阅读说明：本技术 一种二氨基二苯乙烷化合物的合成方法 (Synthesis method of diaminodiphenylethane compound ) 是由 孙绪兵 王同涛 陈永平 杨明生 李和娟 李振兴 于 2019-12-03 设计创作，主要内容包括：本发明公开一种二氨基二苯乙烷化合物的合成方法,涉及化合物制备技术领域；向离子液体催化剂、硝基邻二甲苯中加入碱性溶液,配制成硝基邻二甲苯溶液,硝基邻二甲苯溶液在连续通氧气的作用下进行偶联反应,中和至中性,若碱性溶液中溶剂与水互溶,则过滤、水洗,得到二甲基二硝基二苯乙烷固体,将二甲基二硝基二苯乙烷固体制成二甲基二硝基二苯乙烷溶液,若碱性溶液中溶剂与水不互溶,则分层,得到油层为二甲基二硝基二苯乙烷溶液,将二甲基二硝基二苯乙烷溶液在连续通氢气的作用下进行加氢反应,反应液分层后,油层进行蒸馏,得到二甲基二氨基二苯乙烷。(The invention discloses a synthesis method of a diaminodiphenylethane compound, relating to the technical field of compound preparation; adding an alkaline solution into an ionic liquid catalyst and nitro-o-xylene to prepare a nitro-o-xylene solution, carrying out coupling reaction on the nitro-o-xylene solution under the action of continuous oxygen introduction, neutralizing to neutrality, filtering and washing to obtain a dimethyl dinitro-diphenylethane solid if a solvent in the alkaline solution is mutually soluble with water, preparing the dimethyl dinitro-diphenylethane solid into a dimethyl dinitro-diphenylethane solution, layering if the solvent in the alkaline solution is not mutually soluble with water to obtain a dimethyl dinitro-diphenylethane solution as an oil layer, carrying out hydrogenation reaction on the dimethyl dinitro-diphenylethane solution under the action of continuous hydrogen introduction, and distilling the oil layer after reaction liquid layering to obtain the dimethyl diamino-diphenylethane.)

1. A process for synthesizing diamino-diphenylethane compound features that the alkaline solution is added to ionic liquid catalyst and nitro-o-xylene to obtain nitro-o-xylene solution or

The nitro-o-xylene solution is subjected to coupling reaction under the action of continuous oxygen introduction, neutralized to be neutral,

if the solvent in the alkaline solution is mutually soluble with water, filtering and washing to obtain dimethyl dinitrodiphenylethane solid, preparing the dimethyl dinitrodiphenylethane solid into dimethyl dinitrodiphenylethane solution,

if the solvent in the alkaline solution is not mutually soluble with water, the oil layer is layered to obtain a dimethyl dinitrodiphenylethane solution, the dimethyl dinitrodiphenylethane solution is subjected to hydrogenation reaction under the action of continuously introducing hydrogen, and after the reaction liquid is layered, the oil layer is distilled to obtain the dimethyl diaminodiphenylethane.

2. The synthesis method according to claim 1, wherein the solvent of the alkaline solution includes but is not limited to the following solvents: methanol, ethanol, propanol, butanol, tert-butanol, pentanol, tetrahydrofuran, dioxane, N-dimethylformamide, acetone, butanone, pentanone, dichloroethane, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, cyclohexane, ethyl acetate,

the mass ratio of the solvent of the alkaline solution to the nitro-o-xylene is 1-10: 1.

3. The synthesis process according to claim 1 or 2, characterized in that the dimethyl dinitrodiphenylethane solid is obtained by using but not limited to the following solvents: butanone, pentanone, dichloroethane, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, cyclohexane, ethyl acetate,

preparing a dimethyl dinitrodiphenylethane solution, wherein the mass ratio of the solvent to the nitro-o-xylene is 1-10: 1.

4. The synthesis method according to claim 3, characterized in that the ionic liquid catalyst includes but is not limited to tetrafluoroborated 1-butyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (BDBU) BF4, hexafluorophosphorylated 1-butyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (BDBU) PF6, tetrafluoroborated 1-hexyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (HDBU) BF4, hexafluorophosphorylated 1-hexyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (HDBU) PF6, tetrafluoroborated 1-octyl-1, 8-diazabicyclo (BU 5, 4, 0) undec-7-ene (ODBU) BF4, one or more of hexafluorophosphorylation 1-octyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (ODBU) PF6,

the mass ratio of the ionic liquid catalyst to the nitro-o-xylene is 0.01-1: 1.

5. The synthesis method according to claim 1 or 4, wherein the solute of the alkaline solution includes but is not limited to one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium hydride, sodium ethoxide, triethylamine, triethanolamine, sodium tert-butoxide, potassium tert-butoxide and sodium amide,

the molar ratio of the solute of the alkaline solution to the nitro-o-xylene is 0.1-5: 1.

6. The synthesis process as claimed in claim 5, wherein the coupling reaction is carried out in a microchannel reactor and the hydrogenation reaction is carried out in a fixed bed reactor.

7. The synthesis process as claimed in claim 6, characterized in that the feeding rate of the nitro-o-xylene solution into the fixed bed reactor is from 500kg/h to 4000 kg/h.

8. The synthesis process as claimed in claim 6 or 7, characterized in that the feed rate of oxygen into the fixed-bed reactor is from 30kg/h to 200 kg/h.

9. A diamino diphenylethane compound is characterized by being synthesized by the following method: adding an alkaline solution into an ionic liquid catalyst and the nitro-o-xylene to prepare a nitro-o-xylene solution,

the nitro-o-xylene solution is subjected to coupling reaction under the action of continuous oxygen introduction, neutralized to be neutral,

if the solvent in the alkaline solution is mutually soluble with water, filtering and washing to obtain dimethyl dinitrodiphenylethane solid, preparing the dimethyl dinitrodiphenylethane solid into dimethyl dinitrodiphenylethane solution,

if the solvent in the alkaline solution is not mutually soluble with water, the oil layer is layered to obtain a dimethyl dinitrodiphenylethane solution, the dimethyl dinitrodiphenylethane solution is subjected to hydrogenation reaction under the action of continuously introducing hydrogen, and after the reaction liquid is layered, the oil layer is distilled to obtain the dimethyl diaminodiphenylethane.

10. Use of a diaminodiphenylethane compound according to claim 9.

Technical Field

The invention discloses a synthesis method of a diaminodiphenylethane compound, and relates to the technical field of compound preparation.

Background

The derivatives of the diaminodiphenylethane compound are important intermediates for preparing various chemical raw materials, dyes, medicines, pesticides, various auxiliaries, optical materials, electronic materials and devices thereof.

When the diaminodiphenylethane compound is synthesized, the used solid catalyst must have the conditions of high activity, good selectivity and long-term stability as much as possible, and must also have high mechanical strength and good heat transfer, mass transfer and hydrodynamic properties, the use conditions are harsh, the problems of long reaction period, high consumption, high cost and high waste amount are easily caused, and the large-scale industrial production is not facilitated.

Disclosure of Invention

The invention aims at the problems of the prior art and discloses a method for synthesizing a diaminodiphenylethane compound, which takes 3- (or 4-) nitro-o-xylene as an initial raw material and prepares dimethyl dinitrodiphenylethane through coupling reaction under the strong alkaline condition and the action of an ionic liquid catalyst and under the condition that oxygen is taken as an oxidant; then the dimethyl diamino diphenylethane is prepared by catalytic hydrogenation. The invention provides a synthesis method of a diaminodiphenylethane compound, which has the advantages of high catalytic activity, high yield, continuous operation, less storage of online dangerous materials, safer relative operation, easy stable control, stable product quality, high yield, short reaction period, lower consumption, lower cost and less three wastes, and meets the requirement of clean production by adopting an environment-friendly oxidant, namely oxygen oxidation and hydrogenation reduction, thereby being beneficial to large-scale industrial production.

The specific scheme provided by the invention is as follows:

a method for synthesizing a diaminodiphenylethane compound comprises the following steps: adding an alkaline solution into an ionic liquid catalyst and the nitro-o-xylene to prepare a nitro-o-xylene solution,

the nitro-o-xylene solution is subjected to coupling reaction under the action of continuous oxygen introduction, neutralized to be neutral,

if the solvent in the alkaline solution is mutually soluble with water, filtering and washing to obtain dimethyl dinitrodiphenylethane solid, preparing the dimethyl dinitrodiphenylethane solid into dimethyl dinitrodiphenylethane solution,

if the solvent in the alkaline solution is not mutually soluble with water, the oil layer is layered to obtain a dimethyl dinitrodiphenylethane solution, the dimethyl dinitrodiphenylethane solution is subjected to hydrogenation reaction under the action of continuously introducing hydrogen, and after the reaction liquid is layered, the oil layer is distilled to obtain the dimethyl diaminodiphenylethane.

The solvent of the alkaline solution in the synthesis method includes but is not limited to the following solvents: methanol, ethanol, propanol, butanol, tert-butanol, pentanol, tetrahydrofuran, dioxane, N-dimethylformamide, acetone, butanone, pentanone, dichloroethane, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, cyclohexane, ethyl acetate,

the mass ratio of the solvent of the alkaline solution to the nitro-o-xylene is 1-10: 1.

In the synthesis method, dimethyl dinitrodiphenylethane solid is utilized and is not limited to the following solvents: butanone, pentanone, dichloroethane, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, cyclohexane, ethyl acetate,

preparing a dimethyl dinitrodiphenylethane solution, wherein the mass ratio of the solvent to the nitro-o-xylene is 1-10: 1.

The ionic liquid catalyst in the synthesis method includes, but is not limited to, tetrafluoroborated 1-butyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (BDBU) BF4, hexafluorophosphorylated 1-butyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (BDBU) PF6, tetrafluoroborated 1-hexyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (HDBU) BF4, hexafluorophosphorylated 1-hexyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (HDBU) PF6, tetrafluoroborated 1-octyl-1, 8-diazabicyclo (5, 4, 0) undec-7-ene (ODBU) BF4, hexafluorophosphorylated 1-octyl-1, one or more of 8-diazabicyclo (5, 4, 0) undec-7-ene (ODBU) PF6,

the mass ratio of the ionic liquid catalyst to the nitro-o-xylene is 0.01-1: 1.

The solute of the alkaline solution in the synthesis method comprises but is not limited to one or a mixture of more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium hydride, sodium ethoxide, triethylamine, triethanolamine, sodium tert-butoxide, potassium tert-butoxide and sodium amide,

the molar ratio of the solute of the alkaline solution to the nitro-o-xylene is 0.1-5: 1.

In the synthesis method, the coupling reaction is carried out in a microchannel reactor, and the hydrogenation reaction is carried out in a fixed bed reactor.

In the synthesis method, the feeding rate of the nitro-o-xylene solution entering the fixed bed reactor is 500kg/h-4000 kg/h.

In the synthesis method, the feeding rate of oxygen entering the fixed bed reactor is 30kg/h-200 kg/h.

The catalyst adopted in the hydrogenation reaction in the synthesis method is a Pd/C catalyst.

The coupling reaction equation in the synthesis method is as follows:

or the following steps:

the equation for the hydrogenation reduction reaction is:

or the following steps:

a diaminodiphenylethane compound is synthesized by the following method: adding an alkaline solution into an ionic liquid catalyst and the nitro-o-xylene to prepare a nitro-o-xylene solution,

the nitro-o-xylene solution is subjected to coupling reaction under the action of continuous oxygen introduction, neutralized to be neutral,

if the solvent in the alkaline solution is mutually soluble with water, filtering and washing to obtain dimethyl dinitrodiphenylethane solid, preparing the dimethyl dinitrodiphenylethane solid into dimethyl dinitrodiphenylethane solution,

if the solvent in the alkaline solution is not mutually soluble with water, the oil layer is layered to obtain a dimethyl dinitrodiphenylethane solution, the dimethyl dinitrodiphenylethane solution is subjected to hydrogenation reaction under the action of continuously introducing hydrogen, and after the reaction liquid is layered, the oil layer is distilled to obtain the dimethyl diaminodiphenylethane.

The application of the diaminodiphenylethane compound is provided. For example, derivatives of diaminodiphenylethane compounds are used to prepare chemical raw materials, dyes, medicines, pesticides, various auxiliaries, optical materials, electronic materials and important intermediates of devices thereof.

The invention has the advantages that:

the invention provides a method for synthesizing a diaminodiphenylethane compound, which selects ionic liquid as a catalyst for coupling reaction, overcomes the defects of the existing solid catalyst and homogeneous catalyst, has high catalytic activity and high yield, has less on-line dangerous materials storage in continuous reaction, is relatively safe to operate, is easy to stably control, realizes continuous and stable operation, and is suitable for large-scale industrial mass production. The temperature and the feeding speed can be simply and controllably controlled, the reaction efficiency is correspondingly improved due to the great improvement of the reaction speed, the production process is changed from the existing intermittent operation into the continuous operation, the reaction time is shortened, the energy consumption is reduced, reaction byproducts are correspondingly and greatly reduced due to the great reduction of the reaction time, the selectivity is high, the obtained product has less impurities, and the product purity can reach more than 99.0 percent; the product has high synthesis yield which is more than or equal to 88 percent calculated by the nitro-o-xylene, low consumption and low cost, and simultaneously, the green and environment-friendly oxidant oxygen is adopted for oxidation, and the hydrogenation reduction also meets the requirement of clean production.

Drawings

FIG. 1 is a schematic flow diagram of the process of the present invention.

Detailed Description

The invention provides a synthesis method of diaminodiphenylethane compound, which comprises adding alkaline solution into ionic liquid catalyst and nitro-o-xylene to prepare nitro-o-xylene solution,

the nitro-o-xylene solution is subjected to coupling reaction under the action of continuous oxygen introduction, neutralized to be neutral,

if the solvent in the alkaline solution is mutually soluble with water, filtering and washing to obtain dimethyl dinitrodiphenylethane solid, preparing the dimethyl dinitrodiphenylethane solid into dimethyl dinitrodiphenylethane solution,

if the solvent in the alkaline solution is not mutually soluble with water, the oil layer is layered to obtain a dimethyl dinitrodiphenylethane solution, the dimethyl dinitrodiphenylethane solution is subjected to hydrogenation reaction under the action of continuously introducing hydrogen, and after the reaction liquid is layered, the oil layer is distilled to obtain the dimethyl diaminodiphenylethane.

Simultaneously provides a diaminodiphenylethane compound corresponding to the method, and is synthesized by the method.

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.