Preparation method of trifluoromethylthio-oxime carbonate bifunctional reagent and application of trifluoromethylthio-oxime carbonate bifunctional reagent in olefin

Abstract

The invention provides a novel preparation method of a trifluoromethylthio-oxime carbonate bifunctional reagent. The trifluoromethylthio-oxime carbonate bifunctional reagent is used for preparing a trifluoromethylthio-oxime carbonate bifunctional reagent; the bifunctional reagent and olefin are utilized for the first time, and three different strategies are developed to synthesize the trifluoromethylthio-containing amine compound: direct o-trifluoromethylthio amination of olefin, 1, 4-trifluoromethylthio amination of olefin formed by series connection of two different electrical olefins, and 1, 4-trifluoromethylthio amination of olefin combined with migration reaction of free radical 1, 4-cyano, so that the trifluoromethylthio-containing amine compound is synthesized. And carrying out 2, 3, 5-trifluoromethylthiolation and amination. In addition, a halogen atom extraction strategy is further utilized, and trifluoromethylthiolation halogenation of olefin is achieved. The invention also provides amino-acid ester and amino-nitrile compounds containing SCF3 structural fragments, which cannot be obtained previously and have structural diversity, and the compounds are expected to provide more candidate molecules for developing trifluoromethylthio-containing drugs.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic compound synthesis, and relates to the preparation of a new trifluoromethylthio-carbonate oxime ester bifunctional reagent; and for the first time, a series of important trifluoromethylthio-containing amine compounds and halogenated hydrocarbon compounds are synthesized by using this bifunctional reagent and olefins as reaction objects through methods such as light irradiation. Background Art

[0002] Developing selective and general fluorination strategies has always been the direction of synthetic organic chemistry research. Due to the unique physical and chemical properties of fluorinated organic compounds, they have become important targets in drug and agrochemical discovery work (ACS Omega 2020, 5, 10633 - 10640). In addition to its metabolic stability and electron-withdrawing properties (σ p = 0.50), the trifluoromethylthio (SCF3) group also has a relatively high Hansch hydrophobic parameter (π = 1.44), which has attracted much attention from organic chemists. Its lipophilicity far exceeds that of CF3 (π = 0.88), OCF3 (π = 1.04), etc. (J. Med. Chem. 1973, 16(11), 1207–1216). Therefore, the introduction of the SCF3 structural fragment has attracted great interest in drug and pesticide design.

[0003] Currently, the introduction of the SCF3 fragment into organic molecules by trifluoromethylthiolation reagents provides a strong guarantee for its development. For example, AgSCF3, PhSO2SCF3, PhthNSCF3, saccharine-SCF3, etc. (Acc. Chem. Res. 2015, 48, 1227 - 1236). Among them, the introduction strategies of trifluoromethylthio mainly include -SCF3 and +SCF3 involving nucleophilic and electrophilic ionic methods, and ·SCF3 participating in radical schemes by single electron transfer (SET) (Synthesis 2025, 57(03), 539 - 570). By using these reagents and corresponding introduction methods, the O-H bond of alcohols (Angew. Chem. Int. Ed. 2014, 53, 9316–9320), the Csp 2 -H bond of (hetero)arenes (ACS Sustainable Chem. Eng. 2022, 10, 6889 - 6899), the Csp of alkanes 3-H bond (Nat. Commun. 2019, 10, 4867), trifluoromethylthiolation reactions of alkenes / alkynes and unsaturated carbon-carbon bonds (Angew. Chem. Int. Ed. 2019, 58, 18508 - 18512). Despite great achievements, there are still many drawbacks to these reagents. For example, most reagents are very expensive, have low atom economy, limited initiation methods, and especially lack difunctionalized alkene trifluoromethylthiolation reagents.

[0004] The difunctionalization reaction of alkenes mediated by difunctional reagents is achieved by sequentially or synchronously transferring two different functional groups from the same reagent to the C=C double bond, thus providing an efficient and diverse synthetic strategy for the transformation of alkenes (Nat. Rev. Chem. 2021, 5, 301 - 321). This strategy has received increasing attention due to its advantages such as simple operation, good waste stream inhibition, and precise synthesis. Without a doubt, the design of difunctional reagents and the exploration of related initiation methods are the keys to further developing such elegant reactions. Utilizing the unique reactivity and regioselectivity of radicals, as well as the mild and controllable radical initiation method promoted by visible light catalysis, many radical difunctional reagents have been developed and successfully applied to the difunctionalization reaction of alkenes. However, there is less research on the synthesis of difunctional reagents involving fluorine-containing groups, especially those containing trifluoromethylthiol groups. Therefore, the development of novel trifluoromethylthiolation reagents with difunctional properties and their new initiation methods is of positive significance for the synthesis of bioactive molecules containing both trifluoromethylthiol and other important functional groups and for the late-stage modification of related drugs containing an alkene moiety.

[0005] In recent years, the photoenergy transfer strategy of difunctional reagents based on benzophenone imine groups represents an extraordinary model for the difunctionalization of alkenes involving neutral radical pairs. This mode provides important alkene amino-functionalization reactions, such as oxyamination (Angew. Chem. Int. Ed. 2021, 60, 21997 - 22003), diamination (Nat. Catal. 2022, 5, 1120 - 1130), carbamination (Angew. Chem. Int. Ed. 2020, 59, 3172 - 3177), sulfonylation amination (J. Am. Chem. Soc. 2023, 145, 2364 - 2374), and dihalogenation (Nat. Synth. 2023, 2(5), 439 - 447), etc., by adding highly reactive radicals to alkenes and subsequently capturing carbon radicals through persistent imine radicals. Inspired by these works and our previous work, we designed and synthesized a trifluoromethylthio-carbonyl oxime ester difunctional reagent as a difunctional reagent for the trifluoromethylthiolation amination of alkenes. At the same time, this reagent can also be effectively applied to the trifluoromethylthiolation halogenation reaction of alkenes. Summary of the Invention

[0006] The object of the present invention is to provide a new method for synthesizing trifluoromethylthio-carbonyl oxime ester with safe and reliable operation on a large scale; and for the first time, applying this bifunctional reagent to trifluoromethylthiolation amination of olefins and trifluoromethylthiolation halogenation of olefins.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] In the first aspect of the present invention, a trifluoromethylthio-phosphonium salt is obtained by a continuous deoxidation reaction of a deoxidizing agent and an additive with trifluoromethanesulfonic anhydride, and then reacted with chloroformate oxime ester to obtain a new trifluoromethylthio-carbonyl oxime ester bifunctional reagent, which is characterized in that the reaction equation is as follows:

[0009]

[0010] Wherein, R 1 and R 2 are para-chloro or unsubstituted aryl and alkyl groups.

[0011] This method includes the following steps:

[0012] According to the molar ratio of chloroformate oxime ester, deoxidizing agent, additive and trifluoromethanesulfonic anhydride being (1):(2 - 5):(2 - 5):(1 - 5), add chloroformate oxime ester into solvent-1, and slowly add the deoxidizing agent, additive and trifluoromethanesulfonic anhydride under the condition of -20 to 80°C. After reacting for half an hour, move the reaction mixture to room temperature. After the reaction ends, perform post-treatment on the reaction mixture, and separate by column chromatography to obtain the target compound trifluoromethylthio-carbonyl oxime ester.

[0013] Further, the reaction solvent-1 is any one or a mixture in any proportion of tetrahydrofuran, diethyl ether, dichloromethane, acetonitrile, benzonitrile, chlorobenzene, dichloromethane, 1,2-dichloroethane, chloroform, ethyl acetate, n-butyl acetate, dioxane, methanol, ethanol, N,N-dimethylformamide, and preferably dichloromethane.

[0014] Further, the deoxidizing agent is any one of diethylphenylphosphine, methyldiphenylphosphine, tert-butyldiphenylphosphine, benzyldiphenylphosphine, triphenylphosphine, and preferably triphenylphosphine.

[0015] Further, the additive is any one of tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium fluoride, tetramethylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraheptylammonium bromide, and preferably tetrabutylammonium bromide.

[0016] Further, the reaction temperature-1 is -20 to 80°C, and preferably 0°C.

[0017] Furthermore, the reaction time is 12 to 48 hours, preferably 24 hours.

[0018] In the second aspect of the present invention, the method for preparing the amine compound containing trifluoromethylthio is characterized in that the reaction equation is as follows:

[0019]

[0020] This method comprises the following steps:

[0021] Load a magnetic stir bar into a reaction tube. According to the synthetic route, add a difunctional reagent, olefin-1, olefin-2 photosensitizer, and solvent-2 into the reaction tube, then seal it, displace the inert gas, stir and react at -10 to 60 °C. After irradiating with a blue light lamp for a certain time until the raw materials are consumed, purify the product through post-treatment.

[0022] In the above synthetic route, when R 5 , R 6 is H, R 3 , R 4 is n-butyl, phenethyl, phenyl, substituted phenyl, pyridyl, thienyl, naphthyl, amido, alkoxy, ester group, acyl group, amido, phosphonyl, azide, aldehyde group, cyano group, or silyl group; when R 5 or R 6 is an alkyl group, R 3 , R 4 is an alkyl group, phenyl group, or piperidinyl group.

[0023] Furthermore, the molar ratio of the difunctional reagent A, olefin-1, and Michael acceptor is (1 to 3):(1 to 3):(0 to 4), preferably 2:1:0 or 2:2:1.

[0024] Furthermore, the olefin-1 and olefin-2 are any one of electron-deficient olefins and electron-rich olefins.

[0025] Furthermore, the photosensitizer is any one of [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 4CzIPN, xanthone, and thioxanthone, preferably thioxanthone.

[0026] Furthermore, the dosage of the photosensitizer is 0.5 mol% to 5.0 mol% of the dosage of the difunctional reagent A, preferably 5.0 mol%.

[0027] Furthermore, the reaction solvent-2 is any one or a mixture of any proportions of tetrahydrofuran, dichloromethane, acetonitrile, dichloromethane, chloroform, ethyl acetate, dioxane, acetone, methanol, N,N-dimethylformamide, preferably acetone.

[0028] Further, the temperature -2 is -10 to 60 °C, preferably 25 °C (room temperature).

[0029] Further, the reaction time is 2 to 12 hours, preferably 3 hours.

[0030] Further, the inert gas is selected from any one of nitrogen and argon, preferably argon.

[0031] Further, the wavelength of the blue light lamp is 390 nm to 460 nm, preferably 405 nm.

[0032] Further, the power of the blue light lamp is 3 to 30 W, preferably 6 W.

[0033] In the third aspect of the present invention, there is provided a method for preparing the above-mentioned trifluoromethylthio halogenated hydrocarbon compound, which is characterized in that the reaction equation is as follows:

[0034]

[0035] In the above synthesis route, when R 5 , R 6 is H, R 3 , R 4 are n-butyl, phenethyl, phenyl, substituted phenyl, pyridyl, thienyl, naphthyl, amide group, alkoxy group, ester group, acyl group, amide group, phosphonyl group, azide group, aldehyde group, cyano group, silyl group; when R 5 or R 6 is an alkyl group, R 3 , R 4 are alkyl group, phenyl group, piperidyl group; X = Cl, Br, I.

[0036] The method comprises the following steps:

[0037] Place a magnetic stir bar in a reaction tube. According to the synthesis route, add the bifunctional reagent, olefin, photosensitizer, halogen source and solvent -3 into the reaction tube, seal it, displace the inert gas, stir and react at -10 to 60 °C, and irradiate with a blue light lamp for a certain time. After the raw materials are consumed, purify the product through post-treatment.

[0038] Further, the molar ratio of the bifunctional reagent A, olefin -1 and halogen source is (1 to 2):(1 to 2):(1 to 3), preferably 2:1:2.

[0039] Further, the halogen source is any one of carbon tetrachloride, carbon tetrabromide, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 2-iodopropane, tert-butyl iodide, trichloroisocyanuric acid, preferably N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide.

[0040] Further, the reaction solvent-3 is any one or a mixture of any proportions of tetrahydrofuran, dichloromethane, acetonitrile, dichloromethane, chloroform, ethyl acetate, dioxane, acetone, methanol, N,N-dimethylformamide, preferably acetonitrile.

[0041] Further, the temperature-2 is -10 to 60 °C, preferably 25 °C (room temperature).

[0042] Further, the reaction time is 2 to 12 hours, preferably 3 hours.

[0043] Further, the inert gas is selected from any one of nitrogen and argon, preferably argon.

[0044] Further, the wavelength of the blue light lamp is 390 nm to 460 nm, preferably 405 nm.

[0045] Further, the power of the blue light lamp is 3 to 30 W, preferably 6 W. Detailed implementation manners

[0046] The present invention will be further described in detail below in conjunction with specific embodiments. This detailed description should not be construed as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation manners of the present invention.

[0047] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and drugs, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention.

[0048] Without departing from the scope of the present invention, various improvements and changes can be made to the specific implementation manners of the specification of the present invention, which are obvious to those skilled in the art. Other implementation manners obtained from the specification of the present invention are easily achievable by those skilled in the art. The specification and embodiments of the present invention are merely exemplary.

[0049] Regarding the use of "including", "having", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0050] In the embodiments of the present invention, room temperature refers to "25 ± 5 °C".

[0051] All reactions were carried out in a dried glass reaction tube or round-bottom flask under magnetic stirring in an argon atmosphere. Unless otherwise stated, all reagents were purchased from commercial suppliers and used without further purification. All solvents were purified and dried according to standard methods before use. Organic solutions were concentrated under reduced pressure using a rotary evaporator or an oil pump. The reactions were monitored by thin-layer chromatography (TLC) on silica gel-coated glass plates. The chromatograms were visualized by quenching fluorescence with ultraviolet light at 254 nm. Flash column chromatography was performed using Qingdao Marine column chromatography silica gel (200 - 300 mesh). Nuclear magnetic resonance (NMR) spectra were recorded using deuterated chloroform (400 MHz NMR, internal standard Me4Si) or deuterated water (400 MHz NMR). The NMR data are shown below: 1 1H NMR chemical shifts (ppm), multiplicities (s = singlet; d = doublet; t = triplet; q = quartet; m = multiplet), coupling constants (Hz), and integrals. 13 13C NMR and 19 19F NMR data were reported as chemical shifts. HRMS measurements were performed using a Thermo Scientific Orbitrap Exploris 120 as the mass analyzer.

[0052] An embodiment of the present invention provides a new trifluoromethylthio-carbonate oxime ester bifunctional reagent, the structural general formula of which is:

[0053]

[0054] In the formula, R 1 and R 2 are p-chlorophenyl, phenyl, and methyl.

[0055] An embodiment of the present invention provides a preparation method of a new trifluoromethylthio-carbonate oxime ester bifunctional reagent. Using solvent-1 as the reaction solvent, a continuous deoxygenation reaction occurs between a deoxidizing agent and an additive with trifluoromethanesulfonic anhydride to obtain trifluoromethylthio-phosphonium salt, and then it reacts with chloroformate oxime ester to obtain the trifluoromethylthio-carbonate oxime ester bifunctional reagent.

[0056] In a preferred embodiment of the present invention, the molar ratio of chloroformate oxime ester, deoxidizing agent, additive, and trifluoromethanesulfonic anhydride is (1):(2 - 3):(2):(1 - 2), preferably (1):(3):(2):(2).

[0057] In a preferred embodiment of the present invention, the reaction solvent-1 is any one of tetrahydrofuran and dichloromethane, preferably dichloromethane.

[0058] In a preferred embodiment of the present invention, the deoxidizing agent is any one of methyldiphenylphosphine and triphenylphosphine, preferably triphenylphosphine.

[0059] In a preferred embodiment of the present invention, the additive is any one of tetrabutylammonium bromide and tetrabutylammonium bromide, preferably tetrabutylammonium bromide.

[0060] In a preferred embodiment of the present invention, the reaction temperature is 0 to 25 °C, preferably 0 °C.

[0061] The embodiment of the present invention also provides a trifluoromethylthioamine compound, and its structural general formula is:

[0062]

[0063] The embodiment of the present invention also provides a preparation method of a trifluoromethylthioamine compound. The difunctional reagent and olefin-1 are dissolved in an organic solvent, and irradiated with light at room temperature under the protection of an inert gas. The trifluoromethylthio-carbonooxime ester is formed through energy transfer of transient trifluoromethylthio radicals and persistent imine radicals. The newly generated trifluoromethylthio radicals are added to olefin-1, and the imine radicals are captured to form 1,2-trifluoromethylthiolated amination products; or the generated trifluoromethylthio radicals are added to olefin-1, and the newly formed carbon radicals attack the Michael acceptor, and the imine radicals are captured to form 1,4-trifluoromethylthiolated amination products; or the generated trifluoromethylthio radicals are added to olefin-1 and then undergo a 1,4-cyano migration, and the imine radicals are captured to form 1,5-trifluoromethylthiolated amination products.

[0064] In the formula, when R 5 , R 6 are H, R 3 , R 4 are phenethyl, phenyl, substituted phenyl, pyridyl, thienyl, naphthyl, amide group, alkoxy group, ester group, acyl group, amide group, phosphoryl group, azide group, aldehyde group, cyano group, silicon group; when R 5 or R 6 is an alkyl group, R 3 , R 4 are alkyl groups, phenyl groups.

[0065] In a preferred embodiment of the present invention, the molar ratio of the difunctional reagent A, olefin-1, and Michael acceptor is (1 to 2):1:(0 to 2), preferably 2:1:0 (for two-component reactions) or 2:2:1 (for three-component reactions).

[0066] In a preferred embodiment of the present invention, the olefin-1 is substituted or unsubstituted styrene, unsubstituted or alkyl, phenyl, acyl, amido, aldehyde, ester, amido, phosphonyl, azide, aldehyde-substituted unactivated olefin, electron-rich olefins such as methyldiphenylvinylsilane, vinyl n-butyl ether, vinyl benzoate, N-methylvinylacetamide, N-vinylpyrrolidone, etc., and any one of electron-deficient olefins such as dimethyl itaconate, N,N-dimethylacrylamide, α-methylene-γ-butyrolactone, acrylonitrile, ethyl acrylate, di-tert-butyl 2-methylenemalonate, etc.

[0067] In a preferred embodiment of the present invention, the Michael acceptor is any one of acrylonitrile, ethyl acrylate, and di-tert-butyl 2-methylenemalonate.

[0068] In a preferred embodiment of the present invention, the photosensitizer is any one of [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 and thioxanthone, preferably thioxanthone.

[0069] In a preferred embodiment of the present invention, the dosage of the photosensitizer is 1.0 mol% to 5.0 mol% of the dosage of the bifunctional reagent A, preferably 5.0 mol%.

[0070] In a preferred embodiment of the present invention, the reaction solvent-2 is any one of tetrahydrofuran and acetone, preferably acetone.

[0071] The embodiments of the present invention also provide a trifluoromethylthio halogenated hydrocarbon compound, and its structural general formula is:

[0072]

[0073] In the formula, R 5 , R 6 is H, R 3 , R 4 are amido, ester group, alkoxy group, benzenesulfonyl group, acyl group, phenyl group, m-methylphenyl group, 4-tert-butylphenyl group; X = Cl, Br, I.

[0074] The embodiments of the present invention also provide a preparation method of a trifluoromethylthio halogenated hydrocarbon compound. Dissolve the bifunctional reagent and olefin-1 in an organic solvent, and irradiate with light at room temperature under the protection of an inert gas. The bifunctional reagent generates a transient trifluoromethylthio radical and a persistent imine radical through energy transfer, and then undergoes the addition of the trifluoromethylthio radical to olefin-1 to generate a new carbon radical. Use a halogen source to capture this carbon radical to generate a trifluoromethylthiolated halogenated hydrocarbon compound.

[0075] In a preferred embodiment of the present invention, the halogen source is any one of carbon tetrachloride, N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide, preferably N-chlorosuccinimide, N-bromosuccinimide, or N-iodosuccinimide.

[0076] In a preferred embodiment of the present invention, the reaction solvent-3 is any one of acetonitrile and acetone, preferably acetonitrile.

[0077] In a preferred embodiment of the present invention, the molar ratio of the trifluoromethylthio-carbonooxime bifunctional reagent A, the olefin-1, and the halogen source is 2:1:(1-2), preferably 2:1:2.

[0078] In a preferred embodiment of the present invention, the inert gas is selected from any one of nitrogen and argon.

[0079] The technical solution of the present invention will be further described below by way of examples.

[0080] Example 1:

[0081] Preparation of benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime

[0082] The synthesis route is as follows:

[0083]

[0084] At 0 °C, the chloroformate oxime ester was added to dichloromethane, and then triphenylphosphine (150 mmol, 3 equiv.), tetrabutylammonium bromide (150 mmol, 3 equiv.), and trifluoromethanesulfonic anhydride (100 mmol, 2 equiv.) were slowly added to the dichloromethane solution of the chloroformate oxime ester. The reaction was stirred overnight at 0 °C. After 24 hours of reaction, the mixture was cooled to 0 °C for crystallization, and the triphenylphosphine oxide solid was removed by suction filtration. The product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime was obtained by purification through column chromatography (gradient elution with ethyl acetate and petroleum ether): white solid; 11.7 g; the yield was 70%; 1 H NMR (400 MHz, CDCl3): δ 7.54–7.47 (m, 6H), 7.44–7.40 (m, 2H), 7.36–7.34 (m, 2H); 13 C NMR (100.6 MHz, CDCl3) δ 164.31, 163.92 (q, J C-F = 3.0 Hz), 133.35, 131.81, 130.76, 130.59, 129.10, 129.03, 128.73, 128.48, 127.57 (q, J C-F = 308.8 Hz);19 19F NMR (376 MHz, CDCl3) δ -42.72.

[0085] Example 2:

[0086] Replace triphenylphosphine (150 mmol, 3 equiv.) in Example 1 with triphenylphosphine (100 mmol, 2 equiv.). The remaining procedures and conditions are the same as in Example 1. Purify the obtained product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 8.8 g; yield 54%.

[0087] Example 3:

[0088] Replace trifluoromethanesulfonic anhydride (100 mmol, 2 equiv.) in Example 1 with trifluoromethanesulfonic anhydride (50 mmol, 1 equiv.). The remaining procedures and conditions are the same as in Example 1. Purify the obtained product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 5.2 g; yield 32%.

[0089] Example 4:

[0090] Replace the temperature in Example 1 with 25 °C. The remaining procedures and conditions are the same as in Example 1. Purify the obtained product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 1.2 g; yield 7%.

[0091] Example 5:

[0092] Replace the solvent in Example 1 with tetrahydrofuran. The remaining procedures and conditions are the same as in Example 1. Purify the obtained product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 7.9 g; yield 48%.

[0093] Example 6:

[0094] Replace triphenylphosphine in Example 1 with methyldiphenylphosphine. The remaining procedures and conditions are the same as in Example 1. Purify the obtained product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 8.5 g; yield 52%.

[0095] Example 7:

[0096] Replace tetrabutylammonium bromide in Example 1 with tetramethylammonium bromide. The remaining procedures and conditions are the same as in Example 1. Purify the obtained product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 3.6 g; yield 22%.

[0097] Example 8:

[0098] Preparation of bis(4-chlorophenyl)methanone O-(((trifluoromethyl)thio)carbonyl)oxime

[0099]

[0100] The specific preparation process is the same as that of Example 1, except that benzophenone O-chlorocarbonyl oxime is replaced with bis(4-chlorophenyl)methanone oxime, and the purified product benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime: white solid; 13.3 g; the yield is 68%; 1 1H NMR (400 MHz, CDCl3): δ 7.51–7.37 (m, 6H), 7.29 (d, J = 8.3 Hz, 2H); 13 13C NMR (100.6 MHz, CDCl3) δ 163.47 (q, J C-F = 3.0 Hz), 162.34, 138.50, 137.20, 131.41, 130.47, 130.25, 129.20, 129.03, 128.57, 127.40 (q, J C-F = 308.8 Hz); 19 19F NMR (376 MHz, CDCl3) δ -42.52.

[0101] Example 9:

[0102] Preparation of 1-phenylethyl-1-one O-(((trifluoromethyl)thio)carbonyl)oxime

[0103]

[0104] The specific preparation process is the same as that of Example 1, except that benzophenone O-chlorocarbonyl oxime is replaced with (E)-1-phenylethane-1-one O-chlorocarbonyl oxime, and the purified product 1-phenylethyl-1-one O-(((trifluoromethyl)thio)carbonyl)oxime: colorless oily liquid; 8.7 g; the yield is 66%; 1 1H NMR (400 MHz, CDCl3): δ 7.72–7.67 (m, 2H), 7.55–7.49 (m, 1H), 7.49–7.43 (m, 2H), 2.45 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3) δ 164.05 (q, J C-F = 3.0 Hz), 162.72, 132.97, 131.57, 128.90, 127.59 (q, J C-F = 309.8 Hz), 126.87, 14.59; 19 19F NMR (376 MHz, CDCl3) δ -42.84.

[0105] Example 10:

[0106] Preparation of 1,1-diphenyl-N-(1-phenyl-2-((trifluoromethyl)thio)ethyl)methanimine

[0107]

[0108] The synthetic route is as follows:

[0109] In a 10 mL reaction tube dried in an oven equipped with a magnetic stir bar, styrene (0.3 mmol, 1.0 equiv.), thioxanthone (5 mol%), and the bifunctional reagent benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime (0.6 mmol, 2.0 equiv.) were added. The reaction tube was evacuated and backfilled with argon three times. Subsequently, 3 mL of acetone was added under argon protection. The reaction mixture was stirred under irradiation with a 6 W blue LED (λmax = 405 nm) at room temperature for 3 hours. Then the solution was concentrated under reduced pressure, and the crude product was purified by column chromatography (gradient elution with ethyl acetate and petroleum ether) to obtain 1,1-diphenyl-N-(1-phenyl-2-((trifluoromethyl)thio)ethyl)methanimine: colorless oily liquid; 0.088 g; yield 76%; Colorless oil; (0.088 g, 76%); 1 1H NMR (400 MHz, CDCl3): δ 7.70–7.68 (m, 2H), 7.42–7.24 (m, 11H), 7.04–7.02 (m, 2H), 4.62 (dd, J = 8.8, 4.4 Hz, 1H), 3.44 (dd, J = 12.8, 8.8 Hz, 1H), 3.27 (dd, J = 13.2, 4.8 Hz, 1H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.42, 142.48, 139.38, 136.38, 130.37, 131.16 (q, J C-F = 306.8 Hz), 128.76, 128.62, 128.61, 128.36, 128.07, 127.72, 127.63, 127.08, 65.36, 38.63; 19 19F NMR (376 MHz, CDCl3): δ -41.06 (s, 3F); ESI-HRMS: Calcd for C 22 H 19 F3NS + [M+H] + 386.1185, found 386.1181.

[0110] Example 11:

[0111] Replace the thioxanthone in Example 10 with [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, and the remaining procedures and conditions are the same as in Example 10. The purified product 1,1-diphenyl-N-(1-phenyl-2-((trifluoromethyl)thio)ethyl)methanimine: colorless oily liquid; 0.081 g; the yield is 70%.

[0112] Example 12:

[0113] Replace the thioxanthone (5 mol%) in Example 10 with thioxanthone (1 mol%), and the remaining procedures and conditions are the same as in Example 10. The purified product 1,1-diphenyl-N-(1-phenyl-2-((trifluoromethyl)thio)ethyl)methanimine: colorless oily liquid; 0.054 g; the yield is 47%.

[0114] Example 13:

[0115] Replace the bifunctional reagent benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime (0.6 mmol, 2.0 equiv.) in Example 10 with benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime (0.3 mmol, 1.0 equiv.), and the remaining procedures and conditions are the same as in Example 9. The purified product 1,1-diphenyl-N-(1-phenyl-2-((trifluoromethyl)thio)ethyl)methanimine: colorless oily liquid; 0.063 g; the yield is 54%.

[0116] Example 14:

[0117] Replace the acetone in Example 10 with acetonitrile, and the remaining procedures and conditions are the same as in Example 10. The purified product 1,1-diphenyl-N-(1-phenyl-2-((trifluoromethyl)thio)ethyl)methanimine: colorless oily liquid; 0.060 g; the yield is 47%.

[0118] Example 15:

[0119] Preparation of 4-(1-((dibenzylidene)amino)-2-((trifluoromethyl)thio)ethyl)phenyl acetate

[0120]

[0121] The specific preparation process is the same as in Example 10, except that the raw material styrene is replaced with 4-vinylphenyl acetate. The purified product 4-(1-((dibenzylidene)amino)-2-((trifluoromethyl)thio)ethyl)phenyl acetate: colorless oily liquid; 0.082 g; the yield is 62%; 11H NMR (400 MHz, CDCl3): δ 7.69–7.67 (m, 2H), 7.42–7.37 (m, 4H), 7.35–7.28 (m, 4H), 7.05–7.03 (m, 4H), 4.62 (dd, J = 8.8, 4.4 Hz, 1H), 3.42 (dd, J = 13.2, 8.8 Hz, 1H), 3.25 (dd, J = 13.2, 4.4 Hz, 1H), 2.28 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.61, 169.34, 149.99, 139.92, 139.22, 136.24, 131.10 (q, J C-F = 305.8 Hz), 130.44, 128.74, 128.65, 128.39, 128.06, 127.65, 121.68, 64.79, 38.57, 21.08; 19 19F NMR (376 MHz, CDCl3): δ -41.02 (s, 3F); ESI-HRMS: Calcd for C 24 H 21 F3NO2S + [M+H] + 444.1240, found 444.1235.

[0122] Example 16:

[0123] Preparation of N-[1-(4-tert-butylphenyl)-2-((trifluoromethyl)thio)ethyl]-1,1-diphenylmethanimine

[0124]

[0125] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 4-tert-butylstyrene; the purified product N-[1-(4-tert-butylphenyl)-2-((trifluoromethyl)thio)ethyl]-1,1-diphenylmethanimine: colorless oily liquid; 0.093 g; the yield is 70%; 1 1H NMR (400 MHz, CDCl3): δ 7.69–7.67 (m, 2H), 7.43–7.36 (m, 4H), 7.35–7.31 (m, 4H), 7.22–7.20 (m, 2H), 7.08–7.05 (m, 2H), 4.60 (dd, J = 8.8, 4.0 Hz, 1H), 3.45 (dd, J = 12.8, 8.8 Hz, 1H), 3.26 (dd, J = 12.8, 4.4 Hz, 1H), 1.30 (s, 9H); 1313C NMR (100.6 MHz, CDCl3): δ 169.06, 150.51, 139.48, 139.35, 136.42, 131.20 (q, J C-F = 305.8 Hz), 130.27, 128.75, 128.55, 128.32, 128.03, 127.84, 126.69, 125.50, 65.08, 38.53, 34.51, 31.34; 19 19F NMR (376 MHz, CDCl3): δ -41.05 (s, 3F); ESI-HRMS: Calcd for C 26 H 27 F3NS + [M + H] + 442.1811, found 442.1808.

[0126] Example 17:

[0127] Preparation of N-[1-(naphthalen-2-yl)-2-((trifluoromethyl)thio)ethyl]-1,1-diphenylmethanimine

[0128]

[0129] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 2-vinylnaphthalene, and the purified product N-[1-(naphthalen-2-yl)-2-((trifluoromethyl)thio)ethyl]-1,1-diphenylmethanimine: colorless oily liquid; 0.082 g; yield 63%; 1 1H NMR (400 MHz, CDCl3): δ 7.81–7.77 (m, 3H), 7.73–7.71 (m, 2H), 7.67 (s, 1H), 7.47–7.34 (m, 9H), 7.04–7.03 (m, 2H), 4.79 (dd, J = 8.8, 4.4 Hz, 1H), 3.52 (dd, J = 13.2, 8.8 Hz, 1H), 3.36 (dd, J = 13.0, 4.6 Hz, 1H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.82, 139.97, 139.44, 136.44, 133.43, 133.00, 131.2 (q, J C-F = 306.6 Hz), 130.48, 128.86, 128.72, 128.47, 128.43, 128.15, 128.01, 127.78, 127.72, 126.18, 125.98, 125.95, 125.04, 65.57, 38.65; 1919F NMR (376 MHz, CDCl3): δ -40.97 (s, 3F); ESI-HRMS: Calcd for C 26 H 21 F3NS + [M + H] + 436.1341, found 436.1340.

[0130] Example 18:

[0131] Preparation of 1,1-diphenyl-N-[1-(pyridin-2-yl)-2-((trifluoromethyl)thio)ethyl]methanimine

[0132]

[0133] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 2-vinylpyridine, and the purified product 1,1-diphenyl-N-[1-(pyridin-2-yl)-2-((trifluoromethyl)thio)ethyl]methanimine: colorless oily liquid; 0.070 g; yield 60%; 1 1H NMR (400 MHz, CDCl3): δ 8.56–8.54 (m, 1H), 7.73–7.71 (m, 2H), 7.65 (td, J = 8.0, 2.0 Hz, 1H), 7.44–7.41 (m, 4H), 7.38–7.34 (m, 3H), 7.20–7.16 (m, 1H), 7.10–7.07 (m, 2H), 4.87 (dd, J = 7.6, 4.8 Hz, 1H), 3.59 (dd, J = 12.8, 4.4 Hz, 1H), 3.49 (dd, J = 12.8, 7.6 Hz, 1H); 13 13C NMR (100.6 MHz, CDCl3): δ 170.66, 160.74, 149.26, 139.21, 136.66, 136.05, 131.15 (q, J C-F = 305.8 Hz), 130.58, 128.91, 128.80, 128.56, 128.11, 127.56, 122.51, 122.10, 66.22, 36.83; 19 19F NMR (376 MHz, CDCl3): δ -41.29 (s, 3F); ESI-HRMS: Calcd for C 21 H 18 F3N2S + [M + H] + 387.1137, found 387.1132.

[0134] Example 19:

[0135] Preparation of 1,1-diphenyl-N-[1-((trifluoromethyl)thio)methyl-2,3-dihydro-1H-inden-1-yl]methanimine

[0136]

[0137] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 1-methylene-2,3-dihydro-1H-indene, and the purified product 1,1-diphenyl-N-[1-((trifluoromethyl)thio)methyl-2,3-dihydro-1H-inden-1-yl]methanimine: colorless oily liquid; 0.070 g; the yield is 57%; 1 H NMR(400 MHz, CDCl3): δ 7.55–7.54(m, 2H), 7.38–7.34(m, 1H), 7.31–7.28(m, 3H), 7.20(t, J = 7.4 Hz, 1H), 7.14–7.10(m, 4H), 6.92–6.90(m, 1H), 6.72–6.70(m, 2H), 3.73(d, J = 11.6 Hz, 1H), 3.21(d, J = 11.2 Hz, 1H), 2.76–2.69(m, 1H), 2.34–2.19(m, 3H); 13 C NMR(100.6 MHz, CDCl3): δ 167.84, 147.16, 143.42, 140.92, 137.53, 131.76(q, J C-F = 305.8 Hz), 130.17, 128.41, 128.04, 127.95, 127.77, 127.61, 127.51, 126.55, 124.62, 124.49, 72.51, 45.03, 38.44, 29.85; 19 F NMR(376 MHz, CDCl3): δ -41.43(s, 3F); ESI-HRMS: Calcd for C 24 H 21 F3NS + [M + H] + 412.1341, found 412.1339.

[0138] Example 20:

[0139] Preparation of 1,1-diphenyl-N-[2-phenyl-1-((trifluoromethyl)thio)propan-2-yl]methanimine

[0140]

[0141] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with α-methylstyrene. The purified product 1,1-diphenyl-N-[2-phenyl-1-((trifluoromethyl)thio)propan-2-yl]methanimine: white solid; mp 94–95 °C; 0.070 g; the yield is 57%; White solid; mp 94–95 °C; (0.082 g, 68%); 1 1H NMR (400 MHz, CDCl3): δ 7.59–7.57 (m, 2H), 7.40–7.36 (m, 1H), 7.33–7.29 (m, 2H), 7.20–7.15 (m, 6H), 7.07 (t, J = 7.6 Hz, 2H), 6.57 (d, J = 6.8 Hz, 2H), 3.80 (d, J = 12.0 Hz, 1H), 3.23 (d, J = 11.6 Hz, 1H), 1.47 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 168.07, 146.84, 140.84, 137.98, 131.68 (q, J C-F = 305.8 Hz), 130.21, 128.42, 128.17, 127.98, 127.76, 127.67, 127.34, 127.06, 126.41, 63.13, 48.11, 23.73; 19 19F NMR (376 MHz, CDCl3): δ -41.23 (s, 3F); ESI-HRMS: Calcd for C 23 H 21 F3NS + [M + H] + 400.1341, found 400.1340.

[0142] Example 21:

[0143] Preparation of 1,1-diphenyl-N-[(1R*,2R*)-2-((trifluoromethyl)thio)-2,3-dihydro-1H-inden-1-yl]methanimine

[0144]

[0145] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 1H-indene. The purified product 1,1-diphenyl-N-[(1R*,2R*)-2-((trifluoromethyl)thio)-2,3-dihydro-1H-inden-1-yl]methanimine: white solid; mp 166–168 °C; 0.041 g; the yield is 34%; 11H NMR (400 MHz, CDCl3): δ 7.70–7.69 (m, 2H), 7.49–7.39 (m, 4H), 7.36–7.31 (m, 4H), 7.24–7.22 (m, 3H), 7.07–7.06 (m, 1H), 4.88 (d, J = 8.4 Hz, 1H), 4.21 (dd, J = 18.0, 8.4 Hz, 1H), 3.58 (dd, J = 16.0, 8.0 Hz, 1H), 3.04 (dd, J = 15.6, 10.0 Hz, 1H); 13 13C NMR (100.6 MHz, CDCl3): δ 171.14, 142.40, 140.33, 139.35, 136.20, 130.8 (q, J C-F = 306.8 Hz), 130.48, 128.91, 128.74, 128.65, 128.11, 128.03, 127.91, 127.24, 124.37, 123.82, 71.31, 50.47, 39.99; 19 19F NMR (376 MHz, CDCl3): δ -39.54 (s, 3F); ESI-HRMS: Calcd for C 23 H 19 F3NS + [M+H] + 398.1185, found 398.1181.

[0146] Example 22:

[0147] Preparation of dimethyl 2-((diphenylmethylene)amino)-2-(((trifluoromethyl)thio)methyl)succinate

[0148]

[0149] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by dimethyl itaconate, and the purified product dimethyl 2-((diphenylmethylene)amino)-2-(((trifluoromethyl)thio)methyl)succinate: colorless oily liquid; 0.073 g; the yield is 55%; 1 1H NMR (400 MHz, CDCl3): δ 7.51–7.49 (m, 2H), 7.44–7.37 (m, 4H), 7.32–7.28 (m, 2H), 7.17–7.15 (m, 2H), 3.86 (d, J = 12.8 Hz, 1H), 3.74 (d, J = 12.8 Hz, 1H), 3.64 (s, 3H), 3.25–3.22 (m, 4H), 3.04 (d, J = 16.0 Hz, 1H); 1313C NMR (100.6 MHz, CDCl3): δ 171.22, 170.27, 168.95, 139.75, 135.54, 131.03 (q, J C-F = 306.8 Hz), 130.81, 128.99, 128.66, 128.02, 66.78, 52.15, 51.72, 40.38, 37.61; 19 19F NMR (376 MHz, CDCl3): δ -41.44 (s, 3F); ESI-HRMS: Calcd for C 21 H 21 F3NO4S + [M + H] + 440.1138, found 440.1135.

[0150] Example 23:

[0151] Preparation of 2-((diphenylmethylene)amino)-N,N-dimethyl-3-((trifluoromethyl)thio)acrylamide

[0152]

[0153] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with N,N-dimethylacrylamide, and the purified product 2-((diphenylmethylene)amino)-N,N-dimethyl-3-((trifluoromethyl)thio)acrylamide: colorless oily liquid; 0.068 g; the yield is 60%; 1 1H NMR (400 MHz, CDCl3): δ 7.67–7.65 (m, 2H), 7.52–7.48 (m, 3H), 7.43–7.39 (m, 1H), 7.35–7.31 (m, 2H), 7.20–7.18 (m, 2H), 4.56 (dd, J = 8.4, 5.6 Hz, 1H), 3.52 (dd, J = 14.0, 8.4 Hz, 1H), 3.07 (dd, J = 14.0, 5.6 Hz, 1H), 2.95 (s, 3H), 2.71 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 171.71, 170.04, 138.66, 135.98, 131.15 (q, J C-F = 306.8 Hz), 130.85, 129.10, 128.88, 128.84, 128.08, 127.22, 62.90, 36.64, 36.10, 32.66; 1919F NMR (376 MHz, CDCl3): δ -41.44 (s, 3F); ESI-HRMS: Calcd for C 19 H 20 F3N2OS + [M + H] + 381.1243, found 381.1240.

[0154] Example 24:

[0155] Preparation of 3-((Diphenylmethylene)amino)-3-((trifluoromethylthio)methyl)dihydrofuran-2(3H)-one

[0156]

[0157] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with α-methylene-γ-butyrolactone. The purified product 3-((diphenylmethylene)amino)-3-((trifluoromethylthio)methyl)dihydrofuran-2(3H)-one: colorless oily liquid; 0.052 g; yield 46%; 1 1H NMR (400 MHz, CDCl3): δ 7.57–7.55 (m, 2H), 7.48–7.45 (m, 3H), 7.44–7.40 (m, 1H), 7.34–7.31 (m, 2H), 7.22–7.19 (m, 2H), 4.15 (td, J = 8.8, 6.0 Hz, 1H), 3.82 (td, J = 8.8, 6.0 Hz, 1H), 3.65 (d, J = 12.4 Hz, 1H), 3.11 (d, J = 12.4 Hz, 1H), 2.66–2.59 (m, 1H), 2.53–2.46 (m, 1H); 13 13C NMR (100.6 MHz, CDCl3): δ 175.86, 170.23, 139.47, 135.53, 131.13 (q, J C-F = 306.8 Hz), 131.07, 129.35, 128.74, 128.35, 128.11, 65.56, 64.60, 39.63, 35.55; 19 19F NMR (376 MHz, CDCl3): δ -41.48 (s, 3F); ESI-HRMS: Calcd for C 19 H 17 F3NO2S + [M + H] + 380.0927, found 380.0925.

[0158] Example 25:

[0159] Preparation of N-[1-((diphenylmethylene)amino)-2-((trifluoromethyl)thio)ethyl]-N-methylacetamide

[0160]

[0161] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by N-methyl-N-vinylacetamide, and the purified product N-[1-((diphenylmethylene)amino)-2-((trifluoromethyl)thio)ethyl]-N-methylacetamide: colorless oily liquid; 0.040 g; the yield is 35%; The rotamer ratio was determined to be 1:1.3 by 1 HNMR; 1 H NMR(400 MHz, CDCl3): δ 7.66–7.63(m, 4.5H), 7.54–7.43(m, 9.0H), 7.41–7.32(m, 4.5H), 7.20–7.17(m, 4.5H), 6.17(dd, J = 8.0, 5.6 Hz, 1H), 5.26(dd, J = 8.0, 5.6 Hz, 1.3H), 3.29(dd, J = 14.8, 8.0 Hz, 1.3H), 3.18–3.11(m, 5.3H), 3.03(s, 3.8H), 2.98(dd, J = 13.2, 5.6 Hz, 1.1H), 2.07(s, 3.0H), 1.58(s, 3.8H); 13 C NMR(100.6 MHz, CDCl3): δ 171.52, 171.33, 171.01, 170.16, 138.85, 138.21, 135.83, 135.58, 131.31, 130.92, 130.65(q, J C-F = 306.8 Hz), 130.61(q, J C-F = 305.8 Hz), 129.35, 129.05, 128.89, 128.84, 128.68, 128.26, 128.11, 127.34, 126.99, 72.73, 67.16, 33.19, 32.17, 29.99, 26.71, 22.36, 21.08; 19 F NMR(376 MHz, CDCl3): δ -41.06(s, 3F), -41.43(s, 3F); ESI-HRMS: Calcd for C 19 H 30 F3N2OS + [M + H] +381.1243, found 381.1241.

[0162] Example 26:

[0163] Preparation of 1,1-diphenyl-N-[1-((trifluoromethyl)thio)dodecan-2-yl]methanimine

[0164]

[0165] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 1-dodecene, and the purified product 1,1-diphenyl-N-[1-((trifluoromethyl)thio)dodecan-2-yl]methanimine: colorless oily liquid; 0.071 g; the yield is 53%; 1 H NMR (400 MHz, CDCl3): δ 7.62–7.59 (m, 2H), 7.47–7.30 (m, 6H), 7.19–7.17 (m, 2H), 3.62–3.55 (m, 1H), 3.09 (dddd, J = 12.8, 12.4, 6.8, 5.2 Hz, 2H), 1.65–1.60 (m, 2H), 1.29–1.17 (m, 16H), 0.88 (t, J = 6.8 Hz, 3H); 13 C NMR (100.6 MHz, CDCl3): δ 168.70, 139.61, 136.69, 131.27 (q, J C-F = 305.8 Hz), 130.15, 128.57, 128.38, 128.07, 127.86, 60.70, 36.03, 35.61, 31.89, 29.56, 29.52, 29.46, 29.31, 26.07, 22.67, 14.10; 19 F NMR (376 MHz, CDCl3): δ -41.36 (s, 3F); ESI-HRMS: Calcd for C 26 H 35 F3NS + [M + H] + 450.2437, found 450.2435.

[0166] Example 27:

[0167] Preparation of diethyl 2-[1-((diphenylmethylene)amino)-2-((trifluoromethyl)thio)ethyl]-2-phenylmalonate

[0168]

[0169] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with diethyl 2-phenyl-2-vinylmalonate, and the purified product diethyl 2-[1-((diphenylmethylene)amino)-2-((trifluoromethyl)thio)ethyl]-2-phenylmalonate: colorless oily liquid; 0.085 g; the yield is 52%; 1 H NMR(400MHz, CDCl3): δ7.58–7.56(m, 2H), 7.51–7.49(m, 2H), 7.41–7.30(m, 9H), 6.95–6.93(m, 2H), 4.63(dd, J = 8.4, 3.2Hz, 1H), 4.37–4.13(m, 4H), 3.44(dd, J = 13.6, 3.2Hz, 1H), 3.00(dd, J = 13.6, 8.4Hz, 1H), 1.28(t, J = 7.2Hz, 3H), 1.19(t, J = 7.2Hz, 3H); 13 C NMR(100.6MHz, CDCl3): δ170.61, 169.28, 169.01, 139.81, 135.22, 134.95, 130.81(q, J C-F =306.8Hz), 130.34, 129.65, 128.92, 128.52, 128.48, 127.97, 127.90, 127.83, 127.77, 67.52, 64.60, 61.86, 61.73, 33.53, 13.93, 13.87; 19 F NMR(376MHz, CDCl3): δ-41.90(s, 3F); ESI-HRMS: Calcd for C 29 H 29 F3NO4S + [M+H] + 544.1764, found 544.1760.

[0170] Example 28:

[0171] Preparation of 4-((diphenylmethylene)amino)-N-phenyl-5-((trifluoromethyl)thio)pentanamide

[0172]

[0173] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with N-phenyl-4-pentenamide, and the purified product 4-((diphenylmethylene)amino)-N-phenyl-5-((trifluoromethyl)thio)pentanamide: colorless oily liquid; 0.068 g; the yield is 50%; 11H NMR (400 MHz, CDCl3): δ 7.62–7.60 (m, 2H), 7.41–7.37 (m, 7H), 7.33–7.24 (m, 4H), 7.17–7.16 (m, 2H), 7.07 (t, J = 7.2 Hz, 1H), 3.75–3.69 (m, 1H), 3.13–3.03 (m, 2H), 2.40–2.26 (m, 2H), 2.18–2.01 (m, 2H); 13 13C NMR (100.6 MHz, CDCl3): δ 170.46, 170.10, 139.17, 137.79, 136.14, 131.02 (q, J C-F = 305.8 Hz), 130.51, 128.88, 128.65, 128.59, 128.13, 127.61, 124.18, 119.82, 59.68, 35.64, 33.81, 30.84; 19 19F NMR (376 MHz, CDCl3): δ -41.31 (s, 3F); ESI-HRMS: Calcd for C 25 H 24 F3N2OS + [M + H] + 457.1554 found 457.1556.

[0174] Example 29:

[0175] Preparation of N-[5-phenoxy-1-((trifluoromethyl)thio)pentan-2-yl]-1,1-diphenylmethanimine

[0176]

[0177] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with phenyl-4-penten-1-yl ether, and the purified product N-[5-phenoxy-1-((trifluoromethyl)thio)pentan-2-yl]-1,1-diphenylmethanimine: colorless oily liquid; 0.080 g; yield 60%; 11H NMR (400 MHz, CDCl3): δ 7.62–7.61 (m, 2H), 7.42–7.37 (m, 4H), 7.35–7.31 (m, 2H), 7.27–7.23 (m, 2H), 7.19–7.17 (m, 2H), 6.92 (t, J = 7.2 Hz, 1H), 6.82 (d, J = 8.0 Hz, 2H), 3.88–3.80 (m, 2H), 3.71–3.65 (m, 1H), 3.18–3.08 (m, 2H), 1.92–1.63 (m, 4H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.32, 158.86, 139.33, 136.45, 131.18 (q, J C-F = 305.8 Hz), 130.34, 129.38, 128.64, 128.50, 128.11, 127.75, 120.62, 114.44, 67.33, 60.27, 35.90, 32.00, 25.88; 19 19F NMR (376 MHz, CDCl3): δ -41.29 (s, 3F); ESI-HRMS: Calcd for C 25 H 25 F3NOS + [M+H] + 444.1603, found 444.1602.

[0178] Example 30:

[0179] Preparation of [4-((Diphenylmethylene)amino)-5-((trifluoromethyl)thio)pentyl]diphenylphosphine Oxide

[0180]

[0181] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 4-penten-1-yl diphenylphosphine oxide, and the purified product [4-((diphenylmethylene)amino)-5-((trifluoromethyl)thio)pentyl]diphenylphosphine oxide: colorless oily liquid; 0.103 g; yield 62%; 1 1H NMR (400 MHz, CDCl3): δ 7.71–7.64 (m, 4H), 7.55–7.36 (m, 12H), 7.33–7.29 (m, 2H), 7.05–7.03 (m, 2H), 3.59–3.53 (m, 1H), 3.06–2.98 (m, 2H), 2.20–2.12 (m, 2H), 1.80–1.69 (m, 2H), 1.63–1.46 (m, 2H); 1313C NMR (100.6 MHz, CDCl3): δ 169.29, 139.16, 136.28, 132.90 (d, J C-P = 97.6 Hz), 132.74 (d, J C-P = 98.6 Hz), 131.67 (d, J C-P = 3.0 Hz), 131.64 (d, J C-P = 2.0 Hz), 131.05 (q, J C-F = 305.8 Hz), 132.72 (d, J C-P = 2.0 Hz), 130.61, 130.25, 128.63, 128.61, 128.51, 128.42, 128.38, 128.01, 127.63, 60.10, 36.43 (d, J C-P = 14.1 Hz), 35.68, 29.63 (d, J C-P = 71.4 Hz), 18.29 (d, J C-P = 4.0 Hz); 19 19F NMR (376 MHz, D2O): δ -41.29 (s, 3F); 31 31P NMR (162 MHz, CDCl3): δ 31.99; ESI-HRMS: Calcd for C 31 H 30 F3NOPS + [M + H] + 552.1732, found 552.1730.

[0182] Example 31:

[0183] Preparation of 1,1-diphenyl-N-[6-((trifluoromethylthio)methyl)undecan-6-yl]methanimine

[0184]

[0185] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 6-methylideneundecane, and the purified product 1,1-diphenyl-N-[6-((trifluoromethylthio)methyl)undecan-6-yl]methanimine: colorless oily liquid; 0.063 g; yield 47%; 11H NMR (400 MHz, CDCl3): 7.53–7.51 (m, 2H), 7.41–7.39 (m, 3H), 7.35–7.27 (m, 3H), 7.21–7.18 (m, 2H), 3.18 (s, 2H), 1.50–1.46 (m, 4H), 1.32–1.22 (m, 8H), 1.17–1.10 (m, 4H), 0.86 (t, J = 7.2 Hz, 6H); 13 13C NMR (100.6 MHz, CDCl3): δ 164.50, 141.22, 139.25, 131.69 (q, J C-F = 305.8 Hz), 129.81, 128.29, 128.23, 127.93, 127.91, 127.48, 63.81, 39.10, 38.22, 32.19, 23.43, 22.51, 14.03; 19 19F NMR (376 MHz, CDCl3): δ -41.48 (s, 3F); ESI-HRMS: Calcd for C 26 H 35 F3NS + [M+H] + 450.2437, found 450.2436.

[0186] Example 32:

[0187] (8R, 9S, 13S, 14S)-3-[1-((Diphenylmethylene)amino)-2-((trifluoromethyl)thio)ethyl]-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthren-17-one Preparation

[0188]

[0189] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with (8R, 9S, 13S, 14S)-13-methyl-3-vinyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthren-17-one. The purified product (8R, 9S, 13S, 14S)-3-[1-((diphenylmethylene)amino)-2-((trifluoromethyl)thio)ethyl]-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthren-17-one: colorless oily liquid; 0.091 g; yield 54%; 11H NMR (400 MHz, CDCl3): δ 7.69–7.67 (m, 2H), 7.43–7.32 (m, 6H), 7.24–7.22 (m, 1H), 7.07–7.02 (m, 4H), 4.57 (dd, J = 8.8, 4.4 Hz, 1H), 3.44 (dd, J = 12.8, 8.8 Hz, 1H), 3.26 (dd, J = 13.2, 4.4 Hz, 1H), 2.90–2.88 (m, 2H), 2.50 (dd, J = 19.2, 8.0 Hz, 1H), 2.42–2.39 (m, 1H), 2.31–2.26 (m, 1H), 2.15 (dd, J = 18.8, 8.8 Hz, 1H), 2.09–1.95 (m, 3H), 1.67–1.41 (m, 6H), 0.91 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 220.76, 169.14, 169.12, 139.85, 139.80, 139.46, 139.15, 139.13, 136.78, 136.38, 131.17 (q, J C-F = 305.8 Hz), 130.27, 128.75, 128.57, 128.30, 128.01, 127.82, 127.49, 125.56, 125.54, 124.43, 124.42, 65.07, 65.04, 50.51, 47.94, 44.37, 38.51, 38.06, 35.82, 31.58, 29.44, 29.41, 26.47, 25.65, 25.61, 21.56, 13.82; 19 19F NMR (376 MHz, CDCl3): δ -41.01 (s, 3F); ESI-HRMS: Calcd for C 34 H 35 F3NOS + [M+H] + 562.2386, found 562.2382.

[0190] Example 33:

[0191] (4R)-4-[(8R, 9S, 10S, 13R, 14S, 17R)-10,13-Dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl]pentanoic acid 3-((diphenylmethylene)amino)-4-((trifluoromethyl)thio)butyl ester Preparation

[0192]

[0193] The specific preparation process is the same as that in Example 10, except that the raw material styrene is replaced by but-3-en-1-yl (4R)-4-[(8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl]pentanoate. The purified product, 3-((diphenylmethylene)amino)-4-((trifluoromethyl)thio)butyl (4R)-4-[(8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl]pentanoate, is a white solid; mp 163–165 °C; 0.139 g; the yield is 63%; 1 H NMR (400 MHz, CDCl3): δ 7.61–7.59 (m, 2H), 7.47–7.45 (m, 3H), 7.42–7.38 (m, 1H), 7.35–7.31 (m, 2H), 7.18–7.16 (m, 2H), 4.16–4.08 (m, 1H), 3.97–3.90 (m, 1H), 3.79–3.73 (m, 1H), 3.11 (d, J = 6.0 Hz, 2H), 2.95–2.82 (m, 3H), 2.37–2.08 (m, 10H), 2.05–1.94 (m, 6H), 1.89–1.81 (m, 1H), 1.76–1.70 (m, 1H), 1.62 (td, J = 14.4, 5.2 Hz, 1H), 1.41 (s, 3H), 1.33–1.22 (m, 5H), 1.06 (d, J = 2.8 Hz, 4H), 0.81 (t, J = 7.6 Hz, 3H); 13 C NMR (100.6 MHz, CDCl3): δ 211.93, 209.03, 208.70, 173.81, 169.83, 169.81, 139.16, 136.18, 131.03 (q, J C-F = 305.8 Hz), 130.42, 128.58, 128.46, 128.09, 127.63, 61.06, 57.63, 57.61, 56.82, 51.70, 48.94, 46.79, 45.56, 45.48, 42.75, 38.60, 36.45, 35.97, 35.78, 35.40, 35.39, 35.22, 34.08, 31.23, 31.18, 30.17, 27.56, 27.53, 25.07, 21.86, 18.57, 11.79; 19 F NMR (376 MHz, CDCl3): δ -41.29 (s, 3F); ESI-HRMS: Calcd for C42 H 51 F3NO5S + [M+H] + 738.3435, found 738.3429.

[0194] Example 34:

[0195] ((3aR,5R,5aS,8aS,8bR)-2,2,7,7-Tetramethyltetrahydro-5H-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methyl 4-((diphenylmethylene)amino)-5-((trifluoromethyl)thio)pentanoate Preparation

[0196]

[0197] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with ((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methyl pent-4-enoate, and the purified product ((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methyl 4-((diphenylmethylene)amino)-5-((trifluoromethyl)thio)pentanoate: colorless oily liquid; 0.107 g; the yield is 57%; 1 H NMR (400 MHz, CDCl3): δ 7.60–7.59 (m, 2H), 7.48–7.37 (m, 4H), 7.35–7.31 (m, 2H), 7.19–7.16 (m, 2H), 5.52 (dd, J = 11.2, 4.8 Hz, 1H), 4.59 (td, J = 8.0, 2.4 Hz, 1H), 4.32–4.31 (m, 1H), 4.21–4.09 (m, 3H), 3.99–3.94 (m, 1H), 3.64 (p, J = 6.2 Hz, 1H), 3.14–3.01 (m, 2H), 2.42–2.22 (m, 2H), 2.02 (q, J = 7.3 Hz, 2H), 1.50 (s, 1.4H), 1.48 (s, 1.6H), 1.44 (m, 3H), 1.32 (s, 6H); 13 C NMR (100.6 MHz, CDCl3): δ 172.81, 172.86, 169.72, 139.17, 139.16, 136.23, 131.05 (q, J C-F = 305.8 Hz), 131.04 (q, J C-F= 305.8 Hz), 130.37, 128.62, 128.53, 128.06, 127.67, 127.65, 109.58, 108.71, 108.68, 96.24, 96.23, 71.01, 70.96, 70.66, 70.63, 70.41, 70.36, 65.87, 65.78, 63.54, 63.35, 59.67, 59.62, 35.64, 30.64, 30.57, 30.36, 25.98, 25.91, 24.90, 24.87, 24.44; 19 19F NMR (376 MHz, CDCl3): δ -41.36 (s, 3F); ESI-HRMS: Calcd for C 31 H 37 F3NO7S + [M + H] + 624.2237, found 624.2233.

[0198] Example 35:

[0199] Preparation of Di-tert-butyl 2-(7-bromo-2-(((trifluoromethyl)thio)methyl)heptyl)-2-((diphenylmethylene)amino)malonate

[0200]

[0201] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and 7-bromo-1-heptene. The purified product, di-tert-butyl 2-(7-bromo-2-(((trifluoromethyl)thio)methyl)heptyl)-2-((diphenylmethylene)amino)malonate: colorless oily liquid; 0.150 g; yield 73%; 1 1H NMR (400 MHz, CDCl3): δ 7.56–7.54 (m, 2H), 7.40–7.35 (m, 4H), 7.31–7.24 (m, 4H), 3.33 (t, J = 6.8 Hz, 2H), 3.22 (dd, J = 12.4, 4.8 Hz, 1H), 2.98 (dd, J = 12.4, 6.8 Hz, 1H), 2.28 (dd, J = 14.4, 5.2 Hz, 1H), 2.21 (dd, J = 14.4, 6.8 Hz, 1H), 2.05–2.00 (m, 1H), 1.83–1.76 (m, 2H), 1.53–1.42 (m, 2H), 1.37 (s, 9H), 1.34–1.30 (m, 4H), 1.28 (s, 9H); 1313C NMR (100.6 MHz, CDCl3): δ 168.99, 168.94, 167.16, 141.55, 136.56, 131.13 (q, J C-F = 304.8 Hz), 130.07, 129.07, 128.97, 128.92, 127.87, 127.76, 82.30, 82.21, 75.64, 42.37, 34.80, 34.48, 33.73, 33.60, 32.53, 28.20, 27.80, 27.70, 25.38; 19 19F NMR (376 MHz, CDCl3): δ -40.99 (s, 3F); ESI-HRMS: Calcd for C 33 H 44 BrF3NO4S+ [M + H] + 686.2121, found 686.2114.

[0202] Example 36:

[0203] Preparation of Di-tert-butyl 2-(6-cyano-6-methyl-2-(((trifluoromethyl)thio)methyl)heptyl)-2-((diphenylmethylene)amino)malonate

[0204]

[0205] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and 2,2-dimethyl-6-heptenenitrile. The purified product, di-tert-butyl 2-(6-cyano-6-methyl-2-(((trifluoromethyl)thio)methyl)heptyl)-2-((diphenylmethylene)amino)malonate: colorless oily liquid; 0.132 g; yield 68%; 1 1H NMR (400 MHz, CDCl3): δ 7.57–7.55 (m, 2H), 7.40–7.35 (m, 4H), 7.31–7.25 (m, 4H), 3.22 (dd, J = 12.4, 4.8 Hz, 1H), 3.00 (dd, J = 12.4, 6.8 Hz, 1H), 2.32–2.21 (m, 2H), 2.08–2.05 (m, 1H), 1.53–1.52 (m, 2H), 1.51–1.50 (m, 2H), 1.47–1.41 (m, 2H), 1.36 (s, 9H), 1.30 (s, 9H), 1.27 (s, 3H), 1.25 (s, 3H); 1313C NMR (100.6 MHz, CDCl3): δ 168.91, 168.90, 167.17, 141.54, 136.50, 131.08 (q, J C-F = 305.8 Hz), 130.08, 129.07, 129.01, 128.95, 127.90, 127.77, 124.89, 82.38, 82.28, 75.58, 42.19, 40.93, 34.73, 34.49, 33.61, 32.17, 27.79, 27.71, 26.61, 26.53, 21.86; 19 19F NMR (376 MHz, CDCl3): δ -40.95 (s, 3F); ESI-HRMS: Calcd for C 35 H 46 F3N2O4S + [M + H] + 647.3125, found 647.3117.

[0206] Example 37:

[0207] Preparation of Di-tert-butyl 2-(dibenzylideneamino)-2-(11-oxo-2-(trifluoromethylthio)undecyl)malonate

[0208]

[0209] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and undec-10-enal. The purified product, di-tert-butyl 2-(dibenzylideneamino)-2-(11-oxo-2-(trifluoromethylthio)undecyl)malonate: colorless oily liquid; 0.089 g; yield 44%; 1 1H NMR (400 MHz, CDCl3): δ 9.76 (s, 1H), 7.57–7.55 (m, 2H), 7.39–7.34 (m, 4H), 7.30–7.25 (m, 4H), 3.24 (dd, J = 12.4, 4.8 Hz, 1H), 2.98 (dd, J = 12.0, 6.8 Hz, 1H), 2.40 (td, J = 7.2, 1.6 Hz, 2H), 2.29 (dd, J = 14.8, 4.8 Hz, 1H), 2.18 (dd, J = 14.4, 7.6 Hz, 1H), 2.03 (m, 1H), 1.64–1.56 (m, 2H), 1.50–1.44 (m, 2H), 1.38 (s, 9H), 1.28–1.23 (s, 19H); 1313C NMR (100.6 MHz, CDCl3): δ 202.85, 169.00, 168.99, 167.14, 141.56, 136.63, 131.19 (q, J C-F = 305.8 Hz), 130.01, 129.10, 128.99, 128.87, 127.85, 127.72, 82.23, 82.15, 75.69, 43.86, 42.40, 34.85, 34.53, 33.86, 29.58, 29.24, 29.22, 29.07, 27.81, 27.70, 26.16, 22.04. 19 19F NMR (376 MHz, CDCl3): δ -41.01 (s, 3F); ESI-HRMS: Calcd for C 37 H 51 F3NO5S + [M + H] + 678.3435, found 678.3431.

[0210] Example 38:

[0211] Preparation of Di-tert-butyl 2-(dibenzylideneamino)-2-(6-(4-methoxybenzoyl)-2-(trifluoromethylthio)hexyl)malonate

[0212]

[0213] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and 1-(4-methoxyphenyl)hex-5-en-1-one, and the purified product di-tert-butyl 2-(dibenzylideneamino)-2-(6-(4-methoxybenzoyl)-2-(trifluoromethylthio)hexyl)malonate: colorless oily liquid; 0.161 g; yield 75%; 1 1H NMR (400 MHz, CDCl3): δ 7.87–7.85 (m, 2H), 7.56–7.54 (m, 2H), 7.39–7.31 (m, 4H), 7.28–7.24 (m, 4H), 6.90 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H), 3.25 (dd, J = 12.8, 5.2 Hz, 1H), 3.03 (dd, J = 12.8, 6.8 Hz, 1H), 2.87–2.74 (m, 2H), 2.34–2.22 (m, 2H), 2.11–2.06 (m, 1H), 1.76–1.68 (m, 2H), 1.60–1.55 (m, 2H), 1.36 (s, 9H), 1.29 (s, 9H); 1313C NMR (100.6 MHz, CDCl3): δ 198.35, 168.88, 167.21, 163.29, 141.60, 136.55, 131.11 (q, J C-F = 305.8 Hz), 130.20, 130.00, 129.10, 128.97, 128.89, 127.88, 127.74, 113.60, 82.28, 82.23, 75.67, 55.40, 42.16, 38.11, 34.73, 34.65, 33.38, 27.77, 27.70, 20.82; 19 19F NMR (376 MHz, CDCl3): δ -40.93 (s, 3F); ESI-HRMS: Calcd for C 39 H 47 F3NO6S + [M + H] + 714.3071, found 714.3066.

[0214] Example 39:

[0215] Preparation of Di-tert-butyl 2-(5-(benzoyloxy)-2-(((trifluoromethyl)thio)methyl)pentyl)-2-((diphenylmethylene)amino)malonate

[0216]

[0217] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and 4-pentenyl benzoate, and the purified product di-tert-butyl 2-(5-(benzoyloxy)-2-(((trifluoromethyl)thio)methyl)pentyl)-2-((diphenylmethylene)amino)malonate: colorless oily liquid; 0.149 g; yield 71%; 1 1H NMR (400 MHz, CDCl3): δ 8.04–8.01 (m, 2H), 7.57–7.53 (m, 3H), 7.44–7.41 (m, 2H), 7.39–7.33 (m, 4H), 7.29–7.25 (m, 4H), 4.26 (t, J = 6.4 Hz, 2H), 3.31 (dd, J = 12.4, 4.8 Hz, 1H), 3.02 (dd, J = 12.8, 7.2 Hz, 1H), 2.33 (dd, J = 14.4, 4.8 Hz, 1H), 2.22 (dd, J = 14.4, 7.2 Hz, 1H), 2.15–2.11 (m, 1H), 1.83–1.75 (m, 2H), 1.68–1.62 (m, 2H), 1.37 (s, 9H), 1.27 (s, 9H);13 13C NMR (100.6 MHz, CDCl3): δ 168.95, 168.88, 167.51, 166.53, 141.56, 136.62, 132.82, 131.09 (q, J C-F = 306.8 Hz), 130.32, 130.10, 129.56, 129.13, 128.95, 128.93, 128.30, 127.88, 127.78, 82.37, 82.31, 75.71, 64.79, 42.42, 34.71, 34.46, 30.29, 27.81, 27.70, 25.60; 19 19F NMR (376 MHz, CDCl3): δ -40.91 (s, 3F); ESI-HRMS: Calcd for C 38 H 45 F3NO6S + [M + H] + 700.2914, found 700.2908.

[0218] Example 40:

[0219] Preparation of Di-tert-butyl 2-(7-azido-2-(trifluoromethylthio)heptyl)-2-(dibenzylideneamino)malonate

[0220]

[0221] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and 7-azido-1-heptene, and the purified product is di-tert-butyl 2-(7-azido-2-(trifluoromethylthio)heptyl)-2-(dibenzylideneamino)malonate: colorless oily liquid; 0.105 g; the yield is 54%; 1 1H NMR (400 MHz, CDCl3): δ 7.56–7.55 (m, 2H), 7.40–7.34 (m, 4H), 7.31–7.24 (m, 4H), 3.25–3.17 (m, 3H), 2.98 (dd, J = 12.8, 7.2 Hz, 1H), 2.28 (dd, J = 14.8, 5.2 Hz, 1H), 2.20 (dd, J = 14.4, 7.2 Hz, 1H), 2.06–2.00 (m, 1H), 1.56–1.44 (m, 4H), 1.37 (s, 9H), 1.31–1.26 (m, 13H); 13 13C NMR (100.6 MHz, CDCl3): δ 168.97, 168.94, 167.16, 141.58, 136.58, 131.13 (q, JC-F = 305.8 Hz), 130.04, 129.07, 128.97, 128.91, 127.86, 127.73, 82.29, 82.19, 75.65, 51.34, 42.38, 34.81, 34.50, 33.64, 28.64, 27.78, 27.69, 26.75, 25.73; 19 19F NMR (376 MHz, CDCl3): δ -40.99 (s, 3F); ESI-HRMS: Calcd for C 33 H 44 F3N4O4S + [M + H] + 649.3030, found 649.3025.

[0222] Example 41:

[0223] Preparation of Di-tert-butyl 2-(5-phthalimido-2-(trifluoromethylthio)pentyl)-2-(dibenzylideneamino)malonate

[0224]

[0225] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and N-(4-pentenyl)phthalimide, and the purified product di-tert-butyl 2-(5-phthalimido-2-(trifluoromethylthio)pentyl)-2-(dibenzylideneamino)malonate: colorless oily liquid; 0.137 g; yield 63%; 1 1H NMR (400 MHz, CDCl3): δ 7.84–7.82 (m, 2H), 7.71–7.69 (m, 2H), 7.54–7.52 (m, 2H), 7.38–7.32 (m, 4H), 7.28–7.24 (m, 4H), 3.65–3.61 (m, 2H), 3.26 (dd, J = 12.8, 4.8 Hz, 1H), 2.98 (dd, J = 12.8, 7.2 Hz, 1H), 2.28 (dd, J = 14.4, 4.4 Hz, 1H), 2.17 (dd, J = 14.4, 7.6 Hz, 1H), 2.08–2.06 (m, 1H), 1.73–1.66 (m, 2H), 1.57–1.51 (m, 2H), 1.35 (s, 9H), 1.26 (s, 9H); 13 13C NMR (100.6 MHz, CDCl3): δ 168.88, 168.87, 168.27, 167.48, 141.54, 136.62, 133.84, 132.12, 131.05 (q, JC-F = 304.8 Hz), 130.04, 129.13, 128.96, 128.88, 127.86, 127.76, 123.17, 82.33, 82.27, 75.72, 42.34, 37.92, 34.66, 34.34, 31.13, 27.80, 27.70, 25.44; 19 19F NMR (376 MHz, CDCl3): δ -40.95 (s, 3F); ESI-HRMS: Calcd for C 39 H 44 F3N2O6S + [M + H] + 725.2867, found 725.2863.

[0226] Example 42:

[0227] Preparation of Di-tert-butyl 2-(diphenylmethyleneamino)-2-((8-(trifluoromethylthio)-1,4-dioxaspiro[4.5]dec-8-yl)methyl)malonate

[0228]

[0229] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl-2-methylenemalonate and 1,4-dioxa-8-methylenespiro[4.5]decane. The purified product, di-tert-butyl 2-(diphenylmethyleneamino)-2-((8-(trifluoromethylthio)-1,4-dioxaspiro[4.5]dec-8-yl)methyl)malonate: colorless oily liquid; 0.141 g; yield 71%; 1 1H NMR (400 MHz, CDCl3): δ 7.56–7.54 (m, 2H), 7.38–7.35 (m, 4H), 7.34–7.27 (m, 4H), 3.90 (s, 4H), 3.17 (s, 2H), 2.44 (s, 2H), 1.87–1.80 (m, 2H), 1.78–1.72 (m, 2H), 1.70–1.64 (m, 2H), 1.61–1.54 (m, 2H), 1.27 (s, 18H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.63, 165.66, 142.28, 136.17, 131.00 (q, J C-F = 305.8 Hz), 129.79, 129.74, 129.34, 129.12, 127.83, 127.56, 108.17, 82.30, 75.27, 64.18, 64.09, 45.01, 37.34, 35.99, 32.52, 30.39, 27.55; 19 19F NMR (376 MHz, CDCl3): δ -40.85 (s, 3F); ESI-HRMS: Calcd for C 35 H 45 F3NO6S + [M + H] + 664.2914, found 664.2910.

[0230] Example 43:

[0231] Preparation of Di-tert-butyl 2-(phenyldimethylsilyl-3-(trifluoromethylthio)propyl)-2-(dibenzylideneamino)malonate

[0232]

[0233] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by di-tert-butyl 2-methylenemalonate and dimethylphenylvinylsilane. The purified product, di-tert-butyl 2-(phenyldimethylsilyl-3-(trifluoromethylthio)propyl)-2-(dibenzylideneamino)malonate: colorless oily liquid; 0.105 g; yield 52%; 1 1H NMR (400 MHz, CDCl3): δ 7.53–7.50 (m, 4H), 7.37–7.32 (m, 5H), 7.30–7.25 (m, 4H), 7.12–7.10 (m, 2H), 3.33 (dd, J = 11.6, 6.0 Hz, 1H), 3.23 (dd, J = 11.2, 4.4 Hz, 1H), 2.51 (dd, J = 14.8, 2.0 Hz, 1H), 2.15 (dd, J = 14.8, 12.4 Hz, 1H), 1.62–1.61 (m, 1H), 1.31 (s, 9H), 1.22 (s, 9H), 0.42 (s, 3H), 0.41 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.13, 168.59, 167.10, 141.55, 136.78, 136.56, 134.11, 130.91 (q, J C-F= 305.8 Hz), 129.94, 129.34, 129.17, 129.08, 128.75, 127.87, 127.78, 127.59, 82.17, 82.02, 76.69, 38.04, 31.85, 27.73, 27.65, 22.91, -3.67, -3.72; 19 19F NMR (376 MHz, CDCl3): δ -41.86 (s, 3F); ESI-HRMS: Calcd for C 36 H 45 F3NO4SSi + [M + H] + 672.2785, found 672.2780.

[0234] Example 44:

[0235] Preparation of Di-tert-butyl 2-(2-butoxy-3-(trifluoromethylthio)propyl)-2-(diphenylmethyleneamino)malonate

[0236]

[0237] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and 1-(vinyloxy)butane, and the purified product di-tert-butyl 2-(2-butoxy-3-(trifluoromethylthio)propyl)-2-(diphenylmethyleneamino)malonate: colorless oily liquid; 0.073 g; yield 40%; 1 1H NMR (400 MHz, CDCl3): δ 7.61–7.59 (m, 2H), 7.40–7.35 (m, 4H), 7.31–7.24 (m, 4H), 3.74–3.68 (m, 1H), 3.54–3.48 (m, 1H), 3.37 (q, J = 7.2 Hz, 1H), 3.21 (dd, J = 13.2, 5.6 Hz, 1H), 2.96 (dd, J = 13.2, 6.0 Hz, 1H), 2.57 (dd, J = 14.8, 7.2 Hz, 1H), 2.27 (dd, J = 14.8, 5.2 Hz, 1H), 1.46–1.45 (m, 4H), 1.40 (s, 9H), 1.30 (s, 9H), 0.82 (t, J = 7.6 Hz, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 168.82, 168.44, 167.66, 141.29, 136.72, 131.23 (q, J C-F= 305.8 Hz), 130.12, 128.93, 128.87, 128.84, 127.88, 127.77, 82.31, 81.95, 74.84, 73.86, 70.17, 41.98, 35.08, 31.69, 27.85, 27.73, 19.12, 13.83; 19 19F NMR (376 MHz, CDCl3): δ -41.27 (s, 3F); ESI-HRMS: Calcd for C 32 H 43 F3NO5S + [M + H] + 610.2809, found 610.2805.

[0238] Example 45:

[0239] Preparation of 4-((diphenylmethylene)amino)-5-ethoxy-5-oxo-1-((trifluoromethyl)thio)-2-pentyl benzoate

[0240]

[0241] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with ethyl acrylate and vinyl benzoate, and the purified product 4-((diphenylmethylene)amino)-5-ethoxy-5-oxo-1-((trifluoromethyl)thio)-2-pentyl benzoate: colorless oily liquid; 0. -7 g; the yield is 44%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 1 1H NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.84–7.82 (m, 4H), 7.62–7.53 (m, 6H), 7.40–7.26 (m, 13H), 7.18–7.16 (m, 2H), 7.09–7.07 (m, 1H), 7.03–7.02 (m, 4H), 5.47–5.45 (m, 1H), 5.23–5.20 (m, 1H), 4.27–4.07 (m, 6H), 3.30–3.14 (m, 4H), 2.55–2.49 (m, 3H), 2.36–2.33 (m, 1H), 1.27 (t, J = 7.2 Hz, 4H), 1.21 (t, J = 7.2 Hz, 3H); 13CNMR(100.6 MHz, CDCl3): δ 172.49, 171.52, 171.23, 171.15, 165.63, 165.43, 139.26, 139.03, 135.95, 135.67, 133.16, 133.11, 130.64 (q, J C-F = 306.8 Hz), 130.62 (q, J C-F = 305.8 Hz), 130.54, 129.69, 129.64, 129.54, 129.53, 128.88, 128.84, 128.72, 128.56, 128.48, 128.27, 128.24, 128.16, 128.04, 127.58, 69.95, 69.49, 62.10, 61.50, 61.37, 61.29, 36.79, 36.72, 33.63, 33.57, 14.13, 14.03; 19 F NMR(376 MHz, CDCl3): δ -41.05 (s, 3F), -41.10 (s, 3F); ESI-HRMS: Calcd for C 28 H 27 F3NO4S + [M + H] + 530.1607, found 530.1603.

[0242] Example 46:

[0243] Preparation of 4-cyano-4-((diphenylmethylene)amino)-1-((trifluoromethyl)thio)-2-butyl benzoate

[0244]

[0245] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with vinyl benzoate and acrylonitrile. The purified product 4-cyano-4-((diphenylmethylene)amino)-1-((trifluoromethyl)thio)-2-butyl benzoate: colorless oily liquid; 0.070 g; yield 44%; a mixture of diastereoisomers, dr = 1:1.2 (the ratio was determined by 1 H NMR analysis); 11H NMR (400 MHz, CDCl3): δ 7.86–7.83 (m, 4.4H), 7.62–7.54 (m, 6.7H), 7.47–7.30 (m, 14.4H), 7.21–7.19 (m, 3.2H), 7.18–7.11 (m, 2.2H), 7.09–7.04 (m, 2.2H), 5.59–5.55 (m, 1H), 5.30–5.25 (m, 1.2H), 4.48 (dd, J = 7.2, 6.4 Hz, 1H), 4.33 (dd, J = 10.4, 3.6 Hz, 1.2H), 3.34–3.23 (m, 4.5H), 2.73–2.66 (m, 1.2H), 2.52–2.38 (m, 3.2H); 13 13C NMR (100.6 MHz, CDCl3): δ 175.50, 173.92, 165.35, 165.30, 138.10, 137.86, 134.80, 134.67, 133.48, 133.38, 131.43, 130.44 (q, J C-F = 306.8 Hz), 129.75, 129.64, 129.40, 129.21, 129.06, 129.02, 128.69, 128.41, 128.32, 128.23, 128.21, 127.14, 127.10, 118.97, 118.59, 69.25, 68.41, 49.99, 48.72, 37.85, 37.66, 33.22; 19 19F NMR (376 MHz, CDCl3): δ -40.93 (s, 3F); ESI-HRMS: Calcd for C 26 H 22 F3N2O2S + [M+H] + 483.1349, found 483.1347.

[0246] Example 47:

[0247] Preparation of Di-tert-butyl 2-(4-(2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)-2-(((trifluoromethyl)thio)methyl)butyl)-2-((diphenylmethylene)amino)malonate

[0248]

[0249] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by di-tert-butyl 2-methylenemalonate and but-3-en-1-yl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate. The purified product, di-tert-butyl 2-(4-(2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)-2-(((trifluoromethyl)thio)methyl)butyl)-2-((diphenylmethylene)amino)malonate, is a colorless oily liquid; 0.171 g; the yield is 62%; 1 H NMR(400MHz, CDCl3): δ7.66–7.64(m, 2H), 7.55–7.53(m, 2H), 7.47–7.45(m, 2H), 7.40–7.34(m, 4H), 7.30–7.24(m, 5H), 6.92(d, J = 2.4Hz, 1H), 6.85(d, J = 8.8Hz, 1H), 6.66(dd, J = 9.2, 2.4Hz, 1H), 4.24–4.10(m, 2H), 3.82(s, 3H), 3.59(s, 2H), 3.25(dd, J = 12.4, 4.8Hz, 1H), 2.98(dd, J = 12.8, 6.8Hz, 1H), 2.35–2.30(m, 4H), 2.26–2.17(m, 2H), 1.94–1.79(m, 2H), 1.37(s, 9H), 1.27(s, 9H); 13 C NMR(100.6MHz, CDCl3): δ170.71, 168.84, 168.78, 168.25, 167.64, 156.02, 141.42, 139.18, 136.48, 135.95, 133.87, 131.15, 130.96(q, J C-F = 305.8Hz), 130.72, 130.60, 130.17, 129.08, 129.03, 129.00, 128.97, 127.91, 127.81, 114.95, 112.39, 111.67, 101.11, 82.47, 82.42, 75.47, 62.62, 55.65, 42.17, 34.83, 32.42, 32.34, 30.08, 27.77, 27.67, 13.32; 19 F NMR(376MHz, CDCl3): δ-40.81(s, 3F); ESI-HRMS: Calcd for C 49 H 53 ClF3N2O8S + [M+H] +921.3158, found 921.3157.

[0250] Example 48:

[0251] Preparation of Di-tert-butyl 2-(6-(((3S,8S,9S,10R,13S,14S,17S)-17-acetyl-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl)oxy)-2-(((trifluoromethyl)thio)methyl)hexyl)-2-((diphenylmethylene)amino)malonate

[0252]

[0253] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with di-tert-butyl 2-methylenemalonate and (3S,8S,9S,10R,13S,14S,17S)-3-(hex-5-en-1-yloxy)-10,13-dimethyl-17-acetyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene. The purified product, di-tert-butyl 2-(6-(((3S,8S,9S,10R,13S,14S,17S)-17-acetyl-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl)oxy)-2-(((trifluoromethyl)thio)methyl)hexyl)-2-((diphenylmethylene)amino)malonate: colorless oily liquid; 0.131 g; yield 48%; 1 HNMR(400 MHz, CDCl3): δ 7.56–7.54 (m, 2H), 7.38–7.34 (m, 4H), 7.30–7.25 (m, 4H), 5.33 (s, 1H), 3.41 (t, J = 6.4 Hz, 2H), 3.27 (dd, J = 12.4, 4.8 Hz, 1H), 3.13–3.07 (m, 1H), 2.99 (dd, J = 12.4, 6.8 Hz, 1H), 2.53 (t, J = 8.8 Hz, 1H), 2.36–2.29 (m, 2H), 2.20–2.12 (s, 6H), 2.07–1.98 (m, 4H), 1.87–1.87 (m, 3H), 1.68–1.58 (m, 4H), 1.52–1.44 (12H), 1.38 (s, 9H), 1.27 (s, 9H), 1.00 (s, 3H), 0.63 (s, 3H); 1313C NMR(100.6 MHz, CDCl3): δ 209.39, 168.91, 167.17, 141.52, 141.04, 136.59, 131.13 (q, J C-F = 305.8 Hz), 129.97, 129.07, 128.93, 128.83, 127.81, 127.69, 121.02, 82.19, 82.11, 78.77, 75.66, 67.61, 63.66, 56.88, 50.02, 43.93, 42.32, 39.09, 39.07, 38.80, 37.23, 36.85, 34.80, 34.59, 31.81, 31.76, 31.46, 30.15, 28.37, 28.36, 27.78, 27.66, 24.43, 22.89, 22.77, 21.02, 19.30, 13.16; 19 19F NMR(376 MHz, CDCl3): δ -40.96 (s, 3F); ESI-HRMS: Calcd for C 53 H 73 F3NO6S + [M + H] + 908.5105, found 908.5104.

[0254] Example 49:

[0255] Preparation of 5 - ((diphenylmethylene)amino)-5,5-diphenyl-2-(((trifluoromethyl)thio)methyl)pentanenitrile

[0256]

[0257] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 2,2-diphenyl-5-hexenenitrile, and the purified product 5 - ((diphenylmethylene)amino)-5,5-diphenyl-2-(((trifluoromethyl)thio)methyl)pentanenitrile: colorless oily liquid; 0.090 g; yield 57%; 1 1H NMR(400 MHz, CDCl3): δ 7.70–7.68 (m, 2H), 7.41–7.33 (m, 3H), 7.30–7.27 (m, 4H), 7.20–7.12 (m, 7H), 7.06 (t, J = 7.6 Hz, 2H), 6.49 (d, J = 7.2 Hz, 2H), 2.96–2.84 (m, 2H), 2.70–2.62 (m, 1H), 2.54 (td, J = 12.8, 4.8 Hz, 1H), 2.26 (td, J = 11.2, 4.8 Hz, 1H), 1.69–1.57 (m, 2H);13 13C NMR (100.6 MHz, CDCl3): δ 167.41, 148.88, 148.64, 141.45, 134.86, 130.28 (q, J C-F = 305.8 Hz), 130.16, 128.32, 128.05, 127.93, 127.59, 127.54, 127.51, 127.30, 126.85, 126.20, 126.15, 119.62, 68.40, 37.80, 33.39, 31.41 (q, J C-F = 2.0 Hz), 26.55; 19 19F NMR (376 MHz, CDCl3): δ -40.95 (s, 3F); ESI-HRMS: Calcd for C 32 H 28 F3N2S + [M + H] + 529.1920, found 529.1915.

[0258] Example 50:

[0259] Preparation of 5,5-bis(4-chlorophenyl)-5-((diphenylmethylene)amino)-2-(((trifluoromethyl)thio)methyl)pentanenitrile

[0260]

[0261] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 2,2-bis(4-chlorophenyl)hex-5-enenitrile, and the purified product 5,5-bis(4-chlorophenyl)-5-((diphenylmethylene)amino)-2-(((trifluoromethyl)thio)methyl)pentanenitrile: white solid; mp 135–137 °C; 0.090 g; the yield is 57%; 1 1H NMR (400 MHz, CDCl3): δ 7.67–7.64 (m, 2H), 7.43–7.39 (m, 1H), 7.37–7.33 (m, 2H), 7.24–7.09 (m, 11H), 6.54–6.52 (m, 2H), 2.93 (dq, J = 14.4, 8.8 Hz, 2H), 2.75–2.69 (m, 1H), 2.53 (dt, J = 12.4, 4.8 Hz, 1H), 2.25 (ddd, J = 11.3, 4.8 Hz, 1H), 1.68–1.55 (m, 2H); 1313C NMR (100.6 MHz, CDCl3): δ 168.19, 146.88, 146.67, 141.01, 137.91, 132.29, 132.25, 130.45, 130.24 (q, J C-F = 306.8 Hz), 128.97, 128.91, 128.30, 128.13, 128.11, 127.61, 127.55, 126.75, 119.44, 67.81, 38.21, 33.35, 31.39 (q, J C-F = 2.0 Hz), 26.47; 19 19F NMR (376 MHz, CDCl3): δ -40.89 (s, 3F); ESI-HRMS: Calcd for C 32 H 26 Cl2F3N2S + [M + H] + 597.1140, found 597.1139.

[0262] Example 51:

[0263] Preparation of 2-(trifluoromethylthio)-4-(N-dibenzylidene-9-fluorenylamino)butyronitrile

[0264]

[0265] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 9-(3-butenyl)-9-cyanofluorene, and the purified product 2-(trifluoromethylthio)-4-(N-dibenzylidene-9-fluorenylamino)butyronitrile: colorless oily liquid; 0.073 g; yield 46%; 1 1H NMR (400 MHz, CDCl3): δ 7.56–7.54 (m, 2H), 7.37–7.332 (m, 3H), 7.29–7.25 (m, 2H), 7.22–7.19 (m, 6H), 6.83–6.79 (m, 1H), 6.60 (t, J = 8.0 Hz, 2H), 5.93–5.91 (m, 2H), 2.96–2.95 (m, 2H), 2.80–2.75 (m, 1H), 2.73–2.56 (m, 2H), 1.54–1.45 (m, 2H); 13 13C NMR (100.6 MHz, CDCl3): δ 169.96, 149.83, 140.65, 140.35, 136.43, 130.31 (q, J C-F= 306.8 Hz), 130.10, 128.25, 127.94, 127.77, 127.74, 127.56, 127.50, 126.93, 126.33, 126.26, 123.80, 123.77, 119.85, 119.82, 119.66, 72.14, 41.03, 33.14, 31.28 (q, J C-F = 2.0 Hz), 26.41; 19 19F NMR (376 MHz, CDCl3): δ -41.00 (s, 3F); ESI-HRMS: Calcd for C 32 H 26 F3N2S + [M + H] + 527.1763, found 527.1760.

[0266] Example 52:

[0267] Preparation of 2-((diphenylmethylene)amino)-2-phenyl-5-(((trifluoromethyl)thio)methyl)adiponitrile

[0268]

[0269] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 2-butyl-2-phenylmalononitrile, and the purified product 2-((diphenylmethylene)amino)-2-phenyl-5-(((trifluoromethyl)thio)methyl)adiponitrile: colorless oily liquid; 0.090 g; yield 63%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.69–7.65 (m, 4H), 7.49–7.45 (m, 2H), 7.40–7.33 (m, 16H), 7.28–7.24 (m, 4H), 6.76 (s, 4H), 3.16–3.00 (m, 5H), 2.97–2.90 (m, 1H), 2.76–2.68 (m, 1H), 2.63–2.56 (m, 1H), 2.50–2.43 (m, 1H), 2.35–2.28 (m, 1H), 2.20–2.11 (m, 1H), 2.08–1.92 (m, 2H), 1.91–1.81 (m, 1H); 1313C NMR (100.6 MHz, CDCl3): δ 172.48, 172.31, 141.48, 141.44, 139.38, 134.82, 131.28, 130.27 (q, J C-F = 306.8 Hz), 130.26 (q, J C-F = 307.8 Hz), 129.52, 129.48, 128.97, 128.91, 128.89, 128.48, 128.46, 128.24, 127.87, 127.86, 125.58, 119.16, 119.14, 118.60, 118.53, 64.40, 64.29, 44.90, 44.76, 32.71, 31.43 (q, J C-F = 2.0 Hz), 31.41 (q, J C-F = 2.0 Hz), 27.33, 27.26; 19 19F NMR (376 MHz, CDCl3): δ -40.89 (s, 3F), -40.90 (s, 3F); ESI-HRMS: Calcd for C 27 H 23 F3N3S + [M+H] + 478.1559, found 478.1555.

[0270] Example 53:

[0271] Preparation of 2-cyclopentyl-2-((diphenylmethylene)amino)-5-(((trifluoromethyl)thio)methyl)adiponitrile

[0272]

[0273] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 2-cyclopentyl-2-(3-butenyl)malononitrile, and the purified product 2-cyclopentyl-2-((diphenylmethylene)amino)-5-(((trifluoromethyl)thio)methyl)adiponitrile: colorless oily liquid; 0.063 g; yield 45%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis);; 11H NMR (400 MHz, CDCl3): δ 7.58–7.54 (m, 2H), 7.52–7.45 (m, 3H), 7.44–7.40 (m, 1H), 7.36–7.32 (m, 2H), 7.21–7.19 (m, 2H), 3.12–3.05 (m, 2H), 2.97–2.92 (m, 1H), 2.54–2.48 (m, 1H), 2.35–2.02 (m, 2H), 1.99–1.47 (m, 10H); 13 13C NMR (100.6 MHz, CDCl3): δ 167.89, 167.69, 139.56, 139.53, 135.15, 135.10, 130.80, 130.23 (q, J C-F = 306.8 Hz), 129.49, 128.55, 128.53, 128.37, 128.35, 128.18, 128.11, 128.10, 119.00, 118.96, 118.68, 65.25, 65.04, 50.14, 50.07, 38.03, 37.72, 32.84, 32.77, 31.41 (q, J C-F = 2.0 Hz), 31.31 (q, J C-F = 2.0 Hz), 28.33, 28.08, 27.63, 27.50, 27.00, 26.86, 25.30, 25.26, 25.20, 25.13; 19 19F NMR (376 MHz, CDCl3): δ -40.86 (s, 3F), -40.87 (s, 3F); ESI-HRMS: Calcd for C 26 H 27 F3N3S + [M+H] + 470.1872, found 470.1870.

[0274] Example 54:

[0275] Preparation of methyl 2-butyl-5-cyano-2-((diphenylmethylene)amino)-6-((trifluoromethyl)thio)hexanoate

[0276]

[0277] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by methyl 2-butyl-2-cyano-5-hexenoate. The purified product, methyl 2-butyl-5-cyano-2-((diphenylmethylene)amino)-6-((trifluoromethyl)thio)hexanoate, is a colorless oily liquid; 0.059 g; the yield is 40%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.55–7.53 (m, 2H), 7.41–7.36 (m, 4H), 7.32–7.29 (m, 2H), 7.14–7.12 (m, 2H), 3.33–3.32 (m, 3H), 3.15–3.04 (m, 2H), 2.95–2.90 (m, 1H), 2.19–1.92 (m, 3H), 1.90–1.80 (m, 3H), 1.35–1.26 (m, 4H), 0.92–0.89 (m, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 174.33, 167.01, 166.83, 140.68, 140.66, 136.94, 130.35 (q, J C-F = 306.8 Hz), 130.20, 128.64, 128.44, 128.12, 127.96, 127.86, 119.66, 119.59, 68.38, 68.29, 51.46, 37.72, 37.60, 35.09, 34.64, 33.28, 33.17, 31.43 (q, J C-F = 2.0 Hz), 31.36 (q, J C-F = 2.0 Hz), 26.44, 26.20, 25.80, 25.75, 23.06, 23.04, 13.95, 13.93; 19 19F NMR (376 MHz, CDCl3): δ -40.93 (s, 3F), -40.94 (s, 3F); ESI-HRMS: Calcd for C 26 24 30 H + [M + H] + 491.1975, found 491.1975.

[0278] Example 55:

[0279] Preparation of 5-((Dibenzylidene)amino)-5-phenyl-2-(((trifluoromethyl)thio)methyl)pentanenitrile

[0280]

[0281] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced by 2-phenyl-5-hexenenitrile, and the purified product 5-((dibenzylidene)amino)-5-phenyl-2-(((trifluoromethyl)thio)methyl)pentanenitrile: colorless oily liquid; 0.082 g; the yield is 60%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.69–7.67 (m, 4H), 7.45–7.41 (m, 6H), 7.40–7.33 (m, 6H), 7.31–7.22 (m, 10H), 7.03–7.01 (m, 4H), 4.42–4.37 (m, 2H), 3.00 (d, J = 7.6 Hz, 4H), 2.91–2.77 (m, 2H), 2.23–2.13 (m, 1H), 2.09–2.04 (m, 2H), 2.00–1.91 (m, 1H), 1.75–1.53 (m, 4H); 13 13C NMR (100.6 MHz, CDCl3): δ 167.63, 143.84, 139.43, 136.56, 130.32 (q, J C-F = 306.8 Hz), 130.30 (q, J C-F = 306.8 Hz), 130.21, 128.52, 128.50, 128.08, 127.52, 127.08, 127.03, 126.91, 126.88, 119.60, 119.56, 65.47, 65.26, 36.31, 36.21, 32.92, 32.89, 31.33, 28.43, 28.16; 19 19F NMR (376 MHz, CDCl3): δ -40.95 (s, 3F), -40.95 (s, 3F); ESI-HRMS: Calcd for C 26 28 24 H + [M+H] + 453.1607, found 453.1605.

[0282] Example 56:

[0283] Preparation of 5-((Diphenylmethylene)amino)-5-(thiophen-2-yl)-2-(((trifluoromethyl)thio)methyl)pentanenitrile

[0284]

[0285] The specific preparation process is the same as that of Example 10, except that the raw material styrene is replaced with 5-hexene-2-(2-thienyl)nitrile, and the purified product 5-((diphenylmethylene)amino)-5-(thiophen-2-yl)-2-(((trifluoromethyl)thio)methyl)pentanenitrile: colorless oily liquid; 0.056 g; the yield is 41%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.69–7.67 (m, 4H), 7.45–7.44 (m, 6H), 7.40–7.33 (m, 6H), 7.21–7.20 (m, 2H), 7.11–7.09 (m, 4H), 6.95–6.93 (m, 2H), 6.79–6.77 (m, 2H), 4.76–4.70 (m, 2H), 3.07–3.01 (m, 4H), 2.97–2.88 (m, 1H), 2.84–2.77 (m, 1H), 2.21–1.96 (m, 4H), 1.78–1.64 (m, 4H); 13 13C NMR (100.6 MHz, CDCl3): δ 168.33, 168.29, 147.11, 147.08, 139.19, 139.16, 136.15, 136.12, 130.42, 130.33 (q, J C-F = 306.8 Hz), 130.30 (q, J C-F = 306.8 Hz), 128.70, 128.67, 128.62, 128.12, 127.45, 126.46, 126.40, 124.21, 124.13, 122.88, 122.84, 119.50, 119.49, 61.29, 61.26, 36.69, 36.54, 32.94, 32.83, 31.38 (q, J C-F = 2.0 Hz), 31.36 (q, J C-F = 2.0 Hz), 28.05, 27.83; 1919F NMR (376 MHz, CDCl3): δ -40.94 (s, 3F), -40.95 (s, 3F); ESI-HRMS: Calcd for C 24 H 22 F3N2S2 + [M + H] + 459.1171, found 459.1168.

[0286] Example 57:

[0287] Preparation of methyl 5-cyano-2-((diphenylmethylene)amino)-6-((trifluoromethyl)thio)hexanoate

[0288]

[0289] The specific preparation process was the same as that of Example 10, except that the raw material styrene was replaced with methyl 2-cyano-5-hexenoate, and the purified product methyl 5-cyano-2-((diphenylmethylene)amino)-6-((trifluoromethyl)thio)hexanoate: colorless oily liquid; 0.070 g; yield 54%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.65–7.63 (m, 2H), 7.50–7.47 (m, 3H), 7.44–7.40 (m, 1H), 7.36–7.33 m, 2H), 7.18–7.17 (m, 2H), 4.16–4.11 (m, 1H), 3.73 (s, 3H), 3.08 (d, J = 7.2 Hz, 2H), 3.00–2.84 (m, 1H), 2.23–1.98 (m, 2H), 1.84–1.67 (m, 2H); 13 13C NMR (100.6 MHz, CDCl3): δ 171.81, 171.52, 171.40, 138.97, 137.95, 135.88, 130.66, 130.28 (q, J C-F = 306.8 Hz), 130.26 (q, J C-F = 306.8 Hz), 128.90, 128.78, 128.71, 128.12, 127.54, 119.36, 119.34, 64.03, 63.99, 52.29, 52.28, 32.78, 31.26 (q, J C-F = 2.0 Hz), 31.24 (q, J C-F= 2.0 Hz), 30.59, 30.47, 27.84, 27.76; 19 19F NMR (376 MHz, CDCl3): δ -40.93 (s, 3F); ESI-HRMS: Calcd for C 22 H 22 F3N2O2S + [M + H] + 435.1349, found 435.1345.

[0290] Example 58:

[0291] Preparation of 2-(4-Isobutylphenyl)propyl 4-(4-cyano-1-((diphenylmethylene)amino)-5-((trifluoromethyl)thio)pentyl)benzoate

[0292]

[0293] The specific preparation process was the same as that of Example 10, except that the raw material styrene was replaced with 2-(4-isobutylphenyl)propyl 4-(1-cyano-4-pentenyl)benzoate, and the purified product 2-(4-Isobutylphenyl)propyl 4-(4-cyano-1-((diphenylmethylene)amino)-5-((trifluoromethyl)thio)pentyl)benzoate: colorless oily liquid; 0.097 g; yield 48%; a mixture of diastereoisomers, dr = 1:1 (the ratio was determined by 19 19F NMR analysis); 1 1H NMR (400 MHz, CDCl3): δ 7.93–7.91 (d, J = 8.4 Hz, 4H), 7.69–7.67 (m, 4H), 7.43–7.40 (m, 8H), 7.37–7.31 (m, 8H), 7.20–7.19 (m, 4H), 7.11–7.09 (m, 4H), 6.99–6.97 (m, 4H), 4.46–4.31 (m, 6H), 3.25–3.17 (m, 2H), 3.02 (s, 2H), 3.01 (s, 2H), 2.92–2.78 (m, 2H), 2.46 (s, 2H), 2.44 (s, 2H), 2.23–2.14 (m, 1H), 2.08–2.03 (m, 2H), 1.98–1.92 (m, 1H), 1.90–1.79 (m, 2H), 1.75–1.53 (m, 4H), 1.39 (s, 3H), 1.37 (s, 3H), 0.90 (s, 6H), 0.88 (s, 6H); 1313C NMR (100.6 MHz, CDCl3): δ 168.48, 168.44, 166.32, 149.05, 149.01, 140.31, 140.03, 139.20, 136.43, 136.37, 130.42, 130.30 (q, J C-F = 306.8 Hz), 129.84, 129.20, 128.57, 128.13, 127.38, 127.00, 126.86, 126.84, 119.46, 119.41, 69.99, 65.22, 64.98, 44.99, 38.64, 36.24, 36.11, 32.91, 32.85, 31.34, 30.18, 28.33, 22.35, 22.33, 18.01; 19 19F NMR (376 MHz, CDCl3): δ -40.92 (s, 3F), -40.93 (s, 3F); ESI-HRMS: Calcd for C 40 H 42 F3N2O2S + [M + H] + 671.2914, found 671.2911.

[0294] Example 59:

[0295] Preparation of 2-[4-chloro-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione

[0296]

[0297] The synthetic route is as follows:

[0298] In an oven-dried 10 mL reaction tube equipped with a magnetic stir bar, 2-pent-4-enylisoindole-1,3-dione (0.3 mmol, 1.0 equiv.), N-chlorosuccinimide (0.6 mmol, 2.0 equiv.), thioxanthone (5 mol%), and the bifunctional reagent benzophenone O-(((trifluoromethyl)thio)carbonyl)oxime (0.6 mmol, 2.0 equiv.) were added. The reaction tube was evacuated and backfilled with argon three times. Subsequently, 3 mL of acetonitrile was added under argon protection. The reaction mixture was stirred for 3 hours under irradiation with a 6 W blue LED (λmax = 405 nm) at room temperature. Then the solution was concentrated under reduced pressure, and the crude product was purified by column chromatography (gradient elution with ethyl acetate and petroleum ether) to obtain 2-[4-chloro-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione: a colorless oily liquid; 0.074 g; the yield was 70%; 11H NMR (400 MHz, CDCl3): δ 7.88–7.84 (m, 2H), 7.75–7.71 (m, 2H), 4.14–4.08 (m, 1H), 3.75 (t, J = 6.6 Hz, 2H), 3.26 (dd, J = 14.2, 6.8 Hz, 1H), 3.17 (dd, J = 14.2, 6.8 Hz, 1H), 2.06–1.93 (m, 2H), 1.91–1.71 (m, 2H); 13 13C NMR (100.6 MHz, CDCl3): δ 168.32, 134.03, 131.98, 130.62 (q, J C-F = 304.8 Hz), 123.30, 59.80, 37.35 (q, J C-F = 2.0 Hz), 37.03, 33.88, 25.49; 19 19F NMR (376 MHz, CDCl3): δ -41.05 (s, 3F); ESI-HRMS: Calcd for C 14 H 14 ClF3NO2S + [M+H] + 352.0380, found 352.0376.

[0299] Example 60:

[0300] Replace N-chlorosuccinimide in Example 59 with carbon tetrachloride, and keep the remaining procedures and conditions the same as in Example 59. Purify the obtained product 2-[4-chloro-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione: colorless oily liquid; 0.038 g; yield 36%.

[0301] Example 61:

[0302] Replace acetonitrile in Example 59 with acetone, and keep the remaining procedures and conditions the same as in Example 59. Purify the obtained product 2-[4-chloro-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione: colorless oily liquid; 0.055 g; yield 52%.

[0303] Example 62:

[0304] Replace N-chlorosuccinimide (0.6 mmol, 2.0 equiv.) in Example 59 with N-chlorosuccinimide (0.3 mmol, 1.0 equiv.), and keep the remaining procedures and conditions the same as in Example 59. Purify the obtained product 2-[4-chloro-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione: colorless oily liquid; 0.047 g; yield 44%.

[0305] Example 63:

[0306] Preparation of 4-chloro-5-(trifluoromethylthio)pentyl benzoate

[0307]

[0308] The specific preparation process is the same as that of Example 59, except that the raw material 2-pent-4-enylisoindole-1,3-dione is replaced with 4-penten-1-yl benzoate. The purified product 4-chloro-5-(trifluoromethylthio)pentyl benzoate: colorless oily liquid; 0.053 g; the yield is 54%; 1 H NMR (400 MHz, CDCl3): δ 8.05–8.03 (m, 2H), 7.59–7.55 (m, 1H), 7.45 (t, J = 7.6 Hz, 2H), 4.39–4.36 (m, 2H), 4.17–4.10 (m, 1H), 3.31 (dd, J = 14.2, 6.8 Hz, 1H), 3.19 (dd, J = 14.2, 6.8 Hz, 1H), 2.18–2.05 (m, 2H), 1.97–1.82 (m, 2H); 13 C NMR (100.6 MHz, CDCl3): δ 166.47, 133.02, 130.62 (q, J C-F = 306.8 Hz), 129.53, 128.39, 63.87, 59.94, 37.33 (q, J C-F = 2.0 Hz), 33.31, 25.60; 19 F NMR (376 MHz, CDCl3): δ -41.00 (s, 3F); ESI-HRMS: Calcd for C 13 H 14 ClF3O2S + [M+H] + 327.0428, found 327.0427.

[0309] Example 64:

[0310] Preparation of (2-chloro-5-phenoxypentyl)trifluoromethyl sulfide

[0311]

[0312] The specific preparation process is the same as that of Example 59, except that the raw material 2-pent-4-enylisoindole-1,3-dione is replaced with 4-pentyloxybenzene. The purified product (2-chloro-5-phenoxypentyl)trifluoromethyl sulfide: colorless oily liquid; 0.044 g; the yield is 49%; 11H NMR (400 MHz, CDCl3): δ 7.30–7.26 (m, 2H), 6.95 (t, J = 7.3 Hz, 1H), 6.90–6.88 (m, 2H), 4.17–4.12 (m, 1H), 4.10–3.98 (m, 2H), 3.30 (dd, J = 14.0, 7.2 Hz, 1H), 3.21 (dd, J = 14.0, 6.8 Hz, 1H), 2.22–2.12 (m, 1H), 2.08–2.03 (m, 1H), 1.98–1.82 (m, 2H); 13 13C NMR (100.6 MHz, CDCl3): δ 158.74, 130.70 (q, J C-F = 306.8 Hz), 129.47, 120.84, 114.43, 66.72, 60.28, 37.44 (q, J C-F = 2.0 Hz), 33.54, 26.11; 19 19F NMR (376 MHz, CDCl3): δ -41.01 (s, 3F), ESI-HRMS: Calcd for C 12 H 15 ClF3OS + [M+H] + 299.0479, found 299.0477.

[0313] Example 65:

[0314] Preparation of 2-chloro-5-(phenylsulfonyl)pentyl trifluoromethyl sulfide

[0315]

[0316] The specific preparation process is the same as that of Example 59, except that the raw material 2-pent-4-enylisoindole-1,3-dione is replaced with 4-pentenyl-1-sulfonylbenzene, and the purified product 2-chloro-5-(phenylsulfonyl)pentyl trifluoromethyl sulfide: colorless oily liquid; 0.073 g; the yield is 73%; 1 1H NMR (400 MHz, CDCl3): δ 7.94–7.91 (m, 2H), 7.71–7.67 (m, 1H), 7.62–7.58 (m, 2H), 4.02–3.97 (m, 1H), 3.27 (dd, J = 14.2, 6.8 Hz, 1H), 3.16–3.10 (m, 3H), 2.14–2.04 (m, 2H), 1.91–1.76 (m, 2H); 13 13C NMR (100.6 MHz, CDCl3): δ 138.86, 133.90, 130.52 (q, J C-F= 305.8 Hz), 129.41, 128.03, 59.43, 55.26, 37.14 (q, J C-F = 2.0 Hz), 34.81, 19.84; 19 F NMR (376 MHz, CDCl3): δ -40.96 (s, 3F); ESI-HRMS: Calcd for C 12 H 15 ClF3O2S2 + [M+H] + 347.0149, found 347.0149.

[0317] Example 66:

[0318] Preparation of 4-chloro-N-phenyl-5-(trifluoromethylthio)pentanamide

[0319]

[0320] The specific preparation process is the same as that of Example 59, except that the raw material 2-pent-4-enylisoindole-1,3-dione is replaced by N-phenyl-4-pentenamide, and the purified product 4-chloro-N-phenyl-5-(trifluoromethylthio)pentanamide: colorless oily liquid; 0.042 g; the yield is 45%; 1 H NMR (400 MHz, CDCl3): 7.50–7.43 (m, 3H), 7.34–7.30 (m, 2H), 7.14–7.10 (t, J = 7.4 Hz, 1H), 4.19–4.17 (m, 1H), 3.31–3.18 (m, 2H), 2.68–2.44 (m, 3H), 2.05–1.96 (m, 1H); 13 C NMR (100.6 MHz, CDCl3): δ 169.53, 137.53, 130.60 (q, J C-F = 305.8 Hz), 129.03, 124.54, 119.97, 59.92, 37.42 (q, J C-F = 2.0 Hz), 33.70, 32.01; 19 F NMR (376 MHz, CDCl3): δ -41.03 (s, 3F); ESI-HRMS: Calcd for C 12 H 14 ClF3NOS + [M+H] + 312.0431, found 312.0430.

[0321] Example 67:

[0322] Preparation of 5-chloro-1-(4-methoxyphenyl)-6-(trifluoromethylthio)hexan-1-one

[0323]

[0324] The specific preparation process is the same as that of Example 59, except that the raw material 2-pent-4-enylisoindole-1,3-dione is replaced with 1-(4-methoxyphenyl)hex-5-en-1-one, and the purified product 5-chloro-1-(4-methoxyphenyl)-6-(trifluoromethylthio)hexan-1-one: colorless oily liquid; 0.065 g; the yield is 64%; 1 H NMR(400 MHz, CDCl3): δ 7.94 (d, J = 8.8 Hz, 2H), 6.93 (d, J = 8.8 Hz, 2H), 4.14–4.10 (m, 1H), 3.87 (s, 3H), 3.31–3.18 (m, 2H), 2.98–2.96 (m, 2H), 2.07–1.99 (m, 2H), 1.92–1.77 (m, 2H); 13 C NMR(100.6 MHz, CDCl3): δ 197.79, 163.50, 130.68 (q, J C-F = 305.8 Hz), 130.21, 129.82, 113.73, 60.29, 55.42, 37.29 (q, J C-F = 2.0 Hz), 37.28, 37.03, 20.82; 19 F NMR(376 MHz, CDCl3): δ -41.02 (s, 3F); ESI-HRMS: Calcd for C 14 H 17 ClF3O2S + [M + H] + 341.0584, found 341.0582.

[0325] Example 68:

[0326] Preparation of 2-chloro-2-phenylethyl trifluoromethyl sulfide

[0327]

[0328] The specific preparation process is the same as that of Example 59, except that the raw material 2-pent-4-enylisoindole-1,3-dione is replaced with styrene, and the purified product 2-chloro-2-phenylethyl trifluoromethyl sulfide: colorless oily liquid; 0.054 g; the yield is 75%; 11H NMR (400 MHz, CDCl3): δ 7.40–7.38 (m, 5H), 5.04 (t, J = 7.2 Hz, 1H), 3.58 (dd, J = 14.2, 7.2 Hz, 1H), 3.44 (dd, J = 14.2, 7.6 Hz, 1H); 13 13C NMR (100.6 MHz, CDCl3): δ 138.65, 130.68 (q, J C-F = 306.8 Hz), 129.25, 128.95, 127.18, 60.84, 38.51 (q, J C-F = 2.0 Hz); 19 19F NMR (376 MHz, CDCl3): δ -40.98 (s, 3F); ESI-HRMS: Calcd for C9H9ClF3S + [M+H] + 241.0060, found 241.0060.

[0329] Example 69:

[0330] Preparation of 2-chloro-2-(3-methylphenyl)ethyl trifluoromethyl sulfide

[0331]

[0332] The specific preparation process is the same as that of Example 59, except that the original 2-pent-4-enylisoindole-1,3-dione is replaced with 3-methylstyrene. The purified product 2-chloro-2-(3-methylphenyl)ethyl trifluoromethyl sulfide: colorless oily liquid; 0.047 g; yield 62%; 1 1H NMR (400 MHz, CDCl3): δ 7.29–7.24 (m, 1H), 7.19–7.16 (m, 3H), 5.00 (t, J = 7.2 Hz, 1H), 3.56 (dd, J = 14.2, 7.6 Hz, 1H), 3.44 (dd, J = 14.2, 7.6 Hz, 1H), 2.37 (s, 3H); 13 13C NMR (100.6 MHz, CDCl3): δ 138.81, 138.60, 132.23, 130.72 (q, J C-F = 306.8 Hz), 130.04, 129.19, 128.83, 127.78, 124.20, 60.95, 38.45 (q, J C-F = 2.0 Hz), 21.37; 19 19F NMR (376 MHz, CDCl3): δ -40.99 (s, 3F); ESI-HRMS: Calcd for C10 H 11 ClF3S + [M+H] + 255.0217, found 255.0215.

[0333] Example 70:

[0334] Preparation of 2-bromo-2-[4-(tert-butyl)phenyl]ethyl trifluoromethyl sulfide

[0335]

[0336] The specific preparation process is the same as that of Example 59, except that the raw materials 2-pent-4-enylisoindole-1,3-dione and N-chlorosuccinimide are replaced with 4-tert-butylstyrene and N-bromosuccinimide. The purified product 2-bromo-2-[4-(tert-butyl)phenyl]ethyl trifluoromethyl sulfide: colorless oily liquid; 0.048 g; the yield is 48%; 1 H NMR (400 MHz, CDCl3): δ 7.39 (d, J = 8.4 Hz, 2H), 7.31 d, J = 8.4 Hz, 2H), 5.11 (dd, J = 8.8, 6.8 Hz, 1H), 3.74 (dd, J = 14.2, 6.8 Hz, 1H), 3.62 (dd, J = 14.2, 9.0 Hz, 1H), 1.32 (s, 9H); 13 C NMR (100.6 MHz, CDCl3): δ 152.49, 135.91, 130.64 (q, J C-F = 306.8 Hz), 127.19, 125.96, 50.97, 38.22 (q, J C-F = 2.0 Hz), 34.72, 31.20; 19 F NMR (376 MHz, CDCl3): δ -40.90 (s, 3F), ESI-HRMS: Calcd for C 13 H 17 BrF3S + [M+H] + 341.0181, found 341.0180.

[0337] Example 71:

[0338] Preparation of 2-[4-iodo-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione

[0339]

[0340] The specific preparation process is the same as that of Example 59, except that the raw material N-chlorosuccinimide is replaced by N-iodosuccinimide, and the purified product 2-[4-iodo-5-(trifluoromethylthio)pentyl]isoindole-1,3-dione is obtained: colorless oily liquid; 0.082 g; the yield is 62%; 1 H NMR(400MHz, CDCl3): δ7.87–7.85(m, 2H), 7.74–7.72(m, 2H), 4.23–4.21(m, 1H), 3.75(t, J = 6.4Hz, 2H), 3.57(dd, J = 14.2, 5.6Hz, 1H), 3.33(dd, J = 14.2, 8.8Hz, 1H), 2.04–1.78(m, 4H); 13 C NMR(100.6MHz, CDCl3): δ168.30, 132.00, 131.98, 130.47(q, J C-F = 303.8Hz), 123.30, 39.50(q, J C-F = 2.0Hz), 36.74, 35.34, 30.41, 28.61: 19 F NMR(376MHz, CDCl3): δ-40.69(s, 3F), ESI-HRMS: Calcd for C 14 H 14 F3INO2S + [M+H] + 443.9737, found 443.9736。

[0341] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the content and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A novel trifluoromethylthio-carbonohydroximoyl bifunctional reagent, characterized in that, The structure of the reagent is shown in General Formula A: Among them, R 1 and R 2 are aryl or alkyl which are substituted or unsubstituted by para-chloro etc.

2. The method according to claim 1, wherein According to the molar ratio of chloroformic acid oxime ester, deoxidizer, additive and trifluoromethanesulfonic anhydride being (1):(2 - 5):(2 - 5):(1 - 5), the chloroformic acid oxime ester is added to Solvent-1. Under the condition of -20 to 80 °C, the deoxidizer, additive and trifluoromethanesulfonic anhydride are slowly added. After reacting for half an hour, the reaction mixture is transferred to room temperature. After the reaction ends, the reaction mixture is post-treated, and the target compound trifluoromethylthio-carbonic acid oxime ester A is obtained by column chromatography separation.

3. The method according to claim 2, wherein The described Solvent-1 is any one or a mixture in any proportion of tetrahydrofuran, diethyl ether, dichloromethane, acetonitrile, benzonitrile, chlorobenzene, dichloromethane, 1,2-dichloroethane, chloroform, ethyl acetate, n-butyl acetate, dioxane, methanol, ethanol, N,N-dimethylformamide; the deoxidizer is any one of diethylphenylphosphine, methyldiphenylphosphine, tert-butyldiphenylphosphine, benzyldiphenylphosphine, triphenylphosphine; the additive is any one of tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium fluoride, tetramethylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraheptylammonium bromide; the reaction time is 12 - 48 hours.

4. A new trifluoromethylthio-carbonic acid oxime ester bifunctional reagent A as described in claim 1, its application as an olefin trifluoromethylthiolation amination bifunctional reagent in olefin bifunctionalization to synthesize trifluoromethylthio-containing amine compounds and its application as an olefin trifluoromethylthiolation reagent to synthesize trifluoromethylthio-containing halogenated hydrocarbon compounds.

5. An application as claimed in claim 4, wherein: The described trifluoromethylthio-containing amine compounds and halogenated hydrocarbon compounds have the structures shown below: Among them, when R 5 and R 6 are H, R 3 and R 4 are n-butyl, phenethyl, phenyl, substituted phenyl, pyridyl, thienyl, naphthyl, amide group, alkoxy group, ester group, acyl group, amide group, phosphonyl group, azide group, aldehyde group, cyano group, silyl group; when R 5 or R 6 is an alkyl group, R 3 and R 4 are alkyl group, phenyl group, piperidyl group; X = Cl, Br, I.

6. A preparation method of a trifluoromethylthioamine compound and a halogenated hydrocarbon compound as described in claim 5, characterized in that, Including the following steps: In a 10 mL tube dried in an oven equipped with a magnetic stir bar, after adding the new trifluoromethylthio-carbonic acid oxime ester bifunctional reagent, olefin-1, Michael acceptor, photosensitizer and Solvent-2 to the reaction tube, it is sealed, the protective gas is replaced, and it is stirred and reacted at -10 to 60 °C. After irradiating with a blue light lamp for a certain time until the raw materials are consumed, trifluoromethylthio-containing amine compounds B - D are obtained through post-treatment. In a 10 mL tube dried in an oven equipped with a magnetic stir bar, after adding the new trifluoromethylthio-carbonic acid oxime ester bifunctional reagent A, olefin-1, photosensitizer, halogen source and Solvent-3 to the reaction tube, it is sealed, the inert gas is replaced, and it is stirred and reacted at -10 to 60 °C. After irradiating with a blue light lamp for a certain time until the raw materials are consumed, trifluoromethylthio-containing halogenated hydrocarbon compound E is obtained through post-treatment.

7. The preparation method of the trifluoromethylthioamine compound according to claim 6, characterized in that, The molar ratio of the novel trifluoromethylthio-carbonyl oxime ester bifunctional reagent A, olefin-1 and Michael acceptor is (1 to 3):(1 to 3):(0 to 4); the molar ratio of the novel trifluoromethylthio-carbonyl oxime ester bifunctional reagent A, olefin-1 and halogen source is (1 to 2):(1 to 2):(1 to 3); the olefin-1 is any one of electron-deficient olefins and electron-rich olefins; the Michael acceptor is any one of electron-deficient olefins; the photosensitizer is any one of [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 4CzIPN, xanthone and thioxanthone; the dosage of the photosensitizer is 0.5 mol% to 10 mol% of the dosage of the novel trifluoromethylthio-carbonyl oxime ester bifunctional reagent; the halogen source is any one of carbon tetrachloride, carbon tetrabromide, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 2-iodopropane, tert-butyl iodide, trichloroisocyanuric acid; the solvent-2 is any one or a mixture in any proportion of tetrahydrofuran, dichloromethane, acetonitrile, dichloromethane, chloroform, ethyl acetate, dioxane, acetone, methanol, N,N-dimethylformamide; the protective gas is selected from any one of nitrogen and argon; the wavelength of the blue light lamp is 390 nm to 460 nm; the power of the blue light lamp is 3 to 30 W; the reaction time is 2 to 12 hours;.

8. A novel trifluoromethylthio-carbonyl oxime ester bifunctional reagent as described in claim 1, its application in synthesizing trifluoromethylthio-containing amines, amino acids, aminonitriles, trifluoromethylthio-containing halogenated hydrocarbons, preparing drugs and as an acceptable carrier in pharmacy.

9. A trifluoromethylthio-containing amine compound as described in claim 5, its application in amino acid drugs, terpene drugs and steroid drugs containing trifluoromethylthio structural units.

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