CN101891724A - Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane - Google Patents
Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane Download PDFInfo
- Publication number
- CN101891724A CN101891724A CN2009100845134A CN200910084513A CN101891724A CN 101891724 A CN101891724 A CN 101891724A CN 2009100845134 A CN2009100845134 A CN 2009100845134A CN 200910084513 A CN200910084513 A CN 200910084513A CN 101891724 A CN101891724 A CN 101891724A
- Authority
- CN
- China
- Prior art keywords
- methyl
- synthetic method
- tert butyl
- tert
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane, belonging to the organic synthesis field. The synthesis method comprises the following steps of: (1) reacting 2-methyl-6-tert-butyl-pyrone with malononitrile in an acetic anhydride solution in a refluxing state until the reaction is complete by TLC detection; and (2) concentrating the reaction liquid, and recrystallizing by adding an alcohol solvent. The yield of the method is increased by more than 1/2 compared with the documented yield, and the synthesized product has high purity and can be directly used for preparing DCJTB. In the post-treatment process of the invention, residues remained after the condensation are directly recrystallized with the alcohol solvent, thereby omitting the original documented column chromatography process, simplifying the process flow, and enabling the synthesis method to be applicable to mass production.
Description
Technical field
The invention belongs to the organic synthesis field, relate to the synthetic of ruddiness dopant material DCJTB key intermediate, particularly relate to the synthetic method of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans.
Technical background
Organic electroluminescence device has the efficient height and can produce the glow color that can cover whole visible region, and great application prospect is arranged in flat display technology.
Because performance that organic electroluminescent LED is outstanding and the huge applications prospect in flat display technology have caused people's great attention.In order to realize colored the demonstration, must develop the three-colour light-emitting material of a series of luminous efficiency height, excellent property.Through more than ten years further investigations, developed have high brightness, high efficiency green glow, blue material, but that red light material meets the demands is few relatively.In the organic electroluminescent field, the most extensively the intramolecular charge of utilization transfer class red dye is the DCM series dyes, and people such as Tang had reported and utilized oxine aluminium Alq in 1989
3Make main body luminescent material (C.H.Chen, Tang, C.W., J.Shi, Thin solid Films, 2000,363,327-331), DCM1 and DCJ make the high efficiency red luminescent device of object luminescent material, and since then, DCM class emitting red light dyestuff is studied widely and is applied in the device.And DCM and DCJ have the broken shortcoming of going out of concentration in device application, and for this reason, people such as Tang modify DCJ, and they replace in the C-1 of julolidine and C-4 position and obtain Compound D CJT.Although DCJT has good electroluminescent properties, but there is very big problem in its synthetic purifies and separates process that reaches, this is because the reacting precursor 2 that uses in building-up process, contain two labile methyl groups in 6-dimethyl-(4-dintrile methene)-4H pyrans, therefore DCJT can further generate two condensation by-product 4-(dicyan methene-2, two (julolidine-9-the vinyl)-4H-pyrans (bis-DCJT) of 6-with the aldehyde condensation in building-up process.The generation of two condensation by-product not only causes the reduction of reaction yield, and makes the separation and purification of product become difficult.At the problem that exists in the building-up process, people such as Chen have designed DCJTB owing to improved synthetic method, synthetic and the purifying of compound have good emitting red light characteristic (Chin H.Chen, C.W.Tang, J.Shi, US5935720.).
DCJTB is the most successful material in the present red light material, and brightness, efficient, life-span have all been satisfied commercial applications.The synthetic method of ruddiness dopant material DCJTB is provided in U.S. Pat 5935720, has been generated by two intermediates butt joints, one is 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans, and one is 1,1,7, and 7-tetramethyl--9-network Buddhist nun of a specified duration decides aldehyde.Wherein 1,1,7,7-tetramethyl--9-network Buddhist nun of a specified duration decides aldehyde and is solved, have only the productive rate of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans intermediate very low, cause DCJTB industrialization cost very high, also be restricted in OLED preparation application, so 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans intermediate becomes the industrialized bottleneck of DCJTB.
Because (formula as follows) per step productive rate is all very low in the synthesis technique of main intermediate 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans, the DCJTB price that synthesizes is very expensive, has limited the use of DCJTB.Make DCJTB obtain promoting, intermediate 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans (E in the formula), 5,5-dimethyl-2,4-hexanedial-0,0-boron difluoride (B in the formula), 7-dimethylamino-2,2-dimethyl-6-alkene-3,5-suberic aldehyde-0,0-boron difluoride (C in the formula), the synthesis technique of 2-methyl-6-tert butyl-pyrone (D in the formula) all remain to be improved.
Summary of the invention
On the basis of above-mentioned patent, the invention provides the synthetic method of a kind of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans, its yield is more over half than document yield height, and purity is very high, can be directly used in preparation DCJTB.
The synthetic method of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans comprises the steps:
(1) 2-methyl-6-tert butyl-pyrone and propane dinitrile react in reflux state in the solution of diacetyl oxide,
(2) react completely after, concentration of reaction solution adds the alcoholic solvent recrystallization and gets final product.
Described alcoholic solvent is one or more mixing in methyl alcohol, ethanol, Virahol, the butanols.
The mol ratio of described 2-methyl-6-tert butyl-pyrone and propane dinitrile is 1: 2.
Described step (1) reaction times is 6-15 hour.
The preferred reaction time is 8 hours.
Described reacting completely adopts TLC to detect.
Reaction mechanism of the present invention is that 2-methyl-6-tert butyl-pyrone and propane dinitrile react under the effect of dehydrating agent diacetyl oxide, the present invention adopts reflux temperature control, the boiling point of diacetyl oxide is 139 ℃, because there is water to generate, therefore the temperature of reaction basic controlling becomes more than 130 ℃, speed of response is accelerated, adopt the TLC method to come the terminal point of monitoring reaction simultaneously, therefore reaction is more complete, make that aftertreatment of the present invention is fairly simple, last handling process of the present invention is that the resistates after concentrating is directly come recrystallization with alcoholic solvent, saved former document center pillar chromatography process, yield height and purity are very good, reach more than 99%, can be used as the ruddiness intermediary material, the laserable material intermediate uses.
The mol ratio of 2-methyl-6-tert butyl-pyrone and propane dinitrile is preferably 1: 2, because 2-methyl-6-tert butyl-pyrone is difficult for separating with product, therefore adopt excessive propane dinitrile to make it to react completely, concentrate and unnecessary propane dinitrile and diacetyl oxide can be removed, therefore the mol ratio of 2-methyl-6-tert butyl-pyrone and propane dinitrile is preferably 1: 2, makes 2-methyl-6-tert butyl-pyrone complete reaction.
Technology of the present invention is performed as follows:
2-methyl-6-tert butyl-pyrone, propane dinitrile, diacetyl oxide back flow reaction 6～15 hours concentrate the pure purifying in back; Alcohol can be one or more mixing in methyl alcohol, ethanol, Virahol, the butanols.
The synthesis technique that this patent provides provides technology to compare with american documentation literature, has following characteristics:
(1), the process yield that provides of this patent is more over half than document height, product purity reaches more than 99%.
(2), the reaction conditions gentleness, technology is simple, production easily, cost are low.
(3), the product E purity that obtains is higher, can be directly used in preparation DCJTB.
Specific implementation method
The present invention is described in further detail below in conjunction with embodiment.
2-methyl-6-tert butyl-pyrone can be according to US5935720 disclosed method preparation (seeing the example 3).
Embodiment 1,2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans
In the 25mL three-necked flask, add 2-methyl-6-tert butyl-pyrone 2.21g (0.01mo), the third two eyeball 2.04g (0.02mo), diacetyl oxide 5mL mix stirring, reflux, TLC detects raw material reaction finish (8 hours), stop heating, be spin-dried for mixture, add recrystallizing methanol twice, obtain 2.089 light yellow solids (80%), HPLC detects purity 99%.(US5935720 reports productive rate 50%)
Fusing point: 108-110 ℃
HMNR(CDCl
3，400Hz)：1.31(9H，s)；2.35(3H，s)；6.57(2H，d)。
Claims (6)
1.2-the synthetic method of methyl-6-tert butyl-4-dicyan methene-4H-pyrans comprises the steps:
(1) 2-methyl-6-tert butyl-pyrone and propane dinitrile react in reflux state in the solution of diacetyl oxide,
(2) react completely after, concentration of reaction solution adds the alcoholic solvent recrystallization and gets final product.
2. synthetic method according to claim 1, described alcoholic solvent are one or more mixing in methyl alcohol, ethanol, Virahol, the butanols.
3. synthetic method according to claim 1, the mol ratio of described 2-methyl-6-tert butyl-pyrone and propane dinitrile is 1: 2.
4. synthetic method according to claim 1, described step (1) reaction times is 6-15 hour.
5. synthetic method according to claim 4, the described reaction times is 8 hours.
6. synthetic method according to claim 1, described reacting completely adopts TLC to detect.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100845134A CN101891724A (en) | 2009-05-20 | 2009-05-20 | Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane |
| PCT/CN2010/072453 WO2010133133A1 (en) | 2009-05-20 | 2010-05-05 | Synthetic method of 2-methyl-6-tert-butyl-4-dicyanomethylene-4h-pyran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100845134A CN101891724A (en) | 2009-05-20 | 2009-05-20 | Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101891724A true CN101891724A (en) | 2010-11-24 |
Family
ID=43101099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100845134A Pending CN101891724A (en) | 2009-05-20 | 2009-05-20 | Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101891724A (en) |
| WO (1) | WO2010133133A1 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI291487B (en) * | 2002-01-08 | 2007-12-21 | Chi Mei Optoelectronics Corp | Red-emitting organic electroluminescent compound |
| EP2030266B1 (en) * | 2006-05-15 | 2016-03-23 | Nitto Denko Corporation | Light emitting devices and compositions |
-
2009
- 2009-05-20 CN CN2009100845134A patent/CN101891724A/en active Pending
-
2010
- 2010-05-05 WO PCT/CN2010/072453 patent/WO2010133133A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010133133A1 (en) | 2010-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1861740A (en) | Red light emitting fluorescent dye, synthesizing process and use thereof | |
| CN109400590A (en) | A kind of thermal activation delayed fluorescence material and its application in Organic Light Emitting Diode | |
| CN111825618B (en) | Phenanthroimidazole-containing blue organic semiconductor material and preparation method and application thereof | |
| CN103739607A (en) | Tri-carbazole multi-arm structural red-light--emitting material and preparation method and application thereof | |
| CN104311588A (en) | Silafluorene-based aggregation-induced emission molecule as well as preparation method and application thereof | |
| CN101891759B (en) | Synthesis method of 5,5-dimethyl-2,4-adipaldehyde-O,O-boron difluoride | |
| CN104370887A (en) | 2, 6-bis [3,-(N-carbazolyl) phenyl] pyridine compound | |
| JP6230326B2 (en) | Phosphor and use thereof | |
| CN102775279B (en) | 2,7-dibromo-9-hydroxyl phenanthrene derivatives and preparation method thereof | |
| WO2020237885A1 (en) | Dark blue thermal activation delayed fluorescent material and preparation method therefor, and electroluminescent device | |
| CN101891724A (en) | Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane | |
| CN106749076B (en) | Application of o-hydroxyphenyl azole derivative as organic blue light material | |
| CN109096293A (en) | Preparation method of the one kind containing the benzofuran simultaneously alcohol compound of [2,3-b] pyridine structure | |
| CN107698584B (en) | Blue light material for organic light-emitting diode and synthetic method thereof | |
| TW201217355A (en) | characterized by having 50% higher yield than that in literature, simplifying synthesis flow to be suitable for mass production and providing target compound in a purity of greater than 99% to directly prepare DCJTB | |
| CN101891725B (en) | 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method | |
| CN111100060A (en) | Carbazole thermal activation delayed fluorescent material and preparation method thereof | |
| CN105906636B (en) | A kind of A- π-D- π-A types indoles [3,2-b] carbazole red light material and preparation method thereof | |
| CN107602381B (en) | Naphthoic acid ester derivative and preparation method thereof | |
| CN111777543A (en) | Method for preparing N-phenylcarbazole through copper-catalyzed bromobenzene and carbazole C-N coupling | |
| CN101891758B (en) | Method for synthesizing 7-imethylamino-2, 2-dimethyl-6-ene-3, 5-suberaldehyde-O, O-boron difluoride | |
| CN106397470B (en) | A kind of synthetic method of the fluorenes of 3,3 ' hypoboric acid pinacol ester, 9,9 ' spiral shell two | |
| CN115417805A (en) | Seven-membered ring benzocarbazole organic phosphorescent material intermediate and synthesis method thereof | |
| CN102336753B (en) | Method for synthesizing 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran | |
| CN100408651C (en) | Red fluorescent dye and its systhesis method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1148733 Country of ref document: HK |
|
| ASS | Succession or assignment of patent right |
Owner name: FOSHAN AGLAIA OPTOELECTRONIC MATERIALS CO., LTD. Free format text: FORMER OWNER: AGELEIYA TECH DEVELOPMENT CO., LTD., BEIJING Effective date: 20111114 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100085 HAIDIAN, BEIJING TO: 528300 FOSHAN, GUANGDONG PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20111114 Address after: Five, building 3, No. 518-519 Desheng East Road, Daliang street, Shunde District, Guangdong, Foshan 528300 Applicant after: BEIJING AGLAIA TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 100085, Beijing, Haidian District on the road No. 26, room 1115, room 11 Applicant before: BEIJING AGLAIA TECHNOLOGY & DEVELOPMENT Co.,Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: AGELEIYA TECH DEVELOPMENT CO., LTD., BEIJING Effective date: 20120217 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Five, building 3, No. 518-519 Desheng East Road, Daliang street, Shunde District, Guangdong, Foshan 528300 Applicant after: GUANGDONG AGLAIA OPTOELECTRONIC MATERIALS Co.,Ltd. Address before: Five, building 3, No. 518-519 Desheng East Road, Daliang street, Shunde District, Guangdong, Foshan 528300 Applicant before: BEIJING AGLAIA TECHNOLOGY DEVELOPMENT Co.,Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: FOSHAN AGLAIA PHOTOELECTRIC MATERIALS CO., LTD. TO: GUANGDONG AGLAIA OPTOELECTRONIC MATERIALS CO., LTD. |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20120217 Address after: Five, building 3, No. 518-519 Desheng East Road, Daliang street, Shunde District, Guangdong, Foshan 528300 Applicant after: GUANGDONG AGLAIA OPTOELECTRONIC MATERIALS Co.,Ltd. Co-applicant after: BEIJING AGLAIA TECHNOLOGY & DEVELOPMENT Co.,Ltd. Address before: Five, building 3, No. 518-519 Desheng East Road, Daliang street, Shunde District, Guangdong, Foshan 528300 Applicant before: GUANGDONG AGLAIA OPTOELECTRONIC MATERIALS Co.,Ltd. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20101124 |
|
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1148733 Country of ref document: HK |