CN116178247A - Method for synthesizing tetrapyridyl cyclobutane - Google Patents
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- CN116178247A CN116178247A CN202111417194.1A CN202111417194A CN116178247A CN 116178247 A CN116178247 A CN 116178247A CN 202111417194 A CN202111417194 A CN 202111417194A CN 116178247 A CN116178247 A CN 116178247A
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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Abstract
The invention discloses a simple, green and general method for synthesizing various tetrapyridyl cyclobutanes, which relates to the synthesis of 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane and 1,2,3,4- (2-pyridyl) cyclobutane. The synthetic method takes bipyridyl ethylene (such as 1, 2-di (4-pyridyl) ethylene, 1, 2-di (3-pyridyl) ethylene, 1, 2-di (2-pyridyl) ethylene) as a raw material, and obtains corresponding tetrapyridyl cyclobutane (such as 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane or 1,2,3,4- (2-pyridyl) cyclobutane) after light irradiation, freezing solution of 1, 2-di (3-pyridyl) ethylene or 1, 2-di (2-pyridyl) ethylene solution is frozen, separation and purification are carried out. The method does not need to use organic or metal eutectic molecules, does not need to separate in a later period, does not need to use other organic matters except ethanol, and is simple to operate, green and pollution-free.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing tetrapyridyl cyclobutane.
Background
Tetrapyridylcyclobutane has received much attention as a tetradentate ligand in the field of supermolecule assembly such as metal organic frameworks, coordination polymers, assembled nanoparticles, metal organic cages, and the like. In addition, due to the existence of the conjugated electron-withdrawing pyridine ring, the complex formed by the tetrapyridyl cyclobutane and the metal can realize electron transfer between the metal and the ligand, so that the complex has good electrical property, optical property, magnetic property and the like.
At present, the synthesis method of tetrapyridyl cyclobutane is mainly a eutectic method, namely, a proper eutectic molecule is searched to form eutectic with bipyridyl ethylene, the distance between carbon-carbon double bonds between the bipyridyl ethylene is shortened, and then the bipyridyl ethylene is subjected to [2+2] cycloaddition reaction through ultraviolet irradiation. The Leonard r.macgillivray group reports a method for synthesizing 1,2,3,4- (4-pyridyl) cyclobutane by co-crystal formation of m-diphenol with 1, 2-bis (4-pyridyl) ethylene, followed by ultraviolet irradiation to initiate the [2+2] cycloaddition reaction of 1, 2-bis (4-pyridyl) ethylene. The Leonard r.macgillivray group then reports in turn a process for the synthesis of 1,2,3,4- (3-pyridyl) cyclobutane and 1,2,3,4- (2-pyridyl) cyclobutane by co-crystal formation of ortho-diphenol with 1, 2-bis (3-pyridyl) ethylene and 1, 2-bis (2-pyridyl) ethylene, respectively, followed by ultraviolet irradiation to initiate the [2+2] cycloaddition reaction of 1, 2-bis (3-pyridyl) ethylene and 1, 2-bis (2-pyridyl) ethylene (see j.am. Chem. Soc.2000,122,7817-7818; chem. Commun.2014,50, 15965-15962;ChemPhysChem 2020,21,154-163). The eutectic method has the following defects:
(1) The reported method requires evaporation of large amounts of organic solvents during the eutectic preparation process.
(2) No universal eutectic molecule in the reported method can form a co-crystal with a variety of bipyridylethylenes.
(3) The reported method requires efficient separation of the eutectic molecules to finally obtain tetrapyridylcyclobutane.
Disclosure of Invention
In order to improve the technical problems, the invention provides a synthesis method of tetrapyridyl cyclobutane, which comprises the following steps:
dissolving bipyridyl ethylene in water, and freezing to form a solid freezing solution, and obtaining the tetrapyridyl cyclobutane after illumination.
According to an embodiment of the invention, the bipyridyl ethylene is selected from the group consisting of 1, 2-bis (4-pyridyl) ethylene, 1, 2-bis (3-pyridyl) ethylene and 1, 2-bis (2-pyridyl) ethylene;
according to an embodiment of the invention, the concentration of the bipyridylethylene solution obtained after dissolution in water is 0.2mM-8mM, for example 0.5mM-5mM, exemplified by 2.5mM;
according to an embodiment of the invention, the tetrapyridylcyclobutane is selected from the group consisting of 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane and 1,2,3,4- (2-pyridyl) cyclobutane;
according to an embodiment of the present invention, 1,2,3,4- (4-pyridyl) cyclobutane is prepared after the reaction of 1, 2-bis (4-pyridyl) ethylene is completed; after the reaction of the 1, 2-di (3-pyridyl) ethylene is completed, preparing 1,2,3,4- (3-pyridyl) cyclobutane; and after the reaction of the 1, 2-di (2-pyridyl) ethylene is finished, preparing the 1,2,3,4- (2-pyridyl) cyclobutane.
According to an embodiment of the present invention, the solution formed by dissolving bipyridyl ethylene in water is put under the condition of-10 ℃ to-80 ℃ to form a solid state, for example, the solution is formed under the condition of-20 ℃ to-60 ℃ and the solid state is formed under the condition of-30 ℃ in an exemplary manner;
according to an embodiment of the invention, the temperature of the system upon illumination is such that the bipyridyl ethylene forms a solid state upon dissolution in water, for example-10 ℃ to-80, preferably-20 ℃ to-60 ℃, and exemplary-30 ℃.
According to an embodiment of the invention, the light has a wavelength of 300nm to 1000nm, for example 365nm to 871nm;
according to an embodiment of the invention, the illumination time is more than 0.5h, for example 1-10h, exemplary 1.5h, 8h;
according to an embodiment of the invention, the source of light is a mercury lamp, such as a high pressure mercury lamp.
According to an embodiment of the invention, the synthesis method further comprises: a step of separation and/or purification after the end of the illumination; the step of separation comprises the steps of melting the solid frozen solution to obtain a liquid aqueous solution after illumination is finished, and removing solvent water to obtain the tetrapyridyl cyclobutane; the purification may be recrystallisation of the isolated tetrapyridylcyclobutane from ethanol and water.
According to an exemplary embodiment of the present invention, the synthesis method comprises the steps of:
(1) Taking 1, 2-di (4-pyridyl) ethylene, or 1, 2-di (3-pyridyl) ethylene, or 1, 2-di (2-pyridyl) ethylene, adding water, and dissolving;
(2) Freezing the solution obtained in the step (1) at the temperature of minus 10 ℃ to minus 80 ℃ to form a solid frozen solution, and irradiating the solid frozen solution placed at the temperature of minus 10 ℃ to minus 80 ℃ by using a high-pressure mercury lamp with the wavelength of 365nm to 871nm;
(3) Placing the frozen solution irradiated in the step (2) at room temperature to melt the frozen solution to obtain a liquid aqueous solution, and removing solvent water by reduced pressure evaporation to obtain pale yellow powder;
(4) And (3) recrystallizing and purifying the solid powder obtained in the step (3) by using a mixed solution of ethanol and water to finally obtain transparent crystals of 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane or 1,2,3,4- (2-pyridyl) cyclobutane.
According to the embodiment of the invention, since the bipyridyl ethylene has small solubility in water, the aqueous solution can be prepared by ultrasonic treatment for 0.5-2 h or heating at 60-80 ℃ to accelerate the dissolution.
According to an embodiment of the present invention, the tetrapyridylcyclobutane is synthesized by intermolecular [2+2] cycloaddition of bipyridylethylene under light conditions.
The principle of the synthesis method of the invention is as follows: the low-temperature icing can lead the 1, 2-di (4-pyridyl) ethylene, the 1, 2-di (3-pyridyl) ethylene or the 1, 2-di (2-pyridyl) ethylene to be enriched among ice crystal domains, promote the [2+2] cycloaddition reaction of the 1, 2-di (4-pyridyl) ethylene, the 1, 2-di (3-pyridyl) ethylene or the 1, 2-di (2-pyridyl) ethylene on the surface of ice crystals to be orderly and regularly arranged, ensure that the distance between carbon-carbon double bonds between molecules of the 1, 2-di (4-pyridyl) ethylene, the 1, 2-di (3-pyridyl) ethylene or the 1, 2-di (2-pyridyl) ethylene is in a proper range, thereby realizing the 1, 2-di (4-pyridyl) ethylene, the 1, 2-di (3-pyridyl) ethylene or the 1, 2-di (2-pyridyl) ethylene to obtain 1,2,3,4- (4-pyridyl) cyclobutane, 1, 3- (3-pyridyl) cyclobutane or the 1,2- (3, 3-cyclobutane) cyclobutane under the irradiation of light such as high-pressure mercury lamp.
Advantageous effects
Compared with the prior art, the invention has the following advantages:
1. the invention does not involve the preparation of the co-crystals, the use of co-crystal molecules, and the separation of large amounts of organic solvents and post-co-crystal molecules.
2. The solvent used in the invention is water, so that the method is environment-friendly, high-temperature and high-pressure treatment is not needed in the whole process, and the operation is simple and safe.
3. The present invention is useful for the preparation of a variety of tetrapyridyl cyclobutanes, such as for the synthetic preparation of 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane, and 1,2,3,4- (2-pyridyl) cyclobutane.
Drawings
FIG. 1 is a nuclear magnetic resonance diagram of 1,2,3,4- (4-pyridyl) cyclobutane synthesized in example 1;
FIG. 2 is a nuclear magnetic resonance plot of 1,2,3,4- (3-pyridyl) cyclobutane synthesized in example 2;
FIG. 3 is a nuclear magnetic resonance plot of 1,2,3,4- (2-pyridyl) cyclobutane synthesized in example 3;
FIG. 4 is a single crystal structure diagram of 1,2,3,4- (2-pyridyl) cyclobutane synthesized in example 3.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The invention is further described below with reference to fig. 1 to 4 and examples:
example 1
A method for synthesizing 1,2,3,4- (4-pyridyl) cyclobutane in a simple green color, comprising the following steps:
(1) 36.4mg (0.2 mmol) of 1, 2-bis (4-pyridyl) ethylene was weighed into a 200mL round bottom flask, 80mL of water was added to the round bottom flask, and the mixture was heated and stirred at 80℃to dissolve, followed by standing at room temperature and cooling.
(2) Adding 10mL of the solution prepared in the step (1) into a culture dish with the diameter of 10mm, and standing the culture dish at the temperature of minus 30 ℃ for 1 hour to freeze the solution to form a solid frozen solution.
(3) Placing the freezing solution in the step (2) into a reactor at the temperature of minus 30 ℃ and irradiating the freezing solution for 8 hours by using a high-pressure mercury lamp with the wave band ranging from 365nm to 871 nm.
(4) Repeating the steps (2) and (3) until 80mL of the prepared solution is used up.
(5) The frozen solution after illumination was left at room temperature to melt, collected in a 150mL round bottom flask, and the solvent water was removed using a rotary evaporator to give a pale yellow powder.
(6) The pale yellow powder is dissolved by heating with 2mL of a mixed solution of ethanol and water (volume ratio 1:1), and left at room temperature for 12 hours, and transparent 1,2,3,4- (4-pyridyl) cyclobutane crystals are recrystallized (yield 87%, nuclear magnetic purity characterization > 90%).
FIG. 1 is a nuclear magnetic resonance spectrum of 1,2,3,4- (4-pyridyl) cyclobutane synthesized in this example.
1 H NMR(400MHz,CDCl 3 ,TMS)δ＝4.47(s,4H),6.68-6.69(d,8H),8.42-8.44(d,8H).
Example 2
A method for synthesizing 1,2,3,4- (3-pyridyl) cyclobutane in a simple green color, comprising the following steps:
(1) 36.4mg (0.2 mmol) of 1, 2-bis (3-pyridyl) ethylene was weighed into a 200mL round bottom flask, 80mL of water was added to the round bottom flask, and the mixture was heated and stirred at 80℃to dissolve, followed by standing at room temperature and cooling.
(2) Adding 10mL of the solution prepared in the step (1) into a culture dish with the diameter of 10mm, and standing the culture dish at the temperature of minus 30 ℃ for 1 hour to freeze the solution to form a solid frozen solution.
(3) Placing the freezing solution in the step (2) into a reactor at the temperature of minus 30 ℃ and irradiating the freezing solution for 1.5 hours by using a high-pressure mercury lamp with the wave band ranging from 365nm to 871 nm.
(4) Repeating the steps (2) and (3) until 80mL of the prepared solution is used up.
(5) The frozen solution after illumination was left at room temperature to melt, collected in a 150mL round bottom flask, and the solvent water was removed using a rotary evaporator to give a pale yellow powder.
(6) The pale yellow powder is dissolved by heating with 2mL of a mixed solution of ethanol and water (volume ratio 1:1), and left at room temperature for 12 hours, and transparent 1,2,3,4- (3-pyridyl) cyclobutane crystals are recrystallized (yield 90%, nuclear magnetic purity characterization > 90%).
FIG. 2 is a nuclear magnetic resonance spectrum of 1,2,3,4- (3-pyridyl) cyclobutane synthesized in this example.
1 H NMR(400MHz,CDCl 3 ,TMS)δ＝4.55(s,4H),7.1-7.13(m,4H),7.37-7.4(m,4H),8.37-8.42(m,8H).
Example 3
A method for synthesizing 1,2,3,4- (2-pyridyl) cyclobutane in a simple green color, which comprises the following steps:
(1) 36.4mg (0.2 mmol) of 1, 2-bis (2-pyridyl) ethylene was weighed into a 200mL round bottom flask, 80mL of water was added to the round bottom flask, and the mixture was heated and stirred at 80℃to dissolve, followed by standing at room temperature and cooling.
(2) Adding 10mL of the solution prepared in the step (1) into a culture dish with the diameter of 10mm, and standing the culture dish at the temperature of minus 30 ℃ for 1 hour to freeze the solution to form a solid frozen solution.
(3) Placing the freezing solution in the step (2) into a reactor at the temperature of minus 30 ℃ and irradiating the freezing solution for 1.5 hours by using a high-pressure mercury lamp with the wave band ranging from 365nm to 871 nm.
(4) Repeating the steps (2) and (3) until 80mL of the prepared solution is used up.
(5) The frozen solution after illumination was left at room temperature to melt, collected in a 150mL round bottom flask, and the solvent water was removed using a rotary evaporator to give a pale yellow powder.
(6) The pale yellow powder is dissolved by heating with 2mL of a mixed solution of ethanol and water (volume ratio 1:1), and left at room temperature for 12 hours, and transparent 1,2,3,4- (4-pyridyl) cyclobutane crystals are recrystallized (yield 85%, nuclear magnetic purity characterization > 90%).
FIG. 3 is a nuclear magnetic resonance spectrum of 1,2,3,4- (2-pyridyl) cyclobutane synthesized in this example.
1 H NMR(400MHz,CDCl 3 ,TMS)δ＝5.06(s,4H),6.89-6.93(m,4H),7.05-7.07(d,4H),7.34-7.38(m,4H),8.39-8.4(d,4H).
FIG. 4 is a single crystal structure of 1,2,3,4- (2-pyridyl) cyclobutane synthesized in this example.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing tetrapyridylcyclobutane, comprising the steps of:
dissolving bipyridyl ethylene in water, and freezing to form a solid freezing solution, and obtaining the tetrapyridyl cyclobutane after illumination.
2. The synthetic method of claim 1 wherein the bipyridyl ethylene is selected from the group consisting of 1, 2-bis (4-pyridyl) ethylene, 1, 2-bis (3-pyridyl) ethylene and 1, 2-bis (2-pyridyl) ethylene.
3. A method of synthesis according to claim 1 or 2, characterised in that the concentration of the bipyridyl ethylene in water gives a solution of 0.2mM to 8mM, for example 0.5mM to 5mM.
4. A synthetic method according to any one of claims 1-3, wherein the tetrapyridyl cyclobutane is selected from the group consisting of 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane and 1,2,3,4- (2-pyridyl) cyclobutane;
after the reaction of the 1, 2-di (4-pyridyl) ethylene is finished, preparing 1,2,3,4- (4-pyridyl) cyclobutane; after the reaction of the 1, 2-di (3-pyridyl) ethylene is completed, preparing 1,2,3,4- (3-pyridyl) cyclobutane; and after the reaction of the 1, 2-di (2-pyridyl) ethylene is finished, preparing the 1,2,3,4- (2-pyridyl) cyclobutane.
5. The method according to any one of claims 1 to 4, wherein the dipyridylethylene is dissolved in water to form a solution, and the solution is placed at-10 ℃ to-80 ℃ to form a solid state.
6. A method according to any one of claims 1-5, characterized in that the temperature of the system upon illumination is such that the bipyridyl ethylene forms a solid state after dissolution in water, e.g. from-10 ℃ to-80, preferably from-20 ℃ to-60 ℃.
7. The synthetic method according to any one of claims 1 to 6 wherein the light has a wavelength of 300nm to 1000nm, such as 365nm to 871nm;
preferably, the source of light is a mercury lamp, such as a high pressure mercury lamp.
8. The method of any one of claims 1 to 7, wherein the illumination time is more than 0.5h, such as 1 to 10h.
9. The method of synthesis according to any one of claims 1 to 8, further comprising: a step of separation and/or purification after the end of the illumination; the step of separation comprises the steps of melting the solid frozen solution to obtain a liquid aqueous solution after illumination is finished, and removing solvent water to obtain the tetrapyridyl cyclobutane; the purification is to recrystallize the separated tetrapyridylcyclobutane with ethanol and water.
10. The synthesis method according to any one of claims 1 to 9, comprising the steps of:
(1) Taking 1, 2-di (4-pyridyl) ethylene, or 1, 2-di (3-pyridyl) ethylene, or 1, 2-di (2-pyridyl) ethylene, adding water, and dissolving;
(2) Freezing the solution obtained in the step (1) at the temperature of minus 10 ℃ to minus 80 ℃ to form a solid frozen solution, and irradiating the solid frozen solution placed at the temperature of minus 10 ℃ to minus 80 ℃ by using a high-pressure mercury lamp with the wavelength of 365nm to 871nm;
(3) Placing the frozen solution irradiated in the step (2) at room temperature to melt the frozen solution to obtain a liquid aqueous solution, and removing solvent water by reduced pressure evaporation to obtain pale yellow powder;
(4) And (3) recrystallizing and purifying the solid powder obtained in the step (3) by using a mixed solution of ethanol and water to finally obtain transparent crystals of 1,2,3,4- (4-pyridyl) cyclobutane, 1,2,3,4- (3-pyridyl) cyclobutane or 1,2,3,4- (2-pyridyl) cyclobutane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114716463A (en) * | 2022-05-17 | 2022-07-08 | 淮阴师范学院 | Photoresponse complex and preparation method and application thereof |
| CN114805185A (en) * | 2022-05-10 | 2022-07-29 | 淮阴师范学院 | Homogeneous polycrystalline material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114805185A (en) * | 2022-05-10 | 2022-07-29 | 淮阴师范学院 | Homogeneous polycrystalline material and preparation method and application thereof |
| CN114805185B (en) * | 2022-05-10 | 2023-09-19 | 淮阴师范学院 | Homogeneous polycrystalline material and preparation method and application thereof |
| CN114716463A (en) * | 2022-05-17 | 2022-07-08 | 淮阴师范学院 | Photoresponse complex and preparation method and application thereof |
| CN114716463B (en) * | 2022-05-17 | 2024-02-06 | 淮阴师范学院 | Light response complex and preparation method and application thereof |
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