CN106916082A - A kind of method for synthesizing 3,4,5 trimethoxybenzoyl hydrazines - Google Patents
A kind of method for synthesizing 3,4,5 trimethoxybenzoyl hydrazines Download PDFInfo
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- CN106916082A CN106916082A CN201710293896.0A CN201710293896A CN106916082A CN 106916082 A CN106916082 A CN 106916082A CN 201710293896 A CN201710293896 A CN 201710293896A CN 106916082 A CN106916082 A CN 106916082A
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides the method for one kind 3,4,5 trimethoxybenzoyl hydrazines of synthesis, with 3,4,5 trimethoxy-benzamides, butanone azine and water are raw material to the method, and reaction at a certain temperature prepares 3,4,5 trimethoxybenzoyl hydrazines.Excessive butanone azine and water are added during the course of the reaction so that 3,4, the 5 trimethoxy-benzamides reaction in reaction system is complete, and reaction obtains 3,4,5 trimethoxybenzoyl hydrazines excessive butanone azine and water are distilled off after terminating after.The inventive method process is simple, reaction yield is high, and the reaction time is short, and energy consumption is low；The ammonia and butanone that by-product is reclaimed can be back to synthesis butanone azine, low production cost；Organic brine waste is not produced, waste discharge is few, be a kind of environmental type production technology.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to the side of one kind 3,4,5- trimethoxybenzoyl hydrazines of synthesis
Method.
Background technology
3,4,5- trimethoxybenzoyl hydrazines are white crystalline solid, and fusing point is 159~160 DEG C, is dissolved in water and organic molten
Agent.3,4,5- trimethoxybenzoyl hydrazines are the intermediates for synthesizing the heterocyclic compounds such as methoxybenzyl aminopyrimidine, are also the anti-height of synthesis
Blood pressure drug（Reserpine）Deng the raw material of multi-medicament.
At present, the synthetic method of 3,4,5- trimethoxybenzoyl hydrazines is：First with 3,4,5- trimethoxybenzoic acids as former
Material, methyl alcohol are solvent, with the concentrated sulfuric acid as catalyst, after lower reaction is heated to reflux 10 hours, by reaction solution crystallisation by cooling, mistake
3,4,5- tri-methoxybenzoates are obtained after filter, dry and recrystallization；It is with 3,4,5- tri-methoxybenzoates again
Raw material and hydrazine hydrate being heated to reflux lower reaction 5~6 hours, reaction solution through crystallisation by cooling, filtering, drying, recrystallize after obtain
3,4,5- trimethoxybenzoyl hydrazines.Prior art has the drawback that：（1）Done using the concentrated sulfuric acid in first step esterification
Catalyst, has that corrosivity is strong, can produce a large amount of salt contents organic wastewater high, environmental hazard are big, cost for wastewater treatment is high etc.
Problem；（2）Reaction time is long, and technique is cumbersome, and process is complicated, and yield is low（Only 80% or so）, high energy consumption；（3）In second step hydrazine
It is that production cost is higher with expensive hydrazine hydrate as raw material in solution reaction.
The content of the invention
For the disadvantages mentioned above for overcoming prior art to exist, the invention provides a kind of process is simple, high income, discarded object
Less, the 3,4,5- trimethoxybenzoyl hydrazine new synthetic methods of low production cost, energy-conserving and environment-protective.
The technical solution adopted by the present invention is：With 3,4,5- trimethoxy-benzamides, butanone azine and water are raw material,
Reacted under uniform temperature and prepare 3,4,5- trimethoxybenzoyl hydrazines.Add during the course of the reaction excessive butanone azine and water with
3,4,5- trimethoxy-benzamides in reaction system are made to react complete, the ammonia and butanone generated in course of reaction can be back to
Butanone azine is prepared, reaction obtains 3,4,5- trimethoxybenzoyls excessive butanone azine and water are distilled off after terminating after
Hydrazine.
Specific processing step of the invention is as follows：3,4,5- trimethoxy-benzamides, butanone azine and water are put into instead
In answering kettle, stirring is opened, be heated to backflow, introduce steam into rectifying column, fourth is produced at 75 DEG C~80 DEG C of tower top temperature
Ketone simultaneously reclaims ammonia, reacts 5~6 hours at a reflux temperature, 3,4,5- trimethoxy-benzamide in sampling analysis reaction solution
Content, after treating that 3,4,5- trimethoxy-benzamides have been reacted, the butanone azine and water in reactor are all steamed, then
3,4,5- trimethoxybenzoyl hydrazine finished products will be obtained after solid matter water used wash in reactor, drying, recrystallization.
In above-mentioned steps, the mol ratio of 3,4,5- trimethoxy-benzamides and butanone azine is 1: 1~2, the addition of water
Measure is 0.5~1 times of 3,4,5- trimethoxy-benzamide quality.Its reaction equation is as follows：
Compared with prior art, beneficial effects of the present invention and advantage are as follows：
The present invention with butanone azine that is with low cost, being readily synthesized be the trimethoxybenzoyl hydrazine of Material synthesis 3,4,5-, technique
Simply, reaction yield is high（With butanone azine rate of collecting more than 90%）, the reaction time is short, and energy consumption is low；Ammonia and fourth that by-product is reclaimed
Ketone can be back to synthesis butanone azine, low production cost；Organic brine waste is not produced, waste discharge is few, be a kind of green
Environment-friendly production process.
Specific embodiment
Embodiment 1
3,4,5- trimethoxy-benzamides 211.2g, butanone azine 180g and water 110ml are placed in band stirring, thermometer and essence
In the four-hole boiling flask of fractional distillation column, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated and is risen
Temperature after steam enters rectifying column, butanone is produced at 75~80 DEG C of column top temperature and ammonia is reclaimed to flowing back；In reflux temperature
Lower reaction 5~6 hours, the content of 3,4,5- trimethoxy-benzamides in sampling analysis reaction solution treats 3,4,5- trimethoxies
After benzamide has been reacted, the butanone azine and water in flask are all steamed, then the solid matter in flask is washed with water
Wash, dry, recrystallize after obtain 3,4,5- trimethoxybenzoyl hydrazines 210.5g.
Embodiment 2
3,4,5- trimethoxy-benzamides 211.2g, butanone azine 225g and water 160ml are placed in band stirring, thermometer and essence
In the four-hole boiling flask of fractional distillation column, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated and is risen
Temperature after steam enters rectifying column, butanone is produced at 75~80 DEG C of column top temperature and ammonia is reclaimed to flowing back；In reflux temperature
Lower reaction 5~6 hours, the content of 3,4,5- trimethoxy-benzamides in sampling analysis reaction solution treats 3,4,5- trimethoxies
After benzamide has been reacted, the butanone azine and water in flask are all steamed, then the solid matter in flask is washed with water
Wash, dry, recrystallize after obtain 3,4,5- trimethoxybenzoyl hydrazines 212.9g.
Embodiment 3
3,4,5- trimethoxy-benzamides 211.2g, butanone azine 266g and water 210ml are placed in band stirring, thermometer and essence
In the four-hole boiling flask of fractional distillation column, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated and is risen
Temperature after steam enters rectifying column, butanone is produced at 75~80 DEG C of column top temperature and ammonia is reclaimed to flowing back；In reflux temperature
Lower reaction 5~6 hours, the content of 3,4,5- trimethoxy-benzamides in sampling analysis reaction solution treats 3,4,5- trimethoxies
After benzamide has been reacted, the butanone azine and water in flask are all steamed, then the solid matter in flask is washed with water
Wash, dry, recrystallize after obtain 3,4,5- trimethoxybenzoyl hydrazines 215.3g.
Claims (1)
1. the method that one kind synthesizes 3,4,5- trimethoxybenzoyl hydrazines, it is characterised in that comprise the following steps：By 3,4,5- tri-
Methoxy benzamide, butanone azine and water are put into reactor, open stirring, are heated to backflow, introduce steam into essence
Tower is evaporated, butanone is produced at 75 DEG C~80 DEG C of tower top temperature and ammonia is reclaimed, reacted 5~6 hours at a reflux temperature, sampling point
The content of 3,4,5- trimethoxy-benzamides in analysis reaction solution, after treating that 3,4,5- trimethoxy-benzamides have been reacted, will
Butanone azine and water in reactor are all steamed, then will be obtained after the solid matter water used wash in reactor, drying, recrystallization
To 3,4,5- trimethoxybenzoyl hydrazine finished products；In above-mentioned steps, 3,4,5- trimethoxy-benzamides and butanone azine rub
, than being 1: 1~2, the addition of water is 0.5~1 times of 3,4,5- trimethoxy-benzamide quality for you.
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| CN201710293896.0A CN106916082A (en) | 2017-04-28 | 2017-04-28 | A kind of method for synthesizing 3,4,5 trimethoxybenzoyl hydrazines |
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| CN201710293896.0A CN106916082A (en) | 2017-04-28 | 2017-04-28 | A kind of method for synthesizing 3,4,5 trimethoxybenzoyl hydrazines |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081122A (en) * | 1992-07-10 | 1994-01-26 | 化学工业部西南化工研究院 | Catalyst for synthesizing hydrazine hydrate by ammonia catalytic oxidation |
| US20060231589A1 (en) * | 2005-04-14 | 2006-10-19 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Hydroxynaphthalenedicarboxylic acid hydrazide and derivatives thereof as well as process for preparing them |
| CN105237584A (en) * | 2015-10-26 | 2016-01-13 | 北京科技大学 | Preparation method for N,N'-ferrocenediacetyl-tri(dodecyloxy) benzamide |
| CN105837523A (en) * | 2016-03-30 | 2016-08-10 | 贵州大学 | 1,2,4-triazole compound containing oxime carboxylate, and preparation method and application thereof |
-
2017
- 2017-04-28 CN CN201710293896.0A patent/CN106916082A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081122A (en) * | 1992-07-10 | 1994-01-26 | 化学工业部西南化工研究院 | Catalyst for synthesizing hydrazine hydrate by ammonia catalytic oxidation |
| US20060231589A1 (en) * | 2005-04-14 | 2006-10-19 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Hydroxynaphthalenedicarboxylic acid hydrazide and derivatives thereof as well as process for preparing them |
| CN105237584A (en) * | 2015-10-26 | 2016-01-13 | 北京科技大学 | Preparation method for N,N'-ferrocenediacetyl-tri(dodecyloxy) benzamide |
| CN105837523A (en) * | 2016-03-30 | 2016-08-10 | 贵州大学 | 1,2,4-triazole compound containing oxime carboxylate, and preparation method and application thereof |
Non-Patent Citations (7)
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| QIAN, XUHONG 等: "Syntheses and insecticidal activities of novel 2,5-disubstituted-1,3,4-oxadiazoles", 《JOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY》 * |
| 吴晓旺: "丁酮连氮水解反应精馏工艺的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 孙孟展: "水合肼及其衍生物的合成及绿色化学", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 宋宝安 等: "2-取代硫醚-5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑类化合物的合成、结构与体外抗癌活性", 《化学学报》 * |
| 曲秀艳 等: "2-[(1-取代苯基-1H-1,2,3-三唑-4-基)甲硫基]-5-(3,4,5-三甲氧基苯基)-1,3,4-二唑化合物的合成及抗真菌活性", 《第二军医大学学报》 * |
| 杨懿鑫: "水合肼的合成及其工艺开发研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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