WO2004014925A1 - Process for producing n-phosphonomethylglycine - Google Patents

Process for producing n-phosphonomethylglycine Download PDF

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Publication number
WO2004014925A1
WO2004014925A1 PCT/IB2002/004795 IB0204795W WO2004014925A1 WO 2004014925 A1 WO2004014925 A1 WO 2004014925A1 IB 0204795 W IB0204795 W IB 0204795W WO 2004014925 A1 WO2004014925 A1 WO 2004014925A1
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WO
WIPO (PCT)
Prior art keywords
sulphate
phosphonomethylglycine
phosphonomethyliminodiacetic acid
mixture
oxide
Prior art date
Application number
PCT/IB2002/004795
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French (fr)
Inventor
Pedro Brito Correia
Maria Florbela BENTO MARTINHO DE SÁ PEREIRA
Original Assignee
Pedro Brito Correia
Bento Martinho De Sa Pereira M
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 Pedro Brito Correia, Bento Martinho De Sa Pereira M filed Critical Pedro Brito Correia
Priority to AU2002351013A priority Critical patent/AU2002351013A1/en
Publication of WO2004014925A1 publication Critical patent/WO2004014925A1/en

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    • 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 System
    • 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, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, 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 present invention describes a process for the preparation N- phosphonomethylglycine, by the formation of N-oxide-N- phosphonomethyliminodiacetic acid, with hydrogen peroxide in the presence of a mixture of catalyst containing tungsten and chromium salts, thereafter converting the intermediate N-oxide-N-phosphonomethyliminodiacetic acid to N- phosphonomethylglycine.
  • the present invention describes a process for the production N- phosphonomethylglycine by reacting N-phosphonomethyliminodiacetic acid with hydrogen peroxide in the presence of an effective amount of a catalyst consisting a mixture of alkaline metal tungstates and alkaline metal chromates to form an intermediate N-oxide-N-phosphonomethyliminodiacetic acid, at temperatures of the 71-73°C.
  • the intermediate is than converted to N- phosphonomethylglycine in the presence of iron (II) sulphate, nickel (II) sulphate and cobalt (II) sulphate.
  • the concentration of the hydrogen peroxide is very important for the yield of final reaction, the better results are obtained with concentrations between 35- 45 % on weight.
  • the amount of catalyst to convert the N-phosphonomethyliminodiacetic acid to the intermediate N-oxide-N-phosphonomethyliminodiacetic acid can vary within wide limits. The better results are obtained with concentrations between 0,01 and 0,3 % on the weight of the N-phosphonomethyliminodiacetic acid.

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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)

Abstract

The present invention describes a process for the preparation N-phosphonomethylglycine, by the formation of N-oxide-N-phosphonomethyliminodiacetic acid, with hydrogen peroxide in the presence of a mixture of catalyst containing tungsten and chromium salts, thereafter converting the intermediate N-oxide-N-phosphonomethyliminodiacetic acid to N-phosphonomethylglycine, in the present of a mixture of catalysts containing iron, nickel and cobalt salts, at new particular reaction conditions.

Description

Process for producing N-phosphonomethylglycine
DESCRIPTION
1. Field of invention
Chemical industry.
2. Background of the invention
The present invention describes a process for the preparation N- phosphonomethylglycine, by the formation of N-oxide-N- phosphonomethyliminodiacetic acid, with hydrogen peroxide in the presence of a mixture of catalyst containing tungsten and chromium salts, thereafter converting the intermediate N-oxide-N-phosphonomethyliminodiacetic acid to N- phosphonomethylglycine.
There are many methods for the preparation of the N- phosphonomethylglycine by the oxidation of N-phosphonomethyliminodiacetic acid with hydrogen peroxide1,2'3, using as catalyst noble metals1, silver2, iron2, lead2, manganese2, molybdenum2, mixture of the tungstates3 and molybdates3. Each one of the described methods used specific interval of the temperature and suitable catalyst concentrations.
Although satisfactory results are obtained by the described methods1 ,2,3 to make N-phosphonomethylglycine, all of them present one or more disadvantages, such as the use of excessive amounts of hydrogen peroxide2, elevated temperatures1, side products and elevated amounts of the catalyst3.
The paper4 of the company Interox published the use of sodium tungstate and sodium molibdate as a catalyst in the reaction of oxidation of aminoacids. ..
The patent2 claims protection for the use of iron salts in the oxidation of N- phosphonomethyliminodiacetic acid to N-phosphonomethylglycine.
The patent1- claims protection for a particular range of temperatures and concentrations for the use of both the catalyst sodium tungstate and iron salts in the oxidation of N-phosphonomethyliminodiacetic acid to N- phosphonomethylglycine.
We found that a better range of temperatures and concentrations can be chosen, in order to improve the yield and reducing side productos.
3. Detailed description of the invention
The present invention describes a process for the production N- phosphonomethylglycine by reacting N-phosphonomethyliminodiacetic acid with hydrogen peroxide in the presence of an effective amount of a catalyst consisting a mixture of alkaline metal tungstates and alkaline metal chromates to form an intermediate N-oxide-N-phosphonomethyliminodiacetic acid, at temperatures of the 71-73°C. The intermediate is than converted to N- phosphonomethylglycine in the presence of iron (II) sulphate, nickel (II) sulphate and cobalt (II) sulphate.
Figure imgf000003_0001
The concentration of the hydrogen peroxide is very important for the yield of final reaction, the better results are obtained with concentrations between 35- 45 % on weight. The amount of catalyst to convert the N-phosphonomethyliminodiacetic acid to the intermediate N-oxide-N-phosphonomethyliminodiacetic acid can vary within wide limits. The better results are obtained with concentrations between 0,01 and 0,3 % on the weight of the N-phosphonomethyliminodiacetic acid.
The best results have been obtained when the ratio of alkaline metal tungstates and alkaline metal chromates 70:30.
To catalyse the reaction of the N-oxide-N-phosphonomethyliminodiacetic acid to N-phosphonomethylglycine is used a mixture of iron (II) sulphate, nickel (II) sulphate and cobalt (II) sulphate. Excellent results are obtained with concentrations between 0,5 and 2 % on the weight of the N- phosphonomethyliminodiacetic acid.
EXEMPLE
To a 500 ml round bottom flask was added:
- N-phosphonomethyliminodiacetic acid 113,5 g -Water 170 g
- Sodium tungstate/sodium chromate 0,1 g
The mixture was heated to 71 °C, was added 51 g of the hydrogen peroxide 40 % (1,2 eq) and maintained at this temperature until a solution was obtained (about 1:30 hours). The solution was then allowed to cool to room temperature, was added a aqueous solution of a mixture of iron (II) sulphate and nickel (II) sulphate (0,5 g FeSθ4, 0,5 g NiSO4, 9,0 g water) and maintained the temperature between 50 and 80 °C. The reaction mixture was allowed to cool to room temperature from 12 hours, the solids were filtered and the filtrate and solids were analyzed by HPLC. The conversion of N- phosphonomethyliminodiacetic acid to N-phosphonomethylglycine was 94 %. BIBLIOGRAPHY
1. United States patent; 3,950 ,402 (13-04-1976).
2. Hungarian patent; 187,347 (28-12-1985).
3. European patent; 464,018 (24-01 -1991 ).
4. "Peroxygen Compounds in Organic Synthesis", Interox.

Claims

1. Process for producing N-phosphonomethylglycine by the oxidation of N- phosphonomethyliminodiacetic acid to form an intermediate N-oxide-N- phosphonomethyliminodiacetic acid and converting the intermediate to N- phosphonomethylglycine, characterised for using hydrogen peroxide as oxidative agent and catalytic amount of a mixture of alkaline metal tungstate and alkaline metal chromate, to form N-oxide-N- phosphonomethyliminodiacetic acid at temperature of 71-73°C and thereafter converting the N-oxide-N-phosphonomethyliminodiacetic acid to N- phosphonomethylglycine in the presence of a mixture of iron (II) sulphate and nickel (II) sulphate or cobalt (II) sulphate.
2. In the process of claim 1 wherein the amount of catalyst is between 0,01 % and 0,3 %, based on the weight of the N-phosphonomethyliminodiacetic acid.
3. In the process of claim 2 wherein the catalyst is a mixture of alkaline metal tungstate and alkaline metal chromate.
4. In the process of claim 3 wherein the weight ratio of tungsten compound to chromium compound is 70:30.
5. In process of claim 1 characterised for using to convert the intermediate, N- oxide-N-phosphonomethyliminodiacetic acid to N-phosphonomethylglycine a mixture of iron (II) sulphate and nickel (II) sulphate or cobalt (II) sulphate in concentrations between 0,5 % and 2 % based on the weight of the N- phosphonomethyliminodiacetic acid.
6. In process of claim 5 where the concentration of iron (II) sulphate to nickel (II) sulphate or cobalt (II) sulphate is 10:0,5,to 10:0,1.
PCT/IB2002/004795 2002-08-12 2002-11-18 Process for producing n-phosphonomethylglycine WO2004014925A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002351013A AU2002351013A1 (en) 2002-08-12 2002-11-18 Process for producing n-phosphonomethylglycine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT102827 2002-08-12
PT10282702A PT102827B (en) 2002-08-12 2002-08-12 PROCESS OF PRODUCTION N- (PHOSPHONOMETHYL) GLYCINE

Publications (1)

Publication Number Publication Date
WO2004014925A1 true WO2004014925A1 (en) 2004-02-19

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PCT/IB2002/004795 WO2004014925A1 (en) 2002-08-12 2002-11-18 Process for producing n-phosphonomethylglycine

Country Status (3)

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PT (1) PT102827B (en)
WO (1) WO2004014925A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2808421C1 (en) * 2022-12-28 2023-11-28 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) Method of producing n-(phosphonomethyl)-glycine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0464018A1 (en) * 1990-06-25 1992-01-02 Monsanto Company Process for producing N-phosphonomethylglycine
US5095140A (en) * 1990-06-25 1992-03-10 Monsanto Company Peroxide process for producing N-phosphonomethylglycine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0464018A1 (en) * 1990-06-25 1992-01-02 Monsanto Company Process for producing N-phosphonomethylglycine
US5095140A (en) * 1990-06-25 1992-03-10 Monsanto Company Peroxide process for producing N-phosphonomethylglycine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2808421C1 (en) * 2022-12-28 2023-11-28 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) Method of producing n-(phosphonomethyl)-glycine

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PT102827A (en) 2004-02-27
AU2002351013A1 (en) 2004-02-25
PT102827B (en) 2004-07-30

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