CN109942456A - A kind of method of p-aminophenol synthesis 1,4-benzoquinone list imines - Google Patents
A kind of method of p-aminophenol synthesis 1,4-benzoquinone list imines Download PDFInfo
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- CN109942456A CN109942456A CN201910298768.4A CN201910298768A CN109942456A CN 109942456 A CN109942456 A CN 109942456A CN 201910298768 A CN201910298768 A CN 201910298768A CN 109942456 A CN109942456 A CN 109942456A
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- aminophenol
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Abstract
The invention discloses a kind of methods of p-aminophenol synthesis 1,4-benzoquinone list imines, p-aminophenol is directlyed adopt by one-step method in the present invention and is coupled dehydrogenation oxidation with phenyl boric acid, 1,4-benzoquinone 1,4-benzoquinone list imines is made, it is easy to operate, it is not necessarily to multistep reaction, shorten the reaction time, raw material is cheap, and production cost is low, avoids the use of explosive oxidant, overcome the cumbersome of many more manipulations of art methods, possible high risk of exploding, heavy metal ion high pollution, it is at high cost the disadvantages of.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of method of p-aminophenol synthesis 1,4-benzoquinone list imines.
Background technique
Quinone imines type compound is usually bright compound, quinone imides compound be present in phytochrome,
It may be present in the substances such as dyestuff and indicator, while quinone imides dyestuff is also a kind of more important organic analysis object examination
Agent.Part quinone imides dyestuff also has strong fluorescence, such as safranine T, phenosafraine, nile blue sulfate etc., therefore can benefit
With its stronger fluorescent characteristic, to test and analyze the content of certain metal ions.The quinone imides dye weaker for some fluorescence
Material, such as dimethyl diaminophenazine chloride, but it has deeper color, can use catalytic kinetic spectrophotometry, carries out metal ion catalysis and takes off
Colour response, to realize the detection and analysis of metal ion.In addition, 1,4-benzoquinone list benzene imine structure is present in many antineoplastics
In object structure, especially play an important role in D actinomycin D structure.
The synthesis of 1,4-benzoquinone list benzene imines at present mostly uses p-aminophenol coupling preparation N- phenyl p-aminophenol or N- phenyl
Then 1,4-benzoquinone list benzene imine compound is made by following oxidative dehydrogenation in p-aminophenol ether:
Under nitrogen protection, pass through appropriate silver salt (such as: silver carbonate, silver oxide) and mercury oxide catalysis oxidation N- phenyl
P-aminophenol or the 1,4-benzoquinone list benzene imine compound of N- phenyl p-aminophenol ether preparation, but this method needs nitrogen protection,
Expensive starting materials, it is at high cost, need heavy metal silver salt and mercury salt to be catalyzed, environmental pollution is big.
1,4-benzoquinone list imines is prepared using hypochlorite oxidation's N- phenyl p-aminophenol, is made using N- phenyl p-aminophenol former
Material, expensive, high production cost using strong oxidizer hypochlorite are easy that redox reaction occurs with organic compound,
There is insecurity factor in production.
It is sub- through di-p-methoxy-diphenylamine oxidative synthesis 1,4-benzoquinone list benzene under the conditions of high iodine Dai Si-Martin's oxidant (DMP)
Amine, but reaction raw materials are expensive, high production cost, have potential explosion potential using Dai Si-Martin's oxidant, and anti-
A large amount of organic by-products neighbour phenoxy benzoic acid should be generated in the process.
Summary of the invention
It is an object of the invention to: in view of the above-mentioned problems, 1,4-benzoquinone list benzene imines is directly adopted by one-step method in the present invention
It is coupled dehydrogenation oxidation with phenyl boric acid with p-aminophenol, is made, it is easy to operate, it is not necessarily to multistep reaction, shortens reaction time, raw material
Inexpensively, production cost is low, avoids the use of explosive oxidant.
The technical solution adopted by the invention is as follows:
A kind of method of p-aminophenol synthesis 1,4-benzoquinone list imines: under alkaline condition, using catalyst and catalyst aid
Catalytic coupling and dehydrogenation oxidation reaction, one-step synthesis benzene quinone monoimine are carried out to raw material p-aminophenol and phenyl boric acid.
Further, specific steps are as follows: be dissolved in p-aminophenol, phenyl boric acid, catalyst, catalyst aid and alkaline reagent molten
It is reacted in agent.
Further, reaction condition are as follows: 65-90 DEG C progress back flow reaction 6-18 hours.
It further, further include carrying out cold filtration after reaction, vacuum distillation, then product of distillation is tied again
Crystalline substance filters after recrystallization, and is washed 2-5 times using recrystallization mother liquor.
Further, solvent is ethyl acetate, alkaline condition by potassium carbonate or liquor kalii acetici, catalyst be copper acetate or
Copper chloride, catalyst aid are benzoic acid.
The present invention uses cupric salt as catalyst under alkaline condition, does catalyst aid, p-aminophenyl with benzoic acid
Through catalytic coupling, 1,4-benzoquinone list benzene imines is made in oxidative dehydrogenation for phenol and phenyl boric acid.
N- phenyl p-aminophenol is obtained using p-aminophenol or p-aminophenol and halobenzene or phenyl boric acid coupling in the prior art
Or after N- phenyl p-aminophenol ether, reuses silver catalyst oxidation or directly use oxidant (hypochlorite, high iodine Dai Si-horse
Fourth oxidant) dehydrogenation oxidation obtains product 1,4-benzoquinone list benzene imines.And the present invention using mantoquita there is catalysis C-N to be coupled property,
Using the N- phenyl p-aminophenol of p-aminophenol and phenyl boric acid coupling generation, there is catalysis oxidation using mantoquita in same system
Property obtains product 1,4-benzoquinone list benzene imines with air effect, realizes and carried out coupling and dehydrogenation in same reaction system
Oxidation reaction continuous process, to simplify operation.
Further, the substance of p-aminophenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or copper chloride
The ratio between amount are as follows: 0.8-1.5:0.8-1.5:0.2-0.5:0.8-1.5:0.1-0.2.
Further, the substance of p-aminophenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or copper chloride
The ratio between amount are as follows: 1:1:0.2:1:0.2.
Further, the substance of p-aminophenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or copper chloride
The ratio between amount are as follows: 1:1:0.5:1:0.1.
Further, the substance of p-aminophenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or copper chloride
The ratio between amount are as follows: 1:1:0.5:1:0.2.
Further, product of distillation is recrystallized using petroleum ether.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1, in the present invention, catalyst aid is done with benzoic acid, is passed through as catalyst using cupric salt under alkaline condition
One-step method directlys adopt p-aminophenol and is coupled dehydrogenation oxidation with phenyl boric acid, and 1,4-benzoquinone list imines is made, and the present invention has using mantoquita
There is catalysis C-N coupling property, using the N- phenyl p-aminophenol of p-aminophenol and phenyl boric acid coupling generation, utilize in same system
Mantoquita has the property of catalysis oxidation, obtains product 1,4-benzoquinone list benzene imines with air effect, realizes in same reaction system
In carried out coupling and dehydrogenation oxidation reaction continuous process, thus simplify operation, be not necessarily to multistep reaction, overcome prior art side
The many more manipulations of method it is cumbersome, shorten the time, improve efficiency；
2, in the present invention, reaction process is not necessarily to gas shield, and raw material is cheap, at low cost, without adding heavy metal ion, ring
Border pollution is small；
3, in the present invention, the use of explosive oxidant is avoided, effectively prevents the high risk of explosion；
4, the method according to the invention prepares 1,4-benzoquinone list imines, and yield 55-78% obtains higher yields, has good
Good practical application value.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit
The fixed present invention, i.e., described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
Therefore, the model of claimed invention is not intended to limit to the detailed description in the embodiment of the present invention below
It encloses, but is merely representative of selected embodiment of the invention.Based on the embodiment of the present invention, those skilled in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
It should be noted that the relational terms of term " first " and " second " or the like be used merely to an entity or
Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any
This actual relationship or sequence.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including described
There is also other identical elements in the process, method, article or equipment of element.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of method for p-aminophenol synthesis 1,4-benzoquinone list imines that present pre-ferred embodiments provide, including following step
It is rapid:
In the four-hole boiling flask for being equipped with agitating device, reflux condensate device and thermometer, 150ml ethyl acetate is added,
10mmol amino phenols, 10mmol phenyl boric acid, 2mmol anhydrous cupric acetate, 10mmol potassium carbonate and 5mmol benzoic acid, at 80 DEG C
Lower progress obtains salmon liquid in back flow reaction 8 hours；After completion of the reaction, it is cooled to room temperature, then filters；Filtrate is depressurized
It distills, organic solvent ethyl acetate is recycled in vacuum distillation process, finally obtains deep Orange red solid；Solid is tied again with petroleum ether
Then crystalline substance filters；It is washed 3 times with recrystallization mother liquor and obtains orange/yellow solid product 1.63g, yield 89.1%.
Embodiment 2
A kind of method for p-aminophenol synthesis 1,4-benzoquinone list imines that present pre-ferred embodiments provide, including following step
It is rapid:
In the four-hole boiling flask for being equipped with agitating device, reflux condensate device and thermometer, 150ml ethyl acetate is added,
10mmol amino phenols, 10mmol phenyl boric acid, 2mmol copper chloride dihydrate, 10mmol potassium acetate and 5mmol benzoic acid, at 80 DEG C
Lower progress obtains salmon liquid in back flow reaction 10 hours；After completion of the reaction, it is cooled to room temperature, then filters；Filtrate is subtracted
Pressure is distilled, and organic solvent ethyl acetate is recycled in vacuum distillation process, finally obtains deep Orange red solid；Solid petroleum ether weight
Crystallization, then filters；It is washed 2 times with recrystallization mother liquor and obtains orange/yellow solid product 1.42g, yield 77.6%.
Embodiment 3
A kind of method for p-aminophenol synthesis 1,4-benzoquinone list imines that present pre-ferred embodiments provide, including following step
It is rapid:
In the four-hole boiling flask for being equipped with agitating device, reflux condensate device and thermometer, 150ml ethyl acetate is added,
10mmol amino phenols, 10mmol phenyl boric acid, 2mmol copper acetate dihydrate, 10mmol potassium acetate and 5mmol benzoic acid, 80
It carries out obtaining salmon liquid in back flow reaction 10 hours at DEG C；After completion of the reaction, it is cooled to room temperature, then filters；Filtrate carries out
It is evaporated under reduced pressure, organic solvent ethyl acetate is recycled in vacuum distillation process, finally obtains deep Orange red solid；Solid petroleum ether
Recrystallization, then filters；It is washed 3 times with recrystallization mother liquor and obtains orange/yellow solid product 1.31g, yield 71.6%.
Embodiment 4
A kind of method for p-aminophenol synthesis 1,4-benzoquinone list imines that present pre-ferred embodiments provide, including following step
It is rapid:
In the four-hole boiling flask for being equipped with agitating device, reflux condensate device and thermometer, 150ml ethyl acetate is added,
10mmol amino phenols, 10mmol phenyl boric acid, 1mmol anhydrous cupric acetate, 10mmol potassium carbonate and 5mmol benzoic acid, at 80 DEG C
Lower progress obtains salmon liquid in back flow reaction 15 hours；After completion of the reaction, it is cooled to room temperature, then filters；Filtrate is subtracted
Pressure is distilled, and organic solvent ethyl acetate is recycled in vacuum distillation process, finally obtains deep Orange red solid；Solid petroleum ether weight
Crystallization, then filters；It is washed 2 times with recrystallization mother liquor and obtains orange/yellow solid product 1.14g, yield 62.2%.
Embodiment 5
A kind of method for p-aminophenol synthesis 1,4-benzoquinone list imines that present pre-ferred embodiments provide, including following step
It is rapid:
In the four-hole boiling flask for being equipped with agitating device, reflux condensate device and thermometer, 150ml ethyl acetate is added,
10mmol amino phenols, 10mmol phenyl boric acid, 2mmol anhydrous cupric acetate, 10mmol potassium acetate and 2mmol benzoic acid, at 80 DEG C
Lower progress obtains salmon liquid in back flow reaction 8 hours；After completion of the reaction, it is cooled to room temperature, then filters；Filtrate is depressurized
It distills, organic solvent ethyl acetate is recycled in vacuum distillation process, finally obtains deep Orange red solid；Solid is tied again with petroleum ether
Then crystalline substance filters；It is washed 2 times with recrystallization mother liquor and obtains orange/yellow solid product 1.02g, yield 55.7%.
Above-mentioned products therefrom is detected, hydrogen modal data are as follows:1HNMR(400MHz,Chloroform-d)δ7.42
(t, J=7.7Hz, 2H), 7.26 (d, J=13.1Hz, 2H), 7.12 (s, 1H), 6.92 (d, J=7.7Hz, 2H), 6.63 (d, J
=44.0Hz, 2H).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of method of p-aminophenol synthesis 1,4-benzoquinone list imines, it is characterised in that: under alkaline condition, using catalyst and
Catalyst aid carries out catalytic coupling to raw material p-aminophenol and phenyl boric acid and dehydrogenation oxidation reacts, one-step synthesis benzoquinones Dan Ya
Amine.
2. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 1, it is characterised in that: specific steps
Are as follows: p-aminophenol, phenyl boric acid, catalyst, catalyst aid and alkaline reagent are dissolved in solvent and reacted.
3. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 2, it is characterised in that: the reaction item
Part are as follows: 65-90 DEG C progress back flow reaction 6-18 hours.
4. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 2, it is characterised in that: further include reaction
After carry out cold filtration, be evaporated under reduced pressure, then product of distillation recrystallized, filtered after recrystallization, and using recrystallization
Mother liquor washs 2-5 times.
5. the method for the synthesis 1,4-benzoquinone list imines of the p-aminophenol according to any one of claim 2, it is characterised in that: institute
Stating solvent is ethyl acetate, and for the alkaline condition by potassium carbonate or liquor kalii acetici, the catalyst is copper acetate or copper chloride,
The catalyst aid is benzoic acid.
6. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 2, it is characterised in that: p-aminophenol,
The ratio between phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or the amount of substance of copper chloride are as follows: 0.8-1.5:0.8-1.5:
0.2-0.5:0.8-1.5:0.1-0.2。
7. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 6, it is characterised in that: described to amino
The ratio between phenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or the amount of substance of copper chloride are as follows: 1:1:0.2:1:0.2.
8. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 6, it is characterised in that: described to amino
The ratio between phenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or the amount of substance of copper chloride are as follows: 1:1:0.5:1:0.1.
9. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 6, it is characterised in that: described to amino
The ratio between phenol, phenyl boric acid, benzoic acid, potassium carbonate or potassium acetate, copper acetate or the amount of substance of copper chloride are as follows: 1:1:0.5:1:0.2.
10. the method for p-aminophenol synthesis 1,4-benzoquinone list imines according to claim 4, it is characterised in that: use petroleum
Ether recrystallizes product of distillation.
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| CN201910298768.4A CN109942456B (en) | 2019-04-15 | 2019-04-15 | Method for synthesizing p-benzoquinone monoimine from p-aminophenol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160235A (en) * | 2022-08-10 | 2022-10-11 | 宜宾学院 | 2, 3-dihydroquinazoline-4 (1H) -ketone compound and ultrasonic synthesis method thereof |
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| US4968843A (en) * | 1990-03-08 | 1990-11-06 | The Goodyear Tire & Rubber Company | Preparation of a N-substituted phenylenediamine |
| CN1356979A (en) * | 1998-04-10 | 2002-07-03 | 弗莱克斯塞思美国有限合伙公司 | Prepn. of quinoneimines from hydroxyphenylamines using hydrogen peroxide and catalyst |
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2019
- 2019-04-15 CN CN201910298768.4A patent/CN109942456B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968843A (en) * | 1990-03-08 | 1990-11-06 | The Goodyear Tire & Rubber Company | Preparation of a N-substituted phenylenediamine |
| CN1356979A (en) * | 1998-04-10 | 2002-07-03 | 弗莱克斯塞思美国有限合伙公司 | Prepn. of quinoneimines from hydroxyphenylamines using hydrogen peroxide and catalyst |
Non-Patent Citations (2)
| Title |
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| FABIEN BARAGONA ET AL.: "《Synthesis of 5-substituted 2,3-dihydrobenzofurans in a one-pot oxidation/cyclization reaction》", 《TETRAHEDRON》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160235A (en) * | 2022-08-10 | 2022-10-11 | 宜宾学院 | 2, 3-dihydroquinazoline-4 (1H) -ketone compound and ultrasonic synthesis method thereof |
| CN115160235B (en) * | 2022-08-10 | 2023-12-15 | 宜宾学院 | 2, 3-dihydro-quinazoline-4 (1H) -ketone compound and ultrasonic synthesis method thereof |
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| CN109942456B (en) | 2021-05-04 |
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