Multifunctional naphthalene derivative as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and provides a multifunctional naphthalene derivative as well as a preparation method and application thereof. In the structural formula of the multifunctional naphthalene derivative, R2 is alkyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, an aromatic ring connected with an electron withdrawing group or an aromatic ring connected with an electron donating group, and the electron withdrawing group and the electron donating group comprise methyl, methoxyl, trifluoromethyl or halogen; r3 is H, methyl or methoxyl; r4 is H, methyl, phenyl or alkynyl. According to the preparation method, a 1, 6-diyne-3-alcohol compound is taken as a raw material, [2-(di-tert-butylphosphine) biphenyl] gold chloride (I) and silver tetrafluoroborate are taken as catalysts, intramolecular 6-endo-dig cyclization, 3, 3-Claisen rearrangement and aromatization reaction are performed, and finally, deacylation reaction is performed to obtain the multifunctional naphthalene derivative with phenyl, phenylethynyl and naphthalene ring structures. The method has application value in multiple fields.

Description

Technical Field

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

[0002] Due to the unique properties of the naphthalene ring structure, compounds containing a naphthalene ring skeleton have a wide range of uses in the fields of medicine, pesticides, photo-functional materials, etc. However, at present, the synthesis method of functionalized naphthalene rings is mainly achieved through the electrophilic functionalization reaction of naphthalene. The selectivity of this method is often relatively poor, usually obtaining a mixture of electrophilic addition reactions at different sites, and it is difficult to separate and purify. Another method is to construct a naphthalene ring through a cyclization reaction, and various substituents are introduced in advance on the reaction precursor. This method can obtain highly functionalized naphthalene ring derivatives. There is no relevant literature report on a method for efficiently synthesizing alkynylnaphthalene derivatives using simple and readily available 1,6-diyne-3-ol compounds as starting materials and gold as a catalyst.

[0003] Therefore, it is of great significance to develop a new, simple, and efficient method for synthesizing polyfunctionalized naphthalene derivatives. Summary of the Invention

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

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions: The present invention provides a polyfunctionalized naphthalene derivative, and the structural formula of the polyfunctionalized naphthalene derivative is: ; wherein, 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 is alkynyl, the alkynyl is connected with R 2 .

[0006] Preferably, the structural formula of the polyfunctionalized naphthalene derivative is: , , , , , , , , , , , , , , , , , , , , or .

[0007] The present invention also provides a method for preparing the multifunctionalized naphthalene derivative, and the synthesis route of the multifunctionalized naphthalene derivative is as follows: ; wherein, R 1 is an alkyl group or an aryl group; R 2 is a propyl group, a tert-butyl group, a phenyl group, a 2-naphthyl group, a 1-naphthyl group, a 2-thienyl group, a methylphenyl group, a methoxyphenyl group, a trifluoromethylphenyl group, a chlorophenyl group or a fluorophenyl group; R 3 is H, a methyl group or a methoxy group; R 4 is H, a methyl group, a phenyl group or an alkynyl group. When R 4 is an alkynyl group, the alkynyl group is connected with R 2 ; The method for preparing the multifunctionalized naphthalene derivative comprises the following steps: Mix chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and 1,4-dioxane to obtain a reaction solution, and react the reaction solution with a 1,6-diyne-3-ol compound to obtain the multifunctionalized naphthalene derivative.

[0008] Preferably, the molar ratio of chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and the 1,6-diyne-3-ol compound is 0.04~0.06:0.04~0.06:1.

[0009] Preferably, the molar volume ratio of the 1,6-diyne-3-ol compound and 1,4-dioxane is 0.2 mmol:0.35~0.65 mL.

[0010] 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.

[0011] Preferably, after the reaction is completed, a crude product is obtained, and the crude product is sequentially subjected to rotary evaporation and silica gel column chromatography to obtain the multifunctionalized naphthalene derivative.

[0012] 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.

[0013] The present invention also provides the application of the multi-functionalized naphthalene derivative in fluorescent materials.

[0014] The beneficial effects of the present invention include: In the present invention, 1,6-diyne-3-ol compounds are used as starting materials, and chloro[2-(di-tert-butylphosphino)diphenyl]gold (JohnPhosAuCl) and silver tetrafluoroborate (AgBF4) are used as catalysts. Through intramolecular 6-endo-dig cyclization, 3,3-Claisen rearrangement, aromatization reaction, and finally deacylation reaction, a molecule of carboxylic acid by-product is obtained, and at the same time, a multi-functionalized naphthalene derivative is generated. The multi-functionalized naphthalene derivative of the present invention has phenyl, phenylethynyl, and naphthalene ring structures, and its multiple functional groups make it have application value in multiple fields. For example, there is a conjugated structure, with good optoelectronic properties, suitable for the light-emitting layer or electron transport layer in OLEDs; it has fluorescence characteristics and can be used as a fluorescent probe in biological imaging to assist in studying molecular processes in living organisms; it can be used as an intermediate in organic synthesis to construct more complex molecular structures, especially in the synthesis of polycyclic aromatic hydrocarbons and conjugated systems; it can also be used as a precursor compound in medicinal chemistry to develop bioactive molecules. Specific embodiments

[0015] The present invention provides a multi-functionalized naphthalene derivative, and the structural formula of the multi-functionalized naphthalene derivative is: ; wherein, 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 is alkynyl, the alkynyl is connected to R 2 .

[0016] In the present invention, the structural formula of the multi-functionalized naphthalene derivative is preferably: , , , , , , , , , , , , , , , , , , , , or .

[0017] The present invention also provides a method for preparing the multi-functionalized naphthalene derivative, and the synthetic route of the multi-functionalized naphthalene derivative is as follows:

[0018] wherein, 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 is alkynyl, the alkynyl is connected with R 2 ; The method for preparing the multi-functionalized naphthalene derivative comprises the following steps: Mix chloro[2-(di-tert-butylphosphino)diphenyl]gold (JohnPhosAuCl), silver tetrafluoroborate (AgBF4) and 1,4-dioxane to obtain a reaction solution, and react the reaction solution with a 1,6-diyne-3-ol compound to obtain the multi-functionalized naphthalene derivative.

[0019] In the present invention, the molar ratio of the chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and the 1,6-diyne-3-ol compound is preferably 0.04~0.06:0.04~0.06:1, and more preferably 0.05:0.05:1.

[0020] In the present invention, the molar volume ratio of the 1,6-diyne-3-ol compound and 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.

[0021] In the present invention, the mixing time is preferably 0.8 - 1.2 h, more preferably 1 h, and the mixing is preferably carried out at room temperature; the reaction temperature is preferably 30 - 85 °C, more preferably 35 - 80 °C, still more preferably 50 - 70 °C, and the reaction time is preferably 10.5 - 56 h, more preferably 12.5 - 43 h, still more preferably 14 - 40 h.

[0022] In the present invention, after the reaction is completed, a crude product is obtained. The crude product is preferably subjected to rotary evaporation and silica gel column chromatography in sequence to obtain a polyfunctionalized naphthalene derivative.

[0023] 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.

[0024] The present invention also provides the application of the polyfunctionalized naphthalene derivative in fluorescent materials.

[0025] The technical solutions provided by the present invention will be described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.

[0026] In the examples, JohnPhosAuCl was purchased from Shanghai Bide Pharmaceutical Technology Co., Ltd., with a CAS number of 854045 - 93 - 5, a purity of 98%, and a specification of 1 g; AgBF4 was purchased from Anhui Zesheng Technology Co., Ltd., with a CAS number of 14104 - 20 - 2, a purity of 99%, and a specification of 1 g; Ethyl acetate was purchased from Beijing Merck Technology Co., Ltd., with a CAS number of 141 - 78 - 6, an AR purity of 99%, and a specification of 25 L; Petroleum ether was purchased from Shanghai Jiazu Industry Co., Ltd., with a CAS number of 8032 - 32 - 4, a purity of 99%, and a specification of 25 L; 1,4 - Dioxane was purchased from Beijing Merck Technology Co., Ltd., with a CAS number of 123 - 91 - 1, a purity of 99%, and a specification of 500 mL.

[0027] Example 1

[0028] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 1,5-diphenyl-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-dien-3-ol (1a), and react at 35 °C for 21 h. After the reaction is completed, rotary evaporate to remove 1,4-dioxane, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a).

[0029] 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); 13 C 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. Example 2

[0030] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-(cyclopropyl ethynyl)phenyl)-1,5-diphenylpenta-1,4-diyne-3-ol (1b), and react at 35 °C for 41 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0031] The white solid product 2a in this example was 38.1 mg, and the isolated yield was 63%.

[0032] Example 3 Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-(3,3-dimethylbut-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-diyne-3-ol (1c), and react at 80 °C for 24 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0033] The white solid product 2a in this example was 38.1 mg, and the isolated yield was 61%.

[0034] Example 4

[0035] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-(hept-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-diyne-3-ol (1d), and react at 35 °C for 45.5 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0036] The white solid product 2a in this example was 43.0 mg, and the isolated yield was 71%.

[0037] Example 5

[0038] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-(5-hydroxypent-1-yn-1-yl)phenyl)-1,5-diphenylpent-1,4-diyne-3-ol (1e), and react at 35 °C for 12.5 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0039] The white solid product 2a in this example was 36.0 mg, and the isolated yield was 59%.

[0040] Example 6

[0041] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-((4-methoxyphenyl)ethynyl)phenyl)-1,5-diphenylpent-1,4-diyne-3-ol (1f), and react at 50 °C for 23.5 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 3-phenyl-1-(phenylethynyl)naphthalene (white solid product 2a) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0042] The white solid product 2a in this example was 26.1 mg, and the isolated yield was 43%.

[0043] Example 7

[0044] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di-o-tolylpent-1,4-diyne-3-ol (1g), and react at 35 °C for 21.5 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 3-(o-tolyl)-1-(o-tolylethynyl)naphthalene (yellow liquid product 2g) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 200 - 100:1).

[0045] The yellow liquid product in this example was 44.7 mg for 2 g, and the isolation yield was 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); 13 C 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. Example 8

[0046] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3,3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di-m-tolylpenta-1,4-diyne-3-ol (1h), and react at 35 °C for 21.5 h. After the reaction is completed, rotary evaporate to remove 1,4-dioxane, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-(m-tolyl)-1-(m-tolylethynyl)naphthalene (yellow liquid product 2h).

[0047] The yellow liquid product 2h in this example was 44.6 mg, and the isolation yield was 67%. 11H NMR (400 MHz, Chloroform-d) δ 8.47 (d, J J = 8.0 Hz, 1H), 8.06 (d, J J = 9.3 Hz, 2H), 7.93 (d, J J = 7.9 Hz, 1H), 7.68 – 7.48 (m, 6H), 7.41 (t, J J = 7.5 Hz, 1H), 7.32 (t, J J = 7.6 Hz, 1H), 7.23 (t, J J = 7.8 Hz, 2H), 2.49 (s, 3H), 2.43 (s, 3H); 13 13C 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. Example 9

[0048] To a 4 mL sample vial was added 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-di-p-tolylpenta-1,4-diyne-3-ol (1i) was added, and the reaction was carried out at 35 °C for 21.5 h. After completion of the reaction, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1) was performed to obtain 3-(p-tolyl)-1-(p-tolylethynyl)naphthalene (yellow solid product 2i).

[0049] The yellow solid product 2i of this example was 49.5 mg, and the isolated yield was 74%. 11H NMR (600 MHz, Chloroform-d) δ 8.44 (d, J J = 8.1 Hz, 1H), 8.04 (s, 1H), 8.01 (s, 1H), 7.91 (d, J J = 8.0 Hz, 1H), 7.65 (d, J J = 8.0 Hz, 2H), 7.61 – 7.53 (m, 4H), 7.31 (d, J J = 7.8Hz, 2H), 7.22 (d, J J = 7.8 Hz, 2H), 2.44 (s, 3H), 2.41 (s, 3H); 13 13C 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. Example 10

[0050] 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added to a 4 mL sample vial, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-bis(thiophen-2-yl)penta-1,4-diyne-3-ol (1j) was added, and the reaction was carried out at 35 °C for 22.5 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1) was carried out to obtain 2-((3-(thiophen-2-yl)naphthalen-1-yl)ethynyl)thiophene (yellow solid product 2j).

[0051] The yellow solid product 2j in this example was 28.3 mg, and the isolated yield was 45%. 11H NMR (400 MHz, Chloroform-d) δ 8.34 (dd, J J = 7.6, 1.8 Hz, 1H), 8.04 (q, J J = 1.9 Hz, 2H), 7.87(dd, J J = 7.2, 2.0 Hz, 1H), 7.62 – 7.50 (m, 2H), 7.47 (dd, J J = 3.6, 1.1 Hz, 1H),7.42 (dd, J J = 3.6, 1.2 Hz, 1H), 7.40 – 7.32 (m, 2H), 7.14 (dd, J J = 5.1, 3.6 Hz,1H), 7.08 (dd, J J = 5.2, 3.6 Hz, 1H); 13 13C 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 1 13 8 + H + 14 Example 11

[0052] 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added to a 4 mL sample vial, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 1,5-bis(4-chlorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-dien-3-ol (1k) was added, and the reaction was carried out at 35 °C for 16 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1) was carried out to obtain 3-(4-chlorophenyl)-1-((4-chlorophenyl)ethynyl)naphthalene (yellow solid product 2k).

[0053] The yellow solid product 2k of this example was 46.7 mg, and the isolation 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. Example 12

[0054] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane, stir at room temperature for 1 h, and then add 0.2 mmol of 1,5-bis(3-chlorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyne-3-ol (1l), and react at 35 °C for 35 h. After the reaction is completed, rotary evaporate to remove 1,4-dioxane, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-(3-chlorophenyl)-1-((3-chlorophenyl)ethynyl)naphthalene (yellow solid product 2l).

[0055] The yellow solid product 2l of this example was 51.5 mg, and the separation 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. Example 13

[0056] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 1,5-bis(2-chlorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-dien-3-ol (1m), and react at 35 °C for 22.5 h. After the reaction is completed, rotary evaporate to remove 1,4-dioxane, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-(2-chlorophenyl)-1-((2-chlorophenyl)ethynyl)naphthalene (yellow liquid product 2m).

[0057] 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, 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. Example 14

[0058] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 1,5-bis(4-fluorophenyl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-dien-3-ol (1n), and react at 35 °C for 11 h. After the reaction is completed, rotary evaporate to remove 1,4-dioxane, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-(4-fluorophenyl)-1-((4-fluorophenyl)ethynyl)naphthalene (white solid product 2n).

[0059] The white solid product 2n of 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 / z calculated for C 24 H 15 F2 + [M + H] + : 341.1137, found: 341.1136. Example 15

[0060] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-bis(4-(trifluoromethyl)phenyl)penta-1,4-diyne-3-ol (1o) was added, and the reaction was carried out at 35 °C for 21 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1) was carried out to obtain 3-(4-(trifluoromethyl)phenyl)-1-((4-(tetrafluoromethyl)phenyl)ethynyl)naphthalene (yellow solid product 2o).

[0061] The yellow solid product 2o of 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 = 8.0 Hz, 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 / z calculated for C 26 H 15 F6 + [M+H] + : 441.1073, found: 441.1067. Example 16

[0062] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(2-(prop-1-yn-1-yl)phenyl)-1,5-bis(2-(trifluoromethyl)phenyl)penta-1,4-diyne-3-ol (1p), and react at 35 °C for 18.5 h. After the reaction is complete, remove 1,4-dioxane by rotary evaporation, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-(2-(trifluoromethyl)phenyl)-1-((2-(trifluoromethyl)phenyl)ethynyl)naphthalene (yellow liquid product 2p).

[0063] The yellow liquid product 2p of 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); 13 C 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(377MHz, 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. Example 17

[0064] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added. Then, 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 1,5-bis(naphthalen-1-yl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyne-3-ol (1q) was added, and the reaction was carried out at 35 °C for 14 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 150 - 100:1) was performed to obtain 4'-(naphthalen-1-ylethynyl)-1,2'-binaphthalene (yellow liquid product 2q).

[0065] The yellow liquid product 2q of this example was 59.9 mg, and the separation yield was 74%. 1 H 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. Example 18

[0066] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 1,5-bis(naphthalen-2-yl)-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-diyne-3-ol (1r), and react at 35 °C for 42 h. After the reaction is complete, rotary evaporate to remove 1,4-dioxane, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 4-(naphthalen-2-ylethynyl)-2,2'-binaphthalene (white solid product 2r).

[0067] The white solid product 2r of this example was 52.8 mg, and the isolated yield was 65%. 1 1H 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 19 21 + [M+H] + : 405.1638, found: 405.1633. Example 19

[0068] To a 4 mL sample vial, 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 3-(4-methoxy-2-(prop-1-yn-1-yl)phenyl)-1,5-diphenylpenta-1,4-dien-3-ol (1s) was added, and the reaction was carried out at 35 °C for 14 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100 - 50:1) was carried out to obtain 6-methoxy-3-phenyl-1-(phenylethynyl)naphthalene (yellow solid product 2s).

[0069] 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. Example 20

[0070] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4 - dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-(5 - methyl - 2-(prop - 1 - yn - 1 - yl)phenyl)-1,5 - diphenylpenta - 1,4 - diyn - 3 - ol (1t) and react at 35 °C for 14 h. After the reaction is completed, remove 1,4 - dioxane by rotary evaporation and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 7 - methyl - 3 - phenyl - 1-(phenylethynyl)naphthalene (yellow solid product 2t).

[0071] 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. Example 21

[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. After stirring at room temperature for 1 h, 0.2 mmol of 2,2,8,8-tetramethyl-5-(2-(prop-1-yn-1-yl)phenyl)nona-3,6-diyne-5-ol (1u) was added, and the reaction was carried out at 35 °C for 10.5 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1) was performed to obtain 3-(tert-butyl)-1-(3,3-dimethylbut-1-yn-1-yl)naphthalene (white solid product 2u).

[0073] The white solid product 2u of 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. Example 22

[0074] To a 4 mL sample vial, add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 1,5-dicyclopropyl-3-(2-(prop-1-yn-1-yl)phenyl)penta-1,4-dien-3-ol (1v), and react at 35 °C for 18.5 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and perform silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1) to obtain 3-cyclopropyl-1-(cyclopropyl ethynyl)naphthalene (orange liquid product 2v).

[0075] The orange liquid product 2v in this example is 30.2 mg, and the isolated yield is 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. Example 23

[0076] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 3-phenyl-1-(2-(prop-1-yn-1-yl)phenyl)prop-2-en-1-ol (1w), and react at 35 °C for 21 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 2-phenylnaphthalene (white solid product 2w) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0077] 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. Example 24

[0078] Add 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 to a 4 mL sample vial, then add 0.5 mL of 1,4-dioxane. After stirring at room temperature for 1 h, add 0.2 mmol of 4-phenyl-2-(2-(prop-1-yn-1-yl)phenyl)but-3-yn-2-ol (1x), and react at 35 °C for 43 h. After the reaction is completed, remove 1,4-dioxane by rotary evaporation, and obtain 1-methyl-3-phenylnaphthalene (white solid product 2x) by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).

[0079] The white solid product 2x of 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. Example 25

[0080] 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4 were added to a 4 mL sample vial, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 1,3-diphenyl-1-(2-(prop-1-yn-1-yl)phenyl)prop-2-en-1-ol (1y) was added, and the reaction was carried out at 35 °C for 33 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation, and 1,3-diphenylnaphthalene (white solid product 2y) was obtained by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate was 100:1).

[0081] The white solid product 2y of 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. Example 26

[0082] To a 4 mL sample vial was added 0.01 mmol of JohnPhosAuCl and 0.01 mmol of AgBF4, then 0.5 mL of 1,4-dioxane was added. After stirring at room temperature for 1 h, 0.2 mmol of 6,6-dimethyl-1-phenyl-3-(2-(prop-1-yn-1-yl)phenyl)hepta-1,4-diyne-3-ol (1z) was added, and the reaction was carried out at 35 °C for 41 h. After the reaction was completed, 1,4-dioxane was removed by rotary evaporation. Through silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate was 100:1), a mixture of 1-(3,3-dimethylbut-1-yn-1-yl)-3-phenylnaphthalene (2z) and 3-(tert-butyl)-1-(phenylethynyl)naphthalene (2z’) (yellow liquid product) was obtained.

[0083] The mixture of the yellow liquid products 2z and 2z’ in this example was 37.1 mg (the mass ratio of 2z to 2z’ was 2.58:1), and the total separation yield was 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. It was found through the study of the ultraviolet / visible and fluorescence spectra of the compounds that the yields of most compounds are relatively high. By comparing with naphthalene derivatives without alkynyl groups, it was found that the alkynyl substituents have a significant impact on the optical spectra of the compounds, and the alkynyl substituents play a special role in affecting the absorption onset and fluorescence spectra. The above-mentioned alkynyl naphthalene derivatives can be used as fluorescent probes and have application value in biological imaging.

[0084] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A polyfunctionalized naphthalene derivative, characterized in that, The structural formula of the polyfunctionalized naphthalene derivative is as follows: ； wherein, 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 is alkynyl, the alkynyl is connected to R 2 .

2. The polyfunctionalized naphthalene derivative according to claim 1, wherein The structural formula of the polyfunctionalized naphthalene derivative is as follows: , , , , , , , , , , , , , , , , , , , , or .

3. A method for preparing the polyfunctionalized naphthalene derivative according to claim 1 or 2, characterized in that, The synthetic route of the polyfunctionalized naphthalene derivative is as follows: Among them, R 1 is an alkyl or 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, and when R 4 is alkynyl, the alkynyl is attached to R 2 ; The preparation method of the polyfunctionalized 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 reacts with a 1,6-diyne-3-ol compound to obtain a polyfunctionalized naphthalene derivative.

4. The method for preparing the polyfunctionalized naphthalene derivative according to claim 3, characterized in that, The molar ratio of the chloro[2-(di-tert-butylphosphino)diphenyl]gold, silver tetrafluoroborate and the 1,6-diyne-3-ol compound is 0.04~0.06:0.04~0.06:

1.

5. The method for preparing a polyfunctionalized naphthalene derivative according to claim 3 or 4, characterized in that, The molar volume ratio of the 1,6-diyne-3-ol compound and 1,4-dioxane is 0.2 mmol:0.35~0.65 mL.

6. The preparation method of the polyfunctionalized naphthalene derivative according to claim 5, characterized in that, 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.

7. The method for preparing a polyfunctionalized naphthalene derivative according to claim 6, characterized in that, After the reaction is completed, a crude product is obtained, and the crude product is successively subjected to rotary evaporation and silica gel column chromatography to obtain a polyfunctionalized naphthalene derivative.

8. The method for preparing a polyfunctionalized naphthalene derivative according to claim 7, characterized in that, 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.

9. Use of the polyfunctionalized naphthalene derivative according to claim 1 or 2 in a fluorescent material.

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