CN106674111A - Method for compounding 4-bromine-N-methyl-1(N)-9-anthracene pyridone - Google Patents
Method for compounding 4-bromine-N-methyl-1(N)-9-anthracene pyridone Download PDFInfo
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- CN106674111A CN106674111A CN201611120649.2A CN201611120649A CN106674111A CN 106674111 A CN106674111 A CN 106674111A CN 201611120649 A CN201611120649 A CN 201611120649A CN 106674111 A CN106674111 A CN 106674111A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
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Abstract
The invention discloses a method for compounding 4-bromine-N-methyl-1(N)-9-anthracene pyridone. The method comprises the following steps: adding ethyl alcohol and less potassium tert-butoxide into a reactor, stirring and dissolving; putting an acylation material, namely, 1-(N-methyl) acetamido-4-bromoanthraquinone into the reactor and uniformly stirring; putting less calcium oxide; starting to slowly increase the temperature till reaching a certain temperature; keeping the temperature for several hours; performing HPLC tracking; after the acylation material completely reacts, stopping the temperature preservation, reducing to room temperature, filtering and recycling a mother liquid, washing with hot water and drying; putting the products acquired from ring-closure reaction into a sulfuric acid liquid, pulping for a period of time at room temperature, filtering and recycling the sulfuric acid liquid; soaking the material into the sulfuric acid liquid in the same concentration; performing suction filtration, mixing and collecting the acquired washing liquid and the mother liquid; washing the material with soft water till the washing water is neutral; and discharging and drying. According to the invention, the reaction condition is mild, the temperature is low, the reaction is carried out under normal pressure and the maximal acquired product can reach up to 95%.
Description
Technical field
The present invention relates to a kind of synthetic method of chemical intermediate, and in particular to a kind of bromo- N- methyl isophthalic acids (N) -9- anthracenes of 4-
And the synthetic method of pyridone, belong to organic chemical synthesis field.
Background technology
Bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of 4- are yellow powder, are a kind of important dyestuff intermediates, its knot
Structure formula is：
Following institute can be distinguished by above-mentioned intermediate synthetic red 52, the equal solvent dyestuff of solvent red 149, synthetic route
Show：
(1) solvent red 52
(2) solvent red 149
Above two solvent red dye is widely used, and can both make ink dye, leather dye, coating dyestuff, can also make
Plastic cement dyestuff, tinting strength, tinting power is high, bright in colour, tone becomes clear, and with excellent heat resistance and light resistance, therefore with good
Application prospect, this also promotes bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of 4- sufficient with lifting in the intermediate field of solvent dye
The status of weight, application prospect should not be underestimated.
The synthetic route report on bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of 4- domestic at present is few, but substantially
It is upper with 1- methylamino anthraquinones as raw material, as obtained by bromination, acylation, closed loop, closed loop material are refined, route approximately as：
(1) bromination reaction
(2) acylation reaction
(3) ring-closure reaction
Prior art ring-closure reaction is aqueous phase reactions, therefore cannot avoid hydrolysis and produce bromination material 1- first ammonia
Base -4- bromo anthraquinones, hydrolysis is as follows：
85% or so, bromination material 1- methylamino -4- bromo anthraquinones account for 10% or so to the content of principal product in ring-closure reaction,
Other also a small amount of impurity.In order to ensure the high-purity of bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of 4-, need to be by high concentration
Sulfuric acid is refined to closed loop material, because high-concentration sulfuric acid has certain solubility to principal product, product is not only resulted in so
Yield reduction, and generate substantial amounts of spent acid, bring larger pressure to environmental protection.
The content of the invention
The product yield occurred in above-mentioned product is low, spent acid is more, environmental protection pressure is big in order to overcome for the present invention, it is proposed that a kind of
The synthetic method of bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of new 4-.
In order to solve the above-mentioned technical problem, technical scheme is summarized as follows：One kind synthesis bromo- N- methyl isophthalic acids of 4-
(N) method of -9- Anthrapyridones, comprises the following steps：
(1) ring-closure reaction：
Reaction reagent：
1- (N- methyl) acetamido -4- bromo anthraquinones：Referred to as acylated material, as the initial main material of the invented technology；
Ethanol：Substitution popular response aqueous solvent, it is to avoid substantial amounts of hydrolysis occur；
Potassium tert-butoxide：Conventional use of alkali NaOH of substitution, NaOH does not dissolve in organic solvent, and potassium tert-butoxide is dissolved in second
Alcohol；
Calcium oxide：Due to there is water to produce in reaction, to avoid the occurrence of hydrolysis, plus calcium oxide is used for absorbing reaction process
The water of middle generation.
Operating process：
During ethanol and a small amount of potassium tert-butoxide put into reactor, stirring 0.5h is finished with ensuring potassium tert-butoxide dissolving.
To be stirred in acylated material 1- (N- methyl) acetamido -4- bromo anthraquinones input reactor, then put into a small amount of calcium oxide,
Start to be to slowly warm up to certain temperature, be incubated a few hours, HPLC tracking treats that the reaction of acylated material is finished, you can stop insulation, drop
To normal temperature, mother liquor is recovered by filtration, hot wash is dried, weighed.
(2) refine
Certain density sulfuric acid solution is prepared, during ring-closure reaction products therefrom put into the sulfuric acid solution got ready, often
The lower mashing certain hour of temperature, filtering is reclaimed sulfuric acid solution, then soaks material, suction filtration, gained with the sulfuric acid solution of same concentration
Cleaning solution and mother liquor mixed collection.Soft water washing material to washings are neutrality, discharge, dry, weigh.
(3) recycle
Mixing mother liquor in above-mentioned subtractive process stands two days below 20 DEG C, filtering, mother liquid obtained for clarification is slightly yellow, can
Continue to apply mechanically, gained filter residue amount is few, based on bromination material, content is more than 80%, and bromo- N- methyl isophthalic acids (the N) -9- anthra pyrroles of 4-
Pyridine ketone accounts for 8%~13%.
In one embodiment of the invention, ethanol and the acylated quality for expecting 1- (N- methyl) acetamido -4- bromo anthraquinones
Than being 5:1, ethanol is (20~50) with the mass ratio of potassium tert-butoxide：1, ethanol is (5~20) with the mass ratio of calcium oxide：1.
In one embodiment of the invention, the holding temperature in ring-closure reaction be 30~70 DEG C, soaking time be 5~
12h。
In one embodiment of the invention, the concentration of sulfuric acid is 25w%~60w%, sulfuric acid and material in subtractive process
Mass ratio be 5:1.
Long-term standing, suction filtration below 20 DEG C of the mother liquor produced after refined, are divided into sulfuric acid solution and filter residue, and sulfuric acid solution continues
Apply mechanically, filter residue uses prior art through acylation after repeatedly collecting after, using present invention process, be met industrialized target and produce
Thing.
The present invention has significant advantage compared with prior art：(1) prior art is more based on aqueous phase reactions, needs high temperature
High pressure, reaction condition of the present invention is gentle, and temperature is not high and synthesis under normal pressure；(2) prior art cannot avoid hydrolysis, principal product
85% or so only up to be reached, industrial needs need to could be met by the way that high-concentration sulfuric acid solution (usual more than 70w%) is refined,
Reach more than 98%.Products therefrom of the present invention can reach 95%, and need to be only beaten by low-concentration sulfuric acid solution can be full
Foot industry needs；(3) prior art post processing produces substantial amounts of high concentration spent acid and solid waste, useless in present invention post processing
Acid, solid waste can be recycled easily, not only make process conditions gentle, the yield of product be also improved, while alleviating significantly
The pressure of environmental protection.
Specific embodiment
Specific reactions steps are as follows：
1st, ring-closure reaction：During ethanol and a small amount of potassium tert-butoxide put into reactor, stirring 0.5h is ensuring the tert-butyl alcohol
Potassium dissolving is finished.To be stirred in acylated material 1- (N- methyl) acetamido -4- bromo anthraquinones input reactor, then less investment
The calcium oxide of amount.Ethanol is 5 with the mass ratio of acylated material 1- (N- methyl) acetamido -4- bromo anthraquinones:1, ethanol and the tert-butyl alcohol
The mass ratio of potassium is (20~50)：1, ethanol is (5~20) with the mass ratio of calcium oxide：1.Start to be to slowly warm up to 30~70
DEG C, soaking time is 5~12h.HPLC is tracked, and treats that the reaction of acylated material is finished, you can stop insulation, be down to normal temperature, be recovered by filtration
Mother liquor, hot wash is dried, is weighed.
2nd, refine：Certain density sulfuric acid solution is configured, ring-closure reaction products therefrom is put into the sulfuric acid got ready molten
In liquid, the concentration of sulfuric acid is 25w%~60w% in refinement, and sulfuric acid is 5 with the mass ratio of material:1.One is beaten under normal temperature
Fix time, sulfuric acid solution is reclaimed in filtering, then soak material, suction filtration, gained cleaning solution and mother with the sulfuric acid solution of same concentration
Liquid mixed collection.Soft water washing material to washings are neutrality, discharge, dry, weigh.
3rd, waste liquid, waste residue are recycled：Mixing mother liquor in above-mentioned subtractive process stands two days below 20 DEG C, filtering,
Mother liquid obtained to continue to apply mechanically for clarification is slightly yellow, gained filter residue amount is few, and based on bromination material, content is more than 80%, and 4-
Bromo- N- methyl isophthalic acids (N) -9- Anthrapyridones account for 8%~13%, and filter residue is repeatedly collected, then using prior art through acylation after,
Using present invention process and identical inventory, industrialized target product is met.
Embodiment 1
In the potassium tert-butoxide input reactor of the ethanol of 100g and 2g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 5g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 8h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.2g, content 93.3%, bromine
Material accounts for 4.1%.
Embodiment 2
In the potassium tert-butoxide input reactor of the ethanol of 100g and 2g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 8h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.4g, content 94.7%, bromine
Material accounts for 2.6%.
Embodiment 3
In the potassium tert-butoxide input reactor of the ethanol of 100g and 2g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 20g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 8h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.2g, content 94.4%, bromine
Material accounts for 2.4%.
Embodiment 4
In the potassium tert-butoxide input reactor of the ethanol of 100g and 3g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 6.5h, and reaction finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.32g, content 93.7%,
Bromination material accounts for 3.4%.
Embodiment 5
In the potassium tert-butoxide input reactor of the ethanol of 100g and 4g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 6h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.6g, content 94.1%, bromine
Material accounts for 2.7%.
Embodiment 6
In the potassium tert-butoxide input reactor of the ethanol of 100g and 5g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 5h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.4g, content 94.8%, bromine
Material accounts for 2.9%.
Embodiment 7
In the potassium tert-butoxide input reactor of the ethanol of 100g and 4g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, (30 DEG C) insulations, HPLC under normal temperature
Tracking, is incubated 12h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.8g, content
94.13%, bromination material accounts for 2.9%.
Embodiment 8
In the potassium tert-butoxide input reactor of the ethanol of 100g and 4g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 50 DEG C, HPLC with
Track, is incubated 10h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 18.1g, content 93.8%, bromine
Material accounts for 4.1%.
Embodiment 9
In the potassium tert-butoxide input reactor of the ethanol of 100g and 4g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 60 DEG C, HPLC with
Track, is incubated 7.5h, and reaction finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.2g, content 94.3%,
Bromination material accounts for 3.1%.
Embodiment 10
In the potassium tert-butoxide input reactor of the ethanol of 100g and 4g, 0.5h, the acylated material 1- (N- of input 20g will be stirred
Methyl) acetamido -4- bromo anthraquinones, in stirring a moment, the calcium oxide of 10g is put into reactor, start to warm up to 70 DEG C, HPLC with
Track, is incubated 7h, and reaction is finished, and mother liquor is recovered by filtration, and hot wash is dried, weighed, and obtains dry product 17.6g, content 94.6%, bromine
Material accounts for 2.9%.
Embodiment 11
The sulfuric acid 100g of the crude product of dried 20g and 25w% is put into reactor, 4h is stirred under normal temperature, suction filtration is used
The sulfuric acid 40g immersion material 0.5h of 25w%, suction filtration, soft water washs to neutrality, discharges, dries, weighs, and obtains dry product 19.33g, contains
Amount 98.14%.
Embodiment 12
The sulfuric acid 100g of the crude product of dried 20g and 40w% is put into reactor, 4h is stirred under normal temperature, suction filtration is used
The sulfuric acid 40g immersion material 0.5h of 40w%, suction filtration, soft water washs to neutrality, discharges, dries, weighs, and obtains dry product 18.87g, contains
Amount 98.52%.
Embodiment 13
The sulfuric acid 100g of the crude product of dried 20g and 55w% is put into reactor, 4h is stirred under normal temperature, suction filtration is used
The sulfuric acid 40g immersion material 0.5h of 55w%, suction filtration, soft water washs to neutrality, discharges, dries, weighs, and obtains dry product 18.12g, contains
Amount 98.77%.
Embodiment 14
The sulfuric acid 100g of the crude product of dried 20g and 60w% is put into reactor, 4h is stirred under normal temperature, suction filtration is used
The sulfuric acid 40g immersion material 0.5h of 60w%, suction filtration, soft water washs to neutrality, discharges, dries, weighs, and obtains dry product 17.86g, contains
Amount 98.81%.
Embodiment 15
Long-term below 20 DEG C of sulfate liquor after will be refined to stand, suction filtration gained filter residue is concentrated, drying, takes filter residue material 20g
(bromination material 80% or so, and bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of principal product 4- account for 10% or so), using existing process
Acylation reaction is carried out, dry product 18.99g is obtained, ring-closure reaction is carried out using the present invention, obtain crude product 16.64g, content 86.33%, bromine
Material 7.24%.4h is beaten by the waste acid recovery of 40w%, suction filtration, spent acid immersion, soft water washing are final to obtain dry product 13.32g,
Content 98.21%.
Embodiment 16
The transparent yellow state of waste acid liquor reclaimed from embodiment 15, brominated material 1- first ammonia in the filter residue of recovery
Base -4- bromo anthraquinones content 82.1%, bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones 9.4% of principal product 4-.Therefore, spent acid and filter
Slag can be recycled again.The filter residue that will be reclaimed again is repeatedly concentrated, dried, according to the processing mode of embodiment 15, finally
Obtain dry product 12.73g, content 98.44%.
According to above-described embodiment, it is known that preferred processing condition is：
(1) ethanol described in ring-closure reaction is with the mass ratio of acylated material 1- (N- methyl) acetamido -4- bromo anthraquinones
5:1, ethanol is (20~50) with the mass ratio of potassium tert-butoxide：1, ethanol is (5~20) with the mass ratio of calcium oxide：1.Insulation temperature
Degree is 30~70 DEG C, and soaking time is 5~12h.
(2) concentration of sulfuric acid is 25w%~60w% in refinement, and sulfuric acid is 5 with the mass ratio of material:1.
(3) workshop section is recycled, below 20 DEG C of dwell temperature.
Claims (8)
1. the method for synthesizing bromo- N- methyl isophthalic acids (the N) -9- Anthrapyridones of 4-, it is characterised in that comprise the following steps：
（1）Ring-closure reaction：
During ethanol and a small amount of potassium tert-butoxide put into reactor, stirring and dissolving, will acylated material 1- (N- methyl) acetamido-
Stirred in 4- bromo anthraquinones input reactor, then put into a small amount of calcium oxide, start to be to slowly warm up to certain temperature, protected
Warm a few hours, HPLC tracking treats that the reaction of acylated material is finished, you can stop insulation, be down to normal temperature, mother liquor, hot water wash is recovered by filtration
Wash, dry；
（2）It is refined
During ring-closure reaction products therefrom put into sulfuric acid solution, certain hour is beaten under normal temperature, filtered, reclaim sulfuric acid solution,
Then material, suction filtration, gained cleaning solution and mother liquor mixed collection are soaked with the sulfuric acid solution of same concentration, soft water washing material is extremely
Washings are neutrality, discharging, drying.
2. the method for claim 1, it is characterised in that in ring-closure reaction, ethanol and 1- (N- methyl) acetamido -4-
The mass ratio of bromo anthraquinone is 5:1.
3. the method for claim 1, it is characterised in that in ring-closure reaction, ethanol is with the mass ratio of potassium tert-butoxide（20
~50）：1.
4. the method for claim 1, it is characterised in that in ring-closure reaction, ethanol is with the mass ratio of calcium oxide（5~
20）：1.
5. the method for claim 1, it is characterised in that in ring-closure reaction, holding temperature is 30 ~ 70 DEG C, soaking time
It is 5 ~ 12h.
6. the method for claim 1, it is characterised in that in subtractive process, the concentration of sulfuric acid solution is 25w% ~ 60w%.
7. the method for claim 1, it is characterised in that in subtractive process, sulfuric acid is 5 with the mass ratio of material:1.
8. the method for claim 1, it is characterised in that in subtractive process, the mother liquor that mixed collection is arrived is below 20 DEG C
Two days are stood, gained filter residue can continue to apply mechanically after filtering.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611120649.2A CN106674111A (en) | 2016-12-08 | 2016-12-08 | Method for compounding 4-bromine-N-methyl-1(N)-9-anthracene pyridone |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611120649.2A CN106674111A (en) | 2016-12-08 | 2016-12-08 | Method for compounding 4-bromine-N-methyl-1(N)-9-anthracene pyridone |
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| CN201611120649.2A Pending CN106674111A (en) | 2016-12-08 | 2016-12-08 | Method for compounding 4-bromine-N-methyl-1(N)-9-anthracene pyridone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296999A (en) * | 1999-11-22 | 2001-05-30 | 江苏亚邦集团公司 | Anthrapyridone dye intermediate and production method thereof |
| CN104725315A (en) * | 2013-12-21 | 2015-06-24 | 江苏道博化工有限公司 | Method used for preparing solvent red 149 |
-
2016
- 2016-12-08 CN CN201611120649.2A patent/CN106674111A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296999A (en) * | 1999-11-22 | 2001-05-30 | 江苏亚邦集团公司 | Anthrapyridone dye intermediate and production method thereof |
| CN104725315A (en) * | 2013-12-21 | 2015-06-24 | 江苏道博化工有限公司 | Method used for preparing solvent red 149 |
Non-Patent Citations (2)
| Title |
|---|
| ASHWANI KUMAR,ET AL.: "Anthroneamine based chromofluorogenic probes for Hg detection in aqueous solution", 《TETRAHEDRON LETTERS》 * |
| BO HE，ET AL.: "A divergent route to core- and peripherally functionalized diazacoronenes that act as colorimetric and fluorescence proton sensors", 《CHEM. SCI.》 * |
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Application publication date: 20170517 |