A process for the synthesis of perfluoroalkylated-thioalkylbenzenes

Abstract

The application discloses a synthesis method of perfluoroalkylated-benzene sulfide alkane, and relates to the technical field of organic synthesis; the method comprises the following steps: S1, mixing olefins, perfluoroalkyl iodide, aryl sulfonic sulfonate, an additive and dimethyl sulfoxide solvent in a reaction container; S2, continuously stirring the reaction under light for 4-8 hours at room temperature in a nitrogen atmosphere; S3, after the reaction is completed, washing with water, then extracting with ethyl acetate, drying, removing the solvent through reduced pressure distillation and concentration, and separating the crude product through column chromatography to obtain perfluoroalkylated-benzene sulfide alkane product; the synthesis method is simple and efficient, raw materials are cheap and easy to obtain, operation is simple, the method is suitable for a wide range of applications, and is green and environment-friendly.

Description

Technical Field

[0001] This application relates to the field of organic synthesis technology, and in particular to a method for synthesizing perfluoroalkylated-benzenesulfurized alkanes. Background Technology

[0002] Due to the small atomic radius and high electronegativity of fluorine atoms, the CF bond formed between fluorine and carbon atoms possesses strong bond energy and chemical stability. Introducing fluorine or fluorine-containing groups into organic molecules can alter the physicochemical properties of the parent compound, such as increased metabolic stability, increased lipid solubility, enhanced cell membrane permeability, and changes in intramolecular or intermolecular forces. These properties have led to the widespread application of fluorinated organic compounds in materials, pharmaceuticals, and pesticides. According to reports, over 20% of pharmaceuticals and 30% of agrochemicals contain at least one fluorine source. Popular fluorinated drugs include the antidepressant fluoxetine (Prozac), the cholesterol-lowering drug atorvastatin (Lipitor), and the antibacterial ciprofloxacin (Ciprobay). Despite the importance of fluorinated organic molecules, naturally occurring fluorinated organic compounds are very rare. In recent years, the introduction of fluorine atoms and the construction of new CF bonds have gradually become a major research hotspot, with research on fluorination-related processes such as monofluorination, polyfluorination, fluoroalkylation, and trifluoromethoxylation reaching new heights. Despite the increasing number of reported new methods, developing more efficient, green, and concise synthetic methodologies for selectively introducing fluorine atoms or fluorine-containing groups into organic molecules remains a significant challenge and opportunity, and is currently one of the important directions in organofluorine chemistry research. Furthermore, CS bonds are widely present in natural products, pharmaceuticals, pesticides, and functional materials. Undoubtedly, simultaneously introducing perfluoroalkyl and sulfide groups into organic molecules will further broaden their application potential in medicinal chemistry, agricultural chemistry, and materials chemistry.

[0003] Dilman developed a photoredox / copper-catalyzed radical bifunctionalization of olefins with fluorinated halides and thiolate anions, involving a classical redox-neutral process in which electrophiles and nucleophiles are successively introduced into the C-C double bond. Compared to redox-neutral strategies, the reductive or oxidative bifunctionalization of olefins by using two different nucleophiles or electrophiles is relatively limited. In this context, Song et al. reported a copper / B2pin2 system-catalyzed reductive thiofluoroalkylation of aryl olefins with two electrophilic reactants (BrCF2CO2Et and thiosulfonate). Song also described a photoinduced Ir-catalyzed thiotrifluoromethylation of terminal olefins with CF3SO2Na and benzenesulfonate via a reductive quenching cycle. While these methods are useful, they all require metal catalysts, and stringent metal catalyst residue standards limit their further application in the pharmaceutical industry. Therefore, the continued development of a simpler, more environmentally friendly, and metal-free perfluoroalkylation-sulfurization method for olefins remains of great importance. [References: Müller K, Faeh C, Diederich F. Science, 2007, 317, 1881; Purser S, Moore PR, Swallow S, et al. Chemical Society Reviews, 2008, 37, 320.; Preshlock S, Tredwell M, Gouverneur V. Chemical Reviews, 2016, 116, 719; Wang J, Sanchez-Rosello M, del Pozo C, et al. Chemical Reviews, 2014, 114, 2432; Bégué JP, Bonnet-Delpon D. Journal of Fluorine Chemistry, 2006, 127, 992; Kirk K L. Journal of FluorineChemistry, 2006, 127, 1013; Wong DT, Bymaster FP, Engleman E A. LifeScience, 1995, 57, 411; Roth, BD In Progress in Medicinal Chemistry, Vol.40, Eds.: King FD, Oxford AW, Elsevier, Amsterdam, 2002, pp. 1~22; DrlicaK, Malik M.Current Topics in Medicinal Chemistry, 2003, 3, 249; Xu XH,Matsuzaki K, Shibata N. Chemical Reviews, 2015, 115, 731; Ni C, Hu M, Hu J. Chemistry, 2023, 88, 6252; Kong W, Yu C, An H, Song Q.Organic Letters, 2018, 20, 4975; Kong W, An H, Song Q. ChemicalCommunications, 2017, 53, 8968]. . Summary of the Invention

[0004] The purpose of this application is to provide a method for synthesizing perfluoroalkylated-benzenesulfurized alkanes to solve at least one of the above-mentioned technical problems.

[0005] To address the aforementioned technical problems, this application provides a method for synthesizing perfluoroalkylated-benzenesulfurized alkanes, comprising the following steps:

[0006] S1. Place the olefin, perfluoroalkyl iodide, aryl sulfonate, additive, and dimethyl sulfoxide solvent into a reaction vessel and mix.

[0007] S2. Under a nitrogen atmosphere, at room temperature and under light, the reaction is continuously stirred for 4-8 hours.

[0008] S3. After the reaction is complete, wash with water, then extract with ethyl acetate, dry, concentrate under reduced pressure to remove solvent, and separate the crude product by column chromatography to obtain perfluoroalkylated-benzenesulfurized alkane products.

[0009] Preferably, the perfluoroalkylated-benzenesulfurized alkane product has the following structural formula:

[0010]

[0011] In the structural formula of the perfluoroalkylated-benzenesulfurized alkane product, R is one of benzyl, 1-pentyl, cyclohexyl, and pyrrolidone; Ar is one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-naphthyl, and 2-thiophene. f It is C3F7, C4F9, C5F 11 C6F13 C8F 17 One of CF2CO2Et;

[0012] The aromatic sulfonyl sulfonate has the following structural formula:

[0013] Ar is one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-naphthyl, and 2-thiophene.

[0014] Preferably, the olefin is selected from styrene, 1-octene, cyclohexylethylene, and N-vinylpyrrolidone.

[0015] Preferably, the perfluoroalkyl iodide is selected from C3F7I, C4F9I, and C5F... 11 I, C6F 13 I, C8F 17 I. One of ICF2CO2Et.

[0016] Preferably, the aromatic sulfonate is selected from one of S-benzenesulfonate, S-(p-tolyl)4-methylbenzenesulfonate, S-(p-methoxyphenyl)4-methoxybenzenesulfonate, S-(p-tert-butylphenyl)4-tert-butylbenzenesulfonate, S-(p-methoxyphenyl)4-methoxybenzenesulfonate, S-(naphthyl-2-yl)naphthyl-2-sulfonate, and S-(thiophene-2-yl)thiophene-2-sulfonate.

[0017] Preferably, the additive is selected from one of triethylamine, N,N-diisopropylethylamine, N,N,N',N'-tetramethylethylenediamine, and triethylenediamine.

[0018] Preferably, in step S2, the irradiation light selected under illumination conditions includes one of blue light, white light, and sunlight with a wavelength of 450-460 nm.

[0019] Preferably, the molar ratio between the olefin, perfluoroalkyl iodide, aryl sulfonate, and additive is 1: [1~2]: [1~3]: [1~2].

[0020] Preferably, the concentration of the reaction system of the olefin, perfluoroalkyl iodide, aromatic sulfonate, and additive is 1~2M.

[0021] Compared with the prior art, the beneficial effects of this application are as follows: This application provides a metal-free catalytic method for the highly selective and rapid bifunctionalization of olefins with perfluoroalkyl iodides and aromatic sulfonates to prepare perfluoroalkylated-benzenesulfonated alkanes, which includes at least the following beneficial effects:

[0022] (1) The raw materials are cheap and readily available, and the reaction system is simple and mild. The technical solution provided in this application only requires the use of commercially available tertiary amines that are easy to store, stable in properties, and cheap and readily available as additives, without the need for additional photocatalysts or metals.

[0023] (2) The reaction is simple to operate, has a wide range of substrates, and is green and environmentally friendly; the reaction can be completed using sunlight, which is clean and environmentally friendly.

[0024] (3) No lengthy reaction process is required; the perfluoroalkyl radical R is generated by activating perfluoroalkyl iodides under visible light induction using an electron donor-acceptor (EDA) strategy. f It then undergoes a free radical addition reaction with an olefin to generate a new alkyl radical A, which is subsequently reduced to generate intermediate B. Finally, it undergoes a nucleophilic substitution reaction with an aryl sulfonate to obtain the target product, perfluoroalkylated-benzenesulfonated alkane (TM).

[0025] (4) Good regional chemical selectivity; high yield of target product and low amount of isomers formed. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a schematic diagram of the reaction for preparing perfluoroalkylated-benzenesulfurized alkanes according to one embodiment of this application. Detailed Implementation

[0028] The present invention will be further illustrated by the following examples. These examples are for illustrative purposes only and are not intended to limit the invention in any way. All parameters and descriptions in the examples, unless otherwise stated, are based on quality. Test methods not specifically described in the examples are generally performed under conventional conditions or as recommended by the manufacturer.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be used in the methods of this invention.

[0030] To further understand the invention's content, features, and effects, the following embodiments are provided:

[0031] This application provides a method for synthesizing perfluoroalkylated-phenylsulfide alkanes, comprising the following steps:

[0032] S1. Place the olefin, perfluoroalkyl iodide, aryl sulfonate, additive, and dimethyl sulfoxide solvent into a reaction vessel and mix.

[0033] S2. Under a nitrogen atmosphere, at room temperature and under light, the reaction is continuously stirred for 4-8 hours.

[0034] S3. After the reaction is complete, wash with water, then extract with ethyl acetate, dry, concentrate under reduced pressure to remove solvent, and separate the crude product by column chromatography to obtain perfluoroalkylated-benzenesulfurized alkane products.

[0035] In one embodiment, the perfluoroalkylated-phenylsulfide alkane product has the following structural formula:

[0036]

[0037] In the structural formula of the perfluoroalkylated-benzenesulfurized alkane product, R is one of benzyl, 1-pentyl, cyclohexyl, or pyrrolidone; Ar is one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-naphthyl, or 2-thiophene. f It is C3F7, C4F9, C5F 11 C6F 13 C8F 17 One of CF2CO2Et.

[0038] In one embodiment, the olefin is selected from styrene, 1-octene, cyclohexylethylene, and N-vinylpyrrolidone.

[0039] In one embodiment, the perfluoroalkyl iodide is selected from C3F7I, C4F9I, and C5F. 11 I, C6F 13 I, C8F 17 I. One of ICF2CO2Et.

[0040] In one embodiment, the aromatic sulfonate is selected from one of S-benzenesulfonate, S-(p-tolyl)4-methylbenzenesulfonate, S-(p-methoxyphenyl)4-methoxybenzenesulfonate, S-(p-tert-butylphenyl)4-tert-butylbenzenesulfonate, S-(p-methoxyphenyl)4-methoxybenzenesulfonate, S-(naphthyl-2-yl)naphthyl-2-sulfonate, and S-(thiophene-2-yl)thiophene-2-sulfonate.

[0041] In one embodiment, the additive is selected from triethylamine, N,N-diisopropylethylamine, N,N,N',N'-tetramethylethylenediamine, and triethylenediamine.

[0042] In one embodiment, in step S2, the irradiation light selected under illumination conditions includes one of blue light, white light, and sunlight with a wavelength of 450-460 nm.

[0043] In one embodiment, the molar ratio between the olefin, perfluoroalkyl iodide, aryl sulfonate, and additive is 1: [1~2]: [1~3]: [1~2].

[0044] In one embodiment, the concentration of the reaction system of olefin, perfluoroalkyl iodide, aryl sulfonate, and additive is 1-2 M.

[0045] Example 1

[0046] Synthesis of 3-phenyl-2-phenylthio-1-perfluoropropylpropane.

[0047] 0.2 mmol styrene, 0.3 mmol perfluoroiodopropane, 0.4 mmol S-benzenesulfonate, and 0.4 mmol triethylamine were added to a reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under nitrogen atmosphere at room temperature and under sunlight irradiation for 6 h with continuous stirring. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 60% yield. 1 H NMR (400 MHz, CDCl3): d 7.29–7.27 (m, 2H), 7.23–7.19 (m, 5H), 7.16–7.12 (m, 3H), 3.60–3.53 (m, 1H), 3.05–3.00 (m, 1H), 2.81–2.76 (m, 1H), 2.34–2.23 (m, 2H). 13 C{ 1 H NMR (101 MHz, CDCl3): d 137.6, 133.27, 133.23, 129.3, 129.1, 128.4, 128.0, 126.9, 122.2–119.2(m), 44.7, 41.4 (d, J = 2.7 Hz), 33.01 (d, J = 18.7 Hz).

[0048] Example 2

[0049] Synthesis of 3-phenyl-2-phenylthio-1-perfluorobutylpropane.

[0050] 0.2 mmol styrene, 0.3 mmol perfluoroiodobutane, 0.4 mmol S-benzenesulfonate, and 0.4 mmol N,N-diisopropylethylamine were added to a reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under a nitrogen atmosphere at room temperature and under blue light irradiation at 450–460 nm, with continuous stirring for 5 h. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 64% yield. 1 HNMR (400 MHz, CDCl3): d 7.36 (d, J = 7.5 Hz, 2H), 7.33–7.24 (m, 6H), 7.21 (d, J =7.8 Hz, 2H), 3.74–3.67 (m, 1H), 3.11 (dd, J = 14.4, 5.8 Hz, 1H), 2.94 (dd, J =14.4, 7.8 Hz, 1H), 2.43–2.32 (m, 2H). 13 C{ 1 ¹H NMR (101 MHz, CDCl₃): d 137.6,133.4, 132.6, 129.3, 129.1, 128.4, 127.7, 126.9, 42.7, 41.0, 34.8 (t, J = 21.0Hz), 13 C-NMR for CF2CF2CF2CF3could not be assigned.

[0051] Example 3

[0052] Synthesis of 2-phenylthio-1-perfluorobutyloctane.

[0053] 0.2 mmol 1-octene, 0.3 mmol perfluoroiodobutane, 0.4 mmol S-benzenesulfonylbenzenesulfonate, and 0.4 mmol N,N-diisopropylethylamine were added to the reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under nitrogen atmosphere at room temperature and under white light irradiation for 5 h with continuous stirring. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 60% yield. 1 H NMR (400MHz, CDCl3): d7.41 (d, J = 7.5 Hz, 2H), 7.34–7.27 (m, 3H), 3.49–3.43 (m, 1H), 2.51–2.21 (m, 2H), 1.85–1.76 (m, 1H), 1.67–1.59 (m, 2H), 1.53–1.50 (m, 1H),1.34–1.29 (m, 6H), 0.89 (t, J = 6.4 Hz, 3H). 13 C{ 1 ¹H NMR (101 MHz, CDCl₃): d 133.6,132.6, 129.1, 127.6, 41.5 (d, J = 1.3 Hz), 35.8 (t, J = 20.8 Hz), 34.5 (d, J = 2.2Hz), 31.6, 28.9, 26.3, 22.5, 14.0, 13 C-NMR for CF2CF2CF2CF3could not beassigned.

[0054] Example 4

[0055] Synthesis of 2-cyclohexyl-2-phenylthio-1-perfluorobutylethane.

[0056] 0.2 mmol cyclohexylethylene, 0.3 mmol perfluoroiodobutane, 0.4 mmol S-benzenesulfonate, and 0.4 mmol N,N-diisopropylethylamine were added to a reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under a nitrogen atmosphere at room temperature and under blue light irradiation at 450–460 nm for 6 h with continuous stirring. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 65% yield. 1 H NMR (400 MHz, CDCl3): d 7.44 (d, J = 7.5 Hz, 2H), 7.35–7.27 (m, 3H), 3.46–3.42(m, 1H), 2.60–2.29 (m, 2H), 1.84–1.70 (m, 6H), 1.51–1.42 (m, 1H), 1.31–1.18(m, 4H). 13 C{ 1¹H NMR (101 MHz, CDCl₃): d 135.1, 131.9, 129.1, 127.2, 48.2, 41.8,33.40 (t, J = 21.0 Hz), 30.4, 28.3, 26.34, 26.30, 26.2, 13 C-NMR forCF2CF2CF2CF3could not be assigned.

[0057] Example 5

[0058] Synthesis of 2-pyrrolidone-2-phenylthio-1-perfluorobutylethane

[0059] 0.2 mmol N-vinylpyrrolidone, 0.3 mmol perfluoroiodobutane, 0.4 mmol S-benzenesulfonate, and 0.4 mmol N,N-diisopropylethylamine were added to a reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under a nitrogen atmosphere at room temperature and under blue light irradiation at 450–460 nm, with continuous stirring for 6 h. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 66% yield. 1 H NMR (400 MHz, CDCl3): d 7.44–7.42 (m, 2H), 7.29–7.27 (m, 3H), 6.12–6.09 (m, 1H), 3.56–3.50 (m, 1H), 3.28–3.22 (m, 1H), 2.72–2.46 (m, 2H), 2.27–2.19 (m, 1H), 2.07–1.99 (m, 1H), 1.94–1.87 (m, 1H), 1.82–173 (m, 1H). 13 C{ 1 ¹H NMR (101 MHz, CDCl₃): d 174.6, 133.3, 130.8, 129.0, 128.5, 52.5 (d, J = 3.5 Hz), 41.6, 32.3 (t, J = 21.4 Hz), 30.7, 17.7, 13 C-NMR for CF2CF2CF2CF3could not beassigned.

[0060] Example 6

[0061] Synthesis of 2-pyrrolidone-2-p-toluenethio-1-perfluorobutylethane.

[0062] 0.2 mmol N-vinylpyrrolidone, 0.3 mmol perfluoroiodobutane, 0.5 mmol S-(p-tolyl)-4-methylbenzenesulfonate, and 0.4 mmol N,N-diisopropylethylamine were added to a reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under a nitrogen atmosphere at room temperature and under blue light irradiation at 450–460 nm for 6 h with continuous stirring. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 61% yield. 1 H NMR (400 MHz, CDCl3): d 7.34 (d, J = 7.6 Hz, 2H), 7.11(d, J = 7.6 Hz, 2H), 6.06–6.03 (m, 1H), 3.59–3.54 (m, 1H), 3.29–3.23 (m, 1H), 2.71–2.46 (m, 2H), 2.31 (s, 3H), 2.29–2.21 (m, 1H), 2.10–2.02 (m, 1H), 1.98–1.81 (m, 2H). 13 C{ 1 ¹H NMR (101 MHz, CDCl₃): d 174.6, 139.0, 133.8, 129.9, 127.1,52.8 (d, J = 3.6 Hz), 41.6, 32.2 (t, J = 21.2 Hz), 30.8, 21.1, 17.8, 13 C-NMR forCF2CF2CF2CF3could not be assigned.

[0063] Example 7

[0064] Synthesis of 3-phenyl-2-(thiophene-2-thio)-1-perfluorobutylpropane.

[0065] 0.2 mmol styrene, 0.3 mmol perfluoroiodobutane, 0.4 mmol S-(thiophene-2-yl)thiophene-2-sulfonylsulfonate, and 0.4 mmol triethylamine were added to a reactor, followed by 1 mL of dimethyl sulfoxide solvent. The reaction was carried out under nitrogen atmosphere at room temperature and under sunlight irradiation for 6 h with continuous stirring. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 40% yield. 1 H NMR (400 MHz, CDCl3): d 7.50 (d, J = 5.3 Hz, 1H), 7.41–7.37 (m, 2H), 7.33 (d, J = 7.2Hz, 1H), 7.29–7.27 (m, 2H), 7.21–7.20 (m, 1H), 7.10–7.07 (m, 1H), 3.54–3.47(m, 1H), 3.11–3.00 (m, 2H), 2.58–2.28 (m, 2H). 13 C{ 1 ¹H NMR (101 MHz, CDCl₃): d 137.6, 136.5, 131.2, 130.2, 129.3, 128.5, 127.8, 126.9, 44.6, 40.9, 34.4 (t, J = 20.9 Hz), 13 C-NMR for CF2CF2CF2CF3could not be assigned.

[0066] Example 8

[0067] Synthesis of 3-phenyl-2-phenylthio-1-difluoroethyl ethyl propane.

[0068] 0.2 mmol styrene, 0.3 mmol ethyl difluoroiodoacetate, 0.4 mmol S-benzenesulfonate, and 0.4 mmol triethylamine were added to a reactor, followed by 1 mL dimethyl sulfoxide solvent. The reaction was carried out under nitrogen atmosphere, at room temperature and under sunlight irradiation, with continuous stirring for 6 h. After the reaction was completed, the product was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product in 55% yield. 1 H NMR (400 MHz, CDCl3): d7.45–7.42 (m, 2H), 7.37–7.27 (m, 6H), 7.22–7.20 (m, 2H), 4.32 (q, J =7.2 Hz, 2H), 3.59–3.52 (m, 1H), 3.05–2.94 (m, 2H), 2.49–2.39 (m, 2H), 1.34(t, J = 7.2 Hz, 3H). 13 C{ 1 ¹H NMR (101 MHz, CDCl₃): d 164.05 (t, J = 32.5 Hz), 137.9,133.8, 132.8, 129.4, 129.2, 128.5, 127.8, 126.9, 115.52 (dd, J = 252.3, 249.9Hz), 63.1, 44.1 (d, J =2.9 Hz), 41.8, 38.5 (t, J = 23.6 Hz), 13.9.

[0069] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other.

[0070] The above description is merely a preferred embodiment of this application and is not intended to limit this application in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of this application shall fall within the scope of the technical solution of this application.

Claims

1. A method for synthesizing perfluoroalkylated-phenylsulfide alkanes, characterized in that: Includes the following steps: S1. Place the olefin, perfluoroalkyl iodide, aryl sulfonate, additive, and dimethyl sulfoxide solvent into a reaction vessel and mix. S2. Under a nitrogen atmosphere, at room temperature and under light, the reaction is continuously stirred for 4-8 hours. S3. After the reaction is complete, wash with water, then extract with ethyl acetate, dry, concentrate under reduced pressure to remove solvent, and separate the crude product by column chromatography to obtain perfluoroalkylated-benzenesulfurized alkane product. The perfluoroalkylated-phenylsulfide alkane product has the following structural formula: ； In the structural formula of the perfluoroalkylated-benzenesulfurized alkane product, R is one of benzyl, 1-pentyl, cyclohexyl, and pyrrolidone; Ar is one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-naphthyl, and 2-thiophene. f It is C3F7, C4F9, C5F 11 C6F 13 C8F 17 One of CF2CO2Et; The aromatic sulfonyl sulfonate has the following structural formula: Ar is one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 2-naphthyl, and 2-thiophene. The additive is selected from one of triethylamine, N,N-diisopropylethylamine, N,N,N',N'-tetramethylethylenediamine, and triethylenediamine.

2. The method for synthesizing perfluoroalkylated-benzenesulfide alkanes according to claim 1, characterized in that: The olefin is selected from one of phenylpropene, 1-octene, cyclohexylethylene, and N-vinylpyrrolidone.

3. The method for synthesizing perfluoroalkylated-benzenesulfide alkanes according to claim 1, characterized in that: The perfluoroalkyl iodide is selected from C3F7I, C4F9I, and C5F. 11 I, C6F 13 I, C8F 17 I. One of ICF2CO2Et.

4. The method for synthesizing perfluoroalkylated-phenylsulfide alkanes according to claim 1, characterized in that: The aromatic sulfonate is selected from one of S-benzenesulfonate, S-(p-tolyl)4-methylbenzenesulfonate, S-(p-methoxyphenyl)4-methoxybenzenesulfonate, S-(p-tert-butylphenyl)4-tert-butylbenzenesulfonate, S-(p-methoxyphenyl)4-methoxybenzenesulfonate, S-(naphthyl-2-yl)naphthyl-2-sulfonate, and S-(thiophene-2-yl)thiophene-2-sulfonate.

5. The method for synthesizing perfluoroalkylated-benzenesulfide alkanes according to claim 1, characterized in that: In step S2, the illumination light selected under illumination conditions includes one of blue light, white light, or sunlight with a wavelength of 450-460 nm.

6. The method for synthesizing perfluoroalkylated-benzenesulfide alkanes according to claim 1, characterized in that: The molar ratio between the olefin, perfluoroalkyl iodide, aryl sulfonate, and additive is 1: [1~2]: [1~3]: [1~2].

7. The method for synthesizing perfluoroalkylated-phenylsulfide alkanes according to claim 1, characterized in that: The reaction system of olefins, perfluoroalkyl iodides, aromatic sulfonates, and additives has a concentration of 1-2 M.

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