IL46239A

IL46239A - Fungicidal compositions based on monoesters of phosphonic acid

Info

Publication number: IL46239A
Application number: IL46239A
Authority: IL
Original assignee: Pepro
Priority date: 1973-12-14
Filing date: 1974-12-13
Publication date: 1977-12-30
Also published as: MY7900209A; CA1035277A; NO744515L; GB1449394A; NO141971C; OA04850A; TR18629A; ES432896A1; IT1056093B; IE40852B1; NL164731C; NO141971B; DD117169A5; DK140651C; RO85295A; ATA974674A; HK55479A; CY1002A; AT338563B; PH14371A

Abstract

1449394 Phosphite mono esters and their salts PEPRO SOC POUR LE DEVELOPPEMENT ET LA VENTE DE SPECIALITES CHIMIQUES 12 Dec 1974 [14 Dec 1973 23 Oct 1974] 53752/74 Heading C2P [Also in Division A5] Phosphite mono-esters and their salts of the general Formula I in which R is a linear or branched chain alkyl radical containing from 1-18C atoms which is unsubstituted or substituted by halogen or nitro; an alkenyl, alkinyl, alkoxy alkyl, or alkenoxy alkyl radical, each of which is unsubstituted or substituted by halogen and the hydrocarbon portion of each radical contains from 1-8 C atoms; a cyclohexyl radical; an optionally substituted aryl radical, or aryl alkyl radical; or a heterocyclic radical optionally attached to the oxygen atom through an aliphatic chain, preferably tetrahydro urfuryl, M represents a hydrogen atom, an ammonium cation, ammonium substituted by from 1-4 alkyl or hydroxy alkyl radicals containing from 1-5 C atoms or by 1 or 2 cyclohexyl radicals or a phenyl radical, or a cation of a metal comprising an alkali metal, an alkaline earth metal, or a polyvalent metal, n is an integer equal to the valency of M are prepared, e.g. by (i) transesterifying a dialkyl phosphonate with phosphorous acid in accordance with the equation: (ii) hydrolysing a phosphorous acid dichloride with water in accordance with the equation or (iii) hydrolysing or saponifying an 0,0-dialkylphosphonate in accordance with the equation Several specific compounds which have been prepared are mentioned such compounds including sodium o-methyl phosphonate, sodium o-n-hexadecyl phosphonate, ammonium o-ethyl phosphonate, o-methyl phosphonate, o-cyclohexyl phosphonate, diethyl ammonium o, ethyl phosphonate, tetramethyl ammonium o-methyl phosphonate, calcium o-ethyl phosphonate, and iron o-ethyl phosphonate. The products have fungicidal properties. [GB1449394A]

Description

Fungicidal compoaitione on of phosphonic acid pour le et la Vente de Chimiques This compos itions 01 of acid and their These ere sometimes referred to as phosphi to More par y the invention to which use in in plants and as their active ore to the general in which is optionally or linear or radical containing from to carbon and 1 S carbon an halogenated or alkinyl an an alky the hydrocarbon portion of these four types of containing from to 8 and preferably from 1 to 5 carbon a cyclohexyl radical or a benzyl or an hydrogen represents um ca substituted by a or hydroxy radicals containing from 1 to 5 carbon or by 1 to 2 cyclohexyl radicals or a phen or a cation of a metal from the group the and alkaline earth metals preferably and metals such and is an integer equal Lo the valency Some of these compounds are known per Orlovski et Journal of 192 describe the of numerous salts phosphites in monoethyl phosphites with metallic cations substituted to a greater or although do not mention the that these compounds fungicidal It has now found that the compounds according to the invention show excellent fungicidal especially respect to various types of such as of the vine tobacco mildew and hop These compounds may be obtained by the following methods of phosphonates may prepared by esterifying a dialkyl phospho ate with acid 1107e in with the following was prepared by this an equimolecular mixture of phosphonate and phosphorous acid is heated for 6 hours to A liquid of index and of density d is obtained in The following may also be prepared by this phosphonate phosphonate phospho It is also i to obtain page esters to invention by hydro a phosphorous acid with two equivalents of water in accordance with p osp n part cu ar may e prepare y his So far as the salts are they may be prepared by at least two the first page comprises hydrolysing or an phosphonate in accordance with the following H RO II 0 This method is suitable alkali metal salts and 1 and ammo ium sal s is carried out with a mineral or organic base in aqueous The reaction takes place in 1 to 4 hours at a temperature ranging from ambient to the reflux temperature The products are Liquids or solids generally separated by the and the if Sodium phosphonate was prepared in this One of soda in added stirring to hydroalcoholic solution of diethyl After standing for 2 the alcohol and water are removed by under reduced pressure in a water The solid residue is recrystallised from absolute Melting point 68 Analysis for C P λ C H P Calculated Found The following salts were prepared by this sodium p sodium sodium sodium sodium phosphonate sodium phosphonate p The ammonium salts are obtained in the following manner illustrated ammonium mole of phosphonate are dissolved in a 25 aqueous ammonia After standing for 1 the solution is evaporated under reduced pressure in a water The initially rubbery and colourless residue crystallises Crystals in the of colourless needles are obtained by crystallisation a mixture of ethanol and 87 Analysis C Calculated Found Other alkali metal whose characteristics where the particular preparation conditions are in the following were obtained by the saponi base the radical in the described Substituted amine and Preparation ammonium mole of phosphite is poured into an aqueous solution of one equivalent of The reactio is carried out for 1 hour at the wa er by evaporation leaves a 35 Analy Jsis c H P Calculated Found Similar characteristics are the following were prepared by the same The yields are in excess of 85 in every H t 0 Em irical Physical Centesimal an C H soluble C soluble P C 20 N soluble P ris pages The following compounds were prepared by this mono ammonium phosphonate diethyl ammonium phosphonate trie thy 1 ammonium phosphonate Quaternary ammonium salts Preparation of ammonium phosphonate mole of phosphite is added to an equivalent quantity of trirnethyl amine in solutio in acetone The reaction medium is kept at 50 to for 2 Evaporation of the acetone a highly hygroscopic soluble 77 Analysis for P C P Calculated Found The corresponding and derivatives were obtained by the same the phosphite being replaced by the the propyl respec The is carried a 70 to in onit solids obtained are recrys tallised from phosphonate 94 Analysis for C H P Calculated Found Tetrantethy 1 phosphonate 92 Analysis for C N P Calculated Found Divalent salts A metal is reacted a dialkyl phosphite accordance with the Orlo Calcium phosphonate was prepared in this A mixture of g of calcium chloride g of phosphonate is heated with stirring for 2 hours to The mixture is A precipitate is obtained after and gives crystals melting at in a yield of 96 Analysis 0 P Ca 6 2 C Calculated Found 1 The following salts may be similarly obtained by replacing the barium zinc pho e mole of phosphite is added to a suspension of mole of magnesi in 100 cc of distilled The exothermic reaction is out stirring for 2 hours at After the water is evaporated the leaving a solid which is washed with acetone and then 100 Analysis for C H P Calculated Table shows the characteristics solubility in and analysis of other metal phospbonates obtained in the same way as in the preceding Unless otherwise the yields are in excess of 70 the majority being In the case manganese the metal oxide is replaced by a carbonate Salts obtained by a re via the salt Zinc phosphonate mole of phosphonate and mole of i baryta are dissolved in cc of distilled The phosphonate A solution of mole of zinc sulphate in 20 cc of distilled water is then as a result of which the barium sulphate is It separated by filtration or clear filtrate is evaporated to giving a highly viscous liquid which is dried in This liquid is soluble in 82 Analysis for C b C H P Calculated Found The products whose characteristics are set out the following Table were obtained by changing either the radical or the metal in the procedure described Unless otherwise the yields are in excess of 70 Em irical Physical Centesimal ana formula characteristics calculated C solid H soluble Fe C Cu From the salt phosphonate Sodium p osphonate is A of mole of aluminium nitrate with nine of in 30 cc of distilled added to a solution of of compound in cc of distilled The aluminium phosphonate The precipitate is washed and the with acetone finally dried in giving a white solid which is in 60 Analysis for C H P Calculated Found compounds were prepared by the method phosphonate The iron sal were obtained by replacing the aluminium nitrate with ferric iron The characteristics of all these compounds are set out in the following Unless otherwise the yields are in excess of V salts Iron phosphorate This compound is prepared by the method page comprising r ng ferric chloride 3 equivalent of phosphorous A melting above is obtained after filtration and Analysis for C Fe P Calculated Found ate This is prepared by S method described replacing he soda with It is possibl to obtain the iron salts of the phosphonates such for iron which decomposes at around Analysis for C P Calculated Found The Examples illustrate the fungicidal properti of the following ammonium phosphonate 2 ammonium phosphonate 3 sodium phosphonate 4 calcium phosphonate 5 ammonium phosphonate 6 ammonium phosphonate 7 ammonium phosphonate 8 ammonium phosphonate 9 amnionium 1 phosphonate sodium phosphonate phosphonate phosphonate ammonium ethyl phosphonate ammonium phosphonate ammonium benzyl phosphonate ammonium phosphonate sodium phosphonate ammonium phosphonate dicyclohexyl phosphonate potassium phosphonate magnesium phosphonate baryum phosphonate zi c phosphonate manganese phosphonate aluminium phosphonate phosphonate phosphonate magnesium phosphonate phosphonate calcium phosphonate aluminium phosphonate sodium phosphonate calcium phosphonate ammonium phosphonate aluminium calcium phosphonate sodium ethyl phosphonate magnesium ethyl phosphonate ammonium phos phosphonate EXAMPIB 1 In Lest on in vine plants leaves vine plants sprayed underneath using a spray gun with an aqueous and 40 to 42 aford total whilst compounds 31 and 39 afford good In it was found that none of the compounds tested showed the least phyto oxicit Treatment after The procedure is as described in except that the plants are first of then treated with the active to be the plants being inspected 9 days after contamina Under these cond it was found in a dose 1 compounds 1 to to 36 and 40 to 42 completely stop the development of mildew on the vine Systemic test by root Several vine stocks each a pot containing and a nutritive solution are sprinkled with of a solution containing the to be After 2 the vine is contamina with an aqueous suspension containing Plasmopara The spores are then left to incubate for 48 hours in a room at relative The degree of infestation is assessed after about 9 days in relation to an infested control which has been sprinkled with cc distill Under these it was found in this dose of compounds 1 to 20 35 and 37 to absorbed by the afford total protection to the vine leaves which demons rates clearly the systemic nature of these com test on mildew of the vine Groups of 5 vine stocks are sprayed ever days from the 5th July to the 20th August an aqueous solution containing 200 of active material a wet able powder of the following composition weight active material 50 calcium lignosuiphate 5 sodium alkyl sulphonate 1 silica kaolin 39 The appears from 24th July Natural contamination is con In Augus the stocks are sprayed in such a way that the leaves are The attacks o fungus are considerable in the promoted by particularly At end of the number of mildewed areas is Counted o the leaves vhich have been Under these it was found that the controls show 136 mildewed per whe eas the s treated with compounds numbers 31 and 39 do not show the least sign of the shoots which were not present durin the treatments show only few areas per adeciuately the svstemic character of these under EXAMPLE Test on tobacco Groups of 5 tobacco plants are treated on 15th June with a wettable powder containing 160 of 300 of sodium ethyl phosphonate and 300 of magnesium phosphonate One group is left untreated as After 48 the plants are artificially contaminated finely sprayed The treatment is then continued once An inspection is made on the 2th August by counting the number of mildewed areas per The results are set out in the following 1 Other tests show that two compounds according to invention are also effective against this fungus in EXAMPLE 4 Avocado te t Your avocado plants are planted in soil infested with Phytophtora after which the soil is sprayed with absolution 3 of are left untreated as Under these it was found after days that the roots of the control plants are completely 90 of the roots of the treated plants are PineappLe test Young pineapple plants are contaminated with Phytophtora and then treated after 48 hours by spraying with a solution containing of calcium It was found after 30 days that the fungus was inhibited in the whilst the controls are EXAM Strawberry test Ten strawberry plants Surprise des are treated by soaking for 1 hour in an aqueous solution containing of calcium dried and then planted on the 14th in soil arti icially contaminated with htora Immediately afterward and then once every 8 days until the the plants are with the same solution which corresponds to a total application of g of active material per Plants treated by soakiiig and spraying with water are used as Under these it was found he 24th July that the protection afforded to the strawberry plants is whilst 76 of the control plants are pimento plants Yolo which have already been out are transplanted on the 27th June to pots of artificially with Phytophtor The plants are sprayed immediately and then once every 8 days until the 18th July with an aqueous solution containing zinc phosphonate so as to apply a total of g of treatment per sprayed with water are used as Under these it found that the 10 plants are intact at the end of whilst the control plants have all died by 25th All these Examples clearly shew the remarkable fungicidal activity of the compounds according to the on the one hand a systemic activity both prevents stops the development of vine and on the other on certain phytophtora as they have also found to be extremely effectiv in controlling other types of parasitic fungi such as in Pseudoperonospora Bremia Phytophtora Phyto Phytophtora phascoli Ph h other ε in or plants such as especially sweet in ornamental the compounds according to the invention are particular suitable for use in the preventive or curative treatment fungus disease especially disease caused by phycomycetes and ascomycetes in the vegetables but also more generally in horticul but more especially in The compounds according to the invention may be used with advantage in admixture with one another or other k own such as metal dithiccarbamates basic salts or hydroxides copper ox methyl carbamate 1 or benzenes methyl benzimidazole either to complete the range of activity of the compounds according to the invention or to increase their It has also been found that the compounds according to the invention may be mixed with other phosphorus especially 1 ethyl phosphites and phosphorous acid its The doses in which the compounds according to the invention are used may vary within wide depending both upon the virulence cf fungus and upon the climatic Doses of from to 5 of active material are generally For their practical the compounds according to the invention rarely used on their they generally form part of formulations as a contain a support a surfactant in addition the active material ng to the In the context of the a support is an organic or natural or synthetic material with which the active material is associated to facilitate its i to the to or to or its transportation or i The support can be solid natural or synthetic solid or fluid petroleum chlorinated liquefied The surfactant can be an ionic or emulsi dispersant or wetting agent such for salts of polyacrylic acids and sulphonic condensates of ethylene oxide with fatty fatty acids or fatty amines The prepared suspended concentrates and The wettable powders according to the invention can be prepared in such a way that they contain from 20 to 95 by weight of the active and they normally in addition to a from 0 to by weight of a wetting from 3 to by weight of a dispersant when from 0 to by weight of one or more stabilisers other such as penetration adhesives or One example of the composition of a wettable powder is given active material calcium lignosulphate anionic wetting ilumpi kaolin to 10 of a remainder being hydrdsoluble filler mainly a There is one example of composition of soluble powder active material 70 agent antilumping silica 5 sodium sulfate Aqueous dispersions and for example compositions obtained by diluting with water a wettable powder or an concentrate to the are included within the general of the These can be of the type or of the and can have a thick consistency resembling that of a The compositions according to the invention contain other for example protective adhesives or thixotropic stabilisers or as well as other active materials to have especially acaricides or insufficientOCRQuality

Claims

1. Fungicidal compositions for controlling fungus 'dis a e in plants, distinguished by the fact that, in addition to an inert support and Lhe usual additives, they contain as active material an effective o^tantity of at least one compound corresponding to the general formula in which R is an optionally halogenated or nitrated, linear or branched alkyl radical containing from 1 to 18 carbon atoms and prefera from 1 to 8 carbon atoms, an optionally halogenated alkenvl or alkinyl radical, an alkoxy alkyl radical, an alkenoxy alkyl radical, the hydrocarbon portion of these four types of radicals containing from 1 to 8 and preferably from 1 to 5 carbon atoms, a cyclohexyl radical or a phenyl, benzyl or tetrahydrofurfuryl radical, M represents an ammonium cation, ammonium substituted by 1 to alkyl or hydroxy alkyl radicals containing from 1 to 5 carbon atoms or by 1 to 2 cyclohexyl radicals or a phenyl radical, or a cation of a. metal ' from the group comprising the alkali metals, preferably sodium and potassium, alkaline earth metals, preferably magnesium, barium, calcium, and polyvalent metals • . 46239/2 ■ such as, preferably, zinc, manganese, coppe (I J. ) and (ill), iron, nickel, aluminium, n is an integer equal to the valency of M.. '"

2. Compositions as claimed in Claim.1, wherein M is an anunor.iom cation substituted by 1 to 4 alkyl radicals, or hydroxy alkyl radicals containing from 1 to '5 carbon atoms Or by 1 to 2 cyclohexyl radicals or a phenyl radical. (

3. Compositions as claimed in Claim 1, .wherein M is an ·· alkali metal cation;

4. Compositions as claimed in Claim 1, wherein. is an alkaline earth metal cation.

5. Compositions' as claimed iii- Claim 1, wherein M is. a cation of a metal from the .' group comprising zii'ic, manganese, copper (II) and (ill), iron-(II) and (ill) nickel and aluminium, j

6. Compositions as claimed in any of Claims 1 to 4, wherein j R is an optionally halogenated or nitrated alkyl radical containing from 1 to 8 carbon atoms, an optionally halogenated alkenyl or alkinyl radical,, an alkoxy alkyl radical, an alkenoxy alkyl radical, the hydrocarbon portion of these j radicals containing from 1 to 5 carbon atoms.. <

7. Compositions as claimed in Claim (_», wherein R is an alkyl radical , . a halogenated alkyl radical containing from 1 to 4 carbon atoms, an allyl, propargyl, allyl oxy or alkoxy alkyl radical containing from 2 to 3 carbon atoms. I

8. A composition as claimed in Claim wherein R is the j ethyl radical. « ■ .

9. Compositions as claimed in Claim wherein R is the j isoprcpyl radical.. ' ' I

10. Compositions as claimed in Claim g, wherein the active j material is sodium 0-ethyl phosphonate. j

11. Compositions as claimed in Claim wherein the active [ material is calcium 0-ethyl phosphonate. j

12. Compositions as claia^ed in Claim wherein the active j material is aluminium 0-ethyl phosphonate. j

13. Compositions as claimed in Claim 8, wherein t e active material is magnesium O-ethyl phosphonate. . ,

14. Composi ions a claimed in Claim 8, wherein, the active material is zinc O-eLhyl phosphonate.

15. Compositions' as claimed in Claim v.'herein the active material is cuprous O-ethyl phosphonate . ■·

16. Compositions as- claimed in Claim 9, v.'herein the active material is cup.ric O-ethyl phosphonate..

17. Compositions as claimed in Claim' J.i wherei the active material is sodium O-isopropyl phosphonate.

18.. Compositlons as- claimed in.. Claim vjherein the active .', material is calcium O-isopropyl phosphonate."

19. Compositions as claimed in Claim wherein the active material is aluminium O-is.opropyl phosphonate.

20. Compositions as claimed in Claim- §, wherein the -active material is magnesium O-isopropyl phosphonate.

21. Compositions as "claimed in Claim Ji, wherein the active -material is zinc O-isopropyl phosphonate ..'

22. Compositions as claimed iri Claim 5, wherein the active material is cuprous O-isopropyl phosphonate.

23. Compositions as claimed in Claim ¾, wherein the active material is cupric O-isopropyl phosphonate.

24. Compositions as claimed in any of Claims 1 to 2j, 'wherein they additionally contain a known fungicide.

25. A" process for controlling fungus disease in plants, comprising applying a composition of the kind claimed in . any of Claims 1 to 2 $j for preventive or curative treatment.