CN106885866B - A kind of constituent analysis test method of the 4,6- dihydroxy-pyrimidine reaction solutions of bipolar film process - Google Patents
A kind of constituent analysis test method of the 4,6- dihydroxy-pyrimidine reaction solutions of bipolar film process Download PDFInfo
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Abstract
This application provides the 4 of a kind of bipolar film process, the constituent analysis test method of 6 dihydroxy-pyrimidine reaction solutions, the application to formed using bipolar film process 4,6 dihydroxy-pyrimidine reaction solutions carry out constituent analysis test, analysis test method using the present invention can quick and precisely test out the ingredient of 4,6 dihydroxy-pyrimidine reaction solutions of bipolar film process, convenient for preferably understanding component distributing in 4, the 6 dihydroxy-pyrimidine reaction solution systems using bipolar film process.
Description
Technical field
The present invention relates to technical field of analytical chemistry, 4, the 6- dihydroxy-pyrimidines reaction of more particularly to a kind of bipolar film process
The constituent analysis test method of liquid.
Background technology
4,6- dihydroxy-pyrimidines are widely used in medicine, agriculture usually as fine chemical material or organic synthesis intermediate
The preparation of medicine and fungicide etc., such as can be used in medical industry to produce sulfonamides sulphur Mo Tuoxin, vitamin B4, it is antitumor
The intermediate of medicine and adjuvant class；Further, it is also possible to intermediate for synthesizing methoxy acrylic bactericide etc..Cause
This, 4,6- dihydroxy-pyrimidines have the larger market demand, and then have substantially pulled 4, prepared by the production of 6- dihydroxy-pyrimidines.
During 4,6- dihydroxy-pyrimidines are prepared, a large amount of 4,6- dihydroxy-pyrimidines reaction solution can be formed.For example, with first
When amide, malonate and alkali metal sodium alkoxide prepare 4,6- dihydroxy-pyrimidines for raw material, 4,6- dihydroxy-pyrimidine sodium can be initially formed
Salt, is diluted with water processing, formed the solution comprising 4,6- dihydroxy-pyrimidine sodium salts or comprising 4,6- dihydroxy-pyrimidines sodium salt with
The solution of sodium hydroxide, as 4,6- dihydroxy-pyrimidine reaction solutions, then the reaction solution is acidified and is produced up to 4,6- dihydroxy-pyrimidines
Product.Generally also all it is to be initially formed 4,6- dihydroxy-pyrimidine reaction solutions in other preparation methods, then 4,6- dihydroxy-pyrimidines is reacted
Liquid acidification obtains 4,6- dihydroxy-pyrimidine products.
The component distributing of analysis 4,6- dihydroxy-pyrimidine reaction solutions contributes to after understanding reaction solution system and facilitating adjusting
Acid amount etc. is used in continuous acidification technique, and in the prior art, when testing the analysis of 4,6- dihydroxy-pyrimidines, typically it is being acidified
To after 4,6- dihydroxy-pyrimidine products, the data in terms of testing final products obtained therefrom amount and obtaining product yield or purity, about
The constituent analysis prepared in the 4,6- dihydroxy-pyrimidine reaction solution systems that 4,6- dihydroxy-pyrimidines are formed is but rarely reported.
Invention content
In view of this, the present invention provides a kind of constituent analysis of 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process surveys
Method for testing, analysis test method of the invention can test out in 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process into
Point, convenient for understanding the component distributing of 4, the 6- dihydroxy-pyrimidine reaction solution systems of bipolar film process.
The present invention provides a kind of constituent analysis test method of 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process, packets
Include following steps：
S101：4,6- dihydroxy-pyrimidines standard sample and 4,6- dihydroxy-pyrimidines reaction solution is taken to carry out liquid phase color respectively for sample
Spectrum detection obtains the peak area r of the standard sample1With the peak area r for sample2；
According to formula 1, the reference amount W of 4,6- dihydroxy-pyrimidine sodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution is obtained：
W=(r2×m1×p)/(r1× m) formula 1；
Wherein,
r1For the peak area of 4, the 6- dihydroxy-pyrimidines standard sample, unit mv；
r2The peak area of sample, unit mv are supplied for 4, the 6- dihydroxy-pyrimidines reaction solution；
m1For the quality of 4, the 6- dihydroxy-pyrimidines standard sample, unit g；
Mass fractions of the p for 4, the 6- dihydroxy-pyrimidines standard sample, unit %；
M supplies the quality of sample, unit g for 4, the 6- dihydroxy-pyrimidines reaction solution；
According to formula 2, the reference for obtaining 4,6- dihydroxy-pyrimidine disodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution contains
Measure W1：
W1=W × (M3/M2) formula 2；
Wherein,
M3For the molal weight of sodium hydroxide, unit g/mol；
M2For the molal weight of 4,6- dihydroxy-pyrimidines, unit g/mol；
4,6- dihydroxy-pyrimidine reaction solutions is taken to treat test sample, treat to add in phenolphthalein indicator in test sample to described, and with salt acidity scale
Quasi- solution is titrated to colourless, and record consumes the volume V of hydrochloric acid standard solution；
According to formula 3, total alkali reference content W in 4,6- dihydroxy-pyrimidine reaction solutions is obtained2：
W2=(C × V × M3×10-3)/m2Formula 3；
Wherein,
Concentration of the C for the hydrochloric acid standard solution, unit mol/L；
V by consumption hydrochloric acid standard solution volume, unit mL；
M3For the molal weight of sodium hydroxide, unit g/mol；
m2For the quality for treating test sample, unit g；
S102：Qualitative analysis is carried out to the ingredient in the 4,6- dihydroxy-pyrimidines reaction solution by following discriminant approach：
If (a) W1＜ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and hydroxide in 4,6- dihydroxy-pyrimidines reaction solution
Sodium, without 4,6- dihydroxy-pyrimidines, one sodium salt；
If (b) W1＞ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and 4,6- dihydroxy in 4,6- dihydroxy-pyrimidines reaction solution
One sodium salt of yl pyrimidines, without sodium hydroxide；
The 4,6- dihydroxy-pyrimidines reaction solution is the 4,6- dihydroxy-pyrimidine reaction solutions through bipolar film process；It is described bipolar
The forming process of the 4,6- dihydroxy-pyrimidine reaction solutions of film process is：The raw material synthesized needed for 4,6- dihydroxy-pyrimidines is mixed anti-
Should, form intermediate product；The intermediate product is diluted with water again, forms include 4,6- dihydroxy-pyrimidine sodium salts one time 4,6-
Dihydroxy-pyrimidine reaction solution；Using 4, a 6- dihydroxy-pyrimidine reaction solution described in bipolar film process, bipolar film process is formed
4,6- dihydroxy-pyrimidine reaction solutions.
Preferably, it further includes and following quantitative analysis is carried out to the ingredient in 4,6- dihydroxy-pyrimidine reaction solutions：
For 4,6- dihydroxy-pyrimidine reaction solution systems (a), according to formula 4, obtain in 4,6- dihydroxy-pyrimidine reaction solutions
The mass percentage W of sodium hydroxide3：
W3=W2-W1Formula 4；
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidine disodium salts in 4,6- dihydroxy-pyrimidine reaction solutions4=W ×
(M1/M2)；
Wherein, M1For the molal weight of 4,6- dihydroxy-pyrimidine disodium salts, unit g/mol；
For 4,6- dihydroxy-pyrimidine reaction solution systems (b), according to formula 5, obtain in 4,6- dihydroxy-pyrimidine reaction solutions
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidine disodium salts4＇：
W4＇=C × V × M1×10-3/m2Formula 5；
According to formula 6, the actual mass hundred of 4,6- dihydroxy-pyrimidines, one sodium salt in 4,6- dihydroxy-pyrimidine reaction solutions is obtained
Divide content W5：
W5=W × (M4/M2) formula 6；
Wherein, M4For the molal weight of 4,6- dihydroxy-pyrimidines, one sodium salt, unit g/mol.
Preferably, in the step S101, the chromatographic condition of the liquid chromatographic detection is：
Using C18 chromatographic columns, using acetonitrile as mobile phase A phase, sour aqueous solution is Mobile phase B phase, the mobile phase A phase with
The volume ratio of Mobile phase B phase is (40~50)：(50~60).
Preferably, in the aqueous solution of the acid, sour percentage by volume is 0.3%~0.8%.
Preferably, the acid in the aqueous solution of the acid is acetic acid, phosphoric acid or trifluoroacetic acid.
Preferably, the liquid chromatographic detection wavelength is 195~280nm.
Preferably, the flow rate of mobile phase of the liquid chromatographic detection is 0.5~1.5mL/min.
Preferably, the temperature of the liquid chromatographic detection is 20~40 DEG C.
Preferably, in the step S101, before liquid chromatographic detection is carried out, by 4, the 6- dihydroxy-pyrimidines standard sample
With 4,6- dihydroxy-pyrimidines reaction solution for the sample organic filter membrane filtration that aperture is 0.22~0.45 μm respectively.
Preferably, 4, the 6- dihydroxy-pyrimidines reaction solution is using formamide, malonate and alkali metal sodium alkoxide as raw material
During preparing 4,6- dihydroxy-pyrimidines, 4, the 6- dihydroxy-pyrimidine reaction solutions that are formed.
The present invention provides a kind of constituent analysis test method of 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process, sheets
Invention carries out constituent analysis test to 4, the 6- dihydroxy-pyrimidines reaction solution formed using bipolar film process, using the present invention
Analysis test method can quick and precisely test out the ingredient of 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process, convenient for compared with
Good understanding utilizes component distributing in the 4,6- dihydroxy-pyrimidine reaction solution systems of bipolar film process.
Specific embodiment
The present invention provides a kind of constituent analysis test method of 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process, packets
Include following steps：
S101：4,6- dihydroxy-pyrimidines standard sample and 4,6- dihydroxy-pyrimidines reaction solution is taken to carry out liquid phase color respectively for sample
Spectrum detection obtains the peak area r of the standard sample1With the peak area r for sample2；
According to formula 1, the reference amount W of 4,6- dihydroxy-pyrimidine sodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution is obtained：
W=(r2×m1×p)/(r1× m) formula 1；
Wherein,
r1For the peak area of 4, the 6- dihydroxy-pyrimidines standard sample, unit mv；
r2The peak area of sample, unit mv are supplied for 4, the 6- dihydroxy-pyrimidines reaction solution；
m1For the quality of 4, the 6- dihydroxy-pyrimidines standard sample, unit g；
Mass fractions of the p for 4, the 6- dihydroxy-pyrimidines standard sample, unit %；
M supplies the quality of sample, unit g for 4, the 6- dihydroxy-pyrimidines reaction solution；
According to formula 2, the reference for obtaining 4,6- dihydroxy-pyrimidine disodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution contains
Measure W1：
W1=W × (M3/M2) formula 2；
Wherein,
M3For the molal weight of sodium hydroxide, unit g/mol；
M2For the molal weight of 4,6- dihydroxy-pyrimidines, unit g/mol；
4,6- dihydroxy-pyrimidine reaction solutions is taken to treat test sample, treat to add in phenolphthalein indicator in test sample to described, and with salt acidity scale
Quasi- solution is titrated to colourless, and record consumes the volume V of hydrochloric acid standard solution；
According to formula 3, total alkali reference content W in 4,6- dihydroxy-pyrimidine reaction solutions is obtained2：
W2=(C × V × M3×10-3)/m2Formula 3；
Wherein,
Concentration of the C for the hydrochloric acid standard solution, unit mol/L；
V by consumption hydrochloric acid standard solution volume, unit mL；
Wherein, M3For the molal weight of sodium hydroxide, unit g/mol；
m2For the quality for treating test sample, unit g；
S102：Qualitative analysis is carried out to the ingredient in the 4,6- dihydroxy-pyrimidines reaction solution by following discriminant approach：
If (a) W1＜ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and hydroxide in 4,6- dihydroxy-pyrimidines reaction solution
Sodium, without 4,6- dihydroxy-pyrimidines, one sodium salt；
If (b) W1＞ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and 4,6- dihydroxy in 4,6- dihydroxy-pyrimidines reaction solution
One sodium salt of yl pyrimidines, without sodium hydroxide；
The 4,6- dihydroxy-pyrimidines reaction solution is the 4,6- dihydroxy-pyrimidine reaction solutions through bipolar film process；It is described bipolar
The forming process of the 4,6- dihydroxy-pyrimidine reaction solutions of film process is：The raw material synthesized needed for 4,6- dihydroxy-pyrimidines is mixed anti-
Should, form intermediate product；The intermediate product is diluted with water again, forms include 4,6- dihydroxy-pyrimidine sodium salts one time 4,6-
Dihydroxy-pyrimidine reaction solution；Using 4, a 6- dihydroxy-pyrimidine reaction solution described in bipolar film process, bipolar film process is formed
4,6- dihydroxy-pyrimidine reaction solutions.
In the present invention, test object 4,6- dihydroxy-pyrimidines reaction solution is preferably that 4, the 6- dihydroxy through bipolar film process is phonetic
Pyridine reaction solution；The forming process of the 4,6- dihydroxy-pyrimidine reaction solutions of the bipolar film process is：It is phonetic 4,6- dihydroxy will to be synthesized
Raw material hybrid reaction needed for pyridine forms intermediate product；The intermediate product is diluted with water again, is formed comprising 4,6- dihydroxy
4,6- dihydroxy-pyrimidine reaction solution of pyrimidine sodium salt；It is reacted using a 4,6- dihydroxy-pyrimidine described in bipolar film process
Liquid forms 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process.
In the present invention, the raw material needed for synthesis 4, the 6- dihydroxy-pyrimidines is not particularly limited, to prepare 4,6- dihydroxies
Convenient source used in yl pyrimidines；In the present invention, the raw material preferably includes formamide, malonate and alkali metal alcohol
Sodium.
In the present invention, by raw material hybrid reaction, intermediate product is formed；Dissolving is diluted with water to the intermediate product, is formed
4,6- dihydroxy-pyrimidine reaction solution；Later, the present invention is using 4, a 6- dihydroxy-pyrimidines reaction described in bipolar film process
Liquid obtains 4,6- dihydroxy-pyrimidine reaction solutions.
In the present invention, the source of the Bipolar Membrane is not particularly limited, and is general commercially available product, such as can be purchased from Zhejiang
Jiang Saite membrane technologies Co., Ltd, Langfang City Ya De generation environmental protection equipment Co., Ltd or Hangzhou Lanran Environment Technology Co., Ltd. etc.
The Bipolar Membrane product of producer.
The present invention uses bipolar film process 4,6- dihydroxy-pyrimidine reaction solutions, sodium hydroxide and other components in reaction solution
Separation, comes together in Bipolar Membrane alkali room, advantageously reduces the salt content in wastewater flow rate and waste water；Moreover, in the processing of Bipolar Membrane
Under, it is phonetic that 4, the 6- dihydroxy-pyrimidine disodium salts in 4,6- dihydroxy-pyrimidine reaction solutions are partly or entirely converted into 4,6- dihydroxy
One sodium salt of pyridine, advantageously reduces preparation 4, the sour dosage of acidification technique in 6- dihydroxy-pyrimidine product process.And it thus can also see
Go out, it is relative complex using 4, the 6- dihydroxy-pyrimidine reaction solution system components of bipolar film process, therefore, to the 4 of bipolar film process,
6- dihydroxy-pyrimidines reaction solution carries out constituent analysis test and has been more advantageous to enzymatic hydrolysis system component distributing and the tune convenient for subsequent technique
It is whole.
According to the present invention, the constituent analysis test process of 4,6- dihydroxy-pyrimidine reaction solutions is included：Take 4,6- dihydroxy
Pyrimidine standard sample and 4,6- dihydroxy-pyrimidine reaction solution carry out liquid chromatographic detection respectively for sample, obtain the peak of the standard sample
Area r1With the peak area r for sample2。
In the present invention, 4, the 6- dihydroxy-pyrimidines standard sample can obtain in the following manner：Take 4,6- dihydroxy-pyrimidines
Standard items are diluted to scale in volumetric flask, with the mobile phase of liquid chromatographic detection, and oscillation shakes up, and form 4,6- dihydroxy-pyrimidines
Titer；A certain amount of 4,6- dihydroxy-pyrimidines titer is taken to be diluted in volumetric flask with the mobile phase of liquid chromatographic detection
Scale, oscillation shake up, and form 4,6- dihydroxy-pyrimidine standard samples.In the present invention, 4, the 6- dihydroxy-pyrimidines standard items come
Source is not particularly limited, for general commercially available 4,6- dihydroxy-pyrimidines product；As that can be commercial available quality score is 98%
4,6- dihydroxy-pyrimidine products.
In the present invention, 4, the 6- dihydroxy-pyrimidines reaction solution can obtain in the following manner for sample：Take 4,6- dihydroxies
Yl pyrimidines reaction solution is diluted to scale in volumetric flask, with the mobile phase of liquid chromatographic detection, and oscillation shakes up, and forms 4,6- dihydroxies
Yl pyrimidines reaction solution supplies sample.Wherein, 4,6- dihydroxy-pyrimidines reaction solution is preferably that 4, the 6- dihydroxy through bipolar film process is phonetic
Pyridine reaction solution.
It is excellent after 4,6- dihydroxy-pyrimidines standard sample and 4,6- dihydroxy-pyrimidine reaction solution is obtained for sample in the present invention
Choosing by 4,6- dihydroxy-pyrimidines standard sample and 4,6- dihydroxy-pyrimidine reaction solution for sample respectively organic filter membrane filtration after, then
Liquid chromatographic detection is carried out respectively.In the present invention, the aperture of the organic filter film is preferably 0.22~0.45 μm.It is described organic
The source of filter membrane is not particularly limited, and is general commercially available product.
In the present invention, when carrying out liquid chromatographic detection, it is preferred to use C18 chromatographic columns；The source of the chromatographic column does not have
It is specifically limited, it is general commercially available product.
In the present invention, when carrying out liquid chromatographic detection, preferably using acetonitrile as mobile phase A phase, sour aqueous solution is flowing
Phase B phases.Wherein, the volume ratio of mobile phase A phase and Mobile phase B phase is preferably (40~50)：(50~60), more preferably 45:55.
In the present invention, the acid in sour aqueous solution is preferably acetic acid, phosphoric acid or trifluoroacetic acid.In the aqueous solution of the acid,
The percentage by volume of acid is preferably 0.3%~0.8%, and more preferably 0.5%.
In the present invention, when carrying out liquid chromatographic detection, flow rate of mobile phase is preferably 0.5~1.5mL/min, more preferably
1.0mL/min。
In the present invention, when carrying out liquid chromatographic detection, Detection wavelength is preferably 195~280nm, more preferably 254nm.
The temperature of the detection is preferably room temperature, concretely 20~40 DEG C.
In the present invention, by liquid chromatographic detection, the peak area r to 4,6- dihydroxy-pyrimidine standard samples is obtained respectively1With
4,6- dihydroxy-pyrimidines reaction solution supplies the peak area r of sample2；And according to formula 1, obtain 4, the 6- dihydroxy-pyrimidines reaction solution
The reference amount W of middle 4,6- dihydroxy-pyrimidines sodium salt：
W=(r2×m1×p)/(r1× m) formula 1；
Wherein,
r1For the peak area of 4, the 6- dihydroxy-pyrimidines standard sample, unit mv；
r2The peak area of sample, unit mv are supplied for 4, the 6- dihydroxy-pyrimidines reaction solution；
m1For the quality of 4, the 6- dihydroxy-pyrimidines standard sample, unit g；
Mass fractions of the p for 4, the 6- dihydroxy-pyrimidines standard sample, unit %；
M supplies the quality of sample, unit g for 4, the 6- dihydroxy-pyrimidines reaction solution.
In the present invention, using 4,6- dihydroxy-pyrimidine sodium salts in 4,6- dihydroxy-pyrimidine reaction solutions reference amount W and according to
Formula 2 obtains the reference content W of 4,6- dihydroxy-pyrimidine disodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution1, the W1It is
The reference content of the 4,6- dihydroxy-pyrimidine disodium salts in terms of sodium hydroxide of setting：
W1=W × (M3/M2) formula 2；
Wherein,
M3For the molal weight of sodium hydroxide, unit g/mol；
M2For the molal weight of 4,6- dihydroxy-pyrimidines, unit g/mol.
The analysis test method of the present invention, which further includes, obtains total alkali reference content in 4,6- dihydroxy-pyrimidine reaction solutions.According to
The present invention, the total alkali obtain in the following manner with reference to content：4,6- dihydroxy-pyrimidine reaction solutions is taken to treat test sample, are treated to described
Phenolphthalein indicator is added in test sample, and is titrated to hydrochloric acid standard solution colourless, record consumes the volume of hydrochloric acid standard solution
V；
According to formula 3, total alkali reference content W in 4,6- dihydroxy-pyrimidine reaction solutions is obtained2：
W2=(C × V × M3×10-3)/m2Formula 3；
Wherein,
Concentration of the C for the hydrochloric acid standard solution, unit mol/L；
V by consumption hydrochloric acid standard solution volume, unit mL；
M3For the molal weight of sodium hydroxide, unit g/mol；
m2For the quality for treating test sample, unit g.
In the present invention, the quality m for treating test sample2It is preferred that it is accurate to 0.0002g.
The present invention is to the reference content W of 4,6- dihydroxy-pyrimidine disodium salts in acquisition 4,6- dihydroxy-pyrimidine reaction solutions1With
Total alkali is with reference to content W2Sequence there is no limit, can successively obtain or obtain simultaneously.
According to the present invention, the reference content of 4,6- dihydroxy-pyrimidine disodium salts in 4,6- dihydroxy-pyrimidine reaction solutions are obtained
W1With total alkali with reference to content W2Afterwards, the ingredient in 4, the 6- dihydroxy-pyrimidines reaction solution is determined by following discriminant approach
Property analysis：
If (a) W1＜ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and hydroxide in 4,6- dihydroxy-pyrimidines reaction solution
Sodium, without 4,6- dihydroxy-pyrimidines, one sodium salt；
If (b) W1＞ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and 4,6- dihydroxy in 4,6- dihydroxy-pyrimidines reaction solution
One sodium salt of yl pyrimidines, without sodium hydroxide.
The method according to the invention, in 4, the 6- dihydroxy-pyrimidine reaction solution systems that can accurately analyze bipolar film process
Component type.
According to the present invention, after qualitative analysis goes out the component type of 4,6- dihydroxy-pyrimidine reaction solution systems, preferably pass through
In the following manner carries out quantitative analysis：
For 4,6- dihydroxy-pyrimidine reaction solution systems (a), according to formula 4, obtain in 4,6- dihydroxy-pyrimidine reaction solutions
The mass percentage W of sodium hydroxide3：
W3=W2-W1Formula 4；
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidine disodium salts in 4,6- dihydroxy-pyrimidine reaction solutions4=W ×
(M1/M2)；
Wherein, M1For the molal weight of 4,6- dihydroxy-pyrimidine disodium salts, unit g/mol；
For 4,6- dihydroxy-pyrimidine reaction solution systems (b), according to formula 5, obtain in 4,6- dihydroxy-pyrimidine reaction solutions
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidine disodium salts4＇：
W4＇=C × V × M1×10-3/m2Formula 5；
According to formula 6, the actual mass hundred of 4,6- dihydroxy-pyrimidines, one sodium salt in 4,6- dihydroxy-pyrimidine reaction solutions is obtained
Divide content W5：
W5=W × (M4/M2) formula 6；
Wherein, M4For the molal weight of 4,6- dihydroxy-pyrimidines, one sodium salt, unit g/mol.
Above-mentioned analysis test method provided by the invention can fast and accurately obtain the 4,6- dihydroxy of bipolar film process
The content of each ingredient in pyrimidine reaction solution grasps reaction liquid set member distributed intelligence convenient for technical staff.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only for the feature and advantage that further illustrate the present invention rather than to the claims in the present invention
Limitation.
Embodiment 1
7g formamides with 10g dimethyl malenates are mixed, add in 15g sodium methoxides, after reacting the 1h times at 100 DEG C,
Form the intermediate product for including 4,6- dihydroxy-pyrimidine sodium salts；Dissolving intermediate product is diluted with water, forms 4, a 6- dihydroxy
Pyrimidine reaction solution；Using bipolar film process 4, a 6- dihydroxy-pyrimidine reaction solution, 4, the 6- dihydroxies of bipolar film process are formed
Yl pyrimidines reaction solution.
During bipolar film process 4, a 6- dihydroxy-pyrimidine reaction solution is utilized, irregularly sampled to treatment fluid
Early period is extracted Sample A in detection, processing, and following constituent analysis test is carried out to Sample A：
A.1. the reference content W of 4,6- dihydroxy-pyrimidine disodium salts in Sample A is obtained1With total alkali with reference to content W2：
A.1.1 the reference content W of 4,6- dihydroxy-pyrimidine disodium salts is obtained1：
Liquid chromatographic detection condition：
Instrument：1200 liquid chromatographs of Aglient (band UV detector)；
Chromatographic column：DIKMA Diamonsil C18 (2), 250 × 4.6mm, 5 μm；
Mobile phase：Acetonitrile：Volume ratio=45 of the aqueous solution of acid:55 (sour aqueous solution is：400mL water+2mL acid)；
Detection wavelength：λ=254nm；
Temperature：Room temperature；
Sample size：20μL；
Flow velocity：1.0mL/min.
The measure of 4,6- dihydroxy-pyrimidine standard samples：It is accurate to weigh 4,6- dihydroxy-pyrimidines standard items (mass fraction is
98%) 0.0537g (being accurate to 0.0001g) is placed in 100mL volumetric flasks, is diluted to scale with mobile phase, oscillation shakes up, shape
Into 4,6- dihydroxy-pyrimidine titers.5.0mL4 is accurately drawn again, in 6- dihydroxy-pyrimidines titer to 50mL volumetric flasks, with stream
To scale, oscillation shakes up dynamic phase dilution, forms 4,6- dihydroxy-pyrimidine standard samples.With the organic filter film mistake that aperture is 0.45 μm
Liquid chromatograph is injected into after filtering the standard sample, records the peak area r of 4,6- dihydroxy-pyrimidine standard samples1For
4192.5mv。
4,6- dihydroxy-pyrimidines reaction solution supplies the measure of sample：0.0780g is accurately weighed from Sample A to be placed in for sample
In 100mL volumetric flasks, scale is diluted to mobile phase, oscillation shakes up.After the organic filter membrane filtration that aperture is 0.45 μm
Liquid chromatograph is injected, record 4,6- dihydroxy-pyrimidines reaction solution supplies the peak area r of sample2For 6584.4mv.
The reference amount W of 4,6- dihydroxy-pyrimidine sodium salts in Sample A is obtained as the following formula：
W=(r2×m1×p)/(r1×m)
=[6584.4 × (0.0537/100) × (5/50) × 0.98]/[4192.5 × (0.0780/100)]
=10.60%
The reference content W of 4,6- dihydroxy-pyrimidine disodium salts in Sample A is obtained as the following formula1：
W1=W × (M3/M2)=10.60% × (40/112.09)=3.78%.
A.1.2 total alkali reference content W in Sample A is obtained2：
1.0532g (being accurate to 0.0002g) is accurately weighed from Sample A to be placed in 250mL triangular flasks, is diluted with water to
100mL, add in 2 drop phenolphthalein indicators, be titrated to the hydrochloric acid standard solution of 0.1000mol/L it is colourless, keep 30s it is constant, disappear
The volume for consuming hydrochloric acid standard solution is 22.12mL.
Total alkali reference content W in Sample A is obtained as the following formula2：
W2=(C × V × M3×10-3)/m2=(0.1000 × 22.12 × 0.040)/1.0532=8.40%.
A.2 it qualitatively judges：
W1＜ W2, it follows that using bipolar film process 4, in the treatment fluid sampling early period A of 6- dihydroxy-pyrimidine reaction solutions
Contain 4,6- dihydroxy-pyrimidines disodium salt and sodium hydroxide, without 4,6- dihydroxy-pyrimidines, one sodium salt.As it can be seen that at using Bipolar Membrane
When managing 4,6- dihydroxy-pyrimidine reaction solutions, early period, reaction solution 4 are handled, 6- dihydroxy-pyrimidines disodium salt and sodium hydroxide are total to
Deposit system.
A.3 quantitative analysis：
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidines disodium salt in Sample A4=W × (M1/M2)=10.60% ×
(156.09/112.09)=14.76%；
The mass percentage W of sodium hydroxide in Sample A3=W2-W1=8.40%-3.78%=4.62%.
During bipolar film process 4, a 6- dihydroxy-pyrimidine reaction solution is utilized, sample B is extracted to the processing later stage, it is right
Sample B carries out following constituent analysis test：
B.1. the reference content W of 4,6- dihydroxy-pyrimidine disodium salts in sample B is obtained1With total alkali with reference to content W2：
B.1.1 the reference content W1 of 4,6- dihydroxy-pyrimidine disodium salts is obtained：
Liquid chromatographic detection condition：
Instrument：1200 liquid chromatographs of Aglient (band UV detector)；
Chromatographic column：DIKMA Diamonsil C18 (2), 250 × 4.6mm, 5 μm；
Mobile phase：Acetonitrile：Volume ratio=45 of the aqueous solution of acid:55 (sour aqueous solution is：400mL water+2mL acid)；
Detection wavelength：λ=254nm；
Temperature：Room temperature；
Sample size：20μL；
Flow velocity：1.0mL/min.
The measure of 4,6- dihydroxy-pyrimidine standard samples：It is accurate to weigh 4,6- dihydroxy-pyrimidines standard items (mass fraction is
98%) 0.0537g (being accurate to 0.0001g) is placed in 100mL volumetric flasks, is diluted to scale with mobile phase, oscillation shakes up, shape
Into 4,6- dihydroxy-pyrimidine titers.5.0mL4 is accurately drawn again, in 6- dihydroxy-pyrimidines titer to 50mL volumetric flasks, with stream
To scale, oscillation shakes up dynamic phase dilution, forms 4,6- dihydroxy-pyrimidine standard samples.With the organic filter film mistake that aperture is 0.45 μm
Liquid chromatograph is injected into after filtering the standard sample, records the peak area r of 4,6- dihydroxy-pyrimidine standard samples1For
4192.5mv。
4,6- dihydroxy-pyrimidines reaction solution supplies the measure of sample：0.0420g is accurately weighed from sample B to be placed in for sample
In 50mL volumetric flasks, scale is diluted to mobile phase, oscillation shakes up.With being noted after the organic filter membrane filtration that aperture is 0.45 μm
Enter liquid chromatograph, record 4,6- dihydroxy-pyrimidines reaction solution supplies the peak area r of sample2For 3628.5mv.
The reference amount W of 4,6- dihydroxy-pyrimidine sodium salts in Sample A is obtained as the following formula：
W=(r2×m1×p)/(r1×m)
=[3628.5 × (0.0537/100) × (5/50) × 0.98]/[4192.5 × (0.0420/100)]
=10.84%.
The reference content W of 4,6- dihydroxy-pyrimidine disodium salts in Sample A is obtained as the following formula1：
W1=W × (M3/M2)=10.84% × (40/112.09)=3.87%.
B.1.2 total alkali reference content W in sample B is obtained2：
1.0432g (being accurate to 0.0002g) is accurately weighed from sample B to be placed in 250mL triangular flasks, is diluted with water to
100mL, add in 2 drop phenolphthalein indicators, be titrated to the hydrochloric acid standard solution of 0.1000mol/L it is colourless, keep 30s it is constant, disappear
The volume for consuming hydrochloric acid standard solution is 0.17mL.
Total alkali reference content W in Sample A is obtained as the following formula2：
W2=(C × V × M3×10-3)/m2=(0.1000 × 0.17 × 0.040)/1.0432=0.07%.
B.2 it qualitatively judges：
W1＞ W2, and by 4,6- dihydroxy-pyrimidine sodium salts reference amount 10.84% and total alkali with reference to content 0.07% it is found that
Using bipolar film process 4, without free alkali in the post-processing liquid sampling B of 6- dihydroxy-pyrimidine reaction solutions, contain 4,6- dihydroxy
One sodium salt of pyrimidine and a small amount of 4,6- dihydroxy-pyrimidines disodium salt.As it can be seen that using bipolar film process 4,6- dihydroxy-pyrimidine reaction solutions
When, later stage, reaction solution 4 are handled, system coexists in one sodium salt of 6- dihydroxy-pyrimidines disodium salt and 4,6- dihydroxy-pyrimidine.
B.3 quantitative analysis：
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidine disodium salts in sample B is obtained as the following formula4＇：
W4＇=C × V × M1×10-3/m2=0.1000 × 0.17 × 0.15609/1.0432=0.25%.
The actual mass percentage composition W of one sodium salt of 4,6- dihydroxy-pyrimidines in sample B is obtained as the following formula5：
W5=W × (M4/M2)=10.84% × (134.09/112.09)=12.97%.
The Accuracy Verification of acid base titration experiment：
4,6- dichloro pyrimidine standard samples are provided：It is phonetic accurately to weigh the commercially available 4,6- dichloros of 0.02578g (being accurate to 0.0002g)
Pyridine standard sample (mass fraction 98%) is placed in 250mL triangular flasks, and it is a concentration of accurately to add in 50mL with 50mL pipettes
0.1mol/L sodium hydroxide solutions, fully shaking is completely dissolved sample.With a little distillation water washing triangular flask inner wall, phenol is added in
Phthalein indicator 2 drips, and it is titration end-point to be titrated to red disappear with 0.01005mol/L hydrochloric acid standard solutions, records hydrochloric acid consumer
Product is 27.52mL.Blank control test is done under above-mentioned the same terms, record hydrochloric acid consumption volume is 49.95mL.
Be calculated as follows 4,6- dihydroxy-pyrimidines mass fraction=[(49.95-27.52) × 0.1005 × 0.1121]/
0.2578=98.02%.It follows that free alkali and 4,6- dichloro pyrimidine disodium salt can completely be titrated by hydrochloric acid, Ke Yitong
The mode for crossing acid base titration accurately titrates the content of 4,6- dichloro pyrimidine disodium salts.
As seen from the above embodiment, method using the present invention can accurately analyze 4, the 6- dihydroxy of bipolar film process
The component distributing of pyrimidine reaction solution system effectively grasps the composition information of reaction solution system convenient for technical staff.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.To these embodiments
A variety of modifications will be apparent for those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to the most wide model consistent with the principles and novel features disclosed herein
It encloses.
Claims (7)
1. a kind of constituent analysis test method of 4, the 6- dihydroxy-pyrimidine reaction solutions of bipolar film process, which is characterized in that including
Following steps：
S101：4,6- dihydroxy-pyrimidines standard sample and 4,6- dihydroxy-pyrimidines reaction solution is taken to carry out liquid chromatogram inspection respectively for sample
It surveys, obtains the peak area r of the standard sample1With the peak area r for sample2；
According to formula 1, the reference amount W of 4,6- dihydroxy-pyrimidine sodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution is obtained：
W=(r2×m1×p)/(r1× m) formula 1；
Wherein,
r1For the peak area of 4, the 6- dihydroxy-pyrimidines standard sample, unit mv；
r2The peak area of sample, unit mv are supplied for 4, the 6- dihydroxy-pyrimidines reaction solution；
m1For the quality of 4, the 6- dihydroxy-pyrimidines standard sample, unit g；
Mass fractions of the p for 4, the 6- dihydroxy-pyrimidines standard sample, unit %；
M supplies the quality of sample, unit g for 4, the 6- dihydroxy-pyrimidines reaction solution；
According to formula 2, the reference content W of 4,6- dihydroxy-pyrimidine disodium salts in 4, the 6- dihydroxy-pyrimidines reaction solution is obtained1：
W1=W × (M3/M2) formula 2；
Wherein,
M3For the molal weight of sodium hydroxide, unit g/mol；
M2For the molal weight of 4,6- dihydroxy-pyrimidines, unit g/mol；
4,6- dihydroxy-pyrimidine reaction solutions is taken to treat test sample, treat to add in phenolphthalein indicator in test sample, and molten with normal hydrochloric acid to described
Liquid is titrated to colourless, and record consumes the volume V of hydrochloric acid standard solution；
According to formula 3, total alkali reference content W in 4,6- dihydroxy-pyrimidine reaction solutions is obtained2：
W2=(C × V × M3×10-3)/m2Formula 3；
Wherein,
Concentration of the C for the hydrochloric acid standard solution, unit mol/L；
V by consumption hydrochloric acid standard solution volume, unit mL；
M3For the molal weight of sodium hydroxide, unit g/mol；
m2For the quality for treating test sample, unit g；
S102：Qualitative analysis is carried out to the ingredient in the 4,6- dihydroxy-pyrimidines reaction solution by following discriminant approach：
If (a) W1＜ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt and sodium hydroxide in 4,6- dihydroxy-pyrimidines reaction solution, no
One sodium salt of dihydroxy-pyrimidine containing 4,6-；
If (b) W1＞ W2, then contain 4,6- dihydroxy-pyrimidines disodium salt in 4,6- dihydroxy-pyrimidines reaction solution and 4,6- dihydroxy be phonetic
One sodium salt of pyridine, without sodium hydroxide；
The 4,6- dihydroxy-pyrimidines reaction solution is the 4,6- dihydroxy-pyrimidine reaction solutions through bipolar film process；At the Bipolar Membrane
The forming process of the 4,6- dihydroxy-pyrimidine reaction solutions of reason is：The raw material hybrid reaction needed for 4,6- dihydroxy-pyrimidines will be synthesized,
Form intermediate product；The intermediate product is diluted with water again, forms 4 a, 6- bis- for including 4,6- dihydroxy-pyrimidine sodium salts
Hydroxy pyrimidine reaction solution；Using 4, a 6- dihydroxy-pyrimidine reaction solution described in bipolar film process, the 4 of bipolar film process is formed,
6- dihydroxy-pyrimidine reaction solutions；
In the step S101, the chromatographic condition of the liquid chromatographic detection is：
Using C18 chromatographic columns, using acetonitrile as mobile phase A phase, sour aqueous solution is Mobile phase B phase, the mobile phase A phase and flowing
The volume ratio of phase B phases is (40~50)：(50~60)；
In the aqueous solution of the acid, sour percentage by volume is 0.3%~0.8%；
Acid in the aqueous solution of the acid is acetic acid, phosphoric acid or trifluoroacetic acid.
2. constituent analysis test method according to claim 1, which is characterized in that further include anti-to 4,6- dihydroxy-pyrimidines
The ingredient in liquid is answered to carry out following quantitative analysis：
For 4 in situation (a), 6- dihydroxy-pyrimidine reaction solution systems according to formula 4, obtain the reaction of 4,6- dihydroxy-pyrimidines
The mass percentage W of sodium hydroxide in liquid3：
W3=W2-W1Formula 4；
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidine disodium salts in 4,6- dihydroxy-pyrimidine reaction solutions4=W × (M1/
M2)；
Wherein, M1For the molal weight of 4,6- dihydroxy-pyrimidine disodium salts, unit g/mol；
For 4 in situation (b), 6- dihydroxy-pyrimidine reaction solution systems according to formula 5, obtain the reaction of 4,6- dihydroxy-pyrimidines
The actual mass percentage composition W of 4,6- dihydroxy-pyrimidines disodium salt in liquid4＇：
W4＇=C × V × M1×10-3/m2Formula 5；
According to formula 6, the actual mass percentage for obtaining 4,6- dihydroxy-pyrimidines, one sodium salt in 4,6- dihydroxy-pyrimidine reaction solutions contains
Measure W5：
W5=W × (M4/M2) formula 6；
Wherein, M4For the molal weight of 4,6- dihydroxy-pyrimidines, one sodium salt, unit g/mol.
3. constituent analysis test method according to claim 1, which is characterized in that the liquid chromatographic detection wavelength is
195~280nm.
4. constituent analysis test method according to claim 1, which is characterized in that the mobile phase of the liquid chromatographic detection
Flow velocity is 0.5~1.5mL/min.
5. constituent analysis test method according to claim 1, which is characterized in that the temperature of the liquid chromatographic detection is
20~40 DEG C.
6. constituent analysis test method according to claim 1, which is characterized in that in the step S101, carrying out liquid
Before the detection of phase chromatography, by 4, the 6- dihydroxy-pyrimidines standard sample and 4,6- dihydroxy-pyrimidine reaction solution for sample aperture respectively
For 0.22~0.45 μm of organic filter membrane filtration.
7. constituent analysis test method according to claim 1, which is characterized in that 4, the 6- dihydroxy-pyrimidines reaction solution
Be using formamide, malonate and alkali metal sodium alkoxide as raw material prepare 4,6- dihydroxy-pyrimidines during, formed 4,6-
Dihydroxy-pyrimidine reaction solution.
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