CN106967020A

CN106967020A - A kind of synthetic method of 2 furoyl hydrazine

Info

Publication number: CN106967020A
Application number: CN201710355272.7A
Authority: CN
Inventors: 刘欢
Original assignee: Chongqing Li Cheng Environmental Protection Technology Co Ltd
Current assignee: Chongqing Li Cheng Environmental Protection Technology Co Ltd
Priority date: 2017-05-19
Filing date: 2017-05-19
Publication date: 2017-07-21

Abstract

The invention provides a kind of synthetic method of 2 furoyl hydrazine, this method is using 2 furoylamides, ketazine and water as raw material, the furoyl hydrazine of one-step synthesis method 2.Excessive ketazine and water are added during the course of the reaction so that the 2 furoylamides reaction in reaction system is complete, reaction terminate after using vacuum distillation will butanone azine and water remove after obtain 2 furoyl hydrazines.The inventive method technique is simple, and reaction yield is high, and the few purity of product impurity is high, and waste discharge is few, and the ammonia and acetone that by-product is reclaimed can be back to synthesis ketazine, and production cost is low, is a kind of environmental type production technology.

Description

A kind of synthetic method of 2- furoyls hydrazine

Technical field

The invention belongs to chemosynthesis technical field, and in particular to a kind of synthetic method of 2- furoyls hydrazine.

Background technology

2- furoyls hydrazine also known as furoyl hydrazine, are white to Light yellow crystals powder, fusing point is 78~79 DEG C, is slightly soluble in cold Water, is dissolved in the organic solvent such as hot water and alcohol, ketone.2- furoyl hydrazines are a variety of medicine of synthesis, the important intermediate of agricultural chemicals, are also The important source material of synthesizing heterocyclic compounds.Medically, 2- furoyls hydrazine is as diagnostic reagent, to distinguish people, ox type knot Core bacillus.

At present, the synthetic method of 2- furoyls hydrazine is mainly using 2- furancarboxylic acids as raw material, by two-step reaction（Esterification Reaction and hydrazinolysis reaction）Synthesis：The first step is that the reaction under concentrated sulfuric acid catalyst effect generates 2- with ethanol with 2- furancarboxylic acids Furyl ethyl formate, second step, which is 2- furyl ethyl formates with hydrazine hydrate, obtains 2- furoyl hydrazines being heated to reflux lower reaction. The shortcoming that prior art synthesis 2- furoyls hydrazine is present is as follows：（1）In first step esterification, because being urged using the concentrated sulfuric acid Agent, have that corrosivity is strong, high to equipment requirement, a large amount of acidic organic wastewaters can be produced or neutralized after salt-containing organic wastewater, The problems such as wastewater treatment difficulty is costly greatly, environmental hazard is big；（2）Second step hydrazinolysis reaction in, be typically with it is expensive, Dangerous big hydrazine hydrate is raw material, and overall yield of reaction only has 70% or so, and production cost is higher.

The content of the invention

In order to overcome the disadvantages mentioned above that prior art is present, the invention provides a kind of technique is simple, reaction yield is high, raw The new synthetic method of the production 2- furoyl hydrazines that cost is low, environmental pollution is small.

The technical solution adopted by the present invention is：Using 2- furoylamides, ketazine and water as raw material, at a certain temperature Reaction synthesis 2- furoyl hydrazines.Excessive ketazine and water are added during the course of the reaction so that 2- furans in reaction system Completely, the acetone and ammonia produced in course of reaction can be used for formamide after being reclaimed using rectifier unit and ammonia absorption device Synthesis ketazine, reaction removes water and remaining ketazine after terminating using vacuum distillation, and solid matter is through recrystallizing, doing 2- furoyl hydrazines are obtained after dry.

The specific processing step of the inventive method is as follows：2- furoylamides and ketazine are put into reactor, opened Stirring is opened, 100~120 DEG C are heated to, after 2- furoylamides are all dissolved in ketazine, water is slowly dropped to instead Answer in kettle, controlling reaction temperature is 100 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 Acetone is produced at~58 DEG C and ammonia is reclaimed, water vapour, which is flowed back to after being condensed in rectifying column in reactor, continues to participate in reaction；Water The follow-up continuous insulation reaction of completion of dropping, therebetween in sampling analysis reaction solution 2- furoylamides content, the 2- in question response liquid After furoylamide has been reacted, the ketazine and water in reactor are all steamed with negative pressure, the solids in reactor Matter with ethyl alcohol recrystallization, dry after obtain 2- furoyl hydrazine finished products.

In above-mentioned steps, the mol ratio of 2- furoylamides and ketazine is 1: 1.5~2,2- furoylamides and water Mol ratio be 1: 2.5~4.Its reaction equation is as follows：

Compared with prior art, beneficial effects of the present invention and advantage are as follows：

The present invention is using ketazine that is with low cost, being readily synthesized as raw material, one-step synthesis method 2- furoyl hydrazines, technique letter Single, reaction yield is high（With ketazine rate of collecting more than 90%）, simply, the few purity of product impurity is high for post processing, discarded object row Put few, the ammonia and acetone that by-product is reclaimed can be back to synthesis ketazine, and production cost is low, be a kind of environmental type production work Skill.

Embodiment

Embodiment 1

2- furoylamides 111.1g, ketazine 168g are placed in four mouthfuls with stirring, dropping funel, thermometer and rectifying column In flask, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated to 100~ 120 DEG C, after 2- furoylamides are all dissolved in ketazine, water 45ml is slowly dropped in four-hole boiling flask, control reaction Temperature is 100 DEG C~120 DEG C, and after the gas that reaction is produced enters rectifying column, third is produced at 54 DEG C~58 DEG C of column top temperature Ketone simultaneously reclaims ammonia, is flowed back to after water vapour condensation in flask and continues to participate in reaction；The follow-up continuous insulation reaction of water completion of dropping, therebetween After 2- furoylamides in the content of 2- furoylamides in sampling analysis reaction solution, question response liquid have been reacted, by flask In ketazine and water all steamed with negative pressure, the solid matter in flask with ethyl alcohol recrystallization, dry after obtain 2- furans Formylhydrazine 117.5g.

Embodiment 2

2- furoylamides 111.1g, ketazine 196g are placed in four mouthfuls with stirring, dropping funel, thermometer and rectifying column In flask, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated to 100~ 120 DEG C, after 2- furoylamides are all dissolved in ketazine, water 60ml is slowly dropped in four-hole boiling flask, control reaction Temperature is 100 DEG C~120 DEG C, and after the gas that reaction is produced enters rectifying column, third is produced at 54 DEG C~58 DEG C of column top temperature Ketone simultaneously reclaims ammonia, is flowed back to after water vapour condensation in flask and continues to participate in reaction；The follow-up continuous insulation reaction of water completion of dropping, therebetween After 2- furoylamides in the content of 2- furoylamides in sampling analysis reaction solution, question response liquid have been reacted, by flask In ketazine and water all steamed with negative pressure, the solid matter in flask with ethyl alcohol recrystallization, dry after obtain 2- furans Formylhydrazine 118.8g.

Embodiment 3

2- furoylamides 111.1g, ketazine 224g are placed in four mouthfuls with stirring, dropping funel, thermometer and rectifying column In flask, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated to 100~ 120 DEG C, after 2- furoylamides are all dissolved in ketazine, water 70ml is slowly dropped in four-hole boiling flask, control reaction Temperature is 100 DEG C~120 DEG C, and after the gas that reaction is produced enters rectifying column, third is produced at 54 DEG C~58 DEG C of column top temperature Ketone simultaneously reclaims ammonia, is flowed back to after water vapour condensation in flask and continues to participate in reaction；The follow-up continuous insulation reaction of water completion of dropping, therebetween After 2- furoylamides in the content of 2- furoylamides in sampling analysis reaction solution, question response liquid have been reacted, by flask In ketazine and water all steamed with negative pressure, the solid matter in flask with ethyl alcohol recrystallization, dry after obtain 2- furans Formylhydrazine 119.6g.

Claims

1. a kind of synthetic method of 2- furoyls hydrazine, it is characterised in that comprise the following steps：By 2- furoylamides and acetone Azine is put into reactor, is opened stirring, is heated to 100~120 DEG C, treats that 2- furoylamides are all dissolved in ketazine Afterwards, water is slowly dropped in reactor, controlling reaction temperature is 100 DEG C~120 DEG C, the gas for reacting generation is introduced into rectifying In tower, extraction acetone and ammonia is reclaimed at 54 DEG C~58 DEG C of tower top temperature, water vapour flows back to reaction after being condensed in rectifying column Reaction is continued to participate in kettle；The follow-up continuous insulation reaction of water completion of dropping, therebetween 2- furoylamides in sampling analysis reaction solution After 2- furoylamides in content, question response liquid have been reacted, the ketazine and water in reactor are all steamed with negative pressure Go out, the solid matter in reactor with ethyl alcohol recrystallization, dry after obtain 2- furoyl hydrazine finished products；In above-mentioned steps, 2- furans The mol ratio of formamide and ketazine of muttering is that the mol ratio of 1: 1.5~2,2- furoylamides and water is 1: 2.5~4.