CN106946804A - The preparation technology and its content assaying method of a kind of triazole derivatives preparation - Google Patents
The preparation technology and its content assaying method of a kind of triazole derivatives preparation Download PDFInfo
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- CN106946804A CN106946804A CN201710204768.4A CN201710204768A CN106946804A CN 106946804 A CN106946804 A CN 106946804A CN 201710204768 A CN201710204768 A CN 201710204768A CN 106946804 A CN106946804 A CN 106946804A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The present invention discloses the preparation technology and its content assaying method of a kind of triazole derivatives preparation, o-nitrochlorobenzene is added in there-necked flask, hydrazine hydrate, phase transfer catalyst, magnetic agitation is heated, stop after heating, 40% sodium hydroxide solution is added in reaction solution, then steam using rotary evaporator and reclaim excessive hydrazine hydrate, solution pH value is adjusted to 3.0-3.5, suction filtration and with 10% cryosel water washing, triazole derivatives are produced after vacuum drying, the present invention adds phase transfer catalyst in the solution using phase transfer catalytic technology, one reactant is transferred in the phase containing another reactant, whole reaction is set to have higher reaction speed, solvent use cost can be reduced, it is widely used in industrial production.
Description
Technical field
The present invention relates to chemosynthesis technical field, and in particular to a kind of preparation technology of triazole derivatives preparation and its
Content assaying method.
Background technology
The preparation technology of triazole derivatives preparation, such as building-up process of 1-hydroxy benzo triazole mainly use solvent
Method, i.e., add certain solvent in reaction solution, reaction is carried out in homogeneous.If but this method is applied to greatly industrially
Increase cost.
Based on this, a kind of preparation technology of triazole derivatives preparation has been researched and developed.
The content of the invention
The present invention now provides the preparation technology and its content assaying method of a kind of triazole derivatives preparation, utilizes phase transfer
Catalysis technique, adds phase transfer catalyst, a reactant can be transferred in the phase containing another reactant, improves reaction speed
Degree, the solvent that this preparation method is used is low-toxic organic solvent, and usage amount is few, and product yield is high, is adapted to large-scale production
Prepare triazole derivatives preparation.
The present invention is achieved through the following technical solutions：
A kind of preparation technology of triazole derivatives preparation, adds o-nitrochlorobenzene, hydrazine hydrate, phase turn in there-necked flask
Shifting catalyst, magnetic agitation heating, stops after heating, 40% sodium hydroxide solution is added in reaction solution, then using rotation
Evaporator steams and reclaims excessive hydrazine hydrate, regulation solution pH value to 3.0-3.5, suction filtration and with 10% cryosel water washing,
Triazole derivatives are produced after vacuum drying.
Further, in order to preferably realize the present invention, the triazole derivatives are 1- hydroxy benzo triazoles.
Further, in order to preferably realize the present invention, o-nitrochlorobenzene presses 1 with hydrazine hydrate mol ratio：4 add reaction,
Phase transfer catalyst PEG-800 3mmol are added, back flow reaction 5h, reaction temperature is 110 DEG C, mixing speed 500r/min.
Further, in order to preferably realize the present invention, the addition of the o-nitrochlorobenzene is 0.1mol, hydrazine hydrate
Addition is 0.4mol.
Further, in order to preferably realize the present invention, the o-nitrochlorobenzene, hydrazine hydrate and PEG-800 mol ratios are
1：4：0.03.
A kind of content assaying method of triazole derivatives preparation, by the triazole derivatives preparation prepared using high
Effect liquid phase chromatogram method carries out assay, chromatographic condition：C18 (5um, diameter 4.6mmx150mm), UV detectors, Detection wavelength
254nm, 30 DEG C of column temperature, mobile phase：Methanol aqueous solution 75：25 (v/v), flow velocity is 1.0ml/min, and sample size is 5ul, with standard
Solution concentration is X-axis, and standard curve is made by Y-axis of peak area, and the peak area of the phenylpropyl alcohol triazole measured and standard curve are entered
Row compares, and obtains the content of triazole derivatives preparation.
Further, in order to preferably realize the present invention, the sensitivity of content assaying method is 0.001AUFS.
The present invention compared with prior art, has the following advantages and advantages：
The present invention adds phase transfer catalyst in the solution using phase transfer catalytic technology, and a reactant is transferred to and contained
Have in the phase of another reactant, whole reaction is had higher reaction speed, solvent use cost can be reduced, be widely used in
Industrial production.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, to present invention work
Further to describe in detail, exemplary embodiment and its explanation of the invention is only used for explaining the present invention, is not intended as to this
The restriction of invention.
Embodiment 1：
O-nitrochlorobenzene 0.1mol, hydrazine hydrate 0.4mol, phase transfer catalyst 3mmol, magnetic force are added in there-necked flask
Agitating heating, back flow reaction 5h, reaction temperature is 110 DEG C, and mixing speed is 500r/min, stops heating, is added in reaction solution
Enter 40% sodium hydroxide solution, then steam and reclaim excessive hydrazine hydrate using rotary evaporator, regulation solution pH value to
3.0-3.5, suction filtration and with 10% cryosel water washing, triazole derivatives are produced after vacuum drying, yield is 99.3%.
Wherein, the phase transfer catalyst used in the present embodiment is PEG-800, by quaternary ammonium salt CTMAB, and TBAB is phase transfer
Catalyst is made comparisons with polyethylene glycol (PEG) phase transfer catalyst, and wherein quaternary ammonium salt phase catalyst is easily decomposed, in liquid chromatogram
In analysis chart, it can be seen that generate many accessory substances, from the color and luster of product it can clearly be seen that being urged using quaternary ammonium salt phase transfer
The product colour that agent is obtained mostly yellowish-brown, and the use of polyethylene glycol is that the product that phase transfer catalyst is obtained is white.Its
It is middle when using PEG-800 for phase transfer catalyst, product yield highest.
Wherein, in this preparation technology, the input amount to raw material o-nitrochlorobenzene, hydrazine hydrate is analyzed, and is being added
3mmolPEG-800, back flow reaction 5h, 110 DEG C of reaction temperature, mixing speed 500r/min, at n (hydrazine hydrate)：N (adjacent nitro chlorine
Benzene) it is 4：In the case of 1, yield highest.
Wherein, influence of the mutually quasi- instrument catalyst amount added in the present embodiment to preparation technology to product yield is ground
Study carefully,
O-nitrochlorobenzene 0.1mol and hydrazine hydrate 0.4mol are taken, a certain amount of PEG-800, back flow reaction 5h are taken in proportion,
Reaction temperature is 110 DEG C, and mixing speed is 500r/min, and result of the test is shown, as PEG-800 consumptions increase yield also therewith
Increase, but phase transfer catalyst consumption increases to 3mmol, i.e., be 1 with o-nitrochlorobenzene mol ratio:When 0.03, continue to increase it
Consumption, the influence to product yield is smaller.Therefore optimal PEG-800 consumptions are 3mmol.
Wherein, reaction temperature is larger to the whole influence for preparing reaction, from 90-110 DEG C of increases with reaction temperature,
Product yield is increased considerably, after 110 DEG C, and yield declines, and main cause is in the case where temperature is higher, and portioned product can
Can decompose causes product yield to decline, meanwhile, the too high color and luster that can make product of temperature is deepened, therefore preferable reaction temperature is 110 DEG C.
Wherein, in preparation technology described in the present embodiment, the reaction time also produces influence to product yield：
0.1mol o-nitrochlorobenzenes, 0.4mol hydrazine hydrates and 3mmolPEG -300 are taken, reaction temperature is 110 DEG C, stirring speed
Spend for 500r/min, the differential responses time, (3.5-6h) was contrasted, analysis is understood, with the frame of hating in reaction time, product is received
Rate gradually increases, and after reaction 5h, then extends the reaction time, yield increase is not obvious.Therefore optimum reacting time is 5h.
Wherein, course of reaction described in the present embodiment is heterogeneous system, strengthens stirring, reaction can be made to be smoothed out and carry
High heat transfer efficiency, when low whipping speed is 200-500r/min, yield is steadily improved.After 500r/min, stirring speed is improved
Degree influences smaller to yield, therefore optimal mixing speed is 500r/min.
In summary, it is with the optimum process condition of phase transfer catalysis process synthesizing triazazole derivative：Phase transfer catalyst
PEG-800, o-nitrochlorobenzene, hydrazine hydrate and PEG-800 mol ratios be, 1：4:0.03, reaction temperature is 110 DEG C, reacts 5h, stirs
Speed is mixed for 500r/min.
Embodiment 2：
The triazole derivatives prepared to embodiment 1 carry out content detection, are contained using high performance liquid chromatography
It is fixed to measure, chromatographic condition：C18 (5um, diameter 4.6mmx150mm), UV detectors, Detection wavelength 254nm, 30 DEG C of column temperature, flowing
Phase：Methanol aqueous solution 75：25 (v/v), flow velocity is 1.0ml/min, and sample size is 5ul, using concentration of standard solution as X-axis, with peak
Area makees standard curve for Y-axis, and the peak area of the phenylpropyl alcohol triazole measured and standard curve are compared, and obtains triazole and spreads out
The content of biological agent.
Above-described embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modifications, equivalent substitutions and improvements done etc. all should be included
Within protection scope of the present invention.
Claims (7)
1. a kind of preparation technology of triazole derivatives preparation, it is characterised in that：O-nitrochlorobenzene, water are added in there-necked flask
Hydrazine, phase transfer catalyst are closed, magnetic agitation heating stops after heating, 40% sodium hydroxide solution added in reaction solution, then
Steamed using rotary evaporator and reclaim excessive hydrazine hydrate, regulation solution pH value to 3.0-3.5, suction filtration and with 10% ice
Triazole derivatives are produced after salt water washing, vacuum drying.
2. a kind of preparation technology of triazole derivatives preparation according to claim 1, it is characterised in that：The triazole
Derivative is 1- hydroxy benzo triazoles.
3. a kind of preparation technology of triazole derivatives preparation according to claim 1, it is characterised in that：O-nitrochlorobenzene
1 is pressed with hydrazine hydrate mol ratio：4 add reaction, add phase transfer catalyst PEG-800 3mmol, back flow reaction 5h, reaction temperature
For 110 DEG C, mixing speed 500r/min.
4. a kind of preparation technology of triazole derivatives preparation according to claim 3, it is characterised in that：The adjacent nitro
The addition of chlorobenzene is 0.1mol, and the addition of hydrazine hydrate is 0.4mol.
5. a kind of preparation technology of triazole derivatives preparation according to claim 4, it is characterised in that：The adjacent nitro
Chlorobenzene, hydrazine hydrate and PEG-800 mol ratios are 1：4：0.03.
6. a kind of content assaying method of triazole derivatives preparation, it is characterised in that：Claim 1 to 5 is prepared
Triazole derivatives preparation carries out assay, chromatographic condition using high performance liquid chromatography：C18 (5um, diameter
4.6mmx150mm), UV detectors, Detection wavelength 254nm, 30 DEG C of column temperature, mobile phase：Methanol aqueous solution 75：25 (v/v), flow velocity
For 1.0ml/min, sample size is 5ul, and using concentration of standard solution as X-axis, standard curve is made by Y-axis of peak area, by what is measured
The peak area of phenylpropyl alcohol triazole is compared with standard curve, obtains the content of triazole derivatives preparation.
7. a kind of content assaying method of triazole derivatives preparation according to claim 6, it is characterised in that：Containing measurement
The sensitivity for determining method is 0.001AUFS.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107860735A (en) * | 2017-12-21 | 2018-03-30 | 上海微谱化工技术服务有限公司 | The analysis method of pcb board aqueous cleaning agent |
| CN114907279A (en) * | 2022-03-29 | 2022-08-16 | 金华职业技术学院 | Synthesis method of N-oxyphenyltriazole |
| CN115494183A (en) * | 2022-11-16 | 2022-12-20 | 深圳市海滨制药有限公司 | Method for detecting 1,2, 4-triazole in triazole medicines |
Citations (2)
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| CN102875483A (en) * | 2012-10-26 | 2013-01-16 | 陈守文 | Synthesis technique of benzotriazole |
| CN103450103A (en) * | 2013-05-08 | 2013-12-18 | 如皋市金陵化工有限公司 | Synthesis process of 1-hydroxybenzotriazole |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102875483A (en) * | 2012-10-26 | 2013-01-16 | 陈守文 | Synthesis technique of benzotriazole |
| CN103450103A (en) * | 2013-05-08 | 2013-12-18 | 如皋市金陵化工有限公司 | Synthesis process of 1-hydroxybenzotriazole |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107860735A (en) * | 2017-12-21 | 2018-03-30 | 上海微谱化工技术服务有限公司 | The analysis method of pcb board aqueous cleaning agent |
| CN114907279A (en) * | 2022-03-29 | 2022-08-16 | 金华职业技术学院 | Synthesis method of N-oxyphenyltriazole |
| CN114907279B (en) * | 2022-03-29 | 2023-11-10 | 金华职业技术学院 | Synthesis method of N-oxybenzene propyl triazole |
| CN115494183A (en) * | 2022-11-16 | 2022-12-20 | 深圳市海滨制药有限公司 | Method for detecting 1,2, 4-triazole in triazole medicines |
| CN115494183B (en) * | 2022-11-16 | 2023-03-10 | 深圳市海滨制药有限公司 | Method for detecting 1,2, 4-triazole in triazole medicines |
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Application publication date: 20170714 |