CN110305037A - The synthetic method of the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol - Google Patents
The synthetic method of the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol Download PDFInfo
- Publication number
- CN110305037A CN110305037A CN201910639431.5A CN201910639431A CN110305037A CN 110305037 A CN110305037 A CN 110305037A CN 201910639431 A CN201910639431 A CN 201910639431A CN 110305037 A CN110305037 A CN 110305037A
- Authority
- CN
- China
- Prior art keywords
- resorcinol
- phenylazo
- bis
- chromoisomer
- selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
The invention discloses absorbing materials 2, the synthetic method of the selectivity chromoisomer of 4- bis- (phenylazo) resorcinol, it is first reacted using resorcinol with potassium hydroxide and generates resorcinol monopotassium salt, under phase transfer catalyst presence and solutions of weak acidity, diazonium salt of aniline and resorcinol monopotassium salt carry out coupling reaction in water phase and obtain containing 2,2,4- bis- (phenylazo) resorcinol crude product of 4- bis- (phenylazo) resorcinol Type B chromoisomer；Purified 2,4- bis- (phenylazo) resorcinol Type B chromoisomer for obtaining high-purity again.The method of the present invention, which can be avoided, uses expensive halogenated phenol as substrate, have many advantages, such as that raw material cost is low, high conversion rate, reaction condition are mild, simple to operation, the molar yield (in terms of resorcinol) of final 2,4- bis- (phenylazo) resorcinol Type B constitutional isomer can reach 90% or more.
Description
Technical field
The synthetic method of the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol.
Background technique
2,4- bis- (phenylazo) resorcinols are a kind of orchil, the molecule of 2,4- bis- (phenylazo) resorcinols
Structural formula are as follows:
After study, it has been found that can be formed between the N of 2,4- bis- (phenylazo) resorcinol intramoleculars, H atom faint
Hydrogen bond, different hydrogen bonds collectively form four chromoisomers.Structural formula is as follows:
The physical property that chromoisomer through testing the above-mentioned four kinds of structures isolated is shown is different.A type isomery
External see is in crocus, and Type B isomers appearance is in claret, and c-type isomers appearance is in light yellow, and D type isomers appearance is in
Large red.By largely comparing and solvent screening test discovery, only above-mentioned Type B isomers is configured to 10% ethyl lactate solution
Afterwards, solution is in clear shape, no flocculent undissolved substance.
The comparison tested by UV absorption, it was confirmed that above-mentioned Type B structure has excellent UV absorption performance.Due to B
2,4- bis- (phenylazo) resorcinol of type structure has excellent UV absorption, thunderstorm activity performance, is used in light
The fields such as, electronics, space flight and aviation.It applies in military industry, is even more external right as the invisible coating in national defense industry
The blocking technology in China.
2,4- bis- (phenylazo) resorcinol can be as resorcinol and diazonium salt of aniline through made from coupling reaction.
In resorcinol when carrying out coupling reaction with diazonium salt of aniline, 2,4- bis- (phenylazo) resorcinol of generation
Content is low, and product impurities are complicated, include 4,6- bis- (phenylazo) resorcinol, 2- (phenylazo) resorcinol,
4- (phenylazo) resorcinol, 2,4,6- tri- (phenylazo) resorcinol etc..The structural formula of impurity is as follows:
Different molar ratio, pH value, charging rate etc. can all cause each component proportion in product to significantly change.
United States Patent (USP) US4983492 uses equimolar diazonium salt of aniline and resorcinol coupling reaction in neutral conditions
It is 2 hours, post-treated to obtain 2- (phenylazo) resorcinol and 2, the mixture of 4- bis- (phenylazo) resorcinol, product
In the ratios of two kinds of compositions be about 1:1；
European Patent EP1052244A1 uses molar ratio even in alkali system for the diazonium salt of aniline of 2.2:1 and resorcinol
Reaction 40 minutes is closed, the post-treated content that obtains is 79.5% (phenylazo) resorcinol of 4,6- bis- and 2, the 4,6- tri- of 5%
The mixture product of (phenylazo) resorcinol；
In the existing open source literature for being substrate by diazonium salt of aniline and resorcinol, all do not mention how obtaining 2 in high yield,
4- bis- (phenylazo) resorcinol, how isolated high-purity (phenylazo) resorcinol of 2,4- bis- and how to select
Property separation chromoisomer method.
2,4- bis- (phenylazo) resorcinol of high-purity in order to obtain, the Herbert of Huddersfield
H.Hodgson is taught using m -bromoacetophenone, m-Chlorophenol or iodophenol as substrate, generates 3- halogen through being coupled with diazonium salt of aniline
Generation -2,4- bis- (phenylazo) phenol, then 2,4- bis- (phenylazo) resorcinol is made through hydrolyzing.Reaction equation is as follows:
Herbert H.Hodgson professor has found in article and is referred to when 2,4- bis- (phenylazo) resorcinol is heated to
Discoloration effect has occurred when molten condition, while when being contacted with hydrochloric acid smog, also changing colour.This illustrates bis- (phenyl of 2,4-
Azo) bond energy of hydrogen bond is very weak in resorcinol molecular structure, and it can be heated and extraneous hydrogen ion is influenced.Accordingly,
Herbert professor H.Hodgson illustrate 2,4- bis- (phenylazo) resorcinol contain chromoisomer the fact that.
Unfortunately, Herbert H.Hodgson professor is in article not with regard to 2,4- bis- (phenylazo) resorcinol
How chromoisomer formation mechenism separates chromoisomer and explains.
Using Herbert H.Hodgson professor between halogenated phenol route, there are expensive, source it is rare lack
Point.M -bromoacetophenone and an iodophenol country do not have manufacturer's supply, and import price is up to per ton 500,000 and 2,000,000 respectively
It is more than RMB.Using m-Chlorophenol as raw material, chlorine atom is difficult to hydrolyze, and a large amount of 3- chloro-is still contained in obtained product
2,4- bis- (phenylazo) phenol intermediate structures, reaction yield is low, separation is difficult.
Summary of the invention
The purpose of the present invention is using resorcinol cheap and easy to get as substrate, to obtain 2, the 4- bis- of high-purity in high yield
(phenylazo) resorcinol Type B chromoisomer structure, chemical structure is:
The purpose of the present invention is what is be achieved through the following technical solutions, the chromoisomer of 2,4- bis- (phenylazo) resorcinols
Synthetic method, resorcinol monopotassium salt is first generated using resorcinol and potassium hydroxide, is existed and weak in phase transfer catalyst
Under acid condition, diazonium salt of aniline and resorcinol monopotassium salt are coupled to obtain containing 2,4- bis- (phenylazo) resorcinol Type B
2,4- bis- (phenylazo) resorcinol crude product of chromoisomer；The purified 2,4- bis- (phenylazo) for obtaining high-purity again
Resorcinol Type B chromoisomer.
Chemical equation is as follows:
Firstly, resorcinol monopotassium salt is when carrying out coupling reaction with diazonium salt of aniline, resorcinol monopotassium salt and aniline diazonium
The molar ratio of salt determines the quantity of the phenylazo substituent group of reaction product structure.Diazonium salt of aniline is excessively smaller, reaction
The content of single (phenylazo) resorcinol is bigger in product；Diazonium salt of aniline is excessive bigger, and single in reaction product (phenyl is even
Nitrogen) resorcinol content it is fewer.When diazonium salt of aniline compared with resorcinol mole inventory excessively more than 4:1 when, reaction
Product is essentially all 2,4,6- tri- (phenylazo) resorcinol etc..
Due to 2- (phenylazo) resorcinol, 4- (phenylazo) resorcinol, 5- (phenylazo) resorcinol this
Three list (phenylazo) resorcinols have moderate solubility in most of organic solvents, and reaction product is caused to be difficult to use
The removal of common separation method；And 2,4,6- tri- (phenylazo) resorcinols solubility all very littles in most of organic solvents,
Removal is simple.So the molar feed ratio of aniline and resorcinol of the invention selects (2-3)/1.Make in reaction product in this way
Only micro list (phenylazo) resorcinol, major impurity is 2,4,6- tri- (phenylazo) resorcinols, to react
Crude product is easy to refine.
Secondly, the pH value of reaction system is to be related to connecing ring position and directly determining chromotropism for phenylazo group
The key factor in the hydrogen bond direction of body.It is learnt by a large amount of Comparability tests, pH value is 10 or more, and products therefrom is with 4,6-, bis- (benzene
Base azo) resorcinol be primary product；PH value is between 7-10, and products therefrom is with 2,4,6- tri- (phenylazo) resorcinols
For primary product；When pH value is below 5, reaction almost without；When pH value is between 5-7, reaction principal product is 2,4-, bis- (benzene
Base azo) resorcinol.When pH value is between 5.5-5.8, the yield highest of target product, in terms of resorcinol mole turn
Rate is up to 90% or more.
Reaction carries out in water phase, resorcinol aqueous solution of the homogeneous in order to obtain and pH value between 5-7, the present invention
Resorcinol monopotassium salt is first generated with resorcin reaction using equimolar potassium hydroxide aqueous solution, then adds suitable phosphoric acid
Disodium hydrogen aqueous solution is as PH buffer, when pH value starts that diazonium salt of aniline is added dropwise between 5-7.During dropwise addition, it is whole with
Track pH value needs to add disodium hydrogen phosphate aqueous solution when pH value is lower than 5 with maintenance system pH value between 5-7.
Again, reaction temperature is also to determine target product 2, the key factor of 4- bis- (phenylazo) resorcinol yield.
Reaction temperature is too low, and the solubility decline of resorcinol monopotassium salt in water, raw material is precipitated, and reaction yield is low；Reaction temperature mistake
Height, diazonium salt of aniline are easily decomposed, and reactant molar ratio changes therewith, and reaction conversion ratio and selectivity are all greatly reduced.The present invention
The dropping temperature and holding temperature for selecting diazonium salt of aniline are between 15-20 DEG C.
At this temperature, in order to further increase the solubility of resorcinol monopotassium salt in the above system, increased with reaching
The purpose for adding reaction speed, improving reaction yield, needs to add phase transfer catalyst in system.Using traditional quaternary ammonium
Apparent effect of optimization cannot be obtained after salt, quaternary phosphonium salt class phase transfer catalyst.
The present invention selects to use crown ether compound, the big membered heterocycles of more nitrogen as phase transfer catalyst, this kind of
Catalyst first can form complex, System forming supramolecular structure with the potassium ion of resorcinol monopotassium salt.Catalyst adds
Dosage is the 1-5% of resorcinol quality.Disodium hydrogen phosphate aqueous solution is added again, so that system is able to form homogeneous reaction, with good
Good conversion ratio obtains target product.
After dripping aniline diazo liquid, the extension reaction time is conducive to fully reacting progress.Present invention selection is dripping
After aniline diazo liquid, insulation reaction 1-5 hours between 15-20 DEG C.
Under the conditions of the present invention, gained reaction product be the aforementioned 4 kinds of isomers of 2,4- bis- (phenylazo) resorcinol and
The mixture of 2,4,6- tri- (phenylazo) resorcinols, liquid chromatography results show wherein 2,4- bis- (phenylazo) isophthalic two
The total content of the aforementioned 4 kinds of isomers of phenol reaches as high as 95% or more.
The pH value adjustment of reaction system to 5, filtering are washed with water to neutrality post-processing dilute hydrochloric acid.By filter cake and 3 times of matter
The n,N-Dimethylformamide (DMF) of amount mixes, and is heated to flowing back.20 DEG C are cooled to, filtering.Filter cake is tri- (phenyl of 2,4,6-
Azo) resorcinol, filtrate freezing and crystallizing, before 2,4- bis- (phenylazo) resorcinol of 99% or more purity is obtained by filtration
State 4 kinds of isomer mixtures.
The appearance color of aforementioned 4 kinds of chromoisomers of 2,4- bis- (phenylazo) resorcinols is different, and fusing point differs very
Greatly, and the target isomer of only Type B structure has higher solubility in ethyl lactate.Gained bis- (benzene of 2,4- of the invention
Base azo) the aforementioned 4 kinds of isomer mixtures of resorcinol melting range between 200-207 DEG C, be made into 10% ethyl lactate solution
Afterwards, it can largely dissolve, only a small amount of insoluble matter.This phenomenon illustrates that the target isomer of Type B structure in products obtained therefrom is
Main ingredient.
4 kinds of isomer mixtures of resulting 2,4- bis- (phenylazo) resorcinol are recrystallized with ethyl lactate, are obtained
The target isomer of 2,4- bis- (phenylazo) resorcinol Type B structure of 99% or more purity.Through single crystal X-ray diffraction, really
Product of accepting is the configuration of target chromoisomer.
Test operation of the present invention carries out in the following manner: 1., the resorcinol measured and water being added in bottle, under stirring
Measured 20% potassium hydroxide aqueous solution of stalagmometer.After completion of dropwise addition, the phase transfer catalyst measured is added, property adds again
Enter the disodium hydrogen phosphate aqueous solution measured；2. the aniline measured and water are added in another bottle, cryosel is used under stirring
Cooling 5 DEG C of bath measure hydrochloric acid, sodium nitrite in aqueous solution hereinafter, successively instilling.After completion of dropwise addition, 5 DEG C or less keep the temperature 10 minutes,
Obtain diazonium salt of aniline solution；3. under high-speed stirred, obtained diazonium salt of aniline solution is instilled at 15-20 DEG C above-mentioned
In resorcinol monopotassium salt solution, after completion of dropwise addition, continue heat preservation 2 hours；4. after heat preservation, with dilute hydrochloric acid by reaction solution
PH value adjustment to 5.After high-speed stirred 30 minutes, filtering, filter cake is washed till neutrality with a large amount of clear water, dries.Product after drying
Through DMF dissolution filter, crystallization, then recrystallized with ethyl lactate.Obtain target product, i.e. 2,4- bis- (phenylazo) resorcinol
The target isomer of Type B structure.
Reaction condition of the present invention is mild, simple to operation, and final 2,4- bis- (phenylazo) resorcinol Type B structure is different
Structure body total conversion can reach 90% or more.
Specific embodiment
Example A:
The preparation of aniline diazo liquid:
In the 500ml four-hole boiling flask equipped with mechanical agitator, addition funnel, ice-water bath, air set pipe and thermometer, stirring
Lower addition 28.5g aniline (0.3mol) and 285ml water successively instill 77ml concentrated hydrochloric acid and 86g when temperature is down to 5 DEG C or less
Sodium nitrite (0.3mol) aqueous solution that mass fraction is 24.5%.After completion of dropwise addition, 5 DEG C or less keep the temperature 10 minutes, obtain benzene
Amine diazonium salt solution；It is kept the temperature between 0-5 DEG C spare.
Example B:
The synthesis of 2,4- bis- (phenylazo) resorcinol
Example B-1:
In the 2000ml four-hole boiling flask equipped with mechanical agitator, addition funnel, ice-water bath, air set pipe and thermometer, add
Enter 13g (0.118mol) resorcinol and 50ml deionized water is added in reaction flask, under stirring at room temperature from dropping funel
Potassium hydroxide (0.118mol) aqueous solution that 33g mass fraction is 20% is added dropwise to reaction flask, 30 points are sufficiently stirred after completion of dropwise addition
6 ether of 0.5g18-hat-, then high-speed stirred 3 hours are once added in Zhong Hou.It is 20% that 200g mass fraction, which is added, in property again
Disodium hydrogen phosphate aqueous solution.
Into above-mentioned system, the standby diazonium salt of aniline solution of whole example A institutes is added dropwise, controls rate of addition with guarantee system temperature
Degree is between 15-20 DEG C.Whole constant-current titration reaction solution pH value is adjusted with the disodium hydrogen phosphate aqueous solution that mass fraction is 20%
The entire pH value that process system is added dropwise, makes it stable between 6-6.5.
After completion of dropwise addition, insulation reaction 2 hours between 15-20 DEG C, after heat preservation, with dilute hydrochloric acid by the PH of reaction solution
Value is adjusted to 5.After high-speed stirred 30 minutes, filtering, filter cake is washed till neutrality with a large amount of clear water, dries, obtains the dark red toner of 43.9g
End.Liquid chromatography results show that 2,4- bis- (phenylazo) resorcinol content is 89.37%, between 2,4,6- tri- (phenylazos)
Benzenediol content is that 4.23%, 4- (phenylazo) resorcinol content is 5.98%.
By after drying product and 150mlDMF be added to equipped with mechanical agitator, electric heating cover, reflux condenser and temperature
It spends in the 500ml four-hole boiling flask of meter, is heated with stirring to reflux, be cooled back to 20 DEG C, filtering.Filter cake is that (phenyl is even by 2,4,6- tri-
Nitrogen) resorcinol, filtrate is in subzero 5 DEG C of degree refrigerator overnight crystallization.Next day filtering, after the DMF in filter cake is eluted with water, filter cake
Drying obtains dark red powder after obtaining 38.3g, and liquid chromatography results show that purity is 99.97%.
This 38.3g 500ml ethyl lactate is recrystallized, obtains 31.5g claret powder, liquid-phase chromatographic analysis content is
99.99%.Survey fusing point are as follows: 203.2-204.7 DEG C, melting range is consistent with the standard items that DOW chemical company provides.In terms of resorcinol,
Reacting molar yield is 83.95%.
Example 2
Example B-2:
In the 2000ml four-hole boiling flask equipped with mechanical agitator, addition funnel, ice-water bath, air set pipe and thermometer, add
Enter 11g (0.1mol) resorcinol and 50ml deionized water be added in reaction flask, at room temperature stir under from dropping funel to
Potassium hydroxide (0.1mol) aqueous solution that 28g mass fraction is 20% is added dropwise in reaction flask, is sufficiently stirred after completion of dropwise addition 30 minutes
Afterwards, 0.5g dibenzo -24- crown- 8, then high-speed stirred 3 hours are once added.It is 20% that 200g mass fraction, which is added, in property again
Disodium hydrogen phosphate aqueous solution.
Into above-mentioned system, the standby diazonium salt of aniline solution of whole example A institutes is added dropwise, controls rate of addition with guarantee system temperature
Degree is between 15-20 DEG C.Whole constant-current titration reaction solution pH value is adjusted with the disodium hydrogen phosphate aqueous solution that mass fraction is 20%
The entire pH value that process is added dropwise, makes it stable between 6-6.5.
After completion of dropwise addition, insulation reaction 2 hours between 15-20 DEG C, after heat preservation, with dilute hydrochloric acid by the PH of reaction solution
Value is adjusted to 5.After high-speed stirred 30 minutes, filtering, filter cake is washed till neutrality with a large amount of clear water, dries, obtains the dark red toner of 40.3g
End.Liquid chromatography results show that 2,4- bis- (phenylazo) resorcinol content is 86.42%, between 2,4,6- tri- (phenylazos)
Benzenediol content is that 11.54%, 4- (phenylazo) resorcinol content is 1.03%.
By after drying product and 150mlDMF be added to equipped with mechanical agitator, electric heating cover, reflux condenser and temperature
It spends in the 500ml four-hole boiling flask of meter, is heated with stirring to reflux, be cooled back to 20 DEG C, filtering.Filter cake is that (phenyl is even by 2,4,6- tri-
Nitrogen) resorcinol, filtrate is in subzero 5 DEG C of degree refrigerator overnight crystallization.Next day filtering, after the DMF in filter cake is eluted with water, filter cake
Drying obtains dark red powder after obtaining 30.8g, and liquid chromatography results show that purity is 99.99%.
This 30.8g 500ml ethyl lactate is recrystallized, obtains 26g claret powder, liquid-phase chromatographic analysis content is
100%.Survey fusing point are as follows: 203.0-204.4 DEG C, melting range is consistent with the standard items that DOW chemical company provides.In terms of resorcinol, instead
Answering molar yield is 81.76%.
Example B-3:
In the 2000ml four-hole boiling flask equipped with mechanical agitator, addition funnel, ice-water bath, air set pipe and thermometer, add
Enter 11g (0.1mol) resorcinol and 50ml deionized water be added in reaction flask, at room temperature stir under from dropping funel to
Potassium hydroxide (0.1mol) aqueous solution that 28g mass fraction is 20% is added dropwise in reaction flask, is sufficiently stirred after completion of dropwise addition 30 minutes
Afterwards, 0.5g dibenzo -24- crown- 8, then high-speed stirred 3 hours are once added.It is 20% that 250g mass fraction, which is added, in property again
Disodium hydrogen phosphate aqueous solution.
Into above-mentioned system, the standby diazonium salt of aniline solution of whole example A institutes is added dropwise, controls rate of addition with guarantee system temperature
Degree is between 15-20 DEG C.Whole constant-current titration reaction solution pH value is adjusted with the disodium hydrogen phosphate aqueous solution that mass fraction is 20%
The entire pH value that process is added dropwise, makes it stable between 5.5-5.8.
After completion of dropwise addition, insulation reaction 2 hours between 15-20 DEG C, after heat preservation, with dilute hydrochloric acid by the PH of reaction solution
Value is adjusted to 5.After high-speed stirred 30 minutes, filtering, filter cake is washed till neutrality with a large amount of clear water, dries, obtains the dark red toner of 39.1g
End.Liquid chromatography results show that 2,4- bis- (phenylazo) resorcinol content is 95.71%, between 2,4,6- tri- (phenylazos)
Benzenediol content is that 2.8%, 4- (phenylazo) resorcinol content is 0.22%.
By after drying product and 150mlDMF be added to equipped with mechanical agitator, electric heating cover, reflux condenser and temperature
It spends in the 500ml four-hole boiling flask of meter, is heated with stirring to reflux, be cooled back to 20 DEG C, filtering.Filter cake is that (phenyl is even by 2,4,6- tri-
Nitrogen) resorcinol, filtrate is in subzero 5 DEG C of degree refrigerator overnight crystallization.Next day filtering, after the DMF in filter cake is eluted with water, filter cake
Drying obtains dark red powder after obtaining 33.9g, and liquid chromatography results show that purity is 99.99%.
This 33.9g 500ml ethyl lactate is recrystallized, obtains 29.3g claret powder, liquid-phase chromatographic analysis content is
100%.Survey fusing point are as follows: 203.0-204.4 DEG C, melting range is consistent with the standard items that DOW chemical company provides.In terms of resorcinol, instead
Answering molar yield is 92.14%.
Example B-4:
In the 2000ml four-hole boiling flask equipped with mechanical agitator, addition funnel, ice-water bath, air set pipe and thermometer, add
Enter 16.5g (0.15mol) resorcinol and 50ml deionized water is added in reaction flask, under stirring at room temperature from dropping funel
Potassium hydroxide (0.15mol) aqueous solution that 42g mass fraction is 20% is added dropwise to reaction flask, 30 points are sufficiently stirred after completion of dropwise addition
Zhong Hou, it is primary that 0.2g ring wheel rattan is added rather (Isosorbide-5-Nitrae, 7,10- tetraazacyclododecanands), then high-speed stirred 3 hours.Property adds again
Enter the disodium hydrogen phosphate aqueous solution that 250g mass fraction is 20%.
Into above-mentioned system, the standby diazonium salt of aniline solution of whole example A institutes is added dropwise, controls rate of addition with guarantee system temperature
Degree is between 15-20 DEG C.Whole constant-current titration reaction solution pH value is adjusted with the disodium hydrogen phosphate aqueous solution that mass fraction is 20%
The entire pH value that process is added dropwise, makes it stable between 5.5-5.8.
After completion of dropwise addition, insulation reaction 2 hours between 15-20 DEG C, after heat preservation, with dilute hydrochloric acid by the PH of reaction solution
Value is adjusted to 5.After high-speed stirred 30 minutes, filtering, filter cake is washed till neutrality with a large amount of clear water, dries, obtains the dark red toner of 32.4g
End.Liquid chromatography results show that 2,4- bis- (phenylazo) resorcinol content is 82.81%, between 2,4,6- tri- (phenylazos)
Benzenediol content is that 1.99%, 4- (phenylazo) resorcinol content is 13.64%.
By after drying product and 150mlDMF be added to equipped with mechanical agitator, electric heating cover, reflux condenser and temperature
It spends in the 500ml four-hole boiling flask of meter, is heated with stirring to reflux, be cooled back to 20 DEG C, filtering.Filter cake is that (phenyl is even by 2,4,6- tri-
Nitrogen) resorcinol, filtrate is in subzero 5 DEG C of degree refrigerator overnight crystallization.Next day filtering, after the DMF in filter cake is eluted with water, filter cake
Drying obtains dark red powder after obtaining 23.8g, and liquid chromatography results show that purity is 98.91%.
This 23.8g 500ml ethyl lactate is recrystallized, obtains 21.0g claret powder, liquid-phase chromatographic analysis content is
99.59%.Survey fusing point are as follows: 203.5-204.9 DEG C, melting range is consistent with the standard items that DOW chemical company provides.In terms of resorcinol,
Reacting molar yield is 66.04%.
Claims (6)
1. absorbing material 2, the synthetic method of the selectivity chromoisomer of 4- bis- (phenylazo) resorcinol, molecular structure
Formula is as follows:
Resorcinol monopotassium salt is generated it is characterized in that, first reacting using resorcinol with potassium hydroxide, in phase transfer catalyst
In the presence of and solutions of weak acidity under, diazonium salt of aniline and resorcinol monopotassium salt carry out coupling reaction in water phase, obtain containing 2,
2,4- bis- (phenylazo) resorcinol crude product of 4- bis- (phenylazo) resorcinol selectivity chromoisomer；It is purified again
Obtain 2,4- bis- (phenylazo) resorcinol selectivity chromoisomer of high-purity;
Chemical equation is as follows:
。
2. the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol according to claim 1
Synthetic method, which is characterized in that the molar feed ratio of the diazonium salt of aniline and resorcinol is (2-3)/1.
3. the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol according to claim 1
Synthetic method, which is characterized in that the reaction stops the pH value for being between 5-7, and reaction temperature is temperature between 15-20 DEG C,
The insulation reaction time is 1-5 hours.
4. the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol according to claim 1
Synthetic method, which is characterized in that the phase transfer catalyst is crown ether compound, the big membered heterocycles of more nitrogen, catalysis
The additive amount of agent is the 1-5% of resorcinol quality.
5. the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol according to claim 1
Synthetic method, which is characterized in that the faintly acid system is that addition disodium hydrogen phosphate aqueous solution is slow as PH in the reaction system
What electuary was realized.
6. the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol according to claim 1
Synthetic method, which is characterized in that the purification step refers to, crude reaction first uses n,N-Dimethylformamide as solvent,
Insoluble 2,4,6- tri- (phenylazo) resorcinol of impurity is isolated, then is recrystallized to give 2,4-, bis- (phenyl with ethyl lactate
Azo) resorcinol chromoisomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910639431.5A CN110305037B (en) | 2019-07-16 | 2019-07-16 | Synthesis method of selective isochromic isomer of wave-absorbing material 2, 4-bis (phenylazo) resorcinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910639431.5A CN110305037B (en) | 2019-07-16 | 2019-07-16 | Synthesis method of selective isochromic isomer of wave-absorbing material 2, 4-bis (phenylazo) resorcinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110305037A true CN110305037A (en) | 2019-10-08 |
| CN110305037B CN110305037B (en) | 2022-02-25 |
Family
ID=68080230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910639431.5A Active CN110305037B (en) | 2019-07-16 | 2019-07-16 | Synthesis method of selective isochromic isomer of wave-absorbing material 2, 4-bis (phenylazo) resorcinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110305037B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848438A (en) * | 2020-07-29 | 2020-10-30 | 浙江鼎龙科技有限公司 | Preparation method of 4, 6-diphenyl azoresorcinol and 4, 6-diamino resorcinol |
-
2019
- 2019-07-16 CN CN201910639431.5A patent/CN110305037B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| HIBBERT, FRANK等: "Kinetic studies of the deprotonation of bis(phenylazo)resorcinol monoanions by hydroxide ion", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 2》 * |
| 钟天桂等: "苯胺重氮盐与间苯二酚的偶合反应", 《染料与染色》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848438A (en) * | 2020-07-29 | 2020-10-30 | 浙江鼎龙科技有限公司 | Preparation method of 4, 6-diphenyl azoresorcinol and 4, 6-diamino resorcinol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110305037B (en) | 2022-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SU476748A3 (en) | The method of obtaining bis-stilbene compounds | |
| PT1893587E (en) | Method for producing dihydroquinazolines | |
| CN103265420B (en) | A kind of preparation method of aromatic diketone compound | |
| US4501906A (en) | Monoalkali metal salts of perylene-3,4,9,10-tetracarboxylic acid monoanhydride and process for their manufacturing | |
| Jawaria et al. | Robustness of thioamide dimer synthon, carbon bonding and thioamide–thioamide stacking in ferrocene-based thiosemicarbazones | |
| Potts et al. | Mesoionic compounds. XVI. 1, 4-Dipolar type cycloaddition reactions utilizing pyrimidinium betaines | |
| CN111606845B (en) | Synthesis method of 4-chloro-6-fluoropyridine-2-alcohol | |
| CN110305037A (en) | The synthetic method of the selectivity chromoisomer of absorbing material 2,4- bis- (phenylazo) resorcinol | |
| Qian et al. | Structural characterization of a pyrazolone-based heterocyclic dye and its acid-base adduct | |
| Wiley et al. | Hydrogen cyanide chemistry. 6. Cyanogen condensation with cyanide, C7N7 | |
| US20180186794A1 (en) | Imidazopyrroloquinoline salt, method for producing the same, medicament, cosmetic, and food | |
| KR20090004760A (en) | Azo compound or its salt | |
| Sundberg et al. | Structure of trans-Di (3-iodobenzoato) bis (1, 3-diaminopropane) copper (II), C, H, Cul, N, O | |
| JPS62161767A (en) | Manufacture of imidazole compound | |
| KR100735711B1 (en) | Fluorescent whitening agent and process of producing thereof | |
| Gougoutas et al. | Structure and solid-state chemistry of 3-carboxy-2-naphthalenediazonium bromide | |
| TW201809237A (en) | Intermediates and procedures for the synthesis of functional materials | |
| Novák et al. | Structure of azo dye organotin (IV) compounds containing a C, N‐chelating ligand, part II, and their in vitro antifungal activity | |
| Rosowsky et al. | Quinazolines. VII. Synthesis of 1, 3‐Diamino‐5, 6‐dihydrobenzo [f] quinazolines | |
| Ross et al. | Derivatives of 1-Phenylazo-2-Naphthylamine. The Effect of Substituent on Color | |
| US2335273A (en) | 3,3-dihalogenoxindoles | |
| US1847513A (en) | Pbocess pob pbepabing diazonitjm pittoro-sttlphonates | |
| Arnold et al. | Stereospecificity in the synthesis of the tris ((R)-cysteinato-N, S)-and tris ((R)-cysteinesulfinato-N, S) cobaltate (III) ions | |
| US1817982A (en) | Winfrid hentrich and max habdtmann | |
| Feng et al. | Polymorphism and configurational isomerism in 3-(9-anthryl)-1-(3-hydroxyphenyl) prop-2-en-1-one |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |