CN109232275A - A kind of preparation method of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine - Google Patents
A kind of preparation method of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine Download PDFInfo
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/76—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by nitration
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Abstract
The present invention provides the preparation methods of a kind of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine.The preparation method includes the following steps: that acid anhydrides and/or aromatic acid and aniline are dissolved in organic solvent by (1), carries out ammonolysis or acylation reaction；(2) nitrobenzene and catalyst are added in the solution that step (1) obtains, carry out condensation reaction, generate 4 nitrodiphenyl amine and 4- nitrosodiphenylamine.The present invention replaces aniline to react with nitrobenzene by using aniline with the reaction product of acid anhydrides and/or aromatic acid, on the one hand increases its steric hindrance reacted with nitrobenzene ortho position, effectively inhibits the generation of ortho position byproduct of reaction；On the other hand protective effect is played to amino, the side reaction for avoiding two molecule aniline condensations generation azobenzene reduces the energy consumption of separating-purifying link to improve the yield of target product.And cost is relatively low for raw material acid anhydrides and aromatic acid, is suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine
Preparation method.
Background technique
4-ADPA (4-ADPA), is commonly called as 4-aminodiphenylamine, is the important intermediate of functional polymer, especially rubber work
The important source material of the function additives such as anti-aging agent, stabilizer and antidegradant is produced in industry.Has 4- amino reported in the literature at present
The synthesis technology of diphenylamines has more than ten, at present still in development.But it is used in industrial production there are mainly four types of: aniline
Method, diphenylamines method, formailide method and nitrobenzene method.Four routes respectively have feature:
Aniline process process is simple, at low cost, but reaction temperature is high, and side reaction is more, poor product quality, and only a few is looked forward at present
Industry produces 4-ADPA, such as Bayer A.G using this method.
Diphenylamines method is mainly using diphenylamines as raw material, in the presence of a mineral acid, is carried out in organic solvent with nitrite
Nitrosation obtains N nitrosodiphenyl amine, then is carried out being rearranged into 4- nitrosodiphenylamine hydrochloride with anhydrous hydrogen chloride, in alkali
With rear generation 4- nitrosodiphenylamine, finally restore up to 4-ADPA.The method process flow is simple, reaction condition temperature
With, but have a large amount of reluctant waste water, and cost of material is higher.External many enterprises use the synthetic route, such as U.S.'s health
Pu Dun-You Niluo Ilyushin company, SUMITOMO CHEMICAL chemistry, the emerging chemical company of imperial palace, Russian nitrogen association etc..
Formailide method, aniline first is reacted with formic acid generation formailide, in the presence of acid binding agent potassium carbonate, directly with it is right
Nitro-chlorobenzene condensation, obtains N- formoxyl diphenylamines, and then decarbonylation base generates 4 nitrodiphenyl amine, restores to obtain 4- amino two
Aniline.Accelerate since domestic paranitrochlorobenzene develops, it is of high quality and at a reasonable price, so the method is one of the route used both at home and abroad at present.
But the method can generate a large amount of brine waste due to the addition of acid binding agent potassium carbonate；In addition formic acid is consumed, production is not only increased
Finished product has corrosiveness to equipment, if using sodium sulfide reducing in reducing process, also brings time of a large amount of waste water and dodium thiosulfate
Receipts problem, three-waste pollution are serious.
Nitrobenzene method is the technique that current industry newest in the world is combined to 4-ADPA, is a kind of cleaning green
Technique is quickly grown in recent years, and existing many enterprises use at present or plan is produced using the route.Nitrobenzene method is to adopt
It is raw material with nitrobenzene and aniline, condensation reaction is carried out in the presence of Quaternary Ammonium Alkali Catalyst, obtains 4 nitrodiphenyl amine
4-ADPA can be obtained then by hydro-reduction in (4-NDPA) and 4- nitrosodiphenylamine (4-NODPA).Relatively
In other production technologies, nitrobenzene method raw material is easy to get, and synthesis technology does not generate a large amount of " three wastes ", belongs to relatively green work
Skill.
The reaction process of nitrobenzene method belongs to catalysis nucleophilic attack process, and for aniline in attack nitrobenzene, there are position choosings
Select problem, the ortho para position of nitrobenzene can react with aniline, contraposition product be target product 4 nitrodiphenyl amine and
4- nitrosodiphenylamine, but ortho-product 2- nitrodiphenylamine and 2- nitrosodiphenylamine then belong to by-product, both products
2- amino aniline or closed loop formation azophenlyene easy to form, final to influence the pure of target product 4-ADPA in hydrogenation process
Degree needs multi-step purification that can obtain the higher 4-ADPA of purity.In addition, there is also two molecule benzene in reaction process
Amine condensation generates the side reaction of azobenzene, this portion of product can be reduced to two molecule benzene in the hydrogenation link that 4-aminodiphenylamine synthesizes
Amine both consumes hydrogen, also reduces the yield of product 4-aminodiphenylamine.
During above-mentioned two problems make nitrobenzene method produce 4-ADPA, the public works such as steam, water, electricity
Consumption is very big, is added significantly to industrialization cost, thus is urgently promoted.
Aiming at the problem that reaction of nitrobenzene ortho position, CN 1285344A discloses a kind of by carbanilide preparation 4- nitro
The method of diphenylamines and 4- nitrosodiphenylamine, it is anti-with nitrobenzene instead of aniline with carbanilide (acardite) for starting material
It answers, and adds aniline during the reaction to make up the loss of carbanilide in reaction process.N- phosphinylidyne during the reaction
Aniline is constantly consumed and is regenerated.This method can effectively inhibit aniline to react the by-product generated with nitrobenzene ortho position, improve mesh
Mark the yield of product 4 nitrodiphenyl amine and 4- nitrosodiphenylamine.
But carbanilide is intended only as start material in the technique, since reaction process is unstable, still needs to add
Aniline just can guarantee the good yield of final product, therefore not be avoided that two molecule aniline condensations generate azobenzene.Moreover, raw material
Carbanilide is expensive, although process recovery ratio is high, cost can not also allow most producers to receive, so the industry of the technology
It is very significant to change bottleneck.
Therefore, in this field up for researching and developing a kind of less side reaction, the lower 4 nitrodiphenyl amine of cost and 4- nitrous
The preparation method of base diphenylamines.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of 4 nitrodiphenyl amine and 4- nitroso
The preparation method of diphenylamines.This method can effectively inhibit the generation of by-product, improve 4 nitrodiphenyl amine and 4- nitroso two
The yield and purity of aniline reduce separating-purifying cost.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides the preparation method of a kind of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine, includes the following steps:
(1) acid anhydrides and/or aromatic acid and aniline are dissolved in organic solvent, carry out ammonolysis or acylation reaction；
(2) nitrobenzene and catalyst are added in the solution that step (1) obtains, carry out condensation reaction, generate 4- nitro two
Aniline and 4- nitrosodiphenylamine.
The present invention is contracted using acid anhydrides and/or aromatic acid as the steric group source of aniline in aniline and nitrobenzene
Before conjunction, ammonolysis or acylation reaction first are carried out with acid anhydrides and/or aromatic series and aniline, then under the effect of the catalyst with nitrobenzene
Carry out condensation reaction.With the reaction product of acid anhydrides and/or aromatic acid and aniline replace aniline, on the one hand increase its with
The steric hindrance of nitrobenzene ortho position reaction, effectively inhibits the generation of ortho position reaction product, improves the choosing of contraposition reaction product
Selecting property；On the other hand, play the role of protecting amino, avoid the side reaction that two molecule aniline condensations generate azobenzene.
As the present invention preferably technical solution, the acid anhydrides is in phthalic anhydride, hydrogenation phthalic anhydride or hydrogenated methyl phthalic anhydride
It is a kind of or at least two combination；The combination is typical but non-limiting example has: the combination of phthalic anhydride and hydrogenation phthalic anhydride, phthalic anhydride with
Combination, hydrogenation phthalic anhydride and combination of hydrogenated methyl phthalic anhydride of hydrogenated methyl phthalic anhydride etc..
Preferably, the acid anhydrides is selected from phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthaacid acid
One of acid anhydride, tetrabydrophthalic anhydride or methyl tetrahydrophthalic anhydride or at least two combination；The combination allusion quotation
Type but non-limiting example has: combination, phthalic anhydride and the methyl six of phthalic anhydride and hexahydrophthalic anhydride
Combination, phthalic anhydride and the tetrabydrophthalic anhydride of hydrogen phthalic anhydride, hexahydrophthalic anhydride and tetrahydro are adjacent
Combination, methylhexahydrophthalic anhydride and combination of methyl tetrahydrophthalic anhydride of phthalate anhydride etc..
Preferably, the aromatic acid is selected from one of phthalic acid, M-phthalic acid or terephthalic acid (TPA)
Or at least two combination；The combination is typical but non-limiting example has: the combination of phthalic acid and M-phthalic acid, neighbour
Combination, M-phthalic acid and combination of terephthalic acid (TPA) of phthalic acid and terephthalic acid (TPA) etc..
Due to hydrogenating the higher cost of phthalic anhydride and hydrogenated methyl phthalic anhydride, temperature needed for aromatic acid and aniline reaction
It is higher, and phthalic anhydride is cheap and easy to get, and higher with aniline reaction activity, therefore further excellent in step of the present invention (1)
Choosing carries out ammonolysis reaction using phthalic anhydride and aniline.
As the present invention preferably technical solution, the molar ratio of the acid anhydrides and/or aromatic acid and the aniline
For 0.5-1.5:1；Such as it can be 0.5:1,0.6:1,0.7:1,0.8:1,0.9:1,1:1,1.1:1,1:1.2,1:1.3,1:
1.4 or 1:1.5 etc..
As the present invention preferably technical solution, the organic solvent in ethyl alcohol, pyridine, toluene or hexamethylene one
Kind or at least two combination；The combination is typical but non-limiting example has the combination of ethyl alcohol and pyridine, ethyl alcohol and toluene
Combination, ethyl alcohol and the combination of hexamethylene, the combination of pyridine and toluene, the combination of pyridine and hexamethylene, toluene or hexamethylene group
Close etc..
Preferably, the organic solvent is hexamethylene.
As the present invention preferably technical solution, the temperature of ammonolysis described in step (1) or acylation reaction is 100-200
DEG C, such as can be 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150
DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C or 200 DEG C etc.；Further preferably
It is 160-180 DEG C.
Preferably, the time of ammonolysis described in step (1) or acylation reaction be 30-240min, such as can be 30min,
40min、50min、60min、70min、80min、90min、100min、110min、120min、150min、160min、
180min, 200min, 210min or 240min etc.；Further preferably 30-60min.
As the present invention preferably technical solution, the molar ratio of the nitrobenzene and the aniline is 1:1-10；Such as it can
To be 1:1,1:1.5,1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9 or 1:10 etc..
Preferably, the molar ratio of the nitrobenzene and the catalyst is 1:0.5-1；Such as can be 1:0.5,1:0.6,
1:0.7,1:0.8,1:0.9 or 1:1 etc..
As the present invention preferably technical solution, the catalyst is quaternary amine alkali.
Preferably, the quaternary amine alkali is tetramethylammonium hydroxide.
Preferably, step (2) further includes that highly basic is added into the solution that step (1) obtains.
On the one hand the purpose that highly basic is added is the reaction product of neutralization procedure (1), prevent itself and catalyst reaction, cause not
Necessary waste；On the other hand, in the reaction process of step (2), amide group can be removed from aniline generates carboxylic acid, passes through
Highly basic, which is added, can make carboxylic acid be converted into carboxylate to enter water phase, facilitate its separation with reaction product.
Preferably, the highly basic is sodium hydroxide and/or potassium hydroxide.
Preferably, the molar ratio of the catalyst and the highly basic is 1:0.2-5；Such as it can be 1:0.2,1:0.3,1:
0.5、1:0.6、1:0.8、1:1、1:1.2、1:1.5、1:1.8、1:2、1:2.2、1:2.5、1:2.8、1:3、1:3.2、1:3.5、
1:3.8,1:4,1:4.2,1:4.5,1:4.8 or 1:5 etc..
As the present invention preferably technical solution, the temperature of condensation reaction described in step (2) is 30-150 DEG C, such as can
To be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C
Deng；Preferably 50-100 DEG C.
Preferably, the time of condensation reaction described in step (2) be 0.5-10h, such as can be 0.5h, 0.8h, 1h,
1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h etc.；Further preferably 1-
3h。
Further include step (3) as the present invention preferably technical solution, the preparation method: step (2) being obtained mixed
It closes solution to mix with sodium hydroxide solution, in 20-80 DEG C of (such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 under stirring
DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc.) under reaction, separation water phase and oily phase is hydrolyzed, by oily phase
Vacuum distillation removes the organic solvent and unreacted aniline, obtains 4 nitrodiphenyl amine and the mixing of 4- nitrosodiphenylamine
Object.
Include the following steps: as the present invention preferably technical solution, the preparation method
(1) phthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, in 160-180
Ammonolysis reaction 30-60min at DEG C obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of the phthalic anhydride and the hexamethylene is 1:1-20, the phthalic anhydride with
The molar ratio of the aniline is 0.5-1.5:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Benzophenone amine aqueous solution is passed through in micro passage reaction, the condensation reaction 1-3h at 50-100 DEG C, generate 4 nitrodiphenyl amine and
4- nitrosodiphenylamine；
Wherein, the molar ratio of the nitrobenzene and the aniline is 1:1-10, the nitrobenzene and the tetramethyl hydrogen-oxygen
Change the molar ratio of ammonium as 1:0.5-1, the molar ratio of the tetramethylammonium hydroxide and the sodium hydroxide is 1:0.2-5；
(3) mixed solution that step (2) obtains is mixed with sodium hydroxide solution, under stirring at 20-80 DEG C into
Row hydrolysis, separation water phase and oily phase, by the oil, mutually vacuum distillation removes the organic solvent and unreacted aniline, obtains
To the mixture of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine.
Micro passage reaction described in step (1) and step (2) includes two portions of micro-channel mixer and pipeline reactor
Point, with stronger mass-and heat-transfer efficiency, the yield of ammonolysis reaction is helped to improve, can be used for industrial continuous production.When into
When row continuous production 4 nitrodiphenyl amine and 4- nitrosodiphenylamine, the reaction time described in step (1) and step (2) is object
The residence time of material in the reactor.
Hexamethylene is recycled after the mixture split-phase of the water and hexamethylene that evaporate in the reaction process of step (2)；Not
The adjacent carboxybenzoyl aniline of reaction generates phthalate and aniline, condensation reaction after the hydrolysis in step (3)
The phthalate generated with hydrolysis can be recycled from water phase.
Compared with prior art, the invention has the following advantages:
The present invention by using the reaction product of aniline and acid anhydrides and/or aromatic acid replace aniline and nitrobenzene into
Row reaction, on the one hand increases its steric hindrance reacted with nitrobenzene ortho position, effectively inhibits the generation of ortho position reaction product,
Improve the selectivity of contraposition reaction product；On the other hand, play the role of protecting amino, avoid two molecule aniline condensations
Generate the side reaction of azobenzene.Method provided by the invention prepare 4 nitrodiphenyl amine and 4- nitrosodiphenylamine yield (with
Nitrobenzene meter) it can reach 75% or more, reduce the energy consumption of separating-purifying link, and raw material acid anhydrides and aromatic dicarboxylic used
Cost is relatively low for acid, is suitable for industrialized production.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides the preparation methods of a kind of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine, include the following steps:
(1) phthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, at 160 DEG C
Ammonolysis reaction 60min obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of phthalic anhydride acid anhydrides and hexamethylene is 1:5, the molar ratio of phthalic anhydride and aniline
For 1.5:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Benzophenone amine aqueous solution is passed through in micro passage reaction, the condensation reaction 3h at 50 DEG C, generates 4 nitrodiphenyl amine and 4- nitrous
Base diphenylamines；
Wherein, the molar ratio of nitrobenzene and aniline is 1:1.2, and the molar ratio of nitrobenzene and tetramethylammonium hydroxide is 1:1,
Tetramethylammonium hydroxide and the molar ratio of sodium hydroxide are 1:2.4；
(3) mixed solution that step (2) obtains is mixed with 22% sodium hydroxide solution, under stirring at 80 DEG C
Reaction, separation water phase and oily phase is hydrolyzed, by oil phase vacuum distillation removal organic solvent and unreacted aniline, obtains 4- nitre
The mixture of base diphenylamines and 4- nitrosodiphenylamine, yield (in terms of nitrobenzene) are 93.3%.
Comparative example 1
4 nitrodiphenyl amine and 4- nitrosodiphenylamine directly are prepared using aniline and nitrobenzene as raw material, specific steps are such as
Under:
Aniline is dissolved in hexamethylene, is then passed through micro passage reaction with nitrobenzene, tetramethylammonium hydroxide aqueous solution
In, condensation reaction 3h, stands split-phase after reaction at 50 DEG C, by oily mutually vacuum distillation removal organic solvent and unreacted
Aniline obtains the mixture of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine；
Wherein, the mass ratio of aniline and hexamethylene is 1:3.5, and the molar ratio of nitrobenzene and aniline is 1:1.2, nitrobenzene with
The molar ratio of tetramethylammonium hydroxide is 1:1.
After measured, the yield (in terms of nitrobenzene) for the product that comparative example 1 obtains is 50.5%, far below the present invention.
Embodiment 2
(1) phthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, at 180 DEG C
Ammonolysis reaction 30min obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of phthalic anhydride and hexamethylene is 1:10, and the molar ratio of phthalic anhydride and aniline is
0.5:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Benzophenone amine aqueous solution is passed through in micro passage reaction, the condensation reaction 1h at 100 DEG C, generates 4 nitrodiphenyl amine and 4- nitrous
Base diphenylamines；
Wherein, the molar ratio of nitrobenzene and aniline is 1:3, and the molar ratio of nitrobenzene and tetramethylammonium hydroxide is 1:0.5,
Tetramethylammonium hydroxide and the molar ratio of sodium hydroxide are 1:3；
(3) mixed solution that step (2) obtains is mixed with the sodium hydroxide solution of 22wt%, at 40 DEG C under stirring
Under be hydrolyzed reaction, oily mutually vacuum distillation removal organic solvent and unreacted aniline are obtained 4- by separation water phase and oily phase
The mixture of nitrodiphenylamine and 4- nitrosodiphenylamine, yield (in terms of nitrobenzene) are 79.7%.
Embodiment 3
(1) phthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, at 170 DEG C
Ammonolysis reaction 45min obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of phthalic anhydride and hexamethylene is 1:1, and the molar ratio of phthalic anhydride and aniline is
0.7:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Benzophenone amine aqueous solution is passed through in micro passage reaction, the condensation reaction 1.5h at 80 DEG C, generates 4 nitrodiphenyl amine and 4- is sub-
Nitrodiphenylamine；
Wherein, the molar ratio of nitrobenzene and aniline is 1:5, and the molar ratio of nitrobenzene and tetramethylammonium hydroxide is 1:0.8,
Tetramethylammonium hydroxide and the molar ratio of sodium hydroxide are 1:4；
(3) mixed solution that step (2) obtains is mixed with the sodium hydroxide solution of 22wt%, at 20 DEG C under stirring
Under be hydrolyzed reaction, oily mutually vacuum distillation removal organic solvent and unreacted aniline are obtained 4- by separation water phase and oily phase
The mixture of nitrodiphenylamine and 4- nitrosodiphenylamine, yield (in terms of nitrobenzene) are 76.6%.
Embodiment 4
(1) phthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, at 100 DEG C
Ammonolysis reaction 240min obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of phthalic anhydride and hexamethylene is 1:20, and the molar ratio of phthalic anhydride and aniline is
1:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Benzophenone amine aqueous solution is passed through in micro passage reaction, the condensation reaction 10h at 30 DEG C, generates 4 nitrodiphenyl amine and 4- nitrous
Base diphenylamines；
Wherein, the molar ratio of nitrobenzene and aniline is 1:2, and the molar ratio of nitrobenzene and tetramethylammonium hydroxide is 1:1, four
The molar ratio of ammonium hydroxide and sodium hydroxide is 1:2；
(3) mixed solution that step (2) obtains is mixed with the sodium hydroxide solution of 22wt%, at 60 DEG C under stirring
Under be hydrolyzed reaction, oily mutually vacuum distillation removal organic solvent and unreacted aniline are obtained 4- by separation water phase and oily phase
The mixture of nitrodiphenylamine and 4- nitrosodiphenylamine, yield (in terms of nitrobenzene) are 81.3%.
Embodiment 5
(1) hexahydrophthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, 150
Ammonolysis reaction 90min at DEG C obtains adjacent carboxy cyclohex alkane formailide solution；
Wherein, the mass ratio of hexahydrophthalic anhydride and hexamethylene is 1:15, hexahydrophthalic anhydride and aniline
Molar ratio is 1:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Hexamethylene formailide solution is passed through in micro passage reaction, the condensation reaction 5h at 60 DEG C, generates 4 nitrodiphenyl amine and 4-
Nitrosodiphenylamine；
Wherein, the molar ratio of nitrobenzene and aniline is 1:1.2, and the molar ratio of nitrobenzene and tetramethylammonium hydroxide is 1:1,
Tetramethylammonium hydroxide and the molar ratio of sodium hydroxide are 1:1.2；
(3) mixed solution that step (2) obtains is mixed with the sodium hydroxide solution of 22wt%, at 70 DEG C under stirring
Under be hydrolyzed reaction, oily mutually vacuum distillation removal organic solvent and unreacted aniline are obtained 4- by separation water phase and oily phase
The mixture of nitrodiphenylamine and 4- nitrosodiphenylamine, yield (in terms of nitrobenzene) are 83.5%.
Embodiment 6
(1) phthalic acid is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, the acyl at 200 DEG C
Change reaction 50min, obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of phthalic acid and hexamethylene is 1:8, and the molar ratio of phthalic acid and aniline is 1:1；
(2) the adjacent carboxyl for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Benzophenone amine aqueous solution is passed through in micro passage reaction, the condensation reaction 0.5h at 150 DEG C, generates 4 nitrodiphenyl amine and 4- is sub-
Nitrodiphenylamine；
Wherein, the molar ratio of nitrobenzene and aniline is 1:2, and the molar ratio of nitrobenzene and tetramethylammonium hydroxide is 1:1, four
The molar ratio of ammonium hydroxide and sodium hydroxide is 1:2；
(3) mixed solution that step (2) obtains is mixed with the sodium hydroxide solution of 22wt%, at 80 DEG C under stirring
Under be hydrolyzed reaction, oily mutually vacuum distillation removal organic solvent and unreacted aniline are obtained 4- by separation water phase and oily phase
The mixture of nitrodiphenylamine and 4- nitrosodiphenylamine, yield (in terms of nitrobenzene) are 86.3%.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. the preparation method of a kind of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine, which is characterized in that the preparation method includes
Following steps:
(1) acid anhydrides and/or aromatic acid and aniline are dissolved in organic solvent, carry out ammonolysis or acylation reaction；
(2) nitrobenzene and catalyst are added in the solution that step (1) obtains, carry out condensation reaction, generate 4 nitrodiphenyl amine
With 4- nitrosodiphenylamine.
2. preparation method according to claim 1, which is characterized in that the acid anhydrides is selected from phthalic anhydride, hydrogenation phthalic anhydride or methyl
Hydrogenate the combination of one of phthalic anhydride or at least two；
Preferably, the acid anhydrides is selected from phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, four
One of hydrogen phthalic anhydride or methyl tetrahydrophthalic anhydride or at least two combination, further preferably adjacent benzene
Dicarboxylic acid anhydride；
Preferably, the aromatic acid is selected from one of phthalic acid, M-phthalic acid or terephthalic acid (TPA) or extremely
Few two kinds of combination.
3. preparation method according to claim 1 or 2, which is characterized in that the acid anhydrides and/or aromatic acid and institute
The molar ratio for stating aniline is 0.5-1.5:1.
4. preparation method according to claim 1-3, which is characterized in that the organic solvent is selected from ethyl alcohol, pyrrole
One of pyridine, toluene or hexamethylene or at least two combination；
Preferably, the organic solvent is hexamethylene.
5. preparation method described in any one of -4 according to claim 1, which is characterized in that ammonolysis or acyl described in step (1)
The temperature for changing reaction is 100-200 DEG C, preferably 160-180 DEG C；
Preferably, the time of ammonolysis described in step (1) or acylation reaction is 30-240min, further preferably 30-60min.
6. preparation method according to claim 1-5, which is characterized in that the nitrobenzene rubs with the aniline
You are than being 1:1-10；
Preferably, the molar ratio of the nitrobenzene and the catalyst is 1:0.5-1.
7. preparation method according to claim 1-6, which is characterized in that the catalyst is quaternary amine alkali；
Preferably, the quaternary amine alkali is tetramethylammonium hydroxide；
Preferably, step (2) further includes that highly basic is added into the solution that step (1) obtains；
Preferably, the highly basic is sodium hydroxide and/or potassium hydroxide；
Preferably, the molar ratio of the catalyst and the highly basic is 1:0.2-5.
8. preparation method according to claim 1-7, which is characterized in that condensation reaction described in step (2)
Temperature is 30-150 DEG C, preferably 50-100 DEG C；
Preferably, the time of condensation reaction described in step (2) is 0.5-10h, further preferably 1-3h.
9. preparation method according to claim 1-8, which is characterized in that the preparation method further includes step
(3): the mixed solution that step (2) obtains being mixed with sodium hydroxide solution, is hydrolyzed at 20-80 DEG C under stirring anti-
It answers, separation water phase and oily phase, oily mutually vacuum distillation is removed into the organic solvent and unreacted aniline, obtains 4- nitro hexichol
Amine and 4- nitrosodiphenylamine mixture.
10. -9 described in any item preparation methods according to claim 1, which is characterized in that the preparation method includes following step
It is rapid:
(1) phthalic anhydride is dissolved in hexamethylene, is passed through in micro passage reaction together with aniline, at 160-180 DEG C
Ammonolysis reaction 30-60min obtains adjacent carboxybenzoyl aniline solution；
Wherein, the mass ratio of the phthalic anhydride and the hexamethylene is 1:1-20, the phthalic anhydride with it is described
The molar ratio of aniline is 0.5-1.5:1；
(2) the adjacent carboxyl benzene first for obtaining the aqueous solution of tetramethylammonium hydroxide and sodium hydroxide, nitrobenzene and step (1)
Anilide solution is passed through in micro passage reaction, the condensation reaction 1-3h at 50-100 DEG C, generates 4 nitrodiphenyl amine and 4- is sub-
Nitrodiphenylamine；
Wherein, the molar ratio of the nitrobenzene and the aniline is 1:1-10, the nitrobenzene and the tetramethylammonium hydroxide
Molar ratio be 1:0.5-1, the molar ratio of the tetramethylammonium hydroxide and the sodium hydroxide is 1:0.2-5；
(3) mixed solution that step (2) obtains is mixed with sodium hydroxide solution, carries out water under stirring at 20-80 DEG C
Solution reaction, separation water phase and oily phase, by the oil, mutually vacuum distillation removes the organic solvent and unreacted aniline, obtains 4-
The mixture of nitrodiphenylamine and 4- nitrosodiphenylamine.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101277923A (en) * | 2005-05-16 | 2008-10-01 | 株式会社锦湖石油化学 | Method for preparing 4-aminodiphenylamine |
| CN101665437A (en) * | 2001-07-23 | 2010-03-10 | 弗莱克塞斯美国公司 | Process for preparing 4-aminodiphenylamine |
| CN101735074A (en) * | 2008-11-06 | 2010-06-16 | 南化集团研究院 | Method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbonyl aniline |
| CN102010339A (en) * | 2009-09-04 | 2011-04-13 | 南化集团研究院 | Synthetic method of 4-aminodiphenylamine |
| CN103819346A (en) * | 2014-03-17 | 2014-05-28 | 山东尚舜化工有限公司 | Production equipment and production technology of precursor of 4-aminodiphenylamine |
| WO2014133420A2 (en) * | 2013-02-28 | 2014-09-04 | Godzoev Oleg Alexandrovich | Method for producing 4-aminodiphenylamine and alkylated derivatives thereof |
| US20150045584A1 (en) * | 2012-03-07 | 2015-02-12 | Nocil Limited | Process for preparing 4-aminodiphenylamine |
| CN107311883A (en) * | 2017-06-20 | 2017-11-03 | 四川国光农化股份有限公司 | The synthetic method of one plant growth regulators |
-
2018
- 2018-10-26 CN CN201811257623.1A patent/CN109232275B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665437A (en) * | 2001-07-23 | 2010-03-10 | 弗莱克塞斯美国公司 | Process for preparing 4-aminodiphenylamine |
| CN101277923A (en) * | 2005-05-16 | 2008-10-01 | 株式会社锦湖石油化学 | Method for preparing 4-aminodiphenylamine |
| CN101735074A (en) * | 2008-11-06 | 2010-06-16 | 南化集团研究院 | Method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbonyl aniline |
| CN102010339A (en) * | 2009-09-04 | 2011-04-13 | 南化集团研究院 | Synthetic method of 4-aminodiphenylamine |
| US20150045584A1 (en) * | 2012-03-07 | 2015-02-12 | Nocil Limited | Process for preparing 4-aminodiphenylamine |
| WO2014133420A2 (en) * | 2013-02-28 | 2014-09-04 | Godzoev Oleg Alexandrovich | Method for producing 4-aminodiphenylamine and alkylated derivatives thereof |
| CN103819346A (en) * | 2014-03-17 | 2014-05-28 | 山东尚舜化工有限公司 | Production equipment and production technology of precursor of 4-aminodiphenylamine |
| CN107311883A (en) * | 2017-06-20 | 2017-11-03 | 四川国光农化股份有限公司 | The synthetic method of one plant growth regulators |
Non-Patent Citations (4)
| Title |
|---|
| N.R.AYYANGAR等: ""A NOVSL RSACTION OF ACETANILIDE WITH NITRODBNZBNE IN DMSO - AN UNUSUAL SOLVENT ASSISTRD RBGIOSELECTIVR AROMATIC NUCLEOPHILIC SUBSTITUTION", 《TEMHEDRON LETTERS》 * |
| RUECK-BRAUN, K.，PRIEWISCH, B.: "Nitrosoarenes", 《SCIENCE OF SYNTHESIS》 * |
| 崔小明: "对氨基二苯胺生产技术及其进展", 《化工文摘》 * |
| 薛永震，陈永平: "对氨基二苯胺合成技术进展", 《化学工业与工程技术》 * |
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