CN113683578A - Preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine - Google Patents
Preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006467 substitution reaction Methods 0.000 claims abstract description 35
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229960001413 acetanilide Drugs 0.000 claims abstract description 26
- CHMBIJAOCISYEW-UHFFFAOYSA-N n-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 3
- 230000000850 deacetylating effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000007983 Tris buffer Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000005303 weighing Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 9
- XJLDOQZMHZFDPZ-UHFFFAOYSA-N 4-(2-methylhexan-2-yl)cyclohexa-1,5-diene-1,4-diamine Chemical compound CC(CCCC)(C1(CC=C(C=C1)N)N)C XJLDOQZMHZFDPZ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QRKJNCRCYBKANP-UHFFFAOYSA-N 2-amino-n-phenylacetamide Chemical compound NCC(=O)NC1=CC=CC=C1 QRKJNCRCYBKANP-UHFFFAOYSA-N 0.000 description 1
- CLFLIWXLUUCHDM-UHFFFAOYSA-N 4-N-(2-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(CCCC)(C)NC1=CC=C(C=C1)N CLFLIWXLUUCHDM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FMJYAEKFCVLAKT-UHFFFAOYSA-N [C].[Rh] Chemical class [C].[Rh] FMJYAEKFCVLAKT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, which comprises the following steps: carrying out catalytic hydrogenation reaction on p-aminoacetanilide and methyl isoamyl ketone to obtain N-1, 4-dimethyl amyl p-acetanilide; deacetylating N-1, 4-dimethyl amyl p-acetanilide in an alkali solution to obtain N-1, 4-dimethyl amyl p-acetanilide; cyanuric chloride and N-1, 4-dimethyl amyl p-aniline are subjected to substitution reaction, and after reaction, the 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is obtained by post treatment. The invention has the advantages of high reaction selectivity and yield, less by-products, low cost and good quality.
Description
Technical Field
The invention relates to a preparation method of 2,4, 6-tri (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine, belonging to the technical field of fine chemical engineering.
Background
The alkylaryl anti-aging agents are mainly used for preventing rubber from aging due to heat, ozone, oxygen, mechanical fatigue and the like, but the alkylaryl anti-aging agents are easy to migrate out of vulcanized rubber, react with ozone in the atmospheric environment on the surface of a tire or a rubber product to form a color-changing substance, and seriously affect the appearance of the tire or the rubber, particularly light-colored rubber products. Subsequently, the company Keppie in the United states introduced TAPDT, a product name of Durazone37, a chemical name of 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine, which is an anti-aging agent having characteristics of large relative molecular mass, slow migration speed and the like, and is suitable for antiozonants for heavy tires and agricultural tires.
Experiments prove that the intermediate N-1, 4-dimethyl amyl p-phenylenediamine of the anti-aging agent is prepared by reacting p-phenylenediamine and 5-methyl-2-hexanone, the one-step reaction needs to accurately control the ratio of ketone to amine, the excess proportion of amine is large, the p-phenylenediamine needs to be recovered from a mixture after the reaction is finished, N' -di (dimethyl amyl) p-phenylenediamine (namely the anti-aging agent 4030) is easy to generate, and the selectivity is not high.
The Chinese patent CN108203414A is to use p-nitroaniline and cyanuric chloride as raw materials to prepare an intermediate 2,4, 6-tri- (4-nitroaniline) -1,3, 5-triazine, and then to react with 5-methyl-2-hexanone by reversion hydrogenation to synthesize the product.
Disclosure of Invention
Aiming at the defects of poor selectivity, low yield, high cost, poor process safety and the like in the prior art, the invention provides a preparation method of an anti-aging agent 2,4, 6-tris (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine, wherein p-aminoacetanilide is taken as a raw material and reacts with methyl isoamyl ketone to form the N-1, 4-dimethylpentyl p-acetanilide, and the method has good selectivity, high yield and low cost and provides a new thought for preparing the 2,4, 6-tris (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine.
The specific technical scheme of the invention is as follows:
a preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine comprises the following steps:
(1) carrying out catalytic hydrogenation reaction on p-aminoacetanilide and methyl isoamyl ketone to obtain N-1, 4-dimethyl amyl p-acetanilide;
(2) deacetylating N-1, 4-dimethyl amyl p-acetanilide in an alkali solution to obtain N-1, 4-dimethyl amyl p-acetanilide;
(3) cyanuric chloride and N-1, 4-dimethyl amyl p-aniline are subjected to substitution reaction, and after reaction, the 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is obtained by post treatment.
Furthermore, in the step (1), the molar ratio of the p-aminoacetanilide to the methyl isoamyl ketone is 1: 1-1.5, and preferably 1: 1.1.
Further, in the step (1), the catalyst is a palladium carbon catalyst, a platinum carbon catalyst, a rhodium carbon catalyst or a nickel carbon catalyst. The dosage of the catalyst is 2-4% of the mass of the p-aminoacetanilide.
Further, in the step (1), the reaction is carried out in a solvent, and the solvent is methanol.
Further, in the step (1), the reaction temperature is 60-120 ℃, preferably 80-90 ℃.
Further, in the step (1), during the reaction, the pressure of the hydrogen is kept between 0.3 and 0.4MPa, and when the pressure is lower than 0.1MPa, the hydrogen is supplemented to between 0.3 and 0.4MPa until the reaction is finished when the pressure of the hydrogen is unchanged or basically unchanged.
Further, in the step (2), the N-1, 4-dimethyl amyl p-acetanilide is heated in an ethanol solution of sodium hydroxide or potassium hydroxide for reflux reaction, and acetyl is removed. Wherein the molar ratio of the N-1, 4-dimethyl amyl acetanilide to the sodium hydroxide or the potassium hydroxide is 1: 1-1.3. The concentration of the ethanol solution of sodium hydroxide or potassium hydroxide may be adjusted according to practical needs, for example, 5 to 10 wt%.
Further, in the step (3), the substitution reaction is carried out in three steps, and the substitution reaction comprises the following steps: mixing cyanuric chloride with a solvent to prepare a solution or slurry; mixing N-1, 4-dimethyl amyl p-aniline with a solvent to obtain a solution; the temperature of the cyanuric chloride solution or the pulp is maintained at the primary substitution reaction temperature, then the N-1, 4-dimethyl amyl p-aniline solution is dripped, the temperature is maintained after the dripping is finished to carry out the primary substitution reaction, then the temperature is raised to the secondary substitution reaction temperature to carry out the secondary substitution reaction, and then the temperature is raised to the boiling reflux state to carry out the tertiary substitution reaction.
Furthermore, in the step (3), the dripping time of the N-1, 4-dimethyl amyl p-aniline solution is about 0.5 h.
Further, in the step (3), the temperature of the primary substitution reaction is-10-0 ℃, and the reaction time is 1-2 h; the temperature of the secondary substitution reaction is 25-45 ℃, and the reaction time is 3-4 h; the temperature of the trisubstitution reaction is determined according to the boiling point of the solvent, and the reaction is kept to be in a boiling reflux state for 3-4 h.
Furthermore, in the step (3), the molar ratio of the N-1, 4-dimethyl amyl p-aniline to the cyanuric chloride is 3-3.5: 1, and preferably 3.1: 1.
Further, in the step (3), the solvent is methanol, ethanol, isopropanol, toluene, xylene, benzene or dioxane. The reaction temperature of the trisubstitution reaction differs depending on the solvent. The purpose of the solvent is to provide a reaction environment, and the amount thereof can be selected and adjusted as necessary.
Further, in the step (3), after the substitution reaction is completed, the post-treatment mode is as follows: after the substitution reaction is finished, the temperature of the materials is reduced to 50-60 ℃, sodium hydroxide solution with the same molar weight as hydrogen chloride generated in the reaction is dripped into the materials for neutralization reaction, water is added into the materials after the reaction to separate out solid, and then the solid is filtered, washed and dried to obtain the 2,4, 6-tris (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine.
In one embodiment of the present invention, a method for preparing 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine is disclosed, comprising the following steps:
first, preparation of intermediate N-1, 4-dimethylpentylpetanilide
Dissolving p-aminoacetanilide in methanol and transferring the methanol into a high-pressure kettle, activating a catalyst by using the methanol, adding the activated catalyst into the high-pressure kettle, adding methyl isoamyl ketone into the high-pressure kettle, covering the high-pressure kettle, replacing the activated catalyst by using nitrogen for three times, replacing the activated catalyst by using hydrogen for three times, raising the reaction temperature, introducing the hydrogen for reaction, reducing the temperature and releasing the pressure after the hydrogenation reaction is finished, discharging the material, filtering out the solid catalyst, rotatably evaporating a filtrate to remove the solvent methanol and byproduct alcohol, pouring out the residual material, and cooling to obtain the N-1, 4-dimethyl amyl p-acetanilide for later use. The reaction formula is as follows:
second step, preparation of intermediate N-1, 4-dimethyl amyl p-aniline
Putting the N-1, 4-dimethyl amyl p-acetanilide and an ethanol solution of potassium hydroxide or sodium hydroxide into a reaction kettle, heating to boil for reflux reaction, pouring the solution into ice water after the reaction is finished to obtain the N-1, 4-dimethyl amyl p-acetanilide, filtering and washing the solution to be alkalescent or neutral, and drying the solution for later use. Taking sodium hydroxide as an example, the reaction formula is as follows:
thirdly, preparing 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine
Dissolving cyanuric chloride with a solvent or preparing into slurry, transferring the obtained solution or slurry into a reaction kettle, dissolving N-1, 4-dimethyl amyl p-aniline with the solvent and transferring the solution or slurry into a constant-pressure dropping funnel, firstly, reducing the cyanuric chloride material to a primary substitution reaction temperature, beginning to drop N-1, 4-dimethyl amyl p-aniline solution, reacting for a certain time after dropping, then, raising the material in the reaction kettle to a secondary substitution reaction temperature, and raising the material in the kettle to a boiling reflux state after reacting for a period of time to carry out a tertiary substitution reaction.
After the trisubstitution reaction is finished, the temperature of the materials is reduced to 50-60 ℃, sodium hydroxide solution with the mole number equal to that of chlorine element in cyanuric chloride is dripped, the materials are stirred and reacted for a certain time, then the temperature is reduced, water is added to separate out the product, and the product is washed and dried to obtain the 2,4, 6-tris (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine. The reaction formula is as follows:
the invention has the following beneficial effects:
1. according to the invention, p-aminoacetanilide is selected as a raw material, the p-aminoacetanilide and methyl isoamyl ketone react to form N-1, 4-dimethyl amyl p-acetanilide, and then the N-1, 4-dimethyl amyl p-acetanilide is deacetylated to obtain the N-1, 4-dimethyl amyl p-acetanilide. The process route has the advantages of high reaction selectivity, less side reactions, simple product post-treatment, simple process, high yield and high purity of the obtained intermediate, and avoids the problem of difficult rectification, recovery and separation when p-phenylenediamine is used as a raw material.
2. Compared with p-nitroaniline which is used as a raw material, the p-nitroaniline-containing p-nitroaniline composite material has higher safety, low cost and good industrial application prospect.
Detailed Description
The present invention is illustrated by the following specific examples, which are intended to be merely exemplary and not limiting.
In the following examples, yield = product quality/theoretical quality of product.
Example 1
First, preparation of intermediate N-1, 4-dimethylpentylpetanilide
Weighing 15.02 g (0.1 mol) of p-aminoacetanilide, dissolving in 100ml of methanol and transferring into an autoclave; weighing 0.3 g of palladium-carbon catalyst, washing and activating by using methanol, and then adding into an autoclave; weighing 12.56 g (0.11 mol) of methyl isoamyl ketone, adding the methyl isoamyl ketone into a high-pressure kettle, covering a cover, replacing the mixture with nitrogen for three times, replacing the mixture with hydrogen for three times, raising the reaction temperature to 85 ℃, introducing hydrogen for reaction, stopping introducing the hydrogen when the pressure in the kettle is 0.4MPa each time, introducing the hydrogen again until the pressure in the kettle is reduced to 0.1MPa, introducing the hydrogen again into the kettle to 0.4MPa, stopping introducing the hydrogen when the pressure in the reaction kettle is reduced to 0.1MPa, introducing the hydrogen again when the pressure in the reaction kettle is reduced to 0.1MPa, repeating the steps until the pressure in the kettle is reduced to 0.02MPa within half an hour, determining that the hydrogenation reaction is finished, taking about 32 hours, then reducing the temperature and releasing the pressure to discharge the materials, filtering and filtering out the solid catalyst, removing the solvent methanol and the byproduct alcohol by rotary evaporation from the filtrate, pouring out and cooling the residual materials to obtain 26.07 g (0.099 mol) of N-1, 4-dimethyl amyl p-acetanilide, and detecting the liquid phase purity to be 99.5%, the selectivity was 99.1% and the yield based on p-aminoacetanilide was 98.6%.
Second step, preparation of intermediate N-1, 4-dimethyl amyl p-aniline
Weighing 21.15 g (0.08 mol) of the intermediate, putting the intermediate into a reaction kettle with a reflux device, weighing 5.6 g of potassium hydroxide, dissolving the potassium hydroxide in 100ml of ethanol to prepare a potassium hydroxide ethanol solution, adding the solution into the reaction kettle, heating to boil, carrying out reflux reaction for about 3 hours, neutralizing the pH value of the material with dilute hydrochloric acid to be alkalescent or neutral, pouring the solution into ice water to obtain crystals, filtering, washing the crystals, and drying to obtain 17.62 g (0.08 mol) of N-1, 4-dimethyl amyl p-aniline, wherein the liquid phase purity is 99.7 percent, and the yield is 99.5 percent based on the N-1, 4-dimethyl amyl p-acetanilide.
The third step is 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine group) -1,3, 5-triazine
Weighing 2.98 g (0.0162 mol) of cyanuric chloride, dissolving the cyanuric chloride with 50 ml of isopropanol, transferring the cyanuric chloride into a reaction kettle, weighing 11.07 g (0.05 mol) of N-1, 4-dimethyl amyl p-aniline, dissolving the N-1, 4-dimethyl amyl p-aniline with isopropanol, transferring the solution into a constant-pressure dropping funnel, firstly reducing the cyanuric chloride isopropanol solution to a primary substitution reaction temperature of-5 ℃, beginning to dropwise add the N-1, 4-dimethyl amyl p-aniline isopropanol solution, reacting for 1 hour after the dropwise addition is finished, then increasing the material in the reaction kettle to a secondary substitution reaction temperature of 35 ℃, reacting for 3 hours, then increasing the material in the kettle to a boiling reflux state, and carrying out a tertiary substitution reaction at the temperature of 85 ℃ for 3 hours. After the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, aqueous solution of sodium hydroxide is dripped to carry out neutralization reaction, the materials are stirred to react for 1 hour, then the materials are cooled to room temperature and poured into a beaker, 50 ml of deionized water is added to separate out the product, and the product is washed and dried to obtain 10.99 g (0.016 mol) of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, wherein the liquid phase purity is 99.1 percent, and the yield is 98.3 percent calculated by cyanuric chloride.
Example 2
First, preparation of intermediate N-1, 4-dimethylpentylpetanilide
Weighing 30.04 (0.2 mol) g of p-aminoacetanilide, dissolving the p-aminoacetanilide in 220 ml of methanol, transferring the mixture into a high-pressure kettle, weighing 0.9 g of rhodium-carbon catalyst, washing and activating the rhodium-carbon catalyst by using methanol, adding the activated rhodium-carbon catalyst into the high-pressure kettle, weighing 27.41 g (0.24 mol) of methyl isoamyl ketone, adding the methyl isoamyl ketone into the high-pressure kettle, covering a cover, replacing the rhodium-carbon catalyst for three times by using nitrogen, replacing the rhodium-carbon catalyst for three times by using hydrogen, increasing the reaction temperature to 90 ℃, introducing the hydrogen for reaction, stopping introducing the hydrogen each time until the pressure in the kettle reaches 0.4MPa, introducing the hydrogen into the kettle again until the pressure in the kettle is reduced to 0.1MPa, stopping introducing the hydrogen until the pressure in the reaction kettle is reduced to 0.1MPa, repeatedly introducing the hydrogen again, reducing the pressure until the pressure in the kettle is reduced to less than or equal to 0.02MPa within half an hour, finishing the hydrogenation reaction, keeping the time for about 30 hours, then releasing the pressure and reducing and discharging the material, filtering the solid catalyst, the solvent methanol and the byproduct alcohol are removed from the filtrate by rotary evaporation, and the residual material is poured out and cooled to obtain 51.56 g (0.195 mol) of N-1, 4-dimethyl amyl p-acetanilide, the purity of the liquid phase is 99.8 percent, the selectivity is 98.2 percent, and the yield is 97.5 percent based on the amino acetanilide.
Second step, preparation of intermediate N-1, 4-dimethyl amyl p-aniline
39.66 g (0.15 mol) of the intermediate is weighed and put into a reaction kettle with a reflux device, 6.6 g of sodium hydroxide is weighed and dissolved in 100 g of ethanol to prepare sodium hydroxide ethanol solution which is added into the reaction kettle, the temperature is raised to boiling for reflux reaction for about 4 hours, then the pH value of the material is neutralized to be alkalescent or neutral by dilute hydrochloric acid, then the material is poured into ice water to obtain crystals, the crystals are filtered and washed, and the crystals are dried to obtain 29.89 g (0.135 mol) of N-1, 4-dimethyl amyl p-aniline, the liquid phase purity is 99.8 percent, and the yield is 99 percent based on the N-1, 4-dimethyl amyl p-acetanilide.
The third step is 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine group) -1,3, 5-triazine
Weighing 7.38 g (0.04 mol) of cyanuric chloride, dissolving with 150 ml of isopropanol, transferring into a reaction kettle, weighing 26.57 g (0.12 mol) of N-1, 4-dimethyl amyl p-aniline, dissolving with isopropanol, transferring into a constant pressure dropping funnel, firstly reducing the cyanuric chloride isopropanol solution to a primary substitution reaction temperature of-10 ℃, beginning to dropwise add the N-1, 4-dimethyl amyl p-aniline isopropanol solution, reacting for 1.5 hours after the dropwise addition is finished, then raising the material in the reaction kettle to a secondary substitution reaction temperature of 40 ℃, reacting for 4 hours, then raising the material in the kettle to a boiling reflux state, and carrying out a tertiary substitution reaction at a temperature of 70 ℃ for 4 hours. After the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, 4.8 g of aqueous solution of sodium hydroxide is dripped, the materials are stirred and reacted for 1.5 hours, then the materials are cooled to room temperature and poured into a beaker, 200 ml of deionized water is added to separate out the product, and the product is washed and dried to obtain 27.08 g (0.0391 mol) of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, wherein the liquid phase purity is 99.3 percent, and the yield is 97.7 percent based on cyanuric chloride.
Example 3
First, preparation of intermediate N-1, 4-dimethylpentylpetanilide
Weighing 22.53 (0.15 mol) g of p-aminoacetanilide, dissolving in 180 ml of methanol, transferring to an autoclave, weighing 0.6 g of platinum-carbon catalyst, washing and activating with methanol, adding to the autoclave, weighing 19.7 g (0.173 mol) of methyl isoamyl ketone, adding to the autoclave, covering, replacing with nitrogen for three times, replacing with hydrogen for three times, increasing the reaction temperature to 80 ℃, introducing hydrogen for reaction, stopping introducing hydrogen each time until the pressure in the autoclave reaches 0.4MPa, introducing hydrogen again into the autoclave until the pressure in the autoclave drops to 0.1MPa, stopping introducing hydrogen until the pressure in the autoclave reaches 0.4MPa, stopping introducing hydrogen again until the pressure in the autoclave drops to 0.1MPa, repeating the steps until the pressure in the autoclave drops to 0.02MPa within half an hour, finishing the hydrogenation reaction, reducing the time for about 35 hours, releasing the pressure, discharging the material, filtering and filtering the solid catalyst, the filtrate was subjected to rotary evaporation to remove the solvent methanol and the by-produced alcohol, and the remaining material was poured out and cooled to obtain 38.35 g (0.145 mol) of N-1, 4-dimethylpentyl-p-acetanilide having a liquid phase purity of 99.2%, a selectivity of 97.5% and a yield of 96.7% based on the amount of p-aminoacetanilide.
Second step, preparation of intermediate N-1, 4-dimethyl amyl p-aniline
Weighing 31.73 g (0.12 mol) of the intermediate, putting the intermediate into a reaction kettle with a reflux device, weighing 5.5 g of sodium hydroxide, dissolving the sodium hydroxide in 100 g of ethanol to prepare a sodium hydroxide ethanol solution, adding the sodium hydroxide ethanol solution into the reaction kettle, heating to boil, carrying out reflux reaction for about 4 hours, neutralizing the pH value of the material with dilute hydrochloric acid to be alkalescent or neutral, pouring the neutralized material into ice water to obtain crystals, filtering, washing the crystals, and drying to obtain 26.22 g (0.118 mol) of N-1, 4-dimethyl amyl p-aniline, wherein the liquid phase purity is 99.8 percent, and the yield is 98.7 percent based on the N-1, 4-dimethyl amyl p-acetanilide.
The third step is 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine group) -1,3, 5-triazine
5.535 g (0.03 mol) of cyanuric chloride is weighed and dissolved by 130 ml of isopropanol and transferred to a reaction kettle, 21.04 g (0.095 mol) of N-1, 4-dimethyl amyl p-aniline is weighed and dissolved by isopropanol and transferred to a constant pressure dropping funnel, the cyanuric chloride isopropanol solution is firstly reduced to the primary substitution reaction temperature of-7 ℃, the N-1, 4-dimethyl amyl p-aniline isopropanol solution is started to be dripped, the reaction is carried out for 2 hours after the dripping is finished, then the materials in the reaction kettle are increased to the secondary substitution reaction temperature of 30 ℃ and are reacted for 3.5 hours, then the materials in the kettle are increased to the boiling reflux state for carrying out the tertiary substitution reaction, the temperature is 70 ℃, and the time is 3.5 hours. After the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, 3.72 g of aqueous solution of sodium hydroxide is dripped, the materials are stirred and reacted for 1.5 hours, then the materials are cooled to room temperature and poured into a beaker, 150 ml of deionized water is added to separate out the product, and the product is washed and dried to obtain 20.37 g (0.0294 mol) of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, wherein the liquid phase purity is 99.5 percent, and the yield is 98 percent based on cyanuric chloride.
Example 4
First, preparation of intermediate N-1, 4-dimethylpentylpetanilide
Weighing 22.53 (0.15 mol) g of p-aminoacetanilide, dissolving in 180 ml of methanol, transferring to an autoclave, weighing 0.6 g of platinum-carbon catalyst, washing and activating with methanol, adding to the autoclave, weighing 19.7 g (0.173 mol) of methyl isoamyl ketone, adding to the autoclave, covering, replacing with nitrogen for three times, replacing with hydrogen for three times, increasing the reaction temperature to 60 ℃, introducing hydrogen for reaction, stopping introducing hydrogen each time until the pressure in the autoclave reaches 0.4MPa, introducing hydrogen again into the autoclave until the pressure in the autoclave drops to 0.1MPa, stopping introducing hydrogen until the pressure in the autoclave reaches 0.4MPa, stopping introducing hydrogen again until the pressure in the autoclave drops to 0.1MPa, repeating the steps until the pressure in the autoclave drops to 0.02MPa within half an hour, finishing the hydrogenation reaction, reducing the time for about 38 hours, releasing the pressure, discharging the material, filtering and filtering the solid catalyst, the filtrate was subjected to rotary evaporation to remove the solvent methanol and the by-product alcohol, and the remaining material was poured out and cooled to obtain 37.0 g of N-1, 4-dimethylpentyl-p-acetanilide having a liquid phase purity of 98.9%, a selectivity of 94.3% and a yield of 93.3% based on the p-aminoacetanilide.
Step two, preparing an intermediate N-1, 4-dimethyl amyl p-aniline: the same as in example 3.
Step three, 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine: the same as in example 3.
Example 5
First, preparation of intermediate N-1, 4-dimethylpentylpetanilide
Weighing 22.53 (0.15 mol) g of p-aminoacetanilide, dissolving in 180 ml of methanol, transferring to an autoclave, weighing 0.6 g of platinum-carbon catalyst, washing and activating with methanol, adding to the autoclave, weighing 19.7 g (0.173 mol) of methyl isoamyl ketone, adding to the autoclave, covering, replacing with nitrogen for three times, replacing with hydrogen for three times, increasing the reaction temperature to 120 ℃, introducing hydrogen for reaction, stopping introducing hydrogen each time until the pressure in the autoclave reaches 0.4MPa, introducing hydrogen again into the autoclave until the pressure in the autoclave drops to 0.1MPa, stopping introducing hydrogen until the pressure in the autoclave reaches 0.4MPa, stopping introducing hydrogen again until the pressure in the autoclave drops to 0.1MPa, repeating the steps until the pressure in the autoclave drops to 0.02MPa within half an hour, finishing the hydrogenation reaction, reducing the time for about 32 hours, releasing the pressure, discharging the material, filtering and filtering the solid catalyst, the filtrate was subjected to rotary evaporation to remove the solvent methanol and the by-produced alcohol, and the remaining material was poured out and cooled to obtain 36.64 g of N-1, 4-dimethylpentyl-p-acetanilide having a liquid phase purity of 97.5%, a selectivity of 94.8% and a yield of 92.4% based on the amount of p-aminoacetanilide.
Step two, preparing an intermediate N-1, 4-dimethyl amyl p-aniline: the same as in example 3.
Step three, 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine: the same as in example 3.
Comparative example 1
Weighing 54.07 g (0.5 mol) of p-phenylenediamine, dissolving and transferring the p-phenylenediamine in methanol into an autoclave, sequentially weighing 1.4 g of palladium-carbon catalyst washed and activated by methanol and 40 g (0.35 mol) of methyl isoamyl ketone, adding the palladium-carbon catalyst and the methyl isoamyl ketone into the autoclave, closing a feeding valve, replacing air in the autoclave by nitrogen for 3 times, then replacing gas in the autoclave by hydrogen, heating the autoclave to 85 ℃, then introducing hydrogen into the autoclave to 0.4MPa, introducing hydrogen into the autoclave to 0.4MPa when the pressure in the autoclave is reduced to 0.1MPa, repeating the steps for several times until the pressure in the autoclave is reduced to be less than or equal to 0.02MPa in half an hour, namely finishing the reaction, wherein the reaction time is about 38 hours, then cooling and releasing the material, filtering and filtering out the solid catalyst, carrying out rotary evaporation on filtrate to remove the solvent methanol and byproduct alcohol, then transferring the material into a rectifying tower to carry out rectification and separation, thus obtaining 90.77 g (0.41 mol) of N-1, 4-dimethyl amyl p-aniline, the liquid phase purity is 99.5%, the selectivity is 81.6%, and the yield is 82% by p-phenylenediamine.
Weighing 34.32 g (0.155 mol) of the intermediate, dissolving the intermediate in isopropanol, transferring the solution into a constant-pressure dropping funnel, weighing 9.23 g (0.05 mol) of cyanuric chloride, dissolving the cyanuric chloride in isopropanol, transferring the solution into a reaction kettle, cooling macro materials in the reaction kettle to-10 ℃, starting to dropwise add an intermediate solution, reacting for 1 hour at the temperature after dropwise adding, heating the reaction materials to 35 ℃, reacting for 3 hours at the temperature, heating the reaction materials to about 85 ℃, refluxing and reacting for 3 hours, cooling the materials to 50 ℃ after the reaction is finished, dropwise adding a solution of 6.3 g of sodium hydroxide, stirring and reacting for 1 hour, cooling to room temperature, pouring the mixture into a beaker, adding 150 ml of deionized water to separate out a product, washing and drying to obtain 33.96 g (0.049 mol) of 2,4, 6-tris (N-1, 4-dimethylpentyldiamino) -1,3, 5-triazine, the liquid phase purity of 99.2%, calculated by cyanuric chloride, the yield of 98%, the total yield of 80.4%.
Claims (10)
1. A preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is characterized by comprising the following steps:
(1) carrying out catalytic hydrogenation reaction on p-aminoacetanilide and methyl isoamyl ketone to obtain N-1, 4-dimethyl amyl p-acetanilide;
(2) deacetylating N-1, 4-dimethyl amyl p-acetanilide in an alkali solution to obtain N-1, 4-dimethyl amyl p-acetanilide;
(3) cyanuric chloride and N-1, 4-dimethyl amyl p-aniline are subjected to substitution reaction, and after reaction, the 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is obtained by post treatment.
2. The method of claim 1, wherein: in the step (1), the molar ratio of the p-aminoacetanilide to the methyl isoamyl ketone is 1: 1-1.5, preferably 1: 1.1; in the step (3), the molar ratio of the N-1, 4-dimethyl amyl p-aniline to the cyanuric chloride is 3-3.5: 1, and preferably 3.1: 1.
3. The method according to claim 1 or 2, characterized in that: in the step (1), the catalyst is a palladium carbon catalyst, a platinum carbon catalyst, a rhodium carbon catalyst or a nickel carbon catalyst; preferably, the amount of the catalyst is 2-4% of the mass of the p-aminoacetanilide.
4. The method according to claim 1 or 2, characterized in that: in the step (1), the reaction temperature is 60-120 ℃, and preferably 80-90 ℃.
5. The method according to claim 1 or 2, characterized in that: in the step (1), during the reaction, the pressure of the hydrogen is kept between 0.3 and 0.4MPa, and when the pressure is lower than 0.1MPa, the hydrogen is supplemented to between 0.3 and 0.4MPa until the reaction is finished when the pressure of the hydrogen is unchanged or basically unchanged.
6. The method of claim 1, wherein: in the step (2), heating N-1, 4-dimethyl amyl p-acetanilide in an ethanol solution of sodium hydroxide or potassium hydroxide for reflux reaction to remove acetyl; preferably, the molar ratio of N-1, 4-dimethylpentylpetanilide to sodium or potassium hydroxide is from 1:1 to 1.3.
7. The method according to claim 1 or 2, characterized in that: in the step (3), cyanuric chloride is mixed with a solvent to prepare a solution or slurry; mixing N-1, 4-dimethyl amyl p-aniline with a solvent to obtain a solution; the temperature of the cyanuric chloride solution or the pulp is maintained at the primary substitution reaction temperature, then the N-1, 4-dimethyl amyl p-aniline solution is dripped, the temperature is maintained after the dripping is finished to carry out the primary substitution reaction, then the temperature is raised to the secondary substitution reaction temperature to carry out the secondary substitution reaction, and then the temperature is raised to the boiling reflux state to carry out the tertiary substitution reaction.
8. The method of claim 7, wherein: in the step (3), the primary substitution reaction temperature is-10-0 ℃, and the reaction time is 1-2 h; the temperature of the secondary substitution reaction is 25-45 ℃, and the reaction time is 3-4 h; the temperature of the trisubstitution reaction is determined according to the boiling point of the solvent, and the reaction time is 3-4 h.
9. The method of claim 7, wherein: in the step (3), the solvent is methanol, ethanol, isopropanol, toluene, xylene, benzene or dioxane.
10. The method according to claim 1 or 7, wherein: in the step (3), after the substitution reaction is finished, the post-treatment mode is as follows: after the substitution reaction is finished, the temperature of the materials is reduced to 50-60 ℃, sodium hydroxide solution with the same molar weight as hydrogen chloride generated in the reaction is dripped into the materials for neutralization reaction, water is added into the materials for precipitation and fixation after the reaction, and then the materials are filtered, washed and dried to obtain the 2,4, 6-tris (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050871A (en) * | 1987-08-28 | 1991-04-24 | 尤尼罗亚尔化学公司 | The triazine that the arylidene diamino replaces |
| US5861535A (en) * | 1997-09-23 | 1999-01-19 | Eastman Kodak Company | Reductive alkylation process to prepare tertiary aminoaryl compounds |
| JP2007223964A (en) * | 2006-02-24 | 2007-09-06 | Koei Chem Co Ltd | Method for refining 4-(n-ethyl-n-isopropylamino)aniline |
| CN105478139A (en) * | 2014-09-17 | 2016-04-13 | 江苏圣奥化学科技有限公司 | Catalyst used for preparing N-(1,4-dimethylpentyl)-p-phenylenediamine, preparation method thereof, and preparation method of N-(1,4-dimethylpentyl)-p-phenylenediamine |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050871A (en) * | 1987-08-28 | 1991-04-24 | 尤尼罗亚尔化学公司 | The triazine that the arylidene diamino replaces |
| US5861535A (en) * | 1997-09-23 | 1999-01-19 | Eastman Kodak Company | Reductive alkylation process to prepare tertiary aminoaryl compounds |
| JP2007223964A (en) * | 2006-02-24 | 2007-09-06 | Koei Chem Co Ltd | Method for refining 4-(n-ethyl-n-isopropylamino)aniline |
| CN105478139A (en) * | 2014-09-17 | 2016-04-13 | 江苏圣奥化学科技有限公司 | Catalyst used for preparing N-(1,4-dimethylpentyl)-p-phenylenediamine, preparation method thereof, and preparation method of N-(1,4-dimethylpentyl)-p-phenylenediamine |
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