CN110726801A - Method for monitoring reaction state of alkyl phosphinic acid - Google Patents
Method for monitoring reaction state of alkyl phosphinic acid Download PDFInfo
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- CN110726801A CN110726801A CN201911049668.4A CN201911049668A CN110726801A CN 110726801 A CN110726801 A CN 110726801A CN 201911049668 A CN201911049668 A CN 201911049668A CN 110726801 A CN110726801 A CN 110726801A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/90—Plate chromatography, e.g. thin layer or paper chromatography
Abstract
The invention discloses a method for monitoring the reaction state of alkyl phosphinic acid, which takes methylene chloride and methanol as developing agents and silica gel as an adsorbent, utilizes the difference of the adsorption capacity of the mixture and tracks the organic reaction process by means of adsorption and distribution so as to judge the reaction endpoint. The method is simple and convenient to operate, is a micro and rapid reaction process monitoring method, can track the reaction process and judge the reaction end point in time in the synthesis reaction of the alkyl phosphinic acid, ensures the experiment progress, and has the advantages of high safety coefficient, high efficiency, cost saving and wide application.
Description
Technical Field
The invention relates to a method for monitoring the reaction state of alkyl phosphinic acid, namely a method for tracking the synthesis process of the alkyl phosphinic acid and judging the reaction endpoint, belonging to the technical field of organic synthesis characterization.
Background
The alkyl phosphinate serving as an organic phosphorus flame retardant has the advantages of water resistance, solvent resistance, high flame retardant efficiency, low smoke, no toxicity, small influence on the mechanical properties of materials and the like, so that the organic phosphine flame retardant is favored.
The alkyl phosphinic acid is used as an important intermediate, and a simple and easy analysis method is necessary to be established in order to better track the reaction progress, determine the reaction end point and ensure that experimental projects are carried out in time and order.
CN103073577A discloses the use31The detection of the intermediate by PNMR, Wang Ying et al, introduced the use of Bicycloalkyl phosphinic acid in the article "Synthesis and characterization1HNMR、31The PNMR detection means characterize the intermediate structure. In the article of 'research on preparation of dialkyl phosphinic acid by free radical addition' of Chenqi, characteristic peaks in a product are detected by a gas chromatography-mass spectrometry method, and then the content of the Chenqi is determined. The detection instrument is expensive, the detection instrument needs expensive maintenance cost, most companies cannot support the detection technology, the detection of test samples is finished by external inspection, the problems that the detection result is not timely, the external inspection cost is high and the like exist, the experiment progress is seriously influenced, and the timely accuracy of the experiment cannot be guaranteed.
Disclosure of Invention
In view of the above problems, the present invention adopts a simple, fast and reasonable reaction process monitoring method, namely TLC thin layer chromatography. The method of the invention not only can track the reaction process in time and judge the reaction end point, ensures the experiment progress, but also can save expensive external inspection cost.
The invention aims to provide an accurate, rapid and simple reaction process monitoring method, which can track the reaction process in time and judge the reaction end point.
The technical scheme of the invention is as follows:
a method for monitoring the reaction state of alkyl phosphinic acid by adopting thin layer chromatography detection comprises the following steps:
(1) selecting a reagent which has good solubility to a reactant, can separate components and does not react with a component to be detected or an adsorbent as a solvent, pouring the prepared solvent system into a developing bottle, and putting a piece of filter paper with the diameter of 1.8-2.0cm into the developing bottle;
(2) spotting the compound at the base line marked by the thin plate, and putting the thin plate into a spreading bottle for spreading after spotting;
(3) after the thin plate is unfolded, taking out the thin plate from the unfolding bottle, and waiting for the solvent on the thin plate to be volatilized;
(4) the thin plate is placed under an ultraviolet lamp for observation, the reaction process and the reaction end point are judged according to the observed points with ultraviolet activity, two substances are arranged in the reaction process and correspond to the two ultraviolet activity points, one substance is converted into the other substance along with the reaction, and only the final product is left at the reaction end point and corresponds to one ultraviolet activity point.
Further, the solvent system is a single solvent or a mixed solvent of methanol and dichloromethane.
In the mixed solvent system, a mixed solvent of methanol and dichloromethane is preferable.
In the mixed solvent system, the volume ratio of methanol to dichloromethane is 1: 10-15.
The thin plate is a silica gel plate.
Has the advantages that: compared with the traditional monitoring technology, the invention has the following advantages:
(1) dichloromethane and methanol are used as developing agents, have good solubility to reactants and do not react with the adsorbent;
(2) the method is simple and convenient to operate, and is a micro and rapid reaction process monitoring method;
(3) the method tracks the reaction process in time and judges the reaction end point in the synthesis process of the alkyl phosphinic acid, and ensures the experiment progress;
(4) the invention has high safety factor, high efficiency, cost saving and wide application.
Drawings
FIG. 1 is a view of TLC monitoring of # 1 to # 1 in example 1;
FIG. 2 is a view of 1# -2TLC monitoring in example 2;
FIG. 3 is a view of TLC monitoring of # 1 to # 3 in example 3;
FIG. 4 shows the phosphorus nuclear magnetic resonance spectrum of the intermediate state of reaction No. 1-1 in example 1 (31PNMR)；
FIG. 5 is the NMR spectrum of 1# -3 reaction end point in example 3 (1HNMR)。
Detailed Description
The invention is further described with reference to specific examples, but not in any way limiting the scope of the invention. The following examples illustrate the synthesis of alkylphosphinic acids using the method of the invention of patent CN 108864182 a and monitoring the course of the reaction.
According to the synthesis method of alkyl phosphinic acid in patent CN 108864182A: to the reaction kettle were added 10.56kg hypophosphorous acid (50% aqueous solution) and 9.0kg t-butanol. 10.4kg of a chlorobenzene solution containing 0.4kg of azobisisobutyronitrile and 0.96kg of concentrated sulfuric acid were added dropwise to the system at 70 ℃ over 8 hours, and sampling was performed after completion of the addition (1# -1). 9.0kg of tertiary butanol is added into the system, 10.4kg of chlorobenzene solution containing 0.4kg of azobisisobutyronitrile and 0.96kg of concentrated sulfuric acid are added dropwise within 8 hours at 70 ℃, and the reaction is carried out for 2 hours after the dropwise addition, and sampling (1# -2) is carried out for monitoring. The reaction was carried out at 70 ℃ for 6 hours, and sampling was carried out (1# -3).
Example 1 monitoring of 1# -1 sampling with mixed solvents
(1) Preparing a developing agent, respectively measuring 1ml of methanol and 10ml of dichloromethane, placing the methanol and the dichloromethane into a developing bottle, stirring and mixing the methanol and the dichloromethane uniformly, and placing a piece of filter paper with the diameter of about 1.8-2.0cm to facilitate uniform development;
(2) marking a base line on the silica gel plate by using a pencil, sampling (1# -1), spotting at the base line, and putting the silica gel plate into a developing bottle for developing experiments after spotting is finished;
(3) taking out the silica gel plate after the development is finished, and waiting for the solvent on the silica gel plate to volatilize;
(4) then, the silica gel plate is placed under an ultraviolet lamp for observation, points with ultraviolet activity are observed, two points with similar sizes are observed, and the two substances exist in the reactant, wherein the ratio of the two substances is about 1:1, the reaction is incomplete.
Example 2 monitoring of samples # 1-2 with mixed solvents
(1) Preparing a developing agent, respectively measuring 1ml of methanol and 13ml of dichloromethane, placing the methanol and the dichloromethane into a developing bottle, stirring and mixing the methanol and the dichloromethane uniformly, and placing a piece of filter paper with the diameter of about 1.8-2.0cm to facilitate uniform development;
(2) marking a base line on the silica gel plate by using a pencil, sampling (1# -2) and spotting at the base line, and putting the silica gel plate into a developing bottle for developing experiments after spotting is finished;
(3) taking out the silica gel plate after the development is finished, and waiting for the solvent on the silica gel plate to volatilize;
(4) the silica gel plate was then placed under an ultraviolet lamp for observation, and the points with ultraviolet activity were observed, and two points were observed, indicating that two species were present in the reactants, with a ratio of about 3:1, and the reaction was not complete.
Example 3 monitoring of samples # 1-3 with mixed solvents
(1) Preparing a developing agent, respectively measuring 1ml of methanol and 15ml of dichloromethane, placing the methanol and the dichloromethane into a developing bottle, stirring and mixing the methanol and the dichloromethane uniformly, and placing a piece of filter paper with the diameter of about 1.8-2.0cm to facilitate uniform development;
(2) marking a base line on the silica gel plate by using a pencil, sampling (1# -3) and spotting at the base line, and putting the silica gel plate into a developing bottle for developing experiments after spotting is finished;
(3) taking out the silica gel plate after the development is finished, and waiting for the solvent on the silica gel plate to volatilize;
(4) then the silica gel plate is placed under an ultraviolet lamp for observation, the point with ultraviolet activity is observed, and one point is observed to indicate that only one reactant is left, and the reaction reaches the end point.
Example 4 monitoring of 1# -1 sampling with a single solvent
(1) Preparing a developing agent, measuring dichloromethane with the volume of 20ml, placing the dichloromethane into a developing bottle, and placing a piece of filter paper with the diameter of about 1.8-2.0cm to facilitate uniform development;
(2) marking a base line on the silica gel plate by using a pencil, sampling (1# -1), spotting at the base line, and putting the silica gel plate into a developing bottle for developing experiments after spotting is finished;
(3) taking out the silica gel plate after the development is finished, and waiting for the solvent on the silica gel plate to volatilize;
(4) then, the silica gel plate is placed under an ultraviolet lamp for observation, points with ultraviolet activity are observed, two points with similar sizes are observed, and the two substances exist in the reactant, wherein the ratio of the two substances is about 1:1, the reaction is incomplete.
Example 5 monitoring of samples # 1-3 with a single solvent
(1) Preparing a developing agent, respectively measuring methanol with the volume of 15ml, placing the methanol in a developing bottle, and placing a piece of filter paper with the diameter of about 1.8-2.0cm to facilitate uniform development;
(2) marking a base line on the silica gel plate by using a pencil, sampling (1# -3) and spotting at the base line, and putting the silica gel plate into a developing bottle for developing experiments after spotting is finished;
(3) taking out the silica gel plate after the development is finished, and waiting for the solvent on the silica gel plate to volatilize;
(4) then the silica gel plate is placed under an ultraviolet lamp for observation, the point with ultraviolet activity is observed, and one point is observed to indicate that only one reactant is left, and the reaction reaches the end point.
Comparison of monitoring results
Sampling (1# -1) TLC monitoring of the first stage of the reaction indicated: the proportion of the mono-substituted product and the di-substituted product in the reaction product respectively accounts for 50 percent, the reaction is not complete, raw materials need to be continuously supplemented, and the reaction intermediate state is carried out31PNMR detection, results consistent with TLC monitoring (see fig. 1, fig. 4);
after the raw materials are supplemented, the reaction is carried out for a certain time, and sampling (1# -2) monitoring shows that: the proportion of the disubstituted product is increased, and the reaction is continued to the direction of the disubstituted reaction (see figure 2);
continuing the reaction for a certain time, and sampling (1# -3) TLC monitoring after the reaction is completed and simultaneously carrying out1The HNMR detection shows that the two monitoring results are consistent, and the reaction reaches the end point and is basically completely converted into the double-substituted product (see figure 3 and figure 5).
The method carries out reaction state monitoring in the synthesis process of the alkyl phosphinic acid, judges the reaction process in time, quickly and effectively and determines the reaction end point. Meanwhile, compared with the results of the traditional monitoring means, the detection results are consistent. Compared with the traditional monitoring means, the method has the advantages of better and simpler operation, high safety factor, high efficiency and cost saving.
Claims (5)
1. A method for monitoring the reaction state of alkyl phosphinic acid, which is characterized by adopting thin layer chromatography for detection, and comprises the following steps:
(1) selecting a reagent which has good solubility to a reactant, can separate components and does not react with a component to be detected or an adsorbent as a solvent, pouring the prepared solvent system into a developing bottle, and putting a piece of filter paper with the diameter of 1.8-2.0cm into the developing bottle;
(2) spotting the compound at the base line marked by the thin plate, and putting the thin plate into a developing bottle containing a developing agent for developing after spotting;
(3) after the thin plate is unfolded, taking out the thin plate from the unfolding bottle, and waiting for the solvent on the thin plate to be volatilized;
(4) the thin plate is placed under an ultraviolet lamp for observation, and the reaction progress and the reaction end point are judged according to the observed points with ultraviolet activity.
2. The method of claim 1, wherein the solvent system is a single solvent selected from methanol and dichloromethane, or a mixture thereof.
3. The method of claim 1, wherein the solvent system is a mixture of methanol and dichloromethane.
4. The method of claim 3, wherein the volume ratio of methanol to dichloromethane is 1: 10-15.
5. The method for monitoring the reaction status of alkylphosphinic acids according to any of claims 1 to 4, wherein the thin plate is a silica gel plate.
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Application publication date: 20200124 |