CN115594609A - Preparation method and application of 2-amino-5-chlorodiphenylmethanone oxime - Google Patents
Preparation method and application of 2-amino-5-chlorodiphenylmethanone oxime Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000002923 oximes Chemical class 0.000 title abstract description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZUWXHHBROGLWNH-UHFFFAOYSA-N (2-amino-5-chlorophenyl)-phenylmethanone Chemical compound NC1=CC=C(Cl)C=C1C(=O)C1=CC=CC=C1 ZUWXHHBROGLWNH-UHFFFAOYSA-N 0.000 claims abstract description 23
- GCAVNCINXJNLED-DTQAZKPQSA-N (2-amino-5-chlorophenyl)(phenyl)methanone oxime Chemical compound NC1=CC=C(Cl)C=C1\C(=N\O)C1=CC=CC=C1 GCAVNCINXJNLED-DTQAZKPQSA-N 0.000 claims abstract description 21
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
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- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 14
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- ADIMAYPTOBDMTL-UHFFFAOYSA-N oxazepam Chemical compound C12=CC(Cl)=CC=C2NC(=O)C(O)N=C1C1=CC=CC=C1 ADIMAYPTOBDMTL-UHFFFAOYSA-N 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 abstract description 59
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- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- SVUOLADPCWQTTE-UHFFFAOYSA-N 1h-1,2-benzodiazepine Chemical compound N1N=CC=CC2=CC=CC=C12 SVUOLADPCWQTTE-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method and application of 2-amino-5-chlorodiphenylmethanone oxime, which comprises the following steps: s1, sequentially adding 2-amino-5-chlorobenzophenone and anhydrous sodium acetate, stirring with ethanol, heating and dissolving; s2, cooling to 50-60 ℃, adding hydroxylamine hydrochloride twice, and respectively heating and refluxing to fully react; s3, adding water for distillation until the ethanol is not distilled out; s4, continuously adding water, stirring, filtering, washing to be neutral, and drying to obtain 2-amino-5-chloro-benzophenone oxime; according to the preparation method, the sodium acetate is added for catalytic reaction, and the hydroxylamine hydrochloride is added in batches, so that the reaction process is accelerated, the gas production reaction in the original process is avoided, the reaction is stable and rapid, the conversion rate of the substrate is improved, and the yield of the final product reaches more than 98% and the purity reaches more than 99%.
Description
Technical Field
The invention relates to the technical field of chemical pharmacy, in particular to a preparation method and application of 2-amino-5-chlorodiphenyl methanone oxime.
Background
Oxa Sha Xi (Oxazepam) is benzodiazepine
Sedative hypnotic, which is mainly used for treating anxiety, insomnia and alcohol withdrawal clinically. The oxazepam has the advantages that the oxazepam is simple in metabolic process and is less influenced by age and liver functions; the half-life period is short, and the accumulation in the body is not easy to occur; the drug is less addictive, and is especially suitable for patients with mild liver function damage and the elderly.
2-amino-5-chloro-benzophenone oxime is an important intermediate for the preparation of oxazepam for which the CAS number: 18097-52-4, molecular weight: 246.69g/mol, having the formula:
It should be noted that 2-amino-5-chlorodiphenyl ketone oxime has cis-trans isomer, two product points can be seen by TLC detection, and HPLC detection can also generate two main peaks with one large peak and one small peak, but the next reaction is not influenced.
The conventional preparation method of 2-amino-5-chlorodiphenyl ketoxime at present comprises the following steps: the preparation method comprises the steps of reacting 2-amino-5-chlorobenzophenone with hydroxylamine hydrochloride, carrying out ring opening and reduction on isoxazole to obtain a 2-amino-5-chlorobenzophenone reactant, adding liquid alkali to adjust the pH to 8, filtering while the solution is hot, adding hydroxylamine hydrochloride into filtrate to reflux for 10 hours, recovering ethanol, adding water to dilute until the ethanol concentration is 4-5%, cooling to 30 ℃, adding a saturated solution of sodium carbonate to adjust the pH to 8-9, filtering, washing a filter cake to be neutral by hot water, filtering, and drying at the temperature below 80 ℃ to obtain the 2-amino-5-chlorobenzophenone oxime.
The preparation method has long reaction time, the product generation curve is parabolic, namely the contents of the product and the substrate are not reduced basically after the reaction for a period of time, a small amount of residues still exist, the effect of continuously prolonging the reaction time is slight, the reaction is incomplete, and the total yield is low. And the treatment operation after the reaction is complex, and a large amount of bubbles are generated when a sodium carbonate solution is added, so that the material is easy to wash, therefore, the research on the preparation method of the 2-amino-5-chlorodiphenylketoxime improves the synthesis process, improves the conversion rate of the reaction, improves the quality and yield, reduces the cost, and has important significance.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of 2-amino-5-chlorobenzophenone oxime, and solves the defects of unstable product conversion, low cost and the like of the preparation method in the prior art.
Based on the technical scheme, the invention comprises the following steps:
a preparation method of 2-amino-5-chlorodiphenyl methyl ketoxime comprises the following steps:
s1, sequentially adding 2-amino-5-chlorobenzophenone and anhydrous sodium acetate, and stirring with ethanol, heating and dissolving;
s2, cooling to 50-60 ℃, adding hydroxylamine hydrochloride twice, and respectively heating and refluxing to fully react; the molar ratio of the total amount of hydroxylamine hydrochloride to 2-amino-5-chlorobenzophenone is 1: (0.5-0.7);
s3, adding water for distillation until the ethanol is not distilled out;
and S4, continuously adding water, stirring, filtering, washing to be neutral, and drying to obtain the 2-amino-5-chloro-benzophenone oxime.
As a preferred example, the ratio of the materials used in step S1 is 2-amino-5-chlorobenzophenone: anhydrous sodium acetate: ethanol =1g: (0.3-0.7) g: (2-5) ml.
As a preferable example, in step S2, the added amount of the hydroxylamine hydrochloride for the second time is 30 to 60% of the amount of the hydroxylamine hydrochloride for the first time.
As a preferred example, the ratio of the amount of water used in step S3 to 2-amino-5-chlorobenzophenone is (1.5-3) ml:1g of the total weight of the composition.
As a preferred example, the ratio of the amount of water used in step S4 to 2-amino-5-chlorobenzophenone is (3-5) ml:1g.
As a preferred embodiment, the drying process in step S4 is to pump off the washed material and dry the material in an oven at 60-70 ℃ under reduced pressure.
The invention also provides the application of the preparation method of the 2-amino-5-chlorobenzophenone oxime in preparing oxazepam, and the high-purity intermediate obtained by the preparation method can obviously improve the product quality of oxazepam, reduce the cost and further promote the industrial preparation process of oxazepam.
The invention has the beneficial effects that:
1. according to the preparation method, the sodium acetate is added for catalytic reaction, and the hydroxylamine hydrochloride is added in batches, so that the reaction process is accelerated, the gas production reaction in the original process is avoided, the reaction is stable and quick, the conversion rate of the substrate is improved, and the yield and the purity of the finally prepared 2-amino-5-chlorodiphenylmethanone oxime are obviously improved.
2. The preparation method provided by the invention is easier to purify or can basically save subsequent purification steps to obtain the purity of more than 99%, so that the production cost is effectively reduced; in addition, the reaction process has no pollution to the environment and is suitable for industrial production.
Drawings
FIG. 1 is a chromatogram of 2-amino-5-chlorobenzophenone oxime prepared in example 1 of the present invention.
FIG. 2 is a chromatogram of 2-amino-5-chlorobenzophenone oxime prepared in example 2 of this invention.
FIG. 3 is a chromatogram of 2-amino-5-chlorobenzophenone oxime prepared in example 3 according to the present invention.
FIG. 4 is a chromatogram of 2-amino-5-chlorobenzophenone oxime prepared in comparative example 1 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the field of chemical pharmacy, the drug synthesis route needs to consider not only the quality of the product, such as the purity and yield of the product, but also the reaction parameters of the intermediate process, the properties of raw materials and the reverse transformation of the reaction product which may exist in the intermediate process, so that the research on an optimized preparation process is often limited by various factors. On the other hand, although the principle of the basic chemical reaction is well known to those skilled in the art, designing a single means based on the conversion of the substrate is blind to the conversion of the product, and those skilled in the art cannot predict whether various means can solve the technical problem without grasping various means to improve the conversion rate of the product and thus the quality of the product. Therefore, unlike the prior art preparation process, the preparation process that improves the quality of the product by fusing various means in combination is regarded as an inventive process.
The invention designs a novel preparation process for solving the limitations of the preparation method of 2-amino-5-chlorodiphenyl ketone oxime in the prior art in the aspects of product conversion stability, purity, yield and the like.
In an embodiment of the present invention, a method for preparing 2-amino-5-chlorobenzophenone oxime is provided, which comprises the following steps:
s1, sequentially adding 2-amino-5-chlorobenzophenone and anhydrous sodium acetate, stirring with ethanol, heating and dissolving;
s2, cooling to 50-60 ℃, adding hydroxylamine hydrochloride twice, and respectively heating and refluxing to fully react; the molar ratio of the total amount of hydroxylamine hydrochloride to the 2-amino-5-chlorobenzophenone is 1: (0.5-0.7);
s3, adding water for distillation until the ethanol is not distilled out;
and S4, continuously adding water, stirring, filtering, washing to be neutral, and drying to obtain the 2-amino-5-chlorobenzophenone oxime.
The reaction process comprises the following steps:
according to the preparation method, the sodium acetate is added for catalytic reaction, and the hydroxylamine hydrochloride is added in batches, so that the reaction process is accelerated, the gas production reaction in the original process is avoided, the reaction is stable and quick, the conversion rate of the substrate is improved, and the yield and the purity of the finally prepared 2-amino-5-chlorodiphenylmethanone oxime are obviously improved.
In one embodiment, the ratio of the materials used in step S1 is 2-amino-5-chlorobenzophenone: anhydrous sodium acetate: ethanol =1g: (0.3-0.7) g: (2-5) ml; the anhydrous sodium acetate can catalyze the substrate product, so that the reaction speed is improved, the solubility is improved by the addition of the ethanol, and the product quality can be further improved within the range.
In one embodiment, the hydroxylamine hydrochloride is added in a second amount of 30-60% of the first amount in step S2; adding hydroxylamine hydrochloride twice helps to avoid the reaction curve from presenting a quadratic parabola, and further completely reacts the substrate which is not completely reacted, and finally the substrate can be basically completely reacted.
In one embodiment, the ratio of the amount of water used in step S3 to 2-amino-5-chlorobenzophenone is (1.5-3) ml:1g, for increasing the separation of ethanol upon evaporation.
In one embodiment, the ratio of the amount of water used in step S4 to 2-amino-5-chlorobenzophenone is (3-5) ml to 1g, for enhancing the water washing effect.
In one embodiment, the drying process in step S4 includes pumping out the washed materials, and drying in an oven at 60-70 ℃ under reduced pressure.
The principle of the invention is as follows:
sodium acetate is added in the initial stage of the reaction, hydrochloric acid groups in hydroxylamine hydrochloride are neutralized to a certain extent, so that the reaction can be carried out quickly, and on the other hand, the sodium acetate is combined with generated water to promote the forward reaction, thereby greatly shortening the reaction time. Compared with the prior art, the method has the advantages that the step of adding sodium carbonate is omitted, bubbles are avoided, and the risk of material flushing is reduced; in addition, the reaction process is adjusted by adding hydroxylamine hydrochloride twice in batches, and experiments prove that the second feeding is carried out when the first reaction rate begins to slow down, the reaction curve presents a secondary parabola, the unreacted substrate is further completely reacted, and finally the substrate can be basically completely reacted; according to the preparation method of the 2-amino-5-chlorodiphenylmethanone oxime, the purity of the prepared reaction product reaches more than 99%, other complicated purification steps can be omitted only through simple washing purification, the reaction process is pollution-free to the environment, and the preparation method is suitable for industrial production.
In another embodiment, the 2-amino-5-chlorobenzophenone oxime prepared in the above step reacts with chloroacetyl chloride, and is subjected to ring closure in acetic acid to obtain benzodiazepine-4-oxide, and then the benzodiazepine-4-oxide is deoxidized to obtain oxazepam, and the purity and yield of oxazepam can be further improved by improving the purity of the intermediate.
The following is a preferred embodiment of the present invention for verifying the technical solution and effects of the invention.
In the examples, all the raw materials are industrial and commercial raw materials, the standard is industrial grade, and the purity of the same raw material is the same.
Example 1
100g of 2-amino-5-chlorobenzophenone, 30g of anhydrous sodium acetate and 200ml of ethanol are sequentially added into a clean 1000L reaction bottle, and the mixture is stirred and heated until the mixture is completely dissolved. And (3) cooling to 50 ℃, adding 30g of hydroxylamine hydrochloride, heating, refluxing and preserving heat for reaction. After reacting for 1.5h, 10g of the residual hydroxylamine hydrochloride is added, and the reflux reaction is continued.
And (4) continuing the reaction for 1h, and after the TLC detection confirms that the reaction is complete, adding 150ml of pure water for distillation until the ethanol is not distilled out. Continuously adding 300ml of pure water, stirring for 0.5h, filtering, washing with hot water at 80 ℃ to be nearly neutral, and pumping to dry to obtain a yellow filter cake. Drying in a 65 ℃ oven under negative pressure to obtain 2-amino-5-chlorobenzophenone oxime with yellow crystal, weighing 104.8g, and HPLC purity of 99.48%, wherein the chromatogram is shown in figure 1 (comprising 72.572% and 26.904% of two cis-trans isomers).
Example 2
100g of 2-amino-5-chlorobenzophenone, 50g of anhydrous sodium acetate and 300ml of ethanol are sequentially added into a clean 1000L reaction bottle, and the mixture is stirred and heated until the mixture is completely dissolved. And (3) cooling to 55 ℃, adding 30g of hydroxylamine hydrochloride, heating, refluxing and preserving heat for reaction. After reacting for 1.5h, 15g of the residual hydroxylamine hydrochloride is added, and the reflux reaction is continued.
And (4) continuing the reaction for 1h, and after the TLC detection confirms that the reaction is complete, supplementing 200ml of pure water for distillation until the ethanol is not distilled out. Continuously adding 400ml of pure water, stirring for 0.5h, filtering, washing with hot water at 80 ℃ until the mixture is nearly neutral, and draining to obtain a yellow filter cake. Drying in a 70 ℃ oven under negative pressure to obtain 2-amino-5-chlorobenzophenone oxime with yellow crystals, weighing 104.5g, and having HPLC purity of 99.47%, and the chromatogram is shown in figure 2 (comprising 72.571% and 26.903% of two cis-trans isomers).
Example 3
100g of 2-amino-5-chlorobenzophenone, 70g of anhydrous sodium acetate and 500ml of ethanol are sequentially added into a clean 1000L reaction bottle, and the mixture is stirred and heated until the mixture is completely dissolved. And (3) cooling to 60 ℃, adding 35g of hydroxylamine hydrochloride, heating, refluxing and carrying out heat preservation reaction. After reacting for 1.5h, 25g of the residual hydroxylamine hydrochloride is added, and the reflux reaction is continued.
And (4) continuing the reaction for 1h, and after the TLC detection confirms that the reaction is complete, adding 300ml of pure water for distillation until the ethanol is not distilled out. And continuously adding 500ml of pure water, stirring for 0.5h, filtering, washing with hot water at 80 ℃ to be nearly neutral, and draining to obtain a yellow filter cake. Drying in a 60 ℃ oven under negative pressure to obtain 2-amino-5-chlorobenzophenone oxime with yellow crystals, weighing 103.5g, and having HPLC purity of 99.47%, and the chromatogram is shown in FIG. 3 (comprising 72.576% and 26.898% of two cis-trans isomers).
Comparative example 1
100g of 2-amino-5-chlorobenzophenone, 50g of hydroxylamine hydrochloride and 400ml of ethanol are added into a clean 1000L reaction bottle, stirred and heated to reflux, and the reflux reaction is carried out for 10 hours. Distilling and concentrating until the ethanol does not drip any more, adding 200ml of pure water, cooling to room temperature, starting to slowly drip sodium carbonate aqueous solution (sodium carbonate: water = 42 g: 420 ml), generating a large amount of carbon dioxide bubbles in the dripping process, and dripping until the pH value is 8-9. Filtering, washing with 60 ℃ hot water to be nearly neutral, draining, drying in a 60-70 ℃ oven to obtain 2-amino-5-chlorobenzophenone oxime with yellow crystal, weighing 102.3g, carrying out HPLC (high performance liquid chromatography) with the purity of 93.55% (comprising 69.727% and 23.823% of two cis-trans isomers), carrying out TLC analysis, wherein a small amount of shade of the raw material 2-amino-5-chlorobenzophenone is still remained, and carrying out HPLC (high performance liquid chromatography) to detect the content of 5.439%, wherein the chromatogram is shown in figure 4.
Comparative example 2
The preparation method provided by patent document CN112574064A example 1 is adopted to prepare 2-amino-5-chlorobenzophenone oxime, sodium hydroxide is added in the preparation process, activated carbon is added for reflux reaction for 3 hours, solid is separated out after ethanol is evaporated, acid is added for neutralization, water washing and drying are carried out to obtain the product, the yield is 98.1%, and the HPLC purity is 99.3%.
Comparative example 3
The same preparation process and material ratio as in example 1 were used, except that hydroxylamine hydrochloride was added at one time and reacted, that when the reaction time was 2.5h, TLC detection did not complete reaction, and when the reaction time was 4h, 101.2g of yellow solid was obtained, and hplc purity 94.23%.
Comparative example 4
The same preparation process and material ratio as in example 1 were used, except that anhydrous sodium acetate was not added, TLC detection did not complete reaction when the reaction time was 2.5h, and the product was separated when the reaction time was 4h to give 100.3g of yellow solid with hplc purity 93.52%.
It can be seen from the above examples 1-3 that when the solution is used to add anhydrous sodium acetate and add hydroxylamine hydrochloride twice, the desired conversion rate and purity can be obtained only by simple filtration, washing and purification operations, and the reaction process only requires 2.5h, and the intermediate process only requires ethanol to be distilled to obtain solid precipitate, so that the operation is simple, the preparation efficiency is high, and the method is significantly improved compared with the conventional technology (comparative example 1). In comparative example 2, a reflux reaction mode of sodium hydroxide and activated carbon is adopted, on one hand, excessive alkali is introduced to increase the subsequent acid washing step, on the other hand, the reaction time is 3 hours, the reaction time is relatively long, and the efficiency is lower compared with the scheme. In principle, the comparative example 2 uses the sodium hydroxide only to have the function of reacting with hydroxylamine hydrochloride, and in addition, the addition of hydroxylamine hydrochloride in batches, which is not controlled, objectively still has the property of a transformation quadratic curve, resulting in a prolonged reaction time. Comparative example 3 did not employ the addition of hydroxylamine hydrochloride in portions, and comparative example 4 did not add anhydrous sodium acetate, the reaction time was significantly prolonged, and the purity and conversion of the obtained product were both reduced.
Finally, although the present invention has been described in detail by way of general description and specific examples, the above examples are only intended to illustrate the technical solutions of the present invention, but not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of 2-amino-5-chlorodiphenyl methanone oxime is characterized by comprising the following steps:
s1, sequentially adding 2-amino-5-chlorobenzophenone and anhydrous sodium acetate, and stirring with ethanol, heating and dissolving;
s2, cooling to 50-60 ℃, adding hydroxylamine hydrochloride twice, and respectively heating and refluxing to fully react; the molar ratio of the total amount of hydroxylamine hydrochloride to 2-amino-5-chlorobenzophenone is 1: (0.5-0.7);
s3, adding water for distillation until the ethanol is not distilled out;
and S4, continuously adding water, stirring, filtering, washing to be neutral, and drying to obtain the 2-amino-5-chlorodiphenyl methanone oxime.
2. The method according to claim 1, wherein the ratio of the materials used in step S1 is 2-amino-5-chlorobenzophenone: anhydrous sodium acetate: ethanol =1g: (0.3-0.7) g: (2-5) ml.
3. The method according to claim 1, wherein in the step S2, the hydroxylamine hydrochloride is added in an amount of 30 to 60% in the second time based on the first time.
4. The process according to claim 1, wherein the ratio of the amount of water used in step S3 to 2-amino-5-chlorobenzophenone is (1.5 to 3) ml:1g of the total weight of the composition.
5. The method according to claim 1, wherein the ratio of the amount of water used in step S4 to 2-amino-5-chlorobenzophenone is (3-5) ml:1g.
6. The method according to claim 1, wherein the drying in step S4 is performed by pumping the washed material and drying the material in an oven at 60-70 ℃ under reduced pressure.
7. Use of the process for the preparation of 2-amino-5-chlorobenzophenone oxime according to any one of claims 1 to 6 in the preparation of oxazepam.
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| CN111848549A (en) * | 2019-04-29 | 2020-10-30 | 苏州大学 | Aryl oxime compound and preparation and application thereof |
| CN112500311A (en) * | 2020-12-02 | 2021-03-16 | 河南普美济华医药科技有限公司 | Preparation process of O-3-chloro-2-propenyl hydroxylamine free alkali |
| CN112574064A (en) * | 2021-01-15 | 2021-03-30 | 北京益民药业有限公司 | Preparation method of 2-amino-5 chloro-benzophenone oxime |
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| CN114836098A (en) * | 2022-05-25 | 2022-08-02 | 东营峻茂石油科技有限公司 | Preparation method of anticorrosive paint for offshore petroleum pipeline |
| CN115109003A (en) * | 2022-06-30 | 2022-09-27 | 华中药业股份有限公司 | Preparation method of chlordiazepoxide |
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| CN111848549A (en) * | 2019-04-29 | 2020-10-30 | 苏州大学 | Aryl oxime compound and preparation and application thereof |
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| KR20220097781A (en) * | 2020-12-31 | 2022-07-08 | (주)켐이 | Penothiazine compound, photopolymerization initiator containing the same, and composition for electronic materials containing the same |
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| CN114836098A (en) * | 2022-05-25 | 2022-08-02 | 东营峻茂石油科技有限公司 | Preparation method of anticorrosive paint for offshore petroleum pipeline |
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