CN112239435A - Exterior nadic anhydride crystal form and preparation method thereof - Google Patents
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Abstract
本发明涉及一种外型纳迪克酸酐晶型及其制备方法，属于化合物晶型技术领域。本发明提供了一种外型纳迪克酸酐晶型，在以2θ°表示的粉末XRD射线衍射图谱中，包括在13.082°、16.141°、17.533°、17.809°、18.084°、21.210°、23.521°、24.295°、24.519°、26.003°、26.934°、32.279°、32.619°、33.224°、35.690°、38.384°、51.593°具有衍射峰。该晶型杂质少，纯度高，稳定性好，易于长期保存和运输。本发明还提供了外型纳迪克酸酐晶型的制备方法，该方法简单易操作，设备简单，条件易控，成本低，可操作性强。
The invention relates to an external nadic acid anhydride crystal form and a preparation method thereof, belonging to the technical field of compound crystal forms. The invention provides an external nadic acid anhydride crystal form, which in the powder XRD ray diffraction pattern represented by 2θ°, includes 13.082°, 16.141°, 17.533°, 17.809°, 18.084°, 21.210°, 23.521°, 24.295°, 24.519°, 26.003°, 26.934°, 32.279°, 32.619°, 33.224°, 35.690°, 38.384°, 51.593° have diffraction peaks. The crystal form has few impurities, high purity, good stability, and is easy to store and transport for a long time. The invention also provides a method for preparing an external nadic acid anhydride crystal form, which is simple and easy to operate, simple in equipment, easy to control in conditions, low in cost and strong in operability.
Description
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:
preferably, the exo-nadic anhydride crystalline form has unit cell parameters of
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:
。
3. The crystalline form of exo-nadic anhydride of claim 1 wherein the crystalline form of exo-nadic anhydride has unit cell parameters of
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 ℃.
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|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| Title |
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| GIUSEPPE FILIPPINI ET AL: "The Structure of Bicyclo[2,2,1]hept-5-ene-2,3-exo-dicarboxylic Anhydride", 《ACTA CRYST.》 * |
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