WO2006021743A1 - Process for the preparation of polymorphs of mesotrione - Google Patents
Process for the preparation of polymorphs of mesotrione Download PDFInfo
- Publication number
- WO2006021743A1 WO2006021743A1 PCT/GB2005/003069 GB2005003069W WO2006021743A1 WO 2006021743 A1 WO2006021743 A1 WO 2006021743A1 GB 2005003069 W GB2005003069 W GB 2005003069W WO 2006021743 A1 WO2006021743 A1 WO 2006021743A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mesotrione
- process according
- solution
- crystallisation
- suspension
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
-
- 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
Definitions
- the present invention relates to a process for selectively controlling the crystallisation of polymorphic forms of mesotrione.
- the invention further relates to the use of pH to control the polymorphic formation.
- the invention further relates to a process for converting one polymorphic form to another.
- the invention still further relates to one particular polymorphic form of mesotrione.
- mesotrione (2-(4-methylsulphonyl-2- nitrobenzoyl)cyclohexane- 1 ,3-dione).
- Form 1 is the polymorphic form currently used in commercially available formulations. However,' due to the size of the crystals, milling is required to reduce the crystal size when formulating into an agrochemically acceptable composition.
- Form 2 is already of a size that would be suitable for formulating into an agrochemically acceptable composition. However, Form 2 is thermodynamically unstable and would gradually convert to Form 1; consequently any formulation prepared therefrom would be unstable and would aggregate and settle.
- a first object of the invention is to provide a process for selectively controlling which polymorph is obtained and is stable.
- a second object of the invention is to provide a process for readily converting Form 2 polymorph into Form 1 polymorph.
- the present invention provides a process for selectively controlling the crystallisation of thermodynamically stable Form 1 or kinetically stable Form 2 polymorphs of mesotrione from an aqueous mesotrione solution, said method comprising adjusting the pH of the mesotrione solution to a value wherein said thermodynamically stable Form 1 or kinetically stable Form 2 mesotrione is ultimately obtained.
- the pH of the mesotrione solution is first increased to a pH of >7, suitably MO, and preferably >12.
- the pH can be increased by the addition of a suitable base, for example NaOH, pyridine, triethylamine, Mg(OH) 2 , NH 4 OH etc.
- the addition of the base results in a salt of mesotrione being formed which has a high solubility, ensuring that mesotrione is fully solubilised and that no mesotrione remains out of solution.
- the pH is adjusted to ⁇ 3.0, resulting in the thermodynamically stable Form 1 mesotrione being obtained.
- the pH is adjusted to pH ⁇ 2.5, and preferably to pH 2 ⁇ 0.5.
- the pH is adjusted to greater than 3.0 resulting in the kinetically stable Form 2 mesotrione being obtained.
- the pH is adjusted to a value between about greater than 3.0 and about 5.5, preferably between 3.5 and 5.5.
- the upper value of pH is dependent on which particular mesotrione salt is in solution.
- the adjustment in pH is suitably carried out by the addition of acid to the mesotrione solution.
- the acid is selected from the group consisting of HCl, H 2 SO 4 , HNO 3 etc; preferably HCl.
- Form 1 seed crystals may be beneficial to add some Form 1 seed crystals to the solution after reducing the pH in order to assist crystallisation of Form 1.
- an increase in temperature can aid crystallisation of Form 1.
- the presence of salt and/or solvent can aid crystallisation of Form 1.
- the process is carried out at a temperature of ⁇ 25°C, preferably >40°C.
- a second aspect of the invention provides a process for converting Form 2 mesotrione to Form 1 mesotrione, said process comprising reducing the pH of a Form 2 mesotrione suspension to a pH of ⁇ 3.0.
- the pH is adjusted to pH ⁇ 2.5, and preferably to pH 2 ⁇ 0.5.
- the Form 2 mesotrione has previously been isolated and is resuspended in an appropriate solvent, for example water.
- the Form 2 mesotrione has been formed as a result of the manufacturing process, and has not been isolated; it is therefore already suspended in the mother liquor.
- the pH of the Form 2 mesotrione suspension is first increased to a pH of >7, suitably _d ⁇ , and preferably >12.
- the pH can be increased by the addition of a suitable base, for example NaOH, etc.
- the addition of the base results in a salt of mesotrione being formed, which has a high solubility, resulting in the Form 2 mesotrione going into solution.
- the reduction in pH is suitably carried out by the addition of acid to the mesotrione suspension.
- the acid is selected from the group consisting of HCl, H 2 SO 4 , HNO 3 etc; preferably HCl.
- Form 1 seed crystals may be added to the Form 2 mesotrione suspension after reducing the pH in order to assist crystallisation of Form 1.
- an increase in temperature can aid crystallisation of Form 1.
- the presence of salt and/or solvent can aid crystallisation of Form 1.
- the process is carried out at a temperature of >25°C, preferably >40°C.
- the invention arises from the realisation that pH can be used to control the formation of one particular polymorph over the other or to convert one polymorph to the other. Accordingly, a further aspect of the invention provides the use of pH to control the crystallisation of polymorphs of mesotrione.
- a further aspect of the invention provides a polymorph of mesotrione, wherein said polymorph is characterised by a powder X Ray diffraction pattern and data as given in Figure 2 and C 13 nmr data as given in Figure 4B and 4C.
- Form 2 material was made in the plant via a process upset. Samples of the Form 2 slurry from the crystallizer were taken to the lab where the pH of the solution was adjusted to 2.0 and the material was heated to 40-50 C while agitated. The results are shown in Table 2.
- Example 3 This is an example of converting already isolated Form 2 mesotrione to Form 1 mesotrione by placing the Form 2 material in process filtrate, adding different amounts of TEA and NaCl, adjusting the pH to 2.0, and heating the material to 40-50 C. The results are shown in Table 3.
- Example 5 Isolation of Mesotrione from a Crude Enolate Solution Plant mesotrione enolate suspension was filtered to remove any excess solid enolate. 50ml of the filtered solution was placed in a reaction flask and heated to 40 0 C. A pH probe was placed in the vessel to monitor the pH and the pH was reduced by adding 10% hydrochloric acid in a controlled manner over 20 minutes (the addition can also be done over 5 minutes and Form 1 is still isolated) to 2.8. The crystals were allowed to stir for 20 minutes before being isolated by filtration under reduced pressure, washed with water and sucked dry on the filter. The polymorphic form of the product was confirmed by FT-IR and PXRD as Mesotrione Form 1.
- Example 6 Isolation of Mesotrione from a Laboratory Prepared Enolate Solution The filtrates were placed in a reaction flask, stirred and crystals of Mesotrione added. The pH of the slurry was measured and increased to 10.5 by the addition of 48% sodium hydroxide. The slurry was stirred for 60 minutes and the excess crystals were removed by filtration.
- Form 2 transformed to Form 1 within 1 hour.
- Form 2 was stable but converted to Form 1 when seeded with Form 1 over four hours.
- the suspension could be heated to 40 0 C and 1% by weight of Form 1 seeds added and the Form 2 crystals would not transform to Form 1.
- the polymorphic form of the suspension was determined and was always found to be Form 2. After 3 weeks the monitoring ceased on a regular basis, samples taken several months later still showed that the crystals had not transformed to Form 1.
- Example 8 Stabilising Form 2 Mesotrione in a 0.05% Rhodasurf DA630 Solution 0.5g of Form 2 mesotrione crystals were stirred with a 0.05% Rhodasurf D A630 t
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05767852A EP1786767A1 (en) | 2004-08-26 | 2005-08-03 | Process for the preparation of polymorphs of mesotrione |
BRPI0514645-3A BRPI0514645A (en) | 2004-08-26 | 2005-08-03 | process for preparing mesotrione polymorphs |
CA002575636A CA2575636A1 (en) | 2004-08-26 | 2005-08-03 | Process for the preparation of polymorphs of mesotrione |
AU2005276265A AU2005276265A1 (en) | 2004-08-26 | 2005-08-03 | Process for the preparation of polymorphs of mesotrione |
MX2007002184A MX2007002184A (en) | 2004-08-26 | 2005-08-03 | Process for the preparation of polymorphs of mesotrione. |
US11/574,205 US20080194880A1 (en) | 2004-08-26 | 2005-08-03 | Process For the Preparation of Polymorphs of Mesotrione |
JP2007528954A JP2008510777A (en) | 2004-08-26 | 2005-08-03 | Process for preparing polymorphs of mesotrione |
IL181129A IL181129A0 (en) | 2004-08-26 | 2007-02-01 | Process for the preparation of polymorphs of mesotrione |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0419075.7A GB0419075D0 (en) | 2004-08-26 | 2004-08-26 | Process |
GB0419075.7 | 2004-08-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006021743A1 true WO2006021743A1 (en) | 2006-03-02 |
Family
ID=33104690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2005/003069 WO2006021743A1 (en) | 2004-08-26 | 2005-08-03 | Process for the preparation of polymorphs of mesotrione |
Country Status (19)
Country | Link |
---|---|
US (1) | US20080194880A1 (en) |
EP (1) | EP1786767A1 (en) |
JP (1) | JP2008510777A (en) |
KR (1) | KR20070050449A (en) |
CN (1) | CN101010292A (en) |
AR (1) | AR050609A1 (en) |
AU (1) | AU2005276265A1 (en) |
BR (1) | BRPI0514645A (en) |
CA (1) | CA2575636A1 (en) |
GB (1) | GB0419075D0 (en) |
GT (1) | GT200500227A (en) |
HN (1) | HN2005000482A (en) |
IL (1) | IL181129A0 (en) |
MX (1) | MX2007002184A (en) |
RU (1) | RU2007110952A (en) |
SV (1) | SV2005002209A (en) |
UA (1) | UA89057C2 (en) |
WO (1) | WO2006021743A1 (en) |
ZA (1) | ZA200700925B (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007083242A1 (en) * | 2006-01-18 | 2007-07-26 | Syngenta Participations Ag | Process for the crystallisation of mesotrione |
EP2219646A2 (en) * | 2007-12-21 | 2010-08-25 | University Of Rochester | Method for altering the lifespan of eukaryotic organisms |
WO2011016018A1 (en) | 2009-08-03 | 2011-02-10 | Agan Chemical Manufacturers Ltd. | Crystal modification of mesotrione |
WO2012123314A1 (en) | 2011-03-11 | 2012-09-20 | Syngenta Participations Ag | Solid herbicidal composition comprising mesotrione |
EP2861064A4 (en) * | 2012-06-11 | 2015-12-02 | Syngenta Participations Ag | Producing solids and related mother liquors |
US9629370B1 (en) * | 2015-12-01 | 2017-04-25 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9661851B1 (en) * | 2015-12-03 | 2017-05-30 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9661852B1 (en) * | 2015-12-03 | 2017-05-30 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9668483B1 (en) * | 2015-12-01 | 2017-06-06 | Rotam Agrochem Inernational Company Limited | Synergistic herbicidal composition and use thereof |
US9668484B2 (en) * | 2015-03-30 | 2017-06-06 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9700053B2 (en) * | 2015-10-29 | 2017-07-11 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
WO2018234957A1 (en) * | 2017-06-19 | 2018-12-27 | Upl Ltd | Polymorphs of mesotrione metal chelate and preparation process |
US10421714B2 (en) | 2015-06-08 | 2019-09-24 | Rotam Agrochem International Company Limited | Process for preparing mesotrione |
US10729136B2 (en) | 2015-10-29 | 2020-08-04 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
CN111909066A (en) * | 2020-06-24 | 2020-11-10 | 天津大学 | Crystallization treatment method for improving quality of mesotrione product |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20150023487A (en) * | 2012-05-25 | 2015-03-05 | 바스프 에스이 | Crystalline form a of 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2h-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione |
CN103503862B (en) * | 2013-09-10 | 2015-04-08 | 江苏长青农化股份有限公司 | Mesotrione oil suspension agent composition |
CN114671789B (en) * | 2021-10-25 | 2023-11-03 | 上虞颖泰精细化工有限公司 | Method for continuously crystallizing mesotrione |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0186118A2 (en) | 1984-12-20 | 1986-07-02 | Stauffer Chemical Company | Certain 2-(2'nitrobenzoyl)-1,3-cyclohexanediones |
WO1999028282A1 (en) | 1997-11-27 | 1999-06-10 | Zeneca Limited | Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds |
WO2002076934A2 (en) * | 2001-03-26 | 2002-10-03 | Syngenta Limited | Purification of 2-nitro-4-methylsulphonylbenzoic acid |
WO2005035487A1 (en) | 2003-10-02 | 2005-04-21 | Syngenta Participations Ag | Process for purifying mesotrione |
WO2005092846A1 (en) | 2004-03-26 | 2005-10-06 | Syngenta Participations Ag | Process for purifying mesotrione |
-
2004
- 2004-08-26 GB GBGB0419075.7A patent/GB0419075D0/en not_active Ceased
-
2005
- 2005-08-03 KR KR1020077004525A patent/KR20070050449A/en not_active Application Discontinuation
- 2005-08-03 BR BRPI0514645-3A patent/BRPI0514645A/en not_active IP Right Cessation
- 2005-08-03 MX MX2007002184A patent/MX2007002184A/en not_active Application Discontinuation
- 2005-08-03 UA UAA200702875A patent/UA89057C2/en unknown
- 2005-08-03 CA CA002575636A patent/CA2575636A1/en not_active Abandoned
- 2005-08-03 EP EP05767852A patent/EP1786767A1/en not_active Ceased
- 2005-08-03 CN CNA2005800288179A patent/CN101010292A/en active Pending
- 2005-08-03 JP JP2007528954A patent/JP2008510777A/en active Pending
- 2005-08-03 WO PCT/GB2005/003069 patent/WO2006021743A1/en active Application Filing
- 2005-08-03 RU RU2007110952/04A patent/RU2007110952A/en not_active Application Discontinuation
- 2005-08-03 US US11/574,205 patent/US20080194880A1/en not_active Abandoned
- 2005-08-03 AU AU2005276265A patent/AU2005276265A1/en not_active Withdrawn
- 2005-08-16 AR ARP050103453A patent/AR050609A1/en not_active Application Discontinuation
- 2005-08-25 HN HN2005000482A patent/HN2005000482A/en unknown
- 2005-08-25 GT GT200500227A patent/GT200500227A/en unknown
- 2005-08-26 SV SV2005002209A patent/SV2005002209A/en not_active Application Discontinuation
-
2007
- 2007-01-31 ZA ZA200700925A patent/ZA200700925B/en unknown
- 2007-02-01 IL IL181129A patent/IL181129A0/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0186118A2 (en) | 1984-12-20 | 1986-07-02 | Stauffer Chemical Company | Certain 2-(2'nitrobenzoyl)-1,3-cyclohexanediones |
WO1999028282A1 (en) | 1997-11-27 | 1999-06-10 | Zeneca Limited | Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds |
WO2002076934A2 (en) * | 2001-03-26 | 2002-10-03 | Syngenta Limited | Purification of 2-nitro-4-methylsulphonylbenzoic acid |
WO2005035487A1 (en) | 2003-10-02 | 2005-04-21 | Syngenta Participations Ag | Process for purifying mesotrione |
WO2005092846A1 (en) | 2004-03-26 | 2005-10-06 | Syngenta Participations Ag | Process for purifying mesotrione |
Non-Patent Citations (1)
Title |
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TOMLIN C.D.S: "The Pesticide Manual", 2000, BRITISH CROP PROTECTION COUNCIL, ISBN: 1-901396-12-6, article "500 mesotrione", pages: 602, XP003025445 |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007083242A1 (en) * | 2006-01-18 | 2007-07-26 | Syngenta Participations Ag | Process for the crystallisation of mesotrione |
US8063253B2 (en) | 2006-01-18 | 2011-11-22 | Syngenta Crop Protection, Inc. | Process for the crystallisation of mesotrione |
EP1979310B1 (en) | 2006-01-18 | 2015-03-04 | Syngenta Participations AG | Process for the crystallisation of mesotrione |
EP2219646A2 (en) * | 2007-12-21 | 2010-08-25 | University Of Rochester | Method for altering the lifespan of eukaryotic organisms |
EP2219646A4 (en) * | 2007-12-21 | 2010-12-22 | Univ Rochester | Method for altering the lifespan of eukaryotic organisms |
US8642660B2 (en) | 2007-12-21 | 2014-02-04 | The University Of Rochester | Method for altering the lifespan of eukaryotic organisms |
WO2011016018A1 (en) | 2009-08-03 | 2011-02-10 | Agan Chemical Manufacturers Ltd. | Crystal modification of mesotrione |
US8980796B2 (en) | 2009-08-03 | 2015-03-17 | Agan Chemical Manufacturers Ltd. | Crystal modification of Mesotrione |
WO2012123314A1 (en) | 2011-03-11 | 2012-09-20 | Syngenta Participations Ag | Solid herbicidal composition comprising mesotrione |
EP2861064A4 (en) * | 2012-06-11 | 2015-12-02 | Syngenta Participations Ag | Producing solids and related mother liquors |
GB2555358A (en) * | 2015-03-30 | 2018-04-25 | Rotam Agrochem Int Co Ltd | Synergistic Herbicidal composition and use thereof |
GB2555358B (en) * | 2015-03-30 | 2021-02-03 | Rotam Agrochem Int Co Ltd | Synergistic Herbicidal composition and use thereof |
US9668484B2 (en) * | 2015-03-30 | 2017-06-06 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
WO2017092478A1 (en) * | 2015-03-30 | 2017-06-08 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US10421714B2 (en) | 2015-06-08 | 2019-09-24 | Rotam Agrochem International Company Limited | Process for preparing mesotrione |
US10729136B2 (en) | 2015-10-29 | 2020-08-04 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9700053B2 (en) * | 2015-10-29 | 2017-07-11 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9668483B1 (en) * | 2015-12-01 | 2017-06-06 | Rotam Agrochem Inernational Company Limited | Synergistic herbicidal composition and use thereof |
US9629370B1 (en) * | 2015-12-01 | 2017-04-25 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
GB2555359A (en) * | 2015-12-03 | 2018-04-25 | Rotam Agrochem Int Co Ltd | Synergistic Herbicidal composition and use thereof |
US9661851B1 (en) * | 2015-12-03 | 2017-05-30 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
WO2017092446A1 (en) * | 2015-12-03 | 2017-06-08 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
US9661852B1 (en) * | 2015-12-03 | 2017-05-30 | Rotam Agrochem International Company Limited | Synergistic herbicidal composition and use thereof |
GB2555359B (en) * | 2015-12-03 | 2021-04-14 | Rotam Agrochem Int Co Ltd | Synergistic Herbicidal composition and use thereof |
WO2018234957A1 (en) * | 2017-06-19 | 2018-12-27 | Upl Ltd | Polymorphs of mesotrione metal chelate and preparation process |
US11129384B2 (en) | 2017-06-19 | 2021-09-28 | Upl Ltd | Polymorphs of mesotrione metal chelate and preparation process |
CN111909066A (en) * | 2020-06-24 | 2020-11-10 | 天津大学 | Crystallization treatment method for improving quality of mesotrione product |
Also Published As
Publication number | Publication date |
---|---|
JP2008510777A (en) | 2008-04-10 |
KR20070050449A (en) | 2007-05-15 |
US20080194880A1 (en) | 2008-08-14 |
CA2575636A1 (en) | 2006-03-02 |
CN101010292A (en) | 2007-08-01 |
GT200500227A (en) | 2006-03-21 |
EP1786767A1 (en) | 2007-05-23 |
AR050609A1 (en) | 2006-11-08 |
RU2007110952A (en) | 2008-10-10 |
HN2005000482A (en) | 2009-06-09 |
ZA200700925B (en) | 2008-08-27 |
BRPI0514645A (en) | 2008-06-17 |
SV2005002209A (en) | 2005-12-05 |
MX2007002184A (en) | 2007-04-02 |
UA89057C2 (en) | 2009-12-25 |
GB0419075D0 (en) | 2004-09-29 |
AU2005276265A1 (en) | 2006-03-02 |
IL181129A0 (en) | 2007-07-04 |
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