Halogenated hydrocarbons, process for their preparation and use

Abstract

The application discloses a kind of halogenated hydrocarbon and its preparation method and application, belong to chemical synthesis technology and application field, with the olefin containing R1, R2 Group as raw material, R1 Group is-H;R2 Group is one of-CON(CH3)2, -CONHC2H5, -CONC(CH3)3, join nitrobenzene tetrafluoroboric acid diazonium salt and halogen element sodium salt, under the condition of organic solvent, under visible light, in the presence of quantum dot catalyst, halogenated hydrocarbon is prepared;The halogenated hydrocarbon prepared in the application can be applied to the synthesis of natural product cinnamamide and antibacterial drug, and has great industrial application prospect.

Description

Technical Field

[0001] This application relates to a halohydrocarbon, its preparation method and application, belonging to the field of chemical synthesis technology and application. Background Technology

[0002] In recent years, visible light-induced organic reactions have developed into a friendly and powerful technique for organic synthesis utilizing abundant, safe, clean, and renewable light sources found in nature. Therefore, using visible light as a promoter to directly arylate unfunctionalized alkenes is particularly attractive. Furthermore, functionalized organohalides have been used in various reactions to prepare useful molecules. For example, in reaction with aqueous sodium hydroxide, chlorine atoms can be substituted with hydroxyl groups to generate the corresponding alcohols; in reaction with ammonia or amines, amine derivatives can be obtained. In medicinal chemistry, the introduction of halogen atoms can sometimes improve the properties of drug molecules, such as lipid solubility and metabolic stability.

[0003] Compounds with this structure containing halogenated hydrocarbons are often used as important starting materials in drug synthesis. Halogenated hydrocarbons can serve as starting materials for constructing drug molecular skeletons, and through further structural modifications and functional group transformations, drugs with specific pharmacological activities can be developed. The nitro group can be converted into an amino group through reduction reactions. The amino group is a very important functional group in organic synthesis and can participate in various reactions, such as reacting with acyl chlorides to form amides and reacting with halogenated hydrocarbons to form amine derivatives. Therefore, the nitro group in this compound can serve as a basis for further functional group transformations to synthesize more complex organic compounds.

[0004] Halogenation of alkenes has emerged as a valuable strategy for preparing these compounds in various literature reports, as it allows the introduction of halogen atoms and other functional groups into unsaturated carbon-carbon double bonds. Therefore, developing practical and environmentally friendly synthetic methods for ortho-functionalized organohalides is of great importance. Summary of the Invention

[0005] A first aspect of the present invention is to provide a novel structure of haloalkanes.

[0006] The technical solution adopted in this invention is as follows:

[0007] A halohydrocarbon, with the following structural formula:

[0008]

[0009] In the formula:

[0010] The R1 group is -H;

[0011] The R2 group is one of -CON(CH3)2, -CONHC2H5, and -CONC(CH3)3;

[0012] The X group is one of -F, -Cl, -Br, and -I.

[0013] Furthermore, the halohydrocarbon is selected from any one of the following compounds:

[0014] .

[0015] A halohydrocarbon, with the following structural formula:

[0016] .

[0017] A halohydrocarbon, with the following structural formula:

[0018] .

[0019] A second aspect of the present invention is to provide a method for preparing haloalkanes, comprising the following steps: using the compound shown in Formula 1 as a raw material, adding nitrobenzene tetrafluoroborate diazonium salt and sodium salt of a halogen element, and reacting in the presence of an organic solvent under visible light and in the presence of a quantum dot catalyst to obtain haloalkanes;

[0020]

[0021] In Formula 1: R1 group is -H; R2 group is one of -CON(CH3)2, -CONHC2H5, and -CONC(CH3)3.

[0022] This invention provides a simple and efficient method for synthesizing aryl halogenated hydrocarbons: using inexpensive and readily available raw materials, and under the action of quantum dot catalysts and the induction of visible light, halogenated hydrocarbons are synthesized using diazonium salt of nitrobenzene tetrafluoroborate, olefins containing R1 and R2 groups, and sodium salts of halogen elements.

[0023] The reaction equations involved are as follows:

[0024] .

[0025] In the formula: the R1 group is -H; the R2 group is one of -CON(CH3)2, -CONHC2H5, and -CONC(CH3)3; and the X group is one of -F, -Cl, -Br, and -I.

[0026] Furthermore, in the preparation method:

[0027] The visible light is any one of blue light, green light, or violet light.

[0028] The organic solvent is any one or more of acetonitrile, water, N,N-dimethylformamide, and dimethyl sulfoxide.

[0029] The quantum dot catalyst is selected from one of Ir(dtbpy)(ppy)2PF6, Ru(bpy)3(PF6)2, CuInS2 / ZnS QDs, and CuInS2QDs, with CuInS2 / ZnS QDs being particularly preferred. The amount of the quantum dot catalyst used is preferably 2-8 mol% of the total molar amount of the reactants.

[0030] A third aspect of the present invention is to provide a use for a halohydrocarbon.

[0031] The first application is the synthesis of cinnamamide, a natural product, from halogenated hydrocarbons. Cinnamamide and its derivatives are widely found in natural products and are among the most common and important structural units. These compounds often possess a variety of biological activities, such as protecting the nervous system from Alzheimer's disease, anticonvulsant, anticancer, antibacterial, antitrypanosomiasis, antituberculosis, anti-inflammatory, antiviral, antifungal, antimalarial, tyrosinase inhibitor, and insecticide.

[0032] The second application is in the synthesis of antibacterial drugs. The compounds prepared in this invention have significant inhibitory effects on Staphylococcus aureus and Escherichia coli.

[0033] The beneficial effects of this invention are as follows:

[0034] (1) This invention solves the difficulties of existing processes and provides a safe, green and simple method for preparing haloalkanes, which utilizes visible light-mediated and quantum dot catalysts to achieve rapid preparation.

[0035] (2) This invention utilizes low-cost substrates such as olefins, diazonium salts of nitrobenzene tetrafluoroborate, and sodium salts of halogen elements to synthesize high-value halogenated hydrocarbons under visible light conditions. It has the advantages of low cost, mild reaction conditions, short reaction time, and easy processing.

[0036] (3) The halohydrocarbons prepared by this invention can be used to synthesize natural products cinnamamide and antibacterial drugs, and have great industrial application prospects. Attached Figure Description

[0037] Figure 1 This is the full spectrum of the XPS spectrum of the quantum dot catalyst.

[0038] Figure 2 The Cu spectrum is shown in the XPS spectrum of the quantum dot catalyst.

[0039] Figure 3 The image shows the Zn spectrum in the XPS spectra of the quantum dot catalyst.

[0040] Figure 4 This is the S-spectrum in the XPS spectrum of the quantum dot catalyst.

[0041] Figure 5 The image shows the In spectrum in the XPS spectra of the quantum dot catalyst.

[0042] Figure 6 The image shows the infrared spectrum of the quantum dot catalyst. In the image, blue represents CuInS2 / ZnS, red represents CuInS2, and black represents GSH.

[0043] Figure 7 This is the UV spectrum of the quantum dot catalyst.

[0044] Figure 8 This is the energy band gap diagram of quantum dot catalysts.

[0045] Figure 9 The image shows the XRD pattern of the quantum dot catalyst.

[0046] Figure 10 Transmission electron microscopy of the amplified portion of the quantum dot catalyst before cycling.

[0047] Figure 11A This is a TEM image of the quantum dot catalyst before its recovery.

[0048] Figure 11B The size distribution of the quantum dot catalyst before recovery.

[0049] Figure 12A This is a TEM image of the quantum dot catalyst after recovery.

[0050] Figure 12B The size distribution of the quantum dot catalyst after recovery.

[0051] Figure 13 This is an illustration of the antibacterial activity of Staphylococcus aureus.

[0052] Figure 14 This is a diagram illustrating the antibacterial activity of Escherichia coli. Detailed Implementation

[0053] The following detailed description of specific embodiments of the present invention, in conjunction with the accompanying drawings, does not limit the scope of the claims. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present invention are all prior art or commercially available products.

[0054] In the following embodiments of the present invention, the quantum dot catalyst was prepared by the following method: 0.2 mmol Cu(NO3)2·3H2O, 0.4 mmol In(NO3)3·4H2O, 0.2 mmol thiourea, and 2 mmol GSH were dissolved in deionized water and mixed. Subsequently, 1.0 mol / L sodium hydroxide was added to the above mixed solution to adjust the pH to 10.0. The solution became clear and transparent. The mixture was stirred for 5 min, and then sealed in a 25 mL polytetrafluoroethylene-lined stainless steel autoclave and heated at 110 °C for 40 min. After cooling to room temperature, the prepared shell solution (0.2 mmol Zn(Ac)2·2H2O, 0.1 mmol thiourea, 0.4 mmol GSH) was added to a hydrothermal reactor containing the core solution, sonicated for 5 min, and heated at 110 °C for 1 h. After cooling to room temperature, an aqueous solution of CuInS2 / ZnS quantum dots was obtained. Centrifugation yielded reddish-brown CuInS2 / ZnS quantum dots. The precipitate was washed three times with ethanol and water. The product was dried in a vacuum oven to obtain CuInS2 / ZnS quantum dot powder.

[0055] The structure of quantum dot catalysts has been confirmed:

[0056] according to Figures 1-6 XPS spectral analysis of quantum dot catalysts: Figure 1 The characteristic peaks of Cu 2p, In 3d, S 2p, and Zn 2p appear in the broad spectrum of CuInS2 / ZnS quantum dots, indicating that these elements are present in GSH-terminated CuInS2 / ZnS quantum dots. From Figure 2 As can be seen, the Cu 2p spectrum has two peaks at 951.2 eV and 931.4 eV, corresponding to Cu + Cu 2p state 1 / 2 and Cu 2p 3 / 2 The binding energy of Cu. Furthermore, Cu typically has a binding energy at 942 eV. 2+ The characteristic peaks did not appear in the spectrum. Figure 3 Display Zn 2p 1 / 2 The binding energy is 1044.3 eV, while Zn 2p 3 / 2 The binding energy is 1021.3 eV, which is similar to that of Zn. 2+ The binding energy is consistent. For example... Figure 4 As shown, S 2p 1 / 2 The binding energy is 163.1 eV, while S 2p 3 / 2 The binding energy is 160.9 eV, which is similar to S. 2− The binding energy is consistent. Furthermore, the high-resolution spectrum of In 3d (…) Figure 5 The graph shows two peaks with binding energies of 451.6 eV and 444.2 eV, corresponding to In, respectively.3+ 3D 3 / 2 and In 3+ 3D 5 / 2 This indicates that the In element in the composite is in the +3 state. Therefore, the valence state of the CuInS2 / ZnS quantum dots is Cu. + In 3+ S 2− and Zn 2+ Furthermore, Fourier transform infrared (FT-IR) spectroscopy revealed the composition of the newly synthesized GSH-terminated CuInS2 / ZnS quantum dots. Figure 6 ). 1617 cm -1 The presence of carboxyl stretching vibrations confirms that the CuInS2 / ZnS quantum dot surface is covered by the stabilizer MPA. GSH at 3124 cm⁻¹ -1 and 3026 cm -1 The absorption peak at 2510 cm⁻¹ corresponds to the NH stretching vibration. -1 1617 cm -1 and 1530 cm -1 The characteristic bands at these locations correspond to the stretching vibrations of the -SH group, the stretching vibration of the CO bond, and the torsional vibration of the NH bond in the amide group, respectively. Compared with pure GSH, the -SH vibrations of the GSH ligand on the CuInS2 / ZnS quantum dot surface are more pronounced at 2510 cm⁻¹. -1 The disappearance of the NH twisting vibration band and the weakening of the NH twisting vibration band clearly indicate that GSH has been deprotonated and bound to the quantum dot surface through SH and NHR groups.

[0057] according to Figures 7-12B UV / PL spectral analysis: CuInS2 / ZnS quantum dots exhibit a typical absorption band edge at 405 nm and a distinct first exciton peak at 500 nm. PL spectra show that the quantum dots have a peak at 650 nm with a full width at half maximum (FWHM) of 100 nm and no defect state peaks, indicating good ZnS shell encapsulation and no obvious defects on the quantum dot surface, resulting in a high photogenerated carrier recombination rate. The coordination of CuInS2 and ZnS significantly improves the transport and separation of interfacial charges and suppresses the electron-hole recombination rate. This is crucial for improving efficiency. Furthermore, based on the UV spectra, the band gap energy of CuInS2 / ZnS quantum dots was calculated using the Tauc-plot formula to be approximately 3.61 eV. Figure 8 The results are close to those reported in the literature. This indicates that CuInS2 / ZnS quantum dots can be used as visible light photocatalysts. The separation and transfer efficiency of the photogenerated support in the photocatalyst is a key factor affecting its catalytic performance. The crystal structure, morphology, composition, and size of CuInS2 / ZnS quantum dots were analyzed using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Figure 9X-ray diffraction of CuInS2 / ZnS quantum dots prepared under optimal experimental conditions is shown. Pure CuInS2 exhibits characteristic diffraction peaks at 27.89 °, 46.28 °, and 55.07 °, corresponding to the 112, 220, and 215 crystal planes, respectively (JCPDS No. 38-0777). No other impurity peaks were found in the CuInS2 / ZnS quantum dot sample, indicating good bonding between the two materials. Although no additional peaks were observed, these peaks are expected to appear in the 2q phase of ZnS. 1 / 4 At 29.33, 48.80, and 57.61 (JCPDS No. 05-0566), this clearly indicates that these quantum dots are not a mixture of CuInS2 and ZnS. Instead, some Zn... 2+ Ions diffuse into the CuInS2 nanocrystal structure, leading to an increase in its width and deformation. High-resolution transmission electron microscopy image ( Figure 10 , Figure 11A , Figure 11B , Figure 12A , Figure 12B These images were used to characterize the crystal structure and morphology of quantum dots. Figure 10 The image shows the clear lattice plane of CuInS2 / ZnS quantum dots with a lattice spacing of 4.2 Å. Figure 11A , Figure 11B As shown, these nanocrystals exhibit a narrow size distribution. The CuInS2 / ZnS quantum dots have an average particle size of approximately 2.5 nm, with uniform particle size distribution and clear lattice fringes. From Figure 12A , Figure 12B It can be seen that the size and distribution of CuInS2 / ZnS quantum dots did not change significantly after recycling and remained well dispersed. The size of some quantum dots increased, which may be due to the shedding of some ligands from the quantum dot surface after cycling.

[0058] Example 1

[0059] DMSO (0.2 mL), water (0.4 mL), and acetonitrile (1.4 mL) were added to a 4 mL transparent glass bottle equipped with a magnetic stir bar and a rubber stopper. Then, 4-nitrobenzenetetrafluoroborate diazonium salt (0.2 mmol), N-isopropylacrylamide (0.1 mmol), and sodium chloride (0.5 mmol), along with the quantum dot catalyst CuInS2 / ZnS (3 mg), were added to the bottle. The reaction mixture was reacted at room temperature under a 3 W blue LED (420 nm) for 5 hours. After the reaction (monitored by TLC), the solid was centrifuged, and the organic layer was concentrated. The crude mixture was dried over silica gel (eluted with EA:PE = 1:10), anhydrous sodium sulfate, concentrated under reduced pressure, and purified to obtain the product in 85% yield.

[0060] Product confirmation:

[0061] Compound name: 2-chloro-N-isopropyl-3-(4-nitrophenyl)propionamide.

[0062] The structural formula is:

[0063]

[0064] Product characterization:

[0065] 1 H NMR (400 MHz, Chloroform- d ) δ 8.23 ​​– 8.17 (m, 2H), 7.49 – 7.43 (m,2H), 6.32 (d, J = 7.8 Hz, 1H), 4.60 (dd, J = 7.3, 4.3 Hz, 1H), 4.07 (dp, J = 8.0, 6.6 Hz, 1H), 3.54 (dd, J = 14.2, 4.3 Hz, 1H), 3.43 (dd, J = 14.2, 7.4 Hz, 1H), 1.18 (d, J = 6.6 Hz, 3H), 1.12 (d, J = 6.6 Hz, 3H);

[0066] 13 C NMR (101 MHz, Chloroform- d ) δ 166.29, 147.29, 143.73, 130.84, 123.53, 60.45, 42.30, 40.77, 22.48, 22.42.

[0067] Replacement example

[0068] This example mainly examines the effects of different reaction conditions on the synthesis of haloalkanes.

[0069] The method of Example 1 differs in that the type of reaction catalyst, the type of organic solvent, the type of visible light, the reaction time, etc., are adjusted, and their effects on the reaction are tested, as shown in Table 1.

[0070] Table 1

[0071] .

[0072] In Table 1: the solvent ratio is a volume ratio.

[0073] As shown in Table 1, in the synthesis of haloalkanes, the highest yield of the product was obtained when the reaction time was 5 hours, the reaction system used blue light (3 W) as visible light, CuInS2 / ZnS QDs as catalyst, CH3CN, H2O, and DMSO as solvents, and CH3CN:H2O:DMSO=7:2:1, with a yield of 85%.

[0074] Catalyst cycling experiment

[0075] According to the method of Example 1, the reusability of the catalyst was tested by reaction: after the reaction was completed, the CuInS2 / ZnS quantum dot photocatalyst was recovered by centrifugation, thoroughly cleaned and dried with ethanol / water, and then used to be put back into the reaction to test the cycle performance of the catalyst. The results are shown in Table 2.

[0076] Table 2

[0077] Loop count Yield (%) 1 85 2 84 3 81 4 81 5 79

[0078] As shown in Table 2, the product yield was 79% at the end of the fifth catalytic operation, and the catalytic activity did not decrease significantly. Therefore, it can be seen that the catalyst has good recycling performance and can be applied to industrial production.

[0079] Example 2

[0080] Replacing N-isopropylacrylamide (0.1 mmol) with N-ethylacrylamide (0.1 mmol), and following the same conditions and procedures as in Example 1, yielded the product: 2-chloro-N-ethyl-3-(4-nitrophenyl)propionamide, with a yield of 80%.

[0081] Product confirmation:

[0082] Compound name: 2-chloro-N-ethyl-3-(4-nitrophenyl)propionamide.

[0083] The structural formula is:

[0084]

[0085] Product characterization:

[0086] 1 H NMR (400 MHz, Chloroform- d ) δ 8.24 – 8.16 (m, 2H), 7.48 – 7.42 (m,2H), 6.54 (s, 1H), 4.62 (dd, J = 7.5, 4.3 Hz, 1H), 3.56 (dd, J= 14.3, 4.3 Hz, 1H), 3.41 (dd, J = 14.3, 7.6 Hz, 1H), 3.33 (qd, J = 7.2, 5.6 Hz, 2H), 1.14 (t, J =7.3 Hz, 3H);

[0087] 13 C NMR (101 MHz, Chloroform- d ) δ 167.14, 147.30, 143.76, 130.79, 123.56, 60.51, 40.81, 35.07, 14.56.

[0088] Example 3

[0089] By replacing N-isopropylacrylamide (0.1 mmol) with N,N-dimethylacrylamide (0.1 mmol) and following the same conditions and procedures as in Example 1, the product 2-chloro-N,N-dimethyl-3-(4-nitrophenyl)propionamide was obtained in 80% yield.

[0090] Product confirmation:

[0091] Compound name: 2-chloro-N,N-dimethyl-3-(4-nitrophenyl)propionamide.

[0092] The structural formula is:

[0093]

[0094] Product characterization:

[0095] 1 H NMR (400 MHz, Chloroform- d ) δ 8.18 (dd, J = 8.7, 2.0 Hz, 2H), 7.47(d, J = 8.4 Hz, 2H), 4.63 (t, J = 7.2 Hz, 1H), 3.59 (ddd, J = 14.1, 7.1, 1.5 Hz,1H), 3.31 (dd, J = 14.0, 7.3 Hz, 1H), 3.08 (d, J = 0.8 Hz, 3H), 3.00 (d, J = 1.3Hz, 3H);

[0096] 13 C NMR (101 MHz, Chloroform- d ) δ 167.36, 147.13, 144.71, 130.64, 123.74, 53.40, 40.27, 37.35, 36.32.

[0097] Example 4

[0098] Replacing N-isopropylacrylamide (0.1 mmol) with N-tert-butylacrylamide (0.1 mmol), and following the same conditions and procedures as in Example 1, yielded 2-chloro-N-(tert-butyl)-3-(4-nitrophenyl)propionamide in 82% yield.

[0099] Product confirmation:

[0100] Compound name: 2-chloro-N-(tert-butyl)-3-(4-nitrophenyl)propionamide.

[0101] The structural formula is:

[0102]

[0103] Product characterization:

[0104] 1 H NMR (400 MHz, Chloroform- d ) δ 8.24 – 8.16 (m, 2H), 7.50 – 7.42 (m,2H), 6.33 (s, 1H), 4.53 (dd, J = 7.0, 4.6 Hz, 1H), 3.47 (qd, J = 14.2, 5.8 Hz, 2H), 1.35 (s, 9H);

[0105] 13 C NMR (101 MHz, Chloroform- d ) δ 166.28, 147.28, 143.80, 130.91, 123.51, 60.64, 52.01, 40.70, 28.42.

[0106] Example 5

[0107] Sodium bromide (0.5 mmol) was used instead of sodium chloride (0.5 mmol), and other conditions and procedures were the same as in Example 1, to obtain the product 2-bromo-N-isopropyl-3-(4-nitrophenyl)propionamide in 82% yield.

[0108] Product confirmation:

[0109] Compound name: 2-bromo-N-isopropyl-3-(4-nitrophenyl)propionamide.

[0110] The structural formula is:

[0111]

[0112] Product characterization:

[0113] 1 H NMR (400 MHz, Chloroform- d ) δ 8.24 – 8.16 (m, 2H), 7.52 – 7.39 (m,2H), 6.23 – 6.05 (m, 1H), 4.54 (dd, J = 7.5, 5.3 Hz, 1H), 4.06 (dp, J = 7.8, 6.5Hz, 1H), 3.65 (dd, J = 14.4, 5.3 Hz, 1H), 3.47 (dd, J = 14.4, 7.5 Hz, 1H), 1.16(dd, J = 6.6, 5.0 Hz, 6H);

[0114] 13 C NMR (101 MHz, Chloroform- d ) δ 166.18, 147.27, 144.50, 130.59,123.62, 50.62, 42.56, 41.09, 22.43, 22.36.

[0115] Example 6

[0116] Sodium iodide (0.5 mmol) was used instead of sodium chloride (0.5 mmol), and other conditions and procedures were the same as in Example 1, to obtain the product 2-iodo-N-isopropyl-3-(4-nitrophenyl)propionamide in 80% yield.

[0117] Product confirmation:

[0118] Compound name: 2-iodo-N-isopropyl-3-(4-nitrophenyl)propionamide.

[0119] The structural formula is:

[0120]

[0121] Product characterization:

[0122] 1 H NMR (400 MHz, Chloroform- d ) δ 8.20 – 8.12 (m, 2H), 7.42 – 7.37 (m,2H), 5.56 (d, J = 7.3 Hz, 1H), 4.37 (dd, J = 7.8, 7.0 Hz, 1H), 4.02 (dp, J = 7.7, 6.5 Hz, 1H), 3.63 (dd, J = 14.2, 7.9 Hz, 1H), 3.35 (dd, J = 14.2, 7.0 Hz, 1H), 1.12 (d, J = 6.6 Hz, 3H), 1.07 (d, J = 6.6 Hz, 3H);

[0123] 13 C NMR (101 MHz, Chloroform- d ) δ 167.92, 147.11, 146.19, 130.14,123.84, 42.44, 42.28, 24.51, 22.57, 21.90.

[0124] Example 7

[0125] By replacing 4-nitrobenzenetetrafluoroborate diazonium salt (0.2 mmol) with 2-nitrobenzenetetrafluoroborate diazonium salt (0.2 mmol), and with other conditions and procedures the same as in Example 1, the product 2-chloro-N-isopropyl-3-(2-nitrophenyl)propionamide was obtained in a yield of 49%.

[0126] Product confirmation:

[0127] Compound name: 2-chloro-N-isopropyl-3-(2-nitrophenyl)propionamide.

[0128] The structural formula is:

[0129]

[0130] Product characterization:

[0131] 1 H NMR (400 MHz, Chloroform- d) δ 8.06 – 7.97 (m, 1H), 7.64 – 7.56 (m, 1H), 7.48 (t, J = 7.2 Hz, 2H), 6.15 (s, 1H), 4.63 (ddd, J = 8.7, 5.0, 1.3 Hz,1H), 4.20 – 3.99 (m, 1H), 3.92 (ddd, J = 14.3, 5.0, 1.3 Hz, 1H), 3.47 (ddd, J =14.2, 8.6, 1.3 Hz, 1H), 1.19 (ddd, J = 6.5, 5.1, 1.3 Hz, 7H);

[0132] 13 C NMR (101 MHz, Chloroform- d ) δ 166.75, 133.68, 133.08, 131.66, 128.48, 125.06, 59.78, 42.22, 38.24, 22.48.

[0133] Example 8

[0134] Replacing 0.2 mmol of 3-nitrophenyltetrafluoroborate diazonium salt with 0.2 mmol of 4-nitrophenyltetrafluoroborate diazonium salt, and following the same conditions and procedures as in Example 1, yielded 2-chloro-N-isopropyl-3-(3-nitrophenyl)propionamide in 55% yield.

[0135] Product confirmation:

[0136] Compound name: 2-chloro-N-isopropyl-3-(3-nitrophenyl)propionamide. Structural formula:

[0137]

[0138] Product characterization:

[0139] 1 H NMR (400 MHz, Chloroform- d ) δ 8.27 – 8.04 (m, 2H), 7.62 (d, J = 7.6Hz, 1H), 7.52 (dd, J = 9.1, 7.4 Hz, 1H), 6.32 (d, J= 7.9 Hz, 1H), 4.61 (dd, J =7.2, 4.4 Hz, 1H), 4.21 – 3.96 (m, J = 6.8 Hz, 1H), 3.53 (dd, J = 14.4, 4.4 Hz, 1H), 3.44 (dd, J = 14.4, 7.2 Hz, 1H), 1.14 (dd, J = 28.7, 6.6 Hz, 6H);

[0140] 13 C NMR (101 MHz, Chloroform- d ) δ 166.34, 148.23, 138.10, 136.17, 129.28, 124.77, 122.39, 60.58, 42.29, 40.61, 22.45, 22.41.

[0141] Application Example 1

[0142] This embodiment is mainly applied to the synthesis of the natural product cinnamamide and its derivatives.

[0143] In a 100 mL dry round-bottom flask, add sequentially: 2-chloro-N-isopropyl-3-(4-nitrophenyl)propionamide (2.7 g, 10 mmol), anhydrous ethanol (40 mL) as solvent, and potassium hydroxide (0.84 g, 15 mmol). Attach a reflux condenser to the flask and place it on a heated magnetic stirrer. Attach a drying tube to the top of the condenser to prevent moisture from entering. Turn on the stirrer and heat the reaction mixture to 80°C, and continue stirring at this temperature for 12 hours. During this time, the solution color gradually deepens. After 12 hours, stop heating and cool the reaction mixture to room temperature, then further cool it in an ice-water bath. Carefully add dilute hydrochloric acid to adjust the pH to neutral or weakly acidic to promote solid precipitation. Filter the precipitated solid using a Buchner funnel and wash it several times with a small amount of cold ethanol to obtain the product.

[0144] The reaction equation is as follows:

[0145] .

[0146] By eliminating halogenated products, we successfully synthesized derivatives of the natural product cinnamamide. The product of Experiment 1 was synthesized into a derivative of the natural product cinnamamide via halogen elimination. Cinnamamide and its derivatives are widely found in natural products and are among the most common and important structural units. These compounds often possess a variety of biological activities, such as protecting the nervous system from Alzheimer's disease, anticonvulsant, anticancer, antibacterial, antitrypanosomiasis, antituberculosis, anti-inflammatory, antiviral, antifungal, antimalarial, tyrosinase inhibitor, and insecticide effects. This demonstrates the synthetic application value of this reaction and showcases its potential.

[0147] Application Example 2

[0148] This embodiment mainly examines the antibacterial properties of the compound prepared in Example 1.

[0149] Using DMSO and water as solvents, solutions of the product obtained in Example 1 were prepared at concentrations of 5 mg / mL, 0.25 mg / mL, and 0.05 mg / mL. The inhibitory effects of these solutions on Staphylococcus aureus and Escherichia coli were tested using the plate count method.

[0150] Experimental methods:

[0151] Staphylococcus aureus and Escherichia coli were used as standard test strains, and the inhibition rate was determined by plate counting method. Taking Staphylococcus aureus as an example, the specific steps are as follows: Staphylococcus aureus was activated in advance to achieve an OD600 of 0.6-0.8, and then the bacterial suspension was diluted to an OD600 of 0.08 for later use. The test drug was serially diluted with sterile water to prepare solutions of 10 mg / mL, 0.5 mg / mL, and 0.1 mg / mL, respectively. 50 μL of each concentration of the above drug solution was mixed thoroughly with 50 μL of the prepared bacterial suspension in a sterile EP tube to achieve final effective concentrations of 5 mg / mL, 0.25 mg / mL, and 0.05 mg / mL, respectively. A blank control group was also set up. All mixtures were evenly spread on the surface of solid agar plates, and the plates were incubated upside down in a 37°C incubator overnight. After incubation, the colonies grown on the plates were counted, and the inhibition rate at different concentrations was calculated, as shown in Table 3.

[0152] Table 3: Antibacterial Properties

[0153] .

[0154] Combination Figure 13 , Figure 14As shown: The product obtained in Example 1 exhibited strong inhibitory effects against both Staphylococcus aureus and Escherichia coli, and its antibacterial activity was concentration-dependent. Specifically, the compound showed extremely significant antibacterial effects against Escherichia coli, achieving an inhibition rate of 88.40% at a low concentration of 0.05 mg / mL. The inhibition rate then steadily increased with increasing concentration, reaching 93.04% at 5.00 mg / mL. The compound also showed highly effective inhibitory effects against Staphylococcus aureus. At a concentration of 5.00 mg / mL, it completely inhibited bacterial growth, achieving an inhibition rate of 100%.

[0155] In summary, the product obtained in Example 1 is a substance with broad-spectrum and highly effective antibacterial activity against both Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli), and has excellent development and application potential.

[0156] Summarize:

[0157] This invention uses N-isopropylacrylamide as a bridging unit to achieve a three-component reaction of 4-nitrobenzenetetrafluoroborate diazonium salt and sodium salt of a halogen element to generate haloalkanes under visible light-induced quantum dot catalyst. The reaction conditions are mild, the raw materials are inexpensive and readily available, the operation process is simple, and the reaction has broad applicability. It can effectively produce haloalkanes without the need for complex substrate design. At the same time, since the compounds with haloalkanes as the core have high pharmacological activity and antibacterial properties, it has strong practicality.

[0158] It is understood that the above detailed description of the present invention is for illustrative purposes only and is not intended to limit the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effects; as long as the usage requirements are met, they are all within the protection scope of the present invention.

Claims

1. A halogenated hydrocarbon characterized in that The halogenated hydrocarbon has the following structural formula: 。 2. A halogenated hydrocarbon characterized in that The halogenated hydrocarbon has the following structural formula: 。 3. A process for the preparation of a halogenated hydrocarbon, characterized in that The method comprises the following steps: The compound shown in formula 1 is used as a raw material, nitrobenzene tetrafluoroboric acid diazonium salt and halogen element sodium salt are added, and the reaction is carried out under the condition of an organic solvent, under visible light and in the presence of a quantum dot catalyst to obtain a halogenated hydrocarbon; ； The halogenated hydrocarbon has the following structural formula: ； In the formula, the R1 group is -H; the R2 group is one of -CON(CH3)2, -CONHC2H5 and -CONC(CH3)3; and the X group is one of -F, -Cl, -Br and -I. The visible light is any one of blue light, green light and purple light. The organic solvent is a mixed solvent of CH3CN, H2O and DMSO. The quantum dot catalyst is prepared by the following method: 0.2 mmol of Cu(NO3)2·3H2O, 0.4 mmol of In(NO3)3·4H2O, 0.2 mmol of thiourea and 2 mmol of GSH are dissolved in deionized water and mixed, then 1.0 mol / L of sodium hydroxide is added to the mixed solution to adjust the pH value of the solution to 10.0, the solution is clear and transparent, the mixture is stirred for 5 min, then the mixture is sealed in a 25 mL polytetrafluoroethylene-lined stainless steel autoclave, heated at 110℃ for 40 min, after cooling to room temperature, 0.2 mmol of Zn(Ac)2·2H2O, 0.1 mmol of thiourea and 0.4 mmol of GSH are added to the hydrothermal kettle of the core solution and ultrasonic for 5 min, and then heated at 110℃ for 1 h, after cooling to room temperature, a CuInS2 / ZnS quantum dot aqueous solution is obtained, and a red-brown CuInS2 / ZnS quantum dot is obtained by centrifugation.

4. The process of claim 3 wherein: The catalyst is used in an amount of 2-8 mol% of the total moles of the reactants.

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