CN108250100A - A kind of synthetic method of acethydrazide - Google Patents
A kind of synthetic method of acethydrazide Download PDFInfo
- Publication number
- CN108250100A CN108250100A CN201810081038.4A CN201810081038A CN108250100A CN 108250100 A CN108250100 A CN 108250100A CN 201810081038 A CN201810081038 A CN 201810081038A CN 108250100 A CN108250100 A CN 108250100A
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- reaction
- hydrazine hydrate
- acethydrazide
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/04—Preparation of hydrazides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of acethydrazide, this method is using acetic acid and hydrazine hydrate as raw material, makees catalyst using 5 acidic zeolites of ZSM, the acethydrazide of reaction synthesis at a certain temperature.It keeps hydrazine hydrate excessive in the reaction system, and the water for reacting generation is constantly separated from reaction system, effectively promote the progress of hydrazidesization reaction, shorten the reaction time, improve reaction yield.Compared with prior art, the present invention makees catalyst using 5 acidic zeolites of ZSM, excellent catalytic effect, reaction yield is high, and catalyst is easily recycled, is reusable, without acetic acid is esterified, shorten processing step, production cost is reduced, reduces the discharge of waste, is a kind of environmental type production technology.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of synthetic method of acethydrazide.
Background technology
Acethydrazide is white crystals, and 58~68 °C of fusing point is soluble easily in water, is a kind of important chemical raw material, it can be used
To synthesize analgesic, anticancer drug, tooth corrosion inhibiter, platelet activity index inhibitor, the antifoggant of colored fixing solution, stabilization
Agent, pickling of metal preservative etc..It is that raw material prepares carbamate insecticides especially with acethydrazide, can avoids directly using
Isonitrile acid methyl esters is poisoned caused by human body and environment.
At present, the synthetic method of acethydrazide is mainly using acetic acid, ethyl alcohol and hydrazine hydrate as raw material, by two-step reaction（Ester
Change reaction and hydrazinolysis reaction）It is made：The first step is to carry out esterification life under concentrated sulfuric acid catalyst effect with acetic acid and ethyl alcohol
Into ethyl acetate, second step is that ethyl acetate and hydrazine hydrate heat progress hydrazinolysis in alcohol solvent and acethydrazide are obtained by the reaction.It is existing
The shortcomings that synthesizing acethydrazide with the presence of technology is as follows：（1）In first step esterification, used catalyst concentrated sulfuric acid corrosion
Property it is strong, high to equipment requirement, a large amount of acidic organic wastewaters can be generated, salt content and COD contents after which is handled with alkali neutralization
It is all very high, since treatment of Organic Wastewater difficulty is big, processing cost is high, discharge capacity is big, easily cause environmental pollution；（2）Using two steps
Reaction prepares that acethydrazide is also more there are operating procedure, and technique is cumbersome, and process is complicated, and high energy consumption, side reaction impurity is more, and total recovery is low
（There was only 80~90% with Acetometer）, the problems such as production cost is high.
Invention content
In order to overcome disadvantages mentioned above of the existing technology, the present invention provides one kind is simple for process, reaction yield is high, useless
Gurry discharges less, production cost is low, energy-saving and environment-friendly acethydrazide new synthetic method.
The technical solution adopted by the present invention is：Under nitrogen protection, by acetic acid and hydrazine hydrate under catalyst action and
Hydrazides is carried out under certain temperature, acethydrazide is obtained by the reaction, hydrazine hydrate water that is excessive, and generation will being reacted is kept in reaction system
It is constantly separated from reaction system（Reaction balance is promoted to be moved to positive direction, is received with shortening the reaction time, improving reaction
Rate）, the acetic acid that reaction is had neither part nor lot in reaction solution and hydrazine hydrate are steamed into recycling, acetic acid and hydrazine hydrate after reaction and all steamed
It is recovered by filtration catalyst after going out while hot, acethydrazide finished product is obtained with pure water, vacuum drying after filtrate crystallisation by cooling.Above-mentioned acyl
Hydrazineization reaction used catalyst is ZSM-5 acidic zeolites（Grain size is 1~2mm）, the molecular sieve catalyst through regeneration at
It is reusable after reason.
The specific processing step of the method for the present invention is as follows：Under nitrogen protection, acetic acid, hydrazine hydrate and ZSM-5 acidity are boiled
Stone molecular sieve catalyst is put into the reaction kettle with rectifying column, is opened stirring, reflux is heated to, when steam enters rectifying
After tower, in 98 DEG C~100 DEG C extraction vapor of tower top temperature, react 4~6 hours at a reflux temperature, when rectifying tower top is without cold
React and terminates after condensate outflow, continue heating distillation, produced in 100 DEG C~120 DEG C of tower top temperature have neither part nor lot in the acetic acid of reaction with
Liquid in kettle after acetic acid and hydrazine hydrate are all steamed, is poured out filtering, filtrate is through crystallisation by cooling, pure water by hydrazine hydrate while hot
Acethydrazide finished product is obtained after washing, vacuum drying.ZSM-5 acidic zeolites are obtained after filter cake pure water, drying.
In above-mentioned steps, the mass ratio of acetic acid and hydrazine hydrate is the addition of 1: 1~1.5, ZSM-5 acidic zeolites
It is the 10%~20% of quality of acetic acid, the content of hydrazine hydrate used is more than 80%.
Above-mentioned hydrazides reaction equation is as follows：
CH3COOH + NH2NH2·H2O → CH3CONHNH2 + 2H2O
Compared with prior art, the beneficial effects of the invention are as follows：The present invention is using acetic acid and hydrazine hydrate as raw material, with ZSM-5 acidity
Zeolite molecular sieve makees catalyst, single step reaction synthesis acethydrazide.The synthetic method is easy to operate, and reaction yield is high（With acetic acid and
Hydrazine hydrate rate of collecting is more than 90%）, product impurity lacks purity height, and it is anti-to eliminate esterification for the recyclable reuse of catalyst
Should, processing step is shortened, reduces production cost, reduces the discharge of waste, is a kind of environmental type production technology.
Specific embodiment
Percentage composition as described below is mass fraction, and all steps are completed under nitrogen protection.
Embodiment 1
Acetic acid 300g, the hydrazine hydrate 375g and ZSM-5 acidic zeolite 30g that content is 80% are put into stirring, temperature
In the four-hole boiling flask of meter and rectifying column, stirring is opened, reflux is heated to, after steam enters rectifying column, in column top temperature
98 DEG C~100 DEG C extraction vapor, react 4~6 hours, knot are reacted after rectifying capital evaporated condensation water flows out at a reflux temperature
Beam continues heating distillation, the acetic acid and hydrazine hydrate of reaction is had neither part nor lot in 100 DEG C~120 DEG C recycling of column top temperature, when acetic acid and water
Hydrazine is closed by after whole steamed, liquid in flask is poured out into filtering while hot, filtrate is after crystallisation by cooling, pure water, vacuum drying
Obtain acethydrazide 342.8g.
Embodiment 2
Acetic acid 300g, the hydrazine hydrate 420g and ZSM-5 acidic zeolite 45g that content is 90% are put into stirring, temperature
In the four-hole boiling flask of meter and rectifying column, stirring is opened, reflux is heated to, after steam enters rectifying column, in column top temperature
98 DEG C~100 DEG C extraction vapor, react 4~6 hours, knot are reacted after rectifying capital evaporated condensation water flows out at a reflux temperature
Beam continues heating distillation, the acetic acid and hydrazine hydrate of reaction is had neither part nor lot in 100 DEG C~120 DEG C recycling of column top temperature, when acetic acid and water
Hydrazine is closed by after whole steamed, liquid in flask is poured out into filtering while hot, filtrate is after crystallisation by cooling, pure water, vacuum drying
Obtain acethydrazide 348.2g.
Embodiment 3
Acetic acid 300g, the hydrazine hydrate 450g and ZSM-5 acidic zeolite 60g that content is 99% are put into stirring, temperature
In the four-hole boiling flask of meter and rectifying column, stirring is opened, reflux is heated to, after steam enters rectifying column, in column top temperature
98 DEG C~100 DEG C extraction vapor, react 4~6 hours, knot are reacted after rectifying capital evaporated condensation water flows out at a reflux temperature
Beam continues heating distillation, the acetic acid and hydrazine hydrate of reaction is had neither part nor lot in 100 DEG C~120 DEG C recycling of column top temperature, when acetic acid and water
Hydrazine is closed by after whole steamed, liquid in flask is poured out into filtering while hot, filtrate is after crystallisation by cooling, pure water, vacuum drying
Obtain acethydrazide 353.1g.
Claims (1)
1. a kind of synthetic method of acethydrazide, it is characterised in that include the following steps：Under nitrogen protection, by acetic acid, hydrazine hydrate
It is put into the reaction kettle with rectifying column with catalyst, opens stirring, be heated to reflux, after steam enters rectifying column,
In 98 DEG C~100 DEG C extraction vapor of tower top temperature, react 4~6 hours at a reflux temperature, when rectifying tower top frozen-free flow
Reaction terminates after going out, and continues heating distillation, and the acetic acid and hydrazine hydrate of reaction are had neither part nor lot in 100 DEG C~120 DEG C extraction of tower top temperature,
After acetic acid and hydrazine hydrate are all steamed, liquid in kettle is poured out into filtering while hot, filtrate is through crystallisation by cooling, pure water, very
Acethydrazide finished product is obtained after sky is dry；In above-mentioned steps, the mass ratio of acetic acid and hydrazine hydrate is 1: 1~1.5, and the catalyst is
ZSM-5 acidic zeolites（Grain size is 1~2mm）, the dosage of catalyst is the 10%~20% of quality of acetic acid, hydrazine hydrate used
Content more than 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810081038.4A CN108250100A (en) | 2018-01-28 | 2018-01-28 | A kind of synthetic method of acethydrazide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810081038.4A CN108250100A (en) | 2018-01-28 | 2018-01-28 | A kind of synthetic method of acethydrazide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108250100A true CN108250100A (en) | 2018-07-06 |
Family
ID=62742411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810081038.4A Withdrawn CN108250100A (en) | 2018-01-28 | 2018-01-28 | A kind of synthetic method of acethydrazide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108250100A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516819A (en) * | 2022-02-25 | 2022-05-20 | 顺毅宜昌化工有限公司 | Preparation method of N, N' -diacetyl hydrazine |
-
2018
- 2018-01-28 CN CN201810081038.4A patent/CN108250100A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516819A (en) * | 2022-02-25 | 2022-05-20 | 顺毅宜昌化工有限公司 | Preparation method of N, N' -diacetyl hydrazine |
| CN114516819B (en) * | 2022-02-25 | 2024-02-27 | 顺毅宜昌化工有限公司 | Preparation method of N, N' -diacetyl hydrazine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102364274B1 (en) | Continuous process for the preparation of 2-methylallyl alcohol | |
| CN100463897C (en) | Method for separating sec-butyl acetate from reaction mixture of acetic acid and hybrid C4 | |
| CN115894229A (en) | Selective synthesis process of monoethyl adipate | |
| CN108250100A (en) | A kind of synthetic method of acethydrazide | |
| WO2022007288A1 (en) | Dl-p-hydroxybenzene hydantoin and urea sulfate/ammonium sulfate production process thereof | |
| CN108191704A (en) | A kind of method for synthesizing acethydrazide | |
| CN107056646A (en) | A kind of synthetic method of adipic dihydrazide | |
| CN103145796A (en) | Synthesis process of neotame | |
| CN108191706A (en) | The synthetic method of acethydrazide | |
| CN112047838A (en) | Relay type ethyl acetate industrial preparation process | |
| CN108191707A (en) | The preparation method of acethydrazide | |
| CN108047084A (en) | A kind of preparation method of acethydrazide | |
| CN108191705A (en) | A kind of method for preparing acethydrazide | |
| CN115260029A (en) | Method for producing 2,3,5-trimethylhydroquinone diester by using bubble column reactor | |
| TW202246208A (en) | Process for the ammonolysis of bromoalkanoic acids | |
| CN107963980A (en) | The synthetic method of adipic dihydrazide | |
| CN112645815A (en) | Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent | |
| CN108409597A (en) | A method of synthesis 3,4,5- trimethoxybenzoyl hydrazines | |
| CN113896653B (en) | Synthesis and purification method of 2-chloro-6-fluorobenzonitrile | |
| CN108285433A (en) | A method of synthesis maleic acid hydrazide | |
| CN108178734A (en) | A kind of synthetic method of 3,4,5- trimethoxybenzoyls hydrazine | |
| CN108218741A (en) | A kind of preparation method of adipic dihydrazide | |
| CN108358813A (en) | A kind of method of two hydrazides of synthesizing adipic acid | |
| CN108383751A (en) | A method of synthesis salicylyl hydrazine | |
| CN108299231A (en) | A kind of synthetic method of salicylyl hydrazine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180706 |
|
| WW01 | Invention patent application withdrawn after publication |