CN1322710A - Prepn of triphenylamine derivative - Google Patents

Abstract

The prepn of triphenylamine derivative includes the first step of synthesizing arene iodide with diazo salt or other compound as material and the second step of condensating different aromatic amine compound and arene iodide. Potassium iodide solution produced during the reaction may be recovered for reuse and reduction of potassium iodide. In addition, mixed crown ether as phase transfer catalyst is adopted during the condensation of the second step, and this raises the activity of catalyst while reducing consumption and exhaust of the toxic catalyst.

Description

The preparation method of triphenylamine derivative

The present invention relates to a kind of preparation method of triphenylamine derivative, can efficiently, low consumption prepare important intermediate one triphenylamine derivative of novel photoelectric functional material.

The compound that contains fluorine-triphenylamine structure is novel photoelectric material such as the xerox of preparation, the charge transfer material of laser printer, the important starting material of electroluminescent material etc.General Liv Ullmann (Ullmann) prepared in reaction that adopts, with the difference of the synthetic starting raw material that adopts, the yield of synthetic triphenylamine has bigger difference.If the halogenated aryl hydrocarbon of one of synthesis material adopts iodo aromatic hydrocarbons, the yield of the triphenylamine derivative of gained is best.Simultaneously, because ullmann reaction needs hot conditions, general quaternary ammonium salt-type phase transfer catalyst can not meet the demands, and uses the reaction yield of polyethylene glycols phase-transfer catalyst relatively low, therefore, has only the crown ether-like catalyzer to use.

Adopt method that different aromatic amine compounds and different halogenated aryl hydrocarbon and different phase-transfer catalyst prepare triphenylamine derivative (Gauthier S. etc., J.Org.Chem.54:1476-79 (1989) such as Synthesis 4:383-385 (1987) and Sutaka K.) is existing in the literature and relate to.The preparation method who addresses in the comprehensive literature is so that to adopt iodo aromatic hydrocarbons be one of reaction raw materials and 18-hat-6 ethers are that the effect of phase-transfer catalyst is best.But weak point is: 1. iodo aromatic hydrocarbons relative difficult preparation, raw material are not easy to obtain, usually need preparation in advance before the preparation triphenylamine derivative.And the potassiumiodide that produces in the reaction of preparation triphenylamine derivative can abandon as refuse.The comprehensive consumption of whole technological process is higher.2. though all better as phase-transfer catalyst stability and catalytic effect with 18-hat-6 ethers, price is higher, makes comprehensive consumption big, the more important thing is that its toxicity is bigger, the discharge of wastewater after the reaction can cause environmental pollution.The employing cyclohexanone derivative that other preparation method such as Kikuchi thousand good fortunes etc. are addressed in Chinese patent (publication number 1130174) is that the method for reactant exists deficiencies such as raw material is not easy to obtain.

The objective of the invention is to develop a kind of novel process of synthetic triphenylamine derivative, from the diazols compound, adopt method in common, the first step aromatic hydrocarbons of liquor kalii iodide and diazonium salt prepared in reaction iodo, second step selected for use different aromatic amine compounds and iodo aromatic hydrocarbons to carry out condensation reaction, preparation triphenylamine derivative, the liquor kalii iodide that condensation reaction produces can recycle and reuse, make the potassiumiodide in the whole technological process consume less.In the second step condensation reaction, use the blended crown ether-like phase transfer catalysts, both made the reaction yield of synthetic triphenylamine derivative higher, make the discharging of bigger 18-hat-6 ethers of toxicity less again.Realize purpose efficient, low consumption ground preparation triphenylamine derivative.

Preparation method of the present invention comprises: the first step adopts the general method for preparing diazonium salt to prepare the diazols compound of different structure, with potassiumiodide and diazonium salt prepared in reaction iodo aromatic hydrocarbons, second step was adopted the steps such as cycling and reutilization of compound crown ether Preparation of Catalyst triphenylamine derivative and potassiumiodide.

Method in common is adopted in the preparation of diazonium salt, according to the difference of the triphenylamine derivative structure for preparing, selects for use different arylamine as starting raw material, and the building-up reactions equation is as follows:

The R1 here can be groups such as the methyl, methoxyl group of the contraposition that is substituted in phenyl ring, a position; Acid H ⁺Can be hydrochloric acid or sulfuric acid.Concrete reaction conditions adopts method in common control proportion of raw materials and temperature of reaction.

The preparation of iodo aromatic hydrocarbons is to adopt method in common, with the diazonium salt reaction for preparing in the saturated solution of potassiumiodide and the above-mentioned steps, with diverse ways purification reaction product, can adopt methods such as steam distillation, underpressure distillation, crystallization according to the different mining of the structure of the iodo aromatic hydrocarbons of preparation.Here used liquor kalii iodide will be prepared with commercially available solid when preparing for the first time, can adopt the solution that contains crown ether and cupric ion that reclaims after the condensation reaction in the preparation process afterwards, not influence the yield of iodide reaction with the liquor kalii iodide that reclaims.

After having prepared iodo aromatic hydrocarbons, select for use the reaction of different arylamine and iodo aromatic hydrocarbons can prepare the triphenylamine derivative of different structure, the reaction formula of preparation triphenylamine derivative is as follows:

The R1 here is the same, and R2 can be the contraposition of hydrogen, phenyl ring or methyl that position replaces, methoxyl group etc., and R3 can be hydrogen, phenyl, p-methylphenyl etc.

Because the higher temperature (about 200 ℃) of reaction needed, therefore, the choice of Solvent of reacting required is limited, can only select the solvent of high temperature inert for use, as oil of mirbane, orthodichlorobenzene etc.The boiling temperature and the maintenance backflow that are warmed to solvent can be satisfied the required hot conditions of reaction, and these two kinds of solvents can be removed with the method for wet distillation after reaction finishes.Solvent can recycle after purification, drying.Same reason, the phase-transfer catalyst of this reaction are selected the crown ether-like catalyzer of high-temperature stable for use.In addition, also need to add activated copper powder catalyzer and Anhydrous potassium carbonate in the reaction system as alkaline reagents.

The phase-transfer catalyst that reaction is adopted is a compound crown ether-like catalyzer.Because the solubleness of 18-hat-6 ethers in water is bigger, price is higher, and toxicity is bigger, thereby the consumption of reaction is bigger, discharges comparatively serious to the pollution of water body.The present invention selects dibenzo 18-hat-6 and 18-hat-6 composite composite catalysts of making for use, reduced the consumption of 18-hat-6, simultaneously, because the solvability of dibenzo 18-hat-6 in benzene kind solvent is good than 18-hat-6, and the solvability in the water is relatively poor, not only improve the catalytic activity of composite catalyst effectively, and reduced the content of 18-hat-6 in consumption and the discharge.Concrete composite composition is 3: 1 ratio preparation in molar ratio for dibenzo 18-hat-6 and 18-hat-6.The usage quantity of catalyzer in catalyzed reaction is 1-5% (wt).The structure of dibenzo 18-hat-6 and 18-hat-6 is respectively:

After the reaction of preparation triphenylamine finished, the aqueous solution of recovery proved that through atomic absorption spectrochemical analysis the rate of recovery of iodide ion is generally about 80%.The solution that reclaims is through placing 4 days after-filtration of sedimentation, and the content of cupric ion in solution is 30-60ppm by analysis, and the existence of cupric ion and other impurity is not enough to influence iodination reaction.The KI solution that reclaims can be used to prepare iodo aromatic hydrocarbons.

Adopt above-mentioned technological line, not only make the yield higher (substantially more than 75%) of preparation triphenylamine derivative but also make the discharging of less, the deleterious crown ether-like catalyzer of potassiumiodide consumption in the whole technological process less.

The following examples are to further specify of the present invention, rather than limit scope of the present invention.

Embodiment 1:

Para-totuidine 54 grams are put in the round-bottomed flask of 1000ml, stir the dilute hydrochloric acid 100ml of adding 20% down, and heated and stirred is chilled to this solution below 5 ℃ to the whole dissolvings of solid.Keep temperature to add the sodium nitrite solution for preparing in advance below 5 ℃, be stirred to solution and become blue with the check of KI starch test paper, stop to add sodium nitrite solution, continue to stir 10 minutes, the clear solution that makes is the aqueous solution of diazonium salt.

75 gram KI are dissolved in few water of trying one's best and make KI solution, keeps KI solution being joined in the diazonium salt solution of above-mentioned preparation under 0-5 ℃ the temperature, and constantly stirring.Slowly be warming up to 60-70 ℃, be incubated after 3-4 hour, solution is cooled to room temperature, after the separation water outlet, obtain the thick product of brownish black.Extremely yellow with the solid that the NaOH solution washing obtains, further purification need be carried out wet distillation with solid transfer to distilling flask.The pure product that obtain at last are flaxen waxy solid, productive rate 86%.

In a 500ml there-necked flask that mechanical stirring device, division box and gas gatherer be housed, add 85 gram pentanoic respectively, 120 grams are to toluene iodide, and 70 restrain salt of wormwood, 0.5 the gram activated copper powder, the oil of mirbane of 0.6 gram complex phase transfer catalyst and 240ml.To liquid level, the flow velocity that keeps nitrogen is at 0.01-0.03 cubic meter per hour from the logical nitrogen of gas introduction port.Start mechanical stirring, slowly be warming up to reflux temperature (about 200 ℃), stop to feed nitrogen after backflow 10-16 hour.Stir down reaction solution is cooled to room temperature, changing reaction flask into the wet distillation flask carries out wet distillation, and the solvent oil of mirbane that steams is recycled.Distillation finishes and tells water and oil phase in the distilling flask, and the water that contains a large amount of KI is transferred to and placed sedimentation in the beaker.Oil phase dissolves with toluene, removes by filter solid impurities such as undissolved copper powder.Toluene solution distills after drying, treats that toluene distillation finishes, and changes vacuum distillation apparatus into, distills under the pressure of 5-10 mmhg, collects 180-200 ℃ cut.The product 4-methyl triphenylamine that obtains is flaxen solid, yield 76%.

The above-mentioned aqueous solution that contains KI was placed sedimentation after 4 days, removed by filter the precipitation of container bottom, carried out the atomic absorption spectrum test behind the constant volume.The content of iodine in the solution after tested, the KI that calculates recovery are 65 grams; The content of cupric ion is 43ppm.This KI solution behind a spot of KI solid of complement lysis, the reaction that can be used for preparing iodo aromatic hydrocarbons.

Embodiment 2

Each proportioning raw materials and the concrete technological process that prepare diazonium salt with para-totuidine are identical with the foregoing description 1, and used KI solution is to add 10 gram KI solids by the KI solution 150ml (containing the KI65 gram) that preparation triphenylamine reaction in the foregoing description is reclaimed to make in the iodide reaction.The technology of iodide reaction and the method for purification of product are with embodiment 1, and dried is 84% to the toluene iodide yield.

In a 1000ml there-necked flask that mechanical stirring device, division box and gas gatherer be housed, add 47 gram aniline respectively, 220 grams are to toluene iodide, and 140 restrain salt of wormwood, 0.5 the gram activated copper powder, the orthodichlorobenzene of 0.6 gram complex phase transfer catalyst and 400ml.To liquid level, the flow velocity that keeps nitrogen is at 0.01-0.03 cubic meter per hour from the logical nitrogen of gas introduction port.Start mechanical stirring, guaranteeing to make the speed of stirring big as far as possible under the unlikely situation of overflowing of reaction solution.Slowly be warming up to reflux temperature (about 180 ℃), stop to feed nitrogen after backflow 10-16 hour.Stir down reaction solution is cooled to room temperature, changing reaction flask into the wet distillation flask carries out wet distillation, the orthodichlorobenzene solvent recuperation utilization that steams.Distillation finishes and tells water and oil phase in the distilling flask, and the water that contains a large amount of KI is transferred to and placed sedimentation in the beaker.Oil phase dissolves with toluene, removes by filter solid impurities such as undissolved copper powder.Toluene solution distills after drying, treats that toluene distillation finishes, and changes vacuum distillation apparatus into, distills under the pressure of 5-10 mmhg, collects 200-220 ℃ cut.The product 4 that obtains, 4 '-dimethyl triphenylamine are the xanchromatic solid, yield 70%.

The aqueous solution that contains KI was placed sedimentation after 4 days, removed by filter the precipitation of container bottom, carried out the atomic absorption spectrum test behind the constant volume.The content of iodine in the solution after tested, the KI that calculates recovery are 128 grams; The content of cupric ion is 51ppm.This KI solution behind a spot of KI solid of complement lysis, the reaction that can be used for preparing iodo aromatic hydrocarbons equally.

Embodiment 3

61 gram Para-Anisidines are put in the round-bottomed flask of 1000ml, stir the dilute hydrochloric acid 130ml of adding 20% down, and heated and stirred is chilled to this solution about 0 ℃ to the whole dissolvings of solid.Keep temperature to add the sodium nitrite solution for preparing in advance for about 0 ℃, be stirred to solution and become blue with the check of KI starch test paper, stop to add sodium nitrite solution, continue to stir 10 minutes, the clear solution that makes is the aqueous solution of diazonium salt.

The preparation paraiodoanisole can adopt the KI solution of the processing condition of embodiment 1 with new preparation, also can adopt the method for preparing among the embodiment 2 toluene iodide to adopt the KI solution that reclaims, and the proportioning raw materials of preparation and reaction conditions control are with embodiment 1.The physical properties and the reaction yield of the paraiodoanisole of two kinds of method preparations do not have difference.

In a 500ml there-necked flask that mechanical stirring device, division box and gas gatherer be housed, add 85 gram pentanoic respectively, 70 grams are to toluene iodide, 80 gram salt of wormwood, 0.5 gram activated copper powder, the oil of mirbane of 0.6 gram complex phase transfer catalyst and 250ml.To liquid level, the flow velocity that keeps nitrogen is at 0.01-0.03 cubic meter per hour from the logical nitrogen of gas introduction port.Start mechanical stirring, slowly be warming up to reflux temperature (about 200 ℃), refluxing stopped to feed nitrogen after 10 hours.Stir down reaction solution is cooled to room temperature, changing reaction flask into the wet distillation flask carries out wet distillation, and the solvent oil of mirbane that steams is recycled.Distillation finishes and tells water and oil phase in the distilling flask, and the water that contains a large amount of KI is transferred to and placed sedimentation in the beaker.Oil phase dissolves with toluene, removes by filter solid impurities such as undissolved copper powder.Toluene solution distills after drying, treats that toluene distillation finishes, and product is with 95% ethyl alcohol recrystallization secondary, and the pure product 4-methoxyl group triphenylamine that obtains is flaxen solid, yield 68%.

The treatment process of the aqueous solution that contains KI is with embodiment 1, detects to such an extent that the content of KI is 63 grams through atomic absorption spectrum, and the content of cupric ion is 48ppm.This KI solution can be used for the preparation of iodo aromatic hydrocarbons equally.

Claims (3)

1. the preparation method of a triphenylamine derivative is characterized in that it is the synthetic iodo aromatic hydrocarbons of raw material that the first step adopts the diazols compound, and second step was to carry out condensation reaction with different aromatic amine compounds and iodo aromatic hydrocarbons.

2. the preparation method of triphenylamine derivative according to claim 1, the liquor kalii iodide that its feature produces in the second step condensation reaction can recycling use.

3. the preparation method of triphenylamine derivative according to claim 1, its feature is used the complex phase transfer catalyst of dibenzo 18-hat-6 and 18-hat-6 in the reaction of second step, wherein the mol ratio of dibenzo 18-hat-6 and 18-hat-6 is 3: 1, and the usage quantity of composite catalyst is 1-5% (wt).