IE58475B1 - Microbicidal agents - Google Patents

Microbicidal agents

Info

Publication number
IE58475B1
IE58475B1 IE154486A IE154486A IE58475B1 IE 58475 B1 IE58475 B1 IE 58475B1 IE 154486 A IE154486 A IE 154486A IE 154486 A IE154486 A IE 154486A IE 58475 B1 IE58475 B1 IE 58475B1
Authority
IE
Ireland
Prior art keywords
formula
compound
hydrogen
halogen
active ingredient
Prior art date
Application number
IE154486A
Other versions
IE861544L (en
Original Assignee
Ciba Geigy Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Ag filed Critical Ciba Geigy Ag
Publication of IE861544L publication Critical patent/IE861544L/en
Publication of IE58475B1 publication Critical patent/IE58475B1/en

Links

Classifications

    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5333—Arylalkane phosphine oxides or thioxides
    • 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
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/306—Arylalkanephosphinic acids, e.g. Ar-(CH2)n-P(=X)(R)(XH), (X = O,S, Se; n>=1)
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3882—Arylalkanephosphonic acids
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4056—Esters of arylalkanephosphonic acids
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

1. Claims for the contracting States : BE CH DE FR GB IT LI LU NL SE A microbicidal agent containing as at least one active ingredient a compound of the formula I see diagramm : EP0207890,P22,F1 in which R is C1 -C4 alkyl or OH, R1 is OH X is hydrogen, halogen, C1 -C4 alkyl, C1 -C4 alkoxy, Si(CH3 )3 , -CN, -COOCH3 or -CH2 -CH(NH2 )-P(O)(R)(R1 ) and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl, with the inclusion of the corresponding salts ; together with a suitable carrier and/or wetting agent, a wetting agent always being present, if the active ingredient of the formula I simultaneously has the meanings R=R1 =OH and X=Y= hydrogen. 1. Claims for the Contracting State : AT a microbicidal agent containing as at least one active ingredient a compound of the formula I see diagramm : EP0207890,P23,F2 in which R is C1 -C4 alkyl or OH, R1 is OH X is hydrogen, halogen, C1 -C4 alkyl, C1 -C4 alkoxy, Si(CH3 )3 , -CN, -COOCH3 or -CH2 -CH(NH2 )-P(O)(R)(R1 ) and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl, with the inclusion of the corresponding salts ; together with a suitable carrier and/or wetting agent, a wetting agent always being present, if the active ingredient of the formula I simultaneously has the meanings R=R1 =OH and X=Y= hydrogen.

Description

The present invention relates to microbicidal agents containing as at least one active ingredient a l-amino-2-arylethanephosphonic or 1-amino2-arylethanephosphinic acid derivative of the fonnula I or a salt thereof, and to the preparation and use of these active ingredients for controlling harmful micro-organisms.
The compounds of the present invention have the formula in which R is C1-C4alkyl or OH, R1 is OH, X is hydrogen, halogen, C1-C4alkyl, Cj^-C^alkoxy, Si(CH3)3, -CN, -COOCH3 or -CH2-CH(NH2)-P(0) (R) (Rx) , and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl, with the inclusion of the corresponding salts.
Fonnula I expresses ethanephosphonic acid derivatives if R and Rx are hydroxyl and ethanephosphinic acid derivatives if the substituent R is alkyl.
CL-C4Alkyl· by itself or as moiety of an alkoxy group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
HaLogen is understood as meaning fluorine, chlorine, bromine or iodine.
Cj^-CjHaloalkyl as moiety of a haloalkoxy group or halomethyl is a monohalogenated methyl or ethyl group or a methyl or ethyl group which is polyhalogenated or perhalogenated by a specific halogen atom or by different halogen atoms. Typical examples are CHC12, CHFZ, CH2Cl, CC13, CH2F, CHBr2> CH2CH2C1, CHCl-CHCl, CF3, C2F5, CF2C1, CF2-CF2C1.
Salts of a free hydroxyl group are unsubstituted or substituted ammonium or hydrazinium sales or metal cations.
Examples of metal ions are the cations of the following elements: alkali metals such as lithium, sodium or potasssium; alkaline earth metals such as magnesium, calcium, strontium or barium; elements of the first to eighth Periodic auxiliary group such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, especially iron, manganese, copper and zinc; elements of the third and fourth Periodic main group such as aluminium, silicon, tin, lead, zirconium, titanium, especially aluminium, the metal ions being present in the salts or complexes of the formula I in the valence states appropriate to them.
Phosphonic acid derivatives of the formula I can in principle be obtained by reacting an unsubstituted or substituted 2-phenylacetaldehyde with ammonia and dialkyl phosphite, followed by subsequent hydrolysis with a mineral acid: >-ch2-cho ί ^2 a't kv LC-P-CE-CK 0-a ikv1 I OH [Chalmers and Kosolapoff, J . Am.Chem.Soc. 75, 5278 (1953)].
A mineral acid will be understood as meaning preferably a hydrohalic acid such as hydrochloric or hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, toluenesulfonic acid and the like.
A rather more general method is that proposed by Berlin et al. [J. Org.
Chem. 33., 3090, (1968)], in which a substituted phenylacetyl halide is reacted with a) Ο,Ο,Ο-trialkyl phosphite or b) Ο,Ο-trialkyl phosphonite, and the Intermediate is further reacted, in the presence of hydroxylamine, to give the phosphonyl or phosphinyl oxime, from which che amine can be obtained by hydrogenation; ί In the above formulae, X and Y are as defined for formula I; furthermore X' - H, halogen, C1-C4alkyl, C^-C^alkoxy, Si(CH3)3, -CN, -COOCH3 or -CH2-CHO, alkyl - C1-C4alkyl, X* — H, halogen, C1-C4alkyl, C1-C4alkoxy, Si(CH3)3, -CN, -COOCH3 or -CH2-COHal, X** = H, halogen, C1-C4alkyl, C^C^lkoxy, Si(CH3)3, -CN, -COOCH3 or -CH2-C(O)-P(O) R* (R\), Hal = halogen, preferably Cl or Br, R' - C1-C4alkyl, R* - Cj-C4alkyl or C1-C4alkoxy, R*x - C1-C4alkoxy.
Formula I* embraces only those compounds of the formula I, in which R and R1 have the meaning of R* and R*3. Where R* and/or R\ are C1-C4alkoxy, free hydroxyl groups can be obtained therefrom by hydrolysis with, preferably, a mineral acid. Free OH groups can, if desired, be converted with a base into salts, e.g. metal salts, ammonium salts, alkylammonium salts, dialkylammonium salts or the like.
Compounds of the formula I can be obtained in simple manner and in high yield by a further method by aralkylating the activated Schiff's base obtained from a) aminomethyl phosphonate or aminomethyl phosphinate and b) an aldehyde such as benzaldehyde or a ketone such as phenylacetone or benzophenone, with a suitably substituted benzyl halide (R.W. Ratcliffe and B.G. Christensen, Tetrahedron Letters, 4645 (1973)]: X C Π C=N-CH_-?-R - Kal-CH LiN(iscC,H )? R, j n T1 ' 7 =N-CK-?(R)(R,) m ·* ι * riaiK .-. 0 - ^.-CH2-C;-i-?(R) (R.) M=C Hal - halogen, preferably Br or Cl The activation of the CH2- group vicinal to the P-atom in the starting material can also be effected by other reagents such as butyllithium or sodium hydride in e.g. tetrahydrofuran. R, Rlt X and Y are as defined for formula I, Tx is hydrogen or an aliphatic or aromatic radical and T2 is an aliphatic or aromatic radical.
The last step of the hydrogenolytic cleavage of the Schiff's base to obtain the desired final product of the formula I is carried out by catalytic cleavage with e.g. H2/Pd/C, but can also be performed with hydrogen in the presence of other catalysts (such as platinum or Pt/C). In the presence of a mineral acid such as hydrochloric or hydrobromic acid, it is possible to carry out the cleavage of the Schiff's base and the hydrolysis of an alkoxy group to a hydroxyl group at elevated temperature (40°-150°C) in one reaction step.
It is advantageous to use inert solvents or diluents in all the aforementioned procedures. Examples of customary solvents and diluents are aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzenes, methylene chloride, ethylene chloride, chloroform, tetrachloroethylene; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether and the like), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile, and mixtures of such solvents with one another.
The reaction temperature during the aralkylation (benzylation) is normally in the range from -100’C to +10°C, preferably from -80’C to -20°C. The hydrogenolytic cleavage is conveniently carried out in the temperature range from -20’C to +80°C.
The cited starting compounds are known or are prepared by methods known per se. To prepare the Schiff's base, it is advantageous to carry out the process in an inert gas such as nitrogen or argon. Substituted benzyl bromides can be readily obtained from suitably substituted toluenes by bromination with N-bromosuccinimide in CC14 in the presence of azoisobutyronitrile (catalyst).
The compounds of the formula I are phosphonyl and phosphinyl analogs of β - phenylalanine. As such they possess, adjacent to the P-atom, an asymmetrical carbon atom, such that the structures corresponding to the natural L-a-amino acids have the (R)-configuration, whereas the structures of the formula I corresponding to the D-a-awi.no acids have the (S)-configuration. The respective (R)- or (S)-configurations of a diastereomeric (R,S)-compound can be obtained pure therefrom by fractional crystallisation or chromatography (HPLC). The (R) diastereomers and (S)-diastereoisomers exhibit different microbicidal activity .
The present invention also relates to the above preparation processes, where these lead to novel compounds. The invention further relates to the novel compounds of the formula I in which at least one of the substituents X and Y has a meaning different from hydrogen, provided R and Rx are simultaneously hydroxyl.
Among these, those compounds are preferred in which R - RL - OH, X is hydrogen, fluorine, chlorine or bromine, C1-C4alkyl, CH3O, Si(CH3)3, -CN, -COOCH3 or -CH2-CH(NH2)-P(O)(OH)2, and Y is fluorine, chlorine, bromine, halomethoxy or halomethyl.
Among these last-mentioned compounds, those compounds are particularly preferred in which at least one of the two substituents X and Y is halogen or contains halogen, and, of these, those compounds in which one of the two substituents X and Y is fluorine or contains fluorine.
Derivatives of peptidylaminomethanephosphonic and peptidylaminoethanephosphonic acid are proposed in US Patent Specification 4,016,148 as potentiators for antibiotics. However, no particulars relating to pest control are contained therein and such utility is in no way suggested.
Peptidylaminoalkanephosphonic acid derivatives are proposed as herbicides and retarders of plant growth and plant emergence in US patent specification 4,431,438. However, there is no mention of protecting plants against microbial attack. It must also be added that compositions with general herbicidal or growth-inhibiting properties are of necessity very poorly suited to protecting cultivated plants. l-Amino-2-phenylethanephosphonic acid is mentioned in Agr. Biol. Chem. (5), 1193 [1973] in the context of investigations to obtain phosphorus-containing substances having suspected amino acid-like properties. There is no mention of microbicidal activity.
Surprisingly, it has now been found that aminoethanephosphonic acid derivatives of the formula I mentioned herein and salts thereof not only have no herbicidal properties, but have an unexpectedly potent microbicidal activity which is particularly suitable for imparting lasting protection to plants from attack by fungi and bacteria and for promoting the development of said plants.
The salts of the formula I come into the category of preferred compounds. Especially preferred on account of their fungicidal activity are the metal salts, in particular the aluminium, nickel, manganese and copper salts and the lower alkylammonium salts of the formula I, which are particularly suitable for soil application and as seed dressing agents .
The principal utility of compounds of the formula I is for controlling harmful phytopathogenic fungi. Thus the compounds of the formula I have, for practical purposes, a very useful curative, preventive and systemic action for protecting cultivated plants without adversely affecting said plants by undesirable side-effects. Examples of cultivated plants within the scope of the present invention are; cereals (wheat, barley, rye, oats, rice); beets (sugar-beet and fodder beet); drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); or plants such as maize, tobacco, nuts, coffee, sugar-cane, tea, vines, hops, bananas, avocados, and natural rubber plants, as well as ornamentals.
With the active ingredients of the formula I io is possible to inhibit or destroy the micro-organisms which occur on plants or parts of plants (fruits, blossoms, leaves, stems, tubers, roots) in these and in related crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such micro-organisms. The active ingredients of the formula I are particularly effective against the phytopathogenic fungi belonging to the following classes; Ascomycetes (e.g. Helminthosporium and Fusarium species) and Basidiomycetes (e.g. Tilletia and Ustilago). The compounds of the formula I can therefore also he used as seed dressing agents for the treatment of seeds (fruit, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi which occur in the soil.
Accordingly, the invention also relates to the use of the compounds of the formula I for controlling phytopathogenic micro-organisms and for the preventive treatment of plants to protect them from attack by such micro-organisms .
The active ingredients of the formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further active ingredients. These further active ingredients can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in the art of formulation.
Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner for example to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymeric substances. As with the nature of the agents, the methods of application are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application in agriculture are normally from 50 g to 5 kg of active substance (a.s.) per hectare, preferably from 100 g to 2 kg a.s. /ha, especially from 100 g to 600 g a.s./ha.
Suitable solvents are: aromatic hydrocarbons, preferably the Ca to C12 fractions, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
Particularly advantageous application-promoting adjuvants which are able to reduce substantially the rate of application are also natural (animal or vegetable) or synthetic phospholipids of the series of the cephalins and lecithins, e.g. phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl glycerol or lysolecithin.
Depending on the nature of the active ingredient of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term surfactants will also be understood as comprising mixtures of surfactants.
The surfactants customarily used.in the art of formulation are described, inter alia, in the following publications: McCutcheon's Detergents and Emulsifiers Annual, BC Publishing Corp., Ringwood New Jersey, 1981; Helmut Stache, Tensid-Taschenbuch [Surfactant Handbook], Carl Hanser - Verlag, Munich/Vienna, 1981.
M. and J. Ash, Encyclopedia of Surfactants, Vol. I-III, Chemical Publishing Co., New York, 1980 - 1981.
The agrochemical compositions usually contain 0.1 to 99 X, especially 0.1 to 95 X, of active ingredient of the formula I, 99.9 to 1 X, especially 99.8 to 5 X, of a solid or liquid adjuvant, and 0 to 25 X, especially 0.1 to 25 X, of a surfactant.
Whereas commercial products are preferably concentrated agents, the end user will normally employ dilute agents.
Preparation Examples H -1. Preparation of 1-amino-2 -(4-fluorophenyl)ethanephosohonic acid of the formula a) Preparation of 0.0-diisopropyl-l-N-benzylidenea-mino-2-f4fluorophenyl)ethylphosphonate ( intermediate) With stirring and cooling, .500 ml of n-butyllithium are added to a solution of 113.4 g (0.8 mole) of dilsopropylamine in 750 ml of tetrahydrofuran (THF) . The mixture is cooled to -75°C and then a solution of 226.6 g (0.8 mole) of 0,O-diisopropylbenzylideneaminomethanephosphonate in 600 ml of THF is added dropwise over the course of 1 hour. After stirring for 1 hour, a solution of 151.2 g (0.8 mole) of 4 - fluorobenzyl bromide in 150 ml of THF is added dropwise and stirring is continued for 1 hour. After the reaction mixture has stood overnight at room temperature, the solvent is stripped off and the residue is dissolved in 1 litre of dichloromethane. The solution is washed with three 200 ml portions of water and dried over Na2SO4. The solvent is then removed by evaporation to give 286.3 g (91.4 2 of theory) of the intermediate, which yields 261.2 g (83.4 2 of theory) of pure product after molecular distillation. Boiling point: 160°C/0.1 mbar . b) Hydrogenation of the Intermediate To a solution of 19.6 g (0.05 mole) of the intermediate obtained in la) in 200 ml of isopropanol are added 2 g of Pd/C (5 2 Pd) and the mixture is hydrogenated at room temperature (20°-25<’C). After 62 2 hydrogen uptake, 2 g of Pd/C are again added and, after 90 2 hydrogen uptake, a further 2 g of Pd/C are added. The hydrogen uptake is complete after 19 hours. The reaction mixture is filtered and the filtrate is concentrated hy rotary evaporation. The remaining residue (about 15 g) is distilled in a bulb tube, affording 12.6 g (83.1 2 of theory) of pure 0,0-di isopropyl-1-amino-2 -(4-fluorophenyl)ethylphosphonate in the form of a colourless oil with a boiling point of 170°C/0.08 mbar. c) Preparation of the final product l-amino-2-(4-fluorophenyl)ethanephosphonic acid A mixture of 227.5 g (0.75 mole) of Ο ,O-diisopropyl-1-amino-2-(4fluorophenyl)ethylphosphonate and 750 ml of 20 Z hydrochloric acid is refluxed, with stirring, for 5 hours and stirred for a further 10 hours at room temperature. After addition of 500 ml of water, the residue is filtered and washed with 250 ml of water and 500 ml of methanol, affording 103.3 g of the title compound. The filtrate is concentrated and the residue is recrystallised from methanol/propylene oxide, affording a further 43.3 g of final product. Total yield: 146.6 g (89.2 X of theory). Melting point: 266-27O°C (decomp.).
H-2. Preparation of the optical isomers of l-amino-2-(4-fluorophenyl)ethanephosphonfc acid A. Preparation of the dibenzovl tartrates of O.O-diethyl-l-amino-2-(4f luorophenyl)e thylphosphonate (C,H_COOCH-COOH). dp 2 > Salt a) To a solution of 68.82 g (0.125 mole) of 0,0-diethyl-1-amino i4fluorophenyl)ethylphosphonate in 750 ml of methanol and 750 ml of ethanol are added 47.04 g of dibenzoyltartaric acid (L)(-)xH20 at room temperature. After stirring for 2 hours, the resulting thick white suspension is filtered and the residue is dried. Two recrystallisations from ethanol yield 31.5 g (39.8 X of theory) of salt I of m.p. 179°C (decomp.); [a]g° - -66.4° ± 0.5° (c = 2.077 X in methanol). b) The combined residual filtrates are evaporated and the residue is stirred in 200 ml of IN NaOH. The solution is saturated with sodium chloride and extracted with three 400 ml portions of CH2C12. The organic phase is dried over Na2SO4 and concentrated by evaporation. The residual brown oil (37.5 g) is dissolved in 400 ml of methanol and 400 ml of ethanol and 25.6 g of dibenzoyltartaric acid (D)(+)xH20 are added to the solution. After stirring for 2 hours, 63 g of salt are isolated by filtration and recrystallised from 1200 ml of methanol to give 7.2 g of crude salt II. The filtrate is concentrated and the residue recrystallised from 500 ml of ethanol, affording 17 g of pure salt II; [α]βθ= +67.3’ ± 0.5° (c = 1.998 % in methanol).
B. a) Preparation of (+) O.O-diethyl-l-amino-2-(4-fluorophenvl)ethylphosphonate .34 g of salt I are stirred for 2 hours at room temperature in 100 ml of IN NaOH to effect liberation from the tartrate. The clear solution is saturated with sodium chloride, then 200 ml of CH2C12 are added and the resultant suspension is filtered in vacuo. The residue is washed with two 200 ml portions of CH2Cl2. The organic phase of the combined filtrates is separated off, dried over Na2SO4, filtered, and concentrated by evaporation to give 9.1 g (82.7 X of theory) of the desired final product as a pale yellow oil; (q]q°=- +10.6° ±0.4° 1H-NMR in CDC13: 1.3 (NH2, CH3)(t, 8H); 2.3-3.5 (PCH-CH2) (m, 3H); 4.17 (0CH2)(qu, 4H); 7.1 (m) (4H, phenyl). b) Preparation of (+) l-amino-2-(4-fluorophenyl)ethanephosphonic acid .51 g (0.02 mole) of the (+) phosphonate obtained in a) are refluxed in 40 ml of 20 X hydrochloric acid for 4 hours. The solution is then concentrated and the residue is recrystallised from methanol/propylene oxide, affording 3.7 g (84.5 X of theory) of the desired final product. Melting point: 259-263’C (decomp.); [q]§°= +37.5° ± 0.4° (c = 2.636 in 1 N NaOH).
^-NMR in D20/Na0D: 2.3-3.1 (PCH-CH2)(m, 3H) ; 4.65 (OH, NH2) (S) ; 6.6-7.1 (phenyl, 4H)(m).
C. a) Preparation of (-) 0.O-diethyl-1 - amino-2 -(4-fluorophenyl)ethvlphosphonate in accordance with the method of Ba) from salt II" with IN NaOH solution.
Yield: 95.9 % of theory. Pale yellow oil [q]d°=- -10.3° ± 0.5° (c =- 2.036 X in methanol). b) Preparation of (-) l-amino-2-(4-fluorophenyl)ethanephosphonic acid in accordance with the method of Bb) by hydrolysis of the above (-)phosphonate in 20 X hydrochloric acid. Yield: 77.6 % of theory.
Melting point: 261-263°C (decomp.); [al*0- -36.9° ± 0.5° (c - 2.081 X in IN NaOH). 1H-NMR in D2O/NaOD: 2.5-3.4 (PCH-CH2) (m, 3H) ; 4.85 (OH, NH2) (s) ; 6.8-7.4 (phenyl, 4H) (m).
The following compounds of the formula I, which are obtained as mixtures 15 of diastereomers unless otherwise specifically mentioned, can also be prepared in this manner or by one of the other methods described above.
The 1H-NMR values were determined with a Varian EM-360 spectrometer at 60 MHz in CDC13 with (CH3)4Si as reference substance.
The 31P-NMR values were recorded with a Bruker WP 80 spectrometer at 20 32.28 MHz with 85 X H3POA (externally) as reference substance.
Key: Me = methyl Et = ethyl iPr = isopropyl The temperatures are given in degrees Celsius.
Table 1: ll Intermediates of the formula (R'O) ?-CH(NH )-CH Compound R' X Y Physical data 1.1 Et H H b.p. 170°/0.6 mbar 1.2 iPr H HlH: 1.3(NHz), 2.5-3.5(PCH 7.3 (aromatic-H) 1.3 Et 4-C1 H ηθ° 1.5140 1.4 Et 3-C1 H ‘H:1.3; 2.4-3.5; 7.2 1.5 Et 4-Br H b.p. 125°/0.05 mbar 1.6 Et 4-1 H 1.3; 2.3-3.4; 7.767 1.7 Et 4-F H b.p. 150-160°/0.08 mbar 1.8 iPr 4-F H b.p. 170*70.08 mbar 1.9 iPr 3-F H b.p. 15O°/O.O5 mbar 1.10 iPr 2-F H b.p. 150°/0.08 mbar 1.11 Et 2-C1 4-C1 m.p. 59-62° 1.12 Et 3-C1 4-C1 n™ 1.5272 1.13 Et 4-Me H *H: 1.4; 2.5-3.5; 7.15; 2.32 (X=CH3). 31P: 28.09 1.14 Et 3-Me H n^° 1.5060 1.15 Et 2-He HlH: 1.33; 2.5-3.5; 7.2; 2.33 (X=CHj). 31P: 28.19 1.16 Et H 3-CF3 ηθ° 1.4659 1.17 iPr 4-t-butyl H b.p. 140°/0.01 mbar 1.13 Et 4-HeO H b.p. 16570.2 mbar 1.19 Et 2-MeO H b.p. 12570.1 mbar 1.20 Et 2-F 6-C1 1.21 Et H 4-OCHFz 1.22 . Et H 3-0CHF2 1.23 iPr H 4-OCHFz 1.24 iPr H 4-CF3 1.25 iPr H 4-CHFz Table 1: (continuation) 11 x / Intermediates of the formula (R' C) -CH^··/ Compound R' X Y Physical data 1.26 Et H 4-OC2F 5 1.27 Et H 4-OCFs -CF2C1 1.28 Et 2-Si(Me)3 H b.p. 110° 70.1 mbar 1.29 Et 3-Si(Me)3 H b.p. 150°/0.12 mbar 1.30 Et 4-Si(M.e) 3 H b.p. 120°/0.1 mbar 1.31 iPr 4-CN HlH: 1.35; 2.6-3.5; 1.32 Et 3-F 4-F b.p. 115°/0.1 mbar 1.33 Et 2-F 4-F b.p. 110°/0.08 mbar 1.34 iPr 2-C1 3-C1 b.p. 160°/0.1 mbar 1.35 iPr 3-1 H 1.36 iPr 4-COOCH3 H b.p. 160°/0.08 mbar 1.37 Et 4-CH2-CH- (NHz)-P(O)- (OEt)2 H 1.38 Et 2-C1 4-F 1.39 Et 2-F 6-F b.p. 105°/0.1 mbar 1 . 40 Et 2-F H b.p. 95°/0.1 mbar 17- Table 2: Compounds of the formula Compound X Melting point (m.p.) °C [decomp .] 2.2 4-C1 H 280-282 2.3 3-C1 H 268-272 2.4 4-Br H 284-286 2.5 4-1 H 255-259 2.6 4-F H 266-270 2.7 . 3-F H 278-280 2.8 2-F H 275-276 2.9 2-C1 4-C1 279-280 2.10 3-C1 4-C1 274-278 2.11 4-Me H 276-279 2.12 3-Me H 270-273 2.13 2-Me H 244-245 2.14 H 3-CF3 258-262 2.15 4-t-butyl H 264-268 2.16 4-0Me H 2.17 2-OMe H 2.13 2-F 6-Cl 2.19 H 4-OCKFz 232-236 2.20 H 3-CCHFj 2.21 H 4-CF3 2.22 H 4-CHFz 2.23 H 4-OC2F5 2.24 H 4-OCF2-CF2Cl 2.25 2-Si(Me)3 H 2.26 3-Si(Me)3 H 2.27 4-Si(Me)3 H Table 2: (continuation) Compounds of the formula .?-Cr.(sdor Compound X Melting point (m.p.) °C [decomp .] 2.28 4-CN H 2.29 3-F 4-F 267-269 2.30 2-F 4-F 271-274 2.31 2-Cl 3-C1 2.32 3-1 H 10 2.33 4-CH2-CH(NH2)- P(O)(OH)z H 2.34 2-Cl 4-F 2.35 3-Me 4-C1 2.36 2-Me 4-F 15 2.37 2-F 6-F 258-261 Table 3 Compounds of the formula II KO NH, Compound R X Y m.p. °C 3.1 Me H H 261-262 3.2 Et 2-Me H 234-235 3.3 Et 3-Me H 229-232 3.4 Et 4-Me H 233-236 3.5 Me 4-F . H 254-257 3.6 Me 4-Br H 254-257 3.7 Me 4-C1 H 242-245 3.8 Me 3-Me H 260-262 3.9 Et H H 230-231 3.10 Me 3-C1 H 3.11 Me 3-F H 3.12 Me 2-F H 3.13 Et 2-F 6-C1 3.14 Me 2-C1 4-C1 3.15 Me 3-C1 4-C1 3.16 Et 2-C1 3-C1 3.17 Me H 3-CF3 3.13 Me H 4-OCHFz 3.19 Me 4-OC2H3 H 3.20 Me 4-t-butyl H 3.21 Me H 4-0C 2F5 3.22 Et 2-C1 4-F [decomp.] Table 5: O' !! Compounds of the formula .?_C H(SFo)Cr Compound Μ® X Y Physical data 5.1 Na+ H H m.p. >280° (decomp.) 5 5.2 1/2 Mg++ H H 5-3 1/3 Al+++ H H 5.4 1/2 Mn++ 4-F H 5.5 1/2 Ni++ 4-F H 5.6 1/3 Al+++ 4-F H 10 5.7 1/2 Zn++ 4-F H 5.8 1/4 Zr4+ 4-C1 H 5.9 1/2 Mn++ 4-C1 H 5.10 1/2 Co++ 4-C1 H 5.11 1/3 Al+++ 2-C1 4-F 15 5.12 1/2 Cu++ 2-C1 4-F 5.13 1/2 Cu++ 4-F ff m.p. >300° (decomp.) 5.14 1/3 Fe+++ 4-F H 5.15 1/2 Ca++ H 4-0CHF2 5.16 1/3 Al+++ H 4-OCHF2 20 5.17 1/2 Cu++ 4-CN H 5.13 1/3 Al + + + 2-C1 6-F 5.19 1/2 Mn++ 2-C1 6-F 5.20 1/2 Ca++ 2-Me 4-F 5.21 (MeN’H3) + 4-F H m.p. 27 5-285°(decomp.) 25 5.22 (IsoCjHyNHi) H CF 3 5.23 (CsHsNHj) 2-C1 4-F Formulation Examples for active ingredients of the formula I (X — percent by weight) Fl. Solutions a) b) c) d) active ingredient from the Tables 80 X 10 X 5 X 95 X ethylene glycol monomethyl ether 20 X - - - polyethylene glycol MW 400 - 70 X - - N-methyl-2-pyrrolidone - 20 X - - epoxidised coconut oil - - 1 X 5 X petroleum distillate (boiling range 160-190°C) - - 94 X - (MW — molecular weight) These solutions are suitable for application in the form of microdrops . F2. Granules a) b) active ingredient from the Tables 5 X 10 X kaolin 94 X - highly-disperse silicic acid 1 X - attapulgite - 90 X The active ingredient is dissolved in me thyli ene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. F3. Dusts a) b) active ingredient from the Tables 2 X 5 X highly-disperse silicic acid 1 X 5 X talcum 97 X - kaolin 90 X Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.
F4. Wettable powders active ingredient from the Tables Na lignosulfonate Na lauryl sulfate Na diisobutyInaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly-disperse silicic acid kaolin a) Z Z b) Z Z Z c) Z Z Z The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration and which are particularly suitable for seed dressing.
F5. Emulsifiable concentrate active ingredient from the Tables 10 Z octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 5 Z calcium dodecylbenzenesulfonate 3 Z castor oil polyglycol ether (35 moles of ethylene oxide) 4 Z cyclohexanone 30 Z xylene mixture 50 Z Emulsions of any required concentration can be prepared from this concentrate by dilution with water. These emulsions are particularly suitable for seed dressing.
Biological Examples: Example BI: Action against Botrytis cinerea on beans Residual protective action Bean plants about 10 cm in height are sprayed with a spray mixture (0.02 Z active substance) prepared from a wettable powder of the active ingredient. After 48 hours the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100 X relative humidity and 21 C and then an evaluation of the fungus attack is made. Botrytis attack is 100 X on untreated, infected bean plants. Attack is less than 20 X after treatment with one of the compounds of the formula I. No attack (0-5 X) is observed after treatment with e.g. compounds 1.5, 2.6, 2.11, 3.4, 2.15, 2.37, 5.13 and others .
Example B-2: Seed dressing against Fusarium nivale on rye Rye seeds of the Tetrahell variety which are naturally infected with Fusarium nivale are dressed on a mixer roll with the test fungicide at concentrations of 600 and 200 ppm of active substance (based on the weight of the seeds). The infected and treated rye is sown In October in the open with a seeder in plots 3 metres long and in 6 rows. Three replicates are carried out with each test product at its given concentration. Until evaluation of attack is made, the test plants are cultivated under normal field conditions, preferably In a region with unbroken snow cover during the winter months. To evaluate the phytotoxicity, an assessment is made of emergence in the autumn and of population density and tillering in the spring. To determine the activity of the active ingredients, the percentage of plants attacked by Fusarium is assessed in the spring directly after the snow has melted.
The tested substances of the formula I exhibit scarcely any or no phytotoxicity. Compounds 1.5, 1.8, 2.1, 2.2, 2.6, 2.8, 2.34 and others inhibit Fusarium attack completely at both active ingredient concentrations .
Example B-3; Seed dressing against Helminthosporium gramineum on barley Seeds of winter barley of the Cl variety which are naturally infected with Helminthosporium gramineum are dressed on a mixer roll with the test fungicide at concentrations of 600 and 200 ppm of active substance (based on the weight of the seeds). The infected and treated barley is sown in October in the open with a seeder in plots 2 metres long and in 3 rows. Three replicates are carried out with each test product at its given concentration. Until evaluation is made, the test plants are cultivated under normal field conditions. To evaluate the phytotoxicity, an assessment is made of emergence in the autumn and of population density and tillering in the spring. To determine the activity of the active ingredients, the percentage of stalks attacked by Helminthosporium is assessed at the time of ear emergence.
The tested substances of the formula I exhibit scarcely any or no phytotoxicity. At both concentrations, compounds 1.28, 2.2, 2.6, 2.9, 2.30, 3.5 and others reduce fungus attack to less than 20 X compared with untreated control plants.
Example B-4; Seed dressing against Ustllago nuda on barley Seeds of winter barley of the RMI variety which are naturally infected with Ustilago nuda are dressed on a mixer roll with the test fungicide at concentrations of 600 and 200 ppm of active substance (based on the weight of the seeds) . The infected and treated barley is sown in October in the open with a seeder in plots 2 metres long and in 3 rows. Three replicates are carried out with each test product at its given concentration. Until evaluation is made, the test plants are cultivated under normal field conditions. To determine the activity of the active ingredients, the percentage of ears attacked by Ustilago is assessed during flowering.
Compounds 2.6, 2.10, 2.15, 2.19, 5.21 and others reduce fungus attack at both concentrations to less than 20 X.
Example B-5: Seed dressing against Tilletia tritici on wheat Seeds of winter wheat of the Probus variety which are artificially infected with smut spores of Tilletia tritici (3 g of dry spore material per 1 kg of seeds) are dressed on a mixer roll with the test fungicide at concentrations of 600 and 200 ppm of active substance (based on the weight of the seeds). The infected and treated wheat is sown in October in the open with a seeder in plots 2 metres long and in 3 rows. Three replicates are carried out with each test product at its given concentration. Until ear ripening, the test plants are cultivated under normal field, conditions. To evaluate the phytotoxicity, an assessment is made of emergence in the autumn and of population density and tillering in the spring. To determine the activity of the active ingredients, the percentage of ears attacked by Tilletia is assessed at the time of ear ripening.
At both concentrations, compounds of the formula I, e.g. 1.5, 2.8, 1.28, exhibit a marked protective action against attack by Tilletia tritici, whereby emergence and growth of the wheat plants are favourably influenced.

Claims (21)

1. Patent claims
1. A microbicidal agent containing as at least one active ingredient a compound of the formula I in which R is Cj^-C^alkyl or OH, R 1 is OH, X is hydrogen, halogen, Cq-C^alkyl, Cj^-C^alkoxy, Si(CH 3 ) 3 , -CN, -COOCH 3 or -CHj.-CHCNHzi-PiOXRXRx), and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl, with the inclusion of the corresponding salts; together with a suitable carrier and/or wetting agent, a wetting agent always being present, if the active ingredient of the formula I simultaneously has the meanings R-R 1 -OH and X-Y-hydrogen.
2. An agent according to claim 1, containing a compound of the formula I in which R - Rj = OH, X is hydrogen, fluorine, chlorine or bromine, C 1 -C 4 alkyl, CH 3 O, Si(CH 3 ) 3 , -CN, -COOCHj or -CH 2 -CH(NH 2 )-P(O)(OH) 2 , and Y is fluorine, chlorine, bromine, halomethoxy or halomethyl.
3. An agent according to claim 2, containing a compound of the formula I in which at least one of the two substituents X and Y is halogen or contains halogen.
4. An agent according to claim 3, containing a compound of the formula I in which one of the two substituents X and Y is fluorine or contains fluorine .
5. An agent according to claim 1, containing l-amino-2-(4-tolyl)ethanephosphonic acid as active ingredient. 2Ί .
6. An agent according to ethanephosphonic acid as
7. An agent according to ethanephosphonic acid as claim 1, containing 1-amino-2-phenylactive ingredient. claim 1, containing 1-amino-2 -(4 - fluorophenyl) active ingredient.
8. A process for the preparation of a compound of the formula I n—CK 2~ -z (I) in which R is C 1 -C 4 alkyl or OH, R x is OH,
9. 10 X- is hydrogen, halogen, Cx-C^alkyl, Cq-Cqalkoxy, Si(CH 3 ) 3 , -CN, -COOCH 3 or -CH 2 -CH(NH 2 )-P(O)(R)(R 1 ) , and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl, at least one of the substituents X and Y having a meaning different from hydrogen, provided R and R x are simultaneously hydroxyl, which process 15 comprises activating the CH 2 group of a Schiff's base of the formula /' c=n-ch 2 -p-r then aralkylating the activated base with a suitably substituted benzyl halide of the formula Hal-CHz-20 and cleaving the resulting intermediate of the formula -CH 2 -CH-P(R)(Rx) i=C' hydrogenolytically in the presence of a catalyst, with further treatment with a mineral acid at elevated temperature, provided R and/or R t are alkoxy and are converted into a hydroxyl group, R, R 1( X and Y in the intermediates of the above formulae being as defined for formula I and it being possible for each of R and R x also to be C L -C 4 alkoxy, while T r is hydrogen or an aliphatic or aromatic radical and T 2 is an aliphatic or aromatic radical and Hal is a halogen atom. 5 9. A compound of the formula I as defined in claim 1 or a salt thereof, where at least one of the substituents X or Y has a meaning different from hydrogen, provided R and R! are simultaneously hydroxyl. 10. A compound of the formula I as defined in claim 2.
10. 11. A compound of the formula I as defined in claim 3.
11. 12. A compound of the formula I as defined in claim 4.
12. 13. 1-Amino-2-(4-tolyl)-ethanephosphonic acid.
13.
14. l-Amino-2-(4-fluorophenyl)-ethanephosphonic acid.
15. A method of controlling or preventing an attack by pathogenic microorganisms on cultivated plants, which comprises applying a compound of 15 the formula I according to claim 1 to the plant, to parts of plants or to the locus thereof.
16. A method according to claim 15, wherein the parts of plants to be treated are seeds.
17. A microbicidal agent according to claim 1, substantially as hereinbefore described with particular reference to the accompanying Formulation Examples.
18. A process according to claim 8 for the preparation 5 of a compound of the formula I given and defined therein, substantially as hereinbefore described and exemplified .
19. A compound of the formula I given and defined in claim 8, whenever prepared by a process claimed in 10 claim 8 or 18.
20. A compound according to claim 9, substantially as hereinbefore described and exemplified.
21. A method according to claim 15, substantially as hereinbefore described with particular reference to the 15 accompanying Biological Examples.
IE154486A 1985-06-11 1986-06-10 Microbicidal agents IE58475B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH246285 1985-06-11

Publications (2)

Publication Number Publication Date
IE861544L IE861544L (en) 1986-12-11
IE58475B1 true IE58475B1 (en) 1993-09-22

Family

ID=4234364

Family Applications (1)

Application Number Title Priority Date Filing Date
IE154486A IE58475B1 (en) 1985-06-11 1986-06-10 Microbicidal agents

Country Status (18)

Country Link
EP (1) EP0207890B1 (en)
JP (1) JPH0753743B2 (en)
KR (1) KR940005339B1 (en)
AT (1) ATE50999T1 (en)
AU (1) AU601153B2 (en)
BR (1) BR8602695A (en)
CA (1) CA1313190C (en)
DD (1) DD251913A5 (en)
DE (1) DE3669512D1 (en)
DK (1) DK272886A (en)
ES (1) ES8800954A1 (en)
GR (1) GR861496B (en)
IE (1) IE58475B1 (en)
IL (1) IL79086A0 (en)
NZ (1) NZ216484A (en)
PH (1) PH22874A (en)
PT (1) PT82737B (en)
ZA (1) ZA864321B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5321153A (en) * 1992-06-15 1994-06-14 Monsanto Company Process for making chiral alpha-amino phosphonates selected novel chiral alpha-amino phosphonates
CA2161114A1 (en) * 1993-04-23 1994-11-10 Andrew D. Napper Catalytic antibodies which hydrolyze primary amides and methods for eliciting such antibodies
ZA971253B (en) * 1996-02-16 1998-08-14 Basf Ag Substituted aromatic phosphonic acid derivatives

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL48835A (en) 1975-01-27 1979-05-31 Sparamedica Ag Amino acyl and peptidyl derivatives of phophonic acids, their preparation and pharmaceutical compositions containingthem
DE2966111D1 (en) 1978-10-05 1983-10-06 Ciba Geigy Ag Process for influencing plant growth
US4379146A (en) * 1981-02-17 1983-04-05 Merck & Co., Inc. Substituted phosphonamides as antihypertensives
EP0103867B1 (en) * 1982-09-17 1986-12-17 Kyowa Hakko Kogyo Co., Ltd. Phosphorus-containing peptide derivative
CA1258820A (en) * 1983-03-18 1989-08-29 Hiroshi Asano Electrolyzing dilute caustic soda solution with sequential polarity inversion
SE455259B (en) * 1984-01-30 1988-07-04 Kenogard Ab USE OF CERTAIN AMINOALKANPHOSPHONIC ACIDS FOR COMBATING Fungal DISEASES OF VEGETABLES

Also Published As

Publication number Publication date
PT82737A (en) 1986-07-01
JPS61286395A (en) 1986-12-16
DE3669512D1 (en) 1990-04-19
ES555882A0 (en) 1987-12-01
DK272886A (en) 1986-12-12
DK272886D0 (en) 1986-06-10
KR870000349A (en) 1987-02-18
NZ216484A (en) 1989-11-28
EP0207890A1 (en) 1987-01-07
BR8602695A (en) 1987-03-17
EP0207890B1 (en) 1990-03-14
KR940005339B1 (en) 1994-06-17
IE861544L (en) 1986-12-11
AU601153B2 (en) 1990-09-06
ATE50999T1 (en) 1990-03-15
PT82737B (en) 1988-12-15
IL79086A0 (en) 1986-09-30
JPH0753743B2 (en) 1995-06-07
DD251913A5 (en) 1987-12-02
PH22874A (en) 1989-01-19
CA1313190C (en) 1993-01-26
ZA864321B (en) 1987-02-25
AU5850986A (en) 1986-12-18
ES8800954A1 (en) 1987-12-01
GR861496B (en) 1986-10-10

Similar Documents

Publication Publication Date Title
US4309562A (en) Herbicidal compound, herbicidal composition containing the same, and method of use thereof
US4420436A (en) 2-Substituted 5-phenoxyphenylphosphonic acid derivatives
PL140539B1 (en) Plant growth controlling herbicide and method of obtaining novel derivatives of cyclohexanodionocarboxylic acid
JPH0420912B2 (en)
IL97910A (en) Nematocidal compositions containing benzisothiazoles, certain such novel compounds and their preparation
AU592555B2 (en) 2,2-Difluro 1,3 benzodioxole derivatives
KR920005825B1 (en) Process for preparing 1-aryl-2-fluoro-2-azolyl alkanones and alkanols
US4940799A (en) Preparation of the diastereomeric mixture 2R,4S-1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole
US4001325A (en) α-Chloroacetanilide selective herbicides
IE58475B1 (en) Microbicidal agents
US3238222A (en) (n-3, 4-disubstituted phenyl-3 and/or omega methyl-2-pyrrolidinones and piperidones)
US4776875A (en) Functional acetic acid derivatives containing phosphorus and herbicidal, growth-regulating agents containing them
CA1144167A (en) Substituted naphthyloxy- and naphthylthio-alkylammonium salts, the manufacture thereof, the use thereof for regulating plant growth
US5189030A (en) 1-amino-2-phenylethanephosphonic acids as microbiocides
US5536720A (en) Pesticidal oxadiazines
AU616176B2 (en) Substituted isonicotinoylpyridinylhydrazine derivatives, the preparation thereof, compositions containing them and their use in the protection of plants against attack by harmful microorganisms
NO871536L (en) Microbicides.
KR930011780B1 (en) Process for preparing diphenyl ether derivatives
GB2214184A (en) Amino-oxyalkyl compounds and intermediates therefor
EP0002842A1 (en) Propanthioic acid derivatives, herbicidal and/or plant growth regulating compositions comprising these derivatives and method of destroying or preventing undesirable plant growth
CA1272724A (en) Phytopathogenic microbiocides
JPS60163891A (en) Phenoxypropionyloxyalkane phosphonate
US5677301A (en) Pesticidal oxadiazines
US4564386A (en) Trifluoromethanesulfonanilides, and their production and use
US3714247A (en) Imidoylbenzenesulfonamides

Legal Events

Date Code Title Description
MM4A Patent lapsed