CN108368047A - Novel crystal forms, the preparation method and the usage of ZEN 90160 - Google Patents
Novel crystal forms, the preparation method and the usage of ZEN 90160 Download PDFInfo
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- CN108368047A CN108368047A CN201780004342.2A CN201780004342A CN108368047A CN 108368047 A CN108368047 A CN 108368047A CN 201780004342 A CN201780004342 A CN 201780004342A CN 108368047 A CN108368047 A CN 108368047A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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Abstract
Provide the novel crystal forms of formula (I) compound (ZEN 90160).The novel crystal forms of the ZEN 90160 can be prepared by being crystallized from the solution in suitable solvent.Additionally provide the Fungicidal composition comprising the novel crystal forms, the method for fungal infection for controlling place and the novel crystal forms purposes.
Description
Cross reference to related applications
This application claims in the priority of the January in 2016 of the GB1600977.1 UK Patent Applications submitted on the 19th,
Content is incorporated herein by reference in their entirety.
Technical field
The present invention relates to the novel crystal forms of ZEN 90160 (picoxystrobin).The invention further relates to one kind for making
The method of the standby novel crystal forms.Further, the present invention relates to the purposes of the novel crystal forms.
(chemical name is (E) -3- methoxyl groups -2- [2- (6- trifluoromethyl -2- pyridine oxygen methyls) phenyl] third to ZEN 90160
E pioic acid methyl ester) have following structure formula (I)：
ZEN 90160 belongs to the chemicals of strobilurins (strobilurin) class, is used as fungicide, especially
For controlling leaf rust, brown spot, powdery mildew and net blotch in a series of fungal diseases, including cereal, beans and oilseeds.Pyridine
Oxygen bacterium ester is the preventative and therapeutic fungicide for having systemic cross-film movement, by the Qo for blocking Cytochrome B c1
Electronics transfer at center acts on to inhibit mitochondrial respiratory.
Commercially available ZEN 90160 product usually passes through such as EP 0 278 595, US 6,015,905, CN
Method manufacture described in 102115458A, CN 103030598A and CN 103626691A.
For example, US 6,015,905 is disclosed according to reaction scheme shown in following scheme 1 from methyl -2- (adjacent toluene
Base) acetic acid esters starts to prepare the method for ZEN 90160.
The ZEN 90160 prepared by these above-mentioned methods is unformed, and is difficult to prepare.Particularly, which has
There is high aggregation tendency, especially after long term storage.
Therefore, this field needs to show the pyridine oxygen bacterium of the new model of improved property (such as improved storage stability)
Ester.
Invention content
The new crystal modification that have now been discovered ZEN 90160, be easy to be formulated into agrochemical composition and
The stability of height is shown when preparation.Particularly, the crystal modification (hereinafter referred to as ' crystal modification I ') is shown when preparing
Low-down aggregation tendency.
Therefore, in a first aspect, the present invention provides ZEN 90160 crystal modification I, which is utilizing Cu-K α spokes
It penetrates in the X-ray powder diffraction figure recorded at 25 DEG C and following reflection of at least four as 2 θ values is presented：
2 θ=8.4613 ± 0.2 (1)
2 θ=12.0227 ± 0.2 (2)
2 θ=12.7030 ± 0.2 (3)
2 θ=13.8834 ± 0.2 (4)
2 θ=14.5237 ± 0.2 (5)
2 θ=16.2243 ± 0.2 (6)
2 θ=16.3844 ± 0.2 (7)
2 θ=17.1247 ± 0.2 (8)
2 θ=17.6249 ± 0.2 (9)
2 θ=18.7653 ± 0.2 (10)
2 θ=20.3659 ± 0.2 (11)
2 θ=21.2663 ± 0.2 (12)
2 θ=22.0466 ± 0.2 (13)
2 θ=22.1466 ± 0.2 (14)
2 θ=22.9469 ± 0.2 (15)
2 θ=23.7272 ± 0.2 (16)
2 θ=24.1474 ± 0.2 (17)
2 θ=25.3278 ± 0.2 (18)
2 θ=25.6479 ± 0.2 (19)
2 θ=26.1681 ± 0.2 (20)
2 θ=26.7884 ± 0.2 (21)
2 θ=28.3890 ± 0.2 (22)
2 θ=31.0300 ± 0.2 (23)
2 θ=35.4117 ± 0.2 (24)
As described above, ZEN 90160 crystal modification I is shown in its X-ray powder diffraction figure in reflection listed above
At least four.It is highly preferred that at least five, at least seven in above-mentioned reflection is presented in crystal modification I.
It is highly preferred that the X-ray powder diffraction figure of ZEN 90160 crystal modification I shows at least four in following reflection, more
Preferably at least 5, still more preferably at least 7, even more preferably from all：
2 θ=8.4613 ± 0.2 (1)
2 θ=12.7030 ± 0.2 (3)
2 θ=13.8834 ± 0.2 (4)
2 θ=16.3844 ± 0.2 (7)
2 θ=17.6249 ± 0.2 (9)
2 θ=21.2663 ± 0.2 (12)
2 θ=22.9469 ± 0.2 (15)
2 θ=25.3278 ± 0.2 (18)
In a preferred embodiment, all above-mentioned reflections (1) to (24) are presented in ZEN 90160 crystal modification I.
In a particularly preferred embodiment, ZEN 90160 crystal modification I show substantially with as shown in fig. 1 it is identical
X-ray diffractogram of powder spectrum.
In addition, ZEN 90160 crystal modification I can be characterized alternatively, preferably further characterized by IR spectroscopic methodologies.It is sweeping
Retouch that number is 32 times and resolution is 4cm-1In the case of carry out IR spectroscopic methodologies.The IR spectrograms of ZEN 90160 crystal modification I show
In Fig. 2, key band about 1704.95,1629.04,1577.46,1352.22,1258.08,1201.97,
1124.12,983.51 and 810.19cm-1Place.
ZEN 90160 crystal modification I according to the present invention can be characterized alternatively, preferably further pass through differential scanning amount
Hot method (DSC) characterization, the results are shown in Fig. 3.Show that the endothermic peak at about 79.115 DEG C, initial temperature are about in Fig. 3
73.872℃.The term as used herein " about 79.115 DEG C " means 75 DEG C to 80 DEG C of range.The term as used herein is " about
73.872 DEG C " mean 72 DEG C to 75 DEG C of range.
Particularly preferred ZEN 90160 crystal modification I is that X-ray powder diffraction figure as described above and above-mentioned IR is presented
The crystal modification of one of spectrogram and DSC spectrograms or the two.
The basic crystal structure of studies have shown that the monocrystalline of ZEN 90160 crystal modification I is monoclinic crystal and has space group
P21/c.The characteristic of the crystal structure of ZEN 90160 crystal modification I is shown in the following table 1：
Table 1：The crystallographic data of ZEN 90160 crystal modification I
Wherein：
The length at the edge a, b, c=unit cell (unit cell)
α, the angle of beta, gamma=unit cell
Molecular number in Z=unit cells
The crystal structure of ZEN 90160 crystal modification I is shown in Figure 4.
It can easily prepare the present invention's by crystallizing out crystal modification in the solution of solvent system from ZEN 90160
ZEN 90160 crystal modification I.Any type of ZEN 90160, especially unformed ZEN 90160 can be used molten to prepare this
Liquid.
Therefore, on the other hand, the present invention provides a kind of method of formation ZEN 90160 crystal modification I, this method packets
It includes：
I) ZEN 90160 solution in solvent system comprising one or more of solvents is provided；
Ii) compound of the dissolving is crystallized into the ZEN 90160 crystal modification I with Formulas I；And
Iii crystalline solid) is detached from the solvent system, to generate ZEN 90160 crystal modification I.
As set forth above, it is possible to molten to form ZEN 90160 by the way that the ZEN 90160 of suitable form to be dissolved in solvent system
Liquid.Unformed ZEN 90160 is a kind of preferred starting material to form the solution.
In general, any suitable solvent can be used in solvent system.It is being used to prepare ZEN 90160 crystal modification I's
The preferred solvent used in solvent system is alcohol, especially secondary alcohol and the tertiary alcohol, is optionally mixed with water；Aliphatic alkane or alicyclic ring
Race's alkane, especially C5To C10Alkane, more preferable C5To C7Alkane, the alkane are preferably taken by one or more halogen moieties
Generation；The arsol being substituted, the benzene being especially substituted, the aromatic compounds for especially replacing through nitro and replacing through halogen
Object；Aromatic oxide；Ketone, especially lower alkyl ketone；Nitrile, especially low alkyl group nitrile；And its mixture.
' low alkyl group ' refers to having 1 moieties to 4 carbon atoms.
Preferred halogenic substituent is cl part.
It is preferred that avoid using primary alconol, especially lower alcohol, especially methanol, and the arsol being unsubstituted, such as toluene.
The particularly preferred solvent system for being used to prepare ZEN 90160 crystal modification I include isopropanol, the tert-butyl alcohol, chloroform,
The mixing of dichloroethanes, hexane, nitrobenzene, chlorobenzene, dichloro-benzenes, benzotrifluoride, methyl ethyl ketone, acetonitrile or one or more
Object.Preferred solvent mixture includes chloroform-hexane, THF- hexanes, dichloromethane/hexane and THF- water.
It in the present invention, can be by the way that unformed ZEN 90160 to be dissolved in the solvent comprising a kind of solvent or solvent mixture
ZEN 90160 crystal modification I is prepared in system.Unformed starting material is dissolved in solvent system to form concentrate solution.It is molten
Solution can be heated to carry out to the temperature of solution reflux temperature from room temperature or environment temperature along with by solvent system.It is preferred that
Ground prepares solution under the reflux temperature of solution.Concentration of the ZEN 90160 in final solution, which depends on ZEN 90160, to be made
Solubility in solvent system.
Then gained homogeneous solution can be cooled to required temperature, for example, be cooled to room temperature or environment temperature or be higher than room
The temperature of temperature or environment temperature, to crystallize out desired crystal form from the solution.Alternatively, or additionally, crystal modification I also may be used
With by below the reflux temperature of solution or the reflux temperature of solution, in the case where being with or without vacuum action concentrate homogeneous solution come
Crystallization.
In a preferred embodiment, it is expected that the crystal seed of crystal form (can promote or accelerate to tie by being added during crystallization
Brilliant process) carry out the crystallization of help crystallisation variant I.Based on the weight of ZEN 90160 present in solution, the additive amount of crystal seed is usual
By weight 0.001% to 10%, more preferably 0.002% to 5%, even more preferably from from 0.003% to 2.5%, also more
It is preferred that by weight in the range of from 0.005% to 0.5%.Crystal seed is preferably added at a temperature of less than solution boiling point molten
In liquid.
ZEN 90160 crystal modification I is recycled by detaching the material of crystallization from solvent system.Conjunction for the separation
Suitable technology is known in the art, and includes filtering, centrifugation and decantation.
Hereafter, separated solid is preferably washed with suitable solvent, and the solvent can be to be used for step (i)
Prepare the identical solvent system of concentrate solution or different solvents.Washing usually carries out under cooling, for example, room temperature and 0 DEG C it
Between, to reduce the loss of crystallized product.Wash temperature depends on solubility of the crystal in used solvent system.
The ZEN 90160 crystal modification I of the present invention is especially suitable for being configured to Fungicidal composition.
Therefore, on the other hand, the present invention provides a kind of antifungal combinations including above-mentioned ZEN 90160 crystal modification I
Object.
The Fungicidal composition may include the ZEN 90160 crystal modification I of active amount needed for any be adapted to provide for.It is preferred that
Including being less than the composition of 80%, the more preferable ZEN 90160 crystal modification I for being less than 50% by weight by weight.Including by
The composition of the ZEN 90160 crystal modification I of weight meter about 25% is preferred for many applications.
ZEN 90160 crystal modification I can be prepared in known manner to provide a series of conventional formulations.This kind of preparation
Example includes that suspending agent (SC), oil-based suspension (OD), soluble granule (SG), dispersible agent (DC), missible oil (EC), lotion are mixed
Kind agent, suspension seed dressing, granule (GR), fine granule (MG), suspension emulsion (SE) and water dispersible granules (WG).
Preparations of the ZEN 90160 crystal modification I particularly suitable as suspending agent (SC).In addition to reactive compound, suspending agent is logical
Include often surfactant, and also has (if properly) one or more of thickeners, antifreezing agent, biocide and any
Required auxiliary agent.
ZEN 90160 crystal modification I can be enough to realize that the concentration of dosage needed for this field is present in suspending agent (SC) combination
In object, such as from about 0.1% to about 50% based on the weight of total mixture.It is generally as follows and prepares suspending agent (SC)：In pyridine oxygen bacterium
Solvent, especially water, one or more of dispersants or surfactant are mixed in ester crystal modification I, and one or more of
The other auxiliary agents of kind.
Suitable dispersant is known in the art, and is commercially available.Suitable dispersant includes but unlimited
In the sodium salt, calcium salt and ammonium salt of lignin sulfonic acid (optionally by polyethoxylated)；The sodium salt and ammonium salt of copolymer-maleic anhydride；Contracting
Close the sodium salt of phenolsulfonic acid；With napsylate-formaldehyde condensation products.Lignosulfonates such as sodium lignin sulfonate combines the present invention
Object is particularly useful.The polymer and its salt (such as sodium salt) of napsylate-formaldehyde condensation products such as naphthalene sulfonic acids and formaldehyde are also to the present invention
Composition is particularly useful.
Including suitable thickener in the composition is known in the art, and it is commercially available.Suitably
Thickener includes but not limited to guar gum, pectin, casein, carrageenan, xanthans, alginates, methylcellulose, ethoxy
Cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.Synthetic thickening agent can be used, and include the derivative of mentioned reagent,
And polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, various polyethers, their copolymer and polyacrylic acid and it
Salt.Alkyl polyvinylpyrrolidone is to the particularly useful thickener of the present composition.
Including suitable antifreezing agent in the composition is known in the art, and it is commercially available.Suitably
Antifreezing agent includes liquid polyol, such as ethylene glycol, propylene glycol or glycerine.Total weight based on composition, the presence of antifreezing agent
Amount is especially by weight usually by weight from about 1% to about 20% from about 5% to about 10%.
One or more of biocides or preservative can also be comprised in composition according to the present invention.Suitably
Biocide is known in the art, and includes those of based on isothiazolone, such as from Long Sha companies (Lonza)From Sol chemical company (Thor Chemie)RS comes from Rhom and Hass (Rohm＆
Haas)MK.Total weight based on composition, in composition the amount of preservative usually by weight from
0.05% to 0.5%.
ZEN 90160 crystal modification I can be unique active constituent in pesticidal preparations, or can be with one or more
Kind other active compounds exist, other reactive compounds include one or more of insecticides, attractant, disinfectant,
Fungicide, acaricide, nematicide, fungicide, growth regulatory substance, herbicide, safener, fertilizer and semiochemical.
With the ZEN 90160 crystal modification I preferred reactive compounds being applied in combination gone out up to happy (metalaxyl), bacterium
Clever (dodemorph), Fen Pufu (fenpropimorph), fenpropidin (fenpropidin), Guanoctine (guazatine), spiral shell
Ring bacterium amine (spiroxamine), three obtain fragrant (tridemorph), Pai Meini (pyrimethanil), the third pyrimidine of ring
(cyprodinyl), oxazole (bromoconazole) more hidden than more agricultures (bitertanol), bromine, ring gram seat
(cyproconazole), Ke Li (difenoconazole), olefin conversion (dinitroconazole) are waited for, according to general seat
(epoxiconazole), funk seat (fenbuconazole), Fluquinconazole (fluquinconazole), shield silicon obtain
(flusilazole), Fick sharp (hexaconazole), according to row (imazalil), go out special seat (metconazole), the nitrile bacterium of going out
Azoles (myclobutanil), penconazole (penconazole), Pu Keli (propiconazole), Prochloraz
(prochloraz), prothioconazoles (prothioconazole), Tebuconazole (tebuconazole), triazolone
(triadimefon), Triadimenol (triadimenol), three flumizoles (triflumizole), triticonazole
(triticonazole), according to general with (iprodione), exempt from gram peaceful (vinclozolin), maneb (maneb), a Mancozeb
(mancozeb), so as not to rotten (metiram), grace (thiram), Bai Kelie (boscalid), Bei Fen replace
(carbendazim), Jia Baoxin (carboxin), oxidation it is good protect letter (oxycarboxin), match seat goes out (cyazofamid), nitrile
Thioquinones (dithianon) all is killed with (famoxadone), Fenamidone (fenamidone), Fen Ruimo (fenarimol), good fortune
More peaceful (flutolanil), fast promise fragrant (quinoxyfen), methyl protect net (thiophanate-methyl), ethyl thiophanate more
(thiophanate-ethyl), Sai Funing (triforine), white powder gram (dinocap), nitrophthalic acid-isopropyl ester
(nitrophthal-isopropyl), benzene pyroles (phenylpyrroles), as fenpiclonil (fenpiclonil) or shield are eliminated
Rather (fiudioxonil), my acid benzene-S-methyl (acibenzolar-S-methyl), benzene metsulfovax
(benthiavalicarb), add general amine (carpropamid), tetrachloro isopropyl nitrile (chlorothalonil), the fragrant amine of match
(cyflufenamid), cymoxanil (cymoxanil), fenhexamid (fenhexamid), fentinacetate (fentinacetate),
Fen Nuoni (fenoxanil), help lucky amine (fluazinam), ethane phosphonic acid (fosetyl), aliette (fosetyl-aluminum),
Propineb (iprovalicarb), fragrant agriculture (metrafenone) of going out, seat match amine (zoxamide), Gai Pudan (captan), Fu Er
Train (folpet), dimethomorph (dimethomorph), Ya Tuomin (azoxystrobin), dimoxystrobin (dimoxystrobin),
Fluoxastrobin (fluoxastrobin), gram receipts glad (kresoxim-methyl), SSF 126 (metominostrobin), oxime
Dimoxystrobin (orysastrobin), hectogram quick (pyraclostrobin), prothioconazoles (prothioconazole) or trifluoro are quick
(trifioxystrobin)。
Ring gram seat with the ZEN 90160 crystal modification I particularly preferred active components being applied in combination, the special seat that goes out, penta bacterium
Azoles, Tebuconazole wait for that Ke Li, prothioconazoles, Bai Kelie and hectogram are quick.
Including the present composition of ZEN 90160 crystal modification I all can use known ZEN 90160 preparation controlling
Undesirable fungal pathogens aspect to control is active.What can be controlled causes the fungal pathogens of fungal disease
Including, such as：
Alternaria species (Alternaria on vegetables, rape, beet, soybean, cereal, cotton, fruit and rice
Sp.) (such as the alternaria solani sorauer (A.solani) on potato and other plant or rod method (A.alternata)),
Aphanomyces species (Aphanomyces sp.) on beet and vegetables,
Ascochyta species (Ascochyta sp.) on cotton and rice,
Bipolaris (Bipolaris) on corn, cereal, rice and lawn and Drechslera (Drechslera
Spp.) (for example, the compacted spore of navel (D.teres) in barley filigree on barley, the D.tritci-repentis on wheat),
Wheat powdery mildew (Blumeria graminis) (powdery mildew) on cereal,
The pathogen of Botrytis cinerea (Botrytis cinerea) (gray mold) on strawberry, vegetables, flowers and grapevine,
Two spore species of ball (Botryodiplodia sp.) on cotton,
Lettuce disk on lettuce obstructs mould (Bremia lactucae),
Cercospora species (Cercospora sp.) (such as the beet tail spore on beet on corn and soybean, rice and beet
Bacterium (C.beticula)),
Corn, cereal, cochliobolus category (Cochliobolus) (the standing grain cochliobolus on such as grain on rice
(Cochliobolus sativus), the palace portion cochliobolus (Cochliobolus miyabeanus) on rice)；
Corynespora species (Corynespora sp.) on soybean, cotton and other plant,
Colletotrichum species (Colletotrichum sp.) on soybean, cotton and other plant are (for example, various plants
On sharp spore anthrax-bacilus (C.acutatum)),
Curvularia species (Curvularia sp.) on cereal and rice,
Diplodia species (Diplodia sp.) on cereal and rice,
Prominent navel Helminthosporium species (Exserohilum sp.) on corn,
Two spore powdery mildews (Erysiphe cichoracearum) in cucumber plant and monofilament shell powdery mildew
(Sphaerotheca fuliginea),
Fusarium (Fusarium) and Verticillium sp (Verticillium spp.) on various plants is (for example, eggplant
Verticillium wilt pathogen (V.dahliae)) (for example, Fusarium graminearum (F.graminearum) on wheat),
Gaeumannomyce (Gaeumanomyces graminis) on cereal,
Gibberella species (Gibberella the sp.) (such as gibberella fujikuroi (Gibberella on rice on cereal and rice
Fujikuroi)),
Gram's staining compound (Grainstaining complex) on rice,
Helminthosporium species (Helminthosporium sp.) (for example, H.graminicola) on corn and rice,
Shell ball spore species (Macrophomina sp.) on soybean and cotton,
Michrodochium species on plant, for example, the M.nivale on cereal,
Mycosphaerella (Mycosphaerella) species on cereal, banana and peanut are (for example, the standing grain green-ball chamber on wheat
Bacterium (M.graminicola), the Fijian spherical cavity bacterium (M.fijiesis) on banana),
Mould category (Phaeoisaripsis) species of brown column silk on soybean,
Phakopsora species (Phakopsara sp.) on plant are (for example, Phakopsora pachyrhizi on soy
(P.Pachyrhizi) and mountain horseleech layer rest fungus (Phakopsara meibomiae)),
Phoma species (Phoma sp.) on soybean,
Phomopsis species (Phomopsis sp.) on soybean, sunflower and grapevine are (for example, on grapevine
Grape gives birth to Phomopsis bacterium (P.viticola), the sunflower stem canker (P.helianthii) on sunflower),
Phytophthora infestans (Phytophthora infestans) on potato and tomato,
Grape single shaft on grapevine is mould (Plasmopara viticola),
Penicillium species (Penecilium sp.) on soybean and cotton,
Apple mildew bacterium (Podosphaera leucotricha) on apple,
Wheat Phyllostachys pubescens (Pseudocercosporella herpotrichoides) on cereal,
Pseudoperonospora species (Pseudoperonospora sp.) on hops and cucumber plant are (for example, on cucumber
Pseudoperonospora cubensis (P.cubenis)),
Puccinia species (Puccinia sp.) on cereal, corn and asparagus are (for example, the wheat handle rest fungus on wheat
(P.Triticina) and Stripe Rust (P.Striformis), the asparagus aecidium (P.asparagi) on asparagus),
Pyrenophora species (Pyrenophora sp.) on cereal,
Pyricularia oryzae (Pyricularia oryzae), Bamboo grass wood photovoltaicing leather bacterias (Corticium sasakii), rice broom branch on rice
Mould (Sarocladium oryzae), sheath rot of rice plant bacterium (S.attenuatum), rice leaf smut (Entyloma
Oryzae),
Grey Magnaporthe grisea (Pyricularia grisea) on lawn and cereal,
Pythium (Pythium on lawn, rice, corn, cotton, rape, sunflower, beet, vegetables and other plant
Spp.),
Rhizoctonia on cotton, rice, potato, lawn, corn, rape, potato, beet, vegetables and other plant
Species (Rhizoctonia sp.) (for example, Rhizoctonia solani Kuhn (R.solani)),
Moon ynchosporium species (for example, R.secalis) on rice and cereal,
Sclerotinia species (Sclerotinia sp.) on rape, sunflower and other plant are (for example, sclerotinite
(S.sclerotiorum)),
Wheat septoria (Septoria tritici) on wheat and many spores of clever withered shell (Stagonospora
Nodorum),
Erysiphe (Erysiphe) (different name, grape snag shell (Uncinula necator)) on grapevine,
Prominent navel spore Pseudomonas (Setospaeria sp.) on corn and lawn,
Silk axis smut (Sphacelotheca reilinia) on corn,
Thielaviopsis sp species (Thievaliopsis sp.) on soybean and cotton,
Tilletia foetida species (Tilletia sp.) on cereal,
Ustilago (Ustilago sp.) on cereal, corn and beet, and
Venturia species (Venturia sp.) (sore pinta (scab)) on apple and pears are (for example, the apple on apple
The black star bacterium (V.inaequalis) of fruit).
In another aspect, the present invention provides a kind of method for controlling fungal infection in place, this method includes
ZEN 90160 crystal modification I described above is applied to the place.
Still on the other hand, the present invention provides ZEN 90160 crystal modification I described above in controlling fungal infection
Purposes.
The term as used herein " about " with numerical quantities or range when being used in combination, it is meant that is slightly larger than or slightly smaller than described
Numerical quantities or range deviate ± the 10% of the numerical quantities or endpoints of ranges.
The term as used herein " room temperature " refers to the temperature range from about 20 DEG C to 26 DEG C.
Description of the drawings
Fig. 1 is the X-ray powder diffraction spectrogram of the ZEN 90160 crystal modification I of the present invention；
Fig. 2 is the IR spectrograms of the ZEN 90160 crystal modification I of the present invention；
Fig. 3 is differential scanning calorimetry (DSC) spectrogram of the ZEN 90160 crystal modification I of the present invention；
The crystal structure of the ZEN 90160 crystal modification I of Fig. 4 display present invention；And
Fig. 5 is the X-ray powder diffraction spectrogram of the unformed ZEN 90160 as obtained in embodiment 1 below.
Specific implementation mode
For illustration purposes only, by following embodiment and embodiment of the present invention will be described in reference to the drawings now.
In the examples below, unless otherwise indicated, percentage is weight percent.
Embodiment
The preparation of the unformed ZEN 90160s of embodiment 1-
For comparison purposes, using US 6, method disclosed in 015,905 prepares ZEN 90160.It is followed
The details of program is as follows：
At room temperature, gas chlorination hydrogen (HCl) is bubbled through 3- isochromanomes (2.0g, 13.5mmol) in methanol
Solution in (30mL) continues 0.5 hour.Solution is futher stirred other 2 hours.Remove methanol under reduced pressure, and by institute
Residue is obtained to be dissolved in dichloromethane.Existing insoluble substance is removed by filtration, after this by being oozed on calcium carbonate
It filters to dry solution, to remove water.Finally, solvent is removed, to obtain the methyl 2- chloromethylbenzene yl acetates in grease
(2.62g, 98%) is used for next step without further purification.
It will be in 2- hydroxyl -6- trifluoromethyl pyridines (2.0g, 12.3mmol), the sodium hydroxide in dry toluene (25mL)
The mixture of (0.52g, 12.9mmol) and 15- crown ethers -5 (1 drop) stirs 2 hours under reflux.Toluene is removed under reduced pressure, and
And white salt residue is dissolved in anhydrous dimethyl formamide (DMF) (15mL).By methyl 2- chloromethylbenzene yl acetates
(2.44g, 12.3mmol) is added dropwise with sodium iodide (10mg) in anhydrous DMF (15mL) together.By mixture at 75 DEG C
Stirring 2 hours, is subsequently poured into water, and extracted with ether.Ether extraction liquid is washed with water, it is dry, and under vacuum
Remaining ether is removed, grease is left, is passed through column chromatography (silica gel eluted with 10% ethyl acetate in hexane)
Purifying, to generate methyl 2- (6- tri--Fluoromethylpyridin -2- base oxygroups methyl) phenylacetic acid ester (3.3g, 83%).
At room temperature, under nitrogen atmosphere, by sodium methoxide (0.725g, 13mmol) and methyl formate (0.8mL, 13mmol) point
It criticizes and is added to methyl 2- (6- trifluoromethyl pyridine -2- base oxygroups methyl) phenylacetic acid ester (2.0g, 6.0mmol) in dry toluene
In agitating solution in (15mL).At room temperature after 6 hours, pour the mixture into water, and extracted with ether.Ether is extracted
Liquid is taken to be washed with water, it is dry, and ether is then removed, to generate (E)-methyl 2- [2- (6- trifluoromethyls in yellow colloidal
Pyridine -2- base oxygroups methyl) phenyl]-acrolactic acid ester (95% purity), it is used for lower single order without further purification
Section.
Dimethyl suflfate (0.65mL, 6.9mmol) is added dropwise to (E)-methyl 2- [2- (6- trifluoromethyl pyridines -2-
Base oxygroup methyl) phenyl]-acrolactic acid ester (2.12g, 6mmol) and Anhydrous potassium carbonate (1.2g, 8.7mmol) be anhydrous
In the mixture of DMF (10mL).It after being stirred at room temperature 6 hours, pours the mixture into water, and is extracted with ether.By second
Ether extract liquor is washed with water, dry, and then concentrates, to generate crude product.Crude product (is used in hexane by column chromatography
In 20% ethyl acetate elution silica gel) purifying, to generate unformed (E)-methyl 2- [2- (6- trifluoromethyl pyridines -2-
Base oxygroup methyl) phenyl] -3- methoxy acrylates (98% purity).
Product is analyzed using x-ray powder diffraction instrument.Fig. 5 shows that the X-ray powder diffraction pattern of product is not believed significantly
Number.As a result show that product is unformed.
The preparation (being crystallized from isopropanol) of embodiment 2- ZEN 90160 crystal modifications I
The unformed ZEN 90160 sample that 5g is prepared in embodiment 1 is fitted into the flask containing 35mL isopropanols.It stirs
Mixture is mixed to generate uniform suspension.It will be slowly heated 20 to 25 under stiring in water-bath of the gained suspension at 50 DEG C
Minute is to obtain clear solution.Reaction mixture is set to cool down at room temperature.Crystal is formed during subsequent 45 to 50 hours.It will
Gained crystal is filtered and is dried in vacuo at room temperature, to remove remaining micro isopropanol from crystal.The purity of the crystal is
98%, and produced with the molar yield of 80%w/w.
Crystal is characterized by IR, X-ray powder and single-crystal X-ray diffraction analysis, and it was found that crystal is such as Fig. 1 and figure
ZEN 90160 crystal modification I shown in 2.
Pass through the fusing point of dsc measurement product.Initial temperature is 73.872 DEG C, and maximum peak temperature is 79.115 DEG C.
Fig. 2 show characteristic peaks of the pyrrole ZEN 90160 crystal modification I on IR spectrograms 1704.95,1629.04,
1577.46,1352.22,1258.08,1201.97,1124.12,983.51 and 810.19cm-1Place.
The x-ray diffractogram of powder of the crystal of ZEN 90160 crystal modification I shows reflection as shown in Figure 2, and this
A little values are summarised in the following table 2.
The x-ray diffractogram of powder of 2. ZEN 90160 crystal modification I of table reflects
The characteristic of ZEN 90160 crystal modification I crystal structures is shown in the following table 3.
Table 3：The crystallographic data of ZEN 90160 crystal modification I
Wherein：
The length at a, b, c=unit cell edge
α, the angle of beta, gamma=unit cell
Molecular number in Z=unit cells
The crystal structure of ZEN 90160 crystal modification I is shown in Figure 4.
The preparation (being crystallized from hexane and chloroform) of embodiment 3- ZEN 90160 crystal modifications I
The unformed ZEN 90160 sample that 5g is prepared in embodiment 1 is packed into containing 40mL hexanes and chloroform (1: 1)
In flask.Mixture is stirred until ZEN 90160 dissolves, to generate clear solution.By solution stay on one side and at room temperature not by
Several days are interfered, so that crystallization that is slow and stablizing occurs.The crystal to be formed is recovered by filtration.
As described in example 2 above, the crystal of recycling is characterized by IR, X-ray powder and single-crystal X-ray diffraction analysis.
As a result identical as the result obtained in example 2, this shows that solid product is ZEN 90160 crystal modification I.
Example of formulations
The preparation of the unformed chlorfenapyr suspending agents of embodiment 4- (SC)
The component shown in the following table 4 prepares suspending agent (SC) preparation.
All components are merged and are uniformly mixed.By gained mixture with Dyno-Mill (by Willy A.Bachofen
AG is produced) grinding, to obtain suspending agent.
Table 4
The preparation of embodiment 5- ZEN 90160 crystal modification I suspending agents (SC)
Suspending agent (SC) preparation is prepared by component listed in the following table 5.
All components are merged and are uniformly mixed.By gained mixture with Dyno-Mill (by Willy A.Bachofen
AG is produced) grinding, to obtain suspending agent.
Table 5
Embodiment 6：Compare storage stability
The composition sample prepared in embodiment 6 and embodiment 7 is stored 1 month, 3 months and 6 at a temperature of 54 DEG C
A month.The step of followed, carries out according to CIPAC MT 46.3.
The concentration of ZEN 90160 is measured by HPLC at the end of each Storage period.By observing and measuring aggregation.At each
The initial concentration of ZEN 90160 is 25% in preparation.
As a result it is listed in the table below in 6.
Table 6
* it annotates：
Aggregation extent is indicated, a small amount of aggregation is observed in wherein "+" expression, " +++ ++ " indicate to observe a large amount of gather
Collection, and aggregation is not observed in "-" expression.
It is being listed in table 6 the result shows that, according to prior art step obtain unformed ZEN 90160 product show it is non-
Often poor storage stability wherein the amount of ZEN 90160 significantly reduces in preparation dduring test, and observes that ZEN 90160 is lived
The notable aggregation of property ingredient.On the contrary, the present invention ZEN 90160 crystal modification I show ZEN 90160 active constituent almost without
Degradation, and aggregation is not observed.
Claims (36)
1. the crystal modification I of ZEN 90160, the crystal modification is radiating the x-ray powder recorded at 25 DEG C using Cu-K α
Following reflection of at least four as 2 θ values is presented in diffraction pattern：
2 θ=8.4613 ± 0.2 (1)
2 θ=12.0227 ± 0.2 (2)
2 θ=12.7030 ± 0.2 (3)
20=13.8834 ± 0.2 (4)
2 θ=14.5237 ± 0.2 (5)
2 θ=16.2243 ± 0.2 (6)
2 θ=16.3844 ± 0.2 (7)
2 θ=17.1247 ± 0.2 (8)
2 θ=17.6249 ± 0.2 (9)
2 θ=18.7653 ± 0.2 (10)
2 θ=20.3659 ± 0.2 (11)
2 θ=21.2663 ± 0.2 (12)
2 θ=22.0466 ± 0.2 (13)
2 θ=22.1466 ± 0.2 (14)
2 θ=22.9469 ± 0.2 (15)
2 θ=23.7272 ± 0.2 (16)
2 θ=24.1474 ± 0.2 (17)
2 θ=25.3278 ± 0.2 (18)
2 θ=25.6479 ± 0.2 (19)
2 θ=26.1681 ± 0.2 (20)
2 θ=26.7884 ± 0.2 (21)
2 θ=28.3890 ± 0.2 (22)
2 θ=31.0300 ± 0.2 (23)
2 θ=35.4117 ± 0.2 (24).
2. crystal modification as described in claim 1, wherein at least five in the reflection (1) to (24) is presented.
3. crystal modification as claimed in claim 2, wherein at least seven in the reflection (1) to (24) is presented.
4. crystal modification as described in any one of the preceding claims, wherein the crystal modification is existed using Cu-K α radiation
Following reflection of at least four as 2 θ values is presented in the X-ray powder diffraction figure recorded at 25 DEG C：
2 θ=8.4613 ± 0.2 (1)
2 θ=12.7030 ± 0.2 (3)
2 θ=13.8834 ± 0.2 (4)
2 θ=16.3844 ± 0.2 (7)
2 θ=17.6249 ± 0.2 (9)
2 θ=21.2663 ± 0.2 (12)
2 θ=22.9469 ± 0.2 (15)
2 θ=25.3278 ± 0.2 (18).
5. crystal modification as claimed in claim 4, wherein the reflection (1), (3), (4), (7), (9), (12), (15) are presented
(18) at least five in.
6. crystal modification as claimed in claim 5, wherein the reflection (1), (3), (4), (7), (9), (12), (15) are presented
(18) at least seven in.
7. crystal modification as claimed in claim 5, wherein present all reflections (1), (3), (4), (7), (9), (12),
(15) and (18).
8. crystal modification as claimed in claim 7, wherein all reflections (1) to (24) are presented.
9. crystal modification as described in any one of the preceding claims, wherein shown in the X ray diffracting spectrum and Fig. 1
Scheme essentially identical.
10. the crystal modification I of ZEN 90160, the crystal modification expression characteristics bands of a spectrum about 1704.95,1629.04,
1577.46,1352.22,1258.08,1201.97,1124.12,983.51 and 810.19cm-1The IR spectrograms at place, the IR spectrum
Method is 32 times in scanning times and resolution is 4cm-1Under conditions of carry out.
11. crystal modification as claimed in claim 10, wherein the IR spectrograms of the crystal modification substantially with as shown in Figure 2
It is identical.
12. the crystal modification I of ZEN 90160, the crystal modification, which is presented at about 79.115 DEG C, to be had endothermic peak and originates temperature
Differential scanning calorimetry (DSC) spectrogram that degree is about 73.872 DEG C.
13. crystal modification as claimed in claim 12, wherein the differential scanning calorimetry (DSC) spectrogram substantially with such as scheme
It is identical shown in 3.
14. a kind of method forming ZEN 90160 crystal modification I, the method includes：
I) ZEN 90160 solution in solvent system comprising one or more of solvents is provided；
Ii) compound of dissolving is crystallized into the crystal modification I of the ZEN 90160 with Formulas I；And
Iii crystalline solid) is detached from the solvent system, to generate the ZEN 90160 crystal modification I.
15. method as claimed in claim 14, wherein the solvent system include alcohol, aliphatic alkane or alicyclic alkanes,
Or mixtures thereof arsol, the aromatic oxide being substituted, ketone,.
16. method as claimed in claim 15, the wherein alcohol are secondary alcohol or the tertiary alcohol.
17. the method as described in any one of claim 15 or 16, wherein the alcohol is mixed with water.
18. method as claimed in claim 15, wherein the aliphatic alkane or alicyclic alkanes are by one or more halogen
Plain part replaces.
19. method as claimed in claim 15, wherein the alkane is selected from C5To C10Alkane.
20. method as claimed in claim 19, wherein the alkane is selected from from C5To C7Alkane.
21. method as claimed in claim 15, wherein the arsol is benzene compound.
22. method as claimed in claim 21, wherein the benzene compound is taken by one or more halogens or nitro moiety
Generation.
23. the method as described in any one of claim 14 to 22, wherein the solvent system include isopropanol, the tert-butyl alcohol,
Chloroform, dichloroethanes, hexane, nitrobenzene, chlorobenzene, dichloro-benzenes, benzotrifluoride, methyl ethyl ketone, acetonitrile or its one or more
The mixture of kind.
24. the method as described in any one of claim 14 to 23, wherein the solvent system include selected from chloroform-hexane,
The mixture of the solvent of THF- hexanes, dichloromethane/hexane and THF- water.
25. the method as described in any one of claim 14 to 24, wherein the ZEN 90160 is from room temperature to the solution
It is dissolved at a temperature of reflux temperature in the solvent system.
26. method as claimed in claim 25, wherein the temperature is the reflux temperature of the solution.
27. the method as described in any one of claim 14 to 26, wherein using the crystal modification I being present in the solution
Crystal seed carry out step (ii).
28. method as claimed in claim 27, wherein the crystal seed based on the weight of the solution with 0.005% to 0.5%
Amount exist.
29. a kind of Fungicidal composition, it includes the ZEN 90160 crystal modification I as described in any one of claim 1 to 13.
30. Fungicidal composition as claimed in claim 29, wherein the composition is preparation selected from the following：Suspending agent
(SC), oil-based suspension (OD), soluble granule (SG), dispersible agent (DC), missible oil (EC), lotion seed dressing, suspension are mixed
Kind agent, granule (GR), fine granule (MG), suspension emulsion (SE) and water dispersible granules (WG).
31. the Fungicidal composition as described in any one of claim 29 or 30, wherein the composition is suspending agent (SC).
32. a kind of method of the fungal infection in control place, the method includes applying such as claim 1 to 13 to the place
Any one of described in ZEN 90160 crystal modification I or the composition as described in any one of claim 29 to 31.
33. a kind of use of ZEN 90160 crystal modification I as described in any one of claim 1 to 13 in controlling fungal infection
On the way.
34. a kind of ZEN 90160 crystal modification substantially as described in above referring to figs. 1 to any one in Fig. 4.
35. a kind of method preparing ZEN 90160 crystal modification I substantially as described above.
36. a kind of method for controlling fungal infection substantially as described above.
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| GB1600977.1A GB2546498B (en) | 2016-01-19 | 2016-01-19 | Novel crystalline form of picoxystrobin, method of preparing and use of the same |
| GB1600977.1 | 2016-01-19 | ||
| PCT/CN2017/071499 WO2017125010A1 (en) | 2016-01-19 | 2017-01-18 | Novel crystalline form of picoxystrobin, method of preparing and use of the same |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001538A1 (en) * | 1995-06-28 | 1997-01-16 | Zeneca Limited | Process for the preparation of 2-(6-substituted pyrid-2-yloxymethyl)phenylacetate |
| CN102115458A (en) * | 2010-11-25 | 2011-07-06 | 大连凯飞精细化工有限公司 | Synthesis method of 3-methoxy-2-aryl(methyl)acrylate compounds |
| CN103030598A (en) * | 2012-12-17 | 2013-04-10 | 上海禾本药业有限公司 | Method for preparing strobilurin fungicide |
| CN103626691A (en) * | 2013-11-11 | 2014-03-12 | 上海禾本药业有限公司 | Picoxystrobin preparation method |
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| CN104151233A (en) * | 2014-08-25 | 2014-11-19 | 浙江泰达作物科技有限公司 | Preparation method of agricultural bactericide |
| CN104230794A (en) * | 2014-08-25 | 2014-12-24 | 浙江泰达作物科技有限公司 | Method for synthesizing high-efficiency green agriculture bactericide |
| CN104262239B (en) * | 2014-08-25 | 2016-08-17 | 浙江泰达作物科技有限公司 | A kind of synthesis technique of green high-efficient disinfectant use in agriculture |
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- 2017-01-18 WO PCT/CN2017/071499 patent/WO2017125010A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001538A1 (en) * | 1995-06-28 | 1997-01-16 | Zeneca Limited | Process for the preparation of 2-(6-substituted pyrid-2-yloxymethyl)phenylacetate |
| CN102115458A (en) * | 2010-11-25 | 2011-07-06 | 大连凯飞精细化工有限公司 | Synthesis method of 3-methoxy-2-aryl(methyl)acrylate compounds |
| CN103030598A (en) * | 2012-12-17 | 2013-04-10 | 上海禾本药业有限公司 | Method for preparing strobilurin fungicide |
| CN103626691A (en) * | 2013-11-11 | 2014-03-12 | 上海禾本药业有限公司 | Picoxystrobin preparation method |
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| MX2018007273A (en) | 2018-11-09 |
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| TWI721083B (en) | 2021-03-11 |
| GB2546498A (en) | 2017-07-26 |
| WO2017125010A1 (en) | 2017-07-27 |
| GB201600977D0 (en) | 2016-03-02 |
| TW201731818A (en) | 2017-09-16 |
| BR112017023886A2 (en) | 2018-07-17 |
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