CN105043923B - A kind of detection method of first piperazine and its by-product - Google Patents
A kind of detection method of first piperazine and its by-product Download PDFInfo
- Publication number
- CN105043923B CN105043923B CN201510291859.7A CN201510291859A CN105043923B CN 105043923 B CN105043923 B CN 105043923B CN 201510291859 A CN201510291859 A CN 201510291859A CN 105043923 B CN105043923 B CN 105043923B
- Authority
- CN
- China
- Prior art keywords
- solution
- piperazine
- sample
- detection method
- precipitating
- 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.)
- Active
Links
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The present invention discloses the detection method of a kind of first piperazine and its by-product, weighs first piperazine sample, and lower alcohols solvent is added and dissolves to obtain sample solution；Sample solution is pipetted, low-alcohol solution, crystal aluminum chloride solution is added, sodium tetraphenylborate solution is added and is uniformly mixed, standing at least 10 minutes must precipitate；Precipitating is filtered, washed, drying to constant weight；After precipitating after drying is dissolved with dimethylformamide, it is transferred to be titrated in conical flask；Isopropanol is sequentially added, 2-3 drop thymol blue indicator solutions, it is titration end-point that it is blue, which to be titrated to the solution, with tetrabutylammonium hydroxide standard solution.The detection method can simply, quickly and accurately detect first piperazine content, the content of N- piperidine hydrochloride by-product can be detected simultaneously, it can be applied in the detection of most of first piperazine formulation products, it does not need using expensive analysis instrument, testing cost is low, it is difficult to solve the problems, such as that first piperazine formulation products test and analyze for testing result accurate stable.
Description
Technical field
The present invention relates to the titration determination fields of component in solution, and in particular to the detection of a kind of first piperazine and its by-product
Method.
Background technique
First piperazine (1,1- dimethylpiperidine chloride), also known as mepiquat chloride, the strong element of cotton, help strong element, cotton it is long it is fast, increase cotton
Dissipate, gram this, adjust pyridine, molecular formula C7H16ClN, structural formula such as following formula:
First piperazine has retarding action to vegetation growth of plant, can be conducted by plant leaf blade and root absorption to complete stool, drop
Low plant inner gibberellin activity makes plant shortened internodes to inhibit cell elongation, and leaf green synthesis enhancing can prevent and treat plant
The excessively prosperous growth of strain plays the role of resistant to lodging, volume increase and increases resistance.
There are N- piperidine hydrochloride by-products in first piperazine raw medicine, belong to and must examine in agriculture chemical registration requirement at present
The substance of survey, embodies in testing result are as follows: raw medicine recognizate is N- piperidine hydrochloride, and aqua product is due to can not be direct
N- piperidine hydrochloride is detected, therefore recognizate is sodium chloride and organic chloride.
The detection of first piperazine raw medicine at present is based on professional standard HG/T2856-1997, and basic skills is the precipitation method, should
Method can accurately analyze first piperazine and N- piperidine hydrochloride, be only used for raw medicine measurement in Pesticidal products at present.Multiple
With in product, since with potassium ion, quaternary ammonium salt and some chlorine-containing organic compounds etc. complex reaction can occur for tetraphenylboron sodium, hold
It is influenced vulnerable to auxiliary agents other in compound product or raw medicine, therefore this method is not suitable for the analysis of first piperazine in formulation products.
For compound preparation product, being currently available that detection method, there are following several:
1, for Ion-pair chromalography column in conjunction with electric conductivity detector, IP HPLC is suitble to point of ionic species compound
Analysis, most raw medicines are all non-ionic compounds in pesticide industry, and it is more extensive that general detector can all be equipped with application
UV detector, and many medium-sized and small enterprises will not generally be equipped with electric conductivity detector or ion chromatograph, therefore this method is very much
Enterprise is not prefered method, this is also the reason of domestic raw medicine and aqua standard all do not use the method.
2, for reverse-phase chromatographic column in conjunction with UV detector, this method has two, first is that Detection wavelength is too low, is lower than
The ultraviolet cut-on wavelength (200nm) of water, solvent and impurity effect are bigger, it is thus possible to be only suitable for purer first piperazine list
Agent product；Second is that N- piperidine hydrochloride does not have appearance, required according to newest agriculture chemical registration data review detailed rules and regulations, first piperazine
N- piperidine hydrochloride content must be detected in product, according to the method, be will be unable to detection N- piperidine hydrochloride and contained
Amount, and need to grope other methods to detect.
3, constant-current titration can more accurately obtain first piperazine content using the method in conjunction with paper chromatography, but should
Method disadvantage is also apparent from: determination step is more, needs point sample, chromatographs, colour developing, and the processes such as titration spend the time especially long；It is accurate
Degree is very low, and for low content aqua product, precision is lower.In addition this method is only used for single-dose product, for compound product, by
Contain other auxiliary agents or raw medicine in ingredient, pre-treatment needs further to grope.As contained highly acid substance in compound product
Or metal ion, may will affect chromatographic solution causes content inaccurate；Compounding raw medicine or auxiliary agent contain same chloride ion, can also
Assay can be will affect.
Other methods such as liquid chromatograph mass spectrography is detected, but mass detector price is too high, for Pesticidal products
The testing cost of product is substantially increased for inspection, the practicality is not strong.
Summary of the invention
In view of this, the application provides the detection method of a kind of first piperazine and its by-product, the detection method being capable of letter
Content that is single, quickly and accurately detecting first piperazine and N- piperidine hydrochloride by-product, can be applied to most of first piperazine
Formulation products detection, does not need using expensive analysis instrument, testing cost is low, and testing result accurate stable solves first
Piperazine formulation products test and analyze difficult problem.
In order to solve the above technical problems, technical solution provided by the invention is the detection side of a kind of first piperazine and its by-product
Method, the by-product are N- piperidine hydrochloride, and described detection method includes the following steps:
(1) prepared by sample: weighing first piperazine sample and is no less than 10mg, lower alcohols solvent is added and sufficiently dissolves, obtains sample
Solution；
(2) precipitating preparation: low-alcohol solution, crystal aluminum chloride solution is added in sample solution described in removing step (1),
After mixing, it adds sodium tetraphenylborate solution to be uniformly mixed, standing at least 10 minutes must precipitate；By precipitating filtering, wash
It washs, drying to constant weight；
(3) washing of precipitate: after the precipitating that drying to constant weight described in step (2) is dissolved with dimethylformamide, transfer
It is to be titrated into conical flask；
(4) it titrates: sequentially adding isopropanol in solution to be titrated in step (3) described conical flask, 2-3 drip in hundred
Phenol indigo plant indicator solution, it is titration end-point that it is blue, which to be titrated to the solution, with tetrabutylammonium hydroxide standard titration solution, simultaneously
Do blank titration；
(5) content calculates:
The first piperazine content X indicated with mass percent1, it is calculated by formula I:
(Ⅰ)
M in the formula2It is calculated by formula II:
(Ⅱ)m2=c (V1- V0)×419.5÷1000
The N- piperidine hydrochloride content X indicated with mass percent2, it is calculated by formula III:
(Ⅲ)
In the formula I, II, III:
C --- the concentration of tetrabutylammonium hydroxide standard titration solution, mol/L；
V1--- titration sample solution consumes the volume of tetrabutylammonium hydroxide standard titration solution, mL；
V0--- titration blank solution consumes the volume of tetrabutylammonium hydroxide standard titration solution, mL；
m1--- the quality for the precipitating that drying to constant weight described in step (2), g；
The quality of first piperazine sample, g described in m --- step (1)；
433.5 --- the tetraphenylboron complex compound relative molecular mass of first piperazine；
419.5 --- the tetraphenylboron complex compound relative molecular mass of N- piperidine hydrochloride.
Preferably, in the step (1) lower alcohols solvent or low-alcohol solution be it is at least one selected from methanol, ethyl alcohol,
Ethylene glycol, propylene glycol, the lower alcohols solvent are 35-45mL.
More preferably, lower alcohols solvent or low-alcohol solution are ethyl alcohol in the step (1).
Preferably, in the step (2), the sample solution is first settled to 50mL before pipetting, then be centrifuged
Filter clarifies the sample solution.
Preferably, in the step (2), the sodium tetraphenylborate solution is tetraphenylboron sodium ethanol solution or tetraphenylboron sodium water
Solution, the concentration of the sodium tetraphenylborate solution are 20g/L, volume 50mL.
Preferably, in the step (2), when being filtered by the precipitating, wash, dry, with the glass sand of constant weight
Core funnel is filtered under diminished pressure, and is washed with 40-50mL alcoholic solutions or deionized water, is dried in 105 DEG C of baking ovens.
Preferably, it is characterised in that: in the step (3), the precipitating after the drying is dissolved with dimethylformamide
Afterwards, when being transferred to conical flask, using acetone washing residual solution, it is fully transferred to it in conical flask, the dimethyl
Formamide is 10mL.
Preferably, in the step (1): the weighed first piperazine sample is 15mg, and the sample solution pipetted is
15mL。
Preferably, in the step (2), the crystal aluminum chloride solution is 1-2 drops.
Preferably, in the step (4), the concentration of the tetrabutylammonium hydroxide standard titration solution is 0.02mol/L,
The additional amount of the isopropanol is 20mL.
The application detection method as shown in Figure 1, the first piperazine sample containing by-product N- piperidine hydrochloride are added low
Grade alcoholic solvent, while sample dissolution, the influence of exclusive segment emulsifier and all metal ions to tetraphenylboron sodium forms sample
After solution, tetraphenylboron sodium is added, is used for complex-precipitation first piperazine and N- piperidine hydrochloride, it can by the quality of the precipitating
The gross mass of first piperazine and N- piperidine hydrochloride is calculated, then the precipitating is added with dimethylformamide, due to first piperazine
Complex compound does not dissolve in dimethylformamide, and N- piperidine hydrochloride complex compound dissolves in dimethylformamide, therefore obtains
Be N- piperidine hydrochloride solution, using tetrabutylammonium hydroxide standard titration solution titration N- piperidine hydrochloride it is molten
The quality of N- piperidine hydrochloride can be calculated in liquid, and the quality of N- piperidine hydrochloride is subtracted with gross mass, can obtain
To the quality of first piperazine.
Wherein, the m in formula I1That is the tetraphenylboron complex compound gross mass of nail piperazine and N- piperidine hydrochloride；m2Refer to
The quality of the tetraphenylboron complex compound of N- piperidine hydrochloride.
Compared with prior art, detailed description are as follows by the application: technical scheme provide a kind of first piperazine and
The detection method of its by-product includes the steps that sample preparation, titration, content calculate, will be in first piperazine raw medicine and its preparation
By-product is complexed by tetraphenylboron sodium, then is titrated, and it is miscellaneous that the salts such as the removable inorganic matter of lower alcohols solvent are added before being complexed
The influence of confrontation tetraphenylboron sodium, removes influence of the partial emulsifier to tetraphenylboron sodium complex compound, and the application detection method can avoid
To the influence of chromatographic solution in aqua examination criteria.
Relative to existing analyzing detecting method, the beneficial effect of technical scheme is: technical scheme
Expensive analysis instrument, such as chromatographic apparatus, mass spectrometer are not needed；Its analysis method is simple to operation, does not need paper chromatography
Contact plate, chromatography in method, the cumbersome process such as develop the color, dry；It can be suitable for current raw medicine, aqua product analysis simultaneously,
Alternative existing product analysis standard；Technical scheme has wide range of applications, and in addition to that can survey raw medicine, can also survey list
Agent product, compound product etc., especially compound product, existing aqua product analysis method (chromatography) can not be analyzed, and
This method can be analyzed easily；Furthermore technical scheme is not only applicable to aqua dosage form, can also be applied to it is other not
With analysis of dosage form product, such as missible oil, suspending agent, wettable powder, microemulsion etc.；The process of precipitating is obviously than raw medicine method
Fastly, analysis time is saved；Herein described method can analyze first piperazine and N- piperidine hydrochloride content, and energy simultaneously
Instead of existing aqua product, piperidines salt content is accurately analyzed, analyzes accurate stable.
Detailed description of the invention
Fig. 1 is the flow chart of the application detection method.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The present invention is described in further detail.
Embodiment one
First piperazine raw medicine (crystal) measurement
The present embodiment uses herein described detection method, measures first piperazine raw medicine (crystal), concrete operations are as follows:
First piperazine raw medicine (pulvis) the sample 1.5g is weighed, is placed in 50mL volumetric flask, is settled to ethyl alcohol dissolution
50mL；15.00mL solution is drawn, is placed in 150mL beaker, adds 40mL ethyl alcohol and 1 to drip crystal aluminum chloride solution, shakes up, be added
50mL tetraphenylboron sodium ethanol solution, stirs evenly, and stands 10min, keeps its precipitating complete；With the glass sand core funnel of constant weight into
Row is filtered under diminished pressure, and is precipitated with 40-50mL ethanol washings, and drying to constant weight in 105 DEG C of baking ovens, is weighed；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, the mass percentage of first piperazine and N- piperidine hydrochloride is calculated separately, meanwhile, reference
Quality of HG/T2856-1997 (the first piperazine raw medicine standard) measurement with first piperazine and N- piperidine hydrochloride in a collection of raw medicine
Percentage composition, replication 5 times, as reference examples, as a result such as table 1.
Table 1 first piperazine raw medicine (crystal) measurement result
From determination data as can be seen that with a batch raw medicine, using herein described measuring method, the quality percentage of first piperazine
For content 98.5-98.7%, standard testing result is 98.5-98.8%, it can be clearly seen that, the number of the application measuring method
It is smaller than standard by 0.1% according to fluctuation range；N- piperidine hydrochloride is detected 0.4-0.5%, and standard detection is 0.4-
0.6%, its same data fluctuations range is smaller than standard, it can be said that bright the application measuring method is compared with accurate stable.
Embodiment two
The measurement of 250g/L first piperazine aqua
The present embodiment uses herein described detection method, measures 250g/L first piperazine aqua, and concrete operations are as follows:
The first piperazine water sample 6.00mL is taken, is placed in 50mL capacity, is settled to 50mL with alcoholic solution, the alcohol is molten
Liquid is the mixed solution that the volume ratio of ethyl alcohol and ethylene glycol is 4:1；Pipette samples solution 15.00mL, is placed in 150mL beaker,
Add 40mL alcoholic solution, 1 drop crystal aluminum chloride solution, shakes up, 50mL tetraphenylboron sodium ethanol solution is added, stirs evenly, stand
10min makes its precipitating completely, and the alcoholic solution is the mixed solution that the volume ratio of ethyl alcohol and ethylene glycol is 4:1；With constant weight
Glass sand core funnel is filtered under diminished pressure, and is precipitated with 40-50mL ethanol washings, and drying to constant weight in 105 DEG C of baking ovens, is weighed；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, the mass percentage of first piperazine and N- piperidine hydrochloride is calculated separately, meanwhile, reference
Quality of HG/T2856-1997 (the first piperazine raw medicine standard) measurement with first piperazine and N- piperidine hydrochloride in a collection of raw medicine
Percentage composition, replication 5 times, as reference examples, as a result such as table 2.
2 250g/L first piperazine aqua measurement result of table
From determination data as can be seen that with a batch product, using herein described measuring method, first piperazine testing result
Fluctuation range obviously than standard method detection is small, and the chloride content of standard method detection is contained except N- methyl piperidine salt
Other chloride compositions other than hydrochlorate, therefore result is much higher than the application method.Our company's production in practice
Similar situation is encountered, raw medicine by-product is qualified, and is processed into aqua product, and testing result by-product is exceeded, and reason is exactly
By-product object detecting method is different.It can be said that the bright more acurrate stabilization of the application measuring method.
Embodiment three
The solvable pulvis measurement of 10% first piperazine
The present embodiment uses herein described detection method, measures the 10% solvable pulvis of first piperazine, and concrete operations are as follows:
The solvable pulvis 3.0g (being accurate to 0.0002g) of the 10% first piperazine is weighed, is placed in 50mL volumetric flask, is added
40mL alcoholic solution after being sufficiently mixed sample, is settled to 50mL, and the alcoholic solution is that the volume ratio of ethyl alcohol and propylene glycol is 9:1
Mixed solution；Sample solution is centrifuged, is filtered, filtrate 15mL is drawn, is placed in 150mL beaker, adds 40mL alcoholic solution, 1 drop
Crystal aluminum chloride solution, shakes up, and 50mL tetraphenylboron sodium aqueous solution is added, stirs evenly, and stands 10min, makes its precipitating completely, institute
State the mixed solution that volume ratio that alcoholic solution is ethyl alcohol and propylene glycol is 9:1；It is depressurized with the glass sand core funnel of constant weight
Filtering, washs precipitating with 40mL deionized water, and drying to constant weight in 105 DEG C of baking ovens, weighs；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, precision test is carried out, recovery test the results are shown in Table 3,4.
The solvable pulvis Precision test result of 3 10% first piperazine of table
The solvable pulvis recovery test result of 4 10% first piperazine of table
Wherein, in table 4, " quality in sample ", which is censured, takes the first piperazine product of known content, the product contain it is effective at
Sub-prime amount, " standard specimen quality is added ", which censures, takes first piperazine standard specimen, effective component quality, and both the above component content is accurate
Known, recovery test verifying is the gap of the sample quality of the quality and addition of actual measurement after being added into standard specimen, with
The rate of recovery indicates that the rate of recovery is greater than 97% and belongs to satisfactory value.
Example IV
The measurement of 5% first piperazine missible oil
The present embodiment uses herein described detection method, measures 5% first piperazine missible oil, and concrete operations are as follows:
The 5% first piperazine missible oil 3.0g (being accurate to 0.0002g) is weighed, is placed in 50mL volumetric flask, it is fixed that ethyl alcohol is added
Hold to 50mL；Pipette samples solution 15mL, is placed in 150mL beaker, adds 40mL ethanol solution, 1 drop crystal aluminum chloride solution, shakes
It is even, 50mL sodium tetraphenylborate solution is added, stirs evenly, stands 10min, keeps its precipitating complete；It is leaked with the glass sand core of constant weight
Bucket is filtered under diminished pressure, and is precipitated with 40-50mL ethanol washings, and drying to constant weight in 105 DEG C of baking ovens, is weighed；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, precision test is carried out, recovery test the results are shown in Table 5,6.
5 5% first piperazine missible oil Precision test result of table
6 5% first piperazine missible oil recovery test result of table
Wherein, in table 6, " quality in sample ", which is censured, takes the first piperazine product of known content, the product contain it is effective at
Sub-prime amount, " standard specimen quality is added ", which censures, takes first piperazine standard specimen, effective component quality, and both the above component content is accurate
Known, recovery test verifying is the gap of the sample quality of the quality and addition of actual measurement after being added into standard specimen, with
The rate of recovery indicates that the rate of recovery is greater than 97% and belongs to satisfactory value.
Embodiment five
The measurement of 30% paclobutrazol first piperazine suspending agent
The present embodiment uses herein described detection method, measures 30% paclobutrazol first piperazine suspending agent, specific to grasp
Make as follows:
The 30% paclobutrazol first piperazine suspending agent 3.0g (being accurate to 0.0002g) is weighed, is placed in 50mL volumetric flask,
40mL alcoholic solution is added, after sample is sufficiently mixed, is settled to 50mL, the alcoholic solution is that the volume ratio of methanol and ethylene glycol is
The mixed solution of 7:3；Sample solution is centrifuged, is filtered, filtrate 15mL is drawn, is placed in 150mL beaker, adds 40mL alcoholic solution, 1
Crystal aluminum chloride solution is dripped, is shaken up, 50mL tetraphenylboron sodium ethanol solution is added, stirs evenly, 10min is stood, has precipitated it
Entirely, the alcoholic solution is the mixed solution that the volume ratio of methanol and ethylene glycol is 7:3；It is carried out with the glass sand core funnel of constant weight
It is filtered under diminished pressure, washs precipitating with 40-50mL methanol, drying to constant weight in 105 DEG C of baking ovens, weighs.
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, precision test is carried out, recovery test the results are shown in Table 7,8.
7 30% paclobutrazol first piperazine suspending agent Precision test result of table
8 30% paclobutrazol first piperazine suspending agent recovery test result of table
Wherein, in table 8, " quality in sample ", which is censured, takes the first piperazine product of known content, the product contain it is effective at
Sub-prime amount, " standard specimen quality is added ", which censures, takes first piperazine standard specimen, effective component quality, and both the above component content is accurate
Known, recovery test verifying is the gap of the sample quality of the quality and addition of actual measurement after being added into standard specimen, with
The rate of recovery indicates that the rate of recovery is greater than 97% and belongs to satisfactory value.
Embodiment six
The measurement of 110g/L cyclopropyl amic acid first piperazine aqua
The present embodiment uses herein described detection method, measures 110g/L cyclopropyl amic acid first piperazine aqua, tool
Gymnastics is made as follows:
The 110g/L cyclopropyl amic acid first piperazine aqua 3.0g (being accurate to 0.0002g) is weighed, 50mL capacity is placed in
In bottle, alcoholic solution is added, is settled to 50mL, the alcoholic solution is the mixed solution that the volume ratio of methanol and propylene glycol is 9:1；It will
Sample solution centrifugation, filtering are drawn filtrate 15mL, are placed in 150mL beaker, add 40mL alcoholic solution, 1 drop crystal aluminum chloride molten
Liquid shakes up, and 50mL tetraphenylboron sodium ethanol solution is added, stirs evenly, and stands 10min, makes its precipitating completely, the alcoholic solution is
The volume ratio of methanol and propylene glycol is the mixed solution of 9:1；It is filtered under diminished pressure with the glass sand core funnel of constant weight, with 40-
50mL methanol washing precipitating, drying to constant weight in 105 DEG C of baking ovens, weighs；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, precision test is carried out, recovery test the results are shown in Table 9,10.
9 110g/L cyclopropyl amic acid first piperazine Precision test result of table
10 110g/L cyclopropyl amic acid first piperazine aqua recovery test result of table
Wherein, in table 10, " quality in sample ", which is censured, takes the first piperazine product of known content, the product contain it is effective at
Sub-prime amount, " standard specimen quality is added ", which censures, takes first piperazine standard specimen, effective component quality, and both the above component content is accurate
Known, recovery test verifying is the gap of the sample quality of the quality and addition of actual measurement after being added into standard specimen, with
The rate of recovery indicates that the rate of recovery is greater than 97% and belongs to satisfactory value.
Embodiment seven
The measurement of 30.05% first piperazine triacontanol microemulsion
The present embodiment uses herein described detection method, measures 30.05% first piperazine triacontanol microemulsion, tool
Gymnastics is made as follows:
The 30.05% first piperazine triacontanol microemulsion 3.0g (being accurate to 0.0002g) is weighed, 50mL capacity is placed in
In bottle, alcoholic solution is added, is settled to 50mL, the alcoholic solution is the mixed solution that the volume ratio of ethyl alcohol and propylene glycol is 9:1；It will
Sample solution centrifugation, filtering are drawn filtrate 15mL, are placed in 150mL beaker, add 40mL alcoholic solution, 1 drop crystal aluminum chloride molten
Liquid shakes up, and 50mL tetraphenylboron sodium ethanol solution is added, stirs evenly, and stands 10min, makes its precipitating completely, the alcoholic solution is
The volume ratio of ethyl alcohol and propylene glycol is the mixed solution of 9:1；It is filtered under diminished pressure with the glass sand core funnel of constant weight, with 40-
50mL ethanol washing precipitating, drying to constant weight in 105 DEG C of baking ovens, weighs；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, precision test is carried out, recovery test the results are shown in Table 11,12.
11 30.05% first piperazine triacontanol Precision test result of table
12 30.05% first piperazine triacontanol microemulsion recovery test result of table
Wherein, in table 12, " quality in sample ", which is censured, takes the first piperazine product of known content, the product contain it is effective at
Sub-prime amount, " standard specimen quality is added ", which censures, takes first piperazine standard specimen, effective component quality, and both the above component content is accurate
Known, recovery test verifying is the gap of the sample quality of the quality and addition of actual measurement after being added into standard specimen, with
The rate of recovery indicates that the rate of recovery is greater than 97% and belongs to satisfactory value.
Embodiment eight
The measurement of 30.01% first piperazine brassin lactones microemulsion
The present embodiment uses herein described detection method, measures 30.01% first piperazine brassin lactones microemulsion,
Concrete operations are as follows:
The 30.01% first piperazine brassin lactones microemulsion 3.0g (being accurate to 0.0002g) is weighed, 50mL appearance is placed in
In measuring bottle, alcoholic solution is added, is settled to 50mL, the alcoholic solution is the mixed solution that the volume ratio of ethyl alcohol and propylene glycol is 9:1；
Sample solution is centrifuged, is filtered, filtrate 15mL is drawn, is placed in 150mL beaker, adds 40mL alcoholic solution, 1 drop crystal aluminum chloride molten
Liquid shakes up, and 50mL tetraphenylboron sodium ethanol solution is added, stirs evenly, and stands 10min, makes its precipitating completely, the alcoholic solution is
The volume ratio of ethyl alcohol and propylene glycol is the mixed solution of 9:1；It is filtered under diminished pressure with the glass sand core funnel of constant weight, with 40-
50mL ethanol washing precipitating, drying to constant weight in 105 DEG C of baking ovens, weighs；
By the precipitating in glass sand core funnel, with 10mL dimethylformamide careful dissolution and it is transferred to 150mL conical flask
In, with 30mL acetone washing, add 20mL isopropanol, 3 drop thymol blue indicator solutions, with 0.02mol/L tetrabutylammonium hydroxide mark
It is titration end-point that it is blue, which to be titrated to solution, for quasi- solution, while making blank determination.
Replication 5 times, precision test is carried out, recovery test the results are shown in Table 13,14.
13 30.01% first piperazine brassin lactones Precision test result of table
14 30.01% first piperazine brassin lactones recovery test result of table
Wherein, in table 14, " quality in sample ", which is censured, takes the first piperazine product of known content, the product contain it is effective at
Sub-prime amount, " standard specimen quality is added ", which censures, takes first piperazine standard specimen, effective component quality, and both the above component content is accurate
Known, recovery test verifying is the gap of the sample quality of the quality and addition of actual measurement after being added into standard specimen, with
The rate of recovery indicates that the rate of recovery is greater than 97% and belongs to satisfactory value.
From embodiment three to embodiment eight as can be seen that technical scheme is directed to different dosage forms and different component
Complex agent type, detection first piperazine content value stablize, relative to industry requirement be greater than 97% minimum, add back
Yield is higher, in addition, technical scheme measurement data accurate stable, cost is relatively low, have a good application prospect.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (9)
1. the detection method of a kind of first piperazine and its by-product, the by-product is N- piperidine hydrochloride, it is characterised in that:
It is described that detection method includes the following steps:
(1) prepared by sample: weighing first piperazine sample and is no less than 10mg, lower alcohols solvent is added and sufficiently dissolves, obtains sample solution；
The lower alcohols solvent is at least one selected from methanol, ethyl alcohol, ethylene glycol, propylene glycol；
(2) precipitating preparation: low-alcohol solution, crystal aluminum chloride solution is added in sample solution 15mL described in removing step (1),
After mixing, it adds sodium tetraphenylborate solution to be uniformly mixed, standing at least 10 minutes must precipitate；By precipitating filtering, wash
It washs, drying to constant weight；The sample solution is first settled to 50mL before pipetting, then carries out centrifugal filtration, keeps the sample molten
Liquid clarification；
(3) washing of precipitate: after the precipitating that drying to constant weight described in step (2) is dissolved with dimethylformamide, it is transferred to cone
It is to be titrated in shape bottle；
(4) it titrates: sequentially adding isopropanol in solution to be titrated in step (3) described conical flask, 2-3 drop thymol blue refers to
Show liquid, it is titration end-point that it is blue, which to be titrated to the solution, with tetrabutylammonium hydroxide standard titration solution, while doing blank
Titration；
(5) content calculates:
The first piperazine content X indicated with mass percent1, it is calculated by formula I:
(Ⅰ)
M in the formula2It is calculated by formula II:
(Ⅱ)m2=c (V1- V0)×419.5÷1000
The N- piperidine hydrochloride content X indicated with mass percent2, it is calculated by formula III:
(Ⅲ)
In the formula I, II, III:
C --- the concentration of tetrabutylammonium hydroxide standard titration solution, mol/L；
V1--- titration sample solution consumes the volume of tetrabutylammonium hydroxide standard titration solution, mL；
V0--- titration blank solution consumes the volume of tetrabutylammonium hydroxide standard titration solution, mL；
m1--- the quality for the precipitating that drying to constant weight described in step (2), g；
The quality of first piperazine sample, g described in m --- step (1).
2. a kind of detection method according to claim 1, it is characterised in that: the low-alcohol solution is selected from least one
Methanol, ethyl alcohol, ethylene glycol, propylene glycol.
3. a kind of detection method according to claim 2, it is characterised in that: the lower alcohols solvent or the lower alcohol
Solution is ethyl alcohol.
4. a kind of detection method according to claim 1, it is characterised in that: in the step (2), the tetraphenylboron sodium is molten
Liquid is tetraphenylboron sodium ethanol solution or tetraphenylboron sodium aqueous solution, and the concentration of the sodium tetraphenylborate solution is 20g/L, and volume is
50mL。
5. a kind of detection method according to claim 1, it is characterised in that: in the step (2), the precipitating is carried out
It when being filtered, washed, drying, is filtered under diminished pressure with the glass sand core funnel of constant weight, with 40-50mL alcoholic solutions or deionization
Water washing is dried in 105 DEG C of baking ovens.
6. a kind of detection method according to claim 1, it is characterised in that: in the step (3), after the drying
After precipitating is dissolved with dimethylformamide, when being transferred to conical flask, using acetone washing residual solution, it is made to be fully transferred to institute
It states in conical flask, the dimethylformamide is 10mL.
7. a kind of detection method according to claim 1, it is characterised in that: in the step (1): the weighed first piperazine
Sample is 15mg, and the sample solution pipetted is 15mL.
8. a kind of detection method according to claim 1, it is characterised in that: in the step (2), the crystal aluminum chloride
Solution is 1-2 drops.
9. a kind of detection method according to claim 1, it is characterised in that: in the step (4), the tetrabutyl hydrogen-oxygen
The concentration for changing ammonium standard titration solution is 0.02mol/L, and the additional amount of the isopropanol is 20mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510291859.7A CN105043923B (en) | 2015-06-01 | 2015-06-01 | A kind of detection method of first piperazine and its by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510291859.7A CN105043923B (en) | 2015-06-01 | 2015-06-01 | A kind of detection method of first piperazine and its by-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105043923A CN105043923A (en) | 2015-11-11 |
| CN105043923B true CN105043923B (en) | 2018-12-25 |
Family
ID=54450641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510291859.7A Active CN105043923B (en) | 2015-06-01 | 2015-06-01 | A kind of detection method of first piperazine and its by-product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105043923B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105300978B (en) * | 2015-11-18 | 2018-02-09 | 北京市政路桥建材集团有限公司 | Containing oil soluble amine surfactants warm-mixing agent detection method in a kind of warm-mixed asphalt |
| CN114894938A (en) * | 2022-05-30 | 2022-08-12 | 山东诺正检测有限公司 | Method for detecting brassinolide in soil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271072A (en) * | 2008-04-30 | 2008-09-24 | 河南农大迅捷测试技术有限公司 | Method for measuring kalium in soil by tetraphenylboron sodium nephelometery and its screening agent |
-
2015
- 2015-06-01 CN CN201510291859.7A patent/CN105043923B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271072A (en) * | 2008-04-30 | 2008-09-24 | 河南农大迅捷测试技术有限公司 | Method for measuring kalium in soil by tetraphenylboron sodium nephelometery and its screening agent |
Non-Patent Citations (3)
| Title |
|---|
| 共振光散射法测定甲哌鎓水剂中的氯含量;张涛 等;《农药》;20060228;第45卷(第2期);第111-124页 * |
| 核磁共振法测定甲哌鎓原药的含量;魏泱 等;《农药科学与管理》;20141231;第35卷(第12期);第49-52页 * |
| 高效液相离子对色谱法测定甲哌鎓有效成分含量;邹伟斌 等;《农药》;20100930;第49卷(第9期);第660-663页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105043923A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | A colorimetric method for fluoride determination in aqueous samples based on the hydroxyl deprotection reaction of a cyanine dye | |
| CN106905538B (en) | A kind of zinc-containing metal organic framework materials and its preparation method and application | |
| Lozynska et al. | Spectrophotometric Studies of 4-[N'-(4-Imino-2-oxo-thiazolidin-5-ylidene)-hydrazino]-benzenesulfonic acid as a Reagent for the Determination of Palladium. | |
| CN108822078A (en) | One kind is based on aggregation inducing effect mercury ion fluorescence probe and its preparation and application | |
| CN105043923B (en) | A kind of detection method of first piperazine and its by-product | |
| Wang et al. | Determination of four aromatic amines in water samples using dispersive liquid–liquid microextraction combined with HPLC | |
| CN103728398B (en) | A kind of Ion-pair Liquid Chromatography measures the method for dyeing and finishing auxiliaries for textile neutral line alkyl benzene sulfonate | |
| CN105823738B (en) | A kind of method of transportable property fluorescent brightener levels in measurement paper products | |
| CN105973824A (en) | Method for detecting heavy metals in wastewater | |
| CN102353668A (en) | Method for determining anionic surfactant in surface water | |
| CN110296947A (en) | A kind of cement Cr VI test powder indicator and preparation method thereof | |
| CN104697835B (en) | Aromatic amine detection mixed mark solution of standard and preparation method thereof and purposes in textile | |
| CN104111306B (en) | A kind of method measuring Tea Polyphenols in Tea content | |
| CN108760920A (en) | A method of cyazofamid and its metabolite residue amount are measured based on HPLC-MSMS methods | |
| CN102830114B (en) | Detection method for content of tannin in plant extract liquid | |
| CN104777062A (en) | Method for measuring silicon dioxide content in rare earth concentrate | |
| CN106093012A (en) | The assay method of potassium oxide in a kind of compound fertilizer | |
| Borges et al. | Constant-current coulometry and ion chromatography bromide determination to characterize the purity of the potassium chloride | |
| CN108802083A (en) | A kind of method of sulphur, chlorinity in measurement triphenylphosphine | |
| CN105628669A (en) | Detection method of melamine in milk and milk powder | |
| CN104655610B (en) | The analysis method and assay method of vanadyl oxalate oxalate ion concentration | |
| CN111337611A (en) | Method for detecting malachite green, leucomalachite green, crystal violet and leucocyte crystal violet in aquatic products | |
| CN104215541A (en) | Method for high efficiently and precisely measuring contents of high purity alumina and impurities | |
| RU2283484C1 (en) | Composition of standard samples for controlling error of measurements of oil products content in watery substances | |
| CN110491531A (en) | Zirconium base body removes technique and the burnup measurement method using the technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |