TWI239992B - Method for synthesizing a compound consisting of three types of benzidine with a specific ratio - Google Patents

Abstract

A method for synthesizing a compound consisting of three types of benzidine with a specific ratio is capable of producing a compound consisting of three types of benzidine with a specific ratio in a single operation suitable for being used as an organic photo-sensitive drum charge conductive material, and mainly comprises: using two types of biphenyl amines and a di-halogen biphenyl compound in a specific equivalent ratio as raw material, adding a composite additive formed of an inorganic base, a metal catalyst, and a ligand into the raw material, and performing the reaction in an organic solvent to produce a compound consisting of three types of benzidine with a specific ratio and having specific electrical properties, thereby avoiding the trouble and pollution associated with separately producing three types of compounds while reducing the production cost thereof.

Description

1239992 发明 Description of the invention [Technical field to which the invention belongs] The present invention is a method for synthesizing three types of bibenzylamine compounds in a specific proportion, and in particular, it can be applied in a single synthesis operation in the field of charge conduction layers of organic photoelectric materials Those who have completed the production of benzidine compounds with specific structures and proportions. [Previous technology] Benzaminium compounds are a very important chemical material. Because of their good electrical properties, they can be used as effective charge-conducting layer materials. They are widely used in organic electroluminescent devices, light-emitting diodes, Nonlinear Optics, Dry Photoelectric Imaging, and Charge Transport Layer Materials. According to the Japanese patents JP11282180, JP11087061, JP10017531, German patents DE4427120, DE4427121, European patent EP34425, British patent UK2147897, PCT publication No. 0155087, and US patents US47664625, US5648542, US5648539, US5654482, US6114583 and so on. A series of benzidine-type charge-conducting layer compounds, and these manufacturing methods use copper (Cu), nickel (Ni), palladium (Pd) and other metals in equal or equal catalytic amounts in the presence of different temperatures and different ligands. Halogenated benzene and diphenyl amine compounds are formed by coupling reaction ion in solution, which can synthesize different effective charge-conducting layer compounds. At present, the materials used in the charge-conducting layer of organic photosensitive drums often require the mixing of several benzidine compounds with different structures, which have better electrical properties. The methods described in the above documents have the following disadvantages: 1239992 people (1) are all The preparation methods for the individual synthesis of a single compound need to be physically blended in accordance with the required ratio in order to obtain better electrical characteristics. (2) The production rate of some production methods (US4764625, EP34425 and DE4427121) is lower than 75%, and the recovery rate is too low. (3) Since each benzidine compound is synthesized separately and needs to be blended in a physical manner, the required synthesis time is long and the manufacturing process is continuous, so the cost is expensive. (4) The blending technology is not easy to control, and the control of the required compound ratio cannot be completed in the same batch, the quality is easily affected, and it is not easy to obtain better and stable electrical characteristics. [Summary of the Invention] The present inventors have taken into account the complexity of the current method of making benzidine compound materials for charge-conducting layers, the difficulty of handling, and the poor results, especially using the Ullmann coupling principle and the catalytic amination reaction of BUchwa | d and cleavage Principle 'Provide-a method for manufacturing three types of benzidine compounds in a specific ratio in a single reading' to achieve the invention purpose of simultaneously synthesizing three types of benzidine compounds in a specific ratio. The main purpose of the present invention is to provide a method for synthesizing three types of benzidine compounds with specific proportions. It only needs to perform a single operation reaction, and does not need to synthesize three compounds separately and then blend into specific proportions to achieve simplified charge-conducting material production. Processes, mitigation of recycling or waste disposal work, and those that can save manufacturing costs and meet clean process requirements. Another object of the present invention is to use the method described above to make the three types of compounds of 1239992 have the most appropriate specific ratio (compound 4: compound 5 compound 6 = (86 ± 3%): (13 ± 2%) (· 0.2% ~ 1.5%)). In order to achieve the aforementioned object of the present invention, the technical means used in the present invention is to provide a specific (ratio) dianiline compound (compound 1 and compound 2) and dihalobiphenyl compound (compound 3) as raw materials, wherein The equivalent ratio of each raw material component is: Compound 1: Compound 2: Compound 3 1 · 11 ± 〇3: 5 soil 〇3), the above raw materials are dissolved in an organic solvent

Medium &, and further combined with a combination of additives containing inorganic bases, metal catalysts and ligands, the reaction is heated to a temperature of 100 ~ 200t in the range of stirring = 10 hours and after hot filtration and solvent recrystallization The treatment can complete the purpose of synthesizing three types of benzylamine compounds in a specific ratio at one time. [Embodiment] The method for producing the three types of benzidine compounds of the present invention in a fixed proportion ', and its main synthesis method, please refer to the products of the reaction equations listed below.

10 1239992

x—

—Γ

11 1239992 Its Yin R1 and R2 brand main -π, wind atom, alkyl group with 1-5 carbon atoms, alkoxy group with 1-5 reverse atoms and benzene ring; X series chlorine atom, bromine atom and iodine Atoms; γ-based chlorine, bromine, and iodine atoms; derivation R is 11 atoms; R2 is preferably a hydrogen atom; X is preferably a desert atom; Y is preferably a bromine atom. ,

The above reaction equation shows that the thin two-legged diphenylamine compounds 1 and 2 of the present invention and —dentified biphenyl (compound 3) are used as raw materials in a certain equivalent ratio (compound 1: compound 2: compound 3 is:]: 11 ± 〇 · 3: 5 soil is subjected to thermal transition and solvent recrystallization after treatment, and finally formed three types of benzidine compounds (compounds 4, 5 * 6) in specific proportions, among which the additives are-group organometallic, inorganic base and ligand Combined additives. 0.3) The mixture is mixed for synthesis reaction, and the reaction conditions are: under organic solvents and additives, the reaction is heated to a temperature ranging from 100 to 2000c and stirred for 5 to 10 hours and

The solvent may be a benzene-based solvent, an ether-based solvent, an alcohol-based solvent, a cyanohydrin / mixture, and a combination of the above; the organic metal of the additive is an organic compound selected from palladium, copper, zinc, or nickel; the The inorganic base of the additive is selected from the group consisting of sodium alkoxide, lithium alkoxide, hydroxide, carbonate or bicarbonate; the coordination group with the additive is selected from the group consisting of crown ether, 2, 2, bis (dibenzylphosphine group) , Binap ·· 2,2'-Bis (diphenylphosphino) -l, l, binaphthyl), carbamoylphosphine, alkoxyphosphine'phenylphosphine or pyrimidine compounds. After the synthesis reaction is completed, further The crude mixture is dissolved in a recrystallization solvent, and then heated to tear at a temperature range of 50 to 100 ° C. 12 1239992 is extracted by a liquid-solid phase continuous extraction method and purified by recrystallization, wherein the solvent is recrystallized It is selected from the group consisting of alkane solvents, alkane solvents, benzene solvents, ether solvents, ester solvents or other solvents, and finally obtains high purity three types of benzidine compounds with specific proportions as white crystals. The ratio is compound 4 · compound 5 · compound 6 = (8 6 3%): (1 3 2%) ··· (0 · 2% ~ 1.5%), which is the optimal composition of the benzylamine compound of the charge-conducting layer. In order to make the above and other objects, features, and The advantages can be more obvious and easy to understand, and several examples are given below for detailed description. Read <Implementing Examples> in a 5-liter three-necked round-bottomed bottle (set up mechanical stirring and put a thermometer and install a thermostat) And connect the condenser tube), and pass in nitrogen, put 5qq grams of dibromobiphenyl to wash 13 "〇111〇1 ^ [^ 门 7 丨 (1.6 mol)), 6200 grams of 3-methyldi Aniline (3-methyldiphenylamine (3.4 moles)), 50 grams of diphenylamine (Dipheny | amine (0.3 moles)), oxidized chlorine deoxidation (such as · hydroxide (3 moles)), 112 grams of copper powder ( copper 76 mol)) and 224 ml of Sol 70 (aliphatic mixture with 13-15 carbons purchased from Phillips Chemical Co., Ltd.), the reaction was carried out under nitrogen, and the mixture was heated to 165 degrees Celsius. (: stirring for 7 hours the reaction was completed , And slowly add 25 liters of Sotr〇 丨 / 70 'when the temperature reaches 145 force to remove inorganic solids by hot filtration. 2 liters of methanol was used to force the crystals to pass through, and the crude product was obtained as 0-color mouth-toe 700 {, which is a crude mixture of benzidine, and the yellow solid of the benzidine crude mixture was dissolved in 2 liters of methanol. Oxygen was obtained in 65Q grams of pale yellow product, and then n-sintered and then re-calculated as 13 1239992 to obtain purified white crystals of the final benzidine mixture, with a melting point of 168 to 170. &lt; Example 2> Inside a 5 liter three-necked round wire (set up a mechanical search and put a thermometer, install a temperature controller and connect a condenser tube), pass nitrogen gas, and put 500 g in order. Dibromobiphenyl (1.6 mol), 62 g of 3-methyldiphenylamine (3-4 mol), 50 g of diPhenylamine (0.3 mol) )), Benzene 24 # (T〇 | uene) 27 grams of 1,10-phenoline (1,10-phenanthroline (0.14 mole)), π grams of gasified copper powder (Cuprous Chl〇ride (0-14 moles)) and 168 grams of potassium hydroxide (KOOH (3 moles) and stirred for 30 minutes, then heated to reflux temperature 125 ° C, and stirred for 6 hours to terminate the reaction, 500 milliliters of 曱 was added Benzene, 500 ml of deionized water and gram of acetic acid to neutralize potassium hydroxide. The reaction temperature was kept at 70 ° C and poured into an extraction bottle. After standing for 10 minutes, the layers were separated, and the organic layer was taken out. It was extracted twice with 1 liter of deionized water twice, and the temperature of the organic layer was maintained at 6 CTC, and filtered while hot with 500 g of Woelm neutral alumina. After concentrating the filtrate, 605 g of a white solid was obtained. 500 g of purified white solid of bibenzylamine mixture can be obtained by recrystallization from n-octane. Melting point: 169 ~ 170t: &lt; Example 3 &gt; In a 5 liter di &gt; round-bottomed bottle (set up) Mechanically remove and insert a thermometer, install a thermostat, connect a condenser tube and a Dean-Stark device), and breathe in air, and place 500 g in sequence. Dibromobiphenyl (16 mol )), 620 g of 3-methyldiphenyamine (3 4 mol 14 1239992 ears)), 50 g of diphenylamine (Diphenylamine (0.3 mol)), 2.5 liters of o-xylene, 0.183 G of "Nameba monoacetate (Pd (OAc) 2 (〇_〇51mol%)), 014g of di-tert-butyl scale (P (t-Bu) 3 (0.04 3mol%)) and 350 grams of sodium tert-butyl oxide (NaO- (NBu) (3-64 mol)) and stirred for 30 minutes, then heated to reflux temperature 125 ° C, and stirred for 5 hours to terminate the reaction, and added 500 ml of o-dioxane Benzene, 500 ml of deionized water, the reaction temperature was maintained at 65.0, and poured into a pour bottle. 'Separated by standing for 10 minutes. The organic layer was taken and extracted twice with 1 liter of deionized water twice. The organic layer Temperature dimension 55 ° C, and filtered with 500 grams of Woelm neutral alumina while hot, and concentrated to obtain 6660 grams and then n-octyl :): complete recrystallization to obtain a purified white solid of benzidine mixture 5 8 〇g, melting point 168 ~ 170 ° C. &lt; Example 4 &gt; In a 5-liter three-necked round-bottomed bottle (mechanical stirring and thermometer installation, temperature controller, condensing tube and Dean-Stark device), nitrogen was passed through, in order Put 500 grams of dibromobipheny (1.6 moles), 620 grams of 3-methyldiphenylamine (3.4m moles), and 50 grams of diphenylamine (Diphenylamine (0_3 moles) Ear)), 2.4 liters of toluene, 7.36 g of palladium diphenyl onion (Pd2 (dba) 3 (0.08 mole)) (according to the document J.〇rg.Chem. 2000, 65, p .5330 method), 9.6 grams of diphenylamine di-tert-butylphosphine oxide (P (i-Bu) 2-0-biphenyl (0.032 mole)) (according to the document vJ.Org.Chem. 2000,65 , Ρ · 5330 method) and 350 grams of tert-butyl sodium oxide (Na〇- (i-Bu) (3.64 moles)), and stirred for 30 minutes, and then heated to a temperature of 11CTC and stirred for 5 hours to terminate Add 15 1239992 into 500 $ liters of Jiaben '500 ml of deionized water, keep the reaction temperature to 100% and pour it into the extraction bottle. After standing for 10 minutes, separate the layers. Take the organic layer and repeat 2 liters twice. Deionized water extraction 2 times, the temperature of the organic layer was maintained at 55 ° C., and filtered while hot with 500 g of Woelm ’s neutral alumina. After concentration, 650,000 g of a yellow solid was obtained, and the benzidine mixture was purified by recrystallization from n-octane. 550 grams of white solid, melting point 169 ~ 170 ° C. &Lt; Example 5 &gt; In a 5-liter three-necked round-bottomed bottle (set mechanical stirrer, put a thermometer, install a thermostat, and connect a condenser tube ), And then put in nitrogen, sequentially put in 2.4 liters of xylene, 27 grams of 1,10-morphine (1,10_phenanthr〇 丨 丨 ηθ (0.14 mole)) '420 grams Copper acetate (|) monohydrate (Cupr〇us acetate-monohydrat (2.1 mole)) and 140 grams of zinc (Zn (2 mol)) and 552 grams of carbonic acid (CaC03, (4 Mo (Ear)), and stirred for 30 minutes, then warmed to 120 ° C, and stirred the reaction for 10 hours to terminate, add 500 ml of xylene, 500 ml of deionized water and 350 g of acetic acid, neutralize the carbonic acid dance, the reaction temperature is maintained To 65 ° C and pour it into the extraction bottle. After standing for 10 minutes, the layers are taken into layers. The organic layer is taken and extracted twice with 1.5 l of deionized water twice. 55 ° C 'and filtered with 500 grams of Woelm's neutral oxide while hot, and then add 1 liter of methanol (Me0H) to force crystals, filtered to obtain 595 grams of white solid', and then re-crystallize with n-sinter to obtain Purified aniline mixture was 545 g of white solid with a melting point of 169 ~ 170 ° C. &lt; Example 6 &gt; 16 1239992 In a 5-liter three-necked round-bottomed bottle (set up mechanical stirring and put a thermometer, install a thermostat, connect a condenser tube and a Dean-Stark device), and pass in nitrogen gas. Put 500 grams of dibromobiphenyl (1.6 moles), 620 grams of 3-methyldiphenylamine (3-methyldiphenylamine (3.4m moles)) and 50 grams of diphenylamine (〇 丨 口 [ 16117 丨 311 ^ 116 (0.3 mole)), 2.4 liters of xylene, 27 grams of 1,10-phenoline (1,1〇_phenanthr〇line (〇.i4 mole)), 16 grams of gasified copper (Cuprous chloride (0.14 mole)) and 168 grams of potassium hydroxide (KOH (3 mole)) and stirred for 30 minutes' and then heated to reflux temperature i45 ° C, and stirred; Stir the reaction for 7 hours to terminate. Add 1 liter of o-xylene, 1 liter of deionized water and 400 g of acetic acid 'to neutralize potassium hydroxide. The reaction temperature is maintained at 100 ° C and poured into an extraction bottle. Let stand for 10 minutes. The layers were separated, and the organic layer was taken and extracted twice with 150 ml of deionized water twice. The temperature of the organic layer was maintained at 70 ° C, and filtered while hot with 600 g of Alcoa C g-20 alumina and concentrated. To give a white solid 615 g, n-octane was recrystallized available benzidine mixture was purified 600 g of a white solid, mp 168~170 ° C. &lt; Example 7 &gt; In a 5-liter three-necked round-bottomed bottle (set up mechanical stirring and put a thermometer, install a thermostat, and connect a condenser tube), pass in nitrogen gas, and place it in the order of 2 · 4. Liters of m-xybenzene (m-xy | ene (0.14 mole)), 150 grams of copper powder ((: "Powder (2.4 mole)), and 168 grams of potassium hydroxide (K OH (3 moles)) and 35 grams of 18-crown-6 ether, and stirred for 30 minutes, then heated to reflux temperature 139 ° C, and stirred the reaction for 10 hours to terminate , 17 1239992 Add 1 liter of m-xylene, 1 liter of deionized water and 400 g of acetic acid to neutralize potassium hydroxide. The reaction temperature is kept at 65 ° C and poured into an extraction bottle. After standing for minutes, the layers are taken. The organic layer was extracted twice with 2 liters of deionized water twice, the temperature of the organic layer was maintained at 55 ° C, and filtered with 600 g of Woelm neutral alumina while hot. After concentration, 620 g of white solid was obtained. 600 g of purified white solid of the benzidine mixture was obtained by recrystallization, with a melting point of 169 to 170. &lt; Example 8> In a 5-liter three-necked round-bottomed bottle (mechanical stirring was set up and put into a thermometer and t δ is temperature-controlled and connected to a condensing tube), and nitrogen is passed in, and then a gram of dibromobiphenyl (1.6 mol) and 62 g of 3-fluorenyl diphenylamine (3- methyldiphenylamine (3.4m mole)), 50 grams of diphenylamine in the mouth | ^ (^ | 3 (^ yang (0.3 mole)), 2 liters (30〇Juice〇 丨, 70), 150g of copper Powder (copper powder (2.4 moles)) and 168 g of potassium hydroxide (KOOH (3 moles)) and stirred for 30 minutes, then heated up to 19.0, and stirred for 10 hours to terminate the reaction, add 1 liter of toluene, 1.5 liters of deionized water and 400 g of acetic acid, neutralized potassium hydroxide, the reaction temperature was kept to prevent it and poured into the sampan. 'Stand for 10 minutes to separate, take the organic layer and then After two extractions with 2 liters of deionized water, the temperature of the organic layer was maintained at 55 ° C, and the solution was filtered while hot with 500 g of Woelm neutral alumina. After concentration, 630 g of white solid was obtained; Recrystallize to obtain 60Q g of purified white solid of benzidine mixture, melting point 167 ~ 170 ° C. &Lt; Example 9 &gt; In a 5-liter three-necked round-bottomed bottle (set mechanical stirring and put in a thermometer and 1 8 1239992 Install a thermostat, connect a condenser tube and a Dean-Stark device), pass in nitrogen, and place 500 grams of dibromobiphenyl (1-6 moles) in sequence, 620 grams of 3, 曱Diphenylamine (3.4m mole), 50 grams of diphenylamine (0_3 mole), 2.4 liters of m-xylene (nvXy | ene), 27 grams of phennothroline (0_14 mole )), 16 grams of copper powder (Cuprous chloride (0.14 moles)) and 168 grams of potassium hydroxide (KOH (3 moles)) and stirred for 30 minutes, then heated to reflux temperature i39 ° C, and stirred the reaction After 7 hours, add 1 liter of m-xylene, 1 liter of deionized water and 4qq g of acetic acid to neutralize potassium hydroxide. The reaction temperature is maintained at 65 and poured into an extraction bottle. The layer was washed twice with 2 liters of deionized water. The temperature of the organic layer was maintained at 55 ° C, and filtered with 600 g of Woelm neutral alumina while hot. After concentration, 610 g of a white solid was obtained. Recrystallized to obtain 585 g of purified white solid of benzidine mixture, melting point 169 ~ 170 ° C. Example 10> In a 5-liter three-necked round-bottomed bottle (set up mechanical stirring and put a thermometer, install a thermostat and connect a condenser tube and a Dean-Stark device), pass in nitrogen, and place 2.4 in sequence 1 liter of 10-crown-6 ether (350-Crown-6-ether), 350 grams of tert-butyl sodium oxide (Na〇- (NBu) (3-64 moles)) and 7.36 grams of two onions put Pd2 (dba ) 3 (0.008 moles) and 5.0 grams of 2,2'-bis (diphenylphosphino) -1, Γ-binaphtyl (BINNAP: 2,2, _Β ^ _ηγ1ρ'ρΜη〇) -1, Canabinapthyl ) (0.008 moles) and stirred for 30 minutes, then heated up to 19 1239992 reflux temperature 139 ° C, and stirred the reaction for 6 hours to terminate, add 彳 liters of methane, toluene, 1 liter of deionized water, the reaction temperature is maintained to 65C> c. Pour it into an extraction bottle, and let it stand for 10 minutes to separate the layers. Take the organic layer and take it twice with 2 liters of deionized water. The temperature of the organic layer is maintained at 55 ° C. Neutral oxide was filtered while hot, and crystallized by 1 liter of methanol (Me0H). After filtration, 630 g of a pale yellow solid was obtained, and then purified by n-octane to recrystallize the benzidine mixture. 595 g , Melting point: 169 ~ 17CTC. In each of the above examples, three types of high-purity benzidine compounds with white crystals were obtained in the final examples (see the first and second figures, using nuclear magnetic resonance spectrum (hydrogen spectrum, carbon spectrum)) , And use high-efficiency liquid chromatography analysis (see the third picture) to check the proportion of benzidine compounds, the analysis of the above benzidine mixture of the compound 4, compound 5 and compound 6 three benzidine compounds and photosensitive elements The standard used is correct (the standard is purchased from Syntec, Germany), and its composition ratio is analyzed by high-efficiency liquid chromatography as compound 4: compound 5: compound 6 = (86 ± 3%): (13 ± 2%): (0_2〇 / 〇 ~ 1.5%) is correct. In the third figure, the analysis conditions are as follows: 10 mg of the sample is dissolved in 50 ml of (tetrahydrofuran / methane cyanide = 60/40) solvent and analyzed under the following conditions: HPLC Type:

Pump: Waters 600

Detector: Waters 2996 Photodiode Array Detector Autosampler: Waters 700 plus

Mobile Phase: l% (v / v) Triethylamine, pH7.5 / Acetonitrile = 5/95

Flow Rate: 1.0 mL / min

Column: Luna 5μ Cl8 (2), 4.6 * 250-mm

Column Oven: 40 C

Injection Volume: 10 pL 20 1239992

Wavelength: 340 nm RT: 14.78611 The peak of the company 1 is the retention time of compound 6 ([^ 1 = 11) RT: 17.425 min The peak of the company 1 is the retention time of compound 5 (R1 = H, R2 = H) RT: 20.689111 丨 11 The peak is the retention time RT (retention time) of compound 4 ([^ 2 = «). The photoelectric characteristic test is performed. The general photoelectric characteristic measurement is performed by applying a charge generation layer material on an aluminum substrate by a dip coating method. , And then coated with a charge-conducting layer material. Materials The charge generating layer of each photosensitive drum is composed of 50% type IV polymorph of titanyloxyphthalocyamine and 50. /. Polyvinyl butyral ° Therefore, the charge-conducting layer solution is prepared by mixing a specific proportion of benzidine compound groups and 60% in the examples 1 to 10 of the present invention in a mixture of 40% by weight. The weight ratio of polycarbonate-A (calculated based on the weight of the charge-conducting layer) is dissolved in a mixed solvent (dichloromethane and toluene). Manufacturing process: The charge generating layer material is coated on an aluminum substrate and dried at 100 degrees Celsius for 15 minutes to form a thin layer of 0.3 to 0.5 // m. The charge-conducting layer solution was coated on the charge-generating layer by dip coating, and dried at 100 degrees Celsius for 60 minutes to form a 24 // m-thick charge-conducting layer. Organic photosensitive drum for machine use. Optoelectronic characteristics: The organic photosensitive drum manufactured above was subjected to PDT-2000LA (QEA Inc. 21 1239992. The results are shown in the following table: The following photoelectric values can be obtained.

Distributing potential ____. · Residual sound, bit (when the half-life is six times, it has 1/2: sensitivity (energy required for half of light decay) ', residual potential of inch) DkDec :: dark decay SN: 02021501070217 ) Instrument test The results of the photoelectric characteristics test in Examples 1 to 10 can be compared with the product test of Hp-8, which can meet the physical property requirements of general photoconductor drums, that is, A · σ V〇 (distribution potential) & 670 volt ·

Vr (residual potential) &lt; 60 volt Ει / 2 (sensitivity) · 0.1 ± 0.20 pj / cm2 DkDec (dark decay) &gt; 95% The experimental data show that the method of the present invention can obtain relatively Low residual potential. / ^ From the above-mentioned examples and experimental results, it is known that the present invention provides a novel method that can produce three types of specific proportions of chemicals in a single operation. It mainly uses appropriate reaction conditions and starting materials. Two types of benzidine compounds with specific proportions can be produced at one time, and three types of benzidine mixtures produced can be directly applied to the operation of optoelectronic materials with more excellent properties. Therefore, it is proved that the present invention provides a one-time production The simple method of three types and specific proportions of chemicals does have better effects and industrial applicability. Compared with the methods of synthetically synthesizing three types of benzidine compounds, which are reported in conventional technology or literature, this method is physically combined. The method of the invention only needs to do one step reaction, and can produce specific proportions of three types of benzidine compounds without complicated reactions and physical blending. Therefore, it is more efficient, not only shortening the process time, but also saving manufacturing costs. In addition, because of the simplification of the manufacturing process, the recycling or waste can be reduced. The rational work is to meet the requirements for clean production. As mentioned above, by the method of the present invention, only the appropriate reaction conditions and starting materials need to be selected, and only a single operation can be used to produce three types of benzidine at a specific ratio at a time. The compound is directly applied to the production of the photosensitive drum, which not only greatly simplifies the manufacturing method of the charge-conducting layer of the traditional photoelectric material, makes the # _ clothing production process simple and easy to control, and can reduce the pollution caused by the process. The law has not been used in the same industry, so it has the novelty, practicality and industrial utility of the invention patent application subject, so it has issued a patent application. 23 1239992 [Brief description of the drawings] (I) Part of the drawings: Figures 1 and 2: View the NMR resonance spectrum (hydrogen spectrum and carbon spectrum) of the white crystals of the benzidine compound. Figure 3: High-efficiency liquid phase analyzer analysis for testing the proportion of benzidine compounds. (II) Symbols for components: None

twenty four

Claims (1)

1239992 Pick up and apply for a patent for the production of a synthetic special compound, such as the three types of benzidine compounds. The method is based on two ^., ^ ^ 1U, a reactant known as a dihalogen biphenyl. The reaction formula is as follows: Among them, X and a leaving group representing a gas atom, a bromine atom, and a molybdenum atom; R and R2 represent a hydrogen atom, an alkyl group having 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a benzene ring; / 、 The equivalent ratio of each component when the middle reaction is in progress is: Compound 1: Compound 2 Compound 3 J: 11 ± 〇3: 5 ± 〇3; By mixing the components in the above ratio, the product compound 4: 25 1239992 Compound 5: Compound 6 = (86 ± 3%): (13 ± 2%) m 5%). 〃2: The method according to item 1 of the patent scope, wherein the synthetic reaction is performed in ~! And the solvent is selected from the following groups: benzene solvents, ether solvents, alcohol solvents, and solvents And other solvents. 3. The method according to claim 1 of the patent scope, wherein the reaction is performed in the presence of a combination additive, wherein the combination additive comprises an organic metal, an inorganic base and a ligand. 4. The method according to item 3 of the patent, wherein the organic metal of the additive is an organic compound selected from the group consisting of copper, copper, silicon and zinc. 5. The method according to item 3 of the patent application, wherein the inorganic test of the additive is selected from the group consisting of silk, oxygen scorching, hydroxide, carbonate or bicarbonate. 6 As stated in the method of claim 3, the ligand in the additive is selected from the group consisting of a crown ether, 2,2, -bis (diphenylphosphino) -M, and binaphthyl (B ancestor PJy- BiKdiphenylphosphinoRMi — ^^^ based phosphine, thiophosphine, phenylphosphine, or pyridinoids. 7. Method as described in the above item, please include the product to extract, hot filter or use a recrystallization solvent. 'And the step of obtaining a high-purity product. 8 · The method according to item 7 of the patent application, wherein the extraction method includes a liquid-solid phase continuous extraction method. 9 · The method according to item 7 of the patent application, wherein the hot filtration temperature The range is from 50 ° C to 100 ° C. 26 1239992 1 0 · The method according to item 7 of the patent application range, wherein the recrystallization solvent is selected from the group consisting of: alkane solvents, haloalkane solvents, benzene solvents , Ether solvents, ester solvents or their solvents.