Tetrahydroquinoline substituted trisubstituted olefin compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a green synthesis method and application of tetrahydroquinoline substituted trisubstituted olefin and derivatives thereof. A non-metal organic photocatalyst system is adopted, and one-pot efficient conversion of N-aryl tetrahydroquinoline compounds and phenylacetylene compounds is realized through blue light induced C-H activation / aryl migration cascade reaction under the protection of nitrogen. According to the process, precise fracture of C-N bonds and stereo control of aryl migration are realized in a breakthrough manner, so that gt is reached; and a series of trisubstituted olefin compounds with novel structures are selectively and efficiently constructed according to Z / E ratio of 20: 1. The obtained product can be converted into a tri (hetero) aryl olefin compound with a remarkable aggregation-induced emission (AIE) effect through simple oxidative aromatization. The technology provides a new strategy which is high in atom economy, mild in reaction condition and environment-friendly for precise synthesis of the trisubstituted olefin compound, and has important application prospects in the aspects of preparation of medicines, pesticides, biomedical imaging, intelligent luminescent materials, organic semiconductor precursors and the like. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a trisubstituted olefin compound substituted with tetrahydroquinoline, and a green synthesis method and application thereof. Specifically, it relates to the precise synthesis of such compounds through a transition-metal-free photocatalytic C-H activation / aryl migration cascade reaction, and their application as precursors of aggregation-induced emission (AIE) materials, belonging to the field of organic synthesis. Background Art

[0002] As a typical representative of nitrogen-containing heterocyclic systems, the tetrahydroquinoline skeleton is widely present in natural products and drug molecules with significant biological activities. For example, Hancock alkaloids (angustureine, galipeine, etc.) isolated from Amazonian medicinal plants exhibit potent antimalarial activity, while the synthetic tetrahydroquinoline derivative flumequine, as a precursor of fluoroquinolone antibiotics, has been proven to exert broad-spectrum antibacterial effects by inhibiting DNA gyrase. Its rigid cyclic structure can not only form stable hydrogen bonds with biological targets but also play an important role as a catalyst ligand in organic synthesis. However, traditional synthesis methods such as Povarov cycloaddition and transition-metal-catalyzed hydrogenation have defects such as noble metal dependence (Ir, Rh, etc.), high-temperature and high-pressure conditions (>120 °C), and poor stereoselectivity, severely restricting the precise construction of functionalized tetrahydroquinoline derivatives.

[0003] On the other hand, trisubstituted alkenes (especially those containing aryl groups) serve as the core skeleton of aggregation-induced emission (AIE) materials (Wang S, Chen C, Wu J, Zhang J, Lam JWY, Wang H, Chen L, Tang BZ. Sci China Chem, 2022, 65: 870–876). The precise stereocontrol is the key to determining the material properties. Research has shown that the Z-configuration of triaryl ethylene can increase the solid-state fluorescence quantum yield by more than three times (from 0.25 to 0.78) compared to the E-configuration. However, existing synthetic strategies such as Heck coupling and alkyne insertion have inherent defects: (1) The palladium-catalyzed system is thermodynamically controlled (Oh CH, Jung HH, Kim KS, Kim N. Angew Chem Int Ed, 2003, 42, 805–808), and the product is mainly in the E-configuration; (2) The multi-step reaction leads to a significant reduction in atom economy; (3) The substrate needs to be pre-introduced with a directing group (such as pyridine, amide) (Gao K, Lee PS, Fujita T, Yoshikai N. J Am Chem Soc, 2010, 132, 12249–12251), resulting in limited aryl ring substitution sites (only ortho- and para-modifications are applicable). Especially for triaryl alkenes with AIE effects, the compounds synthesized by existing methods (such as Suzuki coupling) have problems such as a single electronic property of the aryl ring (only electron-rich aryl rings are applicable) and low solid-state fluorescence efficiency, severely restricting their applications in bioimaging and optoelectronic materials.

[0004] Therefore, there is an urgent need to develop a green preparation process with atom economy, stereoselective precision control, and broad functional group tolerance to achieve the efficient synthesis of trisubstituted alkene compounds substituted with tetrahydroquinoline. Such compounds not only have important application prospects in the fields of medicine, pesticides, etc., but also can promote the application of trisubstituted alkene compounds in the field of intelligent optoelectronic materials, showing dual application values in the development of innovative drug lead compounds and the construction of flexible organic semiconductor devices and other frontier fields. Summary of the Invention

[0005] Therefore, the purpose of the present invention is to provide a trisubstituted alkene compound substituted with tetrahydroquinoline and its derivatives.

[0006] Another purpose of the present invention is to provide a synthesis method of a trisubstituted alkene substituted with tetrahydroquinoline and its derivatives. This method has the advantages of simple reaction conditions, no need for transition metal catalysts, convenient operation, high yield, and high Z / E selectivity.

[0007] Thus, a trisubstituted alkene substituted with tetrahydroquinoline and its derivatives of the present invention has the general formula of Formula I:

[0008]

[0009] in:

[0010] R 1 is selected from hydrogen, alkyl, alkoxy, ester, halogen, aryl, heteroaryl, cyano, and nitro;

[0011] R 2 is selected from hydrogen, alkyl, alkoxy, ester, halogen, cyano, nitro, hydroxy, amino, acetylamino, trifluoromethyl, aryl, and heteroaryl;

[0012] R 3 Selected from hydrogen atom, alkyl group, alkoxy group, ester group, halogen, cyano group, nitro group, hydroxyl group, amino group, acetylamino group, trifluoromethyl group, aryl group, heterocyclic aromatic group.

[0013] The present invention also provides a method for synthesizing the trisubstituted olefin containing tetrahydroquinoline and its derivatives as claimed in claim 1, characterized in that the method comprises the following steps under a non-metallic organic photocatalytic system:

[0014] (I) adding an N-aryl tetrahydroquinoline compound, a phenylacetylene compound, a photocatalyst, a base, an additive and an organic solvent into a reaction vessel;

[0015] (II) mixing the reactants thoroughly, irradiating with blue light and heating under nitrogen or argon protection to react;

[0016] (III) Purification to obtain the product.

[0017] Preferably, in the method of the present invention, the general formula of the N-aryl tetrahydroquinoline compound is Formula II:

[0018]

[0019] in:

[0020] R 1 is selected from hydrogen, alkyl, alkoxy, ester, halogen, aryl, heteroaryl, cyano, and nitro;

[0021] R 2 Selected from hydrogen atom, alkyl group, alkoxy group, ester group, halogen, cyano group, nitro group, hydroxyl group, amino group, acetylamino group, trifluoromethyl group, aryl group, heterocyclic aromatic group.

[0022] Preferably, in the method of the present invention, the N-aryl tetrahydroquinoline compounds are selected from: N-phenyl tetrahydroquinoline, N-naphthyl tetrahydroquinoline, N-phenyl-5-methyl tetrahydroquinoline, N-phenyl-6-methyl tetrahydroquinoline, N-phenyl-6-methoxy tetrahydroquinoline, N-phenyl-6-fluoro tetrahydroquinoline, N-phenyl-6-chloro tetrahydroquinoline, N-phenyl-6-bromo tetrahydroquinoline, N-phenyl-6-nitro tetrahydroquinoline, N-phenyl-6-cyano tetrahydroquinoline, N-phenyl-6-nitro tetrahydroquinoline, N-phenyl-6-phenyl tetrahydroquinoline, N-phenyl-6-tetrahydroquinoline carboxylate methyl ester, N-phenyl-7-methyl tetrahydroquinoline, N-phenyl-8-methyl tetrahydroquinoline, N-methyl tetrahydroquinoline, N-benzyl tetrahydroquinoline, N-thienyl tetrahydroquinoline, N-pyridyl tetrahydroquinoline, N-(4-methylphenyl) tetrahydroquinoline, N-(3-methylphenyl) tetrahydroquinoline, N-(2-methylphenyl) tetrahydroquinoline, N-(3,5-dimethylphenyl) tetrahydroquinoline, N-(4-fluorophenyl) tetrahydroquinoline, N-(4-chlorophenyl) tetrahydroquinoline, N-(4-bromophenyl) tetrahydroquinoline, N-(4-methoxyphenyl) tetrahydroquinoline, N-(2-methoxy) tetrahydroquinoline, N-(2,5-dimethoxyphenyl) tetrahydroquinoline, N-(2-isopropylphenyl) tetrahydroquinoline, N-(4-trifluoromethylphenyl) tetrahydroquinoline.

[0023] Preferably, in the method of the present invention, the general formula of the phenylacetylene compounds is III:

[0024]

[0025] Wherein:

[0026] R 3 is selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, an acetylamino group, a trifluoromethyl group, an aryl group, a heteroaryl group.

[0027] Preferably, in the method of the present invention, the phenylacetylene compounds are selected from: phenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-trifluoromethylphenylacetylene, 4-hydroxyphenylacetylene, 2-methylphenylacetylene, 3-methylphenylacetylene, 2-methoxyphenylacetylene, 3-methoxyphenylacetylene, 2-chlorophenylacetylene, 4-ethynylbiphenyl, 1-naphthylacetylene, 2-naphthylacetylene, 4-ethynylbenzoic acid methyl ester, 4-ethynylbenzoic acid ethyl ester, 4-ethynyl-N-methylbenzamide, N-(4-ethynylphenyl)acetamide, 2-ethynylthiophene, 2-ethynylpyridine, 3,5-dimethoxyphenylacetylene, methyl propiolate, ethyl propiolate.

[0028] Preferably, in the method of the present invention, the general formula of the non-metallic photocatalyst is formula IV:

[0029]

[0030] Among them,

[0031] R 4 is selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, an acetylamino group, a trifluoromethyl group, an aryl group, a heteroaryl group;

[0032] R 5 is selected from a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group.

[0033] Preferably, in the method of the present invention, the non-metallic photocatalyst is selected from one of the following compounds:

[0034] Preferably, in the method of the present invention, the base is selected from one of Cs2CO3, CsF, CsCl, CH3COOCs, NaOH, K3PO4, PhCOOK, t-BuOK, K2CO3, KF.

[0035] Preferably, in the method of the present invention, the additive is selected from one of DABCO, NaCl, KI, phthalimide-2-yl benzoate, phthalimide-2-yl 4-methylbenzoate, phthalimide-2-yl 4-methoxybenzoate, phthalimide-2-yl 4-fluorobenzoate, phthalimide-2-yl (4,5,6,7-tetrachlorophthalimido) benzoate.

[0036] Preferably, in the method of the present invention, the organic solvent is selected from one of chlorobenzene, toluene, trifluorotoluene, p-xylene, o-xylene, m-xylene, 1,4-dioxane, dichloromethane, acetonitrile, pyridine, ethylbenzene, anisole, and the amount of the solvent used is: 0.5 - 3.0 mL.

[0037] Preferably, in the method of the present invention, the molar ratio of the N-aryl tetrahydroquinoline compound, the phenylacetylene compound, the photocatalyst, the base, and the additive is 1.0:1.0 - 3.0:0.01 - 0.2:0.5 - 2.0:1.0 - 3.0, the reaction temperature is 20 - 60 °C; the atmosphere in the reaction vessel is: an inert gas atmosphere; the reaction duration is 4 h - 48 h; the light source is: a 35 W blue light lamp or a CFL lamp.

[0038] The present invention also provides a quinoline tris(hetero)aryl-substituted olefin compound, and its general formula is Formula V:

[0039]

[0040] Among them:

[0041] R 1 、R 2 、R 3is the same as the definition of the aforementioned R 1 and R 2 and R 3 ;

[0042] Preferably, the compound of the structure shown in Formula V is selected from one of the following compounds:

[0043]

[0044] The present invention also provides a method for preparing a quinoline tris(hetero)aryl-substituted olefin compound of the structure shown in Formula V, which is characterized in that the method comprises: in the presence of chloroform organic solvent and diethyl azodicarboxylate, oxidizing the trisubstituted olefin substituted with tetrahydroquinoline described in any one of claims 1-2 in an air atmosphere.

[0045] The beneficial effects of the present invention compared with the prior art:

[0046] Under the conditions of a non-metal photocatalyst, a base, an additive and blue light irradiation, the present invention realizes a one-pot reaction of N-aryl tetrahydroquinoline compounds and phenylacetylene compounds in a nitrogen or argon atmosphere, and efficiently and highly selectively obtains a trisubstituted olefin compound substituted with tetrahydroquinoline and its derivatives. The core advantages of this technical solution are reflected in:

[0047] (1) The synthesis route is significantly simplified: breaking through the limitation that the existing technology for synthesizing trisubstituted olefins relies on multiple-step reactions, and directly completing the activation of the C(sp 3 )-H bond of tetrahydroquinoline, the addition with phenylacetylene, the cleavage of the C(sp 2 )-N bond and the stereospecific aryl migration process by using the "one-pot method", omitting the intermediate separation and purification steps, and greatly reducing the time and equipment costs;

[0048] (2) The reaction conditions are mild and controllable: replacing the high temperature and high pressure conditions with blue light, the reaction can be driven at normal temperature and pressure, avoiding the decomposition of the substrate or side reactions of sensitive functional groups, greatly improving the functional group compatibility, and the substrate applicability is very wide;

[0049] (3) It has prominent green economy: no transition metal catalyst or excessive oxidant is required, only a catalytic amount of organic photosensitizer, cheap inorganic base and additive are needed, the atomic economy of the reaction system is high, and the product can meet the purity requirements of pharmaceutical intermediates without complicated post-treatment;

[0050] (4) Precise regulation of Z / E selectivity: Through the strategy of C(sp 2 )-N bond cleavage and stereospecific aryl migration, the efficient and highly selective precise regulation of trisubstituted olefins is realized, which is significantly better than the traditional photochemical method;

[0051] (5) Wide application compatibility: The obtained tetrahydroquinoline-substituted trisubstituted olefin compounds can be used as key intermediates for pesticides (such as fungicide precursors), pharmaceuticals (such as antimalarial drug Galipenine analogs), and bioactive natural products. Additionally, the obtained tetrahydroquinoline-substituted trisubstituted olefins can be converted into tri(hetero)aryl olefin derivatives through simple oxidative aromatization. These compounds, as the core skeletons of aggregation-induced emission (AIE) materials, have important application prospects in the fields of bioimaging and intelligent luminescent materials.

[0052] The present invention will be further described in detail below with reference to the accompanying drawings and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 Synthesis route diagram of the compounds of the present invention.

[0054] Figure 1a and 1b 1H NMR spectrum of the product of Example 1.

[0055] Figure 2a and 2b 1H NMR spectrum of the product of Example 2.

[0056] Figure 3a and 3b 1H NMR spectrum of the product of Example 10.

[0057] Figure 4a and 4b 1H NMR spectrum of the product of Example 13.

[0058] Figure 5a and 5b 1H NMR spectrum of the product of Example 19.

[0059] Figure 6 Optical property test I of the product of Example 19.

[0060] Figure 7 Optical property test II of the product of Example 19.

[0061] Where a is the 1H NMR spectrum and b is the 13C NMR spectrum. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0062] The present invention will now be further described in detail with reference to the following figures. These figures are all simplified schematic diagrams, only illustrating the basic structure of the present invention in a schematic manner, and therefore only showing the components related to the present invention:

[0063]

[0064] Examples 1 - 18

[0065] Comprise the following steps:

[0066] ⑴ Add N-aryl tetrahydroquinoline compounds, phenylacetylene compounds, additives, photocatalysts, bases, and organic solvents into a reaction vessel;

[0067] ⑵ After thoroughly mixing the reactants, evenly heat the reaction vessel (such as by oil bath heating) to the temperature described in Table 1 and irradiate it under blue light. The N-aryl tetrahydroquinoline compounds and phenylacetylene compounds react in the solvent and continue for the time described in Table 1; it should be noted that the reaction atmosphere is selected to be protected by nitrogen or argon;

[0068] ⑶ Purify the product after the reaction.

[0069] The N-aryl tetrahydroquinoline compounds, phenylacetylene compounds, and reaction conditions are shown in Table 1:

[0070] Table 1: Molar ratios of N-aryl tetrahydroquinoline compounds, phenylacetylene compounds, additives, non-metal photocatalysts, bases, and organic solvents, as well as reaction temperatures and reaction times in Examples 1-18

[0071]

[0072]

[0073]

[0074] * Molar ratios of N-aryl tetrahydroquinoline compounds, phenylacetylene compounds, additives, photosensitizers, and bases

[0075] The reaction products, Z / E ratios, and yields are shown in Table 2

[0076] Table 1: Reaction products, yields, and Z / E ratios in Examples 1-18

[0077]

[0078]

[0079] The NMR characterization results of some examples are as follows: 20

[0080] The NMR data of the product of Example 1 are as follows:

[0081] 11H NMR (400 MHz, Chloroform-d) δ 7.33–7.29 (m, 1H), 7.28–7.16 (m, 5H), 7.07 (d, J = 6.8 Hz, 1H), 6.99–6.90 (m, 4H), 6.57 (t, J = 7.6 Hz, 1H), 6.43 (d, J = 8.0 Hz, 1H), 6.21 (d, J = 9.2 Hz, 1H), 4.08–3.82 (m, 1H), 3.79–3.64 (m, 4H), 2.74–2.69 (m, 2H), 2.05–1.92 (m, 1H), 1.90–1.74 (m, 1H). 13 13C NMR (101 MHz, Chloroform-d) δ 156.87, 144.41, 141.08, 138.96, 131.23, 129.31, 129.03, 128.29, 128.24, 127.38, 126.87, 126.61, 120.98, 120.83, 117.05, 114.20, 111.19, 55.61, 51.25, 28.22, 26.05.

[0082] The NMR data of the product of Example 2 are as follows:

[0083] 1 1H NMR (400 MHz, Chloroform-d) δ 7.32–7.20 (m, 5H), 7.19–7.15 (m, 2H), 7.07 (t, J = 8.4 Hz, 2H), 6.99–6.94 (m, 2H), 6.61 (t, J = 7.6 Hz, 1H), 6.48 (d, J = 8.0 Hz, 1H), 6.11 (d, J = 9.2 Hz, 1H), 3.90 (td, J = 9.2, 3.2 Hz, 1H), 3.80 (s, 1H), 2.84–2.67 (m, 2H), 2.02–1.97 (m, 1H), 1.93–1.79 (m, 1H). 13 13C NMR (101 MHz, Chloroform-d) δ 162.29 (d, J = 245 Hz), 143.99, 142.27, 141.76, 135.40, 131.34 (d, J = 7.0 Hz), 131.26, 129.40, 128.41, 127.81, 127.49, 127.00, 121.02, 117.38, 115.49 (d, J = 22 Hz), 114.30, 50.81, 28.72, 26.06.

[0084] The NMR data of the product of Example 3 are as follows:

[0085] 1 H NMR (400 MHz, Chloroform-d) δ 7.51 (d, J = 8.0 Hz, 2H), 7.30–7.20 (m, 5H), 7.08 (d, J = 8.4 Hz, 2H), 7.02–6.90 (m, 2H), 6.61 (t, J = 7.2 Hz, 1H), 6.48 (d, J = 8.0 Hz, 1H), 6.12 (d, J = 9.2 Hz, 1H), 3.89 (td, J = 9.6, 3.2 Hz, 1H), 3.80 (s, 1H), 2.84–2.66 (m, 2H), 2.08–1.92 (m, 1H), 1.94–1.79 (m, 1H). 13 C NMR (101 MHz, Chloroform-d) δ 143.90, 142.11, 141.38, 138.41, 131.70, 131.41, 131.38, 129.39, 128.44, 127.89, 127.50, 127.00, 121.72, 120.98, 117.41, 114.30, 50.79, 28.70, 26.00.

[0086] The NMR data of the product of Example 7 are as follows:

[0087] 1 H NMR (400 MHz, Chloroform-d) δ 7.28–7.23 (m, 5H), 6.97–6.92 (m, 3H), 6.80 (s, 2H), 6.60 (d, J = 7.3 Hz, 1H), 6.47 (d, J = 7.9 Hz, 1H), 6.07 (d, J = 9.3 Hz, 1H), 3.93 (td, J = 9.3, 3.3 Hz, 1H), 3.81 (s, 1H), 2.77–2.74 (m, 2H), 2.31 (s, 6H), 2.05–1.95 (m, 1H), 1.95–1.78 (m, 1H). 13 C NMR (101 MHz, Chloroform-d) δ 144.21, 143.44, 142.05, 139.39, 137.88, 130.56, 129.34, 129.15, 128.27, 127.51, 127.45, 127.35, 126.92, 121.09, 117.19, 114.29, 50.70, 28.71, 26.01, 21.51.

[0088] The NMR data of the product of Example 11 are as follows:

[0089] 11H NMR (400 MHz, Chloroform-d) δ 7.26–7.16 (m, 2H), 7.15–7.07 (m, 3H), 7.01 (d, J = 7.2 Hz, 1H), 6.99–6.82 (m, 4H), 6.58 (t, J = 7.4 Hz, 1H), 6.47 (d, J = 8.0 Hz, 1H), 5.74 (d, J = 9.6 Hz, 1H), 4.11–3.93 (m, 1H), 3.79 (s, 4H), 2.76–2.73 (m, 2H), 2.20 (s, 3H), 2.09–1.96 (m, 1H), 1.82 (dd, J = 12.7, 8.9 Hz, 1H). 13 13C NMR (101 MHz, Chloroform-d) δ 156.37, 144.63, 143.09, 138.61, 135.82, 134.81, 130.91, 130.47, 129.80, 129.35, 129.07, 128.65, 127.07, 126.87, 125.47, 121.08, 120.61, 117.08, 114.26, 110.99, 55.46, 51.20, 28.23, 26.10, 20.20.

[0090] The NMR data of the product of Example 12 are as follows:

[0091] 1 1H NMR (400 MHz, Chloroform-d) δ 7.33 - 7.29 (m, 1H), 7.15–7.10 (m, 2H), 7.09–7.00 (m, 3H), 6.99–6.89 (m, 4H), 6.59 - 6.55 (m, 1H), 6.44–6.42 (d, J = 8.0 Hz, 1H), 6.20 (d, J = 9.2 Hz, 1H), 3.97 (s, 1H), 3.76 (s, 3H), 3.73–3.67 (m, 1H), 2.72 (m, 2H), 2.29 (s, 3H), 1.99–1.94 (m, 1H), 1.91–1.77 (m, 1H). 13 13C NMR (101 MHz, Chloroform-d) δ 156.91, 144.46, 141.09, 139.03, 137.79, 131.30, 131.12, 129.32, 128.97, 128.39, 128.22, 128.20, 127.18, 126.87, 123.96, 121.03, 120.83, 117.03, 114.21, 111.21, 55.64, 51.26, 28.23, 26.06, 21.61.

[0092] The NMR data of the product of Example 16 are as follows:

[0093] 1 H NMR(400MHz,DMSO-d6)δ7.71(d,J=8.0Hz,2H),7.47(d,J=8.0Hz,2H),7.23(d,J=8.4,2H),7.04(d,J=8.8Hz,2H),6.92–6.81(m,2H),6.56(d,J=7.6Hz,1H),6.45(t,J=8.6Hz,1H),6.20(d,J=9.2Hz,1H),5.89(s,1H),3.87–3.82(m,4H),2.75–2.63(m,2H),2.02–1.86(m,1H),1.86–1.67(m,1H). 13 C NMR(101MHz,Chloroform-d)δ156.82,145.76,144.02,137.81,134.44,132.16,131.15,129.72,129.38,127.16,126.99,126.83,121.04,120.95,119.20,117.40,114.33,111.32,110.64,55.58,51.14,28.03,25.81.

[0094] The NMR data of Example 17 are as follows:

[0095] 1H NMR(400MHz,Chloroform-d)δ8.59–8.57(m,1H),7.50(td,J=7.6,2.0Hz,1H),7.38–7.33(m,1H),7.16–7.08(m,2H),7.04–6.96(m,3H),6.96–6.89(m,2H),6.85(d,J=8.0Hz,1H),6.57(t,J=7.3Hz,1H),6.42(d,J=7.9Hz,1H),4.00(s,1H),3.81–3.77(m,1H),3.75(s,4H),2.76–2.69(m,2H),2.06–1.95(m,1H),1.94–1.87(m,1H). 1313C NMR (101 MHz, Chloroform-d) δ 157.50, 157.09, 149.27, 144.27, 138.23, 136.48, 134.49, 131.36, 129.38, 129.26, 126.91, 126.83, 122.11, 121.78, 120.94, 120.93, 116.90, 114.14, 111.16, 55.53, 51.00, 27.97, 26.02.

[0096] Examples 19 - 20

[0097] comprising the following steps:

[0098] ⑴ Add a tetrahydroquinoline-substituted trisubstituted olefin compound, diethyl azodicarboxylate, and chloroform into a reaction vessel;

[0099] ⑵ After thoroughly mixing the reactants, place the reaction vessel at room temperature and stir for 12 h;

[0100] ⑶ After the reaction, perform purification to obtain the product.

[0101] The tetrahydroquinoline-substituted trisubstituted olefin compound, reaction conditions, reaction product, and yield are shown in Table 3:

[0102] Table 3: Reactants and reaction conditions of Examples 19 - 22

[0103]

[0104] The NMR data of the product of Example 19 are as follows:

[0105] 1 1H NMR (400 MHz, Chloroform-d) δ 8.00 (d, J = 9.2 Hz, 1H), 7.73 (d, J = 8.8 Hz, 1H), 7.68–7.60 (m, 2H), 7.47–7.35 (m, 5H), 7.34–7.25 (m, 3H), 7.12–7.09 (m, 1H), 6.98–6.91 (m, 2H), 6.85 (d, J = 8.7 Hz, 1H), 3.56 (s, 3H). 1313C NMR (101 MHz, Chloroform-d) δ 157.62, 157.26, 148.07, 143.94, 141.94, 135.10, 131.82, 129.91, 129.71, 129.41, 129.18, 128.75, 128.28, 128.03, 127.38, 126.99, 126.69, 126.22, 121.25, 121.20, 111.63, 55.70.

[0106] Enlightened by the ideal embodiments of the present invention as described above, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A trisubstituted olefin containing tetrahydroquinoline and its derivatives, which have the general formula I: in: R 1 selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, an aryl group, a heteroaryl group, a cyano group, and a nitro group; R 2 selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, an acetylamino group, a trifluoromethyl group, an aryl group, a heteroaryl group; R 3 Selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, an acetylamino group, a trifluoromethyl group, an aryl group, and a heteroaryl group.

2. A method for synthesizing the tetrahydroquinoline-substituted trisubstituted olefin and its derivatives as claimed in claim 1, characterized in that, In the non-metallic organic photocatalytic system, the following steps are included: (I) adding an N-aryl tetrahydroquinoline compound, a phenylacetylene compound, a photocatalyst, a base, an additive and an organic solvent into a reaction container; (II) mixing the reactants thoroughly, irradiating with blue light and heating under nitrogen or argon protection to react; (III) Purification to obtain the product.

3. The method according to claim 2, wherein The general formula of the N-aryl tetrahydroquinoline compound is Formula II: in: R 1 selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, an aryl group, a heteroaryl group, a cyano group, and a nitro group; R 2 Selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, an acetylamino group, a trifluoromethyl group, an aryl group, a heteroaryl group.

4. The method according to claim 3, wherein The N-aryl tetrahydroquinoline compound is selected from: N-phenyltetrahydroquinoline, N-naphthyltetrahydroquinoline, N-phenyl-5-methyltetrahydroquinoline, N-phenyl-6-methyltetrahydroquinoline, N-phenyl-6-methoxytetrahydroquinoline, N-phenyl-6-fluorotetrahydroquinoline, N-phenyl-6-chlorotetrahydroquinoline, N-phenyl-6-bromotetrahydroquinoline, N-phenyl-6-nitrotetrahydroquinoline, N-phenyl-6-cyanotetrahydroquinoline, N-phenyl-6-nitrotetrahydroquinoline, N-phenyl-6-phenyltetrahydroquinoline, N-phenyl-6-tetrahydroquinoline, methyl N-phenyl-6-tetrahydroquinolinecarboxylate, N-phenyl-7-methyltetrahydroquinoline, N-phenyl-8-methyltetrahydroquinoline, N-methyltetrahydroquinoline, N-benzyltetrahydroquinoline, N-thienyltetrahydroquinoline, N-pyridyltetrahydroquinoline, N-(4-methylphenyl)tetrahydroquinoline, N-(3-methylphenyl)tetrahydroquinoline, N-(2-methylphenyl)tetrahydroquinoline, N-(3,5-dimethylphenyl)tetrahydroquinoline, N-(4-fluorophenyl)tetrahydroquinoline, N-(4-chlorophenyl)tetrahydroquinoline, N-(4-bromophenyl)tetrahydroquinoline, N-(4-methoxyphenyl)tetrahydroquinoline, N-(2-methoxy)tetrahydroquinoline, N-(2,5-dimethoxyphenyl)tetrahydroquinoline, N-(2-isopropylphenyl)tetrahydroquinoline, N-(4-trifluoromethylphenyl)tetrahydroquinoline.

5. The method according to claim 2, wherein The general formula of the phenylacetylene compound is III: in: R 3 Selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, an acetylamino group, a trifluoromethyl group, an aryl group, and a heteroaryl group.

6. The method according to claim 5, characterized in that, The phenylacetylene compound is selected from the group consisting of phenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-trifluoromethylphenylacetylene, 4-hydroxyphenylacetylene, 2-methylphenylacetylene, 3-methylphenylacetylene, 2-methoxyphenylacetylene, 3-methoxyphenylacetylene, 2-chlorophenylacetylene, 4-acetylenic biphenyl, 1-naphthylacetylene, 2-naphthylacetylene, 4-ethynyl methyl benzoate, 4-ethynyl ethyl benzoate, 4-ethynyl-N-methylbenzamide, N-(4-ethynylphenyl)acetamide, 2-ethynylthiophene, 2-acetylenepyridine, 3,5-dimethoxyphenylacetylene, methyl propiolate, and ethyl propiolate.

7. The method according to any one of claims 2-6, characterized in that The general formula of the non-metallic photocatalyst is Formula IV: Wherein, in Formula IV, R 4 selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen, a cyano group, a nitro group, an acetylamino group, a trifluoromethyl group, an aryl group, a heteroaryl group; R 5 Selected from a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group.

8. The method according to claim 7, wherein The non-metallic photocatalyst is selected from one of the following compounds:

9. The method according to any one of claims 2-8, characterized in that, The base is selected from: Cs2CO3, CsF, CsCl, CH3COOCs, NaOH, K3PO4, PhCOOK, t-BuOK, K2CO3, KF.

10. The method according to any one of claims 2-9, characterized in that, The additive is one of the following: DABCO, NaCl, KI, 2-phthalimido benzoate, 2-phthalimido 4-methylbenzoate, 2-phthalimido 4-methoxybenzoate, 2-phthalimido 4-fluorobenzoate, 2-(4,5,6,7-tetrachlorophthalimido) benzoate.

11. The method according to any one of claims 2-10, characterized in that, The organic solvent is selected from one of the following: chlorobenzene, toluene, trifluorotoluene, p-xylene, o-xylene, m-xylene, 1,4-dioxane, dichloromethane, acetonitrile, pyridine, ethylbenzene, anisole, and the amount of the solvent used is 0.5 - 3.0 mL.

12. The method according to any one of claims 2-11, characterized in that, The molar ratio of the N-aryl tetrahydroquinoline compound, phenylacetylene compound, photocatalyst, base, and additive is 1.0:1.0 - 3.0:0.01 - 0.2:0.5 - 2.0:1.0 - 3.0, the reaction temperature is 20 - 60 °C; the atmosphere in the reaction vessel is an inert gas atmosphere; the reaction duration is 4 h - 48 h; the light source is a 35 W blue light lamp or a CFL lamp.

13. A quinoline tri(hetero)aryl substituted olefin compound, whose general formula is Formula V: Wherein: R 1 、R 2 、R 3 are the same as the definition of R 1 、R 2 、R 3 described in any one of claims 1-6; Preferably, the compound of the structure shown in Formula V is selected from one of the following compounds:

14. A method for preparing a quinoline tris(hetero)aryl-substituted olefin compound having the structure shown in Formula V, characterized in that, The method includes: in the presence of chloroform organic solvent and diethyl azodicarboxylate, oxidizing the tetrahydroquinoline-substituted trisubstituted olefin described in any one of Claims 1 - 2 under an air atmosphere.

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