IL46057A - Electrochemical process for the preparation of phosphonomethylglycine - Google Patents
Electrochemical process for the preparation of phosphonomethylglycineInfo
- Publication number
- IL46057A IL46057A IL46057A IL4605774A IL46057A IL 46057 A IL46057 A IL 46057A IL 46057 A IL46057 A IL 46057A IL 4605774 A IL4605774 A IL 4605774A IL 46057 A IL46057 A IL 46057A
- Authority
- IL
- Israel
- Prior art keywords
- salt
- aqueous solution
- phosphonomethylglycine
- solution
- electrolysis
- Prior art date
Links
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000004009 herbicide Substances 0.000 claims abstract description 4
- 229940075397 calomel Drugs 0.000 claims abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 12
- 230000002363 herbicidal effect Effects 0.000 claims description 10
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims description 9
- 238000009472 formulation Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- LIJRZMXBIYZWJX-UHFFFAOYSA-N 2-[[hydroxy(methoxy)phosphoryl]amino]acetic acid Chemical compound COP(O)(=O)NCC(O)=O LIJRZMXBIYZWJX-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000005562 Glyphosate Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229940097068 glyphosate Drugs 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- -1 aliphatic amines Chemical class 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- RSZXXBTXZJGELH-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)naphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=C(C(C)C)C(S(O)(=O)=O)=C21 RSZXXBTXZJGELH-UHFFFAOYSA-N 0.000 description 1
- CBQDTCDOVVBGMN-UHFFFAOYSA-N 2-methyl-3-octylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1C CBQDTCDOVVBGMN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920005550 ammonium lignosulfonate Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- JIJAYWGYIDJVJI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 JIJAYWGYIDJVJI-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
1494197 Electrolytic preparation of N- methylphosphonoglycine IMPERIAL CHEMICAL INDUSTRIES Ltd 6 Nov 1974 [30 Nov 1973] 55663/73 Heading C2P [Also in Division C7] N-phosphonomethylglycine or a salt thereof is prepared by subjecting an aqueous solution of N-phosphonnmethyliminodiacetic acid or a salt thereof to electrolysis. Preferably the anode is maintained at a potential of 0À8 to 1À2 volts with reference to a standard calomel electrode and the electrodes are made of carbon, a noble metal or a metal oxide. Preferably the pH of the aqueous solution is greater than 7 and the solution is stirred or otherwise agitated to bring about movement of the aqueous solution relative to the anode. The electrolysed solutions may be formulated for use as herbicides. Reference has been directed by the Comptroller to Specification 1,428,499.
[GB1494197A]
Description
46057/3 \ ELECTROCHEMICAL PROCESS FOR THE PREPARATION OF PHOSPHONOMETHYLGLYCINE / / / 46057/3 ELECTROCHEMICAL PROCESS FOR THE PREPARATION OF PHOSPHONOMETHYLGLYCINE 46057/2 This invention relates to electrochemical processes, and more particularly to an electrochemical process for preparing the compound N-phosphonomethylglycine, having the formula:= 0 As disclosed in Belgian Patent 774,349, N-phosphonomethylglycine is a broad spectrum herbicide having little or no residual effect. N-Phosphonomethylglycine has been given the common name glyphosate.
A process for the preparation of glyphosate has been published in German O fenlegungschrift 2314134. This process involves the treatment of N-phosphonyl-imino-diacetic acid with a strong acid. The process of the present invention has the advantage that it does not require the use of strong acids, which give rise to problems of waste disposal.
According to the present invention, there is provided a rocess of preparing the compound -eif N-phosphonomethylglycine, or a salt thereof, which comprises subjecting an aqueous solution of N-phosphonomethyliminodiacetic acid or a salt thereof to electrolysis. Preferably the working electrode is maintained at a potential of from 0.8 to 1.2 volts with reference to a standard calomel electrode.
The overall reaction involved in the process of the invention is illustrated by the following reaction scheme :p It will be seen that the reaction is an oxidation in which one of the carboxymethyl groups attached to the nitrogen atom is removed and replaced by a hydrogen atom.
The N-phosphonomethyliminodiacetic acid used as starting material is a known compound, the preparation of which is described for example in Example 2 of United States Patent No.3^55675· The working electrode is preferably a carbon electrode, for example an electrode made of vitreous carbon, porous carbon, or graphite. Electrodes made of other materials, for example metals which are stable in both acid and alkaline media, can also be used. Examples of such metals include the noble metals, for example palladium and platinum. Metal oxides can also be used, for example ruthenium oxide. The secondary electrode may also be a carbon electrode, or may be a platinum or other electrode as described for the working electrode. The secondary electrode may if desired be separated by a porous barrier from the working electrode. By "working electrode" we mean the anode .
When working in alkaline solution, the pH of the aqueous solution is preferably at least 10.
The aqueous solution may be brought to the required pH by including an alkali, for example an alkali metal hydroxide or carbonate, in the solution.
Examples of preferred alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and sodium and potassium carbonates. The required pH may also be attained by addition of ammonia or an aliphatic amine to the solution. Examples of aliphatic amines include primary, secondary and tertiary amines in which the one, two or three aliphatic radicals each contain from 1 to 4 carbon atoms. Where it is not desired to operate in alkaline solution it may still be desirable to add sufficient alkali, ammonia, or amine to form a salt, for example a mono- salt of the N-phosphono-methyliminodiacetic acid, so as to increase the solubility of this substance in the aqueous solution.
The concentration of the N-phosphonomethylimino-diacetic acid or salt thereof is not critical for the success of the process. However, for preparative purposes, it is obviously desirable to avoid very low concentrations, while an upper concentration limit is set by the solubility of N-phosphonomethylimino-diacetic acid or salt thereof in the aqueous solution at any given temperature. A convenient concentration is 0.2 molar, although concentrations of up to 2 molar have been found feasible in the case of the sodium salt, for example. By a molar concentration we mean a concentration of one gram mole per litre.
The temperature at which the electrolysis is carried out may vary from 0° to 100°C or above; since temperatures of above 100°C would require the use of pressure equipment it is generally preferred to operate the process of the invention at below 100°C. A convenient temperature for operating the process is room temperature, for example 15 to 30°C.
Preferably the solution is stirred or otherwise agitated during the electrolysis to cause the aqueous solution to move relative to the working electrode, so that the maximum concentration of starting material is maintained at the electrode surface.
It will be appreciated that the time required for the electrolysis will vary, depending for example upon such factors as the concentration of the reaction solution.
The N-phosphonomethylglycine or salt thereof produced by the process of the invention may if desired be recovered from the reaction solution by conventional methods, such as evaporation of the solution, and extraction and recrytallisation of the residue. Alternatively, it may be preferred not to recover the N-phosphonomethylglycine or salt thereof, but simply to formulate the reaction solution as a herbicidal concentrate on completion of the ^ electrolysis. The herbicidal concentrate may then be sold as such and when required for use as a herbicide may be diluted with water by the end user to provide a dilute composition for spray application. The formulation of the aqueous solution as a herbicidal concentrate requires admixture of adjuvants with the aqueous solution. By adjuvant we mean any of the materials conventionally added to herbicidal formulations; for example viscosity-increasing agents to reduce spray drift when the formulation is sprayed; corrosion inhibitors; stickers to improve the adherence of the formulation to plants; and surface-active agents to improve the dispersibility of the formulation in water and to facilitate the spreading of the dilute spray solution over the whole surface of plants to which it is applied.
Surface active agents used in formulating N-phosphonomethylglycine prepared according to the process of the invention may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include for example quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide Suitable agents of the anionic type include for example soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate; and salts of suiphonated aromatic compounds, for example dodecylbenzenesulphonateg, sodium, calcium and ammonium lignosulphonate , butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropyl- naphthalenesulphonic acid. Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol, and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol monolaurate; the condensation products of the said partial esters with ethylene oxide; and the lecithins.
The amount of surface-active agent to be used in the herbicidal formulation will readily be determined by one skilled in the art, but by way of general guidance, from 5 to 10$ by weight of surface-active agent is usually a suitable amount for inclusion in the concentrate.
The invention is illustrated by the following Examples .
EXAMPLE 1 An electric current was passed through a solution of N-phosphonomethyliminodiacetic acid (0.2 molar) in aqueous sodium hydroxide solution (l. molar).
The elctrodes were both of carbon, and the working electrode was maintained at a potential of 1 volt relative to a saturated calomel electrode. ' The temperature of the solution was 22°C. The amount of current passed was theoretically enough to convert 75% of the starting material to N-phosphonomethyl-glycine assuming a two electron reaction as in the reaction scheme above.
After the passage of current was completed, the solution was examined by nuclear magnetic resonance (NMR) spectroscopy. This indicated the presence of approximately 20% of starting material; a yield of at least 30% of glyphosate; glyoxylic acid; and a mixture of other products.
The peaks due to glyphosate in the NMR spectrum of the reaction mixture were identified by adding a quantity of authentic glyphosate to the solution, when the peaks attributed to glyphosate were increased in height .
EXAMPLE 2 This Example further illustrates the process of the invention. Experiments were carried out as described in Example 1, using various electrodes and solutions of various pH values, and analysing the products by means of NMR spectroscopy as before. The results were as follows:-
Claims (14)
1. A process of preparing the compound N-phosphonomethyl glycine or a salt thereof, which comprises subjecting an aqueous solution of N-phosphonomethyl-iminodiacetic acid or a salt thereof to electrolysis.
2. A process as claimed in claim 1 wherein the working electrode is maintained at a potential of from 0.8 volts to 1.2 volts with reference to a standard calomel electrode.
3. A process as claimed in claim 1 or claim 2 wherein the pH of the aqueous solution is greater than 7.
4. H. A process as claimed in any one of claims 1 to 3 wherein the aqueous solution is stirred or otherwise agitated to bring about movement of the aqueous solution relative to the working electrode.
5. A process as claimed in any one of the preceding claims wherein the concentration of the N-phosphono-methyliminodiacetic acid or salt thereof is at least 0. 2 molar.
6. A process as claimed in any one of the preceding claims wherein the electrodes are made of vitreous carbon, a noble metal, or ruthenium oxide.
7. A process as claimed in any one of the preceding claims wherein the salt of the N-phosphonomethyl-iminodiacetic acid is a sodium salt, a potassium salt, an ammonium salt, or an aIky1ammonium salt.
8. A process as claimed in claim 7 wherein the alkylammonium salt is a salt of isopropylamine .
9. A process as claimed in any one of the previous claims wherein a salt of N-phosphonomethyldiacetic acid is subjected to electrolysis, and wherein on completion of the electrolysis the solution is formulated for use as a herbicide.
10. A process as claimed in claim 9 wherein the formulation of the electrolysed solution comprises the addition of a surface-active agent thereto.
11. N-Phosphonomethylglycine and salts thereof whenever prepared by a process as claimed in any one of claims 1 to 8.
12. Herbicidal compositions comprising N-phosphono-methylglycine or a salt thereof whenever prepared by the process of claim 9 or claim 10. according to claim 1
13. Processes/of preparing N-phosphonomethylglycine and salts thereof, substantially as hereinbefore described. according to claim9
14. Processes/of preparing herbicidal formulations of salts of N-phosphonomethylglycine substantially as hereinbefore described. S.HOROWITZ § CO. AGENTS FOR APPLICANfS JED/GS/SG
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB55663/73A GB1494197A (en) | 1973-11-30 | 1973-11-30 | Electrochemical process for the preparation of n-phosphonomethyl glycine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL46057A0 IL46057A0 (en) | 1975-03-13 |
| IL46057A true IL46057A (en) | 1977-08-31 |
Family
ID=10474522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL46057A IL46057A (en) | 1973-11-30 | 1974-11-15 | Electrochemical process for the preparation of phosphonomethylglycine |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5084532A (en) |
| AT (1) | AT336636B (en) |
| AU (1) | AU7564574A (en) |
| BR (1) | BR7409912A (en) |
| CH (1) | CH594692A5 (en) |
| CU (1) | CU34156A (en) |
| DK (1) | DK600874A (en) |
| EG (1) | EG11659A (en) |
| ES (1) | ES432449A1 (en) |
| FR (1) | FR2253104B1 (en) |
| GB (1) | GB1494197A (en) |
| HU (1) | HU172665B (en) |
| IL (1) | IL46057A (en) |
| OA (1) | OA04849A (en) |
| SE (1) | SE7414840L (en) |
| TR (1) | TR18133A (en) |
| ZA (1) | ZA747254B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX4703E (en) * | 1976-12-20 | 1982-08-04 | Monsanto Co | IMPROVED PROCEDURE FOR THE PREPARATION OF MONKEY AND DISALS OF N-PHOSPHONOMETILGLICINA |
| US4211547A (en) * | 1978-12-22 | 1980-07-08 | Monsanto Company | N-Phosphonomethyliminodiacetonitrile and certain derivatives thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3835000A (en) * | 1972-12-21 | 1974-09-10 | Monsanto Co | Electrolytic process for producing n-phosphonomethyl glycine |
-
1973
- 1973-11-30 GB GB55663/73A patent/GB1494197A/en not_active Expired
-
1974
- 1974-11-12 ZA ZA00747254A patent/ZA747254B/en unknown
- 1974-11-15 IL IL46057A patent/IL46057A/en unknown
- 1974-11-18 CU CU34156A patent/CU34156A/en unknown
- 1974-11-19 DK DK600874A patent/DK600874A/da unknown
- 1974-11-20 AT AT930474A patent/AT336636B/en not_active IP Right Cessation
- 1974-11-22 TR TR18133A patent/TR18133A/en unknown
- 1974-11-22 AU AU75645/74A patent/AU7564574A/en not_active Expired
- 1974-11-26 SE SE7414840A patent/SE7414840L/xx not_active Application Discontinuation
- 1974-11-27 BR BR9912/74A patent/BR7409912A/en unknown
- 1974-11-28 JP JP49135938A patent/JPS5084532A/ja active Pending
- 1974-11-29 CH CH1589574A patent/CH594692A5/xx not_active IP Right Cessation
- 1974-11-29 HU HU74IE00000661A patent/HU172665B/en unknown
- 1974-11-29 OA OA55351A patent/OA04849A/en unknown
- 1974-11-29 FR FR7439210A patent/FR2253104B1/fr not_active Expired
- 1974-11-29 ES ES432449A patent/ES432449A1/en not_active Expired
- 1974-11-30 EG EG531/74A patent/EG11659A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5084532A (en) | 1975-07-08 |
| IL46057A0 (en) | 1975-03-13 |
| EG11659A (en) | 1977-09-30 |
| FR2253104A1 (en) | 1975-06-27 |
| ATA930474A (en) | 1976-09-15 |
| AU7564574A (en) | 1976-05-27 |
| BR7409912A (en) | 1976-05-25 |
| CH594692A5 (en) | 1978-01-31 |
| GB1494197A (en) | 1977-12-07 |
| TR18133A (en) | 1977-03-01 |
| OA04849A (en) | 1980-10-31 |
| DK600874A (en) | 1975-07-28 |
| ZA747254B (en) | 1975-11-26 |
| ES432449A1 (en) | 1976-11-01 |
| FR2253104B1 (en) | 1978-09-22 |
| HU172665B (en) | 1978-11-28 |
| SE7414840L (en) | 1975-06-02 |
| CU34156A (en) | 1980-10-30 |
| AT336636B (en) | 1977-05-10 |
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