Naphthothiophene compound, preparation method and application

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a naphthothiophene compound, a preparation method and application. The naphthothiophene compound is prepared from naphthalene mercaptan and alpha-bromocinnamyl aldehyde as raw materials in the absence of a photocatalyst and an additive at room temperature in an air atmosphere. Compared with a previously reported preparation method, the method has the advantages of being green, environmentally friendly, safe, efficient and energy-saving, the substrate application range is wide, the product functional group compatibility is good, transition metal, a photocatalyst and an external oxidizing agent are not needed, and the organic photoelectric material can be simply and conveniently synthesized through the method.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a naphthothiophene compound, its preparation method, and its application. Background Technology

[0002] Naphthothiophene fused-ring compounds (mainly including naphtho[2,1-) b Thiophene, naphtho[1,2- b Fused structures such as thiophene have attracted much attention due to their unique structure and properties, and have broad application prospects in the field of organic optoelectronic materials. However, traditional synthesis methods for their frameworks still face many challenges. Most existing strategies rely on transition metal catalysis and heating conditions, and usually require stoichiometric oxidants to complete key steps, which not only does not conform to the concept of green chemistry, but also limits their application scope.

[0003] In recent years, with the development of visible light photocatalysis technology, photoredox catalysis has been widely used in the construction of thiophene rings. However, the synthesis of naphthothiophene compounds via the electron donor-acceptor (EDA) complex pathway under visible light induction has not yet been reported in the literature.

[0004] Therefore, developing a green method for the direct cyclization of naphthalenethiophene compounds from naphthalenethiol and α-bromocinnamaldehyde in a mild and neutral system under visible light conditions without the need for external photocatalysts and metal catalysts has become a pressing technical challenge in this field. Summary of the Invention

[0005] In view of this, in order to solve this problem, the present invention discloses a naphthothiophene compound, its preparation method and application.

[0006] It should be noted that this invention provides a simple, green, and easily scalable synthetic method. Using naphthalenethiol and α-bromocinnamaldehyde as raw materials, a series of naphthothiophene compounds can be synthesized under visible light irradiation and at room temperature. This invention is simple to operate, operates under mild conditions, requires no transition metal catalysts, external photosensitizers, or other additives, and can be carried out smoothly in air, demonstrating good atom economy and procedural simplicity. Using this method, structurally diverse naphthothiophene derivatives can be rapidly constructed, leading to the synthesis of organic optoelectronic materials.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] The first technical objective of this invention is to provide a naphthothiophene compound, the structure of which is as follows: ; Wherein, R1 is hydrogen, alkyl, fluorine, chlorine, bromine, or trifluoromethyl; R2 is hydrogen, p-bromosubstituted phenyl, p-nitrosubstituted phenyl, m-bromosubstituted phenyl, or 2,3-dichlorosubstituted phenyl.

[0009] The second technical objective of this invention is to provide a method for preparing the naphthothiophene compounds as described above, the synthetic route of which is as follows: ; R1 and R2 are defined as previously given.

[0010] Specifically, using naphthalenethiol as a raw material and cesium carbonate as a base, it reacts with α-bromocinnamaldehyde under visible light irradiation to generate naphthothiophene compounds.

[0011] Optionally, the molar ratio of naphthalenethiol, α-bromocinnamaldehyde, and cesium carbonate is 1:2:1 to 2:1:1.

[0012] Optionally, the visible light irradiation is selected from one or more light sources selected from 5000-5500 K white light, 395-400 nm violet light, and 460-465 nm blue light, and the power of the irradiation light source is 6-10 W, specifically one of 6 W, 8 W, and 10 W.

[0013] Optionally, the reaction time is 24-30 hours, the reaction temperature is room temperature, and the reaction atmosphere is air.

[0014] Optionally, the reaction solvent is one or more of ethyl acetate and methanol.

[0015] Furthermore, in the method described in this invention, after the reaction is completed, the product is separated and characterized using conventional separation and purification methods to obtain the corresponding product.

[0016] The third technical objective of this invention is to provide an application of the naphthothiophene compounds described above in organic optoelectronic materials.

[0017] Furthermore, the aforementioned naphthothiophene compounds can be used as organic optoelectronic materials.

[0018] It should be noted that naphthothiophene fused-ring compounds (mainly including naphtho[2,1-) b Thiophene, naphtho[1,2- bThiophene and similar structures have broad application prospects in the field of organic optoelectronic materials. These compounds are commonly used as fluorescent dyes, molecular probes, and optoelectronic functional materials, exhibiting excellent photophysical properties and charge transport characteristics. Based on this, the naphthothiophene compounds synthesized / prepared by the method of this invention have application value in the field of organic optoelectronic materials due to the designability of their structures. By introducing specific functional groups, their optoelectronic properties can be precisely controlled. For example, the introduction of an aldehyde group (-CHO) can act as an electron acceptor unit, thereby effectively enhancing the charge transport capability of the material. This technical feature is disclosed in Chinese patent CN117285543A, "An aldehyde monomer and its preparation method and its application in the preparation of two-dimensional covalent organic framework materials." (The last sentence appears to be a separate, unrelated paragraph.) Energy & Environmental Science As mentioned in 2022, 15: 320-333, the introduction of halogen atoms (such as fluorine and chlorine) can effectively improve photovoltaic performance.

[0019] Compared with the prior art, the beneficial effects of the present invention are: This invention prepares naphthothiophene compounds from naphthalenethiol and α-bromocinnamaldehyde at room temperature and in air atmosphere without the need for photocatalysts or additives. Compared with existing synthetic methods, this method has significant advantages such as being green and environmentally friendly, safe to operate, and low in energy consumption. It has broad substrate applicability, the reaction system does not depend on transition metals, photocatalysts, or external oxidants, the conditions are mild, and the post-processing is simple, making it suitable for large-scale preparation. Using this method, diverse naphthothiophene derivatives with excellent photoelectric properties can be constructed, leading to the synthesis of organic optoelectronic materials. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0021] Figure 1These are the hydrogen and carbon spectra of compound 7 of this invention.

[0022] Figure 2 These are the proton, carbon, and fluorine spectra of compound 11 of the present invention.

[0023] Figure 3 These are the proton and carbon spectra of compound 29 of this invention.

[0024] Figure 4 These are the proton and carbon spectra of compound 34 of the present invention.

[0025] Figure 5 These are the proton and carbon spectra of compound 53 of this invention. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0028] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0029] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0030] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0031] This invention discloses a method for preparing naphthothiophene compounds.

[0032] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0033] It should be noted that the reactants and solvents described below are all conventional substances, and the CAS numbers for α-bromocinnamaldehyde, 1-naphthiol, and 2-naphthiol are 5443-49-2, 529-36-2, and 91-60-1, respectively.

[0034] Example 1

[0035] In a 10 mL quartz tube, add 56 μL (0.40 mmol) of 1-naphthiol 1, 42.2 mg (0.20 mmol) of α-bromocinnamaldehyde 6, 65.2 mg (0.2 mmol) of cesium carbonate, and 2 mL of ethyl acetate solution sequentially; incubate the reaction tube at room temperature (25°C). o C. Under irradiation with 8 W blue light (455-460 nm), the reaction was stirred for 24 h. After the reaction was completed, the organic phase was extracted with 50 mL of saturated brine, collected, and then the volatile components were removed under reduced pressure. The product was then separated by thin-layer chromatography (elution buffer: petroleum ether (60-90ºC) / ethyl acetate, v / v = 100:1) to obtain the target product 7 (36.5 mg, yield 63%), which is a pale yellow oily liquid.

[0036] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0037] Example 2

[0038] The reaction steps and operations are the same as in Example 1, except that the raw materials added to the reaction system are ( Z 2-Bromo-3-(3-(trifluoromethyl)phenyl)propenal 8 (1454837-49-0, 55.8 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 9 (15.5 mg, yield 22%) was obtained as a yellow oily liquid.

[0039] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0040] Example 3

[0041] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z10 (1464895-88-2, 45.8 mg, 0.20 mmol) of 2-bromo-3-(4-fluorophenyl)propenal was post-processed to give target product 11 (38.0 mg, 62% yield) as a yellow solid.

[0042] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0043] Example 4

[0044] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z )-2-bromo-3-(4-bromophenyl)propenal 12 (1385030-51-2, 58.0 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 13 (42.84 mg, yield 58%) was obtained as a yellow solid.

[0045] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0046] Example 5

[0047] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z )-2-bromo-3-(4-chlorophenyl)propenal 14 (900506-05-0, 49.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 15 (14.4 mg, yield 22%) was obtained as a yellow solid.

[0048] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0049] Example 6

[0050] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z )-2-bromo-3-(3-chlorophenyl)propenal 16 (1352755-79-3, 49.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 17 (27.5 mg, yield 43%) was obtained as a yellow oily liquid.

[0051] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0052] Example 7

[0053] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z )-2-bromo-3-(2-chlorophenyl)propenal 18 (181352755-80-6, 49.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 19 (45.5 mg, 70% yield) was obtained as a yellow solid.

[0054] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0055] Example 8

[0056] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 2-Bromo-3-(p-Tolyl)propenal 20 (1597410-67-7, 45.0 mg, 0.20 mmol) was added, the reaction was stopped, and the target product 21 (47.6 mg, 79% yield) was obtained as a yellow solid after post-treatment.

[0057] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0058] Example 9

[0059] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 2-Bromo-3-(4-methoxyphenyl)propenal 22 (900506-04-9, 48.2 mg, 0.20 mmol) was used to stop the reaction, and the target product 23 (45.8 mg, 72% yield) was obtained after post-treatment.

[0060] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0061] Example 10

[0062] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 2-Bromo-3-(2-methoxyphenyl)propenal 24 (1464895-94-0, 48.2 mg, 0.20 mmol) was added, the reaction was stopped, and the target product 25 (40.1 mg, 63% yield) was obtained after post-treatment.

[0063] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0064] Example 11

[0065] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 26 (50793-44-78, 64.4 mg, 0.20 mmol)-2-bromo-3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one was reacted with 5-bromo-3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one (50793-44-78, 64.4 mg, 0.20 mmol) to stop the reaction and post-process to give the target product 27 (9.8 mg, 12% yield) as a yellow oily liquid.

[0066] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0067] Example 12

[0068] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 28-Bromo-1-(3-Bromophenyl)-3-phenylprop-2-en-1-one (3081373-02-3, 73.2 mg, 0.20 mmol) was used to stop the reaction, and the target product 29 (54.3 mg, 61% yield) was obtained after post-treatment.

[0069] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0070] Example 13

[0071] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 30 (66.6 mg, 0.20 mmol) of 2-bromo-1-(4-bromophenyl)-3-(3-chlorophenyl)prop-2-en-1-one was added, the reaction was stopped, and the target product 31 (44.5 mg, 45% yield) was obtained after post-treatment.

[0072] At 0°C, a solution of liquid bromine (1.0 mL, 20 mmol, 1.0 equivalent) in dichloromethane (1.0 mL) was slowly added dropwise to a suspension of α,β-unsaturated ketone (20 mmol, 1.0 equivalent) in dichloromethane (30 mL). After the addition was complete, the mixture was stirred at 35°C for 1 hour. Subsequently, triethylamine (4.18 mL, 30 mmol, 1.5 equivalent) was slowly added dropwise to the reaction mixture, and stirring was continued at 35°C overnight. After the reaction was complete, the reaction mixture was diluted with water (30 mL), and the aqueous phase was extracted with dichloromethane (3 × 40 mL). The organic phases were combined and dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 300 / 1–100 / 1, v / v) to obtain the target product (…). Z )-2-bromo-1-(4-bromophenyl)-3-(3-chlorophenyl)prop-2-en-1-one.

[0073] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0074] Example 14

[0075] The reaction steps and operations are the same as in Example 1, except that ( ) are added to the reaction system. Z 32 (24374-10-5, 66.4 mg, 0.20 mmol)-2-bromo-1-(4-nitrophenyl)-3-phenylprop-2-en-1-one was reacted with 2-bromo-1-(4-nitrophenyl)-3-phenylprop-2-en-1-one (24374-10-5, 66.4 mg, 0.20 mmol) to stop the reaction and post-treatment to give the target product 33 (17.1 mg, 21% yield) as a yellow solid.

[0076] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0077] Example 15

[0078] In a 10 mL quartz tube, 2-naphthylthiol 4 (64.1 mg, 0.40 mmol), α-bromocinnamaldehyde 6 (42.2 mg, 0.20 mmol), cesium carbonate (65.2 mg, 0.2 mmol), and 2 mL of ethyl acetate solution were added sequentially; the reaction tube was then incubated at room temperature (25°C). o C. Under irradiation with 8 W blue light (455-460 nm), the reaction was stirred for 24 h. After the reaction was completed, the organic phase was extracted with 50 mL of saturated brine, collected, and then the volatile components were removed under reduced pressure. The organic phase was then separated by thin-layer chromatography (elution buffer: petroleum ether (60-90ºC) / ethyl acetate, v / v = 100:1) to give the target product 34 (46.3 mg, yield 80%) as a yellow solid.

[0079] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0080] Example 16

[0081] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z 2-Bromo-3-(p-Tolyl)propenal 20 (1597410-67-7, 45.0 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 35 (30.7 mg, yield 51%) was obtained as a yellow oily liquid.

[0082] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0083] Example 17

[0084] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z 2-Bromo-3-(4-methoxyphenyl)propenal 22 (900506-04-9, 48.2 mg, 0.20 mmol) was used to stop the reaction, and the target product 36 (39.9 mg, 63% yield) was obtained after post-treatment.

[0085] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0086] Example 18

[0087] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z 2-Bromo-3-(2-methoxyphenyl)propenal 24 (1464895-94-0, 48.2 mg, 0.20 mmol) was added, the reaction was stopped, and the target product 37 (36.6 mg, 57% yield) was obtained after post-treatment.

[0088] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0089] Example 19

[0090] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z)-2-bromo-3-(2-chlorophenyl)propenal 18 (181352755-80-6, 49.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 38 (35.5 mg, yield 55%) was obtained as a yellow oily liquid.

[0091] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0092] Example 20

[0093] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z )-2-bromo-3-(3-chlorophenyl)propenal 16 (1352755-79-3, 49.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 39 (53.0 mg, yield 82%) was obtained as a pale yellow solid.

[0094] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0095] Example 21

[0096] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z )-2-bromo-3-(4-chlorophenyl)propenal 14 (900506-05-0, 49.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 40 (43.1 mg, yield 66%) was obtained as a yellow oily liquid.

[0097] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0098] Example 22

[0099] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z 10 1-2-bromo-3-(4-fluorophenyl)propenal (1464895-88-2, 45.8 mg, 0.20 mmol) was added, the reaction was stopped, and the target product 41 (43.8 mg, 71% yield) was obtained as a yellow solid after post-treatment.

[0100] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0101] Example 23

[0102] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z )-2-bromo-3-(4-bromophenyl)propenal 12 (1385030-51-2, 58.0 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 42 (63.1 mg, yield 86%) was obtained as a pale yellow solid.

[0103] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0104] Example 24

[0105] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z )-2-bromo-3-(4-(trifluoromethyl)phenyl)propenal 43 (1464895-89-3, 64.1 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 44 (61.3 mg, yield 86%) was obtained as a brown solid.

[0106] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0107] Example 25

[0108] The reaction steps and operations are the same as in Example 15, except that the raw materials added to the reaction system are ( Z )-2-bromo-3-(3-(trifluoromethyl)phenyl)propenal 8 (1454837-49-0, 55.8 mg, 0.20 mmol), the reaction was stopped, and after post-treatment, the target product 45 (45.3 mg, yield 63%) was obtained as a yellow solid.

[0109] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0110] Example 26

[0111] The reaction steps and operations were the same as in Example 15, except that (Z)-2-bromo-3-(3-chlorophenyl)-1-phenylprop-2-en-1-one 46 (3027625-24-4, 64.3 mg, 0.20 mmol) was added to the reaction system, the reaction was stopped, and the target product 47 (42.3 mg, yield 54%) was obtained after post-treatment.

[0112] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0113] Example 27

[0114] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z 28 (3081373-02-3, 73.2 mg, 0.20 mmol)-2-bromo-1-(3-bromophenyl)-3-phenylprop-2-en-1-one was added, the reaction was stopped, and the target product 48 (63.1 mg, 71% yield) was obtained after post-treatment.

[0115] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0116] Example 28

[0117] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z 32 (24374-10-5, 66.4 mg, 0.20 mmol)-2-bromo-1-(4-nitrophenyl)-3-phenylprop-2-en-1-one was taken, the reaction was stopped, and the target product 49 (19.2 mg, 23% yield) was obtained after post-treatment.

[0118] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0119] Example 29

[0120] The reaction steps and operations are the same as in Example 15, except that the following difference is found in the reaction system: (Z 50 (71.2 mg, 0.20 mmol) of 2-bromo-1-(3,4-dichlorophenyl)-3-phenylprop-2-en-1-one was added, the reaction was stopped, and the target product 51 (68.5 mg, 79% yield) was obtained as a yellow solid after post-treatment.

[0121] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0122] Example 30

[0123] The reaction steps and operations are the same as in Example 15, except that ( ) are added to the reaction system. Z52 (87.0 mg, 0.20 mmol) of 2-bromo-1-(4-bromophenyl)-3-(3,4-dichlorophenyl)prop-2-en-1-one was added, the reaction was stopped, and the target product 53 (89.8 mg, 88% yield) was obtained after post-treatment.

[0124] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0125] The characterization data of the above compounds are as follows: 3-Phenynaphtho[1,2-] b Thiophene-2-carboxaldehyde (7): TLC (petroleum ether / ethyl acetate = 30:1, v / v), Rf = 0.46; yellow oily liquid (88.3 mg, 87%). 1 H NMR (600 MHz, CDCl3) δ 9.96 (s, 1H), 8.26 - 8.22 (m, 1H), 7.93 (dd, J = 3.8, 3.0 Hz, 1H), 7.73 (d, J = 8.8 Hz, 1H), 7.68 (d, J = 8.8 Hz, 1H), 7.66 - 7.61 (m, 2H), 7.60 - 7.54 (m, 5H). 13 C NMR(150MHz, CDCl3) δ 185.6, 148.6, 142.0, 138.1, 137.0, 132.7, 132.7, 130.7, 129.2,129.1, 129.0, 128.7, 128.1, 127.4, 126.7, 124.6, 122.0HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 12 OSNa + 311.0501; Found 311.0501. 3-(4-chlorophenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (9): TLC (petroleum ether / ethyl acetate = 10:1, v / v), Rf = 0.28; yellow solid (14.4 mg, 22%); mp 164.1 - 164.3 o C. 1H NMR (600 MHz, CDCl3) δ 9.94 (s, 1H), 8.26 - 8.23 ​​(m, 1H), 7.96 - 7.93 (m, 1H), 7.76 (d, J =8.8 Hz, 1H), 7.68 - 7.62 (m, 3H), 7.58 (dt, J = 8.5, 2.3 Hz), 7.52 (dt, J = 8.5, 2.3 Hz). 13 C NMR(150 MHz, CDCl3) δ 185.1, 147.0, 142.1, 138.3, 136.8, 135.6,132.7, 131.9 131.1, 129.3, 129.1, 128.7, 128.2, 127.6, 127.0, 124.6,121.7.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa + 345.0111; Found 345.0112. 3-(4-fluorophenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (11): TLC (petroleum ether / ethyl acetate = 30:1, v / v), Rf = 0.29; yellow solid (38.0 mg, 62%); mp 139.8–140.0 o C. 1 H NMR (600 MHz, CDCl3) δ 9.93 (s, 1H), 8.25 - 8.21 (m, 1H), 7.94 - 7.91 (m, 1H), 7.74 (d, J =8.8 Hz, 1H), 7.66 - 7.61 (m, 3H), 7.57 - 7.52 (m, 2H), 7.30 - 7.25 (m, 2H). 13 CNMR (150 MHz, CDCl3) δ 185.2, 164.2, 162.5, 147.3, 142.0, 138.3, 136.9, 132.7,132.4 (d, J= 8.6 Hz), 129.1, 128.7 - 128.6 (m), 128.2, 127.6, 126.9, 124.6,121.7, 116.2 (d, J = 21.5 Hz). 19 F NMR(565 MHz, CDCl3) δ -33.88 (s).HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 FOSNa + 329.0407; Found 329.0407. 3-(4-bromophenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (13): TLC (petroleum ether / ethyl acetate = 30:1, v / v), Rf = 0.33; yellow solid (42.8 mg, 58%); mp 179.7–179.9 o C. 1 H NMR (600 MHz, CDCl3) δ 9.93 (s, 1H), 8.25 - 8.22 (m, 1H), 7.95 - 7.92 (m, 1H), 7.76 (s, 1H), 7.73 (dt, J =8.3, 2.5 Hz), 7.67-7.62 (m, 3H), 7.44 (dt, J =8.4, 2.3 Hz, 2H). 13 C NMR(150 MHz, CDCl3) δ 185.0, 147.0, 142.1, 138.3, 136.7, 132.7, 132.3,132.2, 131.6, 129.1, 128.7, 128.2, 127.6, 127.0, 124.6, 123.8, 121.6.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 BrOSNa + 388.9606; Found 388.9605. 3-(4-chlorophenyl)naphtho[1,2- bThiophene-2-carboxaldehyde (15): TLC (petroleum ether / ethyl acetate = 10:1, v / v), Rf = 0.28; yellow solid (14.4 mg, 22%); mp 164.1 - 164.3 o C. 1 H NMR (600 MHz, CDCl3) δ 9.94 (s, 1H), 8.26 - 8.23 ​​(m, 1H), 7.96 - 7.93 (m, 1H), 7.76 (d, J =8.8 Hz, 1H), 7.68 - 7.62 (m, 3H), 7.58 (dt, J = 8.5, 2.3 Hz), 7.52 (dt, J = 8.5, 2.3 Hz). 13 C NMR(150 MHz, CDCl3) δ 185.1, 147.0, 142.1, 138.3, 136.8, 135.6,132.7, 131.9 131.1, 129.3, 129.1, 128.7, 128.2, 127.6, 127.0, 124.6,121.7.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa + 345.0111; Found 345.0112. 1-(3-chlorophenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (17): TLC (petroleum ether / ethyl acetate = 30:1, v / v), Rf = 0.29; yellow oily liquid (27.5 mg, 43%). 1 H NMR (600 MHz, CDCl3) δ 9.95 (s,1H), 8.28 - 8.22 (m, 1H), 7.97 - 7.93 (m, 1H), 7.77 (d, J = 8.8 Hz, 1H), 7.69 -7.62 (m, 3H), 7.58 (d, J = 1.8 Hz, 1H), 7.56 - 7.51 (m, 2H), 7.46 (dt, J = 6.8, 1.7 Hz, 1H). 13C NMR(150 MHz, CDCl3) δ 185.0, 146.6, 142.1, 138.5, 136.7,135.1, 134.5, 132.7, 130.5, 130.3, 129.4, 129.2, 128.9, 128.7, 128.3, 127.6,127.1, 124.6, 121.7.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa + 311.0111;Found 311.0110. 3-(3-chlorophenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (19): TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.4; Yellow solid (45.5 mg, 70%); mp 140.5 - 141.0 o C. 1 H NMR (600 MHz, CDCl3) δ 9.83 (s, 1H), 8.26 - 8.25 (m, 1H), 7.94 - 7.92 (m, 1H), 7.73 (d, J =8.8 Hz, 1H), 7.66 - 7.62 (m, 3H), 7.51 - 7.46 (m, 3H), 7.43 (d, J = 8.8 Hz, 1H). 13 C NMR(150 MHz, CDCl3) δ 184.8, 145.1, 141.8, 138.6, 137.0, 134.4, 132.7,132.6, 131.8, 130.7, 130.4, 129.1, 128.8, 128.1, 127.5, 127.1, 126.8, 124.5,121.9.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa + 345.0111; Found 345.0110. 3-(p-Tolyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (21): TLC (petroleum ether / ethyl acetate = 30:1, v / v), Rf = 0.25; Yellow solid (47.6 mg, 79%); mp 171.4 - 171.5 o C. 1 H NMR (600 MHz, CDCl3) δ 9.96 (s, 1H), 8.25 - 8.22 (m, 1H), 7.94 - 7.90 (m, 1H), 7.71 (q, J =8.8 Hz, 2H), 7.65 - 7.60 (m, 2H), 7.46 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 7.8 Hz, 2H), 2.50 (s, 3H). 13 C NMR(150 MHz, CDCl3) δ 185.7, 148.8, 142.0, 139.3, 137.9,137.1, 132.7, 130.6, 129.7, 129.0, 128.7, 128.0, 127.4, 126.6, 124.6, 122.1,21.5.HRMS(ESI) m / z: [M+Na] + Calcd for C 20 H 14 OSNa + 325.0658; Found 325,0658. 3-(4-methoxyphenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (23): TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.18; Yellow solid (45.8 mg, 72%); mp 127.7–127.9 o C. 1 H NMR(600MHz, CDCl3) δ 9.96 (s, 1H), 8.25 - 8.21 (m, 1H), 7.94 - 7.90 (m, 1H), 7.72(q, J = 8.8 Hz, 2H), 7.65 - 7.60 (m, 2H), 7.50 (dt, J = 8.6, 2.9 Hz, 2H), 7.11(dt, J = 8.7, 2.8 Hz, 2H), 3.92 (s, 3H). 13C NMR(150 MHz, CDCl3) δ 185.7, 160.4,148.5, 142.0, 137.8, 137.1, 132.7 132.0, 129.0, 128.8, 128.0, 127.4, 126.6,124.9, 124.6, 122.1, 114.5, 55.6.HRMS(ESI) m / z: [M+Na] + Calcd for C 20 H 14 O2SNa + 341.0607; Found 341.0606. 3-(2-methoxyphenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (25): TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.29; Yellow oil (40.1 mg, 63%). 1 H NMR(400 MHz, CDCl3) δ 9.87(d, J = 0.7 Hz, 1H), 8.24 (d, J = 7.4 Hz, 1H), 7.92 (d, J = 8.1 Hz, 1H), 7.70 (d, J =8.8 Hz, 1H), 7.66 - 7.58 (m, 2H), 7.54 - 7.51 (m, 2 H), 7.40 (d, J = 7.4 Hz,1H), 7.18 - 7.09 (m, 2H), 3.77 (s, 3H). 13 C NMR(100 MHz, CDCl3) δ 185.8, 157.4,144.9, 141.6, 138.1, 137.4, 132.6, 132.5, 130.9, 128.9, 128.8, 127.8, 127.3,126.3, 124.5, 122.4, 121.4, 120.8, 111.5, 55.7.HRMS(ESI) m / z: [M+Na] + Calcdfor C 20 H 14 O2SNa + 341.0607; Found 341.0607. (3-(4-methoxyphenyl)naphtho[1,2- b ]Thiophen-2-yl)(phenyl)methyl ketone (27): TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.42; Yellow oily liquid (9.8 mg, 12%). 1 H NMR(600 MHz, CDCl3)δ 8.24 (dd, J = 7.8, 0.8 Hz, 1H), 7.95 - 7.93 (m, 1H), 7.75 (d, J = 8.8 Hz, 1H), 7.71 (d, J = 8.8 Hz, 1H), 7.65 - 7.59 (m, 4H), 7.36 - 7.33 (m, 1H), 7.25 - 7.23(m, 2H), 7.22 - 7.18 (m, 2H), 6.78 (dt, J = 8.7, 2.9 Hz, 2H), 3.77 (s, 3H). 13 CNMR(100 MHz, CDCl3) δ 191.4, 159.5, 143.0, 140.1, 138.0, 137.3, 132.3, 132.1,131.8, 129.8, 129.0, 128.7, 127.9, 127.3, 127.2, 127.0, 126.4, 124.3, 122.4,113.9, 55.4, 29.9.HRMS(ESI) m / z: [M+Na] + Calcd for C 26 H 18 O2SNa + 417.0920; Found 417.0920. (3-Bromophenyl)(3-Phenynaphtho[1,2-) b ]Thiophene-2-yl)methyl ketone (29):TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.43; Yellow solid (54.3 mg, 61%); mp 159.0 - 159.3 o C. 1 H NMR (600MHz, CDCl3) δ 8.25 (dd, J = 7.8, 0.8 Hz, 1H), 7.96 - 7.92 (m, 1H), 7.75 (d,J =8.8 Hz, 1H), 7.68 (d, J = 8.8 Hz, 1H), 7.66 - 7.60 (m, 3H), 7.54 (dt, J = 7.7,1.1 Hz, 1H), 7.41 - 7.39 (m, 1H), 7.30 - 7.25 (m, 4H), 7.24 - 7.21 (m, 1H),7.04 (t, J = 7.8 Hz, 1H). 13 C NMR(150 MHz, CDCl3) δ 189.8, 143.8, 140.5, 139.6,137.1, 136.8, 134.9, 134.4, 132.7, 132.2, 130.4, 129.5, 129.1, 128.6, 128.5,128.4, 127.9, 127.6, 127.4, 126.7, 124.4, 122.4, 122.0.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 15 BrOSNa + 464.9919; Found 464.9919. (4-Bromophenyl)(3-(3-Chlorophenyl)naphtho[1,2-] b Thiophene-2-yl)methyl ketone (31):TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.54; Yellow solid (34.0 mg, 35%); mp 201.6 - 201.8 o C. 1 HNMR(600 MHz, CDCl3) δ 8.25 - 8.22 (m, 1H), 7.98 - 7.94 (m, 1H), 7.78 (d, J =8.8 Hz, 1H), 7.68 - 7.64 (m, 2H), 7.63 (dd, J = 8.0, 2.3 Hz, 1H), 7.49 (dt, J =8.6, 2.3 Hz, 2H), 7.37 (dt, J= 8.6, 2.2 Hz, 2H), 7.38 - 7.36 (m, 2H), 7.29 -7.26 (m, 2H), 7.25 - 7.19 (m, 2H). 13 C NMR (150 MHz, CDCl3) δ 189.8, 141.7,140.4, 137.1, 136.8, 136.7, 136.2, 134.5, 132.2, 131.4, 130.9, 130.6, 129.8,129.1, 128.6, 128.5, 128.3, 127.7, 127.5, 127.5, 127.0, 124.3, 121.9.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 14 BrClOSNa + 498.9529; Found 498.9529. (4-Nitrophenyl)(3-Phenynaphtho[1,2-] b Thiophene-2-yl)methyl ketone (33):TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.32; Yellow solid (17.1 mg, 21%); mp: 142.3 - 142.8 o C. 1 H NMR (600 MHz, CDCl3) δ 8.35 (dt, J = 8.8, 2.2 Hz, 2H), 8.14 (dt, J = 8.8, 2.2 Hz 2H),7.96 - 7.94 (m, 1H), 7.85 (d, J = 15.7 Hz, 1H), 7.68 - 7.64 (m, 4H), 7.48 (d, J =15.7 Hz, 1H), 7.46 - 7.45 (m, 2H), 7.26 - 7.20 (m, 2H). 13C NMR(150 MHz, CDCl3)δ 189.2, 150.2, 147.0, 143.2, 134.4, 131.4, 130.7, 130.2, 129.6, 129.3,129.1, 129.0, 128.7 - 128.5 (m), 128.0, 127.5, 126.9, 124.5, 124.0, 123.0,122.4, 121.4.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 15 NO3SNa + 432.0665; Found 432.0666. 1-Phenynaphtho[2,1-] b Thiophene-1-carboxaldehyde (34):TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.53; Yellow solid (46.3 mg, 80%); mp: 135.0 - 135.7 o C. 1 H NMR (600 MHz, CDCl3) δ9.68 (s, 1H), 7.90 (d, J = 7.7 Hz, 1H), 7.88 (s, 2H), 7.61-7.55 (m, 3H), 7.53-7.43 (m, 4H), 7.26-7.22 (m, 1H). 13 C NMR (150 MHz, CDCl3) δ 185.6, 149.0, 142.4,139.6, 135.3, 133.8, 132.1, 130.9, 130.2, 130.1, 129.3, 129.2, 129.2, 127.0,125.9, 123.9, 121.1.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 12 OSNa + 311.0501; Found 311.0497. 3-(3-chlorophenyl)naphtho[1,2- b Thiophene-2-carboxaldehyde (35): TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.26; Yellow oily liquid (30.7 mg, 51%).1 H NMR (600 MHz, CDCl3) δ 9.69 (s,1H), 7.93 - 7.90 (m, 1H), 7.89 (s, 2H), 7.59 (d, J = 8.5 Hz, 1H), 7.49 - 7.45(m, 1H), 7.42 - 7.38 (m, 4H), 7.29 - 7.26 (m, 1H), 2.54 (s, 3H). 13 C NMR(150MHz, CDCl3) δ 185.9, 149.3, 142.4, 139.6, 139.1, 133.9, 132.2, 132.1, 131.0,130.2, 130.0, 129.8, 129.3, 126.9, 125.9, 124.0, 121.1, 21.6.HRMS(ESI) m / z:[M+Na] + Calcd for C 20 H 14 OSNa + 325.0658; Found 325.0656. 1-(4-methoxyphenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (36): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.30; Orange solid (39.9 mg, 63%). mp: 119.5 - 120.2 o C. 1 H NMR (600MHz, CDCl3) δ 9.71 (s, 1H), 7.91 (dd, J = 8.0, 0.7 Hz, 1H), 7.88 (s, 2H), 7.62(d, J = 8.5 Hz, 1H), 7.49 - 7.46 (m, 1H), 7.44 (dt, J = 8.6, 2.8 Hz, 2H), 7.29(m, 1H), 7.12 - 7.10 (dt, J = 8.6, 2.8 Hz, 2H), 3.96 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 185.9, 160.3, 148.9, 142.4, 139.7, 134.0, 132.1, 131.3, 131.0, 130.1, 129.3, 127.1, 127.0, 125.6, 123.9, 121.1, 114.6, 55.6.HRMS(ESI) m / z:[M+Na] + Calcd for C 19 H 12 OSNa + 341.0607; Found 341.0608. 2-(2-Methoxyphenyl)-3H-cyclopentano[a]naphthalene-1-carboxaldehyde (37): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.28; Yellow solid (36.5 mg, 57%); mp 134.1 - 134.2 o C. 1 H NMR (600MHz, CDCl3) δ 9.70 (s, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.89 (t, J = 9.1 Hz), 7.70 (dd, J = 8.9, 2.5 Hz, 1H), 7.57 (d, J = 8.5 Hz, 1H), 7.54 (d, J = 2.5 Hz, 1H), 7.49(t, J = 7.4 Hz, 1H), 7.35 - 7.31 (m, 1H), 7.01 (d, J = 8.9 Hz, 1H), 3.66 (s, 3H). 13 C NMR(151 MHz, CDCl3) δ 185.3, 157.0, 143.5, 142.4, 139.5, 134.3, 133.8,133.7, 132.0, 131.0, 130.1, 129.3, 127.2, 126.2, 126.0, 123.3, 121.2, 113.2,113.1, 56.1.HRMS(ESI) m / z: [M+Na] + Calcd for C 20 H 14 O2SNa+ 341.0607; Found 341.0605. 1-(2-chlorophenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (38): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.43; Yellow oily liquid (35.5 mg, 55%). 1 H NMR (400 MHz, CDCl3) δ 9.65 (s,1H), 7.93 (d, J = 10.3 Hz, 3H), 7.67 (d, J = 8.0 Hz, 1H), 7.58 (td, J = 6.5, 2.6Hz, 1H), 7.55 - 7.46 (m, 3H), 7.38 (d, J = 8.3 Hz, 1H), 7.30 (t, J = 7.7 Hz, 1H). 13 C NMR(100 MHz, CDCl3) δ 184.9, 145.2, 142.5, 139.5, 134.6, 134.4, 133.6,1312.0, 130.9, 130.8, 130.4, 130.3, 129.4, 127.5, 127.5, 126.0, 123.1121.1.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa + 345.0111; Found 345.0112. 1-(3-chlorophenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (39): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.51; Yellow oily liquid (53.0 mg, 82%). 1 H NMR (600 MHz, CDCl3) δ 9.69 (s,1H), 7.93 (dd, J = 8.3, 1.1 Hz, 1H), 7.89 (dd). J= 10.2, 9.1 Hz, 2H), 7.62-7.60(m, 1H), 7.56-7.53 (m, 2H), 7.51 - 7.48 (m, 2H), 7.43 (dt, J = 7.5, 1.3 Hz 1H),7.33-7.30 (m, 1H). 13 129.5, 128.3, 127.2,126.1, 123.7, 121.0.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa + 345.0111; Found 345.0111. 1-(4-chlorophenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (40): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.53; Yellow oily liquid (43.1 mg, 66%). 1 H NMR (600 MHz, CDCl3) δ 9.68 (s,1H), 7.95 - 7.92 (m, 1H), 7.91 (s, 2H), 7.59 (dt, J = 8.4, 2.4 Hz, 2H), 7.53 -7.51 (m, 1H), 7.49 (dt, J = 8.3, 2.3 Hz, 3H), 7.33 - 7.30 (m, 1H). 13 C NMR(100MHz, CDCl3) δ 185.2, 147.3, 142.5, 139.8, 135.5, 133.8, 133.6, 132.2 131.5,130.8, 130.4, 129.5, 129.5, 127.2, 126.1, 123.8, 121.1.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 ClOSNa +345.0111; Found 345.0112. 1-(4-fluorophenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (41): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.53; Yellow solid (43.8 mg, 71%); mp: 132.4 - 132.6 o C. 1 H NMR (600 MHz, CDCl3) δ 9.69 (s, 1H), 7.93 (dd, J = 8.2, 1.1 Hz, 1H), 7.91 (s, 2H), 7.53 -7.47 (m, 4H), 7.33 - 7.28 (m, 3H). 13 C NMR(150 MHz, CDCl3) δ 185.3, 164.2,162.5, 147.6, 142.5, 139.9, 133.8, 132.2, 131.9 (d, J = 7.9 Hz), 131.2 (d, J =3.9 Hz), 130.8, 130.4, 129.5, 127.1, 126.0, 123.7, 121.1, 116.5 (d, J = 19.5Hz). 19 F NMR(565 MHz, CDCl3) δ -33.93 (s).HRMS(ESI) m / z: [M+Na] + Calcd forC 19 H 11 FOSNa + 329.0407; Found 329.0408. 1-(4-bromophenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (42): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.53; Yellow oily liquid (63.1 mg, 86%). 1 H NMR (600 MHz, CDCl3) δ 9.67 (s,1H), 7.93 (d, J = 8.0 Hz, 1H), 7.92 - 7.88 (t, J = 10.1 Hz, 2H), 7.74 (dt,J = 8.3,2.3 Hz, 2H), 7.53 - 7.48 (m, 2H), 7.42 (dt, J = 8.3, 2.3 Hz, 2H), 7.32 (m, 1H). 13 C NMR(150 MHz, CDCl3) δ 185.1, 147.2, 142.5, 139.8, 134.3, 133.5, 132.4,132.1, 131.7, 130.7, 130.4, 129.5, 127.2, 126.1, 123.7, 123.6, 121.1.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 11 BrOSNa + 388.9606; Found 388.9605. 1-(4-(trifluoromethyl)phenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (44): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.40; Brown solid (61.3 mg, 86%); mp 140.3 - 140.5 o C. 1 H NMR (600 MHz, CDCl3) δ 9.66 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.93 (s, 1H), 7.91- 7.90 (m, 1H), 7.84 (s, 1H), 7.78 - 7.74 (m, 2H), 7.50 (t, J = 7.6 Hz, 1H), 7.37 (d, J = 8.5 Hz, 1H), 7.27 - 7.29 (m, 1H). 13 C NMR (150 MHz, CDCl3) δ 184.8,146.5, 142.6, 140.1, 136.3, 133.5, 132.2, 131.9, 131.7, 130.6, 130.5, 129.8,129.6, 127.3, 127.0 (q, J = 3.7 Hz), 126.1 (m), 123.5, 121.1. 19F NMR(565 MHz, CDCl3) δ 15.30.HRMS(ESI) m / z: [M+Na] + Calcd for C 20 H 11 F3OSNa + 379.0375; Found 379.0373. 1-(3-(trifluoromethyl)phenyl)naphtho[2,1- b Thiophene-2-carboxaldehyde (45): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.47; Yellow solid (45.3 mg, 63%). mp: 138.9 - 139.5 o C. 1 H NMR (600 MHz, CDCl3) δ 9.65 (s, 1H), 7.94 (d, J = 7.8 Hz, 1H), 7.92 (s, 2H), 7.90 -7.88 (m, 1H), 7.84 (s, 1H), 7.77 - 7.75 (m, 2H), 7.51 - 7.47 (m, 1H), 7.37(d, J = 8.5 Hz, 1H), 7.27 - 7.26 (m, 1H). 13 C NMR(150 MHz, CDCl3) δ 184.8, 146.5,142.6, 140.1, 136.3, 133.53 (d, J = 1.5 Hz), 132.2, 131.9, 131.7, 130.6, 130.5,129.8, 129.6, 127.2, 127.0 (q, J = 3.0 Hz), 126.21 - 126.0 (m), 124.8, 123.5,123.0, 121.1. 19 F NMR(565 MHz, CDCl3) δ -62.60 (s).HRMS(ESI) m / z: [M+Na] + Calcdfor C 20 H 11 F3OSNa + 379.0374; Found 379.0375. (1-(3-chlorophenyl)naphtho[2,1-) b]Thiophene-2-yl)(phenyl)methyl ketone (47): TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.26; Yellow solid (42.3 mg, 54%); mp 176.3–176.5 o C. 1 H NMR (600 MHz, CDCl3) δ 7.94 (d, J = 7.9 Hz, 1H), 7.88 (dd, J = 10.4, 8.9 Hz, 2H), 7.68 (d, J = 7.2 Hz, 2H), 7.54 (d, J = 8.6 Hz, 1H), 7.50 - 7.44 (m, 2H), 7.36 (s,1H), 7.34 - 7.26 (m, 6H). 13 C NMR(150 MHz, CDCl3) δ 191.0, 141.6, 140.3, 139.0,138.7, 137.8, 134.6, 133.3, 132.7, 132.3, 130.5, 130.4, 129.9, 129.5, 129.3,128.9, 128.5, 128.5, 128.1, 126.7, 125.8, 123.8, 120.5.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 15 ClOSNa + 421.0424; Found 421.0424. (3-Bromophenyl)(1-Phenynaphtho[2,1-) b ]Thiophene-2-yl)methyl ketone (48): TLC (petroleum ether / ethyl acetate = 10:1, v / v), R f = 0.45; Yellow solid (63.1 mg, 71%); mp: 141.6–142.6 o C. 1 H NMR (600MHz, CDCl3) δ 7.87 - 7.79 (m, 3H), 7.59 (s, 1H), 7.49 (dd, J = 8.2, 14.6 Hz,2H), 7.41 - 7.36 (m, 2H), 7.28 - 7.18 (m, 5H), 7.15 (t,J = 7.7 Hz, 1H), 7.04(t, J = 7.8 Hz, 1H). 13 C NMR(150 MHz, CDCl3)δ 190.2, 143.8, 140.6, 140.3, 137.3,136.8, 134.9, 133.5, 132.5, 132.3, 130.8, 130.3, 129.6, 129.2, 129.1, 128.7,128.5, 127.7, 126.6, 125.8, 123.9, 122.0, 120.6, 77.4, 77.0.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 15 BrOSNa + 464.9919; Found 464.9919. (4-Nitrophenyl)(1-Phenynaphtho[2,1-) b Thiophene-2-yl)methyl ketone (49):TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.20; Yellow oily liquid (19.2 mg, 23%). 1 H NMR (600 MHz, CDCl3) δ8.01 (dt, J = 8.8, 2.1 Hz, 2H), 7.93 - 7.93 (m, 1H), 7.90 (s, 2H), 7.62 (dt, J =8.8, 2.1 Hz, 2H), 7.51 (d, J = 8.6 Hz, 1H), 7.46 (m, 1H), 7.30 - 7.18 (m, 7H). 13 C NMR(150 MHz, CDCl3) δ 190.1, 149.1, 144.6, 144.1, 141.4, 137.4, 136.6,133.6, 132.3, 130.8, 130.4, 129.8, 129.7, 129.3, 128.8, 128.7, 126.8, 125.9,123.8, 123.0, 120.5.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 15 NO3SNa+ 432.0664;Found 432.0665. (3,4-Dichlorophenyl)(2-phenylnaphtho[2,1-) b Thiophene-1-yl)methyl ketone (51):TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.37; Yellow solid (68.5 mg, 79%); mp: 154.0 - 154.6 o C. 1 HNMR (600 MHz, CDCl3)δ 7.91 (m, 3H), 7.59 (dd, J = 9.6, 5.3 Hz, 2H), 7.48 - 7.43(m, 2H), 7.35 - 7.33 (m, 5H), 7.31 (d, J = 8.3 Hz, 1H), 7.24 - 7.21 (m, 1H). 13 CNMR (150 MHz, CDCl3)δ 189.3, 144.0, 140.8, 138.1, 137.2, 136.7, 136.5, 133.5,132.3, 132.3, 131.5, 130.8, 130.3, 130.1, 129.3, 128.7, 128.6, 128.2, 126.6,125.9, 123.9, 120.6.HRMS(ESI) m / z: [M+Na] + Calcd for C 19 H 12 OSNa + 455.0035; Found 455.0032. (4-Bromophenyl)(1-(3,4-dichlorophenyl)naphtho[2,1- b Thiophene-2-yl)methyl ketone (53):TLC (petroleum ether / ethyl acetate = 30:1, v / v), R f = 0.38; Yellow solid (89.8 mg, 88%); mp: 188.4–189.4 o C. 1 H NMR (600 MHz, CDCl3) δ 7.95 (d, J = 8.0 Hz, 1H), 7.89 (dd, J = 8.8, 13.6Hz, 2H), 7.56 (dd, J= 12.0, 8.5 Hz, 3H), 7.53 - 7.44 (m, 5H), 7.33 (t, J = 7.7Hz, 1H), 7.23 (dd, J = 8.1, 1.9 Hz, 1H). 13 C NMR(150 MHz, CDCl3) δ 188.4, 139.8,139.3, 136.3, 136.1, 135.9, 132.0, 131.9, 131.7, 131.2, 130.9, 130.4, 129.7,129.6, 129.2, 128.4, 128.3, 128.2, 126.7, 125.8, 124.9, 122.5, 119.3.HRMS(ESI) m / z: [M+Na] + Calcd for C 25 H 13 BrCl2OSNa + 532.9139; Found 532.9143. To further demonstrate the beneficial effects of the present invention and to better understand it, the technical features disclosed in the present invention are further illustrated by the following comparative examples, but these should not be construed as limiting the present invention. Other improvements made by those skilled in the art based on the above description of the invention, without inventive effort, are also considered to fall within the protection scope of the present invention.

[0126] Comparative Example 1 The reaction steps and operations were the same as in Example 15, except that the reaction was carried out without light. The reaction was stopped, and the target product 34 was not obtained after the same post-treatment as described above, indicating that the reaction cannot proceed without light.

[0127] Comparative Example 2 The reaction steps and operations were the same as in Example 15, except that the reaction time was 12 h. The reaction was stopped, and after post-processing, the target product 34 (37.7 mg, yield 65%) was obtained, indicating that reducing the reaction time was not conducive to the reaction proceeding.

[0128] Comparative Example 3 The reaction procedure and operation were the same as in Example 15, except that dimethyl sulfoxide was used as the solvent. The reaction was stopped, and after post-treatment, the target product 34 (21.4 mg, yield 37%) was obtained, indicating that using dimethyl sulfoxide as a solvent is not conducive to the reaction.

[0129] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A naphthothiophene compound, characterized in that, The structural formula of the naphthothiophene compound is as follows: ； Wherein, R1 is hydrogen, alkyl, fluorine, chlorine, bromine, or trifluoromethyl; R2 is hydrogen, p-bromosubstituted phenyl, p-nitrosubstituted phenyl, m-bromosubstituted phenyl, or 2,3-dichlorosubstituted phenyl.

2. A method for preparing the naphthothiophene compound as described in claim 1, characterized in that, ； R1-R2 are as defined in claim 1.

3. The method for preparing naphthothiophene compounds according to claim 2, characterized in that, Using naphthalenethiol as a raw material and cesium carbonate as a base, it reacts with α-bromocinnamaldehyde under visible light irradiation to generate naphthothiophene compounds.

4. The method for preparing naphthothiophene compounds according to claim 3, characterized in that, The molar ratio of naphthalenethiol, α-bromocinnamaldehyde, and cesium carbonate is 1:2:1 to 2:1:

1.

5. The method for preparing naphthothiophene compounds according to claim 3, characterized in that, The visible light irradiation is selected from one or more light sources selected from 5000-5500 K white light, 395-400 nm violet light, and 455-460 nm blue light, and the power of the irradiation light source is 6-10W.

6. The method for preparing naphthothiophene compounds according to claim 3, characterized in that, The reaction time is 24-30 hours, the reaction temperature is room temperature, and the reaction atmosphere is air.

7. The method for preparing naphthothiophene compounds according to claim 3, characterized in that, The reaction solvent is one or more of ethyl acetate and methanol.

8. The application of a naphthothiophene compound as described in claim 1 or a naphthothiophene compound prepared by the method described in claims 2 and 3 in organic optoelectronic materials.

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