# Patent

## Title
Method for reducing the phytotoxicity of agricultural machine oil and a

## Abstract

which possesses fungicidal activity as well as herbicidal activity, but not against rice. Some intermediates are also new.

## Background
The invention relates to new phosphorylmethylcarbonyl derivatives, several processes for their preparation and their use as plant protection agents, in particular as herbicides and fungicides.

It is known that certain chlorinated phosphorylacetic acid esters can be used as herbicides (compare, for example, European Pat. No. 1,018). Thus, for example, (1-methyl)-ethyl 2,2-dichloro-2-(diethoxyphosphoryl)acetate can be used for combating weeds. It is also known that certain bis-dithiocarbamates, such as, for example, zinc ethylene-bis-dithiocarbamate, have a fungicidal action (compare U.S. Pat. Nos. 2,457,674 and 3,050,439). However, the action of these compounds is not always adequate, especially when low amounts are employed and in the case of low concentrations.

New chlorinated phosphorylmethylcarbonyl derivatives of the formula (I) ##STR3## in which R.sup.1 represents an optionally substituted radical from the series comprising alkyl, aryl, aralkyl, alkoxy and aralkoxy and comprising alkoxy and aralkoxy, or ##STR4## in which R.sup.4 represents hydrogen or optionally substituted alkyl and optionally substituted pyrazolyl radical; or substituted radical from the series comprising alkyl, cycloalkyl, alkylamino and cycloalkylamino,

have now been found.

The new compounds of the formula (I) are obtained by a process in which

(a) dichloromethanephosphonic acid derivatives of the formula (II) ##STR5## in which R.sup.1 and R.sup.2 represent optionally substituted radicals from the series comprising alkoxy and aralkoxy, or

are reacted with acid halides of the formula (III) ##STR6## in which R.sup.3 has the abovementioned meaning and

in which comprising alkyl and cycloalkyl,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of diluents, or (b) phosphorylmethylcarbonyl compounds of the formula (V) ##STR7## in which R.sup.1, R.sup.2, R.sup.3 and X have the abovementioned meanings,

are reacted with chlorinating agents, if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents.

The new chlorinated phosphorylmethylcarbonyl derivatives of the formula (I) are distinguished by a high herbicidal and fungicidal activity.

Surprisingly, the active compounds of the formula (I) according to the invention are superior to the chlorinated phosphorylacetic acid esters already known (according to European Pat. No. 1,018) against economically important graminaceous weeds in dicotyledonous crops, such as cotton, soy bean, sugarbeet and groundnut. They also have a better systemic action against plant diseases than the bis-thiocarbamates already mentioned (according to U.S. Pat. Nos. 2,457,674 and 3,050,439).

The invention preferably relates to the new chlorinated phosphorylmethylcarbonyl derivatives of the formula (I),

in which carbon atoms, alkoxy with up to 6 carbon atoms and aralkyl and aralkoxy with 6 to 10 carbon atoms in the aryl part and up to 2 carbon atoms in the alkyl part [such as, in particular, benzyl, phenylethyl, benzyloxy and phenylethoxy], in each case optionally monosubstituted or polysubstituted by halogen [such as, in particular, fluorine, chlorine and/or bromine] or C.sub.1 -C.sub.4 -alkoxy, or represents phenyl which is optionally monosubstituted or polysubstituted by halogen [such as, in particular, fluorine, chlorine and/or bromine], nitro, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy and/or C.sub.1 -C.sub.4 -alkoxycarbonyl, and 10 carbon atoms in the aryl part and up to 2 carbon atoms in the alkyl part [such as, in particular, benzyloxy or phenylethoxy], in each case optionally monosubstituted or polysubstituted by halogen [such as, in particular, fluorine, chlorine and/or bromine] or C.sub.1 -C.sub.4 -alkoxy, or alkanedioxy radical with 2 to 5 carbon atoms in the alkyl part, ##STR8## in which R.sup.4 represents hydrogen or alkyl with up to 4 carbon atoms and the alkyl part, or represents an optionally substituted pyrazolyl radical ##STR9## wherein R.sup.7 and R.sup.9 are identical or different and represent hydrogen or C.sub.1 -C.sub.4 -alkyl and C.sub.1 -C.sub.4 -alkyl; or if X represents chlorine, R.sup.3 also may represent alkyl with up to 8 carbon atoms, which is optionally monosubstituted or polysubstituted by halogen, [such as, in particular, fluorine, chlorine and/or bromine], C.sub.1 -C.sub.4 -alkoxy and/or C.sub.3 -C.sub.6 -cycloalkyl, or represents cycloalkyl with 3 to 6 carbon atoms, which is optionally monosubstituted or polysubstituted by C.sub.1 -C.sub.3 -alkyl, or alkylamino with up to 6 carbon atoms in the alkyl part or cycloalkylamino with 3 to 6 carbon atoms.

The invention particularly relates to compounds of the formula (I)

in which

(A) tert.-butoxy, tert.-butoxy, tert.-butyl, cyclopropyl, n-propylamino, i-propylamino, n-butylamino, i-butylamino, sec.-butylamino or tert.-butylamino,

or

(B) tert.-butoxy or phenyl, tert.-butoxy, ##STR10## in which R.sup.4 represents methyl or ethyl and i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, sec.-butoxycarbonyl or tert.-butoxycarbonyl,

or

(C) tert.-butoxy or phenyl, tert.-butoxy, ##STR11## in which R.sup.4 represents hydrogen, methyl, ethyl, n-propyl or i-propyl and ##STR12## wherein R.sup.7 and R.sup.9 are identical or different and represent hydrogen or methyl and

If, for example, O,O-di-n-propyl dichloromethanephosphonate and cyclohexylcarboxylic acid chloride or cyclohexyl isocyanate are used as starting substances, the course of the reaction in process variant (a) according to the invention can be represented by the following equation: ##STR13##

If, for example, sodium hypochlorite is used as the chlorinating agent and 1-(1-pyrazol-1-yl)-ethyl O,O-di-n-propoxy-phosphoryl-acetate is used as the starting substance, the course of the reaction in process variant (b) according to the invention can be represented by the following equation: ##STR14##

Formula (II) provides a definition of the dichloromethanephosphonic acid derivatives to be used as starting substances. In this formula, R.sup.1 and R.sup.2 represent optionally substituted radicals from the series comprising alkoxy and aralkoxy, or together represent an alkanedioxy radical. The preferred and particularly preferred definition of these radicals have already been mentioned in the context of the definition of the substituents for formula (I).

Examples which may be mentioned of the compounds of the formula (II) are: ______________________________________ ##STR15##                    (II) R.sup.1             R.sup.2 ______________________________________ OC.sub.3 H.sub.7n   OC.sub.3 H.sub.7n OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso OC.sub.4 H.sub.9n   OC.sub.4 H.sub.9n OC.sub.4 H.sub.9iso OC.sub.4 H.sub.9iso OC.sub.4 H.sub.9sec. OC.sub.4 H.sub.9sec. OC.sub.4 H.sub.9tert. OC.sub.4 H.sub.9tert. OCH.sub.3           OC.sub.3 H.sub.7n OCH.sub.3           OC.sub.3 H.sub.7iso OCH.sub.3           OC.sub.4 H.sub.9n OCH.sub.3           OC.sub.4 H.sub.9iso OCH.sub.3           OC.sub.4 H.sub.9sec. OCH.sub.3           OC.sub.4 H.sub.9tert. OC.sub.2 H.sub.5    OC.sub.3 H.sub.7n OC.sub.2 H.sub.5    OC.sub.3 H.sub.7iso OC.sub.2 H.sub.5    OC.sub.4 H.sub.9n OC.sub.2 H.sub.5    OC.sub.4 H.sub. 9iso OC.sub.2 H.sub.5    OC.sub.4 H.sub.9sec. OC.sub.2 H.sub.5    OC.sub.4 H.sub.9tert. OC.sub.3 H.sub.7n   OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7n   OC.sub.4 H.sub.9n OC.sub.3 H.sub.7n   OC.sub.4 H.sub.9iso OC.sub.3 H.sub.7n   OC.sub.4 H.sub.9sec. OC.sub.3 H.sub.7n   OC.sub.4 H.sub.9tert. OC.sub.3 H.sub.7i   OC.sub.4 H.sub.9n OC.sub.3 H.sub.7i   OC.sub.4 H.sub.9iso OC.sub.3 H.sub.7i   OC.sub.4 H.sub.9sec. OC.sub.3 H.sub.7i   OC.sub.4 H.sub.9tert. OC.sub.4 H.sub.9n   OC.sub.4 H.sub.9sec. OC.sub.4 H.sub.9n   OC.sub.4 H.sub.9tert. OC.sub.4 H.sub.9iso C.sub.4 H.sub.9sec. OC.sub.4 H.sub.9iso OC.sub.4 H.sub.9tert. OCH.sub.2 CH.sub.2O OCH.sub.2 CH.sub.2 CH.sub.2O ##STR16## ##STR17## ##STR18## ______________________________________

Starting substances of the formula (II) are known and can be prepared by processes which are known per se (Tetrahedron Letters 1975, 609-610).

Formula (III) provides a definition of the acid halides also to be used as starting substances for process variant (a). In this formula, R.sup.3 preferably or particularly preferably represents those radicals which have already been mentioned as preferred or as particularly preferred in the context of the definitions of the substituents for formula (I); Hal represents chlorine or bromine.

Examples which may be mentioned of starting substances of the formula (III) are: the chlorides and bromides of butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid and cyclopropanecarboxylic acid.

Acid halides of the formula (III) are known and can be prepared by customary methods.

The isocyanates of the formula (IV) can also be used as starting substances for process variant (a). In this formula, R.sup.6 preferably represents alkyl with 3 to 6 carbon atoms or cycloalkyl with 3 to 6 carbon atoms. R.sup.6 particularly preferably represents alkyl with 3 to 6 carbon atoms.

Examples which may be mentioned of starting substances of the formula (IV) are: n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl and tert.-butyl isocyanates.

The isocyanates of the formula (IV) are generally known compounds of organic chemistry.

Formula (V) provides a definition of the phosphorylmethylcarbonyl compounds to be used as starting substances for process variant (b). In this formula, R.sup.1, R.sup.2, R.sup.3 and X preferably or particularly preferably represent those radicals which have already been mentioned as preferred or as particularly preferred in the context of the definition of the substituents for formula (I).

Examples which may be mentioned of the starting substances of the formula (V) are: ______________________________________ ##STR19##                    (V) R.sup.1   R.sup.2     XR.sup.3 ______________________________________ OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR20## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR21## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR22## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR23## ##STR24## OC.sub.3 H.sub.7i ##STR25## ##STR26## OC.sub.3 H.sub.7i ##STR27## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR28## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR29## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i HCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR30## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i HOCH.sub.2COOC.sub.2 H.sub.5 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i HOCH.sub.2COOC.sub.4 H.sub.9n OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n ClCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ClCH(CH.sub.3).sub.2 OC.sub.4 H.sub.9i OC.sub.4 H.sub.9i ClCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i HCH(CH.sub.3).sub.2 OC.sub.4 H.sub.9sec. OC.sub.4 H.sub.9sec. ClCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ClC.sub.3 H.sub.7n OC.sub.3 H.sub.7n OC.sub.3 H.sub.7i ClCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i HC.sub.3 H.sub.7n OC.sub.4 H.sub.9i OC.sub.4 H.sub.9i HCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR31## OC.sub.3 H.sub.7i OC.sub.3 H.sub.7i ##STR32## ##STR33## OC.sub.3 H.sub.7i HOCH.sub.2 COOC.sub.2 H.sub.5 ##STR34## OC.sub.3 H.sub.7i HOCH.sub.2 COOC.sub.4 H.sub.9n ##STR35## OC.sub.3 H.sub.7i ##STR36## ##STR37## OC.sub.3 H.sub.7i ##STR38## ##STR39## OC.sub.3 H.sub.7i ##STR40## OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n ##STR41## OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n ##STR42## OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n ##STR43## OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n ##STR44## OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n ##STR45## OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n ##STR46## OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n HOCH.sub.2 COOC.sub.2 H.sub.5 OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n HOCH.sub.2 COOC.sub.2 H.sub.5 OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n HOCH.sub.2 COOC.sub.4 H.sub.9n OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n HOCH.sub.2 COOC.sub.4 H.sub.9n OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n ClCH(CH.sub.3).sub.2 OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n HCH(CH.sub.3).sub.2 OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n ClC.sub.3 H.sub.7n OC.sub.3 H.sub.7n OC.sub.3 H.sub.7n HC.sub.3 H.sub.7n ______________________________________

Some of the starting compounds of the formula (V) have not yet been described in the literature. For example, the compounds of the formula (Va) ##STR47## in which R.sup.1, R.sup.2, R.sup.4 and R.sup.5 have the abovementioned meanings,

are new.

The new compounds of the formula (Va) are obtained by a process in which compounds of the formula (VI) ##STR48## in which R.sup.1 and R.sup.2 have the abovementioned meanings and R.sup.10 represents optionally substituted C.sub.1 -C.sub.4 -alkyl or benzyl,

are heated with halogenoacetic acid esters of the formula (VII) ##STR49## in which R.sup.4 and R.sup.5 have the abovementioned meanings and

to temperatures between 50.degree. C. and 200.degree. C., preferably between 100.degree. C. and 150.degree. C., and the reaction products of the formula Hal.sup.1 -R.sup.10 are removed, if appropriate under reduced pressure.

The compounds of the formula (VI) are generally known compounds of organic chemistry.

Examples which may be mentioned are: the tri-n-propyl ester, tri-i-propyl ester, tri-n-butyl ester, tri-i-butyl ester and tri-sec.-butyl ester of phosphorous acid, and the di-n-propyl ester, di-i-propyl ester, di-n-butyl ester, di-i-butyl ester and di-sec.-butyl ester of phenyl-phosphonous acid.

The halogenoacetic acid esters of the formula (VII) are new. The compounds of the formula (VII) are obtained by reacting halogenoacetic acid halides of the formula (VIII)

in which bromine,

with hydroxy derivatives of the formula (IX) ##STR50## in which R.sup.4 and R.sup.5 have the abovementioned meanings, in the presence of acid acceptors, such as, for example, triethylamine, and in the presence of diluents, such as, for example, methylene chloride, at temperatures between -50.degree. C. and +100.degree. C., preferably between -20.degree. C. and +50.degree. C.

Working up can be carried out by customary methods, for example by washing the organic solution with aqueous sodium bicarbonate solution, drying and filtering the organic phase and distilling off the solvent under reduced pressure.

The starting compounds of the formula (VIII) are generally known compounds of organic chemistry.

The hydroxy derivatives of the formula (IX) are already known (compare, for example, German No. 2,835,158).

Process variant (a) is preferably carried out using diluents.

Suitable diluents are virtually all the inert organic solvents. These include, in particular, aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and dimethylsulphoxide, tetramethylenesulphone, hexamethylphosphoric acid triamide and pyridine.

Process variant (a) is preferably carried out in the presence of acid acceptors. These preferably include alkali metal and alkaline earth metal hydrides, such as, for example, sodium hydride and calcium hydride, organometallic compounds, such as, for example, butyl-lithium or isopropylmagnesium chloride, alcoholates, such as, for example, potassium tert.-butanolate and aluminum isopropylate, and specific amines, such as, for example, diazabicyclooctane, diazabicycloundecene and pyridine.

The reaction temperature can be varied within a substantial range in process (a) for the preparation of the compounds of the formula (I). In general, the reaction is carried out between -120.degree. C. and +100.degree. C., preferably at -70.degree. C. to +50.degree. C. Process (a) is in general carried out under normal pressure.

Equimolar amounts of the starting substances of the formulae (II) and (III) or (II) and (IV) and, in addition, 1 to 2, preferably 1.0 to 1.4, molar equivalents of a suitable base are in general employed for carrying out process (a).

In general, the dichloromethanephosphonic acid derivative of the formula (II) and the base are brought together in a suitable solvent, if appropriate with cooling, and the acid halide of the formula (III) or the isocyanate of the formula (IV) is slowly added, if appropriate in solution. The reaction mixture is stirred until the reaction has ended. Working up can be carried out by customary methods, for example by acidification, for example with sulphuric acid, extraction with methylene chloride, drying and filtration of the organic constituents under reduced pressure and moderately elevated temperature. The residues of low volatility essentially contain compounds of the formula (I), which are characterized by their physico-chemical properties.

Process (b) is carried out using chlorinating agents. Chlorinating agents which may be mentioned are chlorine, sulphuryl chloride and alkali metal or alkaline earth metal hypochlorites, such as, for example, sodium hypochlorite (if appropriate in the form of so-called hypochlorite solution) or calcium hypochlorite. Hypochlorite solution is preferably used.

Process (b) is preferably carried out in the presence of diluents. Possible diluents are, in particular, halogenated hydrocarbons, such as, for example, methylene chloride, ethylene chloride, chloroform and carbon tetrachloride. If hypochlorite solution is employed, water is used as the diluent, and is supplemented, if necessary, by an inert organic solvent.

If appropriate, acid acceptors are used in process (b). If aqueous hypochlorite solutions are employed, the corresponding alkali metal hydroxides or alkaline earth metal hydroxides, such as, for example, sodium hydroxide, potassium hydroxide or calcium hydroxide or calcium hydroxide, are preferably used as the acid-binding agents.

The reaction temperatures can be varied within a substantial range in process (b). In general, the reaction is carried out between -20.degree. C. and +50.degree. C., preferably at 0.degree. C. to 30.degree. C. The process is in general carried out under normal pressure.

For carrying out process (b), between 0.5 and 5, preferably between 0.9 and 3.5, molar equivalents of chlorinating agent are in general employed per mole of phosphorylmethylcarbonyl compound of the formula (V), and the pH value is in general kept between 7 and 14, preferably between 9 and 14.

In general, the chlorinating agent and the diluent are initially introduced into the reaction vessel and the compound of the formula (V) is added, with vigorous stirring. When the reaction has ended, the mixture can be worked up by customary methods, for example by washing the organic solution with aqueous sodium bicarbonate solution, drying and filtering the organic phase and distilling off the solvent under reduced pressure at moderately elevated temperature. The residues of low volatility essentially contain the compounds of the formula (I), which are characterized by their physico-chemical properties.

The active compounds of the formula (I) according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants: Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea. Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita. Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera. Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

The active compounds according to the invention also exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganisms. The active compounds are suitable for use as plant protection agents.

Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating rice diseases such as Pyricularia oryzae.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine capsules in polymeric substances and in coating compositions for seed, and ULV formulations.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents.

In the case of the use of water as an extender, organic solvnts can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions and mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products; as dispersing agents there are suitable: for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixes being possible.

The known herbicides which are suitable for the mixtures are, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione or N-(2-benzothiazolyl)-N,N'-dimethyl-urea, for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one, for combating weeds in sugarbeet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one for combating weeds in soy beans.

Mixing with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, immersion, misting, vaporizing, injecting, forming a slurry, brushing on, dusting, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

The active compounds according to the invention can be applied either before or after emergence of the plants. They are preferably applied before emergence of the plants, that is to say by the pre-emergence method. They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.05 and 10 kg of active compound per ha, preferably between 0.1 and 5 kg/ha.

In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.

The examples which follow serve to illustrate the invention further. ##STR51##

37.4 g (0.15 mole) of diisopropyl dichloromethanephosphonate are initially introduced into 100 ml of tetrahydrofuran, the mixture is cooled to -70.degree. C. and 100 ml of a 15% strength solution of butyl-lithium in n-hexane are added. The mixture is stirred at -70.degree. C. for one hour, 18.1 g (0.15 mole) of isovaleryl chloride are added and the mixture is stirred at -70.degree. C. for a further hour. 50 ml of 1N sulphuric acid are slowly added dropwise at a temperature of 0.degree. C.; the mixture is then extracted three times with methylene chloride, the organic phase is dried and filtered and the solvent is distilled off under reduced pressure.

34.8 g (69% of theory) of 1,1-dichloro-1-(O,O-di-i-propyl-phosphoryl)-4-methyl-pentan-2-one of refractive index n.sub.D.sup.20 1.4455 are obtained. ##STR52##

28 g of hypochlorite solution (containing 11.9% of "active chlorine") are initially introduced into 100 ml of carbon tetrachloride and the mixture is cooled to 0.degree. C. to 5.degree. C. 13.3 g (0.04 mole) of 1-(pyrazol-1-yl)-n-propyl 1-(O,O-di-i-propyl-phosphoryl)-acetate in 50 ml of carbon tetrachloride are added dropwise, with vigorous stirring. The mixture is subsequently stirred at 0.degree. C. for 5.degree. C. for 2 hours and washed with sodium bicarbonate solution, the organic phase is dried over sodium sulphate, filtered and concentrated and the residue is subjected to incipient distillation under a vapour pump at 70.degree. C. for 10 minutes.

6.7 g (46% of theory) of 1-(pyrazol-1-yl)-n-propyl 1-chloro-1-(O,O-di-i-propyl-phosphoryl)-acetate are obtained in the form of an oil of refractive index n.sub.D.sup.20 1.4557.

The compounds of the formula (I) listed in Table 3 which follows were prepared analogously to Example 1 and 2, or analogously to process variant (a) or (b): __________________________________________________________________________ ##STR53##                              (I) Example                             Refractive No.  R.sup.1 R.sup.2 X R.sup.3      index n.sub.D.sup.20 __________________________________________________________________________ 3    OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl CH(CH.sub.3).sub.2 1.4367 4    OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl NHCH(CH.sub.3).sub.2 1.4550 5    OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl ##STR54##   1.4546 6    OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl ##STR55##   1.4385 7    OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl ##STR56##   1.4432 8    OC.sub.3 H.sub.7iso OC.sub.3 H.sub. 7iso Cl ##STR57##   1.4611 9    OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl ##STR58##   1.4681 10   OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso H ##STR59##   1.4658 11 ##STR60## OC.sub.3 H.sub.7iso Cl ##STR61##   1.5265 12   OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso H ##STR62##   1.4711 13   OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso H ##STR63##   1.4795 14   OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso Cl ##STR64##   1.4585 15   OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n H ##STR65##   1.4618 16   OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n Cl ##STR66##   1.4648 17   OC.sub.4 H.sub.9iso OC.sub.4 H.sub.9iso Cl CH.sub.2 CH(CH.sub.3).sub.2 18   OC.sub.4 H.sub.9sec. OC.sub.4 H.sub.9sec. Cl CH.sub.2 CH(CH.sub.3).sub.2 19 ##STR67## OC.sub.3 H.sub.7iso H ##STR68##   1.5295 20   OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso H ##STR69##   1.4689 21   OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n H ##STR70##   1.4694 22 ##STR71## OC.sub.3 H.sub.7iso Cl ##STR72##   1.5183 23   OCH.sub.2 CH.sub.2 Cl OCH.sub.2 CH.sub.2 Cl Cl ##STR73##   1.5009 __________________________________________________________________________ ##STR74##

A mixture of 16.2 g (0.08 mole) of 1-(pyrazol-1-yl)-1-n-propyl 1-chloro-acetate and 18.4 g (0.088 mole) of tri-isopropyl phosphite is stirred at 140.degree. C. for 4 hours and is then subjected to incipient distillation under a vapor pump at 70.degree. C. for 10 minutes.

22.7 g (85% of theory) of 1-(pyrazol-1-yl)-n-propyl 1-(O,O-di-isopropyl-phosphoryl)-acetate of refractive index n.sub.D.sup.20 1.4567 are obtained.

The remaining compounds of the formula (Va) listed in Table 4 were prepared analogously to Example (Va-1): __________________________________________________________________________ ##STR75##                              (Va) Example                              Refractive No.  R.sup.1 R.sup.2 R.sup.4 R.sup.5  index n.sub.D.sup.20 __________________________________________________________________________ Va-2 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso CH.sub.3 COOC.sub.4 H.sub.9n Va-3 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso CH.sub.3 COOC.sub.2 H.sub.5 Va-4 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso C.sub.3 H.sub.7iso ##STR76## 1.4538 Va-5 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso H ##STR77## 1.4635 Va-6 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso C.sub.3 H.sub.7n ##STR78## 1.4595 Va-7 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso CH.sub.3 ##STR79## 1.4539 Va-8 ##STR80## OC.sub.3 H.sub.7iso CH.sub.3 COOC.sub.2 H.sub.5 1.4818 Va-9 ##STR81## OC.sub.3 H.sub.7iso CH.sub.3 ##STR82## 1.4293 Va-10 ##STR83## OC.sub.3 H.sub.7iso CH.sub.3 COOC.sub.4 H.sub.9n 1.4765 Va-11 OC.sub.3 H.sub.7iso OC.sub.3 H.sub.7iso H ##STR84## 1.4579 Va-12 ##STR85## OC.sub.3 H.sub.7iso H ##STR86## 1.5229 Va-13 OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n H ##STR87## 1.4673 Va-14 OC.sub.4 H.sub.9n OC.sub.4 H.sub.9n C.sub.2 H.sub.5 ##STR88## 1.4618 Va-15 ##STR89## OC.sub.3 H.sub.7iso C.sub.2 H.sub.5 ##STR90## __________________________________________________________________________ ##STR91##

12.6 g (0.1 mole) of 1-hydroxy-1-(pyrazol-1-yl)-propane are initially introduced into 100 ml of methylene chloride, the mixture is cooled to 0.degree. C. to 10.degree. C. with ice, 13.3 g (0.13 mole) of triethylamine are added, and 11.3 g (0.10 mole) of chloroacetyl chloride are then slowly added dropwise at 0.degree. C. to 10.degree. C., with vigorous stirring. The mixture is subsequently stirred for 15 to 20 minutes, washed three times with sodium bicarbonate solution, dried and evaporated and the residue is subjected to incipient distillation under a vapor pump at 20.degree. C.

11.3 g (56% of theory) of 1-(pyrazol-1-yl)-n-propyl 1-chloro-acetate of refractive index n.sub.D.sup.20 1.4875  are obtained.

The remaining compounds of the formula (VII) listed in Table 5 were obtained analogously to Example (VII-1): ______________________________________ ##STR92##                   (VII) Example No.    Hal.sup.1 R.sup.4  R.sup.5    Physical constant ______________________________________ VII-2  Cl     CH.sub.3 ##STR93## n.sub.D.sup.20 : 1.4962 VII-3  Cl     H ##STR94## melting point: 58.degree. C. VII-4  Cl     CH.sub.3 COOC.sub.2 H.sub.5 VII-5  Cl     CH.sub.3 COOC.sub.4 H.sub.9 VII-6  Cl     n-C.sub.3 H.sub.7 ##STR95## n.sub.D.sup.20 : 1.4920 VII-7  Cl     iso-C.sub.3 H.sub.7 ##STR96## n.sub.D.sup.20 : 1.4869 VII-8  Cl     H ##STR97## VII-9  Br     CH.sub.3 ##STR98## VII-10 Br     H ##STR99## VII-11 Br     C.sub.2 H.sub.5 ##STR100## ______________________________________ ##STR101##

34 g (0.5 mole) of pyrazole are initially introduced into 250 ml of methylene chloride, and 47 g (0.65 mole) of propionaldehyde are added dropwise at 0.degree. C. to 5.degree. C. The mixture is stirred for about 72 hours and subjected to incipient distillation at 20.degree. C. under a waterpump vacuum.

42 g (67% of theory) of 1-hydroxy-1-(pyrazol-1-yl)-n-propane are obtained as a colorless oil.

The following compounds of the formula (IX) listed in Table 6 were obtained analogously to Example (IX-1): ______________________________________ ##STR102##                   (IX) Example                           Physical No.       R.sup.4   R.sup.5       constant ______________________________________ IX-2      CH.sub.3 ##STR103## IX-3      H ##STR104##   88.degree. C. IX-4      n-C.sub.3 H.sub.7 ##STR105## IX-5      iso-C.sub.3 H.sub.7 ##STR106## ______________________________________

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:

In this test, for example, the following compound according to the preparation examples exhibits an excellent activity: (1).

Pre-emergence test--greenhouse

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:

In this test, for example, the following compound according to the preparation examples exhibits an excellent activity: (9).

Pyricularia test (rice)/systemic

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.

To test for systemic properties, standard soil in which young rice plants have been grown is watered with 40 ml of the preparation of active compound. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Thereafter, the plants remain in a greehouse at a temperature of 25.degree. C. and a relative atmospheric humidity of 100% until they are evaluated.

Evaluation of the disease infestation is carried out 4 days after the inoculation.

In this test, a clearly superior fungicidal activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: (6), (7) and (8), and the rice plants are not injured.

It is understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.

## Claims

1. A chlorinated phosphorylmethylcarbonyl derivative of the formula ##STR107## in which R.sup.1 represents radicals from the series comprising alkyl with up to 6 carbon atoms, alkoxy with up to 6 carbon atoms and aralkyl and aralkoxy with 6 to 10 carbon atoms in the aryl part and up to 2 carbon atoms in the alkyl part, in each case optionally monosubstituted or polysubsttuted by halogen or C.sub.1 -C.sub.4 -alkoxy, or represents phenyl which is optionally monosubstituted or polysubstituted by halogen, nitro, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy and/or C.sub.1 -C.sub.4 -alkoxycarbonyl, and 10 carbon atoms in the alkyl part and up to 2 carbon atoms in the alkyl part, in each case optionally monosubstituted or polysubstituted by halogen or C.sub.1 -C.sub.4 -alkoxy, or R.sup.1 and R.sup.2 together represent a branched or straight-chain alkanedioxy radical with 2 to 5 carbon atoms in the alkyl part, ##STR108## in which R.sup.4 represents hydrogen or alkyl with up to 4 carbon atoms and the alkyl part or represents an optionally substituted pyrazolyl radical ##STR109## wherein R.sup.7 and R.sup.9 are identical or different and represent hydrogen or C.sub.1 -C.sub.4 alkyl and carbon atoms, which is optionally monosubstituted or polysubstituted by C.sub.1 -C.sub.3 -alkyl.

2. A chlorinated phosphorylmethylcarbonyl derivative according to claim 1, in which tert.-butoxy, tert.-butoxy,

3. A chlorinated phosphorylmethylcarbonyl derivative according to claim 1, in which tert.-butoxy or phenyl, tert.-butoxy, ##STR110## in which R.sup.4 represents methyl or ethyl and i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, sec.-butoxycarbonyl or tert.-butoxycarbonyl.

4. A chlorinated phosphorylmethylcarbonyl derivative according to claim 1, in which tert.-butoxy or phenyl, tert.-butoxy, ##STR111## in which R.sup.4 represents hydrogen, methyl, ethyl, n-propyl or i-propyl and ##STR112## wherein R.sup.7 and R.sup.9 are identical or different and represent hydrogen or methyl and

5. A compound according to claim 1, wherein such compound is 1-butoxycarbonyl-ethyl 1,1-dichloro-1-(O,O-di-i-propyl-phosphoryl)-acetate of the formula ##STR113##

6. A compound according to claim 1, wherein such compound is 1-ethoxycarbonyl-ethyl 1,1-dichloro-1-(O,O-di-i-propyl-phosphoryl)-acetate of the formula ##STR114##

7. A compound according to claim 1, wherein such compound is 1,1-dichloro-1-(O,O-di-i-propyl-phosphoryl)-2-cyclopropyl-ethan-2-one of the formula ##STR115##

8. A compound according to claim 1, wherein such compound is (3,5-dimethyl-pyrazol-1yl)-methyl 1,1-dichloro-1-(O,O-di-i-propyl-phosphoryl)-acetate of the formula ##STR116##

9. A fungicidal and selectively herbicidal composition comprising a fungicidally and selectively herbicidally effective amount of a compound according to claim 1 in admixture with a diluent.

10. A method of combating fungi and undesired plants which comprises administering to such fungi or plants or to a habitat thereof a fungicidally or selectively herbicidally effective amount of a compound according to claim 1.

11. The method according to claim 10, wherein the compound is applied to rice or to an area in which rice is to be grown and is 1,1-dichloro-1-(O,O-di-i-propyl-phosphoryl)-acetate.