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WO2011069324A1 - Cristal de sel diméthylaminé de glyphosate, son procédé de préparation et son utilisation - Google Patents

Cristal de sel diméthylaminé de glyphosate, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2011069324A1
WO2011069324A1 PCT/CN2010/001692 CN2010001692W WO2011069324A1 WO 2011069324 A1 WO2011069324 A1 WO 2011069324A1 CN 2010001692 W CN2010001692 W CN 2010001692W WO 2011069324 A1 WO2011069324 A1 WO 2011069324A1
Authority
WO
WIPO (PCT)
Prior art keywords
glyphosate
crystal
salt
dimethylamine
dimethylamine salt
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/CN2010/001692
Other languages
English (en)
Chinese (zh)
Inventor
王伟
周曙光
秦龙
任不凡
钱志刚
刘韬
佘慧玲
章娅仙
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.)
Zhejiang Xinan Chemical Industrial Group Co Ltd
Original Assignee
Zhejiang Xinan Chemical Industrial Group Co Ltd
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 Zhejiang Xinan Chemical Industrial Group Co Ltd filed Critical Zhejiang Xinan Chemical Industrial Group Co Ltd
Priority to US13/514,464 priority Critical patent/US9221853B2/en
Priority to BR112012013914A priority patent/BR112012013914A2/pt
Priority to CN2010800561580A priority patent/CN102803278A/zh
Priority to AU2010330585A priority patent/AU2010330585B2/en
Publication of WO2011069324A1 publication Critical patent/WO2011069324A1/fr
Priority to ZA2012/04116A priority patent/ZA201204116B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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)]
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/04—Mono-, di- or tri-methylamine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the preparation of glyphosate salt is still mainly based on water. Since the liquid contains a large amount of water, it causes inconvenience in packaging, transportation, and storage, and increases costs. With the development and demand of the market, the technical requirements for preparing high-content glyphosate salt solid preparations are becoming more and more urgent.
  • Chinese patent application CN99119971.5 filed by the present applicant discloses a method for preparing glyphosate ammonium salt particles by using glyphosate acid as a raw material, and adding glyphosate acid to an autoclave with a stirrer.
  • the liquid ammonia is reacted, and the weight ratio of glyphosate acid to liquid ammonia is 1 : 0.5-1 : 5 , the reaction heat was removed in time during the reaction.
  • the discharge valve was opened, and the product ammonium glyphosate was pressed into a pressure relief tank to prepare granulated glyphosate ammonium salt particles.
  • the powder has a powder X-ray diffraction pattern having at least one or more peaks at 2 ⁇ (.) ( ⁇ 0.2) of 14.26, 20.44, 20.47, 25.19, 27.49 and 33.51.
  • the organic solvent has a lower ability to dissolve the glyphosate dimethylamine salt than the water to dissolve the glyphosate dimethylamine salt, and is selected from the group consisting of the following organic solvents: Methanol, ethanol, glycerol, butanol, cyclohexanol, acetone, toluene, xylene, diethyl ether, tetrahydrofuran, and mixtures thereof.
  • a method of controlling weeds or unwanted plants comprising applying glyphosate diterpenes according to any one of claims 1 to 7 for the weeds or unwanted plants or their habitats to be dissolved in water.
  • the invention provides a compound of formula (I) in the form of a crystal of the formula (I) N-phosphonomethylglycine dimethylamine salt dimethylamine salt):
  • the powder has a powder X-ray diffraction pattern having at least one or more, for example 2, 3, 4, 5 or 6 at 2 ⁇ (.) ( ⁇ 0.2) of 14.26, 20.44, 20.47, 25.19, 27.49 and 33.51. High intensity diffraction peaks.
  • the powder X-ray diffraction pattern of the crystal also contains 2 turns (.) ( ⁇ 0.2) are 14.16, 14.32, 17.30, 17.40, 17.80, 17.83, 20.27, 21.04, 23.31, 23.45, 25.05, 26.42, 26.46, 27.43, 27.59, 28.70, 28.80, 30.40, 30.43, 30.47, 33.11, 33.31, 33.34
  • the melting point of the glyphosate diamine salt crystal of the present invention was determined to be 155.5 to 156.1 ° C (measuring instrument BUCHI B545 melting point measuring instrument).
  • the present invention preferably controls the reaction temperature to 40 to 90 ° C, more preferably 50 to 70 ° C.
  • the mother liquid after precipitation of the crystal contains a solvent and a small amount of glyphosate dimethylamine salt, and the mother liquor can be returned to the solvent to continue the next batch reaction, and an appropriate amount of the organic solvent is added to make up the solvent caused by the loss of part of the mother liquor. Insufficient problems.
  • the mother liquor can be directly used for recycling, for example, recycling 6 ⁇ 15 batches. After the last batch of mother liquor is distilled or refined to recover the solvent, the residual liquid can be used to prepare glyphosate dimethylamine brine, such as glyphosate II. Indoleamine salt
  • an organic solvent which is miscible or partially miscible with water in an amount of 1 to 10 times by volume is added to the reaction mixture, and is cooled to 15 to 50 ° with slow stirring.
  • C preferably 15 to 35 ° C, the crystals of glyphosate diamine salt crystallized by suction filtration or centrifugation.
  • the ability to dissolve the glyphosate dimethylamine salt should be less than the ability of the water to dissolve the glyphosate dimethylamine salt, including sterol, ethanol, Glycerol, acetone, cyclohexanol, butanol, toluene, xylene, diethyl ether, tetrahydrofuran, and the like, and mixtures thereof.
  • R is preferably a linear or branched, saturated or unsaturated hydrocarbon of from C 6 to C 18 , more preferably from C 8 to C 12 ; n is from 1 to 8, for example, but not limited to, APG0810, APG1214, APG0814, APG0816 , APG 1216, etc.
  • the fatty amine polyoxyethylene ether has the following formula:
  • the glyphosate dimethylamine salt solid herbicidal preparation prepared by using the glyphosate dimethylamine salt crystal of the invention has a high content of glyphosate, which greatly saves the production, packaging, storage and transportation cost of the product; Comparing, the glyphosate diamine salt crystal itself and the glyphosate diamine salt solid preparation having high glyphosate content are more convenient and labor-saving to use and carry; and further, the invention proves that the glyphosate The herbicidal efficacy of the amine salt crystal itself and the high glyphosate content of the glyphosate dimethylamine salt solid preparation is higher than that of the aqueous product.
  • the sample was weighed according to the amount of active ingredient of 60 g/mu (calculated as glyphosate), diluted to 30 liters/mu with water, and the resulting diluted solution was sprayed evenly into the test face plot.
  • the test area was 2 m X 2.5 m and was repeated twice.
  • Weeds are annual weeds that are in a mature period: Gramineae, Goosegrass, and Aphis gossypii, and perennial weeds: Peanuts.
  • the weather was fine on the day of application and the maximum temperature was 37 °C.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un composé actif phytocide, le cristal de sel diméthylaminé de glyphosate, son procédé de préparation, une préparation solide contenant ledit cristal et son utilisation. Le procédé de préparation comprend les étapes suivantes : réaction du glyphosate avec de la diméthylamine gazeuse selon un rapport molaire de 1 à 1,0-3,0 dans un solvant organique à une température d'environ 5 à 90 °C pendant environ 1 h 30 à 5 heures, refroidissement lent jusqu'à environ -5 à 50 °C, addition de germes de cristaux en vue de la cristallisation avec agitation lente pendant environ 1 à 2 heures, filtration et séchage.
PCT/CN2010/001692 2009-12-09 2010-10-25 Cristal de sel diméthylaminé de glyphosate, son procédé de préparation et son utilisation Ceased WO2011069324A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US13/514,464 US9221853B2 (en) 2009-12-09 2010-10-25 Glyphosate dimethylamine salt crystal, preparation method and use thereof
BR112012013914A BR112012013914A2 (pt) 2009-12-09 2010-10-25 sal cristalino de dimetilamina de glifosato e processo de produção e uso do mesmo
CN2010800561580A CN102803278A (zh) 2009-12-09 2010-10-25 草苷膦二甲胺盐晶体及其制法和应用
AU2010330585A AU2010330585B2 (en) 2009-12-09 2010-10-25 Glyphosate dimethylamine salt crystal, preparation method and use thereof
ZA2012/04116A ZA201204116B (en) 2009-12-09 2012-06-05 Glyphosate dimethylamine salt crystal,preparation method and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910154988A CN101723973B (zh) 2009-12-09 2009-12-09 一种制备草甘膦二甲胺盐固体的方法
CN200910154988.6 2009-12-09

Publications (1)

Publication Number Publication Date
WO2011069324A1 true WO2011069324A1 (fr) 2011-06-16

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/001692 Ceased WO2011069324A1 (fr) 2009-12-09 2010-10-25 Cristal de sel diméthylaminé de glyphosate, son procédé de préparation et son utilisation

Country Status (8)

Country Link
US (1) US9221853B2 (fr)
CN (2) CN101723973B (fr)
AR (1) AR079337A1 (fr)
AU (1) AU2010330585B2 (fr)
BR (1) BR112012013914A2 (fr)
UY (1) UY33096A (fr)
WO (1) WO2011069324A1 (fr)
ZA (1) ZA201204116B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101723973B (zh) * 2009-12-09 2012-09-26 浙江新安化工集团股份有限公司 一种制备草甘膦二甲胺盐固体的方法
CN102870803A (zh) * 2011-07-11 2013-01-16 浙江新安化工集团股份有限公司 固体除草剂组合物
CN103819375B (zh) * 2014-01-21 2016-04-13 青岛惠国新材料科技有限公司 一种高纯度固体福美钠的合成方法
CN104592014A (zh) * 2015-01-04 2015-05-06 安徽省化工研究院 一种麦草畏二甲胺盐原料药的制备方法
CN106279271A (zh) * 2015-06-01 2017-01-04 浙江金帆达生化股份有限公司 一种制备高含量草甘膦异丙胺盐的方法
CN106188137B (zh) * 2015-06-01 2018-04-24 浙江金帆达生化股份有限公司 一种制备高含量草甘膦二甲胺盐的方法
CN106259324B (zh) * 2016-07-14 2020-03-17 山东润博生物科技有限公司 一种草甘膦二甲胺盐水溶性粒剂及其制备方法
CN106614719A (zh) * 2016-12-27 2017-05-10 四川福思达生物技术开发有限责任公司 一种含草甘膦二甲胺盐和异壬酸二甲胺盐的农药组合物及其制备方法和应用
CN109757472A (zh) * 2017-11-09 2019-05-17 山东润博生物科技有限公司 一种羧酸类二甲胺盐颗粒剂的制备方法
CN109757484A (zh) * 2017-11-09 2019-05-17 山东润博生物科技有限公司 一种农药二甲胺盐水剂的制备方法
CN109757482A (zh) * 2017-11-09 2019-05-17 山东润博生物科技有限公司 一种农药二甲胺盐水剂的连续化制备方法
CN110437279B (zh) * 2019-08-27 2022-02-08 鹤壁市鹤农生物科技有限公司 一种草甘膦铵盐原药的制备方法

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US3799758A (en) * 1971-08-09 1974-03-26 Monsanto Co N-phosphonomethyl-glycine phytotoxicant compositions
US5324708A (en) * 1991-04-16 1994-06-28 Aklaloida Vegyeszeti Gyar Rt. Non-hygroscopic monoammonium salts of phosphonic and phosphinic acids
HU214948B (hu) * 1992-10-26 1998-08-28 Monsanto Europe S.A. Eljárás nemhigroszkópos N-(foszfono-metil)-glicin-monoammónium-sók előállítására
CN101723973A (zh) * 2009-12-09 2010-06-09 浙江新安化工集团股份有限公司 一种制备草甘膦二甲胺盐固体的方法

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US4659860A (en) * 1971-08-09 1987-04-21 Monsanto Company Thioester of n-phosphonomethylglycine
CN1260344A (zh) 1999-08-13 2000-07-19 浙江新安化工集团股份有限公司 三氯乙酰氯的制备方法
CN1165541C (zh) 2000-08-31 2004-09-08 浙江新安化工集团股份有限公司 草甘膦酸铵合成工艺
CN1244587C (zh) 2002-09-05 2006-03-08 浙江新安化工集团股份有限公司 气－液－固三相反应及溶剂萃取制备草甘膦酸铵
CN101186622B (zh) 2006-11-17 2013-03-20 浙江新安化工集团股份有限公司 一种制备固体草甘膦钾盐的方法
CN1958594B (zh) * 2006-11-17 2011-08-10 浙江新安化工集团股份有限公司 一种制备草甘膦异丙胺盐固体的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3799758A (en) * 1971-08-09 1974-03-26 Monsanto Co N-phosphonomethyl-glycine phytotoxicant compositions
US5324708A (en) * 1991-04-16 1994-06-28 Aklaloida Vegyeszeti Gyar Rt. Non-hygroscopic monoammonium salts of phosphonic and phosphinic acids
HU214948B (hu) * 1992-10-26 1998-08-28 Monsanto Europe S.A. Eljárás nemhigroszkópos N-(foszfono-metil)-glicin-monoammónium-sók előállítására
CN101723973A (zh) * 2009-12-09 2010-06-09 浙江新安化工集团股份有限公司 一种制备草甘膦二甲胺盐固体的方法

Also Published As

Publication number Publication date
AR079337A1 (es) 2012-01-18
US9221853B2 (en) 2015-12-29
ZA201204116B (en) 2013-02-27
AU2010330585B2 (en) 2016-04-21
BR112012013914A2 (pt) 2016-04-26
CN101723973B (zh) 2012-09-26
UY33096A (es) 2011-04-29
AU2010330585A1 (en) 2012-06-21
US20150307528A1 (en) 2015-10-29
CN102803278A (zh) 2012-11-28
CN101723973A (zh) 2010-06-09

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