CN1128747A - Method for prepn. of 1,4-dihydro-9,10 dihydroxy-anthracene - Google Patents
Method for prepn. of 1,4-dihydro-9,10 dihydroxy-anthracene Download PDFInfo
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- CN1128747A CN1128747A CN 95118482 CN95118482A CN1128747A CN 1128747 A CN1128747 A CN 1128747A CN 95118482 CN95118482 CN 95118482 CN 95118482 A CN95118482 A CN 95118482A CN 1128747 A CN1128747 A CN 1128747A
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- anthracene
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Abstract
Tetrahydro-phthalic anhydride is used as the main raw material, by the action of aluminium trichloride, inorganic acid and dehydrator, the product is obtd.. Advantages are as follows: low cost, simple art, and the purity of the product of above 99% can be abtd. without clean-up procedure.
Description
The present invention relates to a kind of preparation of derivative of anthracene compound, particularly 1, the preparation method of 4-dihydro-9,10 dihydroxy-anthracene.
1,4-dihydro-9,10 dihydroxy-anthracene (code name SAQ) is a kind of pulp cooking agent that is used for paper industry in recent years, is the best substitute of anthraquinone.Its molecular formula is C
14H
12O
2, structural formula is:
It has an isometry tautomer (1,4,4a, 9a tetrahydro-anthraquinone), and structural formula is:
This material outward appearance is dark blood red xln, and as easy as rolling off a log oxidation in air is generally all handled with aqueous sodium hydroxide solution, forms 1,4-dihydro-9,10 dihydroxy-anthracene disodium salt, and in time protect with kerosene or white oil, with anti-oxidation.
Preparation method about this material, first delivers people such as U.S. A.Luttringhaus in 1932 with the Diels-Alder reaction method 1,4-naphthoquinones and divinyl are in ethanol medium, and sealed tube internal heating to 100 ℃ makes 1,4,4a, the 9a tetrahydro-anthraquinone prepares the patent of anthraquinone again with atmospheric oxidation, but when attempting industrialization, the success owing to technical obstacle.
In the later stage eighties, Kawasaki, Japan changes into company with this manufactured anthraquinone and its intermediate-1,4,4a, the industrialization of 9a tetrahydro-anthraquinone.
The Kawasaki, Japan company that changes into adopts the interruption method to produce anthraquinone and tetrahydro-anthraquinone.Concrete grammar is: refined naphthalene through the fixed bed multitube oxidizer oxidation get (1,4-naphthoquinones 40.2%, phthalic anhydride 42.6%, unreacted naphthalene 2-7%), water capture solid content be 10% 1,4-naphthoquinones and phthalic acid water soup compound, with the extraction of dimethylbenzene multistage counter current, must contain 1,22% xylene solution of 4-naphthoquinones again, through vacuum concentration, cooling, recrystallization, a part is as 99.7%1,4-naphthoquinones finished product is as commodity selling.And the naphthoquinones xylene solution of lower concentration, with weak base aqueous solution handle remove small amount of residual acid after, in the presence of stopper, carried out addition 3 hours with excess butadiene slightly in 120 ℃, make tetrahydro-anthraquinone, be processed into the tetrahydro-anthraquinone disodium salt with aqueous sodium hydroxide solution again, and with separated from solvent as lower concentration tetrahydro-anthraquinone sodium salt product, seal up for safekeeping as commodity selling with kerosene.
This preparation method's defective is a naphthoquinones raw materials cost height, and can not obtain high purity product.Though the industrialization but production unit is huge of this method, the technical process complexity, investment is big.
The purpose of this invention is to provide a kind of 1, the new preparation method of 4-dihydro-9,10 dihydroxy-anthracene, this method cost is low, raw material is easy to get, the product purity height.
The objective of the invention is to realize by following three-step reaction:
1, the first step reaction is that Tetra Hydro Phthalic Anhydride carries out condensation reaction with benzene under the effect of catalyzer aluminum trichloride (anhydrous), generates o-benzoyl tetrahydrobenzoic acid aluminium double salts and hydrogenchloride;
2, the second step reaction is that the reaction that is hydrolyzed under the mineral acid effect of the o-benzoyl tetrahydrobenzoic acid aluminium double salts that generated generates o-benzoyl tetrahydrobenzoic acid and aluminum chloride;
3, three-step reaction be gained o-benzoyl tetrahydrobenzene formyl under the dewatering agent effect, slough a molecular water and carry out ring-closure reaction, generate 1,4-dihydro-9,10 dihydroxy-anthracene.
The preferred especially hydrochloric acid of wherein said mineral acid, the special preferably phosphoric acid of described dewatering agent, sulfuric acid, phosphorous acid, zinc chloride, metaphosphoric acid.
Represent that with the chemical structure reaction formula said process is as follows:
1. acidylate condensation reaction:
2. hydrolysis reaction (to be example) with concentrated hydrochloric acid:
3. ring-closure reaction:
In preferred version of the present invention, described condensation reaction is carried out under normal pressure, and preferred temperature is 40-65 ℃; Described hydrolysis reaction carries out under normal pressure, and preferred temperature is 35-65 ℃; Described ring-closure reaction is carried out under normal pressure, and preferred temperature is 100-200 ℃.
Method starting material of the present invention are easy to get, cost is low, and facility investment is few, and technology is simple, and directly obtain the product of 99% above purity without purification.Present method also can be used as its isomers 1,4,4a, the preparation method of 9a tetrahydro-anthraquinone.
Describe the present invention in detail below by embodiment.Embodiment:
Prepare the purpose product by following step:
1, condensation reaction: this reaction is the core of whole preparation, and reaction is to be equipped with at the bottom of 1000 milliliters of three mouthfuls of gardens of ring-like reflux condensing tube and to carry out in the flask in that oil sealing agitator and one are housed.Prolong dress monochlor(in)ate suitable for reading calcium absorption pipe is connected with the hydrogen chloride absorption device again.The 3rd mouth of flask is equipped with the soft rubber ball of band thermometer.In there-necked flask, place the Tetra Hydro Phthalic Anhydride and 110 of 32.6 grams (0.2 mole multiple spot) slightly 99.5% or more and restrain the dry-out benzene that contains a small amount of thiophene (below the 50PPM), under strong mixing, divide then and slowly add 60 gram (0.45 mole) aluminum trichloride (anhydrous)s for four times, each add-on 15 grams, behind each adding aluminum chloride, there-necked flask must be built.
Aluminum trichloride (anhydrous) adds the back if temperature of reaction is low for the first time, do not begin, then can adjust jacket temperature, impel reaction normally to begin in temperature of reaction between 40-65 ℃, reaction can reduce temperature or temporarily reaction be relaxed the flask cooling with ice bag when carrying out too acutely.After all aluminum trichloride (anhydrous)s add, in 60-70 ℃ the water-bath with mixture heating up till no longer include hydrogenchloride and emit, be incubated ten minutes and again flask is cooled off, in reaction mixture, slowly and modestly add 200 ice about restraining.
2, hydrolysis reaction: will be added with the concentrated hydrochloric acid that adds (45-50 milliliter) in the aluminium double salts compound solution of 200 gram ice, all dissolvings of the aluminium double salts that makes it to separate out precipitation, also can heat this moment make it temperature at 35-65 ℃ till precipitate CL.And in middle mouthful of importing water vapor of there-necked flask, the side mouth connects prolong, and water steam distillation distillation goes out superfluous benzene (wait to purify and reclaim).With ice oily matter remaining in the flask is cooled off again, make it the cold amorphous sediment that is frozen into.Filter with B then, throw out is with the less water washing of coming down in torrents, and throw out forwards in the flask and to restrain the hot solution that anhydrous sodium carbonates are dissolved in 240 ml waters with 16 and change the o-benzoyl tetrahydrobenzoic acid into sodium salt.For promoting neutralization reaction, can feed a certain amount of water vapor in the flask to whole resolution of precipitates, and behind the heating several minutes, pour into again in the B that is placed with filter paper and filter.It is that 1.19 concentrated hydrochloric acid consumption 20-22 milliliter carries out acidifying that filtrate cooling is poured in the there-necked flask under high degree of agitation with proportion again.Can separate out the o-benzoyl tetrahydrobenzoic acid be oily matter this moment, the solid that congeals in cooling with after stirring, and again with the ice-cooled throw out that filters out, with the less water washing, dry back output is 40 grams (are theoretical yield 85%)
3, ring-closure reaction: at last with the o-benzoyl tetrahydrobenzoic acid that drawn 40 grams with the strong phosphoric acid of 280 gram (7-8 times of weight ratio) 1.63 proportions in 100-200 ℃ of temperature normal pressure till heating is carried out dissolving the dark blood red solution of formation fully to reactant in ring-closure reaction 2-3 hour down, and pour into rapidly on the 4 liter rubble ices, separate out 1.4-dihydro-9.10 dihydroxy-anthracene rapidly, and suction strainer obtains pure product 99% above purity 36.5 more than 99% of theoretical yield of gram in the woven fiber glass funnel).This product be because the as easy as rolling off a log oxidation of pure product must be handled the disodium salt make it shape or 1.4-dihydro-9.10 dihydroxy-anthracene with aqueous sodium hydroxide solution, and seals up for safekeeping with kerosene or white oil and to protect.
Claims (7)
1, a kind of 1,4, the preparation method of-dihydro-9,10 dihydroxy-anthracene is characterized in that comprising the steps:
(1) Tetra Hydro Phthalic Anhydride carries out condensation reaction with benzene under the aluminum chloride effect, generates o-benzoyl tetrahydrobenzoic acid aluminium double salts and hydrogenchloride;
(2) the o-benzoyl tetrahydrobenzoic acid aluminium double salts that is generated generates o-benzoyl tetrahydrobenzoic acid and aluminum chloride under the mineral acid effect;
(3) gained o-benzoyl tetrahydrobenzene formyl is sloughed a molecular water and is carried out ring-closure reaction under the dewatering agent effect, generates 1,4-dihydro-9,10 dihydroxy-anthracene.
2, method as claimed in claim 1 is characterized in that wherein said mineral acid is a hydrochloric acid.
3,, it is characterized in that described dewatering agent is phosphoric acid, sulfuric acid, phosphorous acid, zinc chloride or metaphosphoric acid as the method for claim 1 or 2.
4, method as claimed in claim 1 is characterized in that being reflected under the normal pressure and carries out.
5,, it is characterized in that described step (1) carries out at 40-65 ℃ as the method for claim 1 or 4.
6,, it is characterized in that described step (2) is at 35-65 ℃ as the method for claim 1 or 4
7,, it is characterized in that described step (3) carries out at 100-200 ℃ as the method for claim 1 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95118482 CN1128747A (en) | 1995-11-01 | 1995-11-01 | Method for prepn. of 1,4-dihydro-9,10 dihydroxy-anthracene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95118482 CN1128747A (en) | 1995-11-01 | 1995-11-01 | Method for prepn. of 1,4-dihydro-9,10 dihydroxy-anthracene |
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| Publication Number | Publication Date |
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| CN1128747A true CN1128747A (en) | 1996-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95118482 Pending CN1128747A (en) | 1995-11-01 | 1995-11-01 | Method for prepn. of 1,4-dihydro-9,10 dihydroxy-anthracene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055790A (en) * | 2013-01-18 | 2013-04-24 | 金伟光 | Equipment of preparing anthraquinone by one-kettle method and method of preparing anthraquinone using same |
| CN113999101A (en) * | 2021-10-12 | 2022-02-01 | 广东海洋大学 | Synthetic method of anthraquinone derivative SZ-685C |
-
1995
- 1995-11-01 CN CN 95118482 patent/CN1128747A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055790A (en) * | 2013-01-18 | 2013-04-24 | 金伟光 | Equipment of preparing anthraquinone by one-kettle method and method of preparing anthraquinone using same |
| CN113999101A (en) * | 2021-10-12 | 2022-02-01 | 广东海洋大学 | Synthetic method of anthraquinone derivative SZ-685C |
| CN113999101B (en) * | 2021-10-12 | 2024-03-26 | 广东海洋大学 | Synthesis method of anthraquinone derivative SZ-685C |
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