DD251913A5 - MICROBICIDE MEDIUM - Google Patents

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

Field of application of the invention

The present invention relates to microbicidal compositions containing as at least one active ingredient, a 1-amino-2-arylethanphosphonsäure-, -ethanphosphinsäure- and ethanphosphinoxid derivative of the formula I or a salt thereof, and the use of these agents for controlling harmful microorganisms.

Characteristic of the known technical solutions

In US Patent 4,016,148 Peptidylamino-methanephosphonic acid derivatives and -ethanphosphonsäure derivatives are suggested as potentiators for antibiotics. Advice on pest control is not listed or suggested in any way.

In US Patent 4,431,438 Peptidylamino-alkanephosphonic derivatives are proposed as herbicides and retarders in plant growth and casserole. Information on the protection of plants against microbial attack will not be given. Furthermore, it should be noted that preparations with general herbicidal or growth-inhibiting properties are necessarily very poorly suited for the protection of crops.

Object of the invention

The aim of the invention is the provision of new compounds with strong microbicidal activity, which protect plants against fungal and bacterial infestation permanently and promote their development.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties that are suitable as active ingredient in microbicidal agents.

According to the invention as active ingredient in the new microbicidal agents compounds of the formula

0X

R - P - CH - CH₉ -// K (D

^{1 N}

applied,

wherein R and R _{1 are} independently C ₁ -C ₄ AlkYl, C ₁ -C ₄ AIkOXy or hydroxy, X is hydrogen, halogen, C ₁ -H ₄ AIkYl, C ₁ -C ₄ alkoxy, trimethylsily, cyano, methoxycarbonyl or den ReSt-CH _{2 is} -CH (NH ₂ JP (O) (R) (R ₁ ), and Y is hydrogen, halogen, C ₁ -C ₂ haloalkoxy or Ci-C ₂ haloalkyl, and include corresponding salts, if R and / or R _{1 are} hydroxy.

In Formula I, ethane phosphonic acid derivatives are present when R and R i are hydroxy or alkoxy. Ethanphosphinic acid derivatives are present when one of the two substituents is alkyl, whereas ethane phosphine oxide derivatives are when both substituents R and R _{1 are} alkyl.

C ₁ -C ₄ alkyl alone or as part of an alkoxy group means methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert.

Butyl.

By halogen is meant fluorine, chlorine, bromine or iodine. C! -C ₂ haloalkyl alone or as part of a haloalkoxy group means a methyl or ethyl group which is monohalogenated or is polyhalogenated or perhalogenated by a given halogen atom or by different halogen atoms. Examples are CHCl ₂ , CHF ₂ , CH ₂ Cl, CCI ₃ , CH ₂ F, CHBr ₂ , CH ₂ CH ₂ Cl, CHCl-CHCl, CF ₃ , C ₂ F ₅ , CF ₂ Cl, CF ₂ -CF ₂ Called CI.

Suitable salts of a free HO group are optionally substituted ammonium or hydrazinium salts or metal cations.

As metal ions come ζ. As the cations of the following elements in question: alkali metals such as lithium, sodium or potassium; Alkaline earth metals such as magnesium, calcium, strontium or barium; Elements of the first to eighth subgroups _t such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, in particular iron, manganese, copper and zinc; Elements of the third and fourth main groups such as aluminum, silicon, tin, lead, zirconium, titanium, in particular aluminum, wherein the metal ions are present in the salts or complexes of the formula I in their valences.

Phosphonic acid derivatives of the formula I can be obtained in principle by reaction of an optionally substituted 2-phenylacetaldehyde with ammonia and dialkyl phosphite, optionally followed by hydrolysis with mineral acid:

x \ o

^ -CH-CHO + NH ₃ + HP (Oalkyl)>

film Υ / 0 NH "

" ¹ ^ ί% / H Η0-Ρ-ΓΗ -.

3Ik ₇ IO-P-CH-CH ₂ - '< *. (-> ^H0 j ^CH 2 \

0-alkyl '"· \ V ^0H

(Chalmers and Kosolapoff, J. Am. Chem. Soc. 75, 5278 [1953]).

Among mineral acids are primarily hydrogen halides such as hydrochloric or hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, toluene sulfonic acid and the like. to understand.

A somewhat more general method is that of Berlin et al. (J. Org. Chem. 33, 3090 [1968]), in which a substituted phenylacetyl halide mti optionally a) 0,0,0-Trialkylphosphit, b) 0,0-Trialkylphosphonit or c) 0-Trialkylphosphinit reacted and in The presence of hydroxylamine is converted to the phosphonyl, phosphinyl or oxophosphino-oxime, which can be obtained by hydrogenation of the amine:

Vs " _m ,. γ :. , ν-

> -CH ₉ -COHal + PR τ> \] > -CH ₀ -CO-PR *

\ - U *. ^H 2

/ * - ^CH 2 ~ ^c PR

/ 2

N-OH R ₁ . ^[Ra " ^Ni]

In the aforementioned shape diagrams, X and Y have the meaning given for formula I; furthermore

X '= H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, Si (CH ₃ ) ₃ , -CN, -COOCH ₃ or -CHr-CHO,

alkyl = C, -C ₄ alkyl,

X * = H, halogen, C ₁ -C ₄ AlKyl, C ₁ -C ₄ alkoxy, Si (CH ₃ J ₃ , -CN, -COOCHa or -CH 2 COHal,

X ** = H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, Si (CH ₃ ) ₃ , -CN, -COOCH ₃ or -CH 2 -C (O) -P (O) R * ( Ri), Hal = halogen, preferably Cl or Br,

R '= C 1 -C ₄ -alkyl,

R * = dC ₄ alkyl or C ₁ -C ₄ alkoxy,

Rf = Ci-C ₄ AIkYlOdBrCi-C ₄ AIkOXy.

The formula I * includes only those compounds of formula I wherein R and Ri have the meaning of R * and R *. If R * and / or R * C 1 -C ₄ -alkoxy, they can be prepared from these by hydrolysis with preferably mineral acids, the free hydroxyl groups. Free OH groups can, if desired, be converted into salts with bases, eg. In metal salts, ammonium salts, alkylammonium salts, dialkylammonium salts or the like.

Compounds of the formula I can be prepared by a further method simply and in high yield by reacting the activated Schiff base obtained from a) optionally aminomethyl phosphate, phosphinate or phosphine oxide and b) an aldehyde such as benzaldehyde or ketone such as phenylacetone or benzophenone aralkylated with an appropriately substituted benzyl halide (RW Ratcliffe and BG Christensen, Tetrahedron Letters, 4645 [1973]):

1\

Ί • 2

P = N-CH-P-R + Hal-CH - (

Il = N-CH-P (R) (R _n

Li

LiN (LSOC ₃ H ₇ ) ₂

ν-

N = C

.Λ V

Hal = halogen, preferably Br or Cl

The activation of the P atom adjacent to the adjacent CH ₂ group in the starting material can also by other reagents such as butyl lithium or Na hydride in z. B. tetrahydrofuran carried out. R, Ri, X and Y have the meaning given for formula I, while T _{1 is} H or an aliphatic or aromatic radical and T _{2 is} an aliphatic or aromatic radical. The final stage of the hydrogenolytic cleavage of the Schiff base to obtain the desired end product of formula I is carried out by catalytic cleavage with z. B. H ₂ / Pd / C, but can also be achieved by hydrogen in the presence of other catalysts (such as platinum or Pt / C). In the presence of mineral acids such as hydrochloric acid or hydrobromic acid, the cleavage of the Schiff base and the hydrolysis of an alkoxy group to the HO group, if at least one of the substituents R and / or R, alkoxy, at elevated temperature (40 ⁰ C-150 The use of reaction-inert solvents or diluents is advantageous in all of the preceding processes. Typical solvents and diluents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ethers, halogenated hydrocarbons, such as chlorobenzenes, methylene chloride, Ethylene chloride, chloroform, tetrachlorethylene; ethers and ethereal compounds such as diaryl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether etc.), anisole, dioxane, tetrahydrofuran, nitriles such as acetonitrile, propionitrile and mixtures of such solvents with one another.

The reaction temperatures in the aralkylation (benzylation) are generally between -100 ⁰ C and + 10 ⁰ C, preferably at -8O ⁰ C to -20 ° C. The hydrogenolytic cleavage is advantageously carried out in the temperature range from -20 ⁰ C to + 8O ⁰ C.

The stated starting compounds are known or are prepared by methods known per se. For the production of Schiff's bases, it is expedient to work under protective gas such as nitrogen or argon. Substituted benzyl bromides can easily be obtained from appropriately substituted toluenes by bromination with N-bromosuccinimide in CCI ₄ in the presence of azoisobutyronitrile (catalyst). '

As such, they also have an asymmetric carbon atom adjacent to the P atom, with the structures corresponding to the natural La amino acids having the configuration the structures corresponding to Da amino acids have the formula I (S) configuration. The respective ® or (S) -configurations of a diastereomeric (R, S) compound can be obtained purely from this by fractional crystallisation or chromatography (HPLC). The ® diastereomers and (S) -diastereomers show different microbicidal activity.

The present invention also relates to the said production processes, insofar as they lead to new compounds. Likewise, the invention also relates to the novel compounds of the formula I in which at least one of the substituents X or

Y has a meaning other than hydrogen, provided that R and R _{1 are} simultaneously hydroxy or ethoxy. Compounds of the formula I in which R and R _{1 are} C ₁ -C ₄ -alkoxy represent valuable acaricides (especially against Tetranychus and Amblyomma species) and also insecticides which are active against sucking insects in particular (aphicides).

Preferred microbicides are those compounds of the formula I and their salts in which R is C, -C ₄ alkyl or hydroxyl,

X is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, Si (CH ₃ ) ₃ , -CN, -COOCHa or -CH 1 CHfNHjJ-PFOXRXR,), and

Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl.

Among these, preferred are those in which

R = R ₁ = OH,

X is hydrogen, fluorine, chlorine or bromine, C ₁ -C ₄ AlKyl, CH ₃ O, Si (CH ₃ J ₃ , -CN, -COOCH ₃ or -CH ₂ -CH (NH ₂ ) -P (O) (OH ₂ and

Y is fluorine, chlorine, bromine, halomethoxy or halomethyl.

Particularly preferred among the latter are those compounds in which at least one of the two substituents X and Y is halogen or halogen, and among them those in which one of the two substituents X and Y is fluorine or fluorine.

Another microbicidally important subgroup are compounds of the formula I and their salts, in which R and R ₁ independently of one another are C ₁ -C ₄ AlK ¹ / !, C ₁ -C ₄ alkoxy or hydroxy, X is halogen, d -QAlkyl, C ₁ - C _{4 is} alkoxy, Si {CH ₃ ) ₃ , cyano is OdBr-CH ₂ -CH (NH ₂ JP (O) (R) (R ₁ ), and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl.

Of the latter compounds, those are particularly important in which R, Ri and Y have the meaning mentioned and X is fluorine, chlorine, methyl, ethyl, isopropyl, tert. Butyl, methoxy, ethoxy, isopropoxy or cyano means. Also important are microbicidal agents and their salts in which R and Rj have the meaning given for formula I, while the substituents X are halogen, methyl, methoxy or cyano and Y is hydrogen, halogen, OCHF ₂ or CF ₃ . Another important group are compounds of formula I, wherein R and R _{1 have} the meaning given, while X is hydrogen and Y is difluoromethoxy or trifluoromethyl.

It has now surprisingly been found that the amino-ethanephosphonic acid derivatives of the formula I mentioned herein and their salts not only have no herbicidal properties, but unexpectedly strong microbicidal activity, which is particularly suitable for permanently protecting plants from fungal and bacterial infestation and to promote their development. If at least one of the substituents R and Ri is an OH group, the preferred compounds include the salts of the formula I. Particularly preferred because of their fungicidal action are the metal salts, in particular the aluminum, nickel, manganese and copper salts and the N iederalky! ammonium salts of the formula I, which are particularly suitable for soil application and as a mordant.

The main application of compounds of formula I is in the control of harmful phytopathogenic fungi. Thus, the compounds of formula I have a very favorable for practical needs curative, preventive and systemic action to protect crops without affecting them by unwanted side effects. In the context of the present invention, crop plants are, for example, cereals (wheat, barley, rye, oats, rice); Beets (sugar and fodder beets); Pome, stone and berry fruits (apples, pears, plums, peaches, almonds, cherries, peanuts, cranberries and blackberries); Pulses (beans, lentils, peas, soya, oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts), cucurbits (squash, cucumbers, melons), fibrous plants (cotton, flax, hemp, jute) Citrus fruits (oranges, lemons, grapefruits, mandarins), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers) or vegetable oils Corn, tobacco, nuts, coffee, sugar cane, tea, vines, hops, Bananas, avocados and natural rubber plants as well as ornamental plants.

With the active compounds of the formula I, the occurring microorganisms can be contained or destroyed on plants or on parts of plants (fruits, flowers, foliage, stems, tubers, roots), whereby later growing plant parts are spared from such microorganisms. The active substances are effective, in particular, against the phytopathogenic fungi belonging to the following classes: Ascomycetes (such as Helminthosporium and Fusarium species), Basidiomycetes (such as Tilletia and Ustilago). The compounds of formula I can therefore be used especially as seed for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against occurring in the soil phytopathogenic fungi.

The invention thus further relates to the use of the compounds of the formula I for combating phytopathogenic microorganisms or for the preventive prevention of infestation.

Active ingredients of the formula I are usually used in the form of compositions and can be added to the surface or plant to be treated simultaneously or successively with further active ingredients. These further active ingredients may be fertilizers, trace element mediators or other preparations which influence plant growth. However, they may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with optionally further customary in formulation technology excipients, surfactants or other application-promoting additives.

Suitable carriers and additives may be solid or liquid and correspond to the substances useful in formulation technology, such as. As natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The compounds of formula I are used in unmodified form or preferably together with the usual in formulation technology aids and are therefore z. As to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in z. B. polymeric substances processed in a known manner. The application methods are chosen in the same way as the type of means according to the desired goals and the given conditions. In the agricultural sector are low application rates generally at 50g to 5kg of active ingredient (aa) per ha; preferably 10Og to 2kg AS / ha, especially at 10Og to 600g AS / ha.

Suitable solvents may be: aromatic hydrocarbons, preferably fractions C ₈ to C ₁₂ , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl 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 ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

Particularly advantageous, likungsf ordering additives that can lead to ei η er strong reduction in the application rate, are also natural (animal or vegetable) or synthetic phospholipids from the series of cephalins and lecithins such. B. Phosphatiäylethanolamin, phosphatidylserine, phosphatidylglycerol or lysolecithin.

Depending on the nature of the active compound 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. Surfactants are also surfactant mixtures.

The surfactants commonly used in the formulation technique include i.a. in the following publications: Mc Cutcheon's Detergents and Emulsifiers Annual, BC Publishing Corp., Ringwood New Jersey, 1981;

Helmut Stäche "Tenside Paperback" Carl Hanser-Verlag Munich / Vienna 1981. M. and J. Ash. "Encyclopedia of Surfactants", Vol. Ill., Chemical Publishing Co., New York, 1980-1981.

The agrochemical preparations generally contain from 0.1 to 99%, in particular from 0.1 to 95% of the active ingredient of the formula from 1.99.9 to 1%, in particular from 99.8 to 5%, of a solid or liquid additive and from 0 to 25% , in particular 0.1 to 25% of a

Surfactant. ·

While merchandise is more likely to be concentrated, the end user typically uses diluted funds.

embodiment

The invention is explained in more detail below with reference to some examples.

Preparation Examples

H -1. Preparation of 0,0-diisopropyl-1-amino-2- (4-fluorophenyl) -ethylphosphonate of the formula

ff ^ 2 / - _N

isoC ₃ H ₇ 0-P-CH-CH ₂ - ^^ - F [comp. No. 1.8] OC ₃ H iso

a) Preparation of the Intermediate 0.0-Diisopropyl-1-N-benzylideneamino-2- (4-fluorophenyl) ethylphosphonate

To a solution of 113.4 g (0.8 mol) of diisopropylamine in 750 ml of tetrahydrofuran (THF) are added with stirring and cooling 500 ml of n-butyl lithium. The mixture is cooled to -75 ° C. Over the course of 1 h, a solution of 226.6 g (0.8 mol) of 0.0-diisopropylbenzylideneamino-methane phosphonate in 600 ml of THF is added dropwise. After stirring for 1 h, a solution of 151.2 g (0.8 mol) of 4-fluorobenzyl bromide in 150 ml of THF is added dropwise and stirred for a further hour. After standing overnight at room temperature, the solvent is removed and the residue dissolved in 1 liter of dichloromethane. The solution is washed three times with 200 ml of water and dried over Na ₂ SO ₄ . After evaporation of the solvent, 286.3 g (91.4% of theory) of the intermediate product are obtained, which after molecular distillation gives 261.2 g (83.4% of theory) of pure product; Boiling point 160 ° C / 0.1mbar.

b) Preparation of the final product

To a solution of 19,6g (0.05 Mo!) Of Figure 1 intermediate a) obtained in 200 ml of isopropanol, 2 g Pd / C (5%. Pd) was added and the mixture stirred at room temperature (20-25 ⁰ C) hydrogenated. After 62% of hydrogen has been taken up, a further ₂ g of Pd / C are added and, after 90% H ₂ uptake, another ₂ g of Pd / C are added. After a total of 19 hours, the H ₂ intake is completed. The reaction mixture is filtered and the filtrate is concentrated on a rotary evaporator. The remaining residue of about 15 g is distilled on a bulb tube. This gives 12.6 g (= 83.1% of theory) of pure end product as a colorless oil; Bp 170 ° C / 0.08mbar. H-2. Preparation of 1-amino-2- (4-fluorophenyl) ethane-phosphonic acid [Comp. No. 2.6] A mixture of 227.5 g (0.75 mol) of 0,0-diisopropyl-1-amino-2- (4-fluorophenyl) ethyl phosphonate and 750 ml of 20% strength. Hydrochloric acid is refluxed with stirring for 5 hours and filtered for a further 10 hours at room temperature, and the residue is filtered with 250 ml of water and 500 ml of water and washed with 250 ml of water and 500 ml of methanol. 103.3 g of the title compound are obtained. The filtrate is concentrated and the residue is recrystallized from methanol / propylene oxide, resulting in a further 43.3 g of end product, together 146.6 g (= 89.2% of theory), mp 266-270 ⁰ C (dec.). H-third Preparation of the optical isomers of 1-amino-2- (4-fluorophenyl) ethane phosphonic acid A 'Preparation of the dibenzoyl tartrate of 0,0-diethyl-1-amino-2- (4-fluorophenyl) ethyl phosphonate

(EtO) _n P-CH-CH ₀ -> F + (CH _c C00CH-C00H) "> salt

2L \ / 0 3i

a) 47.04 g of dibenzoyltartaric acid (L) are added at room temperature to a solution of 68.82 g (0.125 mol) of 0,0-diethyl-1-amino-2- (4-fluorophenyl) -ethylphosphonate in 750 ml of methanol and 750 ml of ethanol. (-) xH ₂ O. After stirring for 2 h, the resulting thick white suspension is filtered off and the residue is dried. After twice Urnkristallisation from ethanol to obtain 31.5 g (= 39.8% of theory) "salt I", mp. 179 ° C (dec.), [A] § ° = -66.4 ° ± 0, 5 ° (c = 2.077% in methanol).

b) The remaining filtrates are evaporated together, stirred with 200 ml of 1 N NaOH, saturated with sodium chloride and extracted three times with 400 ml of CH ₂ Cl ₂ . The organic phase is dried over Na ₂ SO ₄ and evaporated. The resulting brown oil (37.5 g) is dissolved in 400 ml of methanol and 400 ml of ethanol and treated with 25.6 g of dibenzoyltartaric acid (D) (+) xH ₂ O. After stirring for 2 hours, 63 g of salt are filtered off, which is recrystallized from 1 200 ml of methanol: 7.2 g of impure "salt II." The filtrate is concentrated and the residue is recrystallized from 500 ml of ethanol to give 17 g of pure "salt II". , [α] § ° = + 67.3 ° ± 0.5 ° (c = 1.998% in methanol).

a) Recovery of the (+) O-diethyl-1-amino-2- (4-fluorophenyl) ethylphosphonate 25.34 g of salt I are stirred for 2 hours at room temperature with 100 ml of 1N NaOH to release it from the tartrate. The solution which has become clear is saturated with sodium chloride, combined with 200 ml of CH ₂ Cl ₂ and filtered as a suspension in vacuo. The residue is washed twice with 200 ml of CH ₂ Cl ₂ . The organic phase of the combined filtrates is separated, dried with NaSO ₄ , filtered and evaporated: 9.1 g (82.7% of theory) of the desired final product as a pale yellow oil, [±] l ° = + 10.6 ° ± 0.4 ° (c = 2.5% in methanol);

¹ H-NMR in CDCl ₃ : 1.3 (NH ₂ , CH ₃ ) (t, 8H); 2.3-3.5 (PCH-CH ₂ ) (m, 3H); 4.17 (OCH ₂ ) (qu, 4H); 7.i (m) (4H, phenyl).

b) Recovery of (+) 1-amino-2- (4-fluorophenyl) -ethanephosphonic acid

5.51 g (0.02 mol) of (+) obtained under a) phosphonate are in 40ml 20% pure. Hydrochloric acid for 4 hrs. To reflux. The solution is then evaporated and the residue is recrystallized from methanol / propylene oxide. This gives 3.7 g (= 84.5% of theory) of the desired end product, mp 259-263 ° C (dec.); [a] o ° = + 37.5 ° ± 0.4 ° (c = 2.636 in 1 N NaOH). ¹ H-NMR in D ₂ 0 / Na0D: 2.3 to 3.1 (PCH-CH ₂₎ (m, 3H); 4.65 (OH, NH ₂ ) (S); 6,6-7,1 (phenyl, 4H) (m)

C.

a) The extraction of (-) 0,0-diethyl-1-amino-2- (4-fluorophenyl) ethyl phosphonate is carried out analogously to the method Ba) from the "salt II" with 1 N NaOH solution:

Yield 95.9% of theory. Pale yellow oil [α] ο ° = -10.3 "± 0.5 ° (c = 2.036% in methanol).

b) The recovery of {-) 1-amino-2- (4-fluorophenyl) -ethanphosphonsäure is carried out analogously to the method

Bb) by hydrolysis of the (-) phosphonate described above in 20%. Hydrochloric acid. Yield 77.6% of

Theory.

Mp. 261-263 ⁰ C (Zers.);

[a] h ° = -36.9 ° ± 0.5 ° (c = 2.081% in 1N NaOH).

¹ H-NMR in D ₂ O / NaOD: 2.5-3.4 (PCH-CH ₂ ) (m, 3H);

4.85 (OH, NH ₂ ) (S); 6.8-7.4 (phenyl, 4H) (m).

In this way, or in the manner of one of the methods given above, it is also possible to prepare the compounds of the formula I listed below which, unless specifically mentioned, are obtained as diastereomer mixtures.

The ¹ H NMR-WeHe were with a Varian EM-360 spectrometer at 6OmHz in CDCI ₃ with (CH ₃ ) ₄ Si as reference substance

determined.

The ³¹ P NMR values were determined using a Bruker WP80 spectrometer at 32.28 MHz at 85%. H ₃ PO ₄ (external) as reference substance

added.

It means:

Me = methyl Et = ethyl iPr = isopropyl temperatures are given in degrees centigrade.

Table 1:

II compounds of the formula (R ¹ O) P-CH (NH) -CH-

Verb. R ' X No. 1.1 et H 1.2 iPRs H 1.3 et 4-CI 1.4 et 3-CI 1.5 et 4-Br 1.6 et 4-J 1.7 et 4-F 1.8 iPr 4-F 1.9 iPr 3-F 1.10 iPr 2-F 1.11 et 2-CI 1.12 et 3-CI 1.13 et 4-Me 1.14 et 3-Me 1.15 et 2-Me 1.16 et 3-CF ₃ 1.17 iPr 4-t-butyl 1.18 et 4-MeO 1.19 et 2-MeO 1.20 et 2-F 1.21 et H 1.22 et H. 1.23 iPr H 1.24 iPr H 1.25 iPRs H

Physical. constant

H Bp 170 ° C / 0,6mbar H ¹ H: 1.3 (NH ₂ ), 2.5-3.5 (PCH- 7.3 (arom-H) H n ° ° 1.5140 H ¹ H: 1.3; 2.4-3.5; 7.2 H Sdp.125 ° C / 0,05bmar H ¹ H: 1.3; 2.3-3.4; 7,767 H Bp 150-160 ° C / 0.08 mbar H Bp 170 ° C / 0.08mbar H Bp 150 ° C / 0.05 mbar H Bp 150 ° C / 0.08 mbar 4-Cl Mp 59-62 ⁰ C 4-CI ng ⁰ 1,5272 H ¹ H: 1.4; 2.5-3.5; 7.15; 2.32 (X = CH ₃ ) - ³¹ P: 28.09 H ng ⁰ 1.5060 H ¹ H: 1.33; 2.5-3.5; 7.2; 2.33 (X = CH ₃ ) - ³¹ P: 28.19 H ng ⁰ 1.4659 H Bp 140 "C / 0.01 mbar H Bp 165 ° C / 0.2 mbar H Bp 125 ° C / 0.1 mbar 6-Cl 4-OCHF ₂ 3-OCHF ₂ 4-OCHF ₂ 4-CF ₃ 4 CHF ₂

Table 1: Continuation)

the formula O X Y Physical. constant links R ' Il (R 'O) P _O-CH (HH ₀₎ -CH Verb. X 4-OC ₂ F ₅ No. et 4-OCF ₂ -CF ₂ Cl 1.26 Et. H . H 'Bp. 110 ° C / 0.1 mbar 1.27 et H H Bp 150 ° C / 0.12 mbar 1.28 et 2-Si (Me) ₃ H Bp 120 ° C / 0.1 mbar 1.29 et 3-Si (Me) ₃ H ¹ H: 1.35; 2.6-3.5; 7.4-7.6 1.30 iPr 4-Si (Me) ₃ . 4-F Bp 115 ° C / 0.1 mbar 1.31 et 4-CN 4-F Bp 110 ° C / 0.08 mbar 1:32 et 3-F 3-CI Boiling point 160 ° C / 0.1 mbar 1:33 iPr 2-F H 1:34 iPr 2-CI H Bp 160 ^o C / 0.08 mbar 1:35 iPr 3-J H 1:36 et 4-COOCH ₃ 4-F 1:37 et 4-CH ₂ -CH (NH ₂ ) -P (O) (OEt) ₂ 6-F Bp 105 ° C / 0.1 mbar 1:38 et 2-CI. H Boiling point 95 ° C / 0.1 mbar 1:39 et 2-F 1:40 2-F Table 2:

Compounds of the formula (HO) ₂ P-CH (NH) CH- '

Verb no.

Melting point (mp.) "C [Ze rs.]

2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 2.20 2.21 2.22 2.23 2.24 2.25 2.26 2.27 2.28 2.29 2.30

4-CI

3-CI

4-Br '

4-J

4-F

3-F

2-F

2-CI

3-CI

4-Me

3-Me

2-Me

4-t-butyl

4-0 Me

2-OMe

2-F

2-Si (Me) ₃

3-Si (Me) ₃

4-Si (Me) ₃

4-CN

3-F

2-F

4-OCHF ₂

3-OCHF ₂

4 CHF ₂

4-OC ₂ F ₅

4-OCF ₂ -CF ₂ Cl

278-282 280-282 268-272 284-286 255-259 266-270 278-280 275-276 279-280 274-278 276-279 270-273 244-245 258-262 264-268

232-236

267-269 271-274

Table 2: Continuation

Compounds of the formula (HO) P-CH (NH) CH - · ^/

Verb. X No. 2.31 2-CI 2:32 3-J 2:33 4-CH ₂ -CH (NH ₂ ) -P (O) (OH) ₂ 2:34 2-CI 2:35 3-Me 2:36 2-Me 2:37 2-F Table 3:

Melting point (mp.) ° C [decomp.]

3-CI

4-F

4-CI

4-F

6-F

258-261

Il / y

Compounds of the formula R-P-CH-CH - ·

Il ² \

HO NH

Verb. R No. 3.1 me 3.2 et 3.3 et 3.4 et 3.5 me 3-6 me 3.7 me 3.8 me 3.9 et 3.10 me 3.11 me 3.12 me 3.13 et 3.14 me 3.15 me 3.16 et 3.17 me 3.18 me 3.19 me 3.20 me 3.21 me 3.22 et Table 4:

Mp. ° C [dec.]

2-Me

3-Me

4-Me

4-F

4-Br

4-CI

3-Me

3-CI

3-F

2-F

2-F

2-CI

3-CI

2-CI

4-OC ₂ H ₅

4-t-butyl

2-CI

3-CF ₃

4-OCHF ₂

4-OC ₂ F ₅

261-262 234-235 229-232 233-236 254-257 254-257 242-245 260-262 230-231

Compounds of the formula (CH) P-CH-CH

NH "

verb

 No.

Physical. constant

4-F 4-CI 2-CI

H H H 4-CI

Bp 160-170 ° C / 0.05 mbar

Table 4: Continuation

Verb. X No. 4.5 2-CI 4.6 H 4-7 H 4.8 4-t-butyl 4.9 4-CN 4.10 4-Si (Me) ₃ 4.11 4-0 ME 4.12 4-0 M E 4.13 H 4.14 2-Me 4.15 2-Me 4.16 3-Me ' 4.17 3-Me 4.18 4-Me 4.19 H 4.20 2-F 4.21 3-F Table 5:

Physical. Constant) ⁰ C [dec.]

4-F

4-OCHF ₂

3-CF ₃

2-CI

3-OCHF ₂

4-CI

2-CI

H.

4-OC ₂ F ₅

6-Cl

Bp 160 ° C / 0.05mbar

Bp 160 ° C / 0.07mbar bp 150-55 ° C / 0.1mbar

Compounds of the formula

often

verb

 No.

Physical constant

5.10

5.11

5.12

5.13

5.14

5.15

5.16

5.17

5.18

5.19

5.20

5.21

6.22

5.23

Na ⁺

VaMg ⁺ +

VsAI ⁺⁺⁺

V2Mn ⁺⁺

V2Ni ⁺⁺

V ₂ Zn ⁺

V2Mn ⁺⁺

V ₂ Co ⁺⁺

VaAI ⁺⁺⁺

V2Cu ⁺⁺

V2Cu ⁺⁺

VsFe ⁺⁺⁺

V ₂ Ca ⁺⁺

VsAI ⁺⁺⁺

V2CU ⁺⁺

V ₃ AI ⁺⁺⁺

V2Mn ⁺⁺

V ₂ Ca ⁺⁺

(MeNH ₃ I ⁺

(ISoC ₃ H ₇ NH ₃ )

(C ₆ H ₅ NH ₃ ) +

4-F

4-F

4-F

4-F

4-CI '

4-CI

4-CI

2-CI

2-CI

4-F

4-F

4-CN

2-CI

2-CI

2-Me

4-F

2-CI

4-OCHF ₂ 4-OCHF ₂

Mp.> 28O ⁰ C (Zers.)

Mp.> 300 ⁰ C (dec.)

Mp. 275-285 ⁰ C (Zers .;

Formuiierungsbeispieie for agents of the formula I.

(% = Weight percent)

F I. Solutions a) b) c) d)

Active ingredient from the tables 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20% - - -

Polyethylene glycolMG400 - 70% - -

N-methyl-2-pyrrolidone - 20% - -

Epoxidized coconut oil - - 1% 5%

Gasoline (boiling limit 160-190 ⁰ C) - - 94% -

(MW = molecular weight)

The solutions are suitable for use in the form of very small drops.

F 2. Granules a) b)

Active substance from the tables 5% 10%

Kaolin - 94% -

Highly disperse silica 1% -

Attapulgite - 90%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

F3. Dusts a) b)

Active ingredient from tables 2% 5%

Highly disperse silica 1% 5%

Talc. 97% -

Kaolin - 90%

Intimately mixing the excipients with the active ingredient gives ready-to-use dusts.

F4. wettable powder • a) b) c) Active ingredient from the tables 25% 50% 75 ° / Na Ligninsulfoant 5% 5% - Na lauryl sulfate 3% , - 5 ° / i Na Diisobutylnaphthalinsulfonat - 6% 10 ° / < octylphenol polyethylene glycol ether - 2% - (7-8 moles of ethylene oxide) Highly dispersed silicic acid 5% 10% 10 ° / ί kaolin 62% 27%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration and which are particularly suitable for seed dressing.

F5. Emulsion concentrate

Active substance from the tables 10%

Octylphenol polyethylene glycol ether 5%

(4-5 mol of ethylene oxide)

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether 4%

(35 moles of ethylene oxide)

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water, which are suitable for pickling seeds.

Biological examples:

Example B-1: Action against Botrytis cinerea on beans Residual protective effect

Approximately 10 cm high bean plants are sprayed with a spraying powder prepared from the active ingredient (0.02% 'active substance). After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After incubation of the infected plants for 3 days at 95-100% relative humidity and 21 ⁰ C, the assessment of fungal infestation takes place. The Botrytis infestation of untreated but infected bean plants is 100%. The infestation after treatment with one of the compounds of formula I is <20%; in case of treatment eg with compounds Nos. 1,5,2.6,2.11, 3,4, 2,15,2,37, 5,13 and others no infestation occurs (0-5%)

Example B-2: Seed pickling of rye against Fusarium nivale

Naturally infected rye of the variety Tetra hei I, which is naturally infected with Fusarium nivale, is stained on a roll with the fungicide to be tested at concentrations of 600 and 200 ppm AS (based on the weight of the seed). The infected and treated rye is sown in October in the field with a seeder on plots of 3m length and 6 rows of seeds. There are 3 repetitions per test product and concentration. Until the infestation evaluation, the plant planting is cultivated under normal field conditions, preferably in a closed snow cover region during the winter months. For assessment and phytotoxicity, the seed boll is rated in autumn and the crop density and tillering in spring. To determine the active substance activity, the percentage of Fusarium-infested plants is counted in the spring, immediately after the snowmelt.

The tested substances of the formula I show little or no phytotoxicity, with the compounds no. 1.5,1.8,2.1,2.2,2.6,2.8, 2.34 and others, the Fusariumbefall is completely prevented at both drug concentrations.

Example B-3: Seed pickling of barley against Helminthosporium gramineum

Helminthosporium gramineum naturally infected winter barley of the variety "Cl" is mixed on a mixing roller with the fungicide to be tested at concentrations of 600 and 200 ppm AS (by weight of seed) .The infected and treated barley is harvested in October Free field seeded on a plot of 2 m in length and 3 rows of seed per test product and concentration 3 replicates are cultivated until the infestation evaluation under normal field conditions in order to assess the phytotoxicity in the autumn of the seed boll and in spring the stock density and tillering To determine the active substance activity, the percentage of helminthosporium-infected stems is counted at the time of ear-picking.

The tested substances of formula I show little or no phytotoxicity. With compounds Nos. 1.28, 2.2, 2.6, 2.9, 2.30, 3.5 and others, fungal infestation at both concentrations is reduced to less than 20% compared to unheated control plants.

Example B-4: Seed dressing of barley against Ustilago nuda

Winter barley of the cultivar "RM1" naturally infected with Ustilago nuda is pickled on a mixing roller with the fungicide to be tested at concentrations of 600 and 200 ppm AS by weight of the seed seeded with a seeder on plots of 2m length and 3 rows of seeds.

For each test product and concentration, 3 repetitions are performed. Until the infestation evaluation, the test plant is cultivated under normal field conditions. To determine the activity of the active ingredient, the percentages of Ustilago-affected spikes are determined during flowering.

With compounds Nos. 2,6, 2,10, 2,15, 2:19, 5:21 and others, fungal infestation is reduced to less than 20% at both concentrations.

Example B-5: Seed pickling wheat against Tilletia tritici

Probus winter wheat (3g dry spore material to 1 kg seed), artificially infected with spores of Tilletia tritici, is stained on a mixing roller with the fungicide to be tested using concentrations of 600 to 200 ppm AS (based on the weight of the seed). The infected and treated wheat is sown in October in the open country with a seeder on plots of 2m length and 3 rows of seeds. For each test product and concentration, 3 repetitions are performed. Until maturity, the trial plant is cultivated under normal field conditions. In order to assess the phytotoxicity, the seed bake is evaluated in autumn and the stock density and tillering in spring. To determine the active ingredient activity at the time of ear maturity, the percentage of ears infected by Tilletia are counted.

Compounds of the formula I, e.g. Nos. 1.5, 2.8, 1.28 show a clear protective effect against Tilletia tritici infestation at both concentrations, whereby the casserole and growth of the wheat plants are favorably influenced.

Claims (16)

1. Microbicidal agent, characterized in that it comprises as at least one active ingredient a compound of formula I. R - P - CH. - CH ₂ - * / C / (D, R-NH "· ' contain, in which RUnOR _{1 is,} independently of one another, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or hydroxyl, X is hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trimethylsilyl, cyano, methoxycarbonyl or the radical CH _{2 is} -CH (NH ₂ JP (O) (R) (R ₁ ), and Y is hydrogen, halo, dC ₂ haloalkoxy or C ₁ -C ₂ haloalkyl, with the inclusion of appropriate salts, if R and / or R ₁ hydroxy, together with a suitable carrier material and / or wetting agent. 2. Means according to item 1, characterized in that they contain a compound of formula I wherein at least one of the substituents X or Y has a meaning other than hydrogen, provided that R and Ri are simultaneously hydroxy or ethoxy. 3. Composition according to item 1, characterized in that they contain a compound of formula I, wherein R Ci-C ₄ AlkyloderOH,
R ₁ OH, X is hydrogen, halogen, Ci-C ₄ AIkYLC ₁ -C ₄ AIkOXy ₇ Si (CH ₃ ) S, -CN, -COOCH ₃ or -CH ₂ - (NH ₂ JP (O) (R) (R ₁ ), and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl. 4. Means according to item 3, characterized in that they contain a compound of formula I, wherein R = R ₁ = OH, X is hydrogen, fluorine, chlorine or bromine, C ₁ -C ₄ AlKyl, CH ₃ O, Si (CH ₃ ) ₃ , -CN, -COOCH ₃ or -CH ₂ -CH (NH ₂ JP) O) (OH) ₂ and Y is fluorine, chlorine, bromine, halomethoxy or halomethyl. 5. A composition according to item 4, characterized in that they contain a compound of formula I wherein at least one of the two substituents X and Y is halogen or halogen. 6. A composition according to item 5, characterized in that they contain a compound of formula I, wherein one of the two substituents X or Y is fluorine or fluorine. 7. A composition according to item 1, characterized in that they contain a compound of formula I wherein R and R independently of one another C ₁ -C ₄ AIkYl, Ci-C ₄ alkoxy or hydroxy, X is halogen, C ₁ -C ₄ A Y y, C ₁ -C ₄ alkoxy, Si (CHg) ₃ , cyano or -CH _r -CH (NH ₂ ) -P (O) (R) {R ₁ ), and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl. 8. A composition according to item 7, characterized in that they contain a compound of formula I, wherein R, Ri and Y have the meaning mentioned and X is fluorine, chlorine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy or cyano means. 9. Composition according to item 1, characterized in that they contain a compound of formula I wherein R and R _{1 have} the meaning given for formula I, while X is halogen, methyl, methoxy or cyano and Y is hydrogen, halogen, difluoromethoxy or Trifluoromethyl means. 10. A composition according to item 1, characterized in that they contain a compound of formula I, wherein R and R _{1 have} the meaning given for formula I, while X is hydrogen and Y is difluoromethoxy or trifluoromethyl. 11. A composition according to item 1, characterized in that they contain as active ingredient i-amino-2-phenylethänphosphonsäure. 12. A composition according to item 1, characterized in that they contain as active ingredient 1-amino-2- (4-fluorophenyl) -ethanephosphonsäure. 13. A method for controlling or preventing a pathogenic microorganism infestation of crop plants, characterized in that applying a compound of formula I according to item 1 to the plant, plant parts or their location. 14. The method according to item 13, characterized in that the plant parts to be treated are the seed. 15. Use of compounds of the formula I according to item 1, characterized in that they are used for the control and / or preventive prevention of infestation of phytopathogenic microorganisms. 16. Use according to item 15, characterized in that the microorganisms are fungi.