CN103509032B - Dioxa anthanthrene class is containing the mass green synthesis method of oxygen fused ring compound - Google Patents
Dioxa anthanthrene class is containing the mass green synthesis method of oxygen fused ring compound Download PDFInfo
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- CN103509032B CN103509032B CN201310339497.5A CN201310339497A CN103509032B CN 103509032 B CN103509032 B CN 103509032B CN 201310339497 A CN201310339497 A CN 201310339497A CN 103509032 B CN103509032 B CN 103509032B
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Abstract
The invention discloses the mass green synthesis method of a kind of dioxa anthanthrene class containing oxygen fused ring compound, comprise: the reaction raw materials containing two hydroxyl is dissolved in high boiling solvent, and add solid-state palladium catalyst, then by reaction system in air ambient in 150-280 DEG C of reflux, from reaction system, solid-state palladium catalyst is isolated after reaction terminates, and recrystallization process is carried out to remaining liquid mixed reactant, obtain dioxa anthanthrene class containing oxygen fused ring compound.Preferably, the method also comprises: in the process of heating reflux reaction, in reaction system, pass into air or oxygen; And after the completion of reaction, recycle palladium catalyst and high boiling solvent.The present invention at least has the following advantages: (1) operation is simple, and reaction conditions is gentle; (2) can avoid using the higher solvent of toxicity, and reaction solvent and catalyzer all can recycles, environmental protection; (3) reaction yield is high, and product is easy to separation and purification, is easy to industrial mass and implements.
Description
Technical field
The present invention be more particularly directed to the mass green synthesis method of a kind of dioxa anthanthrene class containing oxygen fused ring compound, belong to organic photoelectrical material technical field.
Background technology
Dioxa anthanthrene (PXX) is a kind of two dimensional surface condensed ring molecule, it to be replaced by two Sauerstoffatoms and in two anthracenes 6, a kind of novel texture that twelve carbon atom position obtains, due to the existence of its intramolecular two bridging Sauerstoffatoms, this compounds has very good photo-thermal oxidative stability, 200 degree of high temperature can be born under air ambient, neither melting, does not also decompose (" luminous journal ", 2006,27,95).It as far back as 20th century the '20s be just synthesized out (" Ber.Dtsch.Chem.Ges. ", 1926,59,2159), but several years up to date are just taken seriously, 2009, German Merck company took the lead in utilizing such material to make blue-light-emitting OLED (CN101490208A).In the same year, the people such as the N.Kobayashi of Sony utilize the embedding anthracene derivant Ph-PXX of dioxoanthracene to be made into thin film transistor, obtain the high mobility (Chem.Mater.2009,21,552) of 0.4 ~ 0.8cm2/Vs.The full stress-strain TFT driving circuit of the rollable OLED display screen model machine of flexibility that Sony is shown in " SID2009 " meeting utilizes this material evaporation to make and obtains.These application all show the good application prospect of dioxa anthanthrene class material.
Dioxa anthanthrene, as a kind of important photoelectric material, only has a small amount of document to be studied its synthetic method, such as: dinaphthol is dissolved in the aqueous solution of NaOH by the TamotsuInabe study group of Hokkaido, Japan university, adopts Cu (OAc)
2oxidation (Bull.Chem.Soc.Jpn.2001,74,53); The Shen Pei health study group of Zhongshan University adopts microwave carbon bath with Cu (OAc)
2oxidation beta naphthal (luminous journal .2006,27,95), these two kinds of preparation method's productive rates are low, product separation purification difficult, usually just will can obtain purer product through repeatedly distilling.Merck company of Germany adopts transition metal oxide as MnO
2, CuO etc. are oxidized dinaphthol (CN101490208A) under the high temperature conditions, this preparation method's severe reaction conditions, and adopt high toxicity, high boiling oil of mirbane as solvent, purify loaded down with trivial details, productive rate is undesirable equally.Above synthetic method is all not suitable for applying in the large-scale mass production of dioxa anthanthrene.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate, yield is high, green, cheap, be applicable to the preparation method of dioxa anthanthrene compounds of suitability for industrialized production, thus overcome in prior art preparation and the technical problem such as purifying technique is loaded down with trivial details, severe reaction conditions, productive rate are low, separating-purifying is difficult.
For achieving the above object, present invention employs following technical scheme:
A kind of dioxa anthanthrene class is containing the mass green synthesis method of oxygen fused ring compound, comprise: the reaction raw materials containing two hydroxyl is dissolved in high boiling solvent, and add solid-state palladium catalyst, then by reaction system in air ambient in 150-280 DEG C of reflux, from reaction system, solid-state palladium catalyst is isolated after reaction terminates, and recrystallization process is carried out to remaining liquid mixed reactant, obtain dioxa anthanthrene class containing oxygen fused ring compound.
As one of comparatively preferred embodiment, the method also comprises: in the process of heating reflux reaction, in reaction system, pass into air or oxygen.
As one of comparatively preferred embodiment, the method comprises: filtered while hot reaction system after the completion of reaction, reclaims solid-state palladium catalyst, and filtrate recrystallization is obtained dioxa anthanthrene class containing oxygen fused ring compound.
The boiling point of aforementioned high boiling solvent is preferably 150-250 DEG C.
Further, described dioxa anthanthrene class comprises containing the general structure of oxygen fused ring compound:
Further, the general structure of the described reaction raw materials containing two hydroxyl comprises:
Aforementioned R, R
1, R
2at least be selected from following atom and group any one or a few:
Hydrogen;
There is the straight chain of 1 ~ 22 carbon atom, side chain or cyclic alkyl chain;
There is the thiazolinyl of 2 ~ 40 carbon atoms, alkynyl, aryl, arylalkyl;
There is 1 ~ 22 carbon atom, but wherein more than 1 carbon atom by heteroatoms or replace straight chain, side chain or the cyclic alkyl chain that functional group replaces;
There are 2 ~ 40 carbon atoms, but wherein more than 1 carbon atom by heteroatoms or replace thiazolinyl, alkynyl, the aryl that functional group replaces;
There is 1 ~ 22 carbon atom, but hydrogen atom wherein on more than 1 carbon atom is by halogen atom or replace straight chain, side chain or the cyclic alkyl chain that functional group replaces;
There are 2 ~ 40 carbon atoms, but hydrogen atom wherein on more than 1 carbon atom is by halogen atom or replace thiazolinyl, alkynyl, the aryl that functional group replaces;
Described heteroatoms comprises Si, Se, O, S or N, and described replacement functional group comprises thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro;
Aryl in above-mentioned includes but are not limited to the derivative of benzene, biphenyl, naphthalene, anthracene, thiophene, thiophthene, thionaphthene, bithiophene and above all groups.
Described high boiling solvent can be selected from but be not limited to chlorobenzene, p-Xylol, o-Xylol, m-xylene, orthodichlorobenzene, santochlor, N, dinethylformamide, pimelinketone, methyl-sulphoxide, N-Methyl pyrrolidone, oil of mirbane and 1, any one or multiple mixture in 2,4 trichlorobenzene.
Described palladium catalyst comprises palladium carbon.
Further, described palladium carbon comprises 0.5wt% ~ 30wt% palladium, and rest part comprises gac.
Preferably, the molar percentage consumption of described palladium carbon in reaction system is 1% ~ 10%.
As one of comparatively preferred embodiment, in the method, the temperature of reacting by heating is 180 ~ 220 DEG C.
Compared with prior art, the present invention at least has the following advantages: (1) operation is simple, and reaction conditions is gentle; (2) solvent using the toxicity such as oil of mirbane higher can be avoided, and reaction solvent can recycle; (3) reaction yield is high, and product is easy to separation and purification; (4) catalysts can be recycled.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the present invention one better embodiment;
Fig. 2 a is the single crystal structure figure of the wrong embedding anthracene compound B of dioxoanthracene in the embodiment of the present invention 2;
Fig. 2 b is the molecular arrangement schematic diagram of the wrong embedding anthracene compound B of dioxoanthracene in the embodiment of the present invention 2.
Embodiment
As previously mentioned, the problems such as the preparation technology existed in view of existing synthetic method is loaded down with trivial details, use toxic solvents and severe reaction conditions, productive rate is low, separating-purifying is difficult, the present invention proposes the mass green synthesis method of a kind of novel dioxa anthanthrene class containing oxygen fused ring compound, its technical scheme comprises: utilize a small amount of palladium catalyst, hydroxyl raw material reflux generation dehydrocyclization in air ambient is obtained by reacting dioxa anthanthrene class containing oxygen fused ring compound.Simple process is only needed to obtain high-purity product after reaction terminates.And catalysts and solvents is all reusable.
Further, with reference to figure 1, as a better embodiment of the present invention, it can comprise: be dissolved in high boiling solvent by the reaction raw materials containing two hydroxyl, add the palladium carbon of catalytic amount, 150-280 DEG C of reflux; Reaction can be carried out in air ambient, and reaction terminates rear filtered while hot and reclaims catalyzer, and filtrate obtains highly purified dioxa anthanthrene compounds by recrystallization.
Further, described dioxa anthanthrene compounds and previously described general structure can be had containing the reaction raw materials of two hydroxyl, do not repeating herein, and the symbol mod sum label in these general formulas can have following implication: R, R1, R2 are hydrogen or the straight chain with 1 to 22 carbon atom, side chain or cyclic alkyl chain; Or be thiazolinyl, alkynyl, the aryl with 2 to 40 carbon atoms, wherein one or more carbon atoms can by heteroatoms (Si, Se, O, S.N), thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group, nitro replaced, and the hydrogen on one or more carbon atom can be replaced by halogen atom and above-mentioned functional group.
High boiling solvent used is chlorobenzene, p-Xylol, o-Xylol, m-xylene, orthodichlorobenzene, santochlor, N, dinethylformamide, pimelinketone, methyl-sulphoxide, N-Methyl pyrrolidone, oil of mirbane, 1, one or more mixture in 2,4 trichlorobenzene.Especially preferably p-Xylol or orthodichlorobenzene react as solvent.
Palladium catalyst used can adopt palladium carbon, and be generally black powder art or the activated charcoal pellets containing 0.5wt% ~ 30wt% palladium, it adds reaction system after mixing with high boiling solvent in advance, and consumption is at 1% ~ 10%mol.Palladium-carbon catalyst is in suspended state in reaction system, be insoluble to high boiling solvent used, therefore by the modes such as filtered while hot and reactant and product separation, and circulation repeatedly uses, both can be used for short run reaction repeated, also can be used for the continuous batch production mode such as reactor and Flow Control pipe reaction.The growth of the inactivation of palladium catalyst mainly palladium crystal grain makes that its catalytic active area reduces, the covering of impurity and the reason such as poisoning.And palladium there is good corrosion resistance, high-temperature behavior and stable electrology characteristic, make it run off seldom in reaction process, therefore can reuse more completely the palladium catalyst of inactivation.
React in the method and carry out in air atmosphere, instead of carry out under protection of inert gas; In order to accelerated reaction, air or oxygen can be passed in reaction system.Glass reactor, reactor etc. that reaction vessel is glass refluxing unit, can uses in microwave pressurizing device, and be not limited thereto.
Reacting type of heating used in the method is heat-conducting oil heating, electrically heated or microwave heating, and temperature of reaction, in 150 ~ 280 degree Celsius range, especially preferably to be reacted at 180 ~ 220 degrees Celsius.
In the method, the purifying for product can adopt filtration, recrystallization, distillation and distillation etc., especially preferably direct filtration recrystallization obtains high-purity product.
Summarize it, the present invention develops a kind ofly can prepare the preparation method of dioxa anthanthrene compounds by mass, and its reaction yield is high, preparation and purification process is simple, and catalyzer can be recycled, and considerably reduces the pollution to environment, greatly reduce production cost, be applicable to mass production.
Technical scheme of the present invention is further illustrated below by way of two preferred embodiments.Wherein, the synthetic route of these two embodiments and the structure of product can be as follows:
Embodiment 1 oil bath adds the embedding anthracene of hot preparation dioxoanthracene (compd A)
Dinaphthol (1g, 3.5mmol) be dissolved in 50mL orthodichlorobenzene, add catalyst P d/C (Pd:10%) (149mg, 4%mol), 180 degrees Centigrade backflows, reaction is carried out in atmospheric environment, blasts air or oxygen with accelerated reaction in process in reaction system.TLC follows the tracks of reaction process (5h), slightly cools, heat filtering Recover palladium C catalyst about 145 milligrams after reaction terminates, filtrate concentrates, and recrystallization obtains light yellow needles dioxa anthanthrene 0.94g, fusing point 236.5 ~ 237.5 DEG C, purity is greater than 99%, yield 95.3%.
1HNMR(400MHz，DMSO)δ7.49(d，2H)，7.24(dd，2H)，7.18(dd，2H)，7.08(d，2H)，6.76(dd，2H).MS(EI)m/z：282.1(M+)。
The wrong embedding anthracene (compd B) of dioxoanthracene is prepared in embodiment 2 microwave heating
In microwave reaction pipe, add above-mentioned dihydroxy compound (100mg, 0.32mmol), catalyst P d/C (Pd:10%) (34mg, 5%mol) and orthodichlorobenzene 1mL, (model: CEMDiscover under microwave-assisted, microwave irradiation power 300W), 220 degrees Celsius of reaction 60s, after reaction terminates, heat filtering Recover palladium C catalyst, concentrating filter liquor, recrystallization obtains the wrong embedding anthracene 59.2mg of yellow needle-like crystals dioxoanthracene, and purity is greater than 99%, yield 60%, GC-MS (m/z): 308.1 (M+).
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or amendment, all should be encompassed within protection scope of the present invention.
Claims (7)
1. a dioxa anthanthrene class is containing the mass green synthesis method of oxygen fused ring compound, it is characterized in that, comprise: the reaction raw materials containing two hydroxyl is dissolved in high boiling solvent, and add solid-state palladium catalyst, then by reaction system in air ambient in 150-280 DEG C of reflux, from reaction system, isolate solid-state palladium catalyst after reaction terminates, and recrystallization process is carried out to remaining liquid mixed reactant, obtain dioxa anthanthrene class containing oxygen fused ring compound;
The general structure of the described reaction raw materials containing two hydroxyl is:
Aforementioned R, R
1be selected from hydrogen or have in the straight chain of 1 ~ 22 carbon atom, branched alkyl chain any one more than;
Described solid-state palladium catalyst adopts palladium carbon;
Described high boiling solvent is chlorobenzene, p-Xylol, o-Xylol, m-xylene, orthodichlorobenzene, santochlor, DMF, pimelinketone, methyl-sulphoxide, N-Methyl pyrrolidone, oil of mirbane or 1,2,4 trichlorobenzene.
2. dioxa anthanthrene class according to claim 1 is containing the mass green synthesis method of oxygen fused ring compound, and it is characterized in that, the method also comprises: in the process of heating reflux reaction, in reaction system, pass into air or oxygen.
3. dioxa anthanthrene class according to claim 1 and 2 is containing the mass green synthesis method of oxygen fused ring compound, it is characterized in that, the method comprises: filtered while hot reaction system after the completion of reaction, reclaim solid-state palladium catalyst, and filtrate recrystallization is obtained dioxa anthanthrene class containing oxygen fused ring compound.
4. dioxa anthanthrene class according to claim 1 is containing the mass green synthesis method of oxygen fused ring compound, it is characterized in that, described dioxa anthanthrene class containing the general structure of oxygen fused ring compound is:
Aforementioned R, R
1be selected from hydrogen or have in the straight chain of 1 ~ 22 carbon atom, branched alkyl chain any one more than.
5. dioxa anthanthrene class according to claim 1 is containing the mass green synthesis method of oxygen fused ring compound, and it is characterized in that, described palladium carbon comprises 0.5wt% ~ 30wt% palladium, and rest part comprises gac.
6. dioxa anthanthrene class according to claim 1 is containing the mass green synthesis method of oxygen fused ring compound, and it is characterized in that, the molar percentage consumption of described palladium carbon in reaction system is 1% ~ 10%.
7. dioxa anthanthrene class according to claim 1 is containing the mass green synthesis method of oxygen fused ring compound, and it is characterized in that, in the method, the temperature of reacting by heating is 180 ~ 220 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE510443C (en) * | 1927-12-16 | 1930-10-21 | I G Farbenindustrie Akt Ges | Process for the production of dinaphthylene dioxide |
| CN101490208A (en) * | 2006-07-28 | 2009-07-22 | 默克专利有限公司 | Novel materials for organic electroluminescent devices |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE510443C (en) * | 1927-12-16 | 1930-10-21 | I G Farbenindustrie Akt Ges | Process for the production of dinaphthylene dioxide |
| CN101490208A (en) * | 2006-07-28 | 2009-07-22 | 默克专利有限公司 | Novel materials for organic electroluminescent devices |
Non-Patent Citations (3)
| Title |
|---|
| "Synthesis of Dibenzofurans via Palladium-Catalyzed Phenol-Directed";Lei Liu et al.;《Journal of the American Chemical Society》;20110524;第133卷(第24期);第1页右栏第2段至第3页左栏第1段及Table 1和Table 2 * |
| "Synthesis, Properties, and Structures of functionalized Peri-xanthenoxanthene";Na Lv et al.;《Organic Letters》;20130509;第15卷(第10期);全文 * |
| "新型OLED有机光电材料的合成及其性能研究";宋继国;《中国学位论文全文数据库》;20060425;第五章 * |
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