CN110330454B - Synthesis method of pyridine heterocyclic azobenzene - Google Patents
Synthesis method of pyridine heterocyclic azobenzene Download PDFInfo
- Publication number
- CN110330454B CN110330454B CN201910800189.5A CN201910800189A CN110330454B CN 110330454 B CN110330454 B CN 110330454B CN 201910800189 A CN201910800189 A CN 201910800189A CN 110330454 B CN110330454 B CN 110330454B
- Authority
- CN
- China
- Prior art keywords
- solution
- pyridine
- diazonium salt
- carboxypyridine
- azobenzene
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a synthesis method of pyridine heterocyclic azobenzene, which comprises the steps of carrying out diazotization reaction on 5-amino isophthalic acid and sodium nitrite, then carrying out reaction on the reaction product and 1-amino-2-carboxypyridine, 2, 4-dicarboxylpyridine or 2-fluoro-3-carboxypyridine, and filtering and purifying to obtain the pyridine heterocyclic azobenzene, wherein the yield of the pyridine heterocyclic azobenzene is up to more than 59 percent, the product series of heterocyclic azobenzene is widened, and meanwhile, the synthesis process is simple and convenient, few byproducts are produced, and the pyridine heterocyclic azobenzene is easy to purify.
Description
Technical Field
The invention relates to a synthesis method of pyridine heterocyclic azobenzene.
Background
The nitrogen heterocyclic ligand has outstanding physiological activity and good coordination capability, so that the nitrogen heterocyclic ligand has very wide application and research in coordination chemistry, biochemistry, medicine, pesticide, analytical chemistry and fine chemical engineering.
A series of benzo nitrogen-containing heterocyclic pyridyl compounds and azobenzene compounds are synthesized by Leying and the like of the Qinghua university, and are coordinated with rare earth ions to prepare benzo nitrogen-containing heterocyclic pyridyl rare earth complexes, so that the fluorescence performance of the material and the interaction between the benzo nitrogen-containing heterocyclic pyridyl rare earth complexes and biomacromolecule bovine serum albumin are researched.
Li Chaocai et al synthesized a series of liquid crystal compounds based on a dichloropyrazole structure, studied the liquid crystal properties of heterocyclic azobenzene, and found that the molecular structure of azo compounds containing the dichloropyrazole structure had a great influence on the liquid crystal properties of the material, and among the synthesized compounds containing dihydropyrazole azo compounds, compounds containing three aromatic rings had no liquid crystal properties, while compounds containing four aromatic rings all had liquid crystal properties.
However, the study on the heterocyclic azobenzene is still relatively rare, and the study on the performance and structure of the synthesized heterocyclic azobenzene is incomplete.
Disclosure of Invention
Based on the above, the invention aims to provide a synthesis method of pyridine heterocyclic azobenzene. The invention selects aromatic amine containing N heteroatom as raw material, combines diazotization and coupling reaction of aromatic amine, synthesizes a series of novel aromatic heterocyclic azobenzene compounds, and has simple and convenient synthesis method, high product purity and high yield.
The technical scheme of the invention is as follows:
a synthetic method of pyridine heterocyclic azobenzene comprises the following steps:
1) dissolving 5-amino isophthalic acid in dilute hydrochloric acid to prepare a solution I, and placing the solution I in an ice water bath;
2) slowly dripping 1mol/L sodium nitrite aqueous solution into the solution I in the step 1), and stirring for 1-3h at the temperature of 0-5 ℃ to obtain diazonium salt solution, wherein the molar ratio of nitrite to 5-amino isophthalic acid is 1-5: 1;
3) dissolving a pyridine compound in dilute hydrochloric acid, stirring and dissolving at 0-5 ℃ to obtain a solution II, wherein the pyridine compound is one of 1-amino-2-carboxypyridine, 2, 4-dicarboxylpyridine or 2-fluoro-3-carboxypyridine;
4) slowly dropwise adding the diazonium salt solution prepared in the step 2) into the solution II prepared in the step 3) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the pyridine compound in the solution II is 1:1, and after dropwise adding, placing the solution at 0-5 ℃ for reacting for 1-5 hours;
5) and after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, filtering the precipitate, washing, drying, recrystallizing, and then separating and purifying by using a chromatographic column to obtain the pyridine heterocyclic azobenzene.
Preferably, the concentration of the dilute hydrochloric acid in the step 1) and the step 3) is 0.1-2 mol/L.
Preferably, the reagents used in the step 5) for adjusting the pH value of the solution are saturated sodium carbonate and deionized water.
Preferably, the drying temperature in the step 5) is 40 ℃, and the drying time is 24 h.
Preferably, the chromatographic column in the step 5) is a silica gel column, and the eluent for separating and purifying the product by the chromatographic column is dichloromethane and petroleum ether.
The action mechanism of the reaction of the invention adopting three pyridine compounds is as follows:
compared with the prior art, the invention has the following beneficial effects: the invention utilizes 5-amino isophthalic acid to react with a series of micromolecules containing pyridine rings to prepare novel pyridine heterocyclic azobenzene molecules, thereby widening the application of azobenzene in the photoelectric field. The synthesis method is novel and unique, the conception is ingenious, the synthesis process is simple and convenient, and the product purity and the yield are high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 shows the preparation of pyridine heterocyclic azobenzene according to example 1 of the present invention1A HNMR map;
FIG. 2 shows the preparation of pyridine heterocyclic azobenzene according to example 2 of the present invention1A HNMR map;
FIG. 3 shows the preparation of pyridine heterocyclic azobenzene according to example 3 of the present invention1HNMR atlas.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
(1) 10mmol of 5-aminoisophthalic acid are weighed out and dissolved in 40mL of 1mol/L hydrochloric acid solution and placed in an ice-water bath (temperature 0 ℃). 10mL of 1mol/L sodium nitrite (NaNO)2) Slowly dripping the solution into the p-5-amino isophthalic acid solution, and stirring for 1h at the temperature of 0 ℃ to obtain a diazonium salt solution, wherein the yield of diazonium salt is 89%;
(2) dissolving 1-amino-2-carboxypyridine in a hydrochloric acid solution with the concentration of 1mol/L, and stirring the solution at 0 ℃ until the solution is completely dissolved to prepare a 1-amino-2-carboxypyridine solution with the concentration of 0.5 mol/L.
(3) Slowly dropwise adding the diazonium salt solution prepared in the step (1) into the 1-amino-2-carboxypyridine solution prepared in the step (2) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the 1-amino-2-carboxypyridine is 1: 1; then reacted at 0 deg.CThe reaction time is 2 hours; after the reaction is finished, saturated sodium carbonate (Na) is used2CO3) Adjusting the solution to be neutral (pH is 7) with deionized water, filtering the product, washing a filter cake with a large amount of deionized water, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain a crude product; the crude product was recrystallized from a mixed solution of ethanol/water, and purified by column chromatography on silica gel using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1: 3 as an eluent to obtain pyridylheterocycloazobenzene.
FIG. 1 is a representation of the pyridine heterocyclic azobenzene product prepared in example 11HNMR atlas, through recrystallization and silica gel column chromatography separation purification to obtain the product yield about 65%. As can be seen from the figures, it is,1HNMR(500MHz,DMSO-d6):δ＝4.12(s,2H,NH2),8.49(s,2H,Ar-H),8.58(s,1H,Ar-H),8.98(s,1H,Ar-H),9.04(s,1H,Ar-H),11.06(s,3H；COOH)。
example 2
(1) Weighing 10mmol of 5-amino isophthalic acid, dissolving in 40mL of 1mol/L hydrochloric acid solution, placing in an ice water bath (temperature is 0 ℃), and adding 10mL of 1mol/L sodium nitrite (NaNO)2) Slowly dripping the solution into the p-5-amino isophthalic acid solution, and stirring for 1h at 0 ℃ to obtain a diazonium salt solution, wherein the yield of diazonium salt is 89%;
(2) dissolving 2, 4-dicarboxy pyridine in 1mol/L hydrochloric acid solution, stirring at 0 ℃ until the 2, 4-dicarboxy pyridine is completely dissolved to obtain 0.5 mol/L2, 4-dicarboxy pyridine solution;
(3) slowly dropwise adding the diazonium salt solution prepared in the step (1) into the 2, 4-dicarboxy pyridine solution prepared in the step (2) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the 2, 4-dicarboxy pyridine is 1:1, reacting for 3 hours at 0 ℃; with saturated sodium carbonate (Na)2CO3) Adjusting the pH value of the solution to be 7) with deionized water, carrying out suction filtration on the product, washing a filter cake with a large amount of deionized water, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain a crude product; the crude product was recrystallized from a mixed solution of ethanol/water, and purified by column chromatography on silica gel using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1:4 as an eluent to obtain pyridylheterocycloazobenzene.
FIG. 2 is a representation of the pyridine heterocyclic azobenzene product prepared in example 21HNMR atlas, through recrystallization and silica gel column chromatography separation purification to obtain the product yield of about 71%. As can be seen from the figures, it is,1HNMR(500MHz,DMSO-d6):δ＝8.55(s,2H,Ar-H)，9.04(s,1H,Ar-H),9.58(s,2H,Ar-H),11.12(s,4H；COOH)。
example 3
(1) 10mmol of 5-aminoisophthalic acid were weighed out and dissolved in 40mL of 1mol/L hydrochloric acid solution and placed in an ice-water bath (0 ℃ C.). 10mL of 1mol/L sodium nitrite (NaNO)2) The solution was slowly added dropwise to the above-mentioned p-5-aminoisophthalic acid solution, and stirred at 0 ℃ for 1h to give a diazonium salt solution with a diazonium salt yield of 89%.
(2) Dissolving 2-fluoro-3-carboxypyridine in 1mol/L hydrochloric acid solution, and stirring at 0 ℃ until the 2-fluoro-3-carboxypyridine is completely dissolved to prepare a 2-fluoro-3-carboxypyridine solution with the concentration of 0.5 mol/L;
(3) slowly dropwise adding the diazonium salt solution prepared in the step (1) into the 2-fluoro-3-carboxypyridine solution prepared in the step (2) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the 2-fluoro-3-carboxypyridine is 1:1, reacting for 2.5h at 0 ℃; then saturated sodium carbonate (Na) is used2CO3) Adjusting the solution to be neutral (pH is 7) with deionized water, filtering the product, washing a filter cake with a large amount of deionized water, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain a crude product; the crude product was recrystallized from a mixed solution of ethanol/water, and purified by column chromatography on silica gel using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to obtain pyridylheterocycloazobenzene.
FIG. 3 is a representation of the pyridine heterocyclic azobenzene product prepared in example 31HNMR atlas, through recrystallization and silica gel column chromatography separation purification to obtain the product yield about 59%. As can be seen from the figures, it is,1HNMR(500MHz,DMSO-d6):δ＝8.55(s,2H,Ar-H)，8.97(s,1H,Ar-H)，9.11(s,1H,Ar-H),9.62(s,1H,Ar-H),11.09(s,3H；COOH)。
example 4
(1) 25mmol of 5-aminoisophthalic acid was weighed out and dissolved in 50mL of 0.1mol/L hydrochloric acidThe solution was placed in an ice-water bath (temperature 0 ℃). 50mL of 1mol/L sodium nitrite (NaNO)2) Slowly dripping the solution into the p-5-amino isophthalic acid solution, and stirring for 3 hours at the temperature of 2 ℃ to obtain a diazonium salt solution, wherein the yield of the diazonium salt is 65%;
(2) dissolving 2, 4-dicarboxy pyridine in 0.1mol/L hydrochloric acid solution, stirring at 2 deg.C to completely dissolve, and making into 0.42 mol/L2, 4-dicarboxy pyridine solution;
(3) slowly dropwise adding the diazonium salt solution prepared in the step (1) into the 2, 4-dicarboxy pyridine solution prepared in the step (2) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the 2, 4-dicarboxy pyridine is 1:1, reacting for 4 hours at the temperature of 2 ℃; then saturated sodium carbonate (Na) is used2CO3) And deionized water to adjust the solution to neutrality (Ph 7), the product was suction filtered, and the filter cake was washed with copious amounts of deionized water and vacuum dried at 40 ℃ for 24h to afford the crude product. The crude product was recrystallized from a mixed solution of ethanol/water, and purified by column chromatography on silica gel using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1:4 as an eluent to obtain pyridylheterocycloazobenzene.
Example 5
(1) 5mmol of 5-aminoisophthalic acid was weighed, dissolved in 25mL of 1mol/L hydrochloric acid solution, placed in an ice-water bath (temperature 0 ℃) and 25mL of 1mol/L sodium nitrite (NaNO) was added2) The solution was slowly added dropwise to the above-mentioned p-5-aminoisophthalic acid solution, and stirred at 0 ℃ for 1h to give a diazonium salt solution with a diazonium salt yield of 45%.
(2) Dissolving 2-fluoro-3-carboxypyridine in 0.1mol/L hydrochloric acid solution, stirring at 0 ℃ until the 2-fluoro-3-carboxypyridine is completely dissolved to obtain 0.5 mol/L2-fluoro-3-carboxypyridine solution
(3) Slowly dripping the diazonium salt solution prepared in the step (1) into the solution prepared in the step (2) under magnetic stirring, and reacting for 1h at the temperature of 0 ℃; then saturated sodium carbonate (Na) is used2CO3) And deionized water to adjust the solution to neutrality (Ph 7), the product was suction filtered, and the filter cake was washed with copious amounts of deionized water and vacuum dried at 40 ℃ for 24h to afford the crude product. Mixing with ethanol/waterThe crude product was recrystallized from the solution and purified by silica gel column chromatography (using a mixed solvent of dichloromethane and petroleum ether at a volume ratio of 1:2 as an eluent) to obtain pyridylazobenzene.
Example 6
(1) 10mmol of 5-aminoisophthalic acid are weighed out and dissolved in 30mL of 2mol/L hydrochloric acid solution and placed in an ice-water bath (temperature 0 ℃). 30mL of 1mol/L sodium nitrite (NaNO)2) Slowly dripping the solution into the p-5-amino isophthalic acid solution, and stirring for 3 hours at 5 ℃ to obtain a diazonium salt solution, wherein the yield of the diazonium salt is 54%;
(2) dissolving 1-amino-2-carboxypyridine in 1mol/L hydrochloric acid solution, and stirring at 5 ℃ until the 1-amino-2-carboxypyridine is completely dissolved to prepare 1-amino-2-carboxypyridine solution with the concentration of 0.5 mol/L;
(3) slowly dropwise adding the diazonium salt solution prepared in the step (1) into the solution prepared in the step (2) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the 2-fluoro-3-carboxypyridine is 1:1, reacting for 5 hours at 5 ℃; then saturated sodium carbonate (Na) is used2CO3) Adjusting the solution to be neutral (Ph is 7) with deionized water, filtering the product, washing a filter cake with a large amount of deionized water, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain a crude product; the crude product was recrystallized from a mixed solution of ethanol/water, and purified by column chromatography on silica gel using a mixed solvent of dichloromethane and petroleum ether at a volume ratio of 1:2.5 as an eluent to obtain pyridylazobenzene.
Comparative example 1
According to the synthesis method of example 1, 2-hydroxymethyl-4-methoxycarbonylpyridine and 5-amino isophthalic acid are adopted for reaction, and the other process parameters are not changed. The prepared pyridine heterocyclic azobenzene product is detected to have the yield of only 21 percent, more impurities and difficult separation and purification.
Comparative example 2
According to the synthesis method of example 1, m-phthalic acid is diazotized instead of sodium nitrite with 5-aminoisophthalic acid, and the yield of the prepared pyridine heterocyclic azobenzene product is 35% without changing the rest processes. Because the pyridine ring is provided with a heteroatom N atom, the electron-withdrawing ability of N is greater than that of C, the electron cloud density on the pyridine ring is smaller than that of benzene, the activity of pyridine is poorer than that of benzene, the reaction conditions are greatly different, meanwhile, the diazotization reaction of 5-amino isophthalic acid and isophthalic acid is carried out under the condition that PH is 7-9, namely, the diazotization reaction is carried out in an alkaline environment, and the PH is 5-6 during purification needs to be regulated and controlled to precipitate a product, so the purification difficulty is high, and the yield of the product is greatly reduced.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (1)
1. A synthetic method of pyridine heterocyclic azobenzene is characterized by comprising the following steps:
1) dissolving 5-amino isophthalic acid in dilute hydrochloric acid to prepare a solution I, and placing the solution I in an ice water bath;
2) slowly dripping 1mol/L sodium nitrite aqueous solution into the solution I in the step 1), and stirring for 1-3h at the temperature of 0-5 ℃ to obtain diazonium salt solution, wherein the molar ratio of nitrite to 5-amino isophthalic acid is 1-5: 1;
3) dissolving a pyridine compound in dilute hydrochloric acid, stirring and dissolving at 0-5 ℃ to obtain a solution II, wherein the pyridine compound is one of 1-amino-2-carboxypyridine, 2, 4-dicarboxylpyridine or 2-fluoro-3-carboxypyridine;
4) slowly dropwise adding the diazonium salt solution prepared in the step 2) into the solution II prepared in the step 3) under magnetic stirring, wherein the molar ratio of the diazonium salt in the diazonium salt solution to the pyridine compound in the solution II is 1:1, and after dropwise adding, placing the solution at 0-5 ℃ for reacting for 1-5 hours;
5) after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, filtering and precipitating, washing, drying, recrystallizing, and then separating and purifying by using a chromatographic column to obtain pyridine heterocyclic azobenzene;
the concentration of the dilute hydrochloric acid in the step 1) and the step 3) is 0.1-2 mol/L;
step 5) adjusting the pH value of the solution by adopting saturated sodium carbonate and deionized water as reagents;
the drying temperature in the step 5) is 40 ℃, and the drying time is 24 hours;
the chromatographic column in the step 5) is a silica gel column, and the eluent used for separating and purifying the product by the chromatographic column is dichloromethane and petroleum ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910800189.5A CN110330454B (en) | 2019-08-28 | 2019-08-28 | Synthesis method of pyridine heterocyclic azobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910800189.5A CN110330454B (en) | 2019-08-28 | 2019-08-28 | Synthesis method of pyridine heterocyclic azobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110330454A CN110330454A (en) | 2019-10-15 |
| CN110330454B true CN110330454B (en) | 2021-05-14 |
Family
ID=68150201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910800189.5A Active CN110330454B (en) | 2019-08-28 | 2019-08-28 | Synthesis method of pyridine heterocyclic azobenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110330454B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003082881A2 (en) * | 2002-03-28 | 2003-10-09 | Procyon Biopharma Inc. | Pyridoxal-5-phosphate derivatives as hiv integrase inhibitors |
| JP2008101063A (en) * | 2006-10-17 | 2008-05-01 | Tdk Corp | Dye, electrode and photoelectric conversion element |
| CN107814761A (en) * | 2016-09-13 | 2018-03-20 | 天津市化学试剂研究所有限公司 | The preparation method of 4 (pyridylazo of 5 bromine 2) 1,3 diaminobenzenes |
| CN109665973A (en) * | 2017-10-13 | 2019-04-23 | 天津大学 | Three azobenzene molecules and preparation method thereof |
-
2019
- 2019-08-28 CN CN201910800189.5A patent/CN110330454B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110330454A (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111704555B (en) | Method for synthesizing 4-methoxy-2-nitroaniline by adopting continuous flow reactor | |
| JPS63275582A (en) | Production of 1-aminoimidazo(4,5-b)pyridine derivative | |
| CN114605328A (en) | Preparation method of 6-chloro-2-methyl-2H-indazole-5-amine | |
| CN110330454B (en) | Synthesis method of pyridine heterocyclic azobenzene | |
| US20030212277A1 (en) | Process for preparing torsemide intermediate | |
| AU2001247592A1 (en) | Novel processes for preparing torsemide intermediate | |
| JP2904038B2 (en) | Process for producing 4,6-diaminoresorcinol and its precursor | |
| CN113173953B (en) | Purification method of high-purity lobaplatin trihydrate for preparing antitumor drugs | |
| CN109280011B (en) | Synthesis method of OLED intermediate 2-bromopyrene | |
| CN104592122A (en) | Preparation method for 3-(4-methyl-1H-imidazole-1-yl)-5-(trifluoromethyl)aniline | |
| CN108299384A (en) | Trifluoromethylthio transfering reagent compound and its synthetic method | |
| CN106946838A (en) | A kind of quick method for preparing the rhodamine with multiple labile functional groups under temperate condition | |
| WO2016035405A1 (en) | Azo dye composition and method for producing same | |
| CN107915694A (en) | 1 [2 (2,4 3,5-dimethylphenyl sulfydryl) phenyl] piperazine hydrochloride and preparation method thereof | |
| CN114573467B (en) | Synthesis process of 2, 4-dimethyl-3-aminobenzoic acid | |
| US4288620A (en) | Process for the production of 4-acylamido-2-nitro-1-alkoxybenzenes | |
| CN110407702A (en) | A kind of preparation method of eltrombopag olamine key intermediate 3 '-amino -2 '-xenol -3- carboxylic acid | |
| CN114149385B (en) | Synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene | |
| CN112679361B (en) | Synthetic method of 3-fluoro-5-nitropyridine-2-formaldehyde | |
| JP4498923B2 (en) | Method for preparing imidazo (1,2-A) pyridine-3-acetamides | |
| CN112574106B (en) | Synthesis method of 7-amino-5-bromoquinoline | |
| CN102391140A (en) | Preparation method of N-(2- indanyl) amino acid alkyl ester | |
| KR101152607B1 (en) | Process for preparing 6-[4-(2-piperidin-1-yl-ethoxy)-phenyl]-3-pyridin-4-yl-pyrazolo[1,5-a]pyrimidine | |
| JP2513222B2 (en) | Novel pyrimidine derivative | |
| CN113620946A (en) | Preparation method of 2-chloro-1, 8-naphthyridine derivatives |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |