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WO1996019485A1 - Procede de preparation de n-phosphonomethylglycine - Google Patents

Procede de preparation de n-phosphonomethylglycine Download PDF

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Publication number
WO1996019485A1
WO1996019485A1 PCT/SI1995/000029 SI9500029W WO9619485A1 WO 1996019485 A1 WO1996019485 A1 WO 1996019485A1 SI 9500029 W SI9500029 W SI 9500029W WO 9619485 A1 WO9619485 A1 WO 9619485A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphonomethyl
glyphosate
water
wet oxidation
iminodiacetic acid
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.)
Ceased
Application number
PCT/SI1995/000029
Other languages
English (en)
Inventor
Davorin Bauman
Z^¿eljko KNEZ
Vlasta MARC^¿INKO
Branko PETROVIC^¿
Andreja RIZ^¿NER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PINUS DD
Original Assignee
PINUS DD
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 PINUS DD filed Critical PINUS DD
Priority to AU41278/96A priority Critical patent/AU4127896A/en
Publication of WO1996019485A1 publication Critical patent/WO1996019485A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a new process for the preparation of N- phosphonomethyl glycine.
  • N-phosphonomethyl glycine known under the generic name glyphosate as it will be used in the following text of the description, claims, and abstract for the characterisation of N-phosphonomethyl glycine, is an active substance used in ecologically appropriate herbicides. Such herbicides act on numerous annual or perennial, grass or broad-leafed, woody or other weeds. They are used for the control of weeds in stubble fields, in vineyards, orchards, canals, swamps, grasslands, pasture- lands, drained areas, woods, non-cultivated areas, railway tracks, dams and in other places.
  • Glyphosate acts on the system and is rapidly transferred into all vital plant organs (roots, rhizome); therefore plants are completely destroyed by herbicides containing it.
  • Glyphosate encompasses many excellent biological properties: a broad activity spectrum, a non-selective and efficient activity on a high number of annual and perennial weeds.
  • One of its most important properties is the rapid transfer from the plant's leaves into its roots, and thus radically destroying the weeds.
  • the herbicide glyphosate is rapidly adsorbed by the soil where its herbicidal activity is very much diminished.
  • a slight quantity of glyphosate is decomposed via chemical reactions , the majority, however, is decomposed by means of micro-organisms into nutrients for plants, such as: phosphoric acid, ammonia and carbon dioxide.
  • the potential metabolic pathway is described in US Patent No. 3,950,402. Details on the glyphosate metabolism in plants are not well-known.
  • Toxicity of glyphosate - acute oral LD50 for rats: 5600 mg/kg
  • N-phosphonomethyl glycine is a secondary amine of the empirical formula C3H8NO5P and the chemical formula
  • Glyphosate is a white crystalline solid substance.
  • the solubility of glyphosate in water is low, as evident from the following Table 1.
  • Glyphosate is also practically insoluble in the majority of organic solvents, which is an indication for very strong intermolecular hydrogen bonds in its crystalline structure. It is soluble in acids, bases and amines. Hitherto, several processes for preparing glyphosate have been known.
  • the pressure vessel or a glass reaction vessel are filled with a mixture of N-(phosphonomethy])iminodiacetic acid, water and 5% palladium, rhodium, platinum or iridium on carbon.
  • the mixture is heated to 70 - 120 °C and oxygen or pressurised air are continuously fed in.
  • the mixture is then cooled down to room temperature.
  • the catalyst is separated by filtration, and the filtrate sucked off.
  • N-(phosphonomethyl)iminodiacetic acid is mixed at increased temperature with a strong acid having a p K; ⁇ under 2.2. This results in the hydrolysis of N-(phosphonomethyl)iminodiacetic acid into glyphosate and other products.
  • the reaction mixture is then diluted with water and an organic water miscible solvent. Glyphosate precipitates.
  • N-(phosphonomethyl)iminodiacetic acid, water and hydrogen peroxide are heated to 20 - 65 °C in the presence of a catalyst, such as a water soluble molybdenum or wolfram (tungsten) salt. After some time the solution is cooled down and then a water soluble salt of vanadium, iron or copper. The temperature should not exceed 65 °C. Glyphosate precipitates and is isolated by filtration.
  • N-organo-N-(phosphonomethyl)aminodiacetic acid is dissolved in v HC1.
  • an electrolytic cell graphite anode, platinum cathode or a graphite cathode
  • the reaction may be performed at a temperature of 0 - 110 °C.
  • the reaction time is dependant on the current density, concentration on the electrode surface and the volume of the reaction solution.
  • the glyphosate may be isolated by means of extraction and recrystallisation, centrifugation, concentration and the like.
  • N-Benzyl-N-phosphonomethyl glycine and its esters in debenzylation with hydrogen halide acids yield benzyl halides and glyphosate or its esters.
  • the reaction temperature is 40 - 100 °C.
  • the process relates to the preparation of glyphosate by means of acid (HC1, HBr, HJ) catalysed hydrolysis of N-t-butyl-N-phosphonomethyl glycine and its esters.
  • the reaction temperature is 110 - 130 °C.
  • the basic characteristic is the existence ot oxygen, water and organic substances at supercritical conditions in a single homogeneous thud phase.
  • the supercritical water is an excellent medium in which organic substances are oxidised as a result ot high solubility ot organic components and oxygen.
  • the process must be performed in a corrosion resistant reactor
  • the heat generated in the decomposition ot the substances is used in the heating ot the supercritical water.
  • the process in accordance with the present invention may be pertormed in one of the apparatus schematically represented on Fig. 1 and Fig. 2.
  • Fig. 1 is represented an apparatus foi the charge performance of the process in accordance with the invention
  • the reference numei als stand toi : 1 - high-pressui e pump 2 - valve 3 - one-way vaK e
  • Glyphosate was isolated by concentrating the filtrate under reduced pressure in a rotary evaporator, or left to cool down and then sucked off. The formed crystals were dried in a drier for 2 hours at 105 °C. The crystals were analysed by HPLC. The synthesis yield was 80%.
  • Into the reactor represented on Fig. 1 were charged 170 is of water and 15 g of N- (phosphono-methyl)iminodiacetic acid. The reaction mixture was heated to 250 °C, and after that air enriched with oxygen (50%) was blown into it. The pressure in the reactor was 500 bar. In the cell a constant pressure was kept up, and the air flow was 0.1 - 10 g/min. The temperature was maintained by means of a heating jacket. The duration of the reaction was 10 minutes.
  • Glyphosate was isolated by concentrating the filtrate under reduced pressure in a rotary evaporator, or left to cool down and then sucked off. The formed crystals were dried in a drier for 2 hours at 105 °C. The crystals were analysed by HPLC. The synthesis punctd was 92%.
  • Into the reactor represented on Fig. 1 were charged 170 mis of water and 15 g of N- (phosphono-methyl)iminodiacetic acid. The reaction mixture was heated to 400 °C, and after that air enriched with oxygen (50%) was blown into it. The pressure in the reactor was 500 bar. In the cell a constant pressure was kept up, and the air flow was 0.1 - 10 g min. The temperature was maintained by means of a heating jacket. The duration of the reaction was 5 minutes. Glyphosate was isolated by concenti ating the filtrate under reduced pressure in a rotary evaporator, or left to cool down and then sucked off. The formed crystals were dried in a drier tor 2 houi s at 105 °C. The crystals were analysed by HPLC. The synthesis yield was 94%.
  • the duration ot the ieaction was varied in the range of 1 - 100 minutes.

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

Procédé de préparation de N-phosphonométhylglycine par oxydation par voie humide d'acide N-(phosphonométhyl)iminodiacétique à l'aide d'air enrichi en oxygène, ou de peroxyde d'hydrogène sous une pression de 100 à 1000 bars, une température de 50 à 500 °C et pendant un temps de réaction compris entre 0,01 et 10 heures. Le processus peut se dérouler dans des conditions souscritiques ou de préférence surcritiques d'oxydation par voie humide de l'acide N-(phosphonométhyl)iminodiacétique, et de préférence en continu. La N-phosphonométhylglycine connue sous l'appellation générique de glyphosate est une matière active utilisée dans les herbicides écologiques.
PCT/SI1995/000029 1994-12-20 1995-12-18 Procede de preparation de n-phosphonomethylglycine Ceased WO1996019485A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41278/96A AU4127896A (en) 1994-12-20 1995-12-18 Process for preparing n-phosphonomethyl glycine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SIP-9400449 1994-12-20
SI9400449A SI9400449A (en) 1994-12-20 1994-12-20 Process for preparing N-phosphonomethyl glycin

Publications (1)

Publication Number Publication Date
WO1996019485A1 true WO1996019485A1 (fr) 1996-06-27

Family

ID=20431508

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SI1995/000029 Ceased WO1996019485A1 (fr) 1994-12-20 1995-12-18 Procede de preparation de n-phosphonomethylglycine

Country Status (3)

Country Link
AU (1) AU4127896A (fr)
SI (1) SI9400449A (fr)
WO (1) WO1996019485A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092272A3 (fr) * 2000-05-22 2002-05-16 Monsanto Technology Llc Systemes de reaction pour preparer des composes de n-(phosphonomethyl)glycine
US6867326B1 (en) 1999-07-23 2005-03-15 Basf Aktiengesellschaft Method of producing glyphosate or a salt thereof
US7067693B1 (en) 1998-02-25 2006-06-27 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use in preparing N-(phosphonomethyl) glycine compounds
CN1301259C (zh) * 2004-01-16 2007-02-21 广东琪田农药化工有限公司 由双甘膦制备草甘膦的方法
US8252953B2 (en) 2008-05-01 2012-08-28 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
US8703639B2 (en) 2004-09-15 2014-04-22 Monsanto Technology Llc Oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
CN113185548A (zh) * 2021-05-10 2021-07-30 浙江新安化工集团股份有限公司 一种提高亚磷酸二甲酯利用率的草甘膦合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2186477A1 (fr) * 1972-05-31 1974-01-11 Monsanto Co
FR2269533A1 (fr) * 1974-05-01 1975-11-28 Monsanto Co
EP0019445A2 (fr) * 1979-05-11 1980-11-26 Nitrokemia Ipartelepek Procédé de préparation de N-phosphonométhyl-glycine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2186477A1 (fr) * 1972-05-31 1974-01-11 Monsanto Co
FR2269533A1 (fr) * 1974-05-01 1975-11-28 Monsanto Co
EP0019445A2 (fr) * 1979-05-11 1980-11-26 Nitrokemia Ipartelepek Procédé de préparation de N-phosphonométhyl-glycine

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7067693B1 (en) 1998-02-25 2006-06-27 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use in preparing N-(phosphonomethyl) glycine compounds
US8143441B2 (en) 1998-02-25 2012-03-27 Monsanto Technology Llc Deeply reduced oxidation catalyst and its use in preparing N-(phosphonomethyl) glycine compounds
US6867326B1 (en) 1999-07-23 2005-03-15 Basf Aktiengesellschaft Method of producing glyphosate or a salt thereof
EP1676851A3 (fr) * 2000-05-22 2009-06-03 Monsanto Technology, LLC systemes de reaction pour preparer des composes de n-(phosphonomethyl)glycine
US7504534B2 (en) 2000-05-22 2009-03-17 Monsanto Technology Llc Reaction systems for making N-(phosphonomethyl) glycine compounds
WO2001092272A3 (fr) * 2000-05-22 2002-05-16 Monsanto Technology Llc Systemes de reaction pour preparer des composes de n-(phosphonomethyl)glycine
US7015351B2 (en) 2000-05-22 2006-03-21 Monsanto Technology Llc Reaction systems for making N-(phosphonomethyl) glycine compounds
CN1301259C (zh) * 2004-01-16 2007-02-21 广东琪田农药化工有限公司 由双甘膦制备草甘膦的方法
US8703639B2 (en) 2004-09-15 2014-04-22 Monsanto Technology Llc Oxidation catalyst and its use for catalyzing liquid phase oxidation reactions
US8252953B2 (en) 2008-05-01 2012-08-28 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
US9163041B2 (en) 2008-05-01 2015-10-20 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
US9944667B2 (en) 2008-05-01 2018-04-17 Monsanto Technology Llc Metal utilization in supported, metal-containing catalysts
CN113185548A (zh) * 2021-05-10 2021-07-30 浙江新安化工集团股份有限公司 一种提高亚磷酸二甲酯利用率的草甘膦合成方法

Also Published As

Publication number Publication date
SI9400449A (en) 1996-06-30
AU4127896A (en) 1996-07-10

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