WO1996027602A1 - Procede de production de n-phosphonomethylglycine - Google Patents
Procede de production de n-phosphonomethylglycine Download PDFInfo
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- WO1996027602A1 WO1996027602A1 PCT/JP1996/000550 JP9600550W WO9627602A1 WO 1996027602 A1 WO1996027602 A1 WO 1996027602A1 JP 9600550 W JP9600550 W JP 9600550W WO 9627602 A1 WO9627602 A1 WO 9627602A1
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- WIPO (PCT)
- Prior art keywords
- activated carbon
- mol
- pmg
- hydrogen peroxide
- weight
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 58
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 233
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 148
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 238000002955 isolation Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- -1 N-phosphonomethyliminodisulfonic acid Chemical compound 0.000 description 2
- 241000801593 Pida Species 0.000 description 2
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- UVNLAUGZMOPBPR-UHFFFAOYSA-N 1-(2,4-dichlorobenzoyl)-1H-1,2,3-benzotriazole Chemical compound ClC1=CC(Cl)=CC=C1C(=O)N1C2=CC=CC=C2N=N1 UVNLAUGZMOPBPR-UHFFFAOYSA-N 0.000 description 1
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 1
- 241000272875 Ardeidae Species 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000010792 warming Methods 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)]
- C07F9/40—Esters thereof
-
- 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 present invention relates to an improved method for producing N-phosphonomethylglycine used as a raw material or an intermediate of N-phosphonomethylglycine widely used as a herbicide.
- PMIDA N-phosphonomethyliminodisulfonic acid
- water is used as a solvent
- N-phosphonomethylglycine N-phosphonomethylglycine
- activated carbon has a catalytic effect on the decomposition of hydrogen peroxide and is used as a reaction terminator.
- the publication (Example 6 page 9 under Hidarirandai line 5), when producing the PMG guanidine salt, hydrogen peroxide (H 2 0 2) was added to the PM I DA guanidine salt, the reaction After that, excess hydrogen peroxide is decomposed by adding activated carbon. That is, it describes that activated carbon was used as a reaction terminator.
- activated carbon activates hydrogen peroxide and PMIDA and is easily converted to PMG.
- the starting material of the present invention can be prepared by a method well known in the art, for example, the reaction of formaldehyde, iminodi S acid and orthophosphorous acid in the presence of sulfuric acid (JP-A-49-148620), A method of reacting iminodidronic acid with formaldehyde and phosphorous acid in the presence (JP-A-50-160222) or a method of adding phosphorus trichloride to an aqueous solution of sodium salt of iminodidronic acid and reacting it with formaldehyde It can be manufactured by the method described in JP-A-5-3743-1).
- the PMI DA used in the present invention may be manufactured by a method other than the above, and is not particularly limited.
- the activated carbon used in the present invention various types of activated carbon generally commercially available can be used.
- activated carbon on the market.
- classified from raw materials there are beet coal made from peat, lignite coal made from lignite or lignite, coal coal made from bituminous coal, wood and wood.
- activated carbon such as wood charcoal, wood charcoal, and coconut shell charcoal made from coconut husk, etc., and granulated coal, granulated charcoal, crushed charcoal, powdered charcoal, etc. classified according to shape.
- the activated carbon used in the present invention is exemplified below, but not all of them can be shown. However, it is natural that it should not be limited to these.
- Granular white 3 ⁇ 4Gc Granular white: StCc, Granular S Wc, Granular white Oshi WHc, Granular white: 3 ⁇ 4LHc, Granular white ⁇ WHA, Granular white 3 ⁇ 4GOC, Granular white ⁇ APRC: Granola, manufactured by Takeda Pharmaceutical Co., Ltd.
- White 3 ⁇ 4TAC Granulated S3 ⁇ 4MAC, Granulated White Oyster XRC and Granulated White NCC, Granulated White Oshi KL, Granulated White 3 ⁇ 4DC, Granulated White Egret Gx, Granulated White Purple Sx, Granulated White 3 ⁇ 4 Cx, X—7000, X—7100, Granular white 5 GHx, Granular white: KGHxUG, Granular white purple GSlx, Granular white: 3 ⁇ 4GS2x, Granular white 3 ⁇ 4GTx, Granular white GTSx, Granular white 3 ⁇ 4 Gx, Granular white 5 SRCx, Morsibon 3A, Morsibon 4A, Morsibon 5 A and aldenite, carboraffin, strong white 3 ⁇ 4, refined white purple, characteristic white lemon, white KA, white: HM, white 3 ⁇ 4C, white eagle P and white « ⁇ (:,
- BM-WA BM—WD, BM-AL, BM-AH, BM-GB, BM-GA, BM-GCA, MM-CD, MM-CB, MM-CBS, GM manufactured by Mitsui Pharmaceutical Co., Ltd. -GB, GM-GA, GM-GH, GM—AS, GM-AA, PM-PA, PM-PW, PM-PW1, PM-WA. PM-KI, PM-YO, PM-KS, PM-O PM-AA, PM-PE, PM-CR, PM-WA, PM-SX, PM-FZ and PM-SAY,
- Kuraray Coal GG Kuraray Cole GS, Kuraray Cole GC, Kuraray Cole SA, Kuraray Cole KG, Kuraray Cole GM, Kuraray Cole GW, Kuraray Cole GL, Kuraray Cole GLC, Kuraray Cole KW, Kuraray Cole Gulla GWC, Kuraray Cole PW, Kuraray Cole PW—W5, Kuraray Cole PK, Kuraray Cole III, Kuraray Cole II, Kuraray Cole G—II, Kuraray Cole II, S (:,
- Taiko TA Taiko TA, Taiko TS, Taiko TG, Taiko TM, Taiko GL 30, Taiko GL 30 A, Taiko GF 30 A, Taiko GF 50 A, Taiko CW 1303, Taiko CW130 BR, Taiko CW130 manufactured by Nimura Chemical Industry Co., Ltd.
- NOR IT PK NOR IT PKDA 10X30 MESH.
- NOR IT ELOR IT NOR IT AZO, NOR IT GRANULAR DARCO.
- NOR IT HYDRO DARCO NOR IT DARCO 8x30, NOR IT DARCO 12x20 LI, NOR IT DARCO 12x20 DC, NOR IT PETRO DARCO.
- NOR IT DARCO MRX NOR IT HYDRODARCO GCW ⁇ NOR IT HYDRODARCO GCL.
- NOR IT HYDRODARC O GTS NOR IT DARCO CF NOR IT DARCO VAP URE, N0R IT DARCO GCV, NOR IT C-GRANULAR, NOR IT ROW, NOR IT ROW 0.8 SUPER NOR IT RO, NOR IT ROX, NOR IT ROX 0.8, NOR IT RB, NOR IT R.
- NOR IT GL NOR IT CA
- the amount of the activated carbon used may be 0.1 part by weight or more based on 1 part by weight of PM IDA, preferably 0.1 to 0.75 part by weight, and most preferably 0.1 to 0.4 part by weight. If the amount is less than 0.1 part by weight, the reaction is not completed, a side reaction occurs, the purity is reduced, and the object of the present invention cannot be achieved. If the amount exceeds 0.75 parts by weight, the quality and yield are not adversely affected, but the effect is not expected as much as used, and it is not economical. Further, the purpose can be achieved with a smaller amount of powdered activated carbon than in granular form.
- the activated carbon used in the present invention After the activated carbon used in the present invention is used and recovered in the first reaction, it can be reused as it is for the second and subsequent reactions without renewal such as activation.
- One point is a major feature. Even if activated carbon is used multiple times, the activity as a catalyst does not decrease and is extremely economical. If activated carbon is lost in an operation such as filtration by using activated carbon multiple times, the loss may be supplemented.
- the hydrogen peroxide used in the present invention is generally 30-60% by weight commercially available. Aqueous solutions can be used and need not be further diluted with water.
- the amount of hydrogen peroxide used may be 2 moles or more, preferably 2 to 5 moles, and most preferably 2.0 to 2.5 moles, per mole of PMIDA. is there. If the amount is less than 2 mol, the reaction is not completed, and a large amount of PMIDA remains as an unreacted substance. Use of more than 5 moles does not adversely affect the quality and yield, but is not expected to be as effective as used and is not economical.
- the reaction between PMIDA and hydrogen peroxide in the present invention is an exothermic reaction, and the time for adding hydrogen peroxide varies depending on the cooling capacity of the equipment, but it may be within a range in which the heat of reaction can be removed. Since the reaction proceeds rapidly by the addition of hydrogen peroxide, it is not necessary to increase the aging time, and the reaction can be easily controlled. The end point of the reaction can be determined by monitoring the disappearance of PMIDA.
- the reaction of the present invention is completed in about 30 minutes to about 4 hours if the cooling capacity of the reaction equipment is sufficient.
- the reaction in the present invention proceeds in the presence of water, but the amount of water may be within a range in which the reaction solution can be stirred, and is not an amount sufficient to dissolve PMID ⁇ or PMG.
- the ratio is usually 1 part by weight or more with respect to 1 part by weight of PM IDA, and is preferably 2 to 10 parts by weight.
- the reaction temperature in the present invention is preferably 5 0 to 9 O 'C, is a more preferred temperature range face a 6 0 ⁇ 8 0 e C. If the temperature is lower than 50'C, the reaction progresses slowly. If the temperature exceeds 90'C, by-products are generated, and the purity and yield of the target product are reduced.
- the pressure at which the present invention is performed is not particularly limited as long as the object of the present invention is attained.
- the pressure may be lower than atmospheric pressure, atmospheric pressure or higher than atmospheric pressure. Does not need to be carried out above atmospheric pressure, atmospheric pressure is sufficient, and expensive, complicated and dangerous autoclaves such as those using activated carbon and oxygen-containing gas together do not need.
- the generated PMG is precipitated in a crystalline state or dissolved in an aqueous solution state.
- the following operation methods can be mentioned.
- Simplex method (C) In the simplex method (A) and the simplex method (B), hot carbon is filtered to separate activated carbon to obtain a liquid, which is added with a water-soluble organic solvent such as methanol, acetone or Acetonitrile or the like is added in an appropriate amount or more, for example, 1 volume or more with respect to the aqueous solution, and the PMG crystals are crystallized and isolated.
- the isolation method (C) usually increases the yield by several percent over the isolation method (A) or the isolation method (B).
- an inorganic base such as alkali hydroxide, preferably sodium hydroxide, or an organic base such as isopropylamine is used in an amount sufficient to react with the generated PMG to form a salt.
- Add an amine or the like to form a PMG salt form an aqueous solution of the PMG salt, filter the activated carbon, filter the acidified solution with a mineral acid, etc., and crystallize and isolate the PMG .
- the PMG obtained by the method of the present invention can be obtained at a high level and in both purity and yield, and is a satisfactory value for an industrial production method.
- a method of producing PMG by adding 2 to 5 mol of hydrogen peroxide to 1 mol of PM IDA while heating and stirring 1 part by weight of PM IDA, 0.1 to 0.75 parts by weight of activated carbon and water.
- a method for producing PMG by adding 1 to 1 part by weight of PM IDA, 0.1 to 0.75 part by weight of activated carbon and water and adding 2.0 to 2.5 mol of hydrogen peroxide to 1 mol of PM I DA while stirring and mixing.
- a method for producing PMG by adding 1 part by weight of PMI DA, 1 to 0.4 part by weight of activated carbon and water, and adding hydrogen peroxide while heating and stirring.
- a method of producing PMG by adding 1 to 5 parts by weight of PM IDA, 0.1 to 0.4 parts by weight of activated carbon and water and adding 2 to 5 moles of hydrogen peroxide to 1 mole of PM IDA while stirring.
- PIDA PIDA. A method of producing PMG by adding water and hydrogen peroxide to water and recovered activated carbon while heating and stirring.
- (21) A method of producing PMG by adding 1 to 2.5 mol of hydrogen peroxide while heating and stirring 1 mol of PMI DA, water and activated carbon under the IE atmosphere.
- (22) A method for producing PMG by adding hydrogen peroxide under heating and stirring 1 part by weight of PM IDA, 0.1 to 0.75 parts by weight of activated carbon and water under atmospheric pressure.
- (31) A method of producing PMG by adding 1 part by weight of PM IDA, 0.1 to 0.75 parts by weight of recovered activated carbon and water under atmospheric pressure, and adding hydrogen peroxide thereto.
- Examples include the production methods of Embodiments (9), (18), (27) and (36).
- the net yield of PMG is a value calculated by the total yield (Gross) x purity (PMG content) of the crystals obtained by singulation, and the yield is (Net yield of PMG) The theoretical amount of PMG) The value calculated by X100, and the conversion is (content of generated PMG (number of moles) amount of raw material PM IDA used (number of moles)) The value calculated by X100 Shown respectively.
- the content of PMG was determined by high performance liquid chromatography (HPLC).
- activated carbon shelves (1) are manufactured by Mitsui Pharmaceutical Co., Ltd., (2) are manufactured by llmicole, and (3) and (11) are Nimura Chemical ( (4) is made by Kuraray Chemical Co., Ltd. (5) and (12) are made by Takeda Pharmaceutical Co., Ltd. (6) to (9) and (13) to (15) are made by Nippon Norit ( Indicates a product of Hanuri Co., Ltd.
- Example 6 (1) The same reaction was performed 5 times using only the activated carbon recovered and used in the reaction of (1) in Example 6. (2) A similar reaction was performed 10 times using only the activated carbon recovered and used in the reaction of (6) in Example 6. (3) The same reaction was performed five times using only the activated carbon recovered and used in the reaction of (7) in Example 7. (4) The same reaction was performed 10 times using only the activated carbon recovered and used in the reaction of (8) in Example 7. Table 8 shows the results.
- Activated carbon (NOR I T SX—111 ⁇ 13 ⁇ 413 ⁇ 48) with 5.0 £? 20.0 g (0.088 mol) of ⁇ 110 A was added, and oxygen gas was introduced at 60-65 ° C with stirring at a flow rate of 46 ml / min for 8 hours (11.2-fold molar ZPM IDA).
- sodium hydroxide was added to form a PMG salt, and the resulting solution was used as an aqueous solution of the PMG salt.
- the solution was filtered to separate activated carbon, and the amount of PMG determined by HPLC was 3.66 g (0.0216 mol) ( (Conversion rate 24.6%) o
- the method of the present invention can be carried out under atmospheric pressure as compared with the prior art, so no pressure equipment is required, and since no acid is used, there is no problem of corrosion of the reactor, and it is toxic as a catalyst. It does not use metal compounds that may contain complex compounds, so there is no need for processing and it is safe.
- the reaction control is easy, and the used activated carbon can be recycled many times without regenerating. Good purity and yield, suitable for industrial production.
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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)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU48893/96A AU4889396A (en) | 1995-03-07 | 1996-03-07 | Process for producing n-phosphonomethylglycine |
US08/944,029 US5948938A (en) | 1995-03-07 | 1997-08-29 | Process for preparing N-phosphonomethylglycine |
HK98111858A HK1017360A1 (en) | 1995-03-07 | 1998-11-09 | Process for preparing n-phosphonomethylglycine |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4600595 | 1995-03-07 | ||
JP7/46005 | 1995-03-07 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/944,029 Continuation US5948938A (en) | 1995-03-07 | 1997-08-29 | Process for preparing N-phosphonomethylglycine |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996027602A1 true WO1996027602A1 (fr) | 1996-09-12 |
Family
ID=12734963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1996/000550 WO1996027602A1 (fr) | 1995-03-07 | 1996-03-07 | Procede de production de n-phosphonomethylglycine |
Country Status (6)
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999058537A1 (en) * | 1998-05-14 | 1999-11-18 | Calgon Carbon Corporation | Method for the manufacture of n - phosphonomethylglycine from n - phosphonomethyliminodiacetic acid using a catalytic carbon |
DE19938622A1 (de) * | 1999-08-14 | 2001-02-22 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von N-(Phosphonomethyl)glycin |
US6867326B1 (en) | 1999-07-23 | 2005-03-15 | Basf Aktiengesellschaft | Method of producing glyphosate or a salt thereof |
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CN101311183B (zh) * | 2000-05-22 | 2011-08-31 | 孟山都技术有限责任公司 | 制备n-(膦酰基甲基)甘氨酸化合物的反应系统 |
CN1221558C (zh) * | 2000-05-22 | 2005-10-05 | 孟山都技术有限责任公司 | 制备n-(膦酰基甲基)甘氨酸化合物的反应系统 |
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 |
CN104585228B (zh) * | 2005-03-04 | 2017-05-24 | 孟山都技术公司 | 减轻用除草剂草甘膦制剂处理的草甘膦耐受性转基因棉花植物内的坏死 |
CN101092429B (zh) * | 2006-06-23 | 2010-08-11 | 北京紫光英力化工技术有限公司 | 一种催化氧化法制备草甘膦的方法 |
CN101092428B (zh) * | 2006-06-23 | 2011-04-06 | 北京紫光英力化工技术有限公司 | 一种双甘膦空气氧化制备草甘膦的新工艺 |
CN101508701B (zh) * | 2008-12-10 | 2012-09-05 | 上海泰禾(集团)有限公司 | 一种活性碳作催化剂氧气氧化双甘膦制备草甘膦的方法 |
US9359390B2 (en) | 2010-03-31 | 2016-06-07 | Kuraray Chemical Co., Ltd. | Activated carbon and use therefor |
KR101246278B1 (ko) * | 2012-09-18 | 2013-03-22 | 주식회사 천보 | 이미노디아세트산의 합성방법 |
CN104829649A (zh) * | 2015-05-05 | 2015-08-12 | 安徽省益农化工有限公司 | 采用双甘膦为原料生产草甘膦的方法 |
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JPS58219193A (ja) * | 1982-03-08 | 1983-12-20 | ゲシユリ・ラボラトリ−ズ・リミテツド | N−ホスフオノメチルグリシン誘導体 |
JPS597196A (ja) * | 1982-06-25 | 1984-01-14 | ゲシユリ・ラボラトリ−ズ・リミテツド | N−ホスホノメチルグリシン誘導体の製造方法、除草活性化合物および組成物 |
JPS60246328A (ja) * | 1984-05-10 | 1985-12-06 | モンサント コンパニー | 第2アミン及び第1アミンの選択的製造方法 |
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US3969398A (en) * | 1974-05-01 | 1976-07-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
US4624937A (en) * | 1984-05-10 | 1986-11-25 | Monsanto Company | Process for removing surface oxides from activated carbon catalyst |
DE69807061T2 (de) * | 1997-05-09 | 2003-02-27 | The Procter & Gamble Company, Cincinnati | Flexible zusammenlegbare selbsttragende beutel und behälter |
-
1996
- 1996-03-05 TW TW085102684A patent/TW322481B/zh active
- 1996-03-07 AU AU48893/96A patent/AU4889396A/en not_active Abandoned
- 1996-03-07 KR KR1019970706115A patent/KR19980702708A/ko active IP Right Grant
- 1996-03-07 WO PCT/JP1996/000550 patent/WO1996027602A1/ja active IP Right Grant
- 1996-03-07 CN CN96193655A patent/CN1066152C/zh not_active Expired - Fee Related
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1998
- 1998-11-09 HK HK98111858A patent/HK1017360A1/xx not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS58219193A (ja) * | 1982-03-08 | 1983-12-20 | ゲシユリ・ラボラトリ−ズ・リミテツド | N−ホスフオノメチルグリシン誘導体 |
JPS597196A (ja) * | 1982-06-25 | 1984-01-14 | ゲシユリ・ラボラトリ−ズ・リミテツド | N−ホスホノメチルグリシン誘導体の製造方法、除草活性化合物および組成物 |
JPS60246328A (ja) * | 1984-05-10 | 1985-12-06 | モンサント コンパニー | 第2アミン及び第1アミンの選択的製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999058537A1 (en) * | 1998-05-14 | 1999-11-18 | Calgon Carbon Corporation | Method for the manufacture of n - phosphonomethylglycine from n - phosphonomethyliminodiacetic acid using a catalytic carbon |
US6867326B1 (en) | 1999-07-23 | 2005-03-15 | Basf Aktiengesellschaft | Method of producing glyphosate or a salt thereof |
DE19938622A1 (de) * | 1999-08-14 | 2001-02-22 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von N-(Phosphonomethyl)glycin |
DE19938622C2 (de) * | 1999-08-14 | 2002-10-02 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von N-(Phosphonomethyl)glycin |
Also Published As
Publication number | Publication date |
---|---|
AU4889396A (en) | 1996-09-23 |
HK1017360A1 (en) | 1999-11-19 |
KR19980702708A (ko) | 1998-08-05 |
CN1183100A (zh) | 1998-05-27 |
TW322481B (US20020095090A1-20020718-M00002.png) | 1997-12-11 |
CN1066152C (zh) | 2001-05-23 |
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