A CH3 - C - NH - P - OCR3 m.p. 130 - 135"C II II NH O
SC2Hs B CH, - C - NH - P - OC2Hs semicrystalline II II NH 0 oc2HS C CH3 - C - NH - P - OC2Hs m.p. 34 - 35 II II NH S exhibited, even with high dosages of 25 ppm and 50 ppm, no nematocidal action whatsoever.
EXAMPLE 5 Insecticidal action: Dysdercus fasciatus Cotton plants were sprayed with an aqueous emulsion containing 0.05% of the compound to be tested (obtained from a 10% emulsifiable concentrate). After the coating had dried, the plants were infested with larvae of the species Dysdercus fasciatus in the L3-stage. Two plants were used to each test compound, and the destruction rate attained was determined after 2, 4, 8, 24 and 48 hours. The test was carried out at 240C with 60% relative humidity. The compounds Nos. 2, 8, 19 and 23 effected after 8 hours a complete destruction of the larvae.
EXAMPLE 6 Svstemic-insecticidal auction: Aphis fabae In order to determine the systemic action, rooted bean plants (Vicia faba) were placed into a 0.01% aqueous solution of the active substance (obtained from a 10% emulsifiable concentrate). After 24 hours, bean aphids (Aphis fabae) were placed onto the parts of the plants that had been above the soil. By means of a special device, the bean aphids were protected from the effects of contact and gas. The test was carried out at 24"C with 70coo relative humidity.
The compounds Nos. 2, 3 and 8, transported in the sap stream of the plant, effected a complete destruction of the bean aphids.
EXAMPLE 7 Acaricidal action Bean plants (Phaseolus vulgaris) were infested, 12 hours before the test, 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 overflow of the spray liquor. An assessment was made after 2 to 7 days at 250C in a greenhouse, by examination under a binocular microscope, of the living and of the dead larvae, adults and eggs. The compounds of the formula I effected, at the latest after 7 days, a complete destruction both of the larvae and of the adult Acarina species.
WHAT WE CLAIM IS: 1. A compound of the formula I
wherein Rl represents hydrogen, C1-C4 alkyl or cyclopropyl,
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (28)

**WARNING** start of CLMS field may overlap end of DESC **. SC2Hs B CH, - C - NH - P - OC2Hs semicrystalline II II NH 0 oc2HS C CH3 - C - NH - P - OC2Hs m.p. 34 - 35 II II NH S exhibited, even with high dosages of 25 ppm and 50 ppm, no nematocidal action whatsoever. EXAMPLE 5 Insecticidal action: Dysdercus fasciatus Cotton plants were sprayed with an aqueous emulsion containing 0.05% of the compound to be tested (obtained from a 10% emulsifiable concentrate). After the coating had dried, the plants were infested with larvae of the species Dysdercus fasciatus in the L3-stage. Two plants were used to each test compound, and the destruction rate attained was determined after 2, 4, 8, 24 and 48 hours. The test was carried out at 240C with 60% relative humidity. The compounds Nos. 2, 8, 19 and 23 effected after 8 hours a complete destruction of the larvae. EXAMPLE 6 Svstemic-insecticidal auction: Aphis fabae In order to determine the systemic action, rooted bean plants (Vicia faba) were placed into a 0.01% aqueous solution of the active substance (obtained from a 10% emulsifiable concentrate). After 24 hours, bean aphids (Aphis fabae) were placed onto the parts of the plants that had been above the soil. By means of a special device, the bean aphids were protected from the effects of contact and gas. The test was carried out at 24"C with 70coo relative humidity. The compounds Nos. 2, 3 and 8, transported in the sap stream of the plant, effected a complete destruction of the bean aphids. EXAMPLE 7 Acaricidal action Bean plants (Phaseolus vulgaris) were infested, 12 hours before the test, 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 overflow of the spray liquor. An assessment was made after 2 to 7 days at 250C in a greenhouse, by examination under a binocular microscope, of the living and of the dead larvae, adults and eggs. The compounds of the formula I effected, at the latest after 7 days, a complete destruction both of the larvae and of the adult Acarina species. WHAT WE CLAIM IS:
1. A compound of the formula I
wherein Rl represents hydrogen, C1-C4 alkyl or cyclopropyl,
R2 represents Cs-Cs alkyl, R3 represents methyl or ethyl, and Z represents oxygen or sulphur.
2. A compound according to Claim 1, wherein R1 represents hydrogen or methyl, R2 represents n-propyl, and R3 represents ethyl.
3. A compound according to Claim 1 or 2, wherein Z represents oxygen.
4. A compound according to Claim 1, wherein Z represents sulphur, and R3 represents ethyl.
5. A compound according to Claim 2, wherein Z represents sulphur.
6. N-(0-Ethyl-S-n-propyl-thiono-thiol-phosphoryl)-iso.butyramidine of the formula
7. N-(O-Ethyl-S-n-propyl-thiono-thiol-phosphoryl)-acetamidine.
8. N-(O-Ethyl-S-n-propyl-thiophosphoryl)-acetamidine.
9. N-(O-Ethyl-S-sec. -butyl-thiophosphoryl)-acetamidine.
10. N-(O-Ethyl-S-isobutyl-thiophosphoryl)-propionamidine.
11. A process for producing a compound of the formula I of Claim 1, which process comprises reaction of a thiophosphoric acid ester chloride of the formula
(wherein R2, R3 and Z are as defined in claim 1), in the presence of a base at 0 to 1000C, with an amidine of the formula
(wherein R, is as defined as claim 1) or an acid salt thereof.
12. A process for producing a compound as claimed in claim 3, which process comprises hydrolysis of a compound of the formula
(wherein Rl and R3 are as defined in Claim 1) at a temperature of 20" to l()() C with a compound of the formula MeOYHO. (wherein Me represents an alkali metal, alkaline earth metal or NH4, and Y represents oxygen or sulphur); and subsequent alkylation, in a non-aqueous polar solvent, of the intermediate so formed of the formula
(wherein R1, R3 and Me are as defined above) with a compound of the formula RrX (wherein R2 is as defined in claim 1 and X represents halogen or sulphate).
13. A process for producing a compound as claimed in claim l substantially as described in or with reference to any one of Examples 1 to 3.
14. A compound according to claim 1 produced by the process as claimed in any one of claims 11 to 13.
15. A pesticidal composition which comprises, as active ingredient, a compound of the formula I of claim 1 together with a carrier and/or a surface-active additive.
16. A solid pesticidal composition, which contains, as active ingredient, a compound as claimed in claim 1 together with a solid extender and, optionally, a surface active agent.
17. A liquid pesticidal composition which contains, as active ingredient, a compound as claimed in claim 1 together with a liquid diluent and a surface active agent.
18. A pesticidal composition according to any of claims 15 to 17 which contains, as active ingredient, a compound as claimed in claim 2.
19. A pesticidal composition according to any one of claims 15 to 17 which contains, active ingredient, a compound as claimed in claim 3 or 8.
20. A pesticidal composition according to any one of claims 15 to 17 which contains, as active ingredient, a compound as claimed in claim 9 or 10.
21. A pesticidal composition according to any one of claims 15 to 17 which contains, as active ingredient, a compound as claimed in any one of claims 4 to 7.
22. A method of combating pests at a locus which comprises applying to the locus a compound as claimed in claim 1.
23. A method according to claim 22, wherein the pests are nematodes.
24. A method according to claim 23, wherein the nematodes are phytopathogenic nematodes.
25. A method according to any one of claims 22 to 24 wherein there is applied a compound as claimed in claim 2.
26. A method according to any one of claims 22 to 24 wherein there is applied a compound as claimed in claim 3 or 8.
27. A method according to any one of claims 22 to 24 wherein there is applied a compound as claimed in claim 9 or 10.
28. A method according to any one of claims 22 to 24 wherein there is applied a compound as claimed in any one of claims 4 to 7.
GB54180/77A 1976-12-30 1977-12-29 Amidino phorsporic acid thiol esters and their use for combating pests Expired GB1595809A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1647376A CH621045A5 (en) 1976-12-30 1976-12-30 Pesticide containing, as active substance, an amidinophosphoric thioester, and the use of this composition.
CH272177A CH630641A5 (en) 1977-03-04 1977-03-04 Process for the preparation of new amidino-thionophosphoric acid thioesters, their use against nematodes, and pesticides which contain these compounds as active substances

Publications (1)

Publication Number Publication Date
GB1595809A true GB1595809A (en) 1981-08-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
GB54180/77A Expired GB1595809A (en) 1976-12-30 1977-12-29 Amidino phorsporic acid thiol esters and their use for combating pests

Country Status (18)

Country Link
JP (1) JPS5384921A (en)
AT (1) AT355874B (en)
AU (1) AU517698B2 (en)
BR (1) BR7708734A (en)
CA (1) CA1093573A (en)
CS (1) CS194828B2 (en)
DE (1) DE2758173A1 (en)
EG (1) EG12832A (en)
ES (1) ES465545A1 (en)
FR (1) FR2376154A1 (en)
GB (1) GB1595809A (en)
IL (1) IL53707A (en)
NL (1) NL7714370A (en)
OA (1) OA05841A (en)
PL (1) PL107331B1 (en)
PT (1) PT67460B (en)
SU (1) SU745350A1 (en)
TR (1) TR19912A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60105943U (en) * 1983-12-19 1985-07-19 新日本製鐵株式会社 Screw conveyor for transporting waste in melting processing furnace
JPH05240426A (en) * 1992-01-27 1993-09-17 San Frontier Technol:Kk Blowing-out preventive safety device for gas equipment

Also Published As

Publication number Publication date
AT355874B (en) 1980-03-25
FR2376154A1 (en) 1978-07-28
PT67460A (en) 1978-01-01
JPS5384921A (en) 1978-07-26
OA05841A (en) 1981-05-31
BR7708734A (en) 1978-08-15
PL107331B1 (en) 1980-02-29
NL7714370A (en) 1978-07-04
TR19912A (en) 1980-04-28
DE2758173A1 (en) 1978-07-13
AU3199277A (en) 1979-06-28
SU745350A1 (en) 1980-06-30
PL203431A1 (en) 1978-09-25
IL53707A (en) 1982-02-28
CA1093573A (en) 1981-01-13
ATA940577A (en) 1979-08-15
AU517698B2 (en) 1981-08-20
PT67460B (en) 1979-05-25
FR2376154B1 (en) 1980-12-26
EG12832A (en) 1980-03-31
ES465545A1 (en) 1979-01-01
CS194828B2 (en) 1979-12-31
IL53707A0 (en) 1978-03-10

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PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee