CN112239435A - Exterior nadic anhydride crystal form and preparation method thereof - Google Patents

Exterior nadic anhydride crystal form and preparation method thereof Download PDF

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CN112239435A
CN112239435A CN201910650586.9A CN201910650586A CN112239435A CN 112239435 A CN112239435 A CN 112239435A CN 201910650586 A CN201910650586 A CN 201910650586A CN 112239435 A CN112239435 A CN 112239435A
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nadic anhydride
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李涛
万亚萌
何海霞
沙娇
张鹏帅
黄淄博
任保增
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Zhengzhou University
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Abstract

The invention relates to an exterior nadic anhydride crystal form and a preparation method thereof, belonging to the technical field of compound crystal forms. The invention provides an exo-Nadic anhydride crystal form, which comprises diffraction peaks at 13.082 degrees, 16.141 degrees, 17.533 degrees, 17.809 degrees, 18.084 degrees, 21.210 degrees, 23.521 degrees, 24.295 degrees, 24.519 degrees, 26.003 degrees, 26.934 degrees, 32.279 degrees, 32.619 degrees, 33.224 degrees, 35.690 degrees, 38.384 degrees and 51.593 degrees in a powder XRD ray diffraction pattern expressed by 2 theta degrees. The crystal form has the advantages of less impurities, high purity, good stability and easy long-term storage and transportation. The invention also provides a preparation method of the exterior nadic anhydride crystal form, and the method is simple and easy to operate, simple in equipment, easy to control conditions, low in cost and strong in operability.

Description

Exterior nadic anhydride crystal form and preparation method thereof
Technical Field
The invention relates to an exterior nadic anhydride crystal form and a preparation method thereof, belonging to the technical field of compound crystal forms.
Background
Exo-nadic anhydride (cis-5-Norbornene-exo-2,3-dicarboxylic anhydride, CAS:2746-19-2) also known as cis-5-Norbornene-exo-2,3-dicarboxylic anhydride, having the molecular formula C9H8O3. Is an important intermediate of medicines, resins and pesticides. Exo nadic anhydride is a raw material of a novel atypical antipsychotic lurasidone intermediate and is used for synthesizing exo norbornene dicarboximide. It has the advantage of low melting point compared to endo-nadic anhydride (cis-5-norborne-endo-2, 3-dicarboxylic anhydride, CAS: 129-64-6). When used for unsaturated polyester resins, the polyester resin has better air-drying property and heat resistance than tetrahydrophthalic anhydride. Is an important chemical raw material and an intermediate. However, exo-nadic anhydride has strong hygroscopicity and poor stability, and is not favorable for long-term storage and transportation of exo-nadic anhydride.
Disclosure of Invention
The first purpose of the invention is to provide an exterior nadic anhydride crystal form.
The second purpose of the invention is to provide a preparation method of the exo-nadic anhydride crystal form, which is simple, easy to operate and low in cost.
The technical scheme of the invention is as follows:
an exo-nadic anhydride crystal form comprises diffraction peaks at 2 theta-degree positions of 13.082 degrees, 13.829 degrees, 16.141 degrees, 17.533 degrees, 17.809 degrees, 18.084 degrees, 21.210 degrees, 21.919 degrees, 22.246 degrees, 23.219 degrees, 23.521 degrees, 23.953 degrees, 24.295 degrees, 24.519 degrees, 26.003 degrees, 26.934 degrees, 29.627 degrees, 32.279 degrees, 32.619 degrees, 33.224 degrees, 35.690 degrees, 36.152 degrees, 36.467 degrees, 37.950 degrees, 38.384 degrees, 39.909 degrees, 41.694 degrees, 43.018 degrees, 47.640 degrees, 49.938 degrees, 50.091 degrees, 51.593 degrees, 53.889 degrees and 59.248 degrees in a powder XRD ray diffraction pattern expressed by 2 theta degrees, and the error range of the 2 theta degrees is +/-0.1 degrees.
The exterior nadic anhydride crystal form is a new crystal form, has less impurities, high stability and easy long-term storage and transportation, and the purity of the crystal form reaches more than 98 percent.
Preferably, in the powder XRD ray diffraction pattern expressed in 2 θ °, assuming that the relative intensity of the diffraction peak corresponding to 23.521 ° at 2 θ ° is 100, the relative intensities of the diffraction peaks corresponding to 2 θ ° are respectively:
Figure BDA0002135061520000011
Figure BDA0002135061520000021
preferably, the exo-nadic anhydride crystalline form has unit cell parameters of
Figure BDA0002135061520000022
Figure BDA0002135061520000023
α=90°,β=90°,γ=90°。
A preparation method of the exo-nadic anhydride crystal form comprises the following steps: crystallizing the solution dissolved with the exo-nadic anhydride at-15-10 ℃, and separating out a precipitate, namely an exo-nadic anhydride crystal form; the solvent in the solution is one or two of A-type solvent and B-type solvent; the A-type solvent is methyl acetate, ethyl acetate, propyl acetate, acetone, dimethylformamide, N-methylpyrrolidone, 1, 4-dioxane, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether or ethylene glycol butyl ether; the B solvent is methanol, ethanol, butyl acetate or amyl acetate.
The preparation method of the exo-nadic anhydride crystal form only needs to cool the solution dissolved with exo-nadic anhydride, and the exo-nadic anhydride crystal form can be obtained through crystallization. The method is simple and easy to operate, the equipment required in the preparation process is simple, the required conditions are easy to control, the cost is low, and the operability is strong.
It should be noted that, in the process of dissolving exo-nadic anhydride in the organic solvent, the dissolution of exo-nadic anhydride can be promoted by raising the temperature.
Preferably, the exo-nadic anhydride dissolved solution is prepared by a method comprising the steps of: dissolving exo-nadic anhydride in A-type solvent at 25-50 deg.C.
Preferably, the exo-nadic anhydride dissolved solution is prepared by a method comprising the steps of: dissolving exo-nadic anhydride in A-type solvent at 25-50 deg.C, and adding ethanol. The addition of the ethanol can promote the precipitation of the exo-Nadic anhydride crystal form, is beneficial to improving the precipitation rate of the exo-Nadic anhydride crystal form, and improves the purity and the yield of the obtained exo-Nadic anhydride crystal form.
Preferably, the crystallization temperature is-15 to 5 ℃.
Preferably, the group a solvent is acetone or 1, 4-dioxane. Acetone or 1, 4-dioxane is used as an organic solvent, the exo-nadic anhydride precipitation efficiency is high, and the obtained exo-nadic anhydride has high purity and yield.
Preferably, the exo-nadic anhydride dissolved solution is prepared by a method comprising the steps of: dissolving exo-nadic anhydride in B-type solvent at 40-50 deg.C.
Preferably, the crystallization temperature reduction rate of the solution dissolved with the exo-nadic anhydride at-15 to 10 ℃ is 5 ℃/min. The cooling rate of 5 ℃/min is favorable for obtaining the exterior nadic anhydride crystal form.
Preferably, the temperature of the crystallization is-2 to 2 ℃. The temperature is-2 to 2 ℃, which is more beneficial to the crystallization.
Preferably, the crystallization time is 1.5-2.5 h. The crystallization time of 1.5-2.5h can give consideration to both crystallization efficiency and yield, if the crystallization time is too long, the efficiency is lower, and if the crystallization time is too short, the yield is lower.
Drawings
FIG. 1 is XRD ray diffraction patterns of Exo-Nadic anhydride and the crystal form of Exo-Nadic anhydride obtained in example 1, 1a is the XRD ray diffraction pattern of Exo-Nadic anhydride, and 2a is the XRD ray diffraction pattern of the crystal form of Exo-Nadic anhydride;
FIG. 2 is XRD ray diffraction patterns of Exo Nadic anhydride and the crystalline form of Exo Nadic anhydride obtained in example 2, 1b is the XRD ray diffraction pattern of Exo Nadic anhydride, and 2b is the XRD ray diffraction pattern of the crystalline form of Exo Nadic anhydride;
FIG. 3 is XRD ray diffraction patterns of Exo Nadic anhydride and the crystalline form of Exo Nadic anhydride obtained in example 3, 1c is the XRD ray diffraction pattern of Exo Nadic anhydride, and 2c is the XRD ray diffraction pattern of the crystalline form of Exo Nadic anhydride;
FIG. 4 is XRD ray diffraction patterns of Exo Nadic anhydride and the crystalline form of Exo Nadic anhydride obtained in example 4, 1d is the XRD ray diffraction pattern of Exo Nadic anhydride, and 2d is the XRD ray diffraction pattern of the crystalline form of Exo Nadic anhydride;
FIG. 5 is XRD ray diffraction patterns of Exo Nadic anhydride and the crystalline form of Exo Nadic anhydride obtained in example 5, 1e is the XRD ray diffraction pattern of Exo Nadic anhydride, and 2e is the XRD ray diffraction pattern of the crystalline form of Exo Nadic anhydride;
FIG. 6 is XRD ray diffraction patterns of Exo Nadic anhydride and the crystalline form of Exo Nadic anhydride obtained in example 6, 1f is the XRD ray diffraction pattern of Exo Nadic anhydride, and 2f is the XRD ray diffraction pattern of the crystalline form of Exo Nadic anhydride;
FIG. 7 is XRD ray diffraction patterns of Exo Nadic anhydride and the crystalline form of Exo Nadic anhydride obtained in example 7, 1g is the XRD ray diffraction pattern of Exo Nadic anhydride, and 2g is the XRD ray diffraction pattern of the crystalline form of Exo Nadic anhydride;
FIG. 8 is XRD ray diffraction patterns of Exo-Nadic anhydride and the crystalline form of Exo-Nadic anhydride obtained in example 8, 1h is the XRD ray diffraction pattern of Exo-Nadic anhydride, and 2h is the XRD ray diffraction pattern of the crystalline form of Exo-Nadic anhydride.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The specific embodiment of the preparation method of the exo-nadic anhydride crystal form of the invention is as follows:
example 1
The preparation method of the exo-nadic anhydride crystal form of the embodiment is the exo-nadic anhydride crystal form of the embodiment 1, and comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 15g of dioxane at 50 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the separated crystal to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 1, and the product has a purity of 98.94% and a primary precipitation yield of about 62.32% by gas chromatography (GC-7900).
Example 2
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 18g of N-methylpyrrolidone (NMP) at the temperature of 20 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the separated crystal to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 2, and the product is analyzed by gas chromatography (GC-7900) to have a purity of 99.12% and a primary precipitation yield of about 64.46%.
Example 3
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 12g of Dimethylformamide (DMF) at 50 ℃, adding 50mL of ethanol into the solution after the dissolution is finished, cooling the solution to 0 ℃, keeping the temperature for 2h, and performing suction filtration, alcohol washing and drying on the precipitated crystal to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 3, and the product is analyzed by gas chromatography (GC-7900) to have a purity of 99.01% and a primary precipitation yield of about 58.12%.
Example 4
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 16g of methyl acetate at 50 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the precipitated crystals to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 4, and the product is analyzed by gas chromatography (GC-7900) to have a purity of 99.13% and a primary precipitation yield of about 54.18%.
Example 5
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 20g of ethyl acetate at 50 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the precipitated crystals to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 5, and the product has a purity of 98.84% and a primary precipitation yield of about 57.82% by gas chromatography (GC-7900).
Example 6
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 30g of methanol at 50 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the separated crystal to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 6, and the product is analyzed by gas chromatography (GC-7900) to have a purity of 99.02% and a primary precipitation yield of about 51.22%.
Example 7
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 3g of exo-nadic anhydride in 50g of ethanol at 50 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the precipitated crystals to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 7, and the product is analyzed by gas chromatography (GC-7900) to have a purity of 98.92% and a primary precipitation yield of about 57.31%.
Example 8
The preparation method of the exo-nadic anhydride crystal form of the present example comprises the following steps:
stirring and dissolving 5g of exo-nadic anhydride in 15g of acetone at 50 ℃, cooling the solution to 0 ℃ after the dissolution is finished, keeping the temperature for 2 hours, and performing suction filtration, alcohol washing and drying on the precipitated crystals to obtain the exo-nadic anhydride crystal form.
The XRD test results of the exo-nadic anhydride and the crystalline form of the exo-nadic anhydride are shown in figure 8, and the product is analyzed by gas chromatography (GC-7900) to have a purity of 99.25% and a primary precipitation yield of about 67.84%.
Secondly, specific examples of the crystal form of the exo-nadic anhydride of the present invention are as follows:
example 9
The crystal form of exonadic anhydride of the present example, which has a diffraction peak at a 2 θ ° position of 13.082 °, 13.829 °, 16.141 °, 17.533 °, 17.809 °, 18.084 °, 21.210 °, 21.919 °, 22.246 °, 23.219 °, 23.521 °, 23.953 °, 24.295 °, 24.519 °, 26.003 °, 26.934 °, 29.627 °, 32.279 °, 32.619 °, 33.224 °, 35.690 °, 36.152 °, 36.467 °, 37.950 °, 38.384 °, 39.909 °, 41.694 °, 43.018 °, 47.640 °, 49.938 °, 50.091 °, 51.593 °, 53.889 °, and 59.248 °, is included in a powder XRD diffraction pattern expressed by 2 θ °.
Assuming that the relative intensity of the diffraction peak corresponding to 23.521 ° for 2 θ ° is 100, the relative intensity of the diffraction peak corresponding to each 2 θ ° is shown in table 1.
Table 12 relative intensities of diffraction peaks corresponding to θ °
Peak number Angle of diffraction Relative intensity I/I0(%) Peak number Angle of diffraction Relative intensity I/I0(%)
1 13.082° 11.829 18 32.279° 16.878
2 13.829° 5.998 19 32.619° 15.218
3 16.141° 95.21 20 33.224° 12.766
4 17.533° 23.011 21 35.690° 10.406
5 17.809° 17.576 22 36.152° 3.934
6 18.084° 52.200 23 36.467° 4.378
7 21.210° 8.262 24 37.950° 4.408
8 21.919° 2.701 25 38.384° 6.856
9 22.246° 1.582 26 39.909° 2.777
10 23.219° 15.926 27 41.694° 3.605
11 23.521° 100 28 43.018° 4.511
12 23.953° 3.899 29 47.640° 2.382
13 24.295° 9.793 30 49.938° 2.500
14 24.519° 12.143 31 50.091° 0.8535
15 26.003° 17.066 32 51.593° 3.098
16 26.934° 28.544 33 53.889° 3.575
17 29.627° 5.204 34 59.248° 1.499
Examples 10 to 16
The crystalline forms of exo-nadic anhydride of examples 10-16 correspond to the final products of examples 2-8 of the process for preparing the crystalline forms of exo-nadic anhydride, respectively.
Third, related test example
Test examples
1. 10g of exo-nadic anhydride raw material (purity 98.92%, GC-7900) sample and 10g of exo-nadic anhydride crystal form sample (purity 98.84%, GC-7900) prepared in example 5 were placed in a constant temperature and humidity test box, the temperature was controlled at 25 ℃, the humidity was controlled at 30%, and the standing time was 48 hours. And after 48h, performing gas chromatography on the purities of the external Nadic anhydride raw material and the external Nadic anhydride crystal form, wherein the purities are 97.22% and 98.58% respectively.
2. 10g of exo-nadic anhydride raw material (purity 98.92%, GC-7900) sample and 10g of exo-nadic anhydride crystal form sample (purity 98.84%, GC-7900) prepared in example 5 were placed in a constant temperature and humidity test box, the temperature was controlled at 25 ℃, the humidity was controlled at 35%, and the standing time was 48 hours. And after 48h, performing gas chromatography analysis on the purities of the external Nadic anhydride raw material and the external Nadic anhydride crystal form, wherein the purities are 97.16% and 98.51% respectively.
3. 10g of exo-nadic anhydride raw material (purity 98.92%, GC-7900) sample and 10g of exo-nadic anhydride crystal form sample (purity 98.84%, GC-7900) prepared in example 5 were placed in a constant temperature and humidity test box, the temperature was controlled at 25 ℃, the humidity was controlled at 40%, and the standing time was 48 hours. And after 48 hours, performing gas chromatography on the purities of the external Nadic anhydride raw material and the external Nadic anhydride crystal form, wherein the purities are 97.01% and 98.43% respectively.
4. 10g of exo-nadic anhydride raw material (purity 98.92%, GC-7900) sample and 10g of exo-nadic anhydride crystal form sample (purity 98.84%, GC-7900) prepared in example 5 were placed in a constant temperature and humidity test box, the temperature was controlled at 35 ℃, the humidity was controlled at 30%, and the standing time was 48 hours. And after 48 hours, performing gas chromatography on the purities of the external Nadic anhydride raw material and the external Nadic anhydride crystal form, wherein the purities are 97.12% and 98.56% respectively.
5. 10g of exo-nadic anhydride raw material (purity 98.92%, GC-7900) sample and 10g of exo-nadic anhydride crystal form sample (purity 98.84%, GC-7900) prepared in example 5 were placed in a constant temperature and humidity test box, the temperature was controlled at 45 ℃, the humidity was controlled at 30%, and the standing time was 48 hours. And after 48h, performing gas chromatography analysis on the purities of the external Nadic anhydride raw material and the external Nadic anhydride crystal form, wherein the purities are 97.26% and 98.47% respectively.
Therefore, the exo-nadic anhydride crystal form obtained in example 5 of the present invention has better stability, and after being placed under the same temperature and humidity conditions for a period of time, the exo-nadic anhydride crystal form obtained in example 5 of the present invention has higher purity compared to exo-nadic anhydride raw material. Compared with the exo-type nadic anhydride raw material, the novel crystal form has lower sensitivity to environmental temperature and humidity and is beneficial to long-term storage and transportation.

Claims (10)

1. An exo-nadic anhydride crystal form, characterized in that, in a powder XRD ray diffraction pattern expressed by 2 theta degrees, diffraction peaks are provided at 2 theta degrees positions of 13.082 degrees, 13.829 degrees, 16.141 degrees, 17.533 degrees, 17.809 degrees, 18.084 degrees, 21.210 degrees, 21.919 degrees, 22.246 degrees, 23.219 degrees, 23.521 degrees, 23.953 degrees, 24.295 degrees, 24.519 degrees, 26.003 degrees, 26.934 degrees, 29.627 degrees, 32.279 degrees, 32.619 degrees, 33.224 degrees, 35.690 degrees, 36.152 degrees, 36.467 degrees, 37.950 degrees, 38.384 degrees, 39.909 degrees, 41.694 degrees, 43.018 degrees, 47.640 degrees, 49.938 degrees, 50.091 degrees, 51.593 degrees, 53.889 degrees and 59.248 degrees, and the error range of the 2 theta degrees is +/-0.1 degrees.
2. The crystalline form of exo-nadic anhydride of claim 1 wherein, in a powder XRD pattern expressed in 2 Θ °, assuming that the relative intensity of the diffraction peak corresponding to 23.521 ° for 2 Θ ° is 100, the relative intensities of the diffraction peaks corresponding to each 2 Θ ° are respectively:
2θ° relative strength 2θ° Relative strength 13.082° 11.829 32.279° 16.878 13.829° 5.998 32.619° 15.218 16.141° 95.21 33.224° 12.766 17.533° 23.011 35.690° 10.406 17.809° 17.576 36.152° 3.934 18.084° 52.200 36.467° 4.378 21.210° 8.262 37.950° 4.408 21.919° 2.701 38.384° 6.856 22.246° 1.582 39.909° 2.777 23.219° 15.926 41.694° 3.605 23.521° 100 43.018° 4.511 23.953° 3.899 47.640° 2.382 24.295° 9.793 49.938° 2.500 24.519° 12.143 50.091° 0.8535 26.003° 17.066 51.593° 3.098 26.934° 28.544 53.889° 3.575 29.627° 5.204 59.248° 1.499
3. The crystalline form of exo-nadic anhydride of claim 1 wherein the crystalline form of exo-nadic anhydride has unit cell parameters of
Figure FDA0002135061510000021
α=90°,β=90°,γ=90°。
4. A process for the preparation of the exo-nadic anhydride crystalline form of claim 1 comprising the steps of:
crystallizing the solution dissolved with the exo-nadic anhydride at-15-10 ℃, and separating out a precipitate, namely an exo-nadic anhydride crystal form;
the solvent in the solution is one or two of A-type solvent and B-type solvent; the A-type solvent is methyl acetate, ethyl acetate, propyl acetate, acetone, dimethylformamide, N-methylpyrrolidone, 1, 4-dioxane, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether or ethylene glycol butyl ether; the B solvent is methanol, ethanol, butyl acetate or amyl acetate.
5. The method for preparing exo-nadic anhydride in crystalline form according to claim 4, wherein the solution in which exo-nadic anhydride is dissolved is prepared by a method comprising the steps of:
dissolving exo-nadic anhydride in A-type solvent at 25-50 deg.C.
6. The method for preparing exo-nadic anhydride in crystalline form according to claim 4, wherein the solution in which exo-nadic anhydride is dissolved is prepared by a method comprising the steps of:
dissolving exo-nadic anhydride in A solvent at 25-50 deg.C, and adding B solvent.
7. The method for preparing the exo-nadic anhydride crystalline form according to claim 5 or 6, wherein the crystallization temperature is-15 to 5 ℃.
8. The process for the preparation of the crystalline form of exo-nadic anhydride of claim 5 or 6 wherein the group A solvent is acetone or 1, 4-dioxane.
9. The method for preparing exo-nadic anhydride in crystalline form according to claim 4, wherein the solution in which exo-nadic anhydride is dissolved is prepared by a method comprising the steps of:
dissolving exo-nadic anhydride in B-type solvent at 40-50 deg.C.
10. The method for preparing the exo-nadic anhydride crystal form according to claim 4, wherein the crystallization of the solution dissolved with exo-nadic anhydride is performed at a temperature reduction rate of 5 ℃/min at-15 to 10 ℃.
CN201910650586.9A 2019-07-18 2019-07-18 Exterior nadic anhydride crystal form and preparation method thereof Pending CN112239435A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101481368A (en) * 2009-02-25 2009-07-15 濮阳惠成化工有限公司 Production method of 5-norbornene-2,3-anhydride
CN102127039A (en) * 2011-01-20 2011-07-20 濮阳惠成化工有限公司 Preparation method of exterior sodium dick acid anhydride

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101481368A (en) * 2009-02-25 2009-07-15 濮阳惠成化工有限公司 Production method of 5-norbornene-2,3-anhydride
CN102127039A (en) * 2011-01-20 2011-07-20 濮阳惠成化工有限公司 Preparation method of exterior sodium dick acid anhydride

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