CN104155255B - A kind of squaric amide derivant detects the method for RDX explosive - Google Patents

Abstract

The invention relates to a method for detecting RDX explosives by using squaramide derivatives, belonging to the field of chemical sensing materials. The method of the invention adopts the synthesis of an optically active substituted square amido chemical sensor, and after the interaction with the RDX molecule through intermolecular hydrogen bonds, the ultraviolet absorption spectrum of the sensor has obvious absorption intensity around 322nm. The substituted square amide chemical sensor used in the invention has simple synthesis method, wide detection range and high detection sensitivity, is suitable for rapid detection of RDX, and can be widely used in the fields of national defense industry and explosive detection.

Description

A method for detecting RDX explosives with squaramide derivatives

technical field

The invention relates to a method for detecting RDX explosives by using squaramide derivatives, belonging to the field of chemical sensing materials.

Background technique

In today's society, peaceful development is the common theme of all countries in the world. However, in recent years, terrorist activities have been rampant. Using explosives to carry out terrorist attacks is a common method of terrorists, which seriously threatens national security. The research on explosive sensors is not only important for battlefields The detection of a variety of explosive weapons is of great significance, and it also has far-reaching significance in the protection of national people's security in a peaceful society, especially in anti-terrorism.

RDX is one of the high-energy and low-sensitivity single-substance explosives widely used at present. Its detonation velocity reaches about 8700m/s and is easy to detonate. It is one of the main charges of modern weapons and ammunition after TNT explosives. Used in mixed explosives. At present, multiple formulations with RDX as the main explosive are widely used at home and abroad. However, due to frequent reports of explosion accidents in explosive manufacturing workshops this year, as well as terrorist attacks in public places such as downtown areas and airports, scientific researchers and the whole society have attached great importance to explosive detection. Especially in the later stage of explosive production, in the process of pipeline cleaning and waste explosive treatment, knowing the specific explosive type and content contained in it will help to carry out targeted operations, which is of great significance to production safety and cost control. The results of the literature survey found that most of the literature on explosive detection is aimed at TNT explosives, and there are very few literatures on the detection of RDX explosives. Therefore, developing a convenient, rapid and effective method for detecting RDX has become an urgent research topic.

Contents of the invention

The object of the present invention is to provide a method for detecting RDX explosives with squaramide derivatives, which can detect RDX conveniently, rapidly and effectively, and then fill the research gap in RDX explosive detection.

The purpose of the present invention is achieved through the following technical solutions.

A method for detecting RDX explosives with squaramide derivatives, the specific steps are as follows:

Step 1, using an organic solvent to prepare the square amide derivative 1 into a known concentration of the square amide derivative 1 dispersion;

Step 2: Add RDX explosives to the dispersion of squaramide derivatives 1 obtained in step 1, and configure mixed solutions of different concentrations; the molar ratios of RDX explosives and squaramide derivatives are 0.5, 1, 2, 5, 10, respectively. , 20, 50, 100;

Step 3, measure the ultraviolet absorption spectrum of the different mixed solutions of step 2 gained, determine the corresponding relationship with the RDX concentration of the absorbance value at the 272nm place of the ultraviolet absorption spectrum measured, promptly obtain the standard equation y=a+bx of quantitative detection RDX, wherein y is the UV absorbance corresponding to the measured RDX-containing square amide sensor at the maximum absorption wavelength of 272nm, x is the content of RDX in the sample (unit: 10 ^-5 M), a=0.13, b=0.017;

Step 4: Add the sample to be tested containing RDX into N,N-dimethylformamide solution to prepare a solution; then add it into the dispersion of square amide derivative 1 with a known concentration, and measure the ultraviolet absorption spectrum. Substituting the absorbance value at 272nm in the measured ultraviolet absorption spectrum of the sample into the RDX quantitative standard equation obtained in step 3, the content of RDX in the sample can be determined.

The organic solvent in Step 1 includes: N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).

The preparation method of the square amide derivative 1, the specific steps are as follows:

Diethyl squarylate and aniline were added into the container at a molar ratio of 1:1, a mixed solvent of toluene/DMF (v/v, 19/1) was added, and 5% molar amount of Lewis acid was added as a catalyst for the reaction. Heating at 100-130° C. and reacting at a stirring speed of 10-60 r/min for 10-15 hours, centrifuging at high speed, washing the precipitate with anhydrous methanol, and drying to obtain the square amide derivative 1.

In the present invention, the Lewis acid used is zinc trifluoromethanesulfonate and zinc p-toluenesulfonate.

The reaction formula is as follows:

Beneficial effect

1. A method for detecting RDX explosives with squaramide derivatives of the present invention. The squaramide derivative-based chemical sensor prepared by the present invention realizes rapid detection of RDX by using ultraviolet absorption spectrum, and has high sensitivity and good selectivity , low cost, convenient and other characteristics, can quickly and effectively detect trace RDX explosives, can be widely used in the field of defense industry, and produce direct social and economic benefits.

2. A method for detecting RDX explosives with squaramide derivatives of the present invention uses diethyl squarate as a raw material to prepare squaramide derivatives 1 through a one-step synthesis reaction, only one step reaction, mild reaction conditions, post-reaction treatment Simple, the resulting product yield is higher.

Description of drawings

Fig. 1 is the synthetic schematic diagram of square amide derivative 1 in the present invention;

Fig. 2 is the nuclear magnetic hydrogen spectrogram of synthetic square amide derivative 1 in the present invention;

Fig. 3 is the qualitative ultraviolet spectrogram of square amide derivative 1 and RDX explosive in the present invention;

Fig. 4 is the quantitative ultraviolet spectrogram of square amide derivative 1 and RDX explosive in the present invention;

Fig. 5 is a graph showing the relationship between the UV absorbance at 272nm and the concentration of RDX explosives of the square amide derivative 1 in the present invention.

detailed description

The present invention will be further described below in conjunction with the embodiments and accompanying drawings.

Embodiment 1, the preparation of square amide derivatives:

Synthetic route shown in Figure 1, the diethyl squaraine of 50 μ L and the aniline of 60 μ L are dissolved in the 30mL mixed solution of toluene/DMF=19:1, and add 13.8mg zinc trifluoromethanesulfonate catalysts, the temperature From room temperature to 100°C, stirring at a medium speed for 8 hours, the reaction solution was centrifuged at high speed, and the obtained precipitate was washed with anhydrous methanol. The yield was 99%. The H NMR spectrum of the product is shown in Figure 2.

Embodiment 2, the preparation of square amide derivatives:

Dissolve 120 μL of diethyl squarylate and 155 μL of aniline in 30 mL of a mixed solution of toluene/DMF=19:1, add 160 mg of zinc p-toluenesulfonate catalyst, raise the temperature from room temperature to 100 ° C, and stir at a medium speed After 10 hours, the reaction solution was centrifuged at high speed, and the obtained precipitate was washed with anhydrous methanol, and the yield was 96%.

Embodiment 3, the preparation of square amide derivatives:

Dissolve 40 mL of diethyl squarylate and 51 mL of aniline in 100 mL of a mixed solution of toluene/N,N-dimethylformamide = 19:1, raise the temperature from room temperature to 120°C, and stir at medium speed for 9 hours , the reaction solution was centrifuged at high speed, and the resulting precipitate was washed with anhydrous methanol, with a yield of 94%.

Embodiment 4, the preparation of square amide derivative:

Dissolve 100mL of diethyl squarylate and 115mL of aniline in a 150mL mixed solution of toluene/N,N-dimethylformamide=19:1, raise the temperature from room temperature to 100°C, and stir at a medium speed for 12 hours , the reaction solution was centrifuged at high speed, and the precipitate was washed with anhydrous methanol, and the yield was 85%.

Embodiment 5, the preparation of sensor solution

The squaramide derivatives 1 were respectively added into a solvent to prepare a solution with a concentration of 1×10 ^-5 mol/L, and the solvent was DMSO or DMF. The prepared sensor solution can be used for the qualitative and quantitative detection of RDX explosives, as shown in Figure 3-Figure 5. The standard equation for the RDX quantitative detection of the square amide derivatives in the present invention can be obtained from the quantitative analysis data in FIG. 5 .

The quantitative identification and detection of RDX by the present invention will be further described below in conjunction with examples.

Example 6

In order to verify the accuracy and reliability of the RDX detection method of the present invention, five groups of samples containing RDX explosives were artificially prepared, and the RDX contents were respectively 10 ^-5 , 1.5×10 ^-5 , 5×10 ^-5 , 10 ^-4 , 3×10 ^-4 . After fully stirring evenly, the fluorescence spectrum was collected, and the RDX content of the above-mentioned sample was detected by the detection method of the present invention, and the detection results are shown in the following table.

Table 1: Quantitative recognition and detection of RDX in DMF solvent using squaramide derivative 1

sample 1 2 3 4 5 Theoretical content ^10-5 1.5×10 ^-5 5×10 ^{-5 10-4} 3×10 ^-4 Detection content 0.98×10 ^-5 1.47×10 ^-5 4.97×10 ^-5 1.03×10 ^-4 3.02×10 ^-4

As can be seen from the results shown in Table 1, the actual detection value of the RDX content by the method of the present invention is substantially the same as the content value added when making the sample, that is, the theoretical content, and has a smaller error range.

Example 7

Using basically the same detection conditions as in Example 6, the probe compound 1 was used in DMSO solvent to quantitatively identify and detect RDX in the above-mentioned prepared sample, and the specific results are shown in the table below.

Table 2: Quantitative recognition and detection of RDX in DMSO solvent using square amide derivative 1 in the sample

sample 1 2 3 4 5 Theoretical content ^10-5 1.5×10 ^-5 5×10 ^{-5 10-4} 3×10 ^-4 Detection content 0.98×10 ^-5 1.48×10 ^-5 5.02×10 ^-5 1.02×10 ^-4 2.97×10 ^-4

As can be seen from the results shown in Table 2, the actual detection value of the RDX content by the method of the present invention is substantially the same as the content value added when making the sample, i.e. the theoretical content, with a smaller error range.

It can be seen from the results shown that although the probe compound 1 is used in DMF and DMSO respectively, the detection method for RDX content of the present invention can obtain relatively accurate detection results with small errors.

The comprehensive test data shows that the beneficial effect of the method for quantitative detection of RDX by using squaramide derivatives in the present invention is that the equipment with lower cost is used to detect the RDX content, the measurement speed is fast, the operation is simple and convenient, and the measurement results are accurate, reliable and repeatable. Good sex.

Claims (4)

1. detect a method for RDX explosive with squaric amide derivant, it is characterized in that: concrete steps are as follows:

Step one, with organic solvent, squaric amide derivant 1 is mixed with squaric amide derivant 1 dispersion liquid of concentration known;

Step 2, RDX explosive to be joined in squaric amide derivant 1 dispersion liquid of step one gained, be configured to the mixed solution of variable concentrations; The mol ratio of RDX explosive and squaric amide derivant is respectively 0.5, and 1,2,5,10,20,50,100;

The ultra-violet absorption spectrum of the different mixed solution of step 3, determination step two gained, by the ultra-violet absorption spectrum 272nm place absorbance that records with RDX concentration determination corresponding relation, namely the standard equation y=a+bx of RDX is quantitatively detected, wherein y is the surveyed ultraviolet absorptivity corresponding containing RDX squaric amide sensor maximum absorption wavelength 272nm place, x is the content of RDX in sample, and unit is 10 ^-5m, a=0.13, b=0.017;

Step 4, the testing sample containing RDX to be joined in DMF solution, be mixed with solution; Then join in squaric amide derivant 1 dispersion liquid of concentration known, measure ultra-violet absorption spectrum; By in the ultra-violet absorption spectrum of measured sample, the absorbance at 272nm place substitutes in the RDX quantitative criterion equation of step 3 gained, can determine the content of RDX in sample;

The chemical structural formula of described squaric amide derivant 1 is as follows:

2. a kind of squaric amide derivant as claimed in claim 1 detects the method for RDX explosive, it is characterized in that: the organic solvent described in step one comprises: DMF or dimethyl sulfoxide.

3. a kind of squaric amide derivant as claimed in claim 1 detects the method for RDX explosive, it is characterized in that: the preparation method of described squaric amide derivant 1 is: by square diethyl phthalate and aniline in molar ratio for 1:1 joins in container, add the mixed solvent of toluene/DMF, the two v/v is 19/1, adds the catalyzer of lewis acid as reaction of 5% molar weight; Heat at 100 ~ 130 DEG C, reaction after 10 ~ 15 hours under the stirring rate of 10 ~ 60r/min, high speed centrifugation, rinse sediment with absolute methanol, drying can obtain squaric amide derivant 1.

4. a kind of squaric amide derivant as claimed in claim 3 detects the method for RDX explosive, it is characterized in that: described lewis acid is trifluoromethayl sulfonic acid zinc, p-toluenesulfonic acid zinc.