AU601153B2

AU601153B2 - Microbicides

Info

Publication number: AU601153B2
Application number: AU58509/86A
Authority: AU
Inventors: Ludwig Maier
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1985-06-11
Filing date: 1986-06-10
Publication date: 1990-09-06
Anticipated expiration: 2006-06-10
Also published as: BR8602695A; KR870000349A; IE861544L; IL79086A0; PT82737A; ES8800954A1; ATE50999T1; GR861496B; JPH0753743B2; EP0207890A1; DK272886A; EP0207890B1; DD251913A5; PT82737B; DK272886D0; AU5850986A; IE58475B1; NZ216484A; JPS61286395A; ES555882A0

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

FORM 10 V J SPRSON FERGUSON COMMONWEALTH OF AUSTRALiA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: AT SU-pFC U0 NJT .1986 0000 0 00a 00 0 0000 00 00 0 00 00 0 00L' 0 0 00 0 0 0 00 0 00 0 00 0 0 0 4 t 0 0 0 0 00 000 0000 000000 0 0 Class Int. Cla4 Complete Specification Lodged: Accepted: Published: its Priority.- Related Art: Name of Applicant: CIBA-GEIGY AG Address of Applicant: Klybeckstrasse 141, 4002 Basle, Switzerland Actual Inventor: LUDWIG MAIER Address for Service: SIpruson Ferguson, Patent Attorneys, Level 33 St Martins Tower, '31 Market Street, Sydney, New South Wales, 2000, Australia C~omplete Specification far the i-'ention entitled:

"MICROBICIDES"

The following statement is a full description of this in,-ention, including the best method of performing it known to us SBR:eah 134UJ

IA

Microbicides The present invention relates to microbicides containing one active ingredient an l-amino-2-arylethanephosphoric or l-amino-2-arylethanephosphinic acid derivative or l-amino-2-arylethanephosphine oxide derivative of formula I or a salt thereof, and to the use of these compounds for controlling harmful micro-organisms.

According to a broad form of the present invention there is provided a Smicrobicidal compositioi comprising at least one compound of formula 0X D, P- CHCH I R

NH

2

Y

wherein R and R are each independently of the other C -C 4 alkyl, Cl-Calkoxy or hydroxy, X is hydrogen, halogen, C 1

-C

4 alkyl,

C-C

4 alkoxy, trimethylsilyl, cyano, methoxycarbonyl or the radical

S-CH

2

-CH(NH

2 and Y is hydrogen, halogen, C 1

-C

2 haloalkoxy or C -C 2 haloalkyl, or a salt thereof if R and/or R are hydroxy, together with a suitable carrier and/or wetting agent with the proviso that when R and R are simultaneously hydroxy or ethoxy, at least one of X and Y is not hydrogen.

The compounds of the present invention have the formula 0 X R-P-CH-CH

R

1

NH

2

K

Y

wherein R and RI are each independently of the other C.-C 4 alkyl,

C

1

-C

4 alkoxy or hydroxy, X is hydrogen, halogen, C 1

-C

4 alkyl, C -C 4 alkoxy, trimethylsilyl, cyano, methoxycarbonyl or the radical

-CH

2

-CH(NH

2 and Y is hydrogen, halogen, C -C 2 haloalkoxy or C 1

-C

2 haloalkyl, and salts thereof if R and/or R are hydroxy.

TCW/839

A

N

18 Formula I expresses ethanephosphonic acid derivatives if R and RIare hydroxy or alkoxy, ethanephosph,,nic acid derivatives if one of the two substituents R and R1is alkyl, and ethanephosphine, oxide derivatives if both substituents R and Rare alkyl.

CI- C 4 alkyl by itself or as moiety of an alkoxy grou, is fnethyl, cthyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

TCW/839Y I p 2 Halogen denotes fluorine, chlorine, bromine or iodine. C 1 -CaHaloalkyl by itself or as moiety of a haloalkoxy group is a monohalogenated i methyl or ethyl group or a methyl or ethyl group which is perhalogenated by a specific halogen atom or by different halogen atoms.

Typical examples are CHCIa, CHF 2

CH

2 CI, CC13, CH 2 F, CHBr 2

CH

2

CH

2 C1, CHCl-CHCl, CF 3 CaF 5

CF

2 C1, CF 2 -CF2C1.

Salts of a free hydroxyl group are unsubstituted or substituted ammonium or hydrazinium salts or metal cations.

Examples of metal ions are the cations of the following elements: Yj (alkali metals such as lithium, sodium or potassium; alkaline earth metals such as magnesium, calcium, strontium or barium; elements of the first to the eighth Periodic auxiliary group such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, with iron, manganese, copper and zinc being preferred; elements of the third and fourth Periodic main group such as aluminium, silicon, tin, lead, zirconium, titanium, preferably aluminium, which metal ions may be present in the salts or complexes of formula I in the valence states appropriate to them.

Phosphonic acid derivatives of formula I can in principle be obtained by reacting an unsubstituted or substituted 2-phenylacetaldehyde with ammonia and a dialkyl phosphite, followed by optional subsequ ent hydrolysis with a mineral acid: CHZ-C'HO NH 3 H(Oalkyl)a y+ H alkyl-O- H-CH 2 HO- -Calkyl J=Am H 58 [Chalmers and Kosolapoff, J,Am.Chem.Soe. 75, 5278 (1953)1.

-3- 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)1, in which a substituted phenylacetylhalide is reacted with a) 0,0,O-trialkylphosphite, b) 0,0-trialkylphosphonite or c) O-trialkylphosphinite, and the intermediate is further reacted, in the presence of hydroxylamine, to give the phosphonyl, phosphinyl or oxophosphino-oxime, from which the amite can be obtained by hydrogenation: X >al H*-CO- NH0 X\ H H 2 1 a i/o* Ra-Ni] In the above formulae, X and Y are as defined for formula I, and the remaining substituents are defined as follows: xt H, halogen, C 1 -Ctialkyl, Cl-C 4 alkoxy, Si(CH 3 3 -ON, -COOCH 3 or -CH 2

CHO,

alkyl =C 1 -C~alkyl, X* halogen, Cv-C 4 alkyl, Cj-C~alkoxy, Si(CH 3 3 -CN, -COOCH 3 or '-CH 2 -C0Hal, H, halogen, CI-C~alkyl, C 1 -C4alkoxy, Si(C11 3 3 -CN, -COOCH 3 or -CH 2 R* (R* 1 )p Hal -halogen, preferably Cl or Br, R' C 1 -Cijalkyl, R* C1-C4alkyl or Cl-C4alkoxy, R~j =CI-C4alkyl or Ci-C4alkoxy.

4 Formula I* embraces only those compounds of formula I, wherein R and Ri have the meaning of R* and R*

I

Where R* and/or R*i are Ci-Cijalkoxy, 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.

i Compounds of 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) aminomethylphosphonate, aminomethylphosphi- \Q nate or aminomethylphosphine oxide, and b) an aldehyde such as benzaldehyde or a ketone such as phenylacetone or benzophenone, with Sa suitably substituted benzyl halide [RW. Radcliffe and B.G.

SChristensen, Tetrahedron Letters, 4645 (1973)]: q 0 t 2 0X C=N-H-C(R)(Ri) T. i LHis(R)o(Ri) i! T Hal-CH B I Hal halogen, preferably Br or Cl The activation of the -CH 2 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, Ri, X and Y are as defined for formula I, Ti is hydrogen or an aliphatic or aromatic radical and T 2 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 formula I is carried out by catalytic cleavage with e.g. H 2 /Pd/C, but can also be performed with hydrogen in the presence of other catalysts (such as platinum or Pt/C). In the preseni of a mineral acid such as hydrochloric or ii 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 provided at least one of the substituents R and/or Ri is alkoxy at elevated temperature (40 0 -150 0 C) in one reaction step.

SIt 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, O 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 Sanother.

i ,The reaction temperature during the aralkylation (benzylation; is normally in the range from -1000 to +10°C, preferably from -800 to -20 0 C. The hydrogenolytic cleavage is conveniently carried out in the temperature range from -20° to +800i,.

The cited starting compounds are known or are prepared by methods 9o 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 toluenos by bromination with N-bromosuccinimide in CCl in the presence of azoisobutyronitrile (catalyst).

The compounds of formula I are phosphonyl, phosphinyl and oxophosphino analogs of P-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 formula I corresponding to the Q D-N-amino acids have the (S)-configuration. The respective or (S)-configurations of a diastereoisomeric (R,S)-compound can be 6 obtained pure therefrom by fractional crystallisation or chromatography (HPLC). The (R)-diastereoisomers and (S)-diastereoisomers have different microbicidal properties.

The present invention also relates to the above preparatory methods, where thess lead to novel compounds. The invention further relates to the novel compounds of formula I in which at least one of the substituents X and Y has a meaning different from hydrogen, praid4d.R and RI are simultaneously hydroxy or ethoxy, Compounds of formula I, wherein R and Ri are Ci-Coalkoxy, are S valuable acaricides (in particular against Tetranychus and Amblyomma al species) as well as insecticides which are effective in particular against sucking insects (aphicides).

04 Preferred microbicides are compounds of formula I and salts thereof, wherein R is Ci-C4alkyl or OH, RI is OH, X is hydrogen, halogen, Ci-C4alkyl, Ci-Calkoxy, Si(CHa), -CN,

-COOCH

3 or CH 2 -CH(N1 2 and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl.

4o Among these mit,robicides, those compounds are preferred wherein R R1 OH, X is hydrogen, fluorine, chlorine or bromine, C i -Ciialkyl, CH 3 0, I Si(CH 3 3 -CN, -COOCH 3 or -CH 2 -CH(NH2)-P(O)(OH)a, and Y is fluorine, chlorine, bromine, halomethoxy or halomethyl.

Among these last mentioned microbicides, those csnpo:niids are particularly preferred in which at least one of the substituents X and Y is or contains halogen, and, of these, those compounds a1 which one of the substituents X and Y is or contains fluorine.

W6 M ~-OLPC~UI I -7 -7- Another important subgroup of microbicidally active compounds are S-hose compounds of formula I and salts thereof wherein jR and Ri are each independently of the other Ci-Cialkyl, C1-Csialkoxy or hydroxy, X is halogen, Ci-C 4 alkyl, Ci-C 4 alkoxy, Si(CH3) 3 cyano or -CH-CH( Y is hydrogen, halogen, halomethoxy, hclothnxy or halomethyl.

Among these last mentioned microbicides, those compounds are especially important wherein R, RI and v have the given meanings and S X is fluorine, chlorine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy or cyano.

i Also important are microbicidal compounds and salts thereof in which R and RI are as defined for formula I, X is halogen, methyl, methoxy or cyano, and Y is hydrogen, halogen, OCHF 2 or CF 3 Another important group of microbicides comprises those compounds of formula I, wherein R and RI are as previously defined, X is hydrogen and Y is difluoromethoxy or trifluoromethyl.

Derivatives of peptidylaminomethanephospho'ic and peptidylaminophosphinic acid are disclosed ii US patent specification 4 016 148 '0 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 for plant growth and plant emergence in US Spatent 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.

-8 Surprisingly, it has now been found that the aminoethanephcisphonic acid derivatives of torula I 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 bauteria and for promoting the development of said plants.

SProvided at least one of the substituents R and RI is an OH group, i the salts of formula I come into the category of preferred compounds. Especially preferred on account of their fungicidal activity UEO are the metal salts, in particular tle aluminium, nickel, manganese and copper salts and the lower alkylammonium salts of formula I, which are particularly suitable for soil application and as seed dressing agent.

The principal utility of compounds of formula I is for controlling harmful phytopathogepiz fungi. Thus the compounds of formula I have, for practical purposes, a very useful curative, preventive and systemic action for protecting cultivated plants without adversely affecting said plants by undosirable side-effects. Examples of cultivated plants within the scope of this invention are: cereals S 0 (wheat, barley, rye, oats, rice); beet (sugar beet and fodder beot), 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 (cucumber, marrows, 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.

'I

With the compounds of f the micro-organisms whi blossoms, leaves, stems crops of useful plants, which grow later art' al I nisms.

9 ormula I it is possible to inhibit or destroy ch occur in plants or parts of plants (fruit, ,tubers, roots) in these and in related while at the same time the parts of plants so protected from attack by such micro-orgaoi The compounds of formula I are particularly effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes Helminthosporium and Fusarium species) and Basidomycetes }O Tilletia and Ustilago). The compounds of formula I can therefore also be used as seed dressing agents for protecting seeds o o (fruit, tubers, grains) and plant cuttings against fungus infections Sas well as agaiust phytopathogenic fungi which occur in the soil.

0 Accordingly, the invention also relates to the use of compounds of formula I for controlling phytopathogenic micro-organisms and for the preventive treatment of plants to protect them from attack by such micro-organisms.

0 co o 0^ The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be a on treated, simultaneously or in succession, with further compounds.

These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth, They can also be ona selective herbicides, fungicides, bactericides, nematicides, moluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactanta or 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, S dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

LL

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 to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymeric substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, V scattering or pouring, are chosen in accordance with the intended C) objectives and the prevailing cimcimstances, Advantageous rates of application in agriculture are normally from 50 g to 5 kg of' active ingredient per hectare, preferably from 100 g to 2 kg aoi,/ha, most preferably from 100 g to 600 g a.i./ha.

KSuitable solvents are,, aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or K substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalatp, aliphatic hydrocarbons such as cyclohexane or Iiparaffinis, alcohols and glycols and their ethers and esters, such as ethanol, ethylone glycol monomethyl or manoethyl ether, ketones such a cyclohexanone, strongly polar solventa such as N-methyl-2-pyrrolidone, dJimethylsulfoxide or dimethylformamide, as well as epoxidisod vegetable oilo nuch as epoxidised coco.'ut oil or Poytoan oil; or water.

Patvticularly uset-A application-promoting adjuvants which ate, v~ble to reduce substantially the rate of application are also natural V (animal or vegetable) or synthetic phiospholipids of the series of the cophalins and lecithins, e.g. phosphatidyl ethanolamine, phosphatidyl serino, phosphatidyl glycerol or lysolecithin.

Depending on the nature of the compound 94 the fortvI.4 I to be, forrnulatedf suitable 8urfaco-aptiv6 tompoud.a On, ga~n~ and/or anionic sufactants haVing good eMUlA.qifY1n. and wetting propertiea, The. term "sratn-"to an comprisig mixtures of# s'orfaatantai* 11 V The Ourfactants customarily employed in the art of formulation a.

V described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ridgewood, New Jersey, 1981; Helmut Stache "Tensid-Tdschenbuch" (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 preferably 0.1 to 95 of a compound of formula I, 99.9 to 1 preferably 99.8 to 5 of a solid or liquid adjuvant, and 0 to 25 0 preferably 0.1 to 25 of a surfactait.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.

The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein, Parts and percentages are by weight.

Preparatory Examples Examle 1: Prp2arztion nf 0, O-diisopropyl-1-amino-2-(4-fluorophenyl)ethylphosphcnate of formula H-Hn-* [compound 1.8] C oH 7 iso a) Preparation of 0,0-diisopropyl-'1-N-benzylidenamino-2-(4-fluorophenyl)ethvlphosphonate_(intermediate) With stirring and cooling, 500 ml, of n-butyllithium are added to 113.4 g (0.8 mole) of diisopropylamine in 750 ml of tetrahydrofuran (THF). The mixture is cooled to -750f and then a solution of 226.6 g (0.8 mole) of 0,0-diisopropylbenzylideneaminomethanephosphonate in 600 ml of THF is added dropwise over the course of 1 hour. After

-I-

7 :i

.D

(&g r

I

I 12 stirring for 1 hour, a solution of 151.2 g (0.8 mol.e) 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 w-th three 200 ml portions of water and dried over NazSOi,. The solvent is then remov-.1 by evaporation to give 286.3 g (91.4 of theory) of the intermediate, which yields 261.2 g (83.4 of theory) of pure product after molecular distillation. Boiling point: 160°C/0.1 mbar.

b) Preparation of the final product 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 Pd) and the mixture is hydrogenated at room temperature (20 0 After 62 hydrogen uptake, 2 g of Pd/C are again added and, after 90 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 by rotary evaporation. The residue (ca. 15 g) is distilled in a bomb tube, affording 12.6 g (83.1 of theory) of pure final product in the form of a colourless oil with a boiling point of 170°C/0.0 mbar.

Example 2: Preparation of l-amino-2-(4-fluorophenyl)ethanephosphonic acid (compound 2.6) A mixture of 227.5 g (0.75 mole) of O,0-diisopropyl-l-amino-2- (4-fluorophenyl)ethylphosphonate and 750 ml of 20 hydrochloric acid is refluxed, with stirring, for 5 hours and stirred for a further 5 hours at room temperature. After addition of 500 ml of S water, the precipitate is filtered and washed with 250 ml of water and 500 ml of methanol. Yield: 103.3 g of title compound. The filtrate is concentrated and the residue is recrystallised from methaol/propylene oxide, affording a further 43.3 g of final product. Total yield: 146.6 g (89.2 of theory). Melting point: 266 0 -270'C (dec.).

I

U

if if 13 Example 3: Preparation of the optical isomers of I-amino-2-(4-fluotophenyl)ethianephosphonic acid A. Preparation of the dibenzoyl tartrqtes of 0, 0-diethyl-1 -amino- 4-fluoropheqnyl) et'hjosihonate (Et0) 2 P-b1--GH 2

(C

6

H

5 C00&I-COOH) 2 p salt a) To a solution of 68.82 g (0.125 mole) of 0, O-die thyl- I1-amino- 2- (4-fluoropheniyl)e-thylphosphonate in 750 ml of methanol and 750 ml of ethanol are added 47.04 g of dibenz oyl tartaric acid 2

O.

After stirring for 2 hou-rs, the thick white suspension is filtered and the residue is dried. Two recrystallisations from ethanol yield 31.5 g (39.8 of theory) of "salt I" of m.p. 179%C kdec.); D 0.50 (c =2.077 in methanol).

b) The combined residual f~ltrates are evaporated and the residue is stirred in IN NaOH. The so.Lution is saturated with sodium chloride and extracted with three 400 ml portions of CH 2 Gl 2 The organic phase is dr'ied over NaZ9Q4 and concentrated by evaporation, The residual brown oil (37.5 g) is dissolved in 400 ml of methanol and 400 ml of o-thanol and 25.6 g of dibenzoyltartaric acid are added to the solution. Aftcr stirring for 2 hours, 63 g of salt are isolated by filtration and recrystallised from 1200 TDl of methanol to give 7.2 g of crude "salt HI". The filtrate is concentrated and the residue recrystallised from 500 ml of ethanol, affording 17 g of pure "salt IV;~ [a)20. +67.3' 0.5' (c =1.998 in methanol).

B.

a) Preparation of &-diethYl--amino-2-( 4-f luorophenyl) ethylphosphonate 25.34 g of salt I are stirred for 2 hoursa at room temperature in 100 ml of IN N(AOH to e1ffect liberation from the tartrate. The clear solution is saturated1 with sodium chloride, then 200 ml of CH2Cla ifif If if if if ifaif if if -1 14 are added and the resultant suspension is filtered in vacuo. The residue is washed with two 200 ml portions of CH 2 G1 2 The organic phase of the combined filtrates is separated, dried over Na 2 S04, filtered, and concentrated by evaporation to give 9.1 g (82.7 of theory) of the desired final product as a pale yellow oil; [U,2=J +10.60 t 0.40 (c =2.5 in methanol).

IRl-NMR in CDC1 3 1.3 (NH 2

CH

3 811); 2.3-3.5 (PCH-CH 2 (mn, 3H); 4.17 (OCH2)(qu, 4H); 7.1 (in) (4H, phenyl).

b) Preparation of I -amino- 2- (4-f luorophenyl) ethanepho sphonic acid 5.51 g (0.02 mole) of the phosphonate obtained in a) are refluxed in 40 ml of 20 hydrochloric acid for 4 hours. The CIA- solution is then concentrated and the residue is recrystallised from methanol /propylene oxide, affording 3.7 g (84.5 of theory) of the desired final product, Melting point: 259o-263*C (dec.); (a +37.50 t 0.40 (c 2.636 in 1 N NaCH).

1 H-NMR in D 2 0/NaOl: 2.3-3.1 (PCH-CH 2 3H); 4.65 (OH, NH 2 6.6-7.1 (phenyl, 4H)(n).

a) Preparation of 0, O-ciiethyl-l-amino-2-(4-f ltorophenyl) ethylphosphonate in aczcordance with the method of Ba) from "salt II" with IN NaOH solution.

Yield: 95.9 of theory. Pale yellow oil 10.30 0.50 (c 2.036 in methanol).

Preparation ot I -amino-72- (4-f luorophenyl) ethanepbo sphonic A, acid in accordance with the methbsd of Bb) by hydrolysis of the above ()phosphonate in 20 hydrochloric acid. Yield: 77.6 of theory.

Melting point: 261'-263'C (dec.).

(a 0._36.9* 0.50 (c -2.081 in IN NaOH).

15 The following compounds of formula I, which are obtained as mixtures of diastereoisomers unless otherwise specifically mentioned, can also be prepared in this manner or by one of the other methods described above.

The IH-NMR values were determined with a Varian EMK-360 spectrometer at 60 MHz in CDC13 with (CH 3 4 Si as reference substance.

The 31 P-NMR values were recorded with a Bruker WP 80 spectrometer at 32.28 MHz with 85 H 3 P04 (externally) as reference substance.

Key: |0 Me methyl Et ethyl iPr isopropyl The temperatures are given in degrees centigrade.

16 Table 1: Compounds of formula Compound R' X (R'o)J C(H)C2,/ Physical data Et H iPr H

I

C)

4 4 4 44 4, I I 4 4 '44' 1.3 1.4 1.6 1. 7 1.8 1.9 1.10 1 .11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 1.19 1.20 1.21 1.22 1.23 1.24 1.25 4-cl 3-Cl 4-Br 4-1 4-F 4-F 3-F 2-F 2-Cl 3-Cl 4-Me 3-Me 2-Me 3-CF 3 4-t-butyl 4-Me 0 2 -NeO 2-F

H

Hf

H

4-Cl 4-C].

H

6-Cl 4-OCHF 2 3-OCHF.

4-OCHF 2 4-cF3 b.p. 1700/0.6 mbar 'H:1.3(NH 2 2.5-3.5(PCH-CH 2 7.3 (aromatic-H) n 20 1 .5140

D

IH:1.3; 2.4-3.5; 7.2 b.p. 1250/0.05 mbar 1.3; 2.3-3.4; 7.767 b.p. 150-1600/0.08 mnbar b.p. 1700/0.08 mbar b.p. 1500/0.05 mbar h.p. 1500/0.08 rnbar m.p. 59-62* nI2 0 1.5272

D

1.4; 2.5-3.5; 7.15; 2.32 (X-CH 3 31 P: 28.09 n 20 1.5060

D

1.33; 2.5-3.5; 7.12; 2.33 (X=CfH 3 31P: 28.19 n2 0 1 .4659 b.p. 1400/0.01 mbar b.p. 1650/0.2 mbar b.p. l25'/O.1 mbar

A

K

17 Table 1: (continuation) Compounds of formula

(RO)

2

-CH(NH

2

OCH

2 Compound R' X Physical data 1 .26 1.27 1.28 1.29 1 .30 1 .31 1.32 1 .33 1.34 1 .35 1 .36 1 .37

H

2-Si(Me) 3 3-Si(Me) 3 4-Si(Me) 3 4-CN 3-F 2-F 2-Cl 3-1 4-COOCH 3 4-CHa-CH- (NH2-() (OEt) 2 2-Cl 2-F 2-F 4-OC2F 4-OCF 2

CF

2 Cl H b.p.

H b.p.

H 'H: 4-F b.p.

4-F b.p.

3-Cl b.p.

110*/0.1 mbar 1500/0.12 mbar 1200/0.1 mbar 1.35; 2.6-3.5; 7.4-7.6 1150/0.1 mbar 1100/0.08 mbar 1600/0.1 mbar b.p. 160'/0-03 mbar 1 .38 1 .39 1.40 4-F 6-F

H

b.p. 1050/0.1 mbar b.p. 950/0.1 mbar Oo) I I t

I

18 Table 2: Compounds of formula (HO) 2

-CH(NH

2 )CH2/' <e Compound X Melting point [dec.] 2.1 2.2 2.3 2.4 2.6 2.7 2.8 2.9 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 if 4-Cl 3-Cl 4-Br 4-1 4-F 3-F 2-F 2"Cl 3-Cl 4-Me 3-1e 2-(e

H

4-t-butyl 4-OMe 2-OMe 2 -F

H

if fH

H

2-Si(Me) 3 3-Si(MO) 3 4-si(me) 3

H

H-F

H

H-~

H

6-Cl 4-OCHF 2 3-OCHFa 4-CF3 4-CHF 2 4-0C 2 Fs 4-OCF2-CFzC1

H

2 78-282 280 -28 2 268-2 72 284-28 6 2 55-2 59 2 66-2 2 78-2 275-276 279-280 2 74-2 78 276-279 270-273 244-245 2 58-2 62 2 64-26 8 2 32-2 36 19 Table 2: (continuation) Compound X y Melting point [dec.] 2.28 4-CN H 267-269 2.29 3-F 4-F V2.30 2-F 4-F 271-4174 V2.31 2-Cl 3-Cl 2.32 3-1 H K 2.33 4-C11 2

-CH(NH

2 P(o)(0102

H

H2-34 2-Cl 4-F 12.35 3-Me 4-Cl 2.36 2-Me 4-F 2.37 2-F 6-F 258-261 20 Table 3: Compounds of Compound R formula R-P-YH-CH 2 0~

H

6

NH

2 M.P. [dec.i 0 0 0 0 00 0 0 04 0 0 .000 O 009 00 0 a 0 3.1 3.2 3.3 3.4 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 3.15 0.16 3,17 3.18 3.19 3.20 3.21 3.22

H

2-Me 3-Ne 4-Ne 4-,F 4-Br 4-Cl 3-ble

H

3-Cl 3-F 2-F 2-F 2-Cl 3-Cl 2-Cl

H

4-0C 2

HS

4-t-butyl

H

2-Cl H1

H

If

H

6-Cl 4-Cl 4-Cl 3-Cl 3-CF 3 4-0CHF 2

H

4-0C 2

F

261-262 2 34-2 229-232 2.33-236 2 54-2 57 2 54-2 57 242-245 2 60-262 2 30-2 31 -21 Table 4: Compounds of formula e Compound Physical data 4.1 4.2 4.3 4.4 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 4.19 4. 20 4.21

H

4-F 4-Cl 2-Cl 2-Cl

H

4-t-butyl 4-CN 4-Si(Me) 3 4-O~e 4-O~e

H

2-Ne 2 -Me 3-Me 3-Me 4-Me

H

2 -F 3-F

H

4-Cl 4-F 4-OCHF 2 3-CF 3

H

2-Cl 3-OCHF 2

H

4-Cl 2 -CL

H

Hi 4-OC F 6-Cl

H

b.p. 160-170'/0.05 mbar b.p. 1600/0.05 mbar h.p. 1600/0.07 mbar b.p. 150-550/0.1 mbar -22 Table Compounds Compound of formula (1400O) -CH( NHl2)C =-lO.e

MI)

Physical data 5.1 5.2 5.3 5.4 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14 5.15 5.16 5,17 5.18 5.19 5.20 5.21 5.22 5.23 Na~ +H 1/2 Mg+ H 1/3 Al+ H 1/2 Nn+ 4-F 1/2 Ni++ 4-F 1/3 Al 4-F 1 /2 n+ 4-F 14Zr 4+ 4C 1/2 Mn 4-Cl 1/2 Co++ 4-Cl 1/3 Al.. 2-Cl 1/2 Cu~ 2-Cl 1/2 Cu 4-F 1/3 Fe.. 4-F 1/2 Ca H 1/3 H1 1/2 Cu 4-CN 1/3 Al 2-Cl 1/2 Mn 2-Cl 1/2 Ca 2-Me (MeNH,) 4-F (IsO 3

H

7 NH3) +H

(C

6 H6NU 3 +2-Cl m.p. >2800 (dec.) 4-F 4-F

H

4-0CHF2 4-0CHP2

H

TP.p. )300' (dec.) ln.p. 275-285*(doc.) 23 Formulation Examples for active ingredients (compounds) of formula I (throughout, percentages ar by weight) Fl. Solutions a compound of Tables 1 to 5 ethylene, glycol monomethyl ether polyethylene glycol 400 N-methyl--2-pyrrolidone epoxidised coconut oil petroleum distillate (boilipg rangq 1V 160-190') b) 10

C)

5 d) I% 94 These solutions are suitable for applicat.on in the form of micro-, drops, F2. Granulates a compound of Tables 1 to 5 kaolin highly dispersed siipiic acid attapulgite a) 5% b) The active ingredient is dies6 .ved In methylene chloride, the solution Is sprayed onto the carrier, and the solvent is subsequently evaporated off in yac'4o.

r;L0 C F3. Dusts a Compound of Tables 1 to 5 highly dispersed silicip, acid tal1cum~ kaolin a) 2% 1 97 Z b) Ready-for-use dusts are obtainedl by *mtimately miging the carriers with the active ingredient, L- 24 F4. Wettable powders a' b) c) a compound of Tables 1 to 5 25 50 75 sodium lignosulfonate 5 sodium lauryl sulfate 3 5 sodium diisobutylnaphthalenesulfonate 6 10 I octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) 2 highly dispersed silicic acid 5 10 10 Skaolin 62 27 (0 The active ingredient is thoroughly mixed with the adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration and which are particularly suitable for seed dressing.

Emulsifiable concentrate a compound of Tables 1 to 5 10 octylphenol polyethlene glycol ether moles of ethylene oxide) 3 calcium dodecylbenzenesulfonate 3 castor oil polyglycol ether (36 moles of ethylene oxide) 4 cyclohexanone 30 xylene tixture 50 Emulsions of any required concentration can be obtained from this concentrate by dilution with water. These emulsions are particularly suitable for seed dressing.

Biological Examples: Example B11 Action against Botrytis cinerea on beans Residual protective action O Bean plants about 10 cm in height are sprayed with a spray mixture (0.02 prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a 24 F4. Wettable powders a) b) c) a compound of Tables 1 to 5 25 50 75 U sodium lignosulfonate 5 5 sodium lauryl sulfate 3 5 sodium diisobutylnaphthalenesulfonate 6 10 octylphenol po'yethylone glycol ether (7-8 moles of ethylene oxide) 2 highly dispersed silicic acid 5 10 10 kaolin 62 27 l° The active ingredient is thoroughly mixed with thi adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration and which are particularly suitable for seed dressing.

Emulsifiable concentrate a compound of Tables 1 to 5 10 octylphenol polyethlene glycol othe moles of ethylene oxide) 3 calcium dodecylbenzenesulfonate 3 S castor oil polyglycol ether (36 moles of ethylene oxide) 4 cyclohexan.cn 30 xylene mixture 50 Emulsions of any required concentration can be obtained from this concentrate by dilution with water. Thuse emulsions are particularly suitable for seed dressing.

SBiological Examples.

Exam,, e B: Action against Botrytis cinerea on beans Residual protective action S Bean plants about 10 cm in height are sprayed with a spray mixture (0.02 prepared from a wattable powder formulation of the test compound. After 48 hours the treated plants are irt'-ted with a 25 conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100 relative humidity and 21°C and then an evaluation of fungus attack is made. Butrytis attack is 100 on untreated, infected bean plants. Attack is less than 20 after treatment with one of the compounds of formula I. No attack (0-5 is observed af -t treatment with e.g. compounds 1.5, 2.6, 2.11, 3.4, 2.15, .37, 5.13 and others.

Example B2: Action against Fusarlum nivale in rye (seed dressing) Rye seeds of the Tetrahell variety which are naturally infected with S Fusarium nivale are dressed on a mixer roll with the test fungicide at concentrations of 600 and 200 ppm of active ingredient (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 compound at its given concentration. Until evaluation 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 j population density and tillering in the spring. To determine the effectiveness of the test compounds, the percentage of plants attacked by Fusarium is assessed in the spring directly after the snow has melted.

The tested compounds of formula I exhibited scarcely any or no phytoxicity, Compounds 1.5, 1.8, 2.1, 2.2, 2.6, 2.8, 2.34 and others inhibited Fusarium attack completely at both given concentrations.

Example B3: Action against Helminthosporium gramineum on barley (seed dressing) 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 ingredient (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 -1U .I1ICL (AJ IU. Ufl2U±S C 4 26 with each test compound 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 population density and tillering in the sprijg. To determine the effectiveness of the test compounds, the percentage of stalks attacked by Helminthosporium is assessed at the time of car emergence.

The test compounds of formula I exhibited scarcely any or no phytotoxicity. At both given concentrations, compounds 1.28, 2.2, 2.6, 2.9, 2.30, 3.5 and others inhibited fungus attack to less than compared with untreated control plants.

Example B4: Action against Ustilago nuda on barley (seed dressing) SS Seeds of winter barley of the "RM1" variety which are naturally 0O infected with Ustilago nuda are dressed on a mixer roll with the test fungicide at concentrations of 600 and 200 ppm of active n 0 ingredient (based on the weight of the seeds). The infected and o treated barley is sown in October in the open with seeder in plots 2 metres long and in 3 rows. Three replicates are carried out with each test compound at its given concentration. Unt:Ll evaluation is.

made, the test plants are cultivated under normal field condiLions.

o To determine the effectiveness of the test compounds, the percentage S of ears attacked by Ustilago is assessed during flowering.

Compounds 2.6, 2.10, 2.15, 2.19, 5.21 and others reduced fungus attack at both given concentrations to less than 20 Example B5: Action against Tilletia tritici (seed dressing) 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 ~O2 ingredient (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 27 each test compound 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 population density and tillering in the spring. To determine the effectiveness of the test compounds, the percentage of ears attacked by Tilletia tritici is assessed at the time of ear ripening.

At both given concentrations, compounds of formula I, e.g. 1.5, 2.8, 1.28, exhibited a marked protective action against attack by \O Tilletia tritici, whereby emergence and growth of the wheat plants were favourably promoted.

1i

Claims

1. A microbicidal composition comprising at least one compound of formula 0 X R-P-CH-CH R 1 NH Y wherein R and R1 are each independently of the other C 1 -C alkyl, C -C 4 alkoxy or hydroxy, X is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, trimethylsilyl, cyano, methoxycarbonyl or the radical -CH 2 -CH(NH 2 1 and Y is hydrogen, halogen, C 1 -C 2 halo- alkoxy or C 1 -C 2 haloalkyl, or a salt thereof if R and/or R1 are hydroxy, together with a suitable carrier and/or wetting agent with the proviso that when R and R 1 are simultaneously hydroxy or ethoxy, at least one of X and Y is not hydrogen.

2. A composition according to claim 1 which contains a compound of j o formula I, wherein R is C 1 -C alkyl or OH, .S°o R 1 is OH, X is hydrogen, halogen, C 1 'kyl, C -C 4 alkoxy, Si(CH 3 -CN, -COOCH 3 or CH 2 -CH(NH 2 and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl. S3. A composition according to claim 1 or claim 2 which contains a compound of formula I, wherein R Rp OH, X is hydrogen, fluorine, chlorine or bromine, C -C alkyl, CH 3 0, Si(CH 3 3 -CN, -COOCH 3 or -CH 2 -CH(NH 2 2 and Y is fluorine, chlorine, bromine, halomethoxy or halomethyl.

4. A composition according to any one of claims 1 to 3 which contains a compound of formula I, wherein at least one of the substituents X and Y is or contains halogen. A composition according to claim 4 which contains a compound of formula I, wherein one of the substituents X and Y is or contains fluorine.

6. A composition according to any one of claims 1 to 5 which contains a compound of formula I, wherein R and R1 are each independently I /CW 39y V, 1 i;r r ~tLC"C ~~-"liPr ~r~~lrr Y1-II_.ICI.LII_ _I~iYiXl~iiYLY~i*-X~i.l ii i i 44 -29 of the other Cl-C 4 alkyl, C -C 4 alkoxy or hydroxy, X is halogen, C -C 4 alkyl, C 1 -C 4 -alkoxy, SI(CH 3 3 cyano or -CH 2 -CH(NH 2 1 and Y is hydrogen, halogen, halomethoxy, haloethoxy or halomethyl.

7. A composition according to claim 6 which contains a compound of formula I, wherein R, R 1 and Y have the given meanings and X is fluorine, chlorine, methyl, ethyl, Isopropyl, tert-butyl, methoxy, ethoxy, Isopropoxy or cyano.

8. A composition according to any one of claims 1 to 7 which contains a compound o( formula I, wherein R and R1 are as defined for formula I, X is halogen, methyl, methoxy or cyano, and Y Is hydrogen, halogen, difluoromethoxy or trifluoromethyl.

9. A composition according to any one of claims 1 to 8 which contains a compound of formula I, wherein R and R are as defined for formula I, X is hydrogen and Y is difluoromethoxy or trifluoromethyl. A composition according to any one of claims 1 to 9 which contains 1-amino-2-phenylethanephosphonic acid.

11. A composition according to any one of claims 1 to 10 which S contains l-amino-2-(4-fluorophenyl)ethanephosphonic acid.

12. A composition according to any one of claims 1 to 11 which oo contains l-amino-2-(4-tolyl)ethanephosphonic acid.

13. A process for the preparation of a compound of formula I 0 X .006 R-P-CH-CH 2 X RI NH Y wherein R and R are each independently of the other C -C 4 alkyl, Ci-C 4 alkoxy or hydroxy, X is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, TCW/839y -'V 30 trimethylsilyl, cyano, methoxycarbonyl or the radical -CH 2 -CH(N 2 I(R)(R and Y is hydrogen, halogen, C -C haloalkoxy or C1C 2 haloalkyl, with the proviso that at least one of the substltuents SX and Y has a meaning different from hydrogen if R and R1 are simultaneously hydroxy or ethoxy, which process comprises activating the CH 2 group of a Schiff's base of formula T 0 C=N-CH-P- R 2 2 1 and then aralkylating the activated base with a suitably substituted benzyl halide of formula Hal- CH 2 -a !Y and cleaving the intermediate of formula X 0 CH2 CH- P(R)(R) I2 Y T N=C hydrogenolytically in the presence of a catalyst, optionally followed by further treatment with a mineral acid at elevated temperature, provided R and/or R 1 are alkoxy and shall be converted into a hydroxyl group, the substituents R, R I X and Y in thp ~~;cermediates of the above formulae being as defined for formula I, and T 1 is hydrogen or an aliphatic or aromatic radical and T2 is an aliphatic or aromatic radical, and Hal is a halogen atom. jI. A compound of formula I according to claim 1 or a salt thereof, with the proviso that at least one of the substituents X or Y has a meaning different from hydrogen if R and R1 are simultaneously hydroxy or ethoxy. I "tMR/59oy c6? ,I 31 A compound of formula I according to claim 3.

16. A compound of formula I according to claim 4.

17. A compound of formula I according to claim

18. A compound of formula I according to claim 6.

19. A compound of formula I according to claim 7. A compound of formula I according to claim 8.

21. A compound of formula I according to claim 9.

22. l-Amino-2-(4-fluorophenyl)ethanephosphonic acid.

23. l-Amino-2-(2-chloro-4-fluorophenyl)ethanephosphonic acid.

24. l-Amlno-2-(4-tolyl)ethanephosphonic acid. A method of controlling phytopathogenic micro-organisms in cultivated plants or of protecting said plants from attack by such micro- organisms, which comprises applying to said plants, to parts thereof or to the locus thereof a compound of formula I according to claim 1 or a composition containing such a compound.

26. A method according to claim 25, wherein the parts of plants to be treated are seeds.

27. A method according to claim 25, wherein the micro-organisms are phytopathogenic fungi.

28. A method of controlling phytopathogenic micro-organisms in Scultivated plants or of protecting said plants from attack by such micro-organisms, which comprises applying to said plants, to parts thereof or to the locus thereof a compound according to claim 22 or a composition according to claim 11.

29. A method of controlling phytopathogenic micro-organisms in cultivated plants or of protecting said plants from attack by such micro-organisms, which comprises applying to said plants, to parts thereof or to the locus thereof a compound according to claim 24 or a composition according to claim 12. A microbial composition, substantially as hereinbefore described with reference to any o, of Examples Fl to

31. l-Amino-2-arylethanephosphonic or l-amino-2-arylethanephosphonic acid or l-amino-2-arylethanephosphonic oxide derivatives or salts thereof, substantially as hereinbefore described with reference to any one of Compounds 1.2 to 1.40, 2.2 to 2.37, 3.1 to 3.22, 4.1 to 4.21 or 5.1 to 5.23. TCW/839y '^I ~t ~9fl o 99 II 9 9994 I I 900* 4 #0 4 9 449 1 9 94 41 9 9* 99 9 a *99 I 9141 9 94 94 1 4 44 -32 process for the preparation of l-amino-2--aryletLhanephosphonic or 1 -ami no-2-aryl ethanephosphoni c acid or 1 -ami no-2-aryl ethaiiEphosphoni c oxide derivatives or salts thereof, substantially as hereinbefore described with reference to any one of Examples 1 to 3. DATED this TWJENTY-EIGHTH day of SEPTEMBER 1989 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON TMR/590y