1-mercapto-3-alkyl bicyclo [1.1. 1] pentane and synthesis method thereof

Abstract

The invention relates to 1-mercapto-3-alkyl bicyclo [1.1. 1] pentane and a synthesis method thereof. The invention discloses 1-sulfydryl-3-(perfluoro) alkyl bicyclo [1.1. 1] pentane and a synthesis method of the 1-sulfydryl-3-(perfluoro) alkyl bicyclo [1.1. 1] pentane. The synthesis method comprises the following steps: by taking diphenyl disulfide, [1.1. 1] propeller alkane and halogenated hydrocarbon as raw materials and N-methyl pyrrolidone as a solvent at normal temperature, reacting under a photocatalytic condition, and purifying a crude product through silica gel column chromatography (200-300-mesh silica gel) to synthesize the 1-sulfydryl-3-(perfluoro) alkyl bicyclo [1.1. 1] pentane. The method has the advantages of mild reaction conditions, simple experimental operation, good reaction selectivity, high product yield, easy product separation and the like.

Description

Technical Field

[0001] This invention belongs to the field of pharmaceutical and chemical intermediate synthesis technology, specifically relating to 1-mercapto-3-alkylbicyclo[1.1.1]pentane and its synthesis method. Background Technology

[0002] Aryl thiol or alkyl thiol structural units are widely found in natural products, synthetic chemistry, materials, pharmaceuticals, and pesticide molecules. For example, arbidol is commonly used to treat upper respiratory tract infections caused by influenza A and B viruses; vortioxetine hydrochloride is used to treat adult depression; cefazolin is used to treat various infectious diseases such as respiratory tract infections and urinary tract infections caused by susceptible bacteria; and fluticasone propionate is used to treat respiratory allergic diseases such as asthma and allergic rhinitis.

[0003] Halogenated hydrocarbons are widely distributed in nature. The introduction of halogen atoms (such as fluorine) can significantly alter the properties of drug molecules, optimizing efficacy and pharmacokinetic properties by enhancing binding affinity to targets, improving metabolic stability, and regulating lipophilicity. For example, the antidepressant fluoxetine and the antibiotic levofloxacin both benefit from enhanced efficacy due to the presence of fluorine atoms. Perfluoroalkyl groups are used to construct fluorine-containing drug molecules, expanding the diversity of drug structures and aiding in the development of novel drugs. Currently, the pesticide field is dominated by fluorine-containing pesticides, such as fipronil and flonicamid. Leveraging the strong electronegativity and stability of fluorine atoms, these pesticides achieve high insecticidal / fungicidal activity, low toxicity, and environmental compatibility, meeting the demands of modern agriculture for highly efficient and safe pesticides, and becoming an important direction in pesticide molecule design.

[0004] These all demonstrate the application value of substances containing aryl thiol or alkyl thiol structural units, and fluorine-containing substances. If thiol and alkyl groups can be introduced into the bioisostere [1.1.1]pentane (BCP), it will have wider applications in drug synthesis. However, how to construct 1-mercapto-3-alkylbicyclo[1.1.1]pentane in one step under green, simple, and mild reaction conditions has always been a research challenge in the field of organic synthesis. This invention uses [1.1.1]spiroalkyl and readily available diphenyl disulfide and haloalkanes as raw materials, and obtains a series of 1-mercapto-3-alkylbicyclo[1.1.1]pentanes with high selectivity and high yield through a photocatalyst-catalyzed three-component reaction under mild conditions. This compound is a bioisostere of aryl thiol / alkyl thiol or (perfluoro)alkyl groups, and has good research and application value. Summary of the Invention

[0005] In view of the above-mentioned problems existing in the prior art, the present invention provides a simple and efficient method for synthesizing 1-mercapto-3-alkylbicyclo[1.1.1]pentane.

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

[0007] 1-Mercapto-3-(perfluoro)alkylbicyclo[1.1.1]pentane, the structural formula of which is shown in formula (IV):

[0008]

[0009] Where: R 1 It is one of C1-C4 alkyl or substituted alkyl, phenyl, or benzothiazole, wherein the substituent of the substituted alkyl group is benzene; R 2 It is a C1-C10 perfluoroalkyl, methylquinoline, acetate group, cyanomethyl, fluorinated acetate group or difluoroacetate group; X is chlorine, bromine or iodine.

[0010] A method for synthesizing 1-mercapto-3-alkylbicyclo[1.1.1]pentane includes: using a disulfide compound as shown in formula (I), [1.1.1]spiroalkyl as shown in formula (II), and a haloalkane as shown in formula (III) as raw materials, adding the raw materials to an organic solvent, and reacting them in the presence of a catalyst and additives under an inert atmosphere and under blue light irradiation to synthesize 1-mercapto-3-alkylbicyclo[1.1.1]pentane as shown in formula (IV). The reaction equation is as follows:

[0011]

[0012] The substituent R in formula (Ⅰ) 1 The substituent R in formula (II) 2 In the same formula (IV).

[0013] Furthermore, the molar ratio of the disulfide compound, [1.1.1]spiroalkane and haloalkanes is 1:1 to 10:1 to 5, preferably 1:4:3.

[0014] Further, the organic solvent is any one of dichloromethane, 1,2-dichloroethane, ethanol, ethyl acetate, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, or N-methylpyrrolidone, and the volume ratio of the organic solvent to the molar amount of the disulfide compound is 10 to 100:1, preferably 15 to 30:1, with volume in mL and molar amount in mmol.

[0015] Further, the catalyst is any one of 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, meta-triphenylmethylvinyl cationic perchlorate, dicyanoanthracene, phenothiazine, anthraquinone, 4-phenylphenol, 10-methyl-9-trimethylmethylacridine perchlorate, or 3,6-di-tert-butyl-9-trimethylmethyl-10-phenylacridine-10-onium tetrafluoroborate, and the molar ratio of the catalyst to the disulfide compound is 0.01 to 0.1:1, preferably 0.02:1.

[0016] Furthermore, the additive is any one of diisopropylethylamine, triethylamine, and sodium bicarbonate, and the molar ratio of the additive to the disulfide compound is 0.5 to 3:1, preferably 2:1.

[0017] Furthermore, the reaction time is 8 to 24 hours, preferably 12 to 18 hours, and the reaction temperature is room temperature.

[0018] Furthermore, the reaction atmosphere is nitrogen.

[0019] Furthermore, the power of the blue light source is 5W-50W.

[0020] Furthermore, the following post-processing steps are included after the reaction is completed: after the reaction is completed, saturated ammonium chloride aqueous solution is added to quench the reaction, ethyl acetate organic solvent is added for extraction and separation, the organic layer is dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered and concentrated to obtain a brown or yellow crude product, the crude product is purified by column chromatography to obtain 1-mercapto-3-alkylbicyclo[1.1.1]pentane.

[0021] Furthermore, the elution solvent used for column chromatography purification is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:50-500, wherein the volume ratio of ethyl acetate to petroleum ether is preferably 1:50-200.

[0022] The beneficial effects of this invention are as follows: The synthesis method of this invention uses diphenyl disulfide, [1.1.1]spiroalkyl, and haloalkanes as raw materials, reacts them at room temperature with N-methylpyrrolidone as solvent under photocatalytic conditions, and purifies the crude product by silica gel column chromatography (200-300 mesh silica gel) to synthesize 1-mercapto-3-(perfluoro)alkylbicyclo[1.1.1]pentane. This invention has the advantages of mild reaction conditions, simple experimental operation, good reaction selectivity, high product yield, and easy product separation. Attached Figure Description Figure 1 These are the inhibition results of HeLa cells at different final concentrations of the compounds in Examples 10, 12 and 16 of this invention. Detailed Implementation

[0023] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto:

[0024] Example 1:

[0025]

[0026] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen in a double-row tube, N-methylpyrrolidone solvent containing [1.1.1]spiropropane (4 mmol), ethyl bromoacetate (501 mg, 3 mmol), and diisopropylethylamine (258 mg, 2 mmol) was added. The mixture was stirred at room temperature under blue light (455nm, 10W) ​​for 16 hours. After the reaction was completed, 20g of saturated ammonium chloride aqueous solution was added to quench the reaction. Ethyl acetate (30g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 367mg of pale yellow liquid, with a yield of 70%. The purity was determined to be above 99.9% by NMR spectroscopy. 1 H NMR (500MHz, CDCl3) δ7.45–7.41(m,2H),7.32–7.27(m,3H),4.10(q,J=7.2Hz,2H),2.51(s,2H),1.92(s,6H),1.23(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ172.4,135.3,135.1,130.3,129.1,61.9,56.4,43.4,38.6,31.2,15.8; HRMS (ESI+):Calculated for C 15 H 18 O2S:[M+Na] + 301.0869, Found 301.0882.

[0027] Example 2:

[0028]

[0029] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), 2-bromomethylquinoline (666 mg, 3 mmol), and diisopropylethylamine (258 mg, 2 mmol) was added. The N-methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 18 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:80, v / v) to obtain 400 mg of a deep yellow liquid, with a yield of 63%. 1 HNMR(500MHz, CDCl3)δ8.08(d,J=8.5Hz,2H),7.79(d,J=8.1Hz,1H),7.72–7.67(m,1H),7.53–7.49( m,1H),7.39(dt,J=7.5,1.6Hz,2H),7.27–7.23(m,3H),7.21–7.16(m,1H),3.22(s,2H),1.85(s,6H); 13 C NMR (126MHz, CDCl3) δ159.3,136.2,134.0,133.5,129.6,128.8,128.7,127.5,12 7.5,126.7,126.0,122.6,121.6,54.6,42.5,41.5,40.4; HRMS(ESI+):Calculated for C 21 H 19 NS:[M+H] + 318.1311, Found 318.1313.

[0030] Example 3:

[0031]

[0032] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), 2-bromo-N,N-dibutylacetamide (666 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. A solution of N-methylpyrrolidone (20 mL) was stirred at room temperature under blue light (455 nm, 10 W) for 16 hours. After the reaction was complete, a saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:50, v / v) to obtain 421 mg of a pale yellow liquid, with a yield of 61%. 1 H NMR (500MHz, CDCl3) δ7.49–7.39(m,2H),7.31–7.25(m,3H),3.30–3.23(m,2H),3.17–3.09(m,2H ),2.54(s,2H),1.93(s,6H),1.52–1.42(m,4H),1.31–1.25(m,4H),0.92(dt,J=10.3,7.3Hz,6H); 13 CNMR(126MHz, CDCl3)δ169.8,134.0,133.5,128.6,127.5,55.1,48.0,45.5,42.0,38.0,35.5,31.3,30.0,20.3,20.1,13.9,13.8; HRMS(ESI+):Calculated for C 21 H 31 NOS: [M+Na] + 368.2019, Found 368.2017.

[0033] Example 4:

[0034]

[0035] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-methylpropane containing [1.1.1]spiropropane (4 mmol), bromoacetonitrile (360 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. Methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 10 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 267 mg of yellow liquid, with a yield of 62%. 1 HNMR (500MHz, CDCl3) δ7.44 (dt, J = 6.9, 2.1Hz, 2H), 7.35–7.28 (m, 3H), 2.58 (s, 2H), 1.95 (s, 6H); 13 C NMR(126MHz, CDCl3)δ133.9,133.0,129.0,128.0,116.9,54.3,41.9,35.7,20.9; HRMS(ESI+):Calculated for C 13 H 13 NS:[M+Na+O] + 254.061, Found 254.0619.

[0036] Example 5:

[0037]

[0038] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-methylpropionate containing [1.1.1]spiropropane (4 mmol), butylene 2-bromopropionate (666 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. Methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 16 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 332 mg of a dark yellow or pale yellow liquid, with a yield of 55%. 1 H NMR (500MHz, CDCl3) δ7.48–7.40(m,2H),7.34–7.26(m,3H),5.75(td,J=10.2,5.1Hz,1H),5.13–4.99(m,2H),4.10( t,J=6.6Hz,2H),2.60(q,J=6.7Hz,1H),2.36(dd,J=12.8,5.1Hz,2H),1.83(d,J=3.0Hz,6H),1.06(d,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ173.8,134.0,133.8,133.7,128.8,127.6,117.3,63.4,53.0,41.7,41.3,40.7,33.2,13.6; HRMS (ESI+): Calculated for C 18 H 22 O2S:[M+Na] + 325.1233, Found 325.1229.

[0039] Example 6:

[0040]

[0041] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthionyl tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen in a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), S-(2,5-dihydrothiazolyl-2-yl)-2-bromopropylthioester (759 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. A solution of N-methylpyrrolidone (20 mL) was stirred at room temperature under blue light (455 nm, 10 W) for 18 hours. After the reaction was completed, 20 g of saturated ammonium chloride aqueous solution was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:100, v / v) to obtain 426 mg of a dark yellow or pale yellow liquid, with a yield of 61%. 1 H NMR (500MHz, CDCl3) δ7.46–7.42(m,2H),7.34–7.29(m,3H),4.20(q,J=7.2Hz,1H),3. 74(td,J=7.2,2.7Hz,2H),2.69(t,J=7.5Hz,2H),2.10(s,6H),1.69(d,J=7.2Hz,3H); 13 C NMR(126MHz, CDCl3)δ175.1,170.8,133.9,133.1,128.9,128.0,57.3,43.8,42.2,41.5,40.8,28.5,19.0; HRMS(ESI+):Calculated forC 17 H 19 NOS3: [M+Na+O] + 388.047, Found 388.0446.

[0042] Example 7:

[0043]

[0044] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen in a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), 2,2,3,3,3-pentafluoropropyl-2-bromo-2-methylpropionate (894 mg, 3 mmol), and diisopropylethylamine (500 mg, 1 mmol) was added. A 20 mL solution of N-methylpyrrolidone (2 mmol) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 16 hours. After the reaction was completed, a 20 g saturated ammonium chloride aqueous solution was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried over anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 394 mg of a dark yellow or pale yellow liquid, with a yield of 50%. 1 H NMR (500MHz, CDCl3) δ7.46–7.41(m,2H),7.33–7.27(m,3H),4.49(td,J=12.9,1.1Hz,2H),1.81(s,6H),1.14(s,6H); 13 C NMR (126MHz, CDCl3) δ174.0,133.8,133.6,128.8,127.7,59.2(t,J=27.8Hz),51.6,45.5,42.7,40.5,21.8, 13 CNMR for C2F5 could not be assigned; 19 F NMR(471MHz, CDCl3)δ-83.76–-83.84(m),-123.24–-123.36(m); HRMS(ESI+):Calculated for C 18 H 19 F5O2S:[M+Na] + 417.0918, Found 417.0911.

[0045] Example 8:

[0046]

[0047] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), ethyl 2-fluoro-2-iodoacetate (696 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. The N-methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 16 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:120 v / v) to obtain 252 mg of dark yellow or light yellow liquid, with a yield of 45%. 1 H NMR (500MHz, CDCl3) δ7.48–7.40(m,2H),7.31(dd,J=5.1,2.1Hz,3H),4.82(d,J=49.3Hz,1H),4.28–4.20(m,2H),1.96(s,6H),1.28(t,J=7.2Hz,3H); 13 CNMR (126MHz, CDCl3) δ167.5 (d, J = 24.4Hz), 134.0, 133.0, 128.9, 128.0, 86.8 (d, J = 185.8Hz), 61.5, 53.0, 42.3 (d, J = 2.1Hz), 39.2 (d, J = 26.3Hz), 14.3; 19 F NMR(471MHz, CDCl3)δ-192.73; HRMS(ESI+):Calculated for C 15 H 17 FO2S:[M+Na+O] + 319.0775, Found 319.0752.

[0048] Example 9:

[0049]

[0050] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-carbon dioxide containing [1.1.1]spiropropane (4 mmol), ethyl difluorobromoacetate (750 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. Methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 10 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:120 v / v) to obtain 411 mg of a dark yellow or pale yellow liquid, with a yield of 69%. 1 H NMR (500MHz, CDCl3) δ7.87–7.83(m,4H),7.56–7.52(m,2H),7.44–7.42(m,1H),7. 38(dd,J=7.7,1.8Hz,2H),7.29(td,J=6.2,2.8Hz,3H),5.42(s,2H),1.98(s,6H); 13 CNMR(126MHz, CDCl3)δ162.87(t,J=33.2Hz),134.11,133.35,133.08,132.39,131.56,128.98,128.71,128.20,12 8.18,128.11,127.78,126.73,126.58,125.79,112.62(t,J=250.6Hz),68.47,52.20,42.14,39.55(t,J=31.7Hz); 19 F NMR(471MHz, CDCl3)δ-110.16; HRMS(ESI+):Calculated for C 24 H 20 F₂O₂S:[M+Na+O] + 449.09933, Found 449.0963.

[0051] Example 10:

[0052]

[0053] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-carbon gas containing [1.1.1]spiropropane (4 mmol), benzyl difluorobromoacetate (990 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. Methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 12 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:120 v / v) to obtain 484 mg of a dark yellow or pale yellow liquid, with a yield of 59%. 1 H NMR (500MHz, CDCl3) δ7.87–7.83(m,4H),7.56–7.52(m,2H),7.44–7.42(m,1H),7. 38(dd,J=7.7,1.8Hz,2H),7.29(td,J=6.2,2.8Hz,3H),5.42(s,2H),1.98(s,6H); 13 CNMR(126MHz, CDCl3)δ162.87(t,J=33.2Hz),134.11,133.35,133.08,132.39,131.56,128.98,128.71,128.20,12 8.18,128.11,127.78,126.73,126.58,125.79,112.62(t,J=250.6Hz),68.47,52.20,42.14,39.55(t,J=31.7Hz); 19 F NMR(471MHz, CDCl3)δ-110.16; HRMS(ESI+):Calculated for C 24 H 20 F₂O₂S:[M+Na+O] + 449.09933, Found 449.0963.

[0054] Example 11:

[0055]

[0056] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-carbon gas containing [1.1.1]spiropropane (4 mmol), perfluoroiodobutane (1037 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. Methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 12 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:500, v / v) to obtain 489 mg of a dark yellow or pale yellow liquid, with a yield of 62%. 1 H NMR (500MHz, CDCl3) δ7.47–7.42 (m, 2H), 7.34 (dt, J = 4.5, 1.8Hz, 3H), 2.13 (s, 6H); 13 C NMR (126MHz, CDCl3) δ134.3, 132.1, 129.1, 128.4, 52.8, 42.5, 38.1 (t, J = 30.8Hz), 13 C NMR for C4F9could not be assigned; 19 F NMR(471MHz, CDCl3)δ-80.88–-81.29(m),-115.48–-116.09(m),-122.04–-122.50(m),-125.86–-126.39(m); HRMS(ESI+):Calculatedfor C 15 H 11 F9S:[M+Na+O] + 433.0279, Found433.0272.

[0057] Example 12:

[0058]

[0059] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-carbon gas containing [1.1.1]spiropropane (4 mmol), perfluoroiododecane (1938 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. Methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 14 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:500, v / v) to obtain 805 mg of dark yellow or light yellow liquid, with a yield of 58%. 1 H NMR (500MHz, CDCl3) δ7.46 (ddd, J=6.1, 2.9, 1.5Hz, 2H), 7.38–7.31 (m, 3H), 2.14 (s, 6H); 13 C NMR (126MHz, CDCl3) δ133.4,131.1,128.1,127.4,51.8,41.5,37.2(t,J=30.8Hz), 13 C NMR for C 10 F 21 could not be assigned; 19 F NMR(471MHz, CDCl3)δ-81.03–-81.27(m),-115.71–-115.99(m)-120.81–-120.99(m),-121.27–-121.51(m),-121.56–-121.73(m),-12 1.89–-121.97(m),,-122.10–-122.29(m),-122.90–-123.11(m),-126.26–-126.43(m),-126.53–-126.67(m); HRMS(ESI+):Calculated for C 21 H 11 F 21 S:[M+Na+O] + 733.0087, Found 733.0061.

[0060] Example 13:

[0061]

[0062] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-methylpropane containing [1.1.1]spiropropane (4 mmol), dibromodifluoromethane (629 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. The pyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 16 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:100 v / v) to obtain 359 mg of a dark yellow or pale yellow liquid, with a yield of 58%. 1 H NMR (500MHz, CDCl3) δ7.45 (dd, J=6.4, 3.1Hz, 2H), 7.34 (q, J=3.2, 2.6Hz, 3H), 2.14 (s, 6H); 13 C NMR (126MHz, CDCl3) δ134.3, 129.1, 128.4, 127.5, 57.7, 53.1, 46.7 (d, J = 30.4Hz); 19 FNMR(471MHz, CDCl3)δ-51.34; HRMS(ESI+):Calculated for C 12 H 11 BrF2S:[M+H+O] + 320.9755, Found 320.9769.

[0063] Example 14:

[0064]

[0065] Dibenzothiazole disulfide (332 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-mesethyl-10-phenylacridin-10-onium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), ethyl bromoacetate (501 mg, 3 mmol), and diisopropylethylamine (258 mg, 2 mmol) was added. The N-methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 18 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 364 mg of yellow liquid, with a yield of 57%. 1 HNMR(500MHz,; CDCl3)δ7.92(d,J=8.1Hz,1H),7.78(d,J=7.9Hz,1H),7.43(t,J=7.7Hz,1H),7 .32(t,J=7.6Hz,1H),4.15(q,J=7.1Hz,2H),2.61(s,2H),2.28(s,6H),1.27(t,J=7.2Hz,3H); 13 C NMR (126MHz, CDCl3) δ170.7,164.7,153.0,135.7,126.1,124.6,122.2,120.9,60.5,55.7,40.5,38.4,36.9,14.3; HRMS (ESI+): Calculated for C 16 H 17 NO2S2:[M+Na+O] + 358.0542, Found 358.0500.

[0066] Example 15:

[0067]

[0068] Diphenylethyl disulfide (274 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, a mixture containing [1.1.1]spiropropane (4 mmol), ethyl bromoacetate (501 mg, 3 mmol), and diisopropylethylamine (258 mg, 2 mmol) was added. The N-methylpyrrolidone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 18 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 302 mg of yellow liquid, with a yield of 52%. 1 HNMR(500MHz, CDCl3)δ7.30(dd,J=8.1,6.8Hz,2H),7.25–7.16(m,3H),4.13(q,J=7.2Hz,2H),2 .88(dd,J=9.6,6.3Hz,2H),2.77(dd,J=9.5,6.3Hz,2H),2.54(s,2H),1.95(s,6H),1.26(s,3H); 13 C NMR (126MHz, CDCl3) δ171.0,140.6,128.6,128.5,126.4,60.4,54.6,40.6,37.2,37.0,37.0,32.8,14.3; HRMS (ESI+): Calculated for C 17 H 22 O2S: [M+Na+O] + 329.1182, Found 329.1179.

[0069] Example 16:

[0070]

[0071] Diphenyl disulfide (218 mg, 1 mmol) and the photocatalyst 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate (11 mg, 0.02 mmol) were added to a 25 mL Schlenk reactor equipped with a magnetic stirrer. The Schlenk reactor was placed on a magnetic stirrer, and after purging with nitrogen through a double-row tube, N-methylpyrrole containing [1.1.1]spiropropane (4 mmol), estradiol bromoacetate (1170 mg, 3 mmol), and diisopropylethylamine (500 mg, 2 mmol) was added. The ketone solution (20 mL) was stirred and reacted at room temperature under blue light (455 nm, 10 W) for 18 hours. After the reaction was completed, saturated ammonium chloride aqueous solution (20 g) was added to quench the reaction. Ethyl acetate (30 g) was added to extract and separate the layers. The organic layer was dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered, and concentrated to obtain a brown or yellow crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel, eluent: ethyl acetate / petroleum ether = 1:200, v / v) to obtain 496 mg of a deep yellow or pale yellow liquid, with a yield of 51% and a melting point of 118 °C. 1 H NMR (500MHz, CDCl3) δ7.49–7.41(m,2H),7.34–7.26(m,4H),6.82(s,1H),6.77 (d,J=2.5Hz,1H),2.92–2.88(m,2H),2.75(s,2H),2.54–2.48(m,1H),2.41(d, J=3.2Hz,1H),2.28(d,J=4.6Hz,1H),2.19–2.07(m,2H),2.01(s,6H),1.99–1. 91(m,2H),1.60(qd,J=10.8,9.8,7.2Hz,3H),1.52–1.43(m,3H),0.90(s,3H); 13 C NMR (126MHz, CDCl3) δ169.7,148.4,138.1,137.5,133.7,133.6,128.8,127.6,126.4,121.5,118.7,55.0,50. 4,50.0,47.9,44.2,42.0,38.0,37.1,37.0,35.9,31.6,29.4,26.3,25.8,21.6,13.8; HRMS(ESI+):Calculated for C 31 H 34 O3S:[M+Na] + 509.2121, found 509.2111.

[0072] Example 17:

[0073] The reactant ethyl bromoethyl was replaced with an equal molar amount of ethyl chloroethyl, and other operations were the same as in Example 1, yielding 304 mg of pale yellow liquid, with a yield of 58%.

[0074] Example 18:

[0075] The reactant ethyl bromoethyl was replaced with an equal molar amount of ethyl iodoethyl, and other operations were the same as in Example 1, yielding 210 mg of pale yellow liquid, with a yield of 40%.

[0076] Example 19:

[0077] The feed amounts of [1.1.1]spiroline and ethyl bromoacetate were adjusted to make the molar ratio of diphenyl disulfide, [1.1.1]spiroline and ethyl bromoacetate 1:1:1. Other operations were the same as in Example 1, yielding 236 mg of yellow liquid with a yield of 45%.

[0078] Example 20:

[0079] The feed amounts of [1.1.1]spiroline and ethyl bromoacetate were adjusted to make the molar ratio of diphenyl disulfide, [1.1.1]spiroline and ethyl bromoacetate 1:1:5. Other operations were the same as in Example 1, yielding 299 mg of yellow liquid with a yield of 57%.

[0080] Example 21:

[0081] The feed amounts of [1.1.1]spiroline and ethyl bromoacetate were adjusted to make the molar ratio of diphenyl disulfide, [1.1.1]spiroline and ethyl bromoacetate 1:10:1. Other operations were the same as in Example 1, yielding 320 mg of yellow liquid with a yield of 61%.

[0082] Example 22:

[0083] The feed amounts of [1.1.1]spiroline and ethyl bromoacetate were adjusted to make the molar ratio of diphenyl disulfide, [1.1.1]spiroline and ethyl bromoacetate 1:10:5. Other operations were the same as in Example 1, yielding 351 mg of yellow liquid with a yield of 67%.

[0084] Example 23:

[0085] The reaction solvent was changed to an equal volume of dichloromethane, and other operations were the same as in Example 1, yielding 121 mg of yellow liquid, with a yield of 23%.

[0086] Example 24:

[0087] The reaction solvent was changed to an equal volume of 1,2-dichloroethane, and other operations were the same as in Example 1, yielding 147 mg of yellow liquid, with a yield of 28%.

[0088] Example 25:

[0089] The reaction solvent was changed to an equal volume of ethanol, and other operations were the same as in Example 1, yielding 67 mg of yellow liquid, with a yield of 12%.

[0090] Example 26:

[0091] The reaction solvent was changed to an equal volume of ethyl acetate, and other operations were the same as in Example 1, yielding 294 mg of yellow liquid, with a yield of 56%.

[0092] Example 27:

[0093] The reaction solvent was replaced with an equal volume of acetonitrile, and other operations were the same as in Example 1, yielding 304 mg of yellow liquid, with a yield of 58%.

[0094] Example 28:

[0095] The reaction solvent was replaced with an equal volume of N,N-dimethylformamide, and other operations were the same as in Example 1, yielding 225 mg of yellow liquid, with a yield of 43%.

[0096] Example 29:

[0097] The reaction solvent was changed to an equal volume of tetrahydrofuran, and other operations were the same as in Example 1, yielding 121 mg of yellow liquid, with a yield of 23%.

[0098] Example 30:

[0099] The reaction solvent was changed to an equal volume of dimethyl sulfoxide, and other operations were the same as in Example 1, yielding 73 mg of yellow liquid, with a yield of 14%.

[0100] Example 31:

[0101] The reaction catalyst was replaced with an equimolar amount of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, and other operations were the same as in Example 1, yielding 68 mg of yellow liquid, with a yield of 13%.

[0102] Example 32:

[0103] The reaction catalyst was replaced with an equimolar amount of dicyanoanthracene, and other operations were the same as in Example 1, yielding 155 mg of yellow liquid, with a yield of 22%.

[0104] Example 33:

[0105] The reaction catalyst was replaced with an equimolar amount of phenothiazine, and other operations were the same as in Example 1, yielding 131 mg of yellow liquid, with a yield of 25%.

[0106] Example 34:

[0107] The reaction catalyst was replaced with an equal molar amount of anthraquinone, and other operations were the same as in Example 1, yielding 168 mg of yellow liquid, with a yield of 32%.

[0108] Example 35:

[0109] The reaction catalyst was replaced with an equimolar amount of 10-methyl-9-trimethylylacrylidine perchlorate, and other operations were the same as in Example 1, yielding 225 mg of yellow liquid, with a yield of 43%.

[0110] Example 36:

[0111] The amount of catalyst was adjusted so that the molar ratio of 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate to diphenyl disulfide was 0.01:1. Other operations were the same as in Example 1, and 294 mg of yellow liquid was obtained, with a yield of 56%.

[0112] Example 37:

[0113] The amount of catalyst was adjusted so that the molar ratio of 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate to diphenyl disulfide was 0.1:1. Other operations were the same as in Example 1, and 367 mg of yellow liquid was obtained, with a yield of 70%.

[0114] Example 38:

[0115] The reaction additive was replaced with an equimolar amount of triethylamine, and other operations were the same as in Example 1, yielding 294 mg of yellow liquid, with a yield of 56%.

[0116] Example 39:

[0117] The reaction additive was replaced with an equimolar amount of sodium bicarbonate, and other operations were the same as in Example 1, yielding 163 mg of yellow liquid, with a yield of 31%.

[0118] Example 40:

[0119] The amount of additive was adjusted so that the molar ratio of diisopropylethylamine to diphenyl disulfide was 0.5:1. Other operations were the same as in Example 1, yielding 246 mg of yellow liquid with a yield of 47%.

[0120] Example 41:

[0121] The amount of additive was adjusted so that the molar ratio of diisopropylethylamine to diphenyl disulfide was 3:1. Other operations were the same as in Example 1, yielding 356 mg of yellow liquid with a yield of 68%.

[0122] Example 42:

[0123] The reaction time was changed to 8 hours, and other operations were the same as in Example 1, yielding 267 mg of yellow liquid, with a yield of 51%.

[0124] Example 43:

[0125] The reaction time was changed to 24 hours, and other operations were the same as in Example 1, yielding 367 mg of yellow liquid, with a yield of 70%.

[0126] Example 44:

[0127] Thioether derivatives exhibit good antitumor activity. The 1-mercapto-3-alkylbicyclo[1.1.1]pentane obtained in Examples 10, 12, and 16 were tested for in vitro antitumor activity. Based on the MTT assay, to test the inhibitory effect on HeLa cells, the compounds were dissolved in DMSO (dimethyl sulfoxide) to prepare a stock solution, which was then diluted with cell culture medium (ensuring a final DMSO concentration ≤0.1%) and added to cultured HeLa cells for 36 hours. Cell viability was then detected using the MTT assay. The inhibitory results of the compounds from Examples 10, 12, and 16 on HeLa cells at different final concentrations are shown below. Figure 1 As shown, from Figure 1 It can be seen that IC 50 The values ​​were 8.5 (±0.6), 9.8 (±0.5), and 11.2 (±0.8), respectively, indicating that it has a good inhibitory effect on HeLa cells.

[0128] The novel 1-mercapto-3-alkylbicyclo[1.1.1]pentane obtained in the embodiments of the present invention has potential application prospects in the fields of pharmaceuticals, chemicals, materials, and dyes.

[0129] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of this invention should be considered within the scope of protection of this invention.

Claims

1,1-Mercapto-3-(perfluoro)alkylbicyclo[1.1.1]pentane, characterized in that... Its structural formula is shown in equation (IV): Where: R 1 It is one of C1-C4 alkyl or substituted alkyl, phenyl, or benzothiazole, wherein the substituent of the substituted alkyl group is benzene; R 2 It is a C1-C10 perfluoroalkyl, methylquinoline, acetate group, cyanomethyl, fluorinated acetate group or difluoroacetate group; X is chlorine, bromine or iodine.

2. A 1-mercapto-3-alkylbicyclo[] according to claim 1 1.1.1] A method for synthesizing pentane, characterized in that... Using a disulfide compound as shown in formula (I), [1.1.1]spiroalkyl as shown in formula (II), and a haloalkane as shown in formula (III) as raw materials, the raw materials were added to an organic solvent and reacted in an inert atmosphere under blue light irradiation in the presence of a catalyst and additives to synthesize 1-mercapto-3-alkylbicyclo[ ] as shown in formula (IV). 1.1.1] Pentane, the reaction equation is as follows: The substituent R in formula (Ⅰ) 1 The substituent R in formula (II) 2 In the same formula (IV).

3. A 1-mercapto-3-alkylbicyclo[ 1.1.1] A method for synthesizing pentane, characterized in that... The molar ratio of the disulfide compound, [1.1.1]spiroalkane and haloalkanes is 1:1 to 10:1 to 5, preferably 1:4:

3.

4. A 1-mercapto-3-alkylbicyclo[ 1.1.1] A method for synthesizing pentane, characterized in that... The organic solvent is any one of dichloromethane, 1,2-dichloroethane, ethanol, ethyl acetate, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, or N-methylpyrrolidone. The volume ratio of the organic solvent to the molar amount of the disulfide compound is 10 to 100:1, preferably 15 to 30:

1. The volume unit is mL, and the molar amount unit is mmol.

5. A 1-mercapto-3-alkylbicyclo[] according to claim 2 1.1.1] A method for synthesizing pentane, characterized in that... The catalyst is any one of 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, meta-triphenylmethylvinyl cationic perchlorate, dicyanoanthracene, phenothiazine, anthraquinone, 4-phenylphenol, 10-methyl-9-trimethylmethylacridine perchlorate, or 3,6-di-tert-butyl-9-trimethylmethyl-10-phenylacridine-10-onthium tetrafluoroborate, and the molar ratio of the catalyst to the disulfide compound is 0.01 to 0.1:1, preferably 0.02:

1.

6. A 1-mercapto-3-alkylbicyclo[] according to claim 2 1.1.1] A method for synthesizing pentane, characterized in that... The additive is any one of diisopropylethylamine, triethylamine, and sodium bicarbonate, and the molar ratio of the additive to the disulfide compound is 0.5 to 3:1, preferably 2:

1.

7. A 1-mercapto-3-alkylbicyclo[] according to claim 2 1.1.1] A method for synthesizing pentane, characterized in that... The reaction time is 8 to 24 hours, preferably 12 to 18 hours, and the reaction temperature is room temperature.

8. A 1-mercapto-3-alkylbicyclo[] according to claim 2 1.1.1] A method for synthesizing pentane, characterized in that... The reaction atmosphere is nitrogen.

9. A 1-mercapto-3-alkylbicyclo[] according to claim 2 1.1.1] A method for synthesizing pentane, characterized in that... After the reaction is complete, the following post-processing steps are also included: after the reaction is complete, saturated ammonium chloride aqueous solution is added to quench the reaction, ethyl acetate organic solvent is added to extract and separate the layers, the organic layer is dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered and concentrated to obtain a brown or yellow crude product, the crude product is purified by column chromatography to obtain 1-mercapto-3-alkylbicyclo[1.1.1]pentane.

10. A 1-mercapto-3-alkylbicyclo[] according to claim 9 1.1.1] A method for synthesizing pentane, characterized in that... The elution solvent used for column chromatography purification is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:50-500, preferably 1:50-200.

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