5994-61-6

Basic information

• Product Name: N-(Carboxymethyl)-N-(phosphonomethyl)-glycine
• Synonyms: n-(phosphonomethyl)iminodiaceticacidhydrate;n-(carboxymethyl)-n-(phosphonomethyl)-glycine;N-(PHOSPHONOMETHYL)IMINODIACETIC ACID;N-(PHOSPHONOMETHYL)IMINODIACETIC ACID MONOHYDRATE;PMIDA;N-Phosphonomethyl aminodiacetic acid;PMID;N-(PHOSPHONOMETHYL)IMINODIACETIC ACID, 9 5%
• CAS NO: 5994-61-6
• Molecular Formula: C₅H₁₀NO₇P
• Molecular Weight: 227.11
• EINECS: 227-824-5
• Product Categories: Organic Building Blocks;Phosphonic/Phosphinic Acids;Phosphorus Compounds
• Mol File: 5994-61-6.mol
• Article Data: 26

Chemical Properties

• Melting Point: 215 °C (dec.)(lit.)
• Boiling Point: 585.9 °C at 760 mmHg
• Flash Point: 308.2 °C
• Appearance: /
• Density: 1.792 g/cm³
• Vapor Pressure: 3.01E-15mmHg at 25°C
• Refractive Index: 1.577
• PKA: 0.90±0.10(Predicted)
• BRN: 1795744
• CAS DataBase Reference: N-(Carboxymethyl)-N-(phosphonomethyl)-glycine(CAS DataBase Reference)
• NIST Chemistry Reference: N-(Carboxymethyl)-N-(phosphonomethyl)-glycine(5994-61-6)
• EPA Substance Registry System: N-(Carboxymethyl)-N-(phosphonomethyl)-glycine(5994-61-6)

Safety Data

• Hazard Codes: C
• Statements: 34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3261 8/PG 3
• WGK Germany: 1
• Hazardous Substances Data: 5994-61-6(Hazardous Substances Data)

Usage

Uses

N-(Carboxymethyl)-N-(phosphonomethyl)-glycine is used in surface modification of cobalt oxide nanoparticle to overcome any toxic effect while functioning as cancer antigen carrier.

Definition

ChEBI: A tertiary amino compound that consists of iminodiacetic acid bearing an N-phosphonomethyl substituent.

General Description

N-(Phosphonomethyl)iminodiacetic acid hydrate is the hydrated form of N-(phosphonomethyl)iminodiacetic acid (PMIDA; H4pmida). The solubility of PMIDA in various solvents and solvent mixtures has been studied. It is the starting material for the synthesis of N-(phosphonomethyl)iminodiacetate (pmida4-), a multidentate organic ligand. PMIDA undergoes molecular oxygen oxidation in the presence of metal salts to form N-(phosphonomethyl)glycine, also known as glyphosate. H4pmida forms the structural unit of various three-dimensional inorganic-organic hybrid compounds.

InChI:InChI=1/C5H10NO7P/c7-4(8)1-6(2-5(9)10)3-14(11,12)13/h1-3H2,(H,7,8)(H,9,10)(H2,11,12,13)

Synthetic route

formaldehyd (50-00-0) + iminodiacetonitrile (628-87-5) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
Stage #1: iminodiacetonitrile With sodium hydroxide In water at 45 - 50℃; for 1h; Stage #2: With phosphorus trichloride Stage #3: formaldehyd at 115 - 120℃; for 2h;	93.8%
Stage #1: iminodiacetonitrile With hydrogenchloride; sulfuric acid In water at 80 - 160℃; under 1500.15 - 15001.5 Torr; for 6h; Inert atmosphere; Autoclave; Stage #2: formaldehyd With phosphonic Acid In water for 3h; Pressure; Temperature; Inert atmosphere; Autoclave; Reflux;	90.52%

Ν,Ν-biscyanomethyl glycine (31611-66-2) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
Stage #1: Ν,Ν-biscyanomethyl glycine With methanesulfonic acid; phosphorus pentoxide In acetonitrile at 25 - 40℃; for 21h; Stage #2: With water; sodium hydroxide In acetonitrile at 90℃; for 7h; Reagent/catalyst; Time; pH-value; Temperature;	97.3%
Stage #1: Ν,Ν-biscyanomethyl glycine With phosphorus(III) oxide; methanesulfonic acid In acetonitrile at 20 - 40℃; for 21h; Stage #2: In water at 90℃; for 7h; Temperature; Time; Concentration; Reagent/catalyst;	97.3 %Spectr.

formaldehyd (50-00-0) + monosodium salt of iminodiacetic acid → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride; phosphorous acid In water at 115 - 120℃; for 2h;	94.1%
With hydrogenchloride; phosphonic Acid In water

iminodiacetic acid hydrochloride + iminodiacetonitrile (628-87-5) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
Stage #1: iminodiacetonitrile With sodium hydroxide In water at 100 - 110℃; for 1h; Stage #2: iminodiacetic acid hydrochloride With dihydrogen peroxide; pyrographite at 80 - 100℃; for 0.5h; Stage #3: With formaldehyd; phosphoric acid at 110℃; for 3h; Reagent/catalyst;	98.5%

formaldehyd (50-00-0) + iminodiacetic acid monosodium → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride; phosphonic Acid In water at 80 - 110℃; for 5h; Temperature;	94.2%

formaldehyd (50-00-0) + iminodiacetic acid (142-73-4) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride; phosphorous acid In water at 100 - 120℃; under 7500.75 - 9000.9 Torr;	93.1%
With phosphonic Acid for 3h; Reflux; Green chemistry;	90.3%
Stage #1: iminodiacetic acid With phosphonic Acid In water Reflux; Stage #2: formaldehyd In water at 130 - 136℃; for 1.75h; Product distribution / selectivity;	67.3%

phosphorous acid (10294-56-1) + iminodiacetic acid (142-73-4) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With formaldehyd; sulfuric acid	78.2%
With formaldehyd; sulfuric acid	75.3%
With formaldehyd; sulfuric acid	74.2%
With formaldehyd; sulfuric acid In water	59.8%

Ν,Ν-biscyanomethyl glycine (31611-66-2) → phosphonomethylimino-di-acetic acid (5994-61-6) + N,N-bis(cyanomethyl)aminomethylphosphonic acid (76127-84-9)

Conditions	Yield
Stage #1: Ν,Ν-biscyanomethyl glycine With methanesulfonic acid; phosphorus pentoxide In acetonitrile at 25 - 30℃; for 2h; Stage #2: With water; sodium hydroxide at 25℃; Solvent; Time; Temperature; Reagent/catalyst;	A 15.1% B 37.6%
With phosphorus(III) oxide; trifluorormethanesulfonic acid In acetonitrile at 30℃; for 3h; Reagent/catalyst; Temperature; Concentration; Time;	A 13.4 %Spectr. B 65.3 %Spectr.

N-hydroxymethylimino diacetic acid diethyl ester (1531623-12-7) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
Stage #1: N-hydroxymethylimino diacetic acid diethyl ester With methanesulfonic acid; phosphorus pentoxide; Dimethyl phosphite at 50 - 85℃; Stage #2: With water at 85℃; for 1h; Reagent/catalyst; Time; Temperature;	61%

formaldehyd (50-00-0) + 1,4-di(carboxymethyl)-2,5-diketopiperazine (77752-64-8) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride In water	55%

1,3,5-Trioxan (110-88-3) + Diethyl iminodiacetate (6290-05-7) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
Stage #1: 1,3,5-Trioxan; Diethyl iminodiacetate With acetic acid at 80℃; for 6h; Stage #2: With phosphorus pentoxide at 20 - 80℃; for 8h; Stage #3: With water at 100℃; for 6h;	53%

formaldehyd (50-00-0) + phosphorus trichloride hydrolysate + 1,4-di(carboxymethyl)-2,5-diketopiperazine (77752-64-8) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride	88.2%

methyl phosphonic acid monosodium chlorine + iminodiacetic acid disodium salt → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With chlorine; sodium iodide at 80 - 90℃; for 14h;

formaldehyd (50-00-0) + monosodium salt of iminodiacetic acid + phosphorous acid (10294-56-1) → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride	97%, 91%

formaldehyd (50-00-0) + iminodiacetic acid disodium salt → phosphonomethylimino-di-acetic acid (5994-61-6)

Conditions	Yield
With hydrogenchloride; phosphorus trichloride In water Product distribution / selectivity;
With hydrogenchloride; N-methyl N-phosphonomethylglycine; phosphorus trichloride In water Product distribution / selectivity;
With hydrogenchloride; phosphorus trichloride In water Product distribution / selectivity; N-(phosphonomethyl)iminodiacetic acid seeds;

disodium chloromethylphosphonate + disodium salt of bis-carboxymethyl-amine → phosphonomethylimino-di-acetic acid (5994-61-6)

phosphonomethylimino-di-acetic acid (5994-61-6) → N-(phosphonemethyl)glycine (1071-83-6)

Conditions	Yield
Calgon CENTAUR 80-100 mesh (149-177 μm) at 95℃; Product distribution / selectivity;	98.6%
Norit PK at 95℃; Conversion of starting material;	98.3%
Nuchar RGC at 95℃; Conversion of starting material;	98.9%

strontium nitrate + phosphonomethylimino-di-acetic acid (5994-61-6) → [(strontium)2(N-(phosphonomethyl)iminodiacetic acid(-4H))(H2O)]

Conditions	Yield
With 1,3-di(piperidin-4-yl)propane In ethanol; water at 180℃; for 72h; pH=3.42; Autoclave;	81.63%

phosphonomethylimino-di-acetic acid (5994-61-6) + BaCl2*4H2O → [(strontium)2(N-(phosphonomethyl)iminodiacetic acid(-2H))(HPO4)]

Conditions	Yield
With 1,3-di(piperidin-4-yl)propane In ethanol; water at 180℃; for 72h; pH=2.16; Autoclave;	80.74%

phosphonomethylimino-di-acetic acid (5994-61-6) + barium(II) hydroxide → [(barium)2(N-(phosphonomethyl)iminodiacetic acid(-2H))2(H2O)]

Conditions	Yield
With 1,3-di(piperidin-4-yl)propane In ethanol; water at 150℃; for 48h; pH=2.16; Autoclave;	78.87%

phosphonomethylimino-di-acetic acid (5994-61-6) + benzene-1,3,5-tricarboxylic acid (554-95-0) + water (7732-18-5) + magnesium oxide → [Mg15(PMIDA)6(BTC)2(H2O)12]·6H2O

Conditions	Yield
at 180℃; for 168h; pH=5; Autoclave;	77%

phosphonomethylimino-di-acetic acid (5994-61-6) + benzene-1,3,5-tricarboxylic acid (554-95-0) + cobalt(II) diacetate tetrahydrate (6147-53-1) + magnesium oxide → [Co13Mg2(PMIDA)6(BTC)2(H2O)12]·6H2O

Conditions	Yield
With ammonium hydroxide In water at 180℃; for 120h; pH=5; Autoclave;	77%

ammonium molybdate(VI) tetrahydrate + dimethylsulfite (616-42-2) + phosphonomethylimino-di-acetic acid (5994-61-6) → N-(phosphonemethyl)glycine (1071-83-6)

Conditions	Yield
With dihydrogen peroxide In water	76%

erbium(III) chloride hexahydrate + phosphonomethylimino-di-acetic acid (5994-61-6) + iron(II) oxalate dihydrate (6047-25-2) → [ErFe(III)(Fe(II))6(N-(phosphonomethyl)iminodiacetateH)6]*nH2O

Conditions	Yield
With aq. NaOH In further solvent(s) to mixt. of acid, Fe oxalate, ErCl3*6H2O added eutectic mixt. of cholinechloride and malonic acid and aq. NaOH; suspn. magnetically stirred for 1 h at ambient temp.; gel transferred to react. vessel, placed in prehe ated oven (at 150°C) for 90 h; washed 3 times with EtOH with ultrasonic vibration and with water; air dried at ambient temp.;	76%

manganese(II) chloride tetrahydrate + phosphonomethylimino-di-acetic acid (5994-61-6) → Mn(H2O)(N-(phosphonomethyl)iminodiacetate) (821780-71-6)

Conditions	Yield
With tetramethylammonium hydroxide In water High Pressure; to an aq. soln. of Mn-contg. compd. a ligand and TMAOH soln. were added with stirring; the final mixt. with a molar ratio 1 MnCl2*4H2O: 1 H4PMIDA: 4 TMAOH was crystd. in a bomb at 150°C for 5 d; the compd. was filtered and washed with distd. water; elem. anal.; detd.by powder XRD;	75%

phosphonomethylimino-di-acetic acid (5994-61-6) + benzene-1,3,5-tricarboxylic acid (554-95-0) + water (7732-18-5) + nickel(II) acetate tetrahydrate (6018-89-9) + magnesium carbonate → [Mg8Ni12(OH)12(N-(phosphonomethyl)iminodiacetic acid-H4)4(1,3,5-benzenetricarboxylic acid-H3)4(H2O)16]*9H2O

Conditions	Yield
With ammonia at 190℃; for 120h; pH=7; Temperature; pH-value;	75%

barium(II) nitrate + phosphonomethylimino-di-acetic acid (5994-61-6) + cobalt(II) diacetate tetrahydrate (6147-53-1) → [CoBa(PMIDA)(H2O)2]·H2O

Conditions	Yield
With ammonium hydroxide; benzene-1,3,5-tricarboxylic acid In water at 180℃; for 120h; pH=10; Autoclave;	73%

ammonium molybdate(VI) tetrahydrate + phosphonomethylimino-di-acetic acid (5994-61-6) → N-(phosphonemethyl)glycine (1071-83-6)

Conditions	Yield
With sulphur dichloride; dihydrogen peroxide In water	71%
With dihydrogen peroxide In water	68%

cobalt(II) chloride hexahydrate + phosphonomethylimino-di-acetic acid (5994-61-6) → [H3O]6[Co4(H2O)4(N-(phosphonomethyl)iminodiacetic acid(-4H))2(N-(phosphonomethyl)iminodiacetic acid(-3H))2]*2H2O

Conditions	Yield
With (CH3)4NOH; NH4F In ethanol High Pressure; Co salt and NH4F dissolved in EtOH; N-(phosphonomethyl)iminodiacetic acid added with vigorous stirring; Me4NOH added; molar ratio = 1:4:1:1; stirred; mixt. heated at 170°C in autoclave for 5 d; crystals filtered under vac.; washed with EtOH; dried in air; elem. anal.;	70%

fac-[ReI(OH2)3(CO)3](SO3CF3) (1356855-78-1, 811431-04-6) + phosphonomethylimino-di-acetic acid (5994-61-6) → C8H7NO10PRe(2-)

Conditions	Yield
With sodium hydroxide In water at 20℃; for 4h; pH=Ca. 4;	68%

oxovanadium(IV) sulfate + phosphonomethylimino-di-acetic acid (5994-61-6) + sodium hydrogencarbonate (144-55-8) → 2Na(1+)*0.5V2O2(O3PCH2N(CH2CO2)2)2(4-)*5H2O=(Na4[V2O2(O3PCH2N(CH2CO2)2)2]*10H2O)0.5

Conditions	Yield
In water addn. of NaHCO3 (to pH=2 or 4) to mixt. of V-compd. and ligand, stirringat room temp. for 24 h; EtOH addn., crystn. (4°C, 1 week; two crops), collection (filtration), washing (EtOH), drying (vac.); elem. anal.;	67%

Upstream product

• 50-00-0 formaldehyd 
• 142-73-4 iminodiacetic acid 
• 33454-80-7 N-hydroxymethyl iminodiacetic acid 
• 1531623-12-7 N-hydroxymethylimino diacetic acid diethyl ester 
• 110-88-3 1,3,5-Trioxan 
• 628-87-5 iminodiacetonitrile 
• 6290-05-7 Diethyl iminodiacetate 
• 31611-66-2 Ν,Ν-biscyanomethyl glycine 
• 10294-56-1 phosphorous acid 
• 77752-64-8 1,4-di(carboxymethyl)-2,5-diketopiperazine 

Downstream Products

• 1066-51-9 Aminomethylphosphonic acid 
• 1071-83-6 N-(phosphonemethyl)glycine 
• 64-18-6 formic acid 
• 35404-71-8 N-methylaminomethanephosphonic acid 
• 84767-96-4 N-formyl-N-(phosphonomethyl)glycine 
• 68-12-2 N,N-dimethyl-formamide 
• 24569-83-3 N-methyl N-phosphonomethylglycine 
• 50-00-0 formaldehyd 
• 14265-44-2 Phosphate 

Relevant articles and documents

Production method of n-phosphonomethyl iminodiacetic acid

The invention discloses a production method for pmida, comprising the following steps of (1) mixing phosphorous acid, formaldehyde and hydrochloric acid quantitatively, and heating the mixture to a set temperature; (2) dropwise adding an iminodiacetic acid-sodium salt solution into a mixed solution of phosphorous acid, formaldehyde and hydrochloric acid, and keeping the mixture warm at the set temperature until the reaction is completed, thereby obtaining a pmida suspension, wherein the molar ratio of hydrochloric acid to iminodiacetic acid-sodium salt is less than 1.1; (3) cooling the pmida suspension, crystallizing the pmida suspension, separating solids from liquid, and drying to prepare pmida. According to the production method for pmida, the iminodiacetic acid-sodium salt is dropwise added into the mixed solution of phosphorous acid, formaldehyde and hydrochloric acid, and the charging way ensures that hydrogen chloride in a reaction system is always in an excessive state relative to iminodiacetic acid so as to achieve the purposes of reducing the usage amount of hydrochloric acid and the brine wastewater quantity and improving the yield of pmida.

A method for preparing pmida (by machine translation)

The invention provides a preparation method of N-(phosphonomethyl) iminodiacetic acid. The preparation method comprises the steps of enabling disodium iminodiacetate to react with hydrochloric acid to obtain a solution containing monosodium iminodiacetate and sodium chloride; concentrating the solution containing monosodium iminodiacetate and sodium chloride, heating and filtering to obtain a sodium chloride solid and filtrate; mixing the filtrate with hydrochloric acid and phosphorous acid, heating, then adding formaldehyde and reacting to obtain N-(phosphonomethyl) iminodiacetic acid. As monosodium iminodiacetate has relatively large solubility in water and the changes in solubility of sodium chloride along with the temperature are not obvious, sodium chloride obtained by acidification of disodium iminodiacetate by hydrochloric acid is firstly separated, so that the content of sodium chloride is reduced, the precipitation of sodium chloride in the subsequent reaction is avoided, and the reaction yield is improved; meanwhile, the viscosity of raw materials is reduced, so that the mixing of the raw materials becomes more uniform. Secondary, as sodium chloride in the system is reduced, wastewater produced by washing during separation of N-(phosphonomethyl) iminodiacetic acid is reduced. Experimental results show that the yield of N-(phosphonomethyl) iminodiacetic acid prepared by the method provided by the invention can be up to above 93%.

Pmida production and stock solution of phosphorus trichloride in addition to salt recycle method

The invention discloses a method for producing N-(phosphonomethyl)iminodiacetic acid and recycling a mother solution by phosphorus trichloride desalinization, which comprises the following steps: 1) hydrolyzing iminodiacetonitrile with a sodium hydroxide solution to obtain disodium iminodiacetate; 2) adding phosphorus trichloride to acidify the disodium iminodiacetate; 3) adding formaldehyde, heating to react to synthesize the N-(phosphonomethyl)iminodiacetic acid; 4) cooling, crystallizing, separating the solid, and drying to obtain the N-(phosphonomethyl)iminodiacetic acid product; 5) adding phosphorus trichloride into the mother solution subjected to N-(phosphonomethyl)iminodiacetic acid separation until the concentration of the hydrogen chloride is 15-30% so as to precipitate sodium chloride, and separating and taking the sodium chloride out; and 6) returning the hydrogen-chloride/phosphorous-acid-containing mother solution subjected to sodium chloride separation to the step 2) to acidify the disodium iminodiacetate. The method is simple and easy to implement, can avoid the problems of complex process and high energy consumption in the original desalinization technique for concentrating the mother solution, and can recycle excessive phosphorous acid, formaldehyde and dissolved N-(phosphonomethyl)iminodiacetic acid in the mother solution, thereby reducing the raw material consumption and enhancing the yield.