CN109384728A - Fluoxastrobin channel solvates and preparation method thereof - Google Patents

Fluoxastrobin channel solvates and preparation method thereof Download PDF

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Publication number
CN109384728A
CN109384728A CN201710667153.5A CN201710667153A CN109384728A CN 109384728 A CN109384728 A CN 109384728A CN 201710667153 A CN201710667153 A CN 201710667153A CN 109384728 A CN109384728 A CN 109384728A
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China
Prior art keywords
crystal form
solution
basic
dsc
ray powder
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Inventor
徐晓勇
任国宾
李忠
齐明辉
刘鹏建
杜丹
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East China University of Science and Technology
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East China University of Science and Technology
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Priority to CN201710667153.5A priority Critical patent/CN109384728A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • 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
    • 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

Abstract

The present invention provides Fluoxastrobin channel solvates and preparation method thereof.In particular it relates to the channel solvates, preparation method and purposes of (E) -2- { 2- [6- (2- cyano-benzene oxygen) pyrimidine-4-yl oxygroup] phenyl } -3- methoxy-methyl acrylate.

Description

Fluoxastrobin channel solvates and preparation method thereof
Technical field
The invention belongs to field of pesticide chemistry, specifically, the present invention relates to Fluoxastrobin channel solvates, its application And preparation method.
Background technique
Fluoxastrobin (compound of formula I), entitled (E) -2- { 2- [6- (2- cyano-benzene oxygen) pyrimidine-4-yl oxygroup] benzene of chemistry Base } -3- methoxy-methyl acrylate.The compound is a kind of completely new β methoxy acrylic acid lipid fungicide, is able to suppress disease Fungal mitochondria breathing destroys the energy synthesis of germ, has protection, treats and root out triple function.To sac fungus, load The major part disease such as downy mildew, powdery mildew, anthracnose, leaf spot caused by four major class disease fungi of bacterium, Fungi Imperfecti and Oomycete There is good preventive effect.
Same compound, crystal form are different, and solubility may also can have difference, in addition its stability, mobility, can Compressibility, bioavilability may also can be different.And these physicochemical properties can generate certain influence to the application of the compound. According to the preparation method in original chemical patent CN101522639A, the crystal form prepared is named as crystal form A, crystal form A There is a situation where that solubility is low, unstable.
Therefore, this field needs other crystal forms of research and development compound of formula I, it is desirable that preparation method is simple, light and heat stability, Hygroscopicity is low, dissolubility is high, is produced on a large scale.
Summary of the invention
The purpose of the present invention is to provide polymorphics of a kind of Fluoxastrobin and preparation method thereof.
The first aspect of the present invention provides a kind of solvate of compound of formula I,
In another preferred example, the solvate is selected from the group: crystal form B, crystal form C, crystal form D, crystal form E, crystal form F, crystalline substance Type G, crystal form H, crystal form I, crystal form J, crystal form K, crystal form L, crystal form M.
In another preferred example, the X-ray powder diffraction pattern of the crystal form B includes 3 or 3 or more selected from the group below 2 θ values: 7.6 ± 0.2 °, 8.6 ± 0.2 °, 14.4 ± 0.2 °, 16.9 ± 0.2 °, 18.2 ± 0.2 °, 18.8 ± 0.2 °, 20.5 ± 0.2°、21.3±0.2°、22.4±0.2°、22.8±0.2°、24.2±0.2°、26.1±0.2°、26.7±0.2°、28.7± 0.2°、30.4±0.2°、30.9±0.2°、36.0±0.2°、38.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form B includes 5 or 5 or more selected from the group below 2 θ values: 7.6 ± 0.2 °, 8.6 ± 0.2 °, 14.4 ± 0.2 °, 16.9 ± 0.2 °, 18.2 ± 0.2 °, 18.8 ± 0.2 °, 20.5 ± 0.2°、21.3±0.2°、22.4±0.2°、22.8±0.2°、24.2±0.2°、26.1±0.2°、26.7±0.2°、28.7± 0.2°、30.4±0.2°、30.9±0.2°、36.0±0.2°、38.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form B is selected from the group including 10 or 10 or more 2 θ values: 7.6 ± 0.2 °, 8.6 ± 0.2 °, 14.4 ± 0.2 °, 16.9 ± 0.2 °, 18.2 ± 0.2 °, 18.8 ± 0.2 °, 20.5 ± 0.2°、21.3±0.2°、22.4±0.2°、22.8±0.2°、24.2±0.2°、26.1±0.2°、26.7±0.2°、28.7± 0.2°、30.4±0.2°、30.9±0.2°、36.0±0.2°、38.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form B can further comprise 1 or 1 or more and select From 2 θ values of the following group: 11.0 ± 0.2 °, 12.1 ± 0.2 °, 13.8 ± 0.2 °, 15.1 ± 0.2 °, 25.1 ± 0.2 °, 25.7 ± 0.2°、27.4±0.2°、32.4±0.2°、33.8±0.2°、36.7±0.2°、40.8±0.2°、43.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form B is basic as Fig. 1 is characterized.
In another preferred example, the TGA figure of the crystal form B is basic as Fig. 3 is characterized.
In another preferred example, the DSC figure of the crystal form B has heat absorption within the scope of 62~88 DEG C and 100~125 DEG C Peak.
In another preferred example, the DSC figure of the crystal form B is basic as Fig. 2 is characterized.
In another preferred example, the crystal form B purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form C includes 3 or 3 or more selected from the group below 2 θ values: 7.0 ± 0.2 °, 7.3 ± 0.2 °, 7.6 ± 0.2 °, 8.5 ± 0.2 °, 12.1 ± 0.2 °, 13.9 ± 0.2 °, 14.7 ± 0.2°、17.0±0.2°、18.1±0.2°、18.9±0.2°、20.7±0.2°、21.5±0.2°、22.6±0.2°、22.8± 0.2°、24.5±0.2°、25.8±0.2°、26.3±0.2°、26.8±0.2°、27.7±0.2°、28.7±0.2°、29.0± 0.2°、30.6±0.2°、30.8±0.2°、31.2±0.2°、35.0±0.2°、36.2±0.2°、38.5±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form C includes 5 or 5 or more selected from the group below 2 θ values: 7.0 ± 0.2 °, 7.3 ± 0.2 °, 7.6 ± 0.2 °, 8.5 ± 0.2 °, 12.1 ± 0.2 °, 13.9 ± 0.2 °, 14.7 ± 0.2°、17.0±0.2°、18.1±0.2°、18.9±0.2°、20.7±0.2°、21.5±0.2°、22.6±0.2°、22.8± 0.2°、24.5±0.2°、25.8±0.2°、26.3±0.2°、26.8±0.2°、27.7±0.2°、28.7±0.2°、29.0± 0.2°、30.6±0.2°、30.8±0.2°、31.2±0.2°、35.0±0.2°、36.2±0.2°、38.5±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form C is selected from the group including 10 or 10 or more 2 θ values: 7.0 ± 0.2 °, 7.3 ± 0.2 °, 7.6 ± 0.2 °, 8.5 ± 0.2 °, 12.1 ± 0.2 °, 13.9 ± 0.2 °, 14.7 ± 0.2°、17.0±0.2°、18.1±0.2°、18.9±0.2°、20.7±0.2°、21.5±0.2°、22.6±0.2°、22.8± 0.2°、24.5±0.2°、25.8±0.2°、26.3±0.2°、26.8±0.2°、27.7±0.2°、28.7±0.2°、29.0± 0.2°、30.6±0.2°、30.8±0.2°、31.2±0.2°、35.0±0.2°、36.2±0.2°、38.5±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form C can further comprise 1 or 1 or more and select From 2 θ values of the following group: 15.5 ± 0.2 °, 23.5 ± 0.2 °, 25.1 ± 0.2 °, 28.1 ± 0.2 °, 31.5 ± 0.2 °, 32.6 ± 0.2°、33.5±0.2°、33.9±0.2°、37.2±0.2°、40.0±0.2°、40.5±0.2°、41.6±0.2°、42.1± 0.2°、42.8±0.2°、43.8±0.2°、44.5±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form C is basic as Fig. 6 is characterized.
In another preferred example, the TGA figure of the crystal form C is basic as Fig. 8 is characterized.
In another preferred example, the DSC figure of the crystal form C has endothermic peak within the scope of 86~103 DEG C.
In another preferred example, the DSC figure of the crystal form C is basic as Fig. 7 is characterized.
In another preferred example, the crystal form C purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form D includes 3 or 3 or more selected from the group below 2 θ values: 7.6 ± 0.2 °, 8.5 ± 0.2 °, 13.5 ± 0.2 °, 14.4 ± 0.2 °, 16.5 ± 0.2 °, 17.0 ± 0.2 °, 18.2 ± 0.2°、18.7±0.2°、20.6±0.2°、21.0±0.2°、21.3±0.2°、22.4±0.2°、23.6±0.2°、24.1± 0.2°、25.9±0.2°、26.5±0.2°、28.2±0.2°、28.6±0.2°、28.9±0.2°、30.4±0.2°、30.8± 0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form D includes 5 or 5 or more selected from the group below 2 θ values: 7.6 ± 0.2 °, 8.5 ± 0.2 °, 13.5 ± 0.2 °, 14.4 ± 0.2 °, 16.5 ± 0.2 °, 17.0 ± 0.2 °, 18.2 ± 0.2°、18.7±0.2°、20.6±0.2°、21.0±0.2°、21.3±0.2°、22.4±0.2°、23.6±0.2°、24.1± 0.2°、25.9±0.2°、26.5±0.2°、28.2±0.2°、28.6±0.2°、28.9±0.2°、30.4±0.2°、30.8± 0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form D is selected from the group including 10 or 10 or more 2 θ values: 7.6 ± 0.2 °, 8.5 ± 0.2 °, 13.5 ± 0.2 °, 14.4 ± 0.2 °, 16.5 ± 0.2 °, 17.0 ± 0.2 °, 18.2 ± 0.2°、18.7±0.2°、20.6±0.2°、21.0±0.2°、21.3±0.2°、22.4±0.2°、23.6±0.2°、24.1± 0.2°、25.9±0.2°、26.5±0.2°、28.2±0.2°、28.6±0.2°、28.9±0.2°、30.4±0.2°、30.8± 0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form D can further comprise 1 or 1 or more and select From 2 θ values of the following group: 11.9 ± 0.2 °, 15.6 ± 0.2 °, 21.8 ± 0.2 °, 24.5 ± 0.2 °, 25.1 ± 0.2 °, 27.4 ± 0.2°、31.2±0.2°、32.7±0.2°、34.3±0.2°、34.8±0.2°、35.8±0.2°、36.4±0.2°、37.2± 0.2°、38.0±0.2°、40.9±0.2°、41.5±0.2°、43.0±0.2°、43.7±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form D is basic as Figure 13 is characterized.
In another preferred example, the TGA figure of the crystal form D is basic as Figure 15 is characterized.
In another preferred example, the DSC figure of the crystal form D has heat absorption within the scope of 57~87 DEG C and 105~144 DEG C Peak.
In another preferred example, the DSC figure of the crystal form D is basic as Figure 14 is characterized.
In another preferred example, the crystal form D purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form E includes 3 or 3 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.6 ± 0.2 °, 13.4 ± 0.2 °, 14.4 ± 0.2 °, 14.7 ± 0.2 °, 15.6 ± 0.2 °, 16.5 ± 0.2°、18.2±0.2°、19.1±0.2°、20.6±0.2°、21.3±0.2°、22.8±0.2°、24.0±0.2°、24.5± 0.2°、25.3±0.2°、25.8±0.2°、26.6±0.2°、28.6±0.2°、30.2±0.2°、31.3±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form E includes 5 or 5 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.6 ± 0.2 °, 13.4 ± 0.2 °, 14.4 ± 0.2 °, 14.7 ± 0.2 °, 15.6 ± 0.2 °, 16.5 ± 0.2°、18.2±0.2°、19.1±0.2°、20.6±0.2°、21.3±0.2°、22.8±0.2°、24.0±0.2°、24.5± 0.2°、25.3±0.2°、25.8±0.2°、26.6±0.2°、28.6±0.2°、30.2±0.2°、31.3±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form E is selected from the group including 10 or 10 or more 2 θ values: 7.5 ± 0.2 °, 8.6 ± 0.2 °, 13.4 ± 0.2 °, 14.4 ± 0.2 °, 14.7 ± 0.2 °, 15.6 ± 0.2 °, 16.5 ± 0.2°、18.2±0.2°、19.1±0.2°、20.6±0.2°、21.3±0.2°、22.8±0.2°、24.0±0.2°、24.5± 0.2°、25.3±0.2°、25.8±0.2°、26.6±0.2°、28.6±0.2°、30.2±0.2°、31.3±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form E can further comprise 1 or 1 or more and select From 2 θ values of the following group: 11.9 ± 0.2 °, 17.1 ± 0.2 °, 21.8 ± 0.2 °, 27.4 ± 0.2 °, 32.6 ± 0.2 °, 33.4 ± 0.2°、34.2±0.2°、34.6±0.2°、36.4±0.2°、37.3±0.2°、37.8±0.2°、40.2±0.2°、41.0± 0.2°、41.5±0.2°、41.9±0.2°、42.4±0.2°、43.1±0.2°、43.7±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form E is basic as Figure 18 is characterized.
In another preferred example, the TGA figure of the crystal form E is basic as Figure 20 is characterized.
In another preferred example, the DSC figure of the crystal form E has within the scope of 77~100 DEG C and 106~123 DEG C and inhales Thermal spike.
In another preferred example, the DSC figure of the crystal form E is basic as Figure 19 is characterized.
In another preferred example, the crystal form E purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form F includes 3 or 3 or more selected from the group below 2 θ values: 7.1 ± 0.2 °, 8.5 ± 0.2 °, 13.7 ± 0.2 °, 14.5 ± 0.2 °, 16.9 ± 0.2 °, 17.5 ± 0.2 °, 20.1 ± 0.2°、20.6±0.2°、21.2±0.2°、21.7±0.2°、23.2±0.2°、23.6±0.2°、24.6±0.2°、25.1± 0.2°、25.8±0.2°、26.9±0.2°、29.1±0.2°、31.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form F includes 5 or 5 or more selected from the group below 2 θ values: 7.1 ± 0.2 °, 8.5 ± 0.2 °, 13.7 ± 0.2 °, 14.5 ± 0.2 °, 16.9 ± 0.2 °, 17.5 ± 0.2 °, 20.1 ± 0.2°、20.6±0.2°、21.2±0.2°、21.7±0.2°、23.2±0.2°、23.6±0.2°、24.6±0.2°、25.1± 0.2°、25.8±0.2°、26.9±0.2°、29.1±0.2°、31.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form F is selected from the group including 10 or 10 or more 2 θ values: 7.1 ± 0.2 °, 8.5 ± 0.2 °, 13.7 ± 0.2 °, 14.5 ± 0.2 °, 16.9 ± 0.2 °, 17.5 ± 0.2 °, 20.1 ± 0.2°、20.6±0.2°、21.2±0.2°、21.7±0.2°、23.2±0.2°、23.6±0.2°、24.6±0.2°、25.1± 0.2°、25.8±0.2°、26.9±0.2°、29.1±0.2°、31.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form F can further comprise 1 or 1 or more and select From 2 θ values of the following group: 10.9 ± 0.2 °, 11.8 ± 0.2 °, 12.7 ± 0.2 °, 13.3 ± 0.2 °, 15.6 ± 0.2 °, 16.1 ± 0.2°、18.4±0.2°、18.7±0.2°、27.5±0.2°、28.3±0.2°、29.6±0.2°、30.7±0.2°、32.3± 0.2°、33.7±0.2°、33.9±0.2°、35.0±0.2°、35.5±0.2°、36.5±0.2°、36.8±0.2°、38.2± 0.2°、40.5±0.2°、41.3±0.2°、43.2±0.2°、43.7±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form F is basic as Figure 23 is characterized.
In another preferred example, the TGA figure of the crystal form F is basic as Figure 25 is characterized.
In another preferred example, the DSC figure of the crystal form F has endothermic peak within the scope of 106~129 DEG C.
In another preferred example, the DSC figure of the crystal form F is basic as Figure 24 is characterized.
In another preferred example, the crystal form F purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form G includes 3 or 3 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 13.9 ± 0.2 °, 14.3 ± 0.2 °, 14.6 ± 0.2 °, 16.8 ± 0.2 °, 18.1 ± 0.2°、18.9±0.2°、20.6±0.2°、21.2±0.2°、21.4±0.2°、22.4±0.2°、22.8±0.2°、24.3± 0.2°、24.6±0.2°、26.2±0.2°、26.7±0.2°、28.7±0.2°、30.3±0.2°、30.5±0.2°、30.7± 0.2°、31.0±0.2°、31.2±0.2°、36.0±0.2°、38.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form G includes 5 or 5 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 13.9 ± 0.2 °, 14.3 ± 0.2 °, 14.6 ± 0.2 °, 16.8 ± 0.2 °, 18.1 ± 0.2°、18.9±0.2°、20.6±0.2°、21.2±0.2°、21.4±0.2°、22.4±0.2°、22.8±0.2°、24.3± 0.2°、24.6±0.2°、26.2±0.2°、26.7±0.2°、28.7±0.2°、30.3±0.2°、30.5±0.2°、30.7± 0.2°、31.0±0.2°、31.2±0.2°、36.0±0.2°、38.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form G is selected from the group including 10 or 10 or more 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 13.9 ± 0.2 °, 14.3 ± 0.2 °, 14.6 ± 0.2 °, 16.8 ± 0.2 °, 18.1 ± 0.2°、18.9±0.2°、20.6±0.2°、21.2±0.2°、21.4±0.2°、22.4±0.2°、22.8±0.2°、24.3± 0.2°、24.6±0.2°、26.2±0.2°、26.7±0.2°、28.7±0.2°、30.3±0.2°、30.5±0.2°、30.7± 0.2°、31.0±0.2°、31.2±0.2°、36.0±0.2°、38.4±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form G can further comprise 1 or 1 or more and select From 2 θ values of the following group: 6.7 ± 0.2 °, 12.1 ± 0.2 °, 13.2 ± 0.2 °, 15.6 ± 0.2 °, 23.6 ± 0.2 °, 25.5 ± 0.2°、27.3±0.2°、27.9±0.2°、29.5±0.2°、31.5±0.2°、32.5±0.2°、32.9±0.2°、33.9± 0.2°、34.3±0.2°、35.0±0.2°、37.1±0.2°、37.7±0.2°、40.5±0.2°、41.4±0.2°、43.2± 0.2°、43.5±0.2°、44.5±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form G is basic as Figure 26 is characterized.
In another preferred example, the TGA figure of the crystal form G is basic as Figure 28 is characterized.
In another preferred example, the DSC figure of the crystal form G has endothermic peak within the scope of 83~104 DEG C.
In another preferred example, the DSC figure of the crystal form G is basic as Figure 27 is characterized.
In another preferred example, the crystal form G purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form H includes 3 or 3 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.7 ± 0.2 °, 13.5 ± 0.2 °, 14.2 ± 0.2 °, 14.5 ± 0.2 °, 15.6 ± 0.2 °, 18.0 ± 0.2°、19.2±0.2°、20.6±0.2°、21.4±0.2°、22.5±0.2°、23.7±0.2°、24.1±0.2°、25.1± 0.2°、25.5±0.2°、26.3±0.2°、26.8±0.2°、28.3±0.2°、28.5±0.2°、30.0±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form H includes 5 or 5 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.7 ± 0.2 °, 13.5 ± 0.2 °, 14.2 ± 0.2 °, 14.5 ± 0.2 °, 15.6 ± 0.2 °, 18.0 ± 0.2°、19.2±0.2°、20.6±0.2°、21.4±0.2°、22.5±0.2°、23.7±0.2°、24.1±0.2°、25.1± 0.2°、25.5±0.2°、26.3±0.2°、26.8±0.2°、28.3±0.2°、28.5±0.2°、30.0±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form H is selected from the group including 10 or 10 or more 2 θ values: 7.5 ± 0.2 °, 8.7 ± 0.2 °, 13.5 ± 0.2 °, 14.2 ± 0.2 °, 14.5 ± 0.2 °, 15.6 ± 0.2 °, 18.0 ± 0.2°、19.2±0.2°、20.6±0.2°、21.4±0.2°、22.5±0.2°、23.7±0.2°、24.1±0.2°、25.1± 0.2°、25.5±0.2°、26.3±0.2°、26.8±0.2°、28.3±0.2°、28.5±0.2°、30.0±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form H can further comprise 1 or 1 or more and select From 2 θ values of the following group: 11.9 ± 0.2 °, 16.3 ± 0.2 °, 17.3 ± 0.2 °, 27.5 ± 0.2 °, 29.1 ± 0.2 °, 30.7 ± 0.2°、31.2±0.2°、32.0±0.2°、32.9±0.2°、33.3±0.2°、33.8±0.2°、34.7±0.2°、36.0± 0.2°、36.4±0.2°、37.1±0.2°、37.7±0.2°、38.1±0.2°、40.7±0.2°、41.2±0.2°、41.9± 0.2°、43.3±0.2°、43.9±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form H is basic as Figure 29 is characterized.
In another preferred example, the TGA figure of the crystal form H is basic as Figure 31 is characterized.
In another preferred example, the DSC figure of the crystal form H has heat absorption within the scope of 62~81 DEG C and 83~122 DEG C Peak.
In another preferred example, the DSC figure of the crystal form H is basic as Figure 30 is characterized.
In another preferred example, the crystal form H purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form I includes 3 or 3 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 11.0 ± 0.2 °, 13.8 ± 0.2 °, 14.4 ± 0.2 °, 15.9 ± 0.2 °, 16.5 ± 0.2°、17.5±0.2°、19.0±0.2°、20.6±0.2°、21.4±0.2°、22.0±0.2°、22.5±0.2°、22.8± 0.2°、23.9±0.2°、24.4±0.2°、24.9±0.2°、26.3±0.2°、26.7±0.2°、28.4±0.2°、28.9± 0.2°、30.6±0.2°、36.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form I includes 5 or 5 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 11.0 ± 0.2 °, 13.8 ± 0.2 °, 14.4 ± 0.2 °, 15.9 ± 0.2 °, 16.5 ± 0.2°、17.5±0.2°、19.0±0.2°、20.6±0.2°、21.4±0.2°、22.0±0.2°、22.5±0.2°、22.8± 0.2°、23.9±0.2°、24.4±0.2°、24.9±0.2°、26.3±0.2°、26.7±0.2°、28.4±0.2°、28.9± 0.2°、30.6±0.2°、36.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form I is selected from the group including 10 or 10 or more 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 11.0 ± 0.2 °, 13.8 ± 0.2 °, 14.4 ± 0.2 °, 15.9 ± 0.2 °, 16.5 ± 0.2°、17.5±0.2°、19.0±0.2°、20.6±0.2°、21.4±0.2°、22.0±0.2°、22.5±0.2°、22.8± 0.2°、23.9±0.2°、24.4±0.2°、24.9±0.2°、26.3±0.2°、26.7±0.2°、28.4±0.2°、28.9± 0.2°、30.6±0.2°、36.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form I can further comprise 1 or 1 or more and select From 2 θ values of the following group: 6.2 ± 0.2 °, 15.1 ± 0.2 °, 17.1 ± 0.2 °, 18.3 ± 0.2 °, 23.3 ± 0.2 °, 25.4 ± 0.2°、27.2±0.2°、27.8±0.2°、29.5±0.2°、29.9±0.2°、31.2±0.2°、32.0±0.2°、33.7± 0.2°、34.4±0.2°、35.2±0.2°、36.6±0.2°、37.2±0.2°、38.0±0.2°、38.4±0.2°、38.9± 0.2°、39.7±0.2°、41.4±0.2°、43.5±0.2°、43.9±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form I is basic as Figure 32 is characterized.
In another preferred example, the TGA figure of the crystal form I is basic as Figure 34 is characterized.
In another preferred example, the DSC figure of the crystal form I has endothermic peak within the scope of 106~127 DEG C.
In another preferred example, the DSC figure of the crystal form I is basic as Figure 33 is characterized.
In another preferred example, the crystal form I purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form J includes 3 or 3 or more selected from the group below 2 θ values: 7.6 ± 0.2 °, 8.8 ± 0.2 °, 14.4 ± 0.2 °, 17.4 ± 0.2 °, 18.2 ± 0.2 °, 20.6 ± 0.2 °, 21.5 ± 0.2°、22.5±0.2°、22.8±0.2°、26.2±0.2°、26.5±0.2°、28.8±0.2°、29.2±0.2°、30.1± 0.2°、36.2±0.2°、37.9±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form J includes 5 or 5 or more selected from the group below 2 θ values: 7.6 ± 0.2 °, 8.8 ± 0.2 °, 14.4 ± 0.2 °, 17.4 ± 0.2 °, 18.2 ± 0.2 °, 20.6 ± 0.2 °, 21.5 ± 0.2°、22.5±0.2°、22.8±0.2°、26.2±0.2°、26.5±0.2°、28.8±0.2°、29.2±0.2°、30.1± 0.2°、36.2±0.2°、37.9±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form J is selected from the group including 10 or 10 or more 2 θ values: 7.6 ± 0.2 °, 8.8 ± 0.2 °, 14.4 ± 0.2 °, 17.4 ± 0.2 °, 18.2 ± 0.2 °, 20.6 ± 0.2 °, 21.5 ± 0.2°、22.5±0.2°、22.8±0.2°、26.2±0.2°、26.5±0.2°、28.8±0.2°、29.2±0.2°、30.1± 0.2°、36.2±0.2°、37.9±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form J can further comprise 1 or 1 or more and select From 2 θ values of the following group: 7.8 ± 0.2 °, 8.1 ± 0.2 °, 8.3 ± 0.2 °, 11.8 ± 0.2 °, 13.2 ± 0.2 °, 13.4 ± 0.2 °, 14.0±0.2°、15.0±0.2°、15.6±0.2°、16.2±0.2°、17.9±0.2°、18.4±0.2°、19.3±0.2°、 23.5±0.2°、23.8±0.2°、24.4±0.2°、24.9±0.2°、25.6±0.2°、26.8±0.2°、27.6±0.2°、 28.5±0.2°、30.5±0.2°、31.0±0.2°、31.4±0.2°、33.4±0.2°、33.6±0.2°、34.8±0.2°、 35.1±0.2°、36.9±0.2°、38.4±0.2°、40.7±0.2°、44.0±0.2°、44.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form J is basic as Figure 35 is characterized.
In another preferred example, the TGA figure of the crystal form J is basic as Figure 37 is characterized.
In another preferred example, the DSC figure of the crystal form J has endothermic peak within the scope of 110~133 DEG C.
In another preferred example, the DSC figure of the crystal form J is basic as Figure 36 is characterized.
In another preferred example, the crystal form J purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form K includes 3 or 3 or more selected from the group below 2 θ values: 7.7 ± 0.2 °, 8.5 ± 0.2 °, 8.8 ± 0.2 °, 13.4 ± 0.2 °, 14.4 ± 0.2 °, 14.7 ± 0.2 °, 17.4 ± 0.2°、18.2±0.2°、18.6±0.2°、19.0±0.2°、20.7±0.2°、21.3±0.2°、21.6±0.2°、22.5± 0.2°、22.8±0.2°、24.0±0.2°、24.3±0.2°、26.0±0.2°、26.6±0.2°、28.6±0.2°、29.0± 0.2°、30.4±0.2°、36.1±0.2°、36.3±0.2°、37.9±0.2°、38.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form K includes 5 or 5 or more selected from the group below 2 θ values: 7.7 ± 0.2 °, 8.5 ± 0.2 °, 8.8 ± 0.2 °, 13.4 ± 0.2 °, 14.4 ± 0.2 °, 14.7 ± 0.2 °, 17.4 ± 0.2°、18.2±0.2°、18.6±0.2°、19.0±0.2°、20.7±0.2°、21.3±0.2°、21.6±0.2°、22.5± 0.2°、22.8±0.2°、24.0±0.2°、24.3±0.2°、26.0±0.2°、26.6±0.2°、28.6±0.2°、29.0± 0.2°、30.4±0.2°、36.1±0.2°、36.3±0.2°、37.9±0.2°、38.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form K is selected from the group including 10 or 10 or more 2 θ values: 7.7 ± 0.2 °, 8.5 ± 0.2 °, 8.8 ± 0.2 °, 13.4 ± 0.2 °, 14.4 ± 0.2 °, 14.7 ± 0.2 °, 17.4 ± 0.2°、18.2±0.2°、18.6±0.2°、19.0±0.2°、20.7±0.2°、21.3±0.2°、21.6±0.2°、22.5± 0.2°、22.8±0.2°、24.0±0.2°、24.3±0.2°、26.0±0.2°、26.6±0.2°、28.6±0.2°、29.0± 0.2°、30.4±0.2°、36.1±0.2°、36.3±0.2°、37.9±0.2°、38.2±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form K includes 1 or 1 or more selected from the group below 2 θ values: 7.0 ± 0.2 °, 11.1 ± 0.2 °, 15.4 ± 0.2 °, 16.1 ± 0.2 °, 16.8 ± 0.2 °, 18.0 ± 0.2 °, 24.5 ± 0.2°、25.4±0.2°、27.5±0.2°、28.1±0.2°、32.7±0.2°、33.3±0.2°、33.6±0.2°、41.4± 0.2°、44.3±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form K is basic as Figure 38 is characterized.
In another preferred example, the TGA figure of the crystal form K is basic as Figure 40 is characterized.
In another preferred example, the DSC figure of the crystal form K has heat absorption within the scope of 61~79 DEG C and 99~126 DEG C Peak.
In another preferred example, the DSC figure of the crystal form K is basic as Figure 39 is characterized.
In another preferred example, the crystal form K purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form L includes 3 or 3 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 14.0 ± 0.2 °, 14.4 ± 0.2 °, 14.6 ± 0.2 °, 17.1 ± 0.2 °, 18.2 ± 0.2°、19.0±0.2°、20.6±0.2°、21.4±0.2°、22.5±0.2°、22.8±0.2°、24.4±0.2°、26.3± 0.2°、26.8±0.2°、28.8±0.2°、30.5±0.2°、30.9±0.2°、31.2±0.2°、36.1±0.2°、38.4± 0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form L includes 5 or 5 or more selected from the group below 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 14.0 ± 0.2 °, 14.4 ± 0.2 °, 14.6 ± 0.2 °, 17.1 ± 0.2 °, 18.2 ± 0.2°、19.0±0.2°、20.6±0.2°、21.4±0.2°、22.5±0.2°、22.8±0.2°、24.4±0.2°、26.3± 0.2°、26.8±0.2°、28.8±0.2°、30.5±0.2°、30.9±0.2°、31.2±0.2°、36.1±0.2°、38.4± 0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form L is selected from the group including 10 or 10 or more 2 θ values: 7.5 ± 0.2 °, 8.5 ± 0.2 °, 14.0 ± 0.2 °, 14.4 ± 0.2 °, 14.6 ± 0.2 °, 17.1 ± 0.2 °, 18.2 ± 0.2°、19.0±0.2°、20.6±0.2°、21.4±0.2°、22.5±0.2°、22.8±0.2°、24.4±0.2°、26.3± 0.2°、26.8±0.2°、28.8±0.2°、30.5±0.2°、30.9±0.2°、31.2±0.2°、36.1±0.2°、38.4± 0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form L can further comprise 1 or 1 or more and select From 2 θ values of the following group: 12.1 ± 0.2 °, 13.3 ± 0.2 °, 15.1 ± 0.2 °, 15.7 ± 0.2 °, 16.5 ± 0.2 °, 23.6 ± 0.2°、24.7±0.2°、25.1±0.2°、25.7±0.2°、27.4±0.2°、28.1±0.2°、31.6±0.2°、32.6± 0.2°、33.0±0.2°、34.0±0.2°、37.1±0.2°、37.9±0.2°、39.0±0.2°、41.5±0.2°、43.2± 0.2°、43.6±0.2°、44.1±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form L is basic as Figure 41 is characterized.
In another preferred example, the TGA figure of the crystal form L is basic as Figure 43 is characterized.
In another preferred example, the DSC figure of the crystal form L has endothermic peak within the scope of 84~99 DEG C.
In another preferred example, the DSC figure of the crystal form L is basic as Figure 42 is characterized.
In another preferred example, the crystal form L purity is greater than 95%.
In another preferred example, the X-ray powder diffraction pattern of the crystal form M includes 3 or 3 or more selected from the group below 2 θ values: 7.7 ± 0.2 °, 8.7 ± 0.2 °, 11.1 ± 0.2 °, 13.5 ± 0.2 °, 14.0 ± 0.2 °, 14.5 ± 0.2 °, 17.7 ± 0.2°、18.4±0.2°、19.2±0.2°、20.6±0.2°、21.5±0.2°、22.1±0.2°、22.6±0.2°、23.0± 0.2°、24.4±0.2°、25.1±0.2°、26.4±0.2°、26.9±0.2°、29.0±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form M includes 5 or 5 or more selected from the group below 2 θ values: 7.7 ± 0.2 °, 8.7 ± 0.2 °, 11.1 ± 0.2 °, 13.5 ± 0.2 °, 14.0 ± 0.2 °, 14.5 ± 0.2 °, 17.7 ± 0.2°、18.4±0.2°、19.2±0.2°、20.6±0.2°、21.5±0.2°、22.1±0.2°、22.6±0.2°、23.0± 0.2°、24.4±0.2°、25.1±0.2°、26.4±0.2°、26.9±0.2°、29.0±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form M is selected from the group including 10 or 10 or more 2 θ values: 7.7 ± 0.2 °, 8.7 ± 0.2 °, 11.1 ± 0.2 °, 13.5 ± 0.2 °, 14.0 ± 0.2 °, 14.5 ± 0.2 °, 17.7 ± 0.2°、18.4±0.2°、19.2±0.2°、20.6±0.2°、21.5±0.2°、22.1±0.2°、22.6±0.2°、23.0± 0.2°、24.4±0.2°、25.1±0.2°、26.4±0.2°、26.9±0.2°、29.0±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form M can further comprise 1 or 1 or more and select From 2 θ values of the following group: 6.3 ± 0.2 °, 15.2 ± 0.2 °, 16.0 ± 0.2 °, 16.6 ± 0.2 °, 17.2 ± 0.2 °, 27.4 ± 0.2°、28.5±0.2°、29.6±0.2°、30.0±0.2°、31.0±0.2°、32.1±0.2°、32.6±0.2°、33.8± 0.2°、34.6±0.2°、35.4±0.2°、36.2±0.2°、37.2±0.2°、38.1±0.2°、38.6±0.2°、39.7± 0.2°、43.7±0.2°。
In another preferred example, the X-ray powder diffraction pattern of the crystal form M is basic as Figure 44 is characterized.
In another preferred example, the TGA figure of the crystal form M is basic as Figure 46 is characterized.
In another preferred example, the DSC figure of the crystal form M has heat absorption within the scope of 66~80 and 109~126 DEG C Peak.
In another preferred example, the DSC figure of the crystal form M is basic as Figure 45 is characterized.
In another preferred example, the crystal form M purity is greater than 95%.
Second aspect of the present invention provides a kind of composition pesticide, and the composition includes:
(a) solvate as described in the first aspect of the invention, and (b) acceptable carrier in Pesticide Science.
Third aspect present invention, a method of crystal form B described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of 2- butanone dissolved clarification；
(ii) normal heptane is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form B described in first aspect present invention.
Fourth aspect present invention, a method of crystal form C described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of diethy-aceto oxalate dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form C described in first aspect present invention.
Fifth aspect present invention, a method of crystal form D described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of acetone dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form D described in first aspect present invention.
Sixth aspect present invention, a method of crystal form E described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of tetrahydrofuran dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form E described in first aspect present invention.
Seventh aspect present invention, a method of crystal form F described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of 2- methyltetrahydrofuran dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form F described in first aspect present invention.
Eighth aspect present invention, a method of crystal form G described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of butyl acetate dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form G described in first aspect present invention.
Ninth aspect present invention, a method of crystal form H described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of pyridine dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form H described in first aspect present invention.
Tenth aspect present invention, a method of crystal form I described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of propione dissolved clarification；
(ii) n-hexane is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form I described in first aspect present invention.
The tenth one side of the present invention, a method of crystal form J described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of 1,2- dichloroethanes dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form J described in first aspect present invention.
The twelfth aspect of the present invention, a method of crystal form K described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of 1,4- dioxane dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form K described in first aspect present invention.
The 13rd aspect of the present invention, a method of crystal form L described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of butyl acetate dissolved clarification；
(ii) n-hexane is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form L described in first aspect present invention.
Fourteenth aspect of the present invention, a method of crystal form M described in first aspect present invention is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of propione dissolved clarification；
(ii) n-hexane is added in the first solution of Xiang Shangshu, forms the second solution, and carry out at crystallization to the second solution Reason, obtains crystal form M described in first aspect present invention.
The fifteenth aspect of the present invention provides solvate or second aspect of the present invention described in a kind of first aspect present invention The purposes of the composition pesticide, for preventing or controlling disease；Or for inhibiting harmful micro- on agricultural, forestry or gardening Biology.
In another preferred example, the prevention or control are the prevention on agricultural, forestry or gardening or control disease.
In another preferred example, disease plant disease selected from the group below: downy mildew, powdery mildew, anthracnose, tikka Disease, or combinations thereof.
In another preferred example, the harmful microorganism is selected from the group: Ascomycetes, Basidiomycetes, deuteromycetes and Oomycete, or combinations thereof.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 shows the XRPD map of Fluoxastrobin crystal form B
Fig. 2 shows the DSC figure of Fluoxastrobin crystal form B
Fig. 3 shows the TGA figure of Fluoxastrobin crystal form B
Fig. 4 shows crystal form B molecule stereo structure perspective view
Fig. 5 shows that crystal form B structure cell accumulates perspective view
Fig. 6 shows the XRPD map of Fluoxastrobin crystal form C
Fig. 7 shows the DSC figure of Fluoxastrobin crystal form C
Fig. 8 shows the TGA figure of Fluoxastrobin crystal form C
Fig. 9 shows crystal form C molecule stereo structure perspective view
Figure 10 shows that crystal form C structure cell accumulates perspective view
Figure 11 shows five days high-temperature stability XRPD maps of crystal form C
Figure 12 shows ten days high-temperature stability XRPD maps of crystal form C
Figure 13 shows the XRPD map of Fluoxastrobin crystal form D
Figure 14 shows the DSC figure of Fluoxastrobin crystal form D
Figure 15 shows the TGA figure of Fluoxastrobin crystal form D
Figure 16 shows crystal form D molecule stereo structure perspective view
Figure 17 shows that crystal form D structure cell accumulates perspective view
Figure 18 shows the XRPD map of Fluoxastrobin crystal form E
Figure 19 shows the DSC figure of Fluoxastrobin crystal form E
Figure 20 shows the TGA figure of Fluoxastrobin crystal form E
Figure 21 shows crystal form E molecule stereo structure perspective view
Figure 22 shows that crystal form E structure cell accumulates perspective view
Figure 23 shows the XRPD map of Fluoxastrobin crystal form F
Figure 24 shows the DSC figure of Fluoxastrobin crystal form F
Figure 25 shows the TGA figure of Fluoxastrobin crystal form F
Figure 26 shows the XRPD map of Fluoxastrobin crystal form G
Figure 27 shows the DSC figure of Fluoxastrobin crystal form G
Figure 28 shows the TGA figure of Fluoxastrobin crystal form G
Figure 29 shows the XRPD map of Fluoxastrobin crystal form H
Figure 30 shows the DSC figure of Fluoxastrobin crystal form H
Figure 31 shows the TGA figure of Fluoxastrobin crystal form H
Figure 32 shows the XRPD map of Fluoxastrobin crystal form I
Figure 33 shows the DSC figure of Fluoxastrobin crystal form I
Figure 34 shows the TGA figure of Fluoxastrobin crystal form I
Figure 35 shows the XRPD map of Fluoxastrobin crystal form J
Figure 36 shows the DSC figure of Fluoxastrobin crystal form J
Figure 37 shows the TGA figure of Fluoxastrobin crystal form J
Figure 38 shows the XRPD map of Fluoxastrobin crystal form K
Figure 39 shows the DSC figure of Fluoxastrobin crystal form K
Figure 40 shows the TGA figure of Fluoxastrobin crystal form K
Figure 41 shows the XRPD map of Fluoxastrobin crystal form L
Figure 42 shows the DSC figure of Fluoxastrobin crystal form L
Figure 43 shows the TGA figure of Fluoxastrobin crystal form L
Figure 44 shows the XRPD map of Fluoxastrobin crystal form M
Figure 45 shows the DSC figure of Fluoxastrobin crystal form M
Figure 46 shows the TGA figure of Fluoxastrobin crystal form M
Specific embodiment
The present inventor by extensive and in-depth research, be surprised to find that for the first time the solvate of Fluoxastrobin, its application and Preparation method.The solvate purity is high, has good thermal stability and non-hygroscopic, and be better than in terms of solubility Existing Fluoxastrobin.Inhibit harmful microbe composition pesticide suitable for preparation, to sac fungus, basidiomycetes, partly know The major part disease such as downy mildew, powdery mildew, anthracnose, leaf spot caused by four major class disease fungi of bacterium and Oomycete has preferably Preventive effect.In addition, solvate preparation method of the invention is simple, it is suitble to large-scale industrial production.On this basis, inventor Complete the present invention.
Term explanation
Unless otherwise defined, otherwise whole technologies used herein and scientific term all have such as fields of the present invention The normally understood identical meanings of those of ordinary skill.
As used herein, in use, term " about " means that the value can be from enumerating in mentioning the numerical value specifically enumerated Value changes not more than 1%.For example, as used herein, statement " about 100 " include 99 and 101 and between whole values (for example, 99.1,99.2,99.3,99.4 etc.).
As used herein, term " containing " or " including (including) " can be open, semi-enclosed and enclosed.It changes Yan Zhi, the term also include " substantially by ... constitute " or " by ... constitute ".
As used herein, term " n or n or more 2 θ values selected from the group below " refers to including n and any just whole greater than n Number (such as n, n+1 ...), wherein upper limit Nup is the number of all 2 θ peak values in the group.Such as " 1 or 1 or more " is not only Including 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21 ... upper limit Nup is each just whole Number, further includes " 2 or 2 or more ", " 3 or 3 or more ", " 4 or 4 or more ", " 5 or 5 or more ", " 6 or 6 More than a ", " 7 or 7 or more ", " 8 or 8 or more ", " 9 or 9 or more ", " 10 or 10 or more ", etc. ranges. Such as " 3 or 3 or more " not only include 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20, 21 ... each positive integer of upper limit Nup further includes " 4 or 4 or more ", " 5 or 5 or more ", " 6 or 6 or more ", " 7 It is a or 7 or more ", " 8 or 8 or more ", " 9 or 9 or more ", " 10 or 10 or more ", etc. ranges.
Compound of formula I
Fluoxastrobin (compound of formula I), entitled (E) -2- { 2- [6- (2- cyano-benzene oxygen) pyrimidine-4-yl oxygroup] benzene of chemistry Base } -3- methoxy-methyl acrylate.The compound is a kind of completely new β methoxy acrylic acid lipid fungicide, is able to suppress disease Fungal mitochondria breathing, destroys the energy synthesis of germ, and triple function is treated and rooted out in tool protection.To sac fungus, basidiomycetes, The major part disease such as downy mildew, powdery mildew, anthracnose, leaf spot caused by four major class disease fungi of Fungi Imperfecti and Oomycete has Good preventive effect.
Polymorph
It is exactly to exist in the form of crystallization that solid, which is not in the form of unbodied,.In the case where crystal form, molecule is fixed In three-dimensional lattice case.When compound is crystallized out from solution or slurries, the space lattice that it can be different is arranged Crystallization (this property is referred to as " polymorphism "), forms the crystal with different crystal forms, this various crystal form Referred to as " polymorph ".The different polymorphs of given substance can in terms of one or more physical attributes (such as solubility and Rate of dissolution, true specific gravity, crystalline form, accumulation mode, mobility and/or solid-state stability) it is different from each other.
Crystallization
It can be by working solution, so that the solubility limit of compound of interest is exceeded, to complete production scale Crystallization.This can be completed by a variety of methods, for example, dissolved compound at relatively high temperature, then cools down solution To saturation limit.Or by boiling, atmospheric evaporation, vacuum drying or by some other methods reduce liquid bulk Product.It can be come by the way that anti-solvent or compound is added in the mixture of solvent or such solvent wherein with low solubility Reduce the solubility of compound of interest.Another optional method is to adjust pH value to reduce solubility.Related crystallization aspect It is described in detail and refers to Crystallization, the third edition, J W Mullens, Butterworth-Heineman Ltd., 1993,ISBN0750611294。
If it is expected that the formation of salt with crystallization occur simultaneously, if salt is smaller than dissolution of raw material degree in reaction medium, Acid or alkali appropriate, which is added, can lead to the direct crystallization of required salt.Equally, smaller than reactant solubility in finally desired form Medium in, the completion of synthetic reaction can make final product direct crystallization.
The optimization of crystallization may include that the crystal of required form is used to be inoculated in crystallization medium as crystal seed.In addition, many knots Crystal method uses the combination of above-mentioned strategy.One embodiment be at high temperature by interested compound dissolution in a solvent, with The anti-solvent of proper volume is added by controlled way afterwards, so that system is just under saturated level.At this point, needed for being added The crystal seed (and the integrality for keeping crystal seed) of form, system is cooling to complete to crystallize.
Solvate
In compound or drug molecule and solvent molecule contact process, external condition and interior condition factor cause solvent point The situation that son forms eutectic with compound molecule and remains in solid matter is difficult to avoid that.It is formed after compound and solvent crystallization Substance be referred to as solvate (solvate).Be easy with organic compound formed solvate solvent type be water, methanol, Benzene, ethyl alcohol, ether, aromatic hydrocarbons, heterocyclic arene etc..
Hydrate is a kind of special solvate.In pharmaceuticals industry, no matter the synthesis of bulk pharmaceutical chemicals, pharmaceutical preparation, In medicine storage and pharmaceutical activity evaluation, hydrate all has the value individually discussed because of its particularity.
In the present invention, the crystal form of compound shown in Formulas I is channel-style solvate.
Composition pesticide
" active constituent " or " reactive compound " in composition pesticide of the present invention refers to Formulas I of the present invention Object is closed, especially with compound of formula I existing for crystal form of the present invention.
" active constituent " or " reactive compound " and composition pesticide of the present invention can be used for preventing or controlling disease； Or for inhibiting harmful microorganism on agricultural, forestry or gardening.
Differential scanning calorimetry
Also known as " differential scanning calorimetry " (DSC) is during heating, to measure between measured matter and reference substance A kind of technology of relationship between energy difference and temperature.The property of peak position, shape and peak number mesh and substance on DSC map has It closes, therefore can qualitatively be used to identify substance.This method commonly used in the art detects phase transition temperature, the glass transition temperature of substance The many kinds of parameters such as degree, reaction heat.
Preparation method
When the present invention prepares Fluoxastrobin crystal form B, C, H, I, use dissolved is this to be easy and fast to a large amount of industrialized productions Method；The method for preparing Fluoxastrobin crystal form D, E, F, G, H, I, J, K, L, M, it is characterised in that use the method for volatilization, two kinds of sides Method is simple and easy to do, is easy to industrialized production.
Purposes
The present invention provides the purposes of the solvate of Fluoxastrobin and its composition pesticide, the solvate is efficiently wide Spectrum, to downy mildew, powdery mildew, anthracnose, leaf caused by sac fungus, four major class disease fungi of basidiomycetes, Fungi Imperfecti and Oomycete The major part disease such as pinta has good preventive effect.
Main advantages of the present invention
(1) compound of formula I solvate of the invention has good thermal stability and non-hygroscopic, and in solubility Aspect is better than existing Fluoxastrobin.
(2) compound of formula I solvate preparation method of the invention is simple, is suitble to large-scale industrial production.
(3) compound of formula I solvate of the invention can be used for preventing or controlling disease；Or in agricultural, forestry Or inhibit harmful microorganism on gardening.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Experimental material used in following embodiment and reagent can obtain unless otherwise instructed from commercially available channel.Room temperature or Room temperature refers to 4 DEG C -25 DEG C, preferably 15-25 DEG C.
Test method:
XRD (X-ray powder diffraction) method: instrument: Rigaku Ultima IV powder diffractometer, target: Cu-K α (40kV, 40mA) is carried out using D/tex Ultra detector at room temperature.Scanning range, from 3 ° to 45 °, scans in 2 sections θ Speed is 20 °/minute.
By including that many factors below generate measurement difference relevant to this kind of X-ray powder diffraction analysis result: (a) Error in sample preparation object (such as height of specimen), (b) instrument error, (c) calibrate difference, (d) personal error (including The error occurred when measuring peak position), and (e) property (such as preferred orientation error) of substance.Calibration error and sample Height error frequently results in displacement of all peaks in the same direction.When using flat bracket, the small difference of height of specimen will Lead to the big displacement of the peak position XRD.System research shows the peak position that the sample height difference of 1mm can lead to up to 1 ° of 2 θ It moves.These displacements can be identified from X-ray diffractogram, and can be by compensating for the displacement (by system calibration The factor is used for all peak position values) or the recalibration instrument elimination displacement.As described above, being made by application system calibration factor Peak position is consistent, measurement error of the recoverable from different instruments.
TGA (thermogravimetric analysis) method: instrument model: TA Q500 thermogravimetric analyzer, using N2Atmosphere, heating rate 10 ℃/min。
DSC (differential scanning calorimetry) method: instrument model: TA Q2000 differential scanning calorimeter, using N2Atmosphere rises Warm speed is 10 DEG C/min.
The preparation of 1. crystal form A of embodiment
Preparation method in the preparation method referenced patent CN101522639A of crystal form A.
The preparation of 2. crystal form B Fluoxastrobin of embodiment
50mg raw material is weighed in container, 0.5ml 2- butanone dissolved clarification is added, adds 2.5ml normal heptane, is filtered, vacuum Crystal form B Fluoxastrobin (yield 95%) is obtained after drying.
Resulting crystal form B Fluoxastrobin, XRD spectrum are basic as shown in Figure 1, diffraction angular data is substantially as shown in table 1 below.
The XRD data of 1 crystal form B of table
The DSC of crystal form B schemes as shown in Fig. 2, wherein first endothermic peak is corresponding loses dissolving agent process, and second endothermic peak is corresponding Fusion and decomposition process has endothermic peak within the scope of 100~125 DEG C.
The TGA of crystal form B schemes as shown in figure 3, as seen from the figure substantially without weightlessness before decomposition.
In addition, have also obtained crystal form B in embodiment 2 does single crystal X-ray diffraction (SXRD) structure, as shown in Figure 4, Figure 5, Its parameter is as shown in table 2 below:
The single crystal X-ray diffraction parameter of 2 crystal form B of table
The solubility of embodiment 3. crystal form A and crystal form B compares
It weighs excessive crystal form A and crystal form B is suspended in methanol, after shaking 48h, test solubility, test knot using UPLC Fruit is as shown in table 3 below:
The solubility of table 3 crystal form B and crystal form A
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form B 30.0
The solubility of crystal form B in methyl alcohol is greater than crystal form A, about the 1.3 of crystal form A times as can be seen from Table 3.
The preparation of 4. crystal form C Fluoxastrobin of embodiment
50mg raw material is weighed in container, 1.5ml diethy-aceto oxalate dissolved clarification is added, adds 7.5ml hexamethylene, is filtered, Fluoxastrobin crystal form C (yield 97%) is obtained after solid vacuum drying.
Resulting crystal form C Fluoxastrobin, XRD spectrum are basic as shown in fig. 6, diffraction angular data is substantially as shown in table 4 below.
The XRD data of 4 crystal form C of table
The DSC of crystal form C schemes as shown in fig. 7, wherein first endothermic peak is corresponding loses dissolving agent process, and second endothermic peak is corresponding Fusion and decomposition process has endothermic peak within the scope of 86~103 DEG C.
The TGA of crystal form C schemes as shown in figure 8, as seen from the figure substantially without weightlessness before decomposition.
In addition, have also obtained crystal form C in embodiment 4 does single crystal X-ray diffraction (SXRD) structure, such as Fig. 9, Tu10Suo Show, parameter is as shown in table 5 below:
The single crystal X-ray diffraction parameter of 5 crystal form C of table
5. crystal form C Fluoxastrobin study on the stability of embodiment
Crystal form C Fluoxastrobin sample in embodiment 4 is placed in 60 ± 2 DEG C of baking ovens, after 5 days and 10 days by sample take out into Row XRPD test, to investigate sample to the stability of crystal form of temperature.As shown in Figure 11, Figure 12, the results showed that, crystal form under this condition C sample is stablized.
The solubility of embodiment 6. crystal form A and crystal form C compares
It weighs excessive crystal form A and crystal form C is suspended in methanol, after shaking 1h, test solubility, test result using UPLC It is as shown in table 6 below:
The solubility of table 6 crystal form C and crystal form A
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form C 25.1
It can be concluded that the solubility of crystal form C in methyl alcohol is greater than crystal form A, about the 1.1 of crystal form A times.
The preparation of 7. crystal form D Fluoxastrobin of embodiment
50mg raw material is weighed in container, 0.25ml acetone dissolved clarification is added, room temperature volatilization obtains phonetic after solid vacuum drying Bacterium ester crystal form D (yield 97%).
Resulting crystal form D Fluoxastrobin, XRD spectrum is substantially as shown in figure 13, and diffraction angular data is substantially as shown in table 7 below.
The XRD data of 7 crystal form D of table
The DSC figure of crystal form D is as shown in figure 14, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 105~144 DEG C.
The TGA figure of crystal form D is as shown in figure 15, as seen from the figure substantially without weightlessness before decomposition.
In addition, have also obtained crystal form D in embodiment 7 does single crystal X-ray diffraction (SXRD) structure, such as Figure 16, Tu17Suo Show, parameter is as shown in table 8 below:
The single crystal X-ray diffraction parameter of 8 crystal form D of table
The preparation of 8. crystal form E Fluoxastrobin of embodiment
50mg raw material is weighed in container, 0.25ml tetrahydrofuran dissolved clarification is added, room temperature volatilization obtains after solid vacuum drying To Fluoxastrobin crystal form E (yield 95%).
Resulting crystal form E Fluoxastrobin, XRD spectrum is substantially as shown in figure 18, and diffraction angular data is substantially as shown in table 9 below.
The XRD data of 9 crystal form E of table
The DSC figure of crystal form E is as shown in figure 19, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 106~123 DEG C.
The TGA figure of crystal form E is as shown in figure 20, as seen from the figure substantially without weightlessness before decomposition.
In addition, have also obtained crystal form E in embodiment 8 does single crystal X-ray diffraction (SXRD) structure, such as Figure 21, Tu22Suo Show, parameter is as shown in the following table 10:
The single crystal X-ray diffraction parameter of 10 crystal form E of table
The solubility of embodiment 9. crystal form A and crystal form E compares
It weighs excessive crystal form A and crystal form E is suspended in methanol, after shaking 1h, test solubility, test result using UPLC It is as shown in table 11 below:
The solubility of table 11 crystal form E and crystal form A
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form E 25.4
It can be concluded that the solubility of crystal form E in methyl alcohol is greater than crystal form A, about the 1.11 of crystal form A times.
The preparation of 10. crystal form F Fluoxastrobin of embodiment
50mg raw material is weighed in container, 1ml 2- methyltetrahydrofuran dissolved clarification, room temperature volatilization, solid vacuum drying is added After obtain Fluoxastrobin crystal form F (yield 93%).
Resulting crystal form F Fluoxastrobin, XRD spectrum is substantially as shown in figure 23, and diffraction angular data is substantially as shown in table 12 below.
The XRD data of 12 crystal form F of table
2-Theta d(A) I (Height) %
7.1 12.4103 6737
8.5 10.3963 11777
10.9 8.0773 275
11.8 7.4797 177
12.7 6.9742 489
13.3 6.6714 730
13.7 6.4399 2310
14.5 6.1032 1565
15.6 5.6684 492
16.1 5.4881 152
16.9 5.2428 7151
17.5 5.0633 4190
18.4 4.8027 564
18.7 4.7407 987
20.1 4.4053 3863
20.6 4.2996 8003
21.2 4.195 2137
21.7 4.0995 5832
23.2 3.8242 5822
23.6 3.7667 2680
24.6 3.6217 2446
25.1 3.542 1742
25.8 3.4426 1029
26.9 3.3095 2833
27.5 3.2375 282
28.3 3.1489 984
29.1 3.0661 1267
29.6 3.0117 602
30.7 2.9119 272
31.4 2.8484 1221
32.3 2.7707 497
33.7 2.6604 529
33.9 2.6376 499
35.0 2.5628 276
35.5 2.5293 322
36.5 2.461 295
36.8 2.4365 233
38.2 2.3552 352
40.5 2.2229 157
41.3 2.1824 262
43.2 2.0931 189
43.7 2.0696 513
The DSC figure of crystal form F is as shown in figure 24, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 106~129 DEG C.
The TGA figure of crystal form F is as shown in figure 25, as seen from the figure substantially without weightlessness before decomposition.
The preparation of 11. crystal form G Fluoxastrobin of embodiment
50mg raw material is weighed in container, 2ml butyl acetate dissolved clarification is added, room temperature volatilization obtains after solid vacuum drying Fluoxastrobin crystal form G (yield 95%).
Resulting crystal form G Fluoxastrobin, XRD spectrum is substantially as shown in figure 26, and diffraction angular data is substantially as shown in table 13 below.
The XRD data of 13 crystal form G of table
The DSC figure of crystal form G is as shown in figure 27, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 83~104 DEG C.
The TGA figure of crystal form G is as shown in figure 28, as seen from the figure substantially without weightlessness before decomposition.
The solubility of embodiment 12. crystal form A and crystal form G compares
It weighs excessive crystal form A and crystal form G is suspended in methanol, after shaking 1h, test solubility, test result using UPLC It is as shown in table 14 below:
The solubility of table 14 crystal form G and crystal form A
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form G 32.3
It can be concluded that the solubility of crystal form G in methyl alcohol is greater than crystal form A, about the 1.41 of crystal form A times.
The preparation of 13. crystal form H Fluoxastrobin of embodiment
50mg raw material is weighed in container, 0.3ml pyridine dissolved clarification is added, adds 1.5ml hexamethylene, is filtered, solid is true Fluoxastrobin crystal form H (yield 95%) is obtained after sky is dry.
Resulting crystal form H Fluoxastrobin, XRD spectrum is substantially as shown in figure 29, and diffraction angular data is substantially as shown in table 15 below.
The XRD data of 15 crystal form H of table
The DSC figure of crystal form H is as shown in figure 30, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 83~122 DEG C.
The TGA figure of crystal form H is as shown in figure 31, as seen from the figure substantially without weightlessness before decomposition.
The solubility of embodiment 14. crystal form A and crystal form H compares
It weighs excessive crystal form A and crystal form H is suspended in methanol, after shaking 1h, test solubility, test result using UPLC It is as shown in table 16:
The solubility of table 16 crystal form H and crystal form A
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form H 26.6
It can be concluded that the solubility of crystal form H in methyl alcohol is greater than crystal form A, about the 1.16 of crystal form A times.
The preparation of 15. crystal form I Fluoxastrobin of embodiment
50mg raw material is weighed in container, 1ml propione dissolved clarification is added, adds 5ml n-hexane, is filtered, solid vacuum Fluoxastrobin crystal form I (yield 97%) is obtained after drying.
Resulting crystal form I Fluoxastrobin, XRD spectrum is substantially as shown in figure 32, and diffraction angular data is substantially as shown in table 17 below.
The XRD data of 17 crystal form I of table
The DSC figure of crystal form I is as shown in figure 33, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 106~127 DEG C.
The TGA figure of crystal form I is as shown in figure 34, as seen from the figure substantially without weightlessness before decomposition.
The preparation of 16. crystal form J Fluoxastrobin of embodiment
50mg raw material is weighed in container, 0.2ml 1,2- dichloroethanes dissolved clarification is added, then solution is added to 1ml hexamethylene In alkane, filtering obtains Fluoxastrobin crystal form J (yield 97%) after solid vacuum drying.
Resulting crystal form J Fluoxastrobin, XRD spectrum is substantially as shown in figure 35, and diffraction angular data is substantially as shown in table 18 below.
The XRD data of 18 crystal form J of table
The DSC figure of crystal form J is as shown in figure 36, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 110~133 DEG C.
The TGA figure of crystal form J is as shown in figure 37, as seen from the figure substantially without weightlessness before decomposition.
The solubility of embodiment 17. crystal form A and crystal form J compares
It weighs excessive crystal form A and crystal form J is suspended in methanol, after shaking 1h, test solubility, test result using UPLC It is as shown in table 19 below:
The solubility of table 19 crystal form J and crystal form A:
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form J 26.0
It can be concluded that the solubility of crystal form J in methyl alcohol is greater than crystal form A, about the 1.13 of crystal form A times.
The preparation of 18. crystal form K Fluoxastrobin of embodiment
50mg raw material is weighed in container, 0.5ml Isosorbide-5-Nitrae-dioxane dissolved clarification is added, then solution is added to 2.5ml ring Hexane, filtering obtain Fluoxastrobin crystal form K (yield 97%) after solid vacuum drying.
Resulting crystal form K Fluoxastrobin, XRD spectrum is substantially as shown in figure 38, and diffraction angular data is substantially as shown in table 20 below.
The XRD data of 20 crystal form K of table
The DSC figure of crystal form K is as shown in figure 39, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 99~126 DEG C.
The TGA figure of crystal form K is as shown in figure 40, as seen from the figure substantially without weightlessness before decomposition.
The solubility of embodiment 19. crystal form A and crystal form K compares
It weighs excessive crystal form A and crystal form K is suspended in methanol, after shaking 1h, test solubility, test result using UPLC It is as shown in table 21 below:
The solubility of table 21 crystal form K and crystal form A:
Crystal form Solubility (mg/ml)
Crystal form A 22.9
Crystal form K 23.5
It can be concluded that the solubility of crystal form K in methyl alcohol is greater than crystal form A, about the 1.03 of crystal form A times.
The preparation of 20. crystal form L Fluoxastrobin of embodiment
50mg raw material is weighed in container, 2ml butyl acetate dissolved clarification is added, then butyl acetate solution is being added to 10ml just In hexane, filtering obtains Fluoxastrobin crystal form L (yield 93%) after solid vacuum drying.
Resulting crystal form L Fluoxastrobin, XRD spectrum is substantially as shown in figure 41, and diffraction angular data is substantially as shown in table 22 below.
The XRD data of 22 crystal form L of table
The DSC figure of crystal form L is as shown in figure 42, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 84~99 DEG C.
The TGA figure of crystal form L is as shown in figure 43, as seen from the figure substantially without weightlessness before decomposition.
The preparation of 21. crystal form M Fluoxastrobin of embodiment
50mg raw material is weighed in container, 1ml propione dissolved clarification is added, then solution is added in 5ml n-hexane, mistake Filter obtains Fluoxastrobin crystal form M (yield 96%) after solid vacuum drying.
Resulting crystal form M Fluoxastrobin, XRD spectrum is substantially as shown in figure 44, and diffraction angular data is substantially as shown in table 23 below.
The XRD data of 23 crystal form M of table
The DSC figure of crystal form M is as shown in figure 45, wherein first endothermic peak is corresponding to lose dissolving agent process, second endothermic peak pair Fusion and decomposition process is answered, there is endothermic peak within the scope of 109~126 DEG C.
The TGA figure of crystal form M is as shown in figure 46, as seen from the figure substantially without weightlessness before decomposition.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (10)

1. a kind of solvate of compound of formula I,
Preferably, the solvate is selected from the group: crystal form B, crystal form C, crystal form D, crystal form E, crystal form F, crystal form G, crystal form H, crystalline substance Type I, crystal form J, crystal form K, crystal form L, crystal form M.
2. solvate as described in claim 1, which is characterized in that the solvate is crystal form B, and the crystal form B has Feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form B includes 3 or 3 or more 2 θ values selected from the group below: 7.6 ± 0.2 °, 8.6±0.2°、14.4±0.2°、16.9±0.2°、18.2±0.2°、18.8±0.2°、20.5±0.2°、21.3±0.2°、 22.4±0.2°、22.8±0.2°、24.2±0.2°、26.1±0.2°、26.7±0.2°、28.7±0.2°、30.4±0.2°、 30.9±0.2°,36.0±0.2°,38.2±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form B is basic as Fig. 1 is characterized；And/or
(3) the TGA figure of the crystal form B is basic as Fig. 3 is characterized；And/or
(4) the DSC figure of the crystal form B has endothermic peak within the scope of 62~88 DEG C and 100~125 DEG C；And/or
(5) the DSC figure of the crystal form B is basic as Fig. 2 is characterized；And/or
(6) the crystal form B purity is greater than 95%；And/or
The solvate is crystal form C, and the crystal form C has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form C includes 3 or 3 or more 2 θ values selected from the group below: 7.0 ± 0.2 °, 7.3±0.2°、7.6±0.2°、8.5±0.2°、12.1±0.2°、13.9±0.2°、14.7±0.2°、17.0±0.2°、 18.1±0.2°、18.9±0.2°、20.7±0.2°、21.5±0.2°、22.6±0.2°、22.8±0.2°、24.5±0.2°、 25.8±0.2°、26.3±0.2°、26.8±0.2°、27.7±0.2°、28.7±0.2°、29.0±0.2°、30.6±0.2°、 30.8±0.2°,31.2±0.2°,35.0±0.2°,36.2±0.2°,38.5±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form C is basic as Fig. 6 is characterized；And/or
(3) the TGA figure of the crystal form C is basic as Fig. 8 is characterized；And/or
(4) the DSC figure of the crystal form C has endothermic peak within the scope of 86~103 DEG C；And/or
(5) the DSC figure of the crystal form C is basic as Fig. 7 is characterized；And/or
(6) the crystal form C purity is greater than 95%；And/or
The solvate is crystal form D, and the crystal form D has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form D includes 3 or 3 or more 2 θ values selected from the group below: 7.6 ± 0.2 °, 8.5±0.2°、13.5±0.2°、14.4±0.2°、16.5±0.2°、17.0±0.2°、18.2±0.2°、18.7±0.2°、 20.6±0.2°、21.0±0.2°、21.3±0.2°、22.4±0.2°、23.6±0.2°、24.1±0.2°、25.9±0.2°、 26.5±0.2°,28.2±0.2°,28.6±0.2°,28.9±0.2°,30.4±0.2°,30.8±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form D is basic as Figure 13 is characterized；And/or
(3) the TGA figure of the crystal form D is basic as Figure 15 is characterized；And/or
(4) the DSC figure of the crystal form D has endothermic peak within the scope of 57~87 DEG C and 105~144 DEG C；And/or
(5) the DSC figure of the crystal form D is basic as Figure 14 is characterized；And/or
(6) the crystal form D purity is greater than 95%.
3. solvate as described in claim 1, which is characterized in that the solvate is crystal form E, and the crystal form E has Feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form E includes 3 or 3 or more 2 θ values selected from the group below: 7.5 ± 0.2 °, 8.6±0.2°、13.4±0.2°、14.4±0.2°、14.7±0.2°、15.6±0.2°、16.5±0.2°、18.2±0.2°、 19.1±0.2°、20.6±0.2°、21.3±0.2°、22.8±0.2°、24.0±0.2°、24.5±0.2°、25.3±0.2°、 25.8±0.2°,26.6±0.2°,28.6±0.2°,30.2±0.2°,31.3±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form E is basic as Figure 18 is characterized；And/or
(3) the TGA figure of the crystal form E is basic as Figure 20 is characterized；And/or
(4) the DSC figure of the crystal form E has endothermic peak within the scope of 77~100 DEG C and 106~123 DEG C；And/or
(5) the DSC figure of the crystal form E is basic as Figure 19 is characterized；And/or
(6) the crystal form E purity is greater than 95%；And/or
The solvate is crystal form F, and the crystal form F has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form F includes 3 or 3 or more 2 θ values selected from the group below: 7.1 ± 0.2 °, 8.5±0.2°、13.7±0.2°、14.5±0.2°、16.9±0.2°、17.5±0.2°、20.1±0.2°、20.6±0.2°、 21.2±0.2°、21.7±0.2°、23.2±0.2°、23.6±0.2°、24.6±0.2°、25.1±0.2°、25.8±0.2°、 26.9±0.2°,29.1±0.2°,31.4±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form F is basic as Figure 23 is characterized；And/or
(3) the TGA figure of the crystal form F is basic as Figure 25 is characterized；And/or
(4) the DSC figure of the crystal form F has endothermic peak within the scope of 106~129 DEG C；And/or
(5) the DSC figure of the crystal form F is basic as Figure 24 is characterized；And/or
(6) the crystal form F purity is greater than 95%；And/or
The solvate is crystal form G, and the crystal form G has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form G includes 3 or 3 or more 2 θ values selected from the group below: 7.5 ± 0.2 °, 8.5±0.2°、13.9±0.2°、14.3±0.2°、14.6±0.2°、16.8±0.2°、18.1±0.2°、18.9±0.2°、 20.6±0.2°、21.2±0.2°、21.4±0.2°、22.4±0.2°、22.8±0.2°、24.3±0.2°、24.6±0.2°、 26.2±0.2°、26.7±0.2°、28.7±0.2°、30.3±0.2°、30.5±0.2°、30.7±0.2°、31.0±0.2°、 31.2±0.2°,36.0±0.2°,38.4±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form G is basic as Figure 26 is characterized；And/or
(3) the TGA figure of the crystal form G is basic as Figure 28 is characterized；And/or
(4) the DSC figure of the crystal form G has endothermic peak within the scope of 83~104 DEG C；And/or
(5) the DSC figure of the crystal form G is basic as Figure 27 is characterized；And/or
(6) the crystal form G purity is greater than 95%.
4. solvate as described in claim 1, which is characterized in that the solvate is crystal form H, and the crystal form H has Feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form H includes 3 or 3 or more 2 θ values selected from the group below: 7.5 ± 0.2 °, 8.7±0.2°、13.5±0.2°、14.2±0.2°、14.5±0.2°、15.6±0.2°、18.0±0.2°、19.2±0.2°、 20.6±0.2°、21.4±0.2°、22.5±0.2°、23.7±0.2°、24.1±0.2°、25.1±0.2°、25.5±0.2°、 26.3±0.2°,26.8±0.2°,28.3±0.2°,28.5±0.2°,30.0±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form H is basic as Figure 29 is characterized；And/or
(3) the TGA figure of the crystal form H is basic as Figure 31 is characterized；And/or
(4) the DSC figure of the crystal form H has endothermic peak within the scope of 62~81 DEG C and 83~122 DEG C；And/or
(5) the DSC figure of the crystal form H is basic as Figure 30 is characterized；And/or
(6) the crystal form H purity is greater than 95%；And/or
The solvate is crystal form I, and the crystal form I has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form I includes 3 or 3 or more 2 θ values selected from the group below: 7.5 ± 0.2 °, 8.5±0.2°、11.0±0.2°、13.8±0.2°、14.4±0.2°、15.9±0.2°、16.5±0.2°、17.5±0.2°、 19.0±0.2°、20.6±0.2°、21.4±0.2°、22.0±0.2°、22.5±0.2°、22.8±0.2°、23.9±0.2°、 24.4±0.2°、24.9±0.2°、26.3±0.2°、26.7±0.2°、28.4±0.2°、28.9±0.2°、30.6±0.2°、 36.2±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form I is basic as Figure 32 is characterized；And/or
(3) the TGA figure of the crystal form I is basic as Figure 34 is characterized；And/or
(4) the DSC figure of the crystal form I has endothermic peak within the scope of 106~127 DEG C；And/or
(5) the DSC figure of the crystal form I is basic as Figure 33 is characterized；And/or
(6) the crystal form I purity is greater than 95%；And/or
The solvate is crystal form J, and the crystal form J has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form J includes 3 or 3 or more 2 θ values selected from the group below: 7.6 ± 0.2 °, 8.8±0.2°、14.4±0.2°、17.4±0.2°、18.2±0.2°、20.6±0.2°、21.5±0.2°、22.5±0.2°、 22.8±0.2°、26.2±0.2°、26.5±0.2°、28.8±0.2°、29.2±0.2°、30.1±0.2°、36.2±0.2°、 37.9±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form J is basic as Figure 35 is characterized；And/or
(3) the TGA figure of the crystal form J is basic as Figure 37 is characterized；And/or
(4) the DSC figure of the crystal form J has endothermic peak within the scope of 110~133 DEG C；And/or
(5) the DSC figure of the crystal form J is basic as Figure 36 is characterized；And/or
(6) the crystal form J purity is greater than 95%.
5. solvate as described in claim 1, which is characterized in that the solvate is crystal form K, and the crystal form K has Feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form K includes 3 or 3 or more 2 θ values selected from the group below: 7.7 ± 0.2 °, 8.5±0.2°、8.8±0.2°、13.4±0.2°、14.4±0.2°、14.7±0.2°、17.4±0.2°、18.2±0.2°、 18.6±0.2°、19.0±0.2°、20.7±0.2°、21.3±0.2°、21.6±0.2°、22.5±0.2°、22.8±0.2°、 24.0±0.2°、24.3±0.2°、26.0±0.2°、26.6±0.2°、28.6±0.2°、29.0±0.2°、30.4±0.2°、 36.1±0.2°,36.3±0.2°,37.9±0.2°,38.2±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form K is basic as Figure 38 is characterized；And/or
(3) the TGA figure of the crystal form K is basic as Figure 40 is characterized；And/or
(4) the DSC figure of the crystal form K has endothermic peak within the scope of 61~79 DEG C and 99~126 DEG C；And/or
(5) the DSC figure of the crystal form K is basic as Figure 39 is characterized；And/or
(6) the crystal form K purity is greater than 95%；And/or
The solvate is crystal form L, and the crystal form L has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form L includes 3 or 3 or more 2 θ values selected from the group below: 7.5 ± 0.2 °, 8.5±0.2°、14.0±0.2°、14.4±0.2°、14.6±0.2°、17.1±0.2°、18.2±0.2°、19.0±0.2°、 20.6±0.2°、21.4±0.2°、22.5±0.2°、22.8±0.2°、24.4±0.2°、26.3±0.2°、26.8±0.2°、 28.8±0.2°,30.5±0.2°,30.9±0.2°,31.2±0.2°,36.1±0.2°,38.4±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form L is basic as Figure 41 is characterized；And/or
(3) the TGA figure of the crystal form L is basic as Figure 43 is characterized；And/or
(4) the DSC figure of the crystal form L has endothermic peak within the scope of 84~99 DEG C；And/or
(5) the DSC figure of the crystal form L is basic as Figure 42 is characterized；And/or
(6) the crystal form L purity is greater than 95%；And/or
The solvate is crystal form M, and the crystal form M has feature selected from the group below:
(1) X-ray powder diffraction pattern of the crystal form M includes 3 or 3 or more 2 θ values selected from the group below: 7.7 ± 0.2 °, 8.7±0.2°、11.1±0.2°、13.5±0.2°、14.0±0.2°、14.5±0.2°、17.7±0.2°、18.4±0.2°、 19.2±0.2°、20.6±0.2°、21.5±0.2°、22.1±0.2°、22.6±0.2°、23.0±0.2°、24.4±0.2°、 25.1±0.2°,26.4±0.2°,26.9±0.2°,29.0±0.2°；And/or
(2) X-ray powder diffraction pattern of the crystal form M is basic as Figure 44 is characterized；And/or
(3) the TGA figure of the crystal form M is basic as Figure 46 is characterized；And/or
(4) the DSC figure of the crystal form M has endothermic peak within the scope of 66~80 and 109~126 DEG C；And/or
(5) the DSC figure of the crystal form M is basic as Figure 45 is characterized；And/or
(6) the crystal form M purity is greater than 95%.
6. a kind of composition pesticide, the composition includes:
(a) such as solvate as claimed in any one of claims 1 to 5, and (b) acceptable carrier in Pesticide Science.
7. a kind of method for preparing crystal form B described in claim 1, comprising steps of
(i) compound of formula I is provided in the first solution of 2- butanone dissolved clarification；
(ii) normal heptane is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form B described in claim 1；And/or
A method of crystal form C described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of diethy-aceto oxalate dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form C described in claim 1；And/or
A method of crystal form D described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of acetone dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form D described in claim 1；And/or
A method of crystal form E described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of tetrahydrofuran dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form E described in claim 1.
8. a kind of method for preparing crystal form F described in claim 1, comprising steps of
(i) compound of formula I is provided in the first solution of 2- methyltetrahydrofuran dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form F described in claim 1；And/or
A method of crystal form G described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of butyl acetate dissolved clarification；
(ii) it volatilizees to the first solution, obtains crystal form G described in claim 1；And/or
A method of crystal form H described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of pyridine dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form H described in claim 1；And/or
A method of crystal form I described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of propione dissolved clarification；
(ii) n-hexane is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form I described in claim 1.
9. a kind of method for preparing crystal form J described in claim 1, comprising steps of
(i) compound of formula I is provided in the first solution of 1,2- dichloroethanes dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form J described in claim 1；And/or
A method of crystal form K described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of 1,4- dioxane dissolved clarification；
(ii) hexamethylene is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form K described in claim 1；And/or
A method of crystal form L described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of butyl acetate dissolved clarification；
(ii) n-hexane is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form L described in claim 1；And/or
A method of crystal form M described in claim 1 is prepared, comprising steps of
(i) compound of formula I is provided in the first solution of propione dissolved clarification；
(ii) n-hexane is added in the first solution of Xiang Shangshu, forms the second solution, and crystallization processing is carried out to the second solution, obtains To crystal form M described in claim 1.
10. the purposes of a kind of solvate described in claim 1 or composition pesticide as claimed in claim 6, for preventing Or control disease；Or for inhibiting harmful microorganism on agricultural, forestry or gardening.
CN201710667153.5A 2017-08-07 2017-08-07 Fluoxastrobin channel solvates and preparation method thereof Pending CN109384728A (en)

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