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WO2010038008A2 - Co-cristaux - Google Patents

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Publication number
WO2010038008A2
WO2010038008A2 PCT/GB2009/002300 GB2009002300W WO2010038008A2 WO 2010038008 A2 WO2010038008 A2 WO 2010038008A2 GB 2009002300 W GB2009002300 W GB 2009002300W WO 2010038008 A2 WO2010038008 A2 WO 2010038008A2
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WO
WIPO (PCT)
Prior art keywords
powder
ray diffraction
diffraction pattern
crystal
cyprodinil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/GB2009/002300
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WO2010038008A3 (fr
Inventor
James Owen Forrest
Neil George
Rebecca Claire Burton
Manish Maheshbhai Parmar
Gordon Alastair Bell
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Syngenta Ltd
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Syngenta Ltd
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Publication of WO2010038008A2 publication Critical patent/WO2010038008A2/fr
Anticipated expiration legal-status Critical
Publication of WO2010038008A3 publication Critical patent/WO2010038008A3/fr
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    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the present invention relates to novel co-crystals of cyprodinil and pyrimethanil and their use in fungicidal compositions, in particular agrochemical compositions.
  • Cyprodinil and pyrimethanil are anilinopyrimidine fungicides and are thought to act by inhibiting the biosynthesis of methionine and the secretion of fungal hydrolytic enzymes.
  • Cyprodinil is used as a foliar fungicide on cereals, grapes, pome fruit, stone fruit, strawberries, vegetables, field crops and ornamentals and as a seed dressing on barley to control a wide range of pathogens such as Tapesia yallundae and T. acuformis, Erysiphe spp., Pyrenophora teres, Rhynchosporium secalis, Botr ⁇ tis spp., Alternaria spp., Venturia spp.
  • thermodynamic stability of polymorphic forms A and B is enantiotropically related and exhibits a phase transition temperature, which, although sensitive to other conditions, is typically at between 15 and 4O 0 C - certainly within the range of temperature fluctuations that may occur during the processing and storage of agrochemical formulations (typically -1O 0 C and +5O 0 C). Below the phase transition temperature form A is the thermodynamically stable form and above, form B is the thermodynamically stable form. Therefore, under storage conditions a solid state of cyprodinil may undergo transformation by recrystallisation between the two polymorphic forms leading to the generation of large and undesirable particles, which could, for example, block spray nozzles during application of the product.
  • the present invention provides novel co-crystalline forms of cyprodinil or pyrimethanil with improved properties as compared to the commercially available versions of this fungicide.
  • the invention provides a co-crystal of cyprodinil or pyrimethanil with a co-crystal forming compound which has at least one functional group selected from methyl, ether, hydroxyl (including alcohol and phenol), thiol, ketone, amide, primary amine, secondary amine, tertiary amine, sp2 amine, nitrile, pyrrole, pyridine, pyrimidine, thiazole.
  • Suitable co-crystal forming compounds containing at least one hydroxyl functional group include, but are not limited to, 1,8-octanediol, 2-hydroxybenzonitrile, ethyl maltol and N,N-dimethyllactamide.
  • Suitable co-crystal forming compounds containing at least one ketone group include, but are not limited to, 5-methylhydantoin, acethydrazide, ethyl maltol, nicotinic hydrazide, propionamide, succinamide and urea.
  • Suitable co-crystal forming compounds containing at least one amide functional group include, but are not limited to, nicotinic hydrazide, propionamide, urea and N,N- dimethyllactamide.
  • Suitable co-crystal forming compounds containing at least one amine functional group include, but are not limited to, l,5,7-triazabicyclo[4.4.0]dec-5-ene, 2- aminopyrimidine, 5-methylhydantoin, acethydrazide, nicotinic hydrazide, propionamide, succinamide and urea.
  • Suitable co-crystal forming compounds containing at least one nitrile functional group include, but are not limited to, 2-hydroxybenzonitrile.
  • Suitable co -crystal forming compounds containing at least one pyrimidine functional group include, but are not limited to, l,5,7-triazabicyclo[4.4.0]dec-5-ene and 2- aminopyrimidine.
  • the present invention provides a co-crystal of cyprodinil with a co- crystal forming compound as defined above.
  • the co-crystal of cyprodinil is formed using a co-former selected from the group consisting of l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,-8-octanediol, 2- aminopyrimidine, 2-hydroxybenzonitrile, 5-methylhydantoin, acethydrazide, ethyl maltol, nicotinic hydrazide, propionamide, succinimide, urea and N,N-dimethyllactamide.
  • a co-former selected from the group consisting of l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,-8-octanediol, 2- aminopyrimidine, 2-hydroxybenzonitrile, 5-methylhydantoin, acethydrazide, ethyl maltol, nicotinic hydrazide, propionamide, succinimide, urea and N,N
  • the co-crystalline form of cyprodinil or pyrimethanil and the crystal forming compound may be characterised by a crystal morphology (described in terms of the unit cell) or by selected peaks of the powder X-ray diffraction pattern expressed in terms of 2 theta angles.
  • a co-crystal form of cyprodinil and l,5,7-triazabicyclo[4.4.0]dec-5-ene is characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises the 20 angle values listed in Table IA.
  • Table IA shows the 20 values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-1,5,7- triazabicyclo[4.4.0]dec-5-ene co-crystal obtained using the method of Example I a, as well as the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • S strong
  • M medium
  • W weak
  • the diffractogram from which these peak positions are derived is shown in Figure 1.
  • the co-crystal form of cyprodinil and 1,5,7- triazabicyclo[4.4.0]dec-5-ene is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 9.1 ⁇ 0.2, 11.9 ⁇ 0.2, 14.1 ⁇ 0.2, 17.4 ⁇ 0.2, 18.9 ⁇ 0.2, 21.0 ⁇ 0.2 and 25.8 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and 1,5,7- triazabicyclo[4.4.0]dec-5-ene is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table IB, that is, the powder X-ray diffraction pattern comprises the 20 angle values 6.1 ⁇ 0.2, 9.1 ⁇ 0.2, 9.5 ⁇ 0.2, 11.9 ⁇ 0.2, 14.1 ⁇ 0.2, 17.4 ⁇ 0.2, 18.1 ⁇ 0.2, 18.9 ⁇ 0.2, 19.3 ⁇ 0.2, 21.0 ⁇ 0.2, 21.8 ⁇ 0.2, 22.5 ⁇ 0.2, 23.6 ⁇ 0.2, 24.3 ⁇ 0.2, 24.8 ⁇ 0.2, 25.8 ⁇ 0.2 and 27.0 ⁇ 0.2.
  • a co-crystal form of cyprodinil and 1,8-octanediol is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 20 angle values (a) or (b) listed in Table 2 A.
  • Table 2 A shows the 2 ⁇ values of selected peak positions of the powder X-ray diffraction pattern of two cyprodinil- 1,8-octanediol co-crystals obtained using the methods of Example Ia and Ic, respectively, as well as the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • S strong
  • M medium
  • W weak
  • the diffrac to grams from which these peak positions are derived are shown in Figures 3 and 4, respectively.
  • the co-crystal form of cyprodinil and 1,8-octanediol is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 20.1 ⁇ 0.2, 20.5 ⁇ 0.2, 22.7 ⁇ 0.2, 23.6 ⁇ 0.2, 25.6 ⁇ 0.2 and 27.4 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and 1,8-octanediol is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 2B, that is, the powder X-ray diffraction pattern comprises the 20 angle values 6.9 ⁇ 0.2, 11.4 ⁇ 0.2, 13.7 ⁇ 0.2, 15.6 ⁇ 0.2, 18.6 ⁇ 0.2, 20.1 ⁇ 0.2, 20.5 ⁇ 0.2, 22.7 ⁇ 0.2, 23.1 ⁇ 0.2, 23.6 ⁇ 0.2, 25.2 ⁇ 0.2, 25.6 ⁇ 0.2, 26.7 ⁇ 0.2, 27.4 ⁇ 0.2, 31.2 ⁇ 0.2 and 32.0 ⁇ 0.2.
  • a co-crystal form of cyprodinil and 2-aminopyrimidine is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 3 A.
  • Table 3 A shows the 2 ⁇ values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-2-aminopyrimidine co-crystal obtained using the method of Example Ia, as well as the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • S strong
  • M medium
  • W weak
  • the co-crystal form of cyprodinil and 2-aminopyrimidine is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 4.2 ⁇ 0.2, 12.0 ⁇ 0.2, 12.5 ⁇ 0.2, 13.8 ⁇ 0.2, 17.3 ⁇ 0.2, 20.6 ⁇ 0.2, 22.1 ⁇ 0.2, 24.6 ⁇ 0.2, 25.9 ⁇ 0.2 and 31.9 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and 2-aminopyrimidine is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 3B, that is, the powder X-ray diffraction pattern comprises the 29 angle values 4.2 ⁇ 0.2, 8.3 ⁇ 0.2, 10.2 ⁇ 0.2, 12.0 ⁇ 0.2, 12.5 ⁇ 0.2, 13.8 ⁇ 0.2, 14.6 ⁇ 0.2, 17.3 ⁇ 0.2, 20.6 ⁇ 0.2, 20.9 ⁇ 0.2, 22.1 ⁇ 0.2, 24.2 ⁇ 0.2, 24.6 ⁇ 0.2, 25.2 ⁇ 0.2, 25.9 ⁇ 0.2, 29.4 ⁇ 0.2 and 31.9 ⁇ 0.2.
  • AU of the peaks are derived from the powder X-ray diffraction pattern of a cyprodinil-2-aminopyrimidine co- crystal obtained using the method of Example Ib.
  • Table 3B also lists the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • the diffractogram from which these peak positions are derived is shown in Figure 7.
  • a co-crystal form of cyprodinil and 2-hydroxybenzonitrile is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 4A.
  • Table 4A shows the 20 values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-2-hydroxybenzonitrile co-crystal obtained using the method of Example Ia, as well as the intensity of these peaks (strong (S), medium (M) or weak (W)). The diffractogram from which these peak positions are derived is shown in Figure 8.
  • the co-crystal form of cyprodinil and 2-hydroxybenzonitrile is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 14.4 ⁇ 0.2, 17.5 ⁇ 0.2, 21.6 ⁇ 0.2, 22.9 ⁇ 0.2, 26.7 ⁇ 0.2 and 30.8 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and 2-hydroxybenzonitrile is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 20 angle values listed in Table 4B, that is, the powder X-ray diffraction pattern comprises the 20 angle values 6.8 ⁇ 0.2, 11.3 ⁇ 0.2, 13.4 ⁇ 0.2, 14.4 ⁇ 0.2, 15.1 ⁇ 0.2, 15.5 ⁇ 0.2, 16.8 ⁇ 0.2, 17.5 ⁇ 0.2, 18.6 ⁇ 0.2, 19.5 ⁇ 0.2, 20.3 ⁇ 0.2, 21.6 ⁇ 0.2, 22.6 ⁇ 0.2, 22.9 ⁇ 0.2, 25.2 ⁇ 0.2, 26.7 ⁇ 0.2, 30.8 ⁇ 0.2 and 32.1 ⁇ 0.2.
  • a co-crystal form of cyprodinil and 5-methylhydantoin is characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises the 20 angle values listed in Table 5 A.
  • Table 5 A shows the 20 values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-5-methylhydantoin co-crystal obtained using the method of Example Ia as well as the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • S strong
  • M medium
  • W weak
  • the co-crystal form of cyprodinil and 5-methylhydantoin is characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises at least three 20 angle values selected from the group comprising 4.5 ⁇ 0.2, 8.9 ⁇ 0.2, 9.9 ⁇ 0.2, 10.7 ⁇ 0.2, 11.7 ⁇ 0.2, 17.8 ⁇ 0.2, 22.1 ⁇ 0.2 and 24.7 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 20 values.
  • the co- crystal form of cyprodinil and 5-methylhydantoin is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 5B, that is, the powder X-ray diffraction pattern comprises the 20 angle values 4.5 ⁇ 0.2, 8.9 ⁇ 0.2, 9.9 ⁇ 0.2, 10.7 ⁇ 0.2, 11.7 ⁇ 0.2, 13.3 ⁇ 0.2, 17.8 ⁇ 0.2, 18.3 ⁇ 0.2, 19.5 ⁇ 0.2, 20.0 ⁇ 0.2, 20.2 ⁇ 0.2, 22.1 ⁇ 0.2, 24.3 ⁇ 0.2, 24.7 ⁇ 0.2, 25.5 ⁇ 0.2, 26.7 ⁇ 0.2, 31.3 ⁇ 0.2 and 32.9 ⁇ 0.2.
  • a co-crystal form of cyprodinil and acethydrazide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 6A.
  • Table 6A shows the 2 ⁇ values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-acethydrazide co-crystal obtained using the method of Example Ia as well as the intensity of these peaks (strong (S), medium (M) or weak (W)). The diffractogram from which these peak positions are derived is shown in Figure 12.
  • the co-crystal form of cyprodinil and acethydrazide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 7.2 ⁇ 0.2, 14.2 ⁇ 0.2, 25.6 ⁇ 0.2, 26.6 ⁇ 0.2 and 28.6 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and acethydrazide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 6B, that is, the powder X-ray diffraction pattern comprises the 20 angle values 7.2 ⁇ 0.2, 14.2 ⁇ 0.2, 15.6 ⁇ 0.2, 24.3 ⁇ 0.2, 25.6 ⁇ 0.2, 26.6 ⁇ 0.2, 28.6 ⁇ 0.2, 29.1 ⁇ 0.2 and 31.9 ⁇ 0.2.
  • a co-crystal form of cyprodinil and ethyl maltol is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 7A.
  • Table 7A shows the 2 ⁇ values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-ethyl maltol co-crystal obtained using the method of Example Ia as well as the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • S strong
  • M medium
  • W weak
  • the co-crystal form of cyprodinil and ethyl maltol is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 4.1 ⁇ 0.2, 7.9 ⁇ 0.2, 10.8 ⁇ 0.2, 11.9 ⁇ 0.2, 13.4 ⁇ 0.2, 15.2 ⁇ 0.2, 21.8 ⁇ 0.2, 23.9 ⁇ 0.2, 30.9 ⁇ 0.2 and 31.8 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and ethyl maltol is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 20 angle values listed in Table 7B, that is, the powder X-ray diffraction pattern comprises the 2 ⁇ angle values 4.1 ⁇ 0.2, 7.9 ⁇ 0.2, 10.8 ⁇ 0.2, 11.9 ⁇ 0.2, 13.4 ⁇ 0.2, 15.2 ⁇ 0.2, 15.8 ⁇ 0.2, 17.6 ⁇ 0.2, 18.4 ⁇ 0.2, 20.0 ⁇ 0.2, 20.8 ⁇ 0.2, 21.8 ⁇ 0.2, 22.8 ⁇ 0.2, 23.9 ⁇ 0.2, 25.0 ⁇ 0.2, 25.7 ⁇ 0.2, 27.0 ⁇ 0.2, 28.6 ⁇ 0.2, 30.2 ⁇ 0.2, 30.9 ⁇ 0.2, 31.3 ⁇ 0.2 and 31.8 ⁇ 0.2.
  • a co-crystal form of cyprodinil and nicotinic hydrazide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 8 A.
  • Table 8 A shows the 2 ⁇ values of selected peak positions of the powder X- ray diffraction pattern of a cyprodinil-nicotinic hydrazide co-crystal obtained using the method of Example Ic as well as the intensity of these peaks (strong (S), medium (M) or weak (W)).
  • the diffractogram from which these peak positions are derived is shown in Figure 16.
  • the co-crystal form of cyprodinil and nicotinic hydrazide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 5.1 ⁇ 0.2, 9.9 ⁇ 0.2, 17.0 ⁇ 0.2, 18.9 ⁇ 0.2, 19.9 ⁇ 0.2, 25.1 ⁇ 0.2 and 29.9 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and nicotinic hydrazide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 8B, that is, the powder X-ray diffraction pattern comprises the 20 angle values 5.1 ⁇ 0.2, 7.0 ⁇ 0.2, 9.9 ⁇ 0.2, 11.3 ⁇ 0.2, 14.2 ⁇ 0.2, 17.0 ⁇ 0.2, 18.9 ⁇ 0.2, 19.9 ⁇ 0.2, 22.5 ⁇ 0.2, 24.0 ⁇ 0.2, 25.1 ⁇ 0.2, 27.0 ⁇ 0.2, 28.3 ⁇ 0.2 and 29.9 ⁇ 0.2.
  • a co-crystal form of cyprodinil and propionamide is characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises the 20 angle values listed in Table 9 A.
  • Table 9 A shows the 20 values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-propionamide co-crystal obtained using the method of Example Ia as well as the intensity of these peaks (strong (S), medium (M) or weak (W)). The diffractogram from which these peak positions are derived is shown in Figure 18. TABLE 9A
  • the co-crystal form of cyprodinil and propionamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 4.9 ⁇ 0.2, 9.6 ⁇ 0.2, 11.9 ⁇ 0.2, 13.4 ⁇ 0.2, 14.4 ⁇ 0.2 and 21.2 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and propionamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 9B, that is, the powder X-ray diffraction pattern comprises the 2 ⁇ angle values 4.9 ⁇ 0.2, 6.7 ⁇ 0.2, 9.6 ⁇ 0.2, 10.2 ⁇ 0.2, 10.7 ⁇ 0.2, 11.9 ⁇ 0.2, 13.4 ⁇ 0.2, 14.4 ⁇ 0.2, 15.8 ⁇ 0.2, 20.5 ⁇ 0.2, 21.2 ⁇ 0.2, 22.6 ⁇ 0.2, 24.9 ⁇ 0.2, 25.9 ⁇ 0.2 and 26.5 ⁇ 0.2.
  • a co-crystal form of cyprodinil and succinamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 1OA.
  • Table 1OA shows the 2 ⁇ values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-succinamide co-crystal obtained using the method of Example Ia as well as the intensity of these peaks (strong (S), medium (M) or weak (W)). The diffractogram from which these peak positions are derived is shown in Figure 20.
  • the co-crystal form of cyprodinil and succinamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 6.4 ⁇ 0.2, 9.8 ⁇ 0.2, 12.8 ⁇ 0.2, 17.5 ⁇ 0.2, 19.2 ⁇ 0.2, 20.1 ⁇ 0.2, 21.4 ⁇ 0.2, 23.8 ⁇ 0.2 and 28.6 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 20 values.
  • the co-crystal form of cyprodinil and succinamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 1OB, that is, the powder X-ray diffraction pattern comprises the 20 angle values 6.4 ⁇ 0.2, 9.8 ⁇ 0.2, 12.8 ⁇ 0.2, 13.2 ⁇ 0.2, 15.0 ⁇ 0.2, 17.1 ⁇ 0.2, 17.5 ⁇ 0.2, 19.2 ⁇ 0.2, 20.1 ⁇ 0.2, 20.6 ⁇ 0.2, 21.4 ⁇ 0.2, 23.0 ⁇ 0.2, 23.8 ⁇ 0.2, 24.3 ⁇ 0.2, 24.9 ⁇ 0.2, 26.2 ⁇ 0.2, 27.2 ⁇ 0.2, 28.6 ⁇ 0.2.
  • a co-crystal form of cyprodinil and urea is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises the 2 ⁇ angle values listed in Table 1 IA.
  • Table 1 IA shows the 2 ⁇ values of selected peak positions of the powder X-ray diffraction pattern of a cyprodinil-urea co-crystal obtained using the method of Example Ic as well as the intensity of these peaks (strong (S), medium (M) or weak (W)). The diffractogram from which these peak positions are derived is shown in Figure 22.
  • the co-crystal form of cyprodinil and urea is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 4.9 ⁇ 0.2, 9.7 ⁇ 0.2, 13.8 ⁇ 0.2, 16.2 ⁇ 0.2, 16.8 ⁇ 0.2, 17.8 ⁇ 0.2 and 21.3 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and urea is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 1 IB, that is, the powder X-ray diffraction pattern comprises the 2 ⁇ angle values 4.9 ⁇ 0.2, 6.9 ⁇ 0.2, 9.7 ⁇ 0.2, 10.2 ⁇ 0.2, 13.8 ⁇ 0.2, 14.7 ⁇ 0.2, 16.2 ⁇ 0.2, 16.8 ⁇ 0.2, 17.8 ⁇ 0.2, 18.8 ⁇ 0.2, 19.6 ⁇ 0.2, 21.3 ⁇ 0.2, 22.3 ⁇ 0.2, 23.3 ⁇ 0.2, 24.3 ⁇ 0.2, 24.6 ⁇ 0.2, 25.3 ⁇ 0.2, 29.4 ⁇ 0.2 and 31.7 ⁇ 0.2.
  • a co-crystal form of cyprodinil and N,N-dimethyllactamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises at least three 2 ⁇ angle values selected from the group comprising 8.6 ⁇ 0.2, 14.4 ⁇ 0.2, 17.5 ⁇ 0.2, 21.2 ⁇ 0.2, 23.8 ⁇ 0.2, 25.2 ⁇ 0.2 and 31.9 ⁇ 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2 ⁇ values.
  • the co-crystal form of cyprodinil and N,N-dimethyllactamide is characterised by a powder X-ray diffraction pattern expressed in terms of 2 ⁇ angles, wherein the powder X-ray diffraction pattern comprises all the 2 ⁇ angle values listed in Table 12, that is, the powder X-ray diffraction pattern comprises the 2 ⁇ angle values 8.6 ⁇ 0.2, 14.4 ⁇ 0.2, 15.8 ⁇ 0.2, 17.5 ⁇ 0.2, 18.2 ⁇ 0.2, 19.5 ⁇ 0.2, 21.2 ⁇ 0.2, 22.4 ⁇ 0.2, 22.9 ⁇ 0.2 and 23.8 ⁇ 0.2.
  • 'co-crystal means a crystalline material which comprises two or more unique components in a stoichiometric ratio each containing distinctive physical characteristics such as structure, melting point and heat of fusion.
  • a co- crystal is distinct from a crystalline salt as it consists of neutral components and not charged components as would be found in a salt.
  • the co-crystal can be constructed through several modes of molecular recognition including hydrogen-bonding, II (pi)-stacking, guest-host complexation and Van-Der-Waals interactions.
  • co-crystals of the present invention are those where hydrogen bonding occurs between the co-crystal forming compound and the cyprodinil or pyrimethanil. It is noted that, where a co-former has more than one functional group capable of forming, for example, hydrogen bonds, multi-point contacts may be formed in the crystal. For example, two molecules of cyprodinil may form contacts with different functional groups on the same co-former, or, indeed, there may be multi -point contacts between a single molecule of cyprodinil and a single co-former molecule.
  • the co-crystals of the present invention may exist in one or more polymorphic forms.
  • a polymorphic co-crystal may contain any molar ratio of cyprodinil to co-former, but typically will be in the range of 5:1 to 1:5.
  • a polymorphic form may also contain a different isomeric ratio.
  • Each polymorphic form can be defined by one or more solid state analytical techniques including single crystal X-ray diffraction, powder X-ray diffraction, DSC, Raman or Infra-red spectroscopy.
  • the molar ratio of cyprodinil or pyrimethanil to co-crystal forming compound in the co-crystal is in the range of from 5:1 to 1:5. More suitably, the ratio of cyprodinil or pyrimethanil to co-crystal forming compound in the co-crystal is in the range of from 3:1 to 1 :3. Even more suitably, the ratio of cyprodinil or pyrimethanil to co-crystal forming compound is in the range of 2:1 to 1 :1.
  • the co-crystals of the present invention are formed by contacting the cyprodinil or pyrimethanil with the co-crystal forming compound. This may be done by (i) grinding two solids together, (ii) melting, or partially melting, one or both components and allowing them to recrystallise, (iii) solubilising, or partially solubilising, the cyprodinil or pyrimethanil and adding the co-crystal forming compound or (iv) solubilising, or partially solubilising, the co- crystal forming compound and adding the cyprodinil or pyrimethanil.
  • crystallisation is then allowed to occur under suitable conditions.
  • crystallisation may require alteration of a property of the solutions, such as pH or temperature and may require concentration of solute, usually by removal of the solvent and typically by drying the solution.
  • Solvent removal results in the concentration of cyprodinil or pyrimethanil increasing over time so as to facilitate crystallisation.
  • microwave irradiation and/or sonication may be used to facilitate crystallisation.
  • the co-crystal forming compound for use in the process of the invention is as defined above.
  • the co-crystal forming compound is selected from the group consisting of l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-octanediol, 2- aminopyrimidine, 2-hydroxybenzonitrile, 5-methylhydantoin, acethydrazide, ethyl maltol, nicotinic hydrazide, propionamide, succinimide, urea and N,N-dimethyllactamide.
  • Assaying the solid phase for the presence of co-crystals of the cyprodinil or pyrimethanil and the co-crystal forming compound may be carried out by conventional methods known in the art. For example, it is convenient and routine to use powder X-ray diffraction techniques to assess the presence of the co-crystals. This may be effected by comparing the spectra of cyprodinil or pyrimethanil, the co-crystal forming compound and putative co-crystals in order to establish whether or not true co-crystals have been formed.
  • DSC differential scanning calorimetry
  • TGA thermogravimetric analysis
  • Raman or Infra-red spectroscopy NMR, gas chromatography or HPLC.
  • Single crystal X-ray diffraction is especially useful in identifying co-crystal structures.
  • the co-crystals of the invention may be readily incorporated into fungicidal compositions (including agrochemical compositions) by conventional means. Accordingly, the invention also provides a fungicidal composition comprising a co-crystal of the invention as defined above. In one embodiment, the fungicidal composition is an agrochemical composition.
  • the agrochemical compositions comprising the co-crystals of the present invention can be used for the control of plant pathogenic fungi on a number of plant species.
  • the invention also provides a method of preventing/controlling fungal infection on plants or plant propagation material comprising treating the plant or plant propagation material with a fungicidally effective amount of an agricultural composition of the invention.
  • plant propagation material' is meant seeds of all kinds (fruit, tubers, bulbs, grains etc), cuttings, cut shoots and the like.
  • the agrochemical compositions of the invention can be used to control, for example, Cochliobolus sativus, Erysiphe spp. including E. graminis, Leptosphaeria nodorum, Puccinia spp., Pyrenophora teres, Pyrenophora t ⁇ tici-repentis, Rhynchosporium secalis, Septoria spp, Mycosphaerella musicola, Mycosphaerella fijiensis var. difformis, Sclerotinia homoeocarpa, Rhizoctonia solani, Helminthosporium spp.
  • Cochliobolus sativus Erysiphe spp. including E. graminis, Leptosphaeria nodorum, Puccinia spp., Pyrenophora teres, Pyrenophora t ⁇ tici-repentis, Rhynchospor
  • the agrochemical compositions of the present invention are suitable for controlling such disease on a number of plants and their propagation material including, but not limited to the following target crops: cereals (wheat, barley, rye, oats, maize (including field corn, pop corn and sweet corn), rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, eggplants, onions, pepper, tomatoes, potatoes, paprika, okra); plantation crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers); as well as other plants such as vines, bushberries (such as blue
  • ryegrasses such as perennial ryegrass (Lolium perenne L.) and annual (Italian) ryegrass (Lolium multiflorum Lam.)) and warm-season turf grasses (for example, Bermudagrasses (Cynodon L. C. Rich), including hybrid and common
  • Crops' are to be understood to include those crops that have been made tolerant to pests and pesticides, including herbicides or classes of herbicides, as a result of conventional methods of breeding or genetic engineering.
  • Tolerance to e.g. herbicides means a reduced susceptibility to damage caused by a particular herbicide compared to conventional crop breeds.
  • Crops can be modified or bred so as to be tolerant, for example, to HPPD inhibitors such as mesotrione or EPSPS inhibitors such as glyphosate.
  • the rate at which the agrochemical composition of the invention is applied will depend upon the particular type of fungus to be controlled, the degree of control required and the timing and method of application and can be readily determined by the person skilled in the art.
  • the compositions of the invention can be applied at an application rate of between 0.005 kilograms/hectare (kg/ha) and about 5.0kg/ha, based on the total amount of active fungicide in the composition.
  • An application rate of between about 0.1 kg/ha and about 1.5 kg/ha is preferred, with an application rate of between about 0.3 kg/ha and 0.8 kg/ha being especially preferred.
  • the agrochemical compositions comprising the co-crystals of the invention are applied as a formulation containing the various adjuvants and carriers known to or used in the industry. They may thus be formulated as granules, as wettable powders, as emulsifiable concentrates, as suspension concentrates (including oil dispersions), as powders or dusts, as flowables, as solutions, as suspensions or emulsions, suspo-emulsions or as controlled release forms such as microcapsules.
  • the agrochemical composition of the invention may be formulated as a suspension concentrate, a suspo-emulsion or a wet granulation.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Suspension concentrates are formulations in which finely divided solid particles of the active compound are stably suspended.
  • the solid particles may be suspended in an aqueous solution or in an oil (as an oil dispersion).
  • Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor.
  • these concentrates are diluted in water and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and may be applied without dilution to the area in which control of plant pathogenic fungi is required or dispersed in a spray tank before application, for example.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations for use without dilution normally contain about 5% to about 25% active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • active ingredient content may be increased up to 80%.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplets are typically about 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes about 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • formulations described above include wetting, dispersing or emulsifying agents.
  • examples are alkyl and alkylaryl sulphonates and sulphates and their salts, polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines.
  • These agents when used, normally comprise from 0.1% to 40% by weight of the formulation.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art. Suitable examples of the different classes are found in the non- limiting list below.
  • Liquid carriers that can be employed include water and any solvents in which the co- crystal has no or limited solubility e.g.
  • Suitable solid carriers include talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin and the like.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
  • the surface-active agents can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface active agents include salts of alkyl sulphates, such as diethanolammonium lauryl sulphate; alkylarylsulphonate salts, such as calcium dodecylbenzenesulphonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
  • alcohol-alkylene oxide addition products such as tridecyl ' alcohol-C.sub. 16 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalenesulphonate salts such as sodium dibutylnaphthalenesulphonate
  • dialkyl esters of sulphosuccinate salts such as sodium di(2-ethylhexyl) sulphosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • salts of mono and dialkyl phosphate esters such as mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, sticking agents, and the like.
  • compositions may contain other biocidally active ingredients or compositions, in order to broaden the spectrum of activity.
  • the compositions may contain other fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators, in order to broaden the spectrum of activity.
  • Each of the above formulations can be prepared as a package containing the fungicides together with other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.).
  • the formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
  • Dust and liquid compositions can be applied by the use of power-dusters, broom and hand sprayers and spray dusters.
  • the formulations can also be applied from airplanes as a dust or a spray or by rope wick applications.
  • Both solid and liquid formulations may also be applied to the soil in the locus of the plant to be treated allowing the active ingredient to penetrate the plant through the roots.
  • the formulations of the invention may also be used for dressing applications on plant propagation material to provide protection against fungus infections on the plant propagation material as well as against phytopathogenic fungi occurring in the soil.
  • the active ingredient may be applied to plant propagation material to be protected by impregnating the plant propagation material, in particular, seeds, either with a liquid formulation of the fungicide or coating it with a solid formulation.
  • the agrochemical compositions and formulations of the present invention are applied prior to disease development. Rates and frequency of use of the formulations are those conventionally used in the art and will depend on the risk of infestation by the fungal pathogen.
  • FIG.l shows the powder X-Ray diffraction patterns of cyprodinil- 1,5,7- triazabicyclo[4.4.0]dec-5-ene co-crystal obtained using the technique described in Example Ia.
  • FIG.2 shows the powder X-Ray diffraction patterns of (a) 1,5,7- triazabicyclo[4.4.0]dec-5-ene (b) cyprodinil-l,5,7-triazabicyclo[4.4.0]dec-5-ene co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.3 shows the powder X-Ray diffraction patterns of cyprodinil- 1 ,8-octanediol co- crystal obtained using the technique described in Example Ia.
  • FIG .4 shows the powder X-Ray diffraction patterns of cyprodinil- 1,8-octanediol co- crystal obtained using the technique described in Example Ic.
  • FIG.5 shows the powder X-Ray diffraction patterns of (a) 1,8-octanediol, (b) cyprodinil- 1,8-octanediol co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.6 shows the powder X-Ray diffraction patterns of cyprodinil-2-arninopyrimidine co-crystal obtained using the technique described in Example 1 a.
  • FIG.7 shows the powder X-Ray diffraction patterns of (a) 2-aminopyrimidine, (b) cyprodinil-2-aminopyrimidine co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.8 shows the powder X-Ray diffraction patterns of cyprodinil-2- hydroxybenzonitrile co-crystal obtained using the technique described in Example Ia.
  • FIG.9 shows the powder X-Ray diffraction patterns of (a) 2-hydroxybenzonitrile, (b) cyprodinil-2-hydroxybenzonitrile co-crystal obtained using the technique described in Example Ie, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.10 shows the powder X-Ray diffraction patterns of cyprodinil-5- methylhydantoin co-crystal obtained using the technique described in Example Ia.
  • FIG.l 1 shows the powder X-Ray diffraction patterns of (a) 5-methylhydantoin, (b) cyprodinil-5-methylhydantoin co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.12 shows the powder X-Ray diffraction patterns of cyprodinil-acethydrazide co- crystal obtained using the technique described in Example Ia.
  • FIG.13 shows the powder X-Ray diffraction patterns of (a) accethydrazide, (b) cyprodinil-acethydrazide co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.14 shows the powder X-Ray diffraction patterns of cyprodinil-ethyl maltol co- crystal obtained using the technique described in Example Ia.
  • FIG.15 shows the powder X-Ray diffraction patterns of (a) ethyl maltol, (b) cyprodinil-ethyl maltol co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.16 shows the powder X-Ray diffraction patterns of cyprodinil-nicotinic hydrazide co-crystal obtained using the technique described in Example Ic.
  • FIG.17 shows the powder X-Ray diffraction patterns of (a) nicotinic hydrazide, (b) cyprodinil-nicotinic hydrazide co-crystal obtained using the technique described in Example Id, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.18 shows the powder X-Ray diffraction patterns of cyprodinil-propionamide co- crystal obtained using the technique described in Example Ia.
  • FIG.19 shows the powder X-Ray diffraction patterns of (a) propionamide, (b) cyprodinil-propionamide co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.20 shows the powder X-Ray diffraction patterns of cyprodinil-succinamide co- crystal obtained using the technique described in Example Ia.
  • FIG.21 shows the powder X-Ray diffraction patterns of (a) succinamide, (b) cyprodinil-succinamide co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.22 shows the powder X-Ray diffraction patterns of cyprodinil-urea co-crystal obtained using the technique described in Example Ib.
  • FIG.23 shows the powder X-Ray diffraction patterns of (a) urea, (b) cyprodinil-urea co-crystal obtained using the technique described in Example Ib, (c) cyprodinil form A and (d) cyprodinil form B.
  • FIG.24 shows the powder X-Ray diffraction patterns of (a) cyprodinil form A, (b) cyprodinil form B and (c) cyprodinil-N,N-dimethyllactamide co-crystal obtained using the technique described in Example 2.
  • FIG. 25 shows the DSC trace of (a) 2-aminopyrimidine, (b) co-crystal product obtained using the technique described in Example Ib and (c) cyprodinil form B.
  • FIG. 26 shows the DSC trace of (a) 5-methylhydantoin, (b) co-crystal product obtained using the technique described in Example Ib and (c) cyprodinil form B.
  • FIG. 27 shows the DSC trace of (a) ethyl maltol, (b) co-crystal product obtained using the technique described in Example Ib and (c) cyprodinil form B.
  • Figure 28 shows the DSC trace of (a) succinimide, (b) co-crystal product obtained using the technique described in Example Ib and (c) cyprodinil form B.
  • FIG. 29 shows a DSC trace of (a) cyprodinil form B and (b) cyprodinil-N,N- dimethyllactamide co-crystal obtained using the technique described in Example 2.
  • Cyprodinil was dissolved in acetone to make a solution of 0.85 M/l. 94 ⁇ of this solution was charged to a reaction vial and evaporated to dryness under nitrogen. 308 ⁇ of a 0.72 M/l solution of l ,5,7-triazabicyclo[4.4.0]dec-5-ene in methanol was added to the reaction vial and also evaporated to dryness under nitrogen. 500 ⁇ l of methanol was then added and the reaction vial heated to 50°C for 2 hours with stirring to solubilise. The mixture was then cooled to 10°C over 5 hours and then held at 10°C for a further 5 hours. The supernatant liquid was removed from the solution by filtration, any residual solvent allowed to evaporate and the resultant crystals collected.
  • Cyprodinil was dissolved in acetone to make a solution of 1.2 M/l. 100 ⁇ l of this solution was charged to a reaction vial and evaporated to dryness under nitrogen. 64 ⁇ l of a 1.2 M/l solution of 1,8-octanediol 1 in methanol was added to the reaction vial and also evaporated to dryness under nitrogen. 500 ⁇ l of acetonitrile was then added and the reaction vial heated to 50°C for 2 hours with stirring to solubilise. The mixture was then evaporated to dryness under nitrogen and the resultant crystals collected.
  • Powder X-ray diffraction patterns for each of the resultant crystals are shown in Figures 1 to 24 as described above. These powder X-ray diffraction traces clearly show that the product co-crystals bear no resemblance to either of their constituent phases suggesting that a new solid state has been formed.
  • the 2 ⁇ values of selected peak positions of the powder X-ray diffraction patterns of these crystals are shown in Tables 1 to 12 above.
  • Cyprodinil-ethyl maltol crystals obtained from Example Ib were analysed by NMR and displayed a 1 :1 stoichiometric ratio of cyprodinil and ethyl maltol.
  • Cyprodinil-succinamide crystals obtained from Example Ib were analysed by NMR and displayed a 1 :1 stoichiometric ratio of cyprodinil and succinamide.

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Abstract

La présente invention concerne des co-cristaux de cyprodinil ou de pyriméthanil et un composé formant des co-cristaux qui possède au moins un groupe fonctionnel choisi parmi les groupes méthyle, éther, hydroxyle (incluant alcool et phénol), thiol, cétone, amide, amine primaire, amine secondaire, amine tertiaire, amine sp2, nitrile, pyrrole, pyridine, pyrimidine et thiazole.
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WO2013030777A1 (fr) * 2011-08-30 2013-03-07 Basf Se Cocristaux de cyprodinil et de dithianon
WO2013143927A1 (fr) * 2012-03-29 2013-10-03 Basf Se Co-cristaux de dicamba et formeur de co-cristal b
WO2014135392A1 (fr) * 2013-03-07 2014-09-12 Basf Se Cocristaux de pyriméthanyl et de dithiine-tetracarboximide sélectionné

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ATE212337T1 (de) * 1993-11-09 2002-02-15 Syngenta Participations Ag Kristallmodifikation von (4-cyclopropyl-6-methyl- pyrimidin-2-yl)- phenyl-amin, und verfahren zu dessen herstellung
TW200901889A (en) * 2007-02-09 2009-01-16 Basf Se Crystalline complexes of agriculturally active organic compounds
GB0706044D0 (en) * 2007-03-28 2007-05-09 Syngenta Ltd C0-Crystals
GB0716592D0 (en) * 2007-08-24 2007-10-03 Syngenta Ltd Improvements in or relating to organic compounds
AU2008309828B2 (en) * 2007-09-07 2013-09-12 Basf Se Co-crystals of pyrimethanil and dithianon

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EA021892B1 (ru) * 2010-04-15 2015-09-30 Синджента Лимитед Смешанные кристаллы ципродинила
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WO2013030777A1 (fr) * 2011-08-30 2013-03-07 Basf Se Cocristaux de cyprodinil et de dithianon
CN103764632A (zh) * 2011-08-30 2014-04-30 巴斯夫欧洲公司 环丙嘧啶和二噻农的共晶
CN103764632B (zh) * 2011-08-30 2017-05-17 巴斯夫欧洲公司 环丙嘧啶和二噻农的共晶
EA025318B1 (ru) * 2011-08-30 2016-12-30 Басф Се Сокристаллы ципродинила и дитианона
WO2013143927A1 (fr) * 2012-03-29 2013-10-03 Basf Se Co-cristaux de dicamba et formeur de co-cristal b
WO2014135392A1 (fr) * 2013-03-07 2014-09-12 Basf Se Cocristaux de pyriméthanyl et de dithiine-tetracarboximide sélectionné
CN105025723A (zh) * 2013-03-07 2015-11-04 巴斯夫欧洲公司 二甲嘧菌胺和选定的二噻二烯四甲酰亚胺的共晶

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