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CN120271409B - A multifunctional naphthalene derivative and its preparation method and application - Google Patents

A multifunctional naphthalene derivative and its preparation method and application

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Publication number
CN120271409B
CN120271409B CN202510732994.4A CN202510732994A CN120271409B CN 120271409 B CN120271409 B CN 120271409B CN 202510732994 A CN202510732994 A CN 202510732994A CN 120271409 B CN120271409 B CN 120271409B
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multifunctional
naphthalene derivative
phenyl
naphthalene
dioxane
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CN120271409A (en
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李军
臧爽
武彦彬
朱伟东
马睿
马玉勇
王宁伟
卢信清
涂高美
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Zhejiang Normal University CJNU
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Abstract

本发明属于有机合成技术领域，提供了一种多官能化萘衍生物及其制备方法和应用。本发明的多官能化萘衍生物的结构式中，R2为烷基、苯基、2‑萘基、1‑萘基、2‑噻吩基、连有吸电子基团的芳环或连有供电子基团的芳环，吸电子基团和供电子基团包含甲基、甲氧基、三氟甲基或卤素；R3为H、甲基或甲氧基；R4为H、甲基、苯基或炔基。本发明使用1,6‑二炔‑3‑醇类化合物为原料，以[2‑(二叔丁基膦)联苯]氯化金(I)和四氟硼酸银为催化剂，通过分子内6‑endo‑dig环化、3,3‑Claisen重排、芳构化反应，最后脱酰基化反应得到具有苯基、苯乙炔基和萘环结构的多官能化萘衍生物，在多个领域具有应用价值。The invention belongs to the technical field of organic synthesis, and provides a kind of multifunctional naphthalene derivative and its preparation method and application.In the structural formula of the multifunctional naphthalene derivative of the present invention, R2 is alkyl, phenyl, 2 naphthyl, 1 naphthyl, 2 thienyl, the aromatic ring of electron-withdrawing group or the aromatic ring of electron-donating group, electron-withdrawing group and electron-donating group include methyl, methoxyl group, trifluoromethyl or halogen； R3 is H, methyl or methoxyl group； R4 is H, methyl, phenyl or alkynyl. The present invention uses 1,6 diyne 3 alcohol compounds as raw materials, with [2 (di-tert-butylphosphine) biphenyl] gold chloride (I) and silver tetrafluoroborate as catalyst, by intramolecular 6 endo dig cyclization, 3,3 Claisen rearrangement, aromatization reaction, finally deacylation reaction obtains the multifunctional naphthalene derivative with phenyl, phenylethynyl and naphthalene ring structure, has application value in multiple fields.

Description

Multifunctional naphthalene derivative and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a multifunctional naphthalene derivative, a preparation method and application thereof.
Background
Because of the unique property of naphthalene ring structure, the compound containing naphthalene ring skeleton has wide application in the fields of medicines, pesticides, optical functional materials and the like. However, the current synthesis method of functionalized naphthalene ring is mainly realized by electrophilic functionalization reaction of naphthalene, the selectivity of the method is often poor, a mixture of electrophilic addition reactions of different sites is usually obtained, and separation and purification are difficult. Another method is to construct naphthalene rings by cyclization, introducing various substituents on the reaction precursors in advance, which can give highly functionalized naphthalene ring derivatives. A method for efficiently synthesizing alkynyl naphthalene derivatives by taking a simple and easily available 1, 6-diyne-3-ol compound as an initial raw material and gold as a catalyst has not been reported in related literature.
Therefore, the development of a novel simple and efficient method for synthesizing the polyfunctional naphthalene derivative is of great significance.
Disclosure of Invention
The invention aims to provide a multifunctional naphthalene derivative, a preparation method and application thereof, aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a multifunctional naphthalene derivative, which has the structural formula:
;
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, and when R 4 is alkynyl, R 2 is connected to the alkynyl.
Preferably, the polyfunctional naphthalene derivative has the structural formula:
、、、、、、、、、、、、、、、
、、、、、 Or (b) 。
The invention also provides a preparation method of the multifunctional naphthalene derivative, and the synthetic route of the multifunctional naphthalene derivative is as follows:
;
Wherein R 1 is alkyl or aryl;
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, R 2 is connected to the alkynyl;
the preparation method of the polyfunctional naphthalene derivative comprises the following steps:
Mixing chlorine [2- (di-tert-butyl phosphorus) diphenyl ] gold, silver tetrafluoroborate and 1, 4-dioxane to obtain a reaction solution, and reacting the reaction solution with a 1, 6-diyne-3-alcohol compound to obtain the multifunctional naphthalene derivative.
Preferably, the molar ratio of the chlorine [2- (di-tert-butyl phosphorus) diphenyl ] gold, the silver tetrafluoroborate and the 1, 6-diyne-3-ol compound is 0.04-0.06:0.04-0.06:1.
Preferably, the molar volume ratio of the 1, 6-diyne-3-ol compound and the 1, 4-dioxane is 0.2 mmol:0.35-0.65 mL.
Preferably, the mixing time is 0.8-1.2 h, the reaction temperature is 30-85 ℃, and the reaction time is 10.5-56 h.
Preferably, the crude product is obtained after the reaction is completed, and the crude product is sequentially subjected to rotary evaporation and silica gel column chromatography to obtain the polyfunctional naphthalene derivative.
Preferably, the eluent of the silica gel column chromatography is petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 50-200:1.
The invention also provides application of the multifunctional naphthalene derivative in fluorescent materials.
The beneficial effects of the invention include:
According to the invention, 1, 6-diyne-3-alcohol compound is used as an initial raw material, chlorine [2- (di-tert-butyl phosphorus) diphenyl ] gold (JohnPhosAuCl) and silver tetrafluoroborate (AgBF 4) are used as catalysts, and a molecule of carboxylic acid byproduct is obtained through intramolecular 6-endo-dig cyclization, 3-Claisen rearrangement and aromatization reaction, and finally deacylation reaction, and meanwhile, the multifunctional naphthalene derivative is generated. The multifunctional naphthalene derivative has phenyl, phenylethynyl and naphthalene ring structures, and the multifunctional groups have application values in various fields. For example, conjugated structures exist, which have good photoelectric properties, are suitable for luminescent layers or electron transport layers in OLEDs, have fluorescent properties, can be used as fluorescent probes in biological imaging to assist in research of molecular processes in living beings, can be used as intermediates in organic synthesis for constructing more complex molecular structures, particularly in the synthesis of polycyclic aromatic hydrocarbons and conjugated systems, and can also be used as precursor compounds in pharmaceutical chemistry for developing molecules with biological activity.
Detailed Description
The invention provides a multifunctional naphthalene derivative, which has the structural formula:
;
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, and when R 4 is alkynyl, R 2 is connected to the alkynyl.
In the present invention, the structural formula of the polyfunctional naphthalene derivative is preferably:
、、、、、、、、、、、、、、、
、、、、、 Or (b) 。
The invention also provides a preparation method of the multifunctional naphthalene derivative, and the synthetic route of the multifunctional naphthalene derivative is as follows:
Wherein R 1 is alkyl or aryl;
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, R 2 is connected to the alkynyl;
the preparation method of the polyfunctional naphthalene derivative comprises the following steps:
Chlorine [2- (di-tert-butyl phosphorus) diphenyl ] gold (JohnPhosAuCl), silver tetrafluoroborate (AgBF 4) and 1, 4-dioxane are mixed to obtain a reaction solution, and the reaction solution reacts with 1, 6-diyne-3-alcohol compounds to obtain the multifunctional naphthalene derivative.
In the invention, the molar ratio of the chlorine [2- (di-tert-butyl phosphorus) diphenyl ] gold, the 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.
In the invention, the molar volume ratio of the 1, 6-diacetylene-3-alcohol compound to the 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 0.2mmol:0.5mL.
In the invention, the mixing time is preferably 0.8-1.2 h, more preferably 1h, and the mixing is preferably performed at room temperature, the reaction temperature is preferably 30-85 ℃, more preferably 35-80 ℃, more preferably 50-70 ℃, and the reaction time is preferably 10.5-56 h, more preferably 12.5-43 h, more preferably 14-40 h.
In the invention, a crude product is obtained after the reaction is completed, and the crude product is preferably subjected to rotary evaporation and silica gel column chromatography in sequence to obtain the polyfunctional naphthalene derivative.
In the invention, the eluent of the silica gel column chromatography is preferably petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is preferably 50-200:1, more preferably 100-150:1, and the solvent 1, 4-dioxane is removed by rotary evaporation.
The invention also provides application of the multifunctional naphthalene derivative in fluorescent materials.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
In the examples JohnPhosAuCl was purchased from Shanghai Bi medical science and technology Co., ltd, CAS number 854045-93-5, purity 98%, specification 1g;
AgBF 4 was purchased from Anhui Hirudo technologies Co., ltd, CAS number 14104-20-2, purity 99%, specification 1g;
Ethyl acetate was purchased from beijing meruida technologies, ltd, CAS No. 141-78-6, purity AR 99%, 25L gauge;
petroleum ether is purchased from Shanghai Jia foot industries, inc., CAS number 8032-32-4, purity 99% and specification 25L;
1, 4-Dioxa-ring was purchased from Beijing Michael technologies Co., ltd, CAS number 123-91-1, purity 99%, specification 500mL.
Example 1
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-diphenyl-3- (2- (prop-1-yn-1-yl) phenyl) pent-1, 4-diyn-3-ol (1 a) was added and reacted at 35℃for 21h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-phenyl-1- (phenylethynyl) naphthalene (white solid product 2 a) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The white solid product 2a of this example was 46.4mg in isolated yield 77%,1H 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 C24H17 +[M+H]+: 305.1325, found: 305.1326.
Example 2
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (cyclopropylethynyl) phenyl) -1, 5-diphenylpent-1, 4-diyn-3-ol (1 b) was added and reacted at 35℃for 41h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-phenyl-1- (phenylethynyl) naphthalene (white solid product 2 a) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The white solid product 2a of this example was 38.1mg, isolated in 63%.
Example 3
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (3, 3-dimethylbut-1-yn-1-yl) phenyl) -1, 5-diphenylpenta-1, 4-diyn-3-ol (1C) was added and reacted at 80℃for 24h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-phenyl-1- (phenylethynyl) naphthalene (white solid product 2 a) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The white solid product 2a of this example was 38.1mg, isolated in 61% yield.
Example 4
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (hept-1-yn-1-yl) phenyl) -1, 5-diphenylpent-1, 4-diyn-3-ol (1 d) was added and reacted at 35℃for 45.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-phenyl-1- (phenylethynyl) naphthalene (white solid product 2 a) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The white solid product 2a of this example was 43.0mg and isolated in 71% yield.
Example 5
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (5-hydroxypent-1-yn-1-yl) phenyl) -1, 5-diphenylpent-1, 4-diyn-3-ol (1 e) was added and reacted at 35℃for 12.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-phenyl-1- (phenylethynyl) naphthalene (white solid product 2 a) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The white solid product 2a of this example was 36.0mg and isolated in 59% yield.
Example 6
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- ((4-methoxyphenyl) ethynyl) phenyl) -1, 5-diphenylpent-1, 4-diyn-3-ol (1 f) was added and reacted at 50℃for 23.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-phenyl-1- (phenylethynyl) naphthalene (white solid product 2 a) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The white solid product 2a of this example was 26.1mg and isolated in 43% yield.
Example 7
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (prop-1-yn-1-yl) phenyl) -1, 5-di-o-tolylpentan-1, 4-diyn-3-ol (1 g) was added and reacted at 35℃for 21.5h. After the reaction is completed, removing the 1, 4-dioxane by rotary evaporation, and performing silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 200-100:1) to obtain 3- (o-tolyl) -1- (o-tolylethynyl) naphthalene (2 g of yellow liquid product).
The yellow liquid product of this example, 2g, was 44.7mg in isolated yield 67%.1H 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) δ 141.20, 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/z calculated for C26H21 +[M+H]+: 333.1638, found: 333.1635.
Example 8
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3,3- (2- (prop-1-yn-1-yl) phenyl) -1, 5-xylenylpent-1, 4-diyn-3-ol (1 h) was added and reacted at 35℃for 21.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3- (m-tolyl) -1- (m-tolylethynyl) naphthalene (yellow liquid product 2 h) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate: 100:1).
The yellow liquid product of this example was 44.6mg for 2h in isolated yield 67%.1H 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);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 C26H21 +[M+H]+: 333.1638, found: 333.1626.
Example 9
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (prop-1-yn-1-yl) phenyl) -1, 5-di-p-tolylpent-1, 4-diyn-3-ol (1 i) was added and reacted at 35℃for 21.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3- (p-tolyl) -1- (p-tolylethynyl) naphthalene (yellow solid product 2 i) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate: 100:1).
The yellow solid product 2i of this example was 49.5mg in isolated yield 74%.1H 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= 7.8 Hz, 2H), 7.22 (d,J= 7.8 Hz, 2H), 2.44 (s, 3H), 2.41 (s, 3H);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 C26H21 +[M+H]+: 333.1638, found: 333.1634.
Example 10
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, then 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (prop-1-yn-1-yl) phenyl) -1, 5-di (thiophen-2-yl) pent-1, 4-diyn-3-ol (1 j) was added and reacted at 35℃for 22.5h. After the reaction is completed, the 1, 4-dioxane is removed by rotary evaporation, and the 2- ((3- (thiophene-2-yl) naphthalene-1-yl) ethynyl) thiophene (yellow solid product 2 j) is obtained by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100:1).
The yellow solid product 2j of this example was 28.3mg in isolated yield 45%.1H 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);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 C20H13S2 +[M+H]+: 317.0454, found: 317.0451.
Example 11
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-bis (4-chlorophenyl) -3- (2- (prop-1-yn-1-yl) phenyl) penta-1, 4-diyn-3-ol (1 k) was added and reacted at 35℃for 16h. After the reaction, 1, 4-dioxane was removed by rotary evaporation, and 3- (4-chlorophenyl) -1- ((4-chlorophenyl) ethynyl) naphthalene (yellow solid product 2 k) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1).
The yellow solid product 2k of this example was 46.7mg in isolated yield 63%.1H NMR(600 MHz, Chloroform-d) δ 8.40 (d,J= 8.2 Hz, 1H), 8.02 – 7.96 (m, 2H), 7.91 (d,J= 8.0 Hz, 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);13C 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/z calculated for C24H15 35Cl2 +[M+H]+: 373.0546, found: 373.0532; m/z calculated for C24H15 37Cl2 +[M+H]+: 377.0487, found: 377.0489.
Example 12
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-bis (3-chlorophenyl) -3- (2- (prop-1-yn-1-yl) phenyl) penta-1, 4-diyn-3-ol (1 l) was added and reacted at 35℃for 35h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1) was performed to obtain 3- (3-chlorophenyl) -1- ((3-chlorophenyl) ethynyl) naphthalene (yellow solid product 2 l).
The yellow solid product of this example, 2l, was 51.5mg, isolated in yield 68%.1H 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);13C 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 C24H15 35Cl2 +[M+H]+: 373.0546, found: 373.0535; m/z calculated for C24H15 37Cl2 +[M+H]+: 377.0487, found: 377.0491.
Example 13
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, then 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol of 1, 5-bis (2-chlorophenyl) -3- (2- (prop-1-yn-1-yl) phenyl) penta-1, 4-diyn-3-ol (1 m) was added and reacted at 35℃for 22.5h. After the reaction, the 1, 4-dioxane was removed by rotary evaporation, and 3- (2-chlorophenyl) -1- ((2-chlorophenyl) ethynyl) naphthalene (yellow liquid product 2 m) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1).
The yellow liquid product 2m of this example was 58.5mg in isolated yield 78%.1H 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);13C 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 for C24H15 35Cl2 +[M+H]+: 373.0546, found: 373.0540; m/z calculated for C24H15 37Cl2 +[M+H]+: 377.0487, found: 377.0489.
Example 14
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, then 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-bis (4-fluorophenyl) -3- (2- (prop-1-yn-1-yl) phenyl) penta-1, 4-diyn-3-ol (1 n) was added and reacted at 35℃for 11h. After the reaction, 1, 4-dioxane was removed by rotary evaporation, and 3- (4-fluorophenyl) -1- ((4-fluorobenzene) ethynyl) naphthalene (white solid product 2 n) was obtained by silica gel column chromatography (the volume ratio of petroleum ether and ethyl acetate is 100:1).
The white solid product 2n of this example was 49.4mg in isolated yield 73%.1H 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);13C 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;19F NMR(377 MHz, Chloroform-d) δ -110.48, -115.03.GCMS(PCI+) m/z calculated for C24H15F2 +[M+H]+: 341.1137, found: 341.1136.
Example 15
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, then 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (2- (prop-1-yn-1-yl) phenyl) -1, 5-bis (4- (trifluoromethyl) phenyl) pent-1, 4-diyne-3- (1 o) was added and reacted at 35℃for 21h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3- (4- (trifluoromethyl) phenyl) -1- ((4- (tetrafluoromethyl) benzene) ethynyl) naphthalene (yellow solid product 2 o) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate was 100:1).
The yellow solid product 2o of this example was 64.9mg in isolated yield 74%.1H 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);13C 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;19F NMR(377 MHz, Chloroform-d) δ -62.38, -62.74.GCMS(PCI+) m/z calculated for C26H15F6 +[M+H]+: 441.1073, found: 441.1067.
Example 16
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, then 0.5mL 1, 4-dioxane, stirred at room temperature for 1h, then 0.2mmol 3- (2- (prop-1-yn-1-yl) phenyl) -1, 5-bis (2- (trifluoromethyl) phenyl) pent-1, 4-diyn-3-ol (1 p) was added and reacted at 35℃for 18.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3- (2- (trifluoromethyl) phenyl) -1- ((2- (trifluoromethyl) benzene) ethynyl) naphthalene (yellow liquid product 2 p) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate: 100:1).
The yellow liquid product 2p of this example was 37.2mg in isolated yield 42%.1H 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= 30.7 Hz), 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, 90.21.19F NMR(377 MHz, Chloroform-d) δ -56.74, -62.04.GCMS(PCI+) m/z calculated for C26H15F6 +[M+H]+: 441.1073, found: 441.1071.
Example 17
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-bis (naphthalen-1-yl) -3- (2- (prop-1-yn-1-yl) phenyl) pent-1, 4-diyn-3-ol (1 q) was added and reacted at 35℃for 14h. After the reaction is completed, removing the 1, 4-dioxane by rotary evaporation, and performing silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 150-100:1) to obtain 4'- (naphthalene-1-ylethynyl) -1,2' -binaphthyl (yellow liquid product 2 q).
The yellow liquid product 2q of this example was 59.9mg in isolated yield 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);13C 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 for C32H21 +[M+H]+: 405.1638, found: 405.1630.
Example 18
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-bis (naphthalen-2-yl) -3- (2- (prop-1-yn-1-yl) phenyl) pent-1, 4-diyn-3-ol (1 r) was added and reacted at 35℃for 42h. After the reaction, 1, 4-dioxane was removed by rotary evaporation, and the mixture was subjected to silica gel column chromatography (the volume ratio of petroleum ether and ethyl acetate was 100:1) to give 4- (naphthalen-2-ylethynyl) -2,2' -binaphthyl (white solid product 2 r).
The white solid product 2r of this example was 52.8mg in isolated yield 65%.1H NMR(600 MHz, Chloroform-d) δ 8.56 (d,J= 8.2 Hz, 1H), 8.25 (s, 1H), 8.23 (d,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= 8.3 Hz, 1H), 7.67 (t,J= 7.6 Hz, 1H), 7.61 (t,J= 7.5 Hz, 1H), 7.58 – 7.51 (m, 4H);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 C32H21 +[M+H]+: 405.1638, found: 405.1633.
Example 19
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (4-methoxy-2- (prop-1-yn-1-yl) phenyl) -1, 5-diphenylpenta-1, 4-diyn-3-ol (1 s) was added and reacted at 35℃for 14h. After the reaction is finished, removing the 1, 4-dioxane by rotary evaporation, and performing silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 100-50:1) to obtain 6-methoxy-3-phenyl-1- (phenylethynyl) naphthalene (yellow solid product 2 s).
The yellow solid product 2s of this example was 41.8mg in isolated yield 63%.1H 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);13C 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/z calculated for C25H19O+[M+H]+: 335.1431, found: 335.1428.
Example 20
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3- (5-methyl-2- (prop-1-yn-1-yl) phenyl) -1, 5-diphenylpenta-1, 4-diyn-3-ol (1 t) was added and reacted at 35℃for 14h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and the mixture was subjected to silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1) to obtain 7-methyl-3-phenyl-1- (phenylethynyl) naphthalene (yellow solid product 2 t).
The yellow solid product 2t of this example was 46.4mg in isolated yield 73%.1H 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);13C 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 C25H19 +[M+H]+: 319.1482, found: 319.1487.
Example 21
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl, 0.01mmol AgBF 4, then 0.5mL 1, 4-dioxane, stirred at room temperature for 1h, then 0.2mmol 2, 8-tetramethyl-5- (2- (prop-1-yn-1-yl) phenyl) non-3, 6-diyn-5-ol (1 u) was added and reacted at 35℃for 10.5h. After the reaction, 1, 4-dioxane was removed by rotary evaporation, and 3- (tert-butyl) -1- (3, 3-dimethylbut-1-yn-1-yl) naphthalene (white solid product 2 u) was obtained by silica gel column chromatography (volume ratio of petroleum ether to ethyl acetate: 100:1).
The white solid product 2u of this example was 40.2mg in isolated yield 76%.1H 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);13C 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 C20H25 +[M+H]+: 265.1951, found: 265.1952.
Example 22
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 5-dicyclohexyl-3- (2- (prop-1-yn-1-yl) phenyl) penta-1, 4-diyn-3-ol (1 v) was added and reacted at 35℃for 18.5h. After the reaction was completed, 1, 4-dioxane was removed by rotary evaporation, and 3-cyclopropyl-1- (cyclopropylethynyl) naphthalene (orange liquid product 2 v) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The orange liquid product 2v of this example was 30.2mg in isolated yield 65%.1H 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);13C 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 C18H17 +[M+H]+: 233.1325, found: 233.1321.
Example 23
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 3-phenyl-1- (2- (prop-1-yn-1-yl) phenyl) prop-2-en-1-ol (1 w) was added and reacted at 35℃for 21h. After the reaction, 1, 4-dioxane was removed by rotary evaporation, and the mixture was subjected to silica gel column chromatography (the volume ratio of petroleum ether and ethyl acetate was 100:1) to obtain 2-phenyl naphthalene (white solid product 2 w).
The white solid product 2w of this example was 23.6mg in isolated yield 58%.1H 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);13C NMR(101 MHz, Chloroform-d) δ 141.28, 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 C16H13 +[M+H]+: 205.1012, found: 205.1013.
Example 24
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 4-phenyl-2- (2- (prop-1-yn-1-yl) phenyl) but-3-yn-2-ol (1X) was added and reacted at 35℃for 43h. After the reaction, the 1, 4-dioxane was removed by rotary evaporation, and the 1-methyl-3-phenyl naphthalene (white solid product 2 x) was obtained by silica gel column chromatography (the volume ratio of petroleum ether and ethyl acetate was 100:1).
The white solid product 2x of this example was 23.7mg in isolated yield 54%.1H 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);13C NMR(151 MHz, 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/z calculated for C17H15 +[M+H]+: 219.1169, found: 219.1167.
Example 25
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 1, 3-diphenyl-1- (2- (prop-1-yn-1-yl) phenyl) prop-2-en-1-ol (1 y) was added and reacted at 35℃for 33h. After the reaction, the 1, 4-dioxane was removed by rotary evaporation, and 1, 3-diphenylnaphthalene (white solid product 2 y) was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate was 100:1).
The white solid product 2y of this example was 35.6mg in isolated yield 61%.1H 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);13C NMR(151 MHz, 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 C22H17 +[M+H]+: 281.1325, found: 281.1339.
Example 26
To a 4mL sample bottle was added 0.01mmol JohnPhosAuCl mmol AgBF 4, followed by 0.5mL 1, 4-dioxane, and after stirring at room temperature for 1h, 0.2mmol 6, 6-dimethyl-1-phenyl-3- (2- (prop-1-yn-1-yl) phenyl) hept-1, 4-diyn-3-ol (1 z) was added and reacted at 35℃for 41h. After the completion of the reaction, 1, 4-dioxane was removed by rotary evaporation, and a mixture (yellow liquid product) of 1- (3, 3-dimethylbut-1-yn-1-yl) -3-phenylnaphthalene (2 z) and 3- (tert-butyl) -1- (phenylethynyl) naphthalene (2 z') was obtained by silica gel column chromatography (volume ratio of petroleum ether and ethyl acetate: 100:1).
The mixture of the yellow liquid products 2z and 2z 'of this example was 37.1mg (mass ratio of 2z and 2z' is 2.58:1), and the total isolation yield was 57%.1H 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');13C NMR(101 MHz, Chloroform-d) δ 148.14, 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 C22H20Na+[M+Na]+: 307.1458, found: 307.1486.
As a result of ultraviolet/visible light and fluorescence spectrum studies on the compounds, the yields of most compounds were found to be relatively high. Compared with naphthalene derivatives without alkynyl groups, the alkynyl substituent groups have obvious influence on the optical spectrum of the compound, and play a special role in influencing the absorption starting point and the fluorescence spectrum. The alkynyl naphthalene derivative can be used as a fluorescent probe and has application value in biological imaging.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1.一种多官能化萘衍生物的制备方法，其特征在于，多官能化萘衍生物的合成路线为：1. A method for preparing a multifunctional naphthalene derivative, characterized in that the synthetic route of the multifunctional naphthalene derivative is: 其中，R1为烷基或芳基；Wherein, R 1 is an alkyl group or an aryl group; R2为丙基、叔丁基、苯基、2-萘基、1-萘基、2-噻吩基、甲基苯基、甲氧基苯基、三氟甲基苯基、氯苯基或氟苯基； R2 is propyl, tert-butyl, phenyl, 2-naphthyl, 1-naphthyl, 2-thienyl, methylphenyl, methoxyphenyl, trifluoromethylphenyl, chlorophenyl or fluorophenyl; R3为H、甲基或甲氧基； R3 is H, methyl or methoxy; R4为H、甲基、苯基或炔基，当R4为炔基时，炔基上连有R2；R 4 is H, methyl, phenyl or alkynyl. When R 4 is alkynyl, R 2 is attached to the alkynyl. 多官能化萘衍生物的制备方法包含如下步骤：The preparation method of the multifunctional naphthalene derivative comprises the following steps: 将氯[2-(二叔丁基磷)二苯基]金、四氟硼酸银和1,4-二氧六环混合，得到反应液，反应液和1,6-二炔-3-醇类化合物进行反应，得到多官能化萘衍生物。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.根据权利要求1所述的多官能化萘衍生物的制备方法，其特征在于，所述多官能化萘衍生物的结构式为：2. The method for preparing a multifunctional naphthalene derivative according to claim 1, wherein the structural formula of the multifunctional naphthalene derivative is: 3.根据权利要求1所述的多官能化萘衍生物的制备方法，其特征在于，所述氯[2-(二叔丁基磷)二苯基]金、四氟硼酸银和1,6-二炔-3-醇类化合物的摩尔比为0.04～0.06：0.04～0.06：1。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.根据权利要求3所述的多官能化萘衍生物的制备方法，其特征在于，所述1,6-二炔-3-醇类化合物和1,4-二氧六环的摩尔体积比为0.2mmol：0.35～0.65mL。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 to 1,4-dioxane is 0.2 mmol:0.35-0.65 mL. 5.根据权利要求4所述的多官能化萘衍生物的制备方法，其特征在于，所述混合的时间为0.8～1.2h；所述反应的温度为30～85℃，反应的时间为10.5～56h。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.根据权利要求5所述的多官能化萘衍生物的制备方法，其特征在于，反应完成后得到粗产物，粗产物顺次进行旋蒸、硅胶柱层析，得到多官能化萘衍生物。6. The method for preparing a multifunctional naphthalene derivative according to claim 5, wherein a crude product is obtained after the reaction is completed, and the crude product is subjected to rotary evaporation and silica gel column chromatography in sequence to obtain the multifunctional naphthalene derivative. 7.根据权利要求6所述的多官能化萘衍生物的制备方法，其特征在于，硅胶柱层析的洗脱液为石油醚和乙酸乙酯，石油醚和乙酸乙酯的体积比为50～200：1。7 . The method for preparing a multifunctional naphthalene derivative according to claim 6 , wherein 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 to 200:1.
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