HU214947B - Fitoactive compositions containing nonhygroscopyc glyphosate salts as active ingredients and process for producing of the compositions and their active ingredients - Google Patents

Abstract

Solid, non-hygroscopic phytoactive preparations which are in addition to conventional additives and excipients as active ingredients Containing from 0.1 to 95% by weight of formula (I) non-hygroscopic monoammonium salts and not containing diammonium salts of formula III and their production. In the formulas - R1 is hydroxy, -Nammonium ion or C 1-4 alkyl substituted ammonium ion. Solid, non-hygroscopic salts are prepared by to the monoammonium salt of formula (I) by one of the methods known for salt formation during or after the production of a as a by-product of formula III removal and / or formation of diammonium salt Suppress. 0 Ο Λ ® β 11 ® / Fd B (OC-CH2-NH2-CH2-p-oe) -R 1 B OC-CH-NH-CH 2 P e

Description

FIELD OF THE INVENTION The present invention relates to solid herbicidal and plant growth controlling compositions of the formula I containing non-hygroscopic monoammonium salts, and to their preparation. Abbreviations and definitions used in this description:

- R ¹ is hydroxy;

- B is ammonium ion and C 1-4 alkyl ammonium ion;

- "glyphosate" means N-phosphonomethylglycine;

- "IPA" means isopropyl ammonium;

- 'non-hygroscopic' means that the product does not absorb any appreciable amount of water within three weeks at 25 ° C and 60% relative humidity, or that the water uptake is less than 0,1%; "Hygroscopic" means a material which, in such circumstances, absorbs more than 0.11% of water;

- the substance is "insoluble" when not more than 5%, preferably not more than 0,1%, is soluble under the particular conditions;

- 'phytoactive': herbicide and / or herbicide regulator;

- Hyspray® = FAL FINE. Activator of Agrochemicals Ltd. (ethoxylated fatty amine);

- "Lauropal X®" = a polyalkoxylated fatty alcohol excipient of WITCO S.A.

- Atplus 411® = oil based activator of ICI. The herbicide N-phosphonomethylglycine, i.e. glyphosate and its salts (Hungarian Patent No. 174,479) and plant growth regulator (Hungarian Patent No. 167,808), hereafter referred to as phytoactive, are known in the art. Several processes for the preparation of salts are known (for example, Hungarian Patent Nos. 174,479, 184,601, 168,961, 167,343, 165,965). In one method, an organic ammonium salt of a compound of Formula I was prepared in an aqueous medium, the resulting solution was concentrated in vacuo to give a crystalline material from the residual oil (U.S. Pat. No. 4,405,531).

Glyphosate salts are marketed as Roundup®, Glialka® in the form of phytoactive formulations. The formulations are generally not commercially available in solid form, but as an aqueous solution containing up to about 50% by weight of the active ingredient. Therefore, large volumes of transport containers are needed, significant transportation, storage costs, losses from spills and environmental damage. Glyphosate is acidic and chelating in water. It can react with the construction material of metal containers and therefore requires special means of transport. In order to overcome the above disadvantages, it would be desirable to store and package the glyphosate in solid form.

Wettable powders containing the sodium or ammonium salts of glyphosate are known (WO 87/04595, U.S. Patent 4,405,531). The disadvantages of wettable powders were, on the one hand, that the sodium burden on the environment was excessive and, on the other hand, that solid fillers and additives reduced the amount of active ingredient. Because the ammonium salts in the powders were hygroscopic, they decomposed. Special care was therefore taken to store, package and, in the case of partial use, to ensure the stability of the product remaining in the opened packaging. Several solutions have been suggested to overcome the above problem.

Japanese Patent 62,175,407 discloses the preparation of granules by fluid granulation of a solid carrier, additives and 0.5 to 3.5% by weight of active ingredient. Urea and water-soluble inorganic salts are described as carriers in Japanese Patent 62,175,408. Japanese Patent 6,310,701 discloses a particulate composition made by spray-drying an anionic surfactant, additive or solid carrier and a concentrated solution or aqueous dispersion of the active ingredient. Research Disclosure Publication 271-693 (1986), entitled "Increase Glyphosate Acid Wettable Power Formula in Control of Weeds", describes a wettable powder formulation containing glyphosate, nonionic surfactant, diatomaceous earth, inorganic salt and antifoam agent.

In a further method (EP 0206537), the glyphosate salt is mixed with a solvent and a molten surfactant. The solvent was later removed and the surfactant cooled until it solidified. The solid composition is usually dissolved at the site of application with water. It is further known that the acid form of the N-phosphonomethyl-N-carboxymethyl derivative is reacted directly with the liquid amine at ambient temperature until the ammonium salt is obtained or the excess amine is removed from the system. The salt is mixed with a molten surfactant which is solidified at ambient temperature and formed from the resulting blends (Spanish Patent ES 530 743). This reaction was also carried out in other media (benzene and water) (EP 0256608). According to the descriptions, pure active ingredient was obtained.

Reproducing the latter two methods, we found the following:

The resulting products were analyzed for glyphosate content by HPLC and complexometric titration, followed by IR analysis. It was found that a solid mixture of N-phosphonomethylglycine and N-phosphonomethylglycine di [mono (isopropylamine)] salt was not obtained as a homogeneous solid. This is not clear from a simple determination of the active ingredient content, as it may possibly correspond to the value measured for the N-phosphonomethylglycine mono (isopropylammonium) salt (74.1%). It has been observed that the water solubility of free N-phosphonomethylglycine-containing materials is significantly slower than that of the uniform N-phosphonomethylglycine mono (isopropylammonium) salt.

HU 214 947 Β

It was found that the material obtained according to Spanish Patent Specification ES 530743 had a N-phosphonomethylglycine content of 90-93% and a melting point of 196-208 ° C (as compared to the technical N- (phosphonomethyl) glycine mono-isopropyl). m.p. 142-155 ° C] and consists essentially of free N-phosphonomethylglycine in the bulk.

The N-phosphonomethylglycine content of the product according to EP 256608 was found to be 70-85%. FT-IR spectroscopy showed mixtures of N-phosphonomethylglycine and N-phosphonomethylglycine di [mono (isopropylammonium)] salts. The spectrum shows free carbon vibration bands of free N-phosphonomethylglycine at around 1717 and 1733 cm- ^{1 and} vibrations of the N-phosphonomethylglycine di [mono (isopropylamine)] salt 1561 and near 1633 '. Changes in the proportions of these bands closely follow the composition of a given substance. As a control, standard comparisons were made of pre-prepared N-phosphonomethylglycine di [mono (isopropylamine)] salt and N-phosphonomethylglycine and their calibration spectra were recorded.

Also known is a ready-to-use glyphosate-containing composition (Hungarian Patent Application T 54022) which contains a wettable powder composition containing glyphosate or its sodium or potassium salt, enclosed in a bag made of solid water-soluble polymers. Attempts have also been made to prepare a water soluble packaging composition from glyphosate mono (isopropylamine) salt. It has been found that this salt is very poorly crystallizable and therefore cannot be filled into a plastic bag, and the aqueous solution of the salts would dissolve the bag before use.

In our work, it has been surprisingly discovered that the pure salts prepared in our solid crystalline form, unlike those described in the literature, are non-hygroscopic, stable, with a well-defined melting point and with improved water solubility.

We have determined that the above results can be obtained if the following conditions are met:

An organic polar solvent or solvent mixture containing an organic polar solvent in which the salt of the formula I and the acid are insoluble or poorly soluble, and the basic reactant and the diammonium salt of the acid are readily soluble. At this time, the reaction on the surface of the acid particles dispersed in the mixture, since the acid is polybasic, due to the current molar ratios, produces the diammonium salt of the acid which dissolves and the renewed surface reacts continuously as above. After depletion of the basic reactant, the ionic transition between the diammonium salt in solution and the residual acid in the dispersed state results in the formation of a monoammonium salt which in each case has a lower solubility in the solvent used than the diammonium salt.

The solubility data for glyphosate mono- and di-mono-isopropylamine salts are given in Table I in some solvents.

Table I

Solubility of glyphosate salts (g / l)

solvent name mono (isopropyl ) salt di- [mono- (isopropyl NH)] - salt methanol 56.0 570 ethanol 0.7 178 n-butanol <0.1 35 benzyl alcohol 0.5 420 propylene glycol 184.0 244 dimethyl formamide 1.8 22 benzene <0.1 <0.1 i-propylamine <0.1 <0.1 n-propanol 0.9 199 WATER 1470.0 1980

The above reaction pathway is further supported by the changes that are generally well observed during the above reaction: At the start of the reaction, the suspension containing the acid in its dispersed state is a strong white color. During the addition of the basic reactant, it becomes more dull in color, and contains unreacted acid particles in dispersed form, and after addition of the basic reactant, if necessary with heating depending on the solubility of the monoammonium salt in the solvent used, dissolves and can be recovered in a manner known per se.

Using the basic reactant and the acid in a 2: 1 molar ratio rather than an equimolar amount, the diammonium salt of the acid was prepared directly from the solution, the physical constants were determined and reacted with an equimolar amount of the acid, the monoammonium salt.

From the foregoing, it is understood that the process of EP 256,608 and Spanish Patent Specification ES 530,743 does not lead to the formation of a pure mono-salt. Isopropylamine, benzene, etc. in a solvent, the diammonium salt formed on the surface of the acid particles cannot dissolve into the system, the reaction stops after saturation of the surfaces, and the product contains unreacted acid and diammonium salt.

The present invention relates to a process for preparing the glyphosate monoammonium salts of formula I by preparing a solid, non-hygroscopic salt, by preparing the monoammonium salt of formula I by or following one of the known methods of salt formation to remove the or reducing its occurrence.

In the practice of the present invention, it is possible to obtain the solid non-hygroscopic monoammonium salts of glyphosate and to selectively separate them from other possible salts and starting materials by

EN 214 947 Β the following procedural variants, alone or in combination:

a) The acid of Formula II is reacted with a basic reactant capable of forming a B ion in a polar solvent or solvent mixture containing a polar solvent in which the salt of Formula I and the acid of Formula II are not or weakly, while the basic reactant and the diammonium salt of Formula III freely soluble and optionally heating the reaction mixture; obsession

b) reacting the diammonium salt of formula III with an acid of formula II under the conditions given in process variant a); obsession

c) extracting the hygroscopic salt of Formula I with an organic solvent, preferably a polar solvent, or a mixture of organic polar solvents in which the monoammonium salt of Formula I is insoluble and the diammonium salt of Formula III is freely soluble, and the solid crystalline preferably isolated by filtration.

Preferred polar solvents are C1-C8 aliphatic alcohol, dimethylformamide, polyalcohol, C1-C6 aliphatic side chain aromatic alcohol and / or water.

In a very preferred embodiment of the process, glyphosate mono (isopropylammonium) or monoammonium salt is formed in a solvent mixture containing ethanol and / or n-propanol.

The solvents to be used may be selected by taking into account the solubility data given in Table I, or by performing similar pre-tests.

In our work, it has now been surprisingly discovered that, unlike those described in the literature, these salts can be prepared from a water-containing medium by a suitable process in a non-hygroscopic solid crystalline form. Thus, water can also be used as a polar solvent.

According to the present invention, the isopropylamine salt is formed in water or in a solvent mixture containing water, preferably at a low water concentration, and then the water is removed from the reaction mixture or the isopropylammonium salt formed is precipitated.

During the process, or after recovery of the salt, the isopropylammonium salt of the compound of formula I is introduced into, or washed with, an organic polar solvent or solvent mixture containing such solvent, optionally with heating wherein the monoammonium salt of the compound of formula I is and, to a lesser extent, the form of the diammonium salt is highly soluble.

Commonly used methods for removing water from a salt-forming reaction mixture in aqueous or aqueous / solvent media, such as fractional distillation, azeotropic distillation, freezing, ice sublimation, use of water-binding agents, evaporation, spray drying and the like.

At the end of processes a) to d), the salt formed from the reaction mixture can be precipitated, for example, by the use of suitable solvents or solvent mixtures or by salting. Alternatively, the reaction may be carried out in a saturated solution where the monoammonium salt formed is precipitated from the reaction mixture.

It has further been found that the pure crystalline glyphosate mono (isopropylammonium) salt can exist in two crystalline forms, named α and β. These show the following differences: The melting range of the glyphosate mono (isopropylammonium) α-type is 158-163 ° C, with typical absorption values as measured by FT-IR spectroscopy 1660, 1600, 1553, 1545, 1075, 513 and 475 cm -1, while the values of the lattice plane measured by X-ray diffraction are as follows: (11.0; 9.06; 5.94; 5.54; 4.13; 3.71) · 1 (H micrometer.

The melting range of the β-type crystalline glyphosate mono (isopropylammonium) salt is 143-154 ° C, with typical absorption values measured by FT-IR spectroscopy at 1645, 1594, 1561, 1541, 1066, 500 and 455 cm -1. while planar lattice values measured by X-ray diffraction are as follows: (7.00; 4.47; 3.53; 2.815) · 10 to ⁴ micrometers.

The present invention also relates to novel non-hygroscopic crystal forms and their preparation and use. The novel α- and β-crystalline forms are preferably prepared by process variant a).

The advantages of the process according to the present invention over the prior art methods are that they are simple and easy to implement, require only conventional technology, are environmentally friendly, and save energy. The products obtained are solid powder crystals, non-hygroscopic, easy to handle.

The present invention also provides compositions which contain from 0.1 to 95% by weight of the solid non-hygroscopic glyphosate salt of Formula I as an active ingredient, together with customary formulation auxiliaries, preferably in the form of wetting agents, excipients or other excipients.

The salts also retain their advantageous properties in the formulation and lead to a solid formulated composition which has more advantageous properties than the known solid formulations, or which have hitherto only been prepared in the form of a liquid or a tank mix.

The formulations of the present invention may contain, in addition to 0.1 to 95% by weight of the active ingredient salt I, a variety of excipients and auxiliaries commonly used in the manufacture of pesticides or specifically for the use of this product type. For example, cationic, anionic, nonionic and amphoteric surfactants, adhesives, anti-adhesives, antifoams, antifoams, solubilizers, anti-corrosion agents, anti-corrosive additives, activators. They may optionally contain from 0.05% to 95% by weight of one or more solid carriers and from 0.05% to 95% by weight of one or more surfactants.

The agriculturally acceptable carriers are generally known. The carrier is preferably solid, for example, clay, natural or synthetic resins, waxes or solid fertilizers.

The surfactant may be an emulsifying, dispersing, wetting agent of the ionic or nonionic type, or a mixture thereof. These include:

HU 214 947 Β

- water-soluble alkyl sulfonates, alkyl phosphates, alkyl benzene sulfonates,

- naphthyl sulphonates and alkyl naphthyl sulphonates,

- sulphated fatty alcohols, amines, acid amides,

- sulphated or sulphonated fatty acid esters,

- sulphonated vegetable oils,

- alkyl phenols, in particular polyoxyethylene derivatives of isooctylphenol and nonylphenol, and polyoxyethylene derivatives of mono- (long-chain) fatty acid esters of hexital anhydrides,

- polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ethers,

- polyoxyethylene alkyl aryl ether formaldehyde condensates,

- polyoxyethylene alkylene aryl ethers,

- polyoxyethylene alkyl esters,

- polyoxyalkylene sorbital, sorbitan or glycerol esters,

- polyoxyoxyethylene block copolymers,

- polyoxyalkylene alkylsulfonamides,

- polyoxyalkylene alkyl glycerol esters,

- polyoxyalkylene resin esters,

- polyoxypropylene block copolymers,

- polyoxyethylene oleyl ethers,

- polyoxyalkylene alkyl phenols, mixtures thereof and the like,

polyoxyalkylene alkylamines such as ethoxylated tallow amine (most preferably 15-20 moles ethylene oxide), ethoxylated oleinamine, ethoxylated soyamine, ethoxylated cocoaamine, ethoxylated synthetic alkyl amines , propoxylated amines, and mixtures thereof,

- polyoxyalkylene alkyl and alkyl aryl ether sulphates,

- polyoxyalkylene styrylphenyl ether sulphates,

- alkyl naphthalene formaldehyde condensates,

- alkyl diphenyl ether sulfonates,

- polyoxyoxyalkynyl phosphates,

- polyoxyalkylene phenyl ether phosphates,

- polyoxyalkylphenol phosphates,

- polycarboxylates, N-methyl fatty acid laurides, mixtures thereof and the like,

- various amine oxides such as lauryldimethylamine oxide and the like,

- surfactant salts of N-phosphonomethylglycine, such as N, N-bis (hydroxyethyl coconut amine) N-phosphonomethylglycine,

- saturated fatty alcohols, ethyl, sterile, oleyl alcohols, 2-octyldodecanol, isotridecyl alcohol,

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

- fatty acids, fatty acid salts, fatty acid esters,

- ethyl oleate, ethyl stearate, di (n-butyl) adipate,

- lauric hexyl ester, dipropylene glycol pelargonate,

- isopropyl myristate, isopropyl palmitate, isopropyl stearate,

- oleic ester of oleic acid, dodecyl ester of oleic acid, polyglyceryl lauric ester,

- caprylic / capric esters of saturated fatty alcohols, their mixtures and the like,

- glycerol-polyvinyl alcohol derivatives,

- phospholipids, alkyl polyglycoside derivatives,

- methyl, hydroxyethyl, hydroxymethyl and other cellulose derivatives,

- polyvinyl derivatives,

- lignin sulphonates, polymeric alkyl naphthalene sulphonates,

- polymethylene bis (naphthalene sulphonate), N-methyl-N (long-chain) fatty acid laurates,

- quaternary ammonium salts, alkyl or alkylaryl ammonium halides such as C 10 -C 18 alkyldimethyl, alkyltrimethyl, alkylbenzyldimethylammonium chloride, preferably cetyltrimethylammonium chloride,

- anionic, cationic, nonionic or amphoteric fluoroaliphatic wetting agents, silicone copolymer based surfactants,

tetraethoxysilane derivatives and the like.

The compositions may advantageously contain nitrogenous organic or inorganic compounds, urea and urea derivatives, inorganic salts such as calcium, sodium, ammonium chloride, sulfate, phosphate, borate and the like.

Other additives include paraffinic hydrocarbons, aliphatic mineral oil fractions, natural vegetable oils, and organic solvents.

Suitable carriers include diatomaceous earth, kaolin, attapulgite, fuller earth, montmorillonite, bentonite, synthetic silica, thiosulphates.

The solid herbicidal composition containing the salts of the invention may also contain other excipients such as protective colloids, adhesives, thickeners, thixotropic agents, absorption enhancers, stabilizers. In general, it will be appreciated that the compounds used in the present invention may be combined with solid or liquid additives commonly used in the manufacture of pesticides. Particularly preferred are compositions containing salts containing ethoxylated fatty amine and ammonium ions, in particular sulfate.

The composition may contain other pesticidal active ingredients compatible with the active ingredient, preferably insecticides, fungicides, preferably additional herbicides.

The present invention also relates to herbicidal compositions which contain, in addition to the salts of the compound of formula I, the following types of known herbicidal active ingredient compatible herbicides in a total amount of 0.1-95% by weight: glufosinate salt, imidazolinone derivative, phenoxyacetic acid derivative. , diphenyl ether derivative, triazine derivative.

The following is a list of some herbicidal agents that can be advantageously used in the solid compositions of the invention in combination with the glyphosate salt of the invention.

Hormonal Compounds:

- 2,4-D (2,4-dichlorophenoxyacetic acid),

- MCPA (2-methyl-4-chlorophenoxyacetic acid),

- 2,4,5-T (2,4,5-trichlorophenoxyacetic acid),

- dichlorprop [2- (2,4-dichlorophenoxy) propionic acid],

- mecoprop [2- (2-methyl-4-chlorophenoxy) propionic acid],

HU 214 947 Β

- 2,4-DB (2,4-dichlorophenoxy-butyric acid),

- MCPB (2-methyl-4-chlorophenoxy-butyric acid),

- napropamide [2- (1-naphthoxy) -N, N-diethylpropionamide],

- NES (1-naphthyl acetic acid),

- triclopyr (3,5,6-trichloro-2-pyridyloxyacetic acid),

- clopyralid (3,6-dichloropyridine-2-carboxylic acid),

- fluroxypyr (4-amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid),

- picloram (4-amino-3,5,6-trichloro-picolic acid),

- dicamba (2-methoxy-3,6-dichlorobenzoic acid),

- benzac (2,3,6-trichlorobenzoic acid),

- endotal [7-oxabicyclo (2,2,1) heptane-2,3-dicarboxylic acid],

- chlorotetal methyl (2,3,5,6-tetrachlorotereophthalic acid dimethyl ester).

Halogenated alkanoic acids:

- dalapon (2,2-dichloropropionic acid),

TCA (trichloroacetic acid).

triazines:

- simazine [2-chloro-4,6-bis (ethylamino) -striazine],

- atrazine [2-chloro-4- (ethylamino) -6- (isopropylamino) -triazine],

- terbumeton [4- (ethylamino) -2- (tert-butylamino) 6-methoxy-s-triazine],

- cyanazine [2-chloro-4- (ethylamino) -6- (1-cyano-1-methylethylamino) -triazine],

- terbutryn [4- (ethylamino) -2- (tert-butylamino) -6-methylthio-s-triazine],

- metribuzin [4-amino-3- (methylmercapto) -6- (tert-butyl) -1,2,4-triazin-5-one],

- terbuthylazine (4-ethylamino-2-tert-butylamino-6-chloro-triazine).

sulfonylureas:

- fenuron (N, N-dimethyl-N'-phenylurea),

- monuron [1,1-dimethyl-3- (4-chlorophenyl) urea],

- diuron [N '- (3,4-dichlorophenyl) -N, N-dimethylurea],

- methoxuron [N '- (3-chloro-4-methoxyphenyl) -N, N-dimethylurea],

- monolinuron [N- (4-chlorophenyl) -N-methoxy-N-methylurea],

- linuron [N '- (3,4-dichlorophenyl) -N-methoxy-N-methylurea],

- chlorobromuron [N '- (4-bromo-3-chlorophenyl) -Nmethoxy-N-methylurea],

- tebutiuron {N- [5- (1,1-dimethylethyl) -1,3,4-thiadiazol-2-yl] -N, N'-dimethylurea}.

Organophosphorus compounds:

- glufosinate ((3-amino-3-carboxypropyl) methane phosphinic acid),

- bilanaaphos {[4- (hydroxy (methyl) phosphinoyl) -Lhomoalanyl-L-alanyl-L-alanine},

- phosamine ammonium (ammonium ethylcarbanoylphosphonate),

ethephon (2-chloroethylphosphonic acid).

imidazolines:

- imazamethabenzomethyl [2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -? - and -m-toluene-carboxylic acid methyl ester],

- imazapyr [2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid],

- imazaquin {2- [4,5-dihydro-4-methyl-4- (1-methylethyl) 5-oxo-1H-imidazol-2-yl] -3-quinolinecarboxylic acid},

- Imazetapyr {2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -5-ethyl-3-pyridinecarboxylic acid}.

Diphenyl ethers;

- oxyfluorfen [2-chloro-1- (3-ethoxy-4-nitrophenoxy) -4-trifluoromethylbenzene],

- fomesafen {5- [2-chloro-4- (trifluoromethyl) phenoxy] -N-methylsulfonyl-2-nitrobenzamide},

- acifluorfen-Na {Na-5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate},

- bifenox [methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate],

- chloromethoxyphen [4- (2,4-dichlorophenoxy-2-methoxy-1-nitrobenzene)].

Chloroacetamide;

- alachlor [N- (2,6-diethylphenyl) -N- (methoxymethyl) chloroacetamide],

- propachlor (N-isopropyl-2-chloroacetanilide),

- butachlor [N- (butoxymethyl) -2,6-diethyl-2-chloroacetanilide],

- acetochlor [N-ethoxymethyl-2-ethyl-6-methylchloroacetanilide],

- metolachlor [2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) chloroacetanilide],

- propizamide [N- (dimethylpropynyl) -3,5-dichlorobenzamide],

Dinitroanilines:

- pendimethalin [N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline],

- Ethalfluralin [N-ethyl-N- (2-methyl-2-propenyl) -2,6-dinitro-4- (trifluoromethyl) aniline].

Sulfonylureas:

- chlorosulfuron {2-chloro-N - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide},

- Methylsulfuron-methyl / methyl-2 -{ [(4-methoxy-4-methyl-1,3,5-triazin-2-yl) -aminocarbonyl] -aminosulfonyl} -benzoate /

- thifensulfuron-methyl [methyl - {[(4-methoxy-6-methyl-1,3,5-triazin-2-ylamino) carbonyl] amino} sulfonyl] -2-thiophenecarboxylate,

- triazuluron {3- (6-methoxy-4-methyl-1,3,5-triazin2-yl) -1- [2- (2-chloroethoxy) phenylsulfonyl] urea},

- tribenuron-methyl {2-methyl- [N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N- (methylaminocarbonyl) aminosulfonylbenzoate]},

- chlorimuron-ethyl {ethyl 2 - [(4-chloro-6-methoxypyrimidin-2-yl) amino] carbonylaminosulfonyl · benzoate},

- sulfometuron-methyl {2- (3- (4,6-dimethylpyrimidin-2-yl) -ureido-sulfonyl] -benzoic acid methyl ester},

rimriduron {N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl-3-ethylsulfonyl] -2-pyridine sulfonamide},

EN 214 947 Β and other active substances:

- bentazone [3-isopropyl-1,2,3-benzothiadiazinone- (4) 2,2-dioxide],

- oxadiazon {2-tert-butyl-4- [2,4-dichloro-5- (isopropyloxy) -phenyl] -1,3,4-oxo-diazolin-5-one},

- Amitrol (3-amino-1,2,4-triazole),

- Pyridate [O- (6-chloro-3-phenyl-4-pyridazinyl) -S- (noctyl) thiocarbonate],

- paraquat (1,1'-dimethyl-4,4'-bipyridine),

- diquat (1,1 '-ethylene-2,2' -bipyridine),

- dimethipine (2,3-dihydro-5,6-dimethyl-1,4-dithine-1,1,4,4-tetraoxide),

- bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) and nitrogenous organic and inorganic salts and other substances which are useful as additives or modifiers in the efficacy or spectrum of action of glyphosate.

It is expedient to combine the above herbicides with the glyphosate salt of the formula I, based on the glyphosate active ingredient (0.01-4): 1 by weight.

The product can be formulated into any desired shape, for example pellets, powders, tablets, granules, etc., according to the purpose. Forming can be accomplished with suitable equipment such as fluidization techniques, extruder and dryer equipment, and granulation equipment.

1-6. meanings of figures:

Figure 1: X-ray diffraction spectrum of α-crystalline form of glyphosate IPA salt. Angle as a function of intensity.

Figure 2: X-ray diffraction spectrum of the β-crystalline form of glyphosate IPA salt. Angle as a function of intensity.

Figure 3: DSC analysis of the α-crystalline form of glyphosate IPA salt. The heat flow is W / g as a function of temperature ° C.

Figure 4: DSC analysis of the β-crystalline form of glyphosate IPA salt. The heat flow is W / g as a function of temperature ° C.

Figure 5: DSC analysis of glyphosate-IPA salt α and β crystal forms in a 1: 1 mixture. The heat flow is W / g as a function of temperature ° C.

Figure 6: FT-IR spectrum of α-crystalline form of glyphosate IPA salt. Absorption as a function of wave numbers.

The following examples illustrate the invention without limiting it.

Examples

I. Chemical process

1.1. EXAMPLE 1 g N-Phosphonomethylglycine (0.3 mol) was treated with isopropylamine (20 g, 0.34 mol) in methanol (200 ml) at room temperature. The mixture was refluxed at 65 ° C for half an hour, filtered, and the precipitated crystals were filtered off. 69 g (0.3 mol) of N-phosphonomethylglycine mono (isopropylammonium) salt, non-hygroscopic, freely soluble in water, m.p. 148-150 ° C. Active ingredient: 73.5% N-phosphonomethylglycine. Yield: 99.95%.

1.2. example

N-phosphonomethylglycine (100 g, 0.59 mol) was reacted with isopropylamine (35 g, 0.59 mol) in ethanol (400 ml) at room temperature. The suspension, heated to 49 ° C, was heated at 78 ° C for half an hour, refluxed, cooled to room temperature, and filtered. 129.0 g (0.57 mol) of N-phosphonomethylglycine mono (isopropylammonium) salt, non-hygroscopic, freely soluble in water, m.p. 161-162 ° C. Active ingredient content: 74% N-phosphonomethylglycine. Yield: 99.86%.

1.3. example

N-phosphonomethylglycine (100 g, 0.59 mol) was reacted with isopropylamine (35 g, 0.59 mol) in n-propanol (400 ml) at room temperature. The slurry, heated to 49 ° C, is refluxed at 98 ° C for half an hour, cooled to room temperature and filtered. The product

130.7 g (0.57 mol) of N-phosphonomethylglycine mono (isopropylammonium) salt, non-hygroscopic, freely soluble in water, m.p. 159-160 ° C. Active ingredient content: 74% N-phosphonomethylglycine. Yield: 99.9%.

1.4. example

N-phosphonomethylglycine (100 g, 0.59 mol) was reacted with isopropylamine (35 g, 0.59 mol) in n-butanol (400 ml) at room temperature. The slurry, heated to 49 ° C, was heated at less than 100 ° C for half an hour, cooled to room temperature, and filtered. 129.33 g (0.57 mol) of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt, non-hygroscopic, very soluble in water, m.p. 159-160 ° C. Active ingredient: 74% N-phosphonomethylglycine. Yield: 99.91%.

1.5. example

N-phosphonomethylglycine (100 g, 0.59 mol) was reacted with isopropylamine (35 g, 0.59 mol) in namyl alcohol (400 ml) at room temperature. The slurry, heated to 49 ° C, was heated at less than 100 ° C for half an hour, cooled to room temperature, and filtered. The product was 123.7 g (0.54 mol) of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt, non-hygroscopic, freely soluble in water, m.p. 158-159 ° C. Active ingredient content: 73.2% N- (phosphonomethyl) glycine. Yield: 98.7%.

1.6. example

N-phosphonomethylglycine (100 g, 0.59 mol) was reacted with isopropylamine (35 g, 0.59 mol) in dimethylformamide (400 ml) at room temperature. The slurry, heated to 49 ° C, was heated at less than 100 ° C for half an hour, cooled to room temperature, and filtered. The product is crystalline N-phosphonomethylglycine mono (isopropylammonium) salt (115.1 g, 0.5 mol), non-hygroscopic, freely soluble in water, m.p. 148-153 ° C. Active ingredient content: 73.0% N- (phosphonomethyl) glycine. Yield: 98%.

HU 214 947 Β

1.7. example

N-phosphonomethylglycine (200 g, 1.18 mol) was reacted with isopropylamine (140 g, 2.37 mol) in ethanol (600 ml) at room temperature. The slightly opalescent solution, which rose to 58 ° C from the reaction heat, was refluxed for half an hour. The initial crystallization is facilitated by evaporation and cooling, and the crystals are filtered off. 335.8 g (1.17 mol) of fluffy crystalline N- (phosphonomethyl) glycine di (monoisopropylammonium) salt are obtained. The product is freely soluble in water, m.p. 145-150 ° C. Active ingredient content: 57.52% N-phosphonomethylglycine.

1.8. example

In 400 ml of ethanol, 170 g (0.59 mol) of N- (phosphonomethyl) glycine di (isopropylammonium) salt are reacted with 100 g (0.59 mol) of N-phosphonomethylglycine for half an hour. Bring to a boil at 0 ° C. After cooling to room temperature, the milky suspension is filtered and the resulting material is dried. The product is a non-hygroscopic N- (phosphonomethyl) glycine mono (isopropylammonium) salt, m.p. 158-170 ° C. Active ingredient: 74% N-phosphonomethylglycine.

1.9. Example 4a 400 L of ethanol was added to an autoclave with a m ³ stirrer, brine cooling, and isopropylamine, followed by 100 kg (0.59 kmol) of N-phosphonomethylglycine. 35 kg (0.59 kmol) of isopropylamine were added to the autoclave, with stirring under nitrogen stirring, at 20 ° C. The mixture, which was warmed to 45 ° C, was heated to reflux and refluxed for 1 hour. The salt is washed with 30 L of ethanol and dried in a fluid drier after repeated centrifugation. The wash alcohol is combined with the mother liquor. The product was 130.1 kg (0.57 kmol) of N-phosphonomethylglycine mono (isopropylammonium) salt. Active ingredient: 74% N-phosphonomethylglycine. The product is non-hygroscopic, freely soluble in water, m.p. 153-156 ° C.

1:10. example

The procedure of Example 9 was followed, but using 390 L of the mother liquor of Example 9 as a solvent, supplemented with 10 L of ethanol. The product was 131 kg (0.57 kmol) of N (phosphonomethyl) glycine mono (isopropylammonium) salt. The product is non-hygroscopic, freely soluble in water. Active ingredient: 74% N-phosphonomethylglycine. 154-158 ° C.

1:11. example

N-phosphonomethylglycine (360 g, 2.13 mol) was treated with isopropylamine (252 g, 4.3 mol) in water (100 ml) at room temperature, and N-phosphonomethylglycine (360 g) was added and The mixture was heated at <RTI ID = 0.0> C </RTI> for 1 hour, cooled, and the precipitated crystals were filtered, rinsed twice with 200 ml of ethanol and dried. 962 g of the N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. White powdery crystals, non-hygroscopic, freely soluble in water. 151-154 ° C.

Active ingredient content: 74%, yield: 99%.

1:12. example

Glyphosate (360 g, 2.13 mol) was treated with isopropylamine (126 g, 2.13 mol) in water: ethanol (2: 1, 100 ml) at room temperature, heated at <100 ° C for 1 hour, cooled, and the precipitated crystals were filtered off. wash with ethanol and dry. The product is 480 g of glyphosate mono-IPA, a non-hygroscopic, water soluble, m.p. 150-155 ° C. Active ingredient content: 73.5%, yield: 99%.

1:13. example

Glyphosate (360 g, 2.13 mol) was treated with isopropylamine (126 g, 2.13 mol) in water (100 ml) at room temperature and heated at <100 ° C for 1 hour. The resulting oil-like aqueous solution is azeotroped with xylene to remove water. The residual amorphous white material was treated with alcohol, filtered and dried. 485 g of glyphosate mono-IPA salt, non-hygroscopic, easy to handle, water soluble, m.p. 148-150 ° C. Active ingredient content: 73.6%, yield: 99.8%.

1:14. example

Glyphosate (360 g, 2.13 mol) was treated with isopropylamine (126 g, 2.13 mol) in water (100 ml) at room temperature. The system was heated at <100 ° C for one hour and then cooled. To the resulting oily solution was added 1 g of ammonium nitrate and stirred for 10 minutes. The precipitated crystalline material was rinsed with benzyl alcohol and dried after filtration. Well-soluble, water-soluble, m.p. 147-154 ° C. Active ingredient content: 73%, yield: 98%.

1:15. example

1.14. follow the example. The water was removed by evaporation. The resulting glassy product was rinsed with 500 mL of ethanol, refluxed for 0.5 h, cooled, filtered and dried. 485.6 g of powdered crystalline glyphosate IPA salt, non-hygroscopic, freely soluble in water, m.p. 150-155 ° C. Active ingredient content: 73.8%, yield: 99.9%.

1:16. example

1.14. follow the example. To the reaction mixture was cooled to room temperature, 500 ml of ethanol were added and the precipitated white crystalline powder was collected and dried. 480 g of a glyphosate IPA salt, non-hygroscopic, m.p. 148-152 ° C. Active ingredient content: 73.9%, yield: 99%.

1.17. example

1.15. follow the example. The resulting aqueous solution was spray dried and the resulting white material was rinsed with ethanol, filtered and dried. 200 g of a white powder of glyphosate IPA salt, non-hygroscopic, m.p. 141-147 ° C. Active ingredient content: 73.5%, yield: 88%.

HU 214 947 Β

1.18. example

N-phosphonomethylglycine (0.5 mol) was mixed with methanol and 3.5 mol dimethylamine was added. After working up the previous examples, a non-hygroscopic, water-soluble N- (phosphonomethyl) glycine mono (dimethylammonium) salt is obtained. Melting range 118-124 ° C, containing 78.3% of N-phosphonomethylglycine.

1.19. example

0.4 moles of N-phosphonomethylglycine were prepared as described in Example 1.18. Example 1A was reacted with 0.5 moles of ethylamine in isopropanol. Crystalline N-phosphonomethylglycine mono (ethylammonium) salt is obtained, which is freely soluble in water, non-hygroscopic. 131-137 ° C. The N-phosphonomethylglycine content was 77.9%.

1:20. example

360 g (2.13 mol) of N-phosphonomethylglycine were reacted with 126 g (2.13 mol) of isopropylamine in 100 ml of water at room temperature. The resulting mixture was heated at 100 ° C for 1 hour, cooled to room temperature, and after standing for 2 hours, the precipitate was filtered off. The product obtained is hygroscopic. Extract twice (200 mL) with absolute ethanol, then filter and dry. 476.0 g of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water. M.p. 150-154 ° C. Yield: 98%. The N-phosphonomethylglycine content is 74%.

1.21. example

The reaction is illustrated in Figure 1.20. The same procedure was carried out as in Example 1, except that the water was distilled off and the remaining solid hygroscopic salt was treated as described therein. 485.6 g of crystalline N- (phosphonomethyl) glycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water. Melting point: 150-155 ° C. Yield: 99.9%. The N-phosphonomethylglycine content was 73.8%.

1.22. example

360 g (2.13 mol) of N-phosphonomethylglycine are reacted with 252 g of isopropylamine (4.3 mol) in 100 ml of water at room temperature. An additional 360 g of N- (phosphonomethyl) glycine was added and the reaction mixture was heated at a temperature below 100 ° C for 1 hour. After cooling, the precipitate was filtered off. A hygroscopic product is obtained which is extracted twice with 200 ml of absolute ethanol each time, and is then born and dried. 962 g of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water. 154-157 ° C. Yield: 99%. It contains 74% N-phosphonomethylglycine.

1.23. example

360 g of N-phosphonomethylglycine are reacted with 126 g of isopropylamine at room temperature in 100 ml of water. After addition of 500 ml of absolute ethanol, the precipitated product is filtered off, dried and ground. 480 g of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water. 148-152 ° C. Yield: 92%. It contains 73.9% N- (phosphonomethyl) glycine.

1.24. example

1.23. The reaction and the resulting aqueous solution were heated at 100 ° C for 1 hour. An oily product is obtained which is dried in a desiccator over phosphorus pentoxide or calcium chloride for 24 hours at room temperature. The dry product was extracted with 96% ethanol, filtered and dried.

242.5 g of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water. 154-157 ° C. Yield: 99%. It contains 74% N-phosphonomethylglycine.

1:25. example

1.24. The reaction is carried out as in Example 1. To the resulting oily reaction mixture was added 2 g of N-phosphonomethylglycyldi (isopropylammonium) salt. After stirring for 10 minutes, the N-phosphonomethylglycine mono (isopropylammonium) salt precipitates. The white salt was filtered off and extracted with 96% ethanol at room temperature. 480 g of crystalline N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water. 147-152 ° C. Yield: 99%. Active ingredient content: 73.6% N-phosphonomethylglycine.

1.26. example

169.1 g (1 mol) of N-phosphonomethylglycine were reacted at room temperature with 17 g (1 mol) of ammonia previously dissolved at 0 ° C in methanol. The mixture is heated spontaneously to 35 ° C and then heated at 65 ° C for 30 minutes, then cooled, filtered and the crystals dried. 182 g of crystalline N (phosphonometryl) glycine ammonium salt are obtained. The product is non-hygroscopic, freely soluble in water. It contains 90% N-phosphonomethylglycine.

1.27. example

Pure a-crystal

169.1 g (1 mol) of 100% N-phosphonomethylglycine and 59.11 g (1 mol) of 100% isopropylamine are reacted in 700 ml of absolute ethanol at room temperature. The suspension is refluxed for 30 minutes, cooled to room temperature and filtered. 216.78 g (0.95 mol) of N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is crystalline, non-hygroscopic, freely soluble in water, m.p. 161-163 ° C. Characteristic absorption bands (as measured by FT-IR spectroscopy, cm ^-1 ): 1660, 1600, 1553, 1545, 1075, 513, 475. Characteristic crystal lattice plane values as determined by X-ray diffraction: (11.0; 9.06; 5.94; 5.54, 4.13, 3.7 T) -10 ⁴ micrometers, α-truncated crystals (Figures 1, 3, 6).

HU 214 947 Β

1.28. example

N-phosphonomethylglycine (100 g, 0.59 mol) was reacted with isopropylamine (35 g, 0.59 mol) in absolute ethanol (400 ml) at room temperature. The slurry was heated to 49 ° C and refluxed at 78 ° C for another half hour. Cool to room temperature, give birth and dry. 129 g (0.57 mol) of N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is crystalline, non-hygroscopic, freely soluble in water, m.p. 161-162 ° C. N- (phosphonomethyl) glycine content: 74%. Yield: 99.86%. Characteristic absorption bands (as measured by FT-IR spectroscopy, cm ^-1 ): Characteristic lattice plane values of 1660, 1600, 1553, 1545, 1075, 513, 475, X-ray diffraction: (11.0; 9.06; 5 94; 5.54; 4.13; 3.71) 10 ⁴ micrometers (type crystals).

1.28. Example 1 gives the following results:

II. spreadsheet

example amine solvent salt, m.p. production,% *% 1.29. isopropyl n-propanol 130.7 g 159-160 99.9 74 1:30. isopropyl n-butanol 129.33 g 159-160 99.91 74 1.31. isopropyl n-amyl alcohol 123.7 g 158-159 98.7 73.2 1.32. isopropyl dimethylformamide 115.1 g 148-153 98 73.0

* = N-phosphonomethylglycine

I. Example 33

Pure β-crystal

1.27. The procedure of Example 1 is followed except that 70 ml of distilled water is used as solvent and isopropylamine is added slowly. The resulting solution was heated to 100 ° C for 1 hour, cooled to room temperature, and the crystals were filtered off and dried. 228.20 g (1 mol) of N-phosphonomethylglycine mono (isopropylammonium) salt are obtained. The product is non-hygroscopic, freely soluble in water, m.p. 147-153 ° C, β-type crystals (see Figures 2, 4). Characteristic absorption bands (as measured by FT-IR spectroscopy, cm ^-1 ): 1645, 1594, 1561, 1541, 1066, 500, 455, X-ray diffraction pattern characteristic values (7.00; 4.83; 4, 47; 3.35; 2.815) -10 ^-4 micrometers.

II. preparations

II. Example 1

A mixture of 0.5 g of ethoxylated nonylphenol and 2.84 g of ethoxylated alkylamine excipient is dissolved in 40 ml of ethanol at room temperature. Homogenize the solution 60 g 1.2. The glyphosate mono (isopropylammonium) salt prepared according to Example 1 is then removed and the alcohol is removed. The product obtained was 63.3 g of a non-hygroscopic, water-soluble product (active ingredient: 69.6% glyphosate).

II. Example 2

A mixture of 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 polyglycol ether in 30 ml of ethanol is homogenized in 60 g of 1.3. A mixture of glyphosate mono (isopropylamine) salt prepared according to example 1b and 4.4 g of urea. The product obtained after removal of the alcohol is 93 g non-hygroscopic and freely soluble in water [active ingredient: 47.4% N-phosphonomethyl] glycine.

II. Example 3

A mixture of 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 mixture of 30 g of methanol is homogenized in 60 g; A mixture of glyphosate IPA salt prepared according to example 1b, 2.78 g of calcium chloride, 0.03 g of 1-naphthylacetic acid and 0.08 g of boric acid. The product obtained after removal of the alcohol is 82 g, non-hygroscopic and freely soluble in water (active substance content: 53.8% glyphosate).

II. Example 4 g 1.2. The glyphosate mono (isopropylammonium) salt prepared according to example 1b is homogenized with a solution of 40 g of Hyspray® in 60 ml of alcohol. After removal of the alcohol, the resulting water-soluble, non-hygroscopic product weighs 125 g (50.4% glyphosate active ingredient).

II. Example 5 g 1.4. The glyphosate mono (isopropylamine) salt prepared according to Example 1c is homogenized with a mixture of 50 g Hyspray® and 1D g Lauropal®-X in 60 ml alcohol. After drying, the product is a highly water-soluble substance (195 g, 32.3% glyphosate).

II. Example 6 g 1.5. A mixture of the glyphosate mono (isopropylammonium) salt prepared in Example 1 and 50 g of ammonium bicarbonate is homogenized in 50 g of

Hyspray® and 10 g Lauropal®-X excipient in 60 ml of alcohol 10

HU 214 947 Β made with snow. After drying, the product is a 195 g water-soluble particulate material (active ingredient: 32.3% glyphosate).

II. Example 7 A mixture of g Hyspray® and 10 g Lauropal®-X excipient in 100 ml of alcohol was homogenized in 85 g, as described in 1.6. A mixture of glyphosate mono (isopropylammonium) salt prepared according to example 1b, 70 g of ammonium bicarbonate and 50 g of ammonium sulfate. The granular product obtained after removal of the alcohol is 295 g of a dry, water-soluble substance (active ingredient: 21.3% glyphosate).

II. Example 8 g, Example 1.7. The mixture of glyphosate mono (isopropylammonium) salt prepared according to example 1b is homogenized with 50 g of Hyspray® and 10 g of Lauropal®-X in 250 ml of alcohol to a mixture of 50 g of ammonium bicarbonate and 500 g of ammonium sulfate. The wet product is pelletized through a sieve. After drying, 695 g of a water-soluble, non-hygroscopic, granular product (active ingredient: 9% glyphosate) are obtained.

II. Example 9

485 kg; The glyphosate mono-IPA salt prepared according to Example 1b is homogenized in a Nauta mix dryer at 25-30 ° C with a mixture of 4 kg of ethoxylated nonylphenol and 22.7 kg of ethoxylated alkylamine in 1601 ethanol. The alcohol-wet mixture was vacuum dried in the apparatus. The product obtained was 510 kg (70.4% glyphosate active ingredient). The product was dissolved in 590 ml water solution containing the equivalent of 1 m ³ is obtained, known as Glialka®-36, product used as herbicides.

11:10. example

A mixture of 22.5 g of a polyoxyalkylamine excipient is dissolved in 30 ml of ethanol at room temperature. The solution is homogenized with 60 g of the solution of 1.10. The glyphosate mono (isopropylammonium) salt prepared according to Example 1 is then removed and the alcohol is removed. The resulting product (82 g, 53.8% glyphosate active ingredient) was well handled, non-hygroscopic. Dissolve the product thus obtained in 60 ml of water to obtain a solution containing 360 g / l glyphosate corresponding to the product known as Roundup®.

11:11. Example g, Example 1.12. The glyphosate monoIPA salt prepared according to Example 1 was homogenized with a mixture of 52 g of 2,4-D-isopropylammonium salt, 4 g of ethoxylated nonylphenol and 10 g of ethoxylated fatty amine in 20 ml of ethanol and dried in vacuo. 100 g of herbicide combination preparation are obtained.

11:12. Example g, Example 1.12. The solid glyphosate IPA salt prepared in Example 1 and 7 g of glufosinate mono (isopropylammonium) salt were homogenized with 33 g of ammonium sulfate, 2 g of ethoxylated nonylphenol, 3 g of sodium sulfonate, 5 g of silica and 10 g kaolin mixture. 100 g of a combination preparation are obtained.

11:13. Example g, Example 1.13. The glyphosate monoIPA salt of Example 1 and 7 g of dimethipine were homogenized with a mixture of 33 g of ammonium sulfate, 10 g of kaolin, 5 g of silica and 3 g of sodium lignin sulfonate, followed by ethoxylated nonylphenol in 50 ml of ethanol. A water dispersion of the product (100 g) in water can be used in agriculture for weed control.

11:14. Example g, Example 1.14. A mixture of glyphosate monoIPA salt prepared in Example 1 and 4 g of oxifluorophen was homogenized with a solution of 20 g of kaolin, 16 g of silica and 3 g of sodium lignin sulfonate, followed by 2 g of ethoxylated nonylphenol in 50 ml of butanol. The wet product is dried in a vacuum oven.

II. Example 15 g, Example 1.18. A mixture of glyphosate mono (dimethylammonium) salt prepared according to example 1b and 10 g of urea is homogenized with a mixture of 20 g of surfactant in 50 ml of alcohol. The wet product is dried in a vacuum dryer. The resulting granular product is highly water soluble, non-hygroscopic. Once dissolved in water, it can be used in known ways for weed control.

11:16. EXAMPLE 1 A mixture of g of MCPA-isopropylamine and 30 g of glyphosate monoIPA salt was homogenized in a mixture of 2 g of ethoxylated nonylphenol, 5 g of ethoxylated alkylamine, 5 g of isotridecyl alcohol polyglycol ether and 8 g of ethoxylated fatty amine in 50 ml of alcohol. The wet product is dried in a vacuum dryer. 100 g of a non-hygroscopic, water-soluble herbicide product are obtained.

II. Example 17 g, Example 1.10. The glyphosate monoIPA salt prepared in Example 1A is homogenized with 1 g of polyalkoxylated fatty alcohol in 20 ml of butanol and then with 15 g of Atplus 411 oil adjuvant. The product was dried in a vacuum oven at 60 ° C. 99 g of product are obtained which forms an emulsion with water and can thus be used as a herbicide.

11:18. kg is shown in Example 1.13. The dry glyphosate mono-IPA salt prepared according to Example 1 is homogenized in a Nauta-mix apparatus with 6D kg MCPA-isopropylamine salt and then mixed with 20 kg Carbowax-6000 and 10 kg polyoxyethylene (20) sorbitan with stirring. solution of monolaurate excipients in 20 l of ethanol. 10 L of ethanol was distilled off and the wet product was dried in vacuo. The finished product is a 146 kg water-soluble pellet which can be used as a herbicide.

HU 214 947 Β

Π. Example 19 g, Example 1.8. The glyphosate monoIPA salt prepared according to example 1b is homogenized with a mixture of 5 g of imazetapyr (isopropylamine) salt, 3 g of Lauropal®-X and 10 g of Hyspray® in 50 ml of ethanol. The wet product was dried at 40 ° C. 100 g of a combination preparation for use as a herbicide are obtained.

II. Example 20

The glyphosate mono (isopropylammonium) salt (26.82 g, prepared as in Example 5) was homogenized with a mixture of imazetapyr (isopropylammonium) salt (5 g) and polyoxyethylene sorbitan monooleate (13 g) in ethanol (50 ml). The product was dried under vacuum at 60 ° C. The product is 100 g herbicide.

Note: The glyphosate mono-IPA salt used as the active ingredient in the above examples may be in the form of an α or β crystal.

a-type crystals are formed: 96% or more in ethanol or other solvents of the invention (except water and methanol). See 1.2, 1.3,

1.4., I.5., I.7., I.8., I.9., 1.10., 1.11., 1.12., 1.15. examples.

Crystals of type-1 are formed: in aqueous solvents and solvent mixtures less than 96%, in methanol (also 100%), in water. See I.I., I.6, I.8, 1.13,

1.14 .. 1.16..1.17. examples.

III. Analytical tests

III. 1. X-ray diffraction studies

Samples used for the tests were prepared from the N-phosphonomethylglycine mono (isopropylammonium) salts prepared as follows:

III. spreadsheet

example solvent crystal type 1.27. abs. ethanol α 1.9. 961% ethanol α 1:13. WATER β

Method: The experiments were performed on a HZG-4 / C X-ray diffractometer. Radiation source: CoKa 1 = 1.79 ^x 10 ^-4 micrometer, Goniometer sensor speed 1 ° / min. The sample holder is made of aluminum.

The preparation and analysis of the samples were always the same, the lattice plane values were calculated on the basis of the x-rayograms, and the relative intensities were calculated in Table IV. table. Some of the X-rays are a

4 and 5 are also shown. It is clear from the above results that the samples exhibit two different structures, named the α and β crystal types.

ARC. spreadsheet

abs. ethanol 961% ethanol WATER dA 1/10 dA 1/10 dA 1/10 11.0 100 11.0 100 7.00 100 9.06 47 9.09 45 4.83 13 7.41 13 7.39 14 4.54 29 5.94 42 5.95 43 4.47 43 5.54 38 5.56 46 4.26 29 5.38 9 4.17 33 4.98 12 5.0 15 4.05 40 4.85 33 4.86 37 3,937 49 4.55 9 4.56 10 3,820 76 4.37 11 3.62 7 4,298 9 4.30 9 3,515 48 4.13 83 4.13 94 3.351 20 4.08 31 3.30 19 4.01 58 4.01 48 3.195 9 3.82 14 3.83 15 3.136 34 3.782 15 3.79 12 2.912 28 3.710 51 3.71 56 2.815 6 3.59 6 2,737 8 3.48 10 3.488 11 2,650 6 3.403 29 3.403 24 2.545 10 3.295 9 3.293 9 2.502 8 3,257 17 3.259 16 2,420 18 3.189 29 3.191 34 2,405 11 3.035 7 3,037 6 2.34 15 2.985 6 2.983 6 2.929 7 2.932 7 2.909 6 2,790 10 2.789 10 2,688, 2.502 18 2.502 24

d [Á] = dl 0 ⁴ micrometers

III. 2. Moisture absorption

Samples were examined in an open container at 60% humidity at 25 ° C. The results are shown in Table V below:

HU 214 947 Β

Table V.

SALT days 1 2 7 14 30 90 Glyphosate-mono (isopropylammonium) salt * 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% di glyphosate (isopropylammonium) salt ** 13.0% 14,5% 16.1% 18.8% 19.2% 30.9%

appearance:

* The mono (isopropylammonium) salt was unchanged after 30 days.

· * The di (isopropylammonium) salt was sticky and hygroscopic after 1 day and became completely liquid within 14 days. % = weight%

Claims (10)

PATENT CLAIMS A process for preparing glyphosate monoammonium salts of formula (I) -R ¹ is OH, -B is for preparing an ammonium ion or an ammonium ion substituted with C 1-4 alkyl, characterized in that a solid, non-hygroscopic salt is prepared which, at 25 ° C, 60% RH, absorbs <0.1% water over a period of 3 weeks. such that the monoammonium salt of formula (I) - when R ¹ and B are prepared by or after one of the methods known for the salt formation mentioned above, the diammonium salt of the general formula (III) is formed as a by-product; - R ¹ and B represent the above removal and / or suppression thereof by applying the following embodiments, alone or in combination: a) an acid of formula II - R ¹ is a basic reactant capable of forming the above B-ion - B is as defined above in a polar solvent or solvent mixture containing a polar solvent in which the salt of formula I and the acid of formula II are - wherein R ¹ and B are the same as above, while the basic reactant and the by-product diammonium salt of formula III wherein R ¹ and B are as hereinbefore well soluble and optionally heating the reaction mixture; obsession b) a diammonium salt of formula III R ¹ and B are as defined above for an acid of formula II R ¹ and B are as defined above under the conditions of Process a), or c) a salt of formula I in the formula - R ¹ and B are the above which are hygroscopic, i.e. which is at 25 ° C, 15 60% relative humidity It absorbs more than 0.1% water over a period of 3 weeks and is extracted with an organic solvent, preferably a polar solvent or a mixture of organic polar solvents, in which 20 monoammonium salt R ¹ and B are insoluble, while the diammonium salt of formula (III) is highly soluble, and the resulting solid crystalline monoammonium salt of formula (I), wherein R ¹ and B are as defined above, is preferably isolated by filtration. (Priority: 6/11/1992) Process variant (a) according to claim 1, characterized in that it is an acid of formula (II) 30 - ^R1 is capable of forming the ion B is said basic reactant - B is as defined above in a polar solvent or solvent mixture containing a polar solvent in which 35 a salt of Formula I and an acid of Formula II - R ¹ and B are the same as above, while the basic reactant and the by-product diammonium salt of formula III - R ¹ and B are as described above dissolve well and optionally the reaction mixture is heated. (Priority: April 4, 1991) Process according to claim 1 or 2, characterized in that the polar solvent is C 1 -C 8 45 aliphatic alcohols, dimethylformamide and / or water are used. (Priority: 6/11/1992) Process according to process variant a) according to claim 1, characterized in that the glyphosate mono (isopropylammonium) or monoammonium salt is formed in a reaction mixture containing ethanol and / or n-propanol. (Priority: April 4, 1991) Process according to claim 1 or 2, characterized in that the glyphosate mono (isopropylammonium) 55 or monoammonium salt is formed in an aqueous reaction mixture. (Priority: 11/06/1992) 6. A solid non-hygroscopic phytoactive formulation, characterized in that in the manufacture of pesticides 60 commonly used additives 99.9-5% by weight EN 214 947 Β contains from 0.1% to 95% by weight of the non-hygroscopic monoammonium salt of the formula (I) - in the formula - R ¹ is hydroxy, - B is ammonium ion or ammonium ion substituted with C 1 -C 4 alkyl group which, at 25 ° C and 60% RH, absorbs <0.1% water over a period of 3 weeks and does not contain any of the formula (III) - R ¹ and B are as defined above bis ammonium salt. (Priority: April 4, 1991) Composition according to claim 6, characterized in that it contains from 0.1 to 95% by weight of crystalline, non-hygroscopic N-phosphonomethylglycine mono-isopropylammonium salt, m.p. 158-163 ° C, with typical absorption values 1660, 1600, 1553, 1545, 1075, 513 and 475 cm -1 as measured by FT-IR spectroscopy and the values of the lattice plane measured by X-ray diffraction are as follows: ( 11.0, 9.06, 5.94, 5.54, 3.71) -10 ^-4 micrometers. (Priority: April 4, 1991) 8. The composition according to claim 6, wherein the active ingredient comprises from 0.1 to 95% by weight of crystalline, non-hygroscopic N-phosphonomethylglycine mono-isopropylammonium salt, melting range between 143-155 ° C, and wherein the characteristic absorption values measured by FT-IR spectroscopy, 1645, 1594, 1561, 1541, 1066, 500 and 455 ^cm-1 and the lattice plane of the X-ray diffraction values measured as follows: (7 , 00; 4.83; 4.47; 3.35; 2.815) -10 µm. (Priority: April 4, 1991) 9. A 6-8. Composition according to any one of claims 1 to 3, characterized in that, in addition to the solid, non-hygroscopic glyphosate salt, one to more than one known herbicidal active ingredient compatible with the glyphosate salt, based on the glyphosate salt: glufosinate salts, imidazolinone derivatives, phenoxyacetic acid derivatives, diphenyl ether derivatives, triazine derivatives. (Priority: April 4, 1991) 10. Procedure 6-8. The preparation according to any one of claims 1 to 3, characterized in that it is of formula (I) R ¹ and B are solid, non-hygroscopic salts as defined in claim 6, optionally together with an additive and excipient, in accordance with commonly used methods of pesticide manufacture.