CN107033025A

CN107033025A - A kind of preparation method of 2,4,6 trinitrophenyl-hydrazine

Info

Publication number: CN107033025A
Application number: CN201710424098.7A
Authority: CN
Inventors: 李博强
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-06-07
Filing date: 2017-06-07
Publication date: 2017-08-11

Abstract

The invention provides a kind of preparation method of 2,4,6 trinitrophenyl-hydrazines, this method is 2,4,6 trinitrophenyl-hydrazines of reaction synthesis at a certain temperature for raw material with 2,4,6 trinitro-chlorobenzenes, ketazine and sodium hydroxide.Add excessive ketazine and sodium hydroxide during the course of the reaction so that in reaction system 2,4, the reaction of 6 trinitro-chlorobenzenes is complete, reaction removes water and remaining ketazine after terminating using vacuum distillation, solid matter in reactor is dissolved with toluene to be extracted, 2,4,6 trinitrophenyl-hydrazines are obtained after toluene solution vacuum distillation is removed into toluene again.Compared with prior art, the inventive method technique is simple, and side reaction is few, and reaction yield is high, and post processing is simple, and product impurity is few, purity is high, and production cost is low.

Description

A kind of preparation method of 2,4,6- trinitrophenyl-hydrazines

Technical field

The invention belongs to chemosynthesis technical field, and in particular to the preparation method of one kind 2,4,6- trinitrophenyl-hydrazines.

Background technology

2,4,6- trinitrophenyl-hydrazines are salmon pink crystalline powder, and 186 DEG C of fusing point is dissolved in inorganic acid weak solution, hot alcohol, first Benzene, is slightly soluble in water and alcohol.2,4,6- trinitrophenyl-hydrazines are a kind of important fine chemical materials, are the centres for synthesizing schiff bases Body is also inspection and determines the reagent of aldehyde, ketone and sugar.

Current 2, the preparation methods of 4,6- trinitrophenyl-hydrazines be typically with 2,4,6- trinitro-chlorobenzenes and hydrazine hydrate for raw material, It is made with ethanol as solvent heating reflux reaction.The problem of this method is present and have the disadvantage：（1）Side reaction is more, is being heated to reflux Produce during 2,4,6- trinitrophenyl-hydrazines hydrazine hydrate can and ethanol react generation ethyl hydrazine, make the impurity of generation many, Post processing is complicated, and yield is low（Only 80% or so）；（2）During the course of the reaction can by-product and 2,4,6- trinitrophenyl-hydrazine equimolars Hydrazine hydrochloride, hydrazine hydrate consumption is big, and because hydrazine hydrate is expensive, production cost is high.

The content of the invention

In order to overcome the disadvantages mentioned above that prior art is present, the invention provides a kind of side reaction is few, high income, raw material valency The new method for preparing 2,4,6- trinitrophenyl-hydrazines that lattice are cheap, production cost is low.

The technical solution adopted by the present invention is：With 2,4,6- trinitro-chlorobenzenes, ketazine and sodium hydroxide for raw material, Reaction synthesis 2,4,6- trinitrophenyl-hydrazines under certain temperature.Excessive ketazine is added during the course of the reaction（It is both reactant It is also solvent）With sodium hydroxide so that 2,4, the 6- trinitro-chlorobenzenes reaction in reaction system is complete, produced in course of reaction Acetone is reclaimed with rectifier unit, and reaction removes consolidating in water and remaining ketazine, reactor after terminating using vacuum distillation Body material is dissolved with toluene to be extracted, then will obtain 2,4,6- trinitrophenyl-hydrazines after toluene solution vacuum distillation removing toluene.

The specific processing step of the inventive method is as follows：2,4,6- trinitro-chlorobenzenes and ketazine are put into reactor In, stirring is opened, 120 DEG C is heated to, sodium hydroxide solution is slowly dropped in reactor, controlling reaction temperature is 90 DEG C~120 DEG C, the gas that produces will be reacted and be introduced into rectifying column, acetone is produced at 54 DEG C~58 DEG C of tower top temperature, into essence Evaporate tower water vapour and ketazine it is condensed after flow back in reactor and continue to participate in reaction；After sodium hydroxide solution completion of dropping Continue insulation reaction, terminate reaction after rectifying column tower top flows out without acetone, by the water in reactor and ketazine negative pressure All steam, the solid matter in reactor is dissolved with toluene to be extracted, then will be obtained after toluene solution vacuum distillation removing toluene 2,4,6- trinitrophenyl-hydrazines.

In above-mentioned steps, the mol ratio of 2,4,6- trinitro-chlorobenzenes and ketazine is 1: 2~3,2,4,6- trinitro- chlorine The mol ratio of benzene and sodium hydroxide is 1: 1.5~2, and the concentration of sodium hydroxide solution is 20%~30%.Its reaction equation is as follows：

Compared with prior art, the beneficial effects of the invention are as follows：The inventive method technique is simple, and side reaction is few, and post processing is simple, Product impurity is few, purity is high（Content is more than 99%）；Ketazine is with low cost, be readily synthesized, and reaction yield is high（With acetone Azine rate of collecting is more than 90%）, the acetone that by-product is reclaimed during the course of the reaction is the raw material for synthesizing ketazine, recyclable to make With production cost is low.

Embodiment

Embodiment 1

2,4,6- trinitro-chlorobenzenes 247.6g and ketazine 224g are put into stirring, dropping funel, thermometer and rectifying In the four-hole boiling flask of post, open stirring, solution is heated to 120 DEG C, with dropping funel by concentration be 20% sodium hydroxide Solution 300ml is slowly dropped in four-hole boiling flask, and controlling reaction temperature is 90 DEG C~120 DEG C, when the gas that reaction is produced enters After rectifying column, acetone is produced at 54 DEG C~58 DEG C of column top temperature, into rectifying column water vapour and ketazine it is condensed after Flow back in flask and continue to participate in reaction；The follow-up continuous insulation reaction of sodium hydroxide solution completion of dropping, when rectifying column capital receiver Without reaction is terminated after acetone outflow, the water and ketazine in flask are all steamed with negative pressure, the solid matter in flask is used Toluene dissolving is extracted, then will obtain 2,4,6- trinitrophenyl-hydrazine 233.5g after toluene solution vacuum distillation removing toluene.

Embodiment 2

2,4,6- trinitro-chlorobenzenes 247.6g and ketazine 280g are put into stirring, dropping funel, thermometer and rectifying In the four-hole boiling flask of post, open stirring, solution is heated to 120 DEG C, with dropping funel by concentration be 25% sodium hydroxide Solution 280ml is slowly dropped in four-hole boiling flask, and controlling reaction temperature is 90 DEG C~120 DEG C, when the gas that reaction is produced enters After rectifying column, acetone is produced at 54 DEG C~58 DEG C of column top temperature, into rectifying column water vapour and ketazine it is condensed after Flow back in flask and continue to participate in reaction；The follow-up continuous insulation reaction of sodium hydroxide solution completion of dropping, when rectifying column capital receiver Without reaction is terminated after acetone outflow, the water and ketazine in flask are all steamed with negative pressure, the solid matter in flask is used Toluene dissolving is extracted, then will obtain 2,4,6- trinitrophenyl-hydrazine 234.6g after toluene solution vacuum distillation removing toluene.

Embodiment 3

2,4,6- trinitro-chlorobenzenes 247.6g and ketazine 336g are put into stirring, dropping funel, thermometer and rectifying In the four-hole boiling flask of post, open stirring, solution is heated to 120 DEG C, with dropping funel by concentration be 30% sodium hydroxide Solution 240ml is slowly dropped in four-hole boiling flask, and controlling reaction temperature is 90 DEG C~120 DEG C, when the gas that reaction is produced enters After rectifying column, acetone is produced at 54 DEG C~58 DEG C of column top temperature, into rectifying column water vapour and ketazine it is condensed after Flow back in flask and continue to participate in reaction；The follow-up continuous insulation reaction of sodium hydroxide solution completion of dropping, when rectifying column capital receiver Without reaction is terminated after acetone outflow, the water and ketazine in flask are all steamed with negative pressure, the solid matter in flask is used Toluene dissolving is extracted, then will obtain 2,4,6- trinitrophenyl-hydrazine 235.8g after toluene solution vacuum distillation removing toluene.

Claims

1. one kind 2,4, the preparation method of 6- trinitrophenyl-hydrazines, it is characterised in that comprise the following steps：By 2,4,6- trinitro- chlorine Benzene and ketazine are put into reactor, are opened stirring, are heated to 120 DEG C, sodium hydroxide solution is slowly dropped to instead Answer in kettle, controlling reaction temperature is 90 DEG C~120 DEG C, the gas that produces will be reacted and be introduced into rectifying column, in 54 DEG C of tower top temperature Produce acetone at~58 DEG C, into rectifying column water vapour and ketazine it is condensed after flow back in reactor continue to participate in it is anti- Should；The follow-up continuous insulation reaction of sodium hydroxide solution completion of dropping, terminates reaction after rectifying column tower top flows out without acetone, will react Water and ketazine in kettle are all steamed with negative pressure, and the solid matter in reactor is dissolved with toluene to be extracted, then toluene is molten Liquid vacuum distillation obtains 2,4,6- trinitrophenyl-hydrazines after removing toluene；In above-mentioned steps, 2,4,6- trinitro-chlorobenzenes and acetone connect The mol ratio of nitrogen is that the mol ratio of 1: 2~3,2,4,6- trinitro-chlorobenzenes and sodium hydroxide is 1: 1.5~2, sodium hydroxide solution Concentration be 20%~30%.