CN115368351A - Preparation method and application of polysubstituted oxazole compound - Google Patents

Preparation method and application of polysubstituted oxazole compound Download PDF

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CN115368351A
CN115368351A CN202210898185.7A CN202210898185A CN115368351A CN 115368351 A CN115368351 A CN 115368351A CN 202210898185 A CN202210898185 A CN 202210898185A CN 115368351 A CN115368351 A CN 115368351A
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polysubstituted
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oxazole compound
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李先纬
李仲元
霍延平
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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Abstract

The patent application discloses a preparation method and application of a polysubstituted oxazole compound. The method obtains the polysubstituted oxazole compound through multiple dehydrogenation 1,1-double functionalization reaction of N- (1-aryl vinyl) amide catalyzed by trivalent metal and various aromatic heterocyclic nucleophiles such as thiophene, indole and aromatic hydrocarbon respectively. The method has atom and step economy, and directly uses common easily-obtained nucleophilic reagent as raw material, the whole conversion avoids aryl halide and aryl metal reagent as active sites to participate in reaction, and the method meets the development requirement of sustainable chemistry; the substrate for conversion has wide application range, and N- (1-aryl vinyl) amide which is simple and easy to obtain is used as a reaction substrate and simultaneously used as a traceless guide group to participate in the construction of the nitrogen-containing fused heterocycle; the applicant of the present patent also applied the obtained heterocyclic substrate in the hole transport layer of perovskite solar cells.

Description

Preparation method and application of polysubstituted oxazole compound
Technical Field
The patent application relates to the technical field of organic compound synthesis, in particular to a preparation method and application of a polysubstituted oxazole compound.
Background
How to synthesize target structure molecules accurately, efficiently and greenly, and simply construct molecular complexity to enrich the molecular library in the application field of the target structure molecules is always a problem to be faced in the field of synthetic chemistry. On this basis, the dual functionalization of olefins has been demonstrated to be a powerful strategy to rapidly introduce two different functional groups at the carbon-carbon double bond, thereby building molecular complexity in a straightforward manner. In 2001, the Nobel prize was issued to K.Barry Sharpless, ryoji Noyori and William Standard Knowles to show the contribution of the K.Barry Sharpless, ryoji Noyori and William Standard Knowles in the field of chiral catalysis, wherein the osmium developed by Sharpless and the like can catalyze the epoxidation and double hydroxylation reaction of olefin, and the rapid construction of related bioactive molecules can be rapidly realized. Under the initiation, the olefin 1,1-bifunctional and 1,2-bifunctional reactions catalyzed by transition metals such as palladium, nickel and copper are greatly improved, and the olefin 1,1-bifunctional and 1,2-bifunctional reactions are applied to the fields of biological medicines and materials (org. Biomol. Chem.,2020,18,6983-7001).
To achieve the reactivity and site selectivity of the olefin difunctionalization, the major strategies employed by chemists include: 1) Nucleophilic metallation is used to initiate the olefin 1,2-bifunctional Wacker type reaction. For example, the Liu Guosheng topic group explored the high-value metal species for the inclusion of the very challenging C-F, C-OCF 3 Alkene bifunctional reactions involving bond formation (for details, see review: acc. Chem. Res.2016,49, 2413-2423); 2) The site-selective C-H activation of the olefin participated by the guide group further realizes 1,2-dual functionalization. In recent years, the Engle project group at Scripps institute developed a series of alkenes 1,2-dual functionalizations that rapidly acquired the target molecule and greatly expanded the diversity of potential substrates (for a review see: chem. Commun.,2021,57,7610-7624).
The 1,1-bifunctional reaction is slower than 1,2-bifunctional, probably because it is difficult to control the site selectivity of the substrate, so that the catalyst is usually performed by trans-nucleophilic metallation (trans-nucleophilic metallation) when activating the olefin pi-bond, and therefore the 1,1-bifunctional reaction of the olefin has a larger challenge; for example, sanford reports tunable olefins 1,2-and 1,1-arylation with excellent stereoselectivity by using different types of halogenating agents for oxidative interception of Heck reaction intermediates (j.am. Chem. Soc.,2008,130, 2150-2151.). Tose achieves enantioselective 1,1-fluoroarylation of aminoolefins catalyzed by Pd (II)/bisoxazoline (j.am. Chem., soc.2015,137,38, 12207-12210). Sigman developed a series of intermolecular olefins 1,1-difunctionalized with electrophiles and nucleophiles catalyzed by Pd (0) (J.Am.chem.Soc., 2011,133, 5784-5787). Recently, baik and Hong realized cationic palladium catalyzed 1,1-difunctionalization, where two nucleophiles, electron rich arenes and internal hydroxyl groups, were realized by N-quinolinamides, provided synthetically valuable and challenging oxygen containing quaternary carbon centers (j.am. Chem. Soc.,2019,141, 10048-10059).
While 1,1-difunctionalization of olefins based on multiple dehydrogenation strategies, which is more challenging, has been rarely reported.
Content of the patent application
In order to overcome at least one of the problems of the prior art as described above, the present patent application provides a method for preparing a polysubstituted oxazole compound: by the aid of easily obtained traceless weak coordination guide groups, 1,1-dehydrogenation bifunctional of olefin is realized under the catalysis of trivalent metal, and various types of electron-rich aromatic rings are directly used as coupling reagents to construct a multi-connected aromatic heterocyclic molecular skeleton.
It is a further object of the present application to provide the use of the above polysubstituted oxazole compounds. The application of the method simply synthesizes diphenylamine synthetic block-based material molecules through a dehydrogenation 1,1-double functionalization strategy of olefin, finds that the energy level of the diphenylamine synthetic block-based material molecules is matched with a perovskite solar hole transmission material according to a front edge orbit distribution diagram obtained by DFT calculation, and further verifies that the material molecules meet the requirements of a perovskite solar cell hole transmission layer through performance characterization such as ultraviolet absorption, fluorescence emission, cyclic voltammogram and the like.
In order to solve the technical problem, the technical scheme adopted by the patent application is as follows:
a preparation method of a polysubstituted oxazole compound comprises the following steps: in an inert solvent, under the action of a trivalent metal catalyst, reacting an N- (1-aryl vinyl) amide compound (formula II) with an aromatic heterocyclic compound (formula III) to obtain a polysubstituted oxazole compound (formula I), wherein the reaction formula is as follows:
Figure BDA0003769870300000021
wherein Ar is an ortho-substituted, meta-substituted or para-substituted benzene ring or condensed ring compound; r is saturated alkane; het is thiophene compound, polysubstituted indole compound, electron-rich condensed ring aromatic compound and benzene ring compound.
Preferably, the inert solvent is any one or more of toluene, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, N' -dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, 1,2-dichloroethane, ethanol and water.
Preferably, the trivalent metal catalyst is: any one of pentamethylcyclopentadienylrhodium chloride dimer, pentamethylcyclopentadienyliridium chloride dimer, or a combination thereof.
Preferably, the halide ion capturing agent is any one of silver hexafluoroantimonate and silver bis (trifluoromethanesulfonyl) imide or a combination thereof.
Preferably, the oxidant is any one or more of silver acetate, silver carbonate, silver oxide and copper acetate.
Preferably, the additive is any one of pivalic acid, 2,4,6-trimethyl sodium benzoate or their combination.
Preferably, the trivalent metal catalyst is used in an amount of 2mol% based on the amount of the N- (1-arylvinyl) amide compound (formula II).
Preferably, the reaction is carried out at 120 to 140 ℃; the reaction is carried out for 12 to 24 hours.
The preparation method of the polysubstituted oxazole compound in some preferred embodiments of the present patent application comprises the following specific steps:
s1: in a reactor, in the air, 2.5mg of pentamethylcyclopentadienyliridium dichloride dimer, 3.9mg of silver trifluoromethanesulfonimide, 69.5mg of silver oxide, 30.6mg of pivalic acid, 1.0mL of toluene as a solvent, 35.2mg of N- (1- (2,4-dichlorophenyl) vinyl) propionamide, and 49.8mg of 2,2' -bithiophene were sequentially added;
s2: reacting the reaction solution at 140 ℃ for 12 hours;
s3: and after the reaction is finished, separating the mixture by using a column chromatography separation technology to obtain the target compound.
The application also provides a solar cell, wherein the solar cell is a perovskite solar cell, and a hole transport material in the perovskite solar cell adopts the polysubstituted oxazole compound prepared by the preparation method as claimed in claim 1.
Under the condition of inert solvent, under the common promotion of trivalent metal catalyst and silver salt oxidant, the multiple dehydrogenation 1,1 double functionalization of olefin is realized: specifically, firstly, N- (1-aryl vinyl) amide) is used as an easily-obtained and easily-converted raw material, and amide is used as a weakly coordinated traceless guiding group to realize C of olefin SP2 And (3) activating aryl by H, further carrying out enol tautomerism on the amide, and carrying out intramolecular oxidative cyclization with the olefin again, thereby constructing a carbon-carbon bond and a carbon-hetero bond to obtain a multi-dehydrogenation 1,1 bifunctional product of the olefin. The method has high atom economy (the product is obtained by multiple cross dehydrogenation coupling, and the byproduct is H 2 O or H 2 ) And the steps are economical (the raw materials do not need to be halogenated or metallized in advance), a nucleophilic reagent with abundant content in nature is used as the raw materials, the substrate has wide application range, N- (1-aryl vinyl) amide which is simple and easy to obtain is used as a reaction substrate, and simultaneously, the N- (1-aryl vinyl) amide is used as a traceless guiding group to participate in the construction of the nitrogen-containing fused heterocycle, and the obtained heterocycle substrate can be applied to a perovskite solar cell hole transport layer.
Compared with the prior art, the beneficial effect of this patent application is:
the preparation method of the polysubstituted oxazole compound provided by the application has the characteristics of easily obtained raw materials, multiple dehydrogenation, high-efficiency atom economy and step economy, and the obtained heterocyclic substrate can be applied to a hole transport material of a perovskite solar cell.
Drawings
FIG. 1 is a NMR spectrum of Compound 1a prepared in example 1 of the present application;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of Compound 1a prepared in example 1 of the present patent application;
FIG. 3 is a NMR spectrum of Compound 1b prepared in example 2 of the present application;
FIG. 4 is a NMR carbon spectrum of Compound 1b prepared in example 2 of the present application;
FIG. 5 shows the NMR fluorine spectrum of Compound 1b prepared in example 2 of the present application;
FIG. 6 is a NMR spectrum of Compound 1c prepared in example 3 of the present application;
FIG. 7 is a NMR carbon spectrum of Compound 1c prepared in example 3 of the present application;
FIG. 8 is a NMR spectrum of Compound 1d prepared in example 4 of the present application;
FIG. 9 shows a NMR spectrum of Compound 1d prepared in example 4 of the present application;
FIG. 10 is a NMR chart of Compound 1e prepared in example 4 of the present application;
FIG. 11 is a NMR spectrum of Compound 1e prepared in example 5 of the present application;
FIG. 12 is a NMR spectrum of Compound 1f prepared in example 4 of the present application;
FIG. 13 is a NMR carbon spectrum of Compound 1f prepared in example 5 of the present application;
FIG. 14 shows the NMR spectrum of 1g of compound prepared in example 4 of the present patent application;
FIG. 15 is a NMR spectrum of 1g of compound prepared in example 5 of the present patent application;
FIG. 16 is a NMR spectrum of compound 1h prepared in example 4 of the present application for hydrogen;
FIG. 17 is a NMR spectrum of compound 1h prepared in example 5 of the present patent application for C;
FIG. 18 is a NMR spectrum of Compound 1i prepared in example 4 of the present application;
FIG. 19 is a NMR carbon spectrum of Compound 1i prepared in example 5 of the present application;
FIG. 20 is a NMR spectrum of Compound 1j prepared in example 4 of the present application;
FIG. 21 is a NMR carbon spectrum of Compound 1j prepared in example 5 of the present patent application;
FIG. 22 is a front orbital distribution plot of Compound 1j prepared in example 5 of the present patent application;
FIG. 23 is a normalized ultraviolet absorption spectrum and fluorescence emission spectrum of Compound 1j prepared in example 5 of the present patent application;
FIG. 24 is a cyclic voltammogram of Compound 1j prepared in example 5 of the present patent application.
Detailed Description
Embodiments of the present patent application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present patent application and should not be construed as limiting the scope of the present patent application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that:
in the present patent application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated.
In this application, unless otherwise indicated, individual reactions or process steps may be performed sequentially or in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. Moreover, any methods or materials similar or equivalent to those described herein can also be used in the present application.
The application provides a preparation method of a polysubstituted oxazole compound, which comprises the following steps: in an inert solvent, under the action of a trivalent metal catalyst, reacting an N- (1-aryl vinyl) amide compound (formula II) with an aromatic heterocyclic compound (formula III) to obtain a polysubstituted oxazole compound (formula I), wherein the reaction formula in the preparation method is as follows:
Figure BDA0003769870300000051
wherein Ar is an ortho-substituted, meta-substituted or para-substituted benzene ring or condensed ring compound; r is saturated alkane; het is thiophene compound, polysubstituted indole compound, electron-rich fused ring aromatic compound and benzene ring compound.
The preparation method realizes 1,1-dehydrogenation bifunctional of olefin under the catalysis of trivalent metal with the assistance of easily obtained traceless weak coordination guide N- (1-aryl vinyl) amide, and directly uses various types of electron-rich aromatic rings as coupling reagents to construct the multi-connected aromatic heterocyclic molecular skeleton.
Based on the above, the applicant of the present invention also simply synthesizes material molecules based on diphenylamine synthesis building blocks by using an olefin dehydrogenation 1,1-bifunctional strategy, finds that the energy level of the material is matched with that of the perovskite solar hole transport material according to a leading edge trajectory distribution diagram obtained by DFT calculation, and further verifies that the material molecules meet the requirements of the perovskite solar cell hole transport layer through performance characterization such as ultraviolet absorption, fluorescence emission, cyclic voltammogram and the like.
Next, the method for producing a polysubstituted oxazole compound of the present patent application will be described in detail with specific examples.
1. Preparation examples
Example 1- ([ 2,2' -bithiophene ] -5-yl) -4- (2,4-dichlorophenyl) -2-ethyloxazole (1 a)
To a 15mL Schlenk reaction tube under an atmosphere of atmospheric air, N- (1- (2,4-dichlorophenyl) vinyl) propanamide 2 was added in sequencea (35.2mg, 0.20mmol), trivalent iridium catalyst [ Cp IrCl ] 2 ] 2 (2.5mg, 0.004mmol), 2,2' -bithiophene 3a (49.8mg, 0.30mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30.6mg, 0.30mmol), toluene (Tol, 1.0 mL), at a temperature of 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 20:1, the product 5- ([ 2,2' -bithiophene) is obtained in 72% yield]-5-yl) -4- (2,4-dichlorophenyl) -2-ethyl oxazole (1 a).
The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000061
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the chemical combination prepared in example 1 are shown in fig. 1 and fig. 2. As can be seen from fig. 1: 1 H NMR(400MHz,CDCl 3 ) δ 7.53 (d, J =2.1hz, 1h), 7.45 (d, J =8.2hz, 1h), 7.34 (dd, J =2.1hz,8.3hz, 1h), 7.21 (dd, J =1.1hz,5.1hz, 1h), 7.13 (dd, J =1.1hz,3.7hz, 1h), 7.03 (d, J =3.9hz, 1h), 6.99 (dd, J =3.6hz,5.1hz, 1h), 6.93 (d, J =3.8hz, 1h), 2.93-2.86 (m, 2H), 1.42 (dd, J =5.2hz,8.2hz, 3h) molecular hydrogen peaks can correspond to target products one-to one, and are reasonable in number. From FIG. 2, it can be seen that 13 C NMR(100MHz,CDCl 3 ) δ 164.3,142.6,137.9,136.6,135.5,135.2,132.9,130.9,130.0,129.8,129.1,128.2,128.2,127.9,127.5,125.4,125.3,125.0,124.2,124.1,21.7,11.2. The molecular carbon spectrum wave peak energy and the target product correspond to each other one by one, and the quantity is reasonable. The results of the nuclear magnetic hydrogen spectroscopy and the carbon spectrogram show that the product prepared in example 1 is 5- ([ 2,2' -bithiophene]-5-yl) -4- (2,4-dichlorophenyl) -2-ethyl oxazole (1 a).
In this example, N- (1- (2,4-dichlorophenyl) vinyl) propionamide 2a and electron-rich aromatic ring compound 2,2 '-bithiophene 3a were subjected to multiple cross-dehydrogenation coupling reactions to obtain polysubstituted oxazole compound 5- ([ 2,2' -bithiophene ] -5-yl) -4- (2,4-dichlorophenyl) -2-ethyloxazole (1 a).
The synthesis reaction of the polysubstituted oxazole compound in the embodiment has efficient atoms and economical steps, and the common easily-obtained nucleophilic reagent N- (1- (2,4-dichlorophenyl) vinyl) propionamide 2a is directly used as a raw material and simultaneously used as a traceless guide group to participate in the construction of the nitrogen-containing fused heterocycle, so that the aryl halide and the aryl metal reagent are prevented from participating in the reaction as active sites in the whole conversion. In addition, the chemical conversion in the embodiment uses synthetic building block bithiophene (2,2' -bithiophene 3 a) as a raw material, and can be applied to the fields of organic photoelectric materials and the like.
Example 2-methyl-5- (5-methylthiophen-2-yl) -4- (4- (trifluoromethyl) phenyl) oxazole (1 b)
To a 15mL Schlenk reaction tube were added N- (1- (4- (trifluoromethyl) phenyl) vinyl) acetamide 2b (45.8mg, 0.20mmol), 5-methylthiophene 3b (29.4mg, 0.30mmol), and a trivalent rhodium catalyst [ CpRh (CH. Multidot. Rh) (0.30mmol) in this order under an atmospheric air atmosphere 3 CN) 3 Cl 2 ] 2 (3.3 mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9 mg, 0.01mmol), silver oxide (69.5 mg, 0.30mmol), pivalic acid (30.6 mg, 0.30mmol), toluene (toluene, 1.0 mL) at 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10:1, the product 2-methyl-5- (5-methylthiophen-2-yl) -4- (4- (trifluoromethyl) phenyl) oxazole (1 b) was obtained in 65% yield. The corresponding chemical reaction equation of this example is as follows:
Figure BDA0003769870300000071
the nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and nuclear magnetic fluorine spectrum of the compound prepared in example 2 are shown in fig. 3, 4 and 5. As can be seen from fig. 3: 1 H NMR(400MHz,CDCl 3 ) δ 7.58 (d, J =6.7hz, 1h), 7.38 (d, J =5.2hz, 1h), 7.33 (d, J =8.9hz, 1h), 7.23 (s, 1H), 7.19 (dd, J =5.3hz,0.7hz, 1h), 2.58 (s, 3H). The molecular hydrogen spectral peak energies correspond to the target products one by one, and the number is reasonable. As can be seen from fig. 4: 13 C NMR(100MHz,CDCl 3 )δ160.2,156.8(d,J＝250.0Hz),143.3,139.5,132.5,131.6,131.1,130.6,130.4,1298,128.5,119.7,119.5,119.3,117.2,13.9 the molecular carbon spectrum peak energy corresponds to the target product one by one, and the quantity is reasonable. As can be seen from fig. 5: 19 F NMR(300MHz,CDCl 3 ) Delta-118.2. Combining the results of the nuclear magnetic hydrogen, carbon and fluorine spectra, the product obtained in example 2 was 2-methyl-5- (5-methylthiophen-2-yl) -4- (4- (trifluoromethyl) phenyl) oxazole (1 b).
In this example, acetamido group in N- (1- (4- (trifluoromethyl) phenyl) vinyl) acetamide 2b was used as a reaction substrate with traceless directing group, electron rich aromatic ring 5-methylthiophene 3b was used as a coupling reagent, and in a trivalent iridium catalyst [ Cp x IrCl ] in the presence of a trivalent iridium catalyst 2 ] 2 Under the catalysis, 1,1-dehydrogenation bifunctional of olefin is realized, and the poly-aromatic heterocyclic molecular skeleton 2-methyl-5- (5-methylthiophene-2-yl) -4- (4- (trifluoromethyl) phenyl) oxazole (1 b) is constructed. The chemical conversion in this embodiment has high step economy and atom economy, and can be compatible with fluorine elements widely used in the fields of materials and medicines.
Example 3 methyl 4- (5- ([ 2,2
To a 15mL Schlenk reaction tube, methyl 4- (1-acetamidovinyl) benzoate 2c (43.8mg, 0.20mmol), 2,2':5,2' -trithiophene 3c (74.4mg, 0.30mmol), and a trivalent iridium catalyst [ Cp. IrCl ] were sequentially added under an atmospheric pressure air atmosphere 2 ] 2 (2.5mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30.6 mg, 0.30mmol), ethylene glycol dimethyl ether (DME, 1.0 mL) at 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10: the product 4- (5- ([ 2,2]-5-yl) -2-methyloxazol-4-yl) benzoic acid methyl ester (1 c). The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000081
the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the compound prepared in example 3 are shown in fig. 6 and 7. As can be seen from fig. 6: 1 H NMR(400MHz,CDCl 3 ) δ 7.74 (d, J =8.4hz, 2h), 7.49 (d, J =8.4hz, 2h), 7.23 (d, J =5.1hz, 1h), 7.19 (dd, J =6.0hz,3.9hz, 2h), 7.08 (d, J =4.0hz, 3h), 7.03 (dd, J =5.0hz,3.7hz, 1h), 2.54 (s, 3H) molecular hydrogen spectral peak energies correspond one-to-one to the target product, the reasonable number of which can be seen in fig. 7: 13 C NMR(100MHz,CDCl 3 ) δ 160.4,140.5,138.3,137.7,136.9,135.2,134.4,131.3,130.4,129.5,128.4,127.9,126.6,124.8,124.7,124.4,123.9,123.8,94.0,13.9. The molecular carbon spectrum wave peak energy and the target product correspond to each other one by one, and the quantity is reasonable. From the results of the nuclear magnetic hydrogen spectrum and the carbon spectrum, it was found that the product obtained in example 3 was 4- (5- ([ 2,2]-5-yl) -2-methyloxazol-4-yl) benzoic acid methyl ester (1 c).
The synthetic reaction in the embodiment has high-efficiency atom economy and step economy, and uses rich electron-rich aromatic heterocyclic nucleophilic reagent 2,2 '5,2' -trithiophene 3c in nature as a raw material, takes (4- (1-acetamino vinyl) methyl benzoate 2c as a reaction substrate, and simultaneously takes part in the construction of the nitrogen-containing fused heterocyclic ring as a traceless guide group, so that the whole conversion avoids the use of aryl halide and aryl metal reagent, and meets the development requirement of sustainable chemistry.
The chemical conversion in this example uses terthiophene as raw material, terthiophene has many effects, it is monomer precursor of polythiophene, photosensitizer, polycarbonate dopant, it is a very important chemical intermediate; the product synthesized by the embodiment can be applied to the fields of various materials such as electronic liquid crystal, organic electroluminescence and the like.
Example 4- (benzothien-2-yl) -4- (2,4-dichlorophenyl) -2-methyloxazole (1 d)
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d (45.8mg, 0.20mmol), benzothiophene 3d (40.2mg, 0.30mmol), and a trivalent rhodium catalyst [ Cp RhCl [ ], in that order 2 ] 2 (2.5mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30).6mg, 0.30mmol), toluene (Tol, 1.0 mL), at a temperature of 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 20:1, the product 5- (benzothien-2-yl) -4- (2,4-dichlorophenyl) -2-methyloxazole (1 d) was obtained in 49% yield. The corresponding chemical reaction equation of this example is as follows:
Figure BDA0003769870300000101
the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the compound prepared in example 4 are shown in fig. 8 and 9. As can be seen from fig. 8: 1 H NMR(400MHz,CDCl 3 ) δ 7.73 (t, J =8.8hz, 2h), 7.56 (d, J =2.1hz, 1h), 7.46 (d, J =8.3hz, 1h), 7.37 (dd, J =8.2hz,2.1hz, 1h), 7.33 (dd, J =7.0hz,1.7hz, 1h), 7.31 (s, 1H), 2.61 (s, 3H). As can be seen from fig. 9: 13 C NMR(100MHz,CDCl 3 ) δ 160.6,139.4,135.8,135.3,132.9,132.7,130.0,129.5,129.2,127.4,127.4,125.0,124.8,123.9,122.1,121.0,120.8,14.1. Based on the results of the above nuclear magnetic hydrogen spectrum and carbon spectrum, the product obtained in example 4 was 5- (benzothiophen-2-yl) -4- (2,4-dichlorophenyl) -2-methyloxazole (1 d).
The chemical synthesis method in the embodiment has atom and step economy, and directly uses the common easily-obtained electron-rich aromatic heterocyclic nucleophilic reagent benzothiophene 3d and N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d amide which is used as a raw material and is simply and easily obtained as a reaction substrate, and simultaneously participates in the construction of the nitrogen-containing fused heterocycle as a traceless guiding group. .
The chemical conversion in this example uses star molecule benzothiophene in the fields of biomedicine and materials as a raw material, and the synthesized product can be used in the fields of materials such as photochromic materials and optical recording media.
Example 5- (5 '-bromo- [2,2' -bithiophene ] -5-yl) -4- (2,4-dichlorophenyl) -2-methyloxazole (1 e)
To a 15mL Schlenk reaction tube under an atmosphere of atmospheric air was added N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d (45.8 mg)0.20 mmol), 5-bromo-2,2' -bithiophene 3e (73.2mg, 0.30mmol), trivalent iridium catalyst [ Cp x IrCl 2 ] 2 (2.5mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), 2,4,6-sodium trimethylbenzoate (55.8mg, 0.30mmol), toluene (Tol, 1.0 mL), at a temperature of 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 20:1, the product 5- (5 '-bromo- [2,2' -bithiophene) is obtained in 68% yield]-5-yl) -4- (2,4-dichlorophenyl) -2-methyloxazole (1 e). The corresponding chemical reaction equation of this example is as follows:
Figure BDA0003769870300000111
the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the compound prepared in example 5 are shown in fig. 10 and 11. As can be seen from fig. 10: 1 H NMR(400MHz,CDCl 3 ) δ 7.56 (d, J =2.1hz, 1h), 7.46 (d, J =8.3hz, 1h), 7.37 (dd, J =8.3hz,2.1hz, 1h), 6.97 (dd, J =7.3hz,3.9hz, 2h), 6.94 (d, J =3.8hz, 1h), 6.88 (d, J =3.9hz, 1h), 2.60 (s, 3H), as can be seen from fig. 11: 13 C NMR(100MHz,CDCl 3 ) δ 160.1,142.7,138.0,136.8,135.7,135.1,132.8,131.2,130.7,130.0,129.5,129.0,127.5,125.5,124.3,124.2,111.6,13.9. The results of the nuclear magnetic hydrogen spectrum and the carbon spectrum show that the product prepared in example 5 is 5- (5 '-bromo- [2,2' -bithiophene]-5-yl) -4- (2,4-dichlorophenyl) -2-methyloxazole (1 e).
This example is carried out by reacting a trivalent iridium catalyst [ CpIrCl ] in an inert solvent toluene 2 ] 2 Under the promotion of silver oxide, the multi-time dehydrogenation 1,1 double functionalization of olefin is realized. The method has high-efficiency atom economy and step economy, and uses a nucleophile 5-bromo-2,2' -bithiophene 3e which is abundant in nature as a raw material, has wide substrate application range, and takes N- (1- (2,4-dichlorophenyl) ethenyl) acetamide 2d which is simple and easy to obtain as a reaction substrate and simultaneously as a traceless guiding group to participate in the construction of the nitrogenous polysubstituted oxazole compound.
The chemical conversion in this embodiment can be compatible with a variety of aryl halide groups that are incompatible with conventional carbon-hydrogen bond activation reactions, and the aryl halide groups have good chemical activity, such as palladium-catalyzed coupling reactions, ullmann (Ullmann) coupling reactions, and the like, thereby providing a platform for the construction of more complex molecules.
Example 6- (2,4-dichlorophenyl) -2-methyl-5- (1-methyl-2-phenyl-1H-indol-3-yl) oxazole (1 f)
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d (45.8mg, 0.20mmol), 1-methyl-2-phenyl-1H-indole 3f (62.2mg, 0.30mmol), and a trivalent rhodium catalyst [ Cp. Multidot.RhCl ] 2 ] 2 (2.5mg, 0.004mmol), silver hexafluoroantimonate (3.6 mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30.6 mg, 0.30mmol), and toluene (Tol, 1.0 mL) were reacted at 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10:1, the product 4- (2,4-dichlorophenyl) -2-methyl-5- (1-methyl-2-phenyl-1H-indol-3-yl) oxazole (1 f) was obtained in 65% yield. The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000121
the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the compound prepared in example 6 are shown in fig. 12 and 13. As can be seen from fig. 12: 1 H NMR(400MHz,CDCl 3 ) δ 7.76 (d, J =7.9hz, 1h), 7.42 (d, J =8.2hz, 1h), 7.38-7.34 (m, 1H), 7.30-7.27 (m, 2H), 7.25-7.24 (m, 1H), 7.23-7.20 (m, 2H), 7.13 (d, J =1.8hz, 1h), 7.04-7.01 (m, 2H), 6.93 (d, J =1.9hz, 1h), 3.61 (s, 3H), 2.61 (s, 3H), as can be seen from fig. 13: 13 C NMR(100MHz,CDCl 3 ) δ 160.3,144.3,140.2,137.7,137.3,133.9,133.3,132.3,130.5,130.3,129.8,129.2,128.9,128.2,126.4,125.2,122.6,120.8,119.9,109.7,102.1,30.9,14.0. Based on the results of the above nuclear magnetic hydrogen spectrum and carbon spectrum, the product obtained in example 6 was 4- (2,4-dichlorobenzene-2-methyl-5- (1-methyl-2-phenyl-1H-indol-3-yl) oxazole (1 f).
This example is carried out by reacting a trivalent iridium catalyst [ CpIrCl ] in an inert solvent toluene 2 ] 2 Under the promotion of silver oxide, the multi-time dehydrogenation 1,1 double functionalization of olefin is realized. The method has high-efficiency atom economy and step economy, uses the electron-rich aromatic heterocyclic nucleophile 1-methyl-2-phenyl-1H-indole 3f rich in nature as a raw material, has wide substrate application range, and takes N- (1- (2,4-dichlorophenyl) ethenyl) acetamide 2d which is simple and easy to obtain as a reaction substrate and simultaneously as a traceless guide group to participate in the construction of the polysubstituted oxazole compound.
The chemical transformation in this example can modify the biologically active indole compounds and contain halogen functional groups that are easily convertible, thereby providing a platform for the construction of more complex molecules.
Example 7- (4-bromophenyl) -2-methyl-5- (1-methyl-1H-indol-3-yl) oxazole (1 g)
To a 15mL Schlenk reaction tube were added N- (1- (4-bromophenyl) vinyl) acetamide 2e (47.8mg, 0.20mmol), 1-methyl-1H-indole 3g (39.3mg, 0.30mmol), and a trivalent iridium catalyst [ Cp. IrCl ] in that order under an atmospheric air atmosphere 2 ] 2 (2.5mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30.6 mg, 0.30mmol), toluene (Tol, 1.0 mL), at 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10:1, the product 4- (4-bromophenyl) -2-methyl-5- (1-methyl-1H-indol-3-yl) oxazole (1 g) was obtained in 65% yield. The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000131
the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the compound prepared in example 7 are shown in fig. 14 and 15. As can be seen from fig. 14: 1 H NMR(400MHz,CDCl 3 ) δ 7.76 (d, J =7.9hz, 1h), 7.42 (d, J =8.2hz, 1h), 7.38-7.34 (m, 1H), 7.30-7.27 (m, 2H), 7.25-7.24 (m, 1H), 7.23-7.20 (m, 2H), 7.13 (d, J =1.8hz, 1h), 7.04-7.01 (m, 2H), 6.93 (d, J =1.9hz, 1h), 3.61 (s, 3H), 2.61 (s, 3H), as can be seen from fig. 15: 13 C NMR(100MHz,CDCl 3 ) δ 160.3,144.3,140.2,137.7,137.3,133.9,133.3,132.3,130.5,130.3,129.8,129.2,128.9,128.2,126.4,125.2,122.6,120.8,119.9,109.7,102.1,30.9,14.0. The results of the nuclear magnetic hydrogen spectroscopy and the carbon spectroscopy showed that the product obtained in example 7 was 4- (4-bromophenyl) -2-methyl-5- (1-methyl-1H-indol-3-yl) oxazole (1 g).
This example is carried out by reacting a trivalent iridium catalyst [ CpIrCl ] in an inert solvent toluene 2 ] 2 Under the promotion of silver oxide, the multi-dehydrogenation 1,1 double functionalization of olefin is realized. The method has high-efficiency atom economy and step economy, the whole conversion avoids aryl halide and aryl metal reagent as active sites to participate in reaction, 3g of electron-rich aromatic heterocyclic nucleophilic reagent 1-methyl-1H-indole with abundant content in nature is used as a raw material, the substrate application range is wide, and N- (1- (4-bromophenyl) vinyl) acetamide 2e which is simple and easy to obtain is used as a reaction substrate and simultaneously used as a traceless guiding group to participate in the construction of the polysubstituted oxazole compound.
Example 8-methyl-5- (1-methyl-1H-indol-3-yl) -4- (naphthalen-2-yl) oxazole (1H)
To a 15mL Schlenk reaction tube were added N- (1- (naphthalen-2-yl) vinyl) acetamide 2f (42.4 mg, 0.20mmol), 1-methyl-1H-indole 3g (39.3 mg, 0.30mmol), and a trivalent iridium catalyst [ Cp. IrCl ] in that order under an atmospheric pressure air atmosphere 2 ] 2 (2.5mg, 0.004mmol), silver hexafluoroantimonate (3.6mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30.6 mg, 0.30mmol), toluene (Tol, 1.0 mL) at 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10: the product 2-methyl-5- (1-methyl-1H-indol-3-yl) -4- (naphthalen-2-yl) oxazole (1H) was obtained in 63% yield. The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000141
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 8 are shown in fig. 16 and 17. As can be seen from fig. 16: 1 H NMR(400MHz,CDCl 3 ) δ 8.26 (s, 1H), 7.79 (dd, J =3.3hz,6.2hz, 2h), 7.73 (d, J =2.1hz, 1h), 7.56 (d, J =8.0hz, 1h), 7.44 (dd, J =3.2hz,6.2hz, 2h), 7.41-7.35 (m, 3H), 7.31-7.29 (m, 1H), 7.10 (t, J =1.1hz, 1h), 3.83 (s, 3H), 2.64 (s, 3H), as can be seen from fig. 17: 13 C NMR(100MHz,CDCl 3 ) δ 160.0,142.3,136.9,133.5,133.2,132.7,129.8,128.2,128.2,127.9,127.6,126.1,126.0,125.9,125.8,125.1,122.5,121.1,120.5,109.6,103.9,33.1,14.1. Combining the results of the above nuclear magnetic hydrogen and carbon spectrograms, the product obtained in example 8 was 2-methyl-5- (1-methyl-1H-indol-3-yl) -4- (naphthalen-2-yl) oxazole (1H).
This example was carried out over a trivalent iridium catalyst [ CpIrCl ] in the presence of toluene as inert solvent 2 ] 2 Under the promotion of silver oxide, the multi-time dehydrogenation 1,1 double functionalization of olefin is realized. The method has high-efficiency atom economy and step economy, 3g of the electron-rich aromatic heterocyclic nucleophilic reagent 1-methyl-1H-indole which is rich in nature is used as a raw material, the substrate application range is wide, and N- (1- (naphthalene-2-yl) vinyl) acetamide 2f which is simple and easy to obtain is used as a reaction substrate and participates in the construction of the nitrogen-containing fused heterocycle as a traceless guiding group.
The chemical conversion in this example can be applied to fused ring-like materials, bioactive molecules.
Example 9- (4- (2,4-dichlorophenyl) -2-methyloxazol-5-yl) -10-methyl-10H-phenoxazine (1 i)
To a 15mL Schlenk reaction tube under an atmospheric air atmosphere were added N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d (45.8mg, 0.20mmol), 10-methyl-10H-phenoxazine 3H (59.2mg, 0.30mmol), trivalent iridium catalyst [ Cp. IrCl [ ] 2 ] 2 (2.5mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), carbonic acidSilver (82.5mg, 0.30mmol), 2,4,6-trimethylsodium benzoate (55.8mg, 0.30mmol), toluene (Tol, 1.0 mL) were reacted at a temperature of 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10: the product 3- (4- (2,4-dichlorophenyl) -2-methyloxazol-5-yl) -10-methyl-10H-phenoxazine (1 i) is obtained in 46% yield. The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000151
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 9 are shown in fig. 18 and 19 in this order. As can be seen from fig. 18: 1 H NMR(400MHz,CDCl 3 ) δ 7.51 (d, J =2.1hz, 1h), 7.41 (d, J =8.3hz, 1h), 7.32 (dd, J =2.1hz,8.3hz, 1h), 6.86-6.80 (m, 2H), 6.73-6.67 (m, 3H), 6.52 (dd, J =1.3hz,7.9hz, 1h), 6.42 (d, J =8.4hz, 1h), 3.04 (s, 3H), 2.55 (s, 3H), as can be seen from fig. 19: 13 C NMR(100MHz,CDCl 3 ) δ 159.5,145.5,135.0,134.9,132.8,130.7,130.0,129.1,128.2,127.5,126.9,125.3,123.9,123.6,123.3,121.4,121.0,116.3,113.9,111.6,111.3,14.0. The results of the nuclear magnetic hydrogen spectrum and the carbon spectrum show that the product obtained in example 9 is 3- (4- (2,4-dichlorophenyl) -2-methyloxazol-5-yl) -10-methyl-10H-phenoxazine (1 i).
This example is carried out by reacting a trivalent iridium catalyst [ CpIrCl ] in an inert solvent toluene 2 ] 2 Under the promotion of the silver carbonate, the multi-dehydrogenation 1,1 double functionalization of the olefin is realized. The method has high-efficiency atom economy and step economy, takes the electron-rich aromatic heterocyclic nucleophile 10-methyl-10H-phenoxazine 3H rich in nature as a raw material, has wide substrate application range, and takes N- (1- (2,4-dichlorophenyl) ethenyl) acetamide 2d which is simple and easy to obtain as a reaction substrate and simultaneously takes part in the construction of the polysubstituted oxazole compound as a traceless guide group.
The chemical conversion in the embodiment uses a synthetic material intermediate phenoxazine as a raw material, and can be applied to the fields of organic photoelectric materials and the like.
Example 10- (4- (2,4-dichlorophenyl) -2-methyloxazol-5-yl) -N, N-diphenylaniline (1 j)
To a 15mL Schlenk reaction tube were added N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d (45.8mg, 0.20mmol), triphenylamine 3c (73.6mg, 0.30mmol), and a trivalent iridium catalyst [ Cp. IrCl ] in this order under an atmospheric air atmosphere 2 ] 2 (2.5mg, 0.004mmol), silver trifluoromethanesulfonimide (3.9mg, 0.01mmol), silver oxide (69.5mg, 0.30mmol), pivalic acid (30.6 mg, 0.30mmol), ethylene glycol dimethyl ether (DME, 1.0 mL) at 140 ℃ for 12 hours. And (3) carrying out chromatographic separation on the crude product by using a prepared silica gel plate, wherein the volume ratio of the selected developing agent or eluent to the petroleum ether to the ethyl acetate is 10: the product 4- (4- (2,4-dichlorophenyl) -2-methyloxazol-5-yl) -N, N-diphenylaniline (1 j) is obtained in 53% yield. The chemical reaction equation for this example is as follows:
Figure BDA0003769870300000161
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the compound prepared in example 10 are shown in fig. 20 and 21 in this order. As can be seen from fig. 20: 1 H NMR(400MHz,CDCl 3 ) δ 7.48 (d, J =2.1hz, 1h), 7.40 (d, J =8.3hz, 1h), 7.30-7.27 (m, 2H), 7.23-7.16 (m, 5H), 7.10-7.06 (m, 4H), 7.06-7.02 (m, 2H), 6.96 (d, J =8.8hz, 2h), 2.55 (s, 3H). As can be seen from fig. 21: 13 C NMR(100MHz,CDCl 3 ) δ 159.6,147.9,147.2,147.0,135.0,135.0,132.8,131.0,130.2,130.2,129.9,129.4,129.1,128.5,128.3,127.6,127.4,126.9,126.4,125.9,125.3,125.0,123.6,122.3,121.6,114.3,108.5,77.4,77.1,76.8,14.1. The results of the nuclear magnetic hydrogen spectrum and the carbon spectrum showed that the product obtained in example 10 was 4- (4- (2,4-dichlorophenyl) -2-methyloxazol-5-yl) -N, N-diphenylaniline (1 j).
This example is carried out by reacting a trivalent iridium catalyst [ CpIrCl ] in the presence of an inert solvent ethylene glycol dimethyl ether 2 ] 2 Under the promotion of the silver oxide, the multi-time dehydrogenation 1,1 double functionalization of olefin is realized. Such a methodThe method has high-efficiency atom economy and step economy, avoids aryl halide and aryl metal reagent as active sites to participate in reaction in the whole conversion, uses the electron-rich aromatic heterocyclic nucleophilic reagent triphenylamine 3j which is rich in nature as a raw material, has wide substrate application range, and takes the simple and easily obtained N- (1- (2,4-dichlorophenyl) vinyl) acetamide 2d as a reaction substrate and simultaneously as a traceless guide group to participate in the construction of the polysubstituted oxazole compound.
2. Application example
In the material characterization of 1j molecule, we found that it exhibits good performance of hole transport material, specifically, as can be seen from fig. 22, the Highest Occupied Molecular Orbital (HOMO) of 1j is delocalized in the whole molecule, which is favorable for charge transport, the Lowest Unoccupied Molecular Orbital (LUMO) is mainly located on the core skeleton, the overlap of HOMO and LUMO orbitals is favorable for hole extraction, and E of 1j is calculated from density functional theory (DFT for short) to obtain E of 1j HOMO Or E LUMO The value is-5.05/-1.33 eV, which meets the requirements of hole transport materials of perovskite solar cells.
When the 1j molecule is characterized by ultraviolet absorption and fluorescence emission, it can be seen from FIG. 23 that the maximum ultraviolet absorption wavelength is 341nm and the maximum fluorescence emission wavelength is 461nm, and E is estimated 0-0 Is 3.12eV; as can be understood from FIG. 24, the actual value of HOMO is-5.09 eV; therefore, the actual LUMO value is-1.97 eV, which is consistent with the value calculated by DFT, and the feasibility of the 1j molecule as the perovskite solar cell can be further verified by the above characteristics.
Figure BDA0003769870300000171
Note: a) Is a CV measurement. Taking ferrocene as an external standard, and obtaining an HOMO actual value from an oxidation initial potential; b) Is E LUMO Calculation = E HOMO +E 0-0 . Wherein E 0-0 Estimating from the intersection of the normalized ultraviolet absorption and fluorescence emission spectra; c) An estimate is calculated for the DFT.
In the above step, the polysubstituted oxazole compounds are obtained through multiple cross dehydrogenation coupling reactions of trivalent metal catalyzed N- (1-aryl vinyl) amide and four different electron-rich aromatic rings respectively; specifically, under the condition of inert solvent, under the co-promotion of trivalent metal catalyst and silver salt oxidant, the multiple dehydrogenation 1,1-double functionalization of olefin is realized. The method has atom and step economy, and directly uses common and easily-obtained nucleophilic reagent as a raw material, thereby meeting the development requirement of sustainable chemistry; the substrate for conversion has wide application range, and N- (1-aryl vinyl) amide which is simple and easy to obtain is used as a reaction substrate and simultaneously used as a traceless guide group to participate in the construction of the nitrogen-containing fused heterocycle; the obtained heterocyclic substrate is also applied to a perovskite solar cell hole transport layer.
In summary, the patent application relates to a multiple dehydrogenation 1,1-bifunctional reaction of N- (1-aryl vinyl) amide and nucleophilic reagents of thiophene, indole, aromatic hydrocarbon and the like catalyzed by a trivalent metal catalyst, so as to realize the construction of a nitrogen-containing fused heterocycle and further develop the application of the nitrogen-containing fused heterocycle in the field of photoelectric materials. Specifically, under the condition of inert solvent, under the co-promotion of trivalent metal catalyst and silver salt oxidant, the multiple dehydrogenation 1,1 double functionalization of olefin is realized. The method has high-efficiency atom economy and step economy, and uses nucleophilic reagent with rich content in nature as raw material, the substrate has wide application range, and N- (1-aryl vinyl) amide which is simple and easy to obtain is used as a reaction substrate and simultaneously used as a traceless guide group to participate in the construction of the nitrogen-containing fused heterocycle; the obtained heterocyclic substrate can be further applied to a hole transport layer of a perovskite solar cell. In addition, the 1,1-dehydrogenation bifunctional reaction of olefin has more potential advantages, and the method can provide a basis for further multi-functionalization of subsequent products, so that the complexity of molecules is greatly enriched, the multi-connected aromatic heterocyclic skeleton can be quickly constructed, the use of a halogenating reagent and a metal reagent can be reduced, and a new thought is provided for green and efficient construction of functional drug molecules and material molecules.
The dehydrogenation 1,1-bifunctional reaction of olefin disclosed by the patent application has the advantages of good functional group compatibility and wide substrate applicability, can be used for quickly constructing a multi-connected aromatic heterocyclic skeleton, can be used for reducing the use of a halogenating reagent and a metal reagent, and provides a new idea for green and efficient construction of functional drug molecules and material molecules.
In the description herein, references to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present patent application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While several embodiments of the present patent application have been shown and described, it will be appreciated by those of ordinary skill in the art that: numerous changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the present patent application, the scope of which is defined by the claims and their equivalents.

Claims (10)

1. A method for preparing a polysubstituted oxazole compound, characterized in that: in an inert solvent, under the action of a trivalent metal catalyst, reacting an N- (1-aryl vinyl) amide compound (formula II) with an aromatic heterocyclic compound (formula III) to obtain a polysubstituted oxazole compound (formula I), wherein the reaction formula is as follows:
Figure FDA0003769870290000011
wherein Ar is an ortho-substituted, meta-substituted or para-substituted benzene ring compound or a condensed ring compound; r is saturated alkane; het is thiophene compound, polysubstituted indole compound, electron-rich condensed ring aromatic compound and benzene ring compound.
2. A method for preparing a polysubstituted oxazole compound according to claim 1 characterized in that: the inert solvent is any one or more of toluene, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, N' -dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, 1,2-dichloroethane, ethanol and water.
3. The process for producing a polysubstituted oxazole compound according to claim 1 characterized in that: the trivalent metal catalyst is: any one of pentamethylcyclopentadienylrhodium chloride dimer, pentamethylcyclopentadienyliridium chloride dimer, or a combination thereof.
4. The process for producing a polysubstituted oxazole compound according to claim 1 characterized in that: the halide ion capturing agent is any one or the combination of silver hexafluoroantimonate and bis (trifluoromethyl) sulfonyl imide silver.
5. The process for producing a polysubstituted oxazole compound according to claim 1 characterized in that: the oxidant is any one or more of silver acetate, silver carbonate, silver oxide and copper acetate.
6. The process for producing a polysubstituted oxazole compound according to claim 1 characterized in that: the additive is any one of pivalic acid, 2,4,6-trimethyl sodium benzoate or the combination thereof.
7. A process for preparing a polysubstituted oxazole compound according to claim 3 characterized in that: the trivalent metal catalyst is used in an amount of 2mol% based on the amount of the N- (1-arylvinyl) amide compound (formula II).
8. The process for producing a polysubstituted oxazole compound according to claim 1 characterized in that: the reaction is carried out at 120-140 ℃; the reaction is carried out for 12 to 24 hours.
9. The process for producing a polysubstituted oxazole compound according to claim 1 characterized in that: the method comprises the following specific steps:
s1: in a reactor, in the air, 2.5mg of pentamethylcyclopentadienyliridium dichloride dimer, 3.9mg of silver trifluoromethanesulfonimide, 69.5mg of silver oxide, 30.6mg of pivalic acid, 1.0mL of toluene as a solvent, 35.2mg of N- (1- (2,4-dichlorophenyl) vinyl) propionamide, and 49.8mg of 2,2' -bithiophene were sequentially added;
s2: reacting the reaction solution at 140 ℃ for 12 hours;
s3: and after the reaction is finished, separating the mixture by using a column chromatography separation technology to obtain the target compound.
10. A solar cell, characterized by: the solar cell is a perovskite solar cell, and the hole transport material in the perovskite solar cell adopts the polysubstituted oxazole compound prepared by the preparation method as claimed in claim 1.
CN202210898185.7A 2022-07-28 2022-07-28 Preparation method and application of polysubstituted oxazole compound Pending CN115368351A (en)

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