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2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method

A technology of dicyanomethyl group and synthesis method, applied in directions such as organic chemistry, can solve the problems of high cost, reduced reaction yield, low yield and the like, and achieves the effects of mild reaction conditions, easy production and simple process

Active Publication Date: 2010-11-24
GUANGDONG AGLAIA OPTOELECTRONICS MATERIALS
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although DCJT has good electroluminescent properties, there are great problems in its synthesis, purification and separation process, which is due to the reaction precursor 2,6-dimethyl-(4-dinitrile formazan) Alkenyl)-4H pyran contains two active methyl groups, so in the synthesis process DCJT will further condense with aldehydes to generate two condensation by-products 4-(dicyanomethenyl-2,6-bis(julonidine -9-vinyl)-4H-pyran (bis-DCJT)
The formation of dicondensation by-products not only leads to a decrease in reaction yield, but also makes it difficult to separate and purify the product
Among them, 1,1,7,7-tetramethyl-9-juronidine aldehyde has been solved, only 2-methyl-6-tert-butyl-4-dicyanomethenyl-4H-pyran intermediate The production rate is very low, resulting in high cost of DCJTB industrialization, and its application in OLED preparation is also limited. Therefore, 2-methyl-6-tert-butyl-4-dicyanomethenyl-4H-pyran intermediate has become the most important product for DCJTB industrialization. the bottleneck
[0005] Due to the fact that in the synthesis process of the main intermediate 2-methyl-6-tert-butyl-4-dicyanomethenyl-4H-pyran (see the following formula ) The yield of each step is very low, and the price of the synthesized DCJTB is very expensive, which limits the use of DCJTB

Method used

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  • 2-methyl-6-tert-butyl-4-dicyanmethylene-4H-pyran synthesis method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1、5

[0038] Example 1, 5,5-dimethyl-2,4-hexanedialdehyde-O, O-boron difluoride

[0039] Place a 3000ml three-necked flask in an ice-salt bath, under the protection of nitrogen, add 100g of pinacolone and 204g of acetic anhydride, mix and stir, cool with ice-salt, then add 500g of boron trifluoride etherate complex dropwise, after the addition is complete The mixture was reacted overnight at room temperature. Under ice-salt cooling, 10% sodium hydroxide was added dropwise until PH=7, static, liquid separation, and the organic phase was concentrated to precipitate 120 g of a light yellow solid with a yield of 60% (US5935720 reported a yield of 20%).

[0040] Melting point: 82~84℃

[0041] HNMR (CDCl 3 , 400Hz): 1.19(9H, s); 2.2487(3H, s); 5.97(1H, s)

Embodiment 2

[0042] Example 2, 7-dimethylamino-2,2-dimethyl-6-ene-3,5-octanedial-O,O-boron difluoride

[0043] In a 2000ml three-necked flask, under nitrogen protection, add 275g of compound B, 245g of N,N-dimethylacetamide, and 14ml of 2,6-lutidine, and stir. Heated to 30°C, added dropwise N,N-dimethylacetamide dimethyl acetal 388g, after the dropwise addition, kept the temperature and continued to stir for 3 hours, then raised the temperature to 85°C, TLC detected that the reaction of the raw materials was complete, and stopped the reaction (10 hours ), the mixture was a reddish-brown oily liquid, the reaction solution was cooled overnight at -10°C to 0°C, filtered, and the product was washed with petroleum ether to obtain 240 g (85%) of a pale yellow solid. (US5935720 reports 36% yield)

[0044] Melting point: Decompose above 220°C

[0045] 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

[0046] Embodiment 3, 2-methyl-6-tert-butyl-pyrone

[0047] In a 5000ml three-necked flask, add 615g of reaction product C, then add 1080g of water and 1080ml of ethanol in turn, cool with ice water, add 1080ml of 70% perchloric acid, heat and reflux overnight, TLC detects that the reaction of raw materials is complete, stop heating, cool, and rotate to evaporate Spin to dry ethanol, add ammonia water to adjust to alkalinity, a solid precipitates, filter the solid to obtain 300 g (76%) of a yellow product. (US5935720 reports yield 75%)

[0048] HNMR (DMSO, 400Hz): 1.23 (9H, s); 2.25 (3H, s); 6.04 (1H, m); 6.12 (1H, m)

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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 solvents are 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 [0001] The invention belongs to the field of organic synthesis, and relates to the synthesis of a key intermediate of a red light doping material DCJTB, in particular to a synthesis method of 2-methyl-6-tert-butyl-4-dicyanomethenyl-4H-pyran. Background technique [0002] Organic electroluminescent devices have high efficiency and can produce luminescent colors that can cover the entire visible light region, and have great application prospects in flat panel display technology. [0003] Due to the outstanding performance of organic light-emitting diodes and the huge application prospects in flat panel display technology, people have paid great attention to them. In order to realize color display, it is necessary to develop a series of three-color luminescent materials with high luminous efficiency and excellent performance. After more than ten years of in-depth research, green and blue materials with high brightness and high efficiency have been developed, bu...

Claims

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Application Information

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IPC IPC(8): C07D309/34
CPCC07D309/34
Inventor 蔡丽菲戴雷赵洪玉
Owner GUANGDONG AGLAIA OPTOELECTRONICS MATERIALS
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