Synthesis method of dihydroindeno-indene compound

Abstract

The invention discloses a method for synthesizing an indene compound, which comprises the following steps: reacting a 2-iodo styrene compound and diaryl cyclopropenone which are used as raw materials in an organic solvent under the combined action of a palladium catalyst, a ligand and alkali, and carrying out post-treatment after the reaction is finished to obtain the indene compound. The reaction formula of the synthesis method is as follows: in the # imgabs0 # formula, R1 is selected from one of hydrogen atom, alkyl, alkoxy and halogen; r2 is selected from one of a hydrogen atom, an alkyl group, an alkoxy group, an ester group and an acyl group; r is alkyl. According to the present invention, the easily prepared 2-iodo styrene compound and the commercial diaryl cyclopropenone are adopted as the raw materials, three chemical bonds are constructed through the one-pot method, and the rapid synthesis of the indene compound having the four-membered ring structure is achieved; the reaction has the advantages of simplicity in operation, low reaction cost, wide substrate applicability, easiness in separation of a target product and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing indeno[1,2 - b]indene compounds. Background Art

[0002] Indeno[1,2 - b]indene is a complex polycyclic organic compound, whose structure contains four rings, two of which are indene rings and the other two are dihydro - indene rings. The indene ring and dihydro - indene ring can participate in various organic reactions, such as electrophilic substitution, addition reaction, etc. In addition, the indeno[1,2 - b]indene skeleton is widely present in natural products and bioactive molecules and has received extensive attention in the fields of medicine, dyes, pesticides, biology, etc. At present, relatively few synthetic methods for this type of skeleton have been reported, which generally involve the following strategies: (1) Construction through intramolecular cyclization reactions; for example, forming a fused - ring structure through Friedel - Crafts alkylation or acylation reactions. (2) Construction through hydrogenation reactions; through selective hydrogenation of dibenzo[a,e]indene. (3) Construction through Diels - Alder reactions; constructing a polycyclic system by using the cycloaddition reaction of conjugated dienes and dienophiles.

[0003] However, the reported synthetic methods have some limitations: for example, the synthetic steps may require high - temperature or high - pressure conditions, which pose high requirements for experimental equipment and also limit the scope of applicable substrates; in addition, some cyclization reactions require the use of strong acids or strong bases as catalysts, which pose high requirements for the functional - group tolerance of substrates. Moreover, the above synthetic strategies generally involve multiple - step reactions, and the multiple - step reactions and expensive reagents / catalysts may lead to too high synthesis costs, limiting their practical applications. Summary of the Invention

[0004] Aiming at the above problems existing in the prior art, the purpose of the present invention is to provide a method for synthesizing indeno[1,2 - b]indene compounds, which has the advantages of mild reaction conditions, low cost, and simple post - treatment.

[0005] The present invention uses simple and readily available reaction raw materials, and through a reaction process of palladium - catalyzed intermolecular tandem cyclization / C - H activation, synthesizes indeno[1,2 - b]indene compounds in one - pot and multiple - steps.

[0006] To achieve the above purpose, the present invention adopts the following technical scheme:

[0007] A method for synthesizing indeno[1,2 - b]indene compounds, using 2 - iodostyrene compounds and diarylcyclopropenone as raw materials, reacting in an organic solvent under the joint action of a palladium catalyst, a ligand, and a base, and obtaining indeno[1,2 - b]indene compounds after post - treatment after the reaction ends;

[0008] The reaction formula of the said synthesis method is as follows:

[0009]

[0010] In the formula, R 1 is selected from one of hydrogen atom, alkyl, alkoxy and halogen; R 2 One selected from a hydrogen atom, an alkyl group, an alkoxy group, an ester group, and an acyl group; R is an alkyl group.

[0011] Preferably, the molar ratio of the 2-iodostyrene compound, diarylcyclopropenone, palladium catalyst, ligand and base is 1:1.5:0.1:0.2:3.

[0012] Preferably, the concentration of the 2-iodostyrene compound in the reaction solution is 0.05 mol / L.

[0013] Preferably, the palladium catalyst is one of palladium acetate, palladium chloride, palladium trifluoroacetate, tetrakistriphenylphosphine palladium, bis(tricyclohexylphosphine)palladium dichloride or bis(acetonitrile)palladium dichloride.

[0014] Preferably, the ligand is any one of triphenylphosphine, tri(p-methoxyphenyl)phosphine, tri(4-trifluoromethylphenyl)phosphine, tri(p-fluorophenyl)phosphine, tricyclohexylphosphine tetrafluoroborate, tri-tert-butylphosphine tetrafluoroborate, 1,2-bis(diphenylphosphine)ethane, bis(diphenylphosphine)methane, 1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphine)propane, and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthene.

[0015] Preferably, the base is one of cesium carbonate, potassium carbonate, sodium acetate, potassium phosphate and triethylamine.

[0016] Preferably, the organic solvent is one of ethylene glycol dimethyl ether, toluene, dioxane, acetonitrile, tetrahydrofuran or 1,2-dichloroethane.

[0017] Preferably, the reaction temperature is 80-120°C.

[0018] Preferably, the reaction time is 12 to 20 hours.

[0019] Preferably, the post-treatment step is: after the reaction is completed, the reaction system is cooled, the organic solvent is removed by rotary evaporation under reduced pressure, and the residue is mixed with silica gel and separated by column chromatography to obtain a dihydroindenoindene compound.

[0020] Preferably, the eluent for column chromatography separation is a mixture of petroleum ether and ethyl acetate in a volume ratio of 200 to 100:1.

[0021] By adopting the above technology, compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] 1. The reaction raw materials of the present invention are safe and easily available, and have the advantages of good functional group tolerance and wide substrate universality;

[0023] 2. Low cost, one-step construction of indenoindene compounds; the product can be used for drug synthesis; the operation steps are simple; the solvent does not require further treatment. Description of the Drawings

[0024] Figure 1 1H NMR spectrum of the product structure in Example 1;

[0025] Figure 2 1H NMR spectrum of the product structure in Example 2;

[0026] Figure 3 1H NMR spectrum of the product structure in Example 3;

[0027] Figure 4 1H NMR spectrum of the product structure in Example 4;

[0028] Figure 5 1H NMR spectrum of the product structure in Example 5;

[0029] Figure 6 1H NMR spectrum of the product structure in Example 6;

[0030] Figure 7 1H NMR spectrum of the product structure in Example 7;

[0031] Figure 8 1H NMR spectrum of the product structure in Example 8;

[0032] Figure 9 1H NMR spectrum of the product structure in Example 9;

[0033] Figure 10 1H NMR spectrum of the product structure in Example 10;

[0034] Figure 11 1H NMR spectrum of the product structure in Example 11. Detailed Description of the Invention

[0035] The present invention will be further described below in conjunction with specific embodiments. These embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0036] Example 1:

[0037] In this example, the structural formula of the indenoindene compound is:

[0038]

[0039] The synthesis method is as follows: 1-iodo-2-(prop-1-en-2-yl)benzene (48.0 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed and stirred in an oil bath at 100 °C for 16 h. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product (68%) was obtained by column chromatography (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v).

[0040] The detection data of the product are as follows:

[0041] 1 H NMR (400 MHz, CDCl3) δ 7.53 (dd, J = 7.5, 1.7 Hz, 2H), 7.45 (d, J = 7.5 Hz, 1H), 7.41 - 7.26 (m, 5H), 7.20 - 7.10 (m, 3H), 7.03 (dt, J = 20.8, 7.3 Hz, 2H), 2.94 (d, J = 14.4 Hz, 1H), 2.73 (d, J = 14.4 Hz, 1H), 1.34 (d, J = 1.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 158.9, 151.5, 151.4, 146.7, 135.7, 134.9, 133.2, 129.4, 128.5, 127.8, 127.5, 127.0, 126.8, 126.2, 125.1, 122.9, 122.8, 121.5, 62.0, 40.4, 27.2.

[0042] Example 2:

[0043] In this example, the structural formula of the indenoindene compound is:

[0044]

[0045] The synthesis method is as follows: 2-Iodo-4-methoxy-1-(prop-1-en-2-yl)benzene (54.8 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed and stirred in an oil bath at 100 °C for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the target product was obtained by column chromatography separation (petroleum ether / ethyl acetate = 100:1 - 50:1, v / v) (64%).

[0046] The product detection data are as follows:

[0047] 1 H NMR (400 MHz, CDCl3) δ 7.56 - 7.50 (m, 2H), 7.46 - 7.38 (m, 3H), 7.31 (d, J = 7.4 Hz, 1H), 7.23 (dd, J = 18.2, 7.7 Hz, 2H), 7.07 - 6.99 (m, 2H), 6.87 (d, J = 2.4 Hz, 1H), 6.69 (dd, J = 8.1, 2.4 Hz, 1H), 3.71 (s, 3H), 2.93 (d, J = 14.4 Hz, 1H), 2.71 (d, J = 14.4 Hz, 1H), 1.34 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 160.2, 159.4, 151.4, 148.2, 143.8, 135.8, 134.9, 133.1, 129.4, 128.5, 127.8, 127.6, 126.8, 126.2, 123.3, 122.8, 110.4, 107.4, 61.3, 55.6, 40.7, 27.3.

[0048] Example 3:

[0049] In this example, the structural formula of the indenoindene compound is:

[0050]

[0051] The synthesis method is as follows: 4-chloro-2-iodo-1-(prop-1-en-2-yl)benzene (55.6 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed and stirred in an oil bath at 100 °C for 16 h. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product (62%) was obtained by column chromatography (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v).

[0052] The product detection data are as follows:

[0053] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 7.3 Hz, 2H), 7.43 (q, J = 7.3 Hz, 3H), 7.33 (t, J = 7.5 Hz, 1H), 7.27 - 7.25 (m, 2H), 7.22 (d, J = 7.3 Hz, 1H), 7.12 - 7.08 (m, 2H), 7.04 (d, J = 7.5 Hz, 1H), 2.96 (d, J = 14.4 Hz, 1H), 2.73 (d, J = 14.5 Hz, 1H), 1.34 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 160.5, 151.3, 149.6, 148.6, 135.4, 134.3, 133.0, 132.3, 129.3, 128.6, 128.1, 128.0, 127.0, 126.3, 124.9, 123.8, 123.0, 121.6, 61.6, 40.4, 27.2.

[0054] Example 4:

[0055] In this example, the structural formula of the indenoindene compound is:

[0056]

[0057] The synthesis method is as follows: 1-iodo-4-methyl-2-(prop-1-en-2-yl)benzene (51.6 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed and stirred in an oil bath at 100 °C for 16 h. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product (69%) was obtained by column chromatography separation (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v).

[0058] The product detection data are as follows:

[0059] 1 H NMR (400 MHz, CDCl3) δ 7.57 - 7.51 (m, 2H), 7.47 - 7.43 (m, 1H), 7.39 (dd, J = 8.4, 6.7 Hz, 2H), 7.33 - 7.27 (m, 1H), 7.20 (d, J = 7.9 Hz, 3H), 7.07 - 6.99 (m, 3H), 2.93 (d, J = 14.4 Hz, 1H), 2.74 (d, J = 14.4 Hz, 1H), 2.35 (s, 3H), 1.35 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 157.9, 151.8, 151.2, 144.1, 135.9, 135.1, 135.0, 133.3, 129.4, 128.4, 127.72, 127.66, 127.4, 126.8, 126.2, 124.0, 122.7, 121.2, 61.8, 40.4, 27.3, 21.7.

[0060] Example 5:

[0061] In this example, the structural formula of the indenoindene compound is:

[0062]

[0063] The synthesis method is as follows: 4-Fluoro-1-iodo-2-(prop-1-en-2-yl)benzene (52.4 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed and stirred in an oil bath at 100 °C for 16 h. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product was obtained by column chromatography separation (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v) (43%).

[0064] The product detection data are as follows:

[0065] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 7.6 Hz, 2H), 7.47 - 7.35 (m, 3H), 7.33 - 7.27 (m, 1H), 7.21 (dd, J = 8.3, 5.7 Hz, 2H), 7.09 - 6.98 (m, 3H), 6.87 (m, 1H), 2.93 (d, J = 14.4 Hz, 1H), 2.74 (d, J = 14.4 Hz, 1H), 1.33 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 161.7 (d, J = 245.4 Hz), 158.4 (d, J = 4.0 Hz), 153.6 (d, J = 7.7 Hz), 150.9, 142.5 (d, J = 2.4 Hz), 135.6, 134.7, 132.6, 129.4, 128.5, 127.9, 127.6, 126.9, 126.2, 122.6, 122.0 (d, J = 8.6 Hz), 113.7 (d, J = 22.6 Hz), 110.9 (d, J = 22.9 Hz), 61.8 (d, J = 2.3 Hz), 40.2, 27.2.

[0066] Example 6:

[0067] In this example, the structural formula of the indenoindene compound is:

[0068]

[0069] The synthesis method is as follows: 2-Iodo-1-methyl-3-(prop-1-en-2-yl)benzene (51.6 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed, and stirred in an oil bath at 100 °C for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product (57%) was obtained by column chromatography (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v).

[0070] The product detection data are as follows:

[0071] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 6.8 Hz, 1H), 7.41 (dd, J = 8.4, 6.4 Hz, 1H), 7.31 - 7.23 (m, 2H), 7.19 (dd, J = 7.3, 5.5 Hz, 2H), 7.16 - 7.12 (m, 1H), 7.06 - 7.00 (m, 2H), 6.98 - 6.87 (m, 3H), 2.95 (dd, J = 14.5, 1.6 Hz, 1H), 2.74 (d, J = 14.3 Hz, 1H), 1.90 (s, 3H), 1.33 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 159.6, 152.2, 150.9, 144.5, 137.5, 135.9, 134.7, 132.9, 130.7, 130.0, 128.9, 128.2, 128.0, 127.4, 127.2, 126.8, 126.0, 125.1, 122.7, 120.6, 61.1, 40.6, 27.3, 20.4.

[0072] Example 7:

[0073] In this example, the structural formula of the indenoindene compound is:

[0074]

[0075] The synthesis method is as follows: 1-(Hex-1-en-2-yl)-2-iodobenzene (57.2 mg, 0.2 mmol), 2,3-diphenylcycloprop-2-en-1-one (61.8 mg, 0.3 mmol), palladium acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed, and stirred in an oil bath at 100 °C for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the target product was obtained by column chromatography (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v) (54%).

[0076] The product detection data are as follows:

[0077] 1 H NMR (400 MHz, CDCl3) δ 7.57 - 7.52 (m, 2H), 7.47 - 7.39 (m, 3H), 7.35 - 7.28 (m, 3H), 7.19 (ddd, J = 8.8, 7.3, 1.6 Hz, 2H), 7.15 - 7.11 (m, 1H), 7.08 - 6.99 (m, 2H), 2.99 (d, J = 14.5 Hz, 1H), 2.75 (d, J = 14.5 Hz, 1H), 1.96 - 1.87 (m, 1H), 1.63 (td, J = 13.3, 12.5, 4.0 Hz, 1H), 1.06 - 0.94 (m, 3H), 0.76 - 0.68 (m, 1H), 0.62 (t, J = 7.1 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 157.3, 151.8, 150.1, 147.9, 136.2, 135.0, 134.5, 129.5, 128.5, 127.8, 127.5, 127.0, 126.8, 126.1, 124.9, 123.1, 122.6, 121.1, 65.5, 40.2, 40.0, 26.6, 23.2, 14.1.

[0078] Example 8:

[0079] In this example, the structural formula of the indenoindene compound is:

[0080]

[0081] The synthesis method is as follows: 4-chloro-1-iodo-2-(prop-1-en-2-yl)benzene (55.6 mg, 0.2 mmol), 2,3-di-p-tolylcycloprop-2-en-1-one (70.2 mg, 0.3 mmol), palladium acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed, and stirred in an oil bath at 100 °C for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the target product was obtained by column chromatography separation (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v) (58%).

[0082] The product detection data are as follows:

[0083] 1 H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 7.7 Hz, 2H), 7.37 - 7.30 (m, 2H), 7.18 (ddd, J = 22.1, 8.0, 4.8 Hz, 4H), 7.05 (s, 1H), 6.85 (d, J = 7.8 Hz, 1H), 2.89 (d, J = 14.4 Hz, 1H), 2.71 (d, J = 14.5 Hz, 1H), 2.35 (s, 3H), 2.25 (s, 3H), 1.34 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 158.8, 153.0, 151.3, 145.5, 137.8, 137.6, 132.9, 131.63, 131.55, 130.7, 129.22, 129.19, 127.7, 127.1, 127.0, 123.4, 122.6, 122.0, 61.8, 40.1, 27.3, 21.7, 21.5.

[0084] Example 9:

[0085] In this example, the structural formula of the indenoindene compound is:

[0086]

[0087] The synthesis method is as follows: 4-chloro-1-iodo-2-(prop-1-en-2-yl)benzene (55.6 mg, 0.2 mmol), 2,3-bis(4-(tert-butyl)phenyl)cycloprop-2-en-1-one (95.4 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed, and the mixture was stirred in an oil bath at 100 °C for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product was obtained by column chromatography (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v) (52%).

[0088] The product detection data are as follows:

[0089] 1 H NMR (400 MHz, CDCl3) δ 7.49 - 7.40 (m, 5H), 7.33 (d, J = 2.0 Hz, 1H), 7.28 - 7.24 (m, 2H), 7.18 - 7.14 (m, 1H), 7.10 (dd, J = 8.0, 1.8 Hz, 1H), 2.96 - 2.70 (m, 2H), 1.35 (s, 3H), 1.30 (s, 9H), 1.22 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 158.9, 153.2, 151.2, 151.1, 150.8, 131.7, 131.6, 130.7, 129.0, 127.0, 125.4, 124.0, 123.5, 123.3, 122.3, 122.2, 62.0, 40.4, 34.92, 34.86, 31.6, 31.5, 27.4.

[0090] Example 10:

[0091] In this example, the structural formula of the indenoindene compound is:

[0092]

[0093] The synthesis method is as follows: 4-chloro-2-iodo-1-(prop-1-en-2-yl)benzene (55.6 mg, 0.2 mmol), 2,3-bis(4-chlorophenyl)cycloprop-2-en-1-one (82.5 mg, 0.3 mmol), palladium(II) acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) were successively added to a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran was added, the flask was sealed and stirred in an oil bath at 100 °C for 16 h. After the reaction was complete, the solvent was removed by rotary evaporation, and the target product (41%) was obtained by column chromatography separation (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v).

[0094] The product detection data are as follows:

[0095] 1 H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 0.9 Hz, 4H), 7.27 (dd, J = 14.1, 8.0 Hz, 2H), 7.23 - 7.19 (m, 2H), 7.12 (dd, J = 7.9, 1.9 Hz, 1H), 7.02 (dd, J = 8.2, 2.0 Hz, 1H), 2.94 (d, J = 14.7 Hz, 1H), 2.71 (d, J = 14.7 Hz, 1H), 1.33 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 159.4, 153.0, 149.2, 148.0, 134.02, 133.97, 133.6, 133.3, 132.5, 131.6, 130.5, 129.0, 127.4, 126.7, 125.3, 123.9, 123.6, 121.5, 61.9, 40.2, 27.1.

[0096] Example 11:

[0097] In this example, the structural formula of the indenoindene compound is:

[0098]

[0099] The chorusing method is to sequentially add 1-(hex-1-en-2-yl)-2-iodobenzene (57.2 mg, 0.2 mmol), 2,3-bis(4-chlorophenyl)cycloprop-2-en-1-one (82.5 mg, 0.3 mmol), palladium acetate (4.48 mg, 0.02 mmol), tris(4-trifluoromethylphenyl)phosphine (18.6 mg, 0.04 mmol) and potassium carbonate (82.8 mg, 0.6 mmol) into a 25 mL reaction flask. Subsequently, 4.0 mL of tetrahydrofuran is added, the flask is sealed, and it is stirred in an oil bath at 100 °C for 16 hours. After the reaction is complete, the solvent is removed by rotary evaporation, and then the target product (50%) is obtained by column chromatography separation (petroleum ether / ethyl acetate = 200:1 - 100:1, v / v).

[0100] The product detection data is as follows:

[0101] 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.30 (dd, J = 13.7, 7.7 Hz, 2H), 7.21 (dt, J = 13.9, 3.8 Hz, 3H), 7.17 - 7.13 (m, 1H), 7.02 - 6.98 (m, 1H), 2.97 (d, J = 14.8 Hz, 1H), 2.72 (d, J = 14.7 Hz, 1H), 1.89 (ddd, J = 13.2, 11.1, 4.4 Hz, 1H), 1.60 (td, J = 12.7, 4.0 Hz, 1H), 1.04 - 0.90 (m, 3H), 0.63 (t, J = 7.0 Hz, 4H). 13 C NMR (101 MHz, CDCl3) δ 156.3, 153.5, 149.8, 147.3, 134.4, 133.7, 133.4, 133.2, 132.9, 130.6, 128.9, 128.8, 127.2, 127.1, 126.5, 125.3, 123.2, 123.1, 121.0, 65.8, 40.1, 39.8, 26.6, 23.1, 14.1.

[0102] The above are only the preferred embodiments of the present invention, and it is not intended to limit the present invention in other forms. Any person skilled in the art may use the disclosed technical content to make changes or modifications into equivalent embodiments with equivalent changes. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the technical solution content of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A method for synthesizing an indenoindene compound, characterized in that: Using 2-iodostyrene compound and diarylcyclopropenone as raw materials, reacting in an organic solvent through the joint action of a palladium catalyst, a ligand and a base, and after the reaction is completed, post-treatment is performed to obtain a dihydroindenoindene compound; The reaction formula of the synthesis method is as follows: Wherein, R 1 is selected from one of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen; R 2 is selected from one of a hydrogen atom, an alkyl group, an alkoxy group, an ester group, and an acyl group; R is an alkyl group.

2. The synthesis method of the indenoindene compound according to claim 1, characterized in that: The molar ratio of the 2-iodostyrene compound, diarylcyclopropenone, palladium catalyst, ligand and base is 1:1.5:0.1:0.2:

3.

3. The method for synthesizing an indenoindene compound according to claim 1, wherein: The concentration of the 2-iodostyrene compound in the reaction solution is 0.05 mol / L.

4. The synthetic method of the indenoindene compound according to claim 1 or 2, characterized in that: The palladium catalyst is one of palladium acetate, palladium chloride, palladium trifluoroacetate, tetrakistriphenylphosphine palladium, bis(tricyclohexylphosphine)palladium dichloride or bis(acetonitrile)palladium dichloride.

5. The method for synthesizing an indenoindene compound according to claim 1 or 2, characterized in that: The ligand is any one of triphenylphosphine, tri(p-methoxyphenyl)phosphine, tri(4-trifluoromethylphenyl)phosphine, tri(p-fluorophenyl)phosphine, tricyclohexylphosphine tetrafluoroborate, tri-tert-butylphosphine tetrafluoroborate, 1,2-bis(diphenylphosphine)ethane, bis(diphenylphosphine)methane, 1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphine)propane, and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene.

6. The synthetic method of the indenoindene compound according to claim 1 or 2, characterized in that: The base is one of cesium carbonate, potassium carbonate, sodium acetate, potassium phosphate and triethylamine.

7. The method for synthesizing an indenoindene compound according to claim 1 or 2, characterized in that: The organic solvent is one of ethylene glycol dimethyl ether, toluene, dioxane, acetonitrile, tetrahydrofuran or 1,2-dichloroethane.

8. The method for synthesizing an indenoindene compound according to claim 1, wherein: The reaction temperature is 80-120°C, and the reaction time is 12-20h.

9. The synthesis method of the indenoindene compound according to claim 1, wherein: The post-treatment step is: after the reaction is completed, the reaction system is cooled, the organic solvent is removed by rotary evaporation under reduced pressure, and the residue is mixed with silica gel and separated by column chromatography to obtain a dihydroindenoindene compound.

10. The synthetic method of the indenoindene compound according to claim 9, characterized in that: The eluent for column chromatography separation is a mixture of petroleum ether and ethyl acetate in a volume ratio of 200 to 100:1.

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