CN109415303A - Utilize the method for preparing aminoazo-compound of the auxiliary agent dissolved with nitrogen oxides - Google Patents
Utilize the method for preparing aminoazo-compound of the auxiliary agent dissolved with nitrogen oxides Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
Abstract
Relate to the use of the method for preparing aminoazo-compound of the auxiliary agent dissolved with nitrogen oxides, more particularly to the auxiliary agent including that will play stabilizer function (auxiliary substance) is used as reaction medium (reaction medium), heating completes rearrangement technique (rearrangement process) step reset comprising the raw mixture of diazonium compound, auxiliary agent partially and/or is all used as the reaction mixture that reaction medium is prepared from the diazotising continuous processing of amine compounds by the continuous use of above-mentioned raw materials compound, yield, stability and the high new method for preparing aminoazo-compound of economy.
Description
Technical field
The present invention relates to the method for preparing aminoazo-compound by resetting diazonium compound, above-mentioned diazonium compound will
Auxiliary agent is used as reaction medium and prepares from amine compounds, in particular to by continuously resetting comprising 1,3- biphenyl triazenes
The method that mixture prepares p- aminoazabenzol, wherein p- aminoazabenzol is from the aniline as aromatic amine, in promoter effect
The aromatic diazo compound of lower diazotising.More particularly to using p- aminoazabenzol obtained by being hydrocracked preparation virtue
Fragrant race's diamines, the specially method of p-PDA.
Background technique
P-PDA (para-phenylenediamine, p-PDA) is in the widely used most important virtue of chemical field
One of fragrant race's diamines.For example, p-PDA is used as cosmetics, fuel, the raw material of antioxidant or in fuel additive and coloring
The various fields such as agent are used extensively.In addition, being used as manufacture as the functional fiber with drug resistance, heat resistance and high rigidity
Fypro (Aramid fiber), heat resistance and high functionality polyimides or the raw material as polyurethane to benzene two
Isocyanates base stock etc., application range is very wide.
The preparation method of above-mentioned p-PDA, it has been disclosed that have and react nitric acid and ammonia in chlorobenzene and prepare p-NA
(para-nitroaniline), later to the method that it carries out hydrogenation (hydrogenation).But in above-mentioned preparation
In method, in nitrification (nitration) reaction for carrying out chlorobenzene, generated using the ratio of 65:35 weight % as isomerism
Positive (ortho) of object and to (para) nitro-chlorobenzene.In the process, because can not purely separate p- nitro-chlorobenzene (p-
Nitrochlorobenzene), isomer is remained in the p-PDA as end product, thus in the presence of being difficult to make
The shortcomings that p-PDA of standby high-purity.
In addition, direct hydrogenation reaction p-NA prepares the technique of p-PDA, generally p-NA is dissolved in
Polar solvent prepares slurry, under high pressure using noble metal catalyst it is carried out lightization react, accordingly, there exist for recycle
The catalyst of high price and removal are difficult to the higher boiling removed and carry out solution, and the high pressure reactor of complex and expensive, distillation is needed to set
The disadvantage of standby and reclaimer etc..Therefore, it is necessary to have the p-PDA preparation method of the high-purity of economy.
From the above point of view, it is disclosed in each leading document and promising prepares p-PDA diazotising
(diazotization) method of aniline (aniline).The most common method be using inorganic acid (inorganic acid) and
The technique of alkali nitrites (alkaline nitrite).For example, being recorded in U.S.'s registered patent the 2nd, 894,942
There are inorganic acid and alkali nitrites, diazotising aniline is finally prepared under the conditions of 0 DEG C~50 DEG C of temperature
The technique of p-PDA.
But above-mentioned preparation method is used to prepare the intermediate 1 of p-PDA, 3- aminoazabenzol (1,3- in preparation
Diphenyltriazene, 1,3-DPT) in technique, the benzene as reactive very high intermediate is generated as by-product
The diazonium nitrite such as amine diazonium nitrite (aniline diazonium nitrite), potentially there are the danger of explosion.
Therefore, U.S.'s registered patent the 4th, 020, No. 052, the 4th, 279, No. 815 and the 6th, 245,943It is recorded in number
Utilize the technique of nitrogen oxides (nitrogen oxides) diazotising aniline.In this process, aniline is exposed to first and includes
It, then will be remaining to prepare 1,3- aminoazabenzol by diazo-reaction in the gas of 20 DEG C~55 DEG C of nitrogen oxides
Gas be heated to there are the decomposition temperature of the benzene diazonium nitrite of explosion danger (benzene diazonium nitrite) with
On.(rearrangement) 1,3- amino is reset followed by p- aminoazabenzol (p-aminoazobenzene, p-AABz)
Azobenzene.Finally, occurring that hydroperoxide decomposition reaction (hydrogenolysis) is added to generate p-PDA.
In addition, record in U.S.'s registered patent the 4th, 123,466 similar makes in the state of there are sulfuric acid
With the method for nitrogen oxides, and U.S.'s registered patent the 4th, 020,051, the 4th, 275, No. 003 it is equal in record complete
The colleague of Decomposition of benzene diazonium nitrite, the method that aniline is reacted using nitrogen oxides.
Summary of the invention
Problems to be solved by the invention
In the preparation method of the prior art for preparing p-PDA from p-NA, exist the equipment for needing high price or
It is difficult to the shortcomings that obtaining high-purity.In addition, also preparing the p- amino as intermediate using diazo-reaction
During azobenzene, there are safety issues in the diazonium salt for being formed as intermediate, in order to avoid the centre of above-mentioned danger
The generation of body exists and needs by complicated preparation step or have the shortcomings that additional equipment, therefore, it is necessary to solve above-mentioned
Problem develops the preparation method of cheap, safe and effective p- aminoazabenzol, and in order to prepare above-mentioned p- aminoazabenzol,
It is necessary to develop the high preparation process of the yield, stability and the economy that prepare 1,3- aminoazabenzol from aniline.
Solution to the problem
The present inventor, which provides, a kind of not only as reflection reaction medium but also will play the auxiliary agent (auxiliary of stabilizer function
Substance) be used as reaction medium (reaction medium), thus improve the yield of the diazonium compound as product,
The new preparation method of the diazotising amine compounds of stability and economy.
In addition, in the present invention, the preparation method of diazotising amine compounds is characterized in that: by auxiliary agent (auxiliary
Substance) it is used as reaction medium.
In addition, the preparation method of above-mentioned diazotising amine compounds characterized by comprising
(a) the step of supplying amine compounds and auxiliary agent to reactor；
(b) mixture for reacting above-mentioned amine compounds and auxiliary agent, generates comprising the diazonium compound as target product
Primary first-order equation mixture interval (batch) step；
(c) in above-mentioned (b) step, above-mentioned primary first-order equation mixture is recycled while additional input amine, generates packet
The continuous recycling of the secondary response mixture of diazonium compound containing the concentration identical or high with primary first-order equation mixture
(continuous recirculation) step.
In addition, in the present invention, in the technique for preparing diazonium compound, above-mentioned continuous recirculating process can utilize use
The technique of other known batch reactors, semi batch reacor and/or other flow reactors.
In addition, in the present invention, after preparing above-mentioned diazonium compound, can continuously perform and be reset by following step
Technique of the diazonium compound to prepare aminoazo-compound:
(i) prepare the step of including the raw mixture of diazonium compound and auxiliary agent in the reactor；
(ii) rearrangement (rearrangement) step that heating above-mentioned raw materials mixture is reset.
In addition, before rearrangement step, may also include heating after terminating above-mentioned diazo-reaction and/or decompression be anti-
While answering mixture, the step of a part of goods whole of distillation removal auxiliary agent.
In addition, above-mentioned auxiliary agent can be used alone or in mixture of two or more from molten by nitryl compound, ether compound, polarity
The auxiliary agent selected in the group that agent, halogen solvent, alkane compound and aromatic hydrocarbons are constituted.
In addition, above-mentioned auxiliary agent can dissolve nitrogen oxides before being used as reaction medium, dissolved oxygen can be added, and above-mentioned dissolution
Nitrogen oxides and oxygen can dissolve to saturation state.
In addition, above-mentioned amine compounds can be aliphatic amine, aliphatic cyclammonium, aromatic amine, it is raw by diazo-reaction
At product can be aliphatic diazonium compound, aliphatic ring diazonium compound, aromatic diazo compound, and pass through weight
The product that row's reaction generates can be aliphatic amines azo-compound, aliphatic ring type amidogen azo-compound, aromatic amine
Base azo-compound.
In addition, the amine of above-mentioned amine compounds can be aniline (aniline), it can by the product that diazo-reaction generates
To be 1,3- aminoazabenzol (1,3-diphenyltriazene), and can be by the product that above-mentioned rearrangement reaction generates
P- aminoazabenzol (p-aminoazobenzene).
In addition, in the present invention, providing one kind from p- aminoazabenzol obtained above, by adding hydroperoxide decomposition reaction to prepare
The method of p-PDA.
Invention effect
The present invention provides a kind of by the way that auxiliary agent is used as reaction medium, receipts of the raising as the diazonium compound of product
The new aminoazo-compound preparation method of the diazotising amine compounds of rate, stability and economy.
Preferred forms
In the following, of the invention is described in detail.
The diazotising of aniline is that the reaction of 1,3- aminoazabenzol is generated according to following reaction equation.
(reaction equation 1)
In diazo-reaction of the invention, mainly generating object is 1,3- aminoazabenzol (p- aminoazabenzol), and can
According to reaction condition, generated together as by-product to (para) and positive (ortho) aminoazabenzol, right with unreacted aniline
(para) and positive (ortho) aminodiphenyl, to (para) and positive (ortho) nitroaniline, biphenyl and water.The 1,3- generated in this way
Aminoazabenzol again passes by following rearrangement, then can ultimately generate p- aminoazabenzol.
(reaction equation 2)
Above by the p- aminoazabenzol made from rearrangement reaction as target product, again by following reaction formula
3 plus hydroperoxide decomposition reaction be made p-PDA.Above-mentioned plus hydroperoxide decomposition reaction high temperature, high pressure atmosphere of hydrogen and there are catalyst
In the state of carry out, and in the present invention, using Ni catalyst, at 90 DEG C~110 DEG C of temperature and 30bar volume pressure into
Row.In following reaction, aniline produces Main By product, and this can again act as the raw material for preparing p-PDA.
(reaction equation 3)
It in the present invention, is the p- aminoazabenzol for preparing the raw material as p-PDA, using dissolved with nitrogen oxygen
The auxiliary agent of compound.
Refer to for nitrogen oxides of the invention and is typically expressed as NOxNitrification oxygenatedchemicals.It is real of the invention one
It applies in example, nitric oxide (NO) and nitrogen dioxide (NO2) diazo-reaction for use in the present invention.
For auxiliary agent of the invention be can sufficiently dissolve raw material (nitrogen oxides and oxygen including gaseous state) and
Product (including intermediate product) does not have reactive inertia (inert) ingredient to raw material and product, plays simultaneously
The substance for stablizing the stabilizer function of raw material and product is to play the progress for guaranteeing that desired reaction is safe and stable
Reaction medium effect substance.As long as can satisfy the substance of above-mentioned purpose, well known any substance can be used.
In the present invention, preferably, using the sewage auxiliary agent (anhydrous of moisture removal as above-mentioned auxiliary agent
auxiliary substance)。
Specifically, in the present invention, nitryl compound, ether compound, polar solvent, halogen molten can be used as auxiliary agent
Agent, alkane compound and aromatic hydrocarbons.Preferably, nitryl compound can be used alone or in mixture of two or more or contain
Halogen solvent.
Nitryl compound for use in the present invention specifically has following chemical formula (1) and (2):
H3C-R-CN (1)
Here, R is direct key or 1~15 CH2Key.Or
Here, R1And R2For direct key or 1~15 CH2Key.
Ether compound for use in the present invention specifically has following chemical formula (3) to (5):
H3C-R1-O-R2-CH3 (3)
Here, R1And R2For direct key or 1~15 CH2Key.Or
Here, R1To R3For direct key or 1~15 CH2Key.Or
Here, R1To R4For direct key or 1~15 CH2 key.
Specifically, polar solvent for use in the present invention can be from dimethyl sulfoxide (DMSO), dimethylformamide
(DMF), dimethyl acetamide (DMAc) in selection.
Specifically, halogen solvent for use in the present invention can be from chloromethanes (CH3Cl), methylene chloride (CH2Cl2), trichlorine
Methane (chloroform, CHCl3) and tetrachloromethane (CCl4) in selection.
Specifically, alkane compound for use in the present invention can be selected from the n- alkane or cycloalkane that carbon number is 3~40
It selects.
Specifically, the aromatic series carbon that aromatic hydrocarbons for use in the present invention can be 6~40 from carbon number hydrogenates
It closes and is selected in object.
An embodiment according to the present invention is needed first to occur that diazo-reaction in auxiliary agent by by nitrogen oxides
The process being dissolved in auxiliary agent.In addition, being dissolved to saturation state is advisable in order to dissolve the nitrogen oxides of sufficient amount wherein.
An embodiment according to the present invention, more preferably, the temperature for reducing auxiliary agent are dissolved (saturation) process.Preferably,
Temperature range can be 50 DEG C~50 DEG C.More preferably, 10 DEG C~30 DEG C be can be.Most preferably, 0 DEG C~20 DEG C be can be.
An embodiment according to the present invention, during dissolving nitrogen oxides, dissolving together with oxygen is advisable.More preferably
The dissolution of ground, nitrogen oxides or nitrogen oxides and oxygen is carried out to saturation state.
An embodiment according to the present invention is carried out after being once saturated using one of nitrogen oxides, reduces temperature, benefit
Secondary saturation is carried out with nitrogen oxides and oxygen.Alternatively, it is also possible to inversely implement.
An embodiment according to the present invention can be saturated nitrogen dioxide in primary saturation, and in secondary saturation together
It is saturated nitric oxide and oxygen.Alternatively, it is also possible to be saturated nitric oxide in primary saturation, and embezzles in secondary saturation and satisfy together
With nitrogen dioxide and oxygen.
The ratio (oxygen/nitrogen oxides) of an embodiment according to the present invention, above-mentioned oxygen and nitrogen oxides be with mole
Subject to 0 (only saturation nitrogen oxides)~1/20, more preferably 2~1/10, most preferably 1~1/4.Above-mentioned oxygen and nitrogen oxides volume
Molar ratio, in dissolution or saturation, the partial pressure by adjusting oxygen and oxides of nitrogen gas is adjusted.
An embodiment according to the present invention, the auxiliary agent dissolved with nitrogen oxides need to form mixture with raw material.It can incite somebody to action
Auxiliary agent dissolved with nitrogen oxides puts into raw material, or in contrast, can put into raw material dissolved with nitrogen oxides
Auxiliary agent.
An embodiment according to the present invention, above-mentioned raw materials substance can be used together with other substances such as solvents, can also be only
Raw material is direct plungeed into.
An embodiment according to the present invention, the temperature of auxiliary agent and raw material dissolved with nitrogen oxides can be identical or not
Together.In addition, dissolved with nitrogen oxides auxiliary agent and raw material can also be cooled to room temperature it is following.The temperature range of above-mentioned cooling
It is -20 DEG C~20 DEG C, preferably 0 DEG C~10 DEG C.
An embodiment according to the present invention, dissolution or saturation have the auxiliary agent of nitrogen oxides and raw material that can be cooled to often
It is put into while warm following, to form reaction mixture.The temperature range of above-mentioned cooling be -20 DEG C~20 DEG C, preferably 0 DEG C~
10℃。
An embodiment according to the present invention, dissolution or saturation have the muddy shocking milli of the reaction of the auxiliary agent and raw material of nitrogen oxides
Nothing can carry out diazo-reaction while being cooled to room temperature following.The temperature range of above-mentioned cooling is -20 DEG C~20 DEG C, compared with
Good is 0 DEG C~10 DEG C.
An embodiment according to the present invention, aniline can be used in above-mentioned raw materials substance, and acetonitrile can be used in auxiliary agent.
Continuous recirculation reactor can be used in an embodiment according to the present invention, the technique of diazotising aromatic amine.
Batch reactor can be used in the technique of an embodiment according to the present invention, diazotising aromatic amine.
The continuously manufacturing of diazotising aromatic amine may include following steps:
(a) the step of supplying aromatic amine and auxiliary agent to reactor；
(b) mixture for reacting above-mentioned aromatic amine and auxiliary agent, generates comprising the diazonium compound as target product
Primary first-order equation mixture interval (batch) step；
(c) recycle above-mentioned primary first-order equation mixture while additional input aromatic amine, generate comprising with it is primary anti-
Answer mixture identical or the continuous recycling (continuous of the secondary response mixture of the diazonium compound of high concentration
Recirculation) step.
In addition, an embodiment according to the present invention can also pass through interval, half in addition to above-mentioned continuous recirculating process
Continuous reaction process completes diazotization process.
An embodiment according to the present invention is handed over after above-mentioned diazotization process without additional purifying technique or solvent
It changes, the technique for resetting the diazonium compound in above-mentioned secondary response mixture can be continuously performed as follows.This is this hair
Bright feature, because diazotising can be continuously performed using identical auxiliary agent as reaction medium and reset technique.Above-mentioned rearrangement technique
Step are as follows:
(i) after above-mentioned (c) step, continue to heat the step of above-mentioned secondary response mixture completes rearrangement.
An embodiment according to the present invention, after above-mentioned (c) continuous recirculating process step, in above-mentioned (i) diazotising
Before step, it can add and execute while heating and/or depressurizing the above-mentioned secondary response mixture for completing diazo-reaction, steam
Evaporate the step of a part of goods whole except auxiliary agent.
An embodiment according to the present invention, in above-mentioned rearrangement step, the temperature range of heating is 15 DEG C~50 DEG C, preferably
It is 20 DEG C~35 DEG C.
An embodiment according to the present invention, above-mentioned rearrangement reaction time are 1 hour~10 hours, and preferably 2 hours~5 is small
When.
An embodiment according to the present invention may additionally include and steam under normal pressure or reduced pressure after above-mentioned rearrangement reaction
The step of evaporating reaction medium, to prepare p- aminoazabenzol.
An embodiment according to the present invention, above-mentioned distillation may proceed to the water generated in reaction and auxiliary agent forms vapor of mixture
Until object (azeotrope).
An embodiment according to the present invention, there are under the atmosphere of hydrogen of catalyst and high pressure, to comprising by above-mentioned heavy
The reaction medium that row reacts p- aminoazabenzol obtained carries out plus hydroperoxide decomposition reaction, finally prepares p-PDA.
An embodiment according to the present invention, above-mentioned catalyst are Raney nickel, and above-mentioned plus hydroperoxide decomposition reaction is 90 DEG C~110
DEG C temperature range in, in 50bar pressure below, preferably carried out under the pressure of 30bar.
Specific embodiment
(experimental example 1)
By as the acetonitrile of auxiliary agent (acetonitrile) 400g, the nitric oxide that molar ratio is 4:1 is put at 20 DEG C
(NO) and oxygen (O2) in, to prepare reaction medium.By in 18 DEG C of aniline 220g investment reaction medium, add in not additional
In the case where heat or cooling, slowly stirring is put into.It is obtained after diazo-reaction that the results are shown in Table 1.Therefore, aniline is total
Conversion ratio is 25%.
(experimental example 2)
By as the acetonitrile of auxiliary agent (acetonitrile) 800g, carbon dioxide (NO is put at 20 DEG C2) after, 4
The nitric oxide (NO) and oxygen (O that molar ratio is 4:1 are put at DEG C2) in, to prepare reaction medium.By 8~10 DEG C of aniline
400g, slowly stirring is put into reaction medium while cooling.It is obtained after diazo-reaction that the results are shown in Table 1.
Therefore, total conversion ratio of aniline is 24%.
(experimental example 3)
By as the ether of auxiliary agent (diethylether) 80g, the nitric oxide that molar ratio is 4:1 is put at 5 DEG C
(NO) and oxygen (O2) in, to prepare reaction medium.By 10 DEG C of aniline 30g, investment reaction is carried out while slowly stirring
In medium.It is obtained after diazo-reaction that the results are shown in Table 1.Therefore, total conversion ratio of aniline is 20%.
(experimental example 4)
By as the propionitrile of auxiliary agent (propionitrile) 800g, carbon dioxide (NO is put at 18 DEG C2) after, 4
The nitric oxide (NO) and oxygen (O that molar ratio is 4:1 are put at DEG C2) in, to prepare reaction medium.By 8~10 DEG C of aniline
400g, slowly stirring is put into reaction medium while cooling.It is obtained after diazo-reaction that the results are shown in Table 1.
Therefore, total conversion ratio of aniline is 24%.
[table 1]
ACN=acetonitrile；DEE=ether；PN=propionitrile；
A=aniline；B=1,3- aminoazabenzol (1,3-DPT)；
C=p- aminoazabenzol (p-AABz)；D=o- aminoazabenzol；
E=p- aminodiphenyl；F=o- aminodiphenyl；G=biphenyl；
H=p- nitroaniline；H=o- nitroaniline
ND=cannot be detected
In integrated artistic, to improve yield, it is necessary to improve 1,3- aminoazabenzol (the b ingredient in above-mentioned table 1)
Generate ratio.As shown in the result of above-mentioned diazotising experimental example, nitrogen dioxide is saturated to auxiliary agent first, is saturated again at low temperature
It the case where nitric oxide and oxygen and the case where use acetonitrile and propionitrile as auxiliary agent, help to obtain in high yield.
In addition, following Production Example specifically indicates after having the auxiliary agent diazotising aniline of nitrogen oxides using saturation, after
The continuous Production Example reset 1,3- aminoazabenzol and prepare p- aminoazabenzol.After completing rearrangement reaction, carried out using GC/Mass
Constituent analysis.The water generated in auxiliary agent and reaction is not included in the weight % recorded below.Although following Production Examples indicate tool
Body is implemented of the invention as a result, but unrestricted the scope of the present invention.
(Production Example 1)
By as the acetonitrile of auxiliary agent (acetonitrile) 500g, carbon dioxide (NO is put at 18 DEG C2) after, 4
The nitric oxide (NO) and oxygen (O that molar ratio is 4:1 are put at DEG C2) in, to prepare reaction medium.By 8~10 DEG C of aniline
250g, slowly stirring is put into reaction medium while cooling.Above-mentioned diazonium eliminates in terms of input amount that there are subtle
It is actually identical as the method for diazotising experimental example 2 except difference, and the combination after final diazotising is also tested with diazotising
Example 2 is identical.
Above-mentioned diazotizing reaction medium will be completed to heat immediately with 30~35 DEG C of temperature, be evaporated under reduced pressure later to
Until being formed together azeotropic mixture (azeotrope) with the 3.5 weight % of water generated in the reaction.It is removed by vacuum distillation
The acetonitrile of about 90 weight %.Then it, then by mixture is stirred 4 hours under conditions of maintaining 35 DEG C.Final result obtained is such as
Shown in table 2.
(Production Example 2)
By chloroform (chloroform, the CHCl as auxiliary agent3) 150g, the oxygen that molar ratio is 4:1 is put at 20 DEG C
Change nitrogen (NO) and oxygen (O2) in, to prepare reaction medium.By 15 DEG C of aniline 200g, investment is slowly stirred while cooling
Into reaction medium.It will complete above-mentioned diazotizing reaction medium to heat immediately with 28 DEG C of temperature, later to go to dechlorinate
It is imitative to be evaporated under reduced pressure.Pass through the acetonitrile of about 90 weight % of vacuum distillation removal.Then, then by mixture 28 DEG C of item is being maintained
It is stirred 4 hours under part.The results are shown in Table 2 made from final.
(Production Example 3)
By as the acetonitrile of auxiliary agent (acetonitrile) 400g, the nitric oxide that molar ratio is 1:1 is put at 22 DEG C
(NO) and oxygen (O2) in, to prepare reaction medium.By in 25 DEG C of aniline 220g investment reaction medium, add in not additional
In the case where heat or cooling, slowly stirring is put into.It will complete above-mentioned diazotizing reaction medium and carried out immediately with 30 DEG C of temperature
Heating.Then it, then by mixture is stirred 4 hours under conditions of maintaining 30 DEG C.The results are shown in Table 2 made from final.
(Production Example 4)
By tetrachloromethane (tetrachloromethane, the CCl as auxiliary agent4) 100g, molar ratio is put at 20 DEG C
For the nitric oxide (NO) and oxygen (O of 4:12) in, to prepare reaction medium.By 15 DEG C of aniline 50g, stirred while cooling
Investment is mixed into reaction medium.Above-mentioned diazotizing reaction medium will be completed to heat immediately with 22 DEG C of temperature.Then, then
Mixture is stirred 4 hours under conditions of maintaining 22 DEG C.The results are shown in Table 2 made from final.
(Production Example 5)
By n- octane (n-octane) 100g as auxiliary agent, carbon dioxide (NO is used at 5 DEG C2) be saturated after,
The nitric oxide (NO) and oxygen (O for being immediately 4:1 with molar ratio2) be saturated, to prepare reaction medium.By 10 DEG C of aniline
80g, stirring investment is into reaction medium while cooling.Above-mentioned diazotizing reaction medium will be completed immediately with 22 DEG C of temperature
Degree is heated.Then it, then by mixture is stirred 4 hours under conditions of maintaining 22 DEG C.Final result such as 2 institute of table obtained
Show.
(Production Example 6)
By as the dimethyl acetamide of auxiliary agent (dimethylformamide, DMF) 150g, carbon dioxide is used at 5 DEG C
(NO2) be saturated after, the nitric oxide (NO) and oxygen (O that are immediately 4:1 with molar ratio2) be saturated, to prepare to react
Medium.By 10 DEG C of aniline 80g, stirring investment is into reaction medium while cooling.It will complete above-mentioned diazotizing reaction
Medium is heated immediately with 30 DEG C of temperature.Then it, then by mixture is stirred 4 hours under conditions of maintaining 30 DEG C.Finally
It is obtained that the results are shown in Table 2.
[table 2]
ACN=acetonitrile；CHCl3=chloroform (chloroform)；
CCl4=tetrachloromethane；N-Oct=n- octane；DMF=dimethylformamide
A=aniline；B=1,3- aminoazabenzol (1,3-DPT)；
C=p- aminoazabenzol (p-AABz)；D=o- aminoazabenzol；
E=p- aminodiphenyl；F=o- aminodiphenyl；G=biphenyl；
H=p- nitroaniline；H=o- nitroaniline U=unknown compound；ND=cannot be detected
In integrated artistic, to improve yield, it is necessary to improve the life of p- aminoazabenzol (the c ingredient in above-mentioned table 2)
At ratio.From the result of above-described embodiment it is found that acetonitrile and tetrachloromethane are advantageous as auxiliary agent.
In addition, following experimental examples 5 specifically indicate continuously following again for the auxiliary agent diazotising aniline for having nitrogen oxides using saturation
Ring technique.To the mixture obtained by diazo-reaction, constituent analysis is carried out using GC-MS.It is generated in auxiliary agent and reaction
Water is not included in the weight % recorded below.Although following experimental examples indicate that specific implementation is of the invention as a result, but unrestricted
The scope of the present invention.
(experimental example 5)
In the state of filling aniline (aniline, AN) 400g in the reactor that volume is 1500ml, start diazotizing
Intermittent reaction.Above-mentioned reaction utensil is transmitted for substance and heat transmits outstanding recirculation circuit (recirculation
circuit).It is connected positioned at the outlet of reactor lower part with the suction inlet (suction inlet) of circulating pump.The discharge of said pump
The opening (opening) of the perforation reactor of mouth (discharge outlet) and reactor is connected to the pipe of inside reactor
Connection.The reaction that above-mentioned pipe can be emitted on the following position circulation of certain altitude (15cm) of liquid side (liquid level) is mixed
Close object.The flowing of the reaction mixture of circulation is set as 300ml/ points.
NOxSolution is sufficiently to be saturated nitrogen dioxide (NO in the acetonitrile (acetonitrile, ACN) of 656g2) after, 5
Nitric oxide (NO) and oxygen (O are saturated again with 4:1 (molar ratio) at a temperature of DEG C2) preparation.
Above-mentioned solution by while passing through reactor by NOxSolution discharge is to being located at the solution being present in reactor
The isolated pipe of reaction mixture of recycling of lower part pump to reactor, and the flowing velocity of above-mentioned solution is
4.7ml/min。
Reaction heat is removed by the inclusion of the casing of the reactor of the refrigerant of circulation, and reaction temperature is maintained 8~10 DEG C
Temperature range.The interval step of diazotization process terminates after reaction volume reaches 900ml.GC-MS measurement shows complete
The 1,3- ammonia of the ACN of weight %, the AN of 42.7 weight %, 11.6 weight % that mixture at diazotizing product is 44.5
P- aminoazabenzol (the p- of base azobenzene (1,3-diphenyltriazene, 1,3-DPT), 0.35 weight %
Aminoazobenzene, 4-AABz), the 2- aminoazabenzol (2-aminoazobenzene, 2-AABz) of 0.02 weight % and
The 2- aminobphenyl (2-aminobiphenyl, 2-ABPh) of 0.03 weight %, remaining is impurity.
And then implement diazotising recirculation step.Above-mentioned NOxSolution and aniline put into reactor simultaneously.Aniline is by again
After circulating pump discharge, the pipeline of continuous investment to recirculation circuit.Reaction product is obtained from reactor.NOxSolution and benzene
The every 4.7ml/ of the flowing of amine points and 3.6ml/ points.The flow adjustment of product is to maintain reaction volume, as a result its residence time
Calculate to obtain 108 points.The product of above-mentioned successive reaction is gathered in the container of separation.It is measured according to GC-MS, content is 44.1 weights
Measure the ACN of %, the AN of 33.8 weight %, the 1,3-DPT of 20.0 weight %, the 4-AABz of 0.41 weight %, 0.02 weight %
The 2-ABPh of 2-AABz, 0.02 weight %, remaining is other impurities.
In following Production Example 7 and 8, indicate in batch reactor complete aniline diazo-reaction, and then into
The result of the reaction of rearrangement diazonium compound.After completing rearrangement reaction, constituent analysis is carried out using GC/MS.Auxiliary agent and anti-
The water of generation is answered to be not included in the weight % recorded below.Although following Production Examples indicate that knot of the invention is embodied
Fruit, but unrestricted the scope of the present invention.
(Production Example 7)
To prepare the NO for being used as reaction mediumxSolution, by the ACN NO of the 360g of the moisture comprising 0.25 weight %2Sufficiently
After saturation, at 5 DEG C with NO/O2It is successively saturated for 4:1 (molar ratio).
Aniline 320g is slowly put into 2 hours to above-mentioned solution.At this point, the temperature of reactor maintains 8~10 DEG C of range.
After the investment for terminating aniline, the pressure in reactor, distillation removal ACN are slowly reduced.At this point, temperature maintains 28~32 DEG C
Range consumes about 2 hours until the ACN for removing 90%.
After the pressure of reactor is reformed into atmospheric pressure, the mixture at 35 DEG C in heating response device 8 hours,
Carry out the rearrangement process of 1,3-DPT.After reaction terminates, the content of each ingredient through GC measurement is 1.4 weight %, AN of ACN
70.2 weight %, 1,3-DPT, 0.0 weight %, 4-AABz, 21.7 weight %, 2-AABz, 1.6 weight %, 2-ABPh, 0.4 weight
Measure 0.03 weight %, 2-ABPh of %, 3-ABPh, 0.07 weight %, 0.25 weight % of phenylbenzene (BPhA) and remaining impurity.
(Production Example 8)
To prepare the NO for being used as reaction mediumxSolution, by comprising be subject to weight moisture less than 50ppm 360g
ACN NO2Sufficiently after saturation, at 5 DEG C with NO/O2It is successively saturated for 4:1 (molar ratio), with same as Example 2
Method carries out rearrangement technique, and the GC measurement result of the mixture ultimately generated is as follows:
0.0 weight %, 4-AABz of ACN 1.1 weight %, AN, 68.8 weight %, 1,3-DPT, 24.8 weight %, 2-
0.03 weight %, 2-ABPh of AABz 1.82 weight %, 2-ABPh, 0.3 weight %, 3-ABPh, 0.07 weight %, phenylbenzene
(BPhA) 0.21 weight % and remaining impurity.
Following Production Example specifically indicates to make the mixture obtained in above-mentioned Production Example, in the presence of a catalyst
Hydrogenation is carried out, to prepare the Production Example of p-PDA.After completing hydrogenation, constituent analysis is carried out using GC/Mass.
The water generated in auxiliary agent and reaction is not included in the weight % recorded below.Although following Production Examples indicate that this hair is embodied
It is bright as a result, but unrestricted the scope of the present invention.
(Production Example 9)
Will in above-mentioned Production Example 1 solution 200g obtained immediately with Raney's nickel (Raney Ni, Actimet M) 0.45g
It puts into pressurized reactor, is stirred at 90 DEG C of temperature and the pressure of 30bar (hydrogen) together, start hydrogenation.
In the reaction, temperature is slowly risen to 110 DEG C, hydrogenation 3 hours while gentle agitation (mild stirring).
The results are shown in Table 3 made from final.
(Production Example 10)
In addition to using solution obtained in above-mentioned Production Example 2, hydrogenate in method identical with Production Example 9 anti-
It answers.The results are shown in Table 3 made from final.
(Production Example 11)
In addition to using solution obtained in above-mentioned Production Example 3, hydrogenate in method identical with Production Example 9 anti-
It answers.The results are shown in Table 3 made from final.
* (Production Example 12)
In addition to using solution obtained in above-mentioned Production Example 4, hydrogenate in method identical with Production Example 9 anti-
It answers.The results are shown in Table 3 made from final.
(Production Example 13)
In addition to using solution obtained in above-mentioned Production Example 5, hydrogenate in method identical with Production Example 9 anti-
It answers.The results are shown in Table 3 made from final.
(Production Example 14)
In addition to using solution obtained in above-mentioned Production Example 6, hydrogenate in method identical with Production Example 9 anti-
It answers.The results are shown in Table 3 made from final.
(Production Example 15)
Using the solution obtained in above-mentioned Production Example 1, in addition to catalyst is replaced with PriCat Ni55/5P, with
The identical method of Production Example 9 carries out hydrogenation.The results are shown in Table 3 made from final.
[table 3]
A=aniline；C=p- aminoazabenzol (p-AABz)；D=o- aminoazabenzol；
E=p- aminodiphenyl；F=o- aminodiphenyl；G=biphenyl；
H=p- nitroaniline；H=o- nitroaniline；U=unknown compound；
ND=cannot be detected
Above-described embodiment is only to illustrate the present invention rather than limits, those skilled in the art should understand that, it can be with
It modifies, deform or equivalent replacement to the present invention.And do not departing within the spirit and scope of the present invention, it should all cover
In the scope of the claims of the present invention.
Industrial applicibility
It is industrially applicable the present invention relates to the method for preparing aminoazo-compound by resetting diazonium compound.
Claims (16)
1. a kind of method for preparing aminoazo-compound, it is characterised in that: by auxiliary agent, comprising:
(i) prepare the step of including the raw mixture of diazonium compound and auxiliary agent in the reactor；
(ii) rearrangement step that heating above-mentioned raw materials mixture is reset.
2. the method according to claim 1 for preparing aminoazo-compound, it is characterised in that: above-mentioned (i) step it is upper
State raw mixture continuous use part and/or all by auxiliary agent be used as reaction medium, from using batch reactor, it is semicontinuous instead
The technique for answering device or flow reactor, the reaction mixture of diazotising amine compounds preparation.
3. the method according to claim 2 for preparing aminoazo-compound, it is characterised in that: above-mentioned (i) step it is upper
Raw mixture continuous use part is stated and/or all by auxiliary agent as reaction medium, as from the amination included the following steps
Close following 2 secondary response mixtures of the reaction mixture of the diazotising continuous processing preparation of object:
(a) the step of supplying amine compounds and auxiliary agent to reactor；
(b) mixture for reacting above-mentioned amine compounds and auxiliary agent, generates one comprising the diazonium compound as target product
The interval step of secondary response mixture；
(c) above-mentioned primary first-order equation mixture is recycled simultaneously in additional input and the identical or different amine compounds of (b) step, it is raw
At the continuous recycling of the secondary response mixture of the diazonium compound comprising the concentration identical or high with primary first-order equation mixture
Step.
4. the method according to claim 3 for preparing aminoazo-compound, it is characterised in that: after above-mentioned (c) is rapid,
Before above-mentioned (i) step, execution can be added while heating and/or depressurizing above-mentioned raw materials mixture, distillation removal auxiliary agent
A part of goods whole step.
5. the method according to claim 1 or 2 for preparing aminoazo-compound, it is characterised in that: above-mentioned auxiliary agent can be single
Solely or the two or more uses of mixing are from by nitryl compound, ether compound, polar solvent, halogen solvent, alkane compound and virtue
The auxiliary agent selected in the group that fragrant race's hydrocarbon is constituted.
6. the method according to claim 1 or 2 for preparing aminoazo-compound, it is characterised in that: above-mentioned auxiliary agent,
As nitryl compound, such as following chemical formula (1) and (2)
H3C-R-CN (1)
(here, R is direct key or 1~15 CH2Key)
(here, R1And R2For direct key or 1~15 CH2Key)
As for ether compound, such as following chemical formula (3) to (5)
H3C-R1-O-R2-CH3 (3)
(here, R1And R2For direct key or 1~15 CH2Key)
(here, R1To R3For direct key or 1~15 CH2Key)
(here, R1To R4For direct key or 1~15 CH2Key)
As polar solvent, there are dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetamide (DMAc)；
As halogen solvent, there is chloromethanes (CH3Cl), methylene chloride (CH2Cl2), chloroform (chloroform, CHCl3) and four chloromethanes
Alkane (CCl4)；
As alkane compound, having carbon number is 3~40 n- alkane or cycloalkane；
As aromatic hydrocarbons, there are individually or mix the two or more aromatic series love talk compounds by carbon number 6~40
Substance is selected in the group of composition.
7. the method according to claim 1 or 2 for preparing aminoazo-compound, it is characterised in that: above-mentioned reaction medium
It is in above-mentioned auxiliary agent dissolved with nitrogen oxides.
8. the method according to claim 7 for preparing aminoazo-compound, it is characterised in that: above-mentioned reaction medium be
Saturation has nitrogen oxides in above-mentioned auxiliary agent.
9. the method according to claim 8 for preparing aminoazo-compound, it is characterised in that: above-mentioned reaction medium be
Saturation has nitrogen oxides and oxygen in above-mentioned auxiliary agent, and saturation temperature range is 50 DEG C~50 DEG C, and preferably 10 DEG C~30 DEG C, more preferably
It is 0 DEG C~20 DEG C, the ratio (oxygen/nitrogen oxides) of above-mentioned oxygen and nitrogen oxides is 0~1/20 to be subject to mole, preferably
It is 2~1/10, most preferably 1~1/4.
10. the method according to claim 9 for preparing aminoazo-compound, it is characterised in that: above-mentioned reaction medium is
It is carried out after being once saturated in above-mentioned auxiliary agent using nitrogen oxides, reduces temperature, while carrying out using nitrogen oxides and oxygen
Secondary saturation.
11. the method according to claim 10 for preparing aminoazo-compound, it is characterised in that: above-mentioned reaction medium is
It is saturated nitrogen dioxide in primary saturation, and is saturated nitric oxide and oxygen together in secondary saturation.
12. the method according to claim 3 for preparing aminoazo-compound, it is characterised in that: above-mentioned (b) step and/
Or (c) step preferably carries out in 0 DEG C~10 DEG C at -20 DEG C~20 DEG C of temperature range.
13. the method according to claim 1 for preparing aminoazo-compound, it is characterised in that: above-mentioned diazonium compound
It is prepared from amine compounds, above-mentioned amine compounds are preferably aromatic amines compound, more preferably aniline；Above-mentioned diazonium compound is preferable
For aromatic diazo compound, more preferably 1,3- aminoazabenzol；It is even that above-mentioned aminoazo-compound is preferably aromatic series amino
Nitrogen compound, more preferably p- aminoazabenzol.
14. the method according to claim 1 for preparing aminoazo-compound, it is characterised in that: above-mentioned auxiliary agent is anhydrous
Auxiliary agent.
15. the method according to claim 1 for preparing aminoazo-compound, it is characterised in that: above-mentioned heating is 15
DEG C~50 DEG C, preferably at 20 DEG C~35 DEG C, carry out 1~10 hour, preferably 2~5 hours.
16. a pair compound as made from the method according to claim 11 carries out plus hydroperoxide decomposition reaction prepares amine compounds
Method.
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| KR10-2016-0159942 | 2016-11-29 | ||
| KR1020160159942A KR101897210B1 (en) | 2016-11-29 | 2016-11-29 | Continuous recirculation process of diazotization for aromatic amines using an auxiliary substances saturated with nitrogen oxides |
| KR1020160159945A KR101882936B1 (en) | 2016-11-29 | 2016-11-29 | A manufacturing method of aminoazo compounds using nitrogen oxides-dissolved auxiliary substances |
| KR10-2016-0159945 | 2016-11-29 | ||
| PCT/KR2017/013857 WO2018101752A1 (en) | 2016-11-29 | 2017-11-29 | Method for preparing aminoazo compound by using nitrogen oxide-dissolved auxiliary substance |
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|---|---|---|---|---|
| US4020052A (en) * | 1975-11-25 | 1977-04-26 | E. I. Du Pont De Nemours And Company | Treatment of aromatic amines with gas mixtures derived from the oxidation of ammonia to effect diazotization/coupling |
| US4020051A (en) * | 1975-11-25 | 1977-04-26 | E. I. Du Pont De Nemours And Company | Control of nitrogen oxide reactions in off-gases from the diazotization/coupling of aromatic amines |
| KR800001701B1 (en) * | 1976-10-21 | 1980-12-31 | 에이 엔 리이디 | Process for the preparation of 1,3-diaryl triazenes |
| EP0052511A1 (en) * | 1980-11-17 | 1982-05-26 | E.I. Du Pont De Nemours And Company | Production of p-phenylenediamine |
| US4376730A (en) * | 1981-03-13 | 1983-03-15 | Akzo N.V. | Preparation of p-aminoazo-benzene from aniline |
| CN102731320A (en) * | 2012-07-09 | 2012-10-17 | 杭州龙山化工有限公司 | Method for absorbing nitrogen oxide tail gas and generating by-product p-phenylenediamine by using aniline |
| WO2016073275A1 (en) * | 2014-11-04 | 2016-05-12 | The Procter & Gamble Company | Azo direct dyes and method for dyeing hair using these dyes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1589936A (en) * | 1925-11-02 | 1926-06-22 | Newport Co | Process for the reduction of azo compounds to hydrazo compounds |
| DE3160400D1 (en) * | 1980-03-12 | 1983-07-14 | Akzo Nv | Process for the preparation of p-aminoazobenzene from aniline |
| KR101794869B1 (en) * | 2015-11-24 | 2017-12-01 | 휴켐스주식회사 | Manufacturing method of aromatic diamine from aromatic monoamine comprising a step utilizing an auxiliary substance dissolving nitrogen oxides |
-
2017
- 2017-11-29 WO PCT/KR2017/013857 patent/WO2018101752A1/en active Application Filing
- 2017-11-29 JP JP2019520352A patent/JP6718558B2/en active Active
- 2017-11-29 CN CN201780039831.1A patent/CN109415303B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4020052A (en) * | 1975-11-25 | 1977-04-26 | E. I. Du Pont De Nemours And Company | Treatment of aromatic amines with gas mixtures derived from the oxidation of ammonia to effect diazotization/coupling |
| US4020051A (en) * | 1975-11-25 | 1977-04-26 | E. I. Du Pont De Nemours And Company | Control of nitrogen oxide reactions in off-gases from the diazotization/coupling of aromatic amines |
| KR800001701B1 (en) * | 1976-10-21 | 1980-12-31 | 에이 엔 리이디 | Process for the preparation of 1,3-diaryl triazenes |
| EP0052511A1 (en) * | 1980-11-17 | 1982-05-26 | E.I. Du Pont De Nemours And Company | Production of p-phenylenediamine |
| US4376730A (en) * | 1981-03-13 | 1983-03-15 | Akzo N.V. | Preparation of p-aminoazo-benzene from aniline |
| CN102731320A (en) * | 2012-07-09 | 2012-10-17 | 杭州龙山化工有限公司 | Method for absorbing nitrogen oxide tail gas and generating by-product p-phenylenediamine by using aniline |
| WO2016073275A1 (en) * | 2014-11-04 | 2016-05-12 | The Procter & Gamble Company | Azo direct dyes and method for dyeing hair using these dyes |
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| WO2018101752A1 (en) | 2018-06-07 |
| CN109415303B (en) | 2022-01-11 |
| JP2019518803A (en) | 2019-07-04 |
| JP6718558B2 (en) | 2020-07-08 |
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