WO1997005147A1 - Method of preparing n-phosphonomethylglycine esters - Google Patents
Method of preparing n-phosphonomethylglycine esters Download PDFInfo
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- WO1997005147A1 WO1997005147A1 PCT/EP1996/003156 EP9603156W WO9705147A1 WO 1997005147 A1 WO1997005147 A1 WO 1997005147A1 EP 9603156 W EP9603156 W EP 9603156W WO 9705147 A1 WO9705147 A1 WO 9705147A1
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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 System
- 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, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Definitions
- the invention relates to a new process for the preparation of N-phosphonomethylglycine esters, which are known as herbicidally active compounds.
- N-phosphonomethyl-glycine methyl ester is obtained by passing gaseous hydrogen chloride through a suspension of N-phosphonomethyl-glycine in methanol until a clear solution is obtained, the solution is concentrated under reduced pressure, and the residue is removed with a Methanol solution mixed, which contains at least one equivalent of triethylamine, the solvent is removed under reduced pressure, the residue is extracted with ether and then with methanol (cf. DE 2152826 - Example 5, DE 2166573 - Example 3, US 3977860 - Example 5 ).
- the yields vary greatly and the product is usually more or less contaminated by the starting material or by-products.
- the refurbishment is also too complex for industrial purposes.
- N-phosphonomethylglycine esters of the general formula (I) N-phosphonomethylglycine esters of the general formula (I)
- R represents alkyl
- N-phosphonomethylglycine esters of the general formula (I) can be obtained in a technically simple manner in good yields and in high purity using inexpensive auxiliaries by the process according to the invention, the isolation of the products in particular being very simple.
- the method according to the invention thus represents a valuable enrichment of the prior art.
- the invention preferably relates to the preparation of N-phosphonomethylglycine esters of the formula (I) in which
- R represents straight-chain or branched alkyl having 2 to 10 carbon atoms.
- the invention relates in particular to the preparation of N-phosphonom ethyl glycine esters of the formula (I) in which
- R represents ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl.
- the alcohols to be used as starting materials in the process according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (III).
- R preferably or in particular has the meaning which has already been given above for the compounds of the formula (I) to be prepared according to the invention, preferably or as particularly preferred.
- Suitable acids are preferably protonic acids from the mineral acid series, such as Hydrogen chloride (hydrogen chloride), hydrogen bromide
- Hydrogen chloride is very particularly preferred as the acid to be used in the process according to the invention.
- the acid adducts of the compounds of the formula (I) obtained in the process according to the invention are treated with acid binders.
- acid binders Such as come preferably di- (C 3 -C 6 -alkyl) amines with branched alkyl groups, di- (C 5 -C 6 -cycloalkyl) amines, tri- (C j -C 6 -alkyl) amines with straight-chain and / or ver ⁇ branched alkyl groups, N, N-di- (C j -C 6 alkyl) -N- (C 5 -C 6 cycloalkyl) amines with geradkettigten and / or branched alkyl groups, N, N-di - (C 5 -C 6 cycloalkyl) -N- (C j -C 8 alkyl ⁇ amines with straight-chain or branched alkyl groups, N, N-di- (C ] -
- (C r C 6 alkyl) pyridines di (C 1 -C 6 alkyl) pyridines and tri ⁇ j -C 8 alkyl ⁇ pyridines, each with straight-chain or branched alkyl groups.
- Triethylamine is very particularly preferred as an acid binder in the process according to the invention.
- reaction temperatures can be varied within a substantial range when carrying out the process according to the invention.
- the 1st stage is carried out at temperatures between 40 ° C and 150 ° C, preferably between
- the 2nd stage at temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 40 ° C.
- the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under increased or reduced pressure - generally between 0.1 bar and 10 bar
- one mole of phosphonomethylglycine of the formula (II) is generally between 1 and 1000 moles, preferably between 10 and 100 moles of an alcohol of the formula (III) and between 0.5 and 5 moles, preferably between 0.9 and 1.5 mol of an acid and between 0.5 and 5 mol, preferably between 0.9 and 1.5 mol of an acid binder
- the phosphonomethylglycine of the formula (II) is suspended in an alcohol of the formula (III) and an acid is slowly metered in.
- the reaction mixture is then kept at the required temperature until the reaction is practically complete.
- the mixture is then concentrated under reduced pressure, taken up again in an alcohol of the formula (III) and mixed with an acid binder.
- the product of the formula (I) is obtained in crystalline form and can be isolated by suction
- N-phosphonomethylglycine esters of the formula (I) to be prepared by the process according to the invention are already known as herbicidally active compounds (cf. DE 2152826, DE 2166573, US 3977860) Manufacturing examples:
- Hydrogen chloride gas is introduced into a suspension of 200 g (1.2 mol) of N-phosphonomethylglycine in 3000 ml of ethanol until saturation. Then the
- the reaction mixture was heated under reflux for 3 hours and then - after cooling to room temperature - concentrated in a water jet vacuum.
- the residue is dissolved in 1500 ml of ethanol and triethylamine (approx. 140 g) is added dropwise to this solution with vigorous stirring at room temperature (approx. 20 ° C.) until the color changes from reddish brown to light yellow.
- the crystalline product obtained is isolated by suction.
Abstract
Disclosed is a technically simple method of preparing, in very good yields, highly pure N-phosphonomethylglycine esters, having a herbicidal action, of the formula (I) (HO)2P(O)-CH2-NH-CH2-CO-O-R, in which R is alkyl, by reacting N-phosphonomethylglycine of the formula (II) (HO)2P(O)-CH2-NH-CH2-COOH with alcohols of the general formula (III) HO-R at temperatures between 40 and 150 °C in the presence of an acid (1st stage) and then reacting, at temperatures between 0 and 60 °C, the acid adducts of the compounds of formula (I) - optionally after isolating them - with an acid binder selected from the group comprising dialkylamines, dicycloalkylamines, trialkylamines and N,N-dialkyl-N-cycloalkylamines, N,N-dicycloalkyl-N-alkylamines, N,N-dialkylamilines and (N,N)-dialkylbenzylamines plus pyridine, alkylpyridines, dialkylpyridines and trialkylpyridines, the acid binder being measured into the reaction mixture slowly with thorough mixing (2nd stage).
Description
Verfahren zur Herstellung von N-Phosphonomethyl-glvcinesternProcess for the preparation of N-phosphonomethyl glvcine esters
Die Erfindung betrifft ein neues Verfahren zur Herstellung von N-Phosphono- methyl-glycinestern, welche als herbizid wirksame Verbindungen bekannt sind.The invention relates to a new process for the preparation of N-phosphonomethylglycine esters, which are known as herbicidally active compounds.
Es ist bekannt, daß man N-Phosphonomethyl-glycin-methylester erhält, wenn man gasförmigen Chlorwasserstoff durch eine Suspension von N-Phosphonomethyl- glycin in Methanol leitet, bis eine klare Lösung erhalten wird, die Lösung unter vermindertem Druck konzentriert, den Rückstand mit einer Methanollösung ver- mischt, die mindestens ein Äquivalent Triethylamin enthält, das Lösungsmittel bei vermindertem Druck entfernt, den Rückstand mit Ether und dann mit Methanol ex¬ trahiert (vgl. DE 2152826 - Beispiel 5, DE 2166573 - Beispiel 3, US 3977860 - Beispiel 5).It is known that N-phosphonomethyl-glycine methyl ester is obtained by passing gaseous hydrogen chloride through a suspension of N-phosphonomethyl-glycine in methanol until a clear solution is obtained, the solution is concentrated under reduced pressure, and the residue is removed with a Methanol solution mixed, which contains at least one equivalent of triethylamine, the solvent is removed under reduced pressure, the residue is extracted with ether and then with methanol (cf. DE 2152826 - Example 5, DE 2166573 - Example 3, US 3977860 - Example 5 ).
Hierbei werden jedoch stark wechselnde Ausbeuten erzielt und das Produkt ist meist mehr oder weniger stark durch das Ausgangsmaterial oder Nebenprodukte verunreinigt. Die Aufarbeitung ist zudem für industrielle Belange zu aufwendig.However, the yields vary greatly and the product is usually more or less contaminated by the starting material or by-products. The refurbishment is also too complex for industrial purposes.
Es wurde nun gefunden, daß man N-Phosphonomethyl-glycinester der allgemeinen Formel (I)It has now been found that N-phosphonomethylglycine esters of the general formula (I)
(HO)2P(O)-CH2-NH-CH2-CO-O-R (I)(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OR (I)
in welcherin which
R für Alkyl steht,R represents alkyl,
auf technisch einfache Weise in sehr guten Ausbeuten und in hoher Reinheit erhält, wenn man N-Phosphonomethyl-glycin der Formel (II)can be obtained in a technically simple manner in very good yields and in high purity if N-phosphonomethylglycine of the formula (II)
(HO)2P(O)-CH2-NH-CH2-COOH (II)(HO) 2 P (O) -CH 2 -NH-CH 2 -COOH (II)
mit Alkoholen der allgemeinen Formel (III)with alcohols of the general formula (III)
HO-R (III)
in welcherHO-R (III) in which
R die oben angegebene Bedeutung hat,R has the meaning given above,
in Gegenwart einer Säure bei Temperaturen zwischen 40°C und 150°C umsetzt (1. Stufe) und die hierbei gebildeten Säureaddukte der Verbindungen der Formel (I) - gegebenenfalls nach Zwischenisolierung - mit einem Säurebindemittel aus derin the presence of an acid at temperatures between 40 ° C. and 150 ° C. (1st stage) and the acid adducts formed in this way of the compounds of the formula (I) - optionally after intermediate isolation - with an acid binder from the
Reihe der Dialkylamine, Dicycloalkylamine, Trialkylamine, N,N-Dialkyl-N-cyclo- alkylamine, N,N-Dicycloalkyl-N-alkylamine, N,N-Dialkyl-aniline und N,N-Dialkyl- benzylamine sowie Pyridin, Alkylpyridine, Dialkylpyridine und Trialkylpyridine bei Temperaturen zwischen 0°C und 60°C umsetzt, wobei das Säurebindemittel unter guter Durchmischung langsam in das Reaktionsgemisch eindosiert wirdSeries of dialkylamines, dicycloalkylamines, trialkylamines, N, N-dialkyl-N-cycloalkylamines, N, N-dicycloalkyl-N-alkylamines, N, N-dialkyl-anilines and N, N-dialkylbenzylamines and pyridine, alkylpyridines, Reacts dialkylpyridines and trialkylpyridines at temperatures between 0 ° C and 60 ° C, the acid binder being slowly metered into the reaction mixture with thorough mixing
(2. Stufe).(2nd stage).
Überraschenderweise können die N-Phosphonomethyl-glycinester der allgemeinen Formel (I) nach dem erfindungsgemaßen Verfahren auf technisch einfache Weise unter Verwendung preiswerter Hilfsstoffe in guten Ausbeuten und in hoher Rein- heit erhalten werden, wobei insbesondere die Isolierung der Produkte sehr einfach ist. Das erfindungsgemäße Verfahren stellt somit eine wertvolle Bereicherung des Standes der Technik dar.Surprisingly, the N-phosphonomethylglycine esters of the general formula (I) can be obtained in a technically simple manner in good yields and in high purity using inexpensive auxiliaries by the process according to the invention, the isolation of the products in particular being very simple. The method according to the invention thus represents a valuable enrichment of the prior art.
Die Erfindung betrifft vorzugsweise die Herstellung von N-Phosphonomethyl- glycinestern der Formel (I), in welcherThe invention preferably relates to the preparation of N-phosphonomethylglycine esters of the formula (I) in which
R für geradkettiges oder verzweigtes Alkyl mit 2 bis 10 Kohlenstoffatomen steht.R represents straight-chain or branched alkyl having 2 to 10 carbon atoms.
Die Erfindung betrifft insbesondere die Herstellung von N-Phosphonom ethyl - glycinestern der Formel (I), in welcherThe invention relates in particular to the preparation of N-phosphonom ethyl glycine esters of the formula (I) in which
R für Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl steht.R represents ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl.
Verwendet man beispielsweise N-Phosphonomethyl-glycin und Ethanol als Aus¬ gangsstoffe, Hydrogenbromid als Säure und Tributylamin als Säurebindemittel, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren durch das folgende Formelschema skizziert werden:
(HO),P(0)-CH2-NH-CH2-COOHIf, for example, N-phosphonomethylglycine and ethanol are used as starting materials, hydrogen bromide as acid and tributylamine as acid binder, the course of the reaction in the process according to the invention can be outlined using the following formula: (HO), P (0) -CH 2 -NH-CH 2 -COOH
(1) HBr (2) N(C4H9)3 (1) HBr (2) N (C 4 H 9 ) 3
(HO)2P(0)-CH,-NH-CH2-CO - -OC. 2H" ",5(HO) 2 P (0) -CH, -NH-CH 2 -CO - -OC. 2H "", 5
HOC2H5 HOC 2 H 5
Die beim erfindungsgemäßen Verfahren zur Herstellung der Verbindungen der Formel (I) als Ausgangsstoffe zu verwendenden Alkohole sind durch die Formel (III) allgemein definiert. In der Formel (III) hat R vorzugsweise bzw. insbesondere diejenige Bedeutung, die bereits oben bei der Beschreibung der erfindungsgemäß herzustellenden Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für R angegeben wurde.The alcohols to be used as starting materials in the process according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (III). In the formula (III), R preferably or in particular has the meaning which has already been given above for the compounds of the formula (I) to be prepared according to the invention, preferably or as particularly preferred.
Das erfindungsgemäße Verfahren wird unter Verwendung einer Säure durch¬ geführt. Geeignete Säuren sind hierbei vorzugsweise Protonensäuren aus der Reihe der Mineral säuren, wie z.B. Hydrogenchlorid (Chlorwasserstoff), HydrogenbromidThe process according to the invention is carried out using an acid. Suitable acids are preferably protonic acids from the mineral acid series, such as Hydrogen chloride (hydrogen chloride), hydrogen bromide
(Bromwasserstoff), Hydrogeniodid (Iodwasserstoff), Schwefelsäure und Phosphor¬ säure, oder auch organische Protonensäuren vergleichbarer Acidität, wie z.B. Methansulfonsäure, Ethansulfonsäure, Propansulfonsäure, Butansulfonsäure, Tri¬ fluoressigsäure, Trifluormethansulfonsäure, Benzol sulfonsaure und p-Toluol sulf on- säure.(Hydrogen bromide), hydrogen iodide (hydrogen iodide), sulfuric acid and phosphoric acid, or also organic protonic acids of comparable acidity, e.g. Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
Hydrogenchlorid wird als beim erfindungsgemäßen Verfahren einzusetzende Säure ganz besonders bevorzugt.Hydrogen chloride is very particularly preferred as the acid to be used in the process according to the invention.
Die beim erfindungsgemäßen Verfahren anfallenden Säureaddukte der Ver¬ bindungen der Formel (I) werden mit Säurebindemitteln behandelt. Als solche kommen vorzugsweise Di-(C3-C6-alkyl)-amine mit verzweigten Alkylgruppen, Di- (C5-C6-cycloalkyl)-amine, Tri-(Cj-C6-alkyl)-amine mit geradkettigen und/oder ver¬ zweigten Alkylgruppen, N,N-Di-(Cj-C6-alkyl)-N-(C5-C6-cycloalkyl)-amine mit geradkettigten und/oder verzweigten Alkylgruppen, N,N-Di-(C5-C6-cycloalkyl)-N- (Cj-C8-alky^-amine mit geradkettigen oder verzweigten Alkylgruppen, N,N-Di- (C]-C4-alkyl)-aniline und N,N-Di-(C|-C4-alkyl)-benzylamine sowie Pyridin,The acid adducts of the compounds of the formula (I) obtained in the process according to the invention are treated with acid binders. Such as come preferably di- (C 3 -C 6 -alkyl) amines with branched alkyl groups, di- (C 5 -C 6 -cycloalkyl) amines, tri- (C j -C 6 -alkyl) amines with straight-chain and / or ver¬ branched alkyl groups, N, N-di- (C j -C 6 alkyl) -N- (C 5 -C 6 cycloalkyl) amines with geradkettigten and / or branched alkyl groups, N, N-di - (C 5 -C 6 cycloalkyl) -N- (C j -C 8 alkyl ^ amines with straight-chain or branched alkyl groups, N, N-di- (C ] -C 4 alkyl) anilines and N, N-di- (C | to C4 alkyl) -benzylamine and pyridine,
(CrC6-Alkyl)-pyridine, Di-(C1-C6-alkyl)-pyridine und Tri-^j-C8-alky^-pyridine mit jeweils geradkettigen oder verzweigten Alkylgruppen in Betracht.(C r C 6 alkyl) pyridines, di (C 1 -C 6 alkyl) pyridines and tri ^ j -C 8 alkyl ^ pyridines, each with straight-chain or branched alkyl groups.
Von den Pyridinen sind die folgenden von besonderem Interesse: 2-Methyl-, 3-Methyl-, 4-Methyl-, 2,4-Dimethyl-, 2,6-Dimethyl-, 2,4,6-Trimethyl- und 5-Ethyl- 2-methyl-pyridin.
Triethylamin wird als Säurebindemittel beim erfindungsgemäßen Verfahren ganz besonders bevorzugt.Of the pyridines, the following are of particular interest: 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2,4,6-trimethyl and 5- Ethyl 2-methyl pyridine. Triethylamine is very particularly preferred as an acid binder in the process according to the invention.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen führt man die 1. Stufe bei Temperaturen zwischen 40°C und 150°C, vorzugsweise zwischenThe reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, the 1st stage is carried out at temperatures between 40 ° C and 150 ° C, preferably between
60°C und 120°C durch, die 2. Stufe bei Temperaturen zwischen 0°C und 60°C, vorzugsweise zwischen 10°C und 40°C.60 ° C and 120 ° C, the 2nd stage at temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 40 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durch¬ geführt Es ist jedoch auch möglich, das erfindungsgemäße Verfahren unter er- hohtem oder vermindertem Druck - im allgemeinen zwischen 0,1 bar und 10 bar - durchzufuhrenThe process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under increased or reduced pressure - generally between 0.1 bar and 10 bar
Zur Durchfuhrung des erfindungsgemäßen Verfahrens setzt man auf ein Mol Phosphonomethyl-glycin der Formel (II) im allgemeinen zwischen 1 und 1000 Mol, vorzugsweise zwischen 10 und 100 Mol eines Alkohols der Formel (III) und zwischen 0,5 und 5 Mol, vorzugsweise zwischen 0,9 und 1,5 Mol einer Saure sowie zwischen 0,5 und 5 Mol, vorzugsweise zwischen 0,9 und 1,5 Mol eines Saurebindemittels einTo carry out the process according to the invention, one mole of phosphonomethylglycine of the formula (II) is generally between 1 and 1000 moles, preferably between 10 and 100 moles of an alcohol of the formula (III) and between 0.5 and 5 moles, preferably between 0.9 and 1.5 mol of an acid and between 0.5 and 5 mol, preferably between 0.9 and 1.5 mol of an acid binder
In einer bevorzugten Ausführungsform des erfindungsgemaßen Verfahrens wird das Phosphonomethyl-glycin der Formel (II) in einem Alkohol der Formel (III) suspendiert und eine Saure wird langsam eindosiert Die Reaktionsmischung wird dann bei der erforderlichen Temperatur gehalten, bis die Umsetzung praktisch ab¬ geschlossen ist Anschließend wird unter vermindertem Druck eingeengt, wieder in einem Alkohol der Formel (III) aufgenommen und mit einem Saurebindemittel versetzt Das Produkt der Formel (I) fallt dabei in kristalliner Form an und kann durch Absaugen isoliert werdenIn a preferred embodiment of the process according to the invention, the phosphonomethylglycine of the formula (II) is suspended in an alcohol of the formula (III) and an acid is slowly metered in. The reaction mixture is then kept at the required temperature until the reaction is practically complete The mixture is then concentrated under reduced pressure, taken up again in an alcohol of the formula (III) and mixed with an acid binder. The product of the formula (I) is obtained in crystalline form and can be isolated by suction
Die nach dem erfindungsgemaßen Verfahren herzustellenden N-Phosphonomethyl- glycinester der Formel (I) sind bereits als herbizid wirksame Verbindungen bekannt (vgl DE 2152826, DE 2166573, US 3977860)
Herstellungsbeispiele:The N-phosphonomethylglycine esters of the formula (I) to be prepared by the process according to the invention are already known as herbicidally active compounds (cf. DE 2152826, DE 2166573, US 3977860) Manufacturing examples:
Beispiel 1example 1
(HO)2P(O)-CH2-NH-CH2-CO-O-C2H5 (HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OC 2 H 5
In eine Suspension von 200 g (1,2 Mol) N-Phosphonomethyl-glycin in 3000 ml Ethanol wird Chlorwasserstoff-Gas bis zur Sättigung eingeleitet. Dann wird dieHydrogen chloride gas is introduced into a suspension of 200 g (1.2 mol) of N-phosphonomethylglycine in 3000 ml of ethanol until saturation. Then the
Reaktionsmischung 3 Stunden unter Rückfluß erhitzt und anschließend - nach Ab¬ kühlen auf Raumtemperatur - im Wasserstrahlvakuum eingeengt. Der Rückstand wird in 1500 ml Ethanol gelöst und zu dieser Lösung wird unter starkem Rühren bei Raumtemperatur (ca. 20°C) Triethylamin (ca. 140 g) tropfenweise gegeben, bis ein Farbumschlag von rötlich-braun nach hellgelb erfolgt. Das hierbei kristallin an¬ fallende Produkt wird durch Absaugen isoliert.The reaction mixture was heated under reflux for 3 hours and then - after cooling to room temperature - concentrated in a water jet vacuum. The residue is dissolved in 1500 ml of ethanol and triethylamine (approx. 140 g) is added dropwise to this solution with vigorous stirring at room temperature (approx. 20 ° C.) until the color changes from reddish brown to light yellow. The crystalline product obtained is isolated by suction.
Man erhält 201 g (85% der Theorie) N-Phosphonomethyl-glycin-ethylester vom Schmelzpunkt>220°C.
201 g (85% of theory) of N-phosphonomethyl-glycine-ethyl ester with a melting point> 220 ° C. are obtained.
Claims
1. Verfahren zur Herstellung von N-Phosphonomethyl-glycinestern der Formel (I)1. Process for the preparation of N-phosphonomethylglycine esters of the formula (I)
(HO)2P(O)-CH2-NH-CH2-CO-O-R (I)(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OR (I)
in welcherin which
R für Alkyl steht,R represents alkyl,
dadurch gekennzeichnet, daß man N-Phosphonomethyl-glycin der Formel (H)characterized in that N-phosphonomethyl-glycine of the formula (H)
(HO)2P(O)-CH2-NH-CH2-COOH (II)(HO) 2 P (O) -CH 2 -NH-CH 2 -COOH (II)
mit Alkoholen der allgemeinen Formel (III)with alcohols of the general formula (III)
HO-R (III)HO-R (III)
in welcherin which
R die oben angegebene Bedeutung hat,R has the meaning given above,
in Gegenwart einer Säure bei Temperaturen zwischen 40°C und 150°C umsetzt (1. Stufe) und die hierbei gebildeten Säureaddukte der Ver¬ bindungen der Formel (I) - gegebenenfalls nach Zwischenisolierung - mit einem Säurebindemittel aus der Reihe der Dialkylamine, Dicycloalkyl- amine, Trialkylamine, N,N-Dialkyl-N-cycloalkylamine, N,N-Dicycloalkyl- N-alkylamine, N,N-Dialkyl-aniline und N,N-Dialkyl-benzylamine sowie Pyridin, Alkylpyridine, Dialkylpyridine und Trialkylpyridine beiin the presence of an acid at temperatures between 40 ° C. and 150 ° C. (1st stage) and the acid adducts formed in this way of the compounds of the formula (I) - optionally after intermediate isolation - with an acid binder from the series of dialkylamines, dicycloalkyl amines, trialkylamines, N, N-dialkyl-N-cycloalkylamines, N, N-dicycloalkyl-N-alkylamines, N, N-dialkyl-anilines and N, N-dialkyl-benzylamines as well as pyridine, alkylpyridines, dialkylpyridines and trialkylpyridines
Temperaturen zwischen 0°C und 60°C umsetzt, wobei das Säurebindemittel unter guter Durchmischung langsam in das Reaktionsgemisch eindosiert wird (2. Stufe).Reacts temperatures between 0 ° C and 60 ° C, the acid binder is slowly metered into the reaction mixture with thorough mixing (2nd stage).
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die 1. Stufe bei Temperaturen zwischen 60°C und 120°C durchführt. 2. The method according to claim 1, characterized in that one carries out the 1st stage at temperatures between 60 ° C and 120 ° C.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die 2. Stufe bei Temperaturen zwischen 10°C und 40°C durchfuhrt. 3. The method according to claim 1, characterized in that one carries out the second stage at temperatures between 10 ° C and 40 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU67336/96A AU6733696A (en) | 1995-07-31 | 1996-07-18 | Method of preparing n-phosphonomethylglycine esters |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995128060 DE19528060A1 (en) | 1995-07-31 | 1995-07-31 | Process for the preparation of N-phosphonomethyl-glycine esters |
| DE19528060.1 | 1995-07-31 |
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| WO1997005147A1 true WO1997005147A1 (en) | 1997-02-13 |
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| DE (1) | DE19528060A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2152826A1 (en) * | 1971-03-10 | 1972-09-21 | Monsanto Co , St Louis, Mo (V St A ) | New N phosphonomethylglycines and phytotoxic compounds containing such compounds see agents |
| US4428888A (en) * | 1982-08-16 | 1984-01-31 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
-
1995
- 1995-07-31 DE DE1995128060 patent/DE19528060A1/en not_active Withdrawn
-
1996
- 1996-07-18 AU AU67336/96A patent/AU6733696A/en not_active Abandoned
- 1996-07-18 WO PCT/EP1996/003156 patent/WO1997005147A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2152826A1 (en) * | 1971-03-10 | 1972-09-21 | Monsanto Co , St Louis, Mo (V St A ) | New N phosphonomethylglycines and phytotoxic compounds containing such compounds see agents |
| US4428888A (en) * | 1982-08-16 | 1984-01-31 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19528060A1 (en) | 1997-02-06 |
| AU6733696A (en) | 1997-02-26 |
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