CN101891725B - 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method - Google Patents
2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method Download PDFInfo
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Abstract
The invention relates to a 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method, belonging to the field of organic synthesis. The synthesis method comprises the steps of: preparing 5,5-dimethyl-2,4-adipaldehyde-O,O-boron difluoride through the reaction of pinacotone and boron trifluoride diethyl ether; preparing 7-dimethyl amino-2,2-dimethyl-6-ene-3,5-suberic aldehyde-O,O-boron difluoride through the aldolization reaction of the ,5-dimethyl-2,4-adipaldehyde-O,O-boron difluoride and N,N-dimethylacetylamide dimethyl; preparing 2-methyl-6-tertiary butyl-pyrone through perchloric acid cyclization; and reacting 2-methyl-6-tertiary butyl-pyrone with malononitrile to prepare the 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran. The invention is characterized in that alcohol solventsare utilized in the last step for recrystallization. The invention has the advantages of simple operation technology and easy large-scale production and can ensure that the total yield is far higher than the yield provided by the literature and the purity of the final product is very high. The invention can be directly used for preparing DCJTB (4-(Dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran).
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 compound method of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans.
Background technology
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 efficiencies 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 a utilization transfer type 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 in building-up process, uses; Contain two labile methyl groups in 6 one dimethyl-one (4-dintrile methene)-4H pyrans, therefore DCJT can further generate two condensation by-product 4 one (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.To the problem that exists in the building-up process, people such as Chen have designed DCJTB owing to improved compound 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 compound method of ruddiness dopant material DCJTB is provided in U.S. Pat 5935720, has been generated by two midbodys 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 midbody very low; Cause DCJTB industriallization cost very high, also be restricted in OLED preparation application, so 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans midbody 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 very expensive that synthesizes has limited the use of DCJTB.Make DCJTB obtain promoting midbody 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans (E in the formula), 5; 5-dimethyl--2,4-hexanedial-O, O-boron difluoride (B in the formula); 7-dimethylamino-2,2-dimethyl--6-alkene-3,5-suberic aldehyde-O; O-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 present invention provides the compound method of a kind of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans; Its synthetic route is identical therewith, through improving reaction conditions and simplifying finishing sequence, makes its total recovery be higher than the yield that document provides far away; And purity is very high, can directly be used to prepare DCJTB.
The compound method of 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans comprises the steps:
(1) temperature-30-50 ℃ with the nitrogen protection condition under, pinacolone and BFEE react in acetic anhydride solution, obtain 5,5-dimethyl--2,4-hexanedial-O, O-boron difluoride;
(2) temperature 80-100 ℃ with nitrogen protection under, 5,5-dimethyl--2; 4-hexanedial-O, O-boron difluoride and DMAC N,N dimethylacetal are at N; N-N,N-DIMETHYLACETAMIDE, 2 reacts in the 6-lutidine mixed solvent, obtains 7-dimethylamino-2; 2-dimethyl--6-alkene-3,5-suberic aldehyde-O, O-boron difluoride;
(3) 7-dimethylamino-2,2-dimethyl--6-alkene-3,5-suberic aldehyde-O, O-boron difluoride and perchloric acid back flow reaction in ethanol or ethanol-water solution obtains 2-methyl-6-tert butyl-pyrone;
(4) 2-methyl-6-tert butyl-pyrone and propane dinitrile back flow reaction in acetic anhydride solution obtains 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans; Also comprise finishing sequence after reacting completion in the said step (4), said finishing sequence obtains 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans for the concentrated back of reaction solution adding alcoholic solvent recrystallization in resistates is promptly separated.
Said alcoholic solvent is one or more mixing in methyl alcohol, ethanol, Virahol, the butanols.
The reflux time of said step (4) is 6-15 hour, adopts TLC to come the monitoring reaction terminal point.
The mol ratio of pinacolone and BFEE is 1 in the step (1): 1-1: 10.
Preferably: the mol ratio of pinacolone and BFEE is 1: 3-1: 6.
Reaction also comprises finishing sequence after accomplishing in the said step (1), and said finishing sequence makes it to neutral in being lower than room temperature downhill reaction liquid, adding alkaline aqueous solution, and separatory concentrates organic phase, separates out 5,5-dimethyl--2,4-hexanedial-O, O-boron difluoride.
Said alkaline aqueous solution is aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution, aqueous sodium carbonate, wet chemical, potassium hydroxide aqueous solution.
Reaction also comprises finishing sequence after accomplishing in the said step (2); Said finishing sequence is separated out product after cooling off; Separate, use the organic solvent washing product, said organic solvent is the one or more combination in sherwood oil, ETHYLE ACETATE, normal hexane, methyl alcohol, ethanol, the Virahol.
DMAC N,N dimethylacetal in the said step (2) is under 20-50 ℃, to be added drop-wise to 5,5-dimethyl--2, and 4-hexanedial-O, the O-boron difluoride, DMAC N,N, 2, in the mixing solutions of 6-lutidine.
The said back that drips continues to stir 2-5 hour under this temperature, is warming up to 80-100 ℃ of reaction down again.
Perchloric acid in the said step (3) is under-10-40 ℃, to join 7-dimethylamino-2 in batches, 2-dimethyl--6-alkene-3, and 5-suberic aldehyde-O, in the ethanol of O-boron difluoride or the ethanol-water solution.
The present invention adopts the identical reaction scheme of U.S. Pat 5935720, and this patent and analogue compounds synthetic cooked conscientious careful research, has optimized reaction conditions; The isolating aftertreatment technology of product improves, and the yield of per step reaction all is greatly improved than former document, and aftertreatment technology is simple simultaneously; Easy to operate; And easy large-scale production, the product that per step reaction obtains need not pass through special purifying, can directly drop into next step reaction.
Though synthesize similar with intermediate B of many bibliographical informations arranged, and productive rate and reagent additional proportion disunity are difficult to repetition.Produce the acetyl oxonium ion in the intermediate B building-up process; Therefore temperature of reaction needs low temperature; Need take place with boron trifluoride after pinacolone and the acetyl oxonium ion generation condensation; This step is a decision entire reaction speed, and the reaction times reduced because the oily mater that high temperature causes produces at 15 ~ 24 hours.The consumption of boron trifluoride ether solution also is very important to entire reaction, react thing and catalyst action of trifluoro in reaction process; If the quantity not sufficient of using, boride generates not exclusively.In the process of aftertreatment,, and be dissolved in product in the ether because the present invention is keeping subzero treatment (being 90 ℃ of solvent evaporated in the document) always; Utilize the mode of separatory from reaction solution, to extract product, concentrate the B that promptly obtains high yield, saved the time of aftertreatment in a large number; And the low temperature last handling process does not have too many influence to reaction product, does not produce too much impurity, and product can directly be used for step reaction down; The yield of the inventive method is 60%-80%, is more than 3 times of document yield.The subambient temperature that low temperature promptly can reach according to the routine operation in the chemical test, as adopting ice bath, cryosel is bathed, and methods such as dry ice, liquid nitrogen preferably are not higher than and near room temperature, this temperature condition is realized getting final product like ice bath or cryosel bath easily.
The synthetic of Compound C is an aldol condensation, reacts very violent, and temperature is the key factor of decision productive rate; Controlled temperature is at 30 ℃ ~ 80 ℃ in the DMAC N,N dimethylacetal dropping process, drips to finish 80 ℃ ~ 100 ℃ reactions of holding temperature, obtains productive rate and be 2 ~ 3 times of USP.
Synthetic usefulness 70% perchloric acid of Compound D is as cyclization reagent, and perchloric acid has oxidisability, and controlled temperature can reduce by product and generate, and obtains the concentrated solid D that obtains afterwards of product.
The finished product E is under dehydrating agent diacetyl oxide condition, and back flow reaction makes to react completely; Obtain product E, as solvent, recrystallization obtains purity 99% product with alcohols; This product can directly be used for the synthetic of DCJTB, and it is over half that the yield of this step reaction is higher than the document yield, to more than 80%.
The synthetic of compd E can carry out according to following technology:
(1), under-30 ℃ ~ 50 ℃ temperature, suitable temp-30 ℃ ~ 30 ℃; Pinacolone and boron trifluoride ether solution quality mol ratio=1: 1 ~ 1: 10, suitable molar ratio adds at 1: 6; Reaction finishes can water, 10% aqueous sodium hydroxide solution, 10% sodium bicarbonate aqueous solution, 10% aqueous sodium carbonate, 10% wet chemical, 10% potassium hydroxide aqueous solution are handled, and temperature obtains 60 ~ 80% compd Bs not to be higher than room temperature for well.
(2), under 20 ℃ ~ 50 ℃ of the temperature, the DMAC N,N dimethylacetal is added drop-wise in the B mixture, the back is 80 ℃ ~ 100 ℃ reactions, the time, more suitably the time was at 2 ~ 15 hours at 2 ~ 24 hours.Reaction finishes, and-10 ℃ ~ 0 ℃ cooling down, separating prod is used the organic solvent washing product, and organic solvent can be sherwood oil, ETHYLE ACETATE, normal hexane, methyl alcohol, ethanol, Virahol etc., can be the impurity washes clean, and productive rate 60 ~ 90%C.
(3), under-10 ℃ ~ 40 ℃, 70% perchloric acid adds the solution of Compound C in batches, in 1 ~ 24 hour reaction times, concentrates and obtains solid phase prod D, productive rate 70 ~ 80%.
(4), Compound D, propane dinitrile, diacetyl oxide back flow reaction 6 ~ 15 hours, concentrate the back with pure purifying E; 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 exceeds several times than document, product purity reaches more than 99%.
(2), reaction conditions is gentle, technology is simple, production easily, cost are low.
(3), the product E purity that obtains is higher, can be used as the ruddiness intermediary material, the laserable material midbody uses.
The practical implementation method
Embodiment 1,5,5-dimethyl--2,4-hexanedial-O, O-boron difluoride
The 3000ml three-necked flask places cryosel to bathe, and under nitrogen protection, adds pinacolone 100g, acetic anhydride 204g, mixes and stirs, and the cryosel cooling dropwise adds boron trifluoride ethyl ether complex 500g then, adds to react under the mixture room temperature of back to spend the night.The cryosel cooling drips 10% sodium hydroxide down, and till the PH=7, static, separatory concentrates organic phase, separates out light yellow solid 120g, productive rate 60% (US5935720 reports productive rate 20%).
Fusing point: 82 ~ 84 ℃
HNMR(CDCl
3，400Hz)：1.19(9H，s)；2.2487(3H，s)；5.97(1H，s)
Embodiment 2,7-dimethylamino-2,2-dimethyl--6-alkene-3,5-suberic aldehyde-O, O-boron difluoride
In the 2000ml three-necked flask, under the nitrogen protection, add compd B 275g, DMAC N,N 245g, 2,6-lutidine 14ml stirs.Be heated to 30 ℃, dropwise add DMAC N,N dimethylacetal 388g; Dropwise, keep temperature to continue to stir 3 hours, be warming up to 85 ℃; TLC detects raw material reaction to be finished, stopped reaction (10 hours), and mixture is the sorrel oily liquids; Reaction soln filters-10 ℃～0 ℃ cool overnight, and product gets faint yellow solid 240g (85%) with petroleum ether.(US5935720 reports productive rate 36%)
Fusing point: decompose more than 220 ℃
HNMR(CDCl
3，400Hz)：1.29(9H，s)；2.62(3H，s)：3.19(6H，s)；4.88(1H，s)；5.47(1H，s)
Embodiment 3,2-methyl-6-tert butyl-pyrone
In the 5000ml three-necked flask, add reaction product C 615g, add entry 1080g, ethanol 1080ml then successively, the frozen water cooling; Add 1080ml70% perchloric acid, reflux is spent the night, and TLC detects raw material reaction to be finished, and stops heating; Cooling, rotary evaporation revolves dried ethanol, adds ammoniacal liquor and transfers to alkalescence; Have solid to separate out, solids filtered obtains yellow product 300g (76%).(US5935720 reports productive rate 75%)
HNMR(DMSO，400Hz)：1.23(9H，s)；2.25(3H，s)；6.04(1H，m)；6.12(1H，m)
Embodiment 4,2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans
In the 25mL three-necked flask, adding reaction product D 2.2lg (0.01mo), the third two eyeball 2.04g (0.02mo) l, acetic anhydride mixes and stirs; Reflux; TLC detects raw material reaction and finishes (8 hours), stops heating, revolves dry mixture; Add recrystallizing methanol, obtain 2.089 light yellow solids (80%).(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 (8)
1.2-the compound method of methyl-6-tert butyl-4-dicyan methene-4H-pyrans comprises the steps:
(1) temperature-30-50 ℃ with the nitrogen protection condition under, pinacolone and BFEE react in acetic anhydride solution, obtain 5,5-dimethyl--2,4-hexanedial-0,0-boron difluoride;
(2) temperature 80-100 ℃ with nitrogen protection under, 5,5-dimethyl--2; 4-hexanedial-0,0-boron difluoride and DMAC N,N dimethylacetal are at N; N-N,N-DIMETHYLACETAMIDE, 2 reacts in the 6-lutidine mixed solvent, obtains 7-dimethylamino-2; 2-dimethyl--6-alkene-3,5-suberic aldehyde-0,0-boron difluoride;
(3) 7-dimethylamino-2,2-dimethyl--6-alkene-3,5-suberic aldehyde-0,0-boron difluoride and perchloric acid back flow reaction in ethanol or ethanol-water solution obtains 2-methyl-6-tert butyl-pyrone;
(4) 2-methyl-6-tert butyl-pyrone and propane dinitrile back flow reaction in acetic anhydride solution obtains 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans;
Reaction also comprises finishing sequence after accomplishing in the said step (4); Said finishing sequence obtains 2-methyl-6-tert butyl-4-dicyan methene-4H-pyrans for the concentrated back of reaction solution adding alcoholic solvent recrystallization in resistates is promptly separated; The mol ratio of pinacolone and BFEE is 1 in the said step (1): 1-1: 10
Reaction also comprises finishing sequence after accomplishing in the said step (1), and said finishing sequence makes it to neutral in being lower than room temperature downhill reaction liquid, adding alkaline aqueous solution, and separatory concentrates organic phase, separates out 5,5-dimethyl--2,4-hexanedial-0,0-boron difluoride.
2. compound method according to claim 1, said alcoholic solvent are one or more mixing in methyl alcohol, ethanol, Virahol, the butanols.
3. compound method according to claim 1, the reflux time in the said step (4) is 6-15 hour, adopts TLC to come the monitoring reaction terminal point.
4. compound method according to claim 1, the mol ratio of said pinacolone and BFEE are 1: 3-1: 6.
5. compound method according to claim 1, said alkaline aqueous solution are aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution, aqueous sodium carbonate, wet chemical, potassium hydroxide aqueous solution.
6. compound method according to claim 1; Reaction also comprises finishing sequence after accomplishing in the said step (2); Said finishing sequence is separated out product after cooling off; Separate, use the organic solvent washing product, said organic solvent is the one or more combination in sherwood oil, ETHYLE ACETATE, normal hexane, methyl alcohol, ethanol, the Virahol.
7. compound method according to claim 1, the DMAC N,N dimethylacetal in the said step (2) is under 20-50 ℃, to be added drop-wise to 5; 5-dimethyl--2,4-hexanedial-0,0-boron difluoride; DMAC N,N, 2; In the mixing solutions of 6-lutidine, the said back that drips continues to stir 2-5 hour under this temperature, is warming up to 80-100 ℃ of reaction down again.
8. compound method according to claim 1, the perchloric acid in the said step (3) they are under-10-40 ℃, to join 7-dimethylamino-2 in batches, 2-dimethyl--6-alkene-3, and 5-suberic aldehyde-0, in the ethanol of 0-boron difluoride or the ethanol-water solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084515A CN101891725B (en) | 2009-05-20 | 2009-05-20 | 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method |
| PCT/CN2010/072447 WO2010133131A1 (en) | 2009-05-20 | 2010-05-05 | Synthetic method of 2-methyl-6-tert-butyl-4-dicyanomethylene-4h-pyran |
| HK11102712.0A HK1148734A1 (en) | 2009-05-20 | 2011-03-18 |
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| CN200910084515A CN101891725B (en) | 2009-05-20 | 2009-05-20 | 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method |
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| CN101891725A CN101891725A (en) | 2010-11-24 |
| CN101891725B true CN101891725B (en) | 2012-09-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935720A (en) * | 1997-04-07 | 1999-08-10 | Eastman Kodak Company | Red organic electroluminescent devices |
| US6867309B2 (en) * | 2002-01-08 | 2005-03-15 | Chi Mei Optoelectronics Corporation | Red-emitting organic electroluminescent compound |
| WO2007136588A1 (en) * | 2006-05-15 | 2007-11-29 | Nitto Denko Corporation | Light emitting devices and compositions |
-
2009
- 2009-05-20 CN CN200910084515A patent/CN101891725B/en active Active
-
2010
- 2010-05-05 WO PCT/CN2010/072447 patent/WO2010133131A1/en active Application Filing
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2011
- 2011-03-18 HK HK11102712.0A patent/HK1148734A1/xx not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935720A (en) * | 1997-04-07 | 1999-08-10 | Eastman Kodak Company | Red organic electroluminescent devices |
| US6867309B2 (en) * | 2002-01-08 | 2005-03-15 | Chi Mei Optoelectronics Corporation | Red-emitting organic electroluminescent compound |
| WO2007136588A1 (en) * | 2006-05-15 | 2007-11-29 | Nitto Denko Corporation | Light emitting devices and compositions |
Also Published As
| Publication number | Publication date |
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| HK1148734A1 (en) | 2011-09-16 |
| CN101891725A (en) | 2010-11-24 |
| WO2010133131A1 (en) | 2010-11-25 |
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