Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
  • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
  • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
• • 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
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07F9/6533—Six-membered rings
• • 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)]
• • 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
• • 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
  • C07F9/3839—Polyphosphonic acids
  • C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
• • 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)
• • 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
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
  • C07F9/572—Five-membered rings
• • C07F9/5726—
• • 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
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
  • C07F9/572—Five-membered rings
  • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
• • 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
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6524—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having four or more nitrogen atoms as the only ring hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups

Definitions

• the present invention is related to a method for the synthesis of alpha-aminoalkylenephosphonic acid or its phosphonate esters.
• Alpha-amino-phosphonic acid compounds are well known in the art and have found widespread commercial acceptance for a variety of applications including water-treatment, scale-inhibition, detergent additives, sequestrants, marine-oil drilling adjuvants, ion exchange when grafted on resins and as pharmaceutical components. It is well known that such applications preferably require amino alkylenephosphonic acids wherein a majority of the nitrogen substituents are alkylenephosphonic acid groups.
• alpha-aminoalkylenephosphonic acid there are several ways for producing alpha-aminoalkylenephosphonic acid such as those which are for example disclosed in GB 1142294, GB 1230121, U.S. Pat. No. 3,288,846, JP 57075990, U.S. Pat. No. 3,832,393, EP 1681294, EP 1681295 and EP 0638577 patents and in WO 96/40698, JP2007022956 and WO 2009/130322 patent applications among others.
• U.S. Pat. No. 3,796,749 patent discloses a process for producing substantially pure aminomethylenephosphonic acids in a high yield, comprising reacting N-substituted alpha-amino mono- or polycarboxylic acids or their alkali metal salts with phosphorous acid in the presence of water-binding agents at a temperature between about 90° C. and about 160° C.
• Suitable water-binding agents are acid anhydrides which, by combination with water, are converted into the corresponding acids.
• Such agents are, for instance, lower alkanoic acid anhydrides such as acetic acid anhydride, propionic acid anhydride, or inorganic acid anhydrides such as phosphorus pentoxide and the like.
• U.S. Pat. No. 3,816,517 patent discloses a method for the preparation of substantially pure aminomethylenephosphonic acids in a high yield by reacting N-substituted alpha-amino mono- or polycarboxylic acids or their alkali metal salts with phosphorous acid and/or phosphorus trihalogenide, preferably phosphorus trichloride in the presence or absence of an inert diluents. If no phosphorous acid and only phosphorus trichloride is used, a certain amount of water is added to the phosphorus trichloride to form phosphorous acid so that a mixture of phosphorus trichloride and phosphorous acid is present in the reaction mixture. The reaction can also be carried out with phosphorous acid alone. In general, phosphorous acid and/or phosphorus trihalogenide are added to the alpha-aminomethylenecarboxylic acid.
• IN 192483 patent discloses a process for the preparation of ethylene diamine tetra-(methylene phosphonic acid) by reacting ethylenediamino tetra-(acetic acid) with phosphorus trichloride and phosphorous acid.
• EP 2112156 patent application discloses a method for the manufacture of aminoalkylene phosphonic acid, comprising the steps of adding tetraphosphorus hexaoxide to an aqueous reaction medium containing a homogeneous Br ⁇ nsted acid, whereby the tetraphosphorus hexaoxide will substantially qualitatively hydrolyse to phosphorous acid, whereby the free water level in the reaction medium, after the hydrolysis of the tetraphosphorus hexaoxide is completed, is in the range of from 0 to 40% by weight.
• an amine, formaldehyde and additional Br ⁇ nsted acid is added to the reaction medium whereupon the reaction is completed to thus yield the aminoalkylene phosphonic acid
• the amine can be added before or during the tetraphosphorus hexaoxide hydrolysis step.
• the art is thus, as one can expect, crowded and is possessed of methods for the manufacture of such compounds.
• the state-of-the-art manufacture of alpha-aminoalkylenephosphonic acids is premised on converting phosphorous acid resulting from the hydrolysis of phosphorus trichloride or on converting phosphorous acid via the addition of hydrochloric acid which hydrochloric acid can be, in part or in total, added in the form of an amine hydrochloride.
• a carboxyl group of an alpha-aminoalkylenecarboxylic acid can be replaced by a phosphonic acid group through the reaction of the alpha-aminoalkylenecarboxylic acid with tetraphosphorus hexaoxide.
• the carboxyl group reacts with the tetraphosphorus hexaoxide in an entirely different manner.
• the present invention aims to provide a new and efficient synthesis of alpha-aminoalkylenephosphonic acid or its phosphonate esters that does not present the drawbacks of the methods of the prior art. It is another aim of this invention to provide a one step synthesis method capable of selectively delivering superior compound grades at high purity and high yield. Yet another aim of the present invention is to synthesize the phosphonic acid compounds in a shortened and energy efficient manner.
• the present invention discloses a method for the synthesis of an alpha-aminoalkylenephosphonic acid or an ester thereof comprising the steps of:
• R 1 can be a substituted C or substituted S atom
• R 2 can be a H atom, a substituted C or a substituted S atom
• R 3 and R 4 can be independently a H atom or a substituted C atom
• M can be a H atom or an alkaline or alkaline earth metal
• N,N-bis(phosphonomethyl)-4-amino-glutamic acid N,N-bis(phosphonomethyl)-1-amino-ethyl-phosphonic acid, imino (bismethylenephosphonic acid), N-methyl-imino (bismethylenephosphonic acid), N-benzyl-imino (bismethylenephosphonic acid), aminotrismethylenephosphonic acid, ethylene diamino tetra-(methylene phosphonic acid), trans-1,2-cyclohexyldiaminotetramethylenephosphonic acid, 1,4,7,10-tetraazadodecane-1,4,7, 10-tetramethylenephosphonic acid, N-methyl-iminodiphosphonic acid.
• the present invention provides an efficient and economical method for the synthesis of alpha-aminoalkylenephosphonic acid or its phosphonate esters with high selectivity and high yield wherein the phosphonate esters comprise one or more substituted or unsubstituted hydrocarbyl groups which may be branched or unbranched, saturated or unsaturated and may contain one or more rings.
• Suitable hydrocarbyls include alkyl, alkenyl, alkynyl and aryl moieties. They also include alkyl, alkenyl, alkynyl and aryl moieties substituted with other aliphatic or cyclic hydrocarbyl groups, such as alkaryl, alkenaryl and alkynaryl.
• the substituted hydrocarbyl is defined as a hydrocarbyl wherein at least one hydrogen atom has been substituted with an atom other than hydrogen such as an halogen atom, an oxygen atom to form for example an ether or an ester, a nitrogen atom to form an amide or nitrile group or a sulfur atom to form for example a thioether group.
• an atom other than hydrogen such as an halogen atom, an oxygen atom to form for example an ether or an ester, a nitrogen atom to form an amide or nitrile group or a sulfur atom to form for example a thioether group.
• Phosphonate esters in general are prepared by using the P—O—P anhydride moiety comprising compound substituted with the corresponding hydrocarbyl substituents.
• the present method includes an arrangement whereby a P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V), and an alpha-aminoalkylenecarboxylic acid are reacted in the presence of an acid catalyst and optionally a diluent.
• P—O—P anhydride moiety comprising compound is preferably selected from the group consisting of tetraphosphorus hexaoxide and partially hydrolysed species of tetraphosphorus hexaoxide obtained through reaction of 1 mole of tetraphosphorus hexaoxide with 1, 2, 3, 4 and 5 moles of water respectively, it is understood that all compounds comprising at least one P—O—P anhydride moiety wherein one P-atom is at the oxidation state (+III) and the other P-atom is at the oxidation state (+III) or (+V) can be used for the purpose of the invention.
• Suitable P—O—P anhydride moiety comprising compounds can either comprise a P—O—P anhydride moiety in the compound itself (e.g. P 4 O 6 or pyrophosphites (RO) 2 P—O—P(OR) 2 ) or be generated in situ by combining reagents that will form the required P—O—P anhydride moiety upon combination before reacting with the alpha-aminoalkylene carboxylic acid.
• a P—O—P anhydride moiety in the compound itself e.g. P 4 O 6 or pyrophosphites (RO) 2 P—O—P(OR) 2
• RO pyrophosphites
• Suitable reagent combinations are a) compounds containing a least one P—OH moiety (also accessible by tautomerisation of a >P( ⁇ O)H moiety into >P(LP)OH (where LP stands for lone pair of electrons) as possible for dimethylphosphite (MeO) 2 P( ⁇ O)H) and compounds containing at least one P—O—P anhydride moiety e.g. P 2 O 5 or P 4 O 6 and b) partial hydrolysis of a compound containing P—O—P anhydride moieties.
• the P-atom is at the oxidation state (+III) whereas in case b) the P—O—P moieties have one P atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V), in order to form the P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V).
• tetraphosphorus hexaoxide tetraethylpyrophosphite and the combinations of phosphorous acid and tetraphosphorus hexaoxide, of phosphorous acid and tetraphosphorus decaoxide, of dimethylphosphite and tetraphosphorus decaoxide and of tetraphosphorus hexaoxide and water.
• the amount of ‘reactive’ P(+III) atoms that can be converted into phosphonic acids according to this invention is determined by the amount of P(+III) atoms and the amount of P—O—P anhydride moieties. If there are more P—O—P anhydride moieties than P(+III) atoms then all P(+III) atoms are converted into phosphonic acids. If there are less P—O—P anhydride moieties than P(+III) atoms then only a part of P(+III) atoms, equal to the amount of P—O—P anhydride moieties, is converted into phosphonic acids.
• the tetraphosphorus hexaoxide preferably used within the scope of the present invention may be represented by a substantially pure compound containing at least 85%, preferably more than 90%, more preferably at least 95% and in one particular execution at least 97% of P 4 O 6 .
• tetraphosphorus hexaoxide suitable for use within the context of this invention, may be manufactured by any known technology, in preferred executions it is prepared in accordance with the method described in WO 2009/068636 and/or WO 2010/055056 patent applications under the section entitled “Process for the manufacture of P 4 O 6 with improved yield”.
• oxygen, or a mixture of oxygen and inert gas, and gaseous or liquid phosphorus are reacted in essentially stoichiometric amounts in a reaction unit at a temperature in the range from 1600 K to 2000 K, by removing the heat created by the exothermic reaction of phosphorus and oxygen, while maintaining a preferred residence time of from 0.5 seconds to 60 seconds followed by quenching the reaction product at a temperature below 700 K and refining the crude reaction product by distillation.
• the tetraphosphorus hexaoxide so prepared is a pure product containing usually at least 97% of the oxide.
• the so produced P 4 O 6 is generally represented by a liquid material of high purity containing in particular low levels of elementary phosphorus, P 4 , preferably below 1000 ppm, expressed in relation to the P 4 O 6 being 100%.
• the preferred residence time is from 5 seconds to 30 seconds, more preferably from 8 seconds to 30 seconds.
• the reaction product can, in one preferred execution, be quenched to a temperature below 350 K.
• the tetraphosphorus hexaoxide represented by P 4 O 6
• P 4 O 6 is of high purity and contains very low levels of impurities, in particular elemental phosphorus, P 4 , at a level below 1000 ppm, usually below 500 ppm and preferably not more than 200 ppm, expressed in relation to the P 4 O 6 being 100%.
• the alpha-aminoalkylene carboxylic acid comprising compound, used in the present invention can be a molecule, a polymer, a resin or an organic molecule or polymer grafted on an inorganic material and may be represented by the general formula:
• R 1 can be a substituted C or substituted S atom
• R 2 can be a H atom, a substituted C or a substituted S atom
• R 3 and R 4 can be independently a H atom or a substituted C atom
• M can be a H atom or an alkaline or alkaline earth metal.
• the compound containing an alpha-aminocarboxylic acid fragment can be selected from:
• individual species of alpha-aminoalkylenecarboxylic acids of interest may include, N,N-dimethylglycine, N-phthaloglycine, N-phenyl glycine, N-tosyl glycine, N-cyanomethyl glycine, N,N-biscyanomethyl glycine, 4-morpholineacetic acid, pyroglutamic acid, N-acetylglycine, N,N-bis(carboxymethyl)-6-aminohexanoic acid, N,N-bis(carboxymethyl)-1-glutamic acid, N-cyanomethyl alanine, trisodium N,N-bis(carboxymethyl)-alanine, iminodiacetic acid, N-methyl-iminodiacetic acid, N-benzyl iminodiacetic acid nitrilotriacetic acid, ethylene diamino tetraacetic acid, diethylenetriaminepentaacetic acid, N
• the acid catalyst used within the scope of the present invention is preferably a homogeneous Br ⁇ nsted acid catalyst, optionally in the presence of a solvent, or a heterogeneous Br ⁇ nsted acid catalyst, in the presence of a solvent, or a Lewis acid catalyst, in the presence of a solvent or a solvent being a Br ⁇ nsted catalyst.
• the homogeneous Br ⁇ nsted acid catalyst preferably is selected from the group consisting of methanesulfonic acid, fluoromethanesulfonic acid, trichloromethanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid, tert-butyl-sulfonic acid, p-toluenesulfonic acid, naphthalene sulfonic acid, 2,4,6-trimethylbenzene-sulfonic acid, perfluoro or perchloro sulfonic acids, perfluoro or perchloro carboxylic acids, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphorous acid, phosphoric acid and mixtures thereof.
• the Br ⁇ nsted acid catalyst acts as catalyst and as solvent.
• the heterogeneous Br ⁇ nsted acid catalyst is preferably selected from the group of:
• the heterogeneous Br ⁇ nsted catalyst for use in the method of the present invention is preferably selected from the group consisting of macroreticular polymeric resins, representing a continuous open pore structure and comprising sulfonic, carboxylic and/or phosphonic acid moieties.
• the heterogeneous Br ⁇ nsted acid catalyst is substantially insoluble or immiscible in the reaction medium.
• the catalyst can form, at the reaction conditions, in particular the reaction temperature, a second liquid phase and can be recovered at the end of the reaction by conventional techniques such as filtration or phase separation.
• Homogeneous Br ⁇ nsted acid catalysts can leave a residue within the final reaction product. Nevertheless, there are known techniques for recovering the acid catalyst from the reaction medium such as ion exchange, nano filtration or electrodialysis which can be used to solve or mitigate the problems. Alternatively the end product can be separated e.g. by precipitation using a co-solvent and the Br ⁇ nsted catalyst recovered and recycled after removal of the co-solvent.
• the Lewis acid for being included in the solvent in general is a homogeneous or heterogeneous Lewis acid.
• Br ⁇ nsted acidic solvents can be replaced by Lewis acids dissolved or suspended in an organic solvent.
• Preferred homogeneous Lewis acids can be selected from metal salts having the general formula:
• M represents a main group element or transition metal like Li, B, Mg, Al, Bi, Fe, Zn, La, Sc, Yb, or Pd
• X in MX n is typically an anion of an acid or acid derivative like Cl, OTf or NTf 2 , where Tf stands for CF 3 SO 2 and n is equal to the oxidation state of M, which can be from 1 to 5. Possible combinations are e.g.
• a hard metal or a metal on the borderline between hard and soft according to the HSAB (hard soft acid base) concept like Li, Mg, Al, Sc, Zn, Bi, and weakly coordinating anions like OTf or NTf 2 are used.
• Preferred heterogeneous Lewis acids can be represented by species of discretionary selected subclasses created by interaction/bonding of homogeneous Lewis acids e.g. metal complexes, metal salts or organometallic species with polymeric organic or inorganic backbones.
• An example of such subclass is a polystyrene matrix with bonded Sc(OTf) 2 groups.
• Such catalyst can be prepared e.g. by interaction of a polystyrene sulfonic acid resin e.g. Amberlyst 15 with Sc(OTf) 3 .
• the number of equivalents of Lewis acid functions can be determined in this case by different ways e.g. by acid base determination of the unreacted sulfonic acid groups, by quantitative determination of the liberated triflic acid and by ICP measurement of the amount of Sc on the resin.
• Suitable organic solvents are anisole; chlorinated and fluorinated hydrocarbons such as chlorobenzene, fluorobenzene, tetrachloroethane, tetrachloroethylene, dichloroethane, dichloromethane; polar solvents like diglyme, glyme, diphenyloxide, polyalkylene glycol derivatives with capped OH groups such as OR*** where R*** is a low alkyl or acyl group; aliphatic hydrocarbons such as hexane, heptane, cyclohexane; non-cyclic ethers like dibutyl ether, diethyl ether, diisopropyl ether, dipentylether, and butylmethylether; cyclic ethers like tetrahydrofuran, dioxane, and tetrahydropyran; mixed cyclic/non-cyclic ethers like cyclopentylmethylether;
• the method of the present invention is started by mixing the alpha-aminoalkylenecarboxylic acid, the optional diluents and the acid catalyst.
• the alpha-aminoalkylenecarboxylic acid or the mixture of the alpha-aminoalkylene carboxylic acid and the optional diluents is cooled down to a temperature below ambient temperature, preferably to a temperature below about 10° C. before the addition of the acid catalyst, preferably the Br ⁇ nsted acid catalyst.
• the method of the invention comprises the step of forming a reaction mixture by gradually mixing the P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V), preferably tetraphosphorus hexaoxide, and the mixture comprising the aminoalkanecarboxylic acid, the acid catalyst, preferably a Br ⁇ nsted acid catalyst, or a solvent being a Br ⁇ nsted catalyst, and optionally the diluent, standing at an adequate temperature (preferably comprised between about 20° C. and about 120° C.) and maintaining this reaction mixture at an adequate temperature (preferably at a temperature comprised between about 20° C. and about 100° C.), during an adequate period, preferably for at least about 10 minutes after the completion of the mixing process.
• the method comprises the step of forming a reaction mixture by gradually adding the P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V), preferably tetraphosphorus hexaoxide, to the mixture comprising the aminoalkanecarboxylic acid, the acid catalyst, preferably a Br ⁇ nsted acid catalyst or a solvent being a Br ⁇ nsted catalyst, and optionally the diluent, standing at an adequate temperature (preferably comprised between about 20° C. and about 120° C.) and maintaining this reaction mixture at an adequate temperature (preferably at a temperature comprised between about 20° C. and about 100° C.), during an adequate period, preferably for at least about 10 minutes after the completion of the mixing process.
• the P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V),
• the method comprises the step of forming a reaction mixture by gradually adding the mixture comprising the aminoalkanecarboxylic acid, the acid catalyst, preferably a Br ⁇ nsted acid catalyst or a solvent being a Br ⁇ nsted catalyst, and optionally the diluent, standing at an adequate temperature (preferably comprised between about 20° C. and about 120° C.) to the P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V), preferably tetraphosphorus hexaoxide, and maintaining this reaction mixture at an adequate temperature (preferably at a temperature comprised between about 20° C. and about 100° C.), during an adequate period, preferably for at least about 10 minutes after the completion of the mixing process.
• an adequate temperature preferably comprised between about 20° C. and about 120° C.
• the ratio of the moles of acid catalyst to the alpha-aminoalkylene carboxylic acid equivalents is comprised between about 0.01 and about 11.0, preferably between about 0.1 and about 9.0, more preferably between about 1.0 and about 7.0 and most preferably between about 2 and about 5.
• the mixture of alpha-aminoalkylene carboxylic acid and acid catalyst, optionally comprising the diluent(s), is thereafter brought to a temperature comprised between about 20° C. and about 120° C. and preferably between about 20° C. and about 80° C.
• the P—O—P anhydride moiety comprising compound is slowly added, under stirring, in such a way that the temperature of the reaction mixture does not exceed a pre-fixed maximal temperature set-point.
• the equivalent ratio of alpha-aminoalkylenecarboxylic acid to P—O—P anhydride moiety is comprised between about 0.2 and about 4.5, preferably between about 0.3 and about 3.0 and more preferably between about 0.5 and about 1.5.
• the ratio of the alpha-aminoalkylene carboxylic acid equivalents to the moles of tetraphosphorus hexaoxide is comprised between about 1.0 and about 12.0, preferably between about 1.5 and about 8.0 and more preferably between about 2.0 and about 6.0.
• the reaction mixture is kept at the temperature of the mixing process or is heated up or cooled down to a temperature comprised between about 20° C. and about 100° C., preferably between about 40° C. and about 90° C. and more preferably between about 50° C. and about 80° C.
• alpha-aminoalkylenecarboxylic acid into alpha-aminoalkylenephosphonic acid (i.e. the replacement of a carboxylic acid group by a phosphonic acid group).
• CO will leave the reaction mixture as a gas of very high purity.
• This CO gas can be used in many applications like e.g. as a fuel, in combination with hydrogen for methanol and Fischer-Tropsch hydrocarbons manufacture, for hydroformylation reactions, for alcohol carbonylation e.g. carbonylation of methanol to acetic acid or the conversion of methylacetate to acetic anhydride.
• alpha-aminoalkylenecarboxylic acid into alpha-aminoalkylenephosphonic acid, its dehydrated forms or their phosphonate esters
• water is optionally added to the reaction mixture in order to convert the dehydrated forms of alpha-aminoalkylenephosphonic acid or their phosphonate esters into alpha-aminoalkylenephosphonic acid or its phosphonate esters and to hydrolyse the unreacted P—O—P anhydride moieties, if present.
• water is added to the reaction mixture after it is cooled down to room temperature.
• the reaction mixture can be cooled down through the addition of the water.
• This hydrolysis is performed at a temperature comprised between room temperature and about 100° C. for a period comprised between about 10 minutes and about 48 hours and preferably between about 1 hour and about 24 hours.
• Unreacted P—O—P anhydride moieties may be the result of an incomplete conversion or of a non-stoichiometric amount of P—O—P anhydride group comprising compounds, forming the reaction mixture.
• the yield of the conversion of alpha-aminoalkylenecarboxylic acid into alpha-aminoalkylenephosphonic acid, according to the method of the present invention, is preferably at least about 50% advantageously at least about 80% even more advantageously at least about 95%.
• the acetonitrile then was distilled off and the residue was dissolved in 50 ml of water.
• the solution comprising the residue and the water was heated to 90° C. and stirred for 7 hours at 90° C.
• the solution thus obtained was cooled down to ambient temperature upon which 12.67 g of precipitate was formed.
• the precipitate was isolated through filtration. Solid and filtrate were analyzed by 1 H-NMR and 31 P-NMR spectroscopy. The solid was composed of 97.3% weight N,N-phosphonomethyliminodiacetic acid.
• Amberlite IRC 748 is a cation exchange resin consisting of a macroporous styrene divinylbenzene matrix with grafted iminodiacetic acid moieties.
• the beads were filtered off and washed twice with 100 ml H 2 O and kept in a desiccator over P 2 O 5 for overnight.
• the beads were analysed by FTIR-spectroscopy. The bands corresponding to COOH functions had completely disappeared while new bands had appeared in the regions typical for the stretching of P ⁇ O groups of phosphonates.
• Column 7 indicates the ratio of mmoles of alpha-aminoalkylenecarboxylic acid to mmoles of tetraphosphorus hexaoxide or of reactive ‘P(+III)’ atoms with into brackets the ratio of carboxylic acid milliequivalents of the ⁇ -aminoalkylenecarboxylic acid to mmoles of tetraphosphorus hexaoxide or of reactive ‘P(+III)’ atoms.
• Column 10 indicates the temperature (° C.) of the mixture comprising the ⁇ -aminoalkylenecarboxylic acid and catalyst to which the tetraphosphorus hexaoxide or the reactive ‘P(+III)’ atoms is added; this temperature is maintained during the whole tetraphosphorus hexaoxide or reactive ‘P(+III)’ atoms addition.
• alpha-aminoalkylenephosphonic acids prepared in the examples of table 1 are:
• Example 47 to 58 and 63 and 65 to 67 aminotrismethylenephosphonic acid.
• Example 60 iminodiphosphonic acid grafted groups on a macroporous styrene divinylbenzene matrix.
• Example 62 1,4,7,10-tetraazadodecane-1,4,7,10-tetramethylenephosphonic acid
• Example 64 N-methyl-iminodiphosphonic acid.
• the reaction mixture was heated for 1 hr at 100° C.; 6% by weight of aminomethylphosphonic acid was formed through hydrolysis of acetamidomethylphosphonic acid.
• (2*) Pyroglutamic acid is converted into 5-phosphono-2-pyrrolidone (yield: 87.8%).
• the 5-phosphono-2-pyrrolidone is further hydrolyzed and a mixture comprising 11.7% by weight of 5-phosphono-2-pyrrolidone and 77.1% by weight of 4-amino-4-phosphonobutyric acid is obtained.
• the solid is composed for 86.1% by weight of phosphonomethyliminodiacetic acid.
• the obtained solution comprises 13.4% by weight of N-phosphonomethyliminodiacetic acid and 65.3% by weight of N-phosphonomethyliminodiacetonitrile.
• 11* After hydrolysis (stirring 7 hrs at 100° C.), the reactor content was cooled to ambient temperature whereupon a precipitate of phosphonomethyliminodiacetic acid is formed. After filtration the filtrate comprises 26.2% weight of phosphonomethyliminodiacetic acid.
• the solid is composed for 97.3% by weight of phosphonomethyliminodiacetic acid.
• the obtained solution comprises 8.5% by weight of aminotrismethylenephosphonic acid and 9.5% by weight of aminotrismethylenephosphonic acid-N-oxide.
• the obtained solution comprises 82.2% weight of aminotrismethylenephosphonic acid and 0.8% weight of aminotrismethylenephosphonic acid-N-oxide.
• Nafion TM SAC-13 fluorosulfonic acid Nafion TM polymer on amorphous silica, 10-20% (porous nanocomposite).
• the obtained solution comprises comprises 34.9% weight of aminotrismethylenephosphonic acid and 2.4% weight of aminotrismethylenephosphonicacid-N-oxide.
• Amberlite IRC 748 is an iminodiacetic acid chelating cation exchange resin based on a macroporous styrene divinylbenzene matrix. After reaction with P 4 O 6 , the reaction mixture was cooled down to room temperature and the solid was filtered and washed.

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