CN114957659B - Polyoxadiazole and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a polyoxadiazole, a preparation method and application thereof, wherein the method comprises the following steps: respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a dicarboxylic acid compound; and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole. The structure general formula of the polyoxadiazole is as follows:
Description
Technical Field
The invention relates to the technical field of organic heterocyclic polymers, in particular to a polyoxadiazole and a preparation method and application thereof.
Background
Polyoxadiazole (POD) is an important class of functional polymers. Because the macromolecule chain contains oxadiazole rings, the POD has excellent heat resistance and thermal stability; meanwhile, the oxadiazole ring also has a photoelectric effect and is a good electrophilic group, so that the POD also has good application in the aspect of photoelectric materials. In addition, the POD has good film forming and fiber forming properties, and the fiber is widely applied to high-temperature filter materials, protective products, insulating materials and the like. However, the oxadiazole structure-containing polymers which are currently and reported are relatively single in structure and function, and it is difficult to achieve multifunctionality. Therefore, the construction of POD materials with unique structures and advanced functions has important value in both academic and industrial fields, and has received extensive attention from scientists.
Existing POD materials are typically prepared by polymerizing dicarboxylic acid and hydrazine salts in solution or by solid state cyclodehydration of polyhydrazide. This typically requires a cumbersome synthesis procedure.
Accordingly, the prior art is still further developed and improved.
Disclosure of Invention
The invention aims to solve the technical problem that the existing preparation process of the polyoxadiazole is complex.
The invention solves the technical problems by the following technical proposal:
in a first aspect, a polyoxadiazole is provided, wherein the polyoxadiazole has the following structural formula:
wherein n is an integer of 2 to 500; r is R 1 、R 2 Are the same or different organic groups; r is R 3 Is an organic group.
In a second aspect, a polyoxadiazole is provided, wherein the polyoxadiazole has the structural formula:
wherein R is 1 、R 3 Arylene, arylene derivatives, and alkylene radicals, which may be the same or differentA substituent; r is R 4 Selected from any one of the following structural formulas:
R 5 any one selected from the following structural formulas;
* R is hydrogen, halogen atom, nitro, alkyl or alkoxy.
Optionally, the polyoxadiazole wherein R 1 、R 2 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent.
Optionally, the polyoxadiazole wherein R 1 、R 2 Selected from any one of the following structural formulas:
，
* Is a joint; r, R', which are identical or different, are independently hydrogen, a halogen atom, an alkyl group or an alkoxy group, X being selected from the group consisting of oxygen, sulfur or selenium; m, p, q, s, t is an integer of 1-20.
In a third aspect, a method for preparing the polyoxadiazole described above, wherein the method includes:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a dicarboxylic acid compound;
and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
A fourth aspect, a method for preparing the polyoxadiazole described above, wherein the method includes:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a tri-or tetra-carboxylic acid compound;
adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole
Optionally, the preparation method of the polyoxadiazole comprises the step that the organic solvent is selected from one or more of dichloromethane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide and tetrahydrofuran; the precipitant is at least one selected from methanol, diethyl ether, ethanol and acetone.
Optionally, the method for preparing polyoxadiazole, wherein the aldehyde monomer: carboxylic acid monomer: amine monomer: the molar ratio of the isonitrile monomer is 1:1 (2-3) to (2-3).
Optionally, the preparation method of the polyoxadiazole, wherein the amine monomer is selected from one of the following structural formulas:
，
wherein k is an integer of 1 to 20.
In a fifth aspect, the use of the polyoxadiazole described above, wherein the polyoxadiazole is used in the fields of respiratory pattern preparation, visualization and cytofluorescence imaging.
The beneficial effects are that: compared with the prior art, the preparation method provided by the invention has the advantages that the used monomer is cheap and easy to obtain, the yield is good, and the molecular weight of the obtained polymer is high (the absolute weight average molecular weight is up to 5 ten thousand, and the PDI is 1.4-2.1); a series of polyoxadiazoles are efficiently synthesized in one step through a four-component reaction without any catalyst; the polymerization method can be carried out at normal temperature and under air condition, and good results are obtained; the polyoxadiazole product is easy to separate, the polymer with high purity can be obtained only by one-time precipitation in the precipitant, and meanwhile, the prepared polyoxadiazole has good film forming property and unique application value in the fields of respiratory pattern preparation, visualization and cell fluorescence imaging.
Drawings
FIG. 1 is a nuclear magnetic spectrum of polyoxadiazole P1 obtained in example 1 in deuterated dimethyl sulfoxide;
FIG. 2 is a nuclear magnetic spectrum of the polyoxadiazole P2 obtained in example 2 in deuterated dimethyl sulfoxide;
FIG. 3 is a graph showing the photo-induced fluorescence of the polyoxadiazole P2 obtained in example 2 in tetrahydrofuranamine solutions of different water contents;
fig. 4 is a fluorescence photograph of the respiratory pattern prepared by polyoxadiazole P2 obtained in example 2.
Fig. 5 is an SEM photograph of the respiratory pattern prepared from polyoxadiazole P2 obtained in example 2.
FIG. 6 is a nuclear magnetic spectrum of polyoxadiazole P3 in deuterated dimethyl sulfoxide obtained in example 3;
FIG. 7 is a nuclear magnetic spectrum of the polyoxadiazoles P4, P5, P6 obtained in examples 4, 5, 6 in deuterated dimethyl sulfoxide;
FIG. 8 is a graph showing the photo-induced fluorescence of the polyoxadiazole P6 obtained in example 6 in tetrahydrofuranamine solutions of different water contents;
fig. 9 is a plot of fluorescence intensity curves of the resulting polyoxadiazoles P2, P6 of examples 2 and 6 in tetrahydrofuran solutions of different water contents.
Fig. 10 is a confocal image of 4T1 cells stained with lystatter Red (1 μm,30 minutes) and a combined image thereof, and superimposed field images of fluorescent and bright images, respectively, of polyoxadiazoles P2, P6 (10 μm,4 hours) obtained in example 2 and example 6.
Detailed Description
The invention provides a polyoxadiazole, a preparation method and application thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and advantages of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. It should be noted that the process parameters not specifically mentioned can be performed by referring to conventional techniques.
The polyoxadiazole provided by the invention comprises linear polyoxadiazole with the structural general formula shown in the formula (1), hyperbranched polyoxadiazoles with the structural general formulas shown in the formulas (6) and (7),
wherein n is an integer of 2 to 500, such as 100, 300, 500, and the polyoxadiazole having a specific weight average molecule is obtained by controlling the size of n. R is R 1 、R 2 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent.
The polyoxadiazole provided by the invention has good film forming property and unique application value in the fields of respiratory pattern preparation, visualization and cell fluorescence imaging. In other words, the polyoxadiazole can be applied to the fields of respiratory pattern preparation, visualization and cytofluorescence imaging.
The polyoxadiazole can be prepared by the following preparation method,
s10, respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution;
and S20, adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
Specifically, an aldehyde monomer, a carboxylic acid monomer, an amine monomer and an isonitrile are dissolved in a solvent and fully reacted at a proper temperature; after the reaction is completed, the mixture is filtered by neutral alumina, added into a large amount of precipitants for precipitation, filtered and collected, and dried to constant weight, thus obtaining the polyoxadiazole derivative.
In this embodiment, the precipitating agent may be methanol, and the use of methanol as the precipitating agent may well precipitate polyoxadiazole. The aldehyde: carboxylic acid: amine: the molar ratio of the isonitrile monomers is 1:1:2:2. the room temperature is also a general temperature, and means 25 ℃. The reaction time may be 24 hours.
In this embodiment, the structural general formulas of the dialdehyde compound and the dicarboxylic acid compound are shown in formula (2) and formula (3):
OHC-R 1 -CHO formula (2);
HOOC-R 2 -COOH (3)
The structural general formula of the amine compound is shown as formula (4):
the structural formula of the isonitrile compound is shown as formula (5):
the structural general formulas of the tri-and tetra-carboxylic acid compounds are respectively shown as a formula (8) and a formula (9):
it is easy to understand that when the aldehyde monomer is a dialdehyde compound and the carboxylic acid monomer is a dicarboxylic acid compound, linear polyoxadiazole is obtained by the reaction; when the aldehyde monomer is a dialdehyde compound and the carboxylic acid monomer is a ternary or quaternary carboxylic acid compound, hyperbranched polyoxadiazole is obtained by the reaction.
The polyoxadiazole and the preparation method thereof provided by the invention are further explained below through specific preparation examples.
Example 1
A method for preparing linear polyoxadiazole by multicomponent polymerization of binary aromatic aldehyde, binary aromatic carboxylic acid, amine and isonitrile comprises the following steps:
(1) 27.0mg of terephthalaldehyde, 33.0mg of terephthalic acid and 121mg of (isocyanato) triphenylphosphine are added into 1mL of dry dimethyl sulfoxide to be dissolved, 77 mu L of dibenzylamine is added under stirring, and the mixture is stirred at room temperature for reaction for 24 hours;
(2) After the reaction was completed, the reaction mother liquor was diluted with 2mL of methylene chloride, filtered through a 2cm thick neutral alumina column, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 57%, the absolute weight average molecular weight was 14200g/mol and the PDI was 1.4.
The experimental monomers of this example were all obtained by direct purchase.
The polyoxadiazole obtained in this example has a structural formula shown as P1:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of hydrogen spectrum of the polyoxadiazole P1 in the deuterated dimethyl sulfoxide is shown in figure 1. As can be seen from FIG. 1, the solvent and water peaks of deuterated dimethyl sulfoxide are at 2.50 and 3.30ppm, respectively. In addition, the signals are all hydrogen atom signals in the polyoxadiazole, and the signals of several hydrogen atoms can be correspondingly attributed. Wherein 3.70ppm is a characteristic peak of a methylene hydrogen atom in the polymer P1, 5.30ppm is a hydrogen atom of a methine group, and 8.10ppm is a characteristic peak of a hydrogen atom on a benzene ring.
Example 2
A method for preparing polyoxadiazole containing tetraphenyl ethylene structure by multicomponent polymerization of aromatic dibasic aldehyde, aromatic dibasic carboxylic acid, amine and isonitrile containing tetraphenyl ethylene comprises the following steps:
(1) 78.0mg of 4,4' - (1, 2-diphenyl-1, 2-vinylidene) dibenzoaldehyde, 72.0mg of 1, 6-bis (p-carboxyphenoxy) hexane and 121mg of (isocyanatoimino) triphenylphosphine were added to 1mL of dry dimethyl sulfoxide for dissolution, 77. Mu.L of dibenzylamine was added with stirring, and the mixture was stirred at room temperature for reaction for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 57%, the absolute weight average molecular weight was 12000g/mol and the PDI was 1.5.
The 4,4' - (1, 2-diphenyl-1, 2-vinylidene) dibenzoaldehyde and 1, 6-bis (p-carboxyphenoxy) hexane of this example were prepared according to literature (Karaburu, A.; lafzi, F.; bayindir, S.; sevigili,orak, I., the synthesis, current transformer mechanism and structural properties of novel rhodanine-based Al/Bis (Rh) -Ph/p-Si and Al/Bis (Rh) -TPE/p-Si heterojunctions. Journal of Molecular Structure 2021,1231.).
The polyoxadiazole obtained in this example has a structural formula shown as P2:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of hydrogen spectrum of the polyoxadiazole P2 in the deuterated dimethyl sulfoxide is shown in figure 2.
The photo-fluorescence curves of the polyoxadiazole P2 of this example in tetrahydrofuran solutions of different water contents are shown in FIG. 3. As can be seen from fig. 3, the fluorescence of the polymer gradually increases with increasing water content, reaching a maximum at 80% water content. The polymer shows a remarkable aggregation-induced emission phenomenon.
Fig. 4 and 5 are a fluorescence photograph and an SEM photograph of the respiratory pattern prepared from polyoxadiazole P2 obtained in example 2, respectively. The specific operation steps are as follows: dissolving a certain amount of polyoxadiazole in CHCl 3 The solution forms a solution with quantitative concentration, and the polymer is completely dissolved in the solvent by vibrating and ultrasonic for 30 minutes. At room temperature, a clean and pollution-free glass dish is taken, 10mL of deionized water is added, a bracket with a certain height is placed in the glass dish, the surface of the bracket is about 5 mm higher than the liquid level of the deionized water, a clean silicon wafer is placed on the bracket, the whole device is sealed by a plastic preservative film, and the glass dish is placed at room temperature for 2 hours, so that water vapor in a weighing bottle is saturated. Taking 50 microliters of polyoxadiazole solution by using a pinhole injector, penetrating a preservative film, dripping the preservative film on a silicon wafer, immediately sticking pinholes on the preservative film by using a transparent adhesive tape, standing for 30 minutes, and taking out the preservative film to obtain the white polyoxadiazole porous film.
Example 3
A method for preparing linear polyoxadiazole by multicomponent polymerization of dibasic fatty aldehyde, dibasic aromatic carboxylic acid, amine and isonitrile comprises the following steps:
(1) 22.0mg of glutaraldehyde, 33.0mg of terephthalic acid and 121mg of (isocyanimino) triphenylphosphine are added into 1mL of dry dimethyl sulfoxide for dissolution, 77 mu L of dibenzylamine are added under stirring, and the reaction is stirred at room temperature for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 70%, the absolute weight average molecular weight was 12100g/mol and the PDI was 1.6.
The polyoxadiazole obtained in this example has a structural formula shown in P3:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of the hydrogen spectrum of the polyoxadiazole P3 in the deuterated dimethyl sulfoxide is shown in fig. 6.
Example 4
A method for preparing three-arm hyperbranched polyoxadiazole by multicomponent polymerization of dialdehyde, tricarboxylic acid, amine and isonitrile comprises the following steps:
(1) 13.4mg of terephthalaldehyde, 60.5mg of tris (4-biphenylcarboxamide) and 60.5mg of (isocyanato) triphenylphosphine were added to 1mL of dried dimethyl sulfoxide to dissolve, 38.5. Mu.L of dibenzylamine was added under stirring, and the mixture was stirred at room temperature to react for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 70%, the absolute weight average molecular weight was 12100g/mol and the PDI was 1.6.
The polyoxadiazole obtained in this example has a structural formula shown in P4:
the reaction equation according to this example is as follows:
/>
the nuclear magnetic spectrum of hydrogen spectrum of polyoxadiazole P4 in deuterated dimethyl sulfoxide of this example is shown in FIG. 7 (A).
Example 5
A method for preparing three-arm hyperbranched polyoxadiazole containing tetraphenyl ethylene structure by multicomponent polymerization of dialdehyde, tricarboxylic acid containing tetraphenyl ethylene, amine and isonitrile comprises the following steps:
(1) 39.0mg of 4,4' - (1, 2-diphenyl-1, 2-vinylidene) dibenzoaldehyde, 60.5mg of tris (4-biphenylcarboxamide) and 60.5mg of (isocyanatoimino) triphenylphosphine were added to 1mL of dry dimethyl sulfoxide for dissolution, and 38.5. Mu.L of dibenzylamine was added with stirring, and the mixture was stirred at room temperature for reaction for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 70%, the absolute weight average molecular weight was 12100g/mol and the PDI was 1.6.
The polyoxadiazole obtained in this example has a structural formula shown in P5:
the reaction equation according to this example is as follows:
/>
the nuclear magnetic spectrum of hydrogen spectrum of polyoxadiazole P5 in deuterated dimethyl sulfoxide of this example is shown in FIG. 7 (B).
Example 6
A method for preparing four-arm hyperbranched polyoxadiazole by multicomponent polymerization of dialdehyde, tetracarboxylic acid, amine and isonitrile comprises the following steps:
(1) 13.4mg of terephthalaldehyde, 81.2mg of tetra- (4-carboxyl- (1, 1-biphenyl)) ethylene and 60.5mg of (isocyanato) triphenylphosphine are added into 1mL of dry dimethyl sulfoxide for dissolution, 38.5 mu L of dibenzylamine are added under stirring, and the reaction is stirred at room temperature for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 65%, the absolute weight average molecular weight was 65000g/mol and the PDI was 1.4.
The polyoxadiazole obtained in this example has a structural formula shown in P6:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of the hydrogen spectrum of the polyoxadiazole P6 in the deuterated dimethyl sulfoxide is shown in fig. 7 (C).
The photo-fluorescence curves of the polyoxadiazole P6 of this example in tetrahydrofuran solutions of different water contents are shown in FIG. 8. As can be seen from fig. 8, the fluorescence of the polymer gradually increased with increasing water content, reaching a maximum at 70% water content. The polymer shows a remarkable aggregation-induced emission phenomenon.
Fig. 9 is a plot of fluorescence intensity curves of the resulting polyoxadiazoles P2, P6 of examples 2 and 6 in tetrahydrofuran solutions of different water contents.
Fig. 10 is a confocal image of 4T1 cells stained with lystatter Red (1 μm,30 min) and a combined image thereof, and superimposed field images of fluorescent and bright images, respectively, of polyoxadiazoles P2, P6 (10 μm,4 h) obtained in example 2 and example 6.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The polyoxadiazole is characterized by having the following structural general formula:
，
wherein n is an integer of 100 to 500; r is R 1 、R 2 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent.
2. The polyoxadiazole is characterized by having a structural general formula:
or->，
Wherein R is 1 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent; r is R 4 Selected from any one of the following structural formulas:
R 5 any one selected from the following structural formulas;
，
* R is hydrogen, halogen atom, nitro, alkyl or alkoxy.
3. The polyoxadiazole according to claim 1, wherein R 1 、R 2 Selected from any one of the following structural formulas:
，
* Is a joint; r, R', which are identical or different, are independently hydrogen, a halogen atom, an alkyl group or an alkoxy group, X being selected from the group consisting of oxygen, sulfur or selenium; m, p, q, s, t is an integer of 1-20.
4. The polyoxadiazole of claim 2, wherein R 1 Selected from any one of the following structural formulas:
，
* Is a joint; r, R', which are identical or different, are independently hydrogen, a halogen atom, an alkyl group or an alkoxy group, X being selected from the group consisting of oxygen, sulfur or selenium; m, p, q, s, t is an integer of 1-20.
5. A process for the preparation of polyoxadiazole according to claim 1, comprising:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a dicarboxylic acid compound;
and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
6. A process for the preparation of polyoxadiazole according to claim 2, comprising:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a tri-or tetra-carboxylic acid compound;
and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
7. The process for preparing polyoxadiazole according to claim 5 or 6, characterized in that the organic solvent is selected from dichloromethane, dimethyl sulfoxide,N,N-a solvent of the type dimethylformamide, which is chosen,N,N-one or more of dimethylacetamide, tetrahydrofuran; the precipitant is at least one selected from methanol, diethyl ether, ethanol and acetone。
8. The method for producing polyoxadiazole according to claim 5 or 6, characterized in that the aldehyde monomer: carboxylic acid monomer: amine monomer: the molar ratio of the isonitrile monomer is 1:1 (2-3) to (2-3).
9. The method for preparing polyoxadiazole according to claim 5 or 6, characterized in that the amine monomer is selected from one of the following structural formulas:
，
wherein k is an integer of 1 to 20.
10. Use of the polyoxadiazole according to claim 1 or 2, characterized in that it is used in the fields of respiratory patterning, visualization and cytofluorescence imaging.
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| Ali Ramazani et al.,.Novel One-Pot, Four-Component Condensation Reaction: An Efficient Approach for the Synthesis of 2,5-Disubstituted 1,3,4-Oxadiazole Derivatives by a Ugi-4CR/aza-Wittig Sequence.《organic letters》.2010,第12卷(第12期),第2852-2855页. * |
| Ali Ramazani.Four-component Synthesis of 1,3,4-Oxadiazole Derivatives from (N-Isocyanimino)triphenylphosphorane, (E)-Cinnamic Acids, Acetaldehyde and Secondary Amines.《Z. Naturforsch》.2010,第66卷第184-190页. * |
| Ali RAMAZANI.Four-component synthesis of 1,3,4-oxadiazole derivatives from N -isocyaniminotriphenylphosphorane, aromatic carboxylic acids, aromatic bis-aldehydes, and secondary amines.《Turkish Journal of Chemistry》.2012,第36卷第81-91页. * |
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