CN109563044A - The method for being used to prepare Boscalid - Google Patents
The method for being used to prepare Boscalid Download PDFInfo
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- CN109563044A CN109563044A CN201780047243.2A CN201780047243A CN109563044A CN 109563044 A CN109563044 A CN 109563044A CN 201780047243 A CN201780047243 A CN 201780047243A CN 109563044 A CN109563044 A CN 109563044A
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- boscalid
- raised temperature
- crystal modification
- anhydrous
- starting material
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- 239000005740 Boscalid Substances 0.000 title claims abstract description 107
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229940118790 boscalid Drugs 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 61
- 230000004048 modification Effects 0.000 claims abstract description 55
- 238000012986 modification Methods 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000007858 starting material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- JPBWZIPCMDZOPM-UHFFFAOYSA-N 2-(4-chlorophenyl)aniline Chemical compound NC1=CC=CC=C1C1=CC=C(Cl)C=C1 JPBWZIPCMDZOPM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 206010017533 Fungal infection Diseases 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 102000019259 Succinate Dehydrogenase Human genes 0.000 description 1
- 108010012901 Succinate Dehydrogenase Proteins 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical class C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000012866 crystallographic experiment Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- -1 imide compound Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
Classifications
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Provide the method for preparing the crystal modification II of anhydrous Boscalid, this method includes that solid Boscalid starting material is heated to raised temperature, wherein the raised temperature is lower than the fusing point of the solid Boscalid starting material, and is enough to preferentially form the crystal modification II of anhydrous Boscalid.
Description
Cross reference to related applications
This application claims " be used to prepare Boscalid to the entitled of Department of Intellectual Property, Britain submission on August 4th, 2016
The priority of No. 1613457.9 UK Patent Application of method ", entire contents are incorporated herein by reference.
Technical field
The present invention relates to the methods for being used to prepare Boscalid, and in particular to is used to prepare the specific crystal formation of Boscalid
Method.
Background technique
Adopted name is the chloro- N- of compound 2- (4 ' chlorine [1,1 ' xenyl] -2- base)-Niacinamide of Boscalid
With structural formula I:
Boscalid is carboxyl acylamide fungicide, and serve as succinate dehydrogenase inhibitors (SDHI), i.e. mitochondria
Respiration inhibitor.The carboxylic imide compound and its activity of this classification are for the first time in US 4,001,416 and US 5,330,995
It is described.
Boscalid has an activity as fungicide, and its now with it is a series of be used to handle fungal infection and by
The preparation of its generated illness is commercially available.
US 7,087,239 is related to the crystalline hydrate of niacin aniline and Benzanilide derivatives.In US 7,087,239
Specifically illustrate the synthesis and recycling of hydration Boscalid.The hydrate is obtained by preparing anhydrous Boscalid first, should
Anhydrous Boscalid obtains at the end of synthesis process as the solution in hot dimethylbenzene.After cooling, crystallized out from the solution
It Boscalid and is dried in vacuo in an oven.The anhydride is noted with following physical characteristic:
US 7,087,239 discloses the hydrate can be by being dissolved into THF for the anhydride in a solvent at 40 DEG C
In and acquired solution is added in water and is formed.Precipitating and drying is isolated by filtration out, with a water of output Boscalid
Close object.The crystallization that the crystal modification of anhydrous Boscalid disclosed in US 7,087,239 is herein referred to as Boscalid becomes
Body I.
US 7,241,896 is related to for producing 2- halogen-pyridine-2-carboxamide (2-halogen-pyridine-
Carboxylic acid amides) method.Preparation that is open and illustrating Boscalid.In this example, Boscalid
It is to be carried out in dicyandiamide solution (specifically dimethylbenzene) by the chloro- 3- cigarette acyl chloride II of 2- and 2- (4- chlorphenyl) aniline
It reacts to synthesize.After being extracted with sodium carbonate liquor, Boscalid is crystallized by cooling down the organic solution of the compound steadily.
We have found that grinding anhydrous Boscalid disclosed in US 7,087,239 under aqueous conditions or using water
Crystal modification I be difficult.Therefore, directly the crystal modification I of Boscalid is configured to need grinding and/or fine grinding process
Expectation preparation be not a simple task.These preparations are such as granula, microcapsulated granule, tablet, water-dispersible granules, water
Disket, wettable powder or wettable powder, powder preparation and reactive compound for seed treatment are to disperse shape
Preparation existing for formula, such as suspending agent, oil-based suspension, suspended emulsion or the suspending agent for seed treatment.It is being configured to hang
Before floating agent, need the crystal modification aquation of Boscalid.
US 7,501,384 further discloses the new crystal modification claimed as anhydrous Boscalid.In US 7,501,384
Disclosed crystal modification is herein referred to as the crystal modification II of Boscalid.It is proposed in US 7,501,384, pyridine acyl bacterium
The crystal modification II of amine is particularly suited for manufacturing a series of preparations, and otherwise these preparations need interminable grinding/fine grinding process step
Suddenly.
The crystal modification II that US 7,501,384 describes Boscalid can be prepared by the inclusion of the method for following steps:
A) anhydride of the crystal modification I of Boscalid is dissolved in polar organic solvent or aromatic hydrocarbon；And
B) anhydride of the crystal modification II of Boscalid is precipitated by the cooling solvent.
The alternative that the crystal modification II of Boscalid is prepared disclosed in US 7,501,384 includes:
A) the crystal modification I of Boscalid is heated to 150 DEG C or more until fusing；And
B) the thawing object of the crystal seed of the cooling crystal modification II for being added to Boscalid.
The crystal modification II of Boscalid is described as having the property that by US 7,501,384
It is obtained from the Crystallographic Study of the crystal modification II of Boscalid using the single crystal diffractometer of Siemens (Siemens)
The key parameter and structure cell matrix obtained provides as follows in US 7,501,384:
Parameter illustrated above has following meanings:
The rib of a, b, c=structure cell is long；
α, beta, gamma=corresponding angle；And
Molecular number in Z=structure cell.
If the improvement preparation method of the crystal modification II of Boscalid can be provided, it is particularly suitable in commercial size
On application, particularly the method with reproducible high yield and desired Boscalid variant II is provided, will have significant
Advantage.Preferably, this method is easy to operate and easily controllable.
It was unexpectedly determined that it has now been discovered that the crystal modification II for forming the anhydrous Boscalid of high yield is to increase
At a temperature of occur.In contrast, lower temperature leads to the crystal modification I for preferentially forming Boscalid.Specifically, it heats
Crystal modification I is converted crystal modification II by the crystal modification I of Boscalid, especially Boscalid.With US 7,501,384
In introduction on the contrary, surprisingly it has been found that heating Boscalid crystal modification I for formed melt object be not must
Must.On the contrary, the crystal modification II of Boscalid is by being heated to the solid crystal variant I of Boscalid lower than its fusing point
Temperature is formed.
Summary of the invention
Therefore, in a first aspect, the present invention provides the method for the crystal modification II for preparing anhydrous Boscalid, this method
Comprising solid Boscalid starting material is heated to raised temperature, which originates lower than the solid Boscalid
The fusing point of material, and be enough to preferentially form the crystal modification II of anhydrous Boscalid.
In the present invention, Boscalid starting material is converted using raised temperature, and preferentially forms anhydrous pyridine acyl bacterium
The crystal modification II of amine.
Method of the invention uses solid Boscalid starting material.The solid starting material, which can be, to be heated to being lower than
The pyridine acyl bacterium of any suitable solid form of the crystal modification II of anhydrous Boscalid is formed when the raised temperature of its fusing point
Amine.The solid Boscalid starting material is preferably the crystal modification in addition to crystal modification II of anhydrous Boscalid.This hair
Bright method is most preferably using the crystal modification I of anhydrous Boscalid as Boscalid starting material.
In the method for the invention, which is heated to raised temperature.It has been found that rising
High temperature leads to preferentially forming for the crystal modification II of anhydrous Boscalid.Most advantageously, it has been found that, by solid pyridine acyl
The amine-initiated material of bacterium be heated to its fusing point or more than temperature or formed melt object be not required.Therefore, most preferably will
Boscalid starting material is heated to the temperature lower than the starting material of anhydrous Boscalid and the fusing point of both crystal modification II.
Using the crystal modification I of anhydrous Boscalid, the fusing point of the solid form of Boscalid is about 144 DEG C to 145
℃.Therefore, using the crystal modification I of anhydrous Boscalid, starting material is heated to lower than 144 DEG C to 145
DEG C temperature.
Solid Boscalid starting material is heated to raised temperature, that is, is higher than environment temperature or room temperature.This is raised
Temperature is preferably at least 35 DEG C, more preferably at least 40 DEG C, and be still more preferably from least 45 DEG C.For example, it was found that by solid pyridine
The amine-initiated material of acyl bacterium, the solid crystal variant I of especially anhydrous Boscalid are heated to 45 DEG C of temperature, cause anhydrous pyridine acyl
The crystal modification I of bacterium amine is converted by weight 30% crystal modification II.
It is highly preferred that by solid Boscalid starting material be heated at least 50 DEG C, even more preferably at least 55 DEG C, still
More preferably at least 60 DEG C of temperature.In experiments it has been found that the crystal modification I of anhydrous Boscalid is heated to 65 DEG C extremely
70 DEG C of temperature causes the formation of the crystal modification II of by weight 100% anhydrous Boscalid.
As described above, the raised temperature is lower than the fusing point of solid Boscalid starting material.The raised temperature is also low
In the fusing point of the crystal modification II of anhydrous Boscalid.The raised temperature is preferably shorter than 140 DEG C, more preferably less than 130 DEG C, also
More preferably less than 120 DEG C, still more preferably below 110 DEG C.In preferred embodiments, solid Boscalid starting material is added
Heat is extremely lower than 100 DEG C, more preferably less than 90 DEG C, still more preferably less than 85 DEG C, still more preferably below 80 DEG C of raised temperature.
It is preferable to use 30 DEG C to 130 DEG C of raised temperature, more preferably 35 DEG C to 120 DEG C, further preferably 40 DEG C
To 110 DEG C, be still more preferably from 45 DEG C to 100 DEG C, wherein it is preferred that 50 DEG C to 90 DEG C, it is 55 DEG C to 85 DEG C more preferable, still more preferably 60
DEG C to 80 DEG C of temperature.
In the method for the invention, which is heated to raised temperature.Heating can connect
Continue or gradually carry out, or is carried out in a manner of a combination thereof.Preferably, solid Boscalid starting material is in a continuous manner from
Beginning temperature is heated to raised temperature.
Boscalid material can be heated to raised temperature with any suitable rate.It can be using 5 (h) per hour
DEG C to 35 DEG C (DEG C/h) of the rate of heat addition, such as 10 DEG C to 30 DEG C/h.
As described above, it has been found that the effect of heating solid Boscalid starting material causes the crystallization of anhydrous Boscalid
The formation of variant II.Preferably, which is kept into a period of time at elevated temperatures, is especially enough to be formed anhydrous
The desired amount of a period of time of the crystal modification II of Boscalid.For example, the raised temperature can remain up to 45 minutes, it is excellent
Choosing at most 40 minutes, more preferably up to 35 minutes.The shorter time can also be used at elevated temperatures.For example, the solid
Material can be kept 30 seconds to 45 minutes at elevated temperatures, be preferably remained 45 seconds to 40 minutes, and more preferable 1 minute to 25 points
Clock, even more preferably from 1 to 15 minute.
As the crystal modification II for foring anhydrous Boscalid, which can be cooled to room temperature or environment temperature
Degree.Preferably, under an inert atmosphere, cooling Boscalid material under the atmosphere especially substantially free of water (such as nitrogen atmosphere)
Material, to avoid hydrate is formed within this material.
Boscalid material can be cooled to environment temperature from raised temperature with any suitable rate.It can use
The cooling rate of 5 DEG C to 35 DEG C of (h) (DEG C/h) per hour, such as 5 DEG C to 25 DEG C/h.
(such as pass through aeration) Boscalid material can be cooled down by any suitable technology.
Method of the invention can be carried out in a manner of partial or continuous.
Method of the invention can be carried out by using any suitable device.Suitable equipment for carrying out this method is
It is known in the art, and be commercially available.
On the other hand, the present invention provides the crystal modification 1J of the anhydrous Boscalid comprising being prepared by the above method
Fungicide.
Detailed description of the invention
FTIR spectrum method record IR spectrum can be used.
Fig. 1 is the IR spectrum of the crystal modification II of anhydrous Boscalid；
Fig. 2 is the IR spectrum of the crystal modification I of anhydrous Boscalid.
Specific embodiment
Embodiment of the present invention is described by following specific examples only for the purpose of illustration.
In the examples below, unless otherwise indicated, percentage is weight percent.
Embodiment
Embodiment 1
The solid Boscalid starting material (25g) being made of the crystal modification I of anhydrous Boscalid is placed in baking oven
And it is heated to 45 DEG C of raised temperature.The heating carries out in a continuous manner.By the solid material in raised temperature
It is lower to be kept for 30 minutes.Then, the solid material is cooled to room temperature by the rate aeration cooling with 6 DEG C/h to 10 DEG C/h.
The pyridine in obtained solid material is confirmed by melting point analysis (DSC), infrared (IR) spectrum and X-ray diffraction (XRD)
The form of acyl bacterium amine, and the form includes the crystal modification II of anhydrous Boscalid.
Embodiment 2
The solid crystal variant I of the anhydrous Boscalid of 25g is put into the rotating disk in baking oven, and is stablized slowly
It is heated to 45 DEG C of raised temperature.The heating carries out in a continuous manner.The material is kept 30 at such elevated temperature
Minute.Then, which is kept under nitrogen atmosphere, and by external aeration with the cooling velocity of 3 DEG C/h to 10 DEG C/h
It is cooled to room temperature.
The pyridine in obtained solid material is confirmed by melting point analysis (DSC), infrared (IR) spectrum and X-ray diffraction (XRD)
The form of acyl bacterium amine, and the form includes the crystal modification II of anhydrous Boscalid.
In order to further study influence of the temperature to Boscalid material, to be heated to a series of raised temperature of difference,
Repeat step described in Examples 1 and 2.As a result it summarizes in the following table.
The result summarized from upper table can be seen that the form of the anhydrous Boscalid in final solid Boscalid material
Depending on heating solid temperature achieved.Specifically, it is heated to 65 DEG C of temperature, produces 100% anhydrous Boscalid
Crystal modification II.In contrast, 25 DEG C of crystal modification I for only generating anhydrous Boscalid are heated to.
Claims (20)
1. a kind of method for the crystal modification II for preparing anhydrous Boscalid, the method includes that solid Boscalid is originated material
Material is heated to raised temperature, and the raised temperature is lower than the fusing point of the solid Boscalid starting material, and is enough excellent
It is initially formed the crystal modification II of anhydrous Boscalid.
2. according to the method described in claim 1, wherein the Boscalid starting material includes the crystallization of anhydrous Boscalid
Variant I.
3. according to the method described in claim 2, wherein the Boscalid starting material is substantially by the knot of anhydrous Boscalid
Brilliant variant I composition.
4. method according to any preceding claims, wherein the raised temperature is at least 35 DEG C.
5. according to the method described in claim 4, wherein the raised temperature is at least 45 DEG C.
6. according to the method described in claim 5, wherein the raised temperature is at least 50 DEG C.
7. method according to any preceding claims, wherein the raised temperature is lower than 110 DEG C.
8. according to the method described in claim 7, wherein the raised temperature is lower than 100 DEG C.
9. according to the method described in claim 8, wherein the raised temperature is lower than 85 DEG C.
10. method according to any of the preceding claims, wherein the raised temperature is from 45 DEG C to 100 DEG C.
11. according to the method described in claim 10, wherein the raised temperature is from 60 DEG C to 80 DEG C.
12. method according to any preceding claims, wherein the Boscalid starting material is with continuous or gradually
Mode is heated.
13. method according to any preceding claims, wherein heating the Boscalid with the rate of 5 DEG C to 35 DEG C/h
Starting material.
14. method according to any preceding claims, wherein by the Boscalid material at the raised temperature
Kept for a period of time.
15. according to the method for claim 14, wherein the Boscalid material is kept 1 at the raised temperature
To 25 minutes time.
16. method according to any preceding claims, wherein under an inert atmosphere from the cooling institute of the raised temperature
State Boscalid material.
17. method according to any preceding claims, wherein with the rate of 5 DEG C to 35 DEG C/h from the raised temperature
The cooling Boscalid material.
18. method according to any preceding claims, wherein the method carries out or in a continuous manner in a batch manner
It carries out.
19. the method that one kind prepares the crystal modification II of anhydrous Boscalid substantially as described above.
20. a kind of Fungicidal composition, it includes the Boscalid materials prepared by method described in any preceding claims
Material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1613457.9 | 2016-08-04 | ||
| GB1613457.9A GB2552696B (en) | 2016-08-04 | 2016-08-04 | Process for preparing boscalid |
| PCT/CN2017/094633 WO2018024148A1 (en) | 2016-08-04 | 2017-07-27 | Process for preparing boscalid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109563044A true CN109563044A (en) | 2019-04-02 |
Family
ID=60940405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780047243.2A Pending CN109563044A (en) | 2016-08-04 | 2017-07-27 | The method for being used to prepare Boscalid |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN109563044A (en) |
| GB (1) | GB2552696B (en) |
| TW (1) | TWI777967B (en) |
| WO (1) | WO2018024148A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558901A (en) * | 2001-09-25 | 2004-12-29 | �����ɷ� | Crystalline hydrates of nicotinic acid anilide and benzoyl anilide derivatives |
| CN1575281A (en) * | 2001-11-02 | 2005-02-02 | 巴斯福股份公司 | Method for producing 2-halogen-pyridine-carboxylic acid amides |
| CN1751026A (en) * | 2003-02-14 | 2006-03-22 | 巴斯夫股份有限公司 | Novel crystalline modification of the anhydrate of boscalid |
| CN103980192A (en) * | 2014-01-20 | 2014-08-13 | 泰州百力化学股份有限公司 | Selective synthesis method of cyprosulfamide with different crystal forms |
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2016
- 2016-08-04 GB GB1613457.9A patent/GB2552696B/en not_active Expired - Fee Related
-
2017
- 2017-07-27 CN CN201780047243.2A patent/CN109563044A/en active Pending
- 2017-07-27 WO PCT/CN2017/094633 patent/WO2018024148A1/en active Application Filing
- 2017-08-02 TW TW106125995A patent/TWI777967B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558901A (en) * | 2001-09-25 | 2004-12-29 | �����ɷ� | Crystalline hydrates of nicotinic acid anilide and benzoyl anilide derivatives |
| CN1575281A (en) * | 2001-11-02 | 2005-02-02 | 巴斯福股份公司 | Method for producing 2-halogen-pyridine-carboxylic acid amides |
| CN1751026A (en) * | 2003-02-14 | 2006-03-22 | 巴斯夫股份有限公司 | Novel crystalline modification of the anhydrate of boscalid |
| CN103980192A (en) * | 2014-01-20 | 2014-08-13 | 泰州百力化学股份有限公司 | Selective synthesis method of cyprosulfamide with different crystal forms |
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| GB2552696B (en) | 2020-03-04 |
| GB2552696A (en) | 2018-02-07 |
| TW201805272A (en) | 2018-02-16 |
| WO2018024148A1 (en) | 2018-02-08 |
| TWI777967B (en) | 2022-09-21 |
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