EP2451778A1 - Stabiles kristallines polymorph von 2-(2-chloro-4-mesyl- benzoyl)-cyclohexan/-1,3-dion und herstellungsverfahren dafür - Google Patents
Stabiles kristallines polymorph von 2-(2-chloro-4-mesyl- benzoyl)-cyclohexan/-1,3-dion und herstellungsverfahren dafürInfo
- Publication number
- EP2451778A1 EP2451778A1 EP10735359A EP10735359A EP2451778A1 EP 2451778 A1 EP2451778 A1 EP 2451778A1 EP 10735359 A EP10735359 A EP 10735359A EP 10735359 A EP10735359 A EP 10735359A EP 2451778 A1 EP2451778 A1 EP 2451778A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- benzoyl
- chloro
- cyclohexane
- dione
- mesyl
- 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.)
- Withdrawn
Links
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.
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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
PCT/PT2010/000028 WO2011005127A1 (en) | 2009-07-07 | 2010-07-06 | Stable crystalline polymorph of 2-(2-chloro-4-mesyl- benzoyl)-cyclohexane/-1,3-dione and process for preparing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2451778A1 true EP2451778A1 (de) | 2012-05-16 |
Family
ID=42829268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10735359A Withdrawn EP2451778A1 (de) | 2009-07-07 | 2010-07-06 | Stabiles kristallines polymorph von 2-(2-chloro-4-mesyl- benzoyl)-cyclohexan/-1,3-dion und herstellungsverfahren dafür |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2451778A1 (de) |
PT (1) | PT104664A (de) |
WO (1) | WO2011005127A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0186117A2 (de) * | 1984-12-20 | 1986-07-02 | Stauffer Chemical Company | Verfahren zur Herstellung von acylierten diketonischen Verbindungen |
US7211697B2 (en) * | 2002-05-29 | 2007-05-01 | Bayer Cropscience Ag | Method for producing specific crystalline modifications of polmorphous substances |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775411A (en) | 1986-06-09 | 1988-10-04 | Stauffer Chemica Company | Certain substituted 3-amino-2-benzoylcyclohex-2-enones |
US4762551A (en) | 1986-06-09 | 1988-08-09 | Stauffer Chemical Company | Certain 3-(substituted thio)-2-benzoyl-cyclohex-2-enones |
DE59010829D1 (de) * | 1989-10-18 | 1998-07-16 | Hoechst Schering Agrevo Gmbh | Herbizide wirkstoffkombinationen |
DE10152459A1 (de) * | 2001-10-24 | 2003-05-08 | Bayer Cropscience Ag | Neue thermodynamisch stabile Kristallmodifikation von [2-(2-Chloro-4-mesyl-benzoyl)cyclohexane-1,3-dione] |
-
2009
- 2009-07-07 PT PT104664A patent/PT104664A/pt unknown
-
2010
- 2010-07-06 WO PCT/PT2010/000028 patent/WO2011005127A1/en active Application Filing
- 2010-07-06 EP EP10735359A patent/EP2451778A1/de not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0186117A2 (de) * | 1984-12-20 | 1986-07-02 | Stauffer Chemical Company | Verfahren zur Herstellung von acylierten diketonischen Verbindungen |
US7211697B2 (en) * | 2002-05-29 | 2007-05-01 | Bayer Cropscience Ag | Method for producing specific crystalline modifications of polmorphous substances |
Non-Patent Citations (2)
Title |
---|
BAVIN M: "POLYMORPHISM IN PROCESS DEVELOPMENT", CHEMISTRY & INDUSTRY, SOCIETY OF CHEMICAL INDUSTRY. LONDON, GB, vol. 21, 21 August 1989 (1989-08-21), pages 527 - 529, XP001180136, ISSN: 0009-3068 * |
See also references of WO2011005127A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2011005127A1 (en) | 2011-01-13 |
PT104664A (pt) | 2011-01-07 |
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