US3835000A - Electrolytic process for producing n-phosphonomethyl glycine - Google Patents

Electrolytic process for producing n-phosphonomethyl glycine Download PDF

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US3835000A
US3835000A US00385932A US38593273A US3835000A US 3835000 A US3835000 A US 3835000A US 00385932 A US00385932 A US 00385932A US 38593273 A US38593273 A US 38593273A US 3835000 A US3835000 A US 3835000A
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United States
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cell
solution
phosphonomethyl
glycine
phosphonomethyl glycine
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US00385932A
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English (en)
Inventor
J Wagenknecht
H Frazier
L Smith
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Monsanto Co
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Monsanto Co
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Priority to US00385932A priority Critical patent/US3835000A/en
Priority to PH15246A priority patent/PH10205A/en
Priority to BR9442/73A priority patent/BR7309442D0/pt
Priority to RO7377044A priority patent/RO64474A/ro
Priority to ES421614A priority patent/ES421614A1/es
Priority to NL7317370.A priority patent/NL163218C/xx
Priority to AR251626A priority patent/AR216882A1/es
Priority to DD175538A priority patent/DD110503A5/xx
Priority to EG480/73A priority patent/EG11507A/xx
Priority to AU63851/73A priority patent/AU489345B2/en
Priority to SE7317193A priority patent/SE403379B/xx
Priority to FR7345835A priority patent/FR2211468B1/fr
Priority to GB5908373A priority patent/GB1428499A/en
Priority to DE19732363634 priority patent/DE2363634C3/de
Priority to BG025303A priority patent/BG24411A3/xx
Priority to DK694073AA priority patent/DK134559B/da
Priority to SU731978267A priority patent/SU633484A3/ru
Priority to YU3305/73A priority patent/YU37363B/xx
Priority to HUMO891A priority patent/HU168961B/hu
Priority to PL1973167559A priority patent/PL94988B1/pl
Priority to AT1070273A priority patent/AT334395B/de
Priority to IL43880A priority patent/IL43880A/en
Priority to CA188,637A priority patent/CA1001992A/en
Priority to JP48142934A priority patent/JPS5111094B2/ja
Priority to IE2308/73A priority patent/IE38667B1/xx
Priority to CH1796673A priority patent/CH592105A5/xx
Priority to IT3554/73A priority patent/IT1001432B/it
Application granted granted Critical
Publication of US3835000A publication Critical patent/US3835000A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • This disclosure relates to an electrolytic process for producing N-phosphonomethyl glycine compounds by the electrolysis of N-organo-N-phosphonomethylamino acetic acidcompounds.
  • a solution of an N-organo-N-phosphonomethylamino acetic acid compound is subjected to an electromotive force or electric current in an electrolytic cell to be electrolytically oxidized to an N-phosphonomethyl glycine.
  • the N-phosphonomethyl glycines produced are useful as post-emergent herbicides.
  • This invention relates to a method of producing N- phosphonomethyl glycines by the electrolytic oxidation of N-organo-N-phosphonomethylamino acetic acid compounds. More particularly, this invention reates to the production of N-phosphonomethyl glycines by the electolysis of N-organo-N-phosphonomethylamino acetic acid in an aqueous medium.
  • R is alkyl of from 1 to 6 carbon atoms
  • R is hydrogen or R and M
  • M M M and M are each individually hydrogen, alkoxyalkyl groups, alkyl groups, of from '1 to 18 .carbon atoms, preferably lower alkyl, alkali metal, alkaline earth metal, ammonium and organic ammonium, provided that at least one of M, M
  • M is "H, "alkali metal or alkaline earth metal and n islaninteger'gjfil to 6 is charged into an electrolytic cell fitteiwith an anode and a cathode and an electromotive force or electric current impressed upon the cell whereby the Nrgano-N-phosphonomethylamino acetic "Ice acid is electrolytically oxidized to yield an N-phosphonomethyl glycine of the formula wherein M, M and M are as above defined as the principal product.
  • alkoxyalkyl groups represented by M, M M and M include methoxyethyl, 4-ethoxy-2-methylbutyl, 2-ethoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 4-methoxy-2-ethylbutyl, 4-butoxybuty],
  • the alkyl groups represented by R, M, M M M and M include lower alkyls such as methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, as well as the higher alkyls such as heptyl, octyl, dodecyl, octadecyl and the like.
  • alkali metal encompasses lithium, sodium, potassium, cesium and rubidium; and the term alkaline earth metal includes beryllium, magnesium, calcium, strontium and barium.
  • the organic ammonium groups represented by M, M M M and M are those derived from lower molecular Weight organic amines, i.e., those having a molecular weight below about 300.
  • Such organic amines include the alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups, such as methylamine, ethylamine, n-propylamine, isopropylamine, nbutylamine, isobutylamine, sec-butylamine, n-amylarnine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecyl
  • a 2% to 30% solution of the N-organo-N- phosphonom ethylamino acetic acid compound dissolved in 1.0% to 37% hydrochloric acid (1-37% HCl in water) and even more preferred, 10-25% HCl is charged into an electrolytic cell maintained at a temperature of from 25 C. to C. and having noble metal, graphite or carbon electrodes.
  • An electric current is thenirnpressed on the cell by connecting the anode and cathode to a proper source of direct current with controls tomaintain the current density at between 1 and 700 men/cm. for a time sufiicient to oxidize the N-organo-N-phosphonomethylamino acetic acid compound to the N-phosphonomethyl glycine.
  • the resultant reaction solution is then vacuum evaporated to remove the aqueous hydrochloric acid reaction medium and volatile lay-products.
  • the residue is then dissolved in water and recovered by recrystallization upon the cooling of the water solution.
  • concentration of the N-organo-N-phosphonomethylamino acetic acid compound employed in the process of this invention is not critical and is limited only by the solubility of the starting material in water.
  • concentrations as low as 0.01% by weight in water can be employed, for reasons of efiiciency and economy, it is preferred to employ concentrations of from about 5 to about 30% by weight, or even higher, of the N-phosphonomethylamino acetic acid compound in an aqueous electrolyte.
  • the temperature at which the process of the instant invention is conducted is not narrowly critical and can range from as low as 0 C. to as high as 110 C. or even higher if a pressure cell is employed. As is apparent to those skilled in the art, at lower temperature a very dilute solution or a suspension must be employed since the solubility of the N-organo-N-phosphonomethylamino acetic acid starting material is lower at lower temperatures.
  • the process of the instant invention can be conducted at atmospheric pressure, super atmospheric pressures and subatmospheric pressures. For reason of economy and ease of construction of the equipment employed in the process of this invention, it is preferred to conduct this process at approximately atmospheric pressure.
  • the type of electrilytic cell employed in the process of this invention is not critical.
  • the cell can consist of a glass container having one or more anodes and cathodes conncted to a source of direct current, such as a battery and the like or a source of low frequency alternating current.
  • the cell can also consist of the two electrodes separated by an insulator such as a rubber or other non-conducting gasket.
  • the current densities employed in the process of this invention can range from as low as 1 milliampere per square centimeter (ma/cm?) to 700 or more ma./cm.
  • the electrodes i.e., the anode and cathode, employed in the process of this invention can be constructed of a wide variety of materials and combinations oi? materials.
  • the anodes may be constructed. of any conductive substance, such as lead, graphite, lead oxide, lead sulfate, carbon in various forms, platinum, various metal oxides such as manganese dioxide, copper oxide, nickel oxide and the like, and can be in many different forms such as gauze, solids, porous, etc.
  • the cathodes can also be of any conductive substance such as copper, lead, platinum, palladium, lead oxide, graphite, carbon and the like. It is preferred to employ a noble metal such as palladium or platinum or various forms of graphite, carbon or glassy carbon as the elec trodejmaterials employed in the process of this invention. Other electrode materials are less preferred since they corrode rapidly and their ions contaminate the electrolyte, thereby rendering the isolation of the product more expensive and difficult.
  • the acids which can be employed to render the aqueous medium acidic include the hydrohalic acids such as hydrochloric, hydroiodic, hydrobromic and hydrofluoric and other inorganic acids such as sulfuric, nitric, phosphoric, perchloric, tetrafiuoroboric, trifluoroacetic and other strong organic acids such as toluene 'sulfonic' acid, etc. and hexaflu'orophosphonic, etc.
  • hydrohalic acids such as hydrochloric, hydroiodic, hydrobromic and hydrofluoric and other inorganic acids such as sulfuric, nitric, phosphoric, perchloric, tetrafiuoroboric, trifluoroacetic and other strong organic acids such as toluene 'sulfonic' acid, etc. and hexaflu'orophosphonic, etc.
  • the bases which can be employed to render the aque; medium basic include the alkali and alkaline earth metal oxides and hydroxides such-as, for example, sodium, potassium, rubidium, cesium, calcium and barium, oxides and hydroxides, and organic bases such as tetraalkyl am monium hydroxides, tertiary amines and thelike It is, of course, apparent to those skilled in'the art that the aqueous medium must be a conducting aqueous-me dium to obtain the best flow of current. Thus, the acidsior electrolytic solution conductive.” h It is, of course, apparent to those skilled in'the art that the time of reaction is variable and is determined by variables such as current density, electrode area concgntration and volume of the reaction solution. i
  • the N-phosphonomethyl glycine product of the process of the present invention is recovered 'from'the reaction solution by conventional techniques known to-those skilled in the art, such as by extraction and recrystallization, centrifugation, concentration and the like.”--'-
  • the reaction solution can-be vacuum evaporated to eliminate the water, acid, and volatile by-products.
  • the solid which remains can be dissolved in water and then cooled to precipitate theN-phosphon'omethyl glycine, which is recovered by filtration.
  • the product can also be recovered and purified'by crystallization from a mixture of isopropanol and water.
  • the N-organo-N-phosphonomethylamino' acetic acid compounds employed in the process of this invention can be produced by the reaction of the appropriate amine with formaldehyde and phosphorous acid in the presence of hydrochloric acid in accordancewith the process set forth in US. Pat. 3,288,846.
  • reaction mixture was then"ai1alyz'edby 'nliclear magnetic resonance spectral analysis and found to contain 9.2% N-phosphonomethylimino,diaceticacid; 77.5% N- phosphonomethyl. .glycine; 74% N: I, thyl-N-phosphono methyl glycine and 6.1% DUE-dimethyliminornethylene phosphonic acid.
  • EXAMPLE 3v A sandwich cell composed of tw o graphite discs 4% inches in diameter separated by a U-shaped rubber gasket and clamped between twoinsulators with a C clamp and having a volume of about 25ml. was employed. Into this cell was charged 20 ml. of concentrated hydrochloric acid containing N-phosphonomethylimino diacetic acid (4.5 g), dissolved therein. It was necessary to heat the hydrochloric acid to dissolve the imino diacetic acid, however, it remained in solution on cooling. An electrolysis was carried out with the anode potential at 1.05 to 1.17 volts vs. SCE (initial current 300 ma.) for 4 hours and 40 minutes until 0.524 faradays of electricity had been passed.
  • SCE initial current 300 ma.
  • reaction solution was analyzed and found to contain N-phosphonomethyl glycine, some unreacted starting material and N,N-dimethyliminomethylene phosphonic acid and N-methyl-N-phosphonornethyl glycine.
  • EXAMPLE 4 bined with the reaction solution. The solution was then vacuum evaporated to yield 22.6 grams of a White solid. The white solid was assayed and found to contain 39.1% by weight of N-phosphonomethyl glycine, representing a 79.5% yield based upon the starting material.
  • EXAMPLE 5 A series ofexperiments were conducted employing a sandwich cell similar to that employed in Example 3, but employing electrolytically pure graphite and fitted with heating elements to maintain the temperature at 80 C.
  • EXAMPLE 8 A bipolar porous electrode cell was employed in the electrolytic oxidation of N-phosphonomethylimino diacetic acid to N-phosphonomethyl glycine.
  • the cell contained three porous graphite electrodes in series with solution flowing through them.
  • the center electrode had no direct electrical connection but operated as a porous bipolar electrode as evidenced by gas evolution from both surfaces when current was passed through the cell via the end electrodes.
  • a solution of 5% N-phosphonomethylimino diacetic acid in 20 hydrochloric acid was passed through the cell while the current was passing. Analysis of the reaction mixture indicated that there was some conversion of N-phosphonomethylimino diacetic acid to N-phosphonomethyl glycine.
  • EXAMPLE 9 passed through the solution for 5 hours and the current reduced to 0.25 amperes for an additional 1% hours. During this time, water, formaldehyde and hydrochloric acid was distilled off continuously, giving a total of 75 ml. of distillate. The cell was kept at approximately constant volume by the addition of 20% hydrochloric acid. After the electrolysis was completed, the reaction mixture was analyzed by nuclear magnetic resonance spectral analysis and found to contain N-phosphonomethyl glycine. The yield in this experiment was 93% of theory.
  • EXAMPLE 10 In this example, an electrolytic cell comprising two graphite electrodes having surfaces of 28 centimeters by 5 centimeters and separated by an insulating gasket were employed. The cell was open at the top and was equipped with a pump so that the solution could be pumped through the cell and back to a reservoir which was held at 8090 C. The cell was also fitted with heating elements. The reservoir was charged with 50 ml. of a 25% solution of N-phosphonomethylimino diacetic acid dissolved in 20% HCl. This solution was pumped through the cell and back to the reservoir. The cell was heated until reflux was observed in the solution. The flow through the cell was maintainedat about .40-ml.
  • EXAMPLE 12 The electrolysis of N-allyl-N-phosphonomethyl glycine (3 g. in 50 ml. of concentrated HCl) was carried out in an apparatus consisting of a cell, reservoir and pump.
  • the electrolysis cell consisted of a glass tube with a 1-inch diameter by l-inch thick porous graphite anode cemented into the tube. A carbon rod downstream of the anode served as the cathode.
  • the solution was pumped from the reservoir through the cell and back to the reservoir at a rate of 100 ml. per minute during the electrolysis.
  • the electrolysis was carried out at 1 amp for 2 hours at room temperature. After the electrolysis, analysis by proton nuclear magnetic resonance and gas chromatography indicated the presence of N-phosphonomethyl glycine.
  • EXAMPLE 13 The electrolysis of N-benzyl-N-phosphonomethyl glycine grams in 75 ml. of 20% B01) was carried out in the apparatus described in Example 12. The electrolysis was carried out at 0.5 amps for 2 hours at room temperature. After the electrolysis, analysis by proton nuclear magnetic resonance and gas chromatography indicated the presence of N-phosphonomethyl glycine.
  • EXAMPLE 14 The electrolysis of N,N-bis(phosphonomethyl)glycine (5 grams in 50 ml. concentrated HCl) was carried out in the apparatus described in Example 12. The electrolysis was carried out at 1 amp for 2% hours at room temperature. After the electrolysis, analysis by proton nuclear magnetic resonance indicated the presence of N-phosphonomethyl glycine.
  • EXAMPLE 15 The electrolysis of N-phosphonomethylimino diacetic acid (5 grams in 100 ml. of 2% HCl) was carried out in the apparatus described in Example 12, except that the solution in the reservoir was maintained at 80 C. with a heater. The electrolysis was carried out at. 1 amp for 50 minutes and 0.5 amps for 40 minutes at which time no N-phosphonomethylimino diacetic acid remained in the solution (nuclear magnetic analysis). Analysis of the final solution showed 28.44 mg./ml. of N-phosphonomethyl glycine and 5.79 mg./rnl. total phosphorous for a 90.6% yield.
  • EXAMPLE 16 A 5% (W./w.) solution of N-phosphonomethylimino diacetic acid in 20% hydrochloric acid was passed at a rate-of mL/min. through a multi-electrode bipolar cell.
  • the cell consisted of 20 porous graphite blocks, 1" wide x6" highx 1" thick, with electrical connections only on. the end electrodes. Flow was through the 1" thickness.
  • the temperature was 60 C., applied voltage was 57 voltsandburrent lwas50 'amperes.
  • the efiiuent was'shown to contain N-phosphonometliyl glycine in 94% yield based onstarting material.” 7
  • EXAMPLE 17 A 10% (w./w.) solution of 'N-phosphonomethylimino diacetic acid in 20% hydrochloric acid was caused to flow through a multi-electrode monopolar cell at a rate of 8 ml./min.
  • the cell consisted of six porous carbon anodes, 1" Widex 1" thickxZ" high and seven 0.25" diameter graphite rod cathodes mounted between the anodes and at each end. Electrical connection was made to each cathode and each anode. Flow was through the l thckness. The temperature was 5070 C., current was 21 amperes and voltage was 3.3 volts. The etfluen't was shown to contain N-phosphonomethyl glycine in 91.6% yield based on starting material. 1
  • EXAMPLE 18 A 5% (w./w.) solution of N-phosphonomethylimino diacetic acid in 20% hydrochloric acid was caused to flow at a velocity of 5 ft./sec. between a solid graphite anode and a solid graphite cathode. The gap between the electrodes was 1/16, the temperature was 70 C., and the electrode dimensions were 39" x 1". The current density was ma./cm. and 400% of'the theoretical current was used. The efiluent from the cell contained N-phosphonomethyl glycine in 55% yield.
  • R1 is alkyl of from 1 to 6 carbon atoms
  • R5 is H or R
  • n is an integer of 1 to 6
  • M and M are as 9 defined for M, M and M to an electromotive force whereby said acetic acid compound is oxidized to N- phosphonomethyl glycine.
  • a process as claimed in Claim 1 wherein the concentration of the N organo-N-phosphonomethylamino acetic acid compound is from about 5% to about 30% by weight of the aqueous electrolytic medium.
  • N- organo-N-phosphonomethylamino acetic acid compound is N-phosphonomethylimino diacetic acid.
  • N organo-N-phosphonomethylamino acetic acid compound is the isopropylammonium salt of N-phosphonomethylimino diacetic acid.
  • N- organo-N-phosphonomethylamino acetic acid compound is N-allyl-N-phosphonomethylamino acetic acid.
  • N- organo-N-phosphonomethyl acetic acid compound is N- benzyl-N-phosphonomethylamino acetic acid.
  • N- organo-N-phosphonomethyl acetic acid compound is bis- (N-phosphonomethyl)amino acetic acid.

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  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Electrolytic Production Of Metals (AREA)
US00385932A 1972-12-21 1973-08-06 Electrolytic process for producing n-phosphonomethyl glycine Expired - Lifetime US3835000A (en)

Priority Applications (27)

Application Number Priority Date Filing Date Title
US00385932A US3835000A (en) 1972-12-21 1973-08-06 Electrolytic process for producing n-phosphonomethyl glycine
PH15246A PH10205A (en) 1972-12-21 1973-11-21 Electrolytic process for producing n-phosphoromethyl glycine
BR9442/73A BR7309442D0 (pt) 1972-12-21 1973-11-30 Processo para obtencao de n-fosfono metil glicina
RO7377044A RO64474A (fr) 1972-12-21 1973-12-18 Procede d'obtention de la n-phosphonomethyle-glycine
NL7317370.A NL163218C (nl) 1972-12-21 1973-12-19 Werkwijze voor de bereiding van n-fosfonomethylglycine.
ES421614A ES421614A1 (es) 1972-12-21 1973-12-19 Un procedimiento para producir una n-fosfonometilglicina.
PL1973167559A PL94988B1 (xx) 1972-12-21 1973-12-20
EG480/73A EG11507A (en) 1972-12-21 1973-12-20 Process for producing n-phosphonomethyl glycine
AU63851/73A AU489345B2 (en) 1973-12-20 Process for producing n-phosphonomethyl glycine
SE7317193A SE403379B (sv) 1972-12-21 1973-12-20 Forfarande for framstellning av n-fosfonometylglycin genom elektrolytisk oxidation av n-organo-n-fosfonometylaminoettiksyraforeningar
FR7345835A FR2211468B1 (xx) 1972-12-21 1973-12-20
GB5908373A GB1428499A (en) 1972-12-21 1973-12-20 Process for producing n-phosphonomethyl glycine and salts and esters thereof
DE19732363634 DE2363634C3 (de) 1972-12-21 1973-12-20 Verfahren zur Herstellung von N-Phosphonmethylglycin
BG025303A BG24411A3 (en) 1972-12-21 1973-12-20 Method of preparing n-phosphonomethylglycine
AR251626A AR216882A1 (es) 1972-12-21 1973-12-20 Nuevo procedimiento para producir derivados de la n-fosfonometilglicina,que es util como agente activo herbicida
SU731978267A SU633484A3 (ru) 1973-08-06 1973-12-20 Способ получени фосфонометилглицина
YU3305/73A YU37363B (en) 1972-12-21 1973-12-20 Process for obtaining n-phosphonomethylglycine derivatives
HUMO891A HU168961B (xx) 1972-12-21 1973-12-20
DD175538A DD110503A5 (xx) 1972-12-21 1973-12-20
AT1070273A AT334395B (de) 1973-08-06 1973-12-20 Verfahren zur herstellung von n-phosphonomethylglycinen
IL43880A IL43880A (en) 1972-12-21 1973-12-20 Process for the production of N-phosphonomethyl glycines
CA188,637A CA1001992A (en) 1972-12-21 1973-12-20 Process for producing n-phosphonomethyl glycine
JP48142934A JPS5111094B2 (xx) 1972-12-21 1973-12-20
IE2308/73A IE38667B1 (en) 1972-12-21 1973-12-20 Process for producing n-phosphonomethyl glycine and salts and esters thereof
CH1796673A CH592105A5 (xx) 1972-12-21 1973-12-20
IT3554/73A IT1001432B (it) 1972-12-21 1973-12-20 Procedimento per produrre n fosfonometilglicina
DK694073AA DK134559B (da) 1972-12-21 1973-12-20 Fremgangsmåde til fremstilling af N-phosphonomethylglycinforbindelser.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31749872A 1972-12-21 1972-12-21
US00385932A US3835000A (en) 1972-12-21 1973-08-06 Electrolytic process for producing n-phosphonomethyl glycine

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US (1) US3835000A (xx)
JP (1) JPS5111094B2 (xx)
AR (1) AR216882A1 (xx)
BG (1) BG24411A3 (xx)
BR (1) BR7309442D0 (xx)
CA (1) CA1001992A (xx)
CH (1) CH592105A5 (xx)
DD (1) DD110503A5 (xx)
DK (1) DK134559B (xx)
EG (1) EG11507A (xx)
ES (1) ES421614A1 (xx)
FR (1) FR2211468B1 (xx)
GB (1) GB1428499A (xx)
HU (1) HU168961B (xx)
IE (1) IE38667B1 (xx)
IL (1) IL43880A (xx)
IT (1) IT1001432B (xx)
NL (1) NL163218C (xx)
PH (1) PH10205A (xx)
PL (1) PL94988B1 (xx)
RO (1) RO64474A (xx)
SE (1) SE403379B (xx)
YU (1) YU37363B (xx)

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3991095A (en) * 1975-12-29 1976-11-09 Monsanto Company N-thiolcarbonyl derivatives of N-phosphonomethylglycine
US4047927A (en) * 1976-08-13 1977-09-13 Monsanto Company N-(2-hydroxyalkyl) derivatives of N-phosphonomethylglycine and the herbicidal use thereof
US4063922A (en) * 1976-08-13 1977-12-20 Monsanto Company N-(2-hydroxyalkyl) derivatives of N-phosphonomethylglycine for treatment of sugarcane
US4180394A (en) * 1978-07-10 1979-12-25 Monsanto Company Derivatives of N-trifluoroacetyl-N-phosphonomethylglycinates and the herbicidal use thereof
US4218235A (en) * 1978-07-10 1980-08-19 Monsanto Company Ester derivatives of n-trifluoroacetyl-n-phosphonomethylglycine and the herbicidal use thereof
US4251256A (en) * 1978-12-22 1981-02-17 Monsanto Company Herbicidal N-substituted ethylene derivatives of N-phosphonomethylglycine
US4251258A (en) * 1978-09-29 1981-02-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phosphinylmethylglycinates and the herbicidal use thereof
US4261727A (en) * 1979-08-02 1981-04-14 Monsanto Company Herbicidal N-substituted triesters of N-phosphonomethylglycine
US4300942A (en) * 1978-09-29 1981-11-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phos-phinylmethylglycinates and the herbicidal use thereof
US4315765A (en) * 1980-12-04 1982-02-16 Stauffer Chemical Company Trialkylsulfonium salts of n-phosphonomethylglycine and their use as plant growth regulators and herbicides
US4328027A (en) * 1981-04-16 1982-05-04 Stauffer Chemical Company Di-triethylamine salt of N,N'-bis-carboethoxymethyl-N,N'-bis-phosphonomethylurea and its use as a plant growth regulator
US4376644A (en) * 1980-12-04 1983-03-15 Stauffer Chemical Company Tri-mixed alkylsulfonium salts of N-phosphonomethylglycine and their use as plant growth regulators and herbicides
US4384880A (en) * 1980-12-04 1983-05-24 Stauffer Chemical Company Trialkylsulfonium salts of N-phosphonomethyl-glycine and their use as plant growth regulators and herbicides
US4397676A (en) * 1982-03-08 1983-08-09 Geshuri Laboratories Ltd. N-Phosphonomethylglycine derivatives
US4437874A (en) 1981-11-25 1984-03-20 Stauffer Chemical Company Tri-mixed alkylsulfonium salts of N-phosphonomethylgylcine and their use as plant growth regulators and herbicides
US4472189A (en) * 1982-12-27 1984-09-18 Stauffer Chemical Co. Stannic N-phosphonomethyglycine and its use as a herbicide
US4684483A (en) * 1985-09-23 1987-08-04 Monsanto Company Preparation of N-substituted amino acids
US4804500A (en) * 1985-04-22 1989-02-14 Monsanto Company Amine dealkylation process
US4894082A (en) * 1983-07-27 1990-01-16 Rhone-Poulenc Agrochimie N-sulphonyl-N-(N'-phosphonomethylglycyl)amine
US4921991A (en) * 1985-02-22 1990-05-01 Guy Lacroix Preparation of esters of the N-phosphonomethylglycine and the N-phosphonomethyl glycines
US5117043A (en) * 1988-08-18 1992-05-26 Rhone-Poulenc Agrochimie Process for the preparation of n-sulfomethylglycinate
US5187292A (en) * 1988-08-18 1993-02-16 Rhone-Poulenc Agrochimie N-sulfomethylglycinate, use in the preparation of herbicides of the glyphosate type
US6005140A (en) * 1998-02-12 1999-12-21 Monsanto Company Process for making glyphosate by oxidizing N-substituted glyphosates
US6232494B1 (en) 1998-02-12 2001-05-15 Monsanto Company Process for the preparation of N-(phosphonomethyl)glycine by oxidizing N-substituted N-(phosphonomethyl)glycine
US6417133B1 (en) 1998-02-25 2002-07-09 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
US7015351B2 (en) 2000-05-22 2006-03-21 Monsanto Technology Llc Reaction systems for making N-(phosphonomethyl) glycine compounds
US20090011515A1 (en) * 2005-04-01 2009-01-08 Monsanto Technology Llc Control of N-(Phosphonomethyl)Iminodiacetic Acid Conversion in Manufacture of Glyphosate
US20090326262A1 (en) * 2008-05-01 2009-12-31 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
US20100130774A1 (en) * 2004-09-15 2010-05-27 Monsanto Technology Llc Oxidation catalyst and its use for catalyzing liquid phase oxidation reactions

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GB1494197A (en) * 1973-11-30 1977-12-07 Ici Ltd Electrochemical process for the preparation of n-phosphonomethyl glycine
NL7713959A (nl) * 1976-12-20 1978-06-22 Monsanto Co Werkwijze voor het bereiden van n-fosfono- methylglycinezouten.
US4105432A (en) * 1977-07-18 1978-08-08 Monsanto Company Cyclized derivatives of N-(2-hydroxyalkyl)-N-phosphonomethylglycine compounds
FR2560198B1 (fr) * 1984-02-23 1987-05-07 Rhone Poulenc Agrochimie Esters de la famille de la n-phosphonomethylglycine et leur utilisation pour la preparation d'herbicides connus
IL77364A (en) * 1984-12-28 1991-01-31 Monsanto Co Thermal dealkylation of n-alkyl n-phosphono-methylglycine

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US3991095A (en) * 1975-12-29 1976-11-09 Monsanto Company N-thiolcarbonyl derivatives of N-phosphonomethylglycine
US4047927A (en) * 1976-08-13 1977-09-13 Monsanto Company N-(2-hydroxyalkyl) derivatives of N-phosphonomethylglycine and the herbicidal use thereof
US4063922A (en) * 1976-08-13 1977-12-20 Monsanto Company N-(2-hydroxyalkyl) derivatives of N-phosphonomethylglycine for treatment of sugarcane
US4119430A (en) * 1976-08-13 1978-10-10 Monsanto Company N-(2-hydroxyalkyl) derivatives of N-phosphonomethylglycine and herbicidal compositions containing same
US4180394A (en) * 1978-07-10 1979-12-25 Monsanto Company Derivatives of N-trifluoroacetyl-N-phosphonomethylglycinates and the herbicidal use thereof
US4218235A (en) * 1978-07-10 1980-08-19 Monsanto Company Ester derivatives of n-trifluoroacetyl-n-phosphonomethylglycine and the herbicidal use thereof
US4251258A (en) * 1978-09-29 1981-02-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phosphinylmethylglycinates and the herbicidal use thereof
US4300942A (en) * 1978-09-29 1981-11-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phos-phinylmethylglycinates and the herbicidal use thereof
US4251256A (en) * 1978-12-22 1981-02-17 Monsanto Company Herbicidal N-substituted ethylene derivatives of N-phosphonomethylglycine
US4261727A (en) * 1979-08-02 1981-04-14 Monsanto Company Herbicidal N-substituted triesters of N-phosphonomethylglycine
US4315765A (en) * 1980-12-04 1982-02-16 Stauffer Chemical Company Trialkylsulfonium salts of n-phosphonomethylglycine and their use as plant growth regulators and herbicides
US4376644A (en) * 1980-12-04 1983-03-15 Stauffer Chemical Company Tri-mixed alkylsulfonium salts of N-phosphonomethylglycine and their use as plant growth regulators and herbicides
US4384880A (en) * 1980-12-04 1983-05-24 Stauffer Chemical Company Trialkylsulfonium salts of N-phosphonomethyl-glycine and their use as plant growth regulators and herbicides
US4328027A (en) * 1981-04-16 1982-05-04 Stauffer Chemical Company Di-triethylamine salt of N,N'-bis-carboethoxymethyl-N,N'-bis-phosphonomethylurea and its use as a plant growth regulator
US4437874A (en) 1981-11-25 1984-03-20 Stauffer Chemical Company Tri-mixed alkylsulfonium salts of N-phosphonomethylgylcine and their use as plant growth regulators and herbicides
US4397676A (en) * 1982-03-08 1983-08-09 Geshuri Laboratories Ltd. N-Phosphonomethylglycine derivatives
US4472189A (en) * 1982-12-27 1984-09-18 Stauffer Chemical Co. Stannic N-phosphonomethyglycine and its use as a herbicide
US4894082A (en) * 1983-07-27 1990-01-16 Rhone-Poulenc Agrochimie N-sulphonyl-N-(N'-phosphonomethylglycyl)amine
US4921991A (en) * 1985-02-22 1990-05-01 Guy Lacroix Preparation of esters of the N-phosphonomethylglycine and the N-phosphonomethyl glycines
US4804500A (en) * 1985-04-22 1989-02-14 Monsanto Company Amine dealkylation process
US4684483A (en) * 1985-09-23 1987-08-04 Monsanto Company Preparation of N-substituted amino acids
US5117043A (en) * 1988-08-18 1992-05-26 Rhone-Poulenc Agrochimie Process for the preparation of n-sulfomethylglycinate
US5187292A (en) * 1988-08-18 1993-02-16 Rhone-Poulenc Agrochimie N-sulfomethylglycinate, use in the preparation of herbicides of the glyphosate type
US6232494B1 (en) 1998-02-12 2001-05-15 Monsanto Company Process for the preparation of N-(phosphonomethyl)glycine by oxidizing N-substituted N-(phosphonomethyl)glycine
US20040143134A1 (en) * 1998-02-12 2004-07-22 Monsanto Technology Llc Process for the preparation of N-(phosphonomethyl)glycine by oxidizing N-substituted N-(phosphonomethyl)glycine
US7297657B2 (en) 1998-02-12 2007-11-20 Monsanto Technology Llc Process for the preparation of N-(phosphonomethyl)glycine by oxidizing N-substituted N-(phosphonomethyl)glycine
US6005140A (en) * 1998-02-12 1999-12-21 Monsanto Company Process for making glyphosate by oxidizing N-substituted glyphosates
US8143441B2 (en) 1998-02-25 2012-03-27 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use in preparing N-(phosphonomethyl) glycine compounds
US6417133B1 (en) 1998-02-25 2002-07-09 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
US6603039B1 (en) 1998-02-25 2003-08-05 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
US7067693B1 (en) 1998-02-25 2006-06-27 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use in preparing N-(phosphonomethyl) glycine compounds
US20070100161A1 (en) * 1998-02-25 2007-05-03 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use in preparing N-(phosphonomethyl) glycine compounds
US7015351B2 (en) 2000-05-22 2006-03-21 Monsanto Technology Llc Reaction systems for making N-(phosphonomethyl) glycine compounds
US20060079712A1 (en) * 2000-05-22 2006-04-13 Monsanto Technology Llc Reaction systems for making N-(phosphonomethyl) glycine compounds
US7504534B2 (en) 2000-05-22 2009-03-17 Monsanto Technology Llc Reaction systems for making N-(phosphonomethyl) glycine compounds
US20090259068A1 (en) * 2000-05-22 2009-10-15 Monsanto Technology Llc Reaction systems for making n-(phosphonomethyl) glycine compounds
US8703639B2 (en) 2004-09-15 2014-04-22 Monsanto Technology Llc Oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
US20100130774A1 (en) * 2004-09-15 2010-05-27 Monsanto Technology Llc Oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
US7799571B2 (en) 2005-04-01 2010-09-21 Monsanto Technology Llc Control of N-(phosphonomethyl)iminodiacetic acid conversion in manufacture of glyphosate
US20110097810A1 (en) * 2005-04-01 2011-04-28 Monsanto Technology Llc Control of n-(phosphonomethyl)iminodiacetic acid conversion in manufacture of glyphosate
US20090011515A1 (en) * 2005-04-01 2009-01-08 Monsanto Technology Llc Control of N-(Phosphonomethyl)Iminodiacetic Acid Conversion in Manufacture of Glyphosate
US9409935B2 (en) 2005-04-01 2016-08-09 Monsanto Technology Llc Control of N-(phosphonomethyl)iminodiacetic acid conversion in manufacture of glyphosate
US11067502B2 (en) 2005-04-01 2021-07-20 Monsanto Technology Llc Control of n-(phosphonomethyl)iminodiacetic acid conversion in manufacture of glyphosate
US11802835B2 (en) 2005-04-01 2023-10-31 Monsanto Technology Llc Control of N-(phosphonomethyl)iminodiacetic acid conversion manufacture of glyphosate
US20090326262A1 (en) * 2008-05-01 2009-12-31 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
US8252953B2 (en) 2008-05-01 2012-08-28 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
US9163041B2 (en) 2008-05-01 2015-10-20 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
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YU37363B (en) 1984-08-31
ES421614A1 (es) 1976-10-16
HU168961B (xx) 1976-08-28
IL43880A (en) 1976-05-31
GB1428499A (en) 1976-03-17
SE403379B (sv) 1978-08-14
JPS5111094B2 (xx) 1976-04-08
FR2211468A1 (xx) 1974-07-19
FR2211468B1 (xx) 1976-05-07
EG11507A (en) 1977-08-15
JPS4988827A (xx) 1974-08-24
IE38667B1 (en) 1978-05-10
YU330573A (en) 1983-04-27
IL43880A0 (en) 1974-03-14
NL163218B (nl) 1980-03-17
IT1001432B (it) 1976-04-20
PL94988B1 (xx) 1977-09-30
DK134559C (xx) 1977-05-09
PH10205A (en) 1976-09-27
IE38667L (en) 1974-06-21
DD110503A5 (xx) 1974-12-20
AU6385173A (en) 1975-06-26
CH592105A5 (xx) 1977-10-14
CA1001992A (en) 1976-12-21
DE2363634A1 (de) 1974-06-27
DE2363634B2 (de) 1977-06-02
NL7317370A (xx) 1974-06-25
BG24411A3 (en) 1978-02-10
AR216882A1 (es) 1980-02-15
DK134559B (da) 1976-11-29
NL163218C (nl) 1980-08-15
BR7309442D0 (pt) 1974-08-29
RO64474A (fr) 1979-05-15

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