CN110437115A - The method for preparing thiosemicarbazide acetal - Google Patents
The method for preparing thiosemicarbazide acetal Download PDFInfo
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- CN110437115A CN110437115A CN201910655119.5A CN201910655119A CN110437115A CN 110437115 A CN110437115 A CN 110437115A CN 201910655119 A CN201910655119 A CN 201910655119A CN 110437115 A CN110437115 A CN 110437115A
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- thiosemicarbazide
- acetal
- aromatic aldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C337/06—Compounds containing any of the groups, e.g. thiosemicarbazides
- C07C337/08—Compounds containing any of the groups, e.g. thiosemicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. thiosemicarbazones
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method for preparing thiosemicarbazide acetal, comprising steps of a. accelerates after mixing solid-state thiosemicarbazide and solid-state aromatic aldehyde substance, makes its high-speed motion, phase mutual friction, intensified response activity；B., fixed target is set on thiosemicarbazide and the solid-state aromatic aldehyde direction of motion, and the thiosemicarbazide and solid-state aromatic aldehyde of high-speed motion hit the fixation target, and kinetic energy is converted into internal energy of molecular, and molecular scission activation, bonding, synthesizes thiosemicarbazide acetal again.Step a, b periodic cycle carries out, and reacts fully.This method simple process, process is short, few using equipment, and low energy consumption, and the single reaction time is short, and feed stock conversion is greater than 75%, and yield is high, and production capacity is big, and reaction condition is mild, does not use any catalyst or solvent, and three-waste free discharge is not necessarily to environmental improvement.
Description
Technical field
The present invention relates to the preparation methods of thiosemicarbazide acetal, are especially prepared with thiosemicarbazide and aromatic aldehyde substance
The method of thiosemicarbazide acetal.
Background technique
Thiosemicarbazides is a kind of important thiourea derivative, is common pesticide, medicine intermediate, is widely used in pesticide thiophene
Two class fungicide, medical thiacetazone, the synthesis of sulfa drugs.Utilized isothiocyanates and hydrazine reaction for the first time since 1896
Since synthesizing amino thiocarbamide, people are more and more extensive to the research of thiosemicarbazides and its derivative, it not only has extensive life
Reason, pharmacological activity, and be a kind of higher organic reagent of selectivity.Especially in recent years, with the continuous deepening of research, it sends out
The derivative of existing thiosemicarbazides has more extensive purposes and higher physiological activity.People need to introduce also according to different
Different groups is different to achieve the purpose that in such compound, and the research that this allows for thiosemicarbazide compound is more living
Jump.Thiosemicarbazones is a kind of compound being condensed to yield by thiosemicarbazides and aldehydes or ketones appropriate, the amino in thiosemicarbazides
Become thiosemicarbazones with aldehydes or ketones carbonyl condensation, the hydrogen in molecule on nitrogen-atoms can be replaced by alkyl or aryl, to be formed
The (thiosemicarbazone) compound that a series of properties is not quite similar.Different types of aldehydes or ketones are condensed obtained with thiosemicarbazides
Thiosemicarbazones compound can form colored complex respectively as monodentate, bidentate or multidentate ligand and metal ion, be used to
The photometering of sensitive selectivity is carried out, thus thiosemicarbazones is a kind of highly effective analytical reagent.In recent years, it contracts
Thiosemicarbazone derivative is widely applied in terms of medicine, pesticide, the exploitation of electrode new material and development field, is organic chemistry research
Hot spot.
Traditional contracting thiosemicarbazide synthetic method is that a small amount of acetic acid is added and urges using dehydrated alcohol and water as solvent
Agent carries out the condensation of aldehyde radical and amino under counterflow condition.The reaction yield is only 60-80%, and need to consume and largely have
Solvent, the operating time is long, and reaction needs to heat, and energy consumption of reaction is high, there is certain pollution to environment, is not suitable for industrialization rule
Mould production.
Summary of the invention
The purpose of the present invention, be to provide a kind of reaction time is short, yield is high, products pure, can industrial-scale production
Thiosemicarbazide acetal preparation process.
Its technical solution is:
A method of thiosemicarbazide acetal is prepared, comprising steps of
A, after mixing solid-state aromatic aldehyde and solid-state thiosemicarbazide, accelerated with high speed current-carrying gas, make its high-speed motion, phase
Mutual friction, intensified response activity；
B, fixed target is set on aromatic aldehyde and the thiosemicarbazide direction of motion, and the aromatic aldehyde and thiosemicarbazide of high-speed motion are hit
The fixation target is hit, kinetic energy is converted into internal energy of molecular, and molecular scission activation, bonding, synthesizes thiosemicarbazide acetal again.
The aromatic aldehyde is paranitrobenzaldehyde, parahydroxyben-zaldehyde, chooses any one kind of them in 3- hydroxy benzaldehyde.
The aromatic aldehyde and thiosemicarbazide accelerate to 1-3 times of velocity of sound.
The method that aromatic aldehyde and thiosemicarbazide are accelerated is to mix aromatic aldehyde and thiosemicarbazide with high speed carrier gas stream
It closes, aromatic aldehyde is delivered by carrier gas stream and thiosemicarbazide moves.
The carrier gas stream is compressed air.
Step a, the b periodic cycle progress, aromatic aldehyde and thiosemicarbazide collect thiosemicarbazide contracting after sufficiently reacting
Aldehyde.
Above-mentioned product thiosemicarbazide acetal is dried in vacuo, drying temperature≤90 DEG C.
Beneficial effects of the present invention:
Thiosemicarbazide acetal is prepared using the above method, simple process, process is short, and few using equipment, low energy consumption, single
Reaction time is short, and feed stock conversion is greater than 75%, and yield is high, and production capacity is big, and reaction condition is mild, does not use any catalyst
Or solvent, three-waste free discharge are not necessarily to environmental improvement.
Detailed description of the invention
Fig. 1 is process flow and apparatus structure schematic diagram of the invention.
Fig. 2 is product thiosemicarbazide contracting paranitrobenzaldehyde of the invention1H NMR figure.
Fig. 3 is product thiosemicarbazide contracting paranitrobenzaldehyde of the invention13C NMR figure.
Fig. 4 is product thiosemicarbazide contracting parahydroxyben-zaldehyde of the invention1H NMR figure.
Fig. 5 is product thiosemicarbazide contracting parahydroxyben-zaldehyde of the invention13C NMR figure.
Fig. 6 is product thiosemicarbazide contracting 3- hydroxy benzaldehyde of the invention1H NMR figure.
Fig. 7 is product thiosemicarbazide contracting 3- hydroxy benzaldehyde of the invention13C NMR figure.
Specific embodiment
Referring to Fig. 1: the device of one preparation contracting thiosemicarbazide of setting, which includes reactor 4, expansion chamber 3.Expansion
Chamber 3 is located at 4 top of reactor, and the import of the outlet connection reactor 4 of expansion chamber 3, the outlet of reactor 4 is connected by return pipe 7
The import for connecing expansion chamber 3 constitutes a seam loop circulating device.Feed hopper 1, the top of expansion chamber 3 are equipped at the top of expansion chamber 3
Equipped with exhaust outlet 2.One end of reactor 4 is equipped with compressed-air atomizer 5；The other end of reactor 4 is target surface 6.
With embodiment, the present invention will be described in detail below.
Embodiment 1
Parahydroxyben-zaldehyde and thiosemicarbazide are stoichiometrically uniformly mixed, it is spare to be packed into feed hopper 1.
Debugging apparatus: opening nozzle 5, be passed through compressed air to circulator, as the delivery media of reactive material, compression
Air sequentially reacted device 4, return pipe 7, expansion tube 3 are discharged from exhaust outlet 2.The aperture for adjusting nozzle 5 and exhaust outlet 2, makes to follow
Pressure in loop device is stablized in certain certain value, and makes the speed >=2 times velocity of sound for spraying air-flow.Due to circulator each section
Latus rectum is different, and compressed air is also just different in the flow velocity of each section, and the latus rectum of reactor 4 is small, and gas flow rate is high, expansion chamber 3
Latus rectum is very big, and gas flow rate is just very low.
The valve for opening feed hopper 1, puts parahydroxyben-zaldehyde and thiosemicarbazide mixture into circulator, is then turned on
Nozzle 5, is passed through compressed air.The compressed air sprayed through nozzle 5 is a kind of into gas, when reactant enters reactor 4, with
Compressed air mixing, forms gas, solid mixed phase stream, and reactant is accelerated to >=2 times of velocities of sound.At this point, accelerated reactant
There are two features for tool:
1. reactant high-speed motion has very big kinetic energy.
2. it is all disorder that solid formation, which is distributed in a fluid and moves, high speed since gas, solid mixed phase stream are not wadded a quilt with cotton and flowed
Strong friction can occur for the reactant of movement, and activity improves, and energy needed for scission of link reduces.
When mixed phase stream enters the reaction zone of reactor 4, play occurs for the target surface 6 of solid phase reaction substance and reactor 4
Strong collision, the speed moment in the direction of motion are reduced to zero, kinetic energy be converted into reactant molecule can, molecular scission activation, this
When, nucleophilic displacement of fluorine occurs for the amino on carbon-based and thiosemicarbazide on parahydroxyben-zaldehyde, eliminates a molecular water, generates thio
Semicarbazides contracting parahydroxyben-zaldehyde.It is completed from activating to regrouping in moment.
In this example, two kinds of reactive materials are parahydroxyben-zaldehyde and thiosemicarbazide respectively, and generating product is thio ammonia
Base urea contracting parahydroxyben-zaldehyde, reaction equation are as follows:
In general, reacting also insufficient, the mixed phase stream that reactor 4 exports still contains by primary acceleration, collision process
There is still unreacted reactant.When the mixed phase stream flows into expansion chamber 3 through return pipe 7, due to expansion chamber 3 volume very
Greatly, logistics is buffered, and volume expands suddenly, and flow velocity drastically reduces, and gas, solid separation, decrease in air pressure are discharged from exhaust outlet 2,
And solid matter is under its gravity, automatic sedimentation is mixed with compressed air again, participates in reaction.Such periodic cycle,
Until reacting sufficiently, product is collected.
In addition, above-mentioned reaction also generates water (H2O), therefore, the thiosemicarbazide contracting parahydroxyben-zaldehyde being collected into also needs
It is dried, is dehydrated preferably with boulton process, drying temperature is controlled at≤90 DEG C.
The thiosemicarbazide contracting parahydroxyben-zaldehyde prepared with this method, technical performance is excellent, through analytical control, product
's1H NMR is shown in Fig. 4,13C NMR is shown in Fig. 5,13C NMR data is as follows:
13C NMR (150 MHz, DMSO): δ 177.91,159.73,143.17,129.51,125.61,116.01.Simultaneously
Product yield and yield are all 100% as the result is shown.
Embodiment 2
In this example, two kinds of reactive materials are paranitrobenzaldehyde and thiosemicarbazide respectively, and generating product is thio ammonia
Base urea contracting paranitrobenzaldehyde, reaction equation are as follows:
The thiosemicarbazide contracting paranitrobenzaldehyde of preparation, technical performance is excellent, through analytical control, product1 H NMR
See Fig. 2,13C NMR is shown in Fig. 3, and data are as follows:
13C NMR (151 MHz, DMSO): δ 178.95,148.04,141.19,140.01,128.62,124.24.
Remaining is same as Example 1.
Embodiment 3
In this example, two kinds of reactive materials are 3- hydroxy benzaldehyde and thiosemicarbazide respectively, and generating product is thio ammonia
Base urea contracting 3- hydroxy benzaldehyde, reaction equation are as follows:
The thiosemicarbazide contracting 3- hydroxy benzaldehyde of preparation, technical performance is excellent, through analytical control, product1 H NMR
See Fig. 6,13C NMR is shown in Fig. 7,13C NMR data is as follows:
13C NMR(151 MHz,DMSO):δ178.39,158.04,143.08,135.90,130.12,118.87,
117.51,114.13.
Remaining is same as Example 1.
It is above some specific application examples of the invention, this technique is also suitble to other solid-state solid-state aromatic aldehydes, prepares phase
The thiosemicarbazide acetal answered.
This method process conditions are mild, readily satisfy, therefore the apparatus structure for preparing thiosemicarbazide acetal is simple, are easy to add
Work is very suitable to scale industrial production.
Claims (6)
1. a kind of method for preparing thiosemicarbazide acetal, comprising steps of
A, after mixing solid-state thiosemicarbazide and solid-state aromatic aldehyde, accelerated with carrier gas stream, make its high-speed motion, phase mutual friction,
Intensified response activity；
B, fixed target is set on thiosemicarbazide and the aromatic aldehyde direction of motion, and the thiosemicarbazide and aromatic aldehyde of high-speed motion are hit should
Fixed target, kinetic energy are converted into internal energy of molecular, and molecular scission activation, bonding, synthesizes thiosemicarbazide acetal again.
2. the method according to claim 1 for preparing thiosemicarbazide acetal, which is characterized in that the aromatic aldehyde is to nitro
It is benzaldehyde, parahydroxyben-zaldehyde, any in 3- hydroxy benzaldehyde.
3. contraction according to claim 1 is for the method for thiosemicarbazide acetal, which is characterized in that the carrier gas stream is
Compressed air.
4. the method according to claim 1 for preparing thiosemicarbazide acetal, which is characterized in that the aromatic aldehyde and thio ammonia
Base urea accelerates to 1-3 times of velocity of sound.
5. the method according to claim 1 for preparing thiosemicarbazide acetal, which is characterized in that step a, the b period
Property circulation carry out, collection thiosemicarbazide acetal after thiosemicarbazide and aromatic aldehyde sufficiently reacts.
6. the method according to claim 1 for preparing thiosemicarbazide acetal, which is characterized in that further include thiosemicarbazide
The thiosemicarbazide acetal of collection is dried in vacuo, drying temperature≤90 by acetal drying steps0C。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074204A (en) * | 2007-06-16 | 2007-11-21 | 西南科技大学 | Production of schiff base |
| CN102198388A (en) * | 2011-04-02 | 2011-09-28 | 楚士晋 | Method and device for synthesizing compound by solid phase reaction |
| CN102746341A (en) * | 2012-07-20 | 2012-10-24 | 武汉工程大学 | Thiosemicarbazide Schiff alkali bismuth complex and preparation method thereof |
| CN107051364A (en) * | 2017-02-28 | 2017-08-18 | 中国空气动力研究与发展中心高速空气动力研究所 | Hit target formula supersonic flow and accelerate low fever solid phase reaction device and its application process |
-
2019
- 2019-07-19 CN CN201910655119.5A patent/CN110437115A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074204A (en) * | 2007-06-16 | 2007-11-21 | 西南科技大学 | Production of schiff base |
| CN102198388A (en) * | 2011-04-02 | 2011-09-28 | 楚士晋 | Method and device for synthesizing compound by solid phase reaction |
| CN102746341A (en) * | 2012-07-20 | 2012-10-24 | 武汉工程大学 | Thiosemicarbazide Schiff alkali bismuth complex and preparation method thereof |
| CN107051364A (en) * | 2017-02-28 | 2017-08-18 | 中国空气动力研究与发展中心高速空气动力研究所 | Hit target formula supersonic flow and accelerate low fever solid phase reaction device and its application process |
Non-Patent Citations (4)
| Title |
|---|
| JACK BERNSTEIN 等: "The Chemotherapy of Experimental Tuberculosis. III. The Synthesis of Thiosemicarbazones and Related Compounds", 《J.AM.CHEM.SOC.》 * |
| XINGYI ZHU 等: "Mechanically activated synthesis of 1,3,5-triaryl-2-pyrazolines by high speed ball milling", 《GREEN CHEMISTRY》 * |
| 蔡艳华 等: "超音速气流固相反应合成对二甲胺基苯甲醛缩对氨基苯甲酸Schiff碱", 《石油化工》 * |
| 袁邦群 等: "超音速气流条件下芳香醛和丙二酸亚异丙酯的无溶剂缩合反应", 《中国粉体技术》 * |
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Application publication date: 20191112 |