A method of producing glyphosate and oxidation catalyst

 

(57) Abstract:

The invention relates to a method of producing glyphosate-oxidation reaction catalyzed by a noble metal. Glyphosate and its salts suitable for use as a post-harvest herbicide. Describes a method of producing glyphosate, its salt or a complex ester, comprising the contacting of the solution containing N-substituted glyphosate, with oxygen in the presence of a catalyst based on a noble metal selected from the group comprising platinum, palladium, ruthenium, rhodium, iridium and osmium, to increase the number of glyphosate, its salt or a complex ester in solution, where the N-substituted glyphosate has the formula (II)

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R1and R2independently represent a hydrogen atom, a group-RHO3H2, a hydrocarbon radical or substituted hydrocarbon radical, except that R1and R2different from the group-COOH, and the radicals R3, R4and R5independently represent a hydrogen atom, a hydrocarbon radical, a substituted or unsubstituted hydrocarbon radical or agricultural-acceptable cation. The technical result - the creation of a method of producing glyphosate and its complex N-carboxymethyl group. It also describes the oxidation catalyst based on a noble metal selected from the metals of group VIII of the Periodic table. 2 c. and 31 C.p. f-crystals, 2 ill., 9 table.

Background of the invention

This invention generally relates to a method for conversion of N-substituted-N-(phosphonomethyl)glycinol (sometimes referred to as "N-substituted glyphosate"), as well as their esters and salts of N-(phosphonomethyl)glycine (sometimes referred to as "glyphosate") and its esters and salts of the oxidation reaction catalyzed by a noble metal. In particular, this invention is devoted to the transformation of N-substituted glyphosate, as well as their esters and salts, having only N-carboxymethyl functional group.

Glyphosate described by Franz in U.S. patent 3799758 and has the following formula:

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Glyphosate and its salts comfortable in the aqueous formulation for use as a post-harvest herbicide. He is a highly effective and important industrial herbicide broad spectrum of action, used for suppressing the growth of germinating seeds, emerging seedlings, Mature and rooted woody and herbaceous vegetation and aquatic plants.

In engineering WPI is R., clarifies that N-benzylglycine can be phosphonomethylglycine to N-benzoylglycine and then by reaction with Hydrobromic or itestosterone acid, benzyl group is cleaved and the result is glyphosate. In U.S. patent 3927080, Gartner, it follows that N-tert-butylglycol can be phosphonomethylglycine with the formation of N-tert-butylperoxide and then turned into glyphosate by acid hydrolysis. Glyphosate can also be obtained from the N-benzoylglycine by hydrogenolysis, as described, for example, in the application for the European patent 55695 and L. Mayer log Phosphorus, Sulfur and Silicon, I. 61, S. 65-67, 1991. The problem with these methods is that they produce undesirable side products, such as isobutylene and toluene, which create problems due to their potential toxicity. Moreover, acid hydrolysis and hydrogenation of N-substituted glyphosate were demonstrated only for alkyl groups such as tert-butyl-tion and benzyl groups, which are known to be sensitive to these reactions. Dealkylation N-methyl, N-isopropyl and other N-substituted glyphosate that are not so susceptible to acid hydrolysis or catalytic hydrogenation, no prodemo is methyl)iminodiacetic acid (sometimes referred to as FMEC):

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FMEC can be synthesized from trichloride phosphorus, formaldehyde and aqueous solution of disodium salt iminodiacetic acid, as described Gentilcore in U.S. patent 4775498:

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It is well known from the technical field FMEC can be converted to glyphosate by heterogeneous oxidation over carbon catalysts, as described, for example, Franz in U.S. patent 3950402 and Baltazara and others in the U.S. patent 4654429; by homogeneous catalytic oxidation, as described, for example, Riley and others in journals J. Amer.Chem.Soc., so 113, S. 3371-3378, 1991 and Inorq.Chem., so 30, S. 4191-4197, 1991; and by electrochemical oxidation using carbon electrodes, as described by Rasieren and others in the U.S. patent 3835000. However, it was shown that these methods of oxidation are effective only for glyphosate N- (phosphonomethyl)iminodiacetic acid, N-substituted glyphosate, which has two N-carboxymethyl functional groups. None of these known methods of oxidation of the prior art did not specify that they apply to obtain glyphosate N-substituted compounds of glyphosate, with only one N-carboxymethyl functional group, that is, when R' in the formula differs from the group-CH2COOH: the focus of a functional group, different from the group-CH2COOH, in these methods, the level of group-CH2COOH will be split rather than R1and therefore will not be able to obtain glyphosate. It really is so well-known methods, which are aimed at heterogeneous-catalytic oxidation on carbon for electrochemical oxidation using carbon electrodes. The mechanism of these oxidation processes are well known from the literature, in particular for electrochemical oxidation, where he is known as the Kolbe reaction, described in various books on organic electrochemistry, for example in the book S. Torii and H. Tanaka, Organic electrochemistry, S. 535-580 (ed H. Lund, M. M. Baizer, ed. Marcel Dekker, 3rd edition, 1991). Both mechanisms include oxidative decomposition of the carboxylic acid to hydrocarbon radical and carbon dioxide:

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There is no assumption that these mechanisms can be used for cleavage of other functional groups in addition to the group-CH2COOH.

Thus, it is desirable more General way of oxidation of N-substituted glyphosates in glyphosate. This method would use a broader set of N-substituted glycinol as starting materials to obtain the chap who called Yes NMG) - unwanted by-product in the oxidation of N-(phosphonomethyl)iminodiacetic acid (FMEC) catalyzed carbon.

Summary of invention

Thus, one purpose of the invention is to develop a method of producing glyphosate and its esters and salts by oxidation of N-substituted glyphosate, as well as their esters and salts. More specifically, the object of this invention is the provision of a method of producing glyphosate and its esters and salts by oxidation of N-substituted glyphosate, as well as their esters and salts, having only N-carboxymethyl functional group. For example, the purpose of this invention is the provision of a method of producing glyphosate by oxidation of N-methylpyrazine.

Hence briefly the present invention is dedicated to a new way of producing compounds of the formula (I):

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In this formula, R3, R4and R5independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon radical or acceptable for agriculture cation. This invention involves the contacting of the solution with a catalyst based on a noble metal and the introduction of CI is R1and R2independently represent a hydrogen atom, a halogen atom, a group-RHO3H2, -SO3N-NO2or a substituted or unsubstituted hydrocarbon radical, different from the group-COOH. The radicals R3, R4and R5are the same as defined above for formula (I).

In another variant embodiment of this invention, the connection (i.e. the substance of the formula (I)), which can be obtained, is a glyphosate or its salt, a N-substituted glyphosate (i.e., a substance of the formula (II) is N-metalliform or its salt. During the reaction solution having a temperature of from about 125 to 150oWith and in contact with the N-metalliform or its salt, in contact with a catalyst containing a noble metal is platinum. In addition, during the reaction the solution was added 2,2,6,6-tetramethylpiperidine-N-oxide. Additionally, the solution is injected oxygen at a rate that provides the maximum concentration of dissolved oxygen in the solution, which does not exceed 2.0 hours/million

The third variant embodiment of this invention relates to the oxidation catalyst based on a noble metal, on which the adsorbed hydrophobic electroactive molecular cha is alsomany to obtain glyphosate in accordance with this invention, using various N-substituted glycine predecessors.

In Fig.2 summarizes the different substances that can be obtained during the oxidation of N-methylpyrazine.

A detailed description of the preferred embodiment variants of the invention

The present invention provides a new and effective method of producing glyphosate, its salts and esters in the aquatic environment, in which the N-substituted glyphosate or its salt or ester (collectively referred to as "N-substituted glyphosates reagent") is subjected to oxidative cleavage of the oxygen over the catalyst is a noble metal. Advantages of getting a glyphosate N-substituted glyphosate using this method include the simplicity of the method, low cost oxidizer (such as air or molecular oxygen) and the durability of the catalyst (i.e., slight deactivation of the catalyst or the lack of it within a few cycles).

Despite the known from the prior art methods oxidative cleavage of N-substituted glyphosate, this method is not limited to the oxidation FMEC (which has two N-carboxymethyl functional groups). On the contrary, this method can also be used to obtain the glyph, the national group. Therefore, this invention significantly expands the set of N-substituted glyphosate, which can be oxidized with the formation of glyphosate. In turn, this greatly expands the set of N-substituted glycinol (predecessors of many N-substituted glyphosate), which can serve as source material for the production of glyphosate. In addition, this invention is valuable because it provides a method of producing glyphosate N-methylpyrazine - unintended by-product of oxidation FMEC catalyzed carbon.

N-Substituted glyphosate reagents of the present invention have the following formula:

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where preferably R1and R2represent independently a hydrogen atom, a halogen atom, a group-RHO3H2, -SO3N-NO2or a substituted or unsubstituted hydrocarbon radical, different from the group-COOH; and the radicals R3, R4and R5independently are a hydrogen atom, a substituted or unsubstituted hydrocarbon radical or a cation, acceptable for agriculture.

Used herein, the term "hydrocarbon radical" is defined as a radical consisting solely of carbon and hydrogen. This , and may contain one or more rings. Suitable hydrocarbon functional groups include alkyl, alkeline, alkyline and aryl. They also include alkyl, alkeline, alkyline and aryl functional group, substituted with other aliphatic or cyclic hydrocarbon groups such as alkaryl, alkenyl and alkylaryl.

The term "substituted hydrocarbon radical" is defined as radical, in which at least one hydrogen atom is substituted by an atom that is different from hydrogen. For example, the hydrogen atom may be substituted by a halogen atom such as chlorine or fluorine. Alternatively, the hydrogen atom may be replaced by oxygen atom with the formation of, for example, hydroxy-group, simple ester, complex ester, anhydride, aldehyde, ketone or carboxylic acids (except that no1or R2may not be a carboxyl group, i.e.,- COOH). The hydrogen atom can also be substituted by a nitrogen atom with the formation of amide or nitro group. However, preferably should avoid substitution by nitrogen nitrogen with the formation of amine or nitrile group. In addition, the hydrogen atom may be replaced by sulphur atom with the formation of, for example, group-SO3N, although you should avoid substitution with the O. This ring may be either a hydrocarbon or heterocyclic, and at least one hydrogen atom of the ring can be substituted as described above for substituted hydrocarbon functional groups.

In a preferred variant embodiment of the invention, each radical R1, R3, R4and R5represents a hydrogen atom, and R2represents a linear, branched or cyclic hydrocarbon radical, containing approximately up to 19 carbon atoms. In a more preferred embodiment of the invention, each radical R3, R4and R5represents a hydrogen atom and-CHR1R2is stands (i.e., R1and R2are hydrogen atoms), isopropyl (i.e., R1and R2are metelli), benzyl (i.e., R1is a hydrogen atom and R2- phenyl or n-Pentium (i.e., R1is a hydrogen atom and R2is a hydrocarbon radical with up to 4 carbon atoms and a normal chain).

Many N-substituted glyphosate reagents can be obtained by phosphonomethylglycine corresponding N-substituted glycinol, their salts or their amides, for example, by the following reactions:

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Phosphonomethylglycine secondary and the Griffiths & Grayson, published by J. Wiley & Sons, 1976); and in the section entitled "alpha-Substituted phosphonates" in the book P. Mastalerz "Handbook of organophosphorus chemistry", S. 277-375 (Ed. by R. Engel, published by Marcel Dekker, 1992).

For the preparation of N-substituted glycinol and their salts and amides can be used different ways. In one embodiment of this invention, N-substituted glycine was prepared by condensation of hydrogen cyanide, formaldehyde and N-substituted amines with subsequent hydrolysis to N-substituted glycine or salts thereof:

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This reaction is known as the synthesis of Striker. Synthesis of Striker well known in this field of chemistry and described, Dicerem log Angew.Chimie (int. the publication in English. lang.), volume 36, 16, S. 1700-1702 (1997). The resulting N-substituted glycine can be converted into N-substituted glyphosate by reacting with formaldehyde and phosphorous acid (H3RHO3in the presence of a strong acid.

In another variant embodiment of this invention, N-substituted glycine is produced by dehydrogenation of N-substituted ethanolamine in the presence of a base (preferably sodium hydroxide) with the formation of salts of N-substituted glycinol:

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This reaction is described by Francico in U.S. patent 5292936 and 5367112 and Ebner and other means. In the first method, the ketones can condense with monoethanolamine in the presence of hydrogen, solvent and catalyst is a noble metal. This reaction is described by A. C. cope and E. M. Hancock, J. Am.Chem.Soc., so 64, S. 1503-1506 (1942). N-substituted ethanolamines can also be prepared by reacting monosubstituted amine (such as methylamine) with ethylene oxide with the formation of monosubstituted ethanolamines. This reaction was described by Yoshida in the patent application of Japan 95-141575. The resulting salt of N-substituted glycine can be converted into N-substituted glyfo sat by reacting with phosphorus trichloride (PCl3in the water, then the salt is filtered off and added formaldehyde.

In an alternative embodiment of this invention, N-substituted glycine is obtained by condensation of N-substituted amides, formaldehyde and carbon monoxide in the presence of cobalt catalyst:

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This reaction (i.e., karboksimetilirovaniya) described by Bellera etc. in the application for the European patent 0680948; and Knifton, Applied Homogeneous Catalysis, 159-168 (as amended Cornils and others, VCH, Weinheim, Germany, 1996). The product of this reaction is N-acetyl derivative of N-substituted glycine, which can be subjected to hydrolysis in N-substituted glycine. Then N-substituted glits aristoi acid in the presence of a strong acid with the subsequent removal of carboxylic acids well known ways, such as distillation or membrane separation.

In another embodiment of this invention, N-substituted glycine receive rehabilitation alkylation of glycine, which is carried out by interaction of carbonyl compounds with glycine and hydrogen in the presence of a catalyst:

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This reaction is described by Sartori and others in the U.S. patent 4525294. N-substituted glycine can be converted into N-substituted glyphosate by reacting with formaldehyde and phosphorous acid in the presence of a strong acid.

In addition, this invention provides a new and effective way of transformation of N-substituted glyphosate that are not received by phosphonomethylglycine N-substituted glycinol. For example, this method is particularly effective when receiving glyphosate N-methylpyrazine, an unintended by-product of the oxidation FMEC catalyzed carbon.

In Fig.1 summarizes the methods for producing glyphosate of the materials mentioned above. Used in Fig.1 the symbols have the usual meanings, well-known specialists in this field of technology.

In order to oxidize N-substituted glyphosates reagent, it is preferably first mixed with water and patentsthe catalyst - the noble metal N-substituted glyphosates reagent undergoes oxidative transformation of glyphosate and various by-products:

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where R1, R2, R3, R4and R5such as defined above.

In a preferred embodiment, the catalyst is subsequently separated by filtration, and then glyphosate can be isolated by precipitation, for example by evaporation of water and cooling.

The amount of N-substituted glyphosates reagent in aqueous medium is typically from about 1 to 80 wt.% ([mass of N-substituted glyphosates reagent/total reaction mass] 100%). More preferably, the amount of N-substituted glyphosates of the reagent is from about 5 to 50 wt.% and most preferably, from about 20 to 40 wt.%.

Preferably this reaction is carried out at a temperature of approximately from 50 to 200oC. More preferably, the reaction is carried out at a temperature of from about 70 to 150oC and most preferably at a temperature of from about 125 to 150oC.

During the oxidation reactor pressure mainly depends on temperature. Preferably, sufficient is the box is used oxygen-containing gas, also preferred is a pressure, which contributes to the dissolution of oxygen in the reaction mixture at a rate sufficient to maintain the desired reaction rate. Preferably, the pressure at least equal to atmospheric. Preferably, the pressure varies from about 30 to 200 psi (0,21 to 1.4 MPa). More preferably, when the temperature is in the preferred range from about 125 to 150oWith, the pressure is from about 0.28 to 0.7 MPa.

The source of oxygen for the oxidation reaction can be any oxygen-containing gas or a liquid containing dissolved oxygen. Preferably, the oxygen source is an oxygen-containing gas. Used herein, the term "oxygen-containing gas" is any gas mixture containing molecular oxygen, which optionally may contain one or more diluents which do not react with oxygen, or with a reagent or product under the reaction conditions. Examples of such gases is air, pure molecular oxygen or molecular oxygen diluted with helium, argon, neon, nitrogen, or other gases that do not contain molecular molecular oxygen, and more preferably at least about 50% of the oxygen-containing gas is molecular oxygen.

Oxygen can be introduced into the reaction medium by any conventional means so as to maintain the concentration of oxygen dissolved in the reaction mixture at the desired level. If you are using oxygen-containing gas, preferably it is introduced into the reaction mixture in such a way as to provide maximum contact of the gas with the reaction solution. Such contact can be achieved, for example, by dispersing the gas through the diffuser, such as a porous glass plate, or by sintering, shaking or any other means known to specialists in this field of technology.

Preferably, oxygen is supplied into the reaction mixture at a rate that is sufficient to maintain the dissolved oxygen concentration at the maximum level. More preferably, the oxygen is supplied into the reaction mixture at a rate that is sufficient to maintain the dissolved oxygen concentration is not more than approximately 2 hours/million, but at a high enough concentration to provide the desired reaction rate. Not the ion mixture and preferably it is from about 0.5 to 10 ATM (from 0.05 to 1.0 MPa).

Used in this invention, the catalyst includes a noble metal, preferably platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (OS) or gold (Au). In General, more preferred are platinum and palladium, and most preferred is platinum. Because currently, platinum is the most preferred, the subsequent discussion will be mainly devoted to the use of platinum. However, it should be understood that the same discussion will be generally applicable to other noble metals and their combinations.

The catalyst is a noble metal can be nenalezena, for example platinum mobile, industrial available from various sources, such as company Aldrich chemical Co. Inc., Milwaukee, pieces of Wisconsin; Engelhard Bldg., Iselin, items of new Jersey; and Degussa Corp., Ridgefield Park, PCs new Jersey. Alternatively, the catalyst is a noble metal can be deposited on the surface of the carrier, such as carbon, aluminum oxide (Al2ABOUT3), silicon dioxide (SiO2), titanium dioxide (TiO2), zirconium dioxide (ZrO2), siloxane, or barium sulfate (BaSO4), preferably silicon dioxide, titanium dioxide or barium sulfate. Deposited metals is the example, 5% platinum on charcoal from the firm Aldrich, catalog 20593-1; platinum on powdered alumina - Aldrich, catalog 31132-4; palladium (restored) on the barium sulfate - Aldrich, catalog 27799-1; and 5% palladium on charcoal-Aldrich, catalog 20568-0.

As for carbon carriers, it is usually preferred graphite carriers, such as carriers have a high selectivity with respect to glyphosate.

The concentration of the catalyst is a noble metal on the surface of the carrier may vary within wide limits. Preferably, it is in the range from about 0.5 to 20 wt.% ([mass of noble metal/total weight of catalyst] 100%), more preferably, from about 2.5 to 10 weight. %, and most preferably, from about 3 to about 7.5 wt.% At a concentration of greater than about 20 wt.%, there is a tendency to the formation of layers and lumps of precious metal. Thus, there is less surface metal atoms from the total number of used noble metal. This leads to a decrease in catalyst activity and wasteful use of expensive noble metal.

The weight ratio of blah is listello from 1: 500 to 1:5. More preferably, this ratio is from about 1:200 to 1:10 and most preferably, from about 1:50 to 1:10.

In a preferred variant embodiment the catalyst is a noble metal adsorbed electroactive molecular particles (i.e., molecular particles, which are able to reversibly oxidized to recover due to the transition of electrons). In accordance with this invention, it was found that the selectivity and/or conversion for the catalyst is a noble metal can be improved in the presence of electroactive molecular particles, in particular when the catalyst is used to effect the oxidation of N-methylpyrazine with the formation of glyphosate. In this case, the electroactive molecular particles are preferably hydrophobic and have an oxidation potential (E1/2), is at least equal to approximately 0.3 V relative to the saturated calomel electrode. In the literature one can find many substances such oxidative potential. A good range of oxidation potentials of reversible processes for a large number of electroactive molecular particles can be found in Encyclopedia of electrochemistry of the elements (as amended A. demonstrating oxidative potentials for electroactive molecular particles, below: for triphenylmethane - J. Perichon, etc.. encyclopedia of electrochemistry of the elements, I. 11, S. 163 (as amended A. Bard and H. Lund, published by Marcel Dekker, new York, 1978); for N hydroxyphthalimide - M. Masui, etc., J. Chem.Soc. Chem.Comm., S. 479-480 (1983); Tris(4-bromophenyl)amine-S. Dapperheld etc., Chem.Ber., so 124, S. 2557-2567 (1991); 2,2,6,6-tetramethylpiperidine-N-oxide - M. Semmelhack, etc., T. 105, S. 4492-4494 (1983); 5,10,15,20-tetrakis-(pentafluorophenyl)-N, N-porphin chloride iron(III) - D. Dolphin, etc., Acc.Chem.Res., so 30, S. 251-259 (1997); and for various porphyrins - J. H. Fuhrhop. Porphyrins and Metalloporphyrins, 593 (ed K. Smith, ed. Elsevier, New York, 1975).

Electroactive molecular particles are also used in connection with the oxidation of N-isopropylpyrazine with the formation of glyphosate. In this regard, the electroactive molecular particles are preferably adsorbed on the catalyst is a noble metal deposited on a graphitized carbon (carbon as graphite). It was found that in the presence of graphitized carbon media electroactive molecular particles increase the selectivity of the catalyst is a noble metal in respect of glyphosate.

Examples of generally suitable electroactive molecular particles include triphenylmethane; N-hydroxyphthalimide; 5,10,15,20-tympani)amine; 2,2,6,6-tetramethylpiperidine-N-oxide (sometimes referred to as TEMPO); 5,10,15,20-tetraphenyl-N,N-porphin iron(III) chloride (sometimes referred to as Fe(III)TPP chloride); 4,4'-differentfrom; 5,10,15,20-tetraphenyl-N,N-porphin Nickel(II) (sometimes referred to as Ni(II)TPP); and phenothiazines. When the catalyst is a noble metal is used for the catalytic oxidation of N-methylpyrazine in glyphosate, the most preferred electroactive molecular particles include N-hydroxyphthalimide, Tris(4-bromophenyl)amine; 2,2,6,6-tetramethylpiperidine-N-oxide; 5,10,15,20-tetraphenyl-N, N-porphin iron (III) chloride; and 5,10,15,20-tetraphenyl-N,N-porphin Nickel(II).

Electroactive molecular particles can adsorb on the catalyst is a noble metal using various methods well-known in this technical field. Electroactive molecular particles can be added directly to the reaction mixture oxidation, separately from the catalyst is a noble metal. For example 2,2,6,6-tetramethylpiperidine-N-oxide may be added to the reaction mixture without prior adsorption on the catalyst is a noble metal, as shown in Example 13. Using this method, electroactive molecular particles adsorbed on the catalysis of the s adsorbed on the catalyst noble metal before it is added to the reaction mixture oxidation. Usually electroactive molecular particles can adsorb on the catalyst using, for example, deposition from the liquid phase or gas phase. Example 8 illustrates the use of deposition from the liquid phase to the adsorption of electroactive molecular particles.

Preferably the oxidation reaction is carried out in a reactor with a single load in such a way that the reaction mixture may be present in the reactor to complete its transformation into glyphosate. However, you can also use other types of reactors (e.g reactors tanks with continuous mixing), although preferably: 1) must be sufficient contact between the oxygen of N-substituted glyphosate reagent and a catalyst; and 2) it is necessary to ensure adequate residence time of the reaction mixture for a substantial transformation of N-substituted glyphosates reagent glyphosate.

It should be noted that in this invention there is the possibility of oxidation of N-substituted glyphosate in the presence of other chemicals that may occur in the preparation of glyphosate already known methods. For example, in this izobreteniya particles, which are by-products of oxidation FMEC catalyzed carbon, such as aminomethylphosphonic acid (AMPK), N-methylenediphosphonate acid (MMPC) and glyphosate.

In addition, it must be recognized that this method of transformation can be performed while in the reaction mixture is ground in a sub-stoichiometric amount (i.e., less than one equivalent). However, the presence of a base can have a harmful effect on the selectivity of the process in certain conditions.

EXAMPLES

General information

In most examples below are described the oxidation of N-methylpyrazine with the formation of glyphosate. In addition to glyphosate, can also cause the formation of N-methylenediphosphonate acid and phosphoric acid (H3RHO4). In addition, glyphosate product can then be oxidized with the formation of aminomethyl-phosphonic acid. These reactions are summarized in Fig.2.

For analysis of products formed during the reactions considered in the following examples, using a liquid chromatography high pressure (ghvd). Used ion-exchange separation, and the products of the analysis detects, using a UV visible detector emitted to distinguish between N-methylglyoxal, glyphosate and phosphoric acid, but aminomethylphosphonic acid (AMPK) and N-methylenediphosphonate acid (MAMTC) suiryudan together. Because AMPK and MAMTC have, per mol, the same response factor, it is possible to reliably determine the sum of the concentrations AMPK and MMFC. This value is below in the examples as (M)AMPK.

EXAMPLE 1.

This example illustrates a typical synthesis of N-methylpyrazine. About to 89.9 g sarcosine (1.0 mol), 82,0 g of phosphorous acid (1.0 mol) and 110 g of concentrated hydrochloric acid are mixed and refluxed in an oil bath with a temperature of 130oC. and Then added dropwise within 20 minutes 89,3 g of 37% formalin (1.1 mol) and the reaction continued for another 85 minutes. At this point, according to NMR in the mixture have the following products (per mole): 89,9% N-methylpyrazine, 2.1% of phosphorous acid, 1,9% phosphoric acid, 0.4% of hydroxymethylphosphonate acid and 5.7% unknown product (in the NMR spectrum: triplet, 8,59 memorial plaques). After cooling to room temperature, add 40 g of sodium hydroxide and then 250 g of water. This leads to the formation of a white precipitate, which then allocate by filtration and analyzed by the method ghvd. Total yield vydelennogo Similarly you can also get other N-alkylpyridine.

EXAMPLE 2.

This example illustrates the conversion of N-methylpyrazine in glyphosate using a platinum catalyst and oxygen.

Approximately 10.0 g of N-methylpyrazine, 140 g of water and 1.0 g of platinum mobile (Aldrich chemical Co. Inc., Milwaukee, PCs Wisconsin) are mixed in a round bottom flask, equipped with a water cooled reflux condenser and immersed in an oil bath with a temperature of 150oC. the Solution is stirred and within 4 hours after it bubbled oxygen. At the end of this period according to Ehud in the mixture have the following products (per mole): 86.4 per cent of glyphosate, 8.7% of N-methylpyrazine and 2.2% (M)AMPK and 2.7% phosphoric acid. Glyphosate is precipitated from the solution after cooling to room temperature.

In the second experiment a mixture of 10.0 g of N-methylpyrazine, 2.0 g of platinum mobiles and sufficient water to bring the total volume of the mixture to 200 ml), stirred for 2 hours and 40 minutes at a temperature of 80oWith and at the same time in a mixture bubbled oxygen at atmospheric pressure. Analysis of the reaction mixture showed the presence of the following products (per mole): 85.4% glyphosate, 8.1% of phosphoric acid and 6.5% unknown components. N-methylglyoxal was not found.

EXAMPLE 3.

oC. the Solution is stirred and within 18 hours at the surface of the reaction mixture, introducing a stream of oxygen. At the end of this period according to the31P-NMR in the mixture have the following products (per mole): 91% glyphosate, 1% aminophosphonic acid, 6% phosphoric acid and 2% unknown product (in the NMR spectrum: 15,0 memorial plaques). Glyphosate is precipitated from the solution after cooling to room temperature.

EXAMPLE 4.

Use different N-alkylpyridine in the same conditions as described in Example 3, to obtain glyphosate. In other words, the only variable parameter is the radical R1in the following formula:

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Table 1 shows the used alkyl groups (i.e., R1), and also the values of conversion and selectivity to glyphosate.

Example 5.

This example illustrates the conversion of N-methylpyrazine in glyphosate using nenalezena platinum and various catalysts, to the odes and 2.0 g of catalyst 5% platinum on barium sulphate are mixed in a round bottom flask (nabuna water reflux condenser immersed in an oil bath with a temperature of 95oC. the Solution is stirred and for 23 h, and through him bubbled oxygen. At the end of this period according to Ehud in the mixture have the following products (per mole): 78.2% of glyphosate, 2,4% N-methylpyrazine, and 9.4% (M)AMPK and 10.0% phosphoric acid. Glyphosate is precipitated from the solution after cooling to room temperature.

In a separate experience receive data in Table 2, by heating to boiling under reflux a mixture containing 1.0 g of N-methylpyrazine, 20 ml of water and a sufficient amount of catalyst to the content of metallic platinum in a round bottom flask, equipped with a water-cooled reflux condenser and magnetic stirrer, was 5 mg In the mixture for 5 h bubbled oxygen, using a needle. Then the catalyst is removed by filtration and the filtrate analyzed by the method ghvd.

As can be seen from table 2, the tested two catalyst as platinum mobiles. The catalyst for the firm Engelhard V2001 (Engelhard Bldg., Iselin, PCs, new Jersey has a much smaller surface area than platinum mobile firms greater surface area has low selectivity and conversion, even when used in the amount of 30 times (i.e., 150 mg) than the catalyst of the firm Aldrich (i.e., 5 mg).

Was conducted the third experiment, which illustrates that the aluminum oxide and siloxanes (Ciloxan, Degussa Building. , Ridge field Park, PCs, new Jersey can be used as carriers for metal catalysts. The following experiments were conducted during the night when 95oAnd atmospheric pressure, using a sufficient amount of catalyst equivalent to 0.1 g of metallic platinum, 1 g N-methylpyrazine and 10 ml of water. Oxygen is injected through a needle with a speed of 50 ml (standard) per minute. The resulting solution is filtered and analyzed by the method ghvd, and the concentration of dissolved platinum determined by the method of mass spectrometry with inductively coupled plasma. The data are shown in table 3.

EXAMPLE 6.

This example illustrates the use of palladium instead of platinum as catalyst for the oxidation of N-methylpyrazine in glyphosate. A solution containing 3.0 g of N-methylpyrazine, 57 g of water and 0.3 g of palladium mobile, in-air refluxed, cooled by water, from Friday evening until Monday. According to the analysis of NMR in the mixture have the following products: 97,2% N-matilha catalysts, containing graphitized carbon carriers impregnated with platinum, have a high selectivity with respect to glyphosate compared with catalysts containing nepravitelstvennye carbon carriers impregnated with platinum. In addition, this example illustrates that produce less MMPC and AMPK when using catalysts containing graphitized carbon carriers impregnated with platinum.

The following example describes the results of the oxidation of N-methylpyrazine using catalysts containing platinum, dispergirovannoyj available at industrial carbon media. Coal F 106 and the catalyst is platinum on coal F 106 is available from the company Degussa Building. (Ridgefield Park, PCs, new Jersey. Coal Sibunit is made, as described Surovikin and others in the U.S. patent 4978649, and can be delivered from Borisovskoe Institute of catalysis (Novosibirsk, Russia) as canned platinum catalysts supported on carbon Sibunit. However, the catalyst used in this example is prepared from the coal by impregnation with platinum salts and subsequent reduction with sodium borohydride, which is normal when getting deposited platinum catalysts. General A. B. swedene The Stiles, Catalyst carriers and supported catalysts. Theoretical and applied concepts (Butterworths, Boston, items Massachusets, 1987) and in section R. L. moss, Experimental Methods in Catalytic Research, so 2, Chapter 2, S. 43-94 (as amended Anderson and Dawson, Academic Press, new York, 1976). The catalyst was 20% platinum on the corner of Vulcan XC-72R manufactured by the firm Johnson mattey and can be delivered through a firm alpha/Aesar (Ward Hill, items Massachusets). These three types of carbon are respectively neprofessionalnymi, partially graphitized and almost fully graphitized.

Approximately 100 mg of catalyst (except as stated below), 10 ml of water and 1.0 g N-methylpyrazine refluxed for 5 hours and at the same time, bubbled oxygen through a needle. The reaction mixture is filtered and analyzed by the method ghvd. The data are given in table 4.

EXAMPLE 8

This example demonstrates the improvement in selectivity that can be achieved by adsorption of electroactive molecular particles on the catalyst is a noble metal. All electroactive molecular particles adsorbed in this example, undergo oxidation and reduction as a result of electron transfer. Thus, here the use of the elegance predecessors.

This experience is carried out by heating to boiling a mixture containing 1.0 g of N-methylpyrazine, 20 ml of water and 50 mg of platinum metal, round bottom flask, equipped with a water-cooled reflux condenser and a magnetic stirrer. In the mixture for 5 h bubbled oxygen, using a needle. Then the catalyst is removed by filtration and the filtrate analyzed by the method ghvd.

For the preparation of catalysts treated with organic substances, add 0.5 g of platinum mobile (Aldrich chemical Co. Inc., Milwaukee, PCs Wisconsin) in a solution of 25 mg of venom (i.e., electroactive molecular particles) in 50 ml of anhydrous acetonitrile. This mixture clog cap Erlenmeyer flask for 4 days, with the exception of 4,4'-diftorbenzofenon, the solution is treated with the catalyst during the day. In the subsequent catalyst allocate filtration, washed with acetonitrile and diethyl ether and air-dried over night.

2,4,7-Trichlorofluoro the catalyst is prepared using 0.3 g of platinum mobiles and 30 ml of a solution containing 834,5 hours/million 2,4,7-trichlorofluoro in 1% solution of dichloromethane in acetonitrile (used to facilitate dissolution of electroactive molecular particles); solvents give the silt and ethanol and dried in air.

For the preparation of catalysts treated with inorganic substances, mix 0.5 g of platinum mobiles, 50 ml of tetrahydrofuran and either 256 mg, or 100 mg of inorganic electroactive molecular particles. This mixture is stirred for a night at room temperature and sealed in an Erlenmeyer flask with a capacity of 125 ml. of the Catalyst are filtered, washed with diethyl ether and air-dried over night.

All applicable inorganic substances available from the company Aldrich chemical (Milwaukee, PCs Wisconsin) are listed below:

1. 5,10,15,20-tetrakis(pentafluorophenyl)-N,N-porphin iron(III) chloride (abbreviated as Fe(III)TPFPP chloride in the table.5). For the preparation of the catalyst used approximately 25 mg.

2. 5,10,15,20-tetraphenyl-N, N-porphin iron(III) chloride (abbreviated as Fe(III)TPP chloride in the table. 5). For the preparation of the catalyst used approximately 25 mg.

3. 5,10,15,20-tetraphenyl-N,N-porphin Nickel(II) (abbreviated Ni(II)TPP in the table.5). For the preparation of the catalyst used approximately 25 mg.

4. Ruthenium-Tris(2,2'-bipyridine)dichloride (abbreviated as Ru(b)3CL2in table. 5). For the preparation of the catalyst used approximately 100 mg.

5. Ferrocene. For the extreme potential (E1/2for electroactive molecular particles they are listed in the table. 5. This example illustrates that the electroactive molecular particles, which have relative solubility in water (such as ferrocene and Ru(b)3CL2) less effectively increase the selectivity for glyphosate. This example also demonstrated that hydrophobic electroactive molecular particles, having an oxidation potential more negative than approximately 0.3 V relative to the saturated calomel electrode, usually reduce the conversion. Thus, the preferred electroactive molecular particles that increase the selectivity and conversion in the oxidation of N-methylpyrazine may be organic or inorganic, but should be hydrophobic and have an oxidation potential more positive than about 0.3 V relative to the saturated calomel electrode (NEC).

EXAMPLE 9.

This example illustrates the effect of electroactive molecular particles on platinum catalyzed oxidation of N-current IEO-propylpyrazine using a commercial available catalyst (20% PT on the corner of Vulcan XC-72R (produced by the firm Johnson mattey and can be delivered through the fir which was b impregnated two types of electroactive molecular particles: N-hydroxyphthalimide and triphenylmethane.

These catalysts are used for the oxidation of N-isopropylpyrazine according to the method described in the previous example. Instead of N-methylpyrazine using 1 g of N-isopropylpyrazine. The results are shown in table. 6, show that the electroactive molecular particles improve the selectivity of the catalysts of platinum on coal" in this reaction. It was found that the modifiers with less positive oxidation potential, such as triphenylmethane are more effective than modifiers with more positive oxidation potential, such as N-hydroxyphthalimide. This example also demonstrated that the use of graphitized media for platinum is less effective for suppressing undesirable side reactions during the oxidation of N-isopropylpyrazine than in the case of N-methylpyrazine.

EXAMPLE 10.

This example illustrates that the rate of selectivity and conversion can be improved by reducing the dissolved oxygen concentration.

In the reactor-autoclave made of stainless steel 316 (capacity 300 ml) is mixed with 4.4 g of N-methylpyrazine with 1 g of platinum mobile in 145 g of deionized water. The reaction mixture is heated to 70oC at a pressure of 420 kPa is Yu dissolved oxygen is measured, using the dissolved oxygen sensor - Orbiter calibrated to the testimony of 26.4 hours per million of oxygen at saturation of the air in the conditions of the 70oC and a pressure of 420 kPa, and regulate by changing the ratio of nitrogen/oxygen mixture. Spend 2 experience at a concentration of dissolved oxygen at the level of 2-3 hours/million and 10 hours/million During the analysis of the reaction mixture after 2 and 4 hours method ghvd the results obtained are shown in table.7.

EXAMPLE 11.

This example illustrates platinum catalyzed oxidation of N-substituted glyphosates, in which Deputy nitrogen atom, contains atoms different from carbon or hydrogen. In particular, the described oxidation glyphosine (BUT2-CLO2N(CH2RHO3H2)2) and N-hydroxyethylpiperazine who receive phosphonomethyl glycine and N-hydroxyarginine, respectively, by reacting with formaldehyde and phosphorous acid when heated in the presence of a strong acid as described in General in the work of D. Redmore, Topics in Phosphorous Chemistry, so-8, S. 515-585 (ed Griffith and Grayson, publishing house of J. Of Willy and sons, 1976) and in the section entitled "alpha-Substituted phosphonates", in Handbook of organophosphorus chemistry, P. Mastalerz, S. 277-375 (Ed. by R. Engel, published by Marcel Division carried out by the same method, which is used in the oxidation of N-methylpyrazine in Example 8. The distribution of products analyse method31P-NMR. Oxidation glyphosine equal 74,9% with a selectivity for glyphosate of 50.2%. Another main product is bis(phosphonomethyl)amine, (-HN-(CH2RHO3H2)2), which is 39.1% of oxidation products glyphosine. Also, found a small amount AMPK and unidentified products. The use of catalyst - platinum mobiles, treated with Tris(4-bromophenyl) - amine described in Example 8, leads to an increase in conversion to 86.8%, but the selectivity is not changed.

Oxidation of N-hydroxyethylpiperazine leads to the transformation of the substrate equal to 46.7% and distribution products: 61.2% of glyphosate, a 22.4% N-hydroxyethylidenediphosphonic acid and 16.3% phosphoric acid.

EXAMPLE 12.

This example illustrates the speed and selectivity of the oxidation of N-methylpyrazine achieved at elevated temperature on platinum mobiles. Noted that no appreciable deactivation of the catalyst within 7 cycles.

Glass reactor (300 ml), designed for high pressure, equipped with a thermocouple and two filters-the I of the dispersing gas. A second filter located approximately 25 mm from the bottom, but not in the center, is used for the flow. Also provided by the output line gas associated with a back-pressure regulator which is set to maintain a pressure of 350 kPa (50 f/DM2). Charged to the reactor approximately 60 g of N-methylpyrazine, along with 3 g of platinum mobiles from the company Aldrich chemical (Milwaukee, PCs Wisconsin,) and 180 ml of water, together with the mixing device. The reactor is immersed in an oil bath, the mixture is stirred with a magnetic stirrer and heated in a slow stream of nitrogen until the temperature of the mixture reaches 125oWith, forming a homogeneous solution. Then after the reaction mixture was bubbled with oxygen and nitrogen, with a speed of 1.5 and 0.5 normal liters per minute (nl/min), respectively, for 30 minutes, and then an additional 30 minutes the reaction is carried out at flow rates of oxygen and nitrogen is equal to 1 nl/min, and then the last 30 minutes of nitrogen and oxygen is served with speeds of 1.5 and 0.5 nl/min With constant stirring the mixture remained homogeneous during the whole period of 90 minutes. Then set a slow stream of nitrogen for pressure maintenance. The contents of the reactor is brought out through the porous plate to the Vykhino and then remove its traces from the reaction mixture. Then the reactor is allowed to cool. Again, add 60 g of N-methylpyrazine and 180 ml of water and the cycle is repeated. Spend 7 cycles and get the results shown in the table. 8.

The concentration of platinum in the solution at the end of the experience varies from 0.3 to 1.1 hours /million after the first cycle, which was found by the method of mass spectrometry with inductively coupled plasma. Although during the first cycle in the solution passes increased amount of platinum (i.e., the concentration of dissolved platinum is 4.2 hours /million), believe that the greatest part of the lost platinum is an original unrestored platinum on the surface of platinum mobiles.

EXAMPLE 13.

This example illustrates the selectivity that can be achieved in the oxidation of N-alkylglycerol at low flow rates of oxygen and moderate conversion, if the reaction mixture is added electroactive molecular particles, such as 2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO). Requires no pre-treatment of the catalyst. This example also demonstrates that the conversion increases during the first few cycles, when the electroactive molecular particles added to the solution. Finally All.

In the reactor high pressure as described in Example 12, mix approximately 60 g of N-methylpyrazine, 3 g of platinum mobile (Aldrich chemical, Milwaukee, items of Wisconsin), 180 ml of water and 40 mg of TEMPO dissolved in 1 ml of acetonitrile. The mixture is heated to 125oWith stirring under a nitrogen pressure of 350 kPa (50 f/DM2) and a homogeneous mixture is formed, through which bubbled a mixture of nitrogen and oxygen, 75% nitrogen and 25% oxygen by volume) for 90 minutes, with a flow rate of 1 santil/min, maintaining a pressure equal to 350 kPa. Then the reaction mixture is brought out through the plate filter, leaving the catalyst in the reactor. Successively added to the reactor 60 g N-methylpyrazine, 180 ml of water and 40 mg of TEMPO in 1 ml of acetonitrile and the cycle is repeated. Just a 4-cycle. In all cases, the concentration (M)AMPK was below the quantitative level, detected only traces. The only defined quantitatively by-product is phosphoric acid. The values of conversion and selectivity at the end of each of the four cycles shown in the table.9.

As in Example 12, at the end of each experiment to measure the concentration of dissolved platinum by the method of mass spectrometry with inductively coupled plasma. This concentration of RA is 12. As in Example 12, an increased amount of platinum goes into solution during the first cycle (where the concentration of dissolved platinum 8.3 hours/million). However, I believe that the greatest part of the lost platinum is a first unrestored platinum on the surface of platinum mobiles.

EXAMPLE 14.

This example illustrates the selectivity that can be achieved in the case of obtaining N-methylpyrazine by direct phosphonomethylglycine amides of sarcosine, such as N-acetyl - and N-propionylcarnitine or anhydride of sarcosine, and not to sarcosine.

Mix approximately 20,0 g N-acetylcarnosine (152,5 mmol), 12.5 g of phosphorous acid (152,4 mmol) and 37.6 g of concentrated hydrochloric acid and refluxed in an oil bath with a temperature of 120oC. for 20 minutes, added dropwise to 13.6 g of 37% formalin (167,6 mmol). The reaction is continued for 19 hours. According to the analysis ghvd the N-methylpyrazine is 99 mol%. per load.

In the same conditions of 20.0 g of N-propionylcarnitine (137,8 mmol) is transformed into N-methylglyoxal using 11.3 g of phosphorous acid (137,8 mmol), 10.0 g of concentrated hydrochloric acid and 12, is. per load N-propionylcarnitine.

Also in similar conditions of 2.06 g of the anhydride of sarcosine (14.5 mmol) is transformed into N-methylglyoxal using of 2.38 g of phosphorous acid (29,02 mmol), 5.7 g of concentrated hydrochloric acid and 2.6 g of 37% formalin (32,02 mmol). According to the analysis ghvd the N-methylpyrazine is 97,2% mol. per download anhydride sarcosine.

Additional experience mix 2.0 g N-acetylcarnosine of 15.3 mmol) and 1.25 g of phosphorous acid (15,3 mmol) with 3.1 g of concentrated sulfuric acid and 1.7 g of water and then refluxed in an oil bath with a temperature of 120oC. for 20 minutes, added dropwise approximately 1.4 g of 37% formalin at 16.7 mmol). The reaction continued for a further 18 hours. According to analysis31P-NMR was determined that the yield of N-methylpyrazine is 98 mol.% per load N-acetylcarnosine.

EXAMPLE 15.

This example illustrates the oxidation of N-metalliform in conditions that are very close to the conditions in Example 12, except that the reaction mixture is ground in a sub-stoichiometric quantity.

In the reactor described in Example 12 are mixed p is from when the inside temperature of the mixture 125oWith, and at the same time bubbled through a mixture of pure oxygen (0,75 nl/min) under a pressure of 350 kPa. According to the analysis Ehud found that 23.5 percent N-methylpyrazine oxidized with selectivity for glyphosate to 65.7%. Values selectively (M)AMPK and phosphoric acid up to 21.1% and 13.2%, respectively.

From these results it follows that the oxidation of N-methylpyrazine flows, although the values of conversion and selectivity compared with the same indicators for the reaction carried out in the absence of a base.

EXAMPLE 16.

This example demonstrates that N-methylglyoxal can selectively oxidize to glyphosate in the presence of glyphosate and similar substances. Mix 1 g of platinum mobile with 300 g of a solution containing approximately 6% N-methylpyrazine and smaller amounts of glyphosate, AMPK, MAMTC, formaldehyde, formic acid and sodium chloride. The mixture is heated to 150oC for 4 h and at the same time through the mixture bubbled oxygen under pressure of 350 kPa. At the end of the reaction according to analyses of NMR and Ehud found that a large part of the N-methylpyrazine turns into glyphosate.

The above description of the preferred options is intended only is the group for to these professionals could adapt and apply the invention in its various forms in the best possible way in accordance with the requirements of a particular application. Therefore, the present invention is not limited to the above options, and can be variously modified.

1. A method of producing glyphosate, its salt or a complex ester, comprising the contacting of the solution containing N-substituted glyphosate, with oxygen in the presence of a catalyst based on a noble metal selected from the group comprising platinum, palladium, ruthenium, rhodium, iridium and osmium, to increase the number of glyphosate, its salt or a complex ester in solution, where the N-substituted glyphosate has the formula II:

< / BR>
R1and R2independently represent a hydrogen atom, a group - RHO3H2, a hydrocarbon radical or substituted hydrocarbon radical, except that R1and R2different from the group-COOH;

the radicals R3, R4and R5independently represent a hydrogen atom, a hydrocarbon radical, a substituted or unsubstituted hydrocarbon radical or agricultural-acceptable cation.

2. The method according to p. 1, katoey cation.

3. The method according to p. 2, in which R1represents a hydrogen atom, and R2group RHO3H3.

4. The method according to p. 2, in which R1represents a hydrogen atom, and R2is a linear, branched or cyclic hydrocarbon radical containing up to 19 carbon atoms.

5. The method according to p. 4, in which R1represents a hydrogen atom, and R2is unbranched hydrocarbon radical containing 4 carbon atoms.

6. The method according to p. 4, in which R1represents a hydrogen atom, and R2is phenyl.

7. The method according to p. 2, in which R1and R2represent a hydrogen atom.

8. The method according to p. 2, in which the radicals R1and R2represent methyl.

9. The method according to any of paragraphs. 1-8, in which the oxygen is supplied at a rate that provides the maximum concentration of dissolved oxygen in the solution is not more than 2 h/million

10. The method according to any of paragraphs. 1-9, in which the weight ratio of the catalyst noble metal to the N-substituted glyphosate is 1: 500-1: 5.

11. The method according to any of paragraphs. 1-10, in which the weight ratio of the catalyst noble metal to N-Zam is talization noble metal to the N-substituted glyphosate is 1: 50-1: 10.

13. The method according to any of paragraphs. 1-12, in which the process is carried out at a temperature of 50-200oC.

14. The method according to any of paragraphs. 1-13, in which the process is carried out at a temperature of 70-150oC.

15. The method according to any of paragraphs. 1-14, in which the process is carried out at a temperature of 125 to 150oC.

16. The method according to any of paragraphs. 1-15, which is carried out at a temperature of 125 to 150oC and at a pressure of 40-100 pounds/square inch (276-689 kPa).

17. The method according to any of paragraphs. 1-16, which is carried out in a gaseous environment at a partial pressure of oxygen of 0.5 to 10 ATM (51-1013 kPa).

18. The method according to any of paragraphs. 1-18, in which the solution add additional 2,2,6,6-tetramethylpiperidine-N-oxide.

19. The method according to any of paragraphs. 1-18, in which the solution add additional base in a sub-stoichiometric quantity.

20. The method according to any of paragraphs. 1-19, in which the solution further comprises phosphonomethylglycine products in addition to the N-substituted glyphosate.

21. The method according to any of paragraphs. 1-20, in which the solution is obtained by oxidizing N-(phosphonomethyl)iminodiacetic acid.

22. The method according to any of paragraphs. 1-21, in which the solution further comprises glyfo the Method according to any of paragraphs. 1-22, in which a noble metal catalyst selected from the group comprising platinum, palladium, rhodium, iridium or osmium.

24. The method according to any of paragraphs. 1-23, in which the catalyst is a noble metal is on the surface of the substrate, the latter of which includes carbon in form of graphite.

25. The method according to any of paragraphs. 1-24, in which the catalyst is a noble metal comprises palladium or platinum.

26. The method according to p. 25, in which the catalyst is a noble metal includes platinum.

27. The method according to p. 1, comprising the contacting of the solution containing N-substituted glyphosate, with a catalyst comprising platinum, introduction to the solution of 2,2,6,6-tetramethylpiperidine-N-oxide and the introduction of oxygen into the solution at a rate that ensures that the final concentration of dissolved oxygen is not more than 2 ppm, in which the solution has a temperature of 125 to 150oC; N-substituted glyphosate has the formula II

< / BR>
R1and R2represent a hydrogen atom;

R3, R4and R5independently represent a hydrogen atom or agricultural-acceptable cation.

28. The oxidation catalyst comprising a noble metal selected from the group comprising platinum, palladium, rsiste.

29. The oxidation catalyst under item 28, in which the electroactive molecular substances have an oxidation potential of at least about 0.3 V relative to the saturated calomel electrode.

30. The oxidation catalyst under item 28 or 29, in which the electroactive molecular substances are triphenylmethane; N-hydroxyphthalimide; 2,4,7-trichlorofluoro; Tris(4-bromophenyl)amine; 2,2,6,6-tetramethylpiperidine-N-oxide; chloride 5,10,15,20-tetraphenyl-N, N-porphin iron (III) 5,10,15,20-tetraphenyl-N, N-porphin - Nickel(II); 4,4'-differentfrom; chloride of 5,10,15,20-tetrakis(pentafluorophenyl)-N, N-porphin iron(III); or phenothiazines.

31. The oxidation catalyst according to any one of paragraphs. 28-30, in which the noble metal catalyst is on the surface of the carrier, and the carrier includes carbon, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, siloxane or barium sulfate.

32. The oxidation catalyst under item 31, in which the carrier comprises carbon in the form of graphite.

33. The method according to any of paragraphs. 1-23, in which the catalyst based on a noble metal includes the oxidation catalyst according to any one of paragraphs. 28-32.

 

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