CN109503474B - Synthesis method of 2,2',6,6' -tetracarboxyl- [4, 4' -bipyridine ] - Google Patents
Synthesis method of 2,2',6,6' -tetracarboxyl- [4, 4' -bipyridine ] Download PDFInfo
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- CN109503474B CN109503474B CN201811599506.3A CN201811599506A CN109503474B CN 109503474 B CN109503474 B CN 109503474B CN 201811599506 A CN201811599506 A CN 201811599506A CN 109503474 B CN109503474 B CN 109503474B
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- 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
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Abstract
The invention discloses a synthetic method of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine. The method comprises the synthesis of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine and the synthesis of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine, wherein the synthesis of the 2,2' -6,6' -tetramethyl-4, 4' -bipyridine comprises the steps of coupling and air oxidation. The invention uses economical air as oxidant to oxidize the coupling product, thereby being capable of comparing the prior SO in the aspects of reaction control, product separation, raw material recovery and the like2The oxidation method and the Pd catalyst catalysis method have absolute advantages; the full reaction of the metal sodium and the shortening of the reaction time are realized by adding excessive 2, 6-lutidine, and the yield of the product is obviously improved.
Description
Technical Field
The invention belongs to the field of multifunctional coordination materials, supermolecule chemistry and membrane chemistry, and particularly relates to a synthesis method of polycarboxyl bipyridyl, namely a method for aromatizing dihydropyridine by air oxidation.
Background
Multifunctional coordination materials are receiving wide attention due to their diversity in structure and performance. In recent years, memory materials represented by Metal Organic Frameworks (MOFs) and Covalent Organic Frameworks (COFs) are the most popular field of research in inorganic organic materials, and belong to an important class of organic materials. MOFs and COFs have one-dimensional, two-dimensional or three-dimensional structures formed by coordination of organic ligands (or combination of metal atoms or atom clusters), and can be used in a wide range of fields such as molecular storage, catalysts and photochemical reactions. In addition, it is well known that the natural photosynthetic system is assembled from rather complex natural molecules to absorb light and initiate a series of energy transfer processes. Self-assembled monolayer (SAMs) films are particularly attractive for making artificial photosynthetic systems that are simulated by building groups with light harvesting on top of the monolayer. SAMs films are multi-component assembled structures that are non-covalently complexed via metal-ligands.
The bipyridine tetracarboxylic acid ligand contains four carboxyl groups and two pyridine N coordination sites, and can form strong non-covalent bonding capability between molecules by virtue of the carboxyl groups and also can form strong complexing capability between N and metal, thereby becoming the best choice for developing novel MOFs, COFs and SAMs materials. For organic framework materials such as MOFs, COFs and the like, the strength of a molecular framework is ensured by the synergistic effect of multiple carboxyl groups, and the N coordination sites provide potential opportunities for functional modification of the molecular framework materials; for SAMs, the non-covalent bonding of the polycarboxyl groups ensures the strength of the film, and the complexation of the N ligand with the metal ensures the stable deposition of the film on the metal surface without peeling off.
These characteristics lead to a very wide industrial and laboratory demand for polycarboxypyridines, which are ideal alternatives to common organic acids such as aromatic carboxylic acids or fatty acids (e.g., EDTA). Therefore, the development or optimization of a simple, mild, and economical production process is the most urgent task at present. Taking the synthesis example of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine, two methods are most developed at present: one is Na catalyzed coupling, SO2Oxidation process, the greatest disadvantage of which is the use of SO2As an oxidant, the oxidant has high toxicity, complex operation and troublesome post-treatment; secondly, coupling of halogenated pyridine under the action of a noble metal catalyst, and the method has the biggest defects of high cost, strict anhydrous and anaerobic treatment and long reaction time.
Disclosure of Invention
Aiming at the defects of the prior method, the invention provides a method for synthesizing 2,2',6,6' -tetracarboxyl-4, 4 '-bipyridyl, which adopts a green method of Na catalytic coupling and air oxidation aromatization to synthesize the 2,2',6,6 '-tetracarboxyl-4, 4' -bipyridyl with high yield.
The technical scheme of the invention is as follows:
a method for synthesizing 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine comprises the following steps:
(1) synthesis of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine
(A) Coupling: adding Na powder into a double-neck flask under the protection of inert gas, dispersing the Na powder by using anhydrous Tetrahydrofuran (THF), sealing one opening of the flask by using a rubber plug, and injecting 2, 6-lutidine by using a syringe, wherein the molar ratio of the Na powder to the 2, 6-lutidine is 80-140 mmol: 70-100 mmol, adding anhydrous THF, stirring the mixture until the mixture is solidified and no sodium remains, keeping the temperature below 30 ℃ in the stirring process, and standing;
(B) air oxidation: distilling off THF under reduced pressure, and adding water into the reaction solution until most of the solid is dissolved; blowing air until the solution is no longer dark purple and the solid is no longer increased; heating to 45-60 ℃, continuously blowing air for 10-30 min to ensure that the coupling product is fully aromatized, performing suction filtration to obtain a white solid, recrystallizing with dichloromethane and petroleum ether to obtain crystal-shaped 2,2',6,6' -tetramethyl-4, 4' -bipyridine, filtering out excessive raw material 2, 6-lutidine along with a water layer, and performing liquid separation treatment on the water layer to recover the raw material;
(2) synthesis of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine
Dispersing 2,2'-6,6' -tetramethyl-4, 4 '-bipyridyl in a concentrated sulfuric acid solution, wherein the dosage ratio of the 2,2' -6,6 '-tetramethyl-4, 4' -bipyridyl to concentrated sulfuric acid is 8.0-10.5 mmol: 20-40 ml, according to the molar ratio of 0.09-0.12 mol: adding chromium trioxide into concentrated sulfuric acid solution for several times in a proportion of 20-30 ml, continuously stirring for 16-32 hours at room temperature, heating to 45-60 ℃, and continuously maintaining for 1-3 hours; directly adding ice blocks into the reaction mixture to separate out white precipitate, cooling the mixture to-5 ℃, quickly centrifuging to remove the residual chromic acid solution, carrying out suction filtration on the solid, quickly washing the solid with cold water, and drying to obtain white powder.
Further, in the step (A), the using amount ratio of Na powder to tetrahydrofuran is 80-140 mmol: 10-40 ml.
Furthermore, in the step (A), the molar ratio of the 2, 6-lutidine to the metallic sodium is 1.4-1.8: 1.9-2.1, preferably 1.7:2, and in this case, the excess of the 2, 6-lutidine of 70% is maintained, so that the sufficient reaction and the fast reaction speed of the metallic sodium can be better ensured; while avoiding the risk of residual sodium in the next oxidation step.
Further, in the step (A), the addition amount of the additional THF is 1-2 times of the Na powder-dispersed THF.
Further, in the step (A), the standing time is 20-30 hours.
Further, in the step (2), the mass fraction of the concentrated sulfuric acid is 92-98%.
Furthermore, in the step (2), the adding time of the chromium trioxide is controlled to be 20-40 min.
In the step (1), the temperature is kept lower than 30 ℃ during stirring, so that the reduction of the reaction activity and speed caused by the agglomeration of metal sodium can be avoided.
In the step (1), air is directly used as an oxidant, the operation is simple and convenient, the method is economical and practical, and SO is avoided2Complicated preparation, pollution of gas toxicity and trouble of post-treatment.
In the step (1), firstly, oxidizing in a THF solvent, and dispersing a product to facilitate the rapid oxidation; then distilling off the THF solvent and using water as the solvent to ensure complete oxidation of the coupling product included in the solid, wherein the THF distillation is also beneficial to the deposition of the 2,2',6,6' -tetramethyl-4, 4' -bipyridyl solid product.
In the step (1), air is introduced for 30min at room temperature, then the temperature is heated to 50 ℃, and air is continuously introduced for 30 min. The oxidation reaction is prevented from being too fast at room temperature, and the complete oxidation is ensured by heating conditions;
in step (1), the excess 2, 6-lutidine starting material is separated from the aqueous layer and recovered by a liquid separation treatment.
In the step (2), the reaction temperature is controlled below 30 ℃ for a long time (such as 24h) to complete the oxidation of most of methyl, the methyl is completely oxidized when the temperature is increased to 50 ℃, the lower temperature is kept as much as possible to realize the oxidation of the methyl, and the bipyridine skeleton is prevented from being damaged due to the increase of the temperature.
In the step (2), the mixture is cooled to 0 ℃ and then is subjected to centrifugal separation, so that the loss of the product due to water solubility is reduced, and the residual salt and impurities in the product are washed by cold water.
The invention has the beneficial effects that:
(1) the invention uses economical air as oxidant to oxidize the coupling product, thereby controlling the reactionCompared with the prior SO in the aspects of preparation, product separation, raw material recovery and the like2The oxidation method and the Pd catalyst catalysis method have absolute advantages;
(2) the invention realizes the full reaction of the metal sodium and the shortening of the reaction time by adding the excessive 2, 6-dimethylpyridine, thereby obviously improving the yield of the product, while the excessive metal sodium in the literature method has danger in the post-treatment process, and the reaction is slowed down due to the consumption of the 2, 6-dimethylpyridine, thereby causing the reaction to be difficult to be full, and the yield is generally less than 40%;
(3) the air oxidation process is simple to operate, is not influenced by the type and temperature of the solvent, and is full and thorough;
(4) the separation of the product 2,2' -6,6' -tetramethyl-4, 4' -bipyridine is extremely simple, THF used in the first stage is replaced by water after air oxidation, the product is directly separated out, and a pure product can be obtained by filtration;
(5) in the invention, the excessive raw material 2, 6-lutidine is easy to recover, and because the residual raw material 2, 6-lutidine is liquid and is separated from water, the cost is conveniently reduced and the environmental pollution is reduced;
(6) in the step of oxidizing methyl into carboxyl, the invention ensures the sufficient oxidation of methyl and the stability of pyridine skeleton by strictly controlling the temperature of methyl oxidation, almost quantitatively obtains carboxyl, and obviously improves the yield;
(7) the invention reduces the loss of the target product 2,2',6,6' -tetracarboxyl-4, 4' -bipyridyl in the separation process by controlling the temperature during centrifugal separation and washing; not only effectively removing chromium salt and byproducts in the reaction, but also separating the target product to the maximum extent;
(8) the invention uses less chemical and solvent types and small dosage, the used solvent and reagent can be recycled, the cost is reduced, the environmental pollution is reduced, and the method is convenient for continuous operation.
Drawings
FIG. 1 is an H NMR spectrum of a 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine which is a target product of the present invention.
FIG. 2 is a C NMR spectrum of a target product 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine according to the present invention.
FIG. 3 is the MS spectrum of the target product 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine.
FIG. 4 is an H NMR spectrum of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine as an intermediate in the present invention.
FIG. 5 is a C NMR spectrum of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine as an intermediate in the present invention.
FIG. 6 is a MS spectrum of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine as an intermediate product in the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific experimental examples and the accompanying drawings. The target compound 2,2'-6,6' -tetracarboxyl-4, 4 '-bipyridine and the intermediate product 2,2' -6,6 '-tetramethyl-4, 4' -bipyridine are verified by nuclear magnetic and mass spectrometry.
The name of the target compound is 2,2' -6,6' -tetracarboxyl-4, 4' -bipyridine, and the structural formula of the compound is shown as the formula (1):
the route of the compound synthesis thought is shown as formula (2):
as can be seen from formula (2), the specific synthesis thereof is completed in three steps, wherein the coupling of the first reaction step and the air oxidation of the second reaction step are continuously carried out, so that the whole synthesis is divided into two parts:
(1) synthesis of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine. For the first coupling, 2.35g (100mmol) of Na powder was added to a 100mL two-necked flask under inert gas, and the Na powder was rapidly dispersed with 20mL of anhydrous Tetrahydrofuran (THF) and one bite of the same was plugged with a rubber stopper. 9.10g (85mmol) of 2, 6-lutidine was injected via syringe and supplemented with 40mL of anhydrous THF. The mixture was stirred until it solidified and no sodium remained, keeping the temperature below 30 ℃ during stirring and standing overnight.
Secondly, oxidizing the air, distilling off THF under reduced pressure, and adding 40mL of water into the reaction solution until most of the solid is dissolved; blowing air to slowly generate white solid until the solution is not dark purple any more and the solid is not increased any more; heating to 50 deg.C and continuing to blow air for 15min to fully oxidize the coupled product. Filtering to obtain white solid, and recrystallizing with dichloromethane and petroleum ether to obtain crystal 2,2',6,6' -tetramethyl-4, 4' -bipyridine 3.4g with yield of 65%. The excess 2, 6-lutidine starting material was filtered off with the aqueous layer, and the aqueous layer was subjected to a liquid separation treatment to recover the starting material.
(2) Synthesis of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine. 2g (9.4mmol) of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine was dispersed in 25mL of 96% concentrated sulfuric acid, and 11.2g of chromium trioxide (0.11mol) was divided into small portions and added to a concentrated sulfuric acid solution over about 30 min. Stirring was continued for 24h at room temperature, heating to 50 ℃ was continued for 2h, and approximately 20g of ice was added directly to the reaction mixture. A white precipitate separated out, the mixture was cooled to-5 ℃ and the remaining chromic acid solution was removed by flash centrifugation. The solid was filtered with suction, washed rapidly with 2mL of cold water, dried to give 2.9g of white powder, yield: 92 percent.
Referring to FIGS. 1, 2 and 3, respectively, of 2,2' -6,6' -tetracarboxyl-4, 4' -bipyridine prepared by the above-described method1H NMR and13c NMR and MS spectra.
Referring to FIGS. 4, 5 and 6, respectively, there are provided processes for preparing 2,2' -6,6' -tetramethyl-4, 4' -bipyridine by the above-mentioned method1H NMR and13c NMR and MS spectra.
Referring to FIG. 1, is a preparation of 2,2' -6,6' -tetracarboxyl-4, 4' -bipyridine by the above method1H NMR；1H NMR(DMSO-d6):δ(ppm)8.62(s，4H,Pyridine)；13.2(s,br,4H,COOH)；
Referring to FIG. 2, is a preparation of 2,2' -6,6' -tetracarboxyl-4, 4' -bipyridine by the above method13C NMR；13C NMR(DMSO-d6):δ(ppm)165.9,150.2,146.8,125.9；
Referring to FIG. 3, a high resolution mass spectrum of 2,2' -6,6' -tetracarboxyl-4, 4' -bipyridine prepared by the above method is shown. Measured value C14H7N2O8 –[M–H]–331.0209, calculating the following values: 331.0208, respectively; the target product was confirmed by mass spectrometry;
referring to FIG. 4, is a preparation of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine by the above method1H NMR；1H NMR(CDCl3):δ(ppm)7.19(s，4H,Pyridine)；2.62(s,12H,CH3)
Referring to FIG. 5, is a preparation of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine by the above method13C NMR；13C NMR(CDCl3)：δ(ppm)159.2,146.2,106.8,25.0；
Referring to FIG. 6, a high resolution mass spectrum of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine prepared by the above method is shown. Measured value C14H16N2Na+[M+Na]+: 235.1210, calculated as: 235.1206, respectively; the target product was confirmed by mass spectrometry.
Claims (5)
1. A synthetic method of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine is characterized by comprising the following steps:
(1) synthesis of 2,2' -6,6' -tetramethyl-4, 4' -bipyridine
(A) Coupling: adding Na powder into a double-neck flask under the protection of inert gas, dispersing the Na powder by using anhydrous tetrahydrofuran, sealing one opening of the flask by using a rubber plug, and injecting 2, 6-lutidine by using an injector, wherein the molar ratio of the Na powder to the 2, 6-lutidine is 80-140 mmol: 70-100 mmol, adding anhydrous THF, stirring the mixture until the mixture is solidified and no sodium remains, keeping the temperature below 30 ℃ in the stirring process, and standing;
(B) air oxidation: distilling off THF under reduced pressure, and adding water into the reaction solution until most of the solid is dissolved; blowing air until the solution is no longer dark purple and the solid is no longer increased; heating to 45-60 ℃, continuously blowing air for 10-30 min to ensure that the coupling product is fully aromatized, performing suction filtration to obtain a white solid, recrystallizing with dichloromethane and petroleum ether to obtain crystal-shaped 2,2',6,6' -tetramethyl-4, 4' -bipyridine, filtering out excessive raw material 2, 6-lutidine along with a water layer, and performing liquid separation treatment on the water layer to recover the raw material;
(2) synthesis of 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine
Dispersing 2,2'-6,6' -tetramethyl-4, 4 '-bipyridyl in a concentrated sulfuric acid solution, wherein the dosage ratio of the 2,2' -6,6 '-tetramethyl-4, 4' -bipyridyl to concentrated sulfuric acid is 8.0-10.5 mmol: 20-40 ml, according to the molar ratio of 0.09-0.12 mol: 20-30 ml, adding chromium trioxide into the concentrated sulfuric acid solution for several times within 20-40 min, continuously stirring for 16-32 h at room temperature, heating to 45-60 ℃, and continuously maintaining for 1-3 h; directly adding ice blocks into the reaction mixture to separate out white precipitate, cooling the mixture to-5 ℃, quickly centrifuging to remove the residual chromic acid solution, carrying out suction filtration on the solid, quickly washing the solid with cold water, and drying to obtain white powder.
2. The method for synthesizing 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine according to claim 1, wherein in the step (A), the ratio of the amount of Na powder to the amount of tetrahydrofuran is 80-140 mmol: 10-40 ml, and the addition amount of the additional THF is 1-2 times of the Na powder-dispersed THF.
3. The method for synthesizing 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine according to claim 1, wherein in the step (A), the molar ratio of the 2, 6-dimethylpyridine to the metallic sodium is 1.4-1.8: 1.9-2.1.
4. The method for synthesizing 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine according to claim 1, wherein the standing time in the step (A) is 20 to 30 hours.
5. The method for synthesizing 2,2',6,6' -tetracarboxyl-4, 4' -bipyridine according to claim 1, wherein in the step (2), the mass fraction of concentrated sulfuric acid is 92-98%.
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| CN1158852A (en) * | 1996-03-01 | 1997-09-10 | 涿州市桃园农药厂 | Preparation of 4,4-dipyridine |
| US20040110009A1 (en) * | 2002-10-07 | 2004-06-10 | Mcgimpsey William Grant | Non-covalent assembly of multilayer thin film supramolecular structures |
| CN101302188A (en) * | 2008-06-25 | 2008-11-12 | 天津大学 | Bidentate ligand 4,4'- bis (hydroxymethyl)-2,2'dipyridine, preparation thereof and application to polyketone synthesis |
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| CN1158852A (en) * | 1996-03-01 | 1997-09-10 | 涿州市桃园农药厂 | Preparation of 4,4-dipyridine |
| US20040110009A1 (en) * | 2002-10-07 | 2004-06-10 | Mcgimpsey William Grant | Non-covalent assembly of multilayer thin film supramolecular structures |
| CN101302188A (en) * | 2008-06-25 | 2008-11-12 | 天津大学 | Bidentate ligand 4,4'- bis (hydroxymethyl)-2,2'dipyridine, preparation thereof and application to polyketone synthesis |
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| A convenient synthesis of 2,2’,6,6’-tetramethyl-4,4’-bipyridine and its oxidation to 2,2’,6,6’-tetracarboxy-4,4’-bipyridine;Siegfried Huenig;《Synthesis》;19890731(第7期);第552-554页 * |
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