KR960002224B1 - Method of manufacturing n-phosphono methyl glycine - Google Patents
Method of manufacturing n-phosphono methyl glycine Download PDFInfo
- Publication number
- KR960002224B1 KR960002224B1 KR1019880017865A KR880017865A KR960002224B1 KR 960002224 B1 KR960002224 B1 KR 960002224B1 KR 1019880017865 A KR1019880017865 A KR 1019880017865A KR 880017865 A KR880017865 A KR 880017865A KR 960002224 B1 KR960002224 B1 KR 960002224B1
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- general formula
- following general
- compound
- reaction
- Prior art date
Links
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 8
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 239000004009 herbicide Substances 0.000 abstract description 4
- 230000002363 herbicidal effect Effects 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004471 Glycine Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- -1 phosphonate compound Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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)]
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
Description
본 발명은 다음 일반식(Ⅰ)로 표시되는 N-포스포노메틸글라이신의 새로운 제조방법에 관한 것이다.The present invention relates to a novel method for producing N-phosphonomethylglycine represented by the following general formula (I).
상기 일반식(Ⅰ)로 표시되는 N-포스포노메틸글라이신의 화합물은 농약으로 사용되는 제초제로서 살초폭이 넓고 비선택성으로 화본과, 방동사니과, 광염잡초의 1년생, 2년생 및 다년생 초본류에 매우 효과적이며, 또한 많은 잡목림과 교목(喬木)도 방제가능한 발아 후처리용 제초제인 화합물이다.The compound of N-phosphonomethylglycine represented by the general formula (I) is a herbicide used as a pesticide, and has a broader herbicide and a non-selective effect, which is very effective for the first-year, second-year and perennial herbaceous flowers, moths, and weeds. In addition, many woods and arbors are compounds that can control the germination post-treatment herbicides.
종래, 상기 일반식(Ⅰ)로 표시되는 N-포스포노메틸글라이신의 화합물을 합성하는 일반적인 방법은 미국 특허 제4,065,491호 및 제4,237,065호에 소개되어 있는 바, 미국특허 제4,065,491호는 알카리토류 금속수산화물의 수용액 존재하에서 포름알데히드와 글라이신을 반응시키고 여기에다 디알킬포스파이트를 적가하여 상기 일반식(Ⅰ)의 화합물을 제조하는 방법에 관한 것이고, 미국특허 제4,237,065호는 알콜용매 중에서 포름알데히드를 용해하는데 여기에 소량의 트리에틸아민을 사용하고 글라이신을 반응시키면서 과량의 트리에틸아민을 넣어 반응에 직접 적가시킨다. 여기에 디알킬포스파이트를 적가하면서 디알킬-N-포르밀-아미노메틸포스포네이트를 제조한 다음 이를 비누화를 하고 다시 가수분해시켜 상기 일반식(Ⅰ)의 화합물을 제조하는 방법이 기술되어 있다.Conventionally, a general method for synthesizing a compound of N-phosphonomethylglycine represented by the general formula (I) is described in US Pat. Nos. 4,065,491 and 4,237,065, and US Pat. No. 4,065,491 is an alkaline earth metal hydroxide. Formaldehyde is reacted with glycine in the presence of an aqueous solution of and dialkyl phosphite is added to the method for preparing the compound of the general formula (I), US Patent No. 4,237,065, which dissolves formaldehyde in alcohol solvent A small amount of triethylamine is added to the reaction mixture, and excess triethylamine is added dropwise to the reaction while glycine is reacted. Here, a method for preparing the compound of formula (I) is described by preparing dialkyl-N-formyl-aminomethylphosphonate dropwise with dialkylphosphite, followed by saponification and hydrolysis. .
그러나, 이와같은 종래 화합물의 제조방법들은 물의 존재하에서 디알킬포스파이트의 가수분해 등의 영향으로 인하여 손실이 많고 반응시간이 길 뿐만 아니라 반응공정이 매우 복잡한 단점이 있고, 무엇보다도 상기 일반식(Ⅰ)의 목적화합물의 수율이 낮아지는 문제가 있었다.However, the conventional methods for preparing such compounds have disadvantages of high loss and long reaction time due to hydrolysis of dialkyl phosphite in the presence of water, and a very complicated reaction process. ), There was a problem that the yield of the target compound is lowered.
이에 본 발명은 상기와 같은 종래방법에서 제문제점을 해결하고 간단한 공정으로도 빠른 시간내에 고수율로 목적화합물을 제조하기 위하여, 상기와 같은 종래 방법에서 사용되었던 촉매인 트리에틸아민 대신에 알카리금속을 사용하고, 또한 종래에는 포스포네이트화합물을 3차공정으로 제조하였으나, 본 발명은 1차로 생성시킴으로서 기존의 방법보다 정제과정이 매우 간단하여 반응시간이 종래에는 10시간이 소요되었으나 본 발명은 4시간 내에 반응을 진행시킬 수 있음은 물론, 상기 일반식(Ⅰ)의 목적화합물을 고수율로 연속 제조할 수 있도록 한 것이다.Therefore, the present invention solves the problems in the conventional method as described above and to prepare the target compound in a high yield in a short time even in a simple process, using an alkali metal instead of triethylamine which is a catalyst used in the conventional method as described above In addition, conventionally, the phosphonate compound was prepared by the third step, but the present invention was produced by the first step, and thus the purification process was much simpler than the conventional method, so that the reaction time was conventionally 10 hours but the present invention was 4 hours. In addition, the reaction can be carried out in the above, and the target compound of the general formula (I) can be continuously produced in high yield.
즉, 본 발명은 종래의 방법에 비해 간단하고 신속한 공정을 거쳐 고수율로 상기 일반식(Ⅰ)의 화합물을 제조할 수 있는 새로운 방법을 제공하는데 그 안출목적이 있다.That is, the present invention is to provide a new method for producing the compound of the general formula (I) in a high yield through a simple and rapid process compared to the conventional method.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 상기 일반식(Ⅰ)의 화합물을 제조함에 있어서, 다음 일반식(Ⅱ)의 디메틸포스파이트와 다음 일반식(Ⅲ)의 포름알데히드를 출발물질로 하여 다음 일반식(Ⅴ)의 하이드록시메틸-디메틸포스포네이트를 제조한 후 중간체인 다음 일반식(Ⅸ)의 디알킬-N-포르밀-아미노메틸포스포네이트를 제조하고 이를 비누화 및 산가수분해시켜 목적화합물을 제조하는 것을 그 특징으로 한다.In the preparation of the compound of formula (I), the hydroxy of formula (V) is prepared by using dimethyl phosphite of formula (II) and formaldehyde of formula (III) as starting materials. After preparing methyl-dimethylphosphonate, a dialkyl-N-formyl-aminomethylphosphonate of the following general formula (III), which is an intermediate, is prepared, and the target compound is prepared by saponification and acid hydrolysis. It is done.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 상기 일반식(Ⅱ)의 디메틸포스파이트와 상기 일반식(Ⅲ)의 포름알데히드를 반응시켜 상기 일반식(Ⅴ)의 하이드록시메틸-디메틸포스포네이트를 제조하고 여기에다 다음 일반식(Ⅵ)의 티모닐클로라이드 또는 포스포러스펜타클로라이드를 반응시켜 다음 일반식(Ⅶ)의 클로로메틸-디메틸포스포네이트인 중간체로 만들고, 이를 다음 일반식(Ⅷ)의 클라이신과 반응시켜 상기 일반식(Ⅸ)의 디알킬-N-아미노-메틸을 제조하고 이를 비누화 및 산가수분해를 시켜 상기 일반식(Ⅰ)의 화합물을 얻도록 한다.The present invention is prepared by reacting dimethyl phosphite of formula (II) with formaldehyde of formula (III) to prepare hydroxymethyl-dimethylphosphonate of formula (V). ) Thymonyl chloride or phosphorus pentachloride is reacted to give an intermediate which is chloromethyl-dimethylphosphonate of formula (VII), which is then reacted with lysine of formula (VII) to react with The dialkyl-N-amino-methyl is prepared and saponified and acid hydrolyzed to obtain the compound of formula (I).
이와 같은 본 발명에 따라 상기 일반식(Ⅰ)의 화합물을 제조하게 되면 목적 화합물이 70∼80%의 높은 수율로 제조되어지는 바, 이와 같은 본 발명에 따르면 반응용매로 싸이클릭에테르, 싸이클릭아민, 아로마틱아민 또는 그 혼합물용액에 파라포름알데히드를 용해하면서 상기 일반식(Ⅱ)의 화합물을 적하하여 상기 일반식(Ⅴ)의 화합물을 상기 일반식(Ⅵ)의 화합물과 반응시킨 후, 알칼리금속의 수산화물 또는 탄산염 존재하에 상기 일반식(Ⅷ)의 화합물과 반응시킨 다음 이를 비누화 및 산가수분해 하는 것을 특징으로 하고 있으므로, 이와같은 반응용매와 알칼리금속을 촉매로 사용하여 상기 일반식(Ⅰ)의 화합물을 제조하는 경우 공정이 간단할 뿐만 아니라 반응이 신속하게 이루어지고, 높은 수율로 목적하는 상기 일반식(Ⅰ)의 화합물을 제조할 수가 있다.According to the present invention, when the compound of Formula (I) is prepared, the target compound is prepared in high yield of 70 to 80%. According to the present invention, cyclic ether and cyclic amine are used as reaction solvents. And dropping the compound of formula (II) while dissolving paraformaldehyde in an aromatic amine or a mixture thereof, reacting the compound of formula (V) with the compound of formula (VI), and then Since the reaction with the compound of the general formula (Ⅷ) in the presence of a hydroxide or carbonate, and then saponification and acid hydrolysis, the compound of the general formula (I) using such a reaction solvent and an alkali metal as a catalyst In the case of the preparation, not only the process is simple but also the reaction is performed quickly, and the desired compound of general formula (I) can be prepared in high yield. All.
상기와 같은 본 발명을 그 실시예를 들어 더욱 상세히 설명하면 다음과 같지만 본 발명이 본 실시예에만 한정되는 것은 아니다.When the present invention as described above in more detail with reference to the embodiment as follows, but the present invention is not limited to this embodiment.
[실시예 1]Example 1
피리딘 100㎖에 파라포름알데히드 7.5g을 넣어 용해하면서 디메틸포스파이트 27.63g(0.25mole)을 65℃ 내지 75℃에서 30분간 적가하여 30분간 환류 교반하고, 여기에다 티오닐클로라이드 14.875g(0.125mole)을 50℃에서 30분간 적가하여 환류 교반시키고, 탄산나트륨 26.5g(0.25mole)을 첨가하고 환류온도 부근에서 1시간 교반시키면서 글라이신 18.75g(0.25mole)을 넣고 반응시킨 후 0.8몰의 수산화나트륨 수용액을 50㎖를 가하고 30분간 환류시키면서 피리딘을 회수시킨다.After dissolving 7.5 g of paraformaldehyde in 100 ml of pyridine, 27.63 g (0.25 mole) of dimethyl phosphite was added dropwise at 65 ° C to 75 ° C for 30 minutes, followed by stirring under reflux for 30 minutes, and 14.875 g (0.125 mole) of thionyl chloride was added thereto. It was added dropwise at 50 ° C. for 30 minutes and stirred under reflux. 26.5 g (0.25 mole) of sodium carbonate was added thereto, and 18.75 g (0.25 mole) of glycine was added with reaction for 1 hour while stirring at reflux, followed by 50 ml of an aqueous 0.8 mol sodium hydroxide solution. Add pyridine and recover pyridine while refluxing for 30 minutes.
혼합물을 냉각시키고 진한 염산으로 PH를 1까지 조절하면 황색조결정이 석출된다. 이것을 여과하고 메탄올로 3회 씻어 건조하면 백색조결정의 N-포스포노메틸글라이신 28.98g을 얻는다(디에틸포스파이트 98%, 기준수율 70%).Cool the mixture and adjust the pH to 1 with concentrated hydrochloric acid to precipitate yellow crude crystals. This was filtered, washed three times with methanol and dried to obtain 28.98 g of white crude crystal N-phosphonomethylglycine (98% of diethyl phosphite, reference yield 70%).
[실시예 2]Example 2
실시예 1에서 촉매 탄산나트륨을 79.58g(0.75mole)으로 증가시켜 동일한 방법을 반응을 진행시키고 반응을 종료하면 N-포스포노메틸글라이신 31.05g을 얻는다(디에틸 포스파이트 98%, 기준수율 75%).In Example 1, the reaction was carried out by increasing the catalyst sodium carbonate to 79.58 g (0.75 mole) and upon completion of the reaction, 31.05 g of N-phosphonomethylglycine was obtained (diethyl phosphite 98%, reference yield 75%). .
[실시예 3]Example 3
실시예 1에서 티오닐클로라이드 대신 포스포러스 펜타클로라이드 52.125g (0.25mole)을 사용하고 동일한 방법으로 반응을 진행시켜 반응을 종료하면 N-포스포노메틸클로라이드 33.8g을 얻는다(디메틸포스파이트 98%, 기준수율 81.6%).52.125 g (0.25 mole) of phosphorus pentachloride in place of thionyl chloride was used in Example 1, and the reaction was carried out in the same manner to obtain 33.8 g of N-phosphonomethyl chloride (dimethyl phosphite 98%, standard). Yield 81.6%).
[비교예][Comparative Example]
미국특허 제4,237,065호의 제조방법으로 400㎖ 메탄올에 파라포름알데히드 45g(1.5mole)과 트리에틸아민 7㎖을 넣고 10분간 교반하여 용액으로 하고, 글라이신 75g(1mole)을 43℃ 내지 55℃에서 투입하여 교반하고, 트리에틸아민 102g(1mole)을 60분간 60℃ 내지 70℃에서 적가하여 혼합용액을 제조하고, 여기에 디에틸포스파이트 138g(1mole)을 10분간 적가하여 72℃에서 1.5시간 동안 교반하였다.In the manufacturing method of U.S. Patent No. 4,237,065, 45 g (1.5 mole) of paraformaldehyde and 7 ml of triethylamine were added to 400 ml methanol, and stirred for 10 minutes to prepare a solution. 75 g (1 mole) of glycine was added at 43 ° C to 55 ° C. After stirring, 102 g (1 mole) of triethylamine was added dropwise at 60 ° C. to 70 ° C. for 60 minutes to prepare a mixed solution, and 138 g (1 mole) of diethyl phosphite was added dropwise thereto for 10 minutes and stirred at 72 ° C. for 1.5 hours. .
종료 후 냉각시키면서 40% NaOH 수용액 250g을 첨가하여 혼합물을 1.5시간 환류시키면서 메탄올과 트리에틸아민을 회수한 후 105℃ 내지 110℃에서 2시간 가열하였다.250 g of 40% NaOH aqueous solution was added thereto after cooling to recover the mixture, and the mixture was refluxed for 1.5 hours to recover methanol and triethylamine, followed by heating at 105 ° C to 110 ° C for 2 hours.
혼합물을 냉각하여 염산으로 PH를 1.5로 조정하여 N-포스포노메틸글라이신이 4시간에 걸쳐 침전되었다. 이 침전물을 여과 건조시키고 침량한 결과 99.041g(디에틸포스파이트 98%, 기준수율 59.8%)의 백색 결정을 얻어 수율 55% 내지 63%이였다.The mixture was cooled to adjust the pH to 1.5 with hydrochloric acid to precipitate N-phosphonomethylglycine over 4 hours. The precipitate was filtered dried and immersed to obtain 99.041 g (98% of diethyl phosphite, 59.8% of standard yield) as white crystals. The yield was 55% to 63%.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019880017865A KR960002224B1 (en) | 1988-12-29 | 1988-12-29 | Method of manufacturing n-phosphono methyl glycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019880017865A KR960002224B1 (en) | 1988-12-29 | 1988-12-29 | Method of manufacturing n-phosphono methyl glycine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR900009671A KR900009671A (en) | 1990-07-05 |
| KR960002224B1 true KR960002224B1 (en) | 1996-02-13 |
Family
ID=19280895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019880017865A KR960002224B1 (en) | 1988-12-29 | 1988-12-29 | Method of manufacturing n-phosphono methyl glycine |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR960002224B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2862650A1 (en) * | 2003-11-24 | 2005-05-27 | Rhodia Cons Spec Ltd | New dendrimers with phosphonic terminal groups used in surface treatment compositions and as anti-corrosion, lubricant, anti-scale and fire retardant agents |
-
1988
- 1988-12-29 KR KR1019880017865A patent/KR960002224B1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2862650A1 (en) * | 2003-11-24 | 2005-05-27 | Rhodia Cons Spec Ltd | New dendrimers with phosphonic terminal groups used in surface treatment compositions and as anti-corrosion, lubricant, anti-scale and fire retardant agents |
| WO2005052032A1 (en) * | 2003-11-24 | 2005-06-09 | Rhodia Uk Limited | Novel dendritic polymers having monophosphonic terminations, method for preparing them, and their use |
| US8039580B2 (en) | 2003-11-24 | 2011-10-18 | Rhodia Uk Ltd. | Dendritic polymers having monophosphonic terminations, method for preparing them, and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| KR900009671A (en) | 1990-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4519316B2 (en) | Process for the production of glufosinate and intermediates therefor | |
| US4053505A (en) | Preparation of n-phosphonomethyl glycine | |
| EP0221043B1 (en) | Process for the preparation of n-substituted aminomethylphosphonic acids | |
| EP0102694B1 (en) | Method for preparation of n-phosphonomethylglycine | |
| US4422982A (en) | Method for preparation of N-phosphonomethylglycine | |
| EP0085391A1 (en) | Phosphinic acid derivatives and process for preparing the same | |
| KR960002224B1 (en) | Method of manufacturing n-phosphono methyl glycine | |
| US4921991A (en) | Preparation of esters of the N-phosphonomethylglycine and the N-phosphonomethyl glycines | |
| US4804499A (en) | Process for the preparation of N-substituted aminomethylphosphonic acids | |
| KR930002412B1 (en) | Preparation of n-acyl-aminomethyl phosphonates | |
| JPS60163889A (en) | Manufacture of n-phosphonomethylglycin | |
| US5068404A (en) | Thermal dealkylation of N-alkyl N-phosphonomethylglycine | |
| CA1259328A (en) | Thermal dealkylation of n-alkyl n- phosphonomethylglycine | |
| US4160779A (en) | Process for the production of methylaminomethylphosphonic acid and its salts | |
| HU213457B (en) | Process for producing aminomethanephosphonic acid and aminomethyl-phosphinic acid | |
| US4457873A (en) | Process for preparing phosphonomethylated amino acids | |
| CA1256447A (en) | Esters of the family of n-phosphonomethylglycine and their use in the preparation of known herbicides | |
| WO1999019334A1 (en) | Selective functionalization of sodium glycinate | |
| US4548758A (en) | Preparation of phosphonomethylated amino acids | |
| US6040476A (en) | Carbon dioxide assisted hydrolysis of aminophosphonates | |
| US4569802A (en) | Method for preparation of N-phosphonomethylglycine | |
| JPH0225917B2 (en) | ||
| US4548759A (en) | Preparation of phosphonomethylated amino acids | |
| JPH05213978A (en) | Preparation of n-(2-hydroxyalkyl)-n- phosphonomethylglycine | |
| HU208542B (en) | Process for producing n-phosphonomethyl-glycine or alkali-salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| G160 | Decision to publish patent application | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| LAPS | Lapse due to unpaid annual fee |