LT3194B - Novel unhygroscopic ammonium salts - Google Patents

Abstract

New non-absorbent crystal mono-amino saline general I formulas, in which -R1 means hydroxyl or alkyl, -A means groups of C1-4 alkyl amino - or amino alkyl with primary or secondary amino-clumps, the best with - CH2-NH- or -CH(NH2)-CH2- groups.-B means amino ion or amino ion changed with alkyl. There are also methods to obtain this saline, producing the saline of the I formula according to any generally known method for saline abstraction, where - avoiding other pollution - in a saline forming process or after it, the formation of di-ammonium saline general V formula, in which -R1, A and B has the meanings described above, is eliminated or repressed. The described herbicidal or plant growth regulating compositions with this non-absorbent saline, its abstraction methods, and the processing methods of unacceptable plants and weeds, and also tough and flexible dry capsules for storing these compositions are made of polymers which are deliquescent in water.

Description

The present invention relates to novel mono-ammonium salts, their preparation and their use as. pesticide active ingredients.

More particularly, the present invention relates to novel solid non-hygroscopic monoammonium salts of the general formula I which are substantially free of the diammonium salts of the general formula V, to processes for preparing these salts, to pesticidal compositions containing them and to the preparation of said pesticidal compositions. recovery.

In this description, the substituents in the general formula always mean:

-R ¹ - hydroxyl or alkyl groups,

-A-alkylamino or aminoalkyl groups with primary or secondary amino groups, preferably with 20 -CH ₂ -NH- or CH (NH ₂ ) -CH- groups,

-B - an ammonium ion or an alkyl substituted ammonium ion,

-R ² - hydrogen, hydroxy; may be _{4 to 4} alkyl groups or substituted alkyl and aryl or substituted aryl.

Salts of general formula I are known as active ingredients in pesticides, and their preparation and properties are described in the literature. But the mono-ammonium salts of the general formula I have never been described in a state other than hygroscopic products, which are not sensitive to the humidity of normal atmosphere, so their use as pesticides was only possible by dissolving the products in water and selling the aqueous solutions of the product.

This procedure is clearly inconvenient. It was therefore an object of the present invention to provide a method for obtaining the mono-ammonium salt of the general formula I - in particular the N- (phosphonomethyl) glycine mono-isopropylammonium salt and the (3-amino-3-carboxypropyl) -methanephosphinic acid mono-isopropylammonium salt and in this way they can be transported, commercialized and even used in solid form. Alternatively, if aqueous solutions are used directly in the field, to ensure the solubility of the solids prior to use, thus transporting and warehousing at reasonable prices relative to the current situation when transporting and storing aqueous solutions. Commercial aqueous solutions contain a maximum of 30-50% active ingredient. Working with hygroscopic salts also raises environmental and health safety issues that could be avoided with non-stick non-hygroscopic products. Products are mainly acidic and even affect the material in which they are transported, so they require more attention and the right protective material - all of which increases their running costs.

The main constituents of the compounds of the general formula I are the pesticidal ingredients N- (phosphonomethyl) -glycine monoisopropylammonium salt and (3-amino-3-carboxy · propyl) methanephosphate acid monoisopropylammonium salt, but also their ammonium salts.

The salts, their preparation and their use are described in various piblikations: U.S. Pat. No. 3315675, 356672, 4405531, 3868407, 4140513, 4397676 and Hungarian patent no. 184601, as well as U.S. Pat. No. 3288846, 4507250, 4147719, 4487724, German patent no. 3312165, European Patent Nos.

No. 249188, 265412, 301391, and Japanese Patent Nos. No. 60.248190, 02.190196, 59.181288.

In order to avoid the aforementioned consequences, various methods have been developed; Various additives have been proposed - auxiliary agents to ensure the production and application of a wetting powder / fig. European patents no. No. 256942, 352508, Japanese Patent Nos. No. 01.42409, 58.18311, 62.175407, 62.175408 and U.S. Pat. No. 4405531 / Nevertheless, great care must be taken in their practical use to protect the powder from moisture, to fully use open packaging, to store products in suitable conditions, and so on. since add-ons can sometimes not produce the desired results. Another approach to the problem is the idea of spray drying the product / Japanese patent no. 63.10701. Another idea is to mix the salt with the solvent and the molten surfactant to form a mixture from which the solvent is evaporated and the surfactant is frozen until it solidifies, then the product becomes solid (European Patent No. 0206537).

Salts are usually obtained by reacting the acidic and basic components in an aqueous medium (e.g. Hungarian Patent No. 185003, Swiss Patent No. 620812 and German Patent No. 2717440), although the literature also mentions the reaction of the acidic and basic reactants with subsequent addition to the reaction mixture. surfactant, and obtaining the composition after cooling the mixture. / See also Spanish patent no. 530743, wherein the solvents proposed for the analogous method are benzene or water.

What all publications have in common is that, in terms of the quality of the products obtained, they are referred to as hygroscopic / e.g. German patent no. 2717440,

Swiss Pat. 620812 Ammonium salts of glufosinate /, and some publications indicate that solid products are glassy materials that may be crushed in a mortar but still hygroscopic when stored.

Hungarian application no. No. 1322/90 discloses a novel, easy-to-use composition of N (phosphonomethyl) -glycine, which consists of a water-soluble capsule (s) with a hygroscopic powder of the Na or K salt of N- (phosphonomethyl) glycine. The authors state that they have not been able to obtain a similar formulation using the N- (phosphonomethyl) glycine monoisopropylammonium salt due to the extremely hygroscopic nature of the monoisopropylammonium salt. The aqueous solution of N (phosphonomethyl) glycine mono-isopropylammonium salt also did not work as it dissolves the capsule material even before use.

Investigating some of the products obtained by known methods / e.g. repeating the processes according to European patent no. 0256608; and Spanish patent no. 530743 /, we found that the resulting products are not the mono-isopropylammonium salts of the specified acids.

Our invention is based on the claim that mono-isopropylammonium salts, when tested by known methods of analysis, are always products containing certain amounts of the general Form V di-ammonium salts.

The presence of small amounts of di-ammonium salts is not obvious when analyzing products by classical analysis: mono-ammonium salts of general formula I may contain free acids of general formula II together with di35 ammonium salts of general formula V - thus obtaining analytical results concealing di-ammonium salts presence.

By separating the di-ammonium salts from the general formula V, we have found that these salts differ significantly from the monoammonium salts in their hygroscopicity, so that small amounts of the di-ammonium salts strongly influence the hygroscopic properties of such salts.

Examination of the resulting N- (phosphonomethyl) -glycine by known FT-IR spectroscopy revealed that the product spectra contained free carbon- valence oscillations of N- (phosphonomethyl) -glycine at wavelengths 1717 and 1733 cm ^-1 and free carboxylate N (phosphonomethyl). -glycine in diisopropylammonium salt at 1561 and 1633 cm @ ^-1 . The change in the proportions of these relationships represents the change in the ratio of the component. This was demonstrated by preparing standard samples of mono- and diisopropylammonium salts and recording their calibration spectra.

It can be seen from the IR spectroscopy data that glufosinate also exists in two different forms of the porous ionic structure. In this way, the carboxylic group can be expressed both in the dissociated form at 1640 and 1600 cm @ ^-1 and in the undissociated form at 1733 and 1728 cm @ ^-1 .

Samples must be prepared carefully. Occasionally, when the enantiomers are dissolved before the registration of mono-ammonium salts containing di-ammonium as well as free acidic impurities, additional reactions occur, then results are not characteristic of the product.

Compared to the spectra obtained by our methods, it appears that the products of the present invention lose the absorption bands of the undissociated carbonyl group at 1730 cm ^-1 , while the dissociated carboxylation bands at the characteristic salts increase at 1640 and 1600 cm ^-1 .

The above spectroscopic data allow the use of HPLC methods and automated analytical methods to determine the melting point to determine the properties of the new salts.

In accordance with the present invention, the term non-hygroscopic means that there is no appreciable increase in water absorption over a period of 3 weeks at 25 ° C and 60% atmospheric humidity, or less than 0.1%. The salts are crystalline, have ranges of melting points different from those previously reported, and have slightly higher water solubility compared to salts obtained by known methods. The main object of our invention is the non-hygroscopic salts of the general formula I.

The most important products of the present invention are solid non-hygroscopic N- (phosphonomethyl) -glycine monoisopropylammonium salts of the a or / and β crystalline type.

a - The crystalline type has a melting range of 158 ° -163 ° C: Typical crystal lattice levels measured by X-ray diffraction are: 11.0, 9.06, 5.94, 5.54, 4.13, 3.71 and the characteristic absorption bands of the FT-IR spectra are 1660 , 1600, 1553, 1545, 1075, 513 and 475 cm ^-1 .

Other important products of the present invention are solid non-hygroscopic crystalline N- (phosphonomethyl) -glycine mono-isopropylammonium salts of β-crystalline type, with melting range 143-157 ° C, crystalline lattice plane sizes (as measured by retgraph diffraction) 7.00, 4.83, 4.47, 3.35, 2.815 and characteristic absorption bands in the FT-IR spectra of 1645, 1594, 1561, 1541,

1066, 500 and 455 cm ' ¹ .

Thus mono- isopropylammonium salt of N- (phosphonomethyl) glycine. there may be two different crystalline forms which we have named α and β types. None of these have ever been described as a non-hygroscopic crystalline product.

Another important product of the present invention is a solid non-hygroscopic crystalline (3-amino-3-carboxypropyl) methanephosphinic acid mono-isopropylammonium salt with a melting range of 199-203 ° C and characteristic absorption bands in the FT-IR spectrum. 1640, 1601, 1530,

1138, 1037, 750 and 471 cm ^-1 .

Another object of the present invention is a process for synthesizing a solid non-hygroscopic salt by preparing a monoammonium salt of the general formula I according to a commonly known salt process which, while avoiding other contamination, eliminates or inhibits the formation of a di-ammonium salt

Preferred embodiments of the present invention include the use of the following processes, each or a combination thereof:

(a) by reacting an acid of the general Formula II with a basic or alkaline reagent capable of forming an ion B ^{+ in an} organic polar solvent or mixture of solvents containing an organic polar solvent in which the salt and acid of general Formulas I and II are insoluble or poorly soluble; The di-ammonium salt of the general Formula V formed as a by-product is easily soluble and the reaction mixture can then be heated to a high degree: or

(b) the di-ammonium salt of the general formula II is reacted with an acid of the general formula II under reaction conditions as in process (a): or

(c) an acid of general formula II which is reacted with a salt capable of forming an ion B ⁺ under reaction conditions as in process (a): or

d) the hygroscopic salt of the general formula I is extracted with an organic, preferably polar, solvent or mixture of solvents containing an organic polar solvent in which the mono-ammonium salt is insoluble or slightly soluble and the di-ammonium salt is freely soluble: or

(e) removing at room temperature, under vacuum or heating, from the di-ammonium salt of the general formula V or from a mono-ammonium salt contaminated with a di-ammonium salt, an amount of the amine containing B ⁺ ion greater than the molar equivalent: or

f) under reaction conditions as in process a), the acid salt of the general Formula II is treated with a reagent capable of forming a B ⁺ ion and the resulting salt of the general Formula I thus obtained is isolated, preferably by filtration.

In the above processes, N- (phosphonomethyl) glycine of formula III or (3-amino-3-carboxypropyl) methane-phosphinic acid of formula IV is more suitable as starting acids.

Suitable solvents for our process are aliphatic alcohols having from 1 to 6 carbon atoms and / or polyalcohols and / or aromatic alcohols with C 1-8 alkyl side chains. Preferably, the mono-isopropylammonium salt or monoammonium salt of N (phosphonomethyl) glycine is produced in the presence of ethanol and / or propanol. Suitable temperature ranges for reactions according to method c) are 0-150 ° C, most preferably 20-80 ° C.

Essential moment in the process a) Use of a suitable solvent: The latter must be selected in accordance with our invention. As selected, solubility tests should be performed prior to selection. It is important to use solvents in which the salt of the general Formula I and the acid of the general Formula II are practically insoluble or poorly soluble, and the alkaline reagent and the di-ammonium salts of the general Formula V are readily soluble.

The assumption as to how the process may proceed is as follows: The reaction begins on acid particles suspended in a solvent system. Because the acid is 2-base and is an excess of amines, di-ammonium salts are formed on the surface of the acid, which "subsequently leave the surface of the acid particles and dissolve because they are readily soluble in solvent and remain accessible for reaction with new amines. At an analogous rate to that used by the amine or other-basic reagent, the remaining dispersed acid and the di-ammonium salt in the solution can initiate an ion-exchange reaction to form the mono-ammonium salt. Because the solubility of the mono-ammonium salt in the solvent mixture is very low, the mono-ammonium salt is precipitated all the time.

We have found that polar organic solvents or solvent mixtures containing organic polar solvents are suitable for process (a) of the present invention.

The above theory is supported by the changes observed when, for example, N- (phosphonomethyl) -glycine reacts with isopropylamine according to method (a) of our invention:

When a dispersion of N- (phosphonomethyl) -glycine in absolute ethanol is produced, a bright white liquid is obtained. When isopropylamine 7 is subsequently introduced, the color becomes lighter; after addition of all isopropylamine and warming up at the end, the reaction mixture becomes almost clear: after heating, the mono-ammonium salt precipitates.

Knowing that the above method is suitable for obtaining a mono-ammonium salt substantially free of di-ammonium, other methods are also feasible.

To investigate the process, we prepared the di-ammonium salt using double amounts of isopropylamine and tested the product and its solubility / see Tables IV and V. / Then we used these products as starting materials for our process variants b) and e).

The experiments described illustrate why it was not possible to obtain pure mono-ammonium salts according to European patent no. 256608; and Spanish patent no. 530743: They used solvents in which the diisopropylammonium salt did not dissolve readily, resulting in the mono-ammonium salt being significantly contaminated with both the di-ammonium salt and the parent acid.

The advantage of method c) is that the acid of the general formula II is reacted with a salt of a 1- or 2-base carboxylic acid derivative with a pK of 2.27-5.58. The acids may follow the general formula VI.

In this way, the alkyl-ammonium salts are prepared by the method

(c) The use of an acid of the general formula VI may be used

alkylammonium salt which is administered in solid form or in solution.

A more suitable temperature range for the reactions according to method c) is 0-150 ° C, most preferably 20-80 ° C.

Amine salts are used according to our method c). It is usually easier to work with salts than with amines, which have lower boiling points. Of the carboxylic acids, it is preferable, e.g., acrylic, i

benzoic, formic, propane, butyric, valeric and other acids.

The salts may be prepared separately and these isolated salts are added to the acids of the general formula II. However, it is also possible to formulate a salt in solution and inject the solution without isolation after the necessary analytical assessments have been made.

The processes according to our invention are simple, do not require special equipment and do not cause ecological problems, while allowing to obtain new crystalline mono-ammonium salts in accordance with our invention.

It is another object of the present invention to provide herbicidal or plant growth controlling compositions containing an effective amount of the crystalline non-hygroscopic salts of the general Formula I as an active ingredient.

Of particular interest are our inventive herbicidal or plant growth regulating compositions which contain as an active ingredient an effective amount of crystalline non-hygroscopic (3-amino-3-carboxypropyl) methane-phosphinic acid mono-isopropylammonium salt or a and / or β crystalline N- ( phosphonomethyl) -glycine mono-isopropylammonium salts.

12 '

The compositions of the present invention preferably contain from 0.1 to 99.9% of said salts as active ingredients, together with additives and auxiliary products used in the pesticide industry and / or products which modify the properties of the composition in the desired direction in agriculture.

Surfactants which reduce the surface tension and which may be cationic, anionic, nonionic or amphoteric may be used as additives and auxiliary products. Other additives include adjuvants, agents to stimulate and reduce adhesion and foam inhibitors, solubility enhancers, coloring agents, products to enhance rain and corrosion resistance, activators and the like.

The most likely ancillary products are:

- water-soluble alkylsulfonates, alkylphosphates, alkylbenzenesulfonates,

- naphthyl sulphonates, alkyl naphthyl sulphonates,

- sulphated fatty alcohols, amines, acid amides,

- sulphated or sulphonated fatty acid esters,

- sulphonic vegetable oils,

- Alkylphenols such as isooctylphenol and nonylphenol, polyoxyethylene derivatives and hexital anhydrides

- poly (oxyethylene) derivatives of mono- (long-chain) fatty acid esters,

- polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ethers,

- formaldehyde condensates of polyoxyethylene alkylaryl ether,

- polyoxyethylene alkylenaryl ethers,

- polyoxyalkylene alkyl ether,

- polyoxyalkylene sorbits - esters of sorbitan and glycerol,

- polyoxyalkylene block copolymers,

- polyoxyalkylene allylsulfonamides,

- alkyl glycerol esters of polyoxyalkylene,

- esters of polyoxyalkylene resins,

- polyoxypropylene block copolymers, polyoxyethylene oleyl ethers,

- polyoxyalkylene alkylphenols and mixtures thereof,

- polyoxyalkylene alkylamines, leached solid vegetable ethoxylated oleamine such as ethoxy oil amine, ethoxylated soy amine, ethoxylated cocoa amine, ethoxylated synthetic alkyl amines, propoxylated amines and mixtures,

- Pallyloxyalbylene alkyl and alkylaryl ether sulfates,

- Styryl-phenyl ether sulphates of polyoxyalkylene,

- formaldehyde condensates of alkylnaphthalene,

- alkyldiphenyl ether sulfonates, i

polyoxyalkyl alkyl phosphates,

- pilyloxyalkylene-phenyl ether phosphates,

- polyoxyalkyl-phenol phosphates, «

- polycarboxylates, laurides of N-methyl-fatty acid,

- amino oxides such as lauryldimethylamine oxide,

- N- (phosphonomethyl) -glycine surfactant salts, eg N- (phosphonomethyl-glycine N, Nbis (hydroxyethyl-cocosamine salt),

- saturated fatty alcohols,

- esters of organic acids, ethyl ester of lactic acid, dibutyl phthalate, isopropyl ester of adipic acid,

- fatty acids, salts of fatty acids, esters of fatty acids, ethyl oleate, ethyl stearate, di-n-butyl adipate

- lauric acid hexyl ester, dipropylene glycol pelargonate,

- isopropyl methyl myristate, isopropyl palmitate, isopropyl stearate,

- oleic acid, oleyl ester, dodecyl ester of oleic acid, polyglycerol and lauric ester,

- esters of caprylic / capric acid-saturated fatty alcohols,

- glycerol and polyvinyl alcohol derivatives,

- phospholipids, alkyl polyglycoside derivatives,

- methyl, hydroxyethyl, hydroxymethyl and other cellulose derivatives,

- polyvinyl derivatives,

- lignin sulphonates, polymeric alkyl naphthalenesulphonates,

- poly (methylene) -bis- (naphthalenesulfonate), N-methyl-N (long chain) fatty acid laurates,

- quaternary ammonium salts, alkyl and alkyl-aryl ammonium halides, e.g. Alkyl-dimethyl-, alkyl-trimethyl-, alkyl-benzyldimethyl-ammonium chlorides of 10-18 carbon atoms, e.g. cetyl-trimethyl-ammonium chloride,

- anionic, cationic, non-ionic and amphoteric fluoroaliphatic wetting agents,

- surface activators based on silicone copolymers,

- tetraethoxysilane derivatives.

Preferably, the compositions contain additives of specific inorganic or organic products containing nitrogen such as ureas, urea derivatives or inorganic salts such as calcium, sodium, ammonium chloride, sulfate, phosphate, borate and the like.

The compositions may also contain paraffinic hydrocarbons, mineral oil fractions, natural vegetable oils, organic solvents.

Inert binding products such as diatomaceous earth, kaolin, atapulgite, milo clay, montmorillonite, bentonite, synthetic silicylic acids, thiosulphates, and other agents may be adjuvanted using the compositions.

Because these compositions are solid, they can be given various forms, depending on the application requirements, using the right equipment:

pills, powders, tablets, granules.

In addition to the above, the compositions of the present invention may contain products which themselves have pesticidal or other biological activity. These may be insecticides, fungicides, herbicides, growth regulators or chemical fertilizers, trace elements, etc. t.

The best partners of this type in the composition are, for example:

2,4-D = 2,4-Dichloro-phenoxyacetic acid '17 endotal = 7-oxybicyclo / 2,21 / heptene-2,3-dicarboxylic acid

2,4,5-T = 2,4,5-trichlorophenoxyacetic acid,

MCPA = 4-chloro-o-tolyloxyacetic acid,

MCPB = 4-4-chloro-o-tolyloxy acetic acid, glufosinate = ammonium / 3-amino-3-carboxylpropyl / methylphosphinate, bialafos = dl-homoalanine-4-yl-methylphosphinate, etaphone = 2-chloroethane phosphonic acid, mecoprop = 2 - / 2-Methyl-4-chloro-phenoxypropanoic acid, picloram = 4-amino-3,5,6-trichorpicolinic acid, benzak = 2,3,6, -trichlorobenzoic acid, dalapon = 2,2-dichloropropanoic acid, dicamba = 3 6,6-dichloro-o-aniseed acid, dichloroprop = 2- / 2,4-dichlorophenoxy / -propanoic acid, scepter = 2- / 4,5-dihydro-4-methyl-4- / l-methylethyl / 5 -oxo-1H-imidazol-2-yl-3-echinoline carbonic acid,

18pursuit = 2- [4,5-Dihydro-4-methyl-4 / l-methylethyl / -5-oxo-1H-imidazol-2-yl] -5-ethyl-3-pyridine carbonic acid, atrazine = 2-chloro-4 - (ethylamino) -6- (isopropylamino) -s-triazine, simazine = 2-chloro-4,6-bis / ethylamino- (s-triazine), diuran = 3- (3,4-dichlorophenyl) -1,2- dimethylurea, linuron = 3- / 3,4-dichlorophenyl / -1-methoxy-1-methylurea,

NES = 1-naphthylacetic acid, orest = 2- [3- {4,5- (dimethylpyrimidin-2-yl} ureidosulfonyl] benzoic acid, glean = 1- [2-chlorophenylsulfonyl] -3- / 4-methoxy- 6-methyl-1,3,5-triazin-2-yl] urea, allin = methyl 2 - [{4-methoxy-4-methyl-1,3,5-triazin-2-yl} -aminocarbonyl] -aminesulfonyl benzoate, classical = ethyl 2 - [{4-chloro-6-methoxy-pyrimidin-2-yl} -amino] -carbonylamine-sulfonyl-benzoate, fomesafen = 5- [chloro-4- {trifluoromethyl} -phenoxy] -N-methyl-sulfonyl / -2 -nitrobenzamide, oxyfluorophen = [2-chloro-1- {3-ethoxy-4-nitro-phenoxy} -4- / trifluoromethyl] -benzene,

-fero = [phenoxy-prop-ethyl (+ -) ethyl-2,49-6-chloro-2-benzoxazolyl) -oxy-phenoxy] -propanoate,

-alachlor = 2-chloro-2 ', 6'-diethyl-N- / methoxymethyl / -acetanilide,

-propachlor = N-isoporopyl-2-chloro-acetanilide,

-butachlor = N- (butoxymethyl) -2,6-diethyl-2-chloroacetanilide,

-methachlor = 2-chloro-2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) -acetanilide and others.

Further objects of the present invention are methods of making herbicidal or growth-regulating compositions by known methods of producing pesticides, with 0.199.9% of the active ingredient according to our invention and auxiliary products used in the composition of pesticides and / or products that appropriately modify the properties of the active ingredients. products which have biological properties themselves or are known to be active ingredients in pesticides.

Other objects of the present invention are herbicidal or plant growth regulating compositions consisting of a capsule (sachet) which is solid in dry state and is made from a water-soluble polymer-filled composition according to the present invention.

The most suitable products of this type are those containing the N- (phosphonomethyl) -glycine monoisopropylamine or mono-amino salt, or the mono-isopropylammonium or mono-ammonium salt of glufosinate.

Capsules of such measurements are used in the present invention that they contain 0.1 to 10 kg, preferably 0.5 to 5 kg of the inventive composition. Preferably, they are completely filled with the invented composition. But some space may be left to facilitate the introduction of certain materials before use.

At ambient temperature and humidity, the 5 capsules are hard and flexible. Wall thickness - up to

20-100 microns, more preferably 30-60 microns, and are adhered (fused) to at least one side.

The water soluble capsules used in our invention are known as such. The following water-soluble polymers may be used:

- polyvinyl alcohols, in particular polymers of polyvinyl alcohol plasticized with polyvalent alcohols,

- methylcellulose,

- copolymers of ethylene oxide,

- polymers of vinylpyrrolidone or vinyl acetate,

- gelatin, carboxymethylcellulose, dextrose, hydroxyethylcellulose, or

- methylcellulose with polyvalent alcohols such as ethylene glycol, propylene glycol, glycerol, sorbitol, etc.

It may be necessary to protect the capsules by placing them in larger containers or general packages. The latter must be made of cheap material such as plastics, cardboard or aluminum. This does not affect the isolation of the products from the environment since the materials do not come into direct contact with the pesticides inside the polymeric capsules.

According to our invention, the polymeric capsules may contain the mono-ammonium salt of the general formula I alone or may be present in the compositions described above. They may also contain additional protective colloids to increase the density of the stabilizing products. products, products such as thixotropic substances, etc. t,

According to our invention, the capsules are poured into the required 10 volumes of water with vigorous stirring. Within 2 minutes, the polymeric material disappears and the herbicidal composition dissolves or disperses in water, and the resulting liquid can be used in the fields as needed.

Another object of the invention relates to the elimination of undesirable plants or to the regulation of plant growth by the action of an effective amount of a herbicidal or plant growth-controlling composition of the invention. The plants are sprayed with water or aqueous / organic solvent solutions, dispersions or suspensions of this composition.

Figures 1-6 show:

FIG. 1: Diffraction spectrum of α-crystalline glycine mono-isopropylammonium.

FIG. 2: Mono-isopropylammonium ray diffraction spectrum of β-crystalline glycine.

X-rays of N- (phosphonomethyl) salts

X-rays of N- (phosphonomethyl) salts

FIG. 3: DSC studies of a-type crystals of N-phosphonomethyl) -glycine mono-isopropylammonium salt.

FIG. 4: DSC studies of β-type crystals of N- (phosphonomethyl) -glycine mono-isopropylamine salt.

FIG. 5: 1: 1 DSC analysis of a mixture of N- (phosphonomethyl) -glycine mono-isopropylammonium a salt and β-type crystals.

FIG. 6: FT-IR spectrum of a-type crystals of N- (phosphonomethyl) -glycine mono-isopropylammonium salt.

The details of the invention are set forth in the following examples which illustrate but not limit the invention.

I CHEMICAL EXAMPLES

I.1 For example

g 90.3 mole) of N- (phosphonomethyl _r) glycine react at room temperature with 17.5 g (0.3 mole) of isopropylamine in 200 ml of 96% ethanol. The mixture is boiled for one hour, filtered, and recrystallized. dry crystalline Nsu is concentrated by evaporation in a refrigerator,

69 g (0.3 mol) of (phosphonomethyl) glycine mono-isopropylammonium salt are obtained. The product is non-hygroscopic, freely soluble in water. Melting point 161-163 ° C, (phosphonomethyl) -glycine. Yield of absorption band in FT-IR, cm

513, 475; characteristic values measured by X-ray diffraction: 11.0, 9.06, 5.94, 5.54,

4.13, 3.71 (α-type crystals).

has 99.95%

-i

73.9% NB 1660, 1600, crystalline

1553, 1545, 1075, lattice planes

I.2 Eg.

100 g (0.59 mol) of N- (phosphonomethyl) -glycine were treated with 35 g (0.59 mol) of isopropylamine in 400 ml of absolute ethanol at room temperature. The suspension is heated to 49 ° C, then refluxed for half an hour, heated to 78 ° C. After cooling to room temperature, filtration and drying, 129.0 g (0.57 mol) of crystalline N- (phosphonomethyl) -glycine mono-isopropylamine salt are obtained. The product is non-hygroscopic, freely soluble in water, m.p. N- (phosphonomethyl) -glycine, 99.9% yield, characteristic absorption bands in the FT-IR spectrum cm ¹ : 1660,

1600, 1553, 1545, 1075, 513, 475: characteristic values of the crystalline lattice planes measured by X-ray diffraction; 11.0, 9.06, 5.94, 5.54,

4.13, 3.71 (α-type crystals).

Using the example of 1.2, the following results are obtained:

For example .. amine solvent fmg * salt, g melting point ° C yield,% fmg *,% 1.3 isopropyl n.propanol 130.7 159-160 99, 9 74 1.4 isopropyl n.butanol 129.33 159-160 99, 91 74 1.5 isopropyl n. amilo alcohol 123.7 158-159 98.7 73.4 1.6 isopropyl dimethyl foimamid 115.1 148-153 98 73.0

* = N- (phosphonomethyl) -glycine

1.7 Eg.

200 g (1.18 mol) of N- (phosphonomethyl) -glycine are reacted with 140 g of 2.37 mol) of isopropylamine in 600 ml of ethanol and the reaction mixture is heated to reflux and heated to 58 ° C under reflux. hours. After cooling, evaporation and filtration, 335.8 g (1.17 moles) of light are obtained.

· N- (phosphonomethyl) -glycine di- (monoisopropylamino) salts of crystals. The product is freely soluble in water, m.p. t. 145-150 ° C. Contains 57.5% N- (phosphonomethyl) glycine.

170 g (0.59 mol) of N- (phosphonomethyl) -glycine di (mono-isopropylamino) salt are treated with 100 g (0.59 mol) of N- (phosphonomethyl) -glycine in 400 ml of ethanol, refluxed for half an hour, and the milk is filtered off after cooling to room temperature. The product obtained upon drying gives 269.2 g (1.18 mol) of N-phosphonomethyl) -glycine mono-isopropylammonium salt, m.p. temp. 158-160 ° C. The product is non-hygroscopic and contains 74% N-phosphonomethyl) glycine.

I.8 Eg.

Add 100 kg of N- (phosphonomethyl) glycine to a 1 m autoclave vessel with 400 l of ethanol. While stirring, 35 kg of isopropylamine were added to the mixture at 20 ° C under nitrogen. The mixture is warmed to 45 ° C, then heated to reflux and refluxed for one hour. After cooling to 20 ° C, the N- (phosphonomethyl) -glycine mono-isopropylamine salt is centrifuged and washed with 30 L of ethanol and dried after repeated centrifugation. The flush is connected to the mother layer.

130.1 kg of N- (phosphonomethyl) glycine monoisopropylammonium salt are obtained. It contains 74% N- (phosphonomethyl) glycine. Product is non-hygroscopic, freely soluble in water. Melting point 153-156 ° C.

181 g (1 mol) of (3-amino-3-carboxylpropyl) methanephosphinic acid are reacted with 59 g (1 mol) of isopropylamine in 300 ml of methanol. Blend for 30 min. Reflux at 65 ° C, cool, filter and dry the crystals. 232 g of (3-amino-3-carboxylpropyl) -methanephosphinic acid mono-isopropylammonium salt, which is non-hygroscopic, is readily soluble in water: melts at 203-203.5 ° C and has a yield of 75% (3-amino-3-carboxypropyl) -. of methanephosphinic acid. Yield 97%.

Characteristic absorption bands in the FT-IR spectrum are 1640, 1601, 1530, 1138, 1037, 750 and 471 cm ^-1 .

1.10 Eg.

181 g (1 mol) of (3-amino-3-carboxylpropyl) methanephosphinic acid are reacted with 59 g (1.0 mol) of isopropylamine in 800 ml of ethanol at room temperature. Blend for 30 min. Reflux, cool, filter, and dry the crystals.

235.2 g of (3-amino-3-carboxylpropyl) -methanephosphinic acid mono-isopropylammonium salt, which is non-hygroscopic, freely soluble in water, melts at 199203 ° C and contains 74% (3-amino-3-carboxylpropyl) -methanephosphinic acid . Yield 98%.

1.11 Example

181 g (1 mol) of (3-amino-3-carboxylpropyl) -methanephosphinic acid are reacted at room temperature with 17 g (1 mol) of ammonia (previously dissolved in methanol at 0 ° C). The mixture is spontaneously heated to 35 ° C and then boiled Reflux for 30 min at 65 ° C, cool, filter, and dry the crystals to give 193 g (3-amino-3-carboxylic acid 3194B pil) of ammonium salt of methanephosphinic acid, which is non-hygroscopic, freely soluble in water and melts at 207209 ° C. Contains 90% (3-amino-3-carboxylpropyl) methanephosphinic acid in 97.5% yield.

I.12 Example

169.1 g (1 mol) of 100% N-phosphonomethyl) -glycine and 59.11 g (1 mol) of 100% pure isopropylamine are reacted with 700 ml of absolute ethanol at room temperature.

i

The suspension is refluxed for 30 min. cool to room temperature and filter.

216.78 g (0.95 mol) of N-phosphonomethyl) -glycine mono-isopropylammonium salt are obtained. The product is crystalline, non-hygroscopic, freely soluble in water, melts at 161-163 ° C. Characteristic absorption bands in the FT-IR spectrum cm ^-1 : 1660, 1600, 1553, 1545, 1075, 613,

475. Characteristic values of the planes of the crystalline lattice, as measured by X-ray diffraction: 11.0, 9.06, 5.94, 5.54, 4.13, 3.71. (type a crystals). (Fig. 1,3,6).

1.13 Example

Reagents as in Example 1.12. reacts with 70 mL of distilled water by slow addition of isopropylamine. The resulting solution is heated at 100 [deg.] C. for 1 hour, then cooled to room temperature, the crystals are filtered off and dried. 228.20 g (1 mol) of N- (phosphonomethyl) glycine mono-isopropylammonium salt are obtained. The product is non-hygroscopic, freely soluble in water: melting point 147-153 ° C (β-type crystals).

Characteristic absorption bands in the FT-IR spectrum cm ' ¹ : 1645,

1594, 1541, 1066, 500, and 455 cm ¹ are characteristic values of the crystalline lattice planes of ²⁷ as measured by the retgene diffraction method: 7.00, 4.83, 4.47, 3.35, and 2.815. (Fig. 2.4).

1.14 Example

The product obtained according to e.g. 1.12, refluxed for 2x0.5 hours in 700 ml of absolute ethanol: cooled to room temperature, filtered and dried. 220 g of N- (phosphonomethyl) glycine mono-isopropylamine salt are obtained. The product is non-hygroscopic, freely soluble in water: melting point 148-154 ° C (β-type crystals).

1.15 Example

16.9 g (0.1 mol) of N- (phosphonomethyl) -glycine are stirred in 40 ml of absolute ethanol. Add 11.9 g (0.1 mol) of isopropylamine acetate to 80 ° C for 30 min. After cooling to room temperature, the crystals are filtered off, washed with ethanol and dried. Crystalline N- (phosphonomethyl) -glycine mono-isopropylammonium salt is non-hygroscopic; easily soluble in water: melting point 154-157 ° C (type β crystals). Yield 96.9%. Contains 73.8% N- (phosphonomethyl) glycine.

1.16 Example

Repeat the process as in 1.15, except that 14.87 g (0.125 mole) of isopropylamine acetate are used. 21.6 g of crystalline N- (phosphonomethyl) glycine mono-isopropylamine salt are obtained. The product is non-hygroscopic, freely soluble in water, melting point 153-157 ^° C (type β). Yield 95%. Contains 74.1% N- (phosphonomethyl) glycine.

1.17 Example 16.9 g of N- (phosphonomethyl) -glycine are mixed in ml of water and 11.9 g of isopropylamine acetate are added. After a while, the solution becomes clear and is then poured onto the watch glass. Upon storage at room temperature, the water evaporates to give 22.8 g of crystalline N (phosphonomethylglycine mono-isopropylammonium salt) product, non-hygroscopic, freely soluble in water; melting point 148-156 ° C (type β). Contains 74.1% N (phosphonomethyl) ) -glycine.

Example 1.18 16.9 g of n- (phosphonomethyl) glycine are stirred in ml of methanol and 9.1 g of dimethylamine formate are added. By working as in the above examples, 21.31 g of crystalline N- (phosphonomethyl) -glycine mono (dimethylammonium) salt are obtained. Product is non-hygroscopic, freely soluble in water, m.p. temp. Mp 118-124 ° C. Contains 78.3% N- (phosphonomethyl) glycine.

1.19 Example

16.9 g of n- (phosphonomethyl) -glycine are treated as e.g. 1.18

11.9 g ethylamine propionate in 30 ml isopropanol. 19.9 g of crystalline N- (phosphonomethyl) -glycine monoethylammonium salt are obtained. The product is non-hygroscopic, freely soluble in water, melting point 131137 ° C. Yield 93.1%. Contains 77.9% N- (phosphonomethyl) glycine.

1.20 Example

360 g (2.13 moles). N- (Phosphonomethyl) -glycine was treated with 126 g (2.13 mol) of isopropylamine in 100 ml of water at room temperature. The temperature of the mixture reaches almost 100 ° C in 1 hour; the mixture was again cooled to room temperature and maintained for 2 hours. the precipitate is filtered off. The product is hygroscopic. It is extracted twice with 200 ml of absolute ethanol, filtered and dried.

476.0 g of N- (phosphonomethyl) glycine mono-isopropylammonium salt are obtained. Lyd. range 150-154 ° C, freely soluble in water, non-hygroscopic; yield 98%. Contains 74% N- (phosphonomethyl) glycine.

1.21 Example

The reaction is carried out as in 1.20, the difference being that it is removed by evaporation and the remaining solid hygroscopic salt is worked on as above. Incoming

485.6 g of mono- isopropylammonium salt of N- (phosphonomethyl) glycine. Melting point 150-155 ° C, freely soluble in water, non-hygroscopic; yield 99.9%. You have to

73.8 5 N- (Phosphonomethyl) glycine.

1.22 Example

The reaction is carried out as in 1.20, except that the resulting aqueous solution is dried by evaporation and the remaining solid hygroscopic salt is treated as above. The resulting N- (phosphonomethyl) -glycine monoisopropylammonium salt has a melting point of 148152 ° C, freely soluble in water, non-hygroscopic. Yield 99%. Contains 73.9% N- (phosphonomethyl) glycine.

1.23 Example

360 g (2.13 mol) of N- (phosphonomethyl) -glycine are reacted at room temperature with 252 g (4.3 mol) of isopropylamine in 100 ml of water. 360 g of N (phosphonomethyl) -glycine are added and the reaction mixture is heated for 1 hour below 100 ° C. After cooling, the solution is filtered. The hygroscopic product is extracted twice with 200 ml of absolute ethanol, filtered and dried. 962 g of N5 (phosphonomethyl) glycine mono-isopropylammonium salt are obtained. Melting range 154-157 ° C slightly soluble in water, non-hygroscopic. Yield 99%. Contains 74% N- (phosphonomethyl) glycine.

1.24 Example

360 g of N- (phosphonomethyl) glycine are reacted with 126 g of isopropylamine in 100 ml of water at room temperature. The product is precipitated by addition of 500 ml of absolute ethanol and the precipitate is dried to give 480 g of N (phosphonomethyl) glycine mono-isopropylammonium salt. Melting point 148-152 ° C, freely soluble in water, non-hygroscopic; yield 99%. Contains 73.9% N (phosphonomethyl) glycine.

1.25 Example

Following the reaction as-1-24 e.g. and heating the aqueous reaction mixture at 100 ° C for 1 hour, yielding a mixture of oils which is dried at room temperature for 24 hours in a desiccator filled with phosphorus pentoxide or calcium chloride. It is then extracted with 96% ethanol, dried to give 242.5 N- (phosphonomethyl) -glycine mono-isopropylammonium salt.

Melting point 154-157 ° C, freely soluble in water, non-hygroscopic; yield 99% .. Contains 74% N (phosphonomethyl) -glycine.

1.26 Example

The reaction is performed as in Example 1.25. To the oil-like reaction mixture was added 2 g of N- (phosphono-35-methyl) -glycine diisopropylammonium salt after 10 min. after stirring, the N- (phosphonomethyl) -glycine mono-isopropylammonium salt is precipitated. The white salt is filtered off, extracted with 500 ml of absolute ethanol at room temperature, filtered again and dried. 480 g of N- (phosphonomethyl) glycine mono-isopropylammonium salt are obtained. Lyd. temperature 147-152 ° C, freely soluble in water, non-hygroscopic; yield 99%. Contains 73.6% N- (phosphonomethyl) glycine.

i

Example 27 Example g (0.21 mol) N- (phosphonomethyl) -glycine was treated

12.6 g (0.21 mol) of isopropylamine in 100 ml of benzyl alcohol at room temperature. The suspension is warmed to 55 ° C and heated at 100 ° C for 30 min, cooled and filtered. Upon drying, 40.2 g (0.18 mol) of crystalline N- (phosphonomethyl) -glycine monoisopropylammonium salt are obtained. The product is non-hygroscopic, easily soluble in water; melt temp. 158-159 ° C. The active ingredient contains 73.6% N- (phosphonomethyl) glycine. Yield 83%.

1.28 Example g (0.21 mol) of N- (phosphonomethyl) glycine is reacted with

12.6 g (0.21 mol) of isopropylamine in 100 ml of propylene glycol at 10 ° C. The reaction mixture was warmed to almost 50 ° C and then heated at 98 ° C for half an hour. After 24 hours room the crystals are filtered off. Upon drying, 26.3 g (0.11 mol) of N- (phosphonomethyl) -glycine mono-isopropylammonium salt are obtained. Product non-hygroscopic, m.p. temp. 145-147 ° C, containing 73.5% of N- (phosphonomethyl) -glycine. Yield 54%.

II Compositions

11.1 Example

A mixture of 0.5 g of ethoxylated nonylphenol and 2.84 g of alkylamine is dissolved in 40 ml of ethanol at room temperature. After the addition of the N- (phosphonomethyl) -glycine mono-isopropylammonium salt prepared as in Example 1.2. the solution is homogenized and the ethanol is evaporated. 63.3 g of product are obtained, which contains 69.6% of N (phosphonomethyl) -glycine, is non-hygroscopic and readily soluble in water.

11.2 Example

Excipients: 1.1 g of ethoxylated nonylphenol, 6.39 g of ethoxylated alkylamine, 12.69 g of ethoxylated fatty amine and 9.28 g of fatty alcohol and polyglycol ether are made up into a suspension of 30 ml of ethanol. 60 g of N- (phosphonomethyl) -glycine monoisopropylammonium salt prepared as in Example I-3 are added and the suspension is homogenized by adding 4.4 g of urea. Evaporation of ethanol yields 93 g of product containing 47.8% N- (phosphonomethyl) -glycine, non-hygroscopic and freely soluble in water.

11.3 Example

Excipients: 1.53 g of ethoxylated nonylphenol, 3.89 g of ethoxylated alkylamine, 7.92 g of ethoxylated fatty amine and 5.97 g of isotridecanol polyglycol ether in a suspension of 30 ml of methanol. Add 60 g of N- (phosphonomethyl) -glycine mono-isopropylammonium salt prepared as in Example 1.1 and homogenize the suspension by adding a mixture of 2.78 g of potassium chloride, 0.03 g of 1-naphthylacetic acid and 0.08 g of boric acid. Evaporation of the alcohol yields 82 g of a product containing 53.8% N- (phosphonomethyl) -glycine, non-hygroscopic and freely soluble in water.

Example 11.4 5 g of N- (phosphonomethyl) -glycine mono-isopropylammonium salt prepared as in Example 1.2. homogenize with 40 g of Hyspray additive in 60 ml of ethanol. Evaporation of the alcohol yields 125 g of a product which is a non-hygroscopic 10, readily soluble in water and containing 50.4% of N (phosphonomethyl) glycine.

11.5 Example

The procedure used is as in Example 1.11, the difference being that 10 g of Lauropal-X is added to the suspension. The product obtained, - analogous to II. 1, for example, with the same output.

Example II.6

Used in Example 1.12. The difference is that another 50 g of ammonium bicarbonate is added to the suspension and 50 g of the additive Hyspray is used instead of 30 g. Incoming

195 g of a non-hygroscopic, slightly water-soluble product containing 32.3% N- (phosphonomethyl) glycine.

II.7 Example

Applicable II. Example 4 The difference is that 80 g of Hyspray and 10 g of Lauropal-X additives are used in 100 ml of ethanol and 85 g of N- (phosphonomethyl) -glycine monoisopropylammonium salt prepared as in Example 1.2. and 70 g of ammonium bicarbonate and 50 g of ammonium sulfate are added to the suspension.

³⁴

295 g of a non-hygroscopic, easily soluble, aqueous product containing 21.3% of N- (phosphonomethyl) glycine are obtained.

11.8 Example

Applicable to example II.7. Method with the following difference: The quantity of Hyspray additive is 50 g, 100 ml of ethanol is used and 50 g of ammonium sulphate are added. 695 g of product are obtained which is non-hygroscopic, readily soluble in water and contains 9% N- (phosphonomethyl) -glycine.

11.9 Example

Additives - 0.2 g ethoxylated nonylphenol and 1.2 g ethoxylated alkylamine - are dissolved in 10 ml ethanol at room temperature. The solution is homogenized by addition of 24 g (0.1 mol) of (3-amino-3-carboxypropyl) -methanephosphinic acid mono-isopropylammonium salt and the ethanol is evaporated. 25.3 g of a non-hygroscopic product are obtained, which is readily soluble in water and contains 71% of the mono-isopropylammonium salt of (3-amino-3-carboxylpropyl) -methanephosphinic acid.

11.10 Example

Additives - 0.2 g ethoxylated nonylphenol and 7.3 g ethoxylated fatty acid - are mixed with 5 ml ethanol. The resulting suspension is homogenized with 24 g (0.1 mol) of (3-amino-3-carboxylpropyl) methanephosphinic acid mono-isopropylammonium salt prepared as e.g. 1.11, and the ethanol is evaporated. 31.4 g of a non-hygroscopic product are obtained, which is readily soluble in water and contains 57.6% of the mono-isopropylammonium salt of (3-amino-3-carboxypropyl) -methanephosphinic acid.

Example II.11

0.2 g of ethoxylated nonylphenol and 1.2 g of ethoxylated alkylamine are mixed with 8 ml of ethanol. The resulting suspension is homogenized with 19.8% (0.1 mol) of (3-amino-3-carboxypropyl) methanephosphinic acid ammonium salt prepared as II. For example, the alcohol is evaporated. 21.1 g of a non-hygroscopic product are obtained which are readily soluble in water and contain 85% ammonium salt of (3-amino-3-carboxylpropyl) methanephosphinic acid.

11.12 Example

0.2 g of ethoxylated nonylphenol, 1.2 g of ethoxylated alkylamine and 6 g of ethoxylated fatty amine are mixed with 8 ml of ethanol. The resulting suspension is homogenized with 20 g (0.1 mol). Ammonium salts of (3-amino-3-carboxypropyl) methane-phosphinic acid prepared as in Example 1.11. Work as described above gives 26.1 g of the product analogous to the above. The product contains 65% (3-amino-3-carboxypropyl) methanephosphinic acid and is referred to below as acmpa.

Using the above methods ^- ; ' The following compositions are prepared: Water soluble products and solid products capable of wetting or dispersing may be milled or otherwise properly ground.

For example, acmpa- salt acmpa- ¹ small,% % Accessories ethoxylin. nonilfe- hell ethoxylin. fat amine of ammonium sulfate poly-alk sil. rido. alcohol 11.13 isopropyl 98 2 11.14 isopropyl 84 1 15th 11.15 of ammonium 98 2 11.16 of ammonium 80 2 18th 11.17 isopropyl 84 1 10th 5 11.18 of ammonium 68 1 10th 21st 1

Example 11.19 Isopropylamine salt of (3-amino-3-carboxypropyl) methanephosphinic acid 33%

N- (phosphonomethyl) -glycine isopropylamine salt 65%

Ethoxylated nonylphenol 1%

Polyalkoxylated fatty alcohol 1%

Example 11.20 Ammonium salt of (3-amino-3-carboxypropyl) methanephosphinic acid 33% Ammonium salt of N- (phosphonomethyl) glycine 65% Ethoxylated nonylphenol 1% Polyalkoxylated fatty alcohol 1%

Example 11.21 (3-Amino-3-carboxypropyl) -methanephosphinic acid isopropylamine salt 26% N- (phosphonomethyl) -glycine isopropylamine salt 53% Ethoxylated nonylphenol 1% Ammonium sulfate 20%

Example 11.22 Ammonium salt of (3-amino-3-carboxylpropyl) methanephosphinic acid 26%

Ammonium salt of N- (phosphonomethyl) -glycine 53%

Ethoxylated nonylphenol 1%

Ammonium sulphate 20%

Example 11.23 (3-Amino-3-carboxypropyl) -methanephosphinic acid isopropylamine salt 55%

Ethoxylated fatty amine 18%

Imazapril Isopropylamine 27%

Example 11.24 Ammonium salt of (3-amino-3-carboxypropyl) methanephosphinic acid 55%

Ethoxylated alkylphenol 27%

Imazapril Ammonium 27%

Example 11.25 Ammonium salt of (3-amino-3-carboxypropyl) methanephosphinic acid 54%

Ethoxylated fatty amine 19%

Imazapril Ammonium · 27%

Example 11.26 Isopropylamine salt of (3-amino-3-carboxypropyl) -methanephosphinic acid 32%

Ethoxylated alkylamine 4%

2,2-D-isopropylamine salt 64%

Ethoxylated nonylphenol 1%

Example 11.27 (3-Amino-3-carboxypropyl) -methanephosphinic acid isopropylamine salt 30% Polyalkoxylated fatty alcohol 20% Triazine 30% Silica 5% Ammonium sulfate 15%

Example 11.28 Ammonium salts of (3-amino-3-carboxylpropyl) methanephosphinic acid 30% Polyalkoxylated fatty alcohol 15% Triazine 30% Ammonium sulfate 25%

Example 11.29 Ammonium salt of (3-amino-3-carboxypropyl) methanephosphinic acid 68% Oxifluorophene 14% Ethoxylated nonylphenol 1% Polyoxyethyl fatty acid 5% Ammonium sulfate 5% Silica 5%

11.30 Example

With 1 kg of the composition prepared as in the above examples, there is a filling capsule (bag) of a size sufficient to accommodate that amount. The capsule is made of polyvinyl alcohol plasticized with polyvalent alcohol. The capsule is rectangular and closed on three sides. The properties of the powder prepared as mentioned in the examples are such that filling the capsule is not difficult. The capsules are then sealed.

After storage (storage) and delivery to the place of use, the capsules are thrown into the required amount of water with vigorous stirring. The polymeric shell disappears within 2 min. and the herbicidal composition is then completely dissolved or dispersed in water to form a composition which can be applied directly to the field.

The following examples describe various water-soluble or water-wettable solid compositions. The active ingredient, the non-hygroscopic salt of N (phosphonomethyl) -glycine mono-isopropylammonium, is further abbreviated as the solid glyphosate mono-salt.

11.31 Example

Solid glyphosate mono-salt Ethoxylated nonylphenol

11.32 Example

Solid glyphosate mono-bis salt Ethoxylated nonylphenol Ethoxylated alkylamine

11.33 Example

Solid glyphosate mono-ipa salt Ethoxylated nonylphenol Ethoxylated fatty amine

11.34 Example

Solid glyphosate mono-biphenyl salt Ethoxylated nonylphenol

98%

2%

95%

1%

80%

77s

1%

Ethoxylated alkylamine 7% Ethoxylated fatty amine 10% Urea 5%

11.35 Example

Solid glyphosate mono-salt salt 60% Ethoxylated nonylphenol 1% Ethoxylated alkylamine 7% Ethoxylated fatty amine 10% Polyalkoxylated fatty alcohol 2% Ammonium sulfate 20%

II.36 Example

Solid glyphosate mono-salt 70% Ethoxylated nonylphenol 1% Ethoxylated alkylamine 4% Ammonium sulphate 20% Silica 5%

11.37 Example

Solid glyphosate mono-ipa salt 68.00% Ethoxylated nonylphenol 2.00% Ethoxylated alkylamine 4.50% Ethoxylated fatty amine 9, 60% Iso-tridecyl alcohol and polyglycol ether 7.30% KCl 3.45% 1-naphthylacetic acid 0, 05% Boric acid 0.10%

11.38 Example

Solid glyphosate mono-batch salt 50%

2,4-D-Isopropylammonium salt 32% Ethoxylated nonylphenol 1%

Ethoxylated alkylamine 4%

Ammonium sulphate 8%

Silica 5%

11.39 Example

Solid glyphosate mono-bis salt 40%

Glufosinate mono-batch salt 7%

Ethoxylated nonylphenol 2%

Sodium lignin sulphonate 3%

Ammonium sulphate 33%

Silica 5%

Kaolin 10%

11.40 Example

Solid glyphosate mono-bis salt 40%

Dimetipin 7%

Ethoxylated nonylphenol 2%

Sodium lignin sulphonate 3%

Ammonium sulphate 33%

Silica 5%

Kaolin 10%

11.41 Example

Solid glyphosate mono-bis salt 50%

Oxifluorophen 4%

Ethoxylated nonylphenol 2%

Sodium lignin sulphonate 3%

Silica 16%

Kaolin 20%

11.42 Example

Solid glyphosate mono-bis salt 40%

Ethoxylated nonylphenol 1%

Ethoxylated alkylamine 4%

Ethoxylated fatty amine 15%

Ammonium sulphate 30%

Kaolin 10%

11.43 Example

Solid glyphosate mono-bis salt 80%

OPENING 411 19%

Polyalkoxylated fatty alcohol 1%

11.44 Example

Solid glyphosate mono-bis salt 40%

Glufosinate ammonium salt 20%

Ethoxylated nonylphenol 1%

Ethoxylated alkylamine 4%

Ammonium sulphate 35%

11.45 Example

Solid glyphosate mono-batch salt 0.1%

Ammonium sulphate 80.05

Ethoxylated nonylphenol 1.0%

Ethoxylated fatty amine 18.9%

11.46 Example

Solid glyphosate mono-bis salt 99%

Ethoxylated nonylphenol 1%

11.47 Example

Solid glyphosate mono-ipa salt Dissovet S

1%

99%

11.48 Example

Solid glyphosate mono-salt Ammonium sulphate Ammonium nitrate

Polyalkoxylated fatty alcohol

1%

70%

28%

1%

11.49 Example

Solid glyphosate mono-ipa salt Polyalkoxylated fatty alcohol

99.9% 0.1%

11.50 Example g of N- (phosphonomethyl) -glycine mono-isopropylammonium salt, 3 g of 3,6-dichloro-2-pyridine-2-carbonic acid. 10 g of potassium salt of lignin sulphonic acid, 1 g of sodium salt of oleylmethyluric acid, 4 g of polyoxylated nonylphenol, 4 g of polyethylalkylamine and 10 g of synthetic silica are reduced to a particle size of 7-15 µm. A wetting powder is obtained which contains 50% N- (phosphonomethyl) glycine and 17.5% metribezine and can be used in a known manner.

Example 11.51 g of N- (phosphonomethyl) -glycine mono-isopropylammonium salt, 10 g of 2,3-dihydro-5,6-dimethyl-1/4-lithium-1,1,

4,4-Tetroxide, 3 g of polyethoxylated nonylphenol, 7 g of polyethoxylated fatty acid amine, 7 g of lignin sulphonic acid potassium salt and 5 g of synthetic silica are crushed (crushed) to the desired size for agricultural use.

II. Example 52 g of N- (phosphonomethyl) -glycine mono-isopropropylammonium salt, 8.75 g of 4-amino-3-methylmercapto-6-tert-butyl-1,2,4-triazine, 5 g of potassium salt of lignin sulfonic acid, 5 'g of polyethoxylated nonylphenol, 1 g of sodium salt of oleyl lauric acid and 12.25 g of Aerosil are crushed to a size of 7-15 µm. The resulting powder is non-hygroscopic and contains 50% N (phosphonomethyl) -glycine. They can be made into suspensions for agricultural use.

III. ANALYTICAL TESTS

III.l Free Flow Tests

When formulating compositions for use in water-soluble capsules according to the present invention, it is necessary to test the free-spill of the products to determine whether they are suitable for this purpose.

A funnel with a 2 cm wide open channel is filled with 100 g of the proposed non-hygroscopic salt and the time allowed for the product to flow freely. For fine loose powders and the like with good loosening properties, this should occur within 10 seconds. Table I shows the results obtained with some of the products offered.

Table I

An example Breakout Time (sec) 11.31 4.0 11.32 2.0 11.33 4.0 11.34 2.0 11.35 1.5

An example Breakout Time (sec) 11.36 2.0 11.37 7.0 11.38 5, 0 11.39 5.0 11.40 9.5 11.41 7.2 11.42 4.5 11.43 4.0 11.44 3, 0 11.12 5, 0 11.13 5, 0

III.2 X-ray diffraction tests

The following N-(phosphonomethyl) -glycine 5 mono-isopropylammonium salts obtained according to the following examples were tested:

Table II

An example Solvent used Set in crystals type 1.12 abs. ethanol a 1.1 96% ethanol a 1.13 water ............................................ β ...... ..................................... - methanol / diethyl ether * β

* - Freshly made

Methodology: Goniometer holder for beam λ = 1.79 A °

Tests were performed using an HZB-4 / C type X diffractometer. Radiation source: CoKa 30 keV 12 mA ° Fe filter). speed l ° / min. An example (Co tube sensor made from Al.

The preparation and testing of the samples were the same all the time. Lattice d-level values were calculated from radiographs and their relative intensities are shown in Table III. Some radiographs are also shown in Figs. 4 and 5.

The results show that the samples have two different structures, which were marked in Table II as crystal types a and β.

Table II

Abs. ethanol 96% ethanol Methanol- diethyl ether Water o dA I / I _o dA ° I / Io dA ° I / I _o dA ° I / I _o 11.0 100 11.0 100 7, 03 100 7:00 100 9, 06 47 9, 09 45 4, 83 16th 4.83 13th 7.41 13th 7.39 14th 4.56 19th 4.54 29th 5, 94 42 5, 95 43 4.48 46th 4.47 43 5.54 38 5.56 46th 4.27 23rd 4.26 29th 5.38 9th 4.17 46th 4.17 33 4, 98 12th 5.0 15th 4.06 37 4.05 40 4.85 33 4.86 37 3, 937 48 3, 937 49 4.55 9th 4.56 10th 3, 831 65 3.820 76 4.37 11th 3,621 6th 3, 62 7th 4,298 9th 4.30 9th 3,527 55 3,515 48 4.13 83 4.13 94 3.358 21st 3.351 20th 4, 08 31st 3,327 18th 3, 30 19th 4.01 58 4.01 48 3,198 10th 3,195 9th 3, 82 14th 3, 83 15th 3,140 39 3,136 34 3,782 15th 3.79 12th 2, 917 37 2,912 28th 3,710 51 3.71 56 2,821 4 2,815 6th 3.59 6th 2,739 11th 2,737 8th 3.48 10th 3,488 11th 2, 654 6th 2, 650 6th 3, 403 29th 3,403 24th 2,547 7th 2,545 10th 3,295 9th 3,293 9th 2,502 6th 2,502 8th

Abs. ethanol 96% ethanol Methanol- Water diethyl ether dA ° | I / Io dA ° | I / I _o dA ° | I / Io dA ° | I / Io 3.257 17th 3,259 16th 2,421 12th 2,420 18th 3, 189 29th 3,191 34 2.35 21st 2,405 11th  3,035 7th 3, 037 6th 2.34 15th 2, 985 6th 2,983 6th 2, 929 7th 2, 932 7th 2, 909 6th 2,790 10th 2,789 10th 2, 688 2,502 18th 2,502 24th

III.3 Solubility tests

Example 111.3.1 5

Table IV illustrates some of the solubility values of the N- (phosphonomethyl) glycine mono-isopropylammonium salts which may be used to make our proposed preparation practically feasible. All of our solvents can be used in our preparation processes, which have a significant difference in solubility between the salts and the products to be isolated.

Table IV

SOLUBILITY, g / 1

Solvent mono-IPA * salt di-IPA * salt Glyphosate ** water 1470 1980 12th methanol 56 570 <0.3 ethanol 0.2 n-propanol 0.7 170 <0.5 i-propanol <0.5 n-butanol 0.1 35

Solvent mono-IPA * salt di-IPA * salt Glyphosate ** benzyl alcohol 0.5 420 <0.2 propylene glycol 184.0 244 <0 dimethylformamide 1.8 22nd <0.2 benzene <0.1 <0.1 <0.1 isopropylamine <0.1 <0.1

* = isopropylamine ** - N- (phosphonomethyl) -glycine

Example III.32

The values given below can be used to estimate the best solvent to be used for (3-amino-3-carboxylpropyl) -methanephosphinic acid.

Table V

SOLUBILITY, g / 1 (25 ° C)

Solvent mono-ammonium salt mono-ipa salt glufosinate water 2000 1150 99 methanol 14th 260 23rd ethanol 4 5 9th n-propanol 6th 5 9th i-propanol 10th 4 12th benzyl alcohol 9th 300 9th propylene glycol 9th 280 21st dimethylformamide 10th 8th 12th benzene - - 7th

II1.4 Increase in humidity

III.4.1.

Samples were kept in open containers

at 60% humidity and shown in Table VI. Table VI 25 ° C at temperature. Results Salt Daily 1 2 7 14 30 90 N- (phosphonomethyl) glycine * 0.1% 0.1% 0.1% 0.1 % 0.1% 0.1% mono-isopropylammonium salt N- (phosphonomethyl) glycine di- 13.0% 14.5% 16.1% 18.8% 19.2% 30.9% isopropylammonium salt **

Appearance:

* mono-isopropylammonium salt did not change after 30 days ** di-isopropylammonium salt was sticky and hygroscopic after 1 day and completely liquid after 14 days

IV. BIOLOGICAL TESTS

IV. 1

The compositions of formula II.34 are dispersed in water to give 3 g of active ingredient / l of liquid. After 6 mg of the active ingredient, each sample was sprayed onto 15-day-old (aged) barley plants, which were stored in pots in a greenhouse. On the fourth day, the amount of chlorophyll in the plants corresponding to the dry matter unit was determined. The results are shown in Table VII.

Table VII

Control eg. Example II.9 Example II.11

9.26 mg / g

3.42 mg / g

3.43 mg / g

10th It was also fixed are given in Table VIII. Table VIII growth depression: results Control eg. 0 Example II.9 8.75 cm Example 11.11 8.5 cm IV. 2 15th According to the methodology of eg V, 1 15 days (age) bean plants were sprayed with 4.5 mg active ingredient / for a cup (1.5 l of liquid) and the third day set photosynthetic activity. The results are given in IX in the table. 20th Table IX

Checklist Eg.II.9 Eg: II.11 F, mv 685 340 325 F, mv 556 89 116 0.517 0.062 0.134 2,402 0.404 0, 929

0) <') <·

B '(OC A -CH _?

R θ 'c->

I »

H Π - CA - CH ₂ (-)

II .O H

HoC-CH2 ^-Nl OH / P χθω

III (r) i O o

C- CH-C ^ -C ^ · ¹ ω

O CHo ΐιθ ~ '> 3

P

IV

OH o

(1) <-> ii

B O-C-A

- C HO - P)

/ _? .R ¹

R ² - COOH

O ^W

VI

Claims (6)

DEFINITION OF INVENTION A process for preparing the mono-ammonium salts of the general formula (I) (I), wherein R ¹ represents a hydroxy or alkyl group, - A stands for Ο ₄ . ₄ alkylamino or aminoalkyl groups with primary or secondary amino groups, preferably -CH ₂ -NH- or -CH (NH ₂ ) -CH ₂ -, - B represents an ammonium ion or an alkyl-substituted ammonium ion, characterized by the synthesis of a solid non-hygroscopic salt, by preparing a mono-ammonium salt of the general formula (I) according to any known common salt preparation method. (V) di-ammonium salt in which R ¹ , A and B have the above meanings, (V) is eliminated or its production is inhibited, while avoiding other contamination. 2. A process according to claim 1, wherein the following processes or combinations thereof are used: a) general formulas (II) 9 ω R ' ¹ ho-ca-ch ₂ -p ^ _(II) acid in which - R ¹ and A have the above meanings, reacting with a basic (alkaline) reagent capable of forming a B + ion - in which B has the meaning given above in an organic, polar solvent or mixture of solvents containing an organic, polar solvent and in which the salt and acid formed are of general formula (I) and (II) - - in which R ¹ , A and B have the meanings given above - insoluble or only slightly soluble, whereas the basic reagent and the di-ammonium salt of the general formula (V) - R ¹ , A and B have the above meanings which, as a by-product, are readily soluble and the reaction mixture can be substantially heated; or b) a di-ammonium salt of the general formula (V) wherein - R ¹ , A and B have the above meanings, are reacted with an acid of the general formula (II) - R ¹ , A and B have the meanings given above under reaction conditions as in process a); or (c) an acid of the general formula (II) in which - R ¹ and A have the meanings given above, a salt capable of forming a B ⁺ ion wherein B has the meaning given above under reaction conditions as in process a), preferably using a 1- or 2-base carbonic acid salt of the general formula (VI) ) in which -R represents hydrogen, hydroxyl, or C ₁ . _{A 4-} alkyl group (which may be substituted), an aryl group (which may be substituted) having pK values in the range 2,275,58, for example, an acid of the general formula (VI), r ² -cooh (VI) wherein R ² has the above meaning, the trialkylammonium salt by introducing it into the reaction mixture, solid or dissolved, and carrying out the reaction at a temperature of 0-150 ° C, preferably 20-80 ° C; or d) extracting the hygroscopic salt of the general formula (I) wherein R ¹ , A and B have the meanings indicated above, with an organic, preferably polar, solvent or solvent mixture containing an organic polar solvent and wherein the monoammonium salt has the general formula (I) wherein R ¹ , A and B have the above meanings, insoluble or poorly soluble, while the di-ammonium salt of general formula (V) wherein R ¹ , A and B have the above meanings is readily soluble; or e) under vacuum or heating at room temperature, the amino acid is removed from the di-ammonium salt of the general formula (V) wherein R ¹ , A and B have the meanings given above, or from the mono-ammonium salt contaminated with such di-ammonium salt. having a B ⁺ ion in which B has the above value in excess of a molar equivalent; or f) under reaction conditions as in process a), an acid of the general formula (II) in which R ¹ , A and B have the above meanings are reacted with a reagent capable of forming the B ⁺ ion where B has the above meanings and so obtained. isolating, preferably, filtering the salt of the general formula (I) wherein R ¹ , A and B have the above meanings. 3. A process according to any one of claims 1 or 2, wherein the starting acid is N- (phosphonomethyl) glycine of formula (III) (III) or (3-amino-3-carboxypropyl) -methanephosphine (IV). , acid O - C-CH-CH ₂ -CH ₂ -P 9.0+ In the OH (IV) chain, for example as solvents, use aliphatic alcohols having 1 to 6 carbon atoms and / or polyalcohols and / or aromatic alcohols with C 1-8 alkyl in the side preferably ethanol and / or propanol to produce N- (phosphonomethyl) glycine the monoisopropylammonium salt or the monoammonium salt in the presence of ethanol and / or isopropanol, whereby pure N-phosphonomethylglycine mono-isopropylammonium salt of N-phosphonomethylglycine is obtained, melting at 158-163C according to claim 2. at a temperature of (a) A solid non-hygroscopic mono-ammonium salt of the general formula (I) wherein R ¹ , A and B have the above meanings substantially free of the di-ammonium salts of the general formula (V) wherein R ¹ , A and B have the above the crystalline salt of N- (phosphonomethyl) -glycine mono-isopropylammonium has a melting range of 158-163 ° C and is characterized by the following crystalline lattice levels, as measured by X-ray diffraction: 11.0, 9.06, 5.94, 5.54, 4.13, 3.71 A, and the characteristic absorption bands obtained by FT-IR spectroscopy are: 1660, 1600, 1553, 1545, 1075, 513 and 475 cm ^-1 ; and the crystalline salt has a melting range of 143-155 ° C and has the following crystalline lattice values as measured by X-ray diffraction: 7.00, 4.83, 4.47, 3.35, 2.815 and characteristic absorption bands obtained by FT-IR spectroscopy. , 1594, 1561, 1541, 1066, 500 and 455 cm ^-1 , as well as solid non-hygroscopic crystalline (3-amino-3-carboxypropyl) methanthosphinic acid mono-isopropylammonium salt having a melting range of 199-203 ° C and characterized by absorbance bands obtained by FT-IR spectroscopy at 1640, 1601, 1530, 1138, 1037, 750 and 471 cm ^-1 . A herbicidal or plant growth regulating composition comprising an effective amount of the active ingredient, a crystalline non-hygroscopic salt of the general formula (I) wherein R ¹ , A and B have the meanings given above, preferably crystalline non-hygroscopic (3-amino-3- carboxypropyl) methanthosphinic acid mono-isopropylammonium salt or crystalline non-hygroscopic N- (phosphonomethyl) glycine mono-isopropylammonium salt or crystalline type, which may contain additives and auxiliary products used in the pesticide industry and / or products which modify the properties of the product on the farm and / or products which are themselves pesticide ingredients. 6. The herbicidal or plant growth regulating composition of claim 5, characterized in that it consists of a capsule which is in a solid, dry state, made from a water-soluble polymer, and which is filled with the compositions of claim 5.