A multifunctional naphthalene derivative and its preparation method and application

Abstract

The present invention belongs to the technical field of organic synthesis and provides a multifunctional naphthalene derivative and its preparation method and application. In the structural formula of the multifunctional naphthalene derivative of the present invention, R 2 is an alkyl group, a phenyl group, a 2-naphthyl group, a 1-naphthyl group, a 2-thienyl group, an aromatic ring connected to an electron-withdrawing group, or an aromatic ring connected to an electron-donating group, wherein the electron-withdrawing group and the electron-donating group include a methyl group, a methoxy group, a trifluoromethyl group, or a halogen group; R 3 is H, methyl or methoxy; R 4 The present invention uses 1,6-diyne-3-alcohol compounds as raw materials, [2-(di-tert-butylphosphino)biphenyl]gold(I) chloride and silver tetrafluoroborate as catalysts, and obtains multifunctional naphthalene derivatives having phenyl, phenylethynyl and naphthalene ring structures through intramolecular 6-endo-dig cyclization, 3,3-Claisen rearrangement, aromatization reaction, and finally deacylation reaction. The multifunctional naphthalene derivatives have application value in multiple fields.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a multifunctional naphthalene derivative and a preparation method and application thereof. Background Art

[0002] Due to the unique properties of the naphthalene ring structure, compounds containing a naphthalene skeleton have a wide range of applications in medicine, pesticides, optical functional materials, and other fields. However, current methods for synthesizing functionalized naphthalene rings primarily rely on electrophilic functionalization reactions of naphthalene. This method often suffers from poor selectivity, typically yielding a mixture of electrophilic addition reactions at different sites, which is difficult to separate and purify. An alternative approach is to construct the naphthalene ring through cyclization reactions, pre-introducing various substituents onto the reaction precursors. This method can yield highly functionalized naphthalene ring derivatives. However, there are no reports of efficient methods for synthesizing alkynylnaphthalene derivatives using readily available 1,6-diyn-3-ol compounds as starting materials and gold as a catalyst.

[0003] Therefore, it is of great significance to develop new, simple and efficient methods to synthesize multifunctional naphthalene derivatives. Summary of the Invention

[0004] The purpose of the present invention is to provide a multifunctional naphthalene derivative and a preparation method and application thereof in view of the deficiencies in the prior art.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a multifunctional naphthalene derivative, the structural formula of the multifunctional naphthalene derivative is:

[0007] ;

[0008] Among them, R 2 is propyl, tert-butyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, methylphenyl, methoxyphenyl, trifluoromethylphenyl, chlorophenyl or fluorophenyl;

[0009] R 3 is H, methyl or methoxy;

[0010] R 4 is H, methyl, phenyl or alkynyl, when R 4 When it is an alkynyl group, the alkynyl group is connected to R 2 .

[0011] Preferably, the structural formula of the multifunctional naphthalene derivative is:

[0012] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

[0013] 、 、 、 、 、 or .

[0014] The present invention also provides a method for preparing the multifunctionalized naphthalene derivatives. The synthetic route of the multifunctionalized naphthalene derivatives is:

[0015] ;

[0016] Among them, R 1 is an alkyl group or an aryl group;

[0017] R 2 is propyl, tert-butyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, methylphenyl, methoxyphenyl, trifluoromethylphenyl, chlorophenyl or fluorophenyl;

[0018] R 3 is H, methyl or methoxy;

[0019] R 4 is H, methyl, phenyl or alkynyl, when R 4 When it is an alkynyl group, the alkynyl group is connected to R 2 ;

[0020] The preparation method of the multifunctional naphthalene derivative comprises the following steps:

[0021] Chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and 1,4-dioxane are mixed to obtain a reaction solution, and the reaction solution is reacted with a 1,6-diyn-3-ol compound to obtain a multifunctional naphthalene derivative.

[0022] Preferably, the molar ratio of the chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and 1,6-diyn-3-ol compound is 0.04-0.06:0.04-0.06:1.

[0023] Preferably, the molar volume ratio of the 1,6-diyn-3-ol compound to 1,4-dioxane is 0.2 mmol: 0.35-0.65 mL.

[0024] Preferably, the mixing time is 0.8-1.2 h; the reaction temperature is 30-85° C., and the reaction time is 10.5-56 h.

[0025] Preferably, after the reaction is completed, a crude product is obtained, and the crude product is subjected to rotary evaporation and silica gel column chromatography in sequence to obtain a multifunctional naphthalene derivative.

[0026] Preferably, the eluent for silica gel column chromatography is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 50-200:1.

[0027] The present invention also provides application of the multifunctional naphthalene derivative in fluorescent materials.

[0028] The beneficial effects of the present invention include:

[0029] This invention uses 1,6-diyne-3-ol compounds as starting materials, with chloro[2-(di-tert-butylphosphino)diphenyl]gold (JohnPhosAuCl) and silver tetrafluoroborate (AgBF4) as catalysts. Through intramolecular 6-endo-dig cyclization, 3,3-Claisen rearrangement, aromatization, and finally deacylation, a carboxylic acid byproduct is produced, along with a multifunctional naphthalene derivative. These multifunctional naphthalene derivatives possess phenyl, phenylethynyl, and naphthalene ring structures. Their multifunctionality lends them to diverse applications. For example, their conjugated structures offer excellent optoelectronic properties, making them suitable for use as light-emitting layers or electron transport layers in organic light-emitting diodes (OLEDs). Their fluorescent properties make them suitable for use as fluorescent probes in bioimaging, aiding the study of molecular processes within organisms. They can serve as intermediates in organic synthesis, enabling the construction of more complex molecular structures, particularly in the synthesis of polycyclic aromatic hydrocarbons and conjugated systems. They can also serve as precursor compounds in medicinal chemistry, enabling the development of bioactive molecules. DETAILED DESCRIPTION

[0030] The present invention provides a multifunctional naphthalene derivative, the structural formula of the multifunctional naphthalene derivative is:

[0031] ;

[0032] Among them, R 2 is propyl, tert-butyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, methylphenyl, methoxyphenyl, trifluoromethylphenyl, chlorophenyl or fluorophenyl;

[0033] R 3 is H, methyl or methoxy;

[0034] R 4 is H, methyl, phenyl or alkynyl, when R4 When it is an alkynyl group, the alkynyl group is connected to R 2 .

[0035] In the present invention, the structural formula of the multifunctional naphthalene derivative is preferably:

[0036] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

[0037] 、 、 、 、 、 or .

[0038] The present invention also provides a method for preparing the multifunctionalized naphthalene derivatives. The synthetic route of the multifunctionalized naphthalene derivatives is:

[0039]

[0040] Among them, R 1 is an alkyl group or an aryl group;

[0041] R 2 is propyl, tert-butyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, methylphenyl, methoxyphenyl, trifluoromethylphenyl, chlorophenyl or fluorophenyl;

[0042] R 3 is H, methyl or methoxy;

[0043] R 4 is H, methyl, phenyl or alkynyl, when R 4 When it is an alkynyl group, the alkynyl group is connected to R 2 ;

[0044] The preparation method of the multifunctional naphthalene derivative comprises the following steps:

[0045] Chloro[2-(di-tert-butylphosphino)diphenyl]gold (JohnPhosAuCl), silver tetrafluoroborate (AgBF4) and 1,4-dioxane are mixed to obtain a reaction solution, and the reaction solution is reacted with a 1,6-diyn-3-ol compound to obtain a multifunctional naphthalene derivative.

[0046] In the present invention, the molar ratio of the chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and 1,6-diyn-3-ol compound is preferably 0.04-0.06:0.04-0.06:1, and more preferably 0.05:0.05:1.

[0047] In the present invention, the molar volume ratio of the 1,6-diyn-3-ol compound to 1,4-dioxane is preferably 0.2 mmol:0.35-0.65 mL, more preferably 0.2 mmol:0.4-0.6 mL, and even more preferably 0.2 mmol:0.5 mL.

[0048] In the present invention, the mixing time is preferably 0.8 to 1.2 hours, more preferably 1 hour, and the mixing is preferably carried out at room temperature; the reaction temperature is preferably 30 to 85°C, more preferably 35 to 80°C, more preferably 50 to 70°C, and the reaction time is preferably 10.5 to 56 hours, more preferably 12.5 to 43 hours, more preferably 14 to 40 hours.

[0049] In the present invention, a crude product is obtained after the reaction is completed. The crude product is preferably subjected to rotary evaporation and silica gel column chromatography in sequence to obtain a multifunctional naphthalene derivative.

[0050] In the present invention, the eluent for silica gel column chromatography is preferably petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is preferably 50-200:1, more preferably 100-150:1; the solvent 1,4-dioxane is removed by rotary evaporation.

[0051] The present invention also provides application of the multifunctional naphthalene derivative in fluorescent materials.

[0052] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0053] In the examples, JohnPhosAuCl was purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd. with a CAS number of 854045-93-5, a purity of 98%, and a specification of 1 g;

[0054] AgBF4 was purchased from Anhui Zesheng Technology Co., Ltd. with CAS number 14104-20-2, purity 99%, and specification 1g;

[0055] Ethyl acetate was purchased from Beijing Mairuida Technology Co., Ltd. with a CAS number of 141-78-6, a purity AR of 99%, and a specification of 25 L;

[0056] Petroleum ether was purchased from Shanghai Jiazu Industrial Co., Ltd. with CAS number 8032-32-4, purity of 99%, and specification of 25L;

[0057] 1,4-Dioxane was purchased from Beijing Mairida Technology Co., Ltd. with a CAS number of 123-91-1, a purity of 99%, and a specification of 500 mL.

[0058] Example 1

[0059]

[0060] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, and then 0.2 mmol of 1,5-diphenyl-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyn-3-ol (1a) was added. The mixture was reacted at 35°C for 21 h. After the reaction was complete, 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a).

[0061] The white solid product 2a in this example is 46.4 mg, and the isolated yield is 77%. 1 H NMR (400 MHz, Chloroform-d) δ 8.47 (d, J = 8.1 Hz, 1H), 8.07 (d, J = 9.5 Hz, 2H), 7.94 (d, J =7.9 Hz, 1H), 7.76 (d, J = 7.6 Hz, 2H), 7.70 (d, J = 7.1 Hz, 2H), 7.65 – 7.55 (m,2H), 7.52 (t, J = 7.5 Hz, 2H), 7.48 – 7.37 (m, 4H); 13C NMR(151 MHz, Chloroform-d) δ 140.46, 138.28, 133.71, 132.55, 131.85, 130.13, 129.06,128.75, 128.60,127.76, 127.49, 126.98, 126.94, 126.73, 126.21, 123.48, 121.63, 94.47, 87.67;GCMS(PCI+) m / z calculated for C 24 H 17 + [M+H] + : 305.1325, found: 305.1326.

[0062] Example 2

[0063]

[0064] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, followed by the addition of 0.2 mmol of 3-(2-(cyclopropylethynyl)phenyl)-1,5-diphenylpenta-1,4-diyn-3-ol (1b). The mixture was allowed to react at 35°C for 41 h. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (product 2a, a white solid).

[0065] The white solid product 2a in this example was 38.1 mg, and the isolated yield was 63%.

[0066] Example 3

[0067]

[0068] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, followed by the addition of 0.2 mmol of 3-(2-(3,3-dimethylbut-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-diyn-3-ol (1c). The mixture was allowed to react at 80°C for 24 h. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (product 2a), a white solid.

[0069] The white solid product 2a in this example was 38.1 mg, and the isolated yield was 61%.

[0070] Example 4

[0071]

[0072] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(2-(hept-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-diyn-3-ol (1d). The reaction was continued at 35°C for 45.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (product 2a), a white solid.

[0073] The white solid product 2a in this example was 43.0 mg, and the isolated yield was 71%.

[0074] Example 5

[0075]

[0076] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(2-(5-hydroxypent-1-yn-1-yl)phenyl)-1,5-diphenylpent-1,4-diyn-3-ol (1e). The mixture was allowed to react at 35°C for 12.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (product 2a), a white solid.

[0077] The white solid product 2a in this example was 36.0 mg, and the isolated yield was 59%.

[0078] Example 6

[0079]

[0080] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(2-((4-methoxyphenyl)ethynyl)phenyl)-1,5-diphenylpenta-1,4-diyn-3-ol (1f). The reaction was continued at 50°C for 23.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (product 2a), a white solid.

[0081] The amount of the white solid product 2a in this example was 26.1 mg, and the isolated yield was 43%.

[0082] Example 7

[0083]

[0084] To a 4 mL sample vial, add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, followed by 0.5 mL of 1,4-dioxane. Stir at room temperature for 1 hour, then add 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di-o-tolylpenta-1,4-diyn-3-ol (1 g). React at 35°C for 21.5 hours. After completion of the reaction, remove the 1,4-dioxane by rotary evaporation. Silica gel column chromatography (petroleum ether: ethyl acetate, volume ratio: 200-100:1) yields 3-(o-tolyl)-1-(o-tolylethynyl)naphthalene (2 g of a yellow liquid product).

[0085] The yellow liquid product 2g in this example is 44.7mg, and the isolated yield is 67%. 1 H NMR (600 MHz, Chloroform-d) δ 8.53 (d, J = 8.3 Hz, 1H), 7.93 – 7.90 (m, 1H), 7.83 – 7.79 (m,2H), 7.69 – 7.63 (m, 2H), 7.62 – 7.57 (m, 1H), 7.39 – 7.28 (m, 6H), 7.27 –7.23 (m, 1H), 2.66 (s, 3H), 2.37 (s, 3H); 13C NMR(151 MHz, Chloroform-d) δ141.20, 140.29, 139.25, 135.72, 133.35, 132.21,132.19, 132.13, 130.54,130.06, 129.72, 128.70, 128.61, 128.57, 127.76, 126.90, 126.86, 126.24,126.03, 125.83, 123.30, 121.16, 93.38, 91.56, 21.21, 20.67;LCMS(ESI+) m / zcalculated for C 26 H 21 + [M+H] + : 333.1638, found: 333.1635.

[0086] Example 8

[0087]

[0088] To a 4 mL sample vial, add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, followed by 0.5 mL of 1,4-dioxane. Stir at room temperature for 1 hour, then add 0.2 mmol of 3,3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di-m-tolylpenta-1,4-diyn-3-ol (1 hour). React at 35°C for 21.5 hours. After completion of the reaction, remove the 1,4-dioxane by rotary evaporation. Silica gel column chromatography (petroleum ether: ethyl acetate, volume ratio 100:1) yields 3-(m-tolyl)-1-(m-tolylethynyl)naphthalene (yellow liquid product, 2 hours).

[0089] The yellow liquid product 2h in this example is 44.6 mg, and the isolated yield is 67%. 1 H NMR (400 MHz, Chloroform-d) δ 8.47 (d, J = 8.0 Hz, 1H), 8.06 (d, J = 9.3 Hz, 2H), 7.93 (d, J =7.9 Hz, 1H), 7.68 – 7.48 (m, 6H), 7.41 (t, J = 7.5 Hz, 1H), 7.32 (t, J = 7.6 Hz,1H), 7.23 (t, J= 7.8 Hz, 2H), 2.49 (s, 3H), 2.43 (s, 3H); 13 C NMR(101 MHz,Chloroform-d) δ 140.42, 138.64, 138.35, 138.26, 133.69, 132.52,132.40,130.12, 129.48, 128.94, 128.92, 128.70, 128.48, 128.22, 126.90, 126.82,126.59, 126.21, 124.57, 123.28, 121.62, 94.61, 87.36, 21.70, 21.41;LCMS(ESI+)m / z calculated for C 26 H 21 + [M+H] + : 333.1638, found: 333.1626.

[0090] Example 9

[0091]

[0092] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, followed by the addition of 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di-p-tolylpenta-1,4-diyn-3-ol (1i). The mixture was allowed to react at 35°C for 21.5 h. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(p-tolyl)-1-(p-tolylethynyl)naphthalene (yellow solid product 2i).

[0093] The yellow solid product 2i in this example was 49.5 mg, and the isolated yield was 74%. 1 H NMR (600 MHz, Chloroform-d) δ 8.44 (d, J = 8.1 Hz, 1H), 8.04 (s, 1H), 8.01 (s, 1H), 7.91 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.0 Hz, 2H), 7.61 – 7.53 (m, 4H), 7.31 (d, J= 7.8Hz, 2H), 7.22 (d, J = 7.8 Hz, 2H), 2.44 (s, 3H), 2.41 (s, 3H); 13 C NMR (151 MHz, Chloroform-d) δ 138.75, 138.17, 137.58, 133.75, 132.44, 131.74, 129.92,129.78, 129.36, 128.66, 127.29, 126.88, 126.71, 126.25, 126.19,121.75,120.43, 94.60, 87.08, 21.71, 21.30;LCMS(ESI+) m / z calculated for C 26 H 21 + [M+H] + :333.1638, found: 333.1634.

[0094] Example 10

[0095]

[0096] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di(thiophen-2-yl)penta-1,4-diyn-3-ol (1j). The mixture was allowed to react at 35°C for 22.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the mixture was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 2-((3-(thiophen-2-yl)naphthalen-1-yl)ethynyl)thiophene (yellow solid product 2j).

[0097] The yellow solid product 2j in this example was 28.3 mg, and the isolated yield was 45%. 1 H NMR (400 MHz, Chloroform-d) δ 8.34 (dd, J = 7.6, 1.8 Hz, 1H), 8.04 (q, J = 1.9 Hz, 2H), 7.87(dd, J = 7.2, 2.0 Hz, 1H), 7.62 – 7.50 (m, 2H), 7.47 (dd, J= 3.6, 1.1 Hz, 1H),7.42 (dd, J = 3.6, 1.2 Hz, 1H), 7.40 – 7.32 (m, 2H), 7.14 (dd, J = 5.1, 3.6 Hz,1H), 7.08 (dd, J = 5.2, 3.6 Hz, 1H); 13 C NMR(151 MHz, Chloroform-d) δ 143.64,133.64, 132.40, 132.37, 131.58, 128.68, 128.58, 128.36, 127.79, 127.40,127.29, 127.02, 126.23,125.53, 125.19, 123.96, 123.32, 121.49, 91.10, 87.81;LCMS(ESI+) m / z calculated for C 20 H 13 S2 + [M+H] + : 317.0454, found: 317.0451.

[0098] Example 11

[0099]

[0100] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 1,5-bis(4-chlorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyn-3-ol (1k). The mixture was allowed to react at 35°C for 16 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(4-chlorophenyl)-1-((4-chlorophenyl)ethynyl)naphthalene (yellow solid product 2k).

[0101] The yellow solid product 2k in this example was 46.7 mg, and the isolated yield was 63%. 1 H NMR (600 MHz, Chloroform-d) δ 8.40 (d, J = 8.2 Hz, 1H), 8.02 – 7.96 (m, 2H), 7.91 (d, J= 8.0Hz, 1H), 7.66 – 7.61 (m, 3H), 7.61 – 7.55 (m, 3H), 7.49 – 7.44 (m, 2H), 7.41– 7.36 (m, 2H); 13 C NMR(151 MHz, Chloroform-d) δ 138.78, 136.97, 134.69,133.94, 133.61, 133.02, 132.51, 129.78, 129.22, 128.96, 128.78, 128.66, 127.22, 127.20,126.80, 126.09, 121.83, 121.49, 93.49, 88.44;LCMS(ESI+) m / zcalculated for C 24 H 15 35 Cl2 + [M+H] + : 373.0546, found: 373.0532; m / z calculated forC 24 H 15 37 Cl2 + [M+H] + : 377.0487, found: 377.0489.

[0102] Example 12

[0103]

[0104] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, followed by the addition of 0.2 mmol of 1,5-bis(3-chlorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyn-3-ol (1 l). The mixture was allowed to react at 35°C for 35 h. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(3-chlorophenyl)-1-((3-chlorophenyl)ethynyl)naphthalene (yellow solid product 2 l).

[0105] The yellow solid product 21 in this example was 51.5 mg, and the isolated yield was 68%. 1 H NMR (400 MHz, Chloroform-d) δ 8.40 (d, J= 8.1 Hz, 1H), 8.05 – 7.98 (m, 2H), 7.95 – 7.90 (m,1H), 7.72 (t, J = 1.9 Hz, 1H), 7.69 – 7.57 (m, 4H), 7.57 – 7.52 (m, 1H), 7.46 –7.31 (m, 4H); 13 C NMR(151 MHz, Chloroform-d) δ 142.16, 136.79, 135.01, 134.46,133.58, 132.68, 131.67, 130.30, 129.95, 129.93, 129.84, 128.91, 128.87,127.83, 127.56,127.42, 127.26, 127.21, 126.09, 125.60, 125.06, 121.38, 93.20,88.62;LCMS(ESI+) m / z calculated for C 24 H 15 35 Cl2 + [M+H] + : 373.0546, found:373.0535; m / z calculated for C 24 H 15 37 Cl2 + [M+H] + : 377.0487, found: 377.0491.

[0106] Example 13

[0107]

[0108] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 1,5-bis(2-chlorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyn-3-ol (1 m). The mixture was allowed to react at 35°C for 22.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the mixture was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(2-chlorophenyl)-1-((2-chlorophenyl)ethynyl)naphthalene (yellow liquid product, 2 m).

[0109] The yellow liquid product 2m in this example is 58.5 mg, and the isolated yield is 78%. 1 H NMR (400 MHz, Chloroform-d) δ 8.60 (d, J = 8.3 Hz, 1H), 7.92 (d, J = 8.3 Hz, 3H), 7.71 – 7.64(m, 2H), 7.59 (t, J = 7.5 Hz, 1H), 7.53 (dd, J = 7.3, 1.9 Hz, 1H), 7.51 – 7.45(m, 2H), 7.40 – 7.34 (m, 2H), 7.33 – 7.28 (m, 2H); 13 C NMR(101 MHz, Chloroform-d) δ 139.81, 136.63, 136.11, 133.49, 133.15, 132.87, 132.64, 132.29,131.66,130.17, 129.77, 129.53, 129.07, 128.71, 127.48, 127.10, 127.03, 126.70,

[0110] 126.42, 123.47, 120.59, 92.76, 91.26;LCMS(ESI+) m / z calculated forC 24 H 15 35 Cl2 + [M+H] + : 373.0546, found: 373.0540; m / z calculated for C 24 H 15 37 Cl2 + [M+H] + : 377.0487, found: 377.0489.

[0111] Example 14

[0112]

[0113] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 1,5-bis(4-fluorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyn-3-ol (1n). The mixture was allowed to react at 35°C for 11 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(4-fluorophenyl)-1-((4-fluorophenyl)ethynyl)naphthalene (product 2n), a white solid.

[0114] The white solid product 2n in this example was 49.4 mg, and the isolated yield was 73%. 1 H NMR (600 MHz, Chloroform-d) δ 8.41 (d, J = 8.2 Hz, 1H), 7.98 (s, 2H), 7.93 – 7.89 (m, 1H), 7.71 – 7.62 (m, 4H), 7.61 –7.54 (m, 2H), 7.22 – 7.15 (m, 2H), 7.14 – 7.08 (m,2H); 13 C NMR (151 MHz, Chloroform- d ) δ 162.82 (d, J = 247.0 Hz), 162.81 (d, J =249.8 Hz), 137.29, 136.56 (d, J = 3.1 Hz), 133.74 (d, J = 8.6 Hz), 133.67,132.41, 129.91, 129.06 (d, J = 8.1 Hz), 128.72, 127.13, 127.04, 126.61, 126.13,121.57, 119.50 (d, J = 2.2 Hz), 115.97 (d, J = 21.4 Hz), 115.94 (d, J = 22.1 Hz),93.48, 87.22; 19 F NMR (377 MHz, Chloroform- d) δ -110.48, -115.03.GCMS(PCI+) m / zcalculated for C 24 H 15 F2 + [M+H] + : 341.1137, found: 341.1136.

[0115] Example 15

[0116]

[0117] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-bis(4-(trifluoromethyl)phenyl)penta-1,4-diyn-3-(1o). The mixture was allowed to react at 35°C for 21 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the mixture was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(4-(trifluoromethyl)phenyl)-1-((4-(tetrafluoromethyl)phenyl)ethynyl)naphthalene (yellow solid product 2o).

[0118] The yellow solid product 2o in this example was 64.9 mg, and the isolated yield was 74%. 1 H NMR (400 MHz, Chloroform-d) δ 8.43 (d, J = 8.1 Hz, 1H), 8.12 – 8.01 (m, 2H), 7.94 (d, J = 8.0Hz, 1H), 7.82 (d, J = 8.1 Hz, 2H), 7.79 – 7.73 (m, 4H), 7.67 (d, J = 8.5 Hz, 3H),7.65 – 7.58 (m, 1H); 13 C NMR (101 MHz, Chloroform-d) δ 143.75, 136.73, 133.57,132.80, 132.05, 130.38 (q, J = 32.7 Hz), 130.03, 129.90 (q, J = 32.4 Hz), 128.98,127.70, 127.41, 127.09, 126.04, 126.02 (q, J= 3.9 Hz), 125.56 (q, J = 3.7 Hz),124.40 (q, J = 272.0 Hz, CF3), 124.09 (q, J = 272.3 Hz, CF3), 121.33, 93.32,89.71; 19 F NMR (377 MHz, Chloroform- d ) δ -62.38, -62.74.GCMS(PCI+) m / zcalculated for C 26 H 15 F6 + [M+H] + : 441.1073, found: 441.1067.

[0119] Example 16

[0120]

[0121] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-bis(2-(trifluoromethyl)phenyl)penta-1,4-diyn-3-ol (1p). The reaction was continued at 35°C for 18.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(2-(trifluoromethyl)phenyl)-1-((2-(trifluoromethyl)phenyl)ethynyl)naphthalene (yellow liquid product 2p).

[0122] The yellow liquid product 2p in this example is 37.2 mg, and the isolated yield is 42%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.50 (d, J = 8.3 Hz, 1H), 7.90 (d, J = 8.1 Hz, 1H), 7.84 – 7.78(m, 4H), 7.74 (d, J = 7.9 Hz, 1H), 7.69 – 7.59 (m, 3H), 7.57 – 7.50 (m, 2H),7.45 (t, J = 8.5 Hz, 2H); 13C NMR (101 MHz, Chloroform- d ) δ 140.47, 136.98,134.26, 132.82, 132.65, 132.38, 132.13, 131.65, 131.58, 131.46 (q, J = 30.7Hz), 129.49, 128.85 (q, J = 30.7 Hz), 128.70, 128.26, 127.88, 127.54, 127.19,126.33 (q, J = 5.1 Hz), 126.18, 126.11 (q, J = 5.1 Hz), 124.27 (q, J = 274.0 Hz,CF3), 123.87 (q, J = 273.4 Hz, CF3), 121.71, 120.23, 93.14, 90.21. 19 F NMR (377 MHz, Chloroform- d ) δ -56.74, -62.04.GCMS(PCI+) m / z calculated for C 26 H 15 F6 + [M+H] + : 441.1073, found: 441.1071.

[0123] Example 17

[0124]

[0125] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, followed by the addition of 0.2 mmol of 1,5-di(naphthalen-1-yl)-3-(2-(prop-1-yn-1-yl)phenyl)pent-1,4-diyn-3-ol (1q). The mixture was allowed to react at 35°C for 14 h. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 150-100:1) to obtain 4'-(naphthalen-1-ylethynyl)-1,2'-binaphthyl (yellow liquid product 2q).

[0126] The yellow liquid product 2q in this example was 59.9 mg, and the isolated yield was 74%. 1H NMR (400 MHz, Chloroform-d) δ 8.68 (d, J = 8.3 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.09 (d, J =1.6 Hz, 1H), 8.03 – 7.86 (m, 8H), 7.71 (t, 1H), 7.67 – 7.46 (m, 8H); 13 C NMR(151 MHz, Chloroform-d) δ 139.45, 138.11, 133.96, 133.51, 133.40, 133.01,132.56, 131.83, 130.80, 129.82, 129.11, 128.71,128.51, 128.20, 127.44,127.21, 127.10, 127.07, 126.64, 126.48, 126.41, 126.36, 126.09, 126.08,125.56, 125.48, 121.20,121.10, 92.72, 92.47;LCMS(ESI+) m / z calculated forC 32 H 21 + [M+H] + : 405.1638, found: 405.1630.

[0127] Example 18

[0128]

[0129] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 h, followed by the addition of 0.2 mmol of 1,5-di(naphthalen-2-yl)-3-(2-(prop-1-yn-1-yl)phenyl)pent-1,4-diyn-3-ol (1r). The mixture was allowed to react at 35°C for 42 h. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 4-(naphthalen-2-ylethynyl)-2,2'-binaphthyl (product 2r) as a white solid.

[0130] The white solid product 2r in this example was 52.8 mg, and the isolated yield was 65%. 11H NMR (600 MHz, Chloroform-d) δ 8.56 (d, J J = 8.2 Hz, 1H), 8.25 (s, 1H), 8.23 (d, J J = 7.7 Hz, 2H), 8.18 (s, 1H), 8.05 – 7.95 (m, 3H), 7.93 – 7.88 (m, 5H), 7.76 (d, J J = 8.3 Hz, 1H), 7.67 (t, J J = 7.6 Hz, 1H), 7.61 (t, J J = 7.5 Hz, 1H), 7.58 – 7.51 (m, 4H); 13 13C NMR (151 MHz, Chloroform-d) δ 138.13, 137.70, 133.86, 133.79, 133.23, 133.07, 132.92, 132.62, 131.72, 130.31, 128.82, 128.77, 128.61, 128.43, 128.28, 127.99, 127.97, 127.83, 127.07, 127.05, 126.92, 126.78, 126.57, 126.30, 125.63, 121.76, 120.76, 95.00, 88.09; LCMS (ESI+) m / z calculated for C 32 14 21 + [M+H] + : 405.1638, found: 405.1633.

[0131] Example 19

[0132]

[0133] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(4-methoxy-2-(prop-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-diyn-3-ol (1s). The mixture was allowed to react at 35°C for 14 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:50:1) to obtain 6-methoxy-3-phenyl-1-(phenylethynyl)naphthalene (yellow solid product 2s).

[0134] The yellow solid product 2s in this example was 41.8 mg, and the isolated yield was 63%. 1 H NMR (400 MHz, Chloroform-d) δ 8.35 (d, J = 9.0 Hz, 1H), 7.94 (d, J = 1.8 Hz, 1H), 7.91 (d, J =1.7 Hz, 1H), 7.78 – 7.71 (m, 2H), 7.71 – 7.64 (m, 2H), 7.50 (t, J = 7.6 Hz,2H), 7.46 – 7.36 (m, 4H), 7.30 – 7.23 (m, 1H), 7.22 (d, J = 2.5 Hz, 1H), 3.96(s, 3H); 13 C NMR(151 MHz, Chloroform-d) δ 158.49, 140.62, 138.87, 135.00,131.84, 129.02, 128.58, 128.57, 128.07,127.94, 127.79, 127.73, 127.48,125.69, 123.48, 121.42, 119.60, 106.62, 94.14, 87.82, 55.52;LCMS(ESI+) m / zcalculated for C 25 H 19 O + [M+H] + : 335.1431, found: 335.1428.

[0135] Example 20

[0136]

[0137] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 3-(5-methyl-2-(prop-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-diyn-3-ol (1t). The mixture was allowed to react at 35°C for 14 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 7-methyl-3-phenyl-1-(phenylethynyl)naphthalene (yellow solid product 2t).

[0138] The yellow solid product 2t in this example was 46.4 mg, and the isolated yield was 73%. 1 H NMR (400 MHz, Chloroform-d) δ 8.22 (s, 1H), 8.05 (s, 1H), 8.01 (s, 1H), 7.83 (d, J = 8.3 Hz,1H), 7.78 – 7.73 (m,2H), 7.72 – 7.69 (m, 2H), 7.51 (t, J = 7.7 Hz, 2H), 7.47 –7.38 (m, 5H), 2.62 (s, 3H); 13 C NMR(101 MHz, Chloroform-d) δ 140.56, 137.33,136.90, 132.71, 131.95, 131.85, 130.21, 129.22, 129.02, 128.59, 128.53,127.59,127.39, 126.55, 125.19, 123.60, 120.80, 94.21, 87.89, 22.20;LCMS(ESI+)m / z calculated for C 25 H 19 + [M+H] + : 319.1482, found: 319.1487.

[0139] Example 21

[0140]

[0141] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 2,2,8,8-tetramethyl-5-(2-(prop-1-yn-1-yl)phenyl)nona-3,6-diyn-5-ol (1u). The mixture was allowed to react at 35°C for 10.5 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 3-(tert-butyl)-1-(3,3-dimethylbut-1-yn-1-yl)naphthalene (white solid product 2u).

[0142] The white solid product 2u in this example was 40.2 mg, and the isolated yield was 76%. 1 H NMR (400 MHz, Chloroform-d) δ 8.26 (d, J = 8.1 Hz, 1H), 7.80 (d, J = 7.0 Hz, 1H), 7.72 (s, 2H), 7.55 – 7.43 (m, 2H), 1.46 (s, 9H), 1.42 (s, 9H); 13 C NMR(101 MHz, Chloroform-d)δ 148.03, 133.37, 131.90, 128.95, 128.31, 126.24, 125.95, 123.34, 121.36,103.13, 77.53, 34.87, 31.41, 31.33, 28.50;LCMS(ESI+) m / z calculated for C 20 H 25 + [M+H] + : 265.1951, found: 265.1952.

[0143] Example 22

[0144]

[0145] To a 4 mL sample vial, add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, followed by 0.5 mL of 1,4-dioxane. Stir at room temperature for 1 hour, then add 0.2 mmol of 1,5-dicyclopropyl-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyn-3-ol (1v). React at 35°C for 18.5 hours. After completion of the reaction, remove the 1,4-dioxane by rotary evaporation. 3-cyclopropyl-1-(cyclopropylethynyl)naphthalene (orange liquid product 2v) was obtained by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio 100:1).

[0146] The orange liquid product 2v in this example was 30.2 mg, and the isolated yield was 65%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.25 – 8.19 (m, 1H), 7.75 – 7.69 (m, 1H), 7.48 (s, 1H), 7.47– 7.41 (m, 2H), 7.32 (d, J = 1.8 Hz, 1H), 2.06 – 1.97 (m, 1H), 1.64 – 1.56 (m,1H), 1.05 – 0.99 (m, 2H), 0.98 – 0.96 (m, 1H), 0.95 – 0.91 (m, 3H), 0.83 –0.77 (m, 2H); 13 C NMR (101 MHz, Chloroform- d ) δ 140.98, 133.48, 132.18, 128.79,127.65, 126.45, 126.13, 125.60, 124.29, 121.63, 98.24, 73.97, 15.55, 9.14,9.05, 0.61;GCMS(PCI+) m / z calculated for C 18 H 17 + [M+H] + : 233.1325, found:233.1321.

[0147] Example 23

[0148]

[0149] To a 4 mL sample vial, add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, followed by 0.5 mL of 1,4-dioxane. Stir at room temperature for 1 hour, then add 0.2 mmol of 3-phenyl-1-(2-(prop-1-yn-1-yl)phenyl)prop-2-en-1-ol (1w). React at 35°C for 21 hours. After completion of the reaction, remove the 1,4-dioxane by rotary evaporation. 2-phenylnaphthalene (2w) is obtained by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain a white solid product.

[0150] The white solid product 2w in this example was 23.6 mg, and the isolated yield was 58%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.07 (d, J = 1.8 Hz, 1H), 7.97 – 7.86 (m, 3H), 7.81 – 7.73 (m,3H), 7.60 – 7.47 (m, 4H), 7.44 – 7.37 (m, 1H); 13 C NMR (101 MHz, Chloroform- d ) δ141.28, 138.71, 133.83, 132.76, 128.99, 128.55, 128.34, 127.78, 127.57,127.49, 126.42, 126.07, 125.94, 125.73;GCMS(PCI+) m / z calculated for C 16 H 13 + [M+H] + : 205.1012, found: 205.1013.

[0151] Example 24

[0152]

[0153] To a 4 mL sample vial, add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, followed by 0.5 mL of 1,4-dioxane. Stir at room temperature for 1 hour, then add 0.2 mmol of 4-phenyl-2-(2-(prop-1-yn-1-yl)phenyl)but-3-yn-2-ol (1x). React at 35°C for 43 hours. After completion of the reaction, remove the 1,4-dioxane by rotary evaporation. Purify the product by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 1-methyl-3-phenylnaphthalene (2x), a white solid.

[0154] The white solid product 2x in this example was 23.7 mg, and the isolated yield was 54%. 1 H NMR(400 MHz,Chloroform-d) δ 8.08 – 7.99 (m, 1H), 7.97 – 7.89 (m, 2H), 7.80 – 7.71 (m,2H), 7.63 (s, 1H), 7.58 – 7.46 (m, 4H), 7.40 (t, J = 7.4 Hz, 1H); 13 C NMR(151MHz, Chloroform-d) δ 141.34, 138.31, 134.96, 133.99, 131.96, 128.96, 128.92,127.51,127.39, 126.48, 126.13, 125.93, 124.37, 124.12, 19.66;GCMS(PCI+) m / zcalculated for C 17 H 15 + [M+H] + : 219.1169, found: 219.1167.

[0155] Example 25

[0156]

[0157] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 hour, 0.2 mmol of 1,3-diphenyl-1-(2-(prop-1-yn-1-yl)phenyl)prop-2-en-1-ol (1y) was added. The mixture was allowed to react at 35°C for 33 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain 1,3-diphenylnaphthalene (product 2y), a white solid.

[0158] The white solid product 2y in this example was 35.6 mg, and the isolated yield was 61%. 1 H NMR (400 MHz, Chloroform-d) δ 8.09 (s, 1H), 7.99 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H),7.82 – 7.77 (m, 2H), 7.74 (d, J = 1.8 Hz, 1H), 7.61 – 7.38 (m, 10H); 13 C NMR(151MHz, Chloroform-d) δ 141.05, 140.98, 140.82, 138.16, 134.30, 131.00, 130.23,129.01, 128.73, 128.46, 127.58, 127.51,126.83, 126.36, 126.23, 126.05,125.54;LCMS(ESI+) m / z calculated for C 22 H 17 + [M+H] + : 281.1325, found: 281.1339.

[0159] Example 26

[0160]

[0161] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, followed by 0.5 mL of 1,4-dioxane. The mixture was stirred at room temperature for 1 hour, followed by the addition of 0.2 mmol of 6,6-dimethyl-1-phenyl-3-(2-(prop-1-yn-1-yl)phenyl)hept-1,4-diyn-3-ol (1z). The reaction was continued at 35°C for 41 hours. After completion of the reaction, the 1,4-dioxane was removed by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 100:1) to obtain a mixture of 1-(3,3-dimethylbut-1-yn-1-yl)-3-phenylnaphthalene (2z) and 3-(tert-butyl)-1-(phenylethynyl)naphthalene (2z') as a yellow liquid product.

[0162] The yellow liquid product 2z and 2z' mixture of this example is 37.1 mg (the mass ratio of 2z and 2z' is 2.58:1), and the total isolated yield is 57%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.39 (d, J = 8.0 Hz, 0.37H,2z'), 8.33 (d, J = 7.9 Hz, 1H,2z), 7.97 (s, 1H,2z), 7.93 – 7.88 (m, 2.25H),7.85 (d, J = 6.9 Hz, 0.37H,2z'), 7.79 (s, 0.37H,2z'), 7.73 (d, J = 7.3 Hz, 2H,2z),, 7.68 (d, J = 5.9 Hz, 0.77H,2z')z, 7.60 – 7.46 (m, 5H), 7.43 – 7.37 (m,2H), 1.46 (s, 9H,2z), 1.45 (s, 3.49H,2z'); 13 C NMR (101 MHz, Chloroform- d) δ148.14, 140.65, 138.14, 133.65, 133.37, 132.73, 131.80, 131.67, 129.65,129.54, 128.96, 128.61, 128.55, 128.44, 127.60, 127.46, 126.71,126.62,126.50, 126.25, 126.21, 125.91, 125.82, 124.27, 123.61, 122.35, 120.61,103.90, 93.76, 88.07, 34.93 (2z'), 31.33 (2z), 31.32 (2z'), 28.51 (2z);LCMS(ESI+) m / z calculated for C 22 H 20 Na + [M+Na] + : 307.1458, found: 307.1486.

[0163] Ultraviolet / visible light and fluorescence spectroscopy studies of the compounds revealed that most compounds exhibited high yields. Compared to naphthalene derivatives without alkynyl groups, alkynyl substituents significantly influence the optical spectra of the compounds, with the alkynyl substituent playing a particular role in influencing the absorption onset and fluorescence spectra. These alkynyl naphthalene derivatives have potential applications as fluorescent probes in bioimaging.

[0164] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a multifunctional naphthalene derivative, characterized in that: The synthetic route of multifunctional naphthalene derivatives is: Among them, R 1 is an alkyl group or an aryl group; R 2 is propyl, tert-butyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, methylphenyl, methoxyphenyl, trifluoromethylphenyl, chlorophenyl or fluorophenyl; R 3 is H, methyl or methoxy; R 4 is H, methyl, phenyl or alkynyl, when R 4 When it is an alkynyl group, the alkynyl group is connected to R 2 ; The preparation method of the multifunctional naphthalene derivative comprises the following steps: Chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and 1,4-dioxane are mixed to obtain a reaction solution, and the reaction solution is reacted with a 1,6-diyn-3-ol compound to obtain a multifunctional naphthalene derivative.

2. The method for preparing a multifunctional naphthalene derivative according to claim 1, wherein: The structural formula of the multifunctional naphthalene derivative is:

3. The method for preparing a multifunctional naphthalene derivative according to claim 1, wherein: The molar ratio of the chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and 1,6-diyn-3-ol compound is 0.04-0.06:0.04-0.06:

1.

4. The method for preparing a multifunctional naphthalene derivative according to claim 3, wherein: The molar volume ratio of the 1,6-diyn-3-ol compound and 1,4-dioxane is 0.2 mmol: 0.35-0.65 mL.

5. The method for preparing a multifunctional naphthalene derivative according to claim 4, wherein: The mixing time is 0.8 to 1.2 hours; the reaction temperature is 30 to 85° C., and the reaction time is 10.5 to 56 hours.

6. The method for preparing a multifunctional naphthalene derivative according to claim 5, wherein: After the reaction is completed, a crude product is obtained, and the crude product is subjected to rotary evaporation and silica gel column chromatography in sequence to obtain a multifunctional naphthalene derivative.

7. The method for preparing a multifunctional naphthalene derivative according to claim 6, wherein: The eluents for silica gel column chromatography are petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 50-200:1.

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