EP0915892A1 - Procede pour preparer de la n-phosphonomethylglycine - Google Patents
Procede pour preparer de la n-phosphonomethylglycineInfo
- Publication number
- EP0915892A1 EP0915892A1 EP97934517A EP97934517A EP0915892A1 EP 0915892 A1 EP0915892 A1 EP 0915892A1 EP 97934517 A EP97934517 A EP 97934517A EP 97934517 A EP97934517 A EP 97934517A EP 0915892 A1 EP0915892 A1 EP 0915892A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- stage
- alkali
- phosphonomethylglycine
- carried out
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims abstract description 26
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000007513 acids Chemical class 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- ZZLRWERPJLNCEZ-UHFFFAOYSA-N phosphonomethylcarbamic acid Chemical compound OC(=O)NCP(O)(O)=O ZZLRWERPJLNCEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 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 claims description 5
- YIDNMCACBXPAQB-UHFFFAOYSA-N hydroxymethyl(phosphonomethyl)carbamic acid Chemical class OCN(C(O)=O)CP(O)(O)=O YIDNMCACBXPAQB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003112 potassium compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229940018038 sodium carbonate decahydrate Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 102000003960 Ligases Human genes 0.000 description 2
- 108090000364 Ligases Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- -1 aromatic amino acids Chemical class 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000007031 hydroxymethylation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 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
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006215 cyanomethylation reaction Methods 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000009885 systemic effect Effects 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 process for the preparation of N-phosphonomethylglycine from aminomethylphosphonic acid or one of its salts.
- N-phosphonomethylglycine (glyphosate) has been used as a systemic herbicide for more than 20 years. Its effect is based on the inhibition of the plant enzyme 5-enolpyruvylshikimate-3-phosphate synthetase
- a known disadvantage in the hydroxymethylation and cyanomethylation of primary amines is that mixtures of mono- and disubstituted products are generally formed.
- N-phosphonomethyliminodiacetic acid is also obtained as a by-product.
- US Pat. No. 4,221,583 describes the reaction of aminomethylphosphonic acid with formaldehyde and sodium cyanide at pH values from 6.6 to 9.7, N-phosphonomethylglyconitrile being formed in a yield of only 65%.
- EP-A 1 1 2 580 discloses such a synthesis of N-phosphonomethylglycine from Glyci ⁇ . Glycm is first reacted with sodium carbonate in the sodium salt of the corresponding carbamic acid and then with formalin and diethyl phosphite in N- (O, O'- Diethylphosphonomethyl) glyconitrile converted, from which N-phosphonomethylglycine can be obtained by hydrolysis, but even with this method, the yield is extremely low at 36%.
- the invention is therefore based on the object of providing a process for the preparation of N-phosphonomethylglycine which does not have the disadvantages of the prior art mentioned, but rather enables the preparation of this compound in high yield and good purity with little technical outlay.
- N-phosphonomethylglycine in a comparatively low technical outlay in excellent yield with high purity. It is particularly surprising that N-phosphonomethyliminodiacetic acid is formed only to a very small extent ( ⁇ 0.5%) during the reaction and is not contained in the isolated N-phosphonomethylglycine.
- the production of N-phosphonomethylglycine from aminomethylphosphonic acid takes place in several steps, but according to a preferred embodiment the isolation of intermediates is dispensed with and the entire process can be carried out as a one-pot reaction.
- aminomethylphosphonic acid or one of its salts in water is reacted with an alkali carbonate and / or bicarbonate or with carbon dioxide and an alkali metal hydroxide, optionally with the addition of alkali metal lyes, salts of N-phosphonomethyl carbamic acid being the carboxylation of the amino group Formula (I) arise:
- a water-soluble alkali carbonate or / and hydrogen carbonate is preferably used, sodium and potassium salts in particular - partly also in the form of their hydrates - being used can be.
- Sodium or potassium hydroxide solutions are preferred as the alkali hydroxide solution.
- reaction step a) is carried out in water.
- the pH can be varied within wide limits and in particular have values between 7 and 14, preferably between 9 and 11. If alkali carbonates or / and hydrogen carbonates are used, a desired higher pH value can be set by adding alkali lye.
- the molar ratio of aminomethylphosphonic acid or one of its salts to alkali carbonate or bicarbonate can also be varied within wide limits. A molar ratio of 0.9 to 1.2 is preferred.
- appropriate amounts of an alkali metal hydroxide are expediently added before or during the reaction.
- reaction temperature is not critical and is preferably between 0 and 80 ° C. However, temperatures that are too high should be avoided in order to avoid decarboxylation of the carbamic acid or its salts. According to a particularly preferred embodiment, a reaction temperature of 10 to 30 ° C. is selected.
- the concentration of the reaction mixture in reaction step a) is also largely unproblematic. Is preferably carried out in a concentration range of 1 0 to 30 wt .-%, based on the aminomethylphosphonic acid or the corresponding salt.
- the salt of N-phosphonomethyl carbamic acid formed according to a) is, preferably without isolation, with formaldehyde Formation of a salt of N-hydroxymethyl-N-phosphonomethylcarbamic acid of the formula (II)
- Formaldehyde can be used as an aqueous solution (formalin) or in the form of paraformaldehyde.
- the molar ratio of formaldehyde to the aminomethylphosphonic acid used in a) is preferably between 0.9 and 1.2.
- reaction temperature is also not critical and is preferably between 0 and 80 ° C. Excessively high temperatures should, however, be avoided in order to avoid decarboxylation of N-hydroxymethyl-N-phosphonomethylcarbamic acid or its salts. According to a particularly preferred embodiment, a reaction temperature of 10 to 30 ° C. is therefore set.
- reaction step c) the salt of N-hydroxymethyl-N-phosphonomethylcarbamic acid formed according to b), preferably without prior isolation, in aqueous alkaline solution with hydrogen cyanide or a cyanide to a salt of N-carboxy-N-phosphonomethylglyconitrile of the formula ( III) implemented.
- the water-soluble alkali metal cyanides e.g. B. sodium or potassium cyanide is preferred.
- the molar ratio of hydrogen cyanide or cyanide to the aminomethylphosphonic acid used in a) is preferably chosen in a molar ratio of 0.9 to 1.5.
- the reaction temperature and pH are preferably chosen so that they correspond to the conditions for the reaction step b) and a possibly complex change in the reaction procedure is not necessary. If necessary or desired, the pH value can be kept constant by simultaneous dosing of an alkali - preferably sodium hydroxide solution or potassium hydroxide solution.
- reaction step d) of the process according to the invention the salt of N-carboxy-N-phosphonomethylglyconitrile formed according to c) is treated with acids.
- the desired N-phosphonomethylglycine (IV) is formed with decarboxylation and hydrolysis of the nitrile group.
- acids are preferably used as acids, e.g. B. hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid or formic acid and acetic acid.
- acids e.g. B. hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid or formic acid and acetic acid.
- concentrated aqueous hydrochloric acid is used, the molar ratio to the aminomethylphosphonic acid used in a) being about 4 to 8.
- Reaction stage d) is preferably carried out at a temperature of 80 to 120 ° C. in order to ensure a high reaction rate.
- N-phosphonomethylglycine can be isolated from the reaction mixture obtained according to d) by methods known per se. However, the following two routes are preferred: First, the reaction mixture is freed from the aqueous hydrochloric acid by known methods and the residue is taken up in hot water and the pH is adjusted to 1.5 to 3.0 using bases, in particular sodium hydroxide solution. When cooling, the desired reaction product precipitates in the form of fine crystalline powder, which can optionally be washed with water and dried in vacuo.
- the N-phosphonomethylglycine dissolved in hot water can be mixed with methanol, the product then being obtained as a finely crystalline powder on cooling.
- N-phosphonomethylglycine is obtained in yields of up to approx. 88% of theory (based on aminomethylphosphonic acid) and in a purity of approx. 97 to 98%.
- the following examples are intended to explain the invention in more detail.
- 11.1 g (0.1 mol) of aminomethylphosphonic acid are suspended in 35 g of water.
- 28.9 g (0.1 mol) of sodium carbonate decahydrate are added at 20 ° C., the pH of the solution being adjusted to 10 using 25% sodium hydroxide solution after the addition has ended.
- 3.3 g (0.1 1 mol) of paraformaldehyde and 25% sodium hydroxide solution are added to the reaction solution at about 22 ° C. within 35 minutes.
- a total of 1 5.9 g (0.1 mol) of 25% sodium hydroxide solution are consumed.
- 2.97 g (0.11 mol) of hydrocyanic acid are added dropwise to the solution at 22 ° C. over a period of 10 minutes and the mixture is left to stand at room temperature for 2 hours, the pH during and after the addition of the hydrocyanic acid remains at 10.
- N-phosphonomethylglycine 10.7 g (63.9% of theory, based on aminomethylphosphonic acid) of N-phosphonomethylglycine are obtained with a titrimetrically determined content of 95.8%. According to the ion chromatographic analysis, the combined aqueous filter rates still contain 24% N-phosphonomethylglycine. The solution does not contain N-phosphonomethyliminodiacetic acid.
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
Pour préparer de la N-phosphonométhylglycine, on fait réagir (a) de l'acide aminométhylphosphonique ou bien l'un de ses sels dans de l'eau, en y ajoutant éventuellement des lessives alcalines, avec un carbonate alcalin et/ou un carbonate d'hydrogène alcalin ou avec un dioxyde de carbone et une lessive alcaline, (b) on hydroxyméthyle le sel alcalin résultant de l'acide N-phosphonométhylcarbamique avec du formaldéhyde, (c) on fait réagir les sels résultant de l'acide N-hydroxyméthyl-N-phosphonométhylcarbamique, en y ajoutant éventuellement une lessive alcaline, avec de l'acide cyanhydrique et/ou un cyanure, et (d) en ajoutant des acides, on transforme les sels résultant de l'acide N-carboxy-N-phosphonométhylformaldéhyde cyanhydrique en N-phosphonométhylglycine par hydrolyse et décarboxylation. Ce procédé donne d'excellents rendements et un haut degré de pureté de la N-phosphonométhylglycine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19629870 | 1996-07-24 | ||
| DE19629870A DE19629870A1 (de) | 1996-07-24 | 1996-07-24 | Verfahren zur Herstellung von N-Phosphonomethylglycin |
| PCT/EP1997/003955 WO1998003517A1 (fr) | 1996-07-24 | 1997-07-22 | Procede pour preparer de la n-phosphonomethylglycine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0915892A1 true EP0915892A1 (fr) | 1999-05-19 |
Family
ID=7800708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97934517A Withdrawn EP0915892A1 (fr) | 1996-07-24 | 1997-07-22 | Procede pour preparer de la n-phosphonomethylglycine |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6121485A (fr) |
| EP (1) | EP0915892A1 (fr) |
| AU (1) | AU711975B2 (fr) |
| CA (1) | CA2261723A1 (fr) |
| DE (1) | DE19629870A1 (fr) |
| NZ (1) | NZ333097A (fr) |
| WO (1) | WO1998003517A1 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7396922B2 (en) | 2001-11-28 | 2008-07-08 | Angiogenetics Sweden Ab | Regulation of hypoxia-inducible gene expression with antisense Inhibitory PAS domain protein |
| US9090505B2 (en) | 2011-07-15 | 2015-07-28 | Corning Incorporated | Microwave-based glass laminate fabrication |
| CN115057884A (zh) * | 2022-06-06 | 2022-09-16 | 湖北泰盛化工有限公司 | 一种由氨甲基膦酸制备草甘膦的方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221583A (en) * | 1978-12-22 | 1980-09-09 | Monsanto Company | N-Phosphonomethylglycinonitrile and certain derivatives thereof |
| US4439373A (en) * | 1982-12-27 | 1984-03-27 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| US4548760A (en) * | 1983-04-28 | 1985-10-22 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| US4657705A (en) * | 1985-09-23 | 1987-04-14 | Monsanto Company | Process for the preparation of N-substituted aminomethylphosphonic acids |
| PL156933B1 (pl) * | 1988-02-16 | 1992-04-30 | Politechnika Wroclawska | Sposób wytwarzania N-(1-fosfonoalkilo) glicyn, zwlaszcza N-(fosfonometylo) glicyny PL |
| GB9423254D0 (en) * | 1994-11-16 | 1995-01-04 | Zeneca Ltd | Process |
| US5750774A (en) * | 1996-03-11 | 1998-05-12 | Showa Denko K.K. | Method for producing N-phosphonomethylglycine |
| US5948937A (en) * | 1996-09-12 | 1999-09-07 | Monsanto Company | Method for producing N-phosphonomethylglycine and its salts |
-
1996
- 1996-07-24 DE DE19629870A patent/DE19629870A1/de not_active Withdrawn
-
1997
- 1997-07-22 WO PCT/EP1997/003955 patent/WO1998003517A1/fr not_active Application Discontinuation
- 1997-07-22 US US09/194,953 patent/US6121485A/en not_active Expired - Fee Related
- 1997-07-22 EP EP97934517A patent/EP0915892A1/fr not_active Withdrawn
- 1997-07-22 AU AU37701/97A patent/AU711975B2/en not_active Ceased
- 1997-07-22 CA CA002261723A patent/CA2261723A1/fr not_active Abandoned
- 1997-07-22 NZ NZ333097A patent/NZ333097A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9803517A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU711975B2 (en) | 1999-10-28 |
| CA2261723A1 (fr) | 1998-01-29 |
| NZ333097A (en) | 1999-07-29 |
| US6121485A (en) | 2000-09-19 |
| WO1998003517A1 (fr) | 1998-01-29 |
| AU3770197A (en) | 1998-02-10 |
| DE19629870A1 (de) | 1998-01-29 |
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