WO1997005147A1 - Procede de production de n-phosphonomethyl-glycinesters - Google Patents

Procede de production de n-phosphonomethyl-glycinesters Download PDF

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Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
formula
acid
temperatures
stage
phosphonomethylglycine
Prior art date
Application number
PCT/EP1996/003156
Other languages
German (de)
English (en)
Inventor
Hans-Jochem Riebel
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU67336/96A priority Critical patent/AU6733696A/en
Publication of WO1997005147A1 publication Critical patent/WO1997005147A1/fr

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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

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.

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  • 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé de production techniquement simple de N-phosphonométhyl-glycinesters ayant une action herbicide, de la formule (I) (HO)2P(O)-CH2-NH-CH2-CO-O-R où R représente alkyle. Ce procédé permet d'obtenir des substances de la formule (I), d'une grande pureté et avec des rendements élevés, en faisant réagir de la N-phosphonométhyl-glycine de formule générale (II) (HO)2P(O)-CH2-NH-CH2-COOH avec des alcools de formule générale (III) HO-R en présence d'un acide à une température comprise entre 40 °C et 150 °C (1ère étape) puis en faisant réagir les produits d'addition d'acide des composés de la formule (I) ainsi formés - éventuellement après une isolation intermédiaire - avec un liant d'acide de la série des dialkylamines, dicycloalkylamines, trialkylamines, N,N-Dialkyl-N-cycloalkylamines, N,N-dicycloalkyl-N-alkylamines, N,N-dialkyl-anilines et N,N-dialkylbenzylamines ainsi qu'avec de la pyridine, et des alkylpyridines, dialkylpyridines et trialkylpyridines à une température comprise entre 0 °C et 60 °C. Le liant d'acide doit être dosé et ajouté lentement au mélange réactif (2ème étape).
PCT/EP1996/003156 1995-07-31 1996-07-18 Procede de production de n-phosphonomethyl-glycinesters WO1997005147A1 (fr)

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 (de) 1995-07-31 1995-07-31 Verfahren zur Herstellung von N-Phosphonomethyl-glycinestern
DE19528060.1 1995-07-31

Publications (1)

Publication Number Publication Date
WO1997005147A1 true WO1997005147A1 (fr) 1997-02-13

Family

ID=7768295

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003156 WO1997005147A1 (fr) 1995-07-31 1996-07-18 Procede de production de n-phosphonomethyl-glycinesters

Country Status (3)

Country Link
AU (1) AU6733696A (fr)
DE (1) DE19528060A1 (fr)
WO (1) WO1997005147A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2152826A1 (de) * 1971-03-10 1972-09-21 Monsanto Co , St Louis, Mo (V St A ) Neue N Phosphonomethylglycine und solche Verbindungen enthaltende phytotoxi sehe Mittel
US4428888A (en) * 1982-08-16 1984-01-31 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2152826A1 (de) * 1971-03-10 1972-09-21 Monsanto Co , St Louis, Mo (V St A ) Neue N Phosphonomethylglycine und solche Verbindungen enthaltende phytotoxi sehe Mittel
US4428888A (en) * 1982-08-16 1984-01-31 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine

Also Published As

Publication number Publication date
AU6733696A (en) 1997-02-26
DE19528060A1 (de) 1997-02-06

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