TWI246357B - Alkylation of multi-ring aromatic compound and organic electroluminescent device - Google Patents

Abstract

An alkylation of multi-ring aromatic compound and organic electroluminescent device. The process of alkylation includes reacting a multi-ring aromatic compound with an alkyl halide, aluminium chloride, and an ionic liquid (serving as solvent) to obtain an alkylated multi-ring aromatic compound, wherein the yield of the alkylated multi-ring aromatic compound is more than 70%, preferably 85%.

Description

1246357 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for preparing an alkylated polycyclic aromatic compound, and particularly to a method for alkylating a polycyclic aromatic compound using an ionic liquid. [Previous technology] Since 1987, Kodak has developed the first high-efficiency organic electro-optical excitation light element, which has attracted the attention of the industry. Because of its high brightness, self-luminescence, low driving voltage, no viewing angle, The simple manufacturing process is very suitable for flat panel displays. The organic electroluminescent element includes a semiconductor thin film composed of organic electroluminescent material. Under the action of an external electric field, electrons and holes are injected from the cathode and the anode, respectively. When the electron holes are combined in the organic electroluminescent material layer, It emits light. Aromatic compounds with alkyl substitution are suitable as organic electroluminescent materials for organic electroluminescent devices due to their photoelectric properties. Generally speaking, an aromatic compound having an alkyl substitution is prepared by chemically reacting an alkyl halide with an aromatic compound in the presence of a Lewis base. The chemical reaction formula of Friedel-Crafts alkylation is shown in formula (I):

H3C—CI +

AICI3-

+ HCI However, the conversion of this alkylation reaction is not high, so the yield of aromatic compounds with alkyl substitution is generally between 30% and 40%. In addition, since the alkylation reaction must be carried out at a relatively high temperature, the reaction is complicated, and a variety of by-products are formed in the reaction, which makes it difficult to purify the product. Especially in the process of 0424-A20731TWF (N2); 02930032TW; phoelip 5 1246357 reaction, there will be strong corrosive hydrogen halide (hydrogen halide) generation, which increases the danger in operation and handling. In addition, the equivalent number of the Lewis base catalyst used in the alkylation reaction must be 3 to 4 times the equivalent number of the alkane compound, and the solvent used is a general organic solvent, which is flammable and will cause environmental problems. Pollution. Therefore, redesigning and developing a novel method for preparing aromatic compounds with alkyl substitution in order to increase yield, reduce chemical complexity, and simplify purification steps is extremely important for the synthesis of organic electroluminescent materials. Subject. [Summary of the Invention] The purpose of the present invention is to provide a method for preparing alkylated polycyclic aromatic compounds, which can increase the reaction selectivity of polycyclic aromatic compounds in the alkylation reaction and increase the yield of the main product to 70%. In this way, the steps required for purification can be simplified. In addition, another object of the present invention is to provide an organic electroluminescent display device. To achieve the above object, the method for preparing an alkylated polycyclic aromatic compound according to the present invention includes the following steps: In the presence of 60-93_7 wt% ionic liquid and LO_80 wt% aluminum chloride, 5 -30wt% polycyclic aromatic compound and 0.3-2wt% haloalkane are subjected to alkylation reaction to obtain a monoalkylated polycyclic aromatic compound. The yield of the alkylated polycyclic aromatic compound is greater than 70. %, The weight percentage is based on the total weight of the ionic liquid, chloride, polycyclic aromatic compound, and iS compound. The carbon number of the polycyclic aromatic compound is between 13 and 30. The structure of the ionic liquid is a compound having the formula (I), and the haloalkane compound has the formula (II). Compounds: 0424-A20731TWF (N2); 02930032TW; phoelip 6 1246357 r1 ^ N ^ N ^ r2 ίκ3-χ · γ- formula (work) where formula (work) Υ-selection free PF6-, bf4 ·, ( cf3so2) 2n-, cf3scv, cf3co2-, and 2 derivatives thereof, x is fluorine, chlorine, bromine, or iodine, and R1, R2, and R3 are the same or different and are alkane with Ci Or a fluoroalkyl group, and the above compounds having the structure of formula (I) and formula (11), any one or more carbon atoms in the structure, and the hydrogen thereon may be the same or different halogen atoms as required, or Has an alkyl or fluoroalkyl group. In addition, according to another preferred embodiment of the present invention, the organic electroluminescent display device according to the present invention includes a pair of electrodes, and an organic electroluminescent material layer between the pair of electrodes, wherein the organic electroluminescent The optical material layer includes an alkylated polycyclic aromatic compound, which is prepared by the method for preparing an alkylated polycyclic aromatic compound described above. The following describes the methods, features, and advantages of the present invention through several embodiments and the accompanying drawings, but it is not intended to limit the scope of the present invention. The scope of the present invention should be based on the scope of the attached patent application. quasi. [Embodiment] The method for preparing an alkylated polycyclic aromatic compound according to the present invention mainly uses a specific ionic liquid as a reaction solvent and a chlorinated salt as a catalyst, so that the polycyclic aromatic compound and a haloalkane compound are used. The alkylation reaction is carried out to obtain an alkylated polycyclic aromatic compound, which is characterized in that the alkyl group obtained by the alkylation reaction is 0424-A20731TWF (N2); 02930032TW; phoelip 7 1246357 yield of the polycyclic aromatic compound The ratio is greater than 70% and may even be greater than 85%. According to a preferred embodiment of the present invention, in the method for preparing an alkylated polycyclic aromatic compound according to the present invention, the temperature of the alkylation reaction may be in a range of -5 to 100. In between, the reaction can be more selective and the formation of other by-products can be greatly reduced because the reaction of the aromatic compound can be performed without requiring a too high reaction temperature. The ionic liquid system has the characteristics of high thermal stability, no flammability, no ignition point, etc. It is in a liquid state in a wide temperature range and has almost no vapor pressure. The ionic liquid system used in the present invention has a compound represented by formula (I), and it is maintained in a liquid state within a temperature range suitable for a radical polymerization reaction (-lot: to 200 °).

Formula (Engineering) where Y · selects the group consisting of SbF6-, PF6-, BF4-, (CF3S02) 2N_, CF3S03-, CH3C02_, CF3C (V, N03-, Cl ·, Br_, Γ and their derivatives In the formula, R1 and R2 are the same or different and have an alkyl group or a fluoroalkyl group having C ^ o, and the compound having the formula (I) has any one or more carbon atoms on the ring, and hydrogen on the ring. If necessary, it may be substituted with the same or different halogen atom, an alkyl group having C ^ o or a fluoroalkyl group. According to some preferred embodiments of the present invention, the ionic liquid having the structure described in formula (I) may be BmimPF6 (Bmim: l-butyl-3-methyl imidazolium), BmimBF4, BmimCF3S03, BmimCH3C02, BmimCF3C〇2, BmimCl, BmimBr, Bmim (CF3S〇2) 2N, OmimPF6 (Omim: 1-ocazyl-3-methyl OmimBF4, 0mimCF3S03, OmimCH3C〇2, 0mimCF3C02, OmimCl, OmimBr, Omim (CF3S〇2) 2N, 0424-A20731 TWF (N2); 0293032TW; phoelip 8 1246357

DmimPF6 (Dmim: 1-decyl-3-methyl imidazolium), DmimBF4, DmimCF3S〇3-DmimCH3C02 'DmimCF3C〇2 ^ DmimCl ^ DmimBr ^ or Bmim (CF3S02) 2N. The amount of the ionic liquid used is between 60-93.7 wt%, and the weight percentage is based on the total weight of the ionic liquid, aluminum chloride, polycyclic aromatic compound, and compound i. See Table 1 for a list of physical properties of several ionic liquids that conform to the structure described in formula (I). Table 1 Melting point (° C) of ionic liquids Cleavage point (° C) Viscosity (Cp, 25 ° C) Density (kg / m3, 25 ° C) DmimPF6 34 390 — 〇mimPF6 -75 __4_16 1400 BmimPFg 4 3 9〇312 13 7 0 DmimBF4 -77.5 —One BmimBF4 75 219 1119 __ Bmim (CF3S〇2) 2N -89 5 4.2 142 9 In the method for preparing the alkylated polycyclic aromatic compound described in the present invention, "Ring aromatic compound" is an aromatic compound having at least two benzene rings, and the slave number of the multi-frame aromatic compound is between 10 ~ 30, preferably between 13 ~ 30. For example:

0424-A20731TWF (N2); 02930032TW; phoelip 1246357

In addition, the haloalkane compound is a compound having the formula (II): R3-X_ Formula (Engineering) where X is fluorine, gas, bromine, or iodine, and R3 is a C ^ o alkyl group or Fluoroalkyl, and the compound having the structure of formula (II) above, any one or more carbon atoms in the structure, and the hydrogen on it may be the same or different halogen atom, or an alkyl group having C ^ o if necessary Or fluoroalkyl, where R3 is, fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, isopentyl, neopentyl , Hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, heptyl, octyl, decyl, or nonyl. The amount used for the aluminum gasification is between 1-8% by weight, and the amount used for the polycyclic aromatic compound is between 5-30% by weight, and the amount used for the haloalkane compound is between 0.3-2 wt%, the weight percentage is based on the total weight of the ionic liquid, aluminum chloride, polycyclic aromatic compound, and haloalkane compound. In addition, the present invention provides an organic electroluminescent display device 100, as shown in FIG. 1, including a pair of electrodes, that is, a cathode 110 and an anode 120, and an organic electricity between the pair of electrodes. Excitation light material layer 130, wherein the organic electro-excitation light material layer 130 includes an alkylated polycyclic aromatic compound 140, and the alkylated polycyclic aromatic compound is an alkylated polycyclic aromatic compound prepared according to the present invention. Prepared by a compound method. 0424-A20731TWF (N2); 02930032TW; phoelip 10 1246357 Please refer to Table 2, which shows the preferred embodiment of the present invention, and lists the solvents, starting materials and products used in its polycyclic aromatic alkynylation reaction. Table 2

0424-A20731TWF (N2); 02930032TW; phoelip 11 1246357

Example 1 0-lg (2 mmol) of naphthalene was added to a reaction flask, and 2 g of BmimPF6 (l-butyl-3-methyl imidazolium hexafluorophosphate) was added as a solvent. Next, 30 mg of aluminum chloride (A1C13) and 1 ml of tert> butyl chloride were sequentially added to the above reaction bottle, and reacted at C. After tracking reaction on the side of thin layer spot chromatography (TLC) to complete reaction of the third butyl chloride 0424-A20731TWF (N2); 02930032TW; phoelip 12 1246357, the reaction solution was added to n-hexane for extraction three times, filtered and dried After the filtrate, 160 mg of 2,6-di-t-butyl-naphthalene was obtained in a yield of 88%. Example 2 340 mg (2 mmol) of anthracene was added to a reaction flask, and 2 g of BmimPF6 (l-butyl_3-methyl imidazolium hexafluorophosphate) was added as a solvent. Next, 53 mg of aluminum vaporized aluminum (A1C13) and 2 ml of tert-butyl chloride were sequentially added to the above reaction flask, and reacted at 70 ° C. After the reaction on the tracking side of thin layer spot chromatography (TLC) until the third butyl gas was completely reacted, the reaction solution was added to n-hexane and ethyl acetate (95: 5) and extracted three times. After filtering and drying the filtrate, 500 mg of 2,6-bis-tertiary-butyl-anthracene (2,6-earth + 13 plus 71-anthracene) can be obtained with a yield of 90%. Example 6 100 mg (0.5 mmol) of pyrene was added to a reaction flask, and 2 g of BmimPF6 (l-butyl-3_methyl imidazolium hexafluorophosphate) was added as a solvent. Next, 40 mg of aluminum chloride (A1C13) and 1 ml of tert-butyl chloride were sequentially added to the above reaction flask, and reacted at 70 ° C. After the reaction on the tracking side of thin layer spot chromatography (TLC) until the third butyl gas was completely reacted, the reaction solution was added to n-hexane and ethyl acetate (95: 5) and extracted three times. After filtering and drying the filtrate, 150 mg of 1,6-di-t-butyl-pyrene can be obtained with a yield of 96%. Example 7 100 mg (0.5 mmol) of perylene was added to a reaction flask, and 0424- A20731TWF (N2); 02930032TW; phoelip 13 1246357 was added. [Schematic description] Figure 1 shows one of the present invention The organic electroluminescent display device according to the preferred embodiment. [Description of main component symbols] 100 ~ organic electroluminescent display device, 110 ~ cathode; 120 ~ anode; 130 ~ organic electroluminescent material layer; 140 ~ alkylated polycyclic aromatic compound. 0424-A20731TWF (N2); 02930032TW; phoelip 15

Claims (1)

10. Scope of patent application: 1. A method for preparing an alkylated polycyclic aromatic compound, including the following steps: In the presence of 60-93.7 wt% ionic liquid and l_0-8.0 wt% gasification inscription, 5-30 wt% of polycyclic aromatic compounds and 0.3-2 wt% of halogenated compounds are subjected to alkylation reaction, and the temperature of the alkylation reaction is between -5 to 100 ° C to obtain an alkylation reaction. Polycyclic aromatic compounds. The yield of the alkylated polycyclic aromatic compounds is more than 70%. The weight percentage is based on the total weight of the ionic liquid, aluminum chloride, polycyclic aromatic compounds, and haloalkane compounds. The carbon number of the polycyclic aromatic compound is between 13 and 30. The structure of the ionic liquid is a compound having the formula (I), and the haloalkane compound has the formula (II). Compound shown: Formula ⑴ R. —— X formula (II) where Y is selected from the group consisting of PF6-, BF4-, (cf3so2) 2n_, cf3so3-, CF3C02 ·, and derivatives thereof, and X is fluorine, gas, bromine, or iodine , R1, R2 and R3 are the same or different and are C ^ o alkyl or fluoroalkyl, and the above compounds having the structure of formula (I) and formula (II) have any one or more carbons in the structure Atoms, hydrogen on which may be optionally substituted with the same or different halogen atoms, or alkyl or fluoroalkyl groups having Cmo. 2. A method for preparing an alkylated polycyclic aromatic compound 0424-A20731TWF1 (N2); 02930032TW; phoelip 16 1246357 as described in item 1 of the scope of the patent application, wherein the polycyclic aromatic compound has 13 to 30 carbons. Compound system is 3. The method for preparing an alkylated polycyclic aromatic compound as described in item 1 of the scope of the patent application, wherein R3 is fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, and second butyl Base, third butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, 2,2-difluorenylbutyl, 2,3-difluorenylbutyl, Heptyl, octyl, decyl, or nonyl. 4. The method for preparing an alkylated polycyclic aromatic compound according to item 1 of the scope of the patent application, wherein the ionic liquid system having the formula (I) is BmimPF6 (Bmim: 1-butyl-3-methyl imidazolium), BmimBF4 Λ BmimCF3S03, BmimCH3C02, BmimCF3C02, BmimCl, BmimBr, Bmim (CF3S02) 2N, OmimPF6 (Omim: l-octyl-3-methyl imidazolium), OmimBF4 ^ OmimCF3S3 O3 ^ Om OmimCl, OmimBr, 0mim (CF3S02) 2N, DmimPF6 (Dmim: 1-decyl-3-methyl imidazolium), DmimBF4 ^ DmimCF3S〇3, DmimCH3C02, DmimCF3C02, DmimCl, DmimBr, 0424-A20TW1F0294-N20TW Or Bmim (CF3S02) 2N. 5. The method for preparing an alkylated polycyclic aromatic compound according to item 1 of the scope of the patent application, wherein the alkylated polycyclic aromatic compound is an organic electroluminescent display device and an organic electroluminescent material layer Of composition. 0424-A20731TWF1 (N2); 02930032TW; phoelip 18