CN105503847A - Method for synthesizing benzodioxazole type compound - Google Patents
Method for synthesizing benzodioxazole type compound Download PDFInfo
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- CN105503847A CN105503847A CN201610026060.XA CN201610026060A CN105503847A CN 105503847 A CN105503847 A CN 105503847A CN 201610026060 A CN201610026060 A CN 201610026060A CN 105503847 A CN105503847 A CN 105503847A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention discloses a method for synthesizing a benzodioxazole type compound. The synthetic method comprises the following steps of taking a diamino catechol compound and aromatic aldehyde as raw materials and benzene, methylbenzene or xylene as solvent, and stirring the mixture and making the mixture to conduct a reaction for 2-6 hours at the temperature of 80-140 DEG C under the protection of inert gas; cooling reactant to the room temperature, adding 4-methoxy-tetramethyl piperidine oxygen radicals, conducting a reaction for 8-18 hours at the temperature of 80-140 DEG C in air atmosphere, conducting reduced pressure distillation for removing the solvent, and conducting column chromatography isolation, so that the benzodioxazole type compound is obtained. By means of the synthetic method, the catechol type compound and an aromatic aldehyde type compound are converted into the benzodioxazole type compound in a high-activity, high-selectivity and high-yield mode, and the synthetic method has the advantages of being low in reaction temperature, short in time, high in yield and purity, convenient to operate and the like.
Description
Technical field
The present invention relates to a kind of synthetic method of Ben Bing bis-oxazole compounds, with diamino pyrocatechol compounds and aromatic aldehyde for raw material, 4-methoxyl group-tetramethyl piperidine oxyradical (4-Methoxy-TEMPO) is catalyzer, reacts one-step synthesis Ben Bing bis-oxazole quasi-molecule in organic solvent.
Background technology
Organic semiconductor material because of many-sided advantage such as its photoelectric properties excellence, low production cost, complete processing is simple, selection range is broad, satisfactory mechanical property, and all has potential practical value in fields such as Organic Light Emitting Diode (OLED), organic solar batteries (organicSolarcell) and organic thin field-effect body pipes (OFET).Organic semiconductor material can be divided into: (1) Organic micromolecular semiconductor material, is mainly rigidity conjugation small molecules, as pentacene, oligo-thiophenes, Ben Bing bis-oxazole etc.; (2) organic polymer semiconductor material, is mainly the conjugated polymers of amorphous, as polyacetylene, Polythiophene, polyhenylene Ben Bing bis-oxazole etc.
Ben Bing bis-oxazole quasi-molecule is made up of jointly benzo two heterocycle rigid backbone and other functional substituted radical, there are excellent resistance toheat, mechanical property and photoelectric properties, so they are with a wide range of applications in fields such as heat-stable material, matrix material, photoelectric material and high-performance fibers.
Ben Bing bis-oxazole molecule is as the novel organic semiconductor material of a class, and scientists has carried out a series of research to its synthesis side.The synthesis of traditional benzoxazole derivatives mainly adopts piperidines (piperidine), triphenyl phosphorus (PPh
3) and polyphosphoric acid (PPA) as reaction catalyzer.Malika group take piperidines as catalyzer, DMSO is solvent, has been obtained by reacting a series of Ben Bing bis-oxazole compounds (Org.Lett., 2008,10,4915-4918) by diamino Resorcinol and lipoid substance; Colin group is catalyzer with triphenylphosphine, has synthesized a kind of novel cross Ben Bing bis-oxazole compounds (J.Am.Chem.Soc., 2003,125,6030-6031); Chan group, under comparatively gentle condition, take PPA as catalyzer, and it is 82% ~ 90% that single step reaction obtains Ben Bing bis-oxazole family macromolecule compound yield, and find that such compound has good stability (Macromolecules, 1998,31,5639-5646); The people such as Han first with 4-methoxyl group-tetramethyl piperidine oxyradical (4-Methoxy-TEMPO) for catalyzer has synthesized a series of benzoxazole quasi-molecule, yield is 55% ~ 95%(Angew.Chem.Int.Ed., 2008,47,9330-9333).In sum, although the method using these traditional can synthesize Ben Bing bis-oxazole compounds, but the shortcomings such as the severe reaction conditions, the productive rate that substantially all there is compound experiment are low, serious environment pollution, which results in the restriction of their Yong Yu oxazole analog derivatives synthesis.Therefore, the method studying the synthesis Ben Bing bis-oxazole analog derivative of high-efficiency environment friendly is just provided with very important realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method that is easy, Ben Bing bis-oxazole compounds fast, with diamino pyrocatechol compounds and aromatic aldehyde for raw material, 4-methoxyl group-tetramethyl piperidine oxyradical (4-Methoxy-TEMPO) is catalyzer, in organic solvent single step reaction synthesis Ben Bing bis-oxazole compounds.
A synthetic method for Ben Bing bis-oxazole compounds, is characterized in that the step of this synthetic method is as follows:
With diamino pyrocatechol compounds and aromatic aldehyde for raw material, with benzene, toluene or dimethylbenzene for solvent, at 80 ~ 140 ° of C stirring reaction 2 ~ 6h under protection of inert gas; Reactant is cooled to room temperature, adds 4-methoxyl group-tetramethyl piperidine oxyradical, in air atmosphere, 80 ~ 140 ° of C react 8 ~ 18h, and underpressure distillation removes desolventizing, namely obtains benzene and two oxazole compounds through column chromatography for separation.
The mol ratio of described diamino pyrocatechol compounds, aromatic aldehyde, 4-methoxyl group-tetramethyl piperidine oxyradical is 1:2:0.05 ~ 1:4:0.1.
Described aromatic aldehyde is 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde, 2-pyridylaldehyde, 3-pyridylaldehyde, 4-pyridylaldehyde, 2 furan carboxyaldehyde, 3-furtural, 2-pyrimidinecarboxaldehyde or 2-thiazole carboxaldehyde.
Described diamino pyrocatechol compounds is 4,5-diaminostilbene, 2-dihydroxy-benzene, 4, chloro-1, the 2-dihydroxy-benzene of 5-diamino-3-, 4,5-diamino-3-fluoro-1,2-dihydroxy-benzene, 4,5-diamino-3,6-bis-chloro-1,2-dihydroxy-benzene or 4,5-diamino-3,6-bis-fluoro-1,2-dihydroxy-benzene, preferably 4,5-diaminostilbenes, 2-dihydroxy-benzene.
The condition of described column chromatography: filler is 200 ~ 300 order silica gel; Eluent is the mixed solvent of sherwood oil and methylene dichloride; Sherwood oil and methylene chloride volume are than being 1:1 ~ 1:5.
Synthetic method high reactivity of the present invention, highly selective, high yield pyrocatechol compounds is converted into benzene two oxazole compounds with aromatic aldehyde compound, there is the features such as temperature of reaction is low, the time is short, yield is high, purity is high, easy to operate.
Embodiment
The present invention can illustrate with the following example, but the present invention is not by the restriction of listed implementation example.
Embodiment 1
Under protection of inert gas, by 4,5-diaminostilbene, 2-dihydroxy-benzene (1.12g, 4mmol), 2 furan carboxyaldehyde (0.96g, 0.83mL, 10mmol) and toluene (60mL) join in 100mL reaction flask, stir and are heated to 90 ° of C and react 3h.Reactant is cooled to room temperature, adds catalyzer 4-Methoxy-TEMPO(75mg), in air atmosphere, be heated to 100 ° of C react 8h.Underpressure distillation, except desolventizing, through column chromatography for separation, obtains the benzene also two oxazole molecule 1 .08g(3.7mmol that furans replaces), yield 92%.
Embodiment 2
As described in Example 1,2 furan carboxyaldehyde is changed to 2 thiophene carboxaldehyde (1.12g, 0.92mL, 10mmol), stirs and be heated to 80 ° of C and react 3h.Reactant is cooled to room temperature, adds catalyzer 4-Methoxy-TEMPO(75mg), in air atmosphere, be heated to 90 ° of C react 10h.Underpressure distillation, except desolventizing, through column chromatography for separation, obtains the benzene also two oxazole molecule 1 .23g(3.8mmol that thiophene replaces), yield 95%.
Embodiment 3
As described in Example 1,2 furan carboxyaldehyde is changed to 2-pyridylaldehyde (1.07g, 0.95mL, 10mmol), solvent toluene is changed to o-Xylol (60mL), stirs and is heated to 110 ° of C and react 4h.Reactant is cooled to room temperature, adds catalyzer 4-Methoxy-TEMPO(75mg), in air atmosphere, be heated to 120 ° of C react 12h.Underpressure distillation, except desolventizing, through column chromatography for separation, obtains the benzene also two oxazole molecule 1 .13g(3.6mmol that pyridine replaces), yield 90%.
Embodiment 4
As described in Example 1,2 furan carboxyaldehyde is changed to 2-pyrimidinecarboxaldehyde (1.08g, 0.88mL, 10mmol), solvent toluene is changed to o-Xylol (60mL), stirs and is heated to 130 ° of C and react 5h.Reactant is cooled to room temperature, adds catalyzer 4-Methoxy-TEMPO(75mg), in air atmosphere, be heated to 140 ° of C react 15h.Underpressure distillation, except desolventizing, through column chromatography for separation, obtains the benzene also two oxazole molecule 1 .08g(3.4mmol that pyrimidine replaces), yield 86%.
Embodiment 5
As described in Example 1,2 furan carboxyaldehyde is changed to 4-pyridylaldehyde (0.96g, 0.83mL, 10mmol), solvent toluene is changed to o-Xylol (60mL), stirs and is heated to 110 ° of C and react 4h.Reactant is cooled to room temperature, adds catalyzer 4-Methoxy-TEMPO(75mg), in air atmosphere, be heated to 120 ° of C react 12h.Underpressure distillation, except desolventizing, through column chromatography for separation, obtains the benzene also two oxazole molecule 1 .14g(3.6mmol that pyridine replaces), yield 91%.
Claims (6)
1. a synthetic method for benzene two oxazole compounds, is characterized in that the step of this synthetic method is as follows:
With diamino pyrocatechol compounds and aromatic aldehyde for raw material, with benzene, toluene or dimethylbenzene for solvent, at 80 ~ 140 ° of C stirring reaction 2 ~ 6h under protection of inert gas; Reactant is cooled to room temperature, adds 4-methoxyl group-tetramethyl piperidine oxyradical, in air atmosphere, 80 ~ 140 ° of C react 8 ~ 18h, and underpressure distillation removes desolventizing, namely obtains benzene and two oxazole compounds through column chromatography for separation.
2. synthetic method as claimed in claim 1, is characterized in that the mol ratio of described diamino pyrocatechol compounds, aromatic aldehyde, 4-methoxyl group-tetramethyl piperidine oxyradical is 1:2:0.05 ~ 1:4:0.1.
3. synthetic method as claimed in claim 1 or 2, is characterized in that described aromatic aldehyde is 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde, 2-pyridylaldehyde, 3-pyridylaldehyde, 4-pyridylaldehyde, 2 furan carboxyaldehyde, 3-furtural, 2-pyrimidinecarboxaldehyde or 2-thiazole carboxaldehyde.
4. synthetic method as claimed in claim 1 or 2, is characterized in that described diamino pyrocatechol compounds is 4,5-diaminostilbene, 2-dihydroxy-benzene, chloro-1, the 2-dihydroxy-benzene of 4,5-diamino-3-, 4,5-diamino-3-fluoro-1,2-dihydroxy-benzene, 4,5-diamino-3,6-bis-chloro-1,2-dihydroxy-benzene or 4, fluoro-1, the 2-dihydroxy-benzene of 5-diamino-3,6-bis-.
5. synthetic method as claimed in claim 4, is characterized in that described diamino pyrocatechol compounds is 4,5-diaminostilbene, 2-dihydroxy-benzene.
6. synthetic method as claimed in claim 1, is characterized in that the condition of described column chromatography: filler is 200 ~ 300 order silica gel; Eluent is the mixed solvent of sherwood oil and methylene dichloride; The volume ratio of described sherwood oil and methylene dichloride is 1:1 ~ 1:5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2170505A (en) * | 1984-11-20 | 1986-08-06 | Kernforschungsz Karlsruhe | Lasing with substituted 2, 6-diphenyl-benzo-(1.2d;4.5d')- bisoxaszoles and 2,6-diphenyl-benzo-(1.2d;5.4d')- bisoxazoles |
| CN1594398A (en) * | 2004-06-25 | 2005-03-16 | 东华大学 | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
| JP2008266538A (en) * | 2007-04-25 | 2008-11-06 | Toyobo Co Ltd | Polybenzazole film and method for producing the same |
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- 2016-01-15 CN CN201610026060.XA patent/CN105503847A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2170505A (en) * | 1984-11-20 | 1986-08-06 | Kernforschungsz Karlsruhe | Lasing with substituted 2, 6-diphenyl-benzo-(1.2d;4.5d')- bisoxaszoles and 2,6-diphenyl-benzo-(1.2d;5.4d')- bisoxazoles |
| CN1594398A (en) * | 2004-06-25 | 2005-03-16 | 东华大学 | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
| JP2008266538A (en) * | 2007-04-25 | 2008-11-06 | Toyobo Co Ltd | Polybenzazole film and method for producing the same |
Non-Patent Citations (3)
| Title |
|---|
| ABASAHEB V. PATIL，等: "Synthesis and characterization of dithienothiophene vinylene based co-polymer for bulk heterojunction photovoltaic cells", 《SYNTHETIC METALS》 * |
| JARED F. MIKE，等: "An Efficient Synthesis of 2,6-Disubstituted Benzobisoxazoles:New Building Blocks for Organic Semiconductors", 《ORGANIC LETTERS》 * |
| YONG-XING CHEN，等: "Efficient Aerobic Oxidative Synthesis of 2-Substituted Benzoxazoles,Benzothiazoles, and Benzimidazoles Catalyzed by 4-Methoxy-TEMPO", 《ANGEW. CHEM. INT. ED.》 * |
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Application publication date: 20160420 |