CN116621714A - Internal standard for detecting purity of TATB and detection method thereof - Google Patents
Internal standard for detecting purity of TATB and detection method thereof Download PDFInfo
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- CN116621714A CN116621714A CN202310572239.5A CN202310572239A CN116621714A CN 116621714 A CN116621714 A CN 116621714A CN 202310572239 A CN202310572239 A CN 202310572239A CN 116621714 A CN116621714 A CN 116621714A
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- 238000001514 detection method Methods 0.000 title claims abstract description 95
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- FZAZPMLWYUKRAE-UHFFFAOYSA-N 2,4,6-trinitrobenzene-1,3-diamine Chemical compound NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O FZAZPMLWYUKRAE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 20
- 238000000825 ultraviolet detection Methods 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 100
- 239000000243 solution Substances 0.000 claims description 32
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QLZNUFFXTZBJBB-UHFFFAOYSA-N 1-n,3-n-dimethyl-4,6-dinitrobenzene-1,3-diamine Chemical compound CNC1=CC(NC)=C([N+]([O-])=O)C=C1[N+]([O-])=O QLZNUFFXTZBJBB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 5
- 241000720974 Protium Species 0.000 claims description 5
- AEEAZFQPYUMBPY-UHFFFAOYSA-N [I].[W] Chemical compound [I].[W] AEEAZFQPYUMBPY-UHFFFAOYSA-N 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 238000002211 ultraviolet spectrum Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 20
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 239000000523 sample Substances 0.000 description 14
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 13
- 238000004811 liquid chromatography Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- -1 2,4, 6-trinitro-5-ethoxy-1, 3-phenylenediamine Chemical compound 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006396 nitration reaction Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- VNOJQYPHLMLHGQ-UHFFFAOYSA-N 2,4-dichloro-1,3,5-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1Cl VNOJQYPHLMLHGQ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 230000001546 nitrifying effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZPXDNSYFDIHPOJ-UHFFFAOYSA-N 1,5-dichloro-2,4-dinitrobenzene Chemical group [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C=C1Cl ZPXDNSYFDIHPOJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010829 isocratic elution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001035 methylating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WEWRNDOKCPEMIS-UHFFFAOYSA-N 3,5-diamino-2,4,6-trinitrophenol Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(O)=C1[N+]([O-])=O WEWRNDOKCPEMIS-UHFFFAOYSA-N 0.000 description 1
- MKWKGRNINWTHMC-UHFFFAOYSA-N 4,5,6-trinitrobenzene-1,2,3-triamine Chemical compound NC1=C(N)C([N+]([O-])=O)=C([N+]([O-])=O)C([N+]([O-])=O)=C1N MKWKGRNINWTHMC-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
- G01N30/02—Column chromatography
-
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
Abstract
The application discloses an internal standard for detecting TATB purity and a detection method thereof, wherein the internal standard is a benzene internal standard synthesized by a chlorine-containing method, and specifically comprises the following steps: 2,4, 6-trinitro-1, 3-phenylenediamine, N 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine and N 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine. The internal standard is detected by high performance liquid chromatography and ultraviolet detection to determine whether it isCan be used as an internal standard for TATB purity detection. The internal standard substance provided by the application has the advantages of high purity, good stability, simple preparation and the like, and has the advantages of small error, high reproducibility, high precision, high accuracy and the like when being used for detecting the purity of TATB.
Description
Technical Field
The application relates to the field of substance detection, in particular to an internal standard substance for detecting the purity of TATB and a detection method thereof.
Background
TATB (triamino trinitrobenzene) is a high-energy elementary substance insensitive explosive with excellent detonation performance, and as an important high-energy elementary substance insensitive explosive, the purity of a TATB product has a direct influence on an application result, so that the purity of the TATB product needs to be measured.
At present, in the field of material component detection, a liquid chromatography external standard method, an internal standard method, a traditional chemical titration method and a gravimetric analysis method are generally adopted, and in the methods, the liquid chromatography internal standard method is simpler and more convenient to operate, can quickly obtain experimental results and has good reproducibility.
TATB purity is detected by liquid chromatography internal standard method, and proper internal standard is needed to be selected. The internal standard for TATB purity detection requires that several conditions be met: (1) The internal standard has good chemical stability and high purity (more than or equal to 99.8%). Can be stored for a long time without deterioration or decomposition; (2) The internal standard substance can be completely dissolved in a sample to be tested (or the same solvent) and does not react with the sample to be tested; (3) The internal standard substance has a chemical structure similar to that of a substance to be detected and similar ultraviolet spectroscopy behavior; (4) The internal standard substance can be effectively separated from the substance to be detected under proper chromatographic conditions, and the retention time of liquid chromatography is longer than that of the substance to be detected.
2022, all researchers of chemical materials research at the university of southwest science and technology and the China engineering physical institute prepared an internal standard 2,4, 6-trinitro-5-ethoxy-1, 3-phenylenediamine (DATNEB) for analyzing the purity of TATB synthesized by chlorine-containing method through related researches, but subsequent researches find that the DATNEB has poor chemical stability, and ethoxy groups can be changed into methoxy groups when the DATNEB is recrystallized by methanol; after storage at room temperature, the 3, 5-diamino-2, 4, 6-trinitrophenol is decomposed. DATNEB does not fully meet the requirements for use as an internal standard for TATB purity analysis, and a new internal standard for TATB purity analysis is necessary.
Disclosure of Invention
In view of this, the present application provides an internal standard for detecting the purity of TATB and a detection method thereof.
To this end, the first aspect of the present application proposes an internal standard for detecting the purity of TATB, which is a benzene-based internal standard synthesized by chlorine-containing method.
Preferably, the benzene-based internal standard is: 2,4, 6-trinitro-1, 3-phenylenediamine, N 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine and N 1 ,N 3 -any one or more of dimethyl-4, 6-dinitro-1, 3-phenylenediamine.
In a second aspect, the present application provides a detection method for detecting a TATB purity internal standard, wherein the detection method is used for detecting the benzene internal standard; the detection method comprises the following steps: high performance liquid chromatography detection and ultraviolet detection.
Preferably, the high performance liquid chromatography detection method comprises:
4-1: preparing an acetonitrile solution of an internal standard substance with the concentration of 100mg/L and an acetonitrile solution of 100mg/L of TATB for high performance liquid chromatography detection;
4-2: loading an acetonitrile solution of an internal standard and an acetonitrile solution of TATB on a chromatographic column respectively, and measuring a solution liquid chromatograph;
in the step 4-2, the measurement conditions of the liquid chromatograph are as follows: the chromatographic column is a Zorbax-SB-C18 column; the temperature of the chromatographic column is 30 ℃; the sample injection volume of the solution is 20 mu L; the volume ratio of acetonitrile solution to water in the mobile phase is as follows: 6:4, a step of; the flow rate of the mobile phase loaded on the chromatographic column was 1.0mL/min.
Preferably, the ultraviolet detection method comprises:
5-1: preparing an acetonitrile solution with the concentration of 500mg/L of an internal standard substance for detection of ultraviolet spectrum absorption;
5-2: and detecting the ultraviolet absorption wavelength of the internal standard substance by adopting an ultraviolet absorption spectrum, sampling acetonitrile solution, placing the acetonitrile solution in a 1cm quartz cuvette, irradiating the sample by using an iodine tungsten lamp and a protium lamplight source, scanning for three times, and detecting to obtain the ultraviolet maximum absorption wavelength of the internal standard substance.
Preferably, the iodine-tungsten lamp and protium lamp light source provide a detection wavelength in the range of 200-800 nm.
The beneficial effects of the application are as follows: the internal standard substance for detecting the purity of the TATB and the detection method thereof provided by the application provide three brand-new internal standard substances for detecting the purity of the TATB, and the three internal standard substances have the advantages of high purity, good stability, simple preparation and the like, and have the advantages of small error, high reproducibility, high precision, high accuracy and the like when being used for detecting the purity of the TATB.
Drawings
FIG. 1 is a mass spectrum of 2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 2 is a liquid chromatogram of 2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 3 is a liquid chromatogram of 2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 4 is an ultraviolet absorption spectrum of 2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 5 is N 1 ,N 3 -mass spectrum of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 6 is N 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine 1 H NMR spectrum;
FIG. 7 is N 1 ,N 3 -liquid chromatogram of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 8 is N 1 ,N 3 -liquid chromatogram data of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 9 is N 1 ,N 3 -ultraviolet absorption spectrum of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine;
FIG. 10 is N 1 ,N 3 -dimethyl-4, 6-dinitratePhenyl-1, 3-phenylenediamine 1 H NMR spectrum;
FIG. 11 is N 1 ,N 3 -liquid chromatography of dimethyl-4, 6-dinitro-1, 3-phenylenediamine;
FIG. 12 is N 1 ,N 3 -liquid chromatogram data of dimethyl-4, 6-dinitro-1, 3-phenylenediamine;
FIG. 13 is N 1 ,N 3 -ultraviolet absorption spectrum of dimethyl-4, 6-dinitro-1, 3-phenylenediamine.
Detailed Description
Those of ordinary skill in the art will recognize that the embodiments described herein are for the purpose of aiding the reader in understanding the principles of the present application and should be understood that the scope of the application is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
The application will now be described in detail with reference to the drawings and specific examples.
High performance liquid chromatography is an important branch of chromatography, liquid is taken as a mobile phase, a high-pressure infusion system is adopted, a single solvent with different polarities or a mixed solvent with different proportions, buffer solution and other mobile phases are pumped into a chromatographic column filled with a stationary phase, and a sample to be detected enters a detector for detection after components in the column are separated, so that analysis of the sample is realized.
In order to meet the requirement of the internal standard, three suitable internal standard candidates, namely 2,4, 6-trinitro-1, 3-phenylenediamine and N, are obtained by screening 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine, N 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine and is synthesized by a suitable process.
Thus, the present application proposes an internal standard for detecting the purity of TATB, which is a benzene-based internal standard synthesized by chlorine-containing method, as an example, wherein the benzene-based internal standard is: 2,4, 6-trinitro-1, 3-phenylenediamine (2, 4,6-trinitrobenzene-1, 3-dia)Amine), N1, N3-dimethyl-2, 4, 6-trinitro-1, 3-phenylenediamine (N) 1 ,N 3 -dimethyl-2,4,6-trinitrobenzene-1, 3-Diamine) and N 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine (N) 1 ,N 3 -dimethyl-4, 6-dinitabenzen-1, 3-diamine). 2,4, 6-trinitro-1, 3-phenylenediamine, N 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine and N 1 ,N 3 The molecular formula of the-dimethyl-4, 6-dinitro-1, 3-phenylenediamine is respectively as follows:
(1) The synthesis chemistry equation of the internal standard 2,4, 6-trinitro-1, 3-phenylenediamine is as follows:
the synthesis process takes 1, 3-dichlorobenzene as a raw material, and the required target product 2,4, 6-trinitro-1, 3-phenylenediamine is synthesized through two steps of nitration and ammoniation. The intermediate in one step of nitration is 1, 3-dichloro-2, 4,6-trinitrobenzene, the condition in one step of nitration is that nitric acid and sulfuric acid are used for reaction under the high temperature condition, the condition in one step of ammoniation is that ammonia gas is used for reaction, and finally high-purity products are obtained through recrystallization or column chromatography operation.
As an example, the synthesis of the internal standard 2,4, 6-trinitro-1, 3-phenylenediamine is as follows:
and (3) nitrifying: 19.6g (0.2 mol) of concentrated sulfuric acid and 2.05g (0.032 mol) of fuming nitric acid were placed in an ice bath and mixed uniformly. 0.735g (0.05 mol) of m-dichlorobenzene was added to the uniformly mixed nitric-sulfuric mixed acid at room temperature, and the temperature was raised to 150℃for 7 half an hour. After the reaction, cooling to room temperature, filtering to obtain white flocculent solid, and washing with distilled water. Recrystallisation once from ethyl acetate/petroleum ether gives 0.6g of the intermediate 3, 5-dichloro-2, 4, 6-trinitrobenzene. The yield was 48.2%.
An ammoniation step: 0.6g (2 mmol) of 3, 5-dichloro-2, 4,6-trinitrobenzene was weighed and dissolved in 5mL of toluene, ammonia gas was introduced into the solution, the temperature was raised to 40 ℃, and the reaction was carried out for 10 hours, so that a brown yellow solid was produced. The reaction solution was filtered to obtain a brown yellow solid. Acetonitrile followed by methanol recrystallization twice gave 0.3g of product. The yield was 51.9%.
(2) Internal standard N 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine is synthesized by the following equation:
the synthesis process takes 1, 3-dichlorobenzene as raw material, and synthesizes the required target product N through two steps of nitration and methylamine 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine. The one-step intermediate of nitration is 1, 3-dichloro-2, 4, 6-trinitrobenzene. The one-step nitration is carried out by mixing nitric and sulfuric acid at high temperature, and the one-step methylamine is carried out by adding aqueous solution of methylamine. Finally, the high-purity product is obtained through recrystallization or column chromatography operation.
As an example, internal standard N 1 ,N 3 The preparation process of the-dimethyl-2, 4, 6-trinitro-1, 3-phenylenediamine comprises the following steps:
and (3) nitrifying: this step is consistent with the nitration step for the synthesis of 2,4, 6-trinitro-1, 3-phenylenediamine.
A step of methylating: 0.6g (2 mmol) of 3, 5-dichloro-2, 4,6-trinitrobenzene was weighed out and dissolved in 5mL of toluene. 10mL of aqueous methylamine was added dropwise at room temperature and reacted for 8 hours to give a brown yellow solid. The reaction solution was filtered to obtain a brown yellow solid. Acetonitrile followed by methanol recrystallization twice gave 0.30g of product. The yield was 51.9%.
(3) Internal standard N 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine has the chemical equation:
the synthesis process takes 1, 3-dichlorobenzene as raw material, and synthesizes the required target product N through two steps of nitration and methylamine 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine. Intermediate of one step of nitrationThe body is 1, 3-dichloro-4, 6-dinitrobenzene. The one-step nitration is carried out by mixing nitric and sulfuric acid at high temperature, and the one-step methylamine is carried out by adding aqueous solution of methylamine. Finally, the high-purity product is obtained through recrystallization or column chromatography operation.
As an example: n (N) 1 ,N 3 The preparation process of the-dimethyl-4, 6-dinitro-1, 3-phenylenediamine comprises the following steps:
and (3) nitrifying: 19.6g (0.2 mol) of concentrated sulfuric acid and 2.05g (0.032 mol) of fuming nitric acid were placed in an ice bath and mixed uniformly. 0.735g (0.05 mol) of m-dichlorobenzene was added to the uniformly mixed nitric-sulfuric mixed acid at room temperature, and the reaction was carried out at 130℃for 7 half hours. After the reaction, cooling to room temperature, filtering to obtain white flocculent solid, purifying by column chromatography to obtain 0.5g of intermediate 3, 5-dichloro-2, 4,6-trinitrobenzene with a yield of 42.3%.
Column chromatography conditions: isocratic elution, eluting with ethyl acetate: petroleum ether = 1:4.
a step of methylating: 0.6g (2.5 mmol) of 1, 3-dichloro-4, 6-dinitrobenzene was weighed out and dissolved in 5mL of toluene. 10mL of aqueous methylamine was added dropwise at room temperature and reacted for 8 hours to give a brown yellow solid. The reaction solution was filtered to obtain a brown yellow solid. Recrystallisation twice from acetonitrile gives 0.25g of product. The yield was 43.5%.
The three reaction synthesis routes are simple, the operation is simple and convenient, the reaction conditions are mild, and the raw materials are the most common chemical substances in the chemical industry.
Detecting the internal standard according to the related requirements, wherein the detection method comprises the following steps: HPLC-MS detection method, 1 H NMR detection, high performance liquid chromatography, and ultraviolet detection, the first two methods being used to detect the accuracy of the synthesized internal standard, and the second two methods being used to determine whether the synthesized internal standard is capable of being used as an internal standard for TATB purity detection.
The mass spectrum conditions required for the HPLC-MS detection method are as follows: an ESI ionization source, a triple quadrupole tandem mass spectrometer and a positive/negative ion detector; 1 the conditions required for the H NMR detection method are: 600MHz nuclear magnetic resonance spectrometer, TCI three resonance trans ultra-low temperature probe, normal temperature or low temperature detection and deuterated solvent dissolution; high performance liquid chromatographyThe detection method detects the required liquid phase condition: ultra-high performance liquid chromatography system, reversed phase chromatographic column, acetonitrile/water mobile phase and isocratic elution; the ultraviolet detection method detects the required ultraviolet conditions: the light source of the iodine-tungsten lamp and the protium lamp, the holographic reticle grating beam splitting system, the ultraviolet visible near infrared band coverage and the photomultiplier receiver.
HPLC-MS detection of an internal standard substance, wherein the internal standard substance is subjected to HPLC-MS detection under the same liquid chromatography condition in a positive/negative particle mode, the obtained molecular ion peak accords with a mass spectrum detection rule, and the M/z=M+/-1 of the excimer ion peak. The HPLC-MS detection conditions were: the mobile phase is acetonitrile; sample injection volume 5. Mu.L; the detection mode is a negative ion mode.
Internal standard 1 H NMR detection. One-dimensional internal standard 1 H NMR with CDCl3-d or DMSO-d 6 Is a deuterated reagent; detection is performed at room temperature or at low temperature. One-dimensional internal standard 1 The H NMR detection conditions were: DMSO-d 6 Is a deuterated reagent; 600MHz resonance frequency; and (5) detecting at room temperature.
And (5) detecting the high performance liquid chromatography of the internal standard substance. Depending on the selection requirements, the internal standard should have a different liquid chromatography retention time than TATB under the same liquid chromatography conditions and be completely separated from the liquid chromatography peak of TATB. According to preferred conditions, the liquid phase test conditions are: chromatographic column Zorbax-SB-C18 column (250X 4.6mm,5.0 μm); the column temperature is 30 ℃; a sample injection volume of 20 mu L; the mobile phase is acetonitrile: water = 6:4, a step of; the flow rate is 1.0mL/min; the detection wavelength of the ultraviolet detector is 350nm; TATB was prepared as an acetonitrile solution at a concentration of 100 mg/L. The retention time of TATB under this chromatographic condition was 3.62min.
And (5) ultraviolet detection of the internal standard substance. Depending on the selection requirements, the maximum ultraviolet absorption wavelength of the internal standard should be comparable to TATB. The maximum ultraviolet absorption wavelength of TATB is 350nm, so that the maximum ultraviolet absorption wavelength range of the internal standard substance of the internal standard is 320-380 nm.
High performance liquid chromatography detection and ultraviolet detection by internal standard
As an example, three detection methods of internal standard are described, respectively.
(1) The detection method of the internal standard 2,4, 6-trinitro-1, 3-phenylenediamine comprises an HPLC-MS detection method, a high performance liquid chromatography detection method and an ultraviolet detection method, wherein:
HPLC-MS detection method: preparing an acetonitrile solution of 2,4, 6-trinitro-1, 3-phenylenediamine with the concentration of 100mg/L according to the test requirement, detecting the molecular structure information of an internal standard 2,4, 6-trinitro-1, 3-phenylenediamine by adopting HPLC-MS, wherein the test conditions are as follows: sample injection amount is 5 mu L, and ESI ionizes the ionization source; the detecting instrument is as follows: triple quadrupole tandem mass analyzer; the detection mode is as follows: negative ion detector mode. The excimer ion peak m/z= 242.20 is obtained. The mass spectrum is shown in figure 1.
By the above HPLC-MS detection, we can confirm that 2,4, 6-trinitro-1, 3-phenylenediamine can be synthesized by the aforementioned synthesis process.
The high performance liquid chromatography detection method comprises the following steps: according to the test requirement, an acetonitrile solution of 2,4, 6-trinitro-1, 3-phenylenediamine with the concentration of 100mg/L is prepared for detection, and according to the test requirement, the test conditions of liquid chromatography are as follows: chromatographic column Zorbax-SB-C18 column (250X 4.6mm,5.0 μm), column temperature 30 ℃, sample volume 20. Mu.L, mobile phase acetonitrile: water = 6:4, flow rate 1.0mL/min. Through detection, the retention time of the internal standard 2,4, 6-trinitro-1, 3-phenylenediamine is 6.246min, and the purity is 99.77%. The liquid phase test patterns and the data thereof are shown in fig. 2 and 3.
The ultraviolet absorption detection method comprises the following steps: an acetonitrile solution of 2,4, 6-trinitro-1, 3-phenylenediamine at a concentration of 500mg/L was prepared for detection according to the test requirements. The test conditions were: the container is a 1cm quartz cuvette, the detection wavelength range is 200-800nm, and the scanning times are three times. The maximum ultraviolet absorption wavelength of the 2,4, 6-trinitro-1, 3-phenylenediamine is 326nm, and the ultraviolet absorption diagram is shown in figure 4.
Through the high performance liquid chromatography detection and the ultraviolet absorption detection, the 2,4, 6-trinitro-1, 3-phenylenediamine can be determined to be used as an internal standard substance for TATB purity detection.
(2) Internal standard N 1 ,N 3 The detection method of the-dimethyl-2, 4, 6-trinitro-1, 3-phenylenediamine comprises the following steps: HPLC-MS detection method, 1 H NMR detection, high performance liquid chromatography detection, and ultraviolet detection, wherein:
HPLC-MS detection method: according to the testN with required configuration concentration of 100mg/L 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine in acetonitrile for detection and HPLC-MS combined detection of N 1 ,N 3 -molecular structure information of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine. The test conditions were: the sample injection amount is 5 mu L, and the ESI ionization source, the triple quadrupole tandem mass analyzer and the negative ion detector mode are adopted. The excimer ion peak m/z=270.30 was obtained and the mass spectrum is shown in fig. 5.
1 H NMR detection method: configuring N with concentration of 4g/L according to test requirement 1 ,N 3 DMSO-d of-dimethyl-2, 4, 6-trinitro-1, 3-phenylenediamine 6 The solution is used for detection, and 600MHz nuclear magnetic resonance spectrometer is adopted for detection under room temperature condition 1 H NMR to obtain N 1 ,N 3 Hydrogen spectrum information of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine, 1 the H NMR spectrum is shown in FIG. 6.
Detection and detection by HPLC-MS as described above 1 H NMR examination can confirm that N can be synthesized by the aforementioned synthesis procedure 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine.
The high performance liquid chromatography detection method comprises the following steps: configuring N with concentration of 100mg/L according to test requirement 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine in acetonitrile for detection. The test conditions for liquid chromatography were: chromatographic column Zorbax-SB-C18 column (250X 4.6mm,5.0 μm), column temperature 30 ℃, sample volume 20. Mu.L, mobile phase acetonitrile: water = 6:4, the flow rate was 1.0mL/min. Through detection, N 1 ,N 3 The retention time of the-dimethyl-2, 4, 6-trinitro-1, 3-phenylenediamine is 6.95min, the purity is 98.99%, and the liquid phase test patterns and the data thereof are shown in fig. 7 and 8.
The ultraviolet absorption detection method comprises the following steps: configuring N with concentration of 500mg/L according to test requirement 1 ,N 3 -a solution of dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine in acetonitrile for detection, the container being a 1cm quartz cuvette; the detection wavelength range is 200-800nm; the number of scans was three. Detected N 1 ,N 3 The maximum ultraviolet absorption wavelength of the-dimethyl-2, 4, 6-trinitro-1, 3-phenylenediamine is 350.03nm, and the ultraviolet absorption diagram is shown in figure 9.
N can be determined by the HPLC detection and the UV absorption detection 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine can be used as an internal standard for TATB purity detection.
(3) Internal standard N 1 ,N 3 The method for detecting the-dimethyl-4, 6-binitro-1, 3-phenylenediamine comprises the following steps: 1 h NMR detection, high performance liquid chromatography detection, and ultraviolet detection, wherein:
1 h NMR detection method: configuring N with concentration of 4g/L according to test requirement 1 ,N 3 DMSO-d of-dimethyl-4, 6-dinitro-1, 3-phenylenediamine 6 The solution was used for detection. Detection at room temperature using 600MHz nuclear magnetic resonance spectrometer 1 H NMR to obtain N 1 ,N 3 Hydrogen spectrum information of dimethyl-4, 6-dinitro-1, 3-phenylenediamine, 1 the H NMR spectrum is shown in FIG. 10.
By passing through 1 H NMR examination can confirm that N can be synthesized by the aforementioned synthesis procedure 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine.
High performance liquid chromatography detection method, and N with concentration of 100mg/L is configured according to test requirement 1 ,N 3 -acetonitrile solution of dimethyl-4, 6-dinitro-1, 3-phenylenediamine for detection, the test conditions of liquid chromatography are: chromatographic column Zorbax-SB-C18 column (250X 4.6mm,5.0 μm), column temperature 30 ℃, sample volume 20. Mu.L, mobile phase acetonitrile: water = 6:4, flow rate 1.0mL/min. Through detection, N 1 ,N 3 -retention time of dimethyl-4, 6-dinitro-1, 3-phenylenediamine 6.560min, purity 99.9%, liquid phase test pattern and data inspection of FIGS. 11 and 12
The ultraviolet absorption detection method comprises the following steps: configuring N with concentration of 500mg/L according to test requirement 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine in acetonitrile for detection. The container is a quartz cuvette of 1 cm; the detection wavelength range is 200-800nm; the number of scans was three. The maximum ultraviolet absorption wavelength of the detected internal standard 3 is 338nm, and the ultraviolet absorption diagram is shown in figure 13.
Detection by high performance liquid chromatography and ultraviolet absorptionCan determine N 1 ,N 3 -dimethyl-4, 6-dinitro-1, 3-phenylenediamine can be used as an internal standard for the purity detection of TATB.
Claims (6)
1. The internal standard for detecting the purity of TATB is characterized in that the internal standard is a benzene internal standard synthesized by a chlorine-containing method.
2. The internal standard for detecting TATB purity according to claim 1, wherein the benzene-based internal standard is: 2,4, 6-trinitro-1, 3-phenylenediamine, N 1 ,N 3 -dimethyl-2,4, 6-trinitro-1, 3-phenylenediamine and N 1 ,N 3 -any one or more of dimethyl-4, 6-dinitro-1, 3-phenylenediamine.
3. A detection method for detecting an internal standard of TATB purity, characterized in that the detection method is used for detecting the benzene-based internal standard of claim 2; the detection method comprises the following steps: high performance liquid chromatography detection and ultraviolet detection.
4. The method for detecting an internal standard for TATB purity according to claim 3, wherein said high performance liquid chromatography detection method comprises:
4-1: preparing an acetonitrile solution of an internal standard substance with the concentration of 100mg/L and an acetonitrile solution of 100mg/L of TATB for high performance liquid chromatography detection;
4-2: loading an acetonitrile solution of an internal standard and an acetonitrile solution of TATB on a chromatographic column respectively, and measuring a solution liquid chromatograph;
in the step 4-2, the measurement conditions of the liquid chromatograph are as follows: the chromatographic column is a Zorbax-SB-C18 column; the temperature of the chromatographic column is 30 ℃; the sample injection volume of the solution is 20 mu L; the volume ratio of acetonitrile solution to water in the mobile phase is as follows: 6:4, a step of; the flow rate of the mobile phase loaded on the chromatographic column was 1.0mL/min.
5. The method for detecting an internal standard for TATB purity according to claim 3, wherein said ultraviolet detection method comprises:
5-1: preparing an acetonitrile solution with the concentration of 500mg/L of an internal standard substance for detection of ultraviolet spectrum absorption;
5-2: and detecting the ultraviolet absorption wavelength of the internal standard substance by adopting an ultraviolet absorption spectrum, sampling acetonitrile solution, placing the acetonitrile solution in a 1cm quartz cuvette, irradiating the sample by using an iodine tungsten lamp and a protium lamplight source, scanning for three times, and detecting to obtain the ultraviolet maximum absorption wavelength of the internal standard substance.
6. The method according to claim 5, wherein the light source of the iodine-tungsten lamp and the protium lamp provides a detection wavelength in the range of 200-800 nm.
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| GB9925147D0 (en) * | 1999-10-26 | 1999-12-22 | Secr Defence | Synthesis of TATB and DATB |
| CN104237405A (en) * | 2014-09-05 | 2014-12-24 | 北京理工大学 | Method for determining synthesized intermediate and product in wastewater in TATB production by liquid chromatogram |
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| GB9925147D0 (en) * | 1999-10-26 | 1999-12-22 | Secr Defence | Synthesis of TATB and DATB |
| CN104237405A (en) * | 2014-09-05 | 2014-12-24 | 北京理工大学 | Method for determining synthesized intermediate and product in wastewater in TATB production by liquid chromatogram |
| CN112326844A (en) * | 2020-11-30 | 2021-02-05 | 山西北化关铝化工有限公司 | Method for measuring TATB (trans-activator of heavy metals) and HMX (high molecular weight hydrocarbons) content in explosive wastewater |
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