A method for preparing 1,2-diketone compounds by catalytic oxidation of alkynes using a tetradentate nitrogen-containing manganese complex

Abstract

The application discloses a method for preparing 1,2-diketone compounds by catalytic oxidation of acetylenes with tetradentate nitrogen-coordinated manganese, and belongs to the technical field of catalytic oxidation synthesis of organic intermediates. In the method, H2O2 is used as an oxidant, and tetradentate nitrogen-coordinated manganese is used as a catalyst without any additive under mild conditions, so that carbon-carbon triple bonds of various substituted acetylenes are selectively oxidized into corresponding 1,2-diketone compounds. Compared with the prior art, the catalyst used in the application is cheap and easy to obtain, the catalyst consumption is small, the reaction condition is mild, the operation is simple, the functional group compatibility of the substrate is good, H2O2 is used as a clean oxidant, water is the only by-product, the product yield is high, the production cost is low, and the method has a good industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of catalytic oxidation synthesis of organic intermediates. Specifically, this invention relates to a synthetic method for efficiently and selectively converting alkynes into 1,2-diketone compounds using hydrogen peroxide as a green oxidant under the action of a tetradentate nitrogen-coordinated manganese catalyst. Background Technology

[0002] The 1,2-diketone functional group is widely found in natural products and bioactive molecules. Some clinical drugs contain this functional group. For example, rapamycin is a macrolide compound derived from *Streptomyces hygroscopicus*, possessing immunosuppressive and anti-rejection effects and widely used in clinical organ transplantation; indibulin is a synthetic small-molecule microtubule inhibitor containing this functional group, exhibiting antitumor activity and already used in cancer treatment; Biricodar is now used clinically as an antitumor drug; Boceprevir is a synthetic small-molecule drug used to treat chronic hepatitis C; and Fluocortin butyl is a synthetic corticosteroid containing the 1,2-diketone functional group, used to treat rhinitis. Some traditional Chinese medicines also contain 1,2-diketone functional groups. For example, lithodione, a flavonoid isolated from the rhizome of licorice, possesses various pharmacological activities such as antibacterial, antioxidant, and antitumor effects; tanshinone IIA, found in the roots of danshen (Salvia miltiorrhiza), is a transcription factor inhibitor that can inhibit angiogenesis through the protein kinase pathway and has antiarrhythmic and antitumor effects; mansonone C, derived from the bark or root bark of the elm tree (Ulmus parvifolia), has antifungal activity and exhibits larval killing effects against Aedes aegypti mosquitoes; and sophoradione, found in the roots of Sophora flavescens (Sophora flavescens), has inhibitory activity against KB tumor cells. Compounds containing 1,2-diketone functional groups also have wide applications in industry and daily life. In the industrial field, the corrosion rate of low-carbon steel is slowed down in hydrochloric acid solutions containing phenylethylene glycol, and further reduced with increasing phenylethylene glycol concentration or temperature; however, in pure HCl solution, the corrosion rate accelerates with increasing acid concentration or temperature. In everyday life, 1,2-diketones are also commonly used in fragrances and cosmetics. In synthetic chemistry, 1,2-diketones are often used as intermediates or precursors to construct heterocyclic molecules and functional materials. For example, 1,2-diketones can be condensed with 1,2-diamines to synthesize aromatic substituted quinoxaline derivatives, which are widely used as photoinitiators and sensors.

[0003] Although 1,2-diketones have a wide range of applications, their efficient synthesis remains a challenging problem. Currently, the reported synthesis of 1,2-diketones usually involves the dehydrogenation of the hydroxyl group in α-hydroxy ketones or the oxidation of the carbon-carbon triple bond in alkynes. Typically, strong oxidizing agents (such as KMnO4, OsO4) are used for oxidation (J. Chem. Soc., Dalton Trans., 1978, 11, 1599; Org. Lett., 2012, 14, 2976; Chem. Rev., 1980, 80, 187-213), or noble metals (such as Ru, Pd, Cu) are used (J. Am. Chem. Soc., 2000, 122, 11380-11392; Adv. Synth. Catal., 2010, 352, 1424-1428; J. Am. Chem. Soc., 2014, 136, 13987-13990; Org. Lett., 2009, 11, 1841-1844; Adv. Synth. Catalytic oxidation (Catal., 2010, 352, 1630-1634; Synlett, 2013, 24, 2709-2714; Org. Biomol. Chem., 2014, 12, 9909-9913; Tetrahedron Lett., 2019, 60, 843-846) and photocatalytic oxidation (Chem. Commun., 2015, 51, 6568-6571; J. Org. Chem., 2016, 81, 7256−7261; GreenChem., 2016, 18, 6373-6379). Using strong oxidants generates a large amount of waste, and the functional groups in the substrate are difficult to reconcile under strong oxidant conditions. Noble metal catalytic oxidation requires catalyst amounts as high as 10 mol%, and the reaction conditions are quite harsh. Photocatalytic oxidation requires high amounts of photosensitizer, and because the reaction proceeds via a free radical pathway, the selectivity is difficult to control. Furthermore, the reported methods have significant limitations in terms of both substrate types and general applicability. Therefore, developing a green, economical, highly selective, easy-to-operate method for preparing 1,2-diketone compounds with good substrate generality is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide a method for the efficient preparation of 1,2-diketone compounds by selective oxidation of alkynes using H2O2 as an oxidant and inexpensive, easily prepared tetradentate nitrogen-coordinated manganese as a catalyst.

[0005] To achieve the above objectives, the technical solution adopted in this invention is as follows: using tetradentate nitrogen-coordinated manganese as a catalyst and H2O2 as an oxidant, the carbon-carbon triple bond of alkynes represented by formula I, I′, I" or I′" is catalytically oxidized to obtain 1,2-diketone compounds represented by formula II, II′, II" or II′"; the reaction equation is as follows:

[0006]

[0007] In the formula, R 1 R 3 R represents a substituent on the benzene ring. 1 R 3 The group is independently selected from hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, C1-C4 alkyl ester of carboxylic acid, nitro, and amine protected by a protecting group, wherein the benzene ring has one or more identical or different R groups. 1 Or R 3 Substituents; R 2 Representing C1 to C 10 Alkyl groups, protecting groups protecting C1-C 10 Any one of alkylamine groups; the protecting group is selected from any one of tert-butoxycarbonyl, benzyloxycarbonyl, fluorenyloxycarbonyl, phthalimide, and acetyl; M represents O or CH2; R represents hydrogen or phenyl.

[0008] The aforementioned four-toothed nitrogen-coordinated manganese is any one of formula A or formula B:

[0009]

[0010] In formula A, X represents the coordinating anion Cl. - ,Br - I - OAc - OTf - Any one of them; in formula B, Y represents the uncoordinated anion ClO4. - NO3 - BF4 - PF6 - SbF6 - Any one of them, m=2, or Y represents SO4 2- m=1; in formula A or formula B Structural representation , Any one of them, Structural representation , , , , Any one of them, R 1 R 2 R3 R 4 Each is represented independently by H, C1~C 10 Any one of alkyl, C1-C6 alkoxy, nitro, and silyl groups.

[0011] Furthermore, any one of the above-mentioned preferred formulas A-1 to A-4 for the four-toothed nitrogen-coordinated manganese:

[0012]

[0013] Furthermore, the amount of the aforementioned tetradentate nitrogen-coordinated manganese added is 0.1% to 5% of the molar amount of the alkyne, preferably 1% to 3% of the molar amount of the alkyne.

[0014] Furthermore, the amount of H2O2 added is 1 to 10 times the molar amount of the alkyne, preferably 4 to 6 times the molar amount of the alkyne.

[0015] Furthermore, the reaction conditions for the above catalytic oxidation are 20–60 °C for 0.5–12 hours.

[0016] Furthermore, the solvent used in the above method is any one of tert-butanol, acetonitrile, acetone, ethyl acetate, dichloromethane, and trifluoroethanol.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] (1) The catalyst is green, inexpensive and highly active. The tetradentate nitrogen-coordinated manganese catalyst used in this invention is made from inexpensive and readily available raw materials and has a simple synthesis process. It avoids the use of precious metal catalysts (such as Ru, Pd, Au, etc.) and has a low catalyst dosage, which greatly reduces production costs.

[0019] (2) The oxidant is green and environmentally friendly, and the reaction conditions are mild. This invention uses H2O2 as the oxidant, and the only byproduct generated after the reaction is water, avoiding the large amount of toxic or heavy metal waste generated by strong oxidants such as KMnO4 and OsO4. The reaction can be carried out efficiently at room temperature or under mild heating conditions, without the need for high temperature and high pressure, and the operation is simple and safe.

[0020] (3) The system is simple and requires no additional additives. This invention can achieve efficient oxidation of alkynes without any additives or acid-base auxiliaries, avoiding the introduction of additional reagents and subsequent separation steps, and further simplifying the operation process.

[0021] (4) The substrates are widely applicable and have good functional group compatibility. This invention is applicable to a variety of substituted alkynes, including substrates containing functional groups such as alkyl, alkoxy, halogen, ester, nitro and amino protecting groups, which can be successfully converted into the corresponding 1,2-diketone compounds, and are suitable for the later functionalization modification of complex molecules.

[0022] (5) High reaction selectivity and yield. This invention has excellent selective oxidation ability of carbon-carbon triple bonds of alkynes, and no over-oxidation or excessive oxidation side reactions occur during the reaction process, resulting in high yields of 1,2-diketone compounds. Detailed Implementation

[0023] The present invention will be further illustrated below with reference to examples, but the scope of protection of the present invention is not limited to these embodiments.

[0024] The synthesis method of the tetradentate nitrogen-containing coordinated manganese catalyst A-2 used in the following examples is as follows:

[0025] Step 1: Synthesis of (racemic)-1,1'-bis-(3,5-dimethylpyridine)-2,2'-bipiperidine

[0026] 134 mg (0.8 mmol) of bis(3,5-dimethylpyridine) hydrochloride and 326 mg (1.7 mmol) of 2-(chloromethyl)-3,5-dimethylpyridine hydrochloride were weighed into a reaction tube, and 10 mL of dichloromethane was added. Then, 160 mg (4 mmol) of sodium hydroxide was dissolved in 2 mL of deionized water and added dropwise to the reaction tube. The mixture was magnetically stirred at 55 °C for 5 days. After the reaction was completed, the reaction solution was transferred to a 100 mL separatory funnel. 10 mL of deionized water was added, and the mixture was extracted three times with dichloromethane. The organic phases were combined and dried over anhydrous sodium sulfate to remove water. The crude product was then obtained by rotary evaporation. A mixture of petroleum ether, ethyl acetate, and triethylamine in a volume ratio of 50:3:0.5 to 10:1:0.1 was used as the eluent. The crude product was purified by silica gel column chromatography to obtain a white solid (racemic)-1,1'-bis(3,5-dimethylpyridine)-2,2'-bipiperidine 123. mg (yield 38%) and 65 mg (yield 20%) of white solid (meta-1,1'-bis-(3,5-dimethylpyridine)-2,2'-bipiperidine). The reaction equation is as follows:

[0027]

[0028] The spectral data for (racemic)-1,1'-bis-(3,5-dimethylpyridine)-2,2'-bipiperidine are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 8.20 (s, 2H), 7.19 (s, 2H), 4.18 (d, J = 12.4 Hz, 2H), 3.25 (d, J = 12.4 Hz, 2H), 2.63 (t, J= 10.8 Hz, 4H), 2.36 (s, 6H), 2.24 (s,6H), 2.02-1.94 (m, 4H), 1.67-1.64 (m, 2H), 1.47-1.35 (m, 6H), 1.16-1.10 (m,2H); 13 C NMR (100 MHz, CDCl3) d (ppm): 154.6, 146.6, 138.5, 132.1, 131.0,64.0, 59.3, 54.3, 25.9, 24.7, 24.5, 18.7, 17.8; HRMS (ESI) m / z C 26 H 38 N4 [M+Na] + Theoretical value: 429.2989, Measured value: 429.2987. The spectral data for (meracic)-1,1'-bis-(3,5-dimethylpyridine)-2,2'-bipiperidine are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.16 (s, 2H), 7.21 (s, 2H), 4.17 (d, J = 12.4 Hz, 2H), 3.67 (d, J = 12.4 Hz, 2H), 2.82 (s, 2H), 2.66-2.59(m, 2H), 2.32 (s, 6H), 2.32-2.30 (m, 2H), 2.26 (s, 6H), 1.74-1.68 (m, 2H),1.59-1.53 (m, 4H), 1.25-1.10 (m, 2H), 1.09-1.07 (m, 2H), 0.96-0.93 (m, 2H); 13C NMR (100 MHz, CDCl 3) d (ppm): 155.5, 146.0, 138.5, 132.7, 131.1, 58.6, 56.0,48.8, 21.3, 21.1, 20.5, 18.2, 17.8; HRMS (ESI) m / z C 26 H 38 N4 [M+Na] + Theoretical value: 429.2989, measured value: 429.2988.

[0029] Step 2: Synthesis of tetradentate nitrogen-coordinated manganese catalyst A-2

[0030]

[0031] 87 mg (0.25 mmol) of manganese trifluoromethanesulfonate (Mn(OTf)2) and 89 mg (0.25 mmol) of (racemic)-1,1'-bis-(3,5-dimethylpyridine)-2,2'-bispiperidine were weighed sequentially into a 10 mL reaction tube. The nitrogen was replaced three times, and then 3 mL of acetonitrile was added under N2. The reaction was magnetically stirred at 80 °C for 8 hours. After the reaction was stopped, the reaction solution was cooled to room temperature, then transferred to a glove box and filtered with diatomaceous earth to remove the solid precipitate. The solution was then transferred outside the glove box and the solvent was removed by an oil pump to obtain 134 mg of a pale yellow solid (racemic)-1,1'-bis-(3,5-dimethylpyridine)-2,2'-bispiperidine coordinated manganese catalyst (tetradentate nitrogen-containing coordinated manganese catalyst A-2), with a yield of 97%. The structural characterization data are as follows: HRMS (ESI) m / z C 27 H 38 F3MnN4O3S [M-OTf] + Theoretical value: 610.1997, measured value: 610.1993.

[0032] The tetradentate nitrogen-coordinated manganese catalysts A-1, A-3, and A-4 used in the following examples were synthesized using the same method as tetradentate nitrogen-coordinated manganese catalyst A-2, except that 2-(chloromethyl)-3,5-dimethyl-4-methoxypyridine hydrochloride was replaced with equimolar amounts of 2-(chloromethyl)-pyridine hydrochloride, 2-(chloromethyl)-3,5-dimethyl-4-methoxypyridine hydrochloride, and 2-(chloromethyl)-3,5-dimethyl-4-nitropyridine hydrochloride.

[0033] Example 1

[0034] Synthesize 1-(2-oxooxazolidine-3-yl)-2-phenylethane-1,2-dione with the following structural formula.

[0035]

[0036] 94 mg (0.5 mmol) of 3-(phenylethynyl)oxazolidin-2-one was added to a 10 mL clean glass reaction tube containing 1.5 mL of acetonitrile. 7.6 mg (0.01 mmol) of tetradentate nitrogen-coordinated manganese catalyst A-2 was added to the reaction tube. Then, 284 µL (2.5 mmol) of a 30% (w / w) aqueous solution of H₂O₂ was dissolved in 1.5 mL of acetonitrile and added dropwise to the reaction flask over 1 hour using a micro-injection pump. After the addition was complete, the reaction was stirred at room temperature for 30 minutes. After the reaction was complete, the resulting mixture was quenched with saturated sodium sulfite aqueous solution to remove any remaining H₂O₂ and extracted with dichloromethane (3 × 15.0 mL). The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. Column chromatography was used to separate the product, yielding 101.0 mg of a yellow solid, 1-(2-oxooxazolidin-3-yl)-2-phenylethane-1,2-dione, in 92% yield. The spectroscopic data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.88(d, J = 7.9 Hz, 2H), 7.65 (t, J = 7.2 Hz, 1H), 7.54-7.50 (m, 2H), 4.60 (t, J = 8.0 Hz, 2H), 4.12 (t, J = 8.0 Hz, 2H); 13 C NMR (100 MHz, CDCl3) d (ppm):187.8, 166.5, 153.1, 134.9, 132.3, 129.4, 129.0, 64.0, 41.0; HRMS (ESI) m / zC 11 H9NNaO4 [M+Na] + Theoretical value: 242.0424, measured value: 242.0431.

[0037] Example 2

[0038] Synthesize 1-(4-methoxyphenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0039]

[0040] In this embodiment, equimolar amounts of 3-((4-methoxyphenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 99.7 mg of a white solid (1-(4-methoxyphenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, in 80% yield). The spectral data of the product are as follows: 1 HNMR (400 MHz, CDCl3) δ (ppm): 7.85 (d, J = 8.8 Hz, 2H), 7.98 (d, J = 8.8 Hz, 2H), 4.58 (t, J = 8.0 Hz, 2H), 4.15 (t, J = 8.0 Hz, 2H), 3.88 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 186.5, 166.9, 165.1, 153.1, 132.0, 125.5, 114.6,64.0, 55.8, 41.2; HRMS (ESI) m / z C 12 H 11 NNaO5 [M+Na] + Theoretical value: 272.0529, measured value: 272.0526.

[0041] Example 3

[0042] Synthesize 1-(4-methylphenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0043]

[0044] In this embodiment, equimolar amounts of 3-((4-methylphenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 96.7 mg of a white solid, 1-(4-methylphenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, in 83% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.77 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 4.58 (t, J= 8.0 Hz, 2H), 4.15 (t, J = 8.0 Hz, 2H), 2.43 (s, 3H); 13 C NMR (100MHz, CDCl3) d (ppm): 187.7, 166.7, 153.2, 146.3, 130.0, 129.9, 129.5, 64.1,41.0, 22.0; HRMS (ESI) m / z C 12 H 11 NNaO4 [M+Na] + Theoretical value: 256.0580, measured value: 256.0581.

[0045] Example 4

[0046] Synthesize 1-(4-tert-butylphenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0047]

[0048] In this embodiment, equimolar amounts of 3-((4-tert-butylphenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 110.2 mg of a white solid 1-(4-tert-butylphenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, with a yield of 80%. The spectral data of the product are as follows: 1 HNMR (400 MHz, CDCl3) δ (ppm): 7.81 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 4.58 (t, J = 8.0 Hz, 2H), 4.15 (t, J = 8.0 Hz, 2H); 13 C NMR (100 MHz, CDCl3) d (ppm): 187.7, 166.7, 159.0, 153.3, 129.9, 129.4, 126.2, 64.1, 41.0,35.4, 31.0; HRMS (ESI) m / z C 15 H 17 NNaO4 [M+Na] + Theoretical value: 298.1050, measured value: 298.1048.

[0049] Example 5

[0050] Synthesize 1-(4-fluorophenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0051]

[0052] In this embodiment, equimolar amounts of 3-((4-fluorophenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 91.4 mg of a white solid, 1-(4-fluorophenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, with a yield of 77%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.92-7.89 (m, 2H), 7.21-7.17 (m, 2H), 4.60 (t, J =8.0 Hz, 2H), 4.16 (t, J = 8.0 Hz, 2H); 13 C NMR (100 MHz, CDCl3) d (ppm):186.4, 166.8 (d, J = 256.0 Hz), 166.3, 153.2, 132.3 (d, J = 9.7 Hz), 129.0(d, J = 2.7 Hz), 116.6 (d, J = 22.4 Hz), 64.2, 41.1; HRMS (ESI) m / zC 11 H8FNNaO4 [M+Na] + Theoretical value: 260.0330, measured value: 260.0326.

[0053] Example 6

[0054] Synthesize 1-(4-chlorophenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0055]

[0056] In this embodiment, equimolar amounts of 3-((4-chlorophenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 100.2 mg of a white solid, 1-(4-chlorophenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, with a yield of 79%. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.82 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 4.61(t, J = 8.0 Hz, 2H), 4.16 (t, J = 8.0 Hz, 2H); 13 C NMR (100 MHz, CDCl3) d(ppm): 186.7, 166.2, 153.2, 141.6, 130.9, 130.8, 129.6, 64.2, 41.1; HRMS(ESI) m / z C 11 H8ClNNaO4 [M+Na] + Theoretical value: 276.0034, measured value: 276.0031.

[0057] Example 7

[0058] Synthesize 1-(3-fluorophenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0059]

[0060] In this embodiment, equimolar amounts of 3-((3-fluorophenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 94.8 mg of a white solid, 1-(3-fluorophenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, in 80% yield. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.64-7.58 (m, 2H), 7.52-7.47 (m, 1H), 7.37-7.32 (m, 1H), 4.60 (t, J = 8.0 Hz, 2H), 4.15 (t, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) d(ppm): 186.7, 166.0, 163.0 (d, J = 248.0 Hz), 153.3, 134.5 (d, J = 6.6 Hz), 131.0 (d, J = 7.7 Hz), 125.4 (d, J = 3.0 Hz), 122.1 (d, J = 21.4 Hz), 115.8 (d, J = 22.6 Hz), 64.3, 41.1; HRMS (ESI) m / z C 11 H8FNNaO4 [M+Na] + Theoretical value: 260.0330, measured value: 260.0329.

[0061] Example 8

[0062] Synthesize 1-(3-methylphenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0063]

[0064] In this embodiment, equimolar amounts of 3-((3-methylphenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 85.2 mg of a white solid, 1-(3-methylphenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, in 73% yield. The spectral data of the product are as follows: 1 H NMR(400 MHz, CDCl3) δ (ppm): 7.68-7.64 (m, 2H), 7.45-7.43 (m, 1H), 7.40-7.36 (m,1H), 4.56-4.52 (m, 2H), 4.14-4.10 (m, 2H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 188.2, 166.6, 153.3, 139.1, 135.8, 132.4, 129.7, 129.0,126.7, 64.2, 41.0, 21.3; HRMS (ESI) m / z C 12 H 11 NNaO4 [M+Na] +Theoretical value: 256.0580, measured value: 256.0585.

[0065] Example 9

[0066] Synthesize 1-(3,5-dimethylphenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0067]

[0068] In this embodiment, equimolar amounts of 3-((3,5-dimethylphenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 122.3 mg of a white solid, 1-(3,5-dimethylphenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, with a yield of 99%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.48 (s, 2H), 7.27 (s, 1H), 4.56 (t, J = 8.0Hz,, 2H), 4.14 (t, J = 8.0 Hz, 2H), 2.36 (s, 6H); 13 C NMR (100 MHz, CDCl3) d(ppm): 188.4, 166.7, 153.3, 138.9, 136.8, 132.4, 127.1, 64.1, 41.0, 21.2;HRMS (ESI) m / z C 13 H 13 NNaO4 [M+Na] + Theoretical value: 270.0737, measured value: 270.0732.

[0069] Example 10

[0070] Synthesize 1-(2,4,6-trimethylphenyl)-2-(2-oxooxazolidine-3-yl)ethane-1,2-dione with the following structural formula.

[0071]

[0072] In this embodiment, equimolar amounts of 3-((2,4,6-trimethylphenyl)ethynyl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 96.7 mg of a white solid, 1-(2,4,6-trimethylphenyl)-2-(2-oxooxazolidin-3-yl)ethane-1,2-dione, with a yield of 74%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 6.91 (s, 2H), 4.61-4.57 (m, 2H), 4.13-4.09 (m, 2H), 2.41 (s, 6H), 2.31 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm):188.7, 167.2, 153.1, 143.2, 140.0, 130.5, 130.0, 63.8, 42.0, 21.4, 21.1; HRMS(ESI) m / z C 14 H 15 NNaO4 [M+Na] + Theoretical value: 284.0893, measured value: 284.0892.

[0073] Example 11

[0074] Synthesize 1-(2-oxooxazolidine-3-yl)nonane-1,2-dione with the following structural formula.

[0075]

[0076] In this embodiment, equimolar amounts of 3-(non-1-yn-1-yl)oxazolidin-2-one were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 60.3 mg of a colorless oily product, 1-(2-oxooxazolidin-3-yl)nonane-1,2-dione, in 50% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ(ppm): 4.58 (t, J = 8.0 Hz, 2H), 4.02 (t, J = 8.0 Hz, 2H), 2.73-2.69 (m, 2H),1.73-1.65 (m, 2H), 1.36-1.27 (m, 8H), 0.88-0.85 (m, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm): 197.9, 167.4, 153.6, 64.2, 40.9, 39.6, 31.7, 29.1, 28.9,22.7, 22.4, 14.2; HRMS (ESI) m / z C 12 H 19 NNaO4 [M+Na] + Theoretical value: 264.1206, measured value: 264.1202.

[0077] Example 12

[0078] Synthesize 1-(2-oxooxazolidine-3-yl)heptane-1,2-dione with the following structural formula.

[0079]

[0080] In this embodiment, equimolar amounts of 3-(hepta-1-yn-1-yl)oxazolidin-2-one were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 74.6 mg of a colorless oily product, 1-(2-oxooxazolidin-3-yl)heptane-1,2-dione, in 70% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ(ppm): 4.59 (t, J = 8.0 Hz, 2H), 4.02 (t, J = 8.0 Hz, 2H), 2.72 (t, J = 7.4Hz, 2H), 1.72-1.69 (m, 2H), 1.36-1.32 (m, 4H), 0.91-0.88 (m, 3H); 13 C NMR (100MHz, CDCl3) d (ppm): 197.8, 167.4, 153.6, 64.2, 40.9, 39.5, 31.1, 22.5, 22.1,14.0; HRMS (ESI) m / z C 10 H 15 NNaO4 [M+Na] + Theoretical value: 236.0893, measured value: 236.0885.

[0081] Example 13

[0082] Synthesize 1-(2-oxopyrrolidone-1-yl)-2-phenylethane-1,2-dione with the following structural formula.

[0083]

[0084] In this embodiment, equimolar amounts of 1-(phenylethynyl)pyrrolidine-2-one were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 70.7 mg of a colorless oily product, 1-(2-oxopyrrolidine-1-yl)-2-phenylethane-1,2-dione, in 65% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.85 (d, J = 8.2 Hz, 2H), 7.64-7.60 (m, 1H), 7.50 (t, J = 7.7Hz, 2H), 3.94 (t, J = 7.3 Hz, 2H), 2.58 (t, J = 8.1 Hz, 2H), 2.27-2.20 (m,2H); 13 C NMR (100 MHz, CDCl3) d (ppm): 188.9, 175.8, 167.4, 134.5, 132.8,129.3, 129.1, 43.6, 31.9, 18.4; HRMS (ESI) m / z C 12 H 11 NNaO3 [M+Na] + Theoretical value: 240.0631, measured value: 240.0635.

[0085] Example 14

[0086] (S)-1-(2-oxo-4-phenyloxazolidine-3-yl)-2-phenylethane-1,2-dione

[0087]

[0088] In this embodiment, an equimolar amount of (S)-4-phenyl-3-(phenylethynyl)oxazolidin-2-one was used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 65.0 mg of a white solid (S)-1-(2-oxo-4-phenyloxazolidin-3-yl)-2-phenylethane-1,2-dione, with a yield of 44%. The spectral data of the product are as follows: 1 HNMR (400 MHz, CDCl3) δ (ppm): 7.85 (d, J= 8.2 Hz, 2H), 7.64-7.60 (m, 1H),7.50 (t, J = 7.7 Hz, 2H), 3.94 (t, J = 7.3 Hz, 2H), 2.58 (t, J = 8.1 Hz, 2H),2.27-2.20 (m, 2H); 13 C NMR (100 MHz, CDCl3) d (ppm): 188.9, 175.8, 167.4,134.5, 132.8, 129.3, 129.1, 43.6, 31.9, 18.4; HRMS (ESI) m / z C 12 H 11 NNaO3 [M+Na] + Theoretical value: 240.0631, measured value: 240.0635.

[0089] Example 15

[0090] Synthesize 1-(4-methoxyphenyl)-2-phenylethane-1,2-dione with the following structural formula.

[0091]

[0092] In this embodiment, equimolar amounts of 1-methoxy-4-phenylethynylbenzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 99.8 mg of a yellow solid, 1-(4-methoxyphenyl)-2-phenylethane-1,2-dione, in 83% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm):7.98-7.94 (m, 4H), 7.67-7.63 (m, 1H), 7.52-7.48 (m, 2H), 6.98 (d, J = 8.7 Hz, 2H), 3.89 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 195.0, 193.3, 165.1,134.9, 133.4, 132.5, 130.1, 129.1, 126.2, 114.5, 55.8; HRMS (ESI) m / zC 15 H 12 NaO3 [M+Na]+ Theoretical value: 263.0679, measured value: 263.0677.

[0093] Example 16

[0094] Synthesize 1-(4-methoxyphenyl)-2-(p-tolyl)ethane-1,2-dione with the following structural formula.

[0095]

[0096] In this embodiment, equimolar amounts of 1-methoxy-4-[2-(4-methylphenyl)ethynyl]benzene were used instead of 3-(phenylethynyl)oxazolidine-2-one used in Example 1. The other steps were the same as in Example 1, yielding 115.7 mg of a yellow solid 1-(4-methoxyphenyl)-2-(p-tolyl)ethane-1,2-dione, with a yield of 91%. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.94 (d, J = 8.8 Hz, 2H), 7.86 (d, J = 8.1 Hz, 2H), 7.29(d, J = 8.1 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 3.87 (s, 3H), 2.42 (s, 3H); 13 CNMR (100 MHz, CDCl3) (ppm): 194.7, 193.5, 165.0, 146.1, 132.5, 130.9, 130.1,129.8, 126.3, 114.5, 55.8, 22.0; HRMS (ESI) m / z C 16 H 14 NaO3 [M+Na] + Theoretical value: 277.0835, measured value: 277.0832.

[0097] Example 17

[0098] Synthesize 1-(4-methoxyphenyl)-2-(p-fluorophenyl)ethane-1,2-dione with the following structural formula.

[0099]

[0100] In this embodiment, equimolar amounts of 1-methoxy-4-[2-(4-fluorophenyl)ethynyl]benzene were used instead of 3-(phenylethynyl)oxazolidine-2-one used in Example 1. The other steps were the same as in Example 1, yielding 98.3 mg of a yellow solid 1-(4-methoxyphenyl)-2-(p-fluorophenyl)ethane-1,2-dione, with a yield of 76%. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 8.04-7.99 (m, 2H), 7.96-7.92 (m, 2H), 7.20-7.15 (m, 2H), 7.00-6.96 (m, 2H), 3.89 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 193.2,192.8, 166.8 (d, J = 256.4 Hz), 165.3, 132.9 (d, J = 9.7 Hz), 132.6, 129.9 (d, J = 2.8 Hz), 126.1, 116.4 (d, J = 22.0 Hz), 114.6, 55.8; HRMS (ESI) m / zC 15 H 11 FNaO3 [M+Na] + Theoretical value: 281.0584, measured value: 281.0583.

[0101] Example 18

[0102] Synthesize 1-(4-methoxyphenyl)-2-(p-chlorophenyl)ethane-1,2-dione with the following structural formula.

[0103]

[0104] In this embodiment, equimolar amounts of 1-methoxy-4-[2-(4-chlorophenyl)ethynyl]benzene were used instead of 3-(phenylethynyl)oxazolidine-2-one used in Example 1. The other steps were the same as in Example 1, yielding 111.5 mg of a yellow solid 1-(4-methoxyphenyl)-2-(p-chlorophenyl)ethane-1,2-dione, with a yield of 81%. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.95-7.91 (m, 4H), 7.48 (d, J = 8.6 Hz, 2H), 6.98 (d, J= 8.6 Hz, 2H), 3.89 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 193.5, 192.6,165.3, 141.5, 132.6, 131.7, 131.4, 129.5, 126.0, 114.6, 55.8; HRMS (ESI) m / zC 15 H 11 ClNaO3 [M+Na] + Theoretical value: 297.0289, measured value: 297.0290.

[0105] Example 19

[0106] Synthesize 1-(4-methoxyphenyl)-2-(p-bromophenyl)ethane-1,2-dione with the following structural formula.

[0107]

[0108] In this embodiment, equimolar amounts of 1-methoxy-4-[2-(4-bromophenyl)ethynyl]benzene were used instead of 3-(phenylethynyl)oxazolidine-2-one used in Example 1. The other steps were the same as in Example 1, yielding 98.9 mg of a yellow solid 1-(4-methoxyphenyl)-2-(p-bromophenyl)ethane-1,2-dione, with a yield of 62%. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.93 (d, J = 8.9 Hz, 2H), 7.83 (d, J = 8.6 Hz, 2H), 7.64(d, J = 8.6 Hz, 2H), 6.97 (d, J = 8.9 Hz, 2H) 3.88 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 193.7, 192.5, 165.3, 132.6, 132.5, 132.1, 131.4, 130.4,126.0, 114.6, 55.8; HRMS (ESI) m / z C 15 H 11 BrNaO3 [M+Na]+ Theoretical value: 340.9784, measured value: 340.9793.

[0109] Example 20

[0110] Synthesize tert-butyl (4-(2-(4-methoxyphenyl)-2-oxoacetyl)phenyl)carbamate with the following structural formula.

[0111]

[0112] In this embodiment, equimolar amounts of tert-butyl 4-((4-methoxyphenyl)ethynyl)phenylcarbamate were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 126.2 mg of a yellow solid (4-(2-(4-methoxyphenyl)-2-oxoacetyl)phenyl)carbamate, with a yield of 71%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) d (ppm): 7.94-7.88 (m, 4H), 7.48 (d, J =8.8 Hz, 2H), 6.97-6.93 (m, 3H), 3.87 (s, 3H), 1.51 (s, 9H); 13 C NMR (100 MHz, CDCl3) d (ppm): 193.7, 193.5, 165.0, 152.1, 144.7, 132.5, 131.7, 127.8,126.4, 117.8, 114.4, 81.7, 55.8, 28.3; HRMS (ESI) m / z C 20 H 21 Theoretical value of NNaO5 [M+Na]+: 378.1312, measured value: 378.1310.

[0113] Example 21

[0114] Synthesize 4-(2-(4-methoxyphenyl)-2-oxoacetyl)phenylacetamide with the following structural formula.

[0115]

[0116] In this embodiment, equimolar amounts of N-(4-((4-methoxyphenyl)ethynyl)phenyl)acetamide were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 87.9 mg of a white solid, 4-(2-(4-methoxyphenyl)-2-oxoacetyl)phenylacetamide, in 59% yield. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.95-7.92 (m, 4H), 7.64 (d,J = 8.4 Hz, 2H), 7.49 (brs,1H), 6.97 (d, J = 8.8 Hz, 2H), 3.89 (s, 3H), 2.21 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 193.7, 193.4, 168.6, 165.1, 143.8, 132.6, 131.6, 129.0,126.3, 119.2, 114.5, 55.8, 25.0; HRMS (ESI) m / z C 17 H 15 NNaO4 [M+Na] + Theoretical value: 320.0893, measured value: 320.0902.

[0117] Example 22

[0118] Synthesize 1-(4-methoxyphenyl)-2-(m-tolyl)ethane-1,2-dione with the following structural formula.

[0119]

[0120] In this embodiment, equimolar amounts of 1-((4-methoxyphenyl)ethynyl)-3-methylbenzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 111.9 mg of a yellow solid, 1-(4-methoxyphenyl)-2-(m-tolyl)ethane-1,2-dione, in 88% yield. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.94 (d, J = 8.6 Hz, 2H), 7.77-7.75 (m, 2H), 7.46-7.44(m, 1H), 7.39-7.36 (m, 1H), 6.97 (d, J = 8.6 Hz, 2H), 3.87 (s, 3H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 195.2, 193.4, 165.1, 139.0, 135.7,133.3, 132.5, 130.3, 129.0, 127.3, 126.3, 114.5, 55.8, 21.4; HRMS (ESI) m / zC 16H 14 NaO3 [M+Na] + Theoretical value: 277.0835, measured value: 277.0843.

[0121] Example 23

[0122] Synthesize 1-(4-methoxyphenyl)-2-(3-methoxyphenyl)ethane-1,2-dione with the following structural formula.

[0123]

[0124] In this embodiment, equimolar amounts of 1-methoxy-3-((4-methoxyphenyl)ethynyl)benzene were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 54.2 mg of a yellow solid, 1-(4-methoxyphenyl)-2-(m-methoxyphenyl)ethane-1,2-dione, in 40% yield. The spectral data of the product are as follows: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.94 (d, J = 8.8 Hz, 2H), 7.54 (s, 1H), 7.49-7.47 (m,1H), 7.40-7.36 (m, 1H), 7.20-7.18 (m, 1H), 6.97 (d, J = 8.8 Hz, 2H), 3.89 (s, 3H), 3.86 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 194.9, 193.2, 165.1,160.2, 134.7, 132.5, 130.1, 126.3, 123.4, 121.9, 114.5, 113.0, 55.8, 55.7;HRMS (ESI) m / z C 16 H 14 NaO4 [M+Na] + Theoretical value: 293.0784, measured value: 293.0781.

[0125] Example 24

[0126] Synthesize 1-(4-methoxyphenyl)-2-(m-fluorophenyl)ethane-1,2-dione with the following structural formula.

[0127]

[0128] In Example 1, equimolar amounts of 1-fluoro-3-((4-methoxyphenyl)ethynyl)benzene were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 82.7 mg of a yellow solid, 1-(4-methoxyphenyl)-2-(m-fluorophenyl)ethane-1,2-dione, in 64% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.94 (d, J = 8.2 Hz, 2H), 7.73-7.68 (m, 2H), 7.53-7.45 (m,1H), 7.36-7.32 (m, 1H), 6.98 (d, J = 8.2 Hz, 2H), 3.89 (s, 3H); 13 C NMR (100MHz, CDCl3) d (ppm): 193.4, 192.4, 165.3, 163.0 (d, J = 247.9 Hz), 135.4 (d, J = 6.3 Hz), 132.6, 130.8 (d, J = 7.5 Hz), 126.1 (d, J = 3.1 Hz), 126.0, 121.9 (d, J = 21.5 Hz), 116.2 (d, J = 22.4 Hz), 114.6, 55.8; HRMS (ESI) m / zC 15 H 11 FNaO3 [M+Na] + Theoretical value: 281.0584, measured value: 281.0576.

[0129] Example 25

[0130] Synthesize 1-(4-methoxyphenyl)-2-(o-tolyl)ethane-1,2-dione with the following structural formula.

[0131]

[0132] In this embodiment, equimolar amounts of 1-((4-oxyphenyl)ethynyl)-2-methylbenzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 77.7 mg of a yellow solid, 1-(4-methoxyphenyl)-2-(o-tolyl)ethane-1,2-dione, in 61% yield. The spectral data of the product are as follows: 1H NMR (400 MHz, CDCl3) δ (ppm): 7.95 (d, J = 8.7 Hz, 2H), 7.65 (d, J = 7.7 Hz, 1H) 7.49-7.46(m, 1H), 7.33 (d, J = 7.6 Hz, 1H), 7.28-7.24 (m, 1H), 6.98 (d, J = 8.7 Hz,2H), 3.89 (s, 3H), 2.70 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 197.2,193.7, 165.0, 141.4, 133.7, 133.1, 132.6, 132.5, 132.2, 126.4, 126.1, 114.5,55.8, 22.0; HRMS (ESI) m / z C 16 H 14 NaO3 [M+Na] + Theoretical value: 277.0835, measured value: 277.0840.

[0133] Example 26

[0134] Synthesize 1-(4-methoxyphenyl)-2-(o-chlorophenyl)ethane-1,2-dione with the following structural formula.

[0135]

[0136] In this embodiment, equimolar amounts of 1-chloro-2-((4-methoxyphenyl)ethynyl)benzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 89.4 mg of a yellow solid 1-(4-methoxyphenyl)-2-(o-chlorophenyl)ethane-1,2-dione, with a yield of 65%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.01 (d, J = 8.8 Hz, 2H), 7.90-7.87 (m, 1H), 7.54-7.50 (m, 1H), 7.44-7.40 (m, 2H), 7.00 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H); 13C NMR (100MHz, CDCl3) d (ppm): 193.9, 190.8, 164.8, 134.3, 134.1, 133.9, 132.7, 132.2,130.5, 127.3, 125.5, 114.3, 55.6; HRMS (ESI) m / z C 15 H 11 ClNaO3 [M+Na] + Theoretical value: 297.0289, measured value: 297.0293.

[0137] Example 27

[0138] Synthesize 1-(3,5-dimethylphenyl)-2-(4-methoxyphenyl)ethane-1,2-dione with the following structural formula.

[0139]

[0140] In this embodiment, equimolar amounts of 1-((4-methoxyphenyl)ethynyl)-3,5-dimethylbenzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 122.1 mg of a yellow solid 1-(3,5-dimethylphenyl)-2-(4-methoxyphenyl)ethane-1,2-dione, with a yield of 91%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.93 (d, J = 8.8 Hz, 2H), 7.57 (s, 2H), 7.27 (s,1H), 6.97 (d, J = 9.2 Hz, 2H), 3.87 (s, 3H), 2.35 (s, 6H); 13 C NMR (100 MHz, CDCl3) d (ppm): 195.5, 193.6, 165.0, 138.9, 136.6, 133.3, 132.4, 127.7,126.3, 114.4, 55.7, 21.2; HRMS (ESI) m / z C 17 H 16 NaO3 [M+Na] + Theoretical value: 291.0992, measured value: 291.0998.

[0141] Example 28

[0142] Synthesize tert-butyl (4-(2-(4-methoxyphenyl)-2-oxoacetyl)-2-methylphenyl)carbamate with the following structural formula.

[0143]

[0144] In this embodiment, equimolar amounts of tert-butyl (4-((4-methoxyphenyl)ethynyl)-2-methylphenyl)carbamate were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 70.3 mg of a yellow solid (4-(2-(4-methoxyphenyl)-2-oxoacetyl)-2-methylphenyl)carbamate, in 38% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.17 (d, J = 8.8 Hz, 1H), 7.92 (d, J = 8.8 Hz, 2H), 7.80 (d, J = 8.8 Hz, 1H), 7.76 (s, 1H), 6.95(d, J = 8.8 Hz, 2H), 6.60 (s, 1H), 3.87 (s, 3H), 2.27 (s, 3H), 1.52 (s, 9H); 13 C NMR (100 MHz, CDCl3) d (ppm): 194.0, 193.6, 165.0, 152.1, 143.0, 132.5,132.1, 129.9, 127.5, 126.4, 125.3, 118.3, 114.4, 81.8, 55.8, 28.3, 17.7; HRMS(ESI) m / z C 21 H 23 NNaO5 [M+Na] + Theoretical value: 392.1468, measured value: 392.1475.

[0145] Example 29

[0146] Synthesize 1-(5-fluoro-2-methylphenyl)-2-(4-methoxyphenyl)ethane-1,2-dione with the following structural formula.

[0147]

[0148] In this embodiment, equimolar amounts of 4-fluoro-2-((4-methoxyphenyl)ethynyl)-1-methylbenzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 95.4 mg of a yellow solid 1-(5-fluoro-2-methylphenyl)-2-(4-methoxyphenyl)ethane-1,2-dione, with a yield of 70%. The spectral data of the product are as follows: 1 HNMR (400 MHz, CDCl3) δ (ppm): 7.95 (d, J = 8.8 Hz, 2H), 7.37-7.34 (m, 1H), 7.30-7.27 (m, 1H), 7.21-7.16 (m, 1H), 6.99 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H), 2.61 (s, 3H); 13 C NMR (100 MHz, CDCl3) d (ppm): 195.8 (d, J = 2.1 Hz),192.7, 165.2, 160.7 (d, J = 244.8 Hz), 136.7 (d, J = 3.5 Hz), 134.0 (d, J =6.9 Hz), 133.5 (d, J = 5.6 Hz), 132.6, 126.0, 120.7 (d, J = 20.9 Hz), 119.0(d, J = 22.0 Hz), 114.6, 55.8, 21.2; HRMS (ESI) m / z C 16 H 13 FNaO3 [M+Na] + Theoretical value: 295.0741, measured value: 295.0752.

[0149] Example 30

[0150] Synthesize 1-(2,4,6-trimethylphenyl)-2-(4-methoxyphenyl)ethane-1,2-dione with the following structural formula.

[0151]

[0152] In this embodiment, equimolar amounts of 2-((4-methoxyphenyl)ethynyl)-1,3,5-trimethylbenzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 66.4 mg of a yellow solid, 1-(2,4,6-trimethylphenyl)-2-(4-methoxyphenyl)ethane-1,2-dione, with a yield of 47%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.13 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 8.8Hz, 2H), 6.88 (s, 2H), 7.00 (d, J = 8.8 Hz, 2H), 3.91 (s, 3H), 2.30 (s, 3H), 2.27 (s, 6H); 13 C NMR (100 MHz, CDCl3) d (ppm): 198.5, 190.5, 164.8, 141.4,137.3, 133.9, 133.1, 129.5, 125.4, 114.4, 55.7, 21.4, 20.8; HRMS (ESI) m / zC 18 H 18 NaO3 [M+Na] + Theoretical value: 305.1148, measured value: 305.1143.

[0153] Example 31

[0154] Synthesize 1-phenyl-2-(m-tolyl)ethane-1,2-dione with the following structural formula.

[0155]

[0156] In this embodiment, equimolar amounts of 1-methyl-3-(phenylethynyl)benzene were used instead of the 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 58.4 mg of a yellow solid, 1-phenyl-2-(m-tolyl)ethane-1,2-dione, in 52% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.97(d, J= 7.4 Hz, 2H), 7.78-7.76 (m, 2H), 7.67-7.64 (m, 1H), 7.53-7.46 (m, 3H), 7.42-7.38 (m, 1H), 2.41 (s, 3H); 13 HRMS (ESI) m / z C 15 H 12 NaO2 [M+Na] + Theoretical value: 247.0730, measured value: 247.0723.

[0157] Example 32

[0158] Synthesize diphenylethylenedione with the following structural formula

[0159]

[0160] In this embodiment, equimolar amounts of 1,2-diphenylacetylene were used instead of 3-(phenylacetyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 63.2 mg of a yellow solid, diphenylethylenedione, in 60% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.80-7.97 (m, 2H), 7.68-7.64 (m,1H), 7.53-7.50 (m, 2H); 13 C NMR (100 MHz, CDCl3) d (ppm): 194.7, 135.0, 133.2,130.1, 129.2; HRMS (ESI) m / z C 14 H 10 NaO2 [M+Na] + Theoretical value: 233.0573, measured value: 233.0566.

[0161] Example 33

[0162] Synthesize 1-(4-methoxyphenyl)heptane-1,2-dione with the following structural formula.

[0163]

[0164] In this embodiment, equimolar amounts of methyl 1-(hept-1-yn-1-yl)-4-methoxybenzene were used instead of 3-(phenylethynyl)oxazolidine-2-one used in Example 1. The other steps were the same as in Example 1, yielding 82.0 mg of a yellow oily substance, 1-(4-methoxyphenyl)heptane-1,2-dione, in 70% yield. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ(ppm): 7.97 (d, J = 8.8 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 3.88(s, 3H), 2.85(t, J = 7.6 Hz, 2H), 1.70-1.67 (m, 2H), 1.35-1.33 (m, 4H), 0.91-0.88 (m, 3H); 13 C NMR (100 MHz, CDCl3)d (ppm): 204.2, 191.4, 164.9, 132.8, 125.1, 114.4,55.7, 39.0, 31.5, 22.8, 22.5, 14.0; HRMS (ESI) m / z C 14 H 18 NaO2 [M+Na] + Theoretical value: 257.1148, measured value: 257.1151.

[0165] Example 34

[0166] Synthesize 1-(4-methoxyphenyl)octane-1,2-dione with the following structural formula.

[0167]

[0168] In this embodiment, equimolar amounts of methyl 1-methoxy-4-(oct-1-yn-1-yl)benzene were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 78.4 mg of a yellow oily substance, 1-(4-methoxyphenyl)octane-1,2-dione, in 63% yield. The spectral data of the product are as follows: 1H NMR (400 MHz, CDCl3) δ(ppm): 7.96 (d, J = 8.9 Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H), 3.88 (s, 3H), 2.85(t, J = 7.4 Hz, 2H), 1.71-1.63 (m, 2H), 1.39-1.27 (m, 6H), 0.87 (t, J = 6.8Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ (ppm): 204.2, 191.3, 164.9, 132.8, 125.1,114.3, 55.7, 39.0, 31.6, 29.0, 23.0, 22.6, 14.1; HRMS (ESI) m / z C 15 H 20 NaO2 [M+Na] + Theoretical value: 271.1305, measured value: 271.1303.

[0169] Example 35

[0170] Synthesize 2-(4,5-dioxo-5-phenylpentyl)isoindoline-1,3-dione with the following structural formula.

[0171]

[0172] In this embodiment, equimolar amounts of 2-(5-phenylpent-4-yn-1-yl)isoindoline-1,3-dione were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 107.8 mg of a white solid 2-(4,5-dioxo-5-phenylpentyl)isoindoline-1,3-dione, with a yield of 67%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.00 (d, J = 7.6 Hz, 2H), 7.84-7.83 (m, 2H), 7.73-7.70 (m, 2H), 7.64 (t, J = 7.6 Hz, 1H), 7.51-7.47 (m, 2H), 3.82 (t, J = 6.4Hz, 2H), 2.99-2.96 (m, 2H), 2.13-2.09 (m, 2H); 13C NMR (100 MHz, CDCl3) d(ppm): 201.7, 191.8, 168.6, 134.7, 134.1, 132.2, 132.0, 130.3, 129.0, 123.4,37.1, 35.7, 22.1; HRMS (ESI) m / z C 19 H 15 NNaO4 [M+Na] + Theoretical value: 344.0893, measured value: 344.0897.

[0173] Example 36

[0174] Synthesize 2-(5,6-dioxo-6-phenylhexyl)isoindoline-1,3-dione with the following structural formula.

[0175]

[0176] In this embodiment, equimolar amounts of 2-(6-phenylhexyl-5-yn-1-yl)isoindoline-1,3-dione were used instead of 3-(phenylethynyl)oxazolidin-2-one used in Example 1. The other steps were the same as in Example 1, yielding 112.4 mg of a white solid 2-(6-(4-methoxyphenyl)-5,6-dioxohexyl)isoindoline-1,3-dione, with a yield of 67%. The spectral data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.97 (d, J = 7.6 Hz, 2H), 7.85-7.83 (m,2H), 7.72-7.70 (m, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.51-7.47 (m, 2H), 3.73 (t, J = 6.4 Hz, 2H), 2.97-2.93 (m, 2H), 1.78-1.77 (m, 4H); 13 C NMR (100 MHz, CDCl3) d (ppm): 202.7, 192.3, 168.5, 134.7, 134.1, 132.2, 132.0, 130.3,129.0, 123.4, 38.1, 37.6, 28.1, 20.2; HRMS (ESI) m / z C 20 H 17 NNaO4 [M+Na]+ Theoretical value: 358.1050, measured value: 358.1040.

[0177] Example 37

[0178]

[0179] This example demonstrates a gram-scale scale-up experiment of Example 19. The catalyst, acetonitrile, and H₂O₂ used in the experiment were all scaled up simultaneously. 2.22 g (10 mmol) of 1-methoxy-4-[2-(4-methylphenyl)ethynyl]benzene was dissolved in a round-bottom flask equipped with a magnetic stirrer and 30 mL of acetonitrile. Then, 152 mg (0.2 mmol) of tetradentate nitrogen-coordinated manganese catalyst A-2 was added. Next, 5.68 mL (50 mmol) of a 30% (w / w) aqueous solution of H₂O₂ was dissolved in 30 mL of acetonitrile and added dropwise to the reaction flask over 2 hours using a micro-injection pump. After the addition was complete, the reaction was stirred at room temperature for 60 minutes. After the reaction was complete, the resulting mixture was quenched with a saturated sodium sulfite aqueous solution to remove any remaining H₂O₂ and extracted with dichloromethane (3 × 100.0 mL). The organic layer was dried with anhydrous sodium sulfate and the solvent was removed by rotary evaporation. The solution was then separated by column chromatography to give 4.58 g of a yellow solid 1-(4-methoxyphenyl)-2-(p-tolyl)ethane-1,2-dione, with a yield of 90%.

Claims

1. A method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes, characterized in that: Using tetradentate nitrogen-coordinated manganese as a catalyst and H2O2 as an oxidant, the carbon-carbon triple bond of alkynes represented by formula I, I′, I" or I′" is catalytically oxidized to obtain 1,2-diketone compounds represented by formula II, II′, II" or II′; the reaction equations are as follows: In the formula, R 1 R 3 R represents a substituent on the benzene ring. 1 R 3 The group is independently selected from hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, C1-C4 alkyl ester of carboxylic acid, nitro, and amine protected by a protecting group, wherein the benzene ring has one or more identical or different R groups. 1 Or R 3 Substituents; R 2 Representing C1 to C 10 Alkyl groups, protecting groups protecting C1-C 10 Any one of alkylamine groups; the protecting group is selected from any one of tert-butyloxycarbonyl, benzyloxycarbonyl, fluorenyloxycarbonyl, phthalimide, and acetyl; M represents O or CH2; R represents hydrogen or phenyl; The aforementioned four-toothed nitrogen-coordinated manganese is any one of formula A or formula B: In formula A, X represents the coordinating anion Cl. - ,Br - I - OAc - OTf - Any one of them; in formula B, Y represents the uncoordinated anion ClO4. - NO3 - BF4 - PF6 - SbF6 - Any one of them, m=2, or Y represents SO4 2- m=1; in formula A or formula B Structural representation , Any one of them, Structural representation , , , , Any one of them, R 1 R 2 R 3 R 4 Each is represented independently by H, C1~C 10 Any one of alkyl, C1-C6 alkoxy, nitro, and silyl groups.

2. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 1, characterized in that: The tetradentate nitrogen-coordinated manganese is selected from any one of formulas A-1 to A-4: 。 3. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 1 or 2, characterized in that: The amount of the tetradentate nitrogen-coordinated manganese added is 0.1% to 5% of the molar amount of the alkyne.

4. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 3, characterized in that: The amount of the tetradentate nitrogen-coordinated manganese added is 1% to 3% of the molar amount of the alkyne.

5. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 1, characterized in that: The amount of H2O2 added is 1 to 10 times the molar amount of the alkyne.

6. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 5, characterized in that: The amount of H2O2 added is 4 to 6 times the molar amount of alkyne.

7. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 1, characterized in that: The reaction conditions for the catalytic oxidation are 20–60°C for 0.5–12 hours.

8. The method for preparing 1,2-diketone compounds by tetradentate nitrogen-coordinated manganese-catalyzed oxidation of alkynes according to claim 1, characterized in that: The solvent used in the method is any one of tert-butanol, acetonitrile, acetone, ethyl acetate, dichloromethane, and trifluoroethanol.

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