The method of obtaining a mixture of oligoadenylates, the method of obtaining 3-(4-biphenylyl)-4- (4-tert-butylphenyl)-5-(4 - dimethylaminophenyl)-1,2,4-triazole and electroluminescent device

 

(57) Abstract:

The invention relates to methods for organic materials for electroluminescent devices and devices based on them. The invention consists in obtaining a mixture of oligoadenylates (I) containing 8-9 of monomer units, for a hole-transport layer in an electroluminescent device, the interaction monomethylamine of triphenylamine with bromodomain complex with getting dibromsalan of monomethylethanolamine, which is treated with equimolar amounts of activated Mg with the addition of a complex of zero-valent Nickel. The resulting mixture bromodomain oligomers treated with alkyl - or arylalkylamines in the presence of a complex of zero-valent Nickel. The invention relates to a method for the preparation of 3-(4-biphenylyl)-4-(4-tert-butylphenyl)-5-(4-dimethylaminophenyl)-1,2,4-triazole (II) for the active luminescent layer, the interaction of 4-dimethylaminobenzoyl acid with 4-phenylbenzothiazole obtaining 1-(4-dimethylaminobenzoyl)-2-(4-phenylbenzyl)hydrazine, which cyclist in the presence of PCl3and 4-tert-butylaniline. The invention relates to an electroluminescent device, comprising Jenova triazole derivative (II), the hole transport layer based on a mixture of oligoadenylates (I) and an injecting hole of a layer of a mixed oxide of indium and tin (In2O3SnO2). The invention reduces the power consumption at the expense of achieving high brightness at lower currents and can be used for the manufacture of organic electroluminescent displays. 3 c.p. f-crystals.

The invention relates to methods for organic materials for electroluminescent devices and devices based on them.

A method of obtaining a mixture of oligomers,

< / BR>
including interaction monomethylamine of triphenylamine with bromodomain complex with the formation of dibromsalan of monomethylethanolamine, the processing of the last activated magnesium taken in equimolar ratio, with the addition of complex nonvalence Nickel and highlighting mixture bromodomain oligomers (Synthetic Metals, 1991, v 40, N 2, p 231-238) [1]. This mixture has been described to study the electrical conductivity of the material. The applicant is not known applications of these systems as materials for electroluminescent devices.

Also known is a method of obtaining 3-(4-biphenylmethanol acid with 4-phenylbenzothiazole with the formation of 1-(4-dimethylaminobenzoyl)-2-(4-phenylbenzyl) of hydrazine followed by cyclization in the presence of phosphorus trichloride and 4-alkylsilane (Chem. Lett. , 1996, N 1, p 47-48) [2]. The disadvantage of this method is the low yield of the target product -14%.

It is also known electroluminescent device based on organic materials consisting of electronic injects a layer of metal, an active luminescent layer, hole transport layer and the hole injects a layer of a mixed oxide of indium and tin, In2O3-SnO2(ITO) (J. Appl. Phys. , 1994, v.75, No. 3, p 1656-1666) [3]. The use of an intermediate layer with hole conductivity for transport of charge carriers between an injecting hole layer and the active layer caused by the necessity of lowering the energy barrier at the boundary of the active layer [3, 4]. As the hole-transport layer is often used oligomer (dimer) triphenylamine - N,N'-diphenyl-N,N'-(3-were)-1,1'-biphenyl-4,4'-diamine (TPD) (Chem. Communications, 1996, p 2175-2176) [4], which is capable of forming an amorphous film during vacuum deposition and has a high mobility of carriers.

Closest to the present invention, the technical solution is the electroluminescent device on the basis of organic materials consisting of electronic injects a layer of metal, an active luminescent layer of 3-(4 - injects a layer of ITO. The specified device gives the spectrum of electroluminescence with a maximum at a wavelength of 450 nm and half-width (width at half height) of 70 nm [4].

The known device and organic materials used for its preparation, have the following disadvantages. 1) the Morphology of the hole-transport layer, consisting of TPD varies even at room temperature due to a low glass transition temperature (< 60oC). Heating during operation of the device leads to a change in the electrical transport properties of the layer and, as a consequence, the loss of the electroluminescence device, i.e. the loss of life of the device. 2) Low operating characteristics of the device, namely the relatively high current consumption (230 mA/cm3at an operating voltage of 14 V) and relatively high energy costs per unit of luminous intensity (26 watts/CH), and relatively wider spectrum of electroluminescence (70 nm), limiting the possibility of obtaining pure color for use in full-color displays.

The present invention is the creation of materials for electroluminescent device free from the above disadvantages.

The task R is assocom distribution: Mn= 2332 (about 9 units), Mw= 3586 and polydispersity Mw/ Mn= 1.54, including interaction monomethylamine of triphenylamine with bromodomain complex with the formation of dibromsalan of monomethylethanolamine, the processing of the last activated magnesium taken in equimolar ratio, with the addition of complex nonvalence Nickel. The resulting mixture bromodomain oligomers treated with alkyl - or arylalkylamines in the presence of complex nonvalence Nickel.

Additionally, the task is solved by a method of production of new 3-(4-biphenyl)-4-(4-tert. butylphenyl)-5-(4-dimethylaminophenyl)-1,2,4-triazole of the formula

< / BR>
including the interaction of hydrazine with 4-dimethylaminobenzoyl acid with 4-phenylbenzothiazole with the formation of 1-(4-dimethylaminobenzoyl)-2-(4-phenylbenzyl)of hydrazine followed by cyclization in the presence of phosphorus trichloride and 4-tert butylaniline.

This task is solved in that the electroluminescent device consisting of electronic injects a layer based on a magnesium-silver alloy, an active luminescent layer on the basis of a triazole derivative, a hole transport layer on the basis of poly(4,4'-(4"-methyl)tracesthe derived triazole take 3-(4-biphenylyl)-4-(4-tert an bitolterol)-5-(4-dimethylaminophenyl)-1,2,4-triazole

< / BR>
but as poly(4,4'-(4"-methyl)triphenylamine) take the mixture of oligomers of General formula

< / BR>
where n = 8-9,

when the molecular-mass distribution: Mn= 2332 (about 9 units), Mw= 3586 and polydispersity Mw / Mn= 1.54.

This technical result is achieved by the electroluminescent device consisting of electronic injects a layer based on a magnesium-silver alloy, an active luminescent layer on the basis of a triazole derivative, a hole transport layer and the hole injects a layer of a mixed oxide of indium and tin (In2O3-SnO2), as the hole transport layer take dimethylselenide oligo(4,4'-(4"-methyl)triphenylamine (I), General formula

< / BR>
where n = 8-9 (instead of 2 links in normal TPD),

and as an active luminescent layer is used molecule DA-BuTAZ - similar molecules DA-TAZ in which the ethyl substituent in the benzene ring linked to the nitrogen atom, is replaced by tert botilony

< / BR>
The invention consists in that the electroluminescent device using the new material for grocerystores layer and new material for the active luminescent layer that Privol increase the quantum yield and the narrowing of the spectral width of the radiation by 20%.

High glass transition temperature of a mixture of oligomers with the General formula (I) 185oC compared with TPD ensures the preservation of the morphology grocerystores layer even at elevated temperatures. For comparison, the glass transition temperature TPD 60oC, and pentamer of triphenylamine 140oC [4]. Another reason that prevents crystallization of this material is that used oligoadenylates is not an individual connection, and a set of oligomers, which is dominated by compounds with 8-9 Monomeric units. Used as an active luminescent layer DA-BuTAZ characterized by a spectrum of luminescence with a maximum of 427 nm and a width of 57 nm, i.e. has a 20% narrower spectral distribution in the violet region compared with the molecule DA-TAZ (maximum of 450 nm, a width of 70 nm [3].

The invention is illustrated by the following examples.

Example 1. The scheme of synthesis of a mixture of oligomers of triphenylamine (I) (see the end of the description).

1) Synthesis of monomer.

4-Methyldiphenylamine received according to [1].

The mixture 66.68 g (30.6 mol) 4-iodine-toluene, 43.94 g (0.26 mol) of diphenylamine, 41.4 g (0.30 mol) of anhydrous K2CO3and 2.0 g of powder of the com within 24 hours Upon cooling the reaction mass was filtered, the precipitate washed with 100 ml of benzene. The combined filtrate by distillation under reduced pressure to remove the benzene, nitrobenzene, the remains of the-4-iodotoluene, and the residue was distilled in vacuum, collecting the fraction boiling at 180-200oC /3 mm RT. Art. cooling substance was secretarypantyhose. It was purified by chromatographytandem on a short column with Al2O3eluent benzene : hexane (1: 1), with subsequent crystallization from 90% aqueous acetic acid. Received 47.2 pure substance. Output 70.1% of theoretical. So pl. 68.0oC (lit. so pl. 68.8oC [2]).

2) 4,4'-Dibromo-(4"-methyl)triphenylamine was obtained according to the method similar to [3].

To a solution 28.72 g (0.11 mol) of 4-methyldiphenylamine in 140 ml of diethyl ether, cooled to -10oC, was added in small portions during 2 hours 55 g (0.22 mol) of deoxyribose (receipt, see [4]) with continuous stirring. Initial temperature (-10oC) supported the entire period of addition of the reagent and forth, until the termination of allocation of gaseous HBr (only 2.5-3 hours), after which it was heated to room temperature and left for 24 hours. Then the reaction mixture was treated with 20% aqueous NaOH solution (Oh, then drove the solvent under reduced pressure. The resulting crystalline residue was purified on a short column with Al2O3, eluent benzene:hexane (1:4 vol.), followed by recrystallization from 90% aqueous acetic acid. Received 38.2 g of the product. Output 82.6% of theoretical. So pl. 107oC. Elemental analysis: found, %: C: 57.37; H: 3.69; Br: 37.22. C19H15NBr2. Calculated, %: C: 57.71; H: 3.62; Br: 38.31.

3) Synthesis of oligomers.

Oligomerization of the monomer [4,4'-dibromo-(4"-methyl)triphenylamine] were conducted according to a modified method [1].

Oligo(4,4'-(4"-methyl)triphenylamine (blomstermo) (1). 5.21 g (0.133 mol) of potassium Metal was added in small pieces to a solution of 5.54 g (0.058 mol) MgCl2anhydrous 300 ml of dry THF in an atmosphere of dry argon for 0.5 h the mixture is Then boiled under reflux with continuous stirring for 2 h (until the formation of fine metal magnesium). The mixture was cooled to room temperature and over a period of 0.5 h was added a solution 24.52 g (0.059 mol) of 4,4'-dibromo-(4"-methyl)triphenylamine in 50 ml of dry THF. The mixture was stirred at room temperature for 3 h, then was added 0.35 g of catalyst ([1,3-bis(definiltely for another 2 hours Upon cooling, to the mixture was carefully added to 10 ml of ethanol and after 0.5 h the reaction mixture was poured into 1 l of cold ethanol. Formed small flocculent precipitate yellowish-brown color. It was filtered, washed with portions 4 100 ml of 2% hydrochloric acid, then with water until neutral wash water, dried in vacuum at 50oC. Received 15.95 g of the crude product. It was dissolved in 60 ml of benzene, was filtered from the insoluble residue was poured into 350 ml of hexane. Fallen yellow precipitate was filtered, dried in vacuum at 50oC. Received 6.35 g of the product. The yield of the pure product 39% of theoretical. So pl. 183-187oC. Elemental analysis: found, %: C: 82.18; H:4.87; N: 5.15; Br: 7.03. Brutto-formula (C18.6H13.2NBr0.24)n. Calculated, %: C 82.29; H: 5.45; N, 5.05; Br: 7.20. For gross formula (C19N15N)8Br2. Molecular weight distribution: Mn= 1812, Mw= 2802, the polydispersity Mn/ Mw= 1.55V. The glass transition temperature (measured on a differential scanning calorimeter DTAS-1300) is equal to 175oC.

5) Dibromononane of oligomer (I):

Oligo(4,4'-(4"-methyl)triphenylamine (dimethylsiloxane) (II).

To a suspension of 4.13 g (0.17 mol) of metal bauleni about 0.5 h). To the resulting mass was added 0.15 g of catalyst ([1,3-bis(diphenylphosphino)propane]Nickel(II)chloride) (dpppNiCl2) and a solution of 6.0 g (about 0.003 mol) prosteradlo of oligomer (I) in 95 ml of THF. The reaction mixture was stirred at room temperature for 24 h, and then boiled under reflux for a further 2 hours By cooling the reaction mass was carefully poured into 1.5 liters of a 2% aqueous solution of hydrochloric acid. Fell precipitate a light yellow color. It was washed successively with 2% hydrochloric acid, water, ammonium hydroxide, water, then dried in vacuum at 50oC. Received 5.54 g of dry product. Cleaning: previously obtained product was dissolved in 60 ml of benzene and was chromatographically on a short column of silica gel (eluent benzene). The collected eluent was concentrated to a volume of about 740 ml and poured with stirring into 100 ml of hexane. Fell light yellow precipitate. It was filtered, washed with hexane, dried in vacuum at 50oC. Received 3.47 g of substance. The yield of the pure product 61.4% of theoretical. Melting point 206-210oC. the glass transition Temperature by the method of differential thermal analysis 185oC. Elemental analysis: found, %: C: 88.47; H: 5.71; N: 5.83. For gross formula (C17.7. Molecular weight distribution: Mn= 2332 (about 9 units), Mw= 3586, polydispersity Mn/ Mw= 1.54. UV absorption spectrum (solution in chloroform) 313,372 nm.

Example 2. Synthesis of 3-(4-biphenyl)-4-(4-tertbutylphenyl)-5-(4 - dimethylaminophenyl)-1,2,4-triazole (see diagram at the end of the description).

1) EtOH + HCl; 2) OH-H2O; 3) N2H4H2O; 4) 4-phenylbenzophenone; 5) PCl3; 6) 4-tert-butylaniline.

1) Synthesis of ethyl ester of 4-dimethylaminobenzoyl acid (IV).

To of 20.0 g (0.12 mol) of 4-dimethylaminobenzoyl acid was added 200 ml of ethanol and cooled to 10-15oC and stirring was saturated with gaseous HCl. Then the mixture was heated to boiling and boiled for 8 hours At the end of the reaction drove the basic amount of alcohol (about 120 ml). The residue was cooled to 10oC and was added with stirring a solution of 25 g of KOH in 110 ml of water, maintaining the temperature of the reaction mass within 5-10oC (not higher). The precipitate was separated, washed with water, dried, recrystallized from a mixture of benzene-hexane (1:1). Received 15.9 g (IV), the yield of the pure product IV was 54.8% of theoretical. TPL= 64-65oC.

2) Hydrazide 4-dimethylaminobenzoyl calaminariae acid (V), 8.5 g (to 0.17 mol) hydrazinehydrate and the reaction mass was heated to boiling for 8 hours On the partially cooled mass of crystals this way the product was diluted 4-fold volume of water was filtered. The resulting hydrazide (V) was recrystallized from ethanol. Received 10.7 g (92% of theoretical) of product V. TPL= 170-171oC.

3) 1-(4-dimethylaminobenzoyl)-2-(4-phenylbenzyl)hydrazine (VI).

7,56 g (0.035 mol) of 4-Phenylbenzothiazole was dissolved in 50 ml of pyridine. To the solution was added with stirring 6,27 g (0.035 mol) of hydrazine 4-dimethylaminobutyric acid. Then the mixture was heated to boiling and boiled for 0.5 hours, after which it was cooled, diluted 10-fold volume of water. The precipitate was filtered, dried. Then recrystallized from dimethylformamide. Received 9,78 g (VI). The yield of the pure product VI was 78% of theoretical. TPL= 260-261oC.

4) 3-(4-Diphenyl)-4-(4-tert-butylphenyl)-5-(4-dimethylaminophenyl)-1,2,4 - triazole (VII).

A mixture consisting of 8.94 g (0.06 mol) of 4-tert-butylaniline and 3.59 g (0.01 mol) of 1-(4-dimethylaminobenzoyl)-2-(4-phenylbenzyl)hydrazine (VI), 0.96 mol of phosphorus trichloride and 25 ml of 1,2-dichlorobenzene. Was heated to boiling and boiled for 3 hours Then the cooling gap is igenom pressure). The residue was stirred with 20 ml of hexane was obtained crystalline product. For purification it was chromatographically on a column of silica gel. Eluent benzene. Then recrystallized from a mixture of benzene-hexane. Received 2.76 g of pure product (VII). Exit 59% of theoretical. TPL= 205oC. Elemental analysis: found, %: C: 81,77; H: 6,29; N: 11,82. C32H32H4. Calculated, %: C: 81,32; H: 6,82; N Up 11,86.

Example 3. The electroluminescent device ITO/TPD/DA-BuTAZ/Mg:Ag.

Use a glass substrate with a transparent layer of a mixed oxide of indium and tin with resistance 30-70 Ω/square, which by evaporation in vacuum, put a layer of TPD thickness of 0.05 - 0.1 μm. Then also by evaporation in a vacuum is applied to the active layer - DA-BuTAZ thickness of 0.02-0.05 micron. The sample is placed in a vacuum installation VUP-4, pump out in a dynamic mode to vacuum 10-6mm RT.article and sprayed metal electrode by evaporation of an alloy containing magnesium (90%) and silver (10%). The thickness of the metal electrode is about 0.1 μm. The area of the illuminated surface of 4-5 mm2. Received ELU has the following parameters: brightness 144 CD/m2is achieved at a voltage of 13.4 and In the current 42 μa, which corresponds to energopotrebleniem the device ITO/PTA/DA-BuTAZ/Mg:Ag.

The device, as in example 3, but instead of the deposited layer TPD use layer PTA thickness of 0.05-0.1 μm, deposited by centrifuging from a solution in toluene. Received ELU has the following parameters: brightness 144 CD/m2is achieved at a voltage of 10.4 V and a current of 4 mA, which corresponds to a power consumption of 60 W/CH, comparable with that observed for the prototype with the same voltage.

1. The method of obtaining a mixture of oligomers of General formula

< / BR>
where n = 8 - 9

when the molecular-mass distribution: Mn= 2332 (about 9 units), Mw= 3586 and polydispersity Mw/Mn= 1,54, characterized in that monomethylarsonic triphenylamine subjected to interaction with bromodomain complex with the formation of dibromsalan of monomethylethanolamine handle last activated magnesium taken in equimolar ratio, with the addition of a complex of zero-valent Nickel and a mixture bromodomain oligomers, which is treated with alkyl - or arylalkylamines in the presence of complex nonvalence Nickel.

2. The method of obtaining 3-(4-biphenylyl)-4-(4-tert-butylphenyl)-5-(4-dimethylaminophenyl)-1,2,4-triazole of the formula

< / BR>
characterized in that hydrotherapeutic)-2-(4-phenylbenzyl)of hydrazine followed by cyclization in the presence of phosphorus trichloride and 4-tert-butylaniline.

3. The electroluminescent device consisting of electronic injects a layer based on a magnesium-silver alloy, an active luminescent layer on the basis of a triazole derivative, a hole transport layer on the basis of poly(4,4'-(4"-methyl)triphenylamine), an injecting hole of a layer of a mixed oxide of indium and tin (In2O3SnO2), characterized in that as a derivative of triazole take 3-(4-biphenylyl)-4-(4-tert-butylphenyl)-5-(4-dimethylaminophenyl)-1,2,4-triazole of the formula

< / BR>
but as poly(4,4'-(4"-methyl)triphenylamine take a mixture of oligomers of General formula

< / BR>
where n = 8 - 9

when the molecular-mass distribution Mn= 2332 (about 9 units), Mw= 3586 and polydispersity Mw/Mn= 1,54.

 

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