WO1997005148A1 - Procede de production d'esters de n-phosphonomethylglycine - Google Patents
Procede de production d'esters de n-phosphonomethylglycine Download PDFInfo
- Publication number
- WO1997005148A1 WO1997005148A1 PCT/EP1996/003157 EP9603157W WO9705148A1 WO 1997005148 A1 WO1997005148 A1 WO 1997005148A1 EP 9603157 W EP9603157 W EP 9603157W WO 9705148 A1 WO9705148 A1 WO 9705148A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- acid
- phosphonomethylglycine
- temperatures
- stage
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical class OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 150000002924 oxiranes Chemical class 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KETAXFYLSZHQJO-UHFFFAOYSA-N 2-propyloxirane Chemical compound O1CC1CCC.O1CC1CCC KETAXFYLSZHQJO-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- KCNGRSQQOKXAKR-UHFFFAOYSA-N [(2-ethoxy-2-oxoethyl)amino]methylphosphonic acid Chemical compound CCOC(=O)CNCP(O)(O)=O KCNGRSQQOKXAKR-UHFFFAOYSA-N 0.000 description 1
- YYGUXKOBRVTICK-UHFFFAOYSA-N [(2-methoxy-2-oxoethyl)amino]methylphosphonic acid Chemical compound COC(=O)CNCP(O)(O)=O YYGUXKOBRVTICK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Definitions
- the invention relates to a new process for the preparation of N-phosphonomethylglycinestera, 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
- 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 1 to 10 carbon atoms.
- the invention relates in particular to the preparation of N-phosphonomethylglycine 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.
- Formula (I) alcohols to be used as starting materials are represented by the formula (III) generally defined.
- 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 series of mineral acids, such as e.g. Hydrogen chloride (hydrogen chloride), hydrogen bromide (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.
- mineral acids such as e.g. Hydrogen chloride (hydrogen chloride), hydrogen bromide (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, propane
- 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 oxiranes (epoxides) as acid binders.
- Oxiranes (epoxides) with up to 10 carbon atoms which are unsubstituted or substituted once or twice by alkyl or aryl groups are preferred as such. Examples include oxirane (ethylene oxide), methyl oxirane (propylene oxide, 1,2-epoxy propane), ethyl oxirane (1,2-
- Methyl oxirane (propylene oxide, 1,2-epoxypropane) is particularly preferred as an acid binder in the process according to the invention.
- reaction temperatures can be carried out 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 60 ° C and 120 ° C, the 2nd stage at temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 40 ° C.
- 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 moles of an acid and between 1 and 5 moles, preferably between 1.5 and 3.5 moles of one
- Acid binder (oxirane, epoxy).
- 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. It is then concentrated under reduced pressure, taken up again in an alcohol of the formula (III) and mixed with an acid binder (oxirane, epoxy).
- the product of 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).
- 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 propylene oxide (about 150 g) is added dropwise to this solution with vigorous stirring at room temperature (about 150 ° C.) until the color changes from reddish brown to light yellow.
- the crystalline product is isolated by suction.
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
L'invention concerne un procédé de production simple d'esters de N-phosphonométhylglycines 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-phosphonométhylglycine de la formule (II) (HO)2P(O)-CH2-NH-CH2-COOH avec des alcools de la formule générale (III) HO-R, en présence d'un acide, à une température comprise entre 40 °C et 150 °C (1ère étape) et en faisant réagir les produits d'addition d'acide des composés de la formule (I) ainsi obtenus -éventuellement après une isolation intermédiaire - avec un oxyranne (époxyde) comme liant acide à une température comprise entre 0 °C et 60 °C (2ème étape).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU67337/96A AU6733796A (en) | 1995-07-31 | 1996-07-18 | Method of preparing n-phosphonomethylglycine esters |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995128054 DE19528054A1 (de) | 1995-07-31 | 1995-07-31 | Verfahren zur Herstellung von N-Phosphonomethylglycinestern |
| DE19528054.7 | 1995-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997005148A1 true WO1997005148A1 (fr) | 1997-02-13 |
Family
ID=7768290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1996/003157 WO1997005148A1 (fr) | 1995-07-31 | 1996-07-18 | Procede de production d'esters de n-phosphonomethylglycine |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU6733796A (fr) |
| DE (1) | DE19528054A1 (fr) |
| WO (1) | WO1997005148A1 (fr) |
Citations (2)
| 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 |
-
1995
- 1995-07-31 DE DE1995128054 patent/DE19528054A1/de not_active Withdrawn
-
1996
- 1996-07-18 WO PCT/EP1996/003157 patent/WO1997005148A1/fr active Application Filing
- 1996-07-18 AU AU67337/96A patent/AU6733796A/en not_active Abandoned
Patent Citations (2)
| 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 |
|---|---|
| DE19528054A1 (de) | 1997-02-06 |
| AU6733796A (en) | 1997-02-26 |
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