IL45031A - Phosphonic acid derivatives and compositions for regulating plant growth containing them - Google Patents

Description

4 Q31/2 Phosphonic acid derivatives and compositions for regulating plant growth containing them BAYER AKTIBNGESELLSCHAFT C :42963 Type Ila The present invention relates to the use as plant- growth regulators of certain aminomethanephosphonic acid derivatives, some of which are known, and to some that, are new.

The use of certain aminomethanephosphonic acid ' derivatives as additives to antibiotics or as intermediates for t e preparation of phosphonodiazomethane derivatives or of am.inoi'„?thane ho::iphoni'.i acid has already been disclosed (see Sir.iete.v,y Org, Scedinii Sbomik 2, 12-15 (1954); Justus Liebigs Ann, Chem. 748 (1971) 207-210; Chem. Abstr. 4^ (1951) 8444; and Australian Patent Specification 34,471/63).

It has also been disclosed that certain 2-halogenoethyl- ammonium halides, especially (2-chloroethyl)-t imethyl-amm- onium chloride, display plant-growth-regulating properties (see U.S. Patent Specification 3,156,554). Thus (2-chloro-ehyl)-trimethyl-ammonium chloride, in particular, can be used to inhibit the vegetative growth of cereals, for example wheat and. barley. However, the action of this compound is not always satisfactory if low concentrations are used.

It has now been found that the aminomethanephosphonic acid derivatives of the general formula in which R is an NR^ group or an -HH --X radical wherein is one equivalent of an anion of an organic or inorganic acid, and R' and R" , which may be identical or different, are one equivalent of a cation of the formula wherein R^, R2- and R^ , which may be identical or different, are each hydrogen, alkyl, hydrogen, alkyl , hydroxyalkyl , carbethoxyalkyl, carboxyalkyl , or a -C^-C^- H^ group, or R2 and ^ together with the nitrogen atom. form a five or six-membered heterocyclic ring, or R' and R" are hydrogen, provided that R' and R" can simultaneously be hydrogen only if R is an -NH3X radical, display strong plant-growth-regulating properties.

The present invention thus provides a plant-growth-regulating composition containing as active ingredient a compound of the formula (I) above in admixture with a solid ■ or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of regulating the growth of plants, which comprises applying to the plants or a plant habitat a compound of the formula (I) above alone or in the form of a- composition containing as active ingredient a compound of the formula (I) above in admixture with. a diluent or carrier. Θ Preferably, R is an NH2 group or an -ΝΗ3Χθ radical, in θ which X is one equivalent of an anion of an optionally substituted carboxylic acid, of a hydrohalic acid, of a halogen-oxyacid, of nitric acid or of a sulphur-containing acid; and R' and R" are each hydrogen (subject to the above proviso) , straight-chain or branched alkyl with 1 to 4 carbon atoms, one equivalent of a sodium, potassium, calcium or magnesium cation, or one equivalent of a cation of the formula R1 wherein R1, R2 and R3 , which may be identical or different, are each hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms , carbethoxymethylof the formula -CH2-COOC2H5 , carboxymethyl of the formula -CH2-COOH, or a -CH2-CH2-¾H3 group, or R2 and R3 together with the adjacent nitrogen atom form a pyrrolidine, piperidine, imidazole or morpholine ring.

Surprisingly, the aminomethanephosphonic acid derivatives which can be used according to the invention display a substantially greater plant-growth-regulating action than the known compound (2-chloroethyl)-trimethyl-ammonium chloride, which is chemically the nearest active compound of the same type of action. A point to be singled out is that the aminomethanephosphonic acid, derivatives are substantially better suited to inhibiting the vegetative growth of cereals, especially wheat and barley, than is (2-chloroethyl)-trimethyl-ammonium chloride. An inhibitio of the vegetative growth of cereals is of advantage because this produces shorter but thicker stalks, which reduces the danger of the plants kinking (falling-over) before harvesting. The present invention thus represents a valuable enrichment of the art.

The following may be mentioned as examples of the compounds which can be used according to the invention: O-methyl-aminomethanephosphonic acid monoester, 0-ethyl-aminomethanephosphonic acid monoester, O-n-propyl-amino-methanephosphonic acid monoester, O-isopropyl-aminomethane-phosphonic acid monoester, O-n-butyl-aminomethanephosphonic acid monoester,' O-isobutyl-aminomethanephosphonic acid monoester, O-sec.-butyl-aminomethanephosphonic acid monoester, O-tert.-butyl-amiiomethanephosphonic acid monoester, and also the sodium, potassium, ammonium, calcium, magnesium, mono- . methylammonium, dimethylammonium, monoethylammonium, di-ethylammonium and montert.-butylammonium mono-salts of these O-alkyl-aminomethanephosphonic acid monoesters, as well as their mono-salts with pyrrolidine, imidazole, piperidine, morpholine, glycine, glycine ethyl ester and ethanol- amine, as well as 0 , O-dimethyl-aminomethanephosphonic acid diester, 0 ,0-diethyl-aminomethanephosphonic acid diester, 0,0-di-n-propyl-aminomethanephosphonic acid diester, 0,0-di-iso-propyl-aminomethanephosphonic acid diester, 0,0-di-n-butyl-aminomethanephosphonic acid diester, 0,0-di-isobutyl-amino-methanephosphonic acid diester, O,0-di-sec.-butyl-amino-methanephosphonic acid diester, O,0-di-tert.-butyl-amino-methanephosphonic acid diester, as well as potassium aminomethanephosphonate, sodium aminomethanephosphonate, calcium aminomethanephosphonate, magnesium aminomethanephosphonate, ammonium aminomethanephosphonate, methylamine aminomethanephosphonate, dimetbylamine aminomethanephosphonate, trimethyl-amine aminomethanephosphonate, ethylamine aminomethanephosphonate, diethylamine aminomethanephosphonate, triethylamine aminomethanephosphonate, tert.-butylamine aminomethanephosphonate, pyrrolidine aminomethanephosphonate, imidazole aminomethanephosphonate, piperidine aminomethanephosphonate, morpholine aminomethanephosphonate, glycine aminomethanephosphonate, glycine ethyl ester aminomethanephosphonate, 2-aminoethanol aminomethanephosphonate, the corresponding di-salts and also O,0-dimethyl-ammonio-methyl~phosphonic acid chloride, ammonio-methyl-phosphonic acid chloride, ammonio-methyl-phosphonic acid bromide, di-(ammonio-methyl-phosphonic acid) sulphate, ammonio-methyl-phosphonic acid methylsulphonate , ammonio-methyl-phosphonic acid nitrate, ammonio-methyl- 45031/2 phosphonic acid acetate, ammonio-methyl-phosphonic acid di-chloroacetate and ammonio-methyl-phosphonic acid trichloro-acetate.

A number of the compounds to be used according to the invention are known as, for example, in the case of 0, 0-diethyl-aminomethanephosphonic acid diester, 0-ethyl-aminomethanephosphonic acid monoester and its aniline salt (see Sintezy Org. Soedin. Sbovnik 2^ 1 2-14 (1954); Justus Liebigs Ann. Chem. 748. 207-210 ( 1971 ); Chemical Abstracts JL, 8444 ( 1 951 ); and Australian Patent Specification 34, 471 /63 ) . However, their use as plant-growth regulators is new.

Some of the compounds which can be used according to the invention have not hitherto been described in the literature but can be prepared in a simple manner according to known processes.

Thus, for example, the alkali metal salts and ammonium salts of aminomethanephosphonic acid and their salts with nitrogen bases are obtained by adding 1 or 2 equivalents of base., to a suspension of aminomethanephosphonic acid in distilled water. To isolate the reaction products, the reaction solution is evaporated in vacuo at 70°C and the residue which remains- is left for some time at this temperature in vacuo.

The alkaline earth metal salts of aminomethanephosphonic acid are appropriately prepared by adding an equivalent amount of an alkaline earth metal salt solution to the aqueous solution of an alkali metal salt of aminomethanephosphonic acid. The desired products, which precipitate as solids filtration. xThe salts of the monoesters of aminomethanephosphonic acid are prepared in principle in the same manner as the salts of aminomethanephosphonic acid. However, instead of the free aminomethanephosphonic acid an appropriate monoester of this acid serves as the starting material.

The compounds of the formula (I) in which R represents an Θ Q - H-jX radical, are obtainable by addition of a sufficiently-strong acid to aqueous solutions or suspensions of the free aminomethanephosphonic acid or its monoesters or diesters. The compounds can be isolated by evaporating off the excess solvent in vacuo at 70°Ci Aminomethanephosphonic acid, required as a starting material in the preparation of the compounds which can be used according to the invention, is also known,as are the esters of aminomethanephosphonic acid which also serve as starting materials (see Chemical Abstracts 45. 8444 (1951)). The other compounds employed as starting materials are generally known.

The present invention also provides, as new compounds, aminomethanephosphonic acid derivatives of the general formula in which R is -ΘH3X^ radical wherein X® is one equivalent of an anion of an organic or The R.ctive compounds to be used according to the invention affect the physiological metabolism of plant growth and can -therefore be used as plant-growth regulators.

The diverse effects of the active compounds depend essentially on the point in time at which they are used, relative to the stage of development of the seed or of the plant, and on the concentrations used.

Plant-growth regulators are used for various purposes which are related to the stage of development of the plant.

The growth of the plant can be greatly inhibited by means of the compounds according to the invention. This inhibition of growth is of interest in the case of grasses in order to reduce the frequency with which the grass has to be cut. An inhibition of vegetative growth also plays an important role in cereals since this can reduce or complete!" prevent falling-over.

In the case of many crop plants, inhibition of the vegetative growth permits denser planting of the crop so that an increased yield relative to soil area can be achieved. A further mechanism of increasing the yield by means of . growth inhibitors is based on the fact that the nutrients benefit blossoming and fruiting to an increased extent whilst vegetative growth is restricted.

The active compounds to be used according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or 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 solvents can, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alky1 naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes. or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or aceto-nitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for example freon.

As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth-,-or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates. ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and preferred examples of dispersin agents include lignin sulphite waste liquors and methyl cellulose.

The active compounds, to be used according to the invention can be present in the formulations as a mixture with other active compounds.

The formulations in general contain from 0. 1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent.

The active compounds can be used as such, as their formulations or as the application forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, powders, pastes and granules. They may be used in the customary manner, for example by watering, spraying, atomising, dusting, scattering and the like.

The concentrations of active compound in the ready-to-use formulations can be varied within a fairly wide range.

In general, concentrations from 0.0005 to 2%, preferably from 0.01 to 0. $ by weight, are used.

Purthermore, 0,01 to 20kg, preferably 0,1 to 1 0 kg, of active compound are, in general, used per hectare of soil area.

The preferred period of time within which the growth regulators are used depends on the climatic and vegetative circumstances. of the growing a compound of the formula (I) above wae applied talone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention. .

In the test Example which follow the activity as growth regulators of the compounds to be used according to the invention is illustrated,without excluding the possibility of further uses as growth regulators.

Example A Inhibition of growth/wheat Solvent: 10 parts by weight of methanol Emulsifier: 2 parts by weight of polyethylene sorbitan monolaurate To prepare a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent and emulsifier and the mixture was made up to the desired concentration with water.

Young wheat plants, 25 cm high, were sprayed with the preparation of active compound until dripping wet. After 4 weeks, the additional growth was measured and the inhibition of growth in # of the additional growth of the control plants was calculated. 100$ means that growth had stopped and 0# denotes a growth corresponding to that of the untreated plants.

The active compounds, active-compound concentrations and results can be seen from Table A which follows. a l e A Inhibition of growth/wheat Active compound Concen- Inhibition tration. of growth in ppm in ψ of the control Water (control) 0 OH 500 H2N-CH, 85 0 0® H,N-CH2-CH2-0H (16) OH 500 80 H2N-CH2-P 9 NH5-CH(CH5)2 (6) Example B Inhibition of growth/barley Solvent: 10 parts by weight of methanol Emulsifier: 2 parts by weight of polyethylene sorbitan monolaurate To prepare a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent and emulsifier and the mixture was made up to the desired concentration wit water.

After 4 weeks, the additional growth was measured and the inhibition of growth in # of the additional growth of the control plants was calculated. 100$ means that growth had stopped and Oo denotes a growth corresponding to that of the untreated plants.

The active compound , active-compound concentrations and results can be seen from Table B which follows. a b l e B Inhibition of growth/barley Active compound Concen- Inhibi- tration tion of in ppm growth in of the control Water (control) 0 9 C1CH2-CH2-N( CH^ )^ CI Θ 500 35 (known) (6) Example C Inhibition of growth/barley Solvent: 10 parts by weight of methanol Emulsifier: 2 parts by weight of polyethylene sorbitan monolaurate To prepare a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent and emulsifier and the mixture was made up to the desired concentration with water.

Young barley plants, 25 cm high, were sprayed with the preparation of active compound until dripping wet. After 4 weeks, the additional growth was measured and the inhibition of growth in % of the additional growth of the control plants was calculated. 100% means that growth had stopped and 0% denotes a growth corresponding to that of the untreated plants.

The active compounds, active-compound concentrations and results can be seen from Table C which follows. a b l e Inhibition of growth/barley Active compound Concen- Inhibi- tration tion of in ppm growth in of the con- : trol Water (control) (known from DOS 2,113,996} a l e Inhibition of growth/barley Active compound Concen- Inhibl- tratio tion of In ppm growth in i» of the control ^OH Θ ¾Ν-° < 0 Θ 500 80 (6) 0 OH II / H-N-CH--P ζ H3N-CH2-COOH 500 75 The preparation of the compounds to be used according to this invention is illustrated in the following Example. Example 1 ° OH HpN-CH^- (1) ~~^0Na A solution of 4 g (0.1 mole) of sodium hydroxide in 20 ml of distilled water was added to a suspension of 11.11 g (0.1 mole) of aminomethanephosphonic acid in 50 ml of distilled water. Hereupon, salt formation occurred and a clear on r s lt d Th t which hereupon remained was comminuted and left for a further 3 to 60 minutes in vacuo at 70°C. In this way, 6.65 g (100$ of theory) of sodium aminomethanephosphonate were obtained, which decomposed on heating at 320°C.

The following compounds could be prepared by methods analogous to that in Example 1 : - 14a - fc-i Example Content of water Nitrog φ No. Compound of crystallisa- in # 0 OH -CH -P- Q NH2(C2H5)2 15.2 Example Content of water Nitro CD No. Compound of crystallisa- in fo Example 17 O-Ca- 0 H2N-CH2- =0 0=P-CH2-NH2 . H20 (17) CH CH ; ' .' i solution of 8 g (0.2 mole) of sodium hydroxide in '40 ml of distilled water was added to a suspension of 22.22 g (0.2 mole) of aminomethanephosphonic acid in 100 ml of distilled water. A solution of 11.10 g (0.1 mole) of calcium chloride in 40 ml of distilled water was then added to the resulting clear solution of the mono-sodium salt of aminomethanephosphonic acid, whilst stirring. The precipitate which separated out was filtered off, washed with water and then dried. 27.8 g (100$ of theory) of calcium amino- methanephpsphonate, which did not melt oh heating to 355°C, were thus obtained.

Example 18 0 - Mg - 0 H2N-CH2-P=0 0= -CH2-NH2 .4 ¾0 (18) OH OH Magnesium aminomethanephosphonate was also obtained by a method of preparation analogous to that described in Example 17. Yield: 9 # of theory.

On heating this salt, water was slowly released from 100°C onwards; from 264°C onwards, the substance decomposed with foaming.

Example 19 ONa H2N-CH2- =0 . 5 H20 (19) ONa (0.1 mole) of aminomethanephosphonic acid in 50 ml of distilled water. Hereupon. · salt formation occurred and a clear solution was formed. The solution was then evaporated to dryness in vacuo at a bath temperature of 70°C. The residue which hereupon remained was comminuted and left in vacuo at 70°C for a further 30 to 60 minutes. 24.15 (98.6# of theory) of the disodium salt of aminomethanephosphonic acid were thus obtained. On heating, the salt behaved as follows: at 84 to 85°C, liquefaction occurred, and from 124°C onwards the water of crystallisation boiled off and the residue rreessoolliiddiiffiieed and did not melt again up to 355°C.

Example 20 0.1 mole of hydrochloric acid was added to a suspension of 11.11 g (0.1 mole) of aminomethanephosphonic acid in 50 ml of distilled water. Hereupon salt formation occurred and a clear solution resulted. The solution was then evaporated to dryness in vacuo at a bath temperature of 70°C. The residue which hereupon remained was comminuted and was then left for a further 30 to 60 minutes in vacuo at 70°C. 14.6 g (99$ of theory) of ammonium-methyl-phosphonic acid chloride of melting point 170-172°C (decomposition) were thus obtained. Example 21 - - - sulphuric acid. Di-(ammonio-methyl-phosphonic acid) sulphat of melting point 117-119°C was thus obtained. Yield: 00# of theory.

Example 22 | II . OH ® H2N-CH2-P ^ ø H3N-CH2-C00H The mono glycine salt of aminomethanephosphonic acid was prepared, by a method analogous to the one described in Example 1, by reaction of aminomethanephosphonic acid with glycine. Mono glycine salt of aminomethanephosphonic acid of melting point 209 °C (decomposition) was thus obtained. . v

Claims (17)

45031/2 What we claim- is:

1. A plant-growth-regulating composition containing as active ingredient an aminomethanephosphonic acid derivative of the general formula R-CKL-P^ (I), ^OR" in which R is .an NI^ group or an - H ® radical wherein X ^ is one equivalent of an anion of an organic or inorganic acid, and R1 and R" , which may be identical or different, are each alkyl with 1 to 6 carbon atoms, one equivalent of an alkali metal or alkaline earth metal cation,- one equivalent of a cation of the formula H-®/:—Rl wherein R^, R2 and , which may be identical or different, are each hydrogen, alkyl, hydroxyalkyl, carbethoxyalkyl , carboxyalkyl , or a -CH2-CH2-ΘNH3 group, or R2 and R3 together with the nitrogen atom form a five or six membered heterocyclic ring, or R' and R" are hydrogen, provided that R' and R" can simultaneously be hydrogen only if R is an -NH^X^ radical , in admixture with a solid or liquefied gaseous diluent or carrier or in admixture, with a liquid diluent or carrier containing a surface-active agent. 45031/2

2. A plant-growth-regulating composition containing as ^ active ingredient a compound of the formula (I) in Claim 1, * Θ Θ in which R is an H2 group or an -NH-^X radical, in which Xθ is one equivalent- of an anion of an optionally substituted carboxylic acid, of a hydrohalic acid, of a halogen oxyacid, of nitric acid or of a sulphur-containing acid; and R' and R" are each hydrogen (subject to the proviso in Claim 1) straight-chain or branched alkyl with 1 to 4 carbon atoms, one equivalent of a sodium, potassium, calcium or magnesium cation, or one equivalent of a cation of the formula wherein 1 2 3 R , R and R , -which may be identical or different, are each hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms, carbethoxymethylof the formula -CH2-COOC2H5 , carboxymethyl of the formula -CH2-C00H, or a -CH2-CH2-SH3 group, or R2 and R3 together with the adjacent nitrogen atom form a pyrrolidine, piperidine, imidazole or morpholine ring, in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent. - 22 - 45031/2 ^

3. A plant-growth-regulating composition containing as active ingredient the compound of the formula in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

4. plant-growth-regulating composition containing as active ingredient the compound of the formula in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent. - 23 - 45031/2

5. A plant-growth-regulating composition containing as active ingredient the compound of the formula H2N-CH2-P o Θ NH5..CH(CH3)2 (6) in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquids diluen or carrier containing a surface-active agent.

6. A plant-growth-regulating composition containing as active ingredient the compound of the formula 0 0oHø H3øN-CH2-CH2-0H (16) in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

7. A composition according to any of claims 1 to 6, containing from 0.1 to 95% of the active compound, by weight.

8. A composition according to claim 7, containing from 0.5 to 90 of the active compound, by weight.

9. A method of regulating the growth of plants which comprises applying to the plants or a plant habitat a compound of the formula given in any of claims 1 to 6 alone or in the form of a composition containing as active ingredient a compound of the formula given in any of claims 1 to 6 in admixture with a diluent or carrier.

10. A method according to claim 9t in which a composition is used containing from 0.0005 to 2% of the active compound, by weight.

11. A method according to claim 10, in which a composition is used containing from 0.01 to 0.5% of the active compound, by weight.

12. A method according to claim 9» 10 or 11, in which the active compound is applied to an area of agriculture in an amount of 0,01 to 20 tg per hectare. 45031/2 compound is applied to an area of- agriculture in an amount of ,1to 10 kg per hectare.

13. H. A D'ethod according to any of claims 9 to 1?, in which the active compou d is one of tlic e hereinbeiore mentioned in

14. Example A or B.

15. Plants the growth of which has been regulated by their being grown in areas in which immediately prior to and/or during the time of the growing a compound of the formula given in any of claims 1 to 6 was applied alone or in admixture with a diluent or carrier.

16. Aminomethanephosphonic acid derivatives of the general formula in which R is an wherein P is one equivalent of an anion of an organic or inorganic acid, and R' and R" are hydrogen.

17. Compounds according to claim 16 in which is one equivalent of an anion of an optionally substituted carboxylic acid, of a hydrogen halide acid, of a nitric acid or of an acid containing sulphur. the Applicants REINHOLD COH& AND HE:mr