CN104130228A - Method for preparing high-purity cis-5-norbornene-exo-2,3-dicarboxylic anhydride through microwave reaction - Google Patents
Method for preparing high-purity cis-5-norbornene-exo-2,3-dicarboxylic anhydride through microwave reaction Download PDFInfo
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- CN104130228A CN104130228A CN201410329516.0A CN201410329516A CN104130228A CN 104130228 A CN104130228 A CN 104130228A CN 201410329516 A CN201410329516 A CN 201410329516A CN 104130228 A CN104130228 A CN 104130228A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 29
- KNDQHSIWLOJIGP-RNGGSSJXSA-N (3ar,4r,7s,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound C1[C@@H]2[C@@H]3C(=O)OC(=O)[C@@H]3[C@H]1C=C2 KNDQHSIWLOJIGP-RNGGSSJXSA-N 0.000 title abstract 3
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000017105 transposition Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PQXKDMSYBGKCJA-CVTJIBDQSA-N lurasidone Chemical compound C1=CC=C2C(N3CCN(CC3)C[C@@H]3CCCC[C@H]3CN3C(=O)[C@@H]4[C@H]5CC[C@H](C5)[C@@H]4C3=O)=NSC2=C1 PQXKDMSYBGKCJA-CVTJIBDQSA-N 0.000 description 1
- 229960001432 lurasidone Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Furan Compounds (AREA)
Abstract
The invention relates to a method for preparing high-purity cis-5-norbornene-exo-2,3-dicarboxylic anhydride through microwave reaction. According to the invention, cis-5-norbornene-endo-2,3-dicarboxylic anhydride is well mixed with a solvent, and the mixture is placed into a mirowave reaction kettle; temperature and time are set, and a microwave reaction is carried out; oil bath and stirring are carried out, such that crystallization is allowed; the obtained material is cooled to room temperature, and is filtered and dried, such that the product cis-5-norbornene-exo-2,3-dicarboxylic anhydride is obtained. With the method, product yield is up to 80% and purity is up to 98%. Compared to prior arts, the method provided by the invention does not pollute the environment, has clean process, and is environment-friendly. The method is suitable for large-scale productions.
Description
Technical field
The present invention relates to a kind of microwave reaction and prepare the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride.
Background technology
Cis-5-norbornylene-external form-2,3-dicarboxylic anhydride is a kind of important raw material of synthetic antidepressant drug Lurasidone, its structural formula is:
。
In patent application publication number JP2011184340A, disclose with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, by reaching 200 ℃ of heating transpositions of 6 hours high temperature, make, its weak point is: the transposition yield of products therefrom is lower, be only 35%, and because raw material transposition does not thoroughly easily produce the oxide impurity of 12% content, need to add antioxidant addn to reduce oxide impurity, such additive toxicity more greatly and more expensive, is unfavorable for scale operation.
In patent application publication number CN101362751A, disclose: maleimide is reacted with cyclopentadiene and obtain cis-5-norbornylene-external form-2,3-dicarboxylic anhydride, the weak point of the method is: complex operation and product contain cis-5-norbornylene-external form-2,3-dicarboxylic anhydride, cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride and oxide impurity, the product of isolating single configuration is more difficult, is difficult to scale operation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of microwave reaction that utilizes by cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is prepared the cis-5-of high purity norbornylene-external form-2, the method of 3-dicarboxylic anhydride, the method reaction process is simple, and the reaction times is short, without adding additive; By product is few, makes the yield of product up to 80%, and purity, up to 98%, compared with prior art, is a kind of free from environmental pollution, and technique is clean, and environmental friendliness is convenient to the method for large-scale production.
Concrete technical scheme of the present invention is:
A kind of microwave reaction is prepared the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride, and with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, concrete steps are as follows:
(1) by cis-5-norbornylene-Nei type-2 in reactor, 3-dicarboxylic anhydride and stirring solvent are even, put into microwave reaction kettle, design temperature and time, carry out microwave reaction;
(2) after having reacted, by the reactor cooling of step (1), be placed in oil bath stirring and carry out crystallization, be cooled to room temperature, filter, dry, obtain the cis-5-of product white solid norbornylene-external form-2,3-dicarboxylic anhydride.
Solvent described in step (1) is a kind of in toluene or dimethylbenzene or butylacetate or dioxane, is preferably toluene.The effect of described solvent is by white solid cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride dissolves and is dispersed in solvent, under the effect of microwave by cis-5-norbornylene-Nei type-2, the transposition of 3-dicarboxylic anhydride is cis-5-norbornylene-external form-2,3-dicarboxylic anhydride.Why select this several solvents, on the one hand because can dissolve better cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride, and in solvent and under microwave action by cis-5-norbornylene-Nei type-2, the transposition of 3-dicarboxylic anhydride is cis-5-norbornylene-external form-2,3-dicarboxylic anhydride; Because these several solvents, as high boiling solvent, play the effect of insulation when oil bath is stirred in step (2) on the other hand.Why be preferably toluene, when being because selecting toluene as solvent, the cis-5-of its product norbornylene-external form-2, the yield of 3-dicarboxylic anhydride is the highest.
Cis-5-norbornylene-Nei type-2 described in step (1), the quality of 3-dicarboxylic anhydride is 1:1-8 g/mL with the ratio of the volume of solvent, if the too small product purity of ratio is low, if the excessive product yield of ratio is low, is preferably 1:3 g/mL.
Described in step (1), microwave reaction kettle is existing installation, purchases in Guangzhou Wan Cheng microwave equipment company limited.
The temperature that microwave reaction described in step (1) is set is 180 ℃-240 ℃, and the time of setting is 5-10min, is preferably: temperature is 200 ℃, and the time is 8min.If the time is too short, not exclusively, if overlong time, oxidation impurities can increase, and affects yield and the purity of product in reaction.
Described in step (1), in microwave reaction, micro-wave frequency is 0.3GHz-300GHz, the hertzian wave that wavelength is 100cm-1mm; Be preferably 100GHz-200GHz.The microwave of this frequency or wavelength is positioned between the ir radiation (light wave) and radiowave of electromagnetic spectrum, when microwave oven magnetic control pass pipe gives off the microwave of very high frequency, microwave energy field constantly exchanges positive-negative polarity with the speed of 24.5 hundred million times per second, there is great change in molecular motion, molecular arrangement is got up and high-speed motion, collide with each other, rub, push, make kinetic energy-micro-wave energy be converted into heat energy.Because this kind of energy is from cis-5-norbornylene-Nei type-2 that are dissolved in solvent, in 3-dicarboxylic anhydride, itself does not need hot media, and by convection current, its raw material self temperature just can not rise very soon, thereby can be comprehensively, fast, heat equably.That is to say that microwave heating is endogenous thermal source, microwave heating has selectivity.
Due to the type of heating of microwave uniqueness, in reaction, can greatly improve chemical reaction velocity, reduced the activation energy of reaction, changed reaction kinetics.Utilize type of heating and the microwave of microwave uniqueness to have " non-thermal effect " to chemical reaction, can add the carrying out of fast response, demonstrate its be swift in response, completely, high, the good selective of productive rate.
It is 90 ℃-120 ℃ that needed temperature is stirred in the middle oil bath of step (2), and required time is 30min.In order to make purification effect better, be chosen under the oil bath of 90 ℃-120 ℃ and be incubated; If the time is excessive or too small, all can reduce the purity of product.
Described in step (2), dry as forced air drying and dry, temperature required is 50 ℃.
The present inventor on this basis, gives the cis-5-of products obtained therefrom norbornylene-external form-2, and the testing conditions of 3-dicarboxylic anhydride is as follows:
Detector: determination of uv absorption meter; Wavelength: 232nm; Analytical column: Phenomenex Hydro-RP 80A-C18, internal diameter: 4.6mm, length: 250mm; Column temperature: 30 ℃; Moving phase: acetonitrile: water=30:70(V:V); Flow velocity: 1.0mL/min.Detect with this understanding cis-5-norbornylene-external form-2 in products obtained therefrom, the content of 3-dicarboxylic anhydride.
Employing microwave reaction of the present invention is prepared cis-5-norbornylene-external form-2,3-dicarboxylic anhydride, and described method reaction process is simple, and the reaction times is short, without adding additive; By product is few, makes the yield of product up to 80%, and purity, up to 98%, compared with prior art, is a kind of free from environmental pollution, and technique is clean, and environmental friendliness is convenient to the method for large-scale production.
Embodiment
The cis-5-of products obtained therefrom norbornylene-external form-2, the testing conditions of 3-dicarboxylic anhydride is:
Detector: determination of uv absorption meter
Wavelength: 232nm
Analytical column: Phenomenex Hydro-RP 80A-C18, internal diameter: 4.6mm, length: 250mm
Column temperature: 30 ℃
Moving phase: acetonitrile: water=30:70(V:V)
Flow velocity: 1.0mL/min
Content in the present invention all refers to massfraction.
Embodiment 1
A kind of microwave reaction is prepared the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride, and with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, concrete steps are as follows:
(1), in 1L reaction flask, by 100g cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride and 100mL dimethylbenzene stir, and put into microwave reaction kettle, are warming up to 180 ℃, carry out microwave reaction 5 minutes in frequency under the microwave that is 0.3-10GHz;
(2) reacted, by the reactor cooling to 90 ℃ of step (1), be placed in oil bath and stir and carry out crystallization in 30 minutes, be cooled to room temperature, filtered, dried, obtained the cis-5-of product norbornylene-external form-2,3-dicarboxylic anhydride 70.2g; Yield: 70.2%; Purity: 98.6%; Oxide impurity content: 0.05%.
Embodiment 2
A kind of microwave reaction is prepared the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride, and with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, concrete steps are as follows:
(1), in 1L reaction flask, by 200g cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride and 800mL butylacetate stir, and put into microwave reaction kettle, are warming up to 220 ℃, carry out microwave reaction 6 minutes in frequency under the microwave that is 10-100GHz;
(2) reacted, by the reactor cooling to 100 ℃ of step (1), be placed in oil bath and stir and carry out crystallization in 30 minutes, be cooled to room temperature, filtered, dried, obtained the cis-5-of product norbornylene-external form-2,3-dicarboxylic anhydride 145.2g; Yield: 72.6%; Purity: 98.2%; Oxide impurity content: 0.06%.
Embodiment 3
A kind of microwave reaction is prepared the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride, and with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, concrete steps are as follows:
(1), in 1L reaction flask, by 200g cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride and 600mL toluene stir, and put into microwave reaction kettle, are warming up to 200 ℃, carry out microwave reaction 8 minutes in frequency under the microwave that is 100-200GHz;
(2) reacted, by the reactor cooling to 110 ℃ of step (1), be placed in oil bath and stir and carry out crystallization in 30 minutes, be cooled to room temperature, filtered, dried, obtained the cis-5-of product norbornylene-external form-2,3-dicarboxylic anhydride 160.2g; Yield: 80.1%; Purity: 98.2%; Oxide impurity content: 0.06%.
Embodiment 4
A kind of microwave reaction is prepared the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride, and with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, concrete steps are as follows:
(1), in 1L reaction flask, by 100g cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride and 800mL dioxane stir, and put into microwave reaction kettle, are warming up to 240 ℃, carry out microwave reaction 10 minutes in frequency under the microwave that is 200-300GHz;
(2) reacted, by the reactor cooling to 120 ℃ of step (1), be placed in oil bath and stir and carry out crystallization in 30 minutes, be cooled to room temperature, filtered, dried, obtained the cis-5-of product norbornylene-external form-2,3-dicarboxylic anhydride 75.7g; Yield: 75.7%; Purity: 98.2%; Oxide impurity content: 0.06%.
Claims (8)
1. a microwave reaction is prepared the cis-5-of high purity norbornylene-external form-2, the method for 3-dicarboxylic anhydride, and with cis-5-norbornylene-Nei type-2,3-dicarboxylic anhydride is raw material, it is characterized in that: concrete steps are as follows:
(1) by cis-5-norbornylene-Nei type-2 in reactor, 3-dicarboxylic anhydride and stirring solvent are even, put into microwave reaction kettle, design temperature and time, carry out microwave reaction;
(2) after having reacted, by the reactor cooling of step (1), be placed in oil bath stirring and carry out crystallization, be cooled to room temperature, filter, dry, obtain the cis-5-of product white solid norbornylene-external form-2,3-dicarboxylic anhydride;
Solvent described in step (1) is a kind of in toluene or dimethylbenzene or butylacetate or dioxane;
Cis-5-norbornylene-Nei type-2 described in step (1), the quality of 3-dicarboxylic anhydride is 1:1-8 g/mL with the ratio of the volume of solvent.
2. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, and the method for 3-dicarboxylic anhydride, is characterized in that: described in step (1), solvent is toluene.
3. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, the method of 3-dicarboxylic anhydride, it is characterized in that: cis-5-norbornylene-Nei type-2 described in step (1), the quality of 3-dicarboxylic anhydride is 1:3 g/mL with the ratio of the volume of solvent.
4. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, and the method for 3-dicarboxylic anhydride, is characterized in that: the temperature that microwave reaction described in step (1) is set is 180 ℃-240 ℃, and the time of setting is 5-10min.
5. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, and the method for 3-dicarboxylic anhydride, is characterized in that: the temperature that microwave reaction described in step (1) is set is 200 ℃, and the time of setting is 8min.
6. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, and the method for 3-dicarboxylic anhydride, is characterized in that: described in step (1), in microwave reaction, micro-wave frequency is 0.3GHz-300GHz.
7. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, and the method for 3-dicarboxylic anhydride, is characterized in that: described in step (1), in microwave reaction, micro-wave frequency is 100GHz-200GHz.
8. microwave reaction according to claim 1 is prepared the cis-5-of high purity norbornylene-external form-2, and the method for 3-dicarboxylic anhydride, is characterized in that: it is 90 ℃-120 ℃ that needed temperature is stirred in the middle oil bath of step (2), and required time is 30min.
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| CN201410329516.0A CN104130228B (en) | 2014-07-11 | 2014-07-11 | A kind of microwave reaction is prepared the cis-5-of high-purity ENB-external form-2, the method for 3-dicarboxylic anhydride |
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| CN201410329516.0A CN104130228B (en) | 2014-07-11 | 2014-07-11 | A kind of microwave reaction is prepared the cis-5-of high-purity ENB-external form-2, the method for 3-dicarboxylic anhydride |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126738A (en) * | 1976-02-17 | 1978-11-21 | Borg-Warner Corporation | Copolymers of 5-norbornene 2,3-dicarboxylic anhydride and maleic anhydride |
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2014
- 2014-07-11 CN CN201410329516.0A patent/CN104130228B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126738A (en) * | 1976-02-17 | 1978-11-21 | Borg-Warner Corporation | Copolymers of 5-norbornene 2,3-dicarboxylic anhydride and maleic anhydride |
Non-Patent Citations (1)
| Title |
|---|
| 赵忠奎等: "《高效反应技术与绿色化学》", 31 July 2012, 中国石化出版社 * |
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Denomination of invention: A method for preparing high purity cis-5-norbornene-external-2,3-dicarboxylic anhydride by microwave reaction Effective date of registration: 20211230 Granted publication date: 20160511 Pledgee: Industrial Bank Co.,Ltd. Tai'an Branch Pledgor: JEWIM PHARMACEUTICAL (SHANDONG) CO.,LTD. Registration number: Y2021980016939 |
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Denomination of invention: A method for preparing high-purity cis-5-norbornene-exo-2,3-dicarboxylic anhydride by microwave reaction Effective date of registration: 20230210 Granted publication date: 20160511 Pledgee: Industrial Bank Co.,Ltd. Tai'an Branch Pledgor: JEWIM PHARMACEUTICAL (SHANDONG) CO.,LTD. Registration number: Y2023980032425 |
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Denomination of invention: A Method for Preparation of High Purity Cis-5-Norbornene-Exo-2,3-dicarboxylic Anhydride by Microwave Reaction Granted publication date: 20160511 Pledgee: Industrial Bank Co.,Ltd. Tai'an Branch Pledgor: JEWIM PHARMACEUTICAL (SHANDONG) CO.,LTD. Registration number: Y2024980004981 |
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