CN113248390A - N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine and preparation method thereof - Google Patents
N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/51—Phenylenediamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
Abstract
N-phenyl-N '- (1-methyl-4 phenyl) p-phenylenediamine and a preparation method thereof, relating to the technical field of fine chemical engineering, in particular to N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine and a preparation method thereof. The method comprises the following steps: step 1, dissolving sodium alkoxide and ethyl acetoacetate in an alcohol solvent, heating, dropwise adding benzyl chloride, filtering to remove sodium chloride after the reaction is finished, and then distilling to remove the alcohol solvent; adding liquid alkali to perform reflux reaction, heating and stirring to perform decarboxylation reaction, and performing reduced pressure distillation on an organic phase to obtain 4-phenyl-2 butanone; and 2, adding the 4-phenyl-2 butanone, the catalyst and the 4-aminodiphenylamine into a high-pressure reaction kettle, heating, introducing hydrogen under stirring for carrying out hydrogenation reduction reaction, filtering to remove the catalyst after the reaction is finished, and removing the solvent methanol and water under reduced pressure. The invention has the advantages of good static or dynamic ozone erosion resistance, simple production process and low cost.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine and a preparation method thereof.
Background
Currently, widely applied p-phenylenediamine anti-aging agents at home and abroad mainly comprise 4020, 4010NA, 4030, 4050 and the like, and the general formula of the compounds is as follows:
wherein: r is aryl, R' is arylene, and Y is alkyl or cycloalkyl. These compounds are mainly used for preventing rubber from aging due to heat, ozone, oxygen, mechanical fatigue and the like, but they are easy to migrate out of vulcanized rubber, and react with ozone in the atmospheric environment to form discoloring substances on the surface of a tire or rubber product, thereby seriously affecting the appearance of the tire or rubber, particularly light-colored rubber products. Later, the high molecular weight antioxidant Durazone37 was introduced by Kepian, USA, and Irgazone997 was introduced by Pasteur. The two products have the advantages of difficult raw material acquisition, complex production process and high cost, and are rarely used in the market. Therefore, the development of a novel rubber antioxidant is urgently needed.
Disclosure of Invention
The invention aims to provide N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine and a preparation method thereof, so as to achieve the purposes of good static or dynamic ozone erosion resistance, capability of solving the problem of discoloration on the basis of keeping good ozone resistance of a sidewall rubber material, simple production process and low cost.
The invention provides N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine which is characterized in that the molecular structural formula is as follows:
the preparation method of the N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine provided by the invention is characterized by comprising the following steps of:
step 1, preparation of 4-phenyl-2 butanone:
dissolving sodium alkoxide and ethyl acetoacetate in an alcohol solvent, heating, dropwise adding benzyl chloride, filtering to remove sodium chloride after the reaction is finished, and then distilling to remove the alcohol solvent;
adding liquid alkali to perform reflux reaction, adjusting the pH value to 2-3 after the reaction is finished, heating and stirring to perform decarboxylation reaction until no carbon dioxide bubbles are generated, transferring the materials to a separating funnel after the reaction is finished, standing and layering, removing a lower-layer water phase, and washing with water;
carrying out reduced pressure distillation on the organic phase, and collecting 86-88 ℃ fractions for later use to obtain 4-phenyl-2 butanone;
step 2, preparing N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine:
and (2) adding the 4-phenyl-2 butanone obtained in the step (1), a catalyst and 4-aminodiphenylamine into a high-pressure reaction kettle, heating, introducing hydrogen under stirring for carrying out hydrogenation reduction reaction, filtering to remove the catalyst after the reaction is finished, and removing the solvent methanol and water under reduced pressure to obtain the N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine.
Further, in the step 1, the ratio of sodium alkoxide: ethyl acetoacetate: the molar ratio of benzyl chloride is 1 (1-1.2) to 1-1.2, preferably 1:1: 1.05.
Further, in the step 1, refluxing and reacting the ethyl acetoacetate sodium and benzyl chloride for 1-2 hours, preferably 1.5 hours.
Further, in the step 1, liquid alkali is added to carry out reflux reaction for 2-3 hours, preferably 2.5 hours.
Further, in the step 1, the decarboxylation reaction time is 1-2 h, preferably 1.5 h.
Further, in the step 1, the sodium alkoxide is any one or two of sodium methoxide and sodium ethoxide; the alcohol solvent is one or two of methanol and ethanol.
Further, in the step 2, the ratio of 4-aminodiphenylamine: the molar ratio of the 4-phenyl-2 butanone is 1 (1-1.2), preferably 1: 1.05.
Further, in the step 2, the temperature of the hydrogenation reduction reaction is 130-160 ℃, and preferably 140-150 ℃.
Further, in the step 2, the catalyst is one or two of a carbon catalyst and a platinum carbon catalyst, and the catalyst is washed with methanol and then added into the high-pressure reaction kettle.
The N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine and the preparation method thereof provided by the invention have the advantages that the raw materials are conventional chemicals in the market, the purchase is convenient and easy, the production process is simple, and the cost is low. The migration rate in vulcanized rubber is proper, the ozone erosion damage resistance level of the sidewall rubber material is kept in a good continuous state, and the sidewall rubber material has good static or dynamic ozone erosion resistance, so that the color change problem of the sidewall rubber material can be solved on the basis of keeping good ozone resistance. Therefore, the invention has good static or dynamic ozone erosion resistance, can solve the problem of color change of the sidewall rubber on the basis of keeping good ozone resistance, and has the advantages of simple production process and low cost.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, but the scope of the present invention is not limited thereto.
Example 1:
the preparation method of N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine comprises the following steps:
step 1, preparation of 4-phenyl-2 butanone:
dissolving sodium methoxide/sodium ethoxide and ethyl acetoacetate in alcohol solvents such as methanol/ethanol, heating, and dropwise adding benzyl chloride under stirring, wherein the ratio of sodium alkoxide: ethyl acetoacetate: the molar ratio of the benzyl chloride is 1 (1-1.2) to 1-1.2, refluxing and reacting the ethyl acetoacetate sodium and the benzyl chloride for 1-2 hours, filtering to remove the sodium chloride after the reaction is finished, and then distilling to remove alcohol solvents such as methanol/ethanol and the like;
adding liquid alkali to perform reflux reaction for 2-3 h, adjusting the pH value to 2-3 after the reaction is finished, heating and stirring to perform decarboxylation reaction for 1-2 h until no carbon dioxide bubbles are generated, transferring the material to a separating funnel after the reaction is finished, standing and layering, removing a lower-layer water phase, and washing with water;
transferring the organic phase into a gram's bottle, distilling under reduced pressure, and collecting 86-88 ℃ fractions for later use to obtain 4-phenyl-2 butanone;
step 2, preparing N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine:
washing the palladium carbon catalyst or the platinum carbon catalyst with methanol, and then mixing the palladium carbon catalyst or the platinum carbon catalyst with the 4-phenyl-2 butanone and the 4-aminodiphenylamine obtained in the step 1 according to the following ratio of 4-aminodiphenylamine: the mol ratio of the 4-phenyl-2 butanone is 1 (1-1.2), the mixture is added into a high-pressure reaction kettle and heated, hydrogen is introduced into the high-pressure reaction kettle under stirring to carry out hydrogenation reduction reaction at the reaction temperature of 130-160 ℃, the catalyst is removed by filtration after the reaction is finished, and the solvent methanol and water are removed under reduced pressure to obtain N-phenyl-N '- (1-methyl-4 phenyl) p-phenylenediamine, wherein the molecular structural formula of the N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine is as follows:
example 2:
the preparation method of N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine comprises the following steps:
step 1, preparation of 4-phenyl-2 butanone:
dissolving sodium methoxide/sodium ethoxide and ethyl acetoacetate in alcohol solvents such as methanol/ethanol, heating, and dropwise adding benzyl chloride under stirring, wherein the ratio of sodium alkoxide: ethyl acetoacetate: the molar ratio of benzyl chloride is 1:1:1.05, the reflux reaction time of the ethyl acetoacetate sodium and the benzyl chloride is 1.5h, the sodium chloride is removed by filtration after the reaction is finished, and then alcohol solvents such as methanol/ethanol and the like are removed by distillation;
adding liquid alkali to perform reflux reaction for 2.5h, adjusting the pH value to 2-3 after the reaction is finished, heating and stirring to perform decarboxylation reaction for 1.5h until no carbon dioxide bubbles are generated, transferring the material to a separating funnel after the reaction is finished, standing and layering, removing a lower-layer water phase, and washing with water;
transferring the organic phase into a gram's bottle, distilling under reduced pressure, and collecting 86-88 ℃ fractions for later use to obtain 4-phenyl-2 butanone;
step 2, preparing N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine:
washing the palladium carbon catalyst or the platinum carbon catalyst with methanol, and then mixing the palladium carbon catalyst or the platinum carbon catalyst with the 4-aminodiphenylamine and the 4-phenyl-2 butanone obtained in the step 1 according to the following ratio of 4-aminodiphenylamine: adding the 4-phenyl-2 butanone into a high-pressure reaction kettle at a molar ratio of 1:1.05, heating, introducing hydrogen under stirring to perform a hydrogenation reduction reaction at a reaction temperature of 140-150 ℃, filtering to remove the catalyst after the reaction is finished, and removing the solvent methanol and water under reduced pressure to obtain N-phenyl-N '- (1-methyl-4 phenyl) p-phenylenediamine, wherein the molecular structural formula of the N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine is as follows:
example 3:
the preparation method of N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine comprises the following steps:
step 1, preparation of 4-phenyl-2 butanone:
adding 6.81g of sodium ethoxide, 200mL of ethanol and 13g of ethyl acetoacetate into a three-necked bottle, heating, slowly dropwise adding 12.7g of benzyl chloride under stirring, carrying out reflux reaction for 1.5h after dropwise adding is finished, filtering, removing generated sodium chloride, and distilling to remove a solvent ethanol; adding 40g of 10% liquid alkali for reflux reaction for 2.5h, adjusting the pH of the material to 2 to weak acidity by using 19g of 20% hydrochloric acid after the reaction is finished, performing decarboxylation reaction for 1.5h, transferring the material to a separating funnel, standing for layering, discarding the lower water phase, and washing with water to be neutral; and transferring the organic phase into a Kirschner flask for reduced pressure distillation, and collecting 86-88 ℃ (5mmHg) fractions for later use to obtain 13.5g of 4-phenyl-2 butanone with the purity of 99.5% and the yield of 91.1%.
Step 2, preparing N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine:
weighing 12.6g of intermediate 4-phenyl-2 butanone synthesized in the step 1, washing with methanol, adding 0.63g of palladium-carbon catalyst and 14.8g of 4-aminodiphenylamine into an autoclave, replacing for three times with nitrogen, then replacing for three times with hydrogen, setting the pressure in the autoclave to be 2MPa, closing a hydrogen valve, heating to the set temperature of 150 ℃ for reaction, introducing hydrogen to 2MPa when the pressure in the autoclave is reduced to zero, repeating the steps for several times until the reaction is completed when the pressure in the autoclave is maintained at 2MPa and is not reduced any more, and the time is about 10 hours. Discharging the materials in the kettle by pressure relief, filtering the catalyst, and removing low boiling point substances to obtain 23.9g of N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine with the purity of 98% and the yield of 95.2%.
Example 4:
step 1, preparation of 4-phenyl-2 butanone:
adding 10.8g of sodium methoxide, 300mL of methanol and 26g of ethyl acetoacetate into a three-necked bottle, heating, slowly dropwise adding 26.6g of benzyl chloride under stirring, carrying out reflux reaction for 2 hours after dropwise adding is finished, filtering, removing generated sodium chloride, and distilling to remove solvent ethanol; adding 80g of 10% liquid alkali for reflux reaction for 2.5h, adjusting the pH of the material to subacidity by using 38g of 20% hydrochloric acid after the reaction is finished, performing decarboxylation reaction for 2h, transferring the material to a separating funnel, standing for layering, discarding the lower water phase, and washing with water to be neutral; the organic phase is transferred to a Kirschner flask for reduced pressure distillation, and 86-88 ℃ (5mmHg) fractions are collected for later use, so that 26.7g of the organic phase with the purity of 99.7% and the yield of 90% is obtained.
Step 2, preparing N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine:
weighing 22.3g of intermediate 4-phenyl-2 butanone synthesized in the step 1, washing with methanol, adding 1.1g of platinum-carbon catalyst and 26.1g of 4-aminodiphenylamine into an autoclave, replacing for three times with nitrogen, then replacing for three times with hydrogen, setting the pressure in the autoclave to be 2MPa, closing a hydrogen valve, heating to the set temperature of 145 ℃ for reaction, introducing hydrogen to 2MPa when the pressure in the autoclave is reduced to zero, repeating the steps for several times until the reaction is completed when the pressure in the autoclave is maintained at 2MPa and is not reduced any more, and the time is about 10 hours. The pressure was released to discharge the material in the kettle, and the catalyst was filtered off to remove low boiling point material, to obtain 42.7g of N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine with a purity of 98.5% and a yield of 96.5%.
Claims (10)
1. The N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine is characterized in that the molecular structural formula is as follows:
2. the preparation method of N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 1, comprising the following steps:
step 1, preparation of 4-phenyl-2 butanone:
dissolving sodium alkoxide and ethyl acetoacetate in an alcohol solvent, heating, dropwise adding benzyl chloride, filtering to remove sodium chloride after the reaction is finished, and then distilling to remove the alcohol solvent;
adding liquid alkali to perform reflux reaction, adjusting the pH value to 2-3 after the reaction is finished, heating and stirring to perform decarboxylation reaction until no carbon dioxide bubbles are generated, transferring the materials to a separating funnel after the reaction is finished, standing and layering, removing a lower-layer water phase, and washing with water;
carrying out reduced pressure distillation on the organic phase, and collecting 86-88 ℃ fractions for later use to obtain 4-phenyl-2 butanone;
step 2, preparing N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine:
and (2) adding the 4-phenyl-2 butanone obtained in the step (1), a catalyst and 4-aminodiphenylamine into a high-pressure reaction kettle, heating, introducing hydrogen under stirring for carrying out hydrogenation reduction reaction, filtering to remove the catalyst after the reaction is finished, and removing the solvent methanol and water under reduced pressure to obtain the N-phenyl-N' - (1-methyl-4 phenyl) p-phenylenediamine.
3. The method for preparing N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in the step 1, the molar ratio of sodium alkoxide: ethyl acetoacetate: the molar ratio of benzyl chloride is 1 (1-1.2) to 1-1.2, preferably 1:1: 1.05.
4. The preparation method of N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in the step 1, the sodium ethyl acetoacetate and benzyl chloride are refluxed and reacted for 1-2 h, preferably 1.5 h.
5. The preparation method of N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in the step 1, a liquid alkali is added to perform a reflux reaction for 2-3 h, preferably for 2.5 h.
6. The preparation method of N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in the step 1, the decarboxylation reaction time is 1-2 h, preferably 1.5 h.
7. The method for preparing N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in step 1, the sodium alkoxide is any one or two of sodium methoxide and sodium ethoxide; the alcohol solvent is one or two of methanol and ethanol.
8. The method for preparing N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in step 2, the ratio of 4-aminodiphenylamine: the molar ratio of the 4-phenyl-2 butanone is 1 (1-1.2), preferably 1: 1.05.
9. The preparation method of N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein the temperature of the hydrogenation reduction reaction in step 2 is 130-160 ℃, preferably 140-150 ℃.
10. The method for preparing N-phenyl-N' - (1-methyl-4-phenyl) p-phenylenediamine according to claim 2, wherein in the step 2, the catalyst is one or two of a carbon catalyst and a platinum carbon catalyst, and the catalyst is washed with methanol and then added into the high-pressure reaction kettle.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539074A (en) * | 2022-03-02 | 2022-05-27 | 山东阳谷华泰化工股份有限公司 | Refining method of N-alkyl-N' -phenyl-p-phenylenediamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050240058A1 (en) * | 2003-07-04 | 2005-10-27 | Nongyue Wang And Guangqiang Shi | Process for preparing 4-aminodiphenylamine |
| CN103008008A (en) * | 2011-09-22 | 2013-04-03 | 江苏圣奥化学科技有限公司 | Sulfur-containing palladium/carbon catalyst, preparation method thereof, and preparation method of p-phenylenediamine anti-aging agents |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050240058A1 (en) * | 2003-07-04 | 2005-10-27 | Nongyue Wang And Guangqiang Shi | Process for preparing 4-aminodiphenylamine |
| CN103008008A (en) * | 2011-09-22 | 2013-04-03 | 江苏圣奥化学科技有限公司 | Sulfur-containing palladium/carbon catalyst, preparation method thereof, and preparation method of p-phenylenediamine anti-aging agents |
Non-Patent Citations (1)
| Title |
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| 蒋华江等: "《基础实验II》", 31 January 2018, 浙江大学出版社, pages: 113 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539074A (en) * | 2022-03-02 | 2022-05-27 | 山东阳谷华泰化工股份有限公司 | Refining method of N-alkyl-N' -phenyl-p-phenylenediamine |
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Application publication date: 20210813 |