CN104030992A - Dicyclanil medicine crystal form II and preparing method thereof - Google Patents
Dicyclanil medicine crystal form II and preparing method thereof Download PDFInfo
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- CN104030992A CN104030992A CN201410105315.2A CN201410105315A CN104030992A CN 104030992 A CN104030992 A CN 104030992A CN 201410105315 A CN201410105315 A CN 201410105315A CN 104030992 A CN104030992 A CN 104030992A
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- dicyclanil
- crystal
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- drug
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- WSTUXHXGXVLKGF-UHFFFAOYSA-N Cc1c(N)nc(NC2CC2)nc1N Chemical compound Cc1c(N)nc(NC2CC2)nc1N WSTUXHXGXVLKGF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C07D239/50—Three nitrogen atoms
Abstract
The invention belongs to the field of pharmaceutical chemistry and particularly relates to a novel dicyclanil medicine crystal form II suitable for medicine development and a preparing method thereof. The dicyclanil medicine crystal form II and the preparing method thereof are characterized by a N,N-dimethylformamide solvate of a dicyclanil medicine. The crystal space groups of the dicyclanil medicine crystal form II are a monoclinic system. One dicyclanil molecule and one N,N-dimethylformamide molecule are bonded through hydrogen bonds so as to form an elementary structure unit of the dicyclanil medicine crystal form II. A preparation process of the dicyclanil medicine crystal form II adopts the N,N-dimethylformamide as a solvent, and adopts a saturated-solution cooling crystallization method, wherein a solution is saturated due to volatilization by heating so that crystals precipitate in the process of the solvent cooling and volatilization. The dicyclanil medicine crystal form II is capable of preventing larvae of various flies, mosquitoes and fleas from developing to pupae or imagines, and the like, and is obviously improved in solubility, stability and bioavailability.
Description
Technical field
The invention belongs to pharmaceutical chemistry field, be specifically related to a kind of novel Dicyclanil and adapt to a kind of crystal form II of pharmaceutical analysis and preparation method thereof.
Background technology
Dicyclanil (dicyclanil) has another name called the third worm pyridine, chemical name: 4,6-diamino-2-cyclopropylamino pyrimidine-5-nitrile, molecular formula: C
8h
10n
6, Dicyclanil is Novel insect growth regulator, emphasizes pest population control and regulate, optionally effective pest control, can keep normal natural, ecological can not cause environmental pollution again.As veterinary drug of new generation, there is the powerful market requirement, because this medicine is difficult for tolerance, residual value is low, has very high Ecological Society benefit, meets requirement and the target of current environment friendly agricultural.Structural formula is as follows:
At present, patent WO9910333A1 discloses eight kinds of crystal formations of Dicyclanil, is respectively A, B, C, D, E, F, G, H crystal formation.Wherein A crystal formation is stable not, is easily converted into other crystal formation.G, C crystal formation are respectively that these two kinds of crystal formation reaction times are long by A crystal formation 80 ℃ of stirring 16h and 40 ℃ of stirring 24h in water, and temperature is high, is unfavorable for suitability for industrialized production.B crystal formation is obtained by C crystal formation nitrogen drying at 25 ℃.D crystal formation first generates crystal seed could be for industrial production.F crystal formation is to be added to and to be contained stirring at room in water, polyoxyethylene glycol, sorbitanic, mono laurate ester solvent and obtain by A crystal formation.
Patent AU2010201828A1 discloses a kind of new crystal of Dicyclanil, is by Dicyclanil, to add some tensio-active agents and viscosity to modify to obtain.
Affect crystal formation a lot of because have of medicine, such as obtaining different crystal formations by changing solvent, temperature, illumination etc., because of the difference of crystalline network, there is notable difference in same its physical properties of medicine different crystal forms, thereby can exert an influence to the security of medicine, validity.At present, drug crystal forms research has become hot research work.
The solvate of medicine is a kind of new crystal that active constituents of medicine and reagent form by Intermolecular Forces (as hydrogen bond), it can improve physico-chemical property and the bioavailability of active constituents of medicine, the feature with good stability, so the research of relevant drug solvent compound has become the large focus of pharmaceutical field one in recent years.
Therefore, find solubleness good, bioavailability is high, stable, is conducive to 4 of suitability for industrialized production, and 6-diamino-2-cyclopropylamino pyrimidine-5-nitrile new crystal is very necessary.
Summary of the invention
The object of the invention is on the basis of existing technology, a kind of DMF solvate of Dicyclanil medicine of novel texture is provided.Drug crystal forms prepared by the present invention has height killing action what inherited original Dicyclanil medicine to dipteral insect and flea, can stop outside the speciality such as the larvae development pupa worm of various flies, mosquito and flea or adult, in its solvability, stability and bioavailability, have obvious change.
Technical scheme of the present invention is: a kind of Dicyclanil drug crystal forms II, N for Dicyclanil medicine, dinethylformamide solvate, powder X-ray RD collection of illustrative plates is 13.3 ± 0.2 °, 14.18 ± 0.2 °, 15.97 ± 0.2 °, 16.76 ± 0.2 °, 20.22 ± 0.2 °, 21.20 ± 0.2 °, 23.68 ± 0.2 °, 24.49 ± 0.2 °, 26.83 ± 0.2 °, 27.32 ± 0.2 °, 28.76 ± 0.2 °, 29.65 ± 0.2 °, 31.98 ± 0.2 ° at diffraction angle 2 θ and has located characteristic peak.
Using Dicyclanil as active constituents of medicine, take DMF as solvent, the crystal of formation, the spacer of crystal is oblique system, axial length a=7.3744～7.7744, b=17.105～17.505, c=10.950～11.350, α=90, β=96.73～98.73, γ=90.
Powder X-ray RD collection of illustrative plates is 9.44 ± 0.2 ° at diffraction angle 2 θ, 13.3 ± 0.2 °, 14.18 ± 0.2 °, 15.97 ± 0.2 °, 15.16 ± 0.2 °, 16.76 ± 0.2 °, 19.34 ± 0.2 °, 20.22 ± 0.2 °, 21.20 ± 0.2 °, 21.60 ± 0.2 °, 23.68 ± 0.2 °, 24.49 ± 0.2 °, 25.87 ± 0.2 °, 26.83 ± 0.2 °, 27.32 ± 0.2 °, 28.76 ± 0.2 °, 29.65 ± 0.2 °, 31.98 ± 0.2 °, 33.33 ± 0.2 °, 40.65 ± 0.2 °, 42.10 located characteristic peak for ± 0.2 °.
Infared spectrum is at 3423.91 ± 0.2cm
-1, 3331.94 ± 0.2cm
-1, 3203.18 ± 0.2m
-1, 2194.82 ± 0.2cm
-1, 1636.29 ± 0.2cm
-1, 1564.38 ± 0.2cm
-1, 1472.41 ± 0.2cm
-1, 1343.65 ± 0.2cm
-1, 778.43 ± 0.2cm
-1there is absorption peak at place.
1 Dicyclanil molecule and 1 N in crystal, dinethylformamide consists of the basic structural unit of Dicyclanil medicine crystal together hydrogen bonded, N atom in one of them Dicyclanil molecule is as the donor of hydrogen bond, the O atom of a DMF molecule is as the receptor of hydrogen bond and form a hydrogen bond.
A preparation method for described Dicyclanil drug crystal forms II, comprises the steps:
(1) Dicyclanil of A crystal formation is dissolved in DMF solvent, heated and stirred to reach at this temperature hypersaturated state time, filter;
(2) with film, seal the vessel port that Dicyclanil solution is housed, at film, establish volatilization aperture, after standing volatilization 5-7 days,
In container, separate out colourless tabular crystal, isolation of crystalline and get final product.
Heating temperature is: 80-153 ℃.
Dicyclanil drug crystal forms II thermogravimetric curve, first step is since 80 ℃ of decomposition, and 190 ℃ of decomposition complete, weightlessness 28.42%, this step is for losing DMF molecule, second largest step is that 210～330 ℃ of decomposition complete, weightless 66.95.7%, and this step is that Dicyclanil self decomposes.Drug crystal forms II prepared by this present invention has height killing action what inherited original Dicyclanil medicine to dipteral insect and flea, can stop outside the speciality such as the larvae development pupa worm of various flies, mosquito and flea or adult, in its solvability, stability and bioavailability, have obvious change.
The preparation method of drug crystal forms II of the present invention is saturated solution lowering temperature crystallization, and selected solvent is DMF solvent, because heating volatilization reaches capacity solution, therefore have crystal to separate out in the process of solvent cooling and volatilization.
Accompanying drawing explanation
Fig. 1 is Dicyclanil medicine crystal structural unit schematic diagram.
As shown in the figure, 1 Dicyclanil molecule and 1 DMF are by forming the basic structural unit of Dicyclanil medicine crystal together with hydrogen bonded, and the N atom in one of them Dicyclanil molecule is as the donor of hydrogen bond, a N, the O atom of dinethylformamide molecule is as the receptor of hydrogen bond and form a hydrogen bond, its axial length a=7.3744～7.7744, b=17.105～17.505, c=10.950～11.350, α=90, β=96.73～98.73, γ=90.
Fig. 2 is the XRD figure spectrum of Dicyclanil drug crystal forms II.
As shown in the figure, from the X-ray diffraction peak (curve 1) of this synthetic crystal form II, can find out at 9.44 °, 13.3 °, 14.18 °, 15.16 °, 15.97 °, 16.76 °, 19.34 °, 20.22 °, 21.20 °, 21.60 °, 23.68 °, 24.49 °, 25.87 °, 26.83 °, 27.32 °, 28.76 °, 29.65 °, 31.98 °, 33.33 °, 40.65 °, 42.10 ° and occur series of features peak.
Fig. 3 is the thermogravimetric collection of illustrative plates of Dicyclanil drug crystal forms II.
This collection of illustrative plates is under the atmosphere test condition of nitrogen, Dicyclanil crystal form II thermogravimetric curve, first step is since 80 ℃ of decomposition, 190 ℃ of decomposition complete, weightlessness 28.42%, and this step is for losing N, dinethylformamide molecule, second largest step is that 210～330 ℃ of decomposition complete, weightless 66.95.7%, and this step is that Dicyclanil self decomposes.
Fig. 4 is the IR collection of illustrative plates of Dicyclanil drug crystal forms II.
As shown in the figure, the characteristic peak of this new crystal is at 3423.91cm
-1, 3331.94cm
-1, 3203.18cm
-1, 2194.82cm
-1, 1636.29cm
-1, 1564.38cm
-1, 1472.41cm
-1, 1343.65cm
-1, 778.43cm
-1place.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Following specific embodiment is only further used for illustrating the present invention, but not for limiting content of the present invention.
The instrument of detection of drugs crystal form II structure of the present invention and performance thereof is as follows:
1, crystalline structure is measured by X ray single crystal diffractometer, and full name is a Rigaku SCXmini diffractometer.
2, powder diffractometer is produced by German Bruker company, and model is D8-Discover, Cu-K α
, tube voltage 40KV, tube current 30mA, 8 °/min of sweep velocity.
3, thermogravimetric curve is produced by METTLER TOLEDO company, and model is STARe System, adopts nitrogen atmosphere, 10 ℃/min of temperature rise rate.
4, infrared curve is recorded by Fourier infrared spectrograph, and model is NICOLET5700FT-IR.
The transparent glass instrument that the present invention uses is external import, and capacity is 50ml.
A Dicyclanil drug crystal forms II, its powder X-ray RD collection of illustrative plates is 13.3 ± 0.2 °, 14.18 ± 0.2 °, 15.97 ± 0.2 °, 16.76 ± 0.2 °, 20.22 ± 0.2 °, 21.20 ± 0.2 °, 23.68 ± 0.2 °, 24.49 ± 0.2 °, 26.83 ± 0.2 °, 27.32 ± 0.2 °, 28.76 ± 0.2 °, 29.65 ± 0.2 °, 31.98 ± 0.2 ° at diffraction angle 2 θ and has located characteristic peak.
The selected bulk drug Dicyclanil of the present invention is as active constituents of medicine, and the chemical name of Dicyclanil is for having another name called the third worm pyridine, and chinesization formal name used at school is 4,6-diamino-2-cyclopropylamino pyrimidine-5-nitrile, molecular formula C
8h
10n
6, its structural formula is as shown in a; DMF molecular formula C
3h
7oN.
Dicyclanil drug crystal forms II of the present invention is usingd Dicyclanil as active constituents of medicine, with N, dinethylformamide is solvent, the crystal of formation, and its spacer is oblique system, its axial length a=7.3744～7.7744, b=17.105～17.505, c=10.950～11.350, α=90, β=96.73～98.73, γ=90.This crystalline structure simplified summary is as follows: 1 Dicyclanil molecule and 1 N, dinethylformamide consists of the basic structural unit of Dicyclanil medicine crystal together hydrogen bonded, N atom in one of them Dicyclanil molecule is as the donor of hydrogen bond, the O atom of a DMF molecule is as the receptor of hydrogen bond and form a hydrogen bond.
Further, the powder X-ray RD collection of illustrative plates of this Dicyclanil drug crystal forms II is 9.44 ± 0.2 ° at diffraction angle 2 θ, 13.3 ± 0.2 °, 14.18 ± 0.2 °, 15.97 ± 0.2 °, 15.16 ± 0.2 °, 16.76 ± 0.2 °, 19.34 ± 0.2 °, 20.22 ± 0.2 °, 21.20 ± 0.2 °, 21.60 ± 0.2 °, 23.68 ± 0.2 °, 24.49 ± 0.2 °, 25.87 ± 0.2 °, 26.83 ± 0.2 °, 27.32 ± 0.2 °, 28.76 ± 0.2 °, 29.65 ± 0.2 °, 31.98 ± 0.2 °, 33.33 ± 0.2 °, 40.65 ± 0.2 °, located characteristic peak for 42.10 ± 0.2 °.
Further, this Dicyclanil drug crystal forms II has powder X-ray RD collection of illustrative plates substantially as shown in Figure 2.
The infared spectrum of this Dicyclanil drug crystal forms II is at 3423.91 ± 0.2cm
-1, 3331.94 ± 0.2cm
-1, 3203.18 ± 0.2m
-1, 2194.82 ± 0.2cm
-1, 1636.29 ± 0.2cm
-1, 1564.38 ± 0.2cm
-1, 1472.41 ± 0.2cm
-1, 1343.65 ± 0.2cm
-1, 778.43 ± 0.2cm
-1there is absorption peak at place.
The preparation process of Dicyclanil drug crystal forms II of the present invention is as follows:
(1) Dicyclanil is dissolved in DMF solvent, heating for dissolving, to reaching hypersaturated state, stirs 30min～60min, filters;
(2) with film, seal the vessel port that Dicyclanil solution is housed, at film, establish volatilization aperture, after standing volatilization 5-7 days, in container, start to separate out colourless tabular crystal, separated this crystal and get final product.
The present invention further provides a kind of concrete preparation method of Dicyclanil drug crystal forms II: Dicyclanil 1.3～1.7mmol is dissolved in DMF solvent, as for heated and stirred 30min～60min on agitator, filters; With the film of preservative film, seal beaker mouth, with pin, on film, prick several apertures, after standing volatilization 5-7 days, in container, start to separate out colourless sheet shape crystal, i.e. Dicyclanil drug crystal forms II.
Embodiment 1: use the synthetic crystal form II of Dicyclanil and DMF:
Weigh:
A crystal formation Dicyclanil 300mg feeds intake, and with analytical balance, accurately takes.
Bulk drug dissolves:
With transfer pipet, accurately measure 20mlN, dinethylformamide, in 50ml beaker, stirs 30min.
Saturated solution lowering temperature crystallization:
At 153 ℃, after can not dissolving on a small quantity in addition, take out stirrer, with analytical paper, be filled in a clean 50ml transparent glass bottle, with preservative film, seal bottleneck, with the several apertures of pinprick, standing volatilization.After approximately 7 days, in bottle, separate out sheet colourless transparent crystal.
Poisoning test to insect: the insect of selecting is that cotton boll resembles adult
Test method: during experiment respectively by drug crystal forms II of the present invention, by formula, be made into certain density suspensoid respectively with raw material, blank group experiment (other is consistent not add any this medicine composition in formula) is set, adopt and first to soak the method that connects worm after leaf, by contacting after any medicament blade of the same size soaks 5s in the liquid configuring, do not take out, naturally dry, put into insect box, then connect for examination larva, under 25 ℃ of conditions, raise, every processing repeats for 3 times, it is every that to repeat examination borer population used be 50, establish blank simultaneously, in 72h, check dead borer population, calculate mortality ratio and corrected mortality.If contrast mortality ratio is greater than 10%, be considered as invalid experiment.Calculation formula is as follows:
Data by table 1 can find out, drug crystal forms II of the present invention in insect toxic action apparently higher than raw material.
Comparative example:
Use acetonitrile, or acetone solvent according to the method for embodiment 1, to do crystal formation data that same experiment obtains be respectively that crystal formation with raw material is consistent, the position at its powder diffraction spectrum peak is: 7.77 °, 9.87 °, 10.9 °, 11 °, 11.85 °, 15 °, 15.5 °, 17.4 °, 18.79 °, 19.24 °, 21.4 °, 22.2 °, 24 °, 26.2 °, 28.01 °, 29.1 °, 30.1 °, 31.4 °, 33.4 °.
Claims (7)
1. a Dicyclanil drug crystal forms II, it is characterized in that, N for Dicyclanil medicine, dinethylformamide solvate, powder X-ray RD collection of illustrative plates is 13.3 ± 0.2 °, 14.18 ± 0.2 °, 15.97 ± 0.2 °, 16.76 ± 0.2 °, 20.22 ± 0.2 °, 21.20 ± 0.2 °, 23.68 ± 0.2 °, 24.49 ± 0.2 °, 26.83 ± 0.2 °, 27.32 ± 0.2 °, 28.76 ± 0.2 °, 29.65 ± 0.2 °, 31.98 ± 0.2 ° at diffraction angle 2 θ and has located characteristic peak.
2. Dicyclanil drug crystal forms II according to claim 1, is characterized in that, usings Dicyclanil as active constituents of medicine, with N, dinethylformamide is solvent, the crystal of formation, and the spacer of crystal is oblique system, axial length a=7.3744～7.7744, b=17.105～17.505, c=10.950～11.350, α=90, β=96.73～98.73, γ=90.
3. Dicyclanil drug crystal forms II according to claim 1, it is characterized in that, powder X-ray RD collection of illustrative plates is 9.44 ± 0.2 ° at diffraction angle 2 θ, 13.3 ± 0.2 °, 14.18 ± 0.2 °, 15.97 ± 0.2 °, 15.16 ± 0.2 °, 16.76 ± 0.2 °, 19.34 ± 0.2 °, 20.22 ± 0.2 °, 21.20 ± 0.2 °, 21.60 ± 0.2 °, 23.68 ± 0.2 °, 24.49 ± 0.2 °, 25.87 ± 0.2 °, 26.83 ± 0.2 °, 27.32 ± 0.2 °, 28.76 ± 0.2 °, 29.65 ± 0.2 °, 31.98 ± 0.2 °, 33.33 ± 0.2 °, 40.65 ± 0.2 °, located characteristic peak for 42.10 ± 0.2 °.
4. Dicyclanil drug crystal forms II according to claim 1, is characterized in that, infared spectrum is at 3423.91 ± 0.2cm
-1, 3331.94 ± 0.2cm
-1, 3203.18 ± 0.2m
-1, 2194.82 ± 0.2cm
-1, 1636.29 ± 0.2cm
-1, 1564.38 ± 0.2cm
-1, 1472.41 ± 0.2cm
-1, 1343.65 ± 0.2cm
-1, 778.43 ± 0.2cm
-1there is absorption peak at place.
5. Dicyclanil drug crystal forms II according to claim 2, it is characterized in that, 1 Dicyclanil molecule and 1 N in crystal, dinethylformamide consists of the basic structural unit of Dicyclanil medicine crystal together hydrogen bonded, N atom in one of them Dicyclanil molecule is as the donor of hydrogen bond, the O atom of a DMF molecule is as the receptor of hydrogen bond and form a hydrogen bond.
6. a preparation method for the Dicyclanil drug crystal forms II described in claim 1 or 2, is characterized in that, comprises the steps:
(1) Dicyclanil of A crystal formation is dissolved in DMF solvent, heated and stirred to reach at this temperature hypersaturated state time, filter;
(2) with film, seal the vessel port that Dicyclanil solution is housed, at film, establish volatilization aperture, after standing volatilization 5-7 days, in container, separate out colourless tabular crystal, isolation of crystalline and get final product.
7. according to the preparation method of Dicyclanil drug crystal forms II described in claims 6, it is characterized in that, Heating temperature is: 80-153 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268125A (en) * | 1997-08-27 | 2000-09-27 | 诺瓦提斯公司 | Dicyclanil Polymorphs and hydrates and their preparation |
| CN1713891A (en) * | 2002-10-25 | 2005-12-28 | 弗米克斯有限公司 | Cosmetic and pharmaceutical foam |
| WO2008052263A1 (en) * | 2006-11-01 | 2008-05-08 | Veterinary Encapsulation Biosciences Pty Ltd | Delivery system for remote treatment of an animal |
-
2014
- 2014-03-20 CN CN201410105315.2A patent/CN104030992B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268125A (en) * | 1997-08-27 | 2000-09-27 | 诺瓦提斯公司 | Dicyclanil Polymorphs and hydrates and their preparation |
| CN1713891A (en) * | 2002-10-25 | 2005-12-28 | 弗米克斯有限公司 | Cosmetic and pharmaceutical foam |
| WO2008052263A1 (en) * | 2006-11-01 | 2008-05-08 | Veterinary Encapsulation Biosciences Pty Ltd | Delivery system for remote treatment of an animal |
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