WO2011005127A1 - Polymorphe cristallin stable de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione, et procédé d'élaboration correspondant - Google Patents

Polymorphe cristallin stable de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione, et procédé d'élaboration correspondant Download PDF

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Publication number
WO2011005127A1
WO2011005127A1 PCT/PT2010/000028 PT2010000028W WO2011005127A1 WO 2011005127 A1 WO2011005127 A1 WO 2011005127A1 PT 2010000028 W PT2010000028 W PT 2010000028W WO 2011005127 A1 WO2011005127 A1 WO 2011005127A1
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WO
WIPO (PCT)
Prior art keywords
benzoyl
chloro
cyclohexane
dione
mesyl
Prior art date
Application number
PCT/PT2010/000028
Other languages
English (en)
Inventor
José NEVES
Luis Teixeira
Surendra Bhatia
Martin Ermrich
Original Assignee
Sapec-Agro, Sa
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 Sapec-Agro, Sa filed Critical Sapec-Agro, Sa
Priority to EP10735359A priority Critical patent/EP2451778A1/fr
Publication of WO2011005127A1 publication Critical patent/WO2011005127A1/fr

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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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/06—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a new stable crystalline polymorph of 2-(2-cbloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione and to a process for preparing the same. More particularly, it relates to compositions having said polymorph for controlling unwanted plants.
  • biologically active compounds like pharmaceuticals, agrochemicals and other fine chemicals involves synthesis, purification, isolation and recovery by re crystallisation. Many of these biologically active compounds exhibit polymorphism: the ability of a substance to exist in two or more solid forms with different arrangement of atoms or molecules. Different polymorphs of a biologically active compound can have different physical properties, which can be advantageously used to select a specific polymorph for a specific application. There has been an increasingly demand in the development of biologically active compounds with specific crystal polymorphism.
  • 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione (so called Form III in the following description) and to a process for preparing the same. Resulting products from this Form III are efficient when applied as weed controlling agents.
  • the crystalline polymorph of the invention has a density of about 1.474 g/cm 3 .
  • the crystalline polymorph of the invention has a molecular weight of about 328.78 and a volume per atom of about 17.6 A 3 .
  • the present invention also relates to a composition comprising a crystalline polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione as defined above.
  • composition of the invention comprises at least one form of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione which differs from the polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l ,3-dione of the invention.
  • said composition comprises less than about 20% by weight of the at least one form of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3- ⁇ lione which differs from the polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione of the invention.
  • the composition comprises less than about 5% by weight of the at least one form of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione which differs from the polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l ,3-dione of the invention.
  • composition further comprising other herbicides.
  • said herbicides are selected from the group comprising sulfonylureas, chloroacetamides, dinitroanilines, triazines, isoxazoles, oxyacetamides and combinations thereof.
  • the invention further relates to the use of the above composition for controlling unwanted plants, namely for controlling weeds selected from the group comprising Cyperus esculentus, Cyperus rotundas, Chenopodium spp., Amaranthus spp.. Datura stramonium, Polygonum aviculare and Solatium nigrum.
  • the present invention also relates to a process for preparing a crystalline polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l ,3-dione as defined in claim 1, comprising the steps of: 1) preparation of 4-sulfomethyl-2-chloro benzoyl chloride; 2) preparation of enol ester derivative; 3) rearrangement of enol ester derivative to 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione; and 4) purification of 2-(2-chloro- 4-mesyl-benzoyl)-cyclohexane-l,3-dione; wherein in step 1, a reaction of benzoic acid derivative with thionyl chloride in the presence of a catalyst is carried out to produce the benzoyl chloride derivative; in step 2, the benzoyl chloride derivative produced in step 1 is condensed with 1,3-cyclohexane
  • the catalyst of step 1 is DMF
  • the catalyst of step 2 is piperidine
  • the solvent of step 2 is acetonitrile
  • the solvent of step 3 is acetonitrile.
  • the concentration of the alkali solution is in the range of about 5%-20%.
  • the alkali solution is selected from the group comprising sodium, potassium, alkaline earth metal salts and combinations thereof.
  • said concentration of the acid solution is in the range of about 10-20% .
  • the alkali solution in step 4 of the above process, is sodium hydroxide, the organochloride solvent is dichloroethane and the acid solution is hydrochloric acid.
  • Fig. 1 shows the powder X-Ray diffraction spectrum of Form III of 2-(2-chloro- 4-mesyl-benzoyl)-cyclohexane-l,3-dione. The strongest reflections are marked with arrows.
  • Fig. 2 shows the IR spectrum of Form UI of 2-(2-chloro-4-mesyl-benzoyl)- cyclohexane-l,3-dione in the range of 4000-700 cm "1 .
  • Fig 3, 4 and 5 shows the Raman spectrum of Form III of 2-(2-chloro-4-mesyl- benzoyl)-cyclohexane-l,3-dione at Raman's shifts of 3150-2800 cm '1 , 1750-1000 cm 1 and 950-200 cm 1 .
  • the process for preparation of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3- dione of Form III Polymorph of the invention comprises the following steps: Step 1: Preparation of 4-sulfomethyl-2-chloro benzoyl chloride
  • step 1 The benzoyl chloride derivative produced in step 1 is condensed with 1,3-cyclohexane-dione in the presence of piperidine as catalyst, and acetonitrile as solvent. The reaction is carefully monitored for the absence of starting materials, and the product thus obtained is an enol ester derivative.
  • Step 3 Rearrangement of enol ester derivative to 2-(2-chloro-4-mesyl-benzoyl)- cyclohexane-1 ,3-dione.
  • Enol ester dissolved in acetonitrile solvent is rearranged using catalytic amount of CN " .
  • the CN ' can be provided by the use of KCN or Acetone cyanohydrin.
  • Step 4 Purification of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione to produce the specific Form III Polymorph of the invention.
  • 2-(2-chloro-4-mesyl-benzoyl)-cyciohexane-l ,3-dione thus produced is further purified by dissolving it in mild alkaline conditions using an aqueous alkali solution at low concentration (5%-20%).
  • the alkali solution may be any suitable solution.
  • the alkali solution is selected from the group comprising sodium, potassium and alkaline earth metal salts and combinations thereof, which salts are, for example, hydroxides and carbonates.
  • Unwanted by-products which cause instability are extracted using an organochloride solvent, for example, dichlorethane.
  • the resulting aqueous layer is acidified using a diluted acid solution, for example of hydrochloric acid, with a concentration in the range of about 10-20% , to produce 2-(2-chloro-4-mesyl-benzoyl)- cyclohexane-1 ,3-dione in pure form of specific Form HI crystal polymorph.
  • Table 2 shows the crystallographic data of Form III of 2-(2-chloro-4-mesyl- benzoyl)-cyclohexane-l ,3-dione.
  • the analysis was carried out by filling the sample holder and the surface of the sample is carefully smoothed and adjusted against a knife edge.
  • the stable specific Form HI of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane- 1,3-dione according to the invention may be further characterized by IR and Raman spectroscopy. Accordingly, the invention further provides a stable specific Form III of
  • FT-IR spectra were obtained using a B-Optics spectrometer, ALPHA-P model, from Broker. The analysis was carried out by placing the sample into the sample holder and taking the measure.
  • Form in of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione has a Raman spectrum with the bands depicted in Table 4 and the signals shown in Fig. 3 to Fig. 5.
  • Raman spectra were acquired on a FT-Raman 960 spectrometer (Thermo Nicolet) equipped with an indium gallium arsenide (InGaAs) detector. Wavelength verification was performed using sulfur and cyclohexane.
  • Each sample for analysis was prepared by placing the sample into a glass tube and positioning the tube in a gold-coated tube holder. Approximately 0.5 W of Nd: YVCU laser power (1064 nm excitation wavelength) was used to irradiate the sample. Each spectrum represents 256 co-added scans collected at a spectral resolution of 4 cm 1 .
  • the stable crystal polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3- dione of the invention has physicochemical properties such that enable easy handling in formulations.
  • the stable crystal Form in polymorph of 2-(2-chloro-4-mesyl-benzoyl)- cyclohexane-1 ,3-dione of the present invention is particularly suitable for preparing solid and liquid formulations.
  • said formulations are: granules, encapsulated granules, tablets, water-dispersible granules, water-dispersible powders, water- dispersible powders, dust formulations, suspension concentrates, oil-based suspension concentrates, suspoemulsions, or suspension concentrates for plant protection.
  • the stable crystal Form III polymorph of 2-(2-chloro-4-mesyl-benzoyl)- cyclohexane-l,3-dione is highly suitable for preparing compositions for controlling unwanted plants, alone or together with auxiliaries, carriers, and other active compounds.
  • the invention also relates to compositions comprising the stable Form III polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l ,3-dione and at least one form of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione which differs from Form HI polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3-dione.
  • compositions comprising less than about 20% by weight of at least one form of 2-(2-chloro-4-mesyl- benzoyl)-cyclohexane-l,3-dione which differs from Form III polymorph of 2-(2-chloro-4- mesyl-benzoyl)-cyclohexane-l,3-dione are preferred.
  • compositions comprising less than about 15%, much preferably less than about 10%, and most preferably less than about 5%, by weight of at least one form of 2-(2-chloro-4-mesyl- benzoyl)-cyclohexane-l ,3-dione which differs from stable crystal Form III polymorph of 2-(2-chioro-4-mesyl-benzoyl)-cyclohexane-l,3-dione.
  • the stable crystal Form IH polymorph of 2-(2-chloro-4-mesyl-benzoyl)- cyclohexane-l,3-dione of the invention can be preferably employed as a plant protection agent, by controlling a wide range of Dicotyledonous and Monocotyledonous weeds selected from the group comprising Cyperus esculentus, Cyperus rotundus, Chenopodium spp. , Amaranthus spp. , Datura stramonium, Polygonum aviculare and Solarium nigrum.
  • compositions may comprise other herbicides in order to extend the range of weeds to be controlled, particularly some grasses.
  • the herbicides are selected from the group comprising sulfonylureas, chloroacetamides, dinitroanilines, triazines, isoxazoles, oxyacetamides and combinations thereof.
  • the active compound can be formulated into granules, encapsulated granules, tablets, water-dispersible granules, water-dispersible tablets, water-dispersible powders, dust formulations, suspension concentrates, oil-based suspension concentrates, suspoemulsions, suspension concentrates or any other suitable formulations.
  • These formulations are produced in a known manner, for example, by mixing the active compounds liquid solvents and/or solid carriers, optionally with the use of surfactants.
  • a pre-mix of water (45.3 g), MPG (9.Og), Atlox 4913 (3.4 g), Atlox 4894 (2.3 g), Brij-96 (9.9g) and AF9030 (0.1 g) was prepared.
  • 30.5 g of Form HI polymorph of 2-(2-chloro-4-mesyl-benzoyl)-cyclohexane-l,3- ⁇ lione, obtained in Example 1 was added and mixed until homogeneity.
  • the formulation was milled twice in a Dyno-mill, maintaining the temperature of the product below 20 0 C.
  • AF9030 (0.1 g) and thickening agent (9.9 g) was added with gentle stirring.
  • Example 2 Storage Properties The shelf life of the liquid formulation from Example 2 was determined by using the method described in QPAC Handbook, Volume J, MT46.3, pag. 128; Editors W Dobrat and A Martijn; Collaborative International Pesticides Analytical Council Limited, 2000. Samples obtained in the Example 2 were stored at 54 0 C for 14 days. After storage, the samples were brought to room temperature and compared to those freshly prepared. It was observed a slight phase separation but it was readily dispersed. The formulation properties of the formulation did not change after storage.

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

Abstract

La présente invention concerne un nouveau polymorphe cristallin stable de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione, et un procédé d'élaboration correspondant. L'invention concerne plus particulièrement des compositions comportant ledit polymorphe pour lutter contre des plantes parasites. Les différentes étapes du procédé d'élaboration du polymorphe cristallin de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione sont les suivantes: 1) préparation de chlorure de 4-sulfométhyl-2-chloro-benzoyle; 2) préparation de dérivé ester d'énol; 3) réorganisation du dérivé ester d'énol en de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione; et 4) purification du 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione. La structure polymorphe est confirmée par les spectres infrarouges et Raman, ainsi que par les données de cristallographie aux rayons X. Ce polymorphe présente un spectre de diffraction des rayons X de la poudre dont les pics caractéristiques en 2 thêta se situent à 17,6°, 19,1°, 21,0°, 26,0° et 28,7°. Une formulation stable du polymorphe de l'invention est utilisée comme herbicide.
PCT/PT2010/000028 2009-07-07 2010-07-06 Polymorphe cristallin stable de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione, et procédé d'élaboration correspondant WO2011005127A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10735359A EP2451778A1 (fr) 2009-07-07 2010-07-06 Polymorphe cristallin stable de 2-(2-chloro-4-mésyl-benzoyl)-cyclohexane-1,3-dione, et procédé d'élaboration correspondant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT104664 2009-07-07
PT104664A PT104664A (pt) 2009-07-07 2009-07-07 Polimorfo cristalino estável de 2-(2-cloro-4-mesil-benzoil)- ciclo-hexano-1,3-diona e processo para preparar o mesmo

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WO2011005127A1 true WO2011005127A1 (fr) 2011-01-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2530838A (en) * 2015-06-08 2016-04-06 Rotam Agrochem Int Co Ltd Process for preparing mesotrione
CN112198148A (zh) * 2020-10-10 2021-01-08 杭州健澄科技有限公司 利用拉曼光谱检测烯草酮中间体三酮的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0249150A1 (fr) 1986-06-09 1987-12-16 Stauffer Chemical Company 3-(Thio substitué)-2-benzoyl-cyclohex-2-énones
US4775411A (en) 1986-06-09 1988-10-04 Stauffer Chemica Company Certain substituted 3-amino-2-benzoylcyclohex-2-enones
US5447903A (en) * 1989-10-18 1995-09-05 Hoechst Aktiengesellschaft Herbicidal active substance combinations
EP1314724A1 (fr) * 2001-10-24 2003-05-28 Bayer CropScience AG Nouvelle modification crystalline thermodynamiquement stable de (2-(2-Chloro-4-mesyl-benzoyl)cyclohexane-1,3-dione)
EP1517731A1 (fr) 2002-05-29 2005-03-30 Bayer CropScience Aktiengesellschaft Procede de realisation de modifications cristallines specifiques de substances polymorphes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL77350A (en) * 1984-12-20 1991-01-31 Stauffer Chemical Co Production of acylated diketonic compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0249150A1 (fr) 1986-06-09 1987-12-16 Stauffer Chemical Company 3-(Thio substitué)-2-benzoyl-cyclohex-2-énones
US4775411A (en) 1986-06-09 1988-10-04 Stauffer Chemica Company Certain substituted 3-amino-2-benzoylcyclohex-2-enones
US5447903A (en) * 1989-10-18 1995-09-05 Hoechst Aktiengesellschaft Herbicidal active substance combinations
EP1314724A1 (fr) * 2001-10-24 2003-05-28 Bayer CropScience AG Nouvelle modification crystalline thermodynamiquement stable de (2-(2-Chloro-4-mesyl-benzoyl)cyclohexane-1,3-dione)
EP1517731A1 (fr) 2002-05-29 2005-03-30 Bayer CropScience Aktiengesellschaft Procede de realisation de modifications cristallines specifiques de substances polymorphes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2451778A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2530838A (en) * 2015-06-08 2016-04-06 Rotam Agrochem Int Co Ltd Process for preparing mesotrione
WO2016197900A1 (fr) * 2015-06-08 2016-12-15 Rotam Agrochem International Company Limited Procédé de préparation de mésotrione
CN107922327A (zh) * 2015-06-08 2018-04-17 龙灯农业化工国际有限公司 制备硝磺草酮的方法
US10421714B2 (en) 2015-06-08 2019-09-24 Rotam Agrochem International Company Limited Process for preparing mesotrione
GB2530838B (en) * 2015-06-08 2020-01-22 Rotam Agrochem Int Co Ltd Process for purifying mesotrione
CN112198148A (zh) * 2020-10-10 2021-01-08 杭州健澄科技有限公司 利用拉曼光谱检测烯草酮中间体三酮的方法

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PT104664A (pt) 2011-01-07
EP2451778A1 (fr) 2012-05-16

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