WO2000009519A1 - Preparation d'acide formylphosphonique a partir de n-oxydes de (phosphonomethyle) amine - Google Patents

Preparation d'acide formylphosphonique a partir de n-oxydes de (phosphonomethyle) amine Download PDF

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WO2000009519A1
WO2000009519A1 PCT/US1999/017965 US9917965W WO0009519A1 WO 2000009519 A1 WO2000009519 A1 WO 2000009519A1 US 9917965 W US9917965 W US 9917965W WO 0009519 A1 WO0009519 A1 WO 0009519A1
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phosphonomethyl
amine
compound
group
catalyst comprises
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PCT/US1999/017965
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English (en)
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Thaddeus S. Ii Franczyk
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Monsanto Company
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3886—Acids containing the structure -C(=X)-P(=X)(XH)2 or NC-P(=X)(XH)2, (X = O, S, Se)
    • C07F9/3891—Acids containing the structure -C(=X)-P(=X)(XH)2, (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)

Definitions

  • This invention relates to the preparation of formylphosphonic acid, its salts, and its esters, and particularly to novel processes for the preparation of formylphosphonic acid by the catalytic decomposition of a (phosphonomethyl)amine N-oxide compound in the presence of a decomposition catalyst.
  • Phosphorus-containing compounds such as formylphosphonic acid are important precursors for the synthesis of organophosphorus compounds.
  • organophosphorus compounds have numerous applications.
  • formylphosphonic acid can be used as a precursor in the synthesis of N-(phosphonomethyl)glycine, a highly effective commercial herbicide (common name glyphosate, available under the trade name
  • Formylphosphonic acid can alternatively be used as an advanced intermediate in the preparation of medicinally important compounds such as the antiviral agent phosphono hydroxyacetic acid.
  • formylphosphonic acid has potential for chemical transformation at the carbonyl, phosphorus, or hydroxyl moieties.
  • Hershman et al. in U.S. Patent No. 4,072,706, disclose a process in which (phosphonomethyl)amines are oxidized with molecular oxygen in the presence of an activated carbon catalyst to cleave a phosphonomethyl group and produce a secondary amine.
  • formylphosphonic is produced as an intermediate cleavage fragment, with the fragment undergoing hydrolysis in a second step to formic acid and phosphonic acid.
  • Hershman et al. identify formylphosphonic acid as an intermediate cleavage fragment in only one reaction run and although the yield is unreported it is apparently low.
  • Hershman et al. fail to disclose any means to limit the hydrolysis of the intermediate cleavage fragment.
  • N- (phosphonomethyl)iminodiacetic acid N-oxide is catalytically decarboxymethylated to form N-(phosphonomethyl)glycine, carbon dioxide, and formaldehyde.
  • Fields, et al. disclose such a reaction in U.S. Patent No. 5,043,475.
  • the Fields, et al. decarboxymethylation is highly selective for an acetic acid arm of the N-oxide and cleavage of the phosphonomethyl arm is not reported.
  • one aspect of the present invention is directed to a process for the preparation of formylphosphonic acid, its esters, salts, acetals, hemiacetals, and hydrate (collectively herein referred to as formylphosphonic acid derivatives), especially of formylphosphonic acid, wherein the process comprises decomposing a (phosphonomethyl)amine N-oxide compound in the presence of a decomposition catalyst to produce the formylphosphonic acid derivative and a dephosphonomethylated amine.
  • the present invention is also directed to a process for the preparation of formylphosphonic acid, its esters, salts, acetals, hemiacetals, and hydrate, especially of formylphosphonic acid, wherein the process comprises oxidizing nitrilotris(methylenephosphonic acid) or a salt thereof to form nitrilotris(methylenephosphonic acid) N-oxide or a salt thereof, and decomposing the nitrilotris(methylenephosphonic acid) N-oxide or salt thereof in the presence of a decomposition catalyst.
  • Another aspect of the present invention is directed to a process for preparing N- (phosphonomethyl)glycine, or a salt or an ester thereof, wherein the method comprises decomposing a (phosphonomethyl)amine N-oxide compound in the presence of a decomposition catalyst to produce a formylphosphonic acid derivative and a dephosphonomethylated amine, and reacting the formylphosphonic acid derivative to produce N-(phosphonomethyl)glycine or a salt or an ester thereof.
  • N- (phosphonomethyl)glycine is achieved by condensing the formylphosphonic acid derivative with a glycine compound, and reducing the condensed product to produce N- (phosphonomethyl)glycine.
  • Another embodiment which is of particular interest is one in which the formylphosphonic acid derivative is condensed with l-amino-2-hydroxyethane to produce a condensed alcohol intermediate, the condensed alcohol intermediate is reduced to produce an N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound, and the N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound is oxidized to produce N-
  • Figure 1 is a general scheme for the decomposition of a (phosphonomethyl)amine oxide to form a formylphosphonic acid derivative and a dephosphonomethylated amine; the condensation of the formylphosphonic acid derivative with a glycine compound, or a salt, ester, or zwitterion thereof, to form a condensed carboxylate intermediate; and the reduction of the condensed carboxylate intermediate to produce N- (phosphonomethyl)glycine or a salt or an ester thereof.
  • Figure 2 is a general synthetic scheme for the decomposition of a (phosphonomethyl)amine oxide to form a formylphosphonic acid derivative and a dephosphonomethylated amine; the condensation of the formylphosphonic acid derivative with l-amino-2-hydroxyethane to form a condensed alcohol intermediate; the reduction of the condensed alcohol intermediate to produce N-(2-hydroxyethyl)-N- (phosphonomethyl)amine; and the oxidation of N-(2-hydroxyethyl)-N- (phosphonomethyl)amine to form N-(phosphonomethyl)glycine or a salt or an ester thereof.
  • Figure 3 is a general scheme for the decomposition of a (phosphonomethyl)amine oxide to form a formylphosphonic acid derivative and a dephosphonomethylated amine; the condensation of the formylphosphonic acid derivative with a source of ammonia to form an ammonia-formylphosphonic condensate compound; the reduction of the ammonia-formylphosphonic condensate compound to produce an aminomethylphosphonic acid compound; and the reaction of the aminomethylphosphonic acid compound to produce N-(phosphonomethyl)glycine or a salt or an ester thereof.
  • Figure 4 is a graph of selectivity for formylphosphonic acid in the decomposition reaction of nitrilotris(methylenephosphonic acid) N-oxide.
  • Hydrocarbon means a group composed of carbon and hydrogen. This definition includes alkyl, alkenyl, and alkynyl groups which are each straight chain, branched chain, or cyclic hydrocarbons from one to about twenty carbons. Also included in this definition are aryl groups composed of carbon and hydrogen.
  • Hydrocarbyl therefore includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, phenyl, naphthyl, anthracenyl, benzyl, and isomers thereof.
  • Substituted hydrocarbyl means a hydrocarbyl group in which one or more hydrogen has been substituted with a heteroatom-containing group.
  • substituent groups include, for example, halo, oxo, heterocycle, alkoxy, hydroxy, aryloxy, -NO 2 , amino, alkylamino, or amido.
  • the substituted hydrocarbyl can be, for example, an acyl group.
  • Heteroatom means an atom of any element other than carbon or hydrogen which is capable of forming chemical bonds.
  • Heterocycle means a saturated or unsaturated mono- or multi-ring carbocycle wherein at least one carbon atom is replaced by N, S, P, or O. This includes, for example, the following structures:
  • Z, Z', Z", or Z"' is C, S, P, O, or N, with the proviso that one of Z, Z', Z", or
  • Z'" is other than carbon, but is not O or S when attached to another Z atom by a double bond or when attached to another O or S atom.
  • the optional substituents are understood to be attached to Z, Z', Z", or Z'" only when each is C.
  • the point of attachment to the molecule of interest can be at the heteroatom or elsewhere within the ring.
  • Halogen or "halo” means a fluoro, chloro, bromo, or iodo group.
  • NMR nuclear magnetic resonance spectroscopy.
  • Dephosphonomethylated amine means a primary or secondary amine which has been produced by removing at least one phosphonomethyl group from a secondary or tertiary (phosphonomethyl)amine compound.
  • a formylphosphonic acid derivative can surprisingly be obtained in high yield by decomposing a (phosphonomethyl)amine N-oxide compound in the presence of a decomposition catalyst to produce the formylphosphonic acid derivative and a dephosphonomethylated amine.
  • the formylphosphonic acid derivative has the structure of formula (I)
  • the (phosphonomethyl)amine N-oxide has the structure of formula (II)
  • the dephosphonomethylated amine has the structure of formula (III), shown in eq. 1.
  • R 1 and R 2 can independently be H, hydrocarbyl, substituted hydrocarbyl, heterocycle, or a salt-forming cation. Taken together with the oxygen and phosphorus atoms to which they are attached, R 1 and R 2 can optionally form a cyclic structure.
  • examples of salt-forming cations include Na + , K + , Li + , Ca 2+ , NH 4 + , trialkylsulfonium cations, alkylammonium cations, dialkylammonium cations, trialkylammonium cations, and quaternary ammonium cations.
  • R 3 can be -CHO or -CH(OR 8 )(OR 9 ).
  • R 4 and R 5 are independently selected from the group consisting of H, -CH 2 PO(OR 6 )(OR 7 ), hydrocarbyl, substituted hydrocarbyl, and heterocycle. Taken together with the nitrogen atom to which they are attached, R 4 and R 5 can optionally form a cyclic structure.
  • R 6 and R 7 can independently be H, hydrocarbyl, substituted hydrocarbyl, heterocycle, or a salt-fo ⁇ riing cation. Taken together with the oxygen and phosphorus atoms to which they are attached, R 6 and R 7 can optionally form a cyclic structure.
  • R 8 and R 9 can independently be H, hydrocarbyl, substituted hydrocarbyl, or heterocycle. Taken together with the oxygen and carbon atoms to which they are attached, R 8 and R 9 can optionally form a cyclic structure.
  • the process of the present invention may be run in the presence of a solvent, preferably water or an organic solvent.
  • Preferred organic solvents include alcohols.
  • Alcohols useful as solvents include aliphatic alcohols, aromatic alcohols, glycols, polyols, and unsaturated alcohols.
  • the formylphosphonic acid derivative product can comprise the hydrate or a mixture of the hydrate and the aldehyde.
  • the formylphosphonic acid derivative product can comprise an acetal or a mixture of an acetal and the aldehyde.
  • the formylphosphonic acid derivative product can comprise an acetal, a hemiacetal, the hydrate, the aldehyde, or mixtures thereof.
  • the hydrate is represented by formula (I) wherein R 3 is -CH(OR 8 )(OR 9 ), and R 8 and R 9 are both H.
  • the aldehyde is represented by formula (I) wherein R 3 is -CHO.
  • An acetal is represented by formula (I) wherein R 3 is -CH(OR 8 )(OR 9 ), and R 8 and R 9 are independently hydrocarbyl, substituted hydrocarbyl, or heteroaryl.
  • R 8 and R 9 taken together with the oxygen and carbon atoms to which they are attached can optionally form a cyclic structure.
  • a hemiacetal is represented by formula (I) wherein R 3 is -CH(OR 8 )(OR 9 ), one of R 8 and R 9 is H, and the other of R 8 and R 9 is hydrocarbyl, substituted hydrocarbyl, or heteroaryl.
  • the decomposition catalyst used in the present invention can vary widely in its physical and chemical nature.
  • the decomposition catalyst comprises a metal.
  • the metal is iron, zinc, aluminum, vanadium, molybdenum, or copper.
  • the metal is useful as a decomposition catalyst in a variety of valence states.
  • the metal can be present in a zero valence state or in a charged valence state.
  • the metal can be in a metallic form.
  • the metal is in a salt or an oxide form.
  • the decomposition catalyst comprises a vanadium salt, an iron salt, or a copper salt.
  • Suitable decomposition catalysts that can be used in the present process include vanadium pentoxide, vanadyl sulfate, vanadium chloride, ferrous sulfate, ferrous chloride, ferrous bromide, and the like. Still more preferably, the decomposition catalyst comprises a vanadium salt. In an especially preferred embodiment, the decomposition catalyst comprises vanadyl sulfate (NOSO 4 ).
  • the decomposition catalyst can be homogeneous or heterogeneous. When the decomposition catalyst is heterogeneous, it can be present, for example, in a metallic form such as copper metal, iron filings, zinc filings, or aluminum metal.
  • the decomposition catalyst When the decomposition catalyst is homogeneous, it is preferably in the form of a water-soluble compound or a compound which is soluble in the reaction mixture. Surprisingly, a wide range of reaction conditions can be used when practicing the instant invention. Typically the temperature at which the inventive process is run can vary over the range of about 0°C to about 150°C, preferably about 20°C to about 110°C, more preferably about 20°C to about 75°C.
  • reaction times can be used in the process of the present invention.
  • the decomposition reaction is very rapid, having achieved a high rate of conversion of starting material in a short period of time, e.g. minutes.
  • the general stability of the formylphosphonic acid derivative in the product mixture allows longer reaction times to be used, if desired.
  • the initial concentration of the (phosphonomethyl)amine ⁇ -oxide compound can vary widely in the process of the present invention.
  • the process can be run at any convenient initial concentration of the (phosphonomethyl)amine ⁇ -oxide compound.
  • the initial concentration of the (phosphonomethyl)amine ⁇ -oxide compound is less than about 65 wt %, more preferably less than about 50 wt %, still more preferably less than about 35 wt %, and more preferably still less than about 10 wt %.
  • the process of the present invention can be carried out under a wide variety of acidic, basic, or neutral conditions. Preferably at least part of the course of the decomposition reaction is carried out at neutral or acidic conditions, more preferably at about pH 3 or less.
  • the entire course of the decomposition reaction is carried out at about pH 3 or less.
  • at least one of R 4 and R 5 of eq. 1 is -CH 2 PO(OR 6 )(OR 7 ).
  • R 4 and R 5 are independently hydrocarbyl or -CH 2 PO(OR 6 )(OR 7 ).
  • both R 4 and R 5 are -CH 2 PO(OR 6 )(OR 7 ).
  • R 6 and R 7 are independently H or a salt- forming cation. This especially preferred embodiment is illustrated in eq. 2, wherein R 1 , R 2 , and R 3 are as defined for eq. 1.
  • R 4 and R 5 of eq. 1 are both hydrocarbyl.
  • one of R 4 and R 5 of eq. 1 can be hydrocarbyl while the other of R 4 and R 5 is -CH 2 PO(OR 6 )(OR 7 ).
  • one of R 4 and R 5 of eq. 1 is
  • the products of the decomposition reaction comprise a formylphosphonic acid derivative and N-(2-hydroxyethyl)-N-(phosphonomethyl)amine, or salts or zwitterions thereof.
  • the formylphosphonic acid derivative can be used for a variety of purposes as described herein, including the production of N-(phosphonomethyl)glycine.
  • the N-(2- hydroxyethyl)-N-(phosphonomethyl)amine or its salts or zwitterions can be used to directly produce N-(phosphonomethyl)glycine via oxidation as described hereinbelow.
  • An advantage of this process is to recycle the dephosphonomethylated amine, thereby avoiding environmental and economic waste. Eq. 3 shows this dephosphonomethylated amine recycle process.
  • Phosphonomethylation reaction conditions useful in the present invention are well known to those of skill in the art and examples can be found in, e.g., Glyphosate: A Unique Global Herbicide, ACS Monograph 189, J.E. Franz, et al., American Chemical Society, Washington D.C., 1997, pp. 236-245, herein incorporated by reference.
  • the phosphonomethylation reaction conditions can comprise reacting the dephosphonomethylated amine in the presence of phosphorus trichloride, water, and a source of formaldehyde to produce the (phosphonomethyl)amine compound.
  • the phosphonomethylation reaction conditions can comprise reacting the dephosphonomethylated amine in the presence of phosphorous acid, a strong acid, and a source of formaldehyde to produce the (phosphonomethyl)amine compound.
  • the process of the present invention can be operated in a continuous mode wherein the (phosphonomethyl)amine N-oxide compound is continuously or intermittently introduced to a continuous reaction zone and from which a reaction product mixture comprising the formylphosphonic acid derivative is continuously or intermittently withdrawn.
  • a continuous reaction zone useful in the inventive process is a tube reactor packed with a heterogeneous decomposition catalyst.
  • Other examples of continuous reaction zones useful for the inventive process include a continuous stirred tank reactor or a cascade of stirred tanks.
  • the (phosphonomethyl)amine N-oxide useful in the present invention can be prepared by many different methods. For example, Fields, et al. (U.S. Patent No.
  • N- (phosphonomethyl)iminodiacetic acid N-oxide disclose methods for the preparation of N- (phosphonomethyl)iminodiacetic acid N-oxide by treatment of N- (phosphonomethyl)iminodiacetic acid with a peroxide in the presence of an oxidation catalyst.
  • (Phosphonomethyl)amine N-oxides useful in the present invention can be prepared by similar methods. For example, a (phosphonomethyl)amine (formula (VI)) can be treated with an oxidizing agent in the presence of an oxidation catalyst to form the (phosphonomethyl)amine N-oxide.
  • Oxidizing agents useful in the present invention include without limitation peroxides such as hydrogen peroxide, performic acid, peracetic acid, perbenzoic acid, peroxytrifluoroacetic acid, benzoyl peroxide, benzenepersulfonic acid, and combinations thereof. Hydrogen peroxide is a particularly preferred oxidizing agent.
  • Oxidation catalysts useful in the present process include metals and metal complexes. Especially useful oxidation catalysts include transition metals and transition metal complexes. Examples of useful transition metal oxidation catalysts include molybdenum, tungsten, cobalt, silver, iron, nickel, chromium, ruthenium, vanadium, cerium, manganese, and complexes and salts thereof.
  • Suitable salts include manganese acetate, manganese sulfate, manganese (II or III) acetylacetonate, cobalt sulfate, cobalt (II or III) acetylacetonate, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt acetate, eerie ammonium sulfate, eerie ammonium nitrate, ferric ammonium sulfate, nickel bromide, chromium chloride, ruthenium chloride, ruthenium bromide, aluminum nitrate, vanadyl sulfate, vanadium bromide, vanadium chloride, tungstic acid, 1,2-tungstophosphate, barium tungstate, sodium tungstate, potassium tungstate, and the like.
  • a particularly preferred oxidation catalyst is sodium tungstate (Na 2 WO 4 ). Additional oxidation catalysts useful for the preparation of (phosphonomethyl)amine N-oxide compounds are disclosed in Fields, et al., U.S. Patent No. 4,937,376, herein incorporated by reference. The oxidation of a (phosphonomethyl)amine compound with a peroxide to form a
  • (phosphonomethyl)amine N-oxide compound can be aided by adding a catalytic amount of a metabisulfite compound in the presence of a molybdenum oxidation catalyst.
  • Glowka, et al. disclose in U.S. Patent No. 5,047,579 (herein incorporated by reference) a process wherein the yield of N-(phosphonomethyl)iminodiacetic acid N-oxide from the oxidation of N-(phosphonomethyl)iminodiacetic acid in the presence of a water-soluble molybdenum oxidation catalyst is increased by the presence of a metabisulfite compound.
  • Metabisulfite compounds useful in the present invention include, for example, sodium metabisulfite.
  • a (phosphonomethyl)amine compound for example nitrilotris(methylenephosphonic acid)
  • a (phosphonomethyl)amine N-oxide compound for example nitrilotris(methylenephosphonic acid) N-oxide.
  • the (phosphonomethyl)amine N-oxide compound can be catalytically decomposed according to conditions disclosed herein to form a formylphosphonic acid derivative and a dephosphonomethylated amine. This novel sequence is generically shown in eq. 4.
  • the process of the present invention for the production of formylphosphonic acid derivatives from (phosphonomethyl)amine compounds can be carried out in sequential steps, for example, in a series of vessels.
  • the process of the present invention can be carried out in a single step, for example in a single vessel.
  • formylphosphonic acid can be produced in a single step by adding an oxidizing agent to a (phosphonomethyl)amine compound in the presence of one or more catalysts effective for the oxidation of the (phosphonomethyl)amine compound (VI) and for the decomposition of the (phosphonomethyl)a ine N-oxide compound (II) to the formylphosphonic acid derivative (I).
  • Oxidation catalysts useful as decomposition catalysts include vanadium metal, vanadium salts, and vanadium oxides, such as vanadyl sulfate.
  • a mixture of oxidation catalysts and decomposition catalysts can successfully be used in the current embodiment.
  • oxidation catalysts and decomposition catalysts can be added to the single reaction mixture in a sequential fashion.
  • the intermediate (phosphonomethyl)amine N-oxide compound can be isolated or stored in either isolated or unisolated form for a period of time prior to a decomposition step to form the formylphosphonic acid derivative.
  • oxidizing agents such as the peroxides discussed in this disclosure are useful for either the single- step or for the sequentially-stepped production of formylphosphonic acid derivatives from (phosphonomethyl)amine N-oxide compounds.
  • the (phosphonomethyl)amine compounds useful in the present invention include those represented by formula (VI) in eq. 4.
  • the oxidation catalyst for the conversion of the (phosphonomethyl)amine compound to the (phosphonomethyl)amine N- oxide compound comprises or serves as the source of the decomposition catalyst.
  • the reaction of the formylphosphonic acid derivative to produce N-(phosphonomethyl)glycine and its salts and esters can be achieved by a number of different methods.
  • the reaction can be achieved by contacting the formylphosphonic acid derivative with a glycine compound (formula XI) to form a condensed carboxylate intermediate, and reducing the condensed carboxylate intermediate to produce N-(phosphonomethyl)glycine, or a salt or an ester thereof (formula (VIII)).
  • a formylphosphonic acid derivative is condensed with a glycine compound and reduced to produce N-(phosphonomethyl)glycine are disclosed in U.S. Patent No. 4,568,432, herein incorporated by reference.
  • An example of a way in which the reduction of the condensation product of the formylphosphonic acid derivative with the glycine compound can be achieved is by hydrogenation.
  • the condensation product can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst such as a noble metal.
  • a hydrogenation catalyst such as a noble metal.
  • noble metals useful as hydrogenation catalysts include platinum, palladium, nickel, and copper.
  • the catalyst can have a very high surface area, such as Raney nickel.
  • the hydrogenation catalyst can further comprise a solid support such as carbon.
  • the hydrogenation catalyst can comprise a noble metal on carbon.
  • a hydrogenation catalyst useful in the present invention is palladium on carbon.
  • the reaction of formylphosphonic acid to produce N-(phosphonomethyl)glycine or its salts or its esters can also be achieved by condensing the formylphosphonic acid derivative with l-amino-2-hydroxy ethane to form a condensed alcohol intermediate; reducing the condensed alcohol intermediate to produce an N-(2-hydroxyethyl)-N- (phosphonomethyl)amine compound, or a salt or an ester thereof (formula (IX)); and oxidizing the N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound to produce N-(phosphonomethyl)glycine, or a salt or an ester thereof (formula (VIII)).
  • the condensation of a formylphosphonic acid derivative with l-amino-2-hydroxyethane to produce a condensed alcohol intermediate can be performed in a procedure similar to that disclosed in U.S. Patent No. 4,568,432, herein incorporated by reference, for the condensation of glycine with formylphosphonic acid.
  • the reduction of the condensed alcohol intermediate, thereby producing N-(2-hydroxyethyl)-N-(phosphonomethyl)amine can be performed in a manner similar to that disclosed in U.S. Patent No. 4,568,432 for the reduction of the condensation product of glycine with formylphosphonic acid.
  • the condensation product can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst such as a noble metal.
  • a hydrogenation catalyst such as a noble metal.
  • noble metals useful as hydrogenation catalysts include platinum, palladium, nickel, and copper.
  • the catalyst can have a very high surface area, such as Raney nickel.
  • the hydrogenation catalyst can be a supported catalyst such as noble metal on carbon.
  • a useful supported catalyst is palladium on carbon.
  • the oxidation of the N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound to produce N-(phosphonomethyl)glycine, or a salt or an ester thereof can be achieved by a number of different methods.
  • the oxidation of the N-(2-hydroxyethyl)-N- (phosphonomethyl)amine compound can be achieved by dehydrogenated.
  • a useful method for the oxidation via dehydrogenation of N-(2-hydroxyethyl)-N- (phosphonomethyl)amine to produce N-(phosphonomethyl)glycine is disclosed by Ebner, et al., in U.S. Patent No. 5,627,125, herein incorporated by reference.
  • a decomposition catalyst to produce a formylphosphonic acid derivative (formula (III
  • Sources of ammonia which are useful in the present invention include ammonia gas, aqueous ammonium hydroxide, urea, and ammonium salts such as ammonium chloride.
  • Franz, et al. (1997), pp. 254-257, herein incorporated by reference, provide several examples by which aminomethylphosphonic acid compounds are reacted to produce N- (phosphonomethyl)glycine.
  • aminomethylphosphonic acid compounds are reacted to produce N- (phosphonomethyl)glycine.
  • numerous other methods for the reaction of aminomethylphosphonic acid compounds to produce N-(phosphonomethyl)glycine can be employed and are contemplated within the scope of the present invention. This overall process is presented generically in Figure 3 wherein R 1 and R 2 each has the meaning defined previously in this disclosure.
  • the catalyst can have a very high surface area, such as Raney nickel.
  • the hydrogenation catalyst can be a supported catalyst such as noble metal on carbon.
  • a useful supported catalyst is palladium on carbon.
  • Hershman, et al. U.S. Patent No. 4,072,706
  • Hershman, et al. disclosed that under their reaction conditions formylphosphonic acid degrades to formic acid and phosphorous acid. Because of the degradation of formylphosphonic acid, the processes of the prior disclosures show poor selectivities for formylphosphonic acid. Without limitation, it is believed that the increased selectivity of the present inventive reaction conditions for formylphosphonic acid is due in part to the very short reaction times, e.g. minutes, and mild conditions which the present invention allows. Although at high temperatures and long reaction times the present inventive reaction conditions can lead to some hydrolysis of formylphosphonic acid, the overall mild conditions generally allow minimal hydrolysis. Whatever the precise mechanism, the present invention shows high selectivity for formylphosphonic acid as demonstrated by the examples accompanying this disclosure. c. Detailed Preparative Methods
  • Example 1 A 31.4 wt% solution of hydrogen peroxide (1.94 g, 17.9 mmol) was added to nitrilotris(methylenephosphonic acid) (5.00 g, 16.7 mmol) in a 100 mL round bottom flask. A freshly prepared 1.7 wt% solution of Na 2 WO 4 (0.25 g, 0.013 mmol) was then added and the mixture was magnetically stirred under a nitrogen atmosphere while heating at 85°C for 2 hours.
  • NMAO nitrilotris(methylenephosphonic acid) N-oxide
  • Aqueous hydrogen peroxide (30 wt%, 1.99 g, 17.6 mmol) was added over about 30 seconds to a solution of nitrilotris(methylenephosphonic acid) (5.00 g, 16.7 mmol), aqueous vanadyl sulfate (0.27 M, 2.60 microliters, 0.07 mmol), and deionized water (19 mL) at 20-25°C.
  • nitrilotris(methylenephosphonic acid) 5.00 g, 16.7 mmol
  • aqueous vanadyl sulfate (0.27 M, 2.60 microliters, 0.07 mmol
  • deionized water (19 mL) at 20-25°C.
  • Example 4 Aqueous hydrogen peroxide (31 wt%, 2.30 g, 21.2 mmol) was added in one portion to a mixture of N-isopropyl iminobis(methylenephosphonic acid) (5.00 g, 20.2 mmol) and sodium tungstate dihydrate (0.02 g, 0.06 mmol) in water (14 g) at 25°C under nitrogen. The peroxide mixture was then heated at 95°C for 4 hr which, by 31 P NMR, effected 83% conversion of the tertiary amine to the corresponding N-oxide. Aqueous vanadyl sulfate (0.27 M, 300 microliters, 0.08 mmol) was then added to the N-oxide solution at 50°C. Analysis of the resulting mixture after 30 minutes by 31 P NMR revealed about a 46% yield of FPA based on the initial charge of N-isopropyl iminobis(methylenephosphonic acid).
  • Example 5 To a 59% aqueous formylphosphonic acid solution (5.0 g, 0.23 mol) in deionized water (25 mL) was added glycine (1.56 g, 0.021 mol). The pH of the resultant mixture was adjusted to 7.0 by addition of 2.5 N sodium hydroxide. The reaction mixture was then transferred to a 300 mL autoclave, a 10% palladium on carbon catalyst (1.0 g) added, and the reactor was sealed and pressurized with hydrogen to 6.89 x 10 6 N/m 2 gauge. After 60 minutes of reaction at room temperature, 3.2 g of N-(phosphonomethyl)glycine was obtained representing a 91 % yield based on glycine .
  • Example 6 A stock solution of nitrilotris(methylenephosphonic acid) N-oxide (NMAO) was prepared by heating a mixture of purified nitrilotris(methylenephosphonic acid) (NMA, 15.00 g, 50.16 mmol), deionized water (15 g), aqueous hydrogen peroxide (31.4 wt%, 5.72 g, 52.8 mmol), and aqueous sodium tungstate (1.7 wt%, 0.74 g, 0.043 mmol) to 85°C for 2.5 hours under a nitrogen atmosphere.
  • NMA purified nitrilotris(methylenephosphonic acid)
  • deionized water 15 g
  • aqueous hydrogen peroxide 31.4 wt%, 5.72 g, 52.8 mmol
  • aqueous sodium tungstate 1.7 wt%, 0.74 g, 0.043 mmol
  • NMAOjj NMAO concentrations 240 .
  • NMAO/VO 2+ mole ratio NMAO/VO 2+ mole ratio in each vial of 240.
  • the sealed vials were then immersed in a water bath at 65°C for 30 min. Analysis of each sample was performed by 31 P NMR and selectivities were determined from signal integrations by averaging the results of two methods:
  • [FPA] integrated 31 P NMR area for formylphosphonic acid
  • [H 3 PO 3 ] integrated 31 P NMR area for phosphorous acid
  • [H 3 PO 4 ] integrated 31 P NMR area for phosphoric acid
  • [IB] integrated 31 P NMR area for iminobis(methylenephosphonic acid)
  • [NFI] integrated 31 P NMR area for N-formyliminobis(methylene-phosphonic acid).

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Abstract

L'invention concerne des dérivés d'acide formylphosphonique préparés par décomposition catalytique d'un composé de N-oxydes (phosphonométhyle) amine afin de former un dérivé d'acide formylphosphonique et une amine déphosphométhylée.
PCT/US1999/017965 1998-08-12 1999-08-09 Preparation d'acide formylphosphonique a partir de n-oxydes de (phosphonomethyle) amine WO2000009519A1 (fr)

Priority Applications (1)

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AU53441/99A AU5344199A (en) 1998-08-12 1999-08-09 Preparation of formylphosphonic acid from (phosphonomethyl)amine n-oxides

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6441223B1 (en) 2000-11-30 2002-08-27 Monsanto Technology Llc Method of making phosphorus-containing compounds and products thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3907652A (en) * 1974-10-30 1975-09-23 Monsanto Co Electrooxidation of phosphonomethyl amines
US4072706A (en) * 1976-01-02 1978-02-07 Monsanto Company Oxidation of phosphonomethylamines
US5043475A (en) * 1990-06-25 1991-08-27 Monsanto Company Peroxide process for producing N-phosphonomethylglycine
WO1998050391A1 (fr) * 1997-05-05 1998-11-12 Monsanto Company Procede de preparation de l'acide formylphosphonique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907652A (en) * 1974-10-30 1975-09-23 Monsanto Co Electrooxidation of phosphonomethyl amines
US4072706A (en) * 1976-01-02 1978-02-07 Monsanto Company Oxidation of phosphonomethylamines
US5043475A (en) * 1990-06-25 1991-08-27 Monsanto Company Peroxide process for producing N-phosphonomethylglycine
WO1998050391A1 (fr) * 1997-05-05 1998-11-12 Monsanto Company Procede de preparation de l'acide formylphosphonique

Non-Patent Citations (2)

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Title
WAGENKNECHT J H: "Electrochemical oxidation of N-substituted iminodimethylenediphosphonic acids", J. ELECTROCHEM. SOC. (JESOAN);76; VOL.123 (5); PP.620-4, Monsanto Co.;Corp. Res. Dep.; St. Louis; Mo., XP002073454 *
WAGENKNECHT J: "Electrochemical method for the preparation of iminodimethylenediphosphonic acid", SYNTH. REACT. INORG. MET.-ORG. CHEM. (SRIMCN);74; VOL.4 (6); PP.567-72, Monsanto Co.;Corp. Res. Dep.; St. Louis; Mo., XP002073455 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6441223B1 (en) 2000-11-30 2002-08-27 Monsanto Technology Llc Method of making phosphorus-containing compounds and products thereof
WO2002070529A2 (fr) * 2000-11-30 2002-09-12 Monsanto Technology Llc Procede de fabrication de composes contenant du phosphore et produits correspondants
WO2002070529A3 (fr) * 2000-11-30 2003-01-09 Monsanto Technology Llc Procede de fabrication de composes contenant du phosphore et produits correspondants
US6864218B2 (en) 2000-11-30 2005-03-08 Monsanto Technology Llc Method of making phosphorus-containing compounds and products thereof

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