CN113896687A - Preparation method and analysis method of planar explosive LLM-105 solvate - Google Patents
Preparation method and analysis method of planar explosive LLM-105 solvate Download PDFInfo
- Publication number
- CN113896687A CN113896687A CN202111209859.XA CN202111209859A CN113896687A CN 113896687 A CN113896687 A CN 113896687A CN 202111209859 A CN202111209859 A CN 202111209859A CN 113896687 A CN113896687 A CN 113896687A
- Authority
- CN
- China
- Prior art keywords
- llm
- solvate
- crystal
- solvent
- explosive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012453 solvate Substances 0.000 title claims abstract description 35
- 239000002360 explosive Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000004458 analytical method Methods 0.000 title abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 230000003993 interaction Effects 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229920006335 epoxy glue Polymers 0.000 claims description 4
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 claims description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OOSDUBRPGZBAMV-UHFFFAOYSA-N 4,7-dinitro-5,6-dihydro-[1,2,5]oxadiazolo[3,4-b]pyrazine Chemical compound [O-][N+](=O)N1CCN([N+]([O-])=O)C2=NON=C12 OOSDUBRPGZBAMV-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D241/20—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/03—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
- C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a preparation method and an analysis method of a planar explosive LLM-105 solvate, which comprises the following steps: (1) adding the LLM-105 raw material and a solvent into a conical flask, sealing the bottle mouth by using an air balloon, heating in an oil bath pot, and completely dissolving the LLM-105 by magnetic stirring; (2) naturally cooling the LLM-105 solution obtained in the step (1) to room temperature to obtain an LLM-105 supersaturated solution; (3) placing the LLM-105 supersaturated solution in a constant temperature incubator, standing for more than one week to form orange needle-shaped LLM-105 solvent compound crystals at the bottom of the conical flask. The invention realizes the synthesis of the LLM-105 solvate and the crystal structure analysis thereof for the first time.
Description
Technical Field
The invention relates to a preparation method of explosive solvate, in particular to a preparation method and an analysis method of planar explosive LLM-105 solvate.
Background
Solubility is an important parameter in the synthesis, recrystallization and batch manufacturing process design of explosives. The interaction between explosive molecules and solvent molecules is a key factor for determining the solubility of the explosive in an organic solvent and is also a main basis for solvent screening. However, in the solution, both the explosive molecules and the solvent molecules are in the brownian motion state, and the interaction between the explosive molecules and the solvent molecules is difficult to characterize through effective experimental means. Therefore, the analysis of the interaction between explosive molecules and solvent molecules based on the crystal structure of explosive solvates is an important means for studying the solubility of explosives. In addition, solvates are also an important intermediate in the preparation of porous explosives. Researches show that the multilevel pore channel structure of the explosive with special morphology can be obtained through the disassembly and assembly process of the solvate, and the method becomes an important method for regulating and controlling the morphology of the explosive. Therefore, obtaining an explosive solvate structure is of great importance for the application of explosives. LLM-105 (1-oxo-2, 6-diamino-3, 5-dinitropyrazine) is a planar explosive molecule and is a heat-resistant initiating explosive with good application prospect. However, because LLM-105 has very low solubility in common organic solvents, it brings great difficulties to the synthesis, batch preparation and morphology control of LLM-105. The solvents currently used in the recrystallization of LLM-105 explosives are DMF and DMFSO, which also have a solubility of only 0.56 g/100 ml (18 ℃) and 3.63 g/100 ml (18 ℃). Therefore, the LLM-105 solvate is prepared and the crystal structure is obtained, the reasons of the solubility of the LLM-105 in different solvents can be revealed by analyzing the interaction of LLM-105 molecules and solvent molecules in the crystal structure, and meanwhile, the LLM-105 solvate can be utilized for disassembly to obtain the porous LLM-105, so that the special morphology and performance regulation of the LLM-105 are realized. Unfortunately, there is no report of successful synthesis of LLM-105 solvate.
Disclosure of Invention
The invention aims to provide a preparation method and an analysis method of a planar explosive LLM-105 solvate, which realize the synthesis of the LLM-105 solvate and the crystal structure analysis thereof.
In order to achieve the technical effects, the invention provides a preparation method of a planar explosive LLM-105 solvate, which comprises the following steps: (1) adding the LLM-105 raw material and a solvent into a conical flask, sealing the flask opening, heating in an oil bath kettle, and completely dissolving the LLM-105 by magnetic stirring; (2) naturally cooling the LLM-105 solution obtained in the step (1) to room temperature to obtain an LLM-105 supersaturated solution; (3) placing the LLM-105 supersaturated solution in a constant temperature incubator, standing for 7-14 days, and forming orange needle-shaped LLM-105 solvent compound crystals at the bottom of the conical flask.
The further technical scheme is that the solvent is dimethyl sulfoxide or N, N-dimethylformamide.
The further technical scheme is that the mass-volume ratio of the LLM-105 raw material to the solvent is (1-5) g:100 mL.
The further technical scheme is that the heating temperature in the step (1) is 70-80 ℃.
The further technical scheme is that the standing temperature in the step (3) is 5-20 ℃.
A method for resolving a planar explosive LLM-105 solvate, comprising the steps of: (1) dripping epoxy A glue and epoxy B glue on a glass slide, uniformly mixing in equal proportion, sucking the LLM-105 solvent compound crystal prepared by any one preparation method of claims 1-3 by using a glass dropper, and quickly dripping the crystal into the epoxy glue to ensure that the crystal is completely wrapped by the epoxy glue; (2) under an optical microscope, selecting LLM-105 solvate crystals with regular shapes and transparent interiors, and sticking one crystal at the tip of each glass fiber by using a thin glass fiber; (3) inserting the glass fiber into a sample table of a single crystal X-ray diffractometer, screwing and fixing, acquiring single crystal X-ray diffraction data of the LLM-105 solvate by using the single crystal X-ray diffractometer, and analyzing to obtain a crystal structure of the LLM-105 solvate based on the single crystal X-ray diffraction data; (4) the crystal structure of LLM-105 solvate was analyzed using crystallography software to obtain the interaction of LLM-105 with solvent molecules.
Compared with the prior art, the invention has the following beneficial effects: the invention adopts a supersaturation technology and a low-temperature slow crystallization technology to synthesize the LLM-105 solvate, and analyzes the crystal structure of the solvate through single crystal X-ray diffraction (SCXRD). The method of the invention realizes the preparation and crystal structure analysis of LLM-105 solvate for the first time, successfully synthesizes two LLM-105 solvates, LLM-105. DMF and LLM-105. DMSO, obtains the interaction between LLM-105 and the two solvents, can provide important reference for the optimization of the LLM-105 recrystallization process and the screening of the solvents, can also be used for the preparation of porous LLM-105, provides a new thought and method for the morphology control of LLM-105, develops a new application direction for the performance improvement of LLM-105-based initiating explosive, and has important application value.
Drawings
FIG. 1 is a schematic diagram of the synthesis and crystal structure resolution process of LLM-105 solvate;
FIG. 2 is a perspective view of the LLM-105. DMSO crystal structure;
FIG. 3 is a schematic diagram of the intermolecular hydrogen bonding interaction of LLM-105 and DMSO;
FIG. 4 is a perspective view of the LLM-105. DMF crystal structure;
FIG. 5 is a schematic diagram of the intermolecular hydrogen bonding interaction of LLM-105 and DMF.
Detailed Description
Example 1
0.1 g of LLM-105 powder was added to a 10 ml screw glass vial, 2 ml of DMSO was added, the cap was screwed on, the vial was heated to 70 ℃ in an oil bath, and stirring was continued for 1 hour using a magnetic stirrer to completely dissolve the DMSO. Naturally cooling to room temperature, and standing for 7 days to obtain yellow needle crystal precipitate. Sucking a small amount of crystals by a glass dropper, quickly transferring the crystals into AB glue, sticking one crystal by a glass wire, and determining the crystal structure by utilizing single crystal X-ray diffraction. The test result shows that the chemical formula of LLM-105. DMSO is C4H4N6O5·C2H6OS, belonging to monoclinic system, space group P21C, unit cell parameter of β is 101.683(7) °. The molecular packing is shown in FIG. 2. The software analysis shows that the LLM-105 and DMSO have stronger intermolecular hydrogen bonding interaction, as shown in FIG. 3.
Example 2
0.4 g of LLM-105 powder and 35 ml of DMF were added to a 50 ml Erlenmeyer flask, the opening of the Erlenmeyer flask was sealed with a balloon, the mixture was heated to 85 ℃ in an oil bath, and stirred with a magnetic stirrer for 1 hour to completely dissolve the mixture. Naturally cooling to room temperature, transferring the conical flask filled with the LLM-105 supersaturated solution into a low-temperature incubator, keeping the temperature in the incubator at 5 ℃, and standing for 1 hour to obtain yellow needle crystal precipitate. Sucking a small amount of crystals by a glass dropper, quickly transferring the crystals into AB glue, sticking one crystal by a glass wire, and determining the crystal structure by utilizing single crystal X-ray diffraction. The test result shows that the chemical formula of LLM-105. DMF is C4H4N6O 5. C3H7NO, which belongs to a monoclinic system, and the space group is P21Cell parameter ofβ is 96.500(3) °. The molecular packing is shown in FIG. 4. Through software analysis, it can be found that LLM-105 and DMF have strong intermolecular hydrogen bonding interaction, as shown in FIG. 5.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (6)
1. A method for preparing a planar explosive LLM-105 solvate, comprising the steps of: (1) adding the LLM-105 raw material and a solvent into a conical flask, sealing the flask opening, heating in an oil bath kettle, and completely dissolving the LLM-105 by magnetic stirring; (2) naturally cooling the LLM-105 solution obtained in the step (1) to room temperature to obtain an LLM-105 supersaturated solution; (3) placing the LLM-105 supersaturated solution in a constant temperature incubator, standing for 7-14 days, and forming orange needle-shaped LLM-105 solvent compound crystals at the bottom of the conical flask.
2. The method of preparing the planar explosive LLM-105 solvate according to claim 1, wherein said solvent is dimethylsulfoxide or N, N-dimethylformamide.
3. The method of claim 1, wherein the mass-to-volume ratio of the LLM-105 raw material to the solvent is (1-5) g:100 mL.
4. The method for preparing the planar explosive LLM-105 solvate according to claim 1, wherein the heating temperature in the step (1) is 70 to 80 ℃.
5. The method for preparing the planar explosive LLM-105 solvate according to claim 1, wherein the standing temperature in the step (3) is 5 to 20 ℃.
6. A method for resolving a planar explosive LLM-105 solvate, comprising the steps of: (1) dripping epoxy A glue and epoxy B glue on a glass slide, uniformly mixing in equal proportion, sucking the LLM-105 solvent compound crystal prepared by any one preparation method of claims 1-3 by using a glass dropper, and quickly dripping the crystal into the epoxy glue to ensure that the crystal is completely wrapped by the epoxy glue; (2) under an optical microscope, selecting LLM-105 solvate crystals with regular shapes and transparent interiors, and sticking one crystal at the tip of each glass fiber by using a thin glass fiber; (3) inserting the glass fiber into a sample table of a single crystal X-ray diffractometer, screwing and fixing, acquiring single crystal X-ray diffraction data of the LLM-105 solvate by using the single crystal X-ray diffractometer, and analyzing to obtain a crystal structure of the LLM-105 solvate based on the single crystal X-ray diffraction data; (4) the crystal structure of LLM-105 solvate was analyzed using crystallography software to obtain the interaction of LLM-105 with solvent molecules.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111209859.XA CN113896687A (en) | 2021-10-18 | 2021-10-18 | Preparation method and analysis method of planar explosive LLM-105 solvate |
CN202310806963.XA CN116836122A (en) | 2021-10-18 | 2021-10-18 | Planar explosive LLM-105 solvate and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111209859.XA CN113896687A (en) | 2021-10-18 | 2021-10-18 | Preparation method and analysis method of planar explosive LLM-105 solvate |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310806963.XA Division CN116836122A (en) | 2021-10-18 | 2021-10-18 | Planar explosive LLM-105 solvate and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113896687A true CN113896687A (en) | 2022-01-07 |
Family
ID=79192611
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111209859.XA Pending CN113896687A (en) | 2021-10-18 | 2021-10-18 | Preparation method and analysis method of planar explosive LLM-105 solvate |
CN202310806963.XA Pending CN116836122A (en) | 2021-10-18 | 2021-10-18 | Planar explosive LLM-105 solvate and preparation method and application thereof |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310806963.XA Pending CN116836122A (en) | 2021-10-18 | 2021-10-18 | Planar explosive LLM-105 solvate and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN113896687A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107827835A (en) * | 2017-11-22 | 2018-03-23 | 中国工程物理研究院化工材料研究所 | A kind of simple method for preparing of explosive solvate |
-
2021
- 2021-10-18 CN CN202111209859.XA patent/CN113896687A/en active Pending
- 2021-10-18 CN CN202310806963.XA patent/CN116836122A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107827835A (en) * | 2017-11-22 | 2018-03-23 | 中国工程物理研究院化工材料研究所 | A kind of simple method for preparing of explosive solvate |
Non-Patent Citations (3)
Title |
---|
中国食品药品检定研究院: "《中国药品检验标准操作规范》", 31 August 2019 * |
徐容等: "重结晶方法对2,6-二氨基-3,5-二硝基吡嗪-1-氮氧化物晶体特性及性能影响", 《兵工学报》 * |
沈盼盼: "LLM-105的精制及其含能配合物的合成、表征和催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Also Published As
Publication number | Publication date |
---|---|
CN116836122A (en) | 2023-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hao et al. | Reactivity and chemical synthesis of L-pyrrolysine—the 22nd genetically encoded amino acid | |
CN105330606B (en) | 2-aminopyridine is the 5 FU 5 fluorouracil pharmaceutical co-crystals and its preparation method and application of presoma | |
CN113896687A (en) | Preparation method and analysis method of planar explosive LLM-105 solvate | |
CN110093665A (en) | A kind of perovskite crystal growth system and preparation method thereof | |
CN110655914A (en) | Chiral perovskite nanowire crystal and preparation method thereof | |
CN108530354A (en) | A kind of synthetic method of the compound of class containing phenylsulfonylquinoline | |
CN111072588B (en) | Preparation method of sulfur-containing cyano thiazoline compound | |
CN104829673A (en) | Preparation method of sofosbuvir crystal form 6 | |
CN110305131B (en) | Novel crystal form of linagliptin and preparation method thereof | |
CN108530339B (en) | Synthetic method of benzenesulfonyl-containing indole compound | |
CN110372576A (en) | A kind of calcium channel blocking drug molecule eutectic and preparation method thereof | |
CN107686130B (en) | A kind of synthesis of bismuth iodine hybrid material and it is used to prepare BiOI nanometer sheet | |
CN107235887B (en) | Polysubstituted diindolylmethane derivative and preparation method thereof | |
CN105481780B (en) | 2- aminopyrimidine is the 5 FU 5 fluorouracil pharmaceutical co-crystals and its preparation method and application of presoma | |
CN104804018A (en) | Preparation method for type I ceftezole sodium crystal | |
CN113233952A (en) | Preparation method of organic chiral eutectic crystal based on achiral small molecules as donor and acceptor | |
CN115894160A (en) | Method for realizing internal polar phase change of organic eutectic by introducing third element | |
CN116589377A (en) | 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic and preparation method thereof | |
CN111732580A (en) | Preparation method of engagliflozin single crystal | |
Craythorne et al. | A low molecular weight hydro and organogelator derived from an isohexide and sol–gel transcription of the alcogel | |
Larsen et al. | Structures of the optically active monofluoro-substituted mandelic acids: Relation to their racemic counterparts and thermochemical properties | |
CN114105189B (en) | Preparation method of green fluorescent zero-dimensional perovskite | |
KR950004344B1 (en) | Method for growing ktp single crystal by flux method | |
Kulishov et al. | Growth of new linear phenylene-oxazole oligomers with a central benzothiadiazole fragment from solutions of crystals | |
CN116574055A (en) | 4- (8-hydroxy-5-quinolyl azo) benzenesulfonic acid phenanthroline dye eutectic and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220107 |