WO1996020944A1 - Process for producing n-phosphonomethyl glycine - Google Patents
Process for producing n-phosphonomethyl glycine Download PDFInfo
- Publication number
- WO1996020944A1 WO1996020944A1 PCT/EP1995/005095 EP9505095W WO9620944A1 WO 1996020944 A1 WO1996020944 A1 WO 1996020944A1 EP 9505095 W EP9505095 W EP 9505095W WO 9620944 A1 WO9620944 A1 WO 9620944A1
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- Prior art keywords
- catalyst
- activated carbon
- cooh
- temperatures
- reaction
- Prior art date
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 abstract description 6
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 239000004009 herbicide Substances 0.000 abstract 1
- 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 9
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- 229940083542 sodium Drugs 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- -1 alcoholates Chemical class 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229940059913 ammonium carbonate Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940043379 ammonium hydroxide Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ZYMPIVZAUGZPKC-UHFFFAOYSA-N carbonic acid guanidine Chemical compound C(O)(O)=O.NC(=N)N.C(O)(O)=O.NC(=N)N ZYMPIVZAUGZPKC-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
Definitions
- the invention relates to a new process for the preparation of N-phosphonomethylglycine, a compound known to be herbicidally active
- N-phosphonomethyl-glycine is obtained if N-phosphonomethyl-iminodiacetic acid is oxidized with oxygen in the presence of water using an activated carbon catalyst (cf. DE-A 2519388 and EP-A 019445; cf. also EP -A 125363 and US-P 4397676).
- an activated carbon catalyst cf. DE-A 2519388 and EP-A 019445; cf. also EP -A 125363 and US-P 4397676.
- the yields vary greatly and the product is usually more or less contaminated by the starting material or by-products.
- the activated carbon catalysts used contain further, catalytically active constituents.
- the N-phosphonomethylglycine of the formula (I) can be obtained in good yields and in high purity by the process according to the invention in a technically simple manner using inexpensive auxiliaries.
- the method according to the invention thus represents a valuable enrichment of the prior art.
- the process according to the invention is carried out using oxygen.
- atmospheric oxygen can be used.
- pure oxygen that is to say largely freed from the other constituents of the air, is preferably used
- the process according to the invention is carried out in the presence of activated carbon as a catalyst.
- activated carbon Practically all known types of activated carbon come into consideration here, but it is not necessary to use activated carbon which is activated, that is to say which contains additional reaction-accelerating constituents, such as, for example, No ⁇ t pure activated carbon ("p A") can also be used as a catalyst in the process according to the invention
- the process according to the invention is carried out in the presence of a suitable basic reaction auxiliary.
- a suitable basic reaction auxiliary All customary inorganic or organic bases are suitable. These include, for example, alkali metal or alkaline earth metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates , such as lithium, sodium, potassium or calcium hydride, lithium, sodium or potassium amide, sodium or potassium methylate, sodium or potassium ethylate, sodium or potassium propylate, aluminum isopropoxide, sodium - or potassium tert-butoxide, sodium or potassium hydroxide, ammonium hydroxide, sodium, potassium or calcium acetate,
- reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C, especially at temperatures between 80 ° C and 1 10 ° C.
- the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
- 0.5 to 5 mol, preferably 1 to 3 mol of oxygen, 0.1 to 2 mol, preferably 0.5 to 1 mol of basic, are generally employed per mol of starting compound of the formula (II) Reaction aids, 10 to 200 g, preferably 20 to 100 g of activated carbon and 0.5 to 3 liters, preferably 1 to 2 liters of water.
- the N-phosphonomethyl-iminodiacetic acid of the formula (II) is initially introduced into water and the basic reaction auxiliary is added with slow heating. After practically a clear solution has been formed by briefly stirring this mixture at elevated temperature, the activated carbon is added and, at a further elevated temperature, oxygen is passed in via a frit over a period of several hours. When the reaction has ended, the mixture is filtered, if appropriate under reduced pressure, and the filtrate is acidified and concentrated with a strong acid, such as hydrochloric acid. The residue is stirred with a little water and the crystalline product isolated by suction. Manufacturing example
- N-phosphonomethyl-iminodiacetic acid 22.7 g (0.10 mol) of N-phosphonomethyl-iminodiacetic acid are placed in 200 ml of water and, with slow warming to 90 ° C., 9.0 g (0.05 mol) of guanidine carbonate are added after heating for 15 minutes 90 ° C become 5.0 g
- Activated carbon is added and oxygen is introduced into the boiling mixture (approx. 105 ° C) for three hours via a frit. Then it is cooled to room temperature (approx. 20 ° C), concentrated to approx. Half the volume and sucked off
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The active herbicidal agent N-phosphonomethyl glycine (I) (HO)2P(O)-CH2-NH-CH2-COOH is obtained with a good yield and high purity by reacting N-phosphonomethyl iminodiacetic acid of the formula (II) (HO)2P(O)-CH2-N(CH2-COOH)2 with oxygen in the presence of active carbon as the catalyst, of a basic reaction auxiliary and water as the diluent at temperatures of between 0 and 150 °C. Guanidine carbonate is particularly suitable as the basic reaction auxiliary and pure, not particularly activated ('p.A.') active carbon as the catalyst.
Description
Verfahren zur Herstellung von N-PhosphonomethylglvcinProcess for the preparation of N-phosphonomethylglvcin
Die Erfindung betrifft ein neues Verfahren zur Herstellung von N-Phosphono- methyl-glycin, einer als herbizid wirksam bekannten VerbindungThe invention relates to a new process for the preparation of N-phosphonomethylglycine, a compound known to be herbicidally active
Es ist bekannt, daß man N-Phosphonomethyl-glycin erhält, wenn man N- Phosphonomethyl-iminodiessigsäure in Gegenwart von Wasser mit Sauerstoff unter Verwendung eines Aktivkohle-Katalysators oxidiert (vgl. DE-A 2519388 und EP- A 019445; vgl. auch EP-A 125363 und US-P 4397676). Hierbei werden jedoch stark wechselnde Ausbeuten erzielt und das Produkt ist meist mehr oder weniger stark durch das Ausgangsmaterial oder Nebenprodukte verunreinigt. Die ver¬ wendeten Aktivkohle-Katalysatoren enthalten zudem in vielen Fällen weitere, katalytisch wirkende Bestandteile.It is known that N-phosphonomethyl-glycine is obtained if N-phosphonomethyl-iminodiacetic acid is oxidized with oxygen in the presence of water using an activated carbon catalyst (cf. DE-A 2519388 and EP-A 019445; cf. also EP -A 125363 and US-P 4397676). However, the yields vary greatly and the product is usually more or less contaminated by the starting material or by-products. In many cases, the activated carbon catalysts used contain further, catalytically active constituents.
Es wurde nun gefunden, daß man N-Phosphonomethyl-glycin der Formel (I)It has now been found that N-phosphonomethylglycine of the formula (I)
(HO)2P(O)-CH2-NH-CH2-COOH (I)(HO) 2 P (O) -CH 2 -NH-CH 2 -COOH (I)
in guten Ausbeuten und in hoher Reinheit erhält, wenn man N-Phosphonomethyl- iminodiessigsäure der Formel (II)obtained in good yields and in high purity if N-phosphonomethyliminodiacetic acid of the formula (II)
(HO)2P(O)-CH2-N(CH2-COOH)2 (II)(HO) 2 P (O) -CH 2 -N (CH 2 -COOH) 2 (II)
mit Sauerstoff in Gegenwart von Aktivkohle als Katalysator, in Gegenwart eines basischen Reaktionshilfsmittels und in Gegenwart von Wasser als Verdünnungs¬ mittel bei Temperaturen zwischen 0°C und 150°C umsetztwith oxygen in the presence of activated carbon as a catalyst, in the presence of a basic reaction auxiliary and in the presence of water as a diluent at temperatures between 0 ° C. and 150 ° C.
Überraschenderweise kann das N-Phosphonomethyl-glycin der Formel (I) nach dem erfindungsgemäßen Verfahren auf technisch einfache Weise unter Ver¬ wendung preiswerter Hilfsstoffe in guten Ausbeuten und in hoher Reinheit erhalten werden. Das erfindungsgemäße Verfahren stellt somit eine wertvolle Bereicherung des Standes der Technik dar.Surprisingly, the N-phosphonomethylglycine of the formula (I) can be obtained in good yields and in high purity by the process according to the invention in a technically simple manner using inexpensive auxiliaries. The method according to the invention thus represents a valuable enrichment of the prior art.
Der Reaktionsablauf beim erfindungsgemäßen Verfahren kann durch das folgende Formelschema skizziert werden
(HO)2P(0)-CH2-N(CH2COOH)2 — L*. (HO)2P(0)-CH2-NH-CH2-COOHThe course of the reaction in the process according to the invention can be outlined by the following formula (HO) 2 P (0) -CH 2 -N (CH 2 COOH) 2 - L *. (HO) 2 P (0) -CH 2 -NH-CH 2 -COOH
- C02 , -CH2Q- C0 2 , -CH 2 Q
Das erfmdungsgemaße Verfahren wird unter Verwendung von Sauerstoff durchge¬ führt Es kann hierbei Luftsauerstoff eingesetzt werden Vorzugsweise wird jedoch reiner, d h weitgehend von den übrigen Bestandteilen der Luft befreiter Sauerstoff verwendetThe process according to the invention is carried out using oxygen. In this case atmospheric oxygen can be used. However, pure oxygen, that is to say largely freed from the other constituents of the air, is preferably used
Das erfmdungsgemaße Verfahren wird in Gegenwart von Aktivkohle als Kata¬ lysator durchgeführt Es kommen hierbei praktisch alle bekannten Arten von Aktivkohle in Betracht, jedoch ist es nicht notwendig, besonders aktivierte, d h zusätzliche reaktionsbeschleunigende Bestandteile enthaltende Aktivkohle, wie z B Noπt einzusetzen Es kann also mit gutem Erfolg auch reine Aktivkohle ("p A ") als Katalysator beim erfindungsgemaßen Verfahren verwendet werdenThe process according to the invention is carried out in the presence of activated carbon as a catalyst. Practically all known types of activated carbon come into consideration here, but it is not necessary to use activated carbon which is activated, that is to say which contains additional reaction-accelerating constituents, such as, for example, Noπt pure activated carbon ("p A") can also be used as a catalyst in the process according to the invention
Das erfmdungsgemaße Verfahren wird in Gegenwart eines geeigneten basischen Reaktionshilfsmittels durchgeführt Als solche kommen alle üblichen anorgani¬ schen oder organischen Basen infrage Hierzu gehören beispielsweise Alkalimetall- oder Erdalkalimetall-hydπde, -hydroxide, -amide, -alkoholate, -acetate, -carbonate oder -hydrogencarbonate, wie beispielsweise Lithium-, Natrium-, Kalium- oder Calcium-hydπd, Lithium-, Natrium- oder Kahum-amid, Natrium- oder Kalium- methylat, Natrium- oder Kahum-ethylat, Natrium- oder Kahum-propylat, Aluminiumisopropylat, Natrium- oder Kahum-tert-butylat, Natrium- oder Kalium- hydroxid, Ammoniumhydroxid, Natrium-, Kalium- oder Calcium-acetat,The process according to the invention is carried out in the presence of a suitable basic reaction auxiliary. All customary inorganic or organic bases are suitable. These include, for example, alkali metal or alkaline earth metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates , such as lithium, sodium, potassium or calcium hydride, lithium, sodium or potassium amide, sodium or potassium methylate, sodium or potassium ethylate, sodium or potassium propylate, aluminum isopropoxide, sodium - or potassium tert-butoxide, sodium or potassium hydroxide, ammonium hydroxide, sodium, potassium or calcium acetate,
Ammoniumacetat, Natrium-, Kalium- oder Calcium-carbonat, Ammoniumcarbonat, Natrium- oder Kahum-hydrogencarbonat, sowie basische organische Stickstoff Ver¬ bindungen, wie Tπmethylamin, Tπethylamin, Tπpropylamin, Tπbutylamin, Ethyl- dnsopropylamin, N,N-Dιmethylcyclohexylamιn, Dicyclohexylamin, Ethyl-dicyclo- hexylamin, N,N-Dιmethylanιlιn, N,N-Dιmethyl-benzylamιn, Pyπdin, 2-Methyl-, 3-Ammonium acetate, sodium, potassium or calcium carbonate, ammonium carbonate, sodium or potassium hydrogen carbonate, and also basic organic nitrogen compounds, such as tπmethylamine, tπethylamine, tπpropylamine, tπbutylamine, ethyl dnsopropylamine, N, N-dimethylcyclohexylamine, dicyclohexane Ethyl-dicyclo-hexylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, 2-methyl, 3-
Methyl- und 4-Methyl-pyπdιn, 2,4-Dιmethyl-, 2,6-Dιmethyl-, 3,4-Dιmethyl- und 3,5-Dιmethyl-pyπdιn, 5-Ethyl-2-methyl-pyπdιn, N-Methylpipeπdin 4-(N,N-Dι- methylamιno)-pyπdιn, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN oder Diazabicloundecen (DBU), ferner auch Guanidin und dessen Salze, wie z B Guanidin-carbonat
Vorzugsweise wird Guanidin-carbonat als basisches Reaktionshilfsmittel beim er¬ findungsgemäßen Verfahren eingesetzt.Methyl- and 4-methyl-pyπdιn, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyπdιn, 5-ethyl-2-methyl-pyπdιn, N- Methylpipeπdin 4- (N, N-Dι- methylamιno) -pyπdιn, diazabicyclooctane (DABCO), diazabicyclonones (DBN or diazabicloundecene (DBU), and also guanidine and its salts, such as guanidine carbonate Guanidine carbonate is preferably used as the basic reaction auxiliary in the process according to the invention.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 150°C, vorzugsweise bei Temperaturen zwischen 20°C und 120°C, insbesondere bei Temperaturen zwischen 80°C und 1 10°C.The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C, especially at temperatures between 80 ° C and 1 10 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durch¬ geführt. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem Druck - im allgemeinen zwischen 0, 1 bar und 10 bar - zu arbeiten.The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man pro Mol an Aus¬ gangsverbindung der Formel (II) im allgemeinen 0,5 bis 5 Mol, vorzugsweise 1 bis 3 Mol Sauerstoff, 0,1 bis 2 Mol, vorzugsweise 0,5 bis 1 Mol an basischem Re¬ aktionshilfsmittel, 10 bis 200 g, vorzugsweise 20 bis 100 g Aktivkohle und 0,5 bis 3 Liter, vorzugsweise 1 bis 2 Liter Wasser ein.To carry out the process according to the invention, 0.5 to 5 mol, preferably 1 to 3 mol of oxygen, 0.1 to 2 mol, preferably 0.5 to 1 mol of basic, are generally employed per mol of starting compound of the formula (II) Reaction aids, 10 to 200 g, preferably 20 to 100 g of activated carbon and 0.5 to 3 liters, preferably 1 to 2 liters of water.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird die N-Phosphonomethyl-iminodiessigsäure der Formel (II) in Wasser vorgelegt und unter langsamem Erwärmen mit dem basischen Reaktionshilfsmittel versetzt. Nachdem bei kurzem Rühren dieser Mischung bei erhöhter Temperatur praktisch eine klare Lösung entstanden ist, wird die Aktivkohle dazu gegeben und bei weiterhin erhöhter Temperatur über mehrere Stunden verteilt Sauerstoff über eine Fritte eingeleitet. Nach dem Ende der Umsetzung wird - gegebenenfalls unter ver¬ mindertem Druck - filtriert, das Filtrat mit einer starken Säure, wie z.B. Salzsäure, angesäuert und eingeengt. Der Rückstand wird mit wenig Wasser verrührt und das kristallin angefallene Produkt durch Absaugen isoliert.
HerstellungsbeispielIn a preferred embodiment of the process according to the invention, the N-phosphonomethyl-iminodiacetic acid of the formula (II) is initially introduced into water and the basic reaction auxiliary is added with slow heating. After practically a clear solution has been formed by briefly stirring this mixture at elevated temperature, the activated carbon is added and, at a further elevated temperature, oxygen is passed in via a frit over a period of several hours. When the reaction has ended, the mixture is filtered, if appropriate under reduced pressure, and the filtrate is acidified and concentrated with a strong acid, such as hydrochloric acid. The residue is stirred with a little water and the crystalline product isolated by suction. Manufacturing example
(HO)2P(O)-CH2-NH-CH2-COOH (I)(HO) 2 P (O) -CH 2 -NH-CH 2 -COOH (I)
22,7 g (0,10 Mol) N-Phosphonomethyl-iminodiessigsaure werden in 200 ml Wasser vorgelegt und bei langsamem Erwarmen auf 90°C mit 9,0 g (0,05 Mol) Guanidin-carbonat versetzt Nach 15-minutigem Erhitzen auf 90°C werden 5,0 g22.7 g (0.10 mol) of N-phosphonomethyl-iminodiacetic acid are placed in 200 ml of water and, with slow warming to 90 ° C., 9.0 g (0.05 mol) of guanidine carbonate are added after heating for 15 minutes 90 ° C become 5.0 g
Aktivkohle ("p.A ") dazu gegeben und in die siedende Mischung (ca 105°C) wird drei Stunden lang Sauerstoff über eine Fritte eingeleitet Dann wird auf Raum¬ temperatur (ca. 20°C) abgekühlt, auf ca das halbe Volumen eingeengt und abge¬ saugtActivated carbon ("pA") is added and oxygen is introduced into the boiling mixture (approx. 105 ° C) for three hours via a frit. Then it is cooled to room temperature (approx. 20 ° C), concentrated to approx. Half the volume and sucked off
Man erhalt 4,3 g des Guanidin-Salzes von N-Phosphonomethyl-glycin (ent¬ sprechend 19 mMol N-Phosphonomethyl-glycin oder einer Ausbeute von 19% der Theorie) Das Filtrat wird mit konz Salzsaure angesäuert und eingeengt Der Ruckstand wird mit ca 10 ml Wasser verrührt und das kristallin angefallene Produkt durch Absaugen isoliert Man erhalt hierbei 10,4 g N-Phosphonomethyl- glycin (62% der Theorie) vom Schmelzpunkt 235°C4.3 g of the guanidine salt of N-phosphonomethyl-glycine are obtained (corresponding to 19 mmol of N-phosphonomethyl-glycine or a yield of 19% of theory). The filtrate is acidified with concentrated hydrochloric acid and concentrated. The residue is extracted with approx 10 ml of water are stirred and the crystalline product is isolated by suction. This gives 10.4 g of N-phosphonomethylglycine (62% of theory) with a melting point of 235 ° C.
Gesamt- Ausbeute 81% der Theorie
Total yield 81% of theory
Claims
1. Verfahren zur Herstellung von N-Phosphonomethylglycin der Formel (I)1. Process for the preparation of N-phosphonomethylglycine of the formula (I)
(HO)2P(O)-CH2-NH-CH2-COOH (I) ' (HO) 2 P (O) -CH 2 -NH-CH 2 -COOH (I) '
durch Oxidation von N-Phosphonomethyl-iminodiessigsaure der Formel (II)by oxidation of N-phosphonomethyl-iminodiacetic acid of the formula (II)
(HO)2P(O)-CH2-N(CH2-COOH)2 (II)(HO) 2 P (O) -CH 2 -N (CH 2 -COOH) 2 (II)
mit Sauerstoff in Gegenwart eines Katalysators und in Gegenwart von Wasser als Verdünnungsmittel, dadurch gekennzeichnet, daß man die Umsetzung in Gegenwart eines basischen Reaktionshilfsmittels bei Temperaturen zwischen 0°C und 1 50°C durchfuhrt, wobei man als Katalysator Aktivkohle einsetztwith oxygen in the presence of a catalyst and in the presence of water as a diluent, characterized in that the reaction is carried out in the presence of a basic reaction auxiliary at temperatures between 0 ° C and 1 50 ° C, with activated carbon being used as the catalyst
2 Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man die Umsetzung bei Temperaturen zwischen 20°C und 120°C durchführt.2 The method according to claim 1, characterized in that one carries out the reaction at temperatures between 20 ° C and 120 ° C.
3 Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man bei Tempera¬ turen zwischen 80°C und 1 10°C arbeitet3 The method according to claim 1, characterized in that one works at temperatures between 80 ° C and 1 10 ° C.
4 Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man als basisches4 The method according to claim 1, characterized in that as a basic
Reaktionshilfsmittel Guanidin-carbonat einsetztReaction aids used guanidine carbonate
5 Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man als Aktivkohle-Katalysator reine, nicht besonders aktivierte (keine zusatzlichen reaktionsbeschleunigenden Bestandteile enthaltende) Aktivkohle ("p A ") einsetzt 5 The method according to claim 1, characterized in that the activated carbon catalyst is pure, not particularly activated (containing no additional reaction-accelerating constituents) activated carbon ("p A")
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU43471/96A AU4347196A (en) | 1995-01-04 | 1995-12-22 | Process for producing n-phosphonomethyl glycine |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995100121 DE19500121A1 (en) | 1995-01-04 | 1995-01-04 | Process for the preparation of N-phosphonomethylglycine |
| DE19500121.4 | 1995-01-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996020944A1 true WO1996020944A1 (en) | 1996-07-11 |
Family
ID=7750987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1995/005095 WO1996020944A1 (en) | 1995-01-04 | 1995-12-22 | Process for producing n-phosphonomethyl glycine |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU4347196A (en) |
| DE (1) | DE19500121A1 (en) |
| WO (1) | WO1996020944A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058537A1 (en) * | 1998-05-14 | 1999-11-18 | Calgon Carbon Corporation | Method for the manufacture of n - phosphonomethylglycine from n - phosphonomethyliminodiacetic acid using a catalytic carbon |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5942643A (en) * | 1998-05-14 | 1999-08-24 | Calgon Carbon Corporation | Method for the manufacture of N-phosphonomethylglycine from N-phosphonomethyliminodiacetic acid using a low temperature catalytic carbon |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2519388A1 (en) * | 1974-05-01 | 1975-11-13 | Monsanto Co | METHOD FOR PRODUCING N-PHOSPHONE METHYLGLYCINE |
| US4147719A (en) * | 1976-12-20 | 1979-04-03 | Monsanto Company | Process for producing N-phosphonomethylglycine salts |
| EP0088180A1 (en) * | 1982-03-08 | 1983-09-14 | Geshuri Laboratories Ltd. | N-phosphonomethylglycine derivatives |
| EP0125363A1 (en) * | 1983-05-17 | 1984-11-21 | Geshuri Laboratories Ltd. | Process for producing N-phosphonomethylglycine acid |
-
1995
- 1995-01-04 DE DE1995100121 patent/DE19500121A1/en not_active Withdrawn
- 1995-12-22 AU AU43471/96A patent/AU4347196A/en not_active Abandoned
- 1995-12-22 WO PCT/EP1995/005095 patent/WO1996020944A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2519388A1 (en) * | 1974-05-01 | 1975-11-13 | Monsanto Co | METHOD FOR PRODUCING N-PHOSPHONE METHYLGLYCINE |
| US4147719A (en) * | 1976-12-20 | 1979-04-03 | Monsanto Company | Process for producing N-phosphonomethylglycine salts |
| EP0088180A1 (en) * | 1982-03-08 | 1983-09-14 | Geshuri Laboratories Ltd. | N-phosphonomethylglycine derivatives |
| EP0125363A1 (en) * | 1983-05-17 | 1984-11-21 | Geshuri Laboratories Ltd. | Process for producing N-phosphonomethylglycine acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058537A1 (en) * | 1998-05-14 | 1999-11-18 | Calgon Carbon Corporation | Method for the manufacture of n - phosphonomethylglycine from n - phosphonomethyliminodiacetic acid using a catalytic carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19500121A1 (en) | 1996-07-11 |
| AU4347196A (en) | 1996-07-24 |
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