GB2214184A - Amino-oxyalkyl compounds and intermediates therefor - Google Patents

Description

1 2214184 GB 5-16850 Preparation and Biological Activity of

Aminoxyalkyl-phosphonous, -phosphinic and -phosphonic acid Derivatives The present invention relates to new amino oxyalkylphosphonous, -phosphinic and phosphonic acid derivatives and to their salts The invention relates further to the preparation of these derivatives as well as to herbicidal, plant-growth-regulating and phytofungicidal compositions which contain these derivatives as active ingredients.

The invention relates also to the preparation of these compositions and to the use of the active compounds or of the compositions for selectively controlling weeds in cultures of useful plants, for regulating plant-growth or for controlling harmful microorganisms.

The new intermediate products that are necessary for the production of these derivatives are also part of this invention.

The novel phosphonous, phosphinic and phosphonic acid derivatives are of the formula I 2 A-O-CH LRI wherein A is an amino group -NH 2 or the acetoxime rest -N=C(CH 3)2, R is hydrogen, C 1-C 6-alkyl, which is unsubstituted or mono or disubstituted by Cl-C 6-alkoxy or R is hydroxyl, C 1-C 6-alkoxy or a O rest -O Me or -ON(R 4)4, R 1 is hydrogen, C 1-C 6-alkyl, a metal cation Me or an ammonium or substituted ammonium rest -N(R 4)4 and R 2 is hydrogen, Cl-C 6-alkyl, phenyl, benzyl or an aryl rest which is unsubstituted or substituted by halogen, C 1-C 4-alkyl, C 1-C 4-halo- alkyl, C 1-C 4-alkoxy, C 1-C 4-haloalkoxy, nitro, cyano, carboxyl, C 1-C 4-alkoxycarbonyl, amino, C 1-C 4-alkylamino, carbamoyl or acetyl.

R is hydrogen, CI-C 6 alkyl, C 1-C 6 hydroxyalkyl or C 2-C 6 alkoxyalkyl or benzyl.

These derivatives are represented by the formulae Ia and Ib, 2 2 H 2 N O-H R 1 and (CH 3)2 C=N-O-RH-I-R (Ia) A (Ib) wherein R, R 1 and R 2 have the meaning given above.

In these definitions, the alkyl radicals by themselves or as moiety of a combined alkyl ester may be straight chain or branched and contain the indicated number of carbon atoms Representative examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, sec butyl, tert butyl as well as pentyl and hexyl and their isomers.

Halogen comprises fluorine, chlorine, bromine and iodine.

As aryl rests are considered besides phenyl, naphthyl and indan also rests which contain a heteroatom, such as pyridine, chinole, indole, isoindole, furan, benzofuran, thiophen or benzthiophen Alkoxy radicals R can be straight chained and monosubstituted as well as branched and disubstituted, such as e g dialkoxymethylene.

Metal cations are e g lithium, sodium, potassium, zinc, calcium, barium, strontium, magnesium, also iron aluminium, mangan, nickel and chromium These metal-cations are monovalent.

At room temperature, the compounds of the formula I are stable oils, resins or solids They possess valuable herbicidal, plant-growthregulating and phytofungicidal activity and can be used for selec- tively controlling weeds in cultures of useful plants and for regulating plant-growth, in the sense of a reduced growth of the vegetative plant growth, of an improved root-formation or for controlling microorganisms which damage plants The aminooxy-alkyl- phosphonic and phosphinic acids of formula I are well tolerated by culture plants.

Because of their pronounced herbicidal and plant-growth-regulating activities, compounds are preferred, which correspond to the type of substitution or combination of substitutions:

a) Amino-oxyalkyl-phosphonic acid derivative of the formula Ic 2 H 2 N-OH OR (Ic) R' wherein R' and RI independently of each other are hydrogen, Cl-C 6-alkyl, a metal cation Me or an ammonium cation NR 4, R 2 is hydrogen, Cl-C 6-alkyl, phenyl, benzyl or an aryl radical, wherein the benzene ring is unsubstituted or substituted, especially preferred are the compounds (amino-l-oxyeth-1-yl)-diethyl-phosphonate (amino-oxymethyl)-diethyl-phosphonate (amino-l-oxy-prop-l-yl)-diethyl-phosphonate (amino-l-oxy-but-l-yl)diethyl-phosphonate and (amino-l-oxy-2-phenyleth-1-yl)-diethyl-phosphonate.

b) Acetonoxime-oxyalkyl-phosphonic acid derivatives of the for- mula Id (CH)CH 2 (Id) (CH 0)2 C=N-O-CHWR} (Id) 6 R' wherein R', R 1 and R 2 have the meaning given above under the formula Ic Especially active are the compounds acetonoxime-oxymethyl-diethyl-phosphonate, acetonoxime-l-oxyeth-l-yl-diethyl-phosphonate, acetonoxime-l-oxyprop-1-yl-diethyl-phosphonate, acetonoxime-l-oxy-2-phenyleth-1-yl-diethyl-phosphonate, acetonoxime-oxymethyl-phosphonic acid, acetonoxime-l-oxyeth-l-yl-phosphonic acid, acetonoxime-l-oxyprop-l-yl-phosphonic acid.

c) Amino-oxyalkyl phosphonous and phosphinic acid derivatives of the formula Id g 2 H 2 N-O-H OR 1 (Id) wherein R" is hydrogen or C 1-C 6-alkyl, which is unsubstituted or substituted or mono or disubstituted by C 1-C 6-alkoxy, R 1 is hydrogen, Cl-C 6-alkyl, a metal cation Me , or an ammonium cation N(R)4, R 2 is hydrogen, C 1-C 6-alkyl, phenyl, benzyl or an aryl radical whereby the benzene ring is unsubstituted or substituted RX is hydrogen, C 1-C 4-alkyl, Cl-C 4-hydroxyalkyl, C 2-C 6-alkoxyalkyl or benzyl.

Especially active are the compounds amino-oxymethylphosphinic acid-n-propyl ester, amino-oxymethylphosphinic acid, amino-l-oxyeth-l-yl-diethoxymethylphosphinic acid-ethyl ester, amino-l-oxyeth-l-yl-diethoxymethylphosphinic acid, amino-oxymethyl-diethoxymethylphosphinic-acid ethylester, amino-oxymethyl-diethoxymethylphosphinic acid and amino-oxymethyl-phosphonous acid.

d) Amino-oxyalkyl-phosphonous and -phosphinic acid derivatives of the formula Ie 2 (CH 3)2 C=NOH OR 1 (Ie) If wherein R", R 1 and R 2 have the meaning given above, under for- mula Ic.

Of these compounds, only the amino-methylphosphonic acid and its diethyl ester have been disclosed in the literature.

H 2 N-CH 2 OH H See UK Patent 2 071 664 T Denzel et al to E R Squibb + Sons This acid has been prepared according to a method of E Grochowski and J Jurczak in Synthesis 1976 p 682-684 by condensing N-hydroxy- phthalimide with hydroxymethylphosphonic acid diethyl ester in the presence of azodicarbonic acid diethyl ester and triphenylphosphin according to the following reaction scheme:

W COOC 2 H 5 '\'/' E() N COOC 2 H 5 il, JH+HOCH 2 ( O &C 2 H 5)2 I-C O C 2 H 5i p 1 '-OCH 2 &( O C 2 Hs)2 / \ / P(C 6 H 5)s / \/ 8 | + H 2 N-NH 2 H 2 N-OCH 2 (OH)2 HC 1 Hz NOCH 2 (OC 2 H 5)2 Other aminooxyalkylphosphonic acids according to this invention and the novel amino-oxyalkylphosphinic acid derivates according to formula I can be prepared according to this method The literature does not mention anything about the biological action of the above amino-oxymethylphosphonic acid and its diethyl ester.

A process for the production of the amino-oxyalkyl-phosphonic and phosphinic acid derivatives of the formula I according to this invention is characterised by condensing a hydroxyalkylphosphorus- derivative of the formula II HONH-t-OR 1 (II) wherein R, R 1 and R 2 have the meaning given under formula I, with N-hydroxy-phthalimide in an inert organic solvent in the presence of triphenylphosphin and an azodicarbonic acid-dialkyl ester, and splitting the N-phthalimido-oxyalkyl-phosphorous-derivative of the formula III 2 \./x.

wherein R, R 1 and R 2 have the meaning given above under formula I, with hydrazine in an inert organic solvent to give the amino-oxy- alkylphosphor derivative of the formula Ia R 2 H 2 N-ORH I Rl (Ia) wherein R, R 1 and R 2 have the meaning given above, under formula I, and optionally converting this compound, by reaction in an inert organic solvent with a 2,2-dialkoxypropan, with a 2,2-dihalopropan or with aceton, into an acetoxim-oxyalkylphosphor derivative of the formula Ib R 2 (CH 3)2 C=N-OH R 1 (Ib) wherein R, R 1 and R 2 have the meaning given above under the for- mula I.

The acetoxim-oxyalkylphosphonic-, phosphonous and phosphinic-acid derivatives of the formula Ib are advantageously prepared according to another process, in which a tolylsulfonic acid-alkylphosphor compound of the formula IV .- SO 2 CH 3 (I) = R wherein R, R 1 and R 2 have the meaning given above under formula I, is reacted in an inert organic solvent with a metal-salt of acet- oxime of the formula V (CH 3)2 C=NO Me (V) wherein Me is the ion-equivalent of a metal.

The hydroxyalkylphosphor compounds of formula II, which serve as starting material are prepared by reacting aldehydes with phosphite or phosphonite compounds, which have a phosphor-bound hydrogen atom.

The reaction proceeds as follows:

HUGO + Hj R H Oe RI and is described in detail in example 1 It is exothermic and can be conducted with or without solvent.

Appropriate solvents are e g aromatic hydrocarbons, such as benzene or toluene, cyclic ethers such as dioxan or tetrahydrofuran A process for producing hydroxyalkylphosphonic acids and esters is described in Organic Phosphorus Compounds Vol 7 ( 1976).

The intermediates of formula II are novel substances Of special importance are phosphinic acid derivatives, which correspond to formula I Ia H 04--o Ri (I Ia) H -OR 3 RW wherein R 3 and R 4 are Cl-C 6-alkyl while R 1 and R have the meaning given above under formula I, especially important are diethoxymethyl-hydroxymethyl-phosphinic acid ethyl ester, diethoxymethyl-hydroxyeth-l-yl phosphinic acid ethyl ester, diethoxymethyl-l-hydroxy-2-phenyleth-1-yl-phosphinic acid ethyl ester.

The starting material of formula IV is prepared therefrom by condensation with tolylsulfonic acid chloride in an organic solvent in presence of a base.

The compounds of formula IV are new Of special importance are the phosphinic acid derivatives of the formula I Va CH 3 SO 20-OR 1 (I Va) À.= RHOR 3 wherein R 3 and R 4 each are Cl-C 6-alkyl while RI and R 2 have the meaning given above, under formula I.

An example for these compounds is diethoxymethyl-tosyloxymethyl phosphinic acid ethyl ester.

Secondary and tertiary bases are used in these condensations, e.g diethylamine, triethylamine, pyridine, collidine and luthidine.

N-hydroxyphthalamide is prepared by condensation of hydroxylamine and phthalic acid anhydride.

A method for condensing N-hydroxyphthalamide with hydroxyalkylphos- phor derivatives of formula II is described by E Grochowski and J Jurczak, Synthesis 1976 p 682-684 The condensation is carried out in the presence of an azodicarbonic acid dialkyl ester and triphenyl phosphine in an inert organic solvent, such as e g tetra- hydrofuran, dioxan, cyclohexan or benzene The reaction is exo- thermic and has to be cooled It is described in more detail in example 2.

The phthalimido-rest is replaced by amino when the phthalimidooxy-alkylphosphor derivative of the formula III is treated with hydrazine in an inert organic solvent Hydrazine-hydrochloride or -hydrate can be used for this reaction and appropriate organic solvents thereby are alkanols, aromatic hydrocarbons, chlorinated hydrocarbons and ethers, examples are e g ethanol, propanol benzene toluene, hexane, cyclohexan, chloroform ethylene chloride, tetra- hydrofuran and dioxan.

The reaction is exothermic and has to be cooled in the initial stage It is described with more detail in example 3.

In order to transform the amino-oxyalkylphosphor-derivative of the formula Ia into the acetoxim-oxyalkyl-phosphor-derivative of formula Ib, it has to be treated with aceton or with a reactive derivative of aceton, such as e g diketal or 2,2-dihalopropane The reaction is carried out advantageously in an inert organic solvent and in presence of an organic base.

Preferably the acetonoxim-derivatives of formula Ib however are prepared by condensation of the hydroxyalkylphosphor-derivative of the formula II with a metal salt of acetonoxim The hydroxyalkyl- phosphor derivative is first brought into a more reactive form such as into a halide or the toluenesulfonic acid ester and then reacted with the salt of acetonoxime in an organic solvent or diluent.

- Suitable solvents which are advantageously halogenated or aromic hydrocarbons, such as hexan, cyclohexan, chloroform, ethylene/chlo- ride, benzene or toluene The reaction takes place at an elevated temperature of between 200 and 150 C, preferably at the reflux temperature of the solvent or diluant This reaction is described with more details in example 9.

The aminoalkylphosphinic-, -phosphonous and phosphonic acid derivatives of this inventions have precious biological properties.

At low application rates they have good selective-herbicidal properties which are useful for weed control in cultures of culti- vated plants, especially sugar-cane, cereal, cotton, soya, corn and rice It is also possible to control weeds, which could only be controlled with total herbicides up to now.

The mode of action of these derivatives is unusual Many of them are translocatable e g they are absorbed and transported elswhere, in the plant to develop their activity It is thus possible to damage perennial weeds by surface treatment down to their roots The new compounds of formula I are already active at very low application rates in comparison to other herbicidally and plant-growth regula- tingly active substances.

Surprisingly, it has now been found that the novel compounds of the formula I and compositions containing them are characterised in particular by their selective influence on plant metabolism This selective influence on the physiological processes of plant develop- ment makes it possible to use the compounds of formula I for different purposes, especially for those in connnection with increasing the yield of useful plants, with facilitating harvesting, and with labour-saving in measures taken in crops of cultivated plants.

Previous experience with the application of growth regulators has shown that the active ingredients can induce one or more different responses in the plants These different responses depend largely on 11 - the time of application, based on the development state of the seed or plant, as well as on the concentrations of active ingredient applied to the plants or the locus thereof Growth regulators should at all events induce positive responses in the cultivated plants in the desired manner.

Growth regulators may be used e g for inhibiting vegetative plant growth Such a growth inhibition is of economic interest, inter alia, in respect of grasses, as the frequency of cutting in flower gardens, parks, sports fields or road shoulders can thereby be reduced Of importance too is the inhibition of growth of herbaceous and ligneous plants on road shoulders and near transmission lines, or generally in areas in which strong growth is undesirable.

The use of growth regulators for inhibiting the growth in height of cereals is also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting In addition, growth regulators are able to bring about a strengthening of the stalks in crops of cereals and this too counteracts lodging.

Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area A further mechanism of yield increase using growth regulators resides in the fact that nutrients are able increasingly to promote flower formation and fruiting, whilst vegetative growth is inhibited.

Growth regulators are also frequently able to promote vegetative growth This is of great value when the vegetative parts of plants are to be harvested However, promotion of vegetative growth can also result simultaneously in promotion of generative growth, so that e g more or larger fruit is formed.

Yield increases may also often be obtained by influencing the plant metabolism without any visible changes in vegetative growth Growth regulators can also induce a change in the composition of plants, so 12 that the quality of the harvest produce is improved For example, it is possible to increase the sugar content of sugar beet, sugar cane, pineapples and citrus fruit, or to increase the protein content of soya beans or cereals.

The use of growth regulators can lead to the formation of partheno- carpic fruit The sex of blossoms can also be influenced The production or flow of secondary plant substances can also be positively influenced by growth regulators, for example the stimula- tion of the flow of latex in rubber trees.

During plant growth, the development of side-shoots can also be promoted by the chemical interruption of apical dominance using growth regulators This is of interest e g in the propagation of plant cuttings However, it is also possible to inhibit the growth of side-shoots, e g in tobacco plants after decapitation in order to prevent the formation of side-shoots and thus to promote leaf growth.

Premature fruit drop can be prevented by the use of growth regula- tors However, it is also possible to promote fruit drop -e g in fruit crops by means of chemical thinning up to a specific degree.

Growth regulators can also be used for reducing the force necessary for detaching fruit at harvesting, thus making possible mechanical harvesting of plants or facilitating manual harvesting.

With growth regulators it is also possible to speed up or delay the ripening of harvest products before or after harvesting This is particularly advantageous, because a best possible accomodation to market requirements can thereby be achieved In addition, growth regulators can often improve the colour of fruit With the aid of growth regulators is is also possible to concentrate ripening at a particular time The conditions are thus created for a complete mechanical harvesting of e g tobacco, tomatoes or coffee, or for manual harvesting, in only one single operation.

13 - The application of growth regulators can also make it possible to influence the dormancy of seeds and buds of plants, i e the endogenic annual rhythm, so that plants such as pineapples or ornamentals in nurseries germinate, sprout or blossom at a time when they would normally not tend to do so.

With growth regulators it is also possible to delay budding or the germination of seeds, e g in order to avoid damage by late frosts in areas endangered thereby Conversely, root growth and/or forma- tion of shoots can be stimulated, so that growth may be restricted to a shorter period.

Growth regulators can also impart halophilic properties to cultiva- ted plants The conditions are thus created for cultivating plants in salty soil Growth regulators can also impart to plants resi- stance to frost and drought.

Under the influence of growth regulators, the ageing (senescence) of plants or parts of plants can be inhibited or delayed Such an action can be of great economic importance, as the storability of treated parts of plants or whole plants such as fruit, berries, vegetables, salads or ornamentals can be improved or prolonged after harvesting Likewise, a substantial yield increase can be obtained by treating cultivated plants by prolonging the phase of photo- synthetic activity.

A further important field of use for growth regulators is the inhibition of excessive growth of tropical cover crops In tropical and subtropical monocultures, e g in palm tree plantations, cotton and maize fields etc, cover crops, especially species of legumino- sae, are often planted with the object of maintaining or improving the quality of the soil (prevention of desiccation, supplying nitrogen) and for preventing erosion By applying the compounds of this invention it is possible to control the growth of these cover 14 - crops and so to keep the growth in height of these plants at a low level, thus ensuring healthy growth of the cultivated plants and the maintenance of favourable soil conditions.

Surprisingly, it has also been found that, in addition to their advantageous growth regulating properties, the compounds of for- mula I and the compositions containing them also have for practical purposes a very useful microbicidal spectrum A further field of use of the compounds of formula I is therefore the control of harmful microorganisms, especially phytopathogenic fungi The compounds of formula thus have for practical purposes a very useful curative, preventive and systemic action for protecting plants, especially cultivated plants, without adversely affecting them With the compounds of formula I it is possible to inhibit or destroy the microorganisms which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms.

The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e g Ven- turia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidomycetes (e.g the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) In addition, the compounds of formula I have a systemic action They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic microorganisms which occur in the soil.

The compounds of the invention are especially well tolerated by plants.

- Accordingly, the invention also relates to microbicidal compositions and to the use of compounds of the formula I for controlling phytopathogenic microorganisms, especially harmful fungi, and for the preventive treatment of plants to protect them from attack by such microorganisms.

The invention further relates to the preparation of agrochemical compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein The invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of the formula I or the novel compositions.

Target crops to be protected within the scope of the present invention comprise e g the following species of plants:

cereals (wheat, barley, rye, oats, rice, sorghum and related crops); beet (sugar beet and fodder beet); drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sun- flowers, 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); lauraceae (avocados, cinnamon, camphor); or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites), areas of grass, embankments or general low cover crops which counteract erosion or desiccation of the soil and are useful in cultures of trees and perennials (fruit plantations, hop plantations, maize fields, vineyards etc)

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 treated, simultaneously or in succession, with further compounds.

These compounds can be both fertilisers or micronutrient donors or 16 other preparations that influence plant growth They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these composi- tions, if desired together with further carriers, surfactants 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, sol- vents, dispersants, wetting agents, tackifiers, binders or ferti- lisers.

A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is foliar application The number of applications and the rate of application depend on the intensity of infestation by the corresponding pathogen (type of fungus) or on the manner in which growth is influenced However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e g in granular form (soil application) The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or by coating them with a solid formulation In special cases, further types of application are also possible, e g selective treatment of the plant stems or buds.

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 polymer substances As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and 17 - the prevailing circumstances Advantageous rates of application are normally from 10 g to 5 kg of active ingredient (a i) per hectare, preferably from 100 g to 2 kg a i /ha, most preferably from 200 g to 600 g a i /ha.

The formulations, i e the compositions containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in know manner, e g by homo- geneously mixing and/or grinding the active ingredients with extenders, e g solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, 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 monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrro- lidone, dimethylsulfoxide or dimethylformamide, as well as epoxi- dised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e g for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers Suitable granulated adsorp- tive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g especially dolomite or pulverised plant residues Phospholipids are particularly preferred.

18 - Depending on the nature of the 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 The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-C 22), e g the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e g from coconut oil ortallow oil Mention may also be made of fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimid- azole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or sub- stituted ammonium salts and contain a CB-C 22-alkyl radical which also includes the alkyl moiety of acyl radicals, e g the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.

These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts The sulfo- nated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.

Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product Also suitable are corresponding phosphates, e.g salts of the phosphoric acid ester of an adduct of p-nonyl- phenyl with 4 to 14 moles of ethylene oxide.

19 - Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cs-C 22-alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e g stearyl- trimethylammonium chloride or benzyldi( 2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e g in International McCutcheon's Detergents and Emulsi- fiers Annual, MC Publishing Corp Glen Rock, New Jersey, 1985, and M and J Ash, "Encyclopedia of Surfactants", Chemical Publi- shing Co, Inc New York, 1980/1981.

- The agrochemical compositions usually contain 0 1 to 99 %, prefer- ably 0,1 to 95 %, of a compound of the formula I, 1 to 99 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0 1 to 25 % 7 of a surfactant.

Preferred formulations are composed in particular of the constituents (% = percentage by weight):

following Solutions active ingredient:

solvent:

surfactants:

to 95 %, preferably 10 to 80 % to 5 %, preferably 90 to 0 % 1 to 30 %, preferably 2 to 20 % Emulsifiable concentrates active ingredient: 10 to 50 %, surfactant: 5 to 30 %, liquid carrier: 20 to 95 %, Dusts active ingredient:

solid carrier:

preferably 10 to 40 % preferably 10 to 20 % preferably 40 to 80 % 0.5 to 10 %, preferably 2 to 8 % 99.5 to 90 %, preferably 98 to 92 % Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 25 %, preferably 90 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 % Wettable powders active ingredient 5 to 90 %, preferably 10 to 80 %, most preferably 20 to 60 %, surfactant: 0 5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 90 %, preferably 30 to 70 % and 21 - Granulates active ingredient: 0 5 to 30 %, preferably 3 to 15 % solid carrier: 99 5 to 70 %, perferably 97 to 85 %.

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

The formulations can be diluted to a concentration as low as 0.001 %.

The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.

Such agrochemical compositions also constitute an object of the present invention.

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 Example 1: Preparation of (l-hydroxyeth-1-yl)-diethvlphosponate (intermediary product) CH 3, HO HL-(OC 2 Hs)2 At room temperature, 292 ml of acetaldehyde is added dropwise to a stirred solution of 658 5 ml of diethylphosphite lHPO(OC 2 Hs)l in ml of triethylamine The reaction is exothermic and the temperature rises to 70 After the addition is complete, the reaction mixture is kept for 14 hours at room temperature Then the volatile parts are removed on a rotatory evaporator and the residue is 22 - distilled off under high vacuum In this manner 683 5 g title product are obtained in the form of a colourless oil Yield 75 %, boiling point 114-116 /0,2 mbar.

NMR-Spectral data:

1 H-NMR (in CDC 13) 6: 1,35 and 1,5 (t, CH 3 9 H); 4,2 (qui, m, OCH 2, CHP, 5 H); 5,15 (s, OH, 1 H).

In analogy prepared.

Table 1 to this example the compounds listed in table 1 are HO-H (OC 2 H 5) 2 Com R 2 Boiling Yield 1 H-NMR in CDC 13 pound point % R 2 CH 3 OCH 2 PCH OH No C/mbar 1.01 H 110/0,1 85,5 1,32 4,2 3,9 (J 6) 5 15 1.02 CH 3 114-116/0,2 75 1,5 1,35 4,2 4,2 (m) 5,15 1.03 C 2 H 5 111-113/0,1 55,6 0,8-2,0 1,3 4,13 3,c 5,1 1.04 n-C 3 H 7109-112/0,06 40,9 0,7-2,0 1,3 4,15 3,8 4,93 1.05 i-C 3 H 796-102/0,06 60,9 1,43 1,33 4,23 3,37 4,8 1.06 n-C 4 Hg 112-115/0,06 67,4 0,7-2,3 1,4 4,2 3,9 5,0 1.07 Benzyl 135/0,15 60,6 7,3 + 3,1 1,3 4,15 4,0 4,6 1.08 CH 3 SC 2 H 4115/0,2 70,6 2,1 (SCH 3) 1,44,2 4,2 4,9 2,0 (SCH 2) 2,7 (CH 3) Example 2: Preparation of ( 1-phthalimido-N-oxveth-l-yl)-diethyl- phosphonate (intermediary product) V l II >-OCH P(OC 2 Hs)2 %/.

23 - 32.32 g ( 0 2 mol) of Azodicarbonic acid diethyl ester are added dropwise, at a temperature of 0 to 5 to a mixture of 36 34 g ( 0.2 mol) of 1-hydroxyeth-1-yl-diethyl phosphonate (example 1), 32.63 g ( 0 2 mol) of N-hydroxyphthalimide and 52 46 g ( 0 2 mol) of triphenylphosphin l(C 6 Hs)3 Pl in 400 ml tetrahydrofuran The reaction is exothermic and a clear solution forms After the addition is complete, the solution is kept for 14 hours at room temperature, then the volatile parts are removed in a rotatory evaporator The residue is taken up in 200 ml of diethyl ether and stirred for one hour, filtered and the filtrate is again concentrated The residue is subjected to a molecular destillation Thus 80 6 g of title product are obtained as yellow oil with a boiling point of /0 08 mbar The yield is 100 %.

NMR-spectra:

1 H-NMR (in CDC 13) 6: 1,3 und 1,6 (t und d, CH 3 9 H); 4,15 q(qui, OCH 2) und 4,7 ( 2 qu, OCH)( 5 H); 7,3-7,8 (m, C 6 H 4 4 H).

In analogy to this example the compounds listed in table 2 are prepared.

I 11) H (OC 2 Hs) 2 %./ 24 - Table 2

Corm R 2 Boiling Yield 1 H-NMR in CDC 13 pouni point % R 2 CH 3 OCH 2 PCH C 6 H 4 C/mbar 2.01 H chromatogra- phed 1) 70,2 1,4 4,3 4,57 (J 9) 7,4-8,0 2.02 CH 3 175/0 08 100 1,6 1,3 4,15 4,7 7,3-7,8 2.03 C 2 H 5 175/0,06 69,6 1-2,3 1,3 4,17 4,7 7,3-8,0 2.04 n-C 3 H 7 1 crude 0,8-2,2 1,3 4,2 4,7 7,5-7,8 2.05 i-C 3 H 7 further 2.06 n-C 4 H 9 J processed 2.07 Benzyl 180/0,1 56,3 7,4 + 3,33 1,33 4,25,1 7-7,5 1) Lit b p 80-85 GB-A 2 071 664 E R Squibb + Sons Inc.

Example 3: Preparation of ( 1-amino-oxy-eth-l-vl)-diethvlphosphonate (intermediary product) H 3 H 2 N-O-8 H (OC 2 H 5)2 8,94 g ( 0 18 mol) of hydrazine hydrate are added dropwise while stirring to an ice-cold solution of 40 3 g ( 0 1 mol) ( 1-phthalimidoN-oxyeth-l-yl)-diethylphosphonate in 150 ml of methylene chloride.

The reaction is exothermic and a thick suspension forms After the addition is complete, the suspension is stirred for one hour at 0 to 5 and then filtered The filtrate is dried over sodium sulfate and evaporated The residue is 27 8 g of a red oil which is purified by molecular distillation The main fraction 11 8 g distills at /0 06 mbar It is distilled again to yield 9 1 g ( 46 1 %) of pure title product in the form of a clear oil which distills at 77-80 /0 02 mbar.

NMR-spectral data:

1 H-NMR (in CDC 13) 5: 1,35 und 1,5 (t und d, CH 3 9 H); 4,2 (qui, OCH 2, OCH, 5 H); 5 9 (s, NH 2, 2 H).

- In analogy to this example the compounds listed in tables 3 and 4 are prepared.

T 2 a H 2 N-O H ( O C 2 H 5)2 Table 3

Rz Boiling 1 H-NMR in CDC 13 Com point Yield R 2 CH 3 OCH 2 OCH 2 P NH 2 pound C/mbar % (OCHR) 3.01 H 130/0,41) 71 1,35 4,18 4,07 (J 6) 5,93 3.02 CH 3 77-80/0,02 46,1 1,5 1,35 4,2 5,9 3.03 C 2 H 5 86-90/0,04 61,3 1-1,8 1,3 4,2 3,8 5,9 3.04 n-C 3 H 7110/0,06 32,6 0,7 -2,0 1,35 4,2 3,8 5,7 3.05 i-C 3 H 7 3.06 n-C 4 Hg100/0,06 7,3 0,5 -2,0 1,3 4,17 3,8 5,8 3.07 Benzyl 150/0,06 12,4 7,27 + 3,03 1,3 4,17 5,57 1) Lit bp 150 /0,003 mbar GB-A 2 071 664 Analysis:

Compound No C H N P 3.01 3.02 3.03 3.07 Cs H 4 i NO 4 P M.G 183 14 C 6 H 16 NO 4 P M.G 197 17 C 7 H 18 N 04 P M.G 211 2 C 12 H 20 NO 4 P M.G 273 27 cal.

fnd.

cal.

fnd.

cal.

fnd.

cal.

fnd.

32,80 % 32,4 % 36,55 % 37, % 39,81 % 40,9 % 52,75 % 52,0 % 7,11 % 7,6 % 8,18 % 8,1 % 8,39 % 8,6 % 7,38 % 7,3 % 7,65 % 8,0 % 7,10 % 6,1 % 6,63 % 4,8 % 5,13 % 6,2 % 16,92 % 15,6 % 15,71 % 15,2 % 14,67 % 14,5 % 11,34 % 10,3 % 26 - Table 4 2

H 2 N-O-1 Hh R 1 Com R R R 2 Boiling point pound R Cmbar 4.01 O C 2 H 5 C 2 H 5 CH(CH 3)2 Oel 4.02 O C 2 H 5 C 2 H 5 Phenylethyl 132/0,04 4.03 O C 2 H 5 C 2 H 5 C 2 H 4 SCH 3 120/0,02 4.04 CH(OC 2 Hs)2 C 2 Hs C 2 Hs 120/0,1 4.05 CH(OC 2 Hs)2 C 2 H 5 C 3 H 7-n 130/0,1 4.06 CH(OC 2 Hs)2 C 2 H 5 C 2 H 4 SC Hs 108/0,1 4.07 CH(O Cz Hs)2 C 2 Hs H 120-125/0,05 4.08 CH(OC 2 Hs)2 C 2 H 5 Benzyl Oel 4.09 C 2 H 5 CH(CH 3)2 H 115-112/0,02 4.10 C 2 Hs CH(CH 3)2 C 2 H 5 120-125/0,08 Example 4: Preparation of 1-Amino-oxveth-l-yl phosphonic acid H 3 H PN 04 G-H_(OH)2 A mixture of 5 92 g ( 0 03 mol) of ( 1-Amino-oxyeth-1-yl)diethyl- phosphonate (example 3) in 50 ml of 20 % aqueous hydrochloric acid is heated under reflux for four hours Then the reaction mixture is concentrated and the resinous residue is taken up in methanol and brought to boiling A solution forms, which cristallizes upon cooling The precipitate is filtered off, dried and gives 3 7 g ( 73 3 %) of title product in the form of white cristals which melt at 187-189 under decomposition.

NMR spectral data:

1 H-NMR (in D 20): 1,7 ( 2 d, JPCHO, 14 Hz, CH 3 3 H); 4,55 ( 2 qu, JPCH, 8 Hz, CH, 1 H); (s, OH, NH 2, 4 H).

In analogy to this example the compounds listed in table 5 are prepared.

27 - H 2 N -4-XH OH)2 Table 5

R 2 Melting point Yield IH-NMR in Dz O/DC 1 Com C % R CH 2 P OH, NH 2 pound 5.01 H 189-190 dec 1) 75,6 4,7 (J 10) 5,6 5.02 CH 3 187-189 dec 73,3 1,4 (J 14) 4,55 (J 8)5,2 5.03 C 2 H 5184-185 dec 51,6 1,23-2,0 4,45 (m) 5,47 5.04 n-C 3 H 7 5.05 i-C 3 H 7 5.06 n-C 4 Hg 1 H-NMR in Na OD 5.07 I Benzyl I| 72-176 dec | 67,7 7,2 12,5-3,3 | 4,9 1) Lit m p 161-163 C (dec) GB-A 2 071 664 Analysis:

Compound No C H 5.01 C H 6 NO 4 P cal.

M.G 127 4 fnd.

aequivalent wgt cal.

5.02 C 2 H 8 NO 4 P fnd.

M.G 141 06 cal.

aequivalent wgt fnd.

5.03 C 3 Hlo N 04 P cal.

M.G 155 09 fnd.

aequivalent wgt cal.

5.07 Cg H 16 NO 4 P fnd.

M.G 217 16 cal.

9,46 % 9,8 % p K 1 17,03 % 17,0 % p K 1 23,23 % 23,0 % 158 p Kj 44,25 % 43,9 % 4,76 % 4,8 % = 4,29 5,72 % 5,7 % = 4,52 6,5 % 6,4 % = 4,62 5,57 % 5,7 % 11,93 % 24,38 % 10,6 % 23,8 % p K 2 = 6,86 9,93 % 21,96 % 9,6 % 21,8 % p K 2 = 7,28 9,04 % 19,97 % 8,9 % 20,0 % p K 2 = 7,42 6,45 % 14,25 % 6,5 % 14,2 % aequivalent wgt fnd 217 N p 28 - Example 5: Preparation of amino-oxvmethyl-methvlphosphinic acid and n-propvlester (a) Starting from methylphosphonous-n-propyl ester and formaldehyde, 1-hydroxymethyl-phosphinic acid-isopropyl ester is prepared according to the reaction scheme O=CH 2 + H OC 3 H 7-n HOCH 2 OC 3 H 7-n H 3 H 3 boiling point 100 /0 1 mbar yield 62,1 % NMR spectral data:

IH-NMR (CDC 13) 6: 0,9-1,6 (m, C 2 Hs); 1,5 ( 6, JPCH 16) 8 H; 3,85 (m, OCH 2, 4 H); 5,5 (s, OH, 1 H).

(b) Condensation of this ester with N-hydroxyphthalimide in the presence of triphenylphosphine und azodicarbonic acid-diethyl- ester according to the method of example 2 gives phthalimido-N- oxymethvl-methylphosphinic acid-n-propyl ester of the formula:

I II -OCH 2 O C 3 H 7-n oil / \ C>H 3 IH-NMR (CDC 13) 6: 0,8-2,0 (m, C 2 Hs); 1,8 (S,J 15 Hz) 8 H; 4-4,9 (m, OCH 2, 4 H); 7,4-8,0 (m, C 6 H 4, 4 H).

(c) By treating this product with hydrazine according to example 3 amino-oxymethyl-methylphosphinic acid-n-propyl ester of the formula 4.11 H 2 N-O-CH 2 C 3 H 7-n b p 123 /0 02 mb C Hz yield 80,2 %, is obtained.

29 - IH-NMR (in CDC 13) 6: 0,8-2,0 (m, C 2 Hs); 1,37 ( 6,J 16) 8 H; 3,85 (m, OCH 2, 4 H); NH 2 5,77 (s, 2 H).

(d) Saponification of this ester in 6 N HC 1 gives amino-oxymethylmethylphosphinic acid of the formula 4.12 H 2 N-OCH 2OH m p 166-167 H 3 Yield 68 % 1 H-NMR (D 20) 6: 1,3 (d,Jp CH 14, 3 H); 4,1 (d,J, 8 Hz, 2 H); 4,97 (s, NH 2, OH, 3 H).

Example 6: Preparation of 1-amino-oxveth-1-yl-diethoxvmethvlphos- phinic acid and ethylester (a) Diethoxymethylphosphonous acid ethyl ester is prepared by condensing hypophosphorous acid H 2 PO-OH and diethylformiate HC(OC 2 Hs)2 in chloroform in presence of a catalytic amount of paratoluenesulfonic acid according to the method of M J Gallag- her and H Honegger in Australian J Chem 33 p 283 to 294 ( 1980) This product is then treated with acetaldehyde according to example 1 to yield diethoxvmethyl-hydroxy-eth-1-yl-phosphinic acid-ethyl ester of the formula HO-H Cz H 5 b p 125-130 /0,06 mbar CH(OC 2 Hs)2 Yield 71,5 % 1 H-NMR (in CDC 13) 6: 1,25 und 1,3 (m, CH 3, 12 H); 3,7 (m, OCH 2); 4,2 (qui, POCH 2); 4,67 (s, OH); 4,87 (d,J, 9 Hz PCH) ( 9 H).

(b) Reaction of this compound with N-hydroxyphthalimide in presence of triphenylphosphine and azodicarbonic acid-diethyl ester according to example 2 yields diethoxymethyl-( 1-phthalimido-oxy- eth-l-yl)-phosphinic acid-ethyl ester of the formula - if N X-0 CH-?-V-OC 2 H 5 / k / CH(OC 2 Hs)2 1 H-NMR (in CDC 13) 6: 1,2, 1,3, 1,7 (m, CH 3, 12 H); 3,8 (m, OCH 2); 4,1 (qui, POCH 2); 4,5 (m, NOCH); 5,2 (d JPCH 10, PCH)( 8 H); 7,3-7,7 (m, C 6 H 6, 4 H).

(c) By reacting this phthalimide with hydrazine according to example 2 ( 1-amino oxyeth-l-yl)-diethoxymethvl-phosphinic acid-ethyl ester of the formula 4.13 NOH 3 H 2 N-OVH OC 2 H 5 is obtained b p 125 /0,03 mbar t H(OC 2 Hs)2 Yield 66,7 % 1 H-NMR (in CDC 13) 6: 1,3, 1,5 (m, CH 3, 12 H); 3,8 (m, OCH 2, OCH); 4,3 (qui, POCH 2); 4,87 (d, J 9 PCH)( 8 H); 5,8 (s, NH 2, 2 H).

(d) Saponification of this ester in 6 N aqueous hydrochloric acid gives the free (l-amino-oxyeth-1-yl)-phosphonous acid of the formula H 3 H 2 N-0 Z-Ht OH Example 7: Preparation of amino-oxymethyl-diethoxymethyl-phosphinic acid and ethyl ester (a) By condensing according to example 1 diethoxymethyl-phosphonous acid-ethyl ester (which is prepared according to Australian J.

Chem 33 ( 198) p 287-294) with formaldehyde diethoxvmethvlhydroxvmethyl-phosphinic acid ethyl ester is prepared which corresponds to the formula 31 - HOCH 2 -OC 2 H 5 oil.

CH(OC 2 Hs)2 1 H-NMR (in CDC 13) d: 1,2, 1,3 (m, CH 3, 9 H); 3,7 (m, OCH 2); 3,93 (d, J 4, OC Hz P); 4,2 (qui, CH 2 OP)( 8 H); 4,87 (d,J 8, PCH, 1 H); 5,07 (s, OH, 1 H).

(b) This ester is condensed with N-hydroxylphthalimide according to example 2 in the presence of triphenylphosphine und azodicar- bonic acid-diethylester, to give diethoxymethyl-phthalimido-Noxymethyl-phosphinic acid-ethyl ester of the formula / j Ij >-OCH 2 C 2 H 5 \./ \ H(OC 2 Hs)2 (c) This phthalimide is reacted with hydrazine according to example 3 to give amino-oxvmethvl-diethoxvmethylphosphinic acid ethyl ester of the formula H 2 N-OCH 2 z C 2 H 5 b p 120-125 /0,03 mbar H(OC 2 Hs)2 1 H-NMR (in CDC 13) d: 1,6 (m, CH 3, 9 H); 3,6 (m, OCH 2); 4,0 (qui, POCH 2, OCH 2 P) 8 H; 4,7 (d,J 8, CHP, 1 H); 5,7 (s, NH 2 2 H).

(d) Saponification of this ester with 6 N aqueous hydrochloric acid gives the free amino-oxymethyl-phosphonous acid of the formula H 2 N-OCH 2 H 32 - Example 8: Preparation of diethoxymethyl-l-hydroxy-2-phenyleth1-yl-phosphinic acid-ethyl ester (intermediate product) By condensation of diethoxymethylphosphonous acid-ethyl ester (prepared according to Australian J Chem 33 ( 1980) p 287-294) and phenylacetaldehyde, is obtained diethoxymethyl-l-hydroxy-2-phenyl- eth-1-yl-phosphinic acid ethyl ester of the formula .- (H b p 150 /0,08 mbar g \\-CH 2 H-'-OC 2 Hs m p 45-46 C \='/ CH(Oc 2 H 5)2 Yield 79,4 % 1 H-NMR (in CDC 13) d: 1,23 (m, CH 3, 9 H); 2,7-2,9 (m, CH 2); 3,7 (m, OCH 2); 4,17 (m, POCH 2, PCHOH); 4,3 (s, OH)( 1 OH); 4,93 (d, PCH, J 9, 1 H); 7,23 (m, C 6 Hs, 5 H).

Example 9: Preparation of the acetonoximeethers of hvdroxvmethvlphosphonous acid-diethvl ester s \-SO 2-OCH 2 (OC 2 Hs)2 +K-ON=C(CH 2)2 (CH 3)2 C=N-OCH 2 (OC 2 H)2 CH) ( A mixture of 16,12 g ( 0,05 mol) of diethyl-p-tosyloxymethylphos- phonate and 5,6 g ( 0,05 mol) potassium salt of acetonoxim in 200 ml of tetrahydrofuran is stirred ad reflux temperature for 14 hours.

Then 100 ml of water are added thereto, the aqueous phase decanted and extracted 3 times with methylene chloride The organic phases are dried, concentrated and the residue is distilled in a bulb-tube.

Thus 4,8 g of acetonoxim-O-methyl-phosphonic acid-diethyl ester are obtained which correspond to the formula 6.01 (CH 3)2 N=C-OCH 2 V( O C 2 H 5) b p 125 /0,06 mbar Yield 43 % IH-NMR (in CDC 13) 6: 1,3 (t, CH 3, 6 H); 1,85 (s, (CH 3)2 C, 6 H); 4,2 (qui, OCH 2) and 4,43 (d,J 7, H 2, CH 2 P)( 4 H).

33 - analysis found C 43,03 % H 8,13 % N 6,28 % P 13,98 % C 8 H 18 NO 4 P m w 223 21 calc C 43,3 % H 8,2 % N 6,1 % P 13,5 % In analogy to example 9 the compounds of examples 10 to 12 are prepared.

Example 10: Acetonoxim-l-0-eth-1-yl-phosphonic acid-diethyl ester 6.02 (CH 3)2 C=N-OH (OC 2 H 5)2 P 72-77 o/0,04 mbar Yield 31,2 % IH-NMR (in CD C 13) 5: 1,3 (t, CH 3); 1,45 ( 2 d, J Pc H 11)( 9 H); 1,87 (s, C(CH 3)2, 6 H); 4,15 (qui, OCH 2); 4,4 (m, CH)( 5 H).

analysis: Cg H 20 NO 4 P calc C 47,57 % H 8,50 % N 5,91 % P 13,06 % m.w: 237 24 found C 45,2 % H 8,8 % N 5,8 % P 12,3 % Example 11: Acetonoxim-1-O-prop-1-vl-phosphonic acid-diethyl ester 6.03 (CH 3)2 C=N-0 OH ( O C 2 H 5)2 b p77-83 /0,04 mbar Yield 53,4 % H-NMR (in CD C 13) 5: 1,3 (t, CH 3), 1,0-2,0 (m, C 2 Hs)( 11 H); 1,8 (s, (CH 3)2 C, 6 H); 4,13 (qui, OCH 2); 4,3 (m, CH)( 5 H).

analysis: C 1 o H 22 NO 4 P calc C 47,80 % H 8,83 % N 5,58 % P 12,33 % m.w 251 26 found C 47,8 % H 8,7 % N 5,5 % P 12,2 % 34 - Example 12: Acetonoxim-1-0-2-phenvleth-l-yl-phosphonic acid-diethvl ester 6.04 (CH 3)2 C=N-OHJ(OC 2 Hs)2 b p 120-145 /0,06 mbar /: H 2 Yield 68,6 % 1 H-NMR (in CD C 13) in agreement with the expected structure.

Example 13: Preparation of acetonoxim-oxvmethylphosphonic acid 6.05 (CH 3)z C=N-OCH 2-(OH)2 2,77 ml Trimethylbromsilan (CH 3)3 Si Br is added to a solution of 2,23 g of acetonoxim-oxymethylphosphonic acid diethyl ester (example 9) in 5 ml of chloroform and stirred for 2 hours at room temperature The reaction mixture is then evaporated and the residue is distilled in a bulb tube The disilyl ester passes at /0,06 mb in 73,3 % yield The distillate is taken up in 15 ml of methanol and boiled until a clear solution is obtained After evaporation of the methanol acetonoxim-oxymethyl phosphonic acid is obtained as a clear resin Yield 65,9 % 1 H-NMR (in CD 3 OH/D 20) 6: 1,63 ((CH 3)2 C, 6 H); 4,05 (d,J, 8 Hz, CH 2 P, 2 H); 4,63 (s, OH).

In analogy thereto the amino-oxy phosphonic acids of examples 14 and 15 are prepared.

- Example 14:

Acetonoxim-1-O-eth-1-yl-phosphonic acid is prepared starting from the ester of example 10.

(CH 3)2 C=N-OZH-PlO Si(CH 3)31 l 2 Yield 56,8 % (Disilylester) b p 120 /0,08 mbar 1 H-NMR (in CDC 13) 5: 0,1 (s,(CH 3)3 Si, 18 H); 1,3 ( 2 d, JCCH 17 Hz, 3 H); 1,7 (d, (CH 3)2 C; 6 H); 4,2 ( 2 qu, JPCH 10 Hz, 1 H).

6.06 yield 53,9 % (CH 3) C=N H-(OH)2 (free acid) brown resin 1 H-NMR (in CD 30 D) 5: 0,95 ( 2 d, JCC H 16 Hz, 3 H); 1,4 (s, (CH 3)2 C, 6 H); 3,9 ( 2 qu, JPCH 10 Hz, 1 H); 4,7 (s, OH).

Example 15:

Acetonoxim-l-O-prop-l-ylphosphonic acid is prepared from the ester of example 11 according to example 13.

2 H R (CH 3)z C=N-OY{H O Si(CH 3)3 12 Yield 76,6 % (disilyl ester) b p 120 /0,08 mbar IH-NMR (in CDC 13) in agreement with the expected structure 6.07 Yield 76,9 % C 2 H 5 (CH 3)2 C=N-OCH O P(OH)2 (free acid) brown resin 1 H-NMR (in CD 3 OD) 6: 0,5-1,8 (m, C 2 H 5): 1 45 (d, (CH 3)2 C)(ll H); 3,8 ( 2 qu, J,l O Hz, 1 H); 4,83 (s, OH).

36 - Formulation Examples Example 16:

Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) a) Emulsifiable concentrates a compound of formula I calcium dodecylbenzenesulfonate castor oil polyethylene glykol ether ( 36 moles of ethylene oxide) tributylphenoyl polyethylene glykol ether ( 30 moles of ethylene oxide) cyclohexanone xylene mixture Emulsions of any required concentration concentrates by dilution with water.

b) Solutions a compound of examples 4-15 ethylene glykol monomethyl ether polyethylene glykol 400 N-methyl-2-pyrrolidone epoxidised coconut oil petroleum distillate (boiling range 160-190 ) a) % % % b) % 8 % c) % 6 % 12 % 4 % % 20 % % 25 % 20 % can be produced from such a) % on a/ b) % c) d) % 95 % /U /o - % en W z U 'o - 1 % 94 % % These solutions are suitable for application in the drops form of micro- 37 - c) Granulates a compound of formula I kaolin highly dispersed silicic acid attapulgite a) b) % 10 % 94 % - 1 % - % The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently stripped off in vacuo.

d) Dusts a compound of examples 4-15 highly dispersed silicic acid talcum koalin a) b) 2 % 5 % 1 % 5 % 97 % - % Ready-for-use dusts are obtained by intimately with the active ingredient.

mixing the carriers Example 17:

Formulation examples for solid active ingredients of the formula I (throughout, percentages are by weight) a) Wettable powders a compound of examples 4-15 sodium lignosulfonate sodium lauryl sulfate sodium diisobutylnaphthalensulfonate octylphenol polyethylene glykol ether ( 7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) % % b) % % c) % 3 % 5 % 6 % 10 % 2 % - % 10 % 10 % 62 % 27 % - 38 - 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 the desired concentration.

b) Emulsifiable concentrate a compound of formula I 10 % octylphenol polyethylene glykol ether 3 % ( 4-5 moles of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether 4 % ( 36 moles of ethylene oxide) cyclohexanone 30 % xylene mixture 50 % Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

c) Dusts a) b) a compound of examples 4-15 5 % 8 % talcum 95 % - kaolin 92 % Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.

d) Extruder granulate a compound of formula I 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 % The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water The mixture is extruded and then dried in a stream of air.

39 - e) Coated granulate a compound of formula I 3 % polyethylene glykol 200 3 % kaolin 94 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol Non-dusty coated granulates are obtained in this manner.

f) Suspensions-Konzentrat a compound of formula I 40 % ethylene glykol 10 % nonylphenol polyethylene glykol 6 % ( 15 moles of ethylene oxide) sodium lignosulfate 10 % carboxymethylcellulose 1 % 37 % aqueous formaldehyde solution 0,2 % silicone oil in the form of a 75 % 0,8 % aqueous emulsion water 32 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples Example 18: Action against Puccinia graminis on wheat a) Residual-protective action Wheat plants are treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the test compound ( 0.06 %) After 24 hours the treated plants are infected with a uredospore suspension of the fungus The infected plants are incubated for 48 hours at 95-100 % relative humidity and about 20 %C and then stood in a greenhouse at about 22 C Evaluation of rust pustule development is made 12 days after infection.

b) Systemic action Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the test compound ( 0.006 %, based on the volume of the soil) After 48 hours the treated plants are infected with a uredospore suspension of the fungus The plants are then incubated for 48 hours at 95-100 % relative humidity and about 20 %C and then stood in a greenhouse at about 220 C Evaluation of rust pustule development is made 12 days after infection Compounds of Table 1 are effective against Puccinia fungi Puccinia attack is 100 % on untreated and infected control plants Compounds of examples 4 to 15 inhibit Puccinia attack to 0-5 %.

Example 19: Action against Cercospora arachidicola in groundnut plants a) Residual protective action Groundnut plants 10-15 cm in height are sprayed with a spray mixture ( 0.02 %) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus The infected plants are incubated for 72 hours at about 21 %C and high humidity and then stood in a greenhouse until the typical leaf specks occur Evaluation of the fungicidal action is made 12 days after infection and is based on the number and size of the specks.

b) Systemic action Groundnut plants 10-15 cm in height are treated with a spray mixture ( 0.06 %) based on the volume of the soil prepared from the test compound formulated as wettable powder The treated plants are infected 48 hours later with a conidia suspension of the fungus and incubated for 72 hours at about 2100 and high humidity The infected plants are then stood in a greenhouse and evaluation of infestation is made after 11 days.

41 - Compared with untreated and infected controls (number and size of the specks = 100 %), Cercospora attack on groundnut plants treated with compounds of Table 1 is greatly reduced Many compounds inhibit the occurrence of specks in the above tests almost completely ( 0-10 %).

Example 20: Action against Erysiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture ( 0.02 %) prepared from the test compound formulated as a wettable powder The treated plants are dusted with conidia of the fungus after 3-4 hours The infected barley plants are then stood in a greenhouse at about 220 C The extent of the infestation is evaluated after 10 days. b) Systemic action Barley plants about 8 cm in height are treated with a

spray mixture ( 0.006 %) based on the volume of the soil prepared from the test compound formulated as wettable powder Care is taken that the spray mixture does not come in contact with the parts of the plants above the soil The treated plants are infected 48 hours later with a conidia suspension of the fungus The infected barley plants are then stood in a greenhouse at about 22 %C and evaluation of infesta- tion is made after 10 days.

Compounds of the formula I are very effective against Erysiphe fungi Erysiphe attack is 100 % on untreated and infected control plants Among other compounds of examples 4 to 15 inhibit fungus attack on barley to 0-5 %.

42 - Example 21: Residual-protective action against Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture ( 0 06 %) prepared from a wettable powder formulation of the active ingredient The plants are infected 24 hours later with a conidia suspension of the fungus The plants are then incubated for 5 days at 90-100 % relative humidity and stood in a greenhouse for a further 10 days at 20 '-240 C Scab infestation is evaluated 15 days after infection Most compounds inhibit attack to less than 10 % Venturia attack on untreated and infected shoots is %.

Example 22: Action against Botrytis cinerea on beans Residual protective action Bean plants about 10 cm in height are sprayed with a spray mixture ( 0.02 %) prepared from the test compound formulated as wettable powder 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 % relative humidity and 21 'C, and evaluation of the fungus attack is then made Many compounds very strongly inhibit fungus attack At a concentration of 0 02 % compounds of examples 4 to 15 and others are fully effective (attack 0 to 5 %) Botrytis attack on untreated and infected bean plants is 100 % Example 23: Growth inhibition of cereals Summer barley (Hordeum vulgare) and summer rye (Secale) are sown in sterilised soil in plastic beakers in a greenhouse and watered as required The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I The concentration corresponds to 4 and 2 5 kg respectively of active ingredient per hectare Evaluation of the growth of the cereals is made 10 and 21 days after application A comparison with untreated controls shows that the growth of cereal plants treated with compounds of the formula I is substantially reduced.

43 - Example 24: Growth inhibition of grasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Cynodon dactylon are sown in plastic dishes filled with an earth/peat/sand mixture ( 6:3:1), in a greenhouse, and watered as.

required The emergent grasses are cut back weekly to a height of about 4 cm and, about 50 days after sowing and 1 day after the last cut, are sprayed with an aqueous spray mixture of a compound of the formula I The concentration of test compounds correspond to a rate of application of 0 5 and 2 5 kg per hectare respectively The average growth of the grasses is evaluated 10 to 21 days after application The evaluation shows that the compounds of examples 4 to 15 effect a marked reduction in growth.

Example 25: Increase in yield of soybeans Soybeans of the "Hark" variety are sown in plastic containers in an earth/peat/sand mixture ( 6:3:1) The containers are put into a climatic chamber and the plants develop to the 5-6 trefoil leaf stage after about 5 weeks by optimum control of temperature, light, fertiliser addition, and watering The plants are then sprayed with an aqueous mixture of a compound of the formula I until thoroughly wetted The rate of application corresponds to 3 kg a i per hectare Evaluation is made about 5 weeks after application.

Compared with untreated controls, the compounds of table increased the number and weight of the harvested siliques up to 15 %.

Example 26: Growth inhibition of cover crops Test plants of the varieties Psophocarpus palustris and Centrosema pubescens are reared from cuttings in plastic pots filled with an earth/turf/sand mixture ( 1:1:1) After they have grown roots, the plants are transplanted into 9 cm pots and watered as required For further growth the plants are then kept in a greenhouse at a day temperature of 27 %C and a night temperature of 210 C The average light exposure is 14 hours ( 6000 lux) and the humidity is 70 % The plants are cut back to a height of about 15 cm and sprayed 7 days later with a spray mixture of the test compound (corresponding to a rate of application of I and 3 kg/a i /ha respectively) Four weeks 44 - after application the growth of the plants is compared with that of untreated control plants which have been cut back It is found that compounds of Tables 4, 5 and 6 effect a marked growth inhibition of the cover plants.

Example 27: Inhibition of senescence in cereal plants Summer wheat of the "Svenno" variety is sown in pots with compost soil and reared without special climatic conditions About 10 days after emergence, 10 to 12 cm primary leaves are cut off and put individually into the test tubes containing 20 ml of suspension of test compound ( 1 25 to 10 ppm) The test tubes are kept in a climatic room at 23 %C and 70 % relative humidity and irradiated daily for an average of 14 hours ( 10 000 lux) Evaluation of senescence is made 7 days later by comparing the degree of yellowing with still fresh, green leaves This test shows that compounds of examples 4 to 15 markedly inhibit the senescence of the test plants.

They inhibited yellowing of the leaves by more than 80 % during the test period.

Example 28: Inhibition of the growth of solanum and avena Solanum (tomato) and avena (oats) are sown in plastic containers in a 6:3:1 mixture of earth/peat/sand The containers are put into a greenhouse and watered as required Fifteen days after sowing, the plants are sprayed wet with an aqueous spray mixture of a compound of the formula I The rate of application corresponds to 1 to 1 5 kg a.i /ha Evaluation of the growth of the plants is made 7 and 14 days after application and compared with that of not treated plants 100 % The plants are also controlled for symptoms like necrosis, chlorosis of leaf deformation It is observed that the tested compounds substantially inhibit growth without showing phytotoxic symptoms.

Example 29: Advancement of Germination In order to advance the germination of seeds, emulsions of the test substance are sprayed onto the seeds of cotton and corn, so that application rates of 45 to 500 mg per kg of seed is obtained The - seeds are then planted into regular garden earth and the plants are raised in climatic rooms under controlled subtropic temperature conditions After 30 days the shoots are cut at earth-level and the length and fresh-weight is determined The result is expressed in %, % corresponding to the height and weight of shoots of untreated control plants The height of the shoots of corn, whose seed was treated with compounds 4 02, 4 03 and 13 is between 113 and 120 % and the weight between 113 and 118 % of that of untreated corn For the cotton shoots only the length was controlled and was between 103 and 115 % of that of untreated cotton shoots.

Example 30: Growth of roots ( 30-dav-test) Seed of different culture plants are treated with an aqueous emulsion of the substance to be tested so that 45 to 500 mg per kg seed is applied The seed is then sown into boxes filled with garden earth and the boxes are put into climatised rooms under controlled condition, so that the seed can germinate In other tests, the boxes are seeded with untreated seeds and then the test substance is applied at a rate that corresponds to 0 1 to 1 kg/ha In still another modification, the test substance is applied post-emergently onto untreated seed, two weeks after sowing The test is evaluated days after the treatment The shoots are dug out and carefully wasted free from adhering earth The weight and the length of the shoots is determined and compared with that of untreated control plants Tests, which were done with compounds of table 4 showed, that the weight of wheat, corn, soja and cotton shoots was 105 to 123 % of that of untreated controls, the length of the roots varied between 103 and 113 %.

46 -

Claims (26)

Claims:

1 An amino oxyalkyl-phosphonous-, phosphonic or phosphinic-acid derivative of the formula I g 2 A-O-IH OR (I wherein A is an amino group -NH 2 or the acetoxime rest -N=C(CH 3)2, R is hydrogen, Cl-C 6-alkyl, which is unsubstituted or mono or disubstituted by Cl-C 6-alkoxy or R is hydroxyl C 1-C 6-alkoxy a rest -O Me or -ON(R)4, R 1 is hydrogen, C 1-C 6-alkyl, a metal cation-Me or an ammonium or substituted ammonio-rest -N(R 4) and R 2 is hydrogen, C 1-C 6-alkyl, phenyl, benzyl or an aryl rest which is unsubstituted or mono or polysubstituted by halogen, C 1-C 4- alkyl, Cl-C 4-haloalkyl, Cl-C 4-alkoxy, C 1-C 4-haloalkoxy, nitro, cyano, carboxyl, C 1-C 4-alkoxycarbonyl, amino, CI-C 4-alkylamino, carbamoyl or acetyl.

RI is hydrogen, Cl-C 6 alkyl, C 1-C 6 hydroxyalkyl, C 2-C 6 alkoxyalkyl or benzyl.

2 Amino oxyalkyl phosphonous-, phosphonic or phosphinic-acid derivative of the formula Ia g 2 H 2 N-c 4 H#OR (Ia) wherein R, RI and R 2 have the meaning given in claim 1.

3 Amino oxyalkyl phosphonous-, phosphonic or phosphinic-acid derivative of the formula Ib (CH)2 C=NR 2 (Ib) (CH 3)2 C=NO-CH RI (Ib) 47 - wherein R, R 1 and R 2 have the meaning given in claim 1.

4 Amino oxyalkyl phosphonic-acid derivatives of the formula Ic H 2 N-O-H% OR 1 lis (Ic) wherein R' is hydrogen, Ca-C 6-alkyl, a metal cation Me or an ammonium cation N(R 4)e, R 1 is hydrogen, C 1-C 6-alkyl, a metal cation Me or an ammonium cation N(R 4), R 2 is hydrogen, C 1-C 6-alkyl, phenyl, benzyl or an aryl rest which is unsubstituted or substituted by halogen, Cl-C 4-alkyl, C 1-C 4-halo- alkyl, Cl-C 4-alkoxy, Cx-C 4-haloalkoxy, nitro, cyano, carboxyl, Cl-C 4-alkoxycarbonyl, amino, Cl-C 4-alkylamino, carbamoyl or acetyl and R 4 has the meaning given in claim 1.

An amino-oxyalkyl-phosphonic acid derivative according to claim 4 selected from among (amino-l-oxyeth-l-yl)-diethyl-phosphonate, (amino-oxymethyl)-diethyl-phosphonate, (amino-l-oxyprop-l-yl)-diethyl-phosphonate, (amino-l-oxybut-l-yl)diethyl-phosphonate and (amino-l-oxy-2-phenyleth-1-yl)-diethyl-phosphonate.

6 Acetoxim-oxyalkyl-phosphonic acid derivatives of the formula Id (CH 3)2 C=N-O g OR 1 R-' (Id) wherein R', R 1 and R 2 have the meaning given in claim 4.

48 -

7 Acetoxim oxyalkyl-phosphonic acid derivatives according to claim 6 selected from among acetonoxim-oxymethyl-diethyl-phosphonate, acetonoxim-1-oxyeth-1-yl-diethyl-phosphonate, acetonoxim-l-oxyprop-l-yl-diethyl-phosphonate, acetonoxim-l-oxy-2-phenyleth-1-yl-diethyl-phosphonate, acetonoxim-oxymethyl-phosphonic acid, acetonoxim-1-oxyeth-1-yl-phosphonic acid, acetonoxim-l-oxyprop-l-yl-phosphonic acid.

8 Aminooxyalkyl-phosphonous and -phosphinic acid derivatives of the formula Id + 2 9 Id H 2 N-O-H R 1 (Id) wherein R" is hydrogen or Cl-C 6-alkyl, which is unsubstituted or once or twice substituted by C 1-C 6-alkoxy, R 1 is hydrogen, Cl-C 6-alkyl, a metal cation Me, or an ammonium cation -N(R)4, R 2 is hydrogen, Cl-C 6-alkyl, phenyl, benzyl or an aryl rest which is unsubstituted or substituted by halogen, Cl-C 6-alkyl, Cl-C 6-halo- alkyl, Cl-C 6-alkoxy, Cl-C 6-haloalkoxy, nitro, cyano, carboxyl, C 1-C 4-alkoxy carbonyl, amino, C 1-C 4-alkylamino, carbamoyl or acetyl and R 4 has the meaning given in claim 1.

9 An aminooxyalkyl-phosphonous or -phosphinic acid ester according to claim 8 selected from among amino-oxymethyl-o-n-propyl methylphosphinate, amino-oxymethyl methylphosphinic acid, amino-l-oxyeth-l-yl-o-ethyl diethoxymethylphosphinate, amino-l-oxyeth-l-yl-diethoxymethylphosphinic acid, amino-oxymethyl-o-ethyl-diethoxymethylphosphinate, amino-oxymethyl-diethoxymethylphosphinic acid, amino-oxymethyl-phosphonous acid.

49 - Acetoxim oxyalkyl-phosphonous and -phosphinic acid derivatives of the formula Ie (CH 3)2 C=N-06 H-t-ORI (Ie) wherein R", Rl and R 2 have the meaning given in claim 8.

11 Process for the production of an amino oxyalkyl-phosphonous, -phosphinic or -phosphonic acid derivative of the formula I g 2 A-09 H O Ri (I) wherein A is an amino group -NH 2 or the acetoxime rest -N=C(CH 3)2, R is hydrogen, Cl-C 6-alkyl, which is unsubstituted or substituted once or twice by Cl-C 6-alkoxy, hydroxyl C 1-C 6-alkoxy or -O Me or -ON(R 4), R 1 is hydrogen, C 1-C 6-alkyl, a metal cation Mee or an ammonium or cation -N(R 4)4 R 2 is hydrogen, C 1-C 6-alkyl, phenyl, benzyl or an aryl rest which is unsubstituted or substituted by halogen, C 1-C 6-alkyl, C 1-C 6-halo- alkyl, Cl-C 6-alkoxy, Cl-C 6-haloalkoxy, nitro, cyano, carboxyl, Cl-C 4-alkoxycarbonyl, amino, Cl-C 4-alkylamino, carbamoyl or acetyl.

R 4 is hydrogen, CI-C 6 alkyl, Cl-C 6 hydroxyalkyl, C 2-C 6 alkoxyalkyl or benzyl, which is characterized by condensing a hydroxyalkylphosphor deriva- tive of the formula II 182 HOCH RI (II) - wherein R, R 1 and R 2 have the above-given meaning, in an inert organic solvent, in the presence of triphenyl phosphine and an azodicarbondialkyl ester with N-hydroxyphthalimide and splitting the N-phthalimido oxyalkyl-phosphor compound of the formula III obtained, 2 i i N-OH OR 1 (III) %./ / \, wherein R, R 1 and R 2 have the meaning given above, in an inert organic solvent in the presence of hydrazine to give an amino oxyalkyl phosphor compound of the formula Ia 2 H 2 N-OH--0 R 1 (Ia) wherein R, R 1 and R 2 have the meaning given above, and if desired reacting this compound in an inert organic solvent, with a 2,2-di- alkoxypropan or a 2,2-dihalopropan or with aceton to give an acetoxim oxyalkyl-phosphor compound of the formula Ib g 2 (CH 3)2 C=N H 4 R 1 (Ib) wherein R, R 1 and R 2 have the meaning given above.

12 A process for the production of an acetoxim-oxyalkyl-phospho- nous, -phosphinic or phosphonic acid derivative of the formula Ib (CH 3)2 l (lb) (CH 3)2 C=NOC R (Ib) 51 - wherein R is hydrogen, C 1-C 6-alkyl which is unsubstituted or substituted once or twice by C 1-C 6-alkoxy, hydroxyl C 1-C 6-alkoxy or a rest -O Mee or -ON(R 4)4, R 1 is hydrogen, C 1-C 6-alkyl, a metal cation Me or an ammonium 0 cation N(R 4)4, R 2 is hydrogen, C 1-C 6-alkyl, phenyl, benzyl or an aryl radical which is unsubstituted or substituted by halogen, C 1-C 4-alkyl, C 1-C 4-haloalkyl, C 1-C 4-alkoxy, C 1-C 4-haloalkoxy, nitro, cyano, carboxyl, C 1-C 4-alkoxycarbonyl, amino, Cl-C 4-alkylamino, carbamoyl or acetyl, and R 4 is hydrogen, C 1-C 6 alkyl, C 1-C 6 hydroxyalkyl, C 2-C 6 alkoxyalkyl or benzyl, which is characterized by reacting a tolylsufonic acid alkyl-phosphor compound of the formula IV 2 Q CH 3- \ -SO 2 H OR 1 (IV) wherein R, R 1 and R 2 have the meaning given above, in an inert organic solvent or diluent, with a metal salt of acetonoxime of the formula V (CH 3) 2 C=N-O Me (V) wherein Me is the ion-equivalent of a metal.

13 A herbicidal, microbicidal or plant-growth regulating composi- tion, which contains as active component an effective amount of an oxyalkyl-phosphonous, -phosphinic or phosphonic acid derivative according to formula I, claim 1.

52 -

14 A process for the production of a composition according to claim 13 which comprises mixing and grinding intimately an amino oxyalkyl-phosphonous, -phosphinic or -phosphonic acid derivative of the formula I with appropriate liquid or solid carrier material and tensides.

A process for controlling weeds in cultures of cultivated plants, which comprises treating the cultures or their locus with an effective amount of an amino oxyalkyl-phosphonous, -phosphinic or -phosphoric acid derivative according to claim 1.

16 A process for regulating plant growth, which comprises treating plants or parts of plants with an effective amount of an amino oxyalkyl-phosphonous, -phosphinic or -phosphonic acid derivative according to claim 1.

17 A process for controlling or preventing infestation of culti- vated plants by phytopathogenic microorgansims, which comprises treating plants or parts of plants with an effective amount of an amino oxyalkyl-phosphonous, -phosphinic or phosphoric acid deriva- tive according to claim 1.

18 New hydroxyalkyl-phosphonous, -phosphinic and -phosphonic acid derivatives of the formula II R 2 O HO&H-t-OR' wherein R, RI and R 2 have the meaning given in claim 1, as inter- mediates in the production of the compounds of formula I claim 1.

19 New hydroxyalkyl-phosphinic acid derivatives of the formula I Ia H Oz OR 1 (I Ia) H R-OR 3 53 - wherein R 3 and RI are independently of each other C 1-C 6-alkyl while R 1 and R 2 have the meaning given in claim 1, as intermediates.

As new intermediates according to claim 22 (diethoxymethyl)-hydroxymethyl-o-ethyl phosphinate, (diethoxymethyl)-1-hydroxy-1-eth-yl-o-ethyl phosphinate, (diethoxymethyl)-1-hydroxy-2-phenyleth-1-yl-o-ethyl phosphinate.

21 New N-phthalimido-oxyalkyl-phosphonous, -phosphinic and -phos- phonic acid derivatives of the formula III as intermediates I Ii)1-OCH OR 1 (III), wherein R, R 1 and R 2 have the meaning given in claim 1.

22 New tolylsulfonic acid oxyalkyl-phosphonous, -phosphonic and phosphinic acid derivatives of the formula IV as intermediates, CH 3-@/ \ 0-0 k-SO 2-X HRI (IV) wherein R, R 1 and RT have the meaning given in claim 1.

23 New tolyl sulfonic acid oxyalkyl-phosphinic acid derivatives of the formula I Va as intermediates, CH 3- -SO 20 H -k'OR 1 (I Ma) =/ CH(OR 3)OR 4 wherein R 3 and R 4 are independently of each other C 1-C 6-alkyl and RI and R 2 have the meaning given in claim 1.

24 (Diethoxymethyl)-tosyloxymethyl-o-ethyl phosphinate according to claim 23.

54 - Acetonoxim-l-oxyeth-1-yl phosphonic acid trimethylsilyl ester of the formula HH 3 O (CH 3)2 C=N-OZH t O Si(CH 3)3 l as intermediate product.

26 Acetoxim-l-oxyprop-l yl-phosphonic acid trisilylmethyl ester of the formula 2 H 5 Q (CH 3)2 C=N-OCH lO Si(CH 3)3 l as intermediate product.

FO 7 5/NU/cs Published 19 a The P Atent Oce, St te Ho 8 e,88 71 lgh Eoborn,London WC 1 R 4 TP Further copies maybe obtanedm he Patent Oce.

&^ 1 so 2 ran ?s, St Iar: Cr;, Oanon:Ll,1)D 'iinted by Muiplex techniques ltd, St May C My, mnit Ca= 1187