Bio-based carbonylation reagents and uses thereof

Abstract

The application provides a bio-based carbonylation reagent and a preparation method and application thereof. The bio-based carbonylation reagent provided by the application comprises methyl esterified cellulose. The carbonylation reagent provided by the application is convenient to prepare, low in price, stable in property, mild in carbon monoxide releasing condition, and capable of being applied to various carbonylation reactions.

Description

Technical Field

[0001] This invention relates to a bio-based carbonylation reagent and its applications. Background Technology

[0002] Carbonyl structures are not only widely found in pharmaceuticals, agrochemicals, and functional materials, but also serve as various transformative precursor structures in synthetic chemistry. Carbonylation is the most powerful method for constructing carbonyl structures. Introducing carbon monoxide into a molecule is the most direct and effective method for constructing complex carbonyl-containing compounds (Wu, X.-F., Neumann, H., Beller, M. Chem. Soc. Rev. 2011, 40, 4986; Franke, R., Selent, D., (A. Chem. Rev. 2012, 112, 5675.). Although gaseous carbon monoxide has been widely used in organic synthesis through coupling and tandem carbonylation reactions, the high toxicity and flammability of carbon monoxide gas necessitate extremely high skill requirements for storage and use equipment and operation. High-pressure containers and carbon monoxide detectors are typically required, which hinders its safe and convenient use, especially in academic research and laboratories. To overcome the dangers and inconveniences of using carbon monoxide gas, a series of carbon monoxide substitutes, such as formic acid and its derivatives, aldehydes, carboxylic acids, acyl chlorides, carbon dioxide, chloroform, and metal carbonyl compounds, have been developed as carbonylating agents that can release carbon monoxide through reactions (Cao, J., Zheng, Z.-J., Xu, Z., Xu, L.-W. Coord. Chem. Rev. 2017, 336, 43; Morimoto, T., Kakiuchi, K. Angew. Chem. Int. Ed. 2004, 43, 5580; Grushin, VV, Alper, H. Organometallics 1993, 12, 3846; Konishi, H., Manabe, K. Synlett 2014, 25, 1971.), have been widely used in carbonylation synthesis reactions.

[0003] Classic liquid carbonylating agents, such as formic acid, formamide, aldehydes, and acyl chlorides, are typically highly toxic, volatile, and air-sensitive, and often require additional activators, such as metal catalysts and acetic anhydride, to release carbon monoxide during use. Solid carbonylating agents, on the other hand, offer advantages such as greater stability, ease of handling, and lower toxicity. In recent years, research groups such as Wu, Yudin, Skrydstrup, and Manabe have developed more stable and easier-to-operate organic molecular carbonylating agents, such as phenyl-1,3,5-tricarboxylic acid triester (Jiang, L.-B., Qi, X., Wu, X.-F. Tetrahedron Lett. 2016, 57, 3368) and 6-methyl-4,8-dioxo-1,3,6,2-dioxaborane-2-carboxylic acid (Tien, C.-H. et al.). The reported solid carbonylating reagents are: 9-methyl-9H-fluorene-9-carboxyl chloride (Hermange, P. et al. J. Am. Chem. Soc. 2011, 133, 6061) and 3-oxobenzisothiazol-2(3H)-formaldehyde 1,1-dioxide (Ueda, T., Konishi, H., Manabe, K. Angew. Chem. Int. Ed. 2013, 52, 8611). However, the reported precursors for these solid carbonylating reagents are all derived from fossil fuels, which are expensive, require complex synthetic steps, additional activating agents or high temperatures to release carbon monoxide, and have poor compatibility, resulting in a very limited range of carbonylation reactions they can participate in. Therefore, there is an urgent need in the field for a solid carbonylating reagent that is easy to prepare, inexpensive, stable, has mild carbon monoxide release conditions, and can be applied to a variety of carbonylation reactions. Summary of the Invention

[0004] To overcome the shortcomings of existing solid carbonylating reagents, such as complex preparation, high cost, limited types of carbonylation reactions, and poor functional group compatibility, this invention provides a novel carbonylating reagent, its preparation method, and its applications. The carbonylating reagent provided by this invention is a solid carbonylating reagent that is easy to prepare, inexpensive, stable, exhibits mild carbon monoxide release conditions, and can be applied to various types of carbonylation reactions.

[0005] In a first aspect, the present invention provides a bio-based carbonylation reagent comprising methylated cellulose.

[0006] According to some embodiments of the present invention, the methylated cellulose has the structural unit shown in Formula 1:

[0007]

[0008] In Equation 1, R1 R 2 and R 3 For hydrogen or And at least R 1 R 2 and R 3 At least one of them is

[0009] According to some embodiments of the present invention, the degree of substitution of the methyl esterified cellulose is 0.1-3, preferably 0.5-2, more preferably 1-1.5, and most preferably 1.2-1.4.

[0010] In a second aspect, the present invention provides a method for preparing a carbonylating reagent, the method comprising the following steps:

[0011] (1) The cellulose raw material is reacted in a formic acid solution to generate a reaction mixture containing methylated cellulose;

[0012] (2) The reaction mixture is subjected to solid-liquid separation;

[0013] (3) The liquid separated in step (2) is concentrated and dried.

[0014] According to some embodiments of the present invention, the formic acid solution is a formic acid solution with a mass fraction of 10% to 100% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%).

[0015] According to some embodiments of the present invention, the mass-to-volume ratio of the formic acid solution to the cellulose raw material is 1 mL / g to 100 mL / g, for example, 1 mL / g, 10 mL / g, 15 mL / g, 20 mL / g, 30 mL / g, 40 mL / g, 50 mL / g, 60 mL / g, 70 mL / g, 80 mL / g, or 100 mL / g.

[0016] According to some embodiments of the present invention, in step (1), the temperature of the reaction is 10-120°C.

[0017] According to some embodiments of the present invention, in step (1), the reaction time is 1 minute to 24 hours; for example, 1 hour, 2 hours, 4 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours or 22 hours.

[0018] According to some embodiments of the present invention, the reaction includes a first stage and a second stage, wherein the first stage is carried out at 80-120°C, preferably 90-110°C, more preferably 95°C for 4-8 hours, preferably 5-6.5 hours, for example 6 hours; and the second stage is carried out at 20-40°C, preferably 20-30°C, for example 25°C for 8-14 hours, preferably 10-13 hours, for example 12 hours.

[0019] According to some embodiments of the present invention, the first stage is carried out at 90-110°C for 4-8 hours, preferably 5-6.5 hours; the second stage is carried out at 20-30°C for 8-14 hours.

[0020] According to some embodiments of the present invention, the first stage is carried out at 95°C for 6 hours; the second stage is carried out at 20-30°C for 8-14 hours.

[0021] According to some embodiments of the present invention, the degree of substitution of the methylated cellulose obtained in step (1) is 0.1-3, preferably 0.5-2. In some preferred embodiments, the degree of substitution of the methylated cellulose obtained in step (1) is 0.8-2, preferably 1-1.5, and most preferably 1.2-1.4. In one preferred embodiment, the degree of substitution of the methylated cellulose is 1.3-1.4.

[0022] In a third aspect, the present invention provides the application of the carbonylating agent described in the first aspect or the carbonylating agent prepared by the preparation method described in the second aspect in a carbonylation reaction. In some embodiments, a carbonyl group is introduced into the carbonylation reaction. Specifically, it can be an ester group. amide group

[0023] In a fourth aspect, the present invention provides a carbonylation reaction method, comprising:

[0024] Reactant A, reactant B, and the carbonylating reagent described in the first aspect or prepared by the method described in the second aspect are reacted to generate a carbonyl-containing compound. The reactant A is selected from organic compounds having halogen groups, preferably aryl halides or heteroaryl halides. The reactant B is selected from organic compounds having hydroxyl, NH, NH2, terminal alkyne, borate, and / or borate ester groups.

[0025] According to some embodiments of the present invention, the organic compound having a halogen group is as shown in Formula I:

[0026]

[0027] Ring A represents an aryl group having 6-20 carbon atoms or a heteroaryl group having 3-20 carbon atoms;

[0028] In Formula I, R1 represents one or more substituents selected from hydrogen, deuterium, cyano, amino, nitro, C1-C5 alkylamino, halogen, C1-C5 alkyl, C1-C5 alkoxy, phenyl, benzoyl, methoxycarbonyl, and ethoxycarbonyl.

[0029] In some embodiments, ring A is a benzene ring, 4-methylbenzene ring, 4-tert-butylbenzene ring, 4-methoxybenzene ring, 3-methoxybenzene ring, 2-methoxybenzene ring / 4-phenylbenzene ring, 4-benzoylbenzene ring, 4-cyanobenzene ring, 4-methyl ester benzene ring, 4-trifluoromethylbenzene ring, 4-n-butyloxybenzene ring, 2-trifluoromethylbenzene ring, 3,5-dimethylbenzene ring, 3,5-dimethoxybenzene ring, 3,4-dimethoxybenzene ring, 3,4,5-trimethylbenzene ring, 2-naphthyl ring, 1-naphthyl ring, 1,2-methylenedioxybenzene ring, 2,3-dihydrobenzo[b][1,4]dioxin, 2-methylbenzoazole, benzofuran ring, furan ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, fluorene, indole ring, quinoline ring, quinoxaline ring, aminotoluene ring, ethylamine benzene ring, or halogenated benzene ring.

[0030] In some embodiments, the halogen-containing organic compound is selected from one or more of the following compounds:

[0031]

[0032]

[0033] Bromine or iodine are preferred.

[0034] In some embodiments, reactant B is selected from compounds with the following structural formulas:

[0035]

[0036] Where n is 0, 1, 2, 3 or 4; R is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano, halogen, hydroxyl, amino; X and Y are each independently halogen or amino, with halogen preferably being bromine or iodine.

[0037] Examples of reactant B include, but are not limited to:

[0038]

[0039] According to some embodiments of the present invention, the reactant B is selected from organic compounds containing hydroxyl groups, organic compounds containing NH or NH2, organic compounds containing alkyne groups, and organic compounds containing boric acid groups or borate ester groups.

[0040] In some embodiments, the hydroxyl-containing organic compound is an alcohol compound.

[0041] In some embodiments, the alcohol compound is selected from C1-C10 alkyl alcohols, wherein the C1-C10 alkyl group is optionally substituted with a substituent selected from cyano, nitro, halogen, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C6-C10 aryl, amino, C1-C5 alkoxy, and C1-C5 alkyl-substituted amino groups.

[0042] In some embodiments, the alcohol compound is selected from methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, isobutanol, sec-butanol, n-pentanol, 2-pentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, ethylene glycol, benzyl alcohol, phenethyl alcohol, phenylpropanol, etc. Or 1-cyclohexenylmethanol, etc.

[0043] In some embodiments, the organic compound containing NH or NH2 is selected from C3-C10 alkylamines, C6-C20 arylamines, and C3-C20 heteroarylamines. The C3-C10 alkyl group is optionally substituted with a substituent selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C10 aryl, C3-C10 heteroaryl, amino, C1-C5 alkoxy, and C1-C5 alkyl-substituted amino groups. The C6-C20 aryl and C3-C20 heteroaryl groups are optionally substituted with C1-C5 alkyl, C1-C5 alkoxy, halogen, cyano, nitro, and amino groups.

[0044] In some embodiments, the organic compound containing NH or NH2 is selected from one or more of the following compounds:

[0045]

[0046] In some embodiments, the terminal alkyne-containing organic compound is selected from R2D, where R2 represents... D is selected from C3-C10 alkyl, C6-C20 aryl, and C3-C20 heteroaryl, wherein the C3-C10 alkyl, C6-C20 aryl, and C3-C20 heteroaryl are optionally substituted with substituents selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, and C1-C5 alkyl-substituted amino groups;

[0047] In some embodiments, the terminal alkyne-containing organic compound is selected from one or more of the following compounds:

[0048]

[0049] In some embodiments, the organic compound containing a borate group or borate ester group is selected from R3E, wherein R3 is... R4 and R5 are each independently C1-C6 alkyl or linked together to form a 5-6 membered ring; E is selected from C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl, wherein the C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl are optionally substituted with substituents selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, and C1-C5 alkyl-substituted amino groups.

[0050] In some embodiments, the borate compound is selected from...

[0051] In some embodiments, the reaction is carried out in a solvent, which may be one or more of alkane solvents, substituted aromatic hydrocarbon solvents, nitrile solvents, halogenated hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, and amide solvents. The alkane solvent may be n-hexane. The substituted aromatic hydrocarbon solvent may be one or more of chlorobenzene, toluene, and trifluoromethylbenzene. The nitrile solvent may be acetonitrile. The halogenated hydrocarbon solvent may be dichloromethane and chloroform. The ether solvent may be tetrahydrofuran, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, anisole, ethylene glycol dimethyl ether, and 1,4-dioxane. The ketone solvent may be acetone. The ester solvent may be ethyl acetate and ethylene glycol diacetate. The amide solvent may be N,N-dimethylformamide (DMF). The amount of solvent used is not specifically limited, as long as it does not affect the reaction. The solvent may be anhydrous (the anhydrous treatment operation and method are conventional operations and methods in the art).

[0052] In some embodiments, the carbonylation reaction is carried out in an aprotic polar solvent, preferably selected from acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, DMF, or DMSO. Preferably, the solvent is DMF.

[0053] In some embodiments, the carbonylation reaction is carried out under conditions with or without a palladium catalyst and phosphorus ligands.

[0054] In some embodiments, the palladium catalyst may be one or more of palladium acetate, palladium trifluoroacetate, palladium pentavalerate, palladium dichloroacetonitrile, bis(benzonitrile)chloride, palladium chloride, palladium bromide, palladium iodide, palladium tetraacetonitrile tetrafluoroborate, palladium hexafluoroacetylacetonate, bis(acetylacetonate), palladium tetraacetonitrile trifluoromethanesulfonate, palladium neopentanoate, and (1E,4E)-bis(dibenzylacetonate)palladium, or one or more of bis(dibenzylacetonate)dipalladium and tri(dibenzylacetonate)dipalladium;

[0055] In some embodiments, the phosphorus ligand is selected from 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 1,1'-bis(diphenylphosphino)ferrocene, tri-o-toluenephosphine, tricyclohexylphosphine tetrafluoroborate, tri-tert-butylphosphine tetrafluoroborate, di-tert-butylmethylphosphine tetrafluoroborate, triphenylphosphine, 2-di-tert-butylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2'-methylbiphenyl, tri(2-furanyl)phosphine, 2-(dicyclohexylphosphino)biphenyl, n-butylbis(1-adamantyl)phosphine, 2-(di-tert-butylphosphine)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1-biphenyl, 3 2-Bicyclohexylphosphine-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, rac-2-(di-tert-butylphosphine)-1,1′-binaphthyl, 1,3-bis(2,6-diisopropylphenyl)chloroimidazolium, 1,3-bis(diphenylphosphine)propane, 2-diphenylphosphine-2′-(N,N-dimethylamino)biphenyl, tris(4-fluorophenyl)phosphine, 2,2′-bis(diphenylphosphine)-1,1′-binaphthyl, 2 -di-tert-butylphosphine-2′-methylbiphenyl, 2-dicyclohexylphosphine-2′-(N,N-dimethylamine)biphenyl, 1,1′-bis(di-tert-butylphosphine)ferrocene, bis(2-diphenylphosphine) ether, 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene, 1,1′-bis(diisopropylphosphine)ferrocene, 1,2-bis(diphenylphosphine)benzene, 1,2,3,4,5-pentaphenyl-1′-(di-tert-butylphosphine)ferrocene, or bis(diphenylphosphine)methane;

[0056] In some embodiments, the reaction is carried out in the presence of a base, preferably selected from Na3PO4, K3PO4, LiOH, Na2CO3, K2CO3, t-BuOK, t-BuONa, t-BuOLi, NET3, 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylamine, or combinations thereof.

[0057] In some embodiments, in the carbonylation reaction method, the molar ratio of the palladium catalyst to the ligand can be a conventional molar ratio, preferably 2.0:1 to 1.0:3, for example 1:1.5.

[0058] In some embodiments, in the carbonylation reaction method, the concentration of the halogenated product can be a concentration conventional in the art, preferably 0.01 to 5.00 mol / L, and even more preferably 0.01 to 0.20 mol / L.

[0059] In some embodiments, in the carbonylation reaction method, the molar ratio of the alcohol compound to the halide can be 1.0:1 to 100:1, and is preferably 2.5:1 to 3.0:1.

[0060] In some embodiments, the base in the carbonylation reaction method is selected from the group consisting of: Na3PO4, K3PO4, LiOH, Na2CO3, K2CO3, t-BuOK, t-BuONa, t-BuOLi, NET3, 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylamine, or combinations thereof.

[0061] In some embodiments, in the carbonylation reaction method, the molar ratio of the base to the halide is 1-10:1.

[0062] In some embodiments, the carbonylation reaction method may be carried out at a temperature ranging from 0 to 120°C, for example, 0°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 85°C, 90°C, 100°C, 110°C, or 120°C. In some embodiments, the reaction temperature is 20°C-50°C. In some embodiments, the reaction temperature is 20°C-50°C. In some embodiments, the reaction temperature is 60°C-90°C. In some embodiments, the reaction temperature is 80°C-120°C.

[0063] In some embodiments, the carbonylation reaction can be carried out under a protective gas. The protective gas can be nitrogen and / or argon. The progress of the reaction can be monitored using conventional detection methods in the art (e.g., TLC, HPLC, HNMR), preferably with the disappearance or cessation of reaction of the halogenated product as the endpoint. The reaction time can be 1–168 hours.

[0064] The positive and progressive effects of this invention are as follows: the solid carbonylating reagent of this invention is cellulose formate, which is derived from biological materials. The preparation method has high yield, simple preparation, easy separation, good stability, and low price. When applied to carbonylation reactions, it has broad substrate universality and good functional group compatibility. Moreover, it has the advantages of mild reaction conditions and simple operation. Attached Figure Description

[0065] Figure 1 It is the cellulose formate prepared in Example 1. 13 C10 NMR spectrum.

[0066] Figure 2 This is the FT-IR spectrum of the cellulose formate prepared in Example 1.

[0067] Figure 3 This is the thermogravimetric analysis spectrum of the cellulose formate prepared in Example 1. Detailed Implementation

[0068] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention will be further described in detail below.

[0069] Example 1: Preparation of cellulose formate

[0070]

[0071] In a 500 mL round-bottom reaction flask, 10 g of cellulose and 300 mL of formic acid were added in one step under nitrogen or argon protection. The reaction was stirred at 95 °C for 6 hours, then the heating was turned off and the mixture was stirred at room temperature for 12 hours. After the reaction was complete, the solid residue was removed by filtration, and the filtrate was distilled under reduced pressure by rotary evaporation to obtain a solid product. The formic acid obtained from the distillation could be recycled. 400 mL of deionized water was added to the solid product, and the mixture was stirred for 10 minutes. The solid was then collected by filtration. The solid was dried in an oven at 100 °C for 12 hours to obtain the target product, cellulose formate 1. 13 The C NMR spectrum is as follows Figure 1 As shown, the FT-IR spectrum is as follows Figure 2 As shown, the thermogravimetric analysis spectrum is as follows: Figure 3 As shown.

[0072] through 13 C NMR spectroscopy confirmed that the degree of substitution of cellulose formate 1 prepared in this example was 1.27.

[0073] Example 2

[0074] It is basically the same as Example 1, except that the temperature is changed from 95°C to 50°C. 13 C NMR confirmed that the degree of substitution of cellulose formate 2 prepared in this example was 0.8.

[0075] Example 3

[0076] It is basically the same as Example 1, except that the temperature is changed from 95°C to 120°C. 13 C NMR confirmed that the degree of substitution of cellulose formate 3 prepared in this example was 1.34.

[0077] Example 4 uses the cellulose formate prepared in Examples 1-3 as a carbonylating agent in a carbonylation reaction.

[0078] The reaction route is as follows:

[0079]

[0080] General Operating Procedure 1: In a 10 mL reaction tube under nitrogen protection, Pd(OAc)₂ (0.009 mmol, 3 mol%), Xantphos (0.012 mmol, 4 mol%), t-BuOK (1.2 mmol, 4 equiv.), carbonylating agent (105 mg, 1.77 equiv.), aryl halide (0.3 mmol, 1 equiv.), alcohol (6 mmol, 20 equiv.), and anhydrous DMF (3 mL) were stirred at 100 °C for 36 hours. After the reaction was complete, the mixture was diluted with 10 mL of ethyl acetate and washed with water (10 mL × 3). The organic phase was dried over anhydrous MgSO₄, filtered, and the filtrate was concentrated and separated by rapid column chromatography (petroleum ether / ethyl acetate) to obtain the target product.

[0081] The reactants, products, and yields are shown in Table 1.

[0082] Table 1

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] Example 5: Cellulose formate as a carbonylating agent in carbonylation reaction

[0089] The reaction route is as follows:

[0090]

[0091] General Operating Procedure 2: In a 10 mL reaction tube under nitrogen protection, Pd(OAc)₂ (0.012 mmol, 6 mol%), phospholigand dppf (0.02 mmol, 10 mol%), t-BuOK (1.2 mmol, 4 equiv.), cellulose formate 1 prepared as in Example 1 (105 mg, 1.77 equiv.), aryl iodide or aryl bromide (0.3 mmol, 1 equiv.), amine compound (0.4 mmol, 2 equiv.), and anhydrous DMF (2 mL) were stirred at 80 °C for 96 hours. After the reaction was complete, the mixture was diluted with 10 mL of ethyl acetate and washed with water (10 mL × 3). The organic phase was dried over anhydrous MgSO₄, filtered, and the filtrate was concentrated and separated by rapid column chromatography (petroleum ether / ethyl acetate) to obtain the target product.

[0092] Table 2

[0093]

[0094]

[0095]

[0096]

[0097] Example 6: Application of cellulose formate solid carbonylating reagent in carbonylation reaction

[0098]

[0099] General Operating Procedure 3: In a 10 mL reaction tube under nitrogen protection, Pd(OAc)₂ (0.006 mmol, 3 mol%), phosphorus ligand Ph₃P (0.012 mmol, 6 mol%), t-BuOK (0.6 mmol, 3 equiv.), cellulose formate solid carbonylating reagent 1 prepared as in Example 1 (70 mg, 1.77 equiv.), aryl iodide or aryl bromide (0.3 mmol, 1 equiv.), alkyne compound (0.4 mmol, 2 equiv.), and anhydrous DMF (2 mL) were stirred and reacted at room temperature (20-30 °C) for 24 hours. After the reaction was complete, the mixture was diluted with 10 mL of ethyl acetate and washed with water (10 mL × 3). The organic phase was dried over anhydrous MgSO₄, filtered, and the filtrate was concentrated and separated by rapid column chromatography (petroleum ether / ethyl acetate) to obtain the target product.

[0100] Table 3

[0101]

[0102]

[0103]

[0104]

[0105] Example 7: Cellulose formate as a carbonylating agent in carbonylation reaction

[0106] The reaction route is as follows:

[0107]

[0108] General Operating Procedure 4: In a 10 mL reaction tube under nitrogen protection, Pd(OAc)₂ (0.006 mmol, 3 mol%), phosphorus ligand Ph₃P (0.012 mmol, 6 mol%), t-BuOK (0.6 mmol, 3 equiv.), carbonylating reagent (70 mg, 1.77 equiv.), aryl iodide or aryl bromide (0.3 mmol, 1 equiv.), arylboronic acid compound (0.22 mmol, 1.1 equiv.), and anhydrous DMF (2 mL) are added. The mixture is then stirred at 80 °C for 24 hours. After the reaction is complete, the mixture is diluted with 10 mL of ethyl acetate and washed with water (10 mL × 3). The organic phase is dried over anhydrous MgSO₄, filtered, and the filtrate is concentrated and then separated by rapid column chromatography (petroleum ether / ethyl acetate) to obtain the target product.

[0109] Table 4

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] Purification and spectral data of some compounds:

[0116] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product. (X = Br, 49.35 mg, 99% yield; X = I, 49.35 mg, 99% yield). 1 HNMR (500MHz, CDCl3) δ7.90 (d, J = 9Hz, 2H), 6.91 (d, J = 9Hz, 2H), 3.88 (s, 3H), 3.85 (s, 3H). 13 C NMR (125MHz, CDCl3) δ166.82,163.24,131.53,122.49,113.52,55.36,51.83.

[0117] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product. (X = Br, 40.38 mg, 81% yield; X = I, 37.89 mg, 76% yield). 1HNMR (500MHz, CDCl3) δ7.63(d,J=9.5Hz,1H),7.56(d,J=1.5Hz,1H),7.33(t,J=10Hz,1H),7.09(dd,J=3.5,10.5Hz,1H),3.90(s,3H),3.84(s,3H). 13 C NMR (125MHz, CDCl3) δ166.90,159.45,131.34,129.31,121.89,119.43,113.84,55.33,52.11.

[0118] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product. (X = Br, 40.38 mg, 81% yield; X = I, 42.87 mg, 86% yield). 1 H NMR (500MHz, CDCl3) δ7.80 (dd, J = 1.5, 8Hz, 1H), 7.48-7.45 (m, 1H), 6.99-6.96 (m, 2H), 3.90 (s, 3H), 3.89 (s, 3H). 13 C NMR (125MHz, CDCl3) δ166.70,159.07,133.50,131.64,120.10,199.96,111.96,55.95,52.00.

[0119] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (29.29 mg, 65% yield). 1 H NMR (500MHz, CDCl3) δ7.93 (d, J = 10Hz, 2H), 7.23 (d, J = 9.5Hz, 2H), 3.90 (s, 3H), 2.40 (s, 3H). 13 C NMR (125MHz, CDCl3) δ167.15,143.52,129.54,129.03,127.33,51.93,21.62.

[0120] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product. (X = Br, 50.18 mg, 87% yield; X = I, 43.26 mg, 75% yield). 1H NMR (500MHz, CDCl3) δ7.97 (d, J = 10.5Hz, 2H), 7.45 (d, J = 10.5Hz, 2H), 3.90 (s, 3H), 1.34 (s, 9H). 13 C NMR (125MHz, CDCl3) δ167.05,156.43,129.36,127.28,125.25,51.86,34.98,31.03.

[0121] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (29.4 mg, 72% yield). 1 H NMR (500MHz, CDCl3) δ8.05-8.03(m,2H),7.57-7.53(m,1H),7.45-7.41(m,2H),3.91(s,3H). 13 C NMR (125MHz, CDCl3) δ167.04,132.85,130.03,129.48,128.28,52.04.

[0122] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product. (X = Br, 58.58 mg, 92% yield; X = I, 63.04 mg, 99% yield). 1 HNMR (500MHz, CDCl3) δ8.12-8.10(m,2H),7.68-7.66(m,2H),7.64-7.62(m,2H),7.49-7.46(m,2H),7.40(t,J=7.5Hz,1H),3.95(s,3H). 13 C NMR (125MHz, CDCl3) δ167.00,145.61,139.98,130.08,128.90,128.86,128.12,127.26,127.03,52.12.

[0123] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (36.76 mg, 51%, yield). 1H NMR (500MHz, CDCl3) δ8.15 (d, J = 8Hz, 2H), 7.84 (d, J = 8Hz, 2H), 7.80 (d, J = 8Hz, 2H), 7.62 (t, J = 7.5Hz, 1H), 7.50 (t, J = 7.5Hz, 2H), 3.97 (s, 3H). 13 C NMR (125MHz, CDCl3) δ196.03,166.30,141.29,136.91,133.19,132.93,130.09,129.76,129.48,128.44,52.46.

[0124]

[0125] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (26.59 mg, 55% yield). 1 H NMR (500MHz, CDCl3) δ8.15-8.13(m,2H),7.76-7.74(m,2H),3.96(s,3H). 13 C NMR (125MHz, CDCl3) δ165.42,133.90,132.21,130.08,117.95,116.38,52.72.

[0126] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product. (X = Br, 30.54 mg, 62% yield; X = I, 42.86 mg, 87% yield). 1 H NMR (500MHz, CDCl3) δ7.66(s,2H),7.19(s,1H),3.90(s,3H),2.36(s,6H). 13 C NMR (125MHz, CDCl3) δ167.46,138.00,134.55,129.99,127.27,51.99,21.14.

[0127] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product. (X = Br, 42.97 mg, 73% yield; X = I, 54.15 mg, 92% yield). 1HNMR (500MHz, CDCl3) δ7.18 (d, J = 2.5Hz, 2H), 6.64 (t, J = 2.5Hz, 1H), 3.91 (s, 3H), 3.82 (s, 6H). 13 C NMR (125MHz, CDCl3) δ166.84,160.60,131.97,107.07,105.75,55.54,52.23.

[0128] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product. (X = Br, 50.84 mg, 91% yield; X = I, 55.30 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ8.62(s,1H),8.07(dd,J=1,8.5Hz,1H),7.96(d,J=8Hz,1H ),7.89(d,J=8.5Hz,2H),7.59(t,J=7Hz,1H),7.55(t,J=7Hz,1H),3.99(s,3H). 13 C NMR (125MHz, CDCl3) δ167.26,135.49,132.47,131.05,129.34,128.22,128.12,127.74,127.37,126.62,125.21,52.22.

[0129] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product. (X = Br, 45.94 mg, 85% yield; X = I, 53.51 mg, 99% yield). 1 HNMR (500MHz, CDCl3) δ7.63(dd,J=2,10Hz,1H),7.44(s,1H),6.81(d,J=10Hz,1H),6.01(s,2H),3.86(s,3H). 13 C NMR (125MHz, CDCl3) δ166.37,151.48,147.61,125.23,124.04,109.40,107.86,101.71,51.98.

[0130] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product. (X = Br, 48.44 mg, 84% yield; X = I, 44.41 mg, 77% yield). 1H NMR (500MHz, CDCl3) δ8.35 (d, J = 1Hz, 1H), 8.03 (dd, J = 1.5, 8.5Hz, 1H), 7.69 (d, J = 2Hz, 1H), 7.53 (d, J = 9Hz, 1H), 6.84 (dd, J = 0.5, 2Hz, 1H), 3.94 (s, 3H). 13 C NMR (125MHz, CDCl3) δ167.27,157.45,146.21,127.41,126.01,125.15,123.74,111.26,107.11,52.11.

[0131] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (55.36 mg, 96% yield). 1 H NMR (500MHz, CDCl3) δ8.54(s,1H),8.00(d,J=8.5Hz,1H),7.92(d,J=8.5Hz,1H),7.52(d,J=5.5Hz,1H),7.42(d,J=5.5Hz,1H),3.96(s,3H). 13 C NMR (125MHz, CDCl3) δ167.38,144.11,139.31,127.65,126.41,125.53,124.62,124.41,122.34,52.16.

[0132] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (55.06 mg, 97% yield). 1 H NMR (500MHz, CDCl3) δ8.40(d,J=1Hz,1H),7.93(dd,J=4,8.5Hz,1H),7.33(d,J=9H z, 1H), 7.11 (d, J = 3.5Hz, 1H), 6.59 (dd, J = 1, 3.5Hz, 1H), 3.93 (s, 3H), 3.82 (s, 3H). 13 C NMR (125MHz, CDCl3) δ168.26,139.08,130.19,127.93,123.91,122.90,121.32,108.81,102.62,51.81,33.02.

[0133] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (37.07 mg, 66% yield). 1 H NMR (500 MHz, CDCl3) δ9.01 (s, 1H), 8.60 (s, 1H), 8.30 (d, J = 8.5 Hz, 1H), 8.27 (d, J = 8.5 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H), 7.48 (dd, J = 4, 7.5 Hz,1H),4.00(s,3H). 13 CNMR (125 MHz, CDCl3) δ166.59,152.52,150.07,137.33,131.00,129.81,128.94,128.10,127.40,121.84,52.44.

[0134] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (33.31 mg, 59% yield). 1 H NMR (500 MHz, CDCl3) δ9.56(s,1H),8.32-8.30(m,1H),8.21-8.20(m,1H),7.93-7.86(m,2H),4.13(s,3H). 13 C NMR (125 MHz, CDCl3) δ164.66,145.07,143.78,142.33,141.44,132.40,131.08,130.59,129.38,53.42.

[0135] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (38.43 mg, 67% yield). 1 H NMR (500 MHz, CDCl3) δ8.16 (d, J = 1 Hz, 1H), 8.04 (dd, J = 1.5, 9.5 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 3.95 (s, 3H), 2.68 (s, 3H). 13 C NMR (125 MHz, CDCl3) δ166.72,166.69,150.63,145.48,126.66,125.97,119.02,111.90,52.34,14.75.

[0136] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (71.23 mg, 98% yield). 1 H NMR (500 MHz, CDCl3) δ8.83 (d, J = 1 Hz, 1H), 8.24-8.22 (m, 1H), 8.11 (dd, J = 1.5, 8.5 Hz, 1H), 7.89 (d, J = 8.5 Hz,1H),7.87-7.85(m,1H),7.52-7.48(m,2H),4.00(s,3H). 13 C NMR (125 MHz, CDCl3) δ167.18,144.32,139.61,135.51,135.10,127.29,127.23,126.43,124.83,123.11,122.83,122.56,121.90,52.22.

[0137] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (34.32 mg, 51% yield). 1 H NMR (500 MHz, CDCl3) δ7.80 (dd, J = 1, 3.5 Hz, 1H), 7.54 (dd, J = 1, 5 Hz, 1H), 7.10 (dd, J = 3.5, 5 Hz, 1H), 4.11 (d, J = 6.5 Hz,2H),1.82-1.78(m,2H),1.78-1.74(m,2H),1.72-1.67(m,1H),1.32-1.14(m,4H),1.08-1.01(m,2H). 13 C NMR(125 MHz, CDCl3)δ162.36,134.11,133.19,132.12,127.68,70.16,37.22,29.66,26.35,25.67.IR(ATR)ν(cm -1 )=2919,2851,1709,1529,1449,1417,1355,1258,1091,1077,1035,1023,891,751,714.HRMS:m / z(ESI-TOF)calculated[M+H] + :225.0944,measured:225.0945.

[0138] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (44.36 mg, 71% yield). 1 H NMR (500 MHz, CDCl3) δ7.58 (d, J = 1, Hz, 1H), 7.17 (dd, J = 0.5, 3.5 Hz, 1H), 6.50 (dd, J = 1.5, 3.5 Hz, 1H), 4.11 (d, J = 6.5 Hz, 2H), 1.80 (d, J = 12 Hz,2H),1.77-1.74(m,2H),1.70-1.67(m,1H),1.32-1.14(m,4H),1.07-0.99(m,2H). 13 C NMR(125 MHz, CDCl3)δ158.91,146.16,144.88,117.63,111.74,70.00,37.16,29.62,26.33,25.63.IR(ATR)ν(cm -1 )=2919,2851,1719,1445,1088,1080,1032,1023,983,952,890,842,738.HRMS:m / z(ESI-TOF)calculated[M+H] + :209.1172, measured:209.1185.

[0139]

[0140] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (48.65 mg, 90% yield). 1 H NMR (500MHz, CDCl3) δ7.99 (dd, J=2.5, 8.5Hz, 2H), 6.90 (dd, J=2.5, 8.5Hz, 2H), 4.33 (q, J=9Hz, 2H), 3.83 (s, 3H), 1.36 (t, J=9Hz, 3H). 13 C NMR (125MHz, CDCl3) δ166.30,163.13,131.43,122.79,113.42,60.54,55.29,14.29.

[0141]

[0142] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (61.23 mg, 98% yield). 1H NMR (500MHz, CDCl3) δ7.99 (dd, J=2.5, 9Hz, 2H), 6.93-6.89 (m, 2H), 4.28 (t, J=8. 5Hz,2H),3.85(s,3H),1.77-1.70(m,2H),1.51-1.42(m,2H),0.97(t,J=9Hz,3H). 13 C NMR (125MHz, CDCl3) δ166.41,163.15,131.47,122.87,113.47,64.48,55.34,30.76,19.24,13.74.

[0143] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (64.81 mg, 87% yield). 1 H NMR (500MHz, CDCl3) δ8.01-7.99(m,2H),6.93-6.90(m,2H),4.10(d,J=6.5Hz,2H),3.86(s,3H),1.82(d,J= 13Hz,2H),1.79-1.76(m,1H),1.75-1.74(m,1H),1.71-1.67(m,1H),1.33-1.15(m,4H),1.10-1.02(m,2H). 13 C NMR (125MHz, CDCl3) δ166.44,163.21,131.52,122.99,113.53,69.77,55.40,37.30,29.77,26.39,25.72.

[0144] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (39.29 mg, 60% yield). 1 H NMR (500MHz, CDCl3) δ8.06-8.04(m,2H),7.57-7.54(m,1H),7.46-7.43(m,2H),4.14(d,J=6Hz,2H),1.85-1 .81(m,2H),1.80-1.77(m,1H),1.77-1.75(m,1H),1.72-1.68(m,1H),1.33-1.16(m,4H),1.10-1.03(m,2H). 13CNMR (125MHz, CDCl3) δ166.68,132.78,130.53,129.52,128.31,70.06,37.26,29.75,26.37,25.70.

[0145] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (53.78 mg, 74% yield). 1 H NMR (500MHz, CDCl3) δ8.06-8.03(m,2H),7.46-7.44(m,2H),7.42-7.34(m,3H),6.93-6.91(m,2H),5.35(s,2H),3.86(s,3H). 13 C NMR (125MHz, CDCl3) δ166.15,163.36,136.22,131.67,128.52,128.11,128.07,122.44,113.56,66.35,55.39.

[0146] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (30.29 mg, 52% yield). 1 H NMR (500MHz, CDCl3) δ8.09 (s, 4H), 3.94 (s, 6H). 13 C NMR (125MHz, CDCl3) δ166.25,133.83,129.51,52.43.

[0147] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (87.14 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ7.96 (d, J = 9Hz, 2H), 6.88 (d, J = 9Hz, 2H), 4.39 (t, J = 6Hz, 2H), 4.00 (t, J = 6.5Hz, 2H), 2.89 (t, J=6Hz,2H),2.68(q,J=7Hz,4H),1.80-1.74(m,2H),1.52-1.45(m,2H),1.09(t,J=7Hz,6H),0.97(t,J=7.5Hz,3H). 13C NMR (125MHz, CDCl3) δ166.30,162.96,131.55,122.23,114.01,67.83,62.56,50.79,47.64,31.09,19.14,13.78,11.66.

[0148] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product. (X = I, 29.44 mg, 84% yield; X = Br, 28.04 mg, 80% yield). 1 H NMR (500MHz, CDCl3) δ7.52-7.50(m,2H),7.42-7.37(m,3H),3.65(t,J=7Hz,2H),3.42(t,J=6.5Hz,2H),1.99-1.94(m,2H),1.90-1.84(s,2H). 13 C NMR (125MHz, CDCl3) δ169.74,137.23,129.74,128.22,127.07,49.59,46.15,26.38,24.46.

[0149] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give an oily liquid product. (X = I, 35.10 mg, 99% yield; X = Br, 30.13 mg, 85% yield). 1 H NMR (500MHz, CDCl3) δ7.76 (d, J = 8Hz, 2H), 7.46 (t, J = 7.5Hz, 1H), 7.39 (t, J = 7.5Hz, 2H), 6.36 (s,1H),3.43(q,J=6.5Hz,2H),1.61-1.55(m,2H),1.43-1.35(m,2H),0.93(t,J=7.5Hz,3H). 13 C NMR (125MHz, CDCl3) δ167.51, 134.79, 131.20, 128.43, 126.79, 39.74, 31.66, 20.10, 13.73.

[0150] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (31.71 mg, 78% yield). 1H NMR (500MHz, CDCl3) δ7.75 (d, J = 8Hz, 2H), 7.48 (t, J = 7Hz, 1H), 7.42 (t, J = 7.5Hz, 2H), 5.99 (s, 1H), 4.01-3. 94(m,1H),2.04-2.01(m,2H),1.77-1.73(m,2H),1.66-1.64(m,1H),1.47-1.38(m,2H),1.27-1.16(m,3H). 13 CNMR (125MHz, CDCl3) δ166.59,135.08,131.20,128.48,126.79,48.63,33.22,25.55,24.89.

[0151] The reaction was carried out according to general procedure 1, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (27.54 mg, 72% yield). 1 H NMR (500MHz, CDCl3) δ7.42-7.40(m,5H),3.78-3.44(m,8H). 13 C NMR (125MHz, CDCl3) δ170.40,135.28,129.85,128.53,127.05,66.87.

[0152] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a yellow solid product (24.06 mg, 61% yield). 1 H NMR (500MHz, CDCl3) δ7.89-7.86(m,3H),7.65(d,J=7.5Hz,2H),7.55(t,J=7Hz,1H),7.48(t,J=8Hz,2H),7.37(t,J=7.5Hz,2H),7.16(t,J=7.5Hz,1H). 13 C NMR (125MHz, CDCl3) δ165.74,137.89,134.97,131.82,129.08,128.77,127.00,124.55,120.18.

[0153] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product. (X = I, 41.83 mg, 99% yield; X = Br, 30.80 mg, 80% yield). 1H NMR (500MHz, CDCl3) δ7.80–7.78(m,2H),7.50(t,J=7.5Hz,1H),7.44-7.41(m,2H ),7.35(d,J=4.5Hz,4H),7.33-7.28(m,1H),6.51(s,1H),4.64(d,J=5.5Hz,2H). 13 C NMR (125MHz, CDCl3) δ167.33,138.14,134.33,131.52,128.76,128.56,127.89,127.59,126.93,44.10.

[0154] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (44.61 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ7.69(d,J=7.5Hz,2H),7.48(t,J=7.5Hz,1H),7.40(t,J=7.5Hz,2H),7.33 (d,J=7.5Hz,2H),7.24(d,J=8Hz,3H),6.21(s,1H),3.72(q,J=6.5Hz,2H),2.94(t,J=7Hz,2H). 13 C NMR (125MHz, CDCl3) δ167.46,138.87,134.59,131.39,128.80,128.70,128.53,126.78,126.58,41.11,35.67.

[0155] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (38.06 mg, 72% yield). 1 H NMR(500MHz, CDCl3)δ7.80(d,J=7.5Hz,2H),7.45(t,J=7.5Hz,1H),7.39-7.36( m,3H),5.29-5.28(m,1H),3.53(q,J=5Hz,2H),3.38-3.37(m,2H),1.40(s,9H). 13 CNMR (125MHz, CDCl3) δ167.92,157.43,134.06,131.35,128.39,126.98,79.78,41.82,39.91,28.27.

[0156] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (43.42 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ7.42-7.38(m,5H),4.58(d,J=11Hz,1H),3.65(s,1H),3.53(s,2H),2.80(s,1H),2.54(s,1H),1.25(s,3H),1.09(s,3H). 13 C NMR (125MHz, CDCl3) δ170.10,135.55,129.79,128.54,127.07,71.94,53.24,47.49,18.57.

[0157] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (59.23 mg, 93% yield). 1 H NMR (500MHz, CDCl3) δ7.74(d,J=7.5Hz,2H),7.49(t,J=7Hz,1H),7.42(t,J=7.5Hz,2H),6.11(d,J=6.5Hz ,1H),4.59(s,1H),4.09(d,J=3Hz,1H),3.66(s,1H),1.85-1.79(m,4H),1.63-1.62(m,4H),1.44(s,9H). 13 C NMR(125MHz, CDCl3)δ166.76,156.69,134.81,131.39,128.55,126.77,46.34,28.78,28.39,28.18.IR(ATR)ν(cm -1 )=3274,2923,1678,1637,1527,1365,1328,1270,1247,1165,1095,1025,978,875,687.HRMS:m / z(ESI-TOF)calculated[M+Na] + :341.1836, measured:341.1823.

[0158] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a brown solid product (52.93 mg, 99% yield). 1H NMR (500MHz, CDCl3) δ7.74(d,J=7.5Hz,2H),7.44(d,J=7.5Hz,2H),7.35(d,J=4.5Hz,4H),7.31–7.28(m,1H),6.42(s,1H),4.65(s,2H),1.33(s,9H). 13 C NMR (125MHz, CDCl3) δ167.27,155.06,138.28,131.43,128.75,127.89,127.55,126.80,125.53,44.07,34.90,31.14.

[0159] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a pale yellow solid product (43.71 mg, 97% yield). 1 H NMR (500MHz, CDCl3) δ7.69 (d, J = 8Hz, 2H), 7.35 (d, J = 4.5Hz, 4H), 7.32-7.28 ( m,1H),7.23(d,J=8Hz,2H),6.41(s,1H),4.64(d,J=5.5Hz,2H),2.39(s,3H). 13 C NMR (125MHz, CDCl3) δ167.27,141.96,138.26,131.48,129.22,128.75,127.90,127.57,126.92,44.06,21.42.

[0160] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (47.78 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ7.60 (d, J = 8.5Hz, 2H), 7.36-7.33 (m, 4H), 7.32-7.27 ( m,1H),6.91(d,J=9Hz,2H),6.38(s,1H),4.32(d,J=5.5Hz,2H),3.84(s,3H). 13 C NMR (125MHz, CDCl3) δ166.90,162.19,138.36,128.74,127.90,127.54,126.61,113.74,55.39,44.05.

[0161] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (46.55 mg, 81% yield). 1 H NMR (500MHz, CDCl3) δ7.87(d,J=8Hz,2H),7.66(d,J=8.5Hz,2H),7.61(d,J=7.5Hz,2H),7.4 6(t,J=7Hz,2H),7.40-7.36(m,5H),7.33-7.30(m,1H),6.45(s,1H),4.68(d,J=5.5Hz,2H). 13 C NMR (125MHz, CDCl3) δ167.02,144.38,139.95,138.14,132.96,128.90,128.81,128.00,127.95,127.66,127.47,127.26,127.19,44.18.

[0162] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (24.10 mg, 51% yield). 1 H NMR (500MHz, CDCl3) δ7.88 (d, J = 8Hz, 2H), 7.72 (d, J = 8Hz, 2H), 7.38-7.32 (m, 5H), 6.48 (s, 1H), 4.65 (d, J = 5.5Hz, 2H). 13 CNMR (125MHz, CDCl3) δ165.50,138.25,137.48,132.46,128.92,127.99,127.92,127.68,117.93,115.18,44.41.

[0163] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a yellow oily liquid product (45.47 mg, 95% yield). 1 H NMR (500MHz, CDCl3) δ7.40 (s, 2H), 7.36 (d, J = 4.5Hz, 4H), 7.32-7.28 (m, 1H), 7.13 (s, 1H), 6.44 (s, 1H), 4.63 (d, J = 4Hz, 2H), 2.34 (s, 6H). 13C NMR (125MHz, CDCl3) δ167.72,138.25,134.32,133.10,128.73,127.91,127.54,124.71,44.07,21.20.

[0164] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a pale yellow oily liquid product (51.55 mg, 95% yield). 1 H NMR (500MHz, CDCl3) δ7.37-7.34(m,4H),7.32-7.29(m,1H),6.91(d,J=1.5Hz,2H),6.57(s,1H),6.46(s,1H),4.62(d,J=5Hz,2H),3.80(s,6H). 13 CNMR(125MHz, CDCl3)δ167.19,160.86,138.05,136.58,128.75,127.87,127.60,104.89,103.57,55.56,44.15.

[0165] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (37.27 mg, 73% yield). 1 H NMR (500MHz, CDCl3) δ7.35-7.26 (m, 7H), 6.79 (d, J = 8Hz, 1H), 6.48 (s, 1H), 6.00 (s, 2H), 4.58 (d, J = 5.5Hz, 2H). 13 C NMR (125MHz, CDCl3) δ166.64,150.30,147.91,138.20,128.70,128.50,127.82,127.52,121.53,107.92,107.63,101.63,44.09.

[0166] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (27.18 mg, 52% yield). 1 H NMR (500MHz, CDCl3) δ8.31(s,1H),7.88-7.85(m,4H),7.57-7.51(m,2H),7.40-7.35(m,4H),7.32-7.30(m,1H),6.72(s,1H),4.69(d,J=5.5Hz,2H).13 C NMR (125MHz, CDCl3) δ167.41,138.18,134.70,132.55,131.51,128.87,128. 67,128.44,127.93,127.70,127.62,127.59,127.43,126.71,123.56,44.21.

[0167] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give an oily liquid product (33.97 mg, 65% yield). 1 H NMR (500MHz, CDCl3) δ8.35(d,J=8.5Hz,1H),7.91(d,J=8Hz,1H),7.87(d,J=8Hz,1H),7.62(d,J=7Hz,1H),7.58- 7.51(m,2H),7.45(d,J=7.5Hz,1H),7.43-7.36(m,4H),7.31(t,J=7Hz,1H),6.31(s,1H),4.73(d,J=5.5Hz,2H). 13 C NMR (125MHz, CDCl3) δ169.36,138.04,134.26,133.67,130.70,130.14,128. 83,128.30,127.88,127.66,127.16,136.44,125.38,124.89,124.66,44.12.

[0168] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give an oily liquid product. (X = I, 44.23 mg, 88% yield; X = Br, 43.22 mg, 86% yield). 1 HNMR(500MHz, CDCl3)δ8.09(s,1H),7.75(dd,J=1.5,8.5Hz,1H),7.68(d,J=2Hz,1H),7.52(d,J=8.5H z,1H),7.39-7.35(m,4H),7.32-7.29(m,1H),6.81(d,J=2Hz,1H),6.48(s,1H),4.67(d,J=5.5Hz,2H). 13C NMR(125MHz, CDCl3)δ167.53,156.56,146.28,138.24,129.51,128.78,127.93,127.61,127.55,123.37,120.67,111.42,106.96,44.25.IR(ATR)ν(cm -1 )=3264,3110,1632,1540,1450,1413,1322,1263,1174,1119,1103,1025,995,904,881,836,775,745,727,696,662.HRMS:m / z(ESI-TOF)calculated[M+H] + :252.1019, measured:252.1011.

[0169] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give an oily liquid product (33.90 mg, 78% yield). 1 H NMR (500MHz, CDCl3) δ7.88 (d, J = 1.5Hz, 1H), 7.40 (d, J = 5Hz, 1H), 7.35-7.28 (m, 6H), 6.52 (s, 1H), 4.58 (d, J = 6Hz, 2H). 13 CNMR (125MHz, CDCl3) δ162.96,138.14,137.23,128.70,128.35,127.83,127.53,126.46,126.02,43.74.

[0170] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (33.90 mg, 78% yield). 1 H NMR (500MHz, CDCl3) δ6.93 (d, J = 1.5Hz, 1H), 6.89-6.84 (m, 2H), 4.26 (s, 4H), 3.52 (s, 4H), 1.66-1.57 (m, 6H). 13 C NMR (125MHz, CDCl3) δ169.76,144.60,143.23,129.55,120.41,117.09,116.43,64.40,64.26,26.00,24.60.

[0171] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a pale yellow solid product (54.96 mg, 85% yield). 1 H NMR(500MHz, CDCl3)δ7.74(d,J=7.5Hz,1H),7.64-7.62(m,2H),7.60-7.59(m,1H),7.44(s,1H),7.32(s, 1H),7.26-7.22(m,1H),7.03(d,J=8Hz,1H),6.71(d,J=8Hz,1H),4.62-4.55(m,1H),1.35(d,J=6Hz,6H). 13 C NMR (125MHz, CDCl3) δ165.56,158.56,138.59,135.81,132.20,130.19,129.81,128.61,127.23(d,J=31 .9Hz),126.50(q,J=4.8Hz),123.57(d,J=272.1Hz),112.55,112.08,107.86,70.02,22.00.IR(ATR)ν(cm -1 )=3249,2982,1655,1599,1543,1492,1415,1314,1259,1159,1126,1108,1054,1032, 997,980,901,852,775,764,736,678,645,604.HRMS:m / z(ESI-TOF)calculated[M+H] + :324.1206, measured:324.1189.

[0172]

[0173] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a brown solid product (31.96 mg, 51% yield). 1 H NMR (500MHz, CDCl3) δ7.21(d,J=7.5Hz,1H),7.12(br,1H),7.01(s,1H),6.78(s,2H),4.11(s,2H),3.89(s,3H),3.86(s,6H),3.13(t,J=8.5Hz,2H). 13C NMR (125MHz, CDCl3) δ168.55,153.33,142.48,139.69,132.41,132.13,127.20,124.93,123.89,116.90,104.47,60.94,56.24,50.09,28.31.

[0174]

[0175] The reaction was carried out according to general procedure 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (54.48 mg, 76% yield). 1 H NMR (500MHz, CDCl3) δ7.46 (s, 1H), 7.28 (d, J = 8Hz, 3H), 6.90 (d, J = 8.5Hz, 2H), 6.84 (d, J = 8.5Hz, 1H), 6.37 (s, 1H), 4.56 (d, J = 5.5Hz, 2H), 4.09 (t, J = 5.5Hz, 2H), 3.92 (d, J = 7.5Hz, 6H), 2.78 (t, J = 5.5Hz, 2H), 2.38 (s, 6H). 13 C NMR (125MHz, CDCl3) δ166.78,158.19,151.68,148.94,130.57,129.25,127.0 2,119.20,114.75,110.61,110.15,65.76,58.13,56.00,55.97,45.72,43.59.

[0176] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give a white solid product (26.36 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ7.92 (s, 1H), 7.87 (d, J = 7.5Hz, 1H), 7.57 (t, J = 7.5Hz, 1H), 7.49-7.47 (m, 2H), 4.48 (s, 2H). 13 C NMR (125MHz, CDCl3) δ172.15,143.65,132.15,131.68,127.96,123.65,123.15,45.73.

[0177] The reaction was carried out according to general procedure step 2, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 9:1) to give an oily liquid product (21.78 mg, 74% yield). 1H NMR(500MHz, CDCl3)δ8.06(d,J=7.5Hz,1H),7.46-7.43(m,1H),7.35(t,J=7.5Hz,1 H),7.21(d,J=7.5Hz,1H),7.06-6.75(m,1H),3.59-3.56(m,2H),3.01-2.98(m,2H). 13 CNMR (125MHz, CDCl3) δ166.42,138.83,132.10,128.89,127.92,127.21,127.03,40.16,28.29.

[0178] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (40.84 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ8.24-8.22(m,2H),7.71-7.69(m,2H),7.66-7.62(m,1H),7.53(t,J=8Hz,2H),7.50-7.47(m,1H),7.45-7.42(m,2H). 13 C NMR (125MHz, CDCl3) δ178.03,136.87,134.12,133.07,130.79,139.57,128.68,128.62,120.12,93.10,86.87.

[0179] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (41.41 mg, 94% yield). 1 H NMR (500MHz, CDCl3) δ8.25-8.23(m,2H),7.66-7.61(m,2H),7.52(t,J=8Hz,2 H),7.39-7.35(m,1H),7.28(d,J=7.5Hz,1H),7.25-7.22(m,1H),2.59(s,3H). 13 CNMR (125MHz, CDCl3) δ178.00,142.13,136.98,134.00,133.62,130.77,139.84,129.49,128.59,125.90,119.94,92.13,90.71,20.85.

[0180] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (35.68 mg, 81% yield). 1 H NMR (500MHz, CDCl3) δ8.24-8.23(m,2H),7.63(t,J=7.5Hz,1H),7.54-7.50(m,4H),7.33-7.29(m,2H),2.39(s,3H). 13 CNMR (125MHz, CDCl3) δ178.01,138.48,136.87,134.03,133.51,131.72,130.19,139.52,128.57,128.54,119.86,93.47,86.62,21.15.

[0181] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (39.25 mg, 98% yield). 1 H NMR (500MHz, CDCl3) δ8.24-8.22(m,2H),7.64-7.58(m,3H),7.52(t,J=7.5Hz,2H),7.23(d,J=8Hz,2H),2.41(s,3H). 13 C NMR (125MHz, CDCl3) δ178.06,141.54,136.93,133.99,133.10,129.52,129.46,128.56,116.97,93.81,86.75,21.75.

[0182] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (41.58 mg, 88% yield). 1 H NMR (500MHz, CDCl3) δ8.23-8.21(m,2H),7.67-7.61(m,3H),7.53-7.50(m,2H),6.95-6.92(m,2H),3.86(s,3H). 13 C NMR (125MHz, CDCl3) δ178.04,161.72,137.03,135.14,133.89,129.48,128.55,114.41,111.89,94.30,86.86,55.43.

[0183] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (23.34 mg, 55% yield). 1 H NMR (500MHz, CDCl3) δ8.23-8.21(m,2H),7.62-7.59(m,1H),7.53-7.49(m,4H),6.67(d,J=8.5Hz,2H),4.09(s,2H). 13 CNMR(125MHz, CDCl3)δ178.07,149.18,137.23,135.34,133.67,129.42,128.48,114.57,108.58,96.17,87.05.IR(ATR)ν(cm -1 )=3354,3218,2919,2167,1592,1512,1314,1291,1213,1166,1030,1006,826,696.HRMS:m / z(ESI-TOF)calculated[M+H] + :222.0913,measured:222.0903.

[0184] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (39.98 mg, 67% yield). 1 H NMR(500MHz, CDCl3)δ8.22(d,J=7Hz,2H),7.67-7.62(m,3H),7.52(t,J=7.5Hz,2H) ,7.41(d,J=7.5Hz,2H),7.21(t,J=7Hz,1H),7.09-7.07(m,2H),7.01(d,J=9Hz,2H). 13 C NMR (125MHz, CDCl3) δ177.99,160.14,155.43,136.92,135.13,134.01,130.06,129.51,128.58,124.60,120.07,117.98,113.95,93.43,86.90.

[0185] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (45.56 mg, 61% yield). 1H NMR (500MHz, CDCl3) δ8.23-8.21(m,2H),7.61(t,J=7.5Hz,1H),7.53-7.49(m,4H),7.33(t,J=7.5Hz,4H),7.17-7.12(m,6H),7.00(d,J=8.5Hz,2H). 13 C NMR (125MHz, CDCl3) δ177.97,150.32,146.41,137.16,134.55,133.78,129.62,129.44,128.52,125.82,124.59,120.53,111.23,95.21,87.39.

[0186] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (42.23 mg, 77% yield). 1 H NMR (500MHz, CDCl3) δ8.23-8.21(m,2H),7.80(d,J=8Hz,2H),7.70-7.65(m,3H),7.54(t,J=8Hz,2H). 13 C NMR(125MHz,CDCl3)δ177.66,136.55,134.46,133.16,132.24(q,J=32.5Hz),139 .63,128.74,125.63(q,J=3.9Hz),123.95,123.54(q,J=270.9Hz),90.45,88.07.

[0187] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (50.75 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ8.43(d,J=8.5Hz,1H),8.33-8.32(m,2H),8.00-7.96(m,2H),7.92(d,J=8Hz,1H),7.69-7.66(m,2H),7.61-7.51(m,4H). 13 C NMR (125MHz, CDCl3) δ178.01,137.04,134.13,133.63,133.19,133.08,131.49, 129.61,128.70,128.58,127.57,126.96,125.82,125.20,117.71,91.60,91.42.

[0188] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (33.32 mg, 65% yield). 1 H NMR (500MHz, CDCl3) δ8.29-8.26(m,3H),7.89-7.86(m,3H),7.69-7.64(m,2H),7.60-7.54(m,4H). 13 C NMR (125MHz, CDCl3) δ178.00,136.93,134.35,134.12,133.92,132.67,129.60, 128.64,128.50,128.40,128.20,128.02,127.91,127.05,117.28,93.62,87.15.

[0189] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (50.24 mg, 82% yield). 1 H NMR (500MHz, CDCl3) δ8.74-8.71(m,1H),8.69(d,J=8.5Hz,1H),8.53-8.50(m,1H),6.36-8.34(m,2H ),8.30(s,1H),7.93(d,J=8.5Hz,1H),7.77-7.74(m,3H),7.70-7.64(m,2H),7.59(t,J=7.5Hz,2H). 13 CNMR (125MHz, CDCl3) δ177.96,137.05,135.62,134.17,131.28,130.68,130.64,130.06,129.64, 129.14,128.84,128.73,127.61,127.59,127.28,126.63,122.97,122.76,116.65,91.62,91.15.

[0190] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (20.72 mg, 50% yield). 1H NMR(500MHz, CDCl3)δ8.92(s,1H),8.70(d,J=3.5Hz,1H),8.22(d,J=7.5Hz,2H),8 .00-7.98(m,1H),7.66(t,J=7.5Hz,1H),7.54(t,J=7.5Hz,2H),7.41-7.38(m,1H). 13 C NMR (125MHz, CDCl3) δ177.55,153.15,150.65,140.00,136.49,134.48,129.62,128.76,123.28,89.42,88.83.

[0191] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (39.91 mg, 94% yield). 1 H NMR (500MHz, CDCl3) δ8.22-8.20(m,2H),7.86-7.85(m,1H),7.65-7.62(m,1H),7.52(t,J=7.5Hz,2H),7.39-7.38(m,4H),7.33(dd,J=1,5Hz,1H). 13 C NMR (125MHz, CDCl3) δ178.01,136.82,134.08,133.90,130.28,129.52,128.60,126.25,119.38,88.48,87.14.

[0192] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow liquid product (23.55 mg, 56% yield). 1 H NMR (500MHz, CDCl3) δ8.14 (d, J = 8Hz, 2H), 7.59 (t, J = 7Hz, 1H), 7.48 (t, J = 7.5Hz, 2H), 6.58 (s, 1H), 2.28-2.20 (m, 4H), 1.73-1.62 (m, 4H). 13 C NMR (125MHz, CDCl3) δ178.19,142.65,137.01,133.78,129,42,128.46,119.11,95.73,85.17,28.35,26.15,21.92,21.07.

[0193] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily, colorless liquid product (32.45 mg, 81% yield). 1 H NMR (500MHz, CDCl3) δ8.14-8.13(m,2H),7.59(t,J=7Hz,1H),7.47(t,J=8Hz,2H) ,2.50(t,J=7Hz,2H),1.69-1.63(m,2H),1.54-1.47(m,2H),0.96(t,J=7Hz,3H). 13 C NMR (125MHz, CDCl3) δ178.24,136.88,133.83,139.51,128.45,96.83,29.80,22.05,18.88,13.50.

[0194] The reaction was carried out according to general operating procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily yellow liquid product. 1 H NMR (500MHz, CDCl3) δ8.15-8.13(m,2H),7.61-7.58(m,1H),7.47(t,J=7.5Hz,2H),2.49(t,J =7Hz,2H),1.70-1.64(m,2H),1.50-1.44(m,2H),1.35-1.27(m,10H),0.88(t,J=6.5Hz,3H). 13 C NMR (125MHz, CDCl3) δ178.21,136.89,133.81,129.50,128.43,98.89,79.64, 31.81,29.38,29.21,29.01,28.93,27.77,22.62,19.18,14.07.IR(ATR)ν(cm -1 )=2923,2851,2233,2195,1643,1594,1578,1448,1311,1259,1173,906,699.HRMS:m / z(ESI-TOF)calculated[M+H] + :257.1900, measured:257.1886.

[0195] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily yellow liquid product (33.15 mg, 87% yield). 1H NMR (500MHz, CDCl3) δ8.14-8.12(m,2H),7.58(t,J=7Hz,1H),7.47(t,J=8.5Hz,2H),2.71- 2.66(m,1H),1.94-1.91(m,2H),1.79-1.69(m,2H),1.65-1.53(m,3H),1.41-1.39(m,3H). 13 C NMR (125MHz, CDCl3) δ178.30,136.95,133.76,129.46,128.41,100.33,79.47,31.63,29.31,25.58,24.65.

[0196] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (36.39 mg, 77% yield). 1 H NMR (500MHz, CDCl3) δ8.21-8.18(m,2H),7.68-7.66(m,2H),7.49-7.46(m,1H),7.43-7.40(m,2H),6.99(dd,J=2,7Hz,2H),3.90(s,3H). 13 C NMR (125MHz, CDCl3) δ176.65,164.45,132.92,131.95,130.55,130.27,128.62,120.32,113.85,92.27,86.89,55.57.

[0197] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (49.55 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ7.89 (dd, J=1.5, 8Hz, 1H), 7.67-7.65 (m, 2H), 7.61 (d, J=1. 5Hz,1H),7.49-7.46(m,1H),7.42-7.40(m,2H),6.91(d,J=8Hz,1H),6.07(s,2H). 13 C NMR (125MHz, CDCl3) δ176.10,152.85,148.20,132.92,132.06,130.62,128.61,127.20,120.16,108.29,107.99,102.09,92.32,86.74.

[0198] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a brown solid product (50.23 mg, 98% yield). 1 H NMR (500MHz, CDCl3) δ8.80 (s, 1H), 8.23-8.21 (m, 1H), 8.04 (d, J = 8Hz, 1H), 7.94-7.90 (m, 2H), 7 .76-7.74(m,2H),7.66-7.63(m,1H),7.60-7.57(m,1H),7.53-7.50(m,1H),7.47-7.44(m,2H). 13 C NMR (125MHz, CDCl3) δ177.93,136.16,134.43,133.05,132.64,132.41,130.76, 129.88,129.01,128.70,128.54,127.91,126.94,123.97,120.22,93.03,87.06.

[0199] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow oily liquid product (48.26 mg, 98% yield). 1 H NMR(500MHz, CDCl3)δ8.54(d,J=1.5Hz,1H),8.22(dd,J=1.5,8.5Hz,1H),7.73-7.71(m ,3H),7.60(d,J=9Hz,1H),7.51-7.48(m,1H),7.45-7.32(m,2H),6.91d,J=1.5Hz,1H). 13 C NMR (125MHz, CDCl3) δ177.60,158.18,146.67,132.99,132.59,130.68,128.67 ,127.66,126.06,124.29,120.24,111.63,107.38,92.68,87.03.IR(ATR)ν(cm -1 )=3118,3065,2191,1630,1603,1581,1487,1438,1327,1285,1260,1145,1122,1102,1028,1007,995,745,685.HRMS:m / z(ESI-TOF)calculated[M+H] + :247.0754,measured:247.0746.

[0200] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (56.52 mg, 96% yield). 1 H NMR (500MHz, CDCl3) δ8.38 (s, 1H), 8.30 (d, J = 8Hz, 1H), 7.89 (t, J = 8Hz, 2H), 7.73 (d, J=7Hz,2H),7.61(d,J=7Hz,1H),7.52-7.49(m,1H),7.46-7.39(m,4H),4.00(s,2H). 13 C NMR (125MHz, CDCl3) δ177.81,147.60,144.79,143.32,140.33,135.54,133.01,130.66,129 .36,128.67,128.33,127.14,126.00,125.30,121.11,120.32,119.74,92.70,87.24,36.86.

[0201] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow oily liquid product (50.37 mg, 96% yield). 1 H NMR(500MHz, CDCl3)δ8.70(d,J=1Hz,1H),8.18-8.16(m,1H),7.97(d,J=8.5Hz,1H ),7.73-7.71(m,2H),7.55(d,J=5.5Hz,1H),7.51-7.48(m,2H),7.45-7.42(m,2H). 13 C NMR (125MHz, CDCl3) δ177.83,145.37,139.32,133.65,133.00,130.71,128.65 ,128.11,126.07,124.69,124.07,122.60,120.17,92.80,87.02.IR(ATR)ν(cm -1 )=3065,2195,1627,1590,1544,1490,1441,1422,1327,1280,1217,1151,1086 ,1048,994,900,823,785,755,732,682.HRMS:m / z(ESI-TOF)calculated[M+H] + :263.0525,measured:263.0523.

[0202] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow oily liquid product (60.60 mg, 97% yield). 1 H NMR(500MHz, CDCl3)δ8.99(d,J=1.5Hz,1H),8.31(dd,J=1.5,8.5Hz,1H),8.28-8.26(m,1H),7.9 6(d,J=8.5Hz,1H),7.89-7.87(m,1H),7.76-7.74(m,2H),7.55-7.51(m,3H),7.48-7.45(m,2H). 13 CNMR (125MHz, CDCl3) δ177.55,145.87,139.72,135.72,135.06,133.66,133.08,130.82,128.7 4,127.59,127.38,125.06,122.96,122.93,122.80,121.98,120.21,93.17,87.08.IR(ATR)ν(cm -1 )=3062,2923,2202,1647,1601,1584,1547,1489,1444,1317,1268,1227,1193,1 174,1063,1009,991,889,841,781,753,725,681.HRMS:m / z(ESI-TOF)calculated M + 313.0682, measured: 313.0676. The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow oily liquid product (34.39 mg, 81% yield). 1 H NMR (500MHz, CDCl3) δ8.36(dd,J=1,3Hz,1H),7.69-7.65(m,3H),7.50-7.47(m,1H),7.43-7.40(m,2H),7.36(dd,J=2.5,5Hz,1H). 13 C NMR (125MHz, CDCl3) δ171.40,142.96,135.43,132.98,130.74,128.67,126.80,126.79,120.20,91.30,87.28.

[0203] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow oily liquid product (42.03 mg, 99% yield). 1 H NMR (500MHz, CDCl3) δ8.02-8.01(m,1H),7.74-7.73(m,1H),7.67-7.66(m,2H),7.49(d,J=7.5Hz,1H),7.42(t,J=7.5Hz,2H),7.19(t,J=4Hz,1H). 13 C NMR (125MHz, CDCl3) δ169.77,144.93,135.22,135.05,133.02,130.83,128.68,128.32,119.93,91.70,86.46.

[0204] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow oily liquid product (65.63 mg, 95% yield). 1 H NMR (500MHz, CDCl3) δ8.52(s,1H),8.42-8.41(m,1H),8.13(d,J=8Hz,1H),7.68(d,J=7Hz,2H),7.48(t,J=7Hz,1H),7.44-7.36(m,4H),1.74(s,9H). 13 C NMR (125MHz, CDCl3) δ172.29,148.92,135.76,135.68,132.90,130.52,128.65,126.72,1 25.84,124.62,122.48,121.96,120.27,115.10,89.23,87.27,85.70,28.05.IR(ATR)ν(cm -1 )=2978,2931,2187,1740,1623,1540,1485,1448,1368,1307,1278,1231,1134,1103,1048,949,850,833,758,748,688.HRMS:m / z(ESI-TOF)calculated M + :346.1438, measured:346.1425.

[0205] The reaction was carried out according to general procedure 3, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (50.38 mg, 96% yield).1 H NMR (500MHz, CDCl3) δ8.81(d,J=8.5Hz,1H),8.73(s,1H),7.88(d,J=8Hz,1H),7.70-7.68(m,2H),7.55-7.42(m,5H). 13 CNMR (125MHz, CDCl3) δ171.81,142.09,140.25,136.28,135.74,132.89,130.6 4,128.68,126.14,125.86,125.48,122.39,120.13,90.49,87.33.IR(ATR)ν(cm -1 )=3079,2218,2185,1618,1487,1458,1416,1368,1268,1154,1142,1117,1051, 935,859,818,781,767,755,734,705,687.HRMS:m / z(ESI-TOF)calculated[M+H] + :263.0525,measured:263.0526.

[0206] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (30.61 mg, 84% yield). 1 H NMR (500MHz, CDCl3) δ7.83-7.80(m,4H),7.61-7.57(m,2H),7.51-7.47(m,4H). 13 C NMR (125MHz, CDCl3) δ196.76,137.49,132.40,130.03,128.23.

[0207] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (34.38 mg, 81% yield; 30.56 mg, 72% yield). 1 H NMR (500MHz, CDCl3) δ7.85-7.82(m,2H),7.77-7.74(m,2H),7.59-7.55(m,1H),7.49-7.46(m,2H),6.98-6.95(m,2H). 13C NMR (125MHz, CDCl3) δ195.58,163.16,138.20,132.55,131.88,130.07,129.71,128.16,113.50,55.47.

[0208] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (42.88 mg, 83% yield; 32.55 mg, 53% yield). 1 H NMR(500MHz, CDCl3)δ7.91(d,J=8.5Hz,2H),7.86-7.84(m,2H),7.71(d,J=8.5Hz,2 H),7.67-7.65(m,2H),7.61(t,J=7.5Hz,1H),7.53-7.48(m,4H),7.43-7.40(m,1H). 13 C NMR (125MHz, CDCl3) δ196.34,145.21,139.95,137.73,136.20,132.36,130.71,129.98,128.95,128.29,128.16,127.28,126.95.

[0209] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (20.72 mg, 50% yield). 1 H NMR (500MHz, CDCl3) δ7.87 (d, J = 10Hz, 2H), 7.80-7.76 (m, 4H), 7.66-7.62 (m, 1H), 7.53-7.49 (m, 2H). 13 C NMR (125MHz, CDCl3) δ194.99,141.09,136.18,133.27,132.10,130.17,129.99,128.56,117.96,115.53.

[0210] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product. (25.52 mg, 51% yield; 29.52 mg, 59% yield). 1H NMR (500MHz, CDCl3) δ7.90 (d, J = 8Hz, 2H), 7.81 (d, J = 7.5Hz, 2H), 7.76 (d, J = 8Hz, 2H), 7.63 (t, J = 7.5Hz, 1H), 7.51 (t, J = 8Hz, 2H). 13 C NMR (125MHz, CDCl3) δ195.55, 140.70, 136.71, 133.71 (d, J = 32.6Hz), 133.09, 130.13, 130.10, 128.52, 125.34 (q, J = 3.6Hz), 123.64 (q, J = 273Hz).

[0211] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (24.62 mg, 53% yield). 1 H NMR(500MHz, CDCl3)δ8.11(d,J=8.5Hz,1H),8.01(d,J=8Hz,1H),7.94-7.92(m,1 H),7.88-7.87(m,2H),7.62-7.58(m,2H),7.56-7.49(m,3H),7.47(t,J=8Hz,2H). 13 CNMR(125MHz,CDCl3)δ198.01,138.28,136.32,133.69,133.21,131.24,1 30.93,130.39,128.42,128.38,127.75,127.23,126.43,125.67,124.31.

[0212] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (26.94 mg, 58% yield). 1 H NMR (500MHz, CDCl3) δ8.27 (s, 1H), 7.95 (s, 2H), 7.92 (dd, J = 2.5, 8Hz, 2H), 7.88-7.86 (m, 2H), 7.64-7.61 (m, 2H), 7.58-7.51 (m, 3H). 13 C NMR (125MHz, CDCl3) δ196.76,137.87,135.24,134.79,132.37,132.22,131.86,130.08,129.40,128.32,128.31,128.28,127.80,126.78,125.76.

[0213] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product. (42.08 mg, 93% yield; 37.56 mg, 93% yield). 1 H NMR (500MHz, CDCl3) δ7.75-7.73(m,2H),7.56(t,J=7Hz,1H),7.47(t,J=7.5Hz,2H),7.38-7.37(m,2H),6.86(d,J=8Hz,1H),6.06(s,2H). 13 C NMR (125MHz, CDCl3) δ195.11,151.48,147.90,138.09,131.96,131.86,129.67,128.17,126.83,109.88,107.66,101.82.

[0214] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (44.99 mg, 70% yield; 40.49 mg, 63% yield). 1 H NMR(500MHz, CDCl3)δ8.37-8.35(m,1H),8.16(d,J=8Hz,1H),8.08(s,1H),7.89-7.87 (m,2H),7.60(t,J=7.5Hz,1H),7.52(t,J=7.5Hz,2H),7.44-7.38(m,2H),1.70(s,9H). 13 C NMR (125MHz, CDCl3) δ191.37,149.21,139.55,135.51,133.94,132.02,128. 92,128.47,128.32,125.65,124.35,122.59,119.39,114.99,85.44,28.06.

[0215] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (18.82 mg, 50% yield; 24.47 mg, 65% yield). 1 H NMR (500MHz, CDCl3) δ7.94-7.93(m,1H),7.86-7.84(m,2H),7.61-7.57(m,2H),7.49(t,J=8Hz,2H),7.39-7.38(m,1H).13 CNMR (125MHz, CDCl3) δ189.98,141.26,138.59,133.90,132.28,129.34,128.58,128.35,126.18.

[0216] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product. (30.50 mg, 64% yield; 25.26 mg, 53% yield). 1 H NMR (500MHz, CDCl3) δ8.58(d,J=8Hz,1H),8.01(s,1H),7.92(d,J=8Hz,1H),7. 88-7.87(m,2H),7.61(t,J=7.5Hz,1H),7.54-7.50(m,3H),7.48-7.45(m,1H). 13 C NMR (125MHz, CDCl3) δ190.85,140.00,139.25,138.24,137.40,134.77,132.31,129.47,128.41,125.65,125.55,125.15,122.31.

[0217] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a brown solid product (23.43 mg, 50% yield). 1 H NMR (500MHz, CDCl3) δ8.95-8.94(m,2H),8.59(s,1H),8.27-8.23(m,2H),7.89(d,J=7.5Hz,2H),7.65(t,J=7.5Hz,1H),7.53(t,J=8Hz,2H). 13 C NMR (125MHz, CDCl3) δ195.56,146.57,146.01,144.70,142.15,138.59,136.92,133.01,132.51,130.16,130.07,129.97,128.55.

[0218] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (44.42 mg, 94% yield). 1H NMR (500MHz, CDCl3) δ8.07 (d, J = 1Hz, 1H), 7.82 (dd, J = 1.5, 8.5Hz, 1H), 7.74-7.71 ( m,3H),7.57(d,J=8.5Hz,1H),7.29(d,J=8Hz,2H),6.84(t,J=1Hz,1H),2.45(s,3H). 13 C NMR (125MHz, CDCl3) δ196.30,157.06,146.30,142.88,135.45,133.13,130.23,128.90,127.17,126.69,124.27,111.13,107.19,21.61.

[0219] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (46.71 mg, 81% yield; 54.79 mg, 95% yield). 1 HNMR (500MHz, CDCl3) δ8.62 (s, 1H), 8.20-8.19 (m, 1H), 7.96-7.86 (m, 5H), 7.64 (t, J = 7.5Hz, 1H), 7.55-7.48 (m, 4H). 13 C NMR (125MHz, CDCl3) δ196.47,144.08,139.72,137.98,135.45,135.17,133.97,1 32.37,130.06,128.36,128.15,127.41,124.88,123.64,122.94,122.54,121.98.

[0220] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a grayish-white solid product (41.94 mg, 88% yield; 34.79 mg, 73% yield). 1 H NMR (500MHz, CDCl3) δ8.26 (s, 1H), 7.98 (t, J = 8.5Hz, 1H), 7.85-7.83 (m, 3H), 7.61 (t, J = 7.5Hz, 1H), 7.54-7.49 (m, 3H), 7.42 (d, J = 5.5Hz, 1H). 13C NMR (125MHz, CDCl3) δ196.70,143.77,139.03,138.00,133.91,132.23,129.99,128.25,127.82,126.24,125.29,124.50,122.40.

[0221] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (52.98 mg, 98% yield). 1 H NMR (500MHz, CDCl3) δ8.03(s,1H),7.88-7.83(m,5H),7.61(t,J=7.5Hz,2H),7.51(t,J=7.5Hz,2H),7.45-7.37(m,2H),3.97(s,2H). 13 C NMR (125MHz, CDCl3) δ196.74,145.95,144.40,143.06,140.52,138.18,135.85,132. 13,129.94,129.63,128.23,127.96,127.05,126.79,125.24,120.82,119.38,36.89.

[0222] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (28.26 mg, 72% yield). 1 H NMR (500MHz, CDCl3) δ7.79(d,J=9.5Hz,2H),7.73(d,J=10Hz,2H),7.60-7.56(m,1H),7.48(t,J=9.5Hz,2H),7.28(d,J=9.5Hz,2H),2.44(s,3H). 13 C NMR (125MHz, CDCl3) δ196.50,143.22,137.85,134.77,132.13,130.27,129.89,128.92,128.16,21.63.

[0223] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (43.12 mg, 89% yield). 1H NMR (500MHz, CDCl3) δ7.80-7.78(m,4H),6.98-6.95(m,4H),3.89(s,6H). 13 C NMR (125MHz, CDCl3) δ194.47,162.80,132.22,130.72,113.42,55.45.

[0224] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (38.04 mg, 95% yield). 1 H NMR (500MHz, CDCl3) δ7.86-7.84(m,2H),7.78-7.76(m,2H),7.60(t,J=7.5Hz,1H),7.49(t,J=8Hz,2H),7.16(t,J=8.5Hz,2H). 13 C NMR (125MHz, CDCl3) δ195.26, 165.38 (d, J = 252.6Hz), 137.49, 133.78 (d, J = 2 .9Hz), 132.69, 132.54 (d, J = 20.3Hz), 129.86, 128.34, 115.44 (d, J = 21.6Hz).

[0225] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (35.14 mg, 82% yield). 1 H NMR (500MHz, CDCl3) δ7.79-7.77(m,2H),7.59(t,J=7.5Hz,1H),7.50-7.47(m,4H),7.29(t,J=8Hz,1H),2.37(d,J=1.5Hz,3H). 13 C NMR (125MHz, CDCl3) δ195.21, 160.90 (d, J = 245Hz), 137.36, 137.04 (d, J = 6.4Hz), 132.47, 131.28 (d, J = 4.6H z), 130.14 (d, J = 17.4Hz), 129.87, 128.31, 125.77 (d, J = 3.1Hz), 116.47 (d, J = 23.3Hz), 14.81 (d, J = 3.5Hz).

[0226] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (41.27 mg, 92% yield). 1 H NMR (500MHz, CDCl3) δ7.80(d,J=7.5Hz,2H),7.57(t,J=7.5Hz,1H),7.45(t,J =8Hz,2H),7.10(s,1H),7.06(s,1H),2.29(s,3H),2.28(s,3H),2.23(s,3H). 13 C NMR (125MHz, CDCl3) δ198.72,139.25,138.23,135.94,134.46,133.27,132.77,132.39,130.18,130.07,128.32,19.69,19.57,19.17.

[0227] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a white solid product (40.00 mg, 90% yield). 1 H NMR (500MHz, CDCl3) δ8.09(d,J=1.5Hz,1H),7.85-7.80(m,3H),7.71(d,J=2Hz,1H),7.61-7.57(m,2H),7.49(t,J=7.5Hz,2H),6.85(d,J=1.5Hz,1H). 13 C NMR (125MHz, CDCl3) δ196.51,157.15,146.37,138.17,132.76,132.10,129.94,128.19,127.21,126.75,124.46,111.30,107.19.

[0228] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (23.33 mg, 50% yield). 1 H NMR (500MHz, CDCl3) δ9.04 (s, 1H), 8.27-8.16 (m, 4H), 7.87 (d, J = 7.5Hz, 2H), 7.64 (t, J = 7.5Hz, 1H), 7.55-7.49 (m, 3H). 13CNMR (125MHz, CDCl3) δ196.04,152.47,149.70,137.42,137.39,135.48,132.70,131.37,130.10,129.85,129.54,128.56,127.29,121.99.

[0229] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (30.30 mg, 88% yield). 1 H NMR (500MHz, CDCl3) δ7.97-7.96(m,2H),7.71(d,J=1Hz,1H),7.61-7.58(m,1H),7.50(d,J=7.5Hz,2H),7.24-7.23(m,1H),6.60(dd,J=1.5,8.5Hz,1H). 13 C NMR (125MHz, CDCl3) δ182.55,152.25,147.08,137.23,132.55,129.25,128.39,120.55,112.18.

[0230] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give an oily liquid product (27.89 mg, 81% yield). 1 H NMR (500MHz, CDCl3) δ7.92 (s, 1H), 7.86-7.85 (m, 2H), 7.61-7.57 (m, 1H), 7.51-7.48 (m, 3H), 6.91 (d, J = 1Hz, 1H). 13 C NMR (125MHz, CDCl3) δ189.42,148.55,143.94,138.79,132.46,128.80,128.53,126.49,110.19.

[0231] The reaction was carried out according to general procedure 4, and the product was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to give a yellow solid product (37.78 mg, 85% yield). 1 H NMR (500MHz, CDCl3) δ8.26-8.25(m,1H),8.09(s,1H),7.91-7.89(m,2H),7.62(t,J=7.5Hz,1H),7.58-7.51(m,3H),7.44-7.40(m,2H). 13C NMR(125MHz,CDCl3)δ190.21,155.56,152.19,139.24,132.45,128.77,128.64,125.81,125.18,124.52,122.88,121.22,111.48.

Claims

1. A carbonylation reaction method, comprising: Reactant A, reactant B and carbonylating agent are reacted to generate a carbonyl-containing compound, wherein the carbonylating agent includes methylated cellulose; The reactant A is selected from organic compounds having halogen groups, and the organic compounds having halogen groups are aryl halogens or heteroaryl halogens. The reactant B is selected from organic compounds containing hydroxyl groups, organic compounds containing NH or NH2, organic compounds containing terminal alkyne groups, and organic compounds containing borate or borate ester groups. The hydroxyl-containing organic compound is an alcohol; the alcohol is selected from C1-C10 alkyl alcohols, and the C1-C10 alkyl group is optionally substituted by a substituent selected from cyano, nitro, halogen, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C6-C10 aryl, amino, C1-C5 alkoxy, and C1-C5 alkyl-substituted amino groups; The organic compound containing NH or NH2 is selected from C3-C10 alkylamines, C6-C20 arylamines, and C3-C20 heteroarylamines. The C3-C10 alkyl group is optionally substituted with a substituent selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C10 aryl, C3-C10 heteroaryl, amino, C1-C5 alkoxy, and C1-C5 alkyl-substituted amino groups. The C6-C20 aryl and C3-C20 heteroaryl groups are optionally substituted with C1-C5 alkyl, C1-C5 alkoxy, halogen, cyano, nitro, and amino groups. The organic compound containing a terminal alkyne group is selected from R2D, where R2 represents... D is selected from C3-C10 alkyl, C6-C20 aryl, and C3-C20 heteroaryl, wherein the C3-C10 alkyl, C6-C20 aryl, and C3-C20 heteroaryl are optionally substituted with substituents selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, and C1-C5 alkyl-substituted amino groups; The organic compound containing boric acid group or borate ester group is selected from R3E, wherein R3 is or R4 and R5 are each independently C1-C6 alkyl or linked together to form a 5-6 membered ring, E is selected from C6-C20 aryl and C3-C20 heteroaryl, wherein the C6-C20 aryl and C3-C20 heteroaryl are optionally substituted with substituents selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, and C1-C5 alkyl-substituted amino groups; The reaction is carried out in an aprotic polar solvent, which is selected from acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, DMF, and DMSO. The reaction was carried out under conditions of palladium catalyst and in the presence of phosphorus ligands; The reaction is carried out in the presence of a base.

2. The method according to claim 1, characterized in that, The methyl esterified cellulose has the structural unit shown in Formula 1: In Equation 1, R 1 R 2 and R 3 For hydrogen or And at least R 1 R 2 and R 3 At least one of them is .

3. The method according to claim 1, characterized in that, The degree of substitution of the methylated cellulose is 0.1-3.

4. The method according to claim 1, characterized in that, The degree of substitution of the methylated cellulose is 0.5-2.

5. The method according to claim 1, characterized in that, The degree of substitution of the methyl esterified cellulose is 1-1.

5.

6. The method according to claim 1, characterized in that, The degree of substitution of the methyl esterified cellulose is 1.2-1.

4.

7. The method according to claim 1, characterized in that, The preparation method of the carbonylating reagent includes the following steps: (1) The cellulose raw material is reacted in a formic acid solution to generate a reaction mixture containing methylated cellulose; (2) The reaction mixture is subjected to solid-liquid separation; (3) Concentrate and dry the liquid separated in step (2).

8. The method according to claim 7, characterized in that, The formic acid solution is an aqueous solution of formic acid with a mass fraction of 10-100%; and / or, The mass-to-volume ratio of the formic acid solution to the cellulose raw material is 1 mL / g to 100 mL / g; and / or, The reaction temperature is 10-120℃, and the reaction time is 1 minute to 24 hours.

9. The method according to claim 8, characterized in that, The reaction includes a first stage and a second stage. The first stage is carried out at 80-120°C for 4-8 hours, and the second stage is carried out at 20-40°C for 8-14 hours.

10. The method according to claim 9, characterized in that, The first stage is carried out at 90-110℃ for 4-8 hours; the second stage is carried out at 20-30℃ for 8-14 hours.

11. The method according to claim 9, characterized in that, The first stage is carried out at 90-110℃ for 5-6.5 hours; the second stage is carried out at 20-30℃ for 8-14 hours.

12. The method according to claim 9, characterized in that, The first stage is carried out at 90-110℃ for 5-6.5 hours; the second stage is carried out at 20-30℃ for 10-13 hours.

13. The method according to claim 9, characterized in that, The first stage is carried out at 95℃ for 6 hours; the second stage is carried out at 20-30℃ for 8-14 hours.

14. The method according to claim 9, characterized in that, The first stage was conducted at 95℃ for 6 hours; the second stage was conducted at 25℃ for 12 hours.

15. The method according to any one of claims 1-14, characterized in that, The organic compounds having halogen groups are shown in Formula I: Equation I Ring A represents an aryl group having 6-20 carbon atoms or a heteroaryl group having 3-20 carbon atoms; In Formula I, R1 represents one or more substituents selected from hydrogen, deuterium, cyano, amino, nitro, C1-C5 alkylamino, halogen, C1-C5 alkyl, C1-C5 alkoxy, phenyl, benzoyl, methoxycarbonyl, and ethoxycarbonyl.

16. The method according to claim 15, characterized in that, Ring A is a benzene ring, 4-methylbenzene ring, 4-tert-butylbenzene ring, 4-methoxybenzene ring, 3-methoxybenzene ring, 2-methoxybenzene ring / 4-phenylbenzene ring, 4-benzoylbenzene ring, 4-cyanobenzene ring, 4-methyl ester benzene ring, 4-trifluoromethylbenzene ring, 4-n-butyloxybenzene ring, 2-trifluoromethylbenzene ring, 3,5-dimethylbenzene ring, 3,5-dimethoxybenzene ring, 3,4-dimethoxybenzene ring, 3,4,5-trimethylbenzene ring, 2-naphthyl ring, 1-naphthyl ring, 1,2-methylenedioxybenzene ring, 2,3-dihydrobenzo[b][1,4]dioxin, 2-methylbenzoazole, benzofuran ring, furan ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, fluorene, indole ring, quinoline ring, quinoxaline ring, aminotoluene ring, ethylamine benzene ring, or halobenzene ring.

17. The method according to claim 15, characterized in that, The organic compound having a halogen group is selected from one or more of the following compounds: X represents chlorine, bromine, or iodine.

18. The method according to claim 17, characterized in that, X is bromine or iodine.

19. The method according to any one of claims 1-14, characterized in that, The reactant B is selected from compounds with the following structural formulas: Where n is 0, 1, 2, 3 or 4; R is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano, halogen, hydroxyl, amino; X and Y are each independently halogen or amino.

20. The method according to claim 19, characterized in that, Halogens are bromine or iodine.

21. The method according to any one of claims 1-14, characterized in that, The reactant B is selected from: or .

22. The method according to any one of claims 1-14, characterized in that, (1) The alcohol compounds are selected from methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, isobutanol, sec-butanol, n-pentanol, 2-pentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, ethylene glycol, benzyl alcohol, phenethyl alcohol, phenylpropanol, 1-Cyclohexenylmethanol; (2) The organic compound containing NH or NH2 is selected from the following compounds: (3) The organic compound containing a terminal alkyne group is selected from the following compounds: (4) The organic compound containing boric acid group or borate ester group is selected from... .

23. The method according to any one of claims 1-14, characterized in that, The reaction temperature is 20-120℃.

24. The method according to any one of claims 1-14, characterized in that, The palladium catalysts mentioned are palladium acetate, palladium trifluoroacetate, palladium pentavalerate, palladium dichloroacetonitrile, palladium bis(benzonitrile)chloride, palladium chloride, palladium bromide, palladium iodide, palladium tetraacetonitrile tetrafluoroborate, palladium hexafluoroacetylacetonate, palladium di(acetylacetonate), palladium tetraacetonitrile trifluoromethanesulfonic acid, palladium neopentanoate, and (1 E 4 E One or more of bis(dibenzylacetone)palladium, or one or more of bis(dibenzylacetone)dipalladium and tri(dibenzylacetone)dipalladium; and / or The phosphorus ligands are selected from 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 1,1'-bis(diphenylphosphino)ferrocene, tri-o-toluenephosphine, tricyclohexylphosphine tetrafluoroborate, tri-tert-butylphosphine tetrafluoroborate, di-tert-butylmethylphosphine tetrafluoroborate, triphenylphosphine, 2-di-tert-butylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2'-methylbiphenyl, tris(2-furanyl)phosphine, 2-(dicyclohexylphosphine)biphenyl, n-butyldi(1-adamantyl)phosphine, 2-(di-tert-butylphosphine)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1-biphenyl, 3-2- Bicyclohexylphosphine-2',6'-diisopropoxybiphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, rac-2-(di-tert-butylphosphine)-1,1′-binaphthyl, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, 1,3-bis(diphenylphosphino)propane, 2-diphenylphosphine-2′-(N,N-dimethylamino)biphenyl, tris(4-fluorophenyl)phosphine, 2,2′-bis(diphenylphosphine)-1,1′-binaphthyl, 2-di-tert-butylphosphine-2′-methylbiphenyl, 2-dicyclohexylphosphino-2′-(N,N-dimethylamine)biphenyl, 1,1′-bis(di-tert-butylphosphine)ferrocene, bis(2-diphenylphosphine)ether, 4,5- Bis(diphenylphosphine)-9,9-dimethyloxanthracene, 1,1′-bis(diisopropylphosphine)ferrocene, 1,2-bis(diphenylphosphine)benzene, 1,2,3,4,5-pentaphenyl-1′-(di-tert-butylphosphine)ferrocene, or bis(diphenylphosphine)methane.

25. The method according to any one of claims 1-14, characterized in that, The base is selected from Na3PO4, K3PO4, LiOH, Na2CO3, K2CO3, t-BuOK, t-BuONa, t-BuOLi, NET3, 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylamine, or combinations thereof.

26. The method according to any one of claims 1-14, characterized in that, In the carbonylation reaction, the structural formulas of reactants A and B, as well as the carbonyl-containing compound, are shown in any one of reactions 1-124 below: 。

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