CN108203414B - Process for preparing triazine derivatives - Google Patents
Process for preparing triazine derivativesInfo
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- CN108203414B CN108203414B CN201611188018.4A CN201611188018A CN108203414B CN 108203414 B CN108203414 B CN 108203414B CN 201611188018 A CN201611188018 A CN 201611188018A CN 108203414 B CN108203414 B CN 108203414B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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Abstract
The invention provides a preparation method of a triazine derivative, which comprises the following steps of carrying out substitution reaction on paranitroaniline and a compound A to form an intermediate B, and carrying out hydrogenation reduction hydrocarbylation reaction on the intermediate B and the compound C to obtain the triazine derivative. The method provided by the invention adopts a two-step method of substitution and hydrogenation reduction hydrocarbonylation to prepare the triazine derivative, so that the method not only has higher product yield, but also greatly shortens the process flow. Meanwhile, the method effectively avoids the generation of the bi-substituted p-phenylenediamine by-product in the traditional process, so that the separation of the product becomes easy, the cost is greatly reduced, the pollution is avoided, the product quality is high, and the industrialization is easy to realize.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a triazine derivative.
Background
Triazine derivatives having the following structure are an important class of substances (R groups are alkyl groups of C 3～C10). Which is a class of compounds formed by the substitution of a connecting N-substituted p-phenylenediamine at the 1,3,5 carbon atoms of a triazine.
For example, 2,4, 6-tris- (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine (TMPPD for short) is an important one of triazine derivatives, and is a novel rubber antioxidant, also known as TAPDT or DURAZONE37. The antioxidant TMPPD is a novel green pollution-free antioxidant, is mainly used for protecting unsaturated elastomer and elastomer from aging and cracking caused by oxygen and ozone, has super-strong static ozone protection function and excellent dynamic aging resistance function, and is not easy to migrate in the use process.
Regarding the preparation method of TMPPD compounds, all of U.S. Pat. Nos. 4794134, 4794135, 4972010, 5047530 and 5120844 generally report that trichlorotriazines (cyanuric chloride) and N- (1, 4-dimethylpentyl) -p-phenylenediamine (7 PD for short) are used as raw materials, and amino nitrogen atoms are used for replacing chlorine atoms in the trichlorotriazines to generate a target product TMPPD. Among them, N- (1, 4-dimethylpentyl) -p-phenylenediamine (abbreviated as 7 PD) is usually prepared by using p-phenylenediamine or aniline or p-nitrochlorobenzene and 5-methyl-2-hexanone as starting materials, but the side reaction N, N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine (77 PD) is inevitably formed in the synthesis process, which brings much trouble for the subsequent product separation, and the synthesis route is long and the overall yield is not high.
Similar to the rubber antioxidant TMPPD, the existing synthesis process of the triazine derivative has the defects of low yield and long route.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a triazine derivative, which aims to solve the problems of low yield and long route in the synthesis of the triazine derivative in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for producing a triazine derivative, wherein the triazine derivative has the following structural formula:
The preparation method comprises the following steps of carrying out substitution reaction on paranitroaniline and a compound A to form an intermediate B, carrying out hydrogenation reduction hydrocarbylation reaction on the intermediate B and a compound C to obtain a triazine derivative, wherein the compound A has a structure shown in a formula I, the intermediate B has a structure shown in a formula II, and the compound C has a structure shown in a formula III, wherein the formulas I, II and III are as follows:
wherein R is C 3～C10 alkyl, X is halogen atom.
Further, in the step of substitution reaction, the molar ratio of the paranitroaniline to the compound A is 3-10:1, preferably 3-6:1, and more preferably 3-4:1.
Further, the substitution reaction is carried out in an organic solvent selected from one or more of 1, 4-dioxane, N-dimethylformamide, N-hexane, tetrahydrofuran, toluene and isobutane, preferably the water content in the organic solvent is 0 to 5wt%, more preferably 0 to 1wt%, still more preferably 0 to 0.5wt%.
Further, in the step of substitution reaction, the reaction is carried out at the temperature of 0-5 ℃ and then the temperature is raised to the reflux state for reaction.
Further, in the step of hydrogenation reduction hydrocarbylation reaction, the molar ratio of the intermediate B to the compound C is 1:10-60, preferably 1:20-60.
In the hydrogenation reduction hydrocarbonylation reaction step, hydrogen is used as a reducing agent, and the reaction is carried out under the action of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises an active component which is one or more of platinum, palladium, nickel and copper.
Further, the hydrogenation catalyst is one or more of Pt/C catalyst, pd/C catalyst, skeletal nickel catalyst, supported nickel catalyst, amorphous nickel catalyst, cuO/ZnO/Al 2O3 catalyst and CuO/CrO/Al 2O3 catalyst.
Further, when the hydrogenation catalyst is a Pt/C catalyst, the dosage of the hydrogenation catalyst is 2-10% of the weight of the paranitroaniline, when the hydrogenation catalyst is a Pd/C catalyst, the dosage of the hydrogenation catalyst is 3-10% of the weight of the paranitroaniline, when the hydrogenation catalyst is one or more of a skeletal nickel catalyst, a supported nickel catalyst and an amorphous nickel catalyst, the dosage of the hydrogenation catalyst is 10-20% of the weight of the paranitroaniline, and when the hydrogenation catalyst is a CuO/ZnO/Al 2O3 catalyst and/or a CuO/CrO/Al 2O3 catalyst, the dosage of the hydrogenation catalyst is 30-40% of the weight of the paranitroaniline.
Further, in the step of hydrogenation reduction hydrocarbylation reaction, the reaction temperature is 80-200 ℃, preferably 80-160 ℃, and the reaction pressure is 1-10 MPa, preferably 1-6 MPa, and more preferably 1-3 MPa.
Further, after the step of hydrogenation reduction hydrocarbonylation reaction, the method further comprises the steps of filtering a reaction liquid after hydrogenation reduction hydrocarbonylation reaction to obtain a filtrate, and distilling the filtrate to obtain the triazine derivative.
By adopting the technical scheme, the amino group in the paranitroaniline can be used for replacing X in the compound A by utilizing the substitution reaction of the paranitroaniline and the compound A, so that trisubstituted triazine, namely an intermediate B, can be formed. And then, carrying out hydrogenation reduction hydrocarbonylation reaction on the compound C ketone compound and the intermediate B to complete hydrogenation reduction and R group substitution of the nitro group of the intermediate B, thereby obtaining the target product triazine derivative. The triazine derivative prepared by the two-step method of substitution and hydrogenation reduction provided by the invention not only has higher product yield, but also greatly shortens the process flow. Meanwhile, the method effectively avoids the generation of the bi-substituted p-phenylenediamine by-product in the traditional process, so that the separation of the product becomes easy, the cost is greatly reduced, the pollution is avoided, the product quality is high, and the industrialization is easy to realize.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As described in the background section, the existing synthesis process of triazine derivatives has the problems of low yield and long route. In order to solve the problem, the present inventors have provided a method for preparing a triazine derivative having the following structural formula:
The preparation method comprises the following steps of carrying out substitution reaction on paranitroaniline and a compound A to form an intermediate B, carrying out hydrogenation reduction hydrocarbylation reaction on the intermediate B and a compound C to obtain a triazine derivative, wherein the compound A has a structure shown in a formula I, the intermediate B has a structure shown in a formula II, and the compound C has a structure shown in a formula III, wherein the formulas I, II and III are as follows:
wherein R is C 3～C10 alkyl, X is halogen atom.
According to the preparation method provided by the invention, the para-nitroaniline and the compound A are utilized for substitution reaction, so that the amino group in the para-nitroaniline can be used for substituting the X in the compound A to form trisubstituted triazine, namely an intermediate B. And then, carrying out hydrogenation reduction hydrocarbonylation reaction on the compound C ketone compound and the intermediate B to complete hydrogenation reduction and R group substitution of the nitro group of the intermediate B, thereby obtaining the target product triazine derivative. The triazine derivative prepared by the two-step method of substitution and hydrogenation reduction provided by the invention not only has higher product yield, but also greatly shortens the process flow. Meanwhile, the method effectively avoids the generation of the bi-substituted p-phenylenediamine by-product in the traditional process, so that the separation of the product becomes easy, the cost is greatly reduced, the pollution is avoided, the product quality is high, and the industrialization is easy to realize.
Different R groups correspond to different triazine derivatives. Accordingly, the corresponding triazine derivative can be obtained by simply replacing the compound C with the corresponding R-base ketone. Preferably, R is 5-methyl-2-hexyl, 4-methyl-2-pentyl, 2-octyl, cyclohexyl, isopropyl, butyl, 2-pentyl or 2-sunflower. The ketones corresponding to the R groups and the intermediate B have better hydrogenation reduction reaction capability, and the obtained triazine derivative has higher reaction efficiency and higher yield.
The amount relationship between the various reaction materials can be adjusted by those skilled in the art based on the reaction principle of the materials. In a preferred embodiment, in the step of substitution reaction, the molar ratio of paranitroaniline to compound A is 3-10:1, preferably 3-6:1, more preferably 3-4:1. The molar ratio of the paranitroaniline to the compound A is controlled within the range, so that on one hand, the content of the intermediate B in a reaction product is improved, the content of mono-substituted or di-substituted byproducts is reduced, and on the other hand, the reaction energy consumption is reduced, and the cost is saved. Thereby being beneficial to further improving the yield of the target product.
In a preferred embodiment, in the step of hydrogenation reduction alkylation reaction, the molar ratio of the intermediate B to the compound C is 1:10-60, preferably 1:20-60. Similarly, the use amount of the intermediate B and the compound C is controlled within the above range, which is beneficial to improving the yield of the triazine derivative and reducing the occurrence of side reactions.
In a preferred embodiment, the substitution reaction is carried out in an organic solvent which is one or more of 1, 4-dioxane, N-dimethylformamide, N-hexane, tetrahydrofuran, toluene and isobutane. The organic solvents have good compatibility with the reaction raw materials, and can provide a stable reaction environment, so that the stability of the substitution reaction can be maintained.
The water content of the organic solvent used in the reaction also has a large influence on the progress of the substitution reaction. The water content of the organic solvent in the substitution reaction is generally controlled to 0 to 5%, preferably 0 to 1%, more preferably 0 to 0.5%. When the water content in the organic solvent is too high, the compound A is more prone to side reactions such as hydrolysis and the like, which is unfavorable for the main reaction, and further affects the purity and yield of the target product. The water content is controlled within the above range, and the purity and yield of the target product are further improved.
The preparation method provided by the invention has milder overall reaction conditions. In a preferred embodiment, in the step of substitution reaction, the reaction is carried out at a temperature of 0-5 ℃ and then the reaction is carried out at a reflux state after the temperature is raised. The activity of cyanuric chloride is relatively high, the reaction temperature is controlled to be 0-5 ℃, the reaction activity of cyanuric chloride can be properly reduced, so that the substitution reaction between paranitroaniline and a compound A can be better controlled, and after triazine ring is substituted for two aromatic amines, the activity of a third chlorine atom is rapidly reduced due to the conjugated electron donating effect of the aromatic amines, and the temperature must be gradually increased to a reflux state, so that more trisubstituted compounds can be generated. Under such temperature conditions, the purity and yield of intermediate B are higher.
The purpose of the above-described hydrodealkylation reaction is the hydrodeoxygenation of the nitro group and the substitution of the R group of intermediate B. In a preferred embodiment, the hydrogenation reduction hydrocarbylation reaction is carried out by taking hydrogen as a reducing agent and under the action of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises an active component which is one or more of platinum, palladium, nickel and copper. One or more of platinum, palladium, nickel and copper are used as active components of the hydrogenation catalyst, so that the catalytic efficiency of the catalyst can be improved, and the efficiency of hydrogenation reduction reaction is improved.
Specifically, the catalytic efficiency of the catalyst can be effectively improved by taking one or more of platinum, palladium, nickel and copper as the active component of the hydrogenation catalyst. In a preferred embodiment, the hydrogenation catalyst is one or more of a Pt/C catalyst, a Pd/C catalyst, a skeletal nickel catalyst, a supported nickel catalyst, an amorphous nickel catalyst, a CuO/ZnO/Al 2O3 catalyst, and a CuO/CrO/Al 2O3 catalyst. The catalyst has high catalytic efficiency, high stability, good reusability and long activity retention time.
When different catalysts are used for the hydrogenation reduction alkylation reaction, the dosage can be adjusted according to the different catalytic efficiency. In a preferred embodiment, the hydrogenation catalyst is used in an amount of 2-10% by weight of paranitroaniline when the hydrogenation catalyst is a Pt/C catalyst, 3-10% by weight of paranitroaniline when the hydrogenation catalyst is a Pd/C catalyst, 10-20% by weight of paranitroaniline when the hydrogenation catalyst is one or more of a skeletal nickel catalyst, a supported nickel catalyst and an amorphous nickel catalyst, and 30-40% by weight of paranitroaniline when the hydrogenation catalyst is a CuO/ZnO/Al 2O3 catalyst and/or a CuO/CrO/Al 2O3 catalyst. Thus, the reaction rate is improved, and the side reaction is reduced.
Based on a special two-step reaction principle, the process condition for preparing the triazine derivative is mild. In a preferred embodiment, in the step of the hydrodealkylation reaction, the reaction temperature is 80 to 200 ℃, preferably 80 to 160 ℃, and the reaction pressure is 1 to 10mpa, preferably 1 to 6mpa, more preferably 1 to 3mpa.
In the actual process, after the substitution reaction, it is preferable to continue the reaction of adding an acid-binding agent (such as sodium bicarbonate or sodium hydroxide) to the reaction system for a certain period of time for absorbing the acid generated in the reaction.
In a preferred embodiment, the method further comprises the steps of filtering the reaction liquid after the hydrogenation reduction alkylation reaction to obtain a filtrate, and distilling the filtrate to obtain the triazine derivative. Specifically, reduced pressure distillation is carried out, unreacted compound C and a small amount of low-fraction impurities are rectified and recovered at a lower temperature, a small amount of mono-substituted impurities and a large amount of impurities in a higher fraction are recovered at a higher temperature, and finally the obtained residual liquid is the target product triazine derivative.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
(A) Substitution reaction
Adding 0.3mol of paranitroaniline and 225mL of 1, 4-dioxane into a 1000mL four-necked flask, cooling to 0-5 ℃, slowly dropwise adding a cyanuric chloride solution (0.06 mol of cyanuric chloride is dissolved in 180mL of 1, 4-dioxane), maintaining the temperature after the dropwise adding is finished, continuing to react for 1h, heating and refluxing for reacting for 1h, and then adding sodium bicarbonate for reacting for 2h. After the reaction is finished, the feed liquid is washed and filtered to obtain a yellow intermediate 2,4, 6-tri- (4-nitroaniline) -1,3, 5-triazine (intermediate B). The reaction conversion rate is 99.5%, the reaction selectivity is 98%, and the product purity is 98.5%.
(B) Hydrogenation reduction hydrocarbylation reaction
29G (0.06 mol) of 2,4, 6-tris- (4-nitroaniline) -1,3, 5-triazine, 405g (3.55 mol) of 5-methyl-2-hexanone and 3g (relative to the weight of p-nitroaniline) of 3 percent Pt/C catalyst are put into a 1L autoclave at one time, are replaced by N 2、H2 for three times respectively, are stirred, the stirring speed is started for 900r/min, heating and heating are started, the reaction is maintained until no hydrogen is consumed at the temperature of 160 ℃ and the reaction pressure of 1.0-1.5 MPa, the reaction is continued for 3 hours, and after the intermediate is completely converted, the reaction is finished, the temperature reduction, the pressure relief, the kettle opening and the discharging are started. The reaction materials are filtered by a sand core funnel, the catalyst is recovered and reused, the reaction liquid is sampled and analyzed, the reaction conversion rate is 100%, the reaction selectivity is more than 95%, and the purity of the product is 92%.
(C) Post-treatment of hydrogenation liquid
Adding the filtered hydrogenation reducing solution into a 1000mL four-neck flask, carrying out reduced pressure distillation, rectifying and recovering 5-methyl-2-hexanone (MIAK) and a small amount of low fraction impurities at the kettle temperature of 150 ℃ at the vacuum degree of more than or equal to-0.099 MPa, then recovering a small amount of mono-substituted and a small amount of higher fraction impurities at the kettle temperature of 200-260 ℃, and finally obtaining the kettle solution which is the product TMPPD, wherein the purity of the product obtained by HPLC relative area analysis is 93.5%.
The result of the nuclear magnetic detection of the product is as follows ：1H NMR(400MHz,DMSO-d6):δ8.51(s,3H),δ7.36(d,6H),δ6.46(d,6H),δ4.98(s,3H),δ3.29(m,3H),δ1.51(m,3H),δ1.35(m,6H),δ1.23(m,6H),δ1.08(d,9H),δ0.87(d,18H).
Example 2
(A) Substitution reaction
0.12Mol of paranitroaniline and 200mL of N, N-dimethylformamide are added into a 1000mL four-necked flask, the temperature is reduced to 0-5 ℃, then cyanuric chloride solution (0.04 mol of cyanuric chloride is dissolved in 100mL of N, N-dimethylformamide) is slowly added dropwise, and the temperature is maintained for continuous reaction for 1h after the dropwise addition is completed. And then heating and refluxing for reaction for 1h, adding sodium bicarbonate for reaction for 2h, and after the reaction is finished, washing and filtering the feed liquid to obtain a yellow intermediate 2,4, 6-tri- (4-nitroaniline) -1,3,5 triazine. Reaction conversion rate is 99%, reaction selectivity is 98.6%, and product purity is 97.5%
(B) Hydrogenation reduction hydrocarbylation reaction
19.6G (0.04 mol) of 2,4, 6-tris- (4-nitroaniline) -1,3,5 triazine, 270g (2.36 mol) of 5-methyl-2-hexanone and 6g (relative to the weight of p-nitroaniline) of 3% Pd/C catalyst are put into a 1L autoclave at one time, are replaced by N 2、H2 for three times respectively, are stirred, the stirring speed is started for 900r/min, heating and temperature rising are started, the reaction is maintained until no hydrogen is consumed at the temperature of 80 ℃ and the reaction pressure is 1.0-1.5 MPa, the reaction is continued for 3 hours, and after the intermediate is completely converted, the reaction is finished, the temperature reduction, the pressure relief, the kettle opening and the discharging are started. The reaction materials are filtered by a sand core funnel, the catalyst is recovered and reused, the reaction liquid is sampled and analyzed, the reaction conversion rate is 100%, the reaction selectivity is more than 90%, and the purity of the product is 90.2%.
(C) Post-treatment of hydrogenation liquid
Adding the filtered hydrogenation reducing solution into a 1000mL four-neck flask, carrying out reduced pressure distillation, rectifying and recovering 5-methyl-2-hexanone (MIAK) and a small amount of low fraction impurities at the kettle temperature of 150 ℃ at the vacuum degree of more than or equal to-0.099 MPa, then recovering a small amount of primary substitution and a small amount of higher fraction impurities at the kettle temperature of 200-260 ℃, and finally obtaining the kettle solution which is the product TMPPD, wherein the purity of the product obtained by HPLC relative area analysis is 92.9%.
Examples 3 to 7
Triazine derivatives were prepared using the same starting materials and process conditions as in example 2, except that the amount of each starting material was varied and the catalyst was partially varied. The specific dosage relationship and product conditions are as follows:
Examples 8 to 12
Triazine derivatives were prepared using the same relation of the amount of raw materials as in example 2, except that compound a, compound C, and solvent were different. The method comprises the following steps:
examples 10 to 12
Triazine derivatives were prepared using the same starting materials and the same relation of amounts of starting materials as in example 2, except for the differences in process conditions. The method comprises the following steps:
examples 13 to 16
Triazine derivatives were prepared using the same raw materials and the ratio relationship between the raw materials as in example 2, except that the water content of the organic solvent used in the substitution reaction was different. The method comprises the following steps:
as is clear from examples 13 to 16, when the water content of the solvent is controlled to be 0.5% or less, the content of the product TMPPD can be 90% or more, and as the water content of the solvent increases, side reactions such as hydrolysis are increased, and by-products are increased. As is clear from examples 10 to 12, cyanuric chloride is relatively high in reactivity and is liable to deliquesce in the air, and particularly the first chlorine on the triazine ring thereof is liable to be substituted, resulting in other impurities. In the process of synthesizing TMPPD, the reaction temperature is controlled to be 0-5 ℃ firstly, so that the reactivity of cyanuric chloride can be reduced, and groups with the nucleophilicity weaker than that of amino groups in paranitroaniline in a reaction system cannot react with the groups, thereby being more beneficial to substitution reaction between the paranitroaniline and cyanuric chloride, and then the temperature is gradually increased to a reflux state, so that more trisubstituted matters can be generated. As is clear from examples 1 to 7, the ratio of the raw materials is controlled within a specific range, which is advantageous for further improving the yield and purity of the target product.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
The triazine derivative prepared by the two-step method of substitution and hydrogenation reduction has higher product yield and greatly shortens the process flow. Meanwhile, the method effectively avoids the generation of the bi-substituted p-phenylenediamine by-product in the traditional process, so that the separation of the product becomes easy, the cost is greatly reduced, the pollution is avoided, the product quality is high, and the industrialization is easy to realize.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A process for the preparation of a triazine derivative, characterized in that the triazine derivative has the following structural formula:
;
the preparation method comprises the following steps:
the preparation method comprises the steps of carrying out substitution reaction on paranitroaniline and a compound A to form an intermediate B, wherein the molar ratio of the paranitroaniline to the compound A is 3-4:1, in the step of substitution reaction, firstly, the paranitroaniline is reacted at the temperature of 0-5 ℃, then the temperature is increased to a reflux state for reaction, the substitution reaction is carried out in an organic solvent, and the water content in the organic solvent is 0-5wt%;
Carrying out hydrogenation reduction hydrocarbylation reaction on the intermediate B and a compound C to obtain the triazine derivative, wherein the molar ratio of the intermediate B to the compound C is 1:10-60;
Wherein the compound A has a structure shown in a formula I, the intermediate B has a structure shown in a formula II, the compound C has a structure shown in a formula III, and the formula I, the formula II and the formula III are as follows:
,
The method comprises the steps of carrying out hydrogenation reaction by taking hydrogen as a reducing agent in the step of hydrogenation reduction hydrocarbonylation reaction, wherein the R group is C 3~C10 alkyl, the X is a halogen atom, the reaction is carried out under the action of a hydrogenation catalyst, the hydrogenation catalyst is one or more of a Pt/C catalyst, a Pd/C catalyst, a skeletal nickel catalyst, a supported nickel catalyst, an amorphous nickel catalyst, a CuO/ZnO/Al 2O3 catalyst and a CuO/CrO/Al 2O3 catalyst, the dosage of the hydrogenation catalyst is 2-10% of the weight of paranitroaniline when the hydrogenation catalyst is the Pt/C catalyst, the dosage of the hydrogenation catalyst is 3-10% of the weight of the paranitroaniline when the hydrogenation catalyst is the Pd/C catalyst, the dosage of the hydrogenation catalyst is one or more of the skeletal nickel catalyst, the supported nickel catalyst and the amorphous nickel catalyst, the dosage of the hydrogenation catalyst is 10-20% of the weight of the paranitroaniline when the hydrogenation catalyst is the hydrogenation catalyst, the dosage of the hydrogenation catalyst is the ZnO/Al/2O3 ℃ and the hydrogenation catalyst is the hydrogenation reaction is carried out at the temperature of 200-30 MPa, and the hydrogenation reaction is carried out when the hydrogenation catalyst is the temperature of 200-30 MPa.
2. The method according to claim 1, wherein the organic solvent is one or more selected from the group consisting of 1, 4-dioxane, N-dimethylformamide, N-hexane, tetrahydrofuran, toluene and isobutane.
3. The method according to claim 1, wherein the water content in the organic solvent is 0 to 1wt%.
4. The method according to claim 1, wherein the water content in the organic solvent is 0 to 0.5wt%.
5. The method according to any one of claims 1 to 4, wherein in the step of hydrodealkylation reaction, the molar ratio of the intermediate B to the compound C is 1:20 to 60.
6. The method according to claim 1, wherein in the step of hydrogenation reduction alkylation reaction, the reaction temperature is 80-160 ℃ and the reaction pressure is 1-6 mpa.
7. The method according to claim 6, wherein in the step of hydrogenation reduction alkylation reaction, the reaction pressure is 1 to 3mpa.
8. The method of claim 7, further comprising, after the step of hydrodewaxing:
filtering the reaction liquid after the hydrogenation reduction hydrocarbylation reaction to obtain filtrate;
distilling the filtrate to obtain the triazine derivative.
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| CN113563276B (en) * | 2021-07-23 | 2024-04-09 | 山东阳谷华泰化工股份有限公司 | Preparation method of anti-aging agent TAPDT and intermediate thereof |
| CN113429361B (en) * | 2021-07-23 | 2022-08-26 | 山东阳谷华泰化工股份有限公司 | Preparation method of tris (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine and intermediate thereof |
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