WO2021134242A1 - New crystal form of flucarbazone-sodium - Google Patents

New crystal form of flucarbazone-sodium Download PDF

Info

Publication number
WO2021134242A1
WO2021134242A1 PCT/CN2019/130009 CN2019130009W WO2021134242A1 WO 2021134242 A1 WO2021134242 A1 WO 2021134242A1 CN 2019130009 W CN2019130009 W CN 2019130009W WO 2021134242 A1 WO2021134242 A1 WO 2021134242A1
Authority
WO
WIPO (PCT)
Prior art keywords
flucarbazone
sodium
crystal form
new crystal
herbicidal composition
Prior art date
Application number
PCT/CN2019/130009
Other languages
French (fr)
Inventor
James Timothy BRISTOW
Original Assignee
Jiangsu Rotam Chemistry 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 Jiangsu Rotam Chemistry Co., Ltd filed Critical Jiangsu Rotam Chemistry Co., Ltd
Priority to PCT/CN2019/130009 priority Critical patent/WO2021134242A1/en
Priority to CA3166234A priority patent/CA3166234A1/en
Priority to CN201980103367.7A priority patent/CN114929677A/en
Publication of WO2021134242A1 publication Critical patent/WO2021134242A1/en

Links

Images

Classifications

    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to a new crystal of flucarbazone-sodium and a preparation method therefor.
  • Flucarbazone-sodium also known as flucarbazone, which is usually present in the form of a sodium salt. Its English name is flucarbazone-sodium, and its Chinese chemical name is 1H-1, 2, 4-triazolyl-1-carbamoyl-4, 5-2H-3-methoxy-4-methyl-5-O-N- [ [2- (trifluoromethoxy) benzene] sulfonyl] -sodium salt. Flucarbazone-sodium belongs to sulfonylurea herbicides, and is firstly developed by Bayer in 1995 and later acquired by Arysta in 2002.
  • the mechanism of action thereof is to inhibit a reaction of acetolactate synthase (ALS) for producing precursors of side chain amino acids, leucine, isoleucine and valine, after absorption via roots, stems and leaves, thereby killing weeds; it is a selective post-emergence herbicide for treating stems and leaves.
  • ALS acetolactate synthase
  • Flucarbazone-sodium is a highly efficient and broad-spectrum herbicide, which can be applied to prevent and kill gramineae and some important broadleaf weeds in wheat fields and is safe for next-stubble crops.
  • US 5534486 discloses this compound and discloses a synthesis route for this compound and synthesis examples of analogs.
  • CN 106478533 A discloses an improved process for the synthesis of flucarbazone-sodium, wherein methyl isobutyl ketone (MIBK) is used as a solvent, 50%NaOH is then added to form a salt, and after completion, centrifugation is carried out to obtain the flucarbazone-sodium.
  • MIBK methyl isobutyl ketone
  • An object of the present invention is to provide new crystal form I of flucarbazone-sodium, characterized in that an X-ray powder diffraction pattern of said new crystal form I recorded by using Cu-Ka radiation at 25°C shows at least 3 (e.g. 3, 4, 5, 6, 7, 8, 9, 10 or 11) of the following reflections at 2 ⁇ values in any combination:
  • said new crystal form I of flucarbazone-sodium is characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25°C shows at least 4 of the following reflections at 2 ⁇ values in any combination:
  • said new crystal form I of flucarbazone-sodium is characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25°C shows at least 3 of the following reflections at 2 ⁇ values in any combination:
  • said new crystal form I of flucarbazone-sodium has an X-ray powder diffraction pattern as shown in figure 1.
  • Figure 2 is an XRD pattern of the flucarbazone-sodium hemihydrate disclosed in US 10238112 B by Arysta.
  • Another object of the present invention is to provide a method for preparing said new crystal form I of flucarbazone-sodium.
  • the method for preparing the new crystal form I of flucarbazone-sodium, as involved in the present invention comprises the following steps:
  • step b) heating the mixture prepared in step a) to 30°C-100°C, for example, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C; and
  • the “organic solvent” in step a) refers to a nitrile solvent such as acetonitrile; an alcohol solvent such as methanol; a ketone solvent such as acetone; or a mixture of the above-mentioned solvents.
  • a nitrile solvent such as acetonitrile
  • an alcohol solvent such as methanol
  • a ketone solvent such as acetone
  • acetonitrile or a mixture of acetonitrile and other solvents is used as a crystallization solvent.
  • the solution in step b) is preferably heated to 30°C-70°C, especially preferably a temperature of 30°C-60°C, such as 35°C, 40°C, 45°C, 50°C, or 55°C.
  • said separation method involves centrifugation and then filtration.
  • the present invention also provides a herbicidal composition, which contains the new crystal form I of flucarbazone-sodium as an active ingredient and also comprises a filler and/or a surfactant.
  • the herbicidal composition according to the present invention has advantageously improved storage stability, without significant reduction in performance indexes, such as and spontaneous dispersibility, suspensibility after long-term storage.
  • the herbicidal composition of the present invention has significantly improved physical and chemical performance indexes after long-term storage.
  • the content of said active ingredient, the new crystal form I of flucarbazone-sodium accounts for 1%-90%, preferably 10%-90%, preferably 20%-90%, more preferably 30%-90%, more preferably 50%-90%, and more preferably 50%-80%of said herbicidal composition.
  • Dosage forms for the herbicidal composition of the present invention are a suspension concentrate (SC) , an oil-based suspension concentrate (OD) , soluble granules (SG) , a dispersible concentrate (DC) , an emulsifiable concentrate (EC) , a flowable concentrate for seed treatment (FS) , granules (GR) , microgranules (MG) , a suspo-emulsion (SE) , a water soluble powder (WP) and water dispersible granules (WG) .
  • SC suspension concentrate
  • OD oil-based suspension concentrate
  • SG soluble granules
  • DC dispersible concentrate
  • EC emulsifiable concentrate
  • FS flowable concentrate for seed treatment
  • GR granules
  • MG microgranules
  • SE suspo-emulsion
  • WP water soluble powder
  • WP water dispersible granules
  • Said “filler” may be solid or liquid.
  • Suitable liquid carriers include, but are not limited to, water, N, N-Dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidones, ethylene glycol, polypropylene glycol, propylene carbonate, diesters, paraffin, alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, ketones (such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone) , acetates (such as hexyl acetate, heptyl acetate and octyl acetate) , and alcohols (such as methanol, cyclohexanol, decanol, benzyl alcohol and tetrahydrofurfur
  • Suitable solid carriers may be water soluble or water insoluble.
  • Water-soluble solid carriers include, but are not limited to, salts such as alkali metal phosphates (such as sodium dihydrogen phosphate) , alkaline earth metal phosphates, sulfates of sodium, potassium, magnesium and zinc, sodium chloride and potassium chloride, sodium acetate, sodium carbonate and sodium benzoate, sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol.
  • Examples of water-insoluble solid carriers include, but are not limited to, clay, synthetic silica and diatomite, calcium silicate and magnesium silicate, titanium dioxide, aluminum oxide, calcium oxide and zinc oxide, and mixtures thereof.
  • Said “surfactant” includes wetting agents, dispersing agents, thickening agents or mixtures of these surfactants.
  • the wetting agents include, but are not limited to, alkyl sulfosuccinates, laurates, alkyl sulfates, phosphates, acetylenic diols, ethoxylated fluorinated alcohols, ethoxylated silicone, alkylphenol ethoxylates, benzenesulfonates, alkyl-substituted benzenesulfonates, alkyl ⁇ -olefin sulfonates, naphthalenesulfonates, alkyl-substituted naphthalenesulfonates, naphthalenesulfonates, and condensates of alkyl-substituted naphthalenesulfonates and formaldehyde, and alcohol ethoxylates and mixtures thereof.
  • Sodium alkylnaphthalenesulfonate salts are particularly useful for the composition of the present invention.
  • the dispersing agent includes, but is not limited to, sodium, calcium and ammonium salts of lignosulphonic acid (optionally polyethoxylated) ; sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; and naphthalenesulfonic acid-formaldehyde condensates.
  • Lignosulfonates such as sodium lignosulfonate are particularly useful for the composition of the present invention.
  • the thickening agents include, but are not limited to, guar gum, pectin, casein, carrageenan, xanthan gum, alginates, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, and mixtures thereof.
  • Synthetic thickening agents include derivatives of the preceding categories, and also include polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, various polyethers, copolymers thereof, and polyacrylic acid and salts thereof, and mixtures thereof.
  • composition ingredients may also be used in the present invention, such as dyes, desiccants, preservatives, antioxidants, and carriers. These ingredients are known to a person skilled in the art.
  • the present invention further provides the use of said herbicidal composition in controlling the growth of undesired plants.
  • the present invention further provides the use of said herbicidal composition in controlling the growth of gramineae weeds and broadleaf weeds as undesired plants.
  • the present invention further provides the use of said herbicidal composition in controlling the growth of gramineae weeds and broadleaf weeds as undesired plants in wheat fields.
  • the use of the herbicidal composition of the present invention in controlling the growth of Bromus japonicus and Avena fatua as undesired plants in wheat fields is provided.
  • the present invention provides a method for controlling the growth of undesired plants, wherein the herbicidal composition of the present invention is applied to undesired plants or growing sites thereof.
  • a method for controlling the growth of undesired plants comprising: (i) before the germination of the undesired plants; (ii) after the germination of the undesired plants; or (iii) both in (i) and (ii) , a herbicidally effective amount of the herbicidal composition of the present invention is applied to the undesired plants or growing sites thereof.
  • a method for controlling the growth of undesired plants comprising bringing the undesired plants or growing sites thereof into contact with a herbicidally effective amount of the herbicidal composition of the present invention.
  • a method for controlling the growth of undesired plants comprising applying a herbicidally effective amount of the herbicidal composition of the present invention to soil to prevent the germination or growth of undesired plants.
  • herbicidal composition of the present invention is applied to the soil surface before germination, weed seedlings are completely prevented from sprouting, or weeds grow to the cotyledon stage and then, they stop growing and eventually completely die after two to four weeks.
  • said active compound is applied to the green part of a plant after germination, the growth will also stop sharply within a relatively short period of time after treatment, and the weed plant will remain the growth period at the application time point, or will completely die after a certain period of time, so that in this way, competitions caused by weeds which are harmful to crop plants will be eliminated earlier and continuously.
  • the herbicidal composition may be directionally sprayed by means of spraying equipment so that when it reaches the leaves of undesired plants growing below or bare soil, the contact thereof with sensitive crops is minimized.
  • Figure 1 is an X-ray powder diffraction pattern of the new crystal form of flucarbazone-sodium provided by the present invention.
  • Figure 2 is an X-ray powder diffraction pattern of the flucarbazone-sodium hemihydrate reported by Arysta.
  • the resulting solid particles are analyzed by means of X-ray powder diffraction (XRD) , and it is found that they are the new crystal form I of flucarbazone-sodium as shown in figure 1.
  • XRD X-ray powder diffraction
  • the new crystal form I of flucarbazone-sodium obtained in example 3 is analyzed by using X-ray powder diffraction (XRD) , and the result is found to be consistent with that in figure 1.
  • XRD X-ray powder diffraction
  • Samples 1, 2, 3 and 4 prepared in examples 4 and 5 are stored at 54°C for 2 weeks. Comparison is made for the difference in the suspensibility and spontaneous dispersibility of each sample before and after storage. The results are listed in table 3. Test method: CIPAC MT184 for suspensibility, and CIPAC MT 174 for spontaneous dispersibility.
  • results in table 3 further illustrate that the water dispersible granules and wettable powder prepared from the new crystal form I of flucarbazone-sodium provided by the present invention have significantly improved product storage performance, wherein the suspensibility and spontaneous dispersion properties before storage and after storage are both 90%or more which properties are not possessed by the flucarbazone-sodium hemihydrate.

Landscapes

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

Abstract

A new crystal form of flucarbazone-sodium, a preparation method thereof and the use thereof in controlling the growth of undesired plants.

Description

NEW CRYSTAL FORM OF FLUCARBAZONE-SODIUM FIELD
The present invention relates to a new crystal of flucarbazone-sodium and a preparation method therefor.
BACKGROUND
Flucarbazone-sodium, also known as flucarbazone, which is usually present in the form of a sodium salt. Its English name is flucarbazone-sodium, and its Chinese chemical name is 1H-1, 2, 4-triazolyl-1-carbamoyl-4, 5-2H-3-methoxy-4-methyl-5-O-N- [ [2- (trifluoromethoxy) benzene] sulfonyl] -sodium salt. Flucarbazone-sodium belongs to sulfonylurea herbicides, and is firstly developed by Bayer in 1995 and later acquired by Arysta in 2002. The mechanism of action thereof is to inhibit a reaction of acetolactate synthase (ALS) for producing precursors of side chain amino acids, leucine, isoleucine and valine, after absorption via roots, stems and leaves, thereby killing weeds; it is a selective post-emergence herbicide for treating stems and leaves. Flucarbazone-sodium is a highly efficient and broad-spectrum herbicide, which can be applied to prevent and kill gramineae and some important broadleaf weeds in wheat fields and is safe for next-stubble crops.
The molecular formula of flucarbazone-sodium is as follows:
Figure PCTCN2019130009-appb-000001
US 5534486 discloses this compound and discloses a synthesis route for this compound and synthesis examples of analogs.
CN 106478533 A discloses an improved process for the synthesis of flucarbazone-sodium, wherein methyl isobutyl ketone (MIBK) is used as a solvent, 50%NaOH is then added to form a salt, and after completion, centrifugation is carried out to obtain the flucarbazone-sodium.
After comprehensively analyzing the production cost and safety of different  production processes, the following synthesis route is mainly used in industry:
Figure PCTCN2019130009-appb-000002
At present, there are some reports on the study of the crystal form of flucarbazone-sodium, for example, US Patent US 10238112 B discloses a hemihydrate of flucarbazone-sodium, which is characterized by means of XRD and single crystal diffraction. It is reported that a flucarbazone-sodium hemihydrate obtained by treating MSU (a non-sodium salt of flucarbazone) with an aqueous solution of sodium hydroxide under pH control conditions has an advantage in preparation processing.
However, it has been found that solid preparations prepared based on the flucarbazone-sodium hemihydrate, such as water dispersible granules and wettable powders, have reduced product performance indexes, especially a low suspensibility and/or spontaneous dispersibility, after 2 years of shelf storage tests. Therefore, it is necessary to study and develop a new crystal form of flucarbazone-sodium to solve the technical problem of the long-term storage performance indexes of preparation products prepared from flucarbazone-sodium being reduced.
SUMMARY
There are known methods for preparing the flucarbazone-sodium technical material, and reference can be made to methods reported in the prior art, for  example, a conventional preparation process disclosed in US Patent US 5534486, which can be used to obtain flucarbazone-sodium; and as another example, reference can also be made to a method reported in Process Patent CN 1179953 C, which can also be used to prepare flucarbazone-sodium.
An object of the present invention is to provide new crystal form I of flucarbazone-sodium, characterized in that an X-ray powder diffraction pattern of said new crystal form I recorded by using Cu-Ka radiation at 25℃ shows at least 3 (e.g. 3, 4, 5, 6, 7, 8, 9, 10 or 11) of the following reflections at 2θ values in any combination:
2θ = 6.41 ± 0.2°      (1)
2θ = 12.74 ± 0.2°     (2)
2θ = 15.13 ± 0.2°      (3)
2θ = 15.88 ± 0.2°       (4)
2θ = 16.64 ± 0.2°       (5)
2θ = 18.41 ± 0.2°        (6)
2θ = 21.29 ± 0.2°      (7)
2θ = 21.60 ± 0.2°       (8)
2θ = 22.01 ± 0.2°        (9)
2θ = 22.33 ± 0.2°        (10)
2θ = 23.69 ± 0.2°        (11)
2θ = 24.48 ± 0.2°       (12)
2θ = 24.99 ± 0.2°       (13)
2θ = 25.24 ± 0.2°        (14)
2θ = 26.39 ± 0.2°       (15)
2θ = 27.14 ± 0.2°       (16)
2θ = 28.28 ± 0.2°       (17)
2θ = 31.42 ± 0.2°       (18)
2θ = 37.17 ± 0.2°       (19)
Preferably, said new crystal form I of flucarbazone-sodium is characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25℃ shows at least 4 of the following reflections at 2θ values in any combination:
2θ = 6.41 ± 0.2°       (1)
2θ = 12.74 ± 0.2°       (2)
2θ = 15.13 ± 0.2°       (3)
2θ = 15.88 ± 0.2°      (4)
2θ = 16.64 ± 0.2°       (5)
2θ = 18.41 ± 0.2°      (6)
2θ = 21.29 ± 0.2°       (7)
2θ = 21.60 ± 0.2°      (8)
2θ = 22.01 ± 0.2°        (9)
2θ = 22.33 ± 0.2°      (10)
2θ = 23.69 ± 0.2°        (11)
2θ = 24.48 ± 0.2°        (12)
2θ = 24.99 ± 0.2°        (13)
2θ = 25.24 ± 0.2°         (14)
2θ = 26.39 ± 0.2°        (15)
2θ = 27.14 ± 0.2°        (16)
2θ = 28.28 ± 0.2°        (17)
Preferably, said new crystal form I of flucarbazone-sodium is characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25℃ shows at least 3 of the following reflections at 2θ values in any combination:
2θ = 6.41 ± 0.2°        (1)
2θ = 12.74 ± 0.2°       (2)
2θ = 15.13 ± 0.2°         (3)
2θ = 15.88 ± 0.2°        (4)
2θ = 16.64 ± 0.2°         (5)
2θ = 18.41 ± 0.2°         (6)
2θ = 22.01 ± 0.2°      (9)
2θ = 22.33 ± 0.2°        (10)
2θ = 23.69 ± 0.2°        (11)
2θ = 24.48 ± 0.2°       (12)
2θ = 24.99 ± 0.2°         (13)
2θ = 25.24 ± 0.2°      (14)
2θ = 26.39 ± 0.2°       (15)
2θ = 27.14 ± 0.2°        (16)
Preferably, said new crystal form I of flucarbazone-sodium has an X-ray powder diffraction pattern as shown in figure 1.
Figure 2 is an XRD pattern of the flucarbazone-sodium hemihydrate disclosed in US 10238112 B by Arysta.
Another object of the present invention is to provide a method for preparing said new crystal form I of flucarbazone-sodium.
The method for preparing the new crystal form I of flucarbazone-sodium, as involved in the present invention, comprises the following steps:
a) adding a crude synthesized product of flucarbazone-sodium to an organic solvent,
b) heating the mixture prepared in step a) to 30℃-100℃, for example, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, or 95℃; and
c) cooling the resulting dissolved substance, followed by carrying out stirring crystallization and separation to obtain the new crystal form of flucarbazone-sodium.
The “organic solvent” in step a) refers to a nitrile solvent such as acetonitrile; an alcohol solvent such as methanol; a ketone solvent such as acetone; or a mixture of the above-mentioned solvents. Preferably, acetonitrile or a mixture of acetonitrile and other solvents is used as a crystallization solvent.
The solution in step b) is preferably heated to 30℃-70℃, especially preferably a temperature of 30℃-60℃, such as 35℃, 40℃, 45℃, 50℃, or 55℃.
Preferably, said separation method involves centrifugation and then filtration.
The present invention also provides a herbicidal composition, which contains the new crystal form I of flucarbazone-sodium as an active ingredient and also comprises a filler and/or a surfactant.
It has been found that the herbicidal composition according to the present invention has advantageously improved storage stability, without significant reduction in performance indexes, such as and spontaneous dispersibility,  suspensibility after long-term storage. Compared with a herbicidal composition containing a flucarbazone-sodium hemihydrate, the herbicidal composition of the present invention has significantly improved physical and chemical performance indexes after long-term storage.
In the herbicidal composition of the present invention, the content of said active ingredient, the new crystal form I of flucarbazone-sodium, accounts for 1%-90%, preferably 10%-90%, preferably 20%-90%, more preferably 30%-90%, more preferably 50%-90%, and more preferably 50%-80%of said herbicidal composition.
Dosage forms for the herbicidal composition of the present invention are a suspension concentrate (SC) , an oil-based suspension concentrate (OD) , soluble granules (SG) , a dispersible concentrate (DC) , an emulsifiable concentrate (EC) , a flowable concentrate for seed treatment (FS) , granules (GR) , microgranules (MG) , a suspo-emulsion (SE) , a water soluble powder (WP) and water dispersible granules (WG) .
Said “filler” may be solid or liquid.
Suitable liquid carriers include, but are not limited to, water, N, N-Dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidones, ethylene glycol, polypropylene glycol, propylene carbonate, diesters, paraffin, alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, ketones (such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone) , acetates (such as hexyl acetate, heptyl acetate and octyl acetate) , and alcohols (such as methanol, cyclohexanol, decanol, benzyl alcohol and tetrahydrofurfuryl alcohol) , and mixtures thereof.
Suitable solid carriers may be water soluble or water insoluble. Water-soluble solid carriers include, but are not limited to, salts such as alkali metal phosphates (such as sodium dihydrogen phosphate) , alkaline earth metal phosphates, sulfates of sodium, potassium, magnesium and zinc, sodium chloride and potassium chloride, sodium acetate, sodium carbonate and sodium benzoate, sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol. Examples of  water-insoluble solid carriers include, but are not limited to, clay, synthetic silica and diatomite, calcium silicate and magnesium silicate, titanium dioxide, aluminum oxide, calcium oxide and zinc oxide, and mixtures thereof.
Said “surfactant” includes wetting agents, dispersing agents, thickening agents or mixtures of these surfactants.
The wetting agents include, but are not limited to, alkyl sulfosuccinates, laurates, alkyl sulfates, phosphates, acetylenic diols, ethoxylated fluorinated alcohols, ethoxylated silicone, alkylphenol ethoxylates, benzenesulfonates, alkyl-substituted benzenesulfonates, alkyl α-olefin sulfonates, naphthalenesulfonates, alkyl-substituted naphthalenesulfonates, naphthalenesulfonates, and condensates of alkyl-substituted naphthalenesulfonates and formaldehyde, and alcohol ethoxylates and mixtures thereof. Sodium alkylnaphthalenesulfonate salts are particularly useful for the composition of the present invention.
The dispersing agent includes, but is not limited to, sodium, calcium and ammonium salts of lignosulphonic acid (optionally polyethoxylated) ; sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; and naphthalenesulfonic acid-formaldehyde condensates. Lignosulfonates such as sodium lignosulfonate are particularly useful for the composition of the present invention. The thickening agents include, but are not limited to, guar gum, pectin, casein, carrageenan, xanthan gum, alginates, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, and mixtures thereof. Synthetic thickening agents include derivatives of the preceding categories, and also include polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, various polyethers, copolymers thereof, and polyacrylic acid and salts thereof, and mixtures thereof.
Other preparation ingredients may also be used in the present invention, such as dyes, desiccants, preservatives, antioxidants, and carriers. These ingredients are known to a person skilled in the art.
The present invention further provides the use of said herbicidal composition in controlling the growth of undesired plants.
The present invention further provides the use of said herbicidal composition in controlling the growth of gramineae weeds and broadleaf weeds as undesired plants.
The present invention further provides the use of said herbicidal composition in controlling the growth of gramineae weeds and broadleaf weeds as undesired plants in wheat fields.
In particular, the use of the herbicidal composition of the present invention in controlling the growth of Bromus japonicus and Avena fatua as undesired plants in wheat fields is provided.
The present invention provides a method for controlling the growth of undesired plants, wherein the herbicidal composition of the present invention is applied to undesired plants or growing sites thereof.
There is provided a method for controlling the growth of undesired plants, comprising: (i) before the germination of the undesired plants; (ii) after the germination of the undesired plants; or (iii) both in (i) and (ii) , a herbicidally effective amount of the herbicidal composition of the present invention is applied to the undesired plants or growing sites thereof.
There is provided a method for controlling the growth of undesired plants, comprising bringing the undesired plants or growing sites thereof into contact with a herbicidally effective amount of the herbicidal composition of the present invention.
There is provided a method for controlling the growth of undesired plants, comprising applying a herbicidally effective amount of the herbicidal composition of the present invention to soil to prevent the germination or growth of undesired plants.
If the herbicidal composition of the present invention is applied to the soil surface before germination, weed seedlings are completely prevented from sprouting, or weeds grow to the cotyledon stage and then, they stop growing and eventually completely die after two to four weeks.
If said active compound is applied to the green part of a plant after germination, the growth will also stop sharply within a relatively short period of time after  treatment, and the weed plant will remain the growth period at the application time point, or will completely die after a certain period of time, so that in this way, competitions caused by weeds which are harmful to crop plants will be eliminated earlier and continuously.
If the active ingredient cannot be well tolerated by certain crops, the herbicidal composition may be directionally sprayed by means of spraying equipment so that when it reaches the leaves of undesired plants growing below or bare soil, the contact thereof with sensitive crops is minimized.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 is an X-ray powder diffraction pattern of the new crystal form of flucarbazone-sodium provided by the present invention.
Figure 2 is an X-ray powder diffraction pattern of the flucarbazone-sodium hemihydrate reported by Arysta.
DETAILED DESCRIPTION
In order to aid the understanding of the present invention, the following examples are set forth for the present invention. A person skilled in the art should be clear that said examples are provided only for aiding the understanding of the present invention but should not be regarded as particular limitations to the present invention.
Example 1: Preparation of flucarbazone-sodium salt
100 g of methyl isobutyl ketone, 36 g of 2-trifluoromethoxy benzenesulfonamide and 52 g of 5-methoxy-4-methyl-2-phenoxycarbonyl-2, 4-dihydro-1, 2, 4-triazol-3-one are put into a reaction flask, 18 g of a solution of sodium hydroxide at a mass percentage concentration of 50%is dropwise added at 15℃-20℃, and after the dropwise addition is completed, the temperature is maintained at 20℃-25℃, and centrifugation is carried out to obtain 55.2 g of flucarbazone-sodium, the content of which is 96.8%, and the yield of which is 90%based on 2-trifluoromethoxy benzenesulfonamide, wherein the specific reaction is as follows:
Figure PCTCN2019130009-appb-000003
Example 2: Preparation of new crystal form I of flucarbazone-sodium
10 g of flucarbazone-sodium obtained in example 1 is added to a 250 mL three-necked flask, 100 mL of acetonitrile is then added, the mixture is heated to reflux, and an appropriate amount of acetonitrile is supplementary added as necessary until the solid is completely dissolved. It is cooled to room temperature under stirring and left to stand for crystallization; and after the crystallization is completed, separation with a centrifuge and washing are carried out. The filter cake is dried to obtain about 9.5 g of the new crystal form of flucarbazone-sodium. After HPLC (area normalization) analysis, the content thereof is 98.5%.
The resulting solid particles are analyzed by means of X-ray powder diffraction (XRD) , and it is found that they are the new crystal form I of flucarbazone-sodium as shown in figure 1.
A powder X-ray diffraction pattern of the crystal shows the reflections in figure 1; in particular, X-ray powder diffractions expressed as 2θ angles are at 2θ = 6.41 ± 0.2°, 2θ = 12.74 ± 0.2°, 2θ = 15.13 ± 0.2°, 2θ = 15.88 ± 0.2°, 2θ = 16.64 ± 0.2°, 2θ = 18.41 ± 0.2°, 2θ = 21.29 ± 0.2°, 2θ = 21.60 ± 0.2°, 2θ = 22.01 ± 0.2°, 2θ = 22.33 ± 0.2°, 2θ = 23.69 ± 0.2°, 2θ = 24.48 ± 0.2°, 2θ = 24.99 ± 0.2°, 2θ = 25.24 ± 0.2°, 2θ = 26.39 ± 0.2°, 2θ = 27.14 ± 0.2°, 2θ = 28.28 ± 0.2°, 2θ = 31.42 ± 0.2°, and 2θ = 37.17 ± 0.2°. The X-ray powder diffraction pattern is obtained by using a diffractometer and Cu-Ka radiation at 25℃ with an increment of 0.03° in a reflection geometry within the range of 3°-60°.
Example 3 Preparation of new crystal form I of flucarbazone-sodium
12 g of flucarbazone-sodium obtained in example 1 is added to a 250 mL three-necked flask, 80 mL of acetonitrile and 65 mL of methanol are then  respectively added, the mixture is heated to reflux, and an appropriate amount of acetonitrile is supplementary added as necessary until the solid is completely dissolved. It is cooled to room temperature under stirring and left to stand for crystallization; and after the crystallization is complete, separation with a centrifuge and washing are carried out. The filter cake is dried to obtain about 11.6 g of the new crystal form of flucarbazone-sodium. After HPLC analysis (area normalization) , the content thereof is 98.3%.
As described in example 2, the new crystal form I of flucarbazone-sodium obtained in example 3 is analyzed by using X-ray powder diffraction (XRD) , and the result is found to be consistent with that in figure 1.
In particular, the X-ray powder diffraction expressed as 2θ angle has characteristic peaks at 2θ = 6.41 ± 0.2°, 2θ = 12.74 ± 0.2°, 2θ = 15.13 ± 0.2°, 2θ = 15.88 ± 0.2°, 2θ = 16.64 ± 0.2°, 2θ = 18.41 ± 0.2°, 2θ = 21.29 ± 0.2°, 2θ = 21.60 ± 0.2°, 2θ = 22.01 ± 0.2°, 2θ = 22.33 ± 0.2°, 2θ = 23.69 ± 0.2°, 2θ = 24.48 ± 0.2°, 2θ = 24.99 ± 0.2°, 2θ = 25.24 ± 0.2°, 2θ = 26.39 ± 0.2°, 2θ = 27.14 ± 0.2°, 2θ = 28.28 ± 0.2°, 2θ = 31.42 ± 0.2°, and 2θ = 37.17 ± 0.2°.
The above-mentioned characterization results confirm that the obtained product is the new crystal form I of flucarbazone-sodium provided by the present invention.
Example 4: Preparation of water dispersible granule (WDG) formulation
All the components listed in table 1 below are uniformly mixed and pulverized into powder with an average particle size of about 3 um by means of a jet mill. A sufficient amount of water is added to obtain an extrudable paste. The resulting paste passes through an extrusion die or screen and is extruded to form an extrudate. The wet extrudate is dried at 45℃ or less in a vacuum oven and screened through a 0.7-2 mm screen to obtain product particles.
Table 1
Figure PCTCN2019130009-appb-000004
Figure PCTCN2019130009-appb-000005
Example 5: Preparation of wettable powder (WP) formulation
All the components listed in table 2 below are uniformly mixed and pulverized into powder with an average particle size of about 3 um by means of a jet mill to obtain the wettable powder.
Table 2
Figure PCTCN2019130009-appb-000006
Figure PCTCN2019130009-appb-000007
Product performance comparison
Samples 1, 2, 3 and 4 prepared in examples 4 and 5 are stored at 54℃ for 2 weeks. Comparison is made for the difference in the suspensibility and spontaneous dispersibility of each sample before and after storage. The results are listed in table 3. Test method: CIPAC MT184 for suspensibility, and CIPAC MT 174 for spontaneous dispersibility.
Table 3
Figure PCTCN2019130009-appb-000008
Figure PCTCN2019130009-appb-000009
The results in table 3 further illustrate that the water dispersible granules and wettable powder prepared from the new crystal form I of flucarbazone-sodium provided by the present invention have significantly improved product storage performance, wherein the suspensibility and spontaneous dispersion properties before storage and after storage are both 90%or more which properties are not possessed by the flucarbazone-sodium hemihydrate.

Claims (16)

  1. New crystal form I of flucarbazone-sodium, characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25℃ shows at least 3 of the following reflections at 2θ values in any combination:
    2θ = 6.41 ± 0.2°                                 (1)
    2θ = 12.74 ± 0.2°                                (2)
    2θ = 15.13 ± 0.2°                                (3)
    2θ = 15.88 ± 0.2°                                (4)
    2θ = 16.64 ± 0.2°                                (5)
    2θ = 18.41 ± 0.2°                                (6)
    2θ = 21.29 ± 0.2°                                (7)
    2θ = 21.60 ± 0.2°                                (8)
    2θ = 22.01 ± 0.2°                                (9)
    2θ = 22.33 ± 0.2°                                (10)
    2θ = 23.69 ± 0.2°                                (11)
    2θ = 24.48 ± 0.2°                                (12)
    2θ = 24.99 ± 0.2°                                (13)
    2θ = 25.24 ± 0.2°                                (14)
    2θ = 26.39 ± 0.2°                                (15)
    2θ = 27.14 ± 0.2°                                (16)
    2θ = 28.28 ± 0.2°                                (17)
    2θ = 31.42 ± 0.2°                                (18)
    2θ = 37.17 ± 0.2°                                (19) .
  2. The new crystal form I of flucarbazone-sodium according to claim 1, characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25℃ shows at least 4 of the following reflections at 2θ values in any combination:
    2θ = 6.41 ± 0.2°                                 (1)
    2θ = 12.74 ± 0.2°                                (2)
    2θ = 15.13 ± 0.2°                                (3)
    2θ = 15.88 ± 0.2°                                (4)
    2θ = 16.64 ± 0.2°                                (5)
    2θ = 18.41 ± 0.2°                                (6)
    2θ = 21.29 ± 0.2°                                (7)
    2θ = 21.60 ± 0.2°                                (8)
    2θ = 22.01 ± 0.2°                                (9)
    2θ = 22.33 ± 0.2°                                (10)
    2θ = 23.69 ± 0.2°                                (11)
    2θ = 24.48 ± 0.2°                                (12)
    2θ = 24.99 ± 0.2°                                (13)
    2θ = 25.24 ± 0.2°                                (14)
    2θ = 26.39 ± 0.2°                                (15)
    2θ = 27.14 ± 0.2°                                (16)
    2θ = 28.28 ± 0.2°                                (17) .
  3. The new crystal form I of flucarbazone-sodium according to claim 2, characterized in that an X-ray powder diffraction pattern recorded by using Cu-Ka radiation at 25℃ shows at least 3 of the following reflections at 2θ values in any combination:
    2θ = 6.41 ± 0.2°                                 (1)
    2θ = 12.74 ± 0.2°                                (2)
    2θ = 15.13 ± 0.2°                                (3)
    2θ = 15.88 ± 0.2°                                (4)
    2θ = 16.64 ± 0.2°                                (5)
    2θ = 18.41 ± 0.2°                                (6)
    2θ = 22.01 ± 0.2°                                (9)
    2θ = 22.33 ± 0.2°                                (10)
    2θ = 23.69 ± 0.2°                                (11)
    2θ = 24.48 ± 0.2°                                (12)
    2θ = 24.99 ± 0.2°                                (13)
    2θ = 25.24 ± 0.2°                                (14)
    2θ = 26.39 ± 0.2°                                (15)
    2θ = 27.14 ± 0.2°                                (16) .
  4. The new crystal form I of flucarbazone-sodium according to claims 1-3, having an X-ray powder diffraction pattern as shown in figure 1.
  5. A method for preparing the new crystal form I of flucarbazone-sodium according to any one of claims 1-4, comprising the following steps:
    a) adding a crude synthesized product of flucarbazone-sodium to an organic solvent,
    b) heating the mixture prepared in step a) at a temperature of 30℃-100℃, and
    c) cooling the resulting dissolved substance, followed by carrying out stirring crystallization and separation to obtain the new crystal form I of flucarbazone-sodium.
  6. The preparation method according to claim 5, characterized in that the “organic solvent” in step a) refers to a nitrile solvent such as acetonitrile; or an alcohol solvent such as methanol; or a ketone solvent such as acetone; or a mixture of the above-mentioned solvents.
  7. The preparation method according to claim 5, characterized in that acetonitrile or a mixture of acetonitrile and other solvents is used as a crystallization solvent.
  8. The preparation method according to claim 5, characterized in that the solution in step b) is preferably heated at a temperature of 30℃-70℃, especially preferably at a temperature of 30℃-60℃, and then appropriately cooled.
  9. Use of the new crystal form I of flucarbazone-sodium according to claims 1-4 in controlling the growth of undesired plants.
  10. A herbicidal composition, characterized by comprising the new crystal form I of flucarbazone-sodium according to claim 1, a filler and/or a surfactant.
  11. The herbicidal composition according to claim 9, characterized in that dosage forms for the herbicidal composition are a suspension concentrate (SC) , an oil-based suspension concentrate (OD) , soluble granules (SG) , a dispersible concentrate (DC) , an emulsifiable concentrate (EC) , a flowable concentrate for seed treatment (FS) , granules (GR) , microgranules (MG) , a suspo-emulsion (SE) , a water soluble powder (WP) and water dispersible granules (WG) .
  12. Use of the herbicidal composition according to claim 9 in controlling the growth of undesired plants.
  13. Use of the herbicidal composition according to claim 9 in controlling the growth of gramineae weeds and broadleaf weeds as undesired plants.
  14. Use of the herbicidal composition according to claim 9 in controlling the growth of gramineae weeds and broadleaf weeds as undesired plants in wheat fields.
  15. Use of the herbicidal composition according to claim 9 in controlling the growth of Bromus japonicus and Avena fatua as undesired plants in wheat fields.
  16. A method for controlling the growth of undesired plants, comprising: (i) before the germination of the undesired plants; (ii) after the germination of the undesired plants; or (iii) both (i) and (ii) , a herbicidally effective amount of the herbicidal composition according to claim 1 is applied to the undesired plants or growing sites thereof.
PCT/CN2019/130009 2019-12-30 2019-12-30 New crystal form of flucarbazone-sodium WO2021134242A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/CN2019/130009 WO2021134242A1 (en) 2019-12-30 2019-12-30 New crystal form of flucarbazone-sodium
CA3166234A CA3166234A1 (en) 2019-12-30 2019-12-30 New crystal form of flucarbazone-sodium
CN201980103367.7A CN114929677A (en) 2019-12-30 2019-12-30 Novel crystal form of flucarbazone sodium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/130009 WO2021134242A1 (en) 2019-12-30 2019-12-30 New crystal form of flucarbazone-sodium

Publications (1)

Publication Number Publication Date
WO2021134242A1 true WO2021134242A1 (en) 2021-07-08

Family

ID=76687498

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/130009 WO2021134242A1 (en) 2019-12-30 2019-12-30 New crystal form of flucarbazone-sodium

Country Status (3)

Country Link
CN (1) CN114929677A (en)
CA (1) CA3166234A1 (en)
WO (1) WO2021134242A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5534486A (en) * 1991-04-04 1996-07-09 Bayer Aktiengesellschaft Herbicidal sulphonylaminocarbonyl triazolinones having substituents bonded via oxygen
US6160125A (en) * 1999-12-27 2000-12-12 Bayer Corporation Process for the manufacture of sulfonylaminocarbonyl triazolinones in the presence of xylene as solvent
CN1301696A (en) * 1999-12-27 2001-07-04 美国拜尔公司 Method for producing sulfonyl-amino-carbnyl triazolinone salt
CN106478533A (en) * 2016-08-27 2017-03-08 江苏瑞邦农药厂有限公司 A kind of synthetic method of flucarbazone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5534486A (en) * 1991-04-04 1996-07-09 Bayer Aktiengesellschaft Herbicidal sulphonylaminocarbonyl triazolinones having substituents bonded via oxygen
US6160125A (en) * 1999-12-27 2000-12-12 Bayer Corporation Process for the manufacture of sulfonylaminocarbonyl triazolinones in the presence of xylene as solvent
CN1301696A (en) * 1999-12-27 2001-07-04 美国拜尔公司 Method for producing sulfonyl-amino-carbnyl triazolinone salt
CN106478533A (en) * 2016-08-27 2017-03-08 江苏瑞邦农药厂有限公司 A kind of synthetic method of flucarbazone

Also Published As

Publication number Publication date
CA3166234A1 (en) 2021-07-08
CN114929677A (en) 2022-08-19

Similar Documents

Publication Publication Date Title
TWI735574B (en) A novel form of sulfentrazone, a process for its preparation and use the same
CN114920735A (en) Novel crystalline forms of xaflufen, processes for their preparation and their use
CN109790115B (en) Crystal form of spirotetramat, preparation method and application thereof
TWI760427B (en) A novel crystalline form of indoxacarb, a process for its preparation and use of the same
TW201643156A (en) A novel form of RIMSULFURON, a process for its preparation and use of the same
WO2021134242A1 (en) New crystal form of flucarbazone-sodium
TWI778954B (en) A novel form of amicarbazone, a process for its preparation and use of the same
CN109456258B (en) Ivermectin B1a/B1B crystal variant, preparation method and application thereof
AU2016102018A4 (en) A novel crystalline form of chlorfenapyr, a process for its preparation and use of the same
CN109503471B (en) Crystal form of pyriproxyfen, preparation method and application thereof
US9617247B1 (en) Form of halosulfuron-methyl, a process for its preparation and use of the same
US9643936B1 (en) Form of tribenuron-methyl, a process for its preparation and use of the same
CN109790110B (en) Novel crystal form of oxamyl, preparation method and application thereof
US20230348446A1 (en) Type ii crystalline topramezone sodium salt hydrate, preparation method therefor and use thereof
US10059676B2 (en) Process for preparing a novel crystalline form of iodosulfuron-methyl-sodium and use of the same
CN109535034B (en) Novel crystal form of cyflufenamid, preparation method and application thereof
WO2022170964A1 (en) Novel crystalline hydrate of topramezone sodium salt and preparation method therefor
WO2018082456A1 (en) A novel form of penoxsulam, a process for its preparation and use of the same
WO2023040759A1 (en) Crystalline form of methoxyfenozide, process for its preparation and use of the same
WO2017092477A1 (en) Process for preparing novel crystalline form of mesosulfuron-methyl and use thereof
CN111132966B (en) Novel forms of sulfometuron-methyl, process for their preparation and their use
TW202316965A (en) A crystalline form of diflufenican, a process for its preparation and use of the same
US10077248B2 (en) Form of imazapyr, a process for its preparation and use the same
WO2021175029A1 (en) A novel form of metrafenone, a process for its preparation and use of the same
GB2610805A (en) Novel crystalline form of florasulam, preparation and use of the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19958571

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3166234

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19958571

Country of ref document: EP

Kind code of ref document: A1