CN105043923A - Detection method of Mepigtlat-chloride and side product thereof - Google Patents
Detection method of Mepigtlat-chloride and side product thereof Download PDFInfo
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Abstract
The invention discloses a detection method of Mepigtlat-chloride and a side product thereof. The method comprises the following steps of weighing a Mepigtlat-chloride sample, adding a low alcohol solvent to dissolve the solvent to obtain a sample solution; weighing the sample solution, adding a low alcohol solution and an aluminum chloride crystal solution, then adding a sodium tetraphenylborate solution, mixing the solutions uniformly and standing for at least 10 minutes to obtain a sediment; filtering the sediment, washing and drying the sediment to constant weight; and dissolving the dried sediment by using dimethylformamide, transferring the obtained product to a conical flask for titration; orderly adding isopropyl alcohol and 2-3 drops of thymol blue indicating liquid, and titrating by using a tetrabutyl ammonium hydroxide standard solution, and reaching the titration end point until the solution is blue. The detection method is simple, rapid and can accurately detect the Mepigtlat-chloride content, can detect the content of Mepigtlat-chloride piperidine hydrochloride side product at the same time, can be applied to the detection of most of Mepigtlat-chloride preparation products, does not need expensive analytical instruments, has low detection cost, stable and accurate detection result, and solves the problem of difficult detection analysis of the Mepigtlat-chloride preparation products.
Description
Technical field
The present invention relates to the titration determination field of component in solution, be specifically related to the detection method of a kind of first piperazine and accessory substance thereof.
Background technology
First piperazine (1,1-dimethylpiperidine chloride), also known as mepiquat chloride, cotton strong element, help strong element, cotton long fast, increase cotton loose, gram this, regulate pyridine, its molecular formula is C
7h
16clN, structural formula as shown in the formula:
First piperazine has retarding action to vegetation growth of plant, by plant leaf blade and root absorption, conduct to complete stool, reduce plant inner gibberellin active, thus T suppression cell extends, and makes plant shortened internodes, leaf green synthesis strengthens, plant can be prevented and treated and cross prosperous growth, have effect that is resistant to lodging, that increase production and increase resistance.
N-piperidine hydrochloride accessory substance is there is in the former medicine of first piperazine, the material that must detect is belonged at present on agriculture chemical registration requires, testing result is presented as: former medicine inspection effluent is N-piperidine hydrochloride, aqua product is due to cannot direct-detection N-piperidine hydrochloride, and therefore recognizate is sodium chloride and organic chloride.
The detection of the former medicine of current first piperazine is based on industry standard HG/T2856-1997, and its basic skills is the precipitation method, and the method energy accurate analysis goes out first piperazine and N-piperidine hydrochloride, only measures for former medicine at present in Pesticidal products.In compound product, because tetraphenylboron sodium with potassium ion, quaternary ammonium salt and some chlorine-containing organic compounds etc., complex reaction can occur, be easily subject to other auxiliary agent or the impact of former medicine in compound product, therefore the method is not suitable for the analysis of first piperazine in formulation products.
For complex preparation product, detection method available at present exists following several:
1, Ion-pair chromalography post is combined with electric conductivity detector, IP HPLC is applicable to the analysis of ionic species compound, in pesticide industry, most former medicine is all non-ionic compound, general detecting device all can be equipped with Application comparison UV-detector widely, and a lot of medium-sized and small enterprises generally can not be equipped with electric conductivity detector or ion chromatograph, therefore the method is not prefered method in a lot of enterprise, and this is also the reason that domestic former medicine and aqua standard all do not adopt the method.
2, reverse-phase chromatographic column is combined with UV-detector, there is two problems in the method, one is that determined wavelength is too low, lower than the ultraviolet cut-on wavelength (200nm) of water, its solvent and impurity effect larger, therefore may be only suitable for purer first piperazine single-dose product; Two is that N-piperidine hydrochloride does not go out peak, according to up-to-date agriculture chemical registration data review detailed rules and regulations requirement, N-piperidine hydrochloride content must be detected in first piperazine product, according to the method, N-piperidine hydrochloride content cannot be detected, and need to grope other method to detect.
3, potentiometric titration is combined with paper chromatography, and adopt the method can obtain first piperazine content more accurately, but the method shortcoming also clearly: determination step is many, needs point sample, chromatography, colour developing, the processes such as titration, spended time is long especially; Precision is very low, and for low content aqua product, precision is lower.The method is only for single-dose product in addition, and for compound product, owing to containing other auxiliary agent or former medicine in composition, its pre-treatment needs to grope further.As contained highly acid material or metallic ion in compound product, chromatographic solution may be affected and cause content inaccurate; Composite former medicine or auxiliary agent contain same chlorion, also may affect assay.
Additive method such as liquid chromatograph mass spectrography detects, but mass detector price is too high, and for Pesticidal products inspection, substantially increase the testing cost of product, its 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 accessory substance thereof, described detection method can detect the content of first piperazine and N-piperidine hydrochloride accessory substance simply, quickly and accurately, can be applicable to most first piperazine formulation products detect, do not need to use expensive analytical instrument, testing cost is low, testing result accurate stable, solves first piperazine formulation products and detects the problem analyzing difficulty.
For solving above technical matters, technical scheme provided by the invention is the detection method of a kind of first piperazine and accessory substance thereof, and described accessory substance is N-piperidine hydrochloride, and described detection method comprises the following steps:
(1) sample preparation: take first piperazine sample and be no less than 10mg, add lower alcohols solvent and fully dissolve, obtain sample solution;
(2) precipitation: sample solution described in removing step (1), adds low-alcohol solution, crystal aluminum chloride solution, after mixing, then adds sodium tetraphenylborate solution and mixes, and leaves standstill and must precipitate at least 10 minutes; By described sedimentation and filtration, washing, oven dry to constant weight;
(3) washing of precipitate: by drying described in step (2) to the precipitation dimethyl formamide dissolving of constant weight, be transferred in conical flask to be titrated;
(4) titration: add isopropyl alcohol successively in solution to be titrated in step (3) described conical flask, 2-3 thymol blue indicator solutions, being titrated to described solution with TBAH standard solution is that blueness is titration end-point, does blank titration simultaneously;
(5) cubage:
The first piperazine content X represented with mass percent
1, calculate by formula I:
(Ⅰ)X
1＝(m
1－m
2)×115.08÷m
M in described formula
2calculate by formula II:
(Ⅱ)m
2＝c(V
1－V
0)×419.5÷1000
The N-piperidine hydrochloride content X represented with mass percent
2, calculate by formula III:
(Ⅲ)X
2＝c(V
1－V
0)×45.22÷m
In described formula I, II, III:
C---the concentration of TBAH standard titration solution, mol/L;
V
1---titration sample solution, consumes the volume of TBAH standard titration solution, mL;
V
0---titration blank solution, consumes the volume of TBAH standard titration solution, mL;
M
1---dry the quality of the precipitation to constant weight described in step (2), g;
The quality of first piperazine sample described in m---step (1), g.
Preferably, in described step (1), lower alcohols solvent or low-alcohol solution are that at least one is selected from methyl alcohol, ethanol, ethylene glycol, propylene glycol, and described lower alcohols solvent is 35-45mL.
More preferred, in described step (1), lower alcohols solvent or low-alcohol solution are ethanol.
Preferably, in described step (2), described sample solution, before pipetting, is first settled to 50mL, then carries out centrifugal filtration, and described sample solution is clarified.
Preferably, in described step (2), described sodium tetraphenylborate solution is tetraphenylboron sodium ethanolic solution, or tetraphenylboron sodium aqueous solution, and the concentration of described sodium tetraphenylborate solution is 20g/L, and volume is 50mL.
Preferably, in described step (2), described precipitation carried out filter, wash, when drying, carry out filtration under diminished pressure with the glass sand core funnel of constant weight, wash with 40-50mL alcoholic solution or deionized water, dry in 105 DEG C of baking ovens.
Preferably, it is characterized in that: in described step (3), after the precipitation dimethyl formamide after described oven dry is dissolved, when being transferred to conical flask, adopt acetone wash residual solution, make it all be transferred in described conical flask, described dimethyl formamide is 10mL.
Preferably, in described step (1): described in the first piperazine sample that takes be 15mg, described in the sample solution that pipettes be 15mL.
Preferably, in described step (2), described crystal aluminum chloride solution is 1-2.
Preferably, in described step (4), the concentration of described TBAH standard solution is 0.02mol/L, and the addition of described isopropyl alcohol is 20mL.
The application's detection method as shown in Figure 1, first piperazine sample containing accessory substance N-piperidine hydrochloride, add lower alcohol solvent, while sample dissolution, exclusive segment emulsifying agent and all metal ions are on the impact of tetraphenylboron sodium, after forming sample solution, add tetraphenylboron sodium, for complex-precipitation first piperazine and N-piperidine hydrochloride, the gross mass of first piperazine and N-piperidine hydrochloride can be calculated by the quality of described precipitation, described precipitation is added again with dimethyl formamide, because first piperazine complex compound is insoluble to dimethyl formamide, and N-piperidine hydrochloride complex compound dissolves in dimethyl formamide, what therefore obtain is N-piperidine hydrochloride solution, adopt TBAH standard solution titration N-piperidine hydrochloride solution, the quality of N-piperidine hydrochloride can be calculated, the quality of N-piperidine hydrochloride is deducted by gross mass, the quality of first piperazine can be obtained.
Wherein, the m in formula I
1the i.e. tetraphenylboron complex compound gross mass of nail piperazine and N-piperidine hydrochloride; m
2namely the quality of the tetraphenylboron complex compound of N-piperidine hydrochloride is referred to.
The application compared with prior art, it is described in detail as follows: technical scheme provides the detection method of a kind of first piperazine and accessory substance thereof, comprise the step of sample preparation, titration, cubage, by the accessory substance in former for first piperazine medicine and preparation thereof by tetraphenylboron sodium complexing, carry out titration again, add lower alcohols solvent before complexing and can remove the salt impurity such as inorganics to the impact of tetraphenylboron sodium, remove partial emulsifier to the impact of tetraphenylboron sodium complex compound, the application's detection method can avoid the impact on chromatographic solution in aqua examination criteria.
Relative to existing analyzing detecting method, the beneficial effect of technical scheme is: technical scheme does not need expensive analytical instrument, as chromatographic apparatus, mass spectrometer etc.; Its analytical approach is simple to operation, the loaded down with trivial details process such as does not need the some plate in paper chromatography, chromatography, develops the color, dries; Current former medicine, aqua product analysis can be suitable for, alternative existing product analysis standard simultaneously; Technical scheme has wide range of applications, except former medicine can be surveyed, single-dose product, compound product etc. can also be surveyed, especially compound product, existing aqua product analytical approach (chromatography) cannot be analyzed, and this method can easily analyze; In addition technical scheme is not only applied to aqua formulation, can also be applied to the analysis of other different dosage form product, such as missible oil, suspending agent, wettable powder, microemulsion etc.; The process of precipitation is obviously fast than former prescription method, saves analysis time; Method described in the application can analyze first piperazine and N-piperidine hydrochloride content simultaneously, and can replace existing aqua product, and accurate analysis goes out piperidinium salt content, analyzes accurate stable.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the application's detection method.
Embodiment
In order to make those skilled in the art understand technical scheme of the present invention better, below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment one
The former medicine of first piperazine (crystal) measures
The present embodiment adopts detection method described in the application, and measure the former medicine of first piperazine (crystal), its concrete operations are as follows:
Take described first piperazine former medicine (pulvis) sample 1.5g, be placed in 50mL volumetric flask, dissolve with ethanol and be settled to 50mL; Draw 15.00mL solution, be placed in 150mL beaker, add 40mL ethanol and 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium ethanolic solution, stir, leave standstill 10min, make it precipitate completely; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, with the washing precipitation of 40-50mL ethanol, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, calculate the mass percentage of first piperazine and N-piperidine hydrochloride respectively, simultaneously, the mass percentage with the first piperazine in a collection of former medicine and N-piperidine hydrochloride is measured with reference to HG/T2856-1997 (first piperazine former medicine standard), replication 5 times, example in contrast, result is as table 1.
The former medicine of table 1 first piperazine (crystal) measurement result
As can be seen from determination data, with a collection of former medicine, adopt assay method described in the application, the mass percentage of first piperazine is 98.5-98.7%, standard testing result is 98.5-98.8%, can obviously find out, the data fluctuations scope of the application's assay method is less than standard by 0.1%; N-piperidine hydrochloride detects 0.4-0.5%, and standard detection is 0.4-0.6%, and its data fluctuations scope is less than standard equally, and therefore the application's assay method comparatively accurate stable can be described.
Embodiment two
250g/L first piperazine aqua measures
The present embodiment adopts detection method described in the application, and measure 250g/L first piperazine aqua, its concrete operations are as follows:
Get described first piperazine water sample 6.00mL, be placed in 50mL capacity, be settled to 50mL with alcoholic solution, described alcoholic solution is the volume ratio of ethanol and ethylene glycol is the mixed solution of 4:1; Pipette samples solution 15.00mL, is placed in 150mL beaker, adds 40mL alcoholic solution, 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium ethanolic solution, stir, leave standstill 10min, make it precipitate completely, described alcoholic solution is the volume ratio of ethanol and ethylene glycol is the mixed solution of 4:1; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, with the washing precipitation of 40-50mL ethanol, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, calculate the mass percentage of first piperazine and N-piperidine hydrochloride respectively, simultaneously, the mass percentage with the first piperazine in a collection of former medicine and N-piperidine hydrochloride is measured with reference to HG/T2856-1997 (first piperazine former medicine standard), replication 5 times, example in contrast, result is as table 2.
Table 2250g/L first piperazine aqua measurement result
As can be seen from determination data, with a collection of product, adopt assay method described in the application, the fluctuation range that its first piperazine testing result obviously detects than standard method is little, and the chloride content that standard method detects contains other chloride composition except N-piperidine hydrochloride, therefore result is much higher than the application's method.In our company's production reality, also run into analogue, former medicine accessory substance is qualified, and is processed into aqua product, and testing result accessory substance exceeds standard, and reason is exactly that accessory substance detection method is different.Therefore the application's assay method more accurate stable can be described.
Embodiment three
The solvable pulvis of 10% first piperazine measures
The present embodiment adopts detection method described in the application, and measure the solvable pulvis of 10% first piperazine, its concrete operations are as follows:
Take the solvable pulvis 3.0g (being accurate to 0.0002g) of described 10% first piperazine, be placed in 50mL volumetric flask, add 40mL alcoholic solution, after sample is fully mixed, be settled to 50mL, described alcoholic solution is the volume ratio of ethanol and propylene glycol is the mixed solution of 9:1; Sample solution is centrifugal, filter, draw filtrate 15mL, be placed in 150mL beaker, add 40mL alcoholic solution, 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium aqueous solution, stir, leave standstill 10min, make it precipitate completely, described alcoholic solution is the volume ratio of ethanol and propylene glycol is the mixed solution of 9:1; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, with the washing precipitation of 40mL deionized water, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, carries out precision test, recovery test, the results are shown in Table 3,4.
The solvable pulvis Precision test result of table 310% first piperazine
Table 410% first piperazine solvable pulvis recovery test result
Wherein, in table 4, " in sample quality " censures the first piperazine product getting known content, the effective constituent quality that this product contains, and first piperazine standard specimen is got in " adding standard specimen quality " denotion, its effective constituent quality, above two kinds of component contents are accurately known, and what recovery test was verified is after being added into standard specimen, the quality of actual measurement and the gap of the sample quality added, represent with the recovery, the recovery is greater than 97% and namely belongs to satisfactory value.
Embodiment four
5% first piperazine missible oil measures
The present embodiment adopts detection method described in the application, and measure 5% first piperazine missible oil, its concrete operations are as follows:
Take described 5% first piperazine missible oil 3.0g (being accurate to 0.0002g), be placed in 50mL volumetric flask, add ethanol and be settled to 50mL; Pipette samples solution 15mL, is placed in 150mL beaker, adds 40mL ethanolic solution, 1 crystal aluminum chloride solution, shakes up, add 50mL sodium tetraphenylborate solution, stir, and leaves standstill 10min, makes it precipitate completely; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, with the washing precipitation of 40-50mL ethanol, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, carries out precision test, recovery test, the results are shown in Table 5,6.
Table 55% first piperazine missible oil Precision test result
Table 65% first piperazine missible oil recovery test result
Wherein, in table 6, " in sample quality " censures the first piperazine product getting known content, the effective constituent quality that this product contains, and first piperazine standard specimen is got in " adding standard specimen quality " denotion, its effective constituent quality, above two kinds of component contents are accurately known, and what recovery test was verified is after being added into standard specimen, the quality of actual measurement and the gap of the sample quality added, represent with the recovery, the recovery is greater than 97% and namely belongs to satisfactory value.
Embodiment five
30% paclobutrazol first piperazine suspending agent measures
The present embodiment adopts detection method described in the application, and measure 30% paclobutrazol first piperazine suspending agent, its concrete operations are as follows:
Take described 30% paclobutrazol first piperazine suspending agent 3.0g (being accurate to 0.0002g), be placed in 50mL volumetric flask, add 40mL alcoholic solution, after sample is fully mixed, be settled to 50mL, described alcoholic solution is the volume ratio of methyl alcohol and ethylene glycol is the mixed solution of 7:3; Sample solution is centrifugal, filter, draw filtrate 15mL, be placed in 150mL beaker, add 40mL alcoholic solution, 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium ethanolic solution, stir, leave standstill 10min, make it precipitate completely, described alcoholic solution is the volume ratio of methyl alcohol and ethylene glycol is the mixed solution of 7:3; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, by 40-50mL methanol wash precipitation, dry in 105 DEG C of baking ovens to constant weight, weigh.
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, carries out precision test, recovery test, the results are shown in Table 7,8.
Table 730% paclobutrazol first piperazine suspending agent Precision test result
Table 830% paclobutrazol first piperazine suspending agent recovery test result
Wherein, in table 8, " in sample quality " censures the first piperazine product getting known content, the effective constituent quality that this product contains, and first piperazine standard specimen is got in " adding standard specimen quality " denotion, its effective constituent quality, above two kinds of component contents are accurately known, and what recovery test was verified is after being added into standard specimen, the quality of actual measurement and the gap of the sample quality added, represent with the recovery, the recovery is greater than 97% and namely belongs to satisfactory value.
Embodiment six
110g/L ring malonamic acid first piperazine aqua measures
The present embodiment adopts detection method described in the application, and measure 110g/L ring malonamic acid first piperazine aqua, its concrete operations are as follows:
Take described 110g/L ring malonamic acid first piperazine aqua 3.0g (being accurate to 0.0002g), be placed in 50mL volumetric flask, add alcoholic solution, be settled to 50mL, described alcoholic solution is the volume ratio of methyl alcohol and propylene glycol is the mixed solution of 9:1; Sample solution is centrifugal, filter, draw filtrate 15mL, be placed in 150mL beaker, add 40mL alcoholic solution, 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium ethanolic solution, stir, leave standstill 10min, make it precipitate completely, described alcoholic solution is the volume ratio of methyl alcohol and propylene glycol is the mixed solution of 9:1; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, by 40-50mL methanol wash precipitation, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, carries out precision test, recovery test, the results are shown in Table 9,10.
Table 9110g/L ring malonamic acid first piperazine Precision test result
Table 10110g/L ring malonamic acid first piperazine aqua recovery test result
Wherein, in table 10, " in sample quality " censures the first piperazine product getting known content, the effective constituent quality that this product contains, and first piperazine standard specimen is got in " adding standard specimen quality " denotion, its effective constituent quality, above two kinds of component contents are accurately known, and what recovery test was verified is after being added into standard specimen, the quality of actual measurement and the gap of the sample quality added, represent with the recovery, the recovery is greater than 97% and namely belongs to satisfactory value.
Embodiment seven
30.05% first piperazine triacontanol microemulsion measures
The present embodiment adopts detection method described in the application, and measure 30.05% first piperazine triacontanol microemulsion, its concrete operations are as follows:
Take described 30.05% first piperazine triacontanol microemulsion 3.0g (being accurate to 0.0002g), be placed in 50mL volumetric flask, add alcoholic solution, be settled to 50mL, described alcoholic solution is the volume ratio of ethanol and propylene glycol is the mixed solution of 9:1; Sample solution is centrifugal, filter, draw filtrate 15mL, be placed in 150mL beaker, add 40mL alcoholic solution, 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium ethanolic solution, stir, leave standstill 10min, make it precipitate completely, described alcoholic solution is the volume ratio of ethanol and propylene glycol is the mixed solution of 9:1; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, with the washing precipitation of 40-50mL ethanol, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, carries out precision test, recovery test, the results are shown in Table 11,12.
Table 1130.05% first piperazine triacontanol Precision test result
Table 1230.05% first piperazine triacontanol microemulsion recovery test result
Wherein, in table 12, " in sample quality " censures the first piperazine product getting known content, the effective constituent quality that this product contains, and first piperazine standard specimen is got in " adding standard specimen quality " denotion, its effective constituent quality, above two kinds of component contents are accurately known, and what recovery test was verified is after being added into standard specimen, the quality of actual measurement and the gap of the sample quality added, represent with the recovery, the recovery is greater than 97% and namely belongs to satisfactory value.
Embodiment eight
30.01% first piperazine brassin lactones microemulsion measures
The present embodiment adopts detection method described in the application, and measure 30.01% first piperazine brassin lactones microemulsion, its concrete operations are as follows:
Take described 30.01% first piperazine brassin lactones microemulsion 3.0g (being accurate to 0.0002g), be placed in 50mL volumetric flask, add alcoholic solution, be settled to 50mL, described alcoholic solution is the volume ratio of ethanol and propylene glycol is the mixed solution of 9:1; Sample solution is centrifugal, filter, draw filtrate 15mL, be placed in 150mL beaker, add 40mL alcoholic solution, 1 crystal aluminum chloride solution, shake up, add 50mL tetraphenylboron sodium ethanolic solution, stir, leave standstill 10min, make it precipitate completely, described alcoholic solution is the volume ratio of ethanol and propylene glycol is the mixed solution of 9:1; Carry out filtration under diminished pressure with the glass sand core funnel of constant weight, with the washing precipitation of 40-50mL ethanol, dry in 105 DEG C of baking ovens to constant weight, weigh;
By the precipitation in glass sand core funnel, be transferred in 150mL conical flask with 10mL dimethyl formamide careful dissolution, wash with 30mL acetone, add 20mL isopropyl alcohol, 3 thymol blue indicator solutions, being titrated to solution with 0.02mol/L TBAH standard solution is that blueness is titration end-point, does blank determination simultaneously.
Replication 5 times, carries out precision test, recovery test, the results are shown in Table 13,14.
Table 1330.01% first piperazine brassin lactones Precision test result
Table 1430.01% first piperazine brassin lactones recovery test result
Wherein, in table 14, " in sample quality " censures the first piperazine product getting known content, the effective constituent quality that this product contains, and first piperazine standard specimen is got in " adding standard specimen quality " denotion, its effective constituent quality, above two kinds of component contents are accurately known, and what recovery test was verified is after being added into standard specimen, the quality of actual measurement and the gap of the sample quality added, represent with the recovery, the recovery is greater than 97% and namely belongs to satisfactory value.
As can be seen from embodiment three to embodiment eight, technical scheme is directed to the complex agent type of different dosage form and different component, its first piperazine content value detected is stablized, relative to industry requirement be greater than 97% minimum, its TIANZHU XINGNAO Capsul is higher, in addition, the data accurate stable that technical scheme measures, cost are lower, have good application prospect.
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred implementation should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a detection method for first piperazine and accessory substance thereof, described accessory substance is N-piperidine hydrochloride, it is characterized in that: described detection method comprises the following steps:
(1) sample preparation: take first piperazine sample and be no less than 10mg, add lower alcohols solvent and fully dissolve, obtain sample solution;
(2) precipitation: sample solution described in removing step (1), adds low-alcohol solution, crystal aluminum chloride solution, after mixing, then adds sodium tetraphenylborate solution and mixes, and leaves standstill and must precipitate at least 10 minutes; By described sedimentation and filtration, washing, oven dry to constant weight;
(3) washing of precipitate: by drying described in step (2) to the precipitation dimethyl formamide dissolving of constant weight, be transferred in conical flask to be titrated;
(4) titration: add isopropyl alcohol successively in solution to be titrated in step (3) described conical flask, 2-3 thymol blue indicator solutions, being titrated to described solution with TBAH standard solution is that blueness is titration end-point, does blank titration simultaneously;
(5) cubage:
The first piperazine content X represented with mass percent
1, calculate by formula I:
(Ⅰ)X
1＝(m
1－m
2)×115.08÷m
M in described formula
2calculate by formula II:
(Ⅱ)m
2＝c(V
1－V
0)×419.5÷1000
The N-piperidine hydrochloride content X represented with mass percent
2, calculate by formula III:
(Ⅲ)X
2＝c(V
1－V
0)×45.22÷m
In described formula I, II, III:
C---the concentration of TBAH standard titration solution, mol/L;
V
1---titration sample solution, consumes the volume of TBAH standard titration solution, mL;
V
0---titration blank solution, consumes the volume of TBAH standard titration solution, mL;
M
1---dry the quality of the precipitation to constant weight described in step (2), g;
The quality of first piperazine sample described in m---step (1), g.
2. a kind of detection method according to claim 1, it is characterized in that: in described step (1), lower alcohols solvent or low-alcohol solution are that at least one is selected from methyl alcohol, ethanol, ethylene glycol, propylene glycol, and described lower alcohols solvent is 35-45mL.
3. a kind of detection method according to claim 2, is characterized in that: in described step (1), lower alcohols solvent or low-alcohol solution are ethanol.
4. a kind of detection method according to claim 1, is characterized in that: in described step (2), described sample solution, before pipetting, is first settled to 50mL, then carries out centrifugal filtration, and described sample solution is clarified.
5. a kind of detection method according to claim 1, it is characterized in that: in described step (2), described sodium tetraphenylborate solution is tetraphenylboron sodium ethanolic solution, or tetraphenylboron sodium aqueous solution, the concentration of described sodium tetraphenylborate solution is 20g/L, and volume is 50mL.
6. a kind of detection method according to claim 1, it is characterized in that: in described step (2), described precipitation carried out filter, wash, when drying, filtration under diminished pressure is carried out with the glass sand core funnel of constant weight, with 40-50mL alcoholic solution or deionized water washing, dry in 105 DEG C of baking ovens.
7. a kind of detection method according to claim 1, it is characterized in that: in described step (3), after precipitation dimethyl formamide after described oven dry is dissolved, when being transferred to conical flask, adopt acetone wash residual solution, make it all be transferred in described conical flask, described dimethyl formamide is 10mL.
8. a kind of detection method according to claim 1, is characterized in that: in described step (1): described in the first piperazine sample that takes be 15mg, described in the sample solution that pipettes be 15mL.
9. a kind of detection method according to claim 1, is characterized in that: in described step (2), and described crystal aluminum chloride solution is 1-2.
10. a kind of detection method according to claim 1, is characterized in that: in described step (4), and the concentration of described TBAH standard solution is 0.02mol/L, and the addition of described isopropyl alcohol is 20mL.
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