Preparation method of mono-cyano diarylethene compound

Abstract

The invention discloses a preparation method of a mono-cyano diarylethene compound, which comprises the following steps: in a solvent, carrying out heating reaction on substituted aryl benzaldehyde and substituted benzyl cyanide under the action of alkali; the structure of the mono-cyano diarylethene compound is # imgabs0 #; the structure of substituted aryl benzaldehyde is L-CHO; the substituted benzyl cyanide is benzyl cyanide containing an electron withdrawing group. The preparation method provided by the invention has the advantages of simple operation, wide substrate application range, high yield, easily available reaction raw materials, low cost, less pollution and the like.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing a monocyanodiarylethene compound. Background Art

[0002] Luminescent materials have a wide range of applications in the fields of light sources, optoelectronic devices, chemical sensors, biological probes, etc. However, traditional organic luminescent materials have an insurmountable problem: aggregation leads to luminescence quenching effect, that is, the luminescent molecules can emit light efficiently in dilute solutions, but in high-concentration solutions or solid states, their fluorescence is significantly weakened or even disappears, which greatly limits their application. In 2001, Academician Tang Benzhong proposed the scientific concept of "aggregation-induced emission" (AIE), that is, the molecules hardly emit light in solution, but emit strong fluorescence in the aggregated state or solid film. The discovery of AIE broke the shackles of traditional concepts and opened up new ways for the design and functional development of luminescent materials. Monocyanodiarylethene, that is, monocyano functionalized diarylethene, as a typical aggregation-induced emission molecule, is favored for its unique aggregation-induced fluorescence enhancement performance and the characteristics of adjustable fluorescence during isomerization. It has been widely used in liquid crystal display, sensors, information storage and encryption, shape-adjustable smart materials and biomedical imaging.

[0003] At present, there are mainly the following methods for synthesizing monocyanodiarylethene derivatives: (A) Metal or photocatalyzed olefin cyanation reaction: This method uses CN -As a nitrile source, olefin derivatives are cyanated by metal-catalyzed CC bond coupling reaction or photocatalyzed CH bond activation (Hallberg, A. et al. J. Org. Chem. 2000, 65, 7984-7989; Studer, A. et al. Angew. Chem. Int. Ed. 2018, 57, 11792-11796); (B) Metal or photocatalyzed α-olefination of aromatic vinyl: This method firstly dehydrogenates aromatic benzyl alcohols to aromatic aldehydes by metal or photocatalysis, and then reacts with aromatic benzyl cyanide to form monocyano diaryl vinyl derivatives (Milstein, D. et al. al.J.Am.Chem.Soc.2017,139,11710-11713); (C) Base-catalyzed classic Knoevenagel reaction: This reaction uses aromatic benzaldehyde and aromatic benzyl cyanide as starting reactants and undergoes a Knoevenagel condensation reaction under base catalysis. Although great progress has been made in the synthesis of monocyanodiarylethylene derivatives, there are still some limitations: (1) Both method A and method B have disadvantages such as low yield, poor regioselectivity and poor substrate adaptability; (2) The reaction system requires the use of some transition metal catalysts, which are expensive, have harsh reaction conditions, cause high pollution and are difficult to post-process; (3) As a conventional method for preparing monocyanodiarylethylene derivatives, the Knoevenagel condensation reaction has made great progress in the construction of asymmetric monocyanodiarylethylene derivatives, but for the construction of symmetrical monocyanodiarylethylene derivatives, it is necessary to simultaneously prepare aromatic benzaldehyde derivatives and aromatic phenylacetonitrile derivatives with the same structure as starting materials; and the preparation of aromatic phenylacetonitrile derivatives generally requires the use of highly toxic reagents such as sodium cyanide or potassium cyanide, which has high synthesis risks, high environmental pollution and high cost. Therefore, it is very necessary to develop a method for preparing monocyanodiarylethylene derivatives with symmetrical structures that is low in cost, low in pollution, high in efficiency and simple to operate. Summary of the invention

[0004] In view of the above technical problems, the present invention provides a method for preparing monocyanodiarylethene compounds. The preparation method provided by the present invention has the advantages of mild reaction conditions, high synthesis efficiency, good yield and strong substrate adaptability.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] In one aspect, the present invention provides a method for preparing a monocyano diarylethylene compound, comprising the following steps: in a solvent, heating a substituted aryl benzaldehyde and a substituted phenylacetonitrile under the action of a base to obtain the monocyano diarylethylene compound;

[0007] The structure of the monocyano diarylethene compound is The structure of L is shown in formula (1) or formula (2):

[0008]

[0009] In formula (1), is any one of a heterocyclic group or a benzene ring group; is an aryl group having 6 to 30 carbon atoms; Z is a substituent on the aryl group;

[0010] The structure of the substituted aryl benzaldehyde is L-CHO; and the substituted benzyl cyanide is benzyl cyanide containing an electron-withdrawing group.

[0011] In the technical scheme of the present invention, the substituent Z is a monocyclic hydrocarbon group, a polycyclic hydrocarbon group, a monoheterocyclic hydrocarbon group or a polyheterocyclic hydrocarbon group formed by connecting to adjacent groups, and the substitution position is not particularly limited.

[0012] As a preferred embodiment, the substituent Z is selected from Any one of; wherein X is selected from at least one of H, F, Cl, Br, Me; In the figure, the substituent Z is the structure to which it is bonded on the left side of the dotted line.

[0013] As a preferred embodiment, It is a thiophene ring or a benzene ring.

[0014] As a preferred embodiment, the electron-withdrawing group is selected from at least one of trifluoromethyl, F, Cl and Br; the aromatic acetonitrile can specifically include 3,5-bis(trifluoromethyl)benzyl acetonitrile, 3,5-difluorobenzyl acetonitrile, 2,6-difluorobenzyl acetonitrile, 3,5-dichlorobenzyl acetonitrile, 3,5-dibromobenzyl acetonitrile, p-trifluoromethylbenzyl acetonitrile, 3,4,5-trifluorobenzyl acetonitrile, 2,5,6-trifluorobenzyl acetonitrile, 2,4,6-trifluorobenzyl acetonitrile, pentafluorobenzyl acetonitrile, etc., preferably 2,3,6-trifluorobenzyl acetonitrile and 3,5-bis(trifluoromethyl)benzyl acetonitrile.

[0015] In the technical solution of the present invention, the base is selected from at least one of potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide, sodium methoxide and sodium ethoxide, preferably potassium tert-butoxide.

[0016] In the technical solution of the present invention, the solvent is selected from at least one of methanol, ethanol and tert-butanol, preferably ethanol.

[0017] As a preferred embodiment, the temperature of the heating reaction is 80 to 100° C., preferably 100° C.; the time of the heating reaction is 24 to 36 hours.

[0018] In certain specific embodiments, the preparation method comprises the following steps: dispersing substituted aromatic benzaldehyde, substituted benzyl cyanide and a base in a solvent, reacting at 80 to 100° C. for 24 to 36 hours, quenching the reaction, and obtaining the monocyano diarylethylene compound by purification.

[0019] In the technical solution of the present invention, the molar ratio of the substituted aromatic benzaldehyde, the substituted benzyl cyanide and the base is 1:(1.5-3):(1-3), preferably 1:(1.5-2.5):(1.5-2.5), and more preferably 1:2:2.

[0020] In another aspect, the present invention provides monocyanodiarylethene compounds obtained by the above preparation method.

[0021] In another aspect, the present invention provides use of the above-mentioned monocyanodiarylethene compounds in the preparation of luminescent materials and biological imaging.

[0022] The beneficial effects of the present invention are:

[0023] The present invention uses substituted aryl benzaldehyde as a starting material and commercially available substituted benzyl cyanide as a cyano source to synthesize a series of monocyano diarylethene derivatives with symmetrical structures. The preparation method provided by the present invention has a simple reaction system, a wide substrate adaptability range, a high yield, easy availability of reaction raw materials, low cost and less pollution. In addition, the monocyano diarylethene derivatives synthesized by the present invention have excellent aggregation-induced luminescence properties and are expected to be applied to functional luminescent materials and biological imaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 1 and 1. The fluorescence spectrum (a) and fluorescence intensity variation trend (b) of compound CS-3 in Example 3 of the present invention in solvents with different water contents.

[0025] Figure 2 The fluorescence spectrum (a) and fluorescence intensity variation trend diagram (b) of compound CS-9 in Example 9 of the present invention in solvents with different water contents.

[0026] Figure 3 It is the fluorescence spectrum diagram (a) and the fluorescence intensity variation trend diagram (b) of the compound CS-13 in Example 13 of the present invention in solvents with different water contents. DETAILED DESCRIPTION

[0027] The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

[0028] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0029] Example 1

[0030] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0031]

[0032] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-1 (0.456 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (40 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a white solid CS-1 with a yield of 56%.

[0033] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-1 prepared in this example are as follows:

[0034] 1 H NMR (400MHz, CDCl3, δ): 5.04 (s, ArCH2O, 4H), 5.05 (s, ArCH2O, 4H), 6.58 (t, J = 2.1Hz, ArH, 1H), 6.66 (t, J = 2.1Hz, ArH, 1H), 6.89 (d, J = 2.1 Hz, ArH, 2H), 7.12 (d, J = 2.1 Hz, ArH, 2H), 7.34 (s, ArH, 12H), 7.41 (s, ArCH = C (CN) Ar, 1H).

[0035] 13C NMR (100MHz, CDCl3, δ):159.8,159.6,142.5,139.8,139.7,136.6,135.4,135.3, 135.3,128.3,125.6,117.8,112.0,108.5,105.8,105.1,102.8,77.2,68.7,68.7.

[0036] HRMS-ESI,m / z:Calcd for C 43 H 28 NO4Cl8 + ([M+H] + ):905.94621,Found:905.94678.

[0037] Example 2

[0038] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0039]

[0040] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-2 (0.318 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a white solid CS-2 with a yield of 51%.

[0041] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-2 prepared in this example are as follows:

[0042] 1 H NMR (400MHz, CDCl3, δ): 5.08 (s, ArCH2O, 4H), 5.09 (s, ArCH2O, 4H), 6.64 (s, ArH, 1H), 6.70 (s,ArH,1H),6.89(s,ArH,2H),7.13(s,ArH,2H),7.34-7.45(m,PhH+ArCH=C(CN)Ar,21H).

[0043] 13C NMR (100MHz, CDCl3, δ): 160.3, 160.1, 142.6, 136.5, 136.5, 135.3, 128.7, 128. 7,128.2,128.2,127.7,118.0,111.9,108.3,105.6,105.1,102.9,70.4,70.3.

[0044] HRMS-ESI,m / z:Calcd for C 43 H 36 NO4 + ([M+H] + ):630.26389,Found:630.26154.

[0045] Example 3

[0046] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0047]

[0048] In a 100mL reaction tube equipped with a stirring magnetic bar, A-3 (0.390g, 1.0mmol), 2,3,6-trifluorophenylacetonitrile (0.342g, 2.0mmol), potassium tert-butoxide (0.224g, 2.0mmol) and ultra-dry ethanol (40mL) were added in sequence; the reaction was carried out in a metal bath at 100°C under nitrogen protection for 24h, during which the reaction progress was tracked by TLC; after the reaction was completed, the mixture was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a white solid CS-3 with a yield of 41%.

[0049] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-3 prepared in this example are as follows:

[0050] 1 H NMR(400MHz,CDCl3,δ):5.08(s,ArCH2O,4H),5.09(s,ArCH2O,4H),6.57(s,ArH,1H),6.66(s,ArH,1H),6.78-6.80(t,ArH ,4H),6.88(d,J=1.9Hz,ArH,2H),6.97(s,ArH,4H),6.98(s,ArH,4H),7.11(d,J=1.6Hz,2H),7.41(s,ArCH=C(CN)Ar,1H).

[0051] 13C NMR (100MHz, CDCl3, δ): 163.2 (dd, J1=12.5Hz, J2=249.1Hz), 159.8, 159.6, 142.4, 140.4 (dd, J1=9.2Hz, J2=18.1Hz), 136.6, 135.4, 117.8, 11 2.0, 109.9 (dd, J1 = 7.0Hz, J2 = 18.8Hz), 108.5, 107.0, 105.8, 105.2, 103.7 (d, J = 7.0Hz), 103.5 (d, J = 6.9Hz), 103.2 (d, J = 7.2Hz), 102.9, 68.9.

[0052] HRMS-ESI,m / z:Calcd for C 43 H 28 F8NO4 + ([M+H] + ):774.18851,Found:774.18744.

[0053] Example 4

[0054] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0055]

[0056] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-4 (0.634 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (50 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a white solid CS-4 with a yield of 53%.

[0057] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-4 prepared in this example are as follows:

[0058] 1H NMR(400MHz,CDCl3,δ):5.04(s,ArCH2O,4H),5.05(s,ArCH2O,4H),6.58(s,ArH,1H),6.66(s,ArH,1H) ,6.89(s,ArH,2H),7.13(s,ArH,2H),7.42(s,ArCH=C(CN)Ar,1H),7.54(s,ArH,8H),7.65(s,ArH,4H).

[0059] 13 C NMR (100MHz, CDCl3, δ): 159.7, 159.5, 140.2, 139.9, 137.5, 133.8, 133.8, 129.0, 128.8, 128.7, 123.3, 108.6, 107.5, 102.3, 68.6.

[0060] HRMS-ESI,m / z:Calcd for C 43 H 28 Br8NO4 + ([M+H] + ):1261.53980,Found:1261.53906.

[0061] Example 5

[0062] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0063]

[0064] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-5 (0.425 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (50 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a white solid CS-5 with a yield of 61%.

[0065] The characterization data of the hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrum of CS-5 prepared in this example are as follows:

[0066] 1H NMR(400MHz,CDCl3,δ):5.09(s,ArCH2O,2H),5.14(s,ArCH2O,2H),5.16(s,ArCH2O,4H),5.18(s,ArCH2O,4 H),6.90(s,ArH,2H),7.15(s,ArH,1H),7.19(s,ArH,2H),7.27-7.29(m,PhH,5H),7.32-7.44(m,PhH,25H).

[0067] 13 C NMR (100MHz, CDCl3, δ):153.1,152.9,141.6,140.4,139.3,137.5,136.7,130.2,129.0,128.7,128.6, 128.6,128.3,128.1,128.1,128.0,127.6,127.5,118.4,110.1,108.8,105.9,75.3,75.3,71.5,71.2.

[0068] HRMS-ESI,m / z:Calcd for C 57 H 48 NO6 + ([M+H] + ):842.34761,Found:842.34747.

[0069] Example 6

[0070] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0071]

[0072] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-6 (0.631 g, 1.0 mmol), 3,5-bis(trifluoromethyl)benzyl cyanide (0.506 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (70 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a light green solid CS-6 with a yield of 53%.

[0073] The characterization data of the hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrum of CS-6 prepared in this example are as follows:

[0074] 1H NMR(400MHz,CDCl3,δ):5.01(s,ArCH2O,2H),5.06(s,ArCH2O,2H),5.10(s,ArCH2O,4H),5.11(s,ArCH2O,4H) ,6.90(s,ArH,2H),7.19(s,ArH,2H),7.20(s,ArCH=C(CN)Ar,1H),7.30(s,ArH,4H),7.33-7.35(m,ArH,14H).

[0075] 13 C NMR (100MHz, CDCl3, δ):155.8,155.5,144.9,144.8,143.8,143.8,142.9,142.0,138.5,138.1,133.9, 132.8,131.6,131.6,131.4,129.5,129.5,128.9,128.9,121.3,113.8,112.1,109.3,73.2,73.0,71.1.

[0076] HRMS-ESI,m / z:Calcd for C 57 H 36 NO6Cl 12 + ([M+H] + ):1255.87110,Found:1255.87110.

[0077] Example 7

[0078] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0079]

[0080] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-7 (0.509 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (60 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a white solid CS-7 with a yield of 53%.

[0081] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-7 prepared in this example are as follows:

[0082] 1 H NMR(400MHz,CDCl3,δ):2.24(s,ArCH3,12H),2.32(s,ArCH3,24H),5.00(s,ArCH2O,2H),5.04(s,ArCH2O,2H),5.10(s,ArCH2O,4H),5.11(s,ArCH 2O,4H),6.92(s,ArH,2H),6.95(s,ArH,2H),6.97(s,ArH,4H),7.06(s,ArH,4H),7.11(s,ArH,8H),7.23(s,ArCH=C(CN)Ar,1H),7.23(s,ArH,2H).

[0083] 13 C NMR (100MHz, CDCl3, δ):153.4,153.2,141.7,140.7,139.7,138.1,138.1,137.8,137.4,136.7,130.3,129.7 ,129.6,129.2,126.4,126.3,125.5,125.4,118.4,110.3,109.1,106.3,75.3,75.3,71.7,71.5,21.3,21.2.

[0084] HRMS-ESI,m / z:Calcd for C 69 H 72 NO6 + ([M+H] + ):1010.53542,Found:1010.53576.

[0085] Example 8

[0086] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0087]

[0088] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-8 (0.201 g, 1.0 mmol), 3,5-bis(trifluoromethyl)benzyl cyanide (0.506 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (20 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain an orange-red solid CS-8 with a yield of 56%.

[0089] The characterization data of the hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrum of CS-8 prepared in this example are as follows:

[0090] 1 H NMR (400MHz, CDCl3, δ): 1.97 (d, J=3.6Hz, ArCH2CH2CH2N, 8H), 2.77 (s, ArCH2CH2CH2N, 8H), 3.17 (s, ArCH2C H2CH2N,4H),3.23(s,ArCH2CH2CH2N,4H),7.04(s,ArH,2H),7.07(s,ArCH=C(CN)Ar,1H),7.36(s,ArH,2H).

[0091] 13 C NMR (100MHz, CDCl3, δ): 144.1, 142.7, 138.1, 128.3, 124.0, 122.8, 121.6, 120.7, 120.0, 116.5, 104.0, 50.0, 27.8, 27.7, 21.9, 21.7.

[0092] HRMS-ESI,m / z:Calcd for C 27 H 30 N3 + ([M+H] + ):396.24342,Found:394.22766.

[0093] Example 9

[0094] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0095]

[0096] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-9 (0.273 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (20 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a yellow solid CS-9 with a yield of 45%.

[0097] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-9 prepared in this example are as follows:

[0098] 1 H NMR (400MHz, CDCl3, δ): 7.04-7.16 (m, ArH+ArCH=C(CN)Ar, 17H), 7.29-7.33 (m, ArH, 8H), 7.49 (d, J=8.6Hz, ArH, 2H), 7.75 (d, J=8.7Hz, ArH, 2H).

[0099] 13 C NMR (100MHz, CDCl3, δ):149.6,148.3,147.2,146.7,139.6,130.4,129.6,129.5 ,128.4,126.9,126.5,125.6,124.9,124.3,123.6,122.9,121.2,118.9,107.5.

[0100] HRMS-ESI,m / z:Calcd for C 39 H 30 N3 + ([M+H] + ):540.24342,Found:540.24319.

[0101] Example 10

[0102] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0103]

[0104] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-10 (0.350 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a yellow solid CS-10 with a yield of 67%.

[0105] The hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum characterization data of CS-10 prepared in this example are as follows:

[0106] 1H NMR (400MHz, CDCl3, δ): 7.03-7.07 (m, ArH, 4H), 7.13-7.15 (m, ArH, 12H), 7.26-7.30 (m, ArH, 8H), 7.51 (t, J = 8.1Hz, ArH, 4H), 7.57 (s ,ArCH=C(CN)Ar,1H),7.64(d,J=8.5Hz,ArH,2H),7.67(d,J=8.5Hz,ArH,2H),7.74(d,J=8.4Hz,ArH,2H),7.97(d,J=8.4Hz,ArH,2H).

[0107] 13 C NMR (100MHz, CDCl3, δ):148.0,147.8,147.5,147.5,142.6,141.4,141.1,133.5,133.3,132.9,132.2,129.9 ,129.4,129.4,127.7,127.7,127.1,126.9,126.4,124.8,124.7,123.6,123.4,123.3,123.2,118.3,110.4.

[0108] Embodiment 11

[0109] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0110]

[0111] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-11 (0.356 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain red solid CS-11 with a yield of 42%.

[0112] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-11 prepared in this example are as follows:

[0113] 1H NMR(400MHz,CDCl3,δ):7.05-7.07(m,ArH,8H),7.12-7.14(m,ArH,8H),7.22-7.30(s,ArH,1 1H),7.37(s,ArCH=C(CN)Ar,1H),7.43(s,ArH,1H),7.45(s,ArH,1H),7.47-7.52(m,ArH,3H).

[0114] 13 C NMR (100MHz, CDCl3, δ):149.0,148.4,147.9,147.3,147.2,144.6,137.3,136.1,134.9,133.8,131.1,129.5 ,129.4,127.8,127.2,127.0,126.9,126.5,124.9,124.8,123.6,123.5,123.2,122.9,122.7,117.1,101.8.

[0115] HRMS-ESI,m / z:Calcd for C 47 H 34 N3S2 + ([M+H] + ):704.21887,Found:704.21814.

[0116] Example 12

[0117] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0118]

[0119] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-12 (0.384 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a red solid CS-12 with a yield of 67%.

[0120] The hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum characterization data of CS-12 prepared in this example are as follows:

[0121] 1H NMR (400MHz, CDCl3, δ): 2.33 (s, ArCH3, 12H), 6.99-7.03 (m, ArH, 12H), 7.08-7.10 (m, ArH, 8H), 7.14 (d, J=8.4Hz, ArH, 2H), 7.21 ( d,J=3.8Hz,ArH,1H),7.24(d,J=3.8Hz,ArH,1H),7.37(s,ArCH=C(CN)Ar,1H),7.41(d,J=3.7Hz,ArH,1H),7.47-7.49(m,ArH,3H).

[0122] 13 C NMR (100MHz, CDCl3, δ):149.2,148.7,148.3,144.8,144.7,137.1,135.8,133.8,133.3,133.2,131.0,1 30.1,127.7,126.8,126.4,126.3,126.0,125.2,125.1,122.6,122.4,121.9,121.6,117.2,101.6,20.9.

[0123] Embodiment 13

[0124] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0125]

[0126] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-13 (0.361 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a yellow solid CS-13 with a yield of 51%.

[0127] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-13 prepared in this example are as follows:

[0128] 1H NMR (400MHz, CDCl3, δ): 7.03 (s, ArH, 14H), 7.11 (s, ArH, 20H), 7.33 (s, ArCH=C(CN)Ar, 1H), 7.36 (d, J=7.8Hz, ArH, 2H), 7.60 (d, J=7.8Hz, ArH, 2H).

[0129] 13 C NMR (100MHz, CDCl3, δ):146.4,144.8,143.4,143.3,143.2,142.3,142.0,141.2,140.1,140.0,132.5,132.0 ,131.9,131.7,131.4,131.3,128.7,127.9,127.9,127.8,127.7,126.9,126.8,126.7,125.1,118.1,110.4.

[0130] HRMS-ESI,m / z:Calcd for C 55 H 40 N + ([M+H] + ):714.31553,Found:714.31583.

[0131] Embodiment 14

[0132] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0133]

[0134] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-14 (0.443 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain orange solid CS-14 with a yield of 40%.

[0135] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-14 prepared in this example are as follows:

[0136] 1H NMR (400MHz, CDCl3, δ): 7.04-7.13 (m, ArH, 35H), 7.18 (d, J = 3.5Hz, ArH, 2H), 7.33 (d, J = 8.0Hz ,ArH,2H),7.36(s,ArCH=C(CN)Ar,1H),7.40(d,J=7.8Hz,ArH,2H),7.46(d,J=3.0Hz,ArH,1H).

[0137] 13 C NMR (100MHz, CDCl3, δ):148.9,144.6,143.6,143.4,141.7,141.6,140.1,137.9,136.7,133.8,132.1 ,131.4,131.3,131.2,127.9,127.8,127.7,126.7,126.7,125.3,124.9,123.8,123.6,117.0,102.2.

[0138] HRMS-ESI,m / z:Calcd for C 63 H 44 NS2 + ([M+H] + ):878.29097,Found:878.29077.

[0139] Embodiment 15

[0140] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0141]

[0142] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-15 (0.421 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the obtained crude product was purified by silica gel flash column chromatography to obtain a yellow solid CS-15 with a yield of 51%.

[0143] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-15 prepared in this example are as follows:

[0144] 1H NMR (400MHz, CDCl3, δ): 6.76-6.80 (m, ArH, 6H), 6.82 (d, J = 1.8Hz, ArH, 1H), 6. 84(d,J=1.8Hz,ArH,1H),7.12-7.17(m,ArH,6H),7.36-7.43(m,ArH,8H),7.66( s,ArCH=C(CN)Ar,1H),7.75-7.83(m,ArH,6H),7.87(d,J=7.6Hz,ArH,4H),7.9 3 (d, J = 7.6 Hz, ArH, 2H), 8.05 (d, J = 8.4 Hz, ArH, 2H), 8.09 (d, J = 7.4 Hz, ArH, 2H).

[0145] 13 C NMR (100MHz, CDCl3, δ):149.1,148.8,148.6,148.6,148.6,143.4,142.6,142.2,141.8,141.4,141.4,139.8,133.5,132.8,1 29.9,128.2,127.9,127.9,127.7,127.0,127.0,126.4,124.5,124.5,124.2,124.1,120.1,118.7,118.6,118.2,110.9,65.8.

[0146] HRMS-ESI,m / z:Calcd for C 65 H 40 N + ([M+H] + ):834.31553,Found:834.31512.

[0147] Example 16

[0148] This example synthesizes a monocyano diarylethene compound, and the preparation process is as follows:

[0149]

[0150] In a 100 mL reaction tube equipped with a stirring magnetic bar, A-16 (0.421 g, 1.0 mmol), 2,3,6-trifluorophenylacetonitrile (0.342 g, 2.0 mmol), potassium tert-butoxide (0.224 g, 2.0 mmol) and ultra-dry ethanol (30 mL) were added in sequence; the reaction was carried out in a metal bath at 100 ° C under nitrogen protection for 24 h, and the reaction progress was tracked by TLC during the reaction; after the reaction was completed, it was cooled to room temperature, a large amount of product precipitated, filtered, and the solid crude product was washed with a large amount of ethanol; the crude product was purified by silica gel flash column chromatography to obtain a yellow solid CS-16 with a yield of 51%.

[0151] The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high-resolution mass spectrometry characterization data of CS-16 prepared in this example are as follows:

[0152] 1 H NMR (400MHz, CDCl3, δ): 6.72 (s, ArH, 1H), 6.73 (d, J = 2.3Hz, ArH, 1H), 6.77 (d, J = 7.6Hz, ArH, 4H),6.97(d,J=7.8Hz,ArH,2H),7.11(t,J=7.4Hz,ArH,6H),7.37(t,J=7.4Hz,ArH,6H),7.42 (s,ArCH=C(CN)Ar,1H),7.45-7.51(m,ArH,4H),7.57(d,J=8.2Hz,ArH,2H),7.64(t,J=8.7Hz , ArH, 2H), 7.80 (d, J = 8.1 Hz, ArH, 2H), 7.86 ( d, J = 7.6 Hz, ArH, 6H), 7.91 ( d, J = 8.0 Hz, ArH, 2H).

[0153] 13 C NMR (100MHz, CDCl3, δ):149.7,149.7,149.3,148.6,148.6,142.9,141.8,141.7,141.6,141.2,141.1,139.6,139.6,133.2,132.5,1 29.7,128.1,128.0,127.9,127.6,127.4,126.9,126.9,126.1,124.2,122.6,122.5,120.5,120.5,120.2,120.1,118.0,110.7,66.1.

[0154] HRMS-ESI,m / z:Calcd for C 65 H 40 N + ([M+H] +):834.31553,Found:834.31579.

[0155] It can be seen from the above examples that the preparation method provided by the present invention can synthesize a series of monocyanodiarylethene compounds with symmetrical structures, has a simple reaction system, a wide substrate adaptability, a high yield, easy availability of reaction raw materials, low cost and less pollution.

[0156] Application Examples

[0157] This example tests and characterizes the aggregation-induced emission properties of the monocyanodiarylethene compounds CS-3, CS-9 and CS-13 in Examples 3, 9 and 13. Taking compound CS-3 as an example, the test process is as follows:

[0158] Take a 100mL volumetric flask and prepare 10 -3 mol / L tetrahydrofuran solution of compound CS-3;

[0159] Take 11 10 mL sample bottles, numbered 0 to 10, and add 0.5 mL of the tetrahydrofuran solution of the above compound CS-3 into each sample bottle using a pipette;

[0160] Tetrahydrofuran 9.5mL, 8.5mL, 7.5mL, 6.5mL, 5.5mL, 5.5mL, 3.5mL, 2.5mL, 1.5mL, and 0.5mL were added to the test tubes labeled 0 to 9, respectively; then deionized water 1.0mL, 2.0mL, 3.0mL, 4.0mL, 5.0mL, 6.0mL, 7.0mL, 8.0mL, 9.0mL, and 9.5mL were added to the test tubes labeled 1 to 10, respectively, to obtain 5×10 - 5 mol / L solution of compound CS-3; the prepared solution was sonicated in an ultrasonic instrument for 60 seconds and then subjected to fluorescence spectrum testing.

[0161] Figure 1-3The fluorescence spectra and fluorescence enhancement trend diagrams of compounds CS-3, CS-9 and CS-13 in the dissolved state and the aggregated state are respectively shown. It can be seen from the figures that the compounds CS-3, CS-9 and CS-13 synthesized by the present invention have the characteristics of aggregation-induced phosphorescence, wherein the luminescence efficiency of CS-3 in the aggregated state (tetrahydrofuran-water mixed solution with a water content of 95 vol%) is 8.1 times higher than that in the dissolved state (tetrahydrofuran solution), the luminescence efficiency of CS-9 in the aggregated state (tetrahydrofuran-water mixed solution with a water content of 95 vol%) is 9.7 times higher than that in the dissolved state (tetrahydrofuran solution), and the luminescence efficiency of CS-13 in the aggregated state (tetrahydrofuran-water mixed solution with a water content of 95 vol%) is 68.5 times higher than that in the dissolved state (tetrahydrofuran solution).

[0162] It can be seen from the application examples that the monocyanodiarylethene compounds synthesized by the preparation method provided by the present invention have excellent aggregation-induced emission properties and are expected to be applied in the fields of functional luminescent materials and biological imaging.

[0163] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a monocyanodiarylethene compound, characterized in that: The following steps are included: In a solvent, substituted aryl benzaldehyde and substituted phenylacetonitrile are subjected to heating reaction under the action of a base to obtain the monocyano diarylethene compound; The structure of the monocyano diarylethene compound is The structure of L is shown in formula (1) or formula (2): In formula (1), is any one of a heterocyclic group or a benzene ring group; is an aryl group having 6 to 30 carbon atoms; Z is a substituent on the aryl group; The structure of the substituted aryl benzaldehyde is L-CHO; and the substituted benzyl cyanide is benzyl cyanide containing an electron-withdrawing group.

2. The preparation method according to claim 1, characterized in that: The substituent Z is a monocyclic hydrocarbon group, a polycyclic hydrocarbon group, a monoheterocyclic hydrocarbon group or a polyheterocyclic hydrocarbon group formed by mono-, di- or tri-substitution or by bonding to adjacent groups.

3. The preparation method according to claim 1, characterized in that: The substituent Z is selected from Any one of; wherein X is selected from at least one of H, F, Cl, Br, Me; In the figure, the substituent Z is the structure to which it is bonded on the left side of the dotted line.

4. The preparation method according to claim 1, characterized in that: A thiophene ring or a benzene ring; Preferably, the electron withdrawing group is selected from at least one of trifluoromethyl, F, Cl and Br.

5. The preparation method according to claim 1, characterized in that: The base is selected from at least one of potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide, sodium methoxide and sodium ethoxide, preferably potassium tert-butoxide.

6. The preparation method according to claim 1, characterized in that: The solvent is selected from at least one of methanol, ethanol and tert-butanol, preferably ethanol.

7. The preparation method according to claim 1, characterized in that: The temperature of the heating reaction is 80-100° C., preferably 100° C.; the time of the heating reaction is 24-36 hours.

8. The preparation method according to claim 1, characterized in that: The molar ratio of the substituted aryl benzaldehyde, the substituted benzyl cyanide and the base is 1:(1.5-3):(1-3), preferably 1:(1.5-2.5):(1.5-2.5), and more preferably 1:2:

2.

9. The monocyanodiarylethene compound obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the monocyanodiarylethene compound according to claim 9 in the preparation of luminescent materials and bio-imaging.

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